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CHEMISTRY
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Flowers, Theopold and Langley

Chemistry (OpenStax)
Flowers, Theopold and Langley

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TABLE OF CONTENTS
Licensing
1: Essential Ideas
1.1: Introduction
1.2: Chemistry in Context
1.3: Phases and Classi cation of Matter
1.4: Physical and Chemical Properties
1.5: Measurements
1.6: Measurement Uncertainty, Accuracy, and Precision
1.7: Mathematical Treatment of Measurement Results
1.8: Key Terms
1.9: Key Equations
1.10: Summary
1.11: Exercises
2: Atoms, Molecules, and Ions

2.1: Introduction
2.2: Early Ideas in Atomic Theory
2.3: Evolution of Atomic Theory
2.4: Atomic Structure and Symbolism
2.5: Chemical Formulas
2.6: The Periodic Table
2.7: Molecular and Ionic Compounds
2.8: Chemical Nomenclature
2.9: Key Terms
2.10: Key Equations
2.11: Summary
2.12: Exercises
3: Composition of Substances and Solutions

3.1: Introduction
3.2: Formula Mass and the Mole Concept
3.3: Determining Empirical and Molecular Formulas
3.4: Molarity
3.5: Other Units for Solution Concentrations
3.6: Key Terms
3.7: Key Equations
3.8: Summary
3.9: Exercises
4: Stoichiometry of Chemical Reactions

4.1: Introduction
4.2: Writing and Balancing Chemical Equations
4.3: Classifying Chemical Reactions
4.4: Reaction Stoichiometry
4.5: Reaction Yields
1 https://chem.libretexts.org/@go/page/414775
4.6: Quantitative Chemical Analysis
4.7: Key Terms
4.8: Key Equations
4.9: Summary
4.10: Exercises
5: Thermochemistry
5.1: Introduction
5.2: Energy Basics
5.3: Calorimetry
5.4: Enthalpy
5.5: Key Terms
5.6: Key Equations
5.7: Summary
5.8: Exercises
6: Electronic Structure and Periodic Properties

6.1: Introduction
6.2: Electromagnetic Energy
6.3: The Bohr Model
6.4: Development of Quantum Theory
6.5: Electronic Structure of Atoms (Electron Con gurations)
6.6: Periodic Variations in Element Properties
6.7: Key Terms
6.8: Key Equations
6.9: Summary
6.10: Exercises
7: Chemical Bonding and Molecular Geometry

7.1: Introduction
7.2: Ionic Bonding
7.3: Covalent Bonding
7.4: Lewis Symbols and Structures
7.5: Formal Charges and Resonance
7.6: Strengths of Ionic and Covalent Bonds
7.7: Molecular Structure and Polarity
7.8: Key Terms
7.9: Key Equations
7.10: Summary
7.11: Exercises
8: Advanced Theories of Covalent Bonding

8.1: Introduction
8.2: Valence Bond Theory
8.3: Hybrid Atomic Orbitals
8.4: Multiple Bonds
8.5: Molecular Orbital Theory
8.6: Key Terms
8.7: Key Equations
8.8: Summary
8.9: Exercises
9: Gases
9.1: Introduction
9.2: Gas Pressure
9.3: Relating Pressure, Volume, Amount, and Temperature - The Ideal Gas Law
9.4: Stoichiometry of Gaseous Substances, Mixtures, and Reactions
9.5: Effusion and Diffusion of Gases
9.6: The Kinetic-Molecular Theory
9.7: Non-Ideal Gas Behavior
9.8: Key Terms
9.9: Key Equations
9.10: Summary
9.11: Exercises
10: Liquids and Solids

10.1: Introduction
10.2: Intermolecular Forces
10.3: Properties of Liquids
10.4: Phase Transitions
10.5: Phase Diagrams
10.6: The Solid State of Matter
10.7: Lattice Structures in Crystalline Solids
10.8: Key Terms
10.9: Key Equations
10.10: Summary
10.11: Exercises
11: Solutions and Colloids

11.1: Introduction
11.2: The Dissolution Process
11.3: Electrolytes
11.4: Solubility
11.5: Colligative Properties
11.6: Colloids
11.7: Key Terms
11.8: Key Equations
11.9: Summary
11.10: Exercises
12: Kinetics
12.1: Introduction
12.2: Chemical Reaction Rates
12.3: Factors Affecting Reaction Rates
12.4: Rate Laws
12.5: Integrated Rate Laws
12.6: Collision Theory
12.7: Reaction Mechanisms
12.8: Catalysis
12.9: Key Terms
12.10: Key Equations
12.11: Summary
12.12: Exercises
13: Fundamental Equilibrium Concepts

13.1: Introduction
13.2: Chemical Equilibria
13.3: Equilibrium Constants
13.4: Shifting Equilibria- Le Châtelier’s Principle
13.5: Equilibrium Calculations
13.6: Key Terms
13.7: Key Equations
13.8: Summary
13.9: Exercises
14: Acid-Base Equilibria

14.1: Introduction
14.2: Brønsted-Lowry Acids and Bases
14.3: pH and pOH
14.4: Relative Strengths of Acids and Bases
14.5: Hydrolysis of Salt Solutions
14.6: Polyprotic Acids
14.7: Buffers
14.8: Acid-Base Titrations
14.9: Key Terms
14.11: Summary
14.12: Exercises
15: Equilibria of Other Reaction Classes

15.1: Introduction
15.2: Precipitation and Dissolution
15.3: Lewis Acids and Bases
15.4: Coupled Equilibria
15.5: Key Terms
15.6: Key Equations
15.7: Summary
15.8: Exercises
16: Thermodynamics
16.1: Introduction
16.2: Spontaneity
16.3: Entropy
16.4: The Second and Third Laws of Thermodynamics
16.5: Free Energy
16.6: Key Terms
16.7: Key Equations
16.8: Summary
16.9: Exercises
17: Electrochemistry
17.1: Introduction
17.2: Review of Redox Chemistry
17.3: Galvanic Cells
17.4: Electrode and Cell Potentials
17.5: Potential, Free Energy, and Equilibrium
17.6: Batteries and Fuel Cells
17.7: Corrosion
17.8: Electrolysis
17.9: Key Terms
17.11: Summary
17.12: Exercises
18: Representative Metals, Metalloids, and Nonmetals

18.1: Introduction
18.2: Periodicity
18.3: Occurrence and Preparation of the Representative Metals
18.4: Structure and General Properties of the Metalloids
18.5: Structure and General Properties of the Nonmetals
18.6: Occurrence, Preparation, and Compounds of Hydrogen
18.7: Occurrence, Preparation, and Properties of Carbonates
18.8: Occurrence, Preparation, and Properties of Nitrogen
18.9: Occurrence, Preparation, and Properties of Phosphorus
18.10: Occurrence, Preparation, and Compounds of Oxygen
18.11: Occurrence, Preparation, and Properties of Sulfur
18.12: Occurrence, Preparation, and Properties of Halogens
18.13: Occurrence, Preparation, and Properties of the Noble Gases
18.14: Key Terms
18.15: Summary
18.16: Exercises
19: Transition Metals and Coordination Chemistry

19.1: Introduction
19.2: Occurrence, Preparation, and Properties of Transition Metals and Their Compounds
19.3: Coordination Chemistry of Transition Metals
19.4: Spectroscopic and Magnetic Properties of Coordination Compounds
19.5: Key Terms
19.6: Summary
19.7: Exercises
20: Organic Chemistry

20.1: Introduction
20.2: Hydrocarbons
20.3: Alcohols and Ethers
20.4: Aldehydes, Ketones, Carboxylic Acids, and Esters
20.5: Amines and Amides
20.6: Key Terms
20.7: Summary
20.8: Exercises
21: Nuclear Chemistry
21.1: Introduction
21.2: Nuclear Structure and Stability
21.3: Nuclear Equations
21.4: Radioactive Decay
21.5: Transmutation and Nuclear Energy
21.6: Uses of Radioisotopes
21.7: Biological Effects of Radiation
21.8: Key Terms
21.9: Key Equations
21.10: Summary
21.11: Exercises
22: Appendices
22.2: Essential Mathematics
22.3: Units and Conversion Factors
22.4: Fundamental Physical Constants
22.5: Water Properties
22.6: Composition of Commercial Acids and Bases
22.7: Standard Thermodynamic Properties for Selected Substances
22.8: Ionization Constants of Weak Acids
22.9: Ionization Constants of Weak Bases
22.10: Solubility Products
22.11: Formation Constants for Complex Ions
22.12: Standard Electrode (Half-Cell) Potentials
22.13: Half-Lives for Several Radioactive Isotopes
22.14: Answer Key
22.14.1: Chapter 1
22.14.2: Chapter 2
22.14.3: Chapter 3
22.14.4: Chapter 4
22.14.5: Chapter 5
22.14.6: Chapter 6
22.14.7: Chapter 7
22.14.8: Chapter 8
22.14.9: Chapter 9
22.14.10: Chapter 10
22.14.11: Chapter 11
22.14.12: Chapter 12
22.14.13: Chapter 13
22.14.14: Chapter 14
22.14.15: Chapter 15
22.14.16: Chapter 16
22.14.17: Chapter 17
22.14.18: Chapter 18
22.14.19: Chapter 19
22.14.20: Chapter 20
22.14.21: Chapter 21
Index
Glossary
Detailed Licensing
Detailed Licensing
Licensing
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CHAPTER OVERVIEW
1: Essential Ideas
A general chemistry Libretexts Textbook remixed and remastered from

OpenStax's textbook:
General Chemistry
Most everything you do and encounter during your day involves chemistry. Making coffee, cooking eggs, and toasting bread
involve chemistry. The products you use—like soap and shampoo, the fabrics you wear, the electronics that keep you connected to
your world, the gasoline that propels your car—all of these and more involve chemical substances and processes. Whether you are
aware or not, chemistry is part of your everyday world. In this course, you will learn many of the essential principles underlying the
chemistry of modern-day life.
1.1: Introduction
1.3: Phases and Classification of Matter
1.5: Measurements
1.8: Key Terms
1.9: Key Equations
1.10: Summary
1.11: Exercises
This page titled 1: Essential Ideas is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content
that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request.
1
1.1: Introduction
Figure 1.1 Chemical substances and processes are essential for our existence, providing sustenance, keeping us clean and healthy,
fabricating electronic devices, enabling transportation, and much more. (credit “left”: modification of work by “vxla”/Flickr; credit
“left middle”: modification of work by “the Italian voice”/Flickr; credit “right middle”: modification of work by Jason Trim; credit
“right”: modification of work by “gosheshe”/Flickr)
Chapter Outline
1.1 Chemistry in Context
1.2 Phases and Classification of Matter
1.3 Physical and Chemical Properties
1.4 Measurements
1.5 Measurement Uncertainty, Accuracy, and Precision
1.6 Mathematical Treatment of Measurement Results
Your alarm goes off and, after hitting “snooze” once or twice, you pry yourself out of bed. You make a cup of coffee to help you
get going, and then you shower, get dressed, eat breakfast, and check your phone for messages. On your way to school, you stop to
fill your car’s gas tank, almost making you late for the first day of chemistry class. As you find a seat in the classroom, you read the
question projected on the screen: “Welcome to class! Why should we study chemistry?”
Do you have an answer? You may be studying chemistry because it fulfills an academic requirement, but if you consider your daily
activities, you might find chemistry interesting for other reasons. Most everything you do and encounter during your day involves
chemistry. Making coffee, cooking eggs, and toasting bread involve chemistry. The products you use—like soap and shampoo, the
fabrics you wear, the electronics that keep you connected to your world, the gasoline that propels your car—all of these and more
involve chemical substances and processes. Whether you are aware or not, chemistry is part of your everyday world. In this course,
you will learn many of the essential principles underlying the chemistry of modern-day life.
1.1: Introduction is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.
1.1.1 https://chem.libretexts.org/@go/page/415138
 Learning Objectives
By the end of this section, you will be able to:

Outline the historical development of chemistry
Provide examples of the importance of chemistry in everyday life
Describe the scientific method
Differentiate among hypotheses, theories, and laws
Provide examples illustrating macroscopic, microscopic, and symbolic domains
Throughout human history, people have tried to convert matter into more useful forms. Our Stone Age ancestors chipped pieces of
flint into useful tools and carved wood into statues and toys. These endeavors involved changing the shape of a substance without
changing the substance itself. But as our knowledge increased, humans began to change the composition of the substances as well
—clay was converted into pottery, hides were cured to make garments, copper ores were transformed into copper tools and
weapons, and grain was made into bread.
Humans began to practice chemistry when they learned to control fire and use it to cook, make pottery, and smelt metals.
Subsequently, they began to separate and use specific components of matter. A variety of drugs such as aloe, myrrh, and opium
were isolated from plants. Dyes, such as indigo and Tyrian purple, were extracted from plant and animal matter. Metals were
combined to form alloys—for example, copper and tin were mixed together to make bronze—and more elaborate smelting
techniques produced iron. Alkalis were extracted from ashes, and soaps were prepared by combining these alkalis with fats.
Alcohol was produced by fermentation and purified by distillation.
Attempts to understand the behavior of matter extend back for more than 2500 years. As early as the sixth century BC, Greek
philosophers discussed a system in which water was the basis of all things. You may have heard of the Greek postulate that matter
consists of four elements: earth, air, fire, and water. Subsequently, an amalgamation of chemical technologies and philosophical
speculations was spread from Egypt, China, and the eastern Mediterranean by alchemists, who endeavored to transform “base
metals” such as lead into “noble metals” like gold, and to create elixirs to cure disease and extend life (Figure 1.2).
Figure 1.2 (a) This portrayal shows an alchemist’s workshop circa 1580. Although alchemy made some useful contributions to how
to manipulate matter, it was not scientific by modern standards. (b) While the equipment used by Alma Levant Hayden in this 1952
picture might not seem as sleek as you might find in a lab today, her approach was highly methodical and carefully recorded. A
department head at the FDA, Hayden is most famous for exposing an aggressively marketed anti-cancer drug as nothing more than
an unhelpful solution of common substances. (credit a: Chemical Heritage Foundation; b: NIH History Office)
From alchemy came the historical progressions that led to modern chemistry: the isolation of drugs from natural sources, such as
plants and animals. But while many of the substances extracted or processed from those natural sources were critical in the
treatment of diseases, many were scarce. For example, progesterone, which is critical to women's health, became available as a
Access for free at OpenStax 1.2.1 https://chem.libretexts.org/@go/page/414594

medicine in 1935, but its animal sources produced extremely small quantities, limiting its availability and increasing its expense.
Likewise, in the 1940s, cortisone came into use to treat arthritis and other disorders and injuries, but it took a 36-step process to
synthesize. Chemist Percy Lavon Julian turned to a more plentiful source: soybeans. Previously, Julian had developed a lab to
isolate soy protein, which was used in firefighting among other applications. He focused on using the soy sterols—substances
mostly used in plant membranes—and was able to quickly produce progesterone and later testosterone and other hormones. He
later developed a process to do the same for cortisone, and laid the groundwork for modern drug design. Since soybeans and
similar plant sources were extremely plentiful, the drugs soon became widely available, saving many lives.
1.2.0.1: Chemistry: The Central Science

Chemistry is sometimes referred to as “the central science” due to its interconnectedness with a vast array of other STEM
disciplines (STEM stands for areas of study in the science, technology, engineering, and math fields). Chemistry and the language
of chemists play vital roles in biology, medicine, materials science, forensics, environmental science, and many other fields (Figure
1.3). The basic principles of physics are essential for understanding many aspects of chemistry, and there is extensive overlap
between many subdisciplines within the two fields, such as chemical physics and nuclear chemistry. Mathematics, computer
science, and information theory provide important tools that help us calculate, interpret, describe, and generally make sense of the
chemical world. Biology and chemistry converge in biochemistry, which is crucial to understanding the many complex factors and
processes that keep living organisms (such as us) alive. Chemical engineering, materials science, and nanotechnology combine
chemical principles and empirical findings to produce useful substances, ranging from gasoline to fabrics to electronics.
Agriculture, food science, veterinary science, and brewing and wine making help provide sustenance in the form of food and drink
to the world’s population. Medicine, pharmacology, biotechnology, and botany identify and produce substances that help keep us
healthy. Environmental science, geology, oceanography, and atmospheric science incorporate many chemical ideas to help us better
understand and protect our physical world. Chemical ideas are used to help understand the universe in astronomy and cosmology.
Figure 1.3 Knowledge of chemistry is central to understanding a wide range of scientific disciplines. This diagram shows just some
of the interrelationships between chemistry and other fields.
What are some changes in matter that are essential to daily life? Digesting and assimilating food, synthesizing polymers that are
used to make clothing, containers, cookware, and credit cards, and refining crude oil into gasoline and other products are just a few
examples. As you proceed through this course, you will discover many different examples of changes in the composition and
structure of matter, how to classify these changes and how they occurred, their causes, the changes in energy that accompany them,
and the principles and laws involved. As you learn about these things, you will be learning chemistry, the study of the composition,
properties, and interactions of matter. The practice of chemistry is not limited to chemistry books or laboratories: It happens
whenever someone is involved in changes in matter or in conditions that may lead to such changes.

1.2.0.1: The Scientific Method
Chemistry is a science based on observation and experimentation. Doing chemistry involves attempting to answer questions and
explain observations in terms of the laws and theories of chemistry, using procedures that are accepted by the scientific community.
There is no single route to answering a question or explaining an observation, but there is an aspect common to every approach:
Each uses knowledge based on experiments that can be reproduced to verify the results. Some routes involve a hypothesis, a
tentative explanation of observations that acts as a guide for gathering and checking information. A hypothesis is tested by
experimentation, calculation, and/or comparison with the experiments of others and then refined as needed.
Some hypotheses are attempts to explain the behavior that is summarized in laws. The laws of science summarize a vast number of
experimental observations, and describe or predict some facet of the natural world. If such a hypothesis turns out to be capable of
explaining a large body of experimental data, it can reach the status of a theory. Scientific theories are well-substantiated,
comprehensive, testable explanations of particular aspects of nature. Theories are accepted because they provide satisfactory
explanations, but they can be modified if new data become available. The path of discovery that leads from question and
observation to law or hypothesis to theory, combined with experimental verification of the hypothesis and any necessary
modification of the theory, is called the scientific method (Figure 1.4).
Figure 1.4 The scientific method follows a process similar to the one shown in this diagram. All the key components are shown, in
roughly the right order. Scientific progress is seldom neat and clean: It requires open inquiry and the reworking of questions and
ideas in response to findings.
1.2.0.1: The Domains of Chemistry

Chemists study and describe the behavior of matter and energy in three different domains: macroscopic, microscopic, and
symbolic. These domains provide different ways of considering and describing chemical behavior.
Macro is a Greek word that means “large.” The macroscopic domain is familiar to us: It is the realm of everyday things that are
large enough to be sensed directly by human sight or touch. In daily life, this includes the food you eat and the breeze you feel on
your face. The macroscopic domain includes everyday and laboratory chemistry, where we observe and measure physical and
chemical properties such as density, solubility, and flammability.
Micro comes from Greek and means “small.” The microscopic domain of chemistry is often visited in the imagination. Some
aspects of the microscopic domain are visible through standard optical microscopes, for example, many biological cells. More

sophisticated instruments are capable of imaging even smaller entities such as molecules and atoms (see Figure 1.5 (b)).
However, most of the subjects in the microscopic domain of chemistry are too small to be seen even with the most advanced
microscopes and may only be pictured in the mind. Other components of the microscopic domain include ions and electrons,
protons and neutrons, and chemical bonds, each of which is far too small to see.
The symbolic domain contains the specialized language used to represent components of the macroscopic and microscopic
domains. Chemical symbols (such as those used in the periodic table), chemical formulas, and chemical equations are part of the
symbolic domain, as are graphs, drawings, and calculations. These symbols play an important role in chemistry because they help
interpret the behavior of the macroscopic domain in terms of the components of the microscopic domain. One of the challenges for
students learning chemistry is recognizing that the same symbols can represent different things in the macroscopic and microscopic
domains, and one of the features that makes chemistry fascinating is the use of a domain that must be imagined to explain behavior
in a domain that can be observed.
A helpful way to understand the three domains is via the essential and ubiquitous substance of water. That water is a liquid at
moderate temperatures, will freeze to form a solid at lower temperatures, and boil to form a gas at higher temperatures (Figure 1.5)
are macroscopic observations. But some properties of water fall into the microscopic domain—what cannot be observed with the
naked eye. The description of water as comprising two hydrogen atoms and one oxygen atom, and the explanation of freezing and
boiling in terms of attractions between these molecules, is within the microscopic arena. The formula H2O, which can describe
water at either the macroscopic or microscopic levels, is an example of the symbolic domain. The abbreviations (g) for gas, (s) for
solid, and (l) for liquid are also symbolic.
Figure 1.5 (a) Moisture in the air, icebergs, and the ocean represent water in the macroscopic domain. (b) At the molecular level
(microscopic domain), gas molecules are far apart and disorganized, solid water molecules are close together and organized, and
liquid molecules are close together and disorganized. (c) The formula H2O symbolizes water, and (g), (s), and (l) symbolize its
phases. Note that clouds are actually comprised of either very small liquid water droplets or solid water crystals; gaseous water in
our atmosphere is not visible to the naked eye, although it may be sensed as humidity. (credit a: modification of work by
“Gorkaazk”/Wikimedia Commons)
This page titled 1.2: Chemistry in Context is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via
source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request.


Describe the basic properties of each physical state of matter: solid, liquid, and gas
Distinguish between mass and weight
Apply the law of conservation of matter
Classify matter as an element, compound, homogeneous mixture, or heterogeneous mixture with regard to its physical state
and composition
Define and give examples of atoms and molecules
Matter is defined as anything that occupies space and has mass, and it is all around us. Solids and liquids are more obviously
matter: We can see that they take up space, and their weight tells us that they have mass. Gases are also matter; if gases did not take
up space, a balloon would not inflate (increase its volume) when filled with gas.
Solids, liquids, and gases are the three states of matter commonly found on earth (Figure 1.6). A solid is rigid and possesses a
definite shape. A liquid flows and takes the shape of its container, except that it forms a flat or slightly curved upper surface when
acted upon by gravity. (In zero gravity, liquids assume a spherical shape.) Both liquid and solid samples have volumes that are very
nearly independent of pressure. A gas takes both the shape and volume of its container.
Figure 1.6 The three most common states or phases of matter are solid, liquid, and gas.
A fourth state of matter, plasma, occurs naturally in the interiors of stars. A plasma is a gaseous state of matter that contains
appreciable numbers of electrically charged particles (Figure 1.7). The presence of these charged particles imparts unique
properties to plasmas that justify their classification as a state of matter distinct from gases. In addition to stars, plasmas are found
in some other high-temperature environments (both natural and man-made), such as lightning strikes, certain television screens,
and specialized analytical instruments used to detect trace amounts of metals.

Figure 1.7 A plasma torch can be used to cut metal. (credit: “Hypertherm”/Wikimedia Commons)
1.3.0.1: Link to Learning

In a tiny cell in a plasma television, the plasma emits ultraviolet light, which in turn causes the display at that location to
appear a specific color. The composite of these tiny dots of color makes up the image that you see. Watch this video to learn
more about plasma and the places you encounter it.
Some samples of matter appear to have properties of solids, liquids, and/or gases at the same time. This can occur when the sample
is composed of many small pieces. For example, we can pour sand as if it were a liquid because it is composed of many small
grains of solid sand. Matter can also have properties of more than one state when it is a mixture, such as with clouds. Clouds appear
to behave somewhat like gases, but they are actually mixtures of air (gas) and tiny particles of water (liquid or solid).
The mass of an object is a measure of the amount of matter in it. One way to measure an object’s mass is to measure the force it
takes to accelerate the object. It takes much more force to accelerate a car than a bicycle because the car has much more mass. A
more common way to determine the mass of an object is to use a balance to compare its mass with a standard mass.
Although weight is related to mass, it is not the same thing. Weight refers to the force that gravity exerts on an object. This force is
directly proportional to the mass of the object. The weight of an object changes as the force of gravity changes, but its mass does
not. An astronaut’s mass does not change just because she goes to the moon. But her weight on the moon is only one-sixth her
earth-bound weight because the moon’s gravity is only one-sixth that of the earth’s. She may feel “weightless” during her trip when
she experiences negligible external forces (gravitational or any other), although she is, of course, never “massless.”
The law of conservation of matter summarizes many scientific observations about matter: It states that there is no detectable
change in the total quantity of matter present when matter converts from one type to another (a chemical change) or changes
among solid, liquid, or gaseous states (a physical change). Brewing beer and the operation of batteries provide examples of the
conservation of matter (Figure 1.8). During the brewing of beer, the ingredients (water, yeast, grains, malt, hops, and sugar) are
converted into beer (water, alcohol, carbonation, and flavoring substances) with no actual loss of substance. This is most clearly
seen during the bottling process, when glucose turns into ethanol and carbon dioxide, and the total mass of the substances does not
change. This can also be seen in a lead-acid car battery: The original substances (lead, lead oxide, and sulfuric acid), which are

capable of producing electricity, are changed into other substances (lead sulfate and water) that do not produce electricity, with no
change in the actual amount of matter.
Figure 1.8 (a) The mass of beer precursor materials is the same as the mass of beer produced: Sugar has become alcohol and carbon
dioxide. (b) The mass of the lead, lead oxide, and sulfuric acid consumed by the production of electricity is exactly equal to the
mass of lead sulfate and water that is formed.
Although this conservation law holds true for all conversions of matter, convincing examples are few and far between because,
outside of the controlled conditions in a laboratory, we seldom collect all of the material that is produced during a particular
conversion. For example, when you eat, digest, and assimilate food, all of the matter in the original food is preserved. But because
some of the matter is incorporated into your body, and much is excreted as various types of waste, it is challenging to verify by
measurement.
1.3.0.1: Classifying Matter

Matter can be classified into several categories. Two broad categories are mixtures and pure substances. A pure substance has a
constant composition. All specimens of a pure substance have exactly the same makeup and properties. Any sample of sucrose
(table sugar) consists of 42.1% carbon, 6.5% hydrogen, and 51.4% oxygen by mass. Any sample of sucrose also has the same
physical properties, such as melting point, color, and sweetness, regardless of the source from which it is isolated.
Pure substances may be divided into two classes: elements and compounds. Pure substances that cannot be broken down into
simpler substances by chemical changes are called elements. Iron, silver, gold, aluminum, sulfur, oxygen, and copper are familiar
examples of the more than 100 known elements, of which about 90 occur naturally on the earth, and two dozen or so have been
created in laboratories.
Pure substances that are comprised of two or more elements are called compounds. Compounds may be broken down by chemical
changes to yield either elements or other compounds, or both. Mercury(II) oxide, an orange, crystalline solid, can be broken down
by heat into the elements mercury and oxygen (Figure 1.9). When heated in the absence of air, the compound sucrose is broken
down into the element carbon and the compound water. (The initial stage of this process, when the sugar is turning brown, is
known as caramelization—this is what imparts the characteristic sweet and nutty flavor to caramel apples, caramelized onions, and
caramel). Silver(I) chloride is a white solid that can be broken down into its elements, silver and chlorine, by absorption of light.
This property is the basis for the use of this compound in photographic films and photochromic eyeglasses (those with lenses that
darken when exposed to light).

Figure 1.9 (a) The compound mercury(II) oxide, (b) when heated, (c) decomposes into silvery droplets of liquid mercury and
invisible oxygen gas. (credit: modification of work by Paul Flowers)

Many compounds break down when heated. This site shows the breakdown of mercury oxide, HgO. You can also view an
example of the photochemical decomposition of silver chloride (AgCl), the basis of early photography.
The properties of combined elements are different from those in the free, or uncombined, state. For example, white crystalline
sugar (sucrose) is a compound resulting from the chemical combination of the element carbon, which is a black solid in one of its
uncombined forms, and the two elements hydrogen and oxygen, which are colorless gases when uncombined. Free sodium, an
element that is a soft, shiny, metallic solid, and free chlorine, an element that is a yellow-green gas, combine to form sodium
chloride (table salt), a compound that is a white, crystalline solid.
A mixture is composed of two or more types of matter that can be present in varying amounts and can be separated by physical
changes, such as evaporation (you will learn more about this later). A mixture with a composition that varies from point to point is
called a heterogeneous mixture. Italian dressing is an example of a heterogeneous mixture (Figure 1.10). Its composition can vary
because it may be prepared from varying amounts of oil, vinegar, and herbs. It is not the same from point to point throughout the
mixture—one drop may be mostly vinegar, whereas a different drop may be mostly oil or herbs because the oil and vinegar
separate and the herbs settle. Other examples of heterogeneous mixtures are chocolate chip cookies (we can see the separate bits of
chocolate, nuts, and cookie dough) and granite (we can see the quartz, mica, feldspar, and more).
A homogeneous mixture, also called a solution, exhibits a uniform composition and appears visually the same throughout. An
example of a solution is a sports drink, consisting of water, sugar, coloring, flavoring, and electrolytes mixed together uniformly
(Figure 1.10). Each drop of a sports drink tastes the same because each drop contains the same amounts of water, sugar, and other
components. Note that the composition of a sports drink can vary—it could be made with somewhat more or less sugar, flavoring,
or other components, and still be a sports drink. Other examples of homogeneous mixtures include air, maple syrup, gasoline, and a
solution of salt in water.

Figure 1.10 (a) Oil and vinegar salad dressing is a heterogeneous mixture because its composition is not uniform throughout. (b) A
commercial sports drink is a homogeneous mixture because its composition is uniform throughout. (credit a “left”: modification of
work by John Mayer; credit a “right”: modification of work by Umberto Salvagnin; credit b “left: modification of work by Jeff
Bedford)
Although there are just over 100 elements, tens of millions of chemical compounds result from different combinations of these
elements. Each compound has a specific composition and possesses definite chemical and physical properties that distinguish it
from all other compounds. And, of course, there are innumerable ways to combine elements and compounds to form different
mixtures. A summary of how to distinguish between the various major classifications of matter is shown in (Figure 1.11).
Figure 1.11 Depending on its properties, a given substance can be classified as a homogeneous mixture, a heterogeneous mixture, a
compound, or an element.
Eleven elements make up about 99% of the earth’s crust and atmosphere (Table 1.1). Oxygen constitutes nearly one-half and
silicon about one-quarter of the total quantity of these elements. A majority of elements on earth are found in chemical
combinations with other elements; about one-quarter of the elements are also found in the free state.
Elemental Composition of Earth
Element Symbol Percent Mass Element Symbol Percent Mass
oxygen O 49.20 chlorine Cl 0.19
silicon Si 25.67 phosphorus P 0.11
aluminum Al 7.50 manganese Mn 0.09
iron Fe 4.71 carbon C 0.08
calcium Ca 3.39 sulfur S 0.06
sodium Na 2.63 barium Ba 0.04
potassium K 2.40 nitrogen N 0.03
magnesium Mg 1.93 fluorine F 0.03
hydrogen H 0.87 strontium Sr 0.02
titanium Ti 0.58 all others - 0.47
Table 1.1

1.3.0.1: Atoms and Molecules
An atom is the smallest particle of an element that has the properties of that element and can enter into a chemical combination.
Consider the element gold, for example. Imagine cutting a gold nugget in half, then cutting one of the halves in half, and repeating
this process until a piece of gold remained that was so small that it could not be cut in half (regardless of how tiny your knife may
be). This minimally sized piece of gold is an atom (from the Greek atomos, meaning “indivisible”) (Figure 1.12). This atom would
no longer be gold if it were divided any further.
Figure 1.12 (a) This photograph shows a gold nugget. (b) A scanning-tunneling microscope (STM) can generate views of the
surfaces of solids, such as this image of a gold crystal. Each sphere represents one gold atom. (credit a: modification of work by
United States Geological Survey; credit b: modification of work by “Erwinrossen”/Wikimedia Commons)
The first suggestion that matter is composed of atoms is attributed to the Greek philosophers Leucippus and Democritus, who
developed their ideas in the 5th century BCE. However, it was not until the early nineteenth century that John Dalton (1766–1844),
a British schoolteacher with a keen interest in science, supported this hypothesis with quantitative measurements. Since that time,
repeated experiments have confirmed many aspects of this hypothesis, and it has become one of the central theories of chemistry.
Other aspects of Dalton’s atomic theory are still used but with minor revisions (details of Dalton’s theory are provided in the
chapter on atoms and molecules).
An atom is so small that its size is difficult to imagine. One of the smallest things we can see with our unaided eye is a single thread
of a spider web: These strands are about 1/10,000 of a centimeter (0.0001 cm) in diameter. Although the cross-section of one strand
is almost impossible to see without a microscope, it is huge on an atomic scale. A single carbon atom in the web has a diameter of
about 0.000000015 centimeter, and it would take about 7000 carbon atoms to span the diameter of the strand. To put this in
perspective, if a carbon atom were the size of a dime, the cross-section of one strand would be larger than a football field, which
would require about 150 million carbon atom “dimes” to cover it. (Figure 1.13) shows increasingly close microscopic and atomic-
level views of ordinary cotton.
Figure 1.13 These images provide an increasingly closer view: (a) a cotton boll, (b) a single cotton fiber viewed under an optical
microscope (magnified 40 times), (c) an image of a cotton fiber obtained with an electron microscope (much higher magnification

than with the optical microscope); and (d and e) atomic-level models of the fiber (spheres of different colors represent atoms of
different elements). (credit c: modification of work by “Featheredtar”/Wikimedia Commons)
An atom is so light that its mass is also difficult to imagine. A billion lead atoms (1,000,000,000 atoms) weigh about 3 × 10−13
grams, a mass that is far too light to be weighed on even the world’s most sensitive balances. It would require over
300,000,000,000,000 lead atoms (300 trillion, or 3 × 1014) to be weighed, and they would weigh only 0.0000001 gram.
It is rare to find collections of individual atoms. Only a few elements, such as the gases helium, neon, and argon, consist of a
collection of individual atoms that move about independently of one another. Other elements, such as the gases hydrogen, nitrogen,
oxygen, and chlorine, are composed of units that consist of pairs of atoms (Figure 1.14). One form of the element phosphorus
consists of units composed of four phosphorus atoms. The element sulfur exists in various forms, one of which consists of units
composed of eight sulfur atoms. These units are called molecules. A molecule consists of two or more atoms joined by strong
forces called chemical bonds. The atoms in a molecule move around as a unit, much like the cans of soda in a six-pack or a bunch
of keys joined together on a single key ring. A molecule may consist of two or more identical atoms, as in the molecules found in
the elements hydrogen, oxygen, and sulfur, or it may consist of two or more different atoms, as in the molecules found in water.
Each water molecule is a unit that contains two hydrogen atoms and one oxygen atom. Each glucose molecule is a unit that
contains 6 carbon atoms, 12 hydrogen atoms, and 6 oxygen atoms. Like atoms, molecules are incredibly small and light. If an
ordinary glass of water were enlarged to the size of the earth, the water molecules inside it would be about the size of golf balls.
Figure 1.14 The elements hydrogen, oxygen, phosphorus, and sulfur form molecules consisting of two or more atoms of the same
element. The compounds water, carbon dioxide, and glucose consist of combinations of atoms of different elements.
1.3.0.1: Chemistry in Everyday Life

1.3.0.0.1: Decomposition of Water / Production of Hydrogen
Water consists of the elements hydrogen and oxygen combined in a 2 to 1 ratio. Water can be broken down into hydrogen and
oxygen gases by the addition of energy. One way to do this is with a battery or power supply, as shown in (Figure 1.15).

Figure 1.15 The decomposition of water is shown at the macroscopic, microscopic, and symbolic levels. The battery provides
an electric current (microscopic) that decomposes water. At the macroscopic level, the liquid separates into the gases hydrogen
(on the left) and oxygen (on the right). Symbolically, this change is presented by showing how liquid H2O separates into H2
and O2 gases.
The breakdown of water involves a rearrangement of the atoms in water molecules into different molecules, each composed of
two hydrogen atoms and two oxygen atoms, respectively. Two water molecules form one oxygen molecule and two hydrogen
molecules. The representation for what occurs, 2H O(l) ⟶ 2H (g) + O (g), will be explored in more depth in later
2 2 2
chapters.
The two gases produced have distinctly different properties. Oxygen is not flammable but is required for combustion of a fuel,
and hydrogen is highly flammable and a potent energy source. How might this knowledge be applied in our world? One

application involves research into more fuel-efficient transportation. Fuel-cell vehicles (FCV) run on hydrogen instead of
gasoline (Figure 1.16). They are more efficient than vehicles with internal combustion engines, are nonpolluting, and reduce
greenhouse gas emissions, making us less dependent on fossil fuels. FCVs are not yet economically viable, however, and
current hydrogen production depends on natural gas. If we can develop a process to economically decompose water, or
produce hydrogen in another environmentally sound way, FCVs may be the way of the future.
Figure 1.16 A fuel cell generates electrical energy from hydrogen and oxygen via an electrochemical process and produces
only water as the waste product.

1.3.0.0.2: Chemistry of Cell Phones
Imagine how different your life would be without cell phones (Figure 1.17) and other smart devices. Cell phones are made
from numerous chemical substances, which are extracted, refined, purified, and assembled using an extensive and in-depth
understanding of chemical principles. About 30% of the elements that are found in nature are found within a typical smart

phone. The case/body/frame consists of a combination of sturdy, durable polymers composed primarily of carbon, hydrogen,
oxygen, and nitrogen [acrylonitrile butadiene styrene (ABS) and polycarbonate thermoplastics], and light, strong, structural
metals, such as aluminum, magnesium, and iron. The display screen is made from a specially toughened glass (silica glass
strengthened by the addition of aluminum, sodium, and potassium) and coated with a material to make it conductive (such as
indium tin oxide). The circuit board uses a semiconductor material (usually silicon); commonly used metals like copper, tin,
silver, and gold; and more unfamiliar elements such as yttrium, praseodymium, and gadolinium. The battery relies upon
lithium ions and a variety of other materials, including iron, cobalt, copper, polyethylene oxide, and polyacrylonitrile.
Figure 1.17 Almost one-third of naturally occurring elements are used to make a cell phone. (credit: modification of work by
John Taylor)
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OpenStax via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request.


Identify properties of and changes in matter as physical or chemical
Identify properties of matter as extensive or intensive
The characteristics that distinguish one substance from another are called properties. A physical property is a characteristic of
matter that is not associated with a change in its chemical composition. Familiar examples of physical properties include density,
color, hardness, melting and boiling points, and electrical conductivity. Some physical properties, such as density and color, may be
observed without changing the physical state of the matter. Other physical properties, such as the melting temperature of iron or the
freezing temperature of water, can only be observed as matter undergoes a physical change. A physical change is a change in the
state or properties of matter without any accompanying change in the chemical identities of the substances contained in the matter.
Physical changes are observed when wax melts, when sugar dissolves in coffee, and when steam condenses into liquid water
(Figure 1.18). Other examples of physical changes include magnetizing and demagnetizing metals (as is done with common
antitheft security tags) and grinding solids into powders (which can sometimes yield noticeable changes in color). In each of these
examples, there is a change in the physical state, form, or properties of the substance, but no change in its chemical composition.
Figure 1.18 (a) Wax undergoes a physical change when solid wax is heated and forms liquid wax. (b) Steam condensing inside a
cooking pot is a physical change, as water vapor is changed into liquid water. (credit a: modification of work by
“95jb14”/Wikimedia Commons; credit b: modification of work by “mjneuby”/Flickr)
The change of one type of matter into another type (or the inability to change) is a chemical property. Examples of chemical
properties include flammability, toxicity, acidity, and many other types of reactivity. Iron, for example, combines with oxygen in
the presence of water to form rust; chromium does not oxidize (Figure 1.19). Nitroglycerin is very dangerous because it explodes
easily; neon poses almost no hazard because it is very unreactive.

Figure 1.19 (a) One of the chemical properties of iron is that it rusts; (b) one of the chemical properties of chromium is that it does
not. (credit a: modification of work by Tony Hisgett; credit b: modification of work by “Atoma”/Wikimedia Commons)
A chemical change always produces one or more types of matter that differ from the matter present before the change. The
formation of rust is a chemical change because rust is a different kind of matter than the iron, oxygen, and water present before the
rust formed. The explosion of nitroglycerin is a chemical change because the gases produced are very different kinds of matter
from the original substance. Other examples of chemical changes include reactions that are performed in a lab (such as copper
reacting with nitric acid), all forms of combustion (burning), and food being cooked, digested, or rotting (Figure 1.20).

Figure 1.20 (a) Copper and nitric acid undergo a chemical change to form copper nitrate and brown, gaseous nitrogen dioxide. (b)
During the combustion of a match, cellulose in the match and oxygen from the air undergo a chemical change to form carbon
dioxide and water vapor. (c) Cooking red meat causes a number of chemical changes, including the oxidation of iron in myoglobin
that results in the familiar red-to-brown color change. (d) A banana turning brown is a chemical change as new, darker (and less

tasty) substances form. (credit b: modification of work by Jeff Turner; credit c: modification of work by Gloria Cabada-Leman;
credit d: modification of work by Roberto Verzo)
Properties of matter fall into one of two categories. If the property depends on the amount of matter present, it is an extensive
property. The mass and volume of a substance are examples of extensive properties; for instance, a gallon of milk has a larger mass
than a cup of milk. The value of an extensive property is directly proportional to the amount of matter in question. If the property of
a sample of matter does not depend on the amount of matter present, it is an intensive property. Temperature is an example of an
intensive property. If the gallon and cup of milk are each at 20 °C (room temperature), when they are combined, the temperature
remains at 20 °C. As another example, consider the distinct but related properties of heat and temperature. A drop of hot cooking
oil spattered on your arm causes brief, minor discomfort, whereas a pot of hot oil yields severe burns. Both the drop and the pot of
oil are at the same temperature (an intensive property), but the pot clearly contains much more heat (extensive property).

1.4.0.0.1: Hazard Diamond
You may have seen the symbol shown in Figure 1.21 on containers of chemicals in a laboratory or workplace. Sometimes
called a “fire diamond” or “hazard diamond,” this chemical hazard diamond provides valuable information that briefly
summarizes the various dangers of which to be aware when working with a particular substance.
Figure 1.21 The National Fire Protection Agency (NFPA) hazard diamond summarizes the major hazards of a chemical
substance.
The National Fire Protection Agency (NFPA) 704 Hazard Identification System was developed by NFPA to provide safety
information about certain substances. The system details flammability, reactivity, health, and other hazards. Within the overall
diamond symbol, the top (red) diamond specifies the level of fire hazard (temperature range for flash point). The blue (left)
diamond indicates the level of health hazard. The yellow (right) diamond describes reactivity hazards, such as how readily the
substance will undergo detonation or a violent chemical change. The white (bottom) diamond points out special hazards, such
as if it is an oxidizer (which allows the substance to burn in the absence of air/oxygen), undergoes an unusual or dangerous

reaction with water, is corrosive, acidic, alkaline, a biological hazard, radioactive, and so on. Each hazard is rated on a scale
from 0 to 4, with 0 being no hazard and 4 being extremely hazardous.
While many elements differ dramatically in their chemical and physical properties, some elements have similar properties. For
example, many elements conduct heat and electricity well, whereas others are poor conductors. These properties can be used to sort
the elements into three classes: metals (elements that conduct well), nonmetals (elements that conduct poorly), and metalloids
(elements that have intermediate conductivities).
The periodic table is a table of elements that places elements with similar properties close together (Figure 1.22). You will learn
more about the periodic table as you continue your study of chemistry.
Figure 1.22 The periodic table shows how elements may be grouped according to certain similar properties. Note the background
color denotes whether an element is a metal, metalloid, or nonmetal, whereas the element symbol color indicates whether it is a
solid, liquid, or gas.
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1.5: Measurements

Explain the process of measurement
Identify the three basic parts of a quantity
Describe the properties and units of length, mass, volume, density, temperature, and time
Perform basic unit calculations and conversions in the metric and other unit systems
Measurements provide much of the information that informs the hypotheses, theories, and laws describing the behavior of matter
and energy in both the macroscopic and microscopic domains of chemistry. Every measurement provides three kinds of
information: the size or magnitude of the measurement (a number); a standard of comparison for the measurement (a unit); and an
indication of the uncertainty of the measurement. While the number and unit are explicitly represented when a quantity is written,
the uncertainty is an aspect of the measurement result that is more implicitly represented and will be discussed later.
The number in the measurement can be represented in different ways, including decimal form and scientific notation. (Scientific
notation is also known as exponential notation; a review of this topic can be found in Appendix B.) For example, the maximum
takeoff weight of a Boeing 777-200ER airliner is 298,000 kilograms, which can also be written as 2.98 × 105 kg. The mass of the
average mosquito is about 0.0000025 kilograms, which can be written as 2.5 × 10−6 kg.
Units, such as liters, pounds, and centimeters, are standards of comparison for measurements. A 2-liter bottle of a soft drink
contains a volume of beverage that is twice that of the accepted volume of 1 liter. The meat used to prepare a 0.25-pound
hamburger weighs one-fourth as much as the accepted weight of 1 pound. Without units, a number can be meaningless, confusing,
or possibly life threatening. Suppose a doctor prescribes phenobarbital to control a patient’s seizures and states a dosage of “100”
without specifying units. Not only will this be confusing to the medical professional giving the dose, but the consequences can be
dire: 100 mg given three times per day can be effective as an anticonvulsant, but a single dose of 100 g is more than 10 times the
lethal amount.
The measurement units for seven fundamental properties (“base units”) are listed in Table 1.2. The standards for these units are
fixed by international agreement, and they are called the International System of Units or SI Units (from the French, Le Système
International d’Unités). SI units have been used by the United States National Institute of Standards and Technology (NIST) since
1964. Units for other properties may be derived from these seven base units.
Base Units of the SI System
Property Measured Name of Unit Symbol of Unit
length meter m
mass kilogram kg
time second s
temperature kelvin K
electric current ampere A
amount of substance mole mol
luminous intensity candela cd
Table 1.2

Everyday measurement units are often defined as fractions or multiples of other units. Milk is commonly packaged in containers of
1 gallon (4 quarts), 1 quart (0.25 gallon), and one pint (0.5 quart). This same approach is used with SI units, but these fractions or
multiples are always powers of 10. Fractional or multiple SI units are named using a prefix and the name of the base unit. For
example, a length of 1000 meters is also called a kilometer because the prefix kilo means “one thousand,” which in scientific
notation is 103 (1 kilometer = 1000 m = 103 m). The prefixes used and the powers to which 10 are raised are listed in Table 1.3.
Common Unit Prefixes
Prefix Symbol Factor Example
femto f 10−15 1 femtosecond (fs) = 1 × 10−15 s (0.000000000000001 s)
pico p 10−12 1 picometer (pm) = 1 × 10−12 m (0.000000000001 m)
nano n 10−9 4 nanograms (ng) = 4 × 10−9 g (0.000000004 g)
micro µ 10−6 1 microliter (μL) = 1 × 10−6 L (0.000001 L)
milli m 10−3 2 millimoles (mmol) = 2 × 10−3 mol (0.002 mol)
centi c 10−2 7 centimeters (cm) = 7 × 10−2 m (0.07 m)
deci d 10−1 1 deciliter (dL) = 1 × 10−1 L (0.1 L )
kilo k 103 1 kilometer (km) = 1 × 103 m (1000 m)
mega M 106 3 megahertz (MHz) = 3 × 106 Hz (3,000,000 Hz)
giga G 109 8 gigayears (Gyr) = 8 × 109 yr (8,000,000,000 yr)
tera T 1012 5 terawatts (TW) = 5 × 1012 W (5,000,000,000,000 W)
Table 1.3

Need a refresher or more practice with scientific notation? Visit this site to go over the basics of scientific notation.
1.5.0.1: SI Base Units

The initial units of the metric system, which eventually evolved into the SI system, were established in France during the French
Revolution. The original standards for the meter and the kilogram were adopted there in 1799 and eventually by other countries.
This section introduces four of the SI base units commonly used in chemistry. Other SI units will be introduced in subsequent
chapters.
1.5.0.0.1: Length
The standard unit of length in both the SI and original metric systems is the meter (m). A meter was originally specified as
1/10,000,000 of the distance from the North Pole to the equator. It is now defined as the distance light in a vacuum travels in
1/299,792,458 of a second. A meter is about 3 inches longer than a yard (Figure 1.23); one meter is about 39.37 inches or 1.094
yards. Longer distances are often reported in kilometers (1 km = 1000 m = 103 m), whereas shorter distances can be reported in
centimeters (1 cm = 0.01 m = 10−2 m) or millimeters (1 mm = 0.001 m = 10−3 m).

Figure 1.23 The relative lengths of 1 m, 1 yd, 1 cm, and 1 in. are shown (not actual size), as well as comparisons of 2.54 cm and 1
in., and of 1 m and 1.094 yd.
1.5.0.0.2: Mass
The standard unit of mass in the SI system is the kilogram (kg). The kilogram was previously defined by the International Union of
Pure and Applied Chemistry (IUPAC) as the mass of a specific reference object. This object was originally one liter of pure water,
and more recently it was a metal cylinder made from a platinum-iridium alloy with a height and diameter of 39 mm (Figure 1.24).
In May 2019, this definition was changed to one that is based instead on precisely measured values of several fundamental physical
constants.1. One kilogram is about 2.2 pounds. The gram (g) is exactly equal to 1/1000 of the mass of the kilogram (10−3 kg).
Figure 1.24 This replica prototype kilogram as previously defined is housed at the National Institute of Standards and Technology
(NIST) in Maryland. (credit: National Institutes of Standards and Technology)

1.5.0.0.3: Temperature
Temperature is an intensive property. The SI unit of temperature is the kelvin (K). The IUPAC convention is to use kelvin (all
lowercase) for the word, K (uppercase) for the unit symbol, and neither the word “degree” nor the degree symbol (°). The degree
Celsius (°C) is also allowed in the SI system, with both the word “degree” and the degree symbol used for Celsius measurements.
Celsius degrees are the same magnitude as those of kelvin, but the two scales place their zeros in different places. Water freezes at
273.15 K (0 °C) and boils at 373.15 K (100 °C) by definition, and normal human body temperature is approximately 310 K (37
°C). The conversion between these two units and the Fahrenheit scale will be discussed later in this chapter.
1.5.0.0.4: Time
The SI base unit of time is the second (s). Small and large time intervals can be expressed with the appropriate prefixes; for
example, 3 microseconds = 0.000003 s = 3 × 10−6 and 5 megaseconds = 5,000,000 s = 5 × 106 s. Alternatively, hours, days, and
years can be used.
1.5.0.1: Derived SI Units

We can derive many units from the seven SI base units. For example, we can use the base unit of length to define a unit of volume,
and the base units of mass and length to define a unit of density.
1.5.0.0.1: Volume
Volume is the measure of the amount of space occupied by an object. The standard SI unit of volume is defined by the base unit of
length (Figure 1.25). The standard volume is a cubic meter (m3), a cube with an edge length of exactly one meter. To dispense a
cubic meter of water, we could build a cubic box with edge lengths of exactly one meter. This box would hold a cubic meter of
water or any other substance.
A more commonly used unit of volume is derived from the decimeter (0.1 m, or 10 cm). A cube with edge lengths of exactly one
decimeter contains a volume of one cubic decimeter (dm3). A liter (L) is the more common name for the cubic decimeter. One liter
is about 1.06 quarts.
A cubic centimeter (cm3) is the volume of a cube with an edge length of exactly one centimeter. The abbreviation cc (for cubic
centimeter) is often used by health professionals. A cubic centimeter is equivalent to a milliliter (mL) and is 1/1000 of a liter.
Figure 1.25 (a) The relative volumes are shown for cubes of 1 m3, 1 dm3 (1 L), and 1 cm3 (1 mL) (not to scale). (b) The diameter of
a dime is compared relative to the edge length of a 1-cm3 (1-mL) cube.

1.5.0.0.2: Density
We use the mass and volume of a substance to determine its density. Thus, the units of density are defined by the base units of mass
and length.
The density of a substance is the ratio of the mass of a sample of the substance to its volume. The SI unit for density is the kilogram
per cubic meter (kg/m3). For many situations, however, this is an inconvenient unit, and we often use grams per cubic centimeter
(g/cm3) for the densities of solids and liquids, and grams per liter (g/L) for gases. Although there are exceptions, most liquids and
solids have densities that range from about 0.7 g/cm3 (the density of gasoline) to 19 g/cm3 (the density of gold). The density of air
is about 1.2 g/L. Table 1.4 shows the densities of some common substances.
Densities of Common Substances
Solids Liquids Gases (at 25 °C and 1 atm)
ice (at 0 °C) 0.92 g/cm3 water 1.0 g/cm3 dry air 1.20 g/L
oak (wood) 0.60–0.90 g/cm3 ethanol 0.79 g/cm3 oxygen 1.31 g/L
iron 7.9 g/cm3 acetone 0.79 g/cm3 nitrogen 1.14 g/L
copper 9.0 g/cm3 glycerin 1.26 g/cm3 carbon dioxide 1.80 g/L
lead 11.3 g/cm3 olive oil 0.92 g/cm3 helium 0.16 g/L
silver 10.5 g/cm3 gasoline 0.70–0.77 g/cm3 neon 0.83 g/L
gold 19.3 g/cm3 mercury 13.6 g/cm3 radon 9.1 g/L
Table 1.4
While there are many ways to determine the density of an object, perhaps the most straightforward method involves separately
finding the mass and volume of the object, and then dividing the mass of the sample by its volume. In the following example, the
mass is found directly by weighing, but the volume is found indirectly through length measurements.
mass
density =
volume
1.5.0.1: Example 1.1

1.5.0.0.3: Calculation of Density
Gold—in bricks, bars, and coins—has been a form of currency for centuries. In order to swindle people into paying for a brick
of gold without actually investing in a brick of gold, people have considered filling the centers of hollow gold bricks with lead
to fool buyers into thinking that the entire brick is gold. It does not work: Lead is a dense substance, but its density is not as
great as that of gold, 19.3 g/cm3. What is the density of lead if a cube of lead has an edge length of 2.00 cm and a mass of 90.7
g?
1.5.0.0.4: Solution
The density of a substance can be calculated by dividing its mass by its volume. The volume of a cube is calculated by cubing
the edge length.
3
volume of lead cube = 2.00 cm × 2.00 cm × 2.00 cm = 8.00 cm
mass 90.7 g 3
density = = = 11.3 g/cm
3
volume 8.00 cm
(We will discuss the reason for rounding to the first decimal place in the next section.)
1.5.0.0.5: Check Your Learning
(a) To three decimal places, what is the volume of a cube (cm3) with an edge length of 0.843 cm?
(b) If the cube in part (a) is copper and has a mass of 5.34 g, what is the density of copper to two decimal places?

1.5.0.1: Answer:
(a) 0.599 cm3; (b) 8.91 g/cm3

To learn more about the relationship between mass, volume, and density, use this interactive simulator to explore the density of
different materials.
1.5.0.1: Example 1.2

1.5.0.0.6: Using Displacement of Water to Determine Density
This exercise uses a simulation to illustrate an alternative approach to the determination of density that involves measuring the
object’s volume via displacement of water. Use the simulator to determine the densities iron and wood.
1.5.0.0.7: Solution
Click the “turn fluid into water” button in the simulator to adjust the density of liquid in the beaker to 1.00 g/mL. Remove the
red block from the beaker and note the volume of water is 25.5 mL. Select the iron sample by clicking “iron” in the table of
materials at the bottom of the screen, place the iron block on the balance pan, and observe its mass is 31.48 g. Transfer the iron
block to the beaker and notice that it sinks, displacing a volume of water equal to its own volume and causing the water level to
rise to 29.5 mL. The volume of the iron block is therefore:
viron = 29.5 mL– 25.5 mL = 4.0 mL
The density of the iron is then calculated to be:

mass 31.48 g
density = = = 7.9 g/mL
volume 4.0 mL
Remove the iron block from the beaker, change the block material to wood, and then repeat the mass and volume
measurements. Unlike iron, the wood block does not sink in the water but instead floats on the water’s surface. To measure its
volume, drag it beneath the water’s surface so that it is fully submerged.
mass 1.95 g
density = = = 0.65 g/mL
volume 3.0 mL
Note: The sink versus float behavior illustrated in this example demonstrates the property of “buoyancy” (see end of chapter
Exercise 1.42 and Exercise 1.43).
Following the water displacement approach, use the simulator to measure the density of the foam sample.
1.5.0.1: Answer:
0.230 g/mL
1.5.0.1: Footnotes
1For details see https://www.nist.gov/pml/weights-and.../si-units-mass
This page titled 1.5: Measurements is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source
content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request.


Define accuracy and precision
Distinguish exact and uncertain numbers
Correctly represent uncertainty in quantities using significant figures
Apply proper rounding rules to computed quantities
Counting is the only type of measurement that is free from uncertainty, provided the number of objects being counted does not
change while the counting process is underway. The result of such a counting measurement is an example of an exact number. By
counting the eggs in a carton, one can determine exactly how many eggs the carton contains. The numbers of defined quantities are
also exact. By definition, 1 foot is exactly 12 inches, 1 inch is exactly 2.54 centimeters, and 1 gram is exactly 0.001 kilogram.
Quantities derived from measurements other than counting, however, are uncertain to varying extents due to practical limitations of
the measurement process used.
1.6.0.1: Significant Figures in Measurement

The numbers of measured quantities, unlike defined or directly counted quantities, are not exact. To measure the volume of liquid
in a graduated cylinder, you should make a reading at the bottom of the meniscus, the lowest point on the curved surface of the
liquid.
Figure 1.26 To measure the volume of liquid in this graduated cylinder, you must mentally subdivide the distance between the 21
and 22 mL marks into tenths of a milliliter, and then make a reading (estimate) at the bottom of the meniscus.
Refer to the illustration in Figure 1.26. The bottom of the meniscus in this case clearly lies between the 21 and 22 markings,
meaning the liquid volume is certainly greater than 21 mL but less than 22 mL. The meniscus appears to be a bit closer to the 22-
mL mark than to the 21-mL mark, and so a reasonable estimate of the liquid’s volume would be 21.6 mL. In the number 21.6, then,
the digits 2 and 1 are certain, but the 6 is an estimate. Some people might estimate the meniscus position to be equally distant from
each of the markings and estimate the tenth-place digit as 5, while others may think it to be even closer to the 22-mL mark and

estimate this digit to be 7. Note that it would be pointless to attempt to estimate a digit for the hundredths place, given that the
tenths-place digit is uncertain. In general, numerical scales such as the one on this graduated cylinder will permit measurements to
one-tenth of the smallest scale division. The scale in this case has 1-mL divisions, and so volumes may be measured to the nearest
0.1 mL.
This concept holds true for all measurements, even if you do not actively make an estimate. If you place a quarter on a standard
electronic balance, you may obtain a reading of 6.72 g. The digits 6 and 7 are certain, and the 2 indicates that the mass of the
quarter is likely between 6.71 and 6.73 grams. The quarter weighs about 6.72 grams, with a nominal uncertainty in the
measurement of ± 0.01 gram. If the coin is weighed on a more sensitive balance, the mass might be 6.723 g. This means its mass
lies between 6.722 and 6.724 grams, an uncertainty of 0.001 gram. Every measurement has some uncertainty, which depends on
the device used (and the user’s ability). All of the digits in a measurement, including the uncertain last digit, are called significant
figures or significant digits. Note that zero may be a measured value; for example, if you stand on a scale that shows weight to the
nearest pound and it shows “120,” then the 1 (hundreds), 2 (tens) and 0 (ones) are all significant (measured) values.
A measurement result is properly reported when its significant digits accurately represent the certainty of the measurement process.
But what if you were analyzing a reported value and trying to determine what is significant and what is not? Well, for starters, all
nonzero digits are significant, and it is only zeros that require some thought. We will use the terms “leading,” “trailing,” and
“captive” for the zeros and will consider how to deal with them.
Starting with the first nonzero digit on the left, count this digit and all remaining digits to the right. This is the number of
significant figures in the measurement unless the last digit is a trailing zero lying to the left of the decimal point.
Captive zeros result from measurement and are therefore always significant. Leading zeros, however, are never significant—they
merely tell us where the decimal point is located.
The leading zeros in this example are not significant. We could use exponential notation (as described in Appendix B) and express
the number as 8.32407 × 10−3; then the number 8.32407 contains all of the significant figures, and 10−3 locates the decimal point.
The number of significant figures is uncertain in a number that ends with a zero to the left of the decimal point location. The zeros
in the measurement 1,300 grams could be significant or they could simply indicate where the decimal point is located. The
ambiguity can be resolved with the use of exponential notation: 1.3 × 103 (two significant figures), 1.30 × 103 (three significant
figures, if the tens place was measured), or 1.300 × 103 (four significant figures, if the ones place was also measured). In cases
where only the decimal-formatted number is available, it is prudent to assume that all trailing zeros are not significant.

When determining significant figures, be sure to pay attention to reported values and think about the measurement and significant
figures in terms of what is reasonable or likely when evaluating whether the value makes sense. For example, the official January
2014 census reported the resident population of the US as 317,297,725. Do you think the US population was correctly determined
to the reported nine significant figures, that is, to the exact number of people? People are constantly being born, dying, or moving
into or out of the country, and assumptions are made to account for the large number of people who are not actually counted.
Because of these uncertainties, it might be more reasonable to expect that we know the population to within perhaps a million or so,
in which case the population should be reported as 3.17 × 108 people.
1.6.0.1: Significant Figures in Calculations

A second important principle of uncertainty is that results calculated from a measurement are at least as uncertain as the
measurement itself. Take the uncertainty in measurements into account to avoid misrepresenting the uncertainty in calculated
results. One way to do this is to report the result of a calculation with the correct number of significant figures, which is determined
by the following three rules for rounding numbers:
1. When adding or subtracting numbers, round the result to the same number of decimal places as the number with the least
number of decimal places (the least certain value in terms of addition and subtraction).
2. When multiplying or dividing numbers, round the result to the same number of digits as the number with the least number of
significant figures (the least certain value in terms of multiplication and division).
3. If the digit to be dropped (the one immediately to the right of the digit to be retained) is less than 5, “round down” and leave the
retained digit unchanged; if it is more than 5, “round up” and increase the retained digit by 1. If the dropped digit is 5, and it’s
either the last digit in the number or it’s followed only by zeros, round up or down, whichever yields an even value for the
retained digit. If any nonzero digits follow the dropped 5, round up. (The last part of this rule may strike you as a bit odd, but
it’s based on reliable statistics and is aimed at avoiding any bias when dropping the digit “5,” since it is equally close to both
possible values of the retained digit.)
The following examples illustrate the application of this rule in rounding a few different numbers to three significant figures:
0.028675 rounds “up” to 0.0287 (the dropped digit, 7, is greater than 5)
18.3384 rounds “down” to 18.3 (the dropped digit, 3, is less than 5)
6.8752 rounds “up” to 6.88 (the dropped digit is 5, and a nonzero digit follows it)
92.85 rounds “down” to 92.8 (the dropped digit is 5, and the retained digit is even)
Let’s work through these rules with a few examples.
1.6.0.1: Example 1.3

1.6.0.0.1: Rounding Numbers
Round the following to the indicated number of significant figures:
(a) 31.57 (to two significant figures)
(b) 8.1649 (to three significant figures)
(c) 0.051065 (to four significant figures)
(d) 0.90275 (to four significant figures)
1.6.0.0.2: Solution
(a) 31.57 rounds “up” to 32 (the dropped digit is 5, and the retained digit is even)
(b) 8.1649 rounds “down” to 8.16 (the dropped digit, 4, is less than 5)
(c) 0.051065 rounds “down” to 0.05106 (the dropped digit is 5, and the retained digit is even)
(d) 0.90275 rounds “up” to 0.9028 (the dropped digit is 5, and the retained digit is even)

Round the following to the indicated number of significant figures:
(a) 0.424 (to two significant figures)
(b) 0.0038661 (to three significant figures)
(c) 421.25 (to four significant figures)
(d) 28,683.5 (to five significant figures)
1.6.0.1: Answer:
(a) 0.42; (b) 0.00387; (c) 421.2; (d) 28,684
1.6.0.1: Example 1.4

1.6.0.0.4: Addition and Subtraction with Significant Figures
Rule: When adding or subtracting numbers, round the result to the same number of decimal places as the number with the
fewest decimal places (i.e., the least certain value in terms of addition and subtraction).
(a) Add 1.0023 g and 4.383 g.
(b) Subtract 421.23 g from 486 g.
1.6.0.0.5: Solution
(a) 1.0023 g
+ 4.383 g
5.3853 g
Answer is 5.385 g (round to the thousandths place; three decimal places)
(b) 486 g
−421.23 g
64.77 g
Answer is 65 g (round to the ones place; no decimal places)

(a) Add 2.334 mL and 0.31 mL.
(b) Subtract 55.8752 m from 56.533 m.
1.6.0.1: Answer:
(a) 2.64 mL; (b) 0.658 m
1.6.0.1: Example 1.5

1.6.0.0.7: Multiplication and Division with Significant Figures
Rule: When multiplying or dividing numbers, round the result to the same number of digits as the number with the fewest
significant figures (the least certain value in terms of multiplication and division).
(a) Multiply 0.6238 cm by 6.6 cm.
(b) Divide 421.23 g by 486 mL.
1.6.0.0.8: Solution
2 2
0.6238 cm × 6.6 cm = 4.11708 cm ⟶ result is 4.1 cm (round to two significant figures)
(a)
four significant figures × two significant figures ⟶ two significant figures answer
421.23 g
= 0.866728... g/mL ⟶ result is 0.867 g/mL (round to three significant figures)
486 mL
(b) five significant figures
⟶ three significant figures answer
three significant figures

(a) Multiply 2.334 cm and 0.320 cm.
(b) Divide 55.8752 m by 56.53 s.
1.6.0.1: Answer:
(a) 0.747 cm2 (b) 0.9884 m/s
In the midst of all these technicalities, it is important to keep in mind the reason for these rules about significant figures and
rounding—to correctly represent the certainty of the values reported and to ensure that a calculated result is not represented as
being more certain than the least certain value used in the calculation.
1.6.0.1: Example 1.6

1.6.0.0.10: Calculation with Significant Figures
One common bathtub is 13.44 dm long, 5.920 dm wide, and 2.54 dm deep. Assume that the tub is rectangular and calculate its
approximate volume in liters.
1.6.0.0.11: Solution
V = l × w × d
= 13.44 dm × 5.920 dm × 2.54 dm
3
= 202.09459... dm (value from calculator)
3
= 202 dm , or 202 L (answer rounded to three significant figures)

What is the density of a liquid with a mass of 31.1415 g and a volume of 30.13 cm3?
1.6.0.1: Answer:
1.034 g/mL
1.6.0.1: Example 1.7

1.6.0.0.13: Experimental Determination of Density Using Water Displacement

A piece of rebar is weighed and then submerged in a graduated cylinder partially filled with water, with results as shown.
(a) Use these values to determine the density of this piece of rebar.
(b) Rebar is mostly iron. Does your result in (a) support this statement? How?
The volume of the piece of rebar is equal to the volume of the water displaced:
3
volume = 22.4 mL − 13.5 mL = 8.9 mL = 8.9 cm
(rounded to the nearest 0.1 mL, per the rule for addition and subtraction)
The density is the mass-to-volume ratio:
mass 69.658 g 3
density = = = 7.8 g/cm
3
volume 8.9 cm
(rounded to two significant figures, per the rule for multiplication and division)
From Table 1.4, the density of iron is 7.9 g/cm3, very close to that of rebar, which lends some support to the fact that rebar is
mostly iron.

An irregularly shaped piece of a shiny yellowish material is weighed and then submerged in a graduated cylinder, with results
as shown.
(a) Use these values to determine the density of this material.
(b) Do you have any reasonable guesses as to the identity of this material? Explain your reasoning.
1.6.0.1: Answer:
(a) 19 g/cm3; (b) It is likely gold; the right appearance for gold and very close to the density given for gold in Table 1.4.
1.6.0.1: Accuracy and Precision

Scientists typically make repeated measurements of a quantity to ensure the quality of their findings and to evaluate both the
precision and the accuracy of their results. Measurements are said to be precise if they yield very similar results when repeated in
the same manner. A measurement is considered accurate if it yields a result that is very close to the true or accepted value. Precise
values agree with each other; accurate values agree with a true value. These characterizations can be extended to other contexts,
such as the results of an archery competition (Figure 1.27).
Figure 1.27 (a) These arrows are close to both the bull’s eye and one another, so they are both accurate and precise. (b) These
arrows are close to one another but not on target, so they are precise but not accurate. (c) These arrows are neither on target nor
close to one another, so they are neither accurate nor precise.

Suppose a quality control chemist at a pharmaceutical company is tasked with checking the accuracy and precision of three
different machines that are meant to dispense 10 ounces (296 mL) of cough syrup into storage bottles. She proceeds to use each
machine to fill five bottles and then carefully determines the actual volume dispensed, obtaining the results tabulated in Table 1.5.
Volume (mL) of Cough Medicine Delivered by 10-oz (296 mL) Dispensers
Dispenser #1 Dispenser #2 Dispenser #3
283.3 298.3 296.1
284.1 294.2 295.9
283.9 296.0 296.1
284.0 297.8 296.0
284.1 293.9 296.1
Table 1.5
Considering these results, she will report that dispenser #1 is precise (values all close to one another, within a few tenths of a
milliliter) but not accurate (none of the values are close to the target value of 296 mL, each being more than 10 mL too low).
Results for dispenser #2 represent improved accuracy (each volume is less than 3 mL away from 296 mL) but worse precision
(volumes vary by more than 4 mL). Finally, she can report that dispenser #3 is working well, dispensing cough syrup both
accurately (all volumes within 0.1 mL of the target volume) and precisely (volumes differing from each other by no more than 0.2
mL).
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upon request.


Explain the dimensional analysis (factor label) approach to mathematical calculations involving quantities
Use dimensional analysis to carry out unit conversions for a given property and computations involving two or more
properties
It is often the case that a quantity of interest may not be easy (or even possible) to measure directly but instead must be calculated
from other directly measured properties and appropriate mathematical relationships. For example, consider measuring the average
speed of an athlete running sprints. This is typically accomplished by measuring the time required for the athlete to run from the
starting line to the finish line, and the distance between these two lines, and then computing speed from the equation that relates
these three properties:
distance
speed =
time
An Olympic-quality sprinter can run 100 m in approximately 10 s, corresponding to an average speed of

100 m
= 10 m/s
10 s
(For this and the next calculation, assume the trailing zeros are significant digits.) Note that this simple arithmetic involves dividing
the numbers of each measured quantity to yield the number of the computed quantity (100/10 = 10) and likewise dividing the units
of each measured quantity to yield the unit of the computed quantity (m/s = m/s). Now, consider using this same relation to predict
the time required for a person running at this speed to travel a distance of 25 m. The same relation among the three properties is
used, but in this case, the two quantities provided are a speed (10 m/s) and a distance (25 m). To yield the sought property, time, the
equation must be rearranged appropriately:
distance
time =
speed
The time can then be computed as:

25 m
= 2.5 s
10 m/s
Again, arithmetic on the numbers (25/10 = 2.5) was accompanied by the same arithmetic on the units (m/(m/s) = s) to yield the
number and unit of the result, 2.5 s. Note that, just as for numbers, when a unit is divided by an identical unit (in this case, m/m),
the result is “1”—or, as commonly phrased, the units “cancel.”
These calculations are examples of a versatile mathematical approach known as dimensional analysis (or the factor-label method).
Dimensional analysis is based on this premise: the units of quantities must be subjected to the same mathematical operations as
their associated numbers. This method can be applied to computations ranging from simple unit conversions to more complex,
multi-step calculations involving several different quantities.
1.7.0.1: Conversion Factors and Dimensional Analysis

A ratio of two equivalent quantities expressed with different measurement units can be used as a unit conversion factor. For
example, the lengths of 2.54 cm and 1 in. are equivalent (by definition), and so a unit conversion factor may be derived from the
ratio,
2.54 cm cm
(2.54 cm = 1 in.) or 2.54
1 in. in.
Several other commonly used conversion factors are given in Table 1.6.
Common Conversion Factors

Length Volume Mass
1 m = 1.0936 yd 1 L = 1.0567 qt 1 kg = 2.2046 lb
1 in. = 2.54 cm (exact) 1 qt = 0.94635 L 1 lb = 453.59 g
1 km = 0.62137 mi 1 ft3 = 28.317 L 1 (avoirdupois) oz = 28.349 g
1 mi = 1609.3 m 1 tbsp = 14.787 mL 1 (troy) oz = 31.103 g
Table 1.6
When a quantity (such as distance in inches) is multiplied by an appropriate unit conversion factor, the quantity is converted to an
equivalent value with different units (such as distance in centimeters). For example, a basketball player’s vertical jump of 34 inches
can be converted to centimeters by:
2.54 cm
34 in. × = 86 cm
1 in.
Since this simple arithmetic involves quantities, the premise of dimensional analysis requires that we multiply both numbers and
units. The numbers of these two quantities are multiplied to yield the number of the product quantity, 86, whereas the units are
multiplied to yield . Just as for numbers, a ratio of identical units is also numerically equal to one,
in. × cm
in.
= 1, and the unit
in.
in.
product thus simplifies to cm. (When identical units divide to yield a factor of 1, they are said to “cancel.”) Dimensional analysis
may be used to confirm the proper application of unit conversion factors as demonstrated in the following example.
1.7.0.1: Example 1.8

1.7.0.0.1: Using a Unit Conversion Factor
The mass of a competition frisbee is 125 g. Convert its mass to ounces using the unit conversion factor derived from the
relationship 1 oz = 28.349 g (Table 1.6).
1.7.0.0.2: Solution
Given the conversion factor, the mass in ounces may be derived using an equation similar to the one used for converting length
from inches to centimeters.
x oz = 125 g × unit conversion factor
The unit conversion factor may be represented as:

1 oz 28.349 g
and
28.349 g 1 oz
The correct unit conversion factor is the ratio that cancels the units of grams and leaves ounces.
1 oz
x oz = 125 g ×
28.349 g
125
= ( ) oz
28.349
= 4.41 oz (three significant figures)

Convert a volume of 9.345 qt to liters.
1.7.0.1: Answer:
8.844 L
Beyond simple unit conversions, the factor-label method can be used to solve more complex problems involving computations.
Regardless of the details, the basic approach is the same—all the factors involved in the calculation must be appropriately oriented

to ensure that their labels (units) will appropriately cancel and/or combine to yield the desired unit in the result. As your study of
chemistry continues, you will encounter many opportunities to apply this approach.
1.7.0.1: Example 1.9

1.7.0.0.4: Computing Quantities from Measurement Results and Known Mathematical Relations
What is the density of common antifreeze in units of g/mL? A 4.00-qt sample of the antifreeze weighs 9.26 lb.
1.7.0.0.5: Solution
Since density = mass
, we need to divide the mass in grams by the volume in milliliters. In general: the number of units of
volume
B = the number of units of A × unit conversion factor. The necessary conversion factors are given in Table 1.6: 1 lb = 453.59
g; 1 L = 1.0567 qt; 1 L = 1,000 mL. Mass may be converted from pounds to grams as follows:
453.59 g
3
9.26 lb × = 4.20 × 10 g
1 lb
Volume may be converted from quarts to milliliters via two steps:

1. Step 1. Convert quarts to liters.
1 L
4.00 qt × = 3.78 L
1.0567 qt
2. Step 2. Convert liters to milliliters.

1000 mL 3
3.78 L × = 3.78 × 10 mL
1 L
Then,
3
4.20 × 10 g
density = = 1.11 g/mL
3
3.78 × 10 mL
Alternatively, the calculation could be set up in a way that uses three unit conversion factors sequentially as follows:
9.26 lb 453.59 g 1.0567 qt 1 L

× × × = 1.11 g/mL
4.00 qt 1000 mL
1 lb 1 L

What is the volume in liters of 1.000 oz, given that 1 L = 1.0567 qt and 1 qt = 32 oz (exactly)?
1.7.0.1: Answer:
2.956 × 10−2 L
1.7.0.1: Example 1.10

1.7.0.0.7: Computing Quantities from Measurement Results and Known Mathematical Relations
While being driven from Philadelphia to Atlanta, a distance of about 1250 km, a 2014 Lamborghini Aventador Roadster uses
213 L gasoline.
(a) What (average) fuel economy, in miles per gallon, did the Roadster get during this trip?
(b) If gasoline costs $3.80 per gallon, what was the fuel cost for this trip?
1.7.0.0.8: Solution
(a) First convert distance from kilometers to miles:
0.62137 mi
1250 km × = 777 mi
1 km
and then convert volume from liters to gallons:

1.0567 qt 1 gal
213 L × × = 56.3 gal
1 L 4 qt
Finally,
777 mi
(average) mileage = = 13.8 miles/gallon = 13.8 mpg
56.3 gal
Alternatively, the calculation could be set up in a way that uses all the conversion factors sequentially, as follows:
1250 km 1 L 4 qt
0.62137 mi
× × × = 13.8 mpg
213 L 1 km 1.0567 qt 1 gal
(b) Using the previously calculated volume in gallons, we find:

$3.80
56.3 gal × = $214
1 gal

A Toyota Prius Hybrid uses 59.7 L gasoline to drive from San Francisco to Seattle, a distance of 1300 km (two significant
digits).
(a) What (average) fuel economy, in miles per gallon, did the Prius get during this trip?
(b) If gasoline costs $3.90 per gallon, what was the fuel cost for this trip?
1.7.0.1: Answer:
(a) 51 mpg; (b) $62
1.7.0.1: Conversion of Temperature Units

We use the word temperature to refer to the hotness or coldness of a substance. One way we measure a change in temperature is to
use the fact that most substances expand when their temperature increases and contract when their temperature decreases. The
liquid in a common glass thermometer changes its volume as the temperature changes, and the position of the trapped liquid's
surface along a printed scale may be used as a measure of temperature.
Temperature scales are defined relative to selected reference temperatures: Two of the most commonly used are the freezing and
boiling temperatures of water at a specified atmospheric pressure. On the Celsius scale, 0 °C is defined as the freezing temperature
of water and 100 °C as the boiling temperature of water. The space between the two temperatures is divided into 100 equal
intervals, which we call degrees. On the Fahrenheit scale, the freezing point of water is defined as 32 °F and the boiling
temperature as 212 °F. The space between these two points on a Fahrenheit thermometer is divided into 180 equal parts (degrees).
Defining the Celsius and Fahrenheit temperature scales as described in the previous paragraph results in a slightly more complex
relationship between temperature values on these two scales than for different units of measure for other properties. Most
measurement units for a given property are directly proportional to one another (y = mx). Using familiar length units as one
example:
1 ft
length in feet = ( ) × length in inches
12 in.
where y = length in feet, x = length in inches, and the proportionality constant, m, is the conversion factor. The Celsius and
Fahrenheit temperature scales, however, do not share a common zero point, and so the relationship between these two scales is a
linear one rather than a proportional one (y = mx + b). Consequently, converting a temperature from one of these scales into the
other requires more than simple multiplication by a conversion factor, m; it also must take into account differences in the scales’
zero points (b).
The linear equation relating Celsius and Fahrenheit temperatures is easily derived from the two temperatures used to define each
scale. Representing the Celsius temperature as x and the Fahrenheit temperature as y, the slope, m, is computed to be:

Δy 212 °F − 32 °F 180 °F 9 °F
m = = = =
Δx 100 °C − 0 °C 100 °C 5 °C
The y-intercept of the equation, b, is then calculated using either of the equivalent temperature pairs, (100 °C, 212 °F) or (0 °C, 32
°F), as:
9 °F
b = y − mx = 32 °F − × 0 °C = 32 °F
5 °C
The equation relating the temperature (T) scales is then:

9 °F
T°F = ( × T°C ) + 32 °F
5 °C
An abbreviated form of this equation that omits the measurement units is:
9
T°F = ( × T°C ) + 32
5
Rearrangement of this equation yields the form useful for converting from Fahrenheit to Celsius:
5
T°C = (T°F − 32)
9
As mentioned earlier in this chapter, the SI unit of temperature is the kelvin (K). Unlike the Celsius and Fahrenheit scales, the
kelvin scale is an absolute temperature scale in which 0 (zero) K corresponds to the lowest temperature that can theoretically be
achieved. Since the kelvin temperature scale is absolute, a degree symbol is not included in the unit abbreviation, K. The early
19th-century discovery of the relationship between a gas’s volume and temperature suggested that the volume of a gas would be
zero at −273.15 °C. In 1848, British physicist William Thompson, who later adopted the title of Lord Kelvin, proposed an absolute
temperature scale based on this concept (further treatment of this topic is provided in this text’s chapter on gases).
The freezing temperature of water on this scale is 273.15 K and its boiling temperature is 373.15 K. Notice the numerical
difference in these two reference temperatures is 100, the same as for the Celsius scale, and so the linear relation between these two
temperature scales will exhibit a slope of 1 K
°C
. Following the same approach, the equations for converting between the kelvin and
Celsius temperature scales are derived to be:
TK = T°C + 273.15
T°C = TK − 273.15
The 273.15 in these equations has been determined experimentally, so it is not exact. Figure 1.28 shows the relationship among the
three temperature scales.

Figure 1.28 The Fahrenheit, Celsius, and kelvin temperature scales are compared.
Although the kelvin (absolute) temperature scale is the official SI temperature scale, Celsius is commonly used in many scientific
contexts and is the scale of choice for nonscience contexts in almost all areas of the world. Very few countries (the U.S. and its
territories, the Bahamas, Belize, Cayman Islands, and Palau) still use Fahrenheit for weather, medicine, and cooking.
1.7.0.1: Example 1.11

1.7.0.0.1: Conversion from Celsius
Normal body temperature has been commonly accepted as 37.0 °C (although it varies depending on time of day and method of
measurement, as well as among individuals). What is this temperature on the kelvin scale and on the Fahrenheit scale?
1.7.0.0.2: Solution
K = °C + 273.15 = 37.0 + 273.2 = 310.2 K
9 9
°F = °C + 32.0 = ( × 37.0) + 32.0 = 66.6 + 32.0 = 98.6 °F
5 5

Convert 80.92 °C to K and °F.
1.7.0.1: Answer:
354.07 K, 177.7 °F
1.7.0.1: Example 1.12

1.7.0.0.4: Conversion from Fahrenheit
Baking a ready-made pizza calls for an oven temperature of 450 °F. If you are in Europe, and your oven thermometer uses the
Celsius scale, what is the setting? What is the kelvin temperature?
1.7.0.0.5: Solution
5 5 5
°C = (°F − 32) = (450 − 32) = × 418 = 232 °C ⟶ set oven to 230 °C (two significant figures)
9 9 9
2
K = °C + 273.15 = 230 + 273 = 503 K ⟶ 5.0 × 10 K (two significant figures)

Convert 50 °F to °C and K.
1.7.0.1: Answer:
10 °C, 280 K
This page titled 1.7: Mathematical Treatment of Measurement Results is shared under a CC BY 4.0 license and was authored, remixed, and/or
upon request.

1.8: Key Terms
accuracy
how closely a measurement aligns with a correct value
atom
smallest particle of an element that can enter into a chemical combination
Celsius (°C)
unit of temperature; water freezes at 0 °C and boils at 100 °C on this scale
chemical change
change producing a different kind of matter from the original kind of matter
chemical property
behavior that is related to the change of one kind of matter into another kind of matter
chemistry
study of the composition, properties, and interactions of matter
compound
pure substance that can be decomposed into two or more elements
cubic centimeter (cm3 or cc)

volume of a cube with an edge length of exactly 1 cm
cubic meter (m3)

SI unit of volume
density
ratio of mass to volume for a substance or object
dimensional analysis
(also, factor-label method) versatile mathematical approach that can be applied to computations ranging from simple unit
conversions to more complex, multi-step calculations involving several different quantities
element
substance that is composed of a single type of atom; a substance that cannot be decomposed by a chemical change
exact number
number derived by counting or by definition
extensive property
property of a substance that depends on the amount of the substance
Fahrenheit
unit of temperature; water freezes at 32 °F and boils at 212 °F on this scale
gas
state in which matter has neither definite volume nor shape
heterogeneous mixture
combination of substances with a composition that varies from point to point
homogeneous mixture
(also, solution) combination of substances with a composition that is uniform throughout
hypothesis
tentative explanation of observations that acts as a guide for gathering and checking information
intensive property
property of a substance that is independent of the amount of the substance
kelvin (K)
SI unit of temperature; 273.15 K = 0 ºC
kilogram (kg)
standard SI unit of mass; 1 kg = approximately 2.2 pounds
law
statement that summarizes a vast number of experimental observations, and describes or predicts some aspect of the natural
world
law of conservation of matter

when matter converts from one type to another or changes form, there is no detectable change in the total amount of matter
present
length
measure of one dimension of an object
liquid
state of matter that has a definite volume but indefinite shape
liter (L)
(also, cubic decimeter) unit of volume; 1 L = 1,000 cm3
macroscopic domain
realm of everyday things that are large enough to sense directly by human sight and touch
mass
fundamental property indicating amount of matter
matter
anything that occupies space and has mass
meter (m)
standard metric and SI unit of length; 1 m = approximately 1.094 yards
microscopic domain
realm of things that are much too small to be sensed directly
milliliter (mL)
1/1,000 of a liter; equal to 1 cm3
mixture
matter that can be separated into its components by physical means
molecule
bonded collection of two or more atoms of the same or different elements
physical change
change in the state or properties of matter that does not involve a change in its chemical composition
physical property
characteristic of matter that is not associated with any change in its chemical composition
plasma
gaseous state of matter containing a large number of electrically charged atoms and/or molecules
precision
how closely a measurement matches the same measurement when repeated
pure substance
homogeneous substance that has a constant composition
rounding
procedure used to ensure that calculated results properly reflect the uncertainty in the measurements used in the calculation
scientific method
path of discovery that leads from question and observation to law or hypothesis to theory, combined with experimental
verification of the hypothesis and any necessary modification of the theory
second (s)
SI unit of time
SI units (International System of Units)

standards fixed by international agreement in the International System of Units (Le Système International d’Unités)
significant figures
(also, significant digits) all of the measured digits in a determination, including the uncertain last digit
solid
state of matter that is rigid, has a definite shape, and has a fairly constant volume
symbolic domain
specialized language used to represent components of the macroscopic and microscopic domains, such as chemical symbols,
chemical formulas, chemical equations, graphs, drawings, and calculations
temperature
intensive property representing the hotness or coldness of matter
theory
well-substantiated, comprehensive, testable explanation of a particular aspect of nature
uncertainty
estimate of amount by which measurement differs from true value
unit
standard of comparison for measurements
unit conversion factor

ratio of equivalent quantities expressed with different units; used to convert from one unit to a different unit
volume
amount of space occupied by an object
weight
force that gravity exerts on an object
1.8: Key Terms is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.
1.9: Key Equations
mass
density =
volume
5
T°C = × (T°F − 32)
9
9
T°F = ( × T°C ) + 32
5
TK = °C + 273.15
T°C = K − 273.15
1.9: Key Equations is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.
1.10: Summary
1.1 Chemistry in Context
Chemistry deals with the composition, structure, and properties of matter, and the ways by which various forms of matter may be
interconverted. Thus, it occupies a central place in the study and practice of science and technology. Chemists use the scientific
method to perform experiments, pose hypotheses, and formulate laws and develop theories, so that they can better understand the
behavior of the natural world. To do so, they operate in the macroscopic, microscopic, and symbolic domains. Chemists measure,
analyze, purify, and synthesize a wide variety of substances that are important to our lives.
1.2 Phases and Classification of Matter

Matter is anything that occupies space and has mass. The basic building block of matter is the atom, the smallest unit of an element
that can enter into combinations with atoms of the same or other elements. In many substances, atoms are combined into
molecules. On earth, matter commonly exists in three states: solids, of fixed shape and volume; liquids, of variable shape but fixed
volume; and gases, of variable shape and volume. Under high-temperature conditions, matter also can exist as a plasma. Most
matter is a mixture: It is composed of two or more types of matter that can be present in varying amounts and can be separated by
physical means. Heterogeneous mixtures vary in composition from point to point; homogeneous mixtures have the same
composition from point to point. Pure substances consist of only one type of matter. A pure substance can be an element, which
consists of only one type of atom and cannot be broken down by a chemical change, or a compound, which consists of two or more
types of atoms.
1.3 Physical and Chemical Properties

All substances have distinct physical and chemical properties, and may undergo physical or chemical changes. Physical properties,
such as hardness and boiling point, and physical changes, such as melting or freezing, do not involve a change in the composition
of matter. Chemical properties, such flammability and acidity, and chemical changes, such as rusting, involve production of matter
that differs from that present beforehand.
Measurable properties fall into one of two categories. Extensive properties depend on the amount of matter present, for example,
the mass of gold. Intensive properties do not depend on the amount of matter present, for example, the density of gold. Heat is an
example of an extensive property, and temperature is an example of an intensive property.
1.4 Measurements
Measurements provide quantitative information that is critical in studying and practicing chemistry. Each measurement has an
amount, a unit for comparison, and an uncertainty. Measurements can be represented in either decimal or scientific notation.
Scientists primarily use SI (International System) units such as meters, seconds, and kilograms, as well as derived units, such as
liters (for volume) and g/cm3 (for density). In many cases, it is convenient to use prefixes that yield fractional and multiple units,
such as microseconds (10−6 seconds) and megahertz (106 hertz), respectively.
1.5 Measurement Uncertainty, Accuracy, and Precision

Quantities can be defined or measured. Measured quantities have an associated uncertainty that is represented by the number of
significant figures in the quantity’s number. The uncertainty of a calculated quantity depends on the uncertainties in the quantities
used in the calculation and is reflected in how the value is rounded. Quantities are characterized with regard to accuracy (closeness
to a true or accepted value) and precision (variation among replicate measurement results).
1.6 Mathematical Treatment of Measurement Results

Measurements are made using a variety of units. It is often useful or necessary to convert a measured quantity from one unit into
another. These conversions are accomplished using unit conversion factors, which are derived by simple applications of a
mathematical approach called the factor-label method or dimensional analysis. This strategy is also employed to calculate sought
quantities using measured quantities and appropriate mathematical relations.
1.10: Summary is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.
1.11: Exercises
1.11.0.1: 1.1 Chemistry in Context
1.
Explain how you could experimentally determine whether the outside temperature is higher or lower than 0 °C (32 °F) without
using a thermometer.
2.
Identify each of the following statements as being most similar to a hypothesis, a law, or a theory. Explain your reasoning.
(a) Falling barometric pressure precedes the onset of bad weather.
(b) All life on earth has evolved from a common, primitive organism through the process of natural selection.
(c) My truck’s gas mileage has dropped significantly, probably because it’s due for a tune-up.
3.
Identify each of the following statements as being most similar to a hypothesis, a law, or a theory. Explain your reasoning.
(a) The pressure of a sample of gas is directly proportional to the temperature of the gas.
(b) Matter consists of tiny particles that can combine in specific ratios to form substances with specific properties.
(c) At a higher temperature, solids (such as salt or sugar) will dissolve better in water.
4.
Identify each of the underlined items as a part of either the macroscopic domain, the microscopic domain, or the symbolic domain
of chemistry. For any in the symbolic domain, indicate whether they are symbols for a macroscopic or a microscopic feature.
(a) The mass of a lead pipe is 14 lb.
(b) The mass of a certain chlorine atom is 35 amu.
(c) A bottle with a label that reads Al contains aluminum metal.
(d) Al is the symbol for an aluminum atom.
5.
Identify each of the underlined items as a part of either the macroscopic domain, the microscopic domain, or the symbolic domain
of chemistry. For those in the symbolic domain, indicate whether they are symbols for a macroscopic or a microscopic feature.
(a) A certain molecule contains one H atom and one Cl atom.
(b) Copper wire has a density of about 8 g/cm3.
(c) The bottle contains 15 grams of Ni powder.
(d) A sulfur molecule is composed of eight sulfur atoms.
6.
According to one theory, the pressure of a gas increases as its volume decreases because the molecules in the gas have to move a
shorter distance to hit the walls of the container. Does this theory follow a macroscopic or microscopic description of chemical
behavior? Explain your answer.
7.
The amount of heat required to melt 2 lbs of ice is twice the amount of heat required to melt 1 lb of ice. Is this observation a
macroscopic or microscopic description of chemical behavior? Explain your answer.
1.11.0.1: 1.2 Phases and Classification of Matter

8.
Why is an object’s mass, rather than its weight, used to indicate the amount of matter it contains?
9.

What properties distinguish solids from liquids? Liquids from gases? Solids from gases?
10.
How does a heterogeneous mixture differ from a homogeneous mixture? How are they similar?
11.
How does a homogeneous mixture differ from a pure substance? How are they similar?
12.
How does an element differ from a compound? How are they similar?
13.
How do molecules of elements and molecules of compounds differ? In what ways are they similar?
14.
How does an atom differ from a molecule? In what ways are they similar?
15.
Many of the items you purchase are mixtures of pure compounds. Select three of these commercial products and prepare a list of
the ingredients that are pure compounds.
16.
Classify each of the following as an element, a compound, or a mixture:
(a) copper
(b) water
(c) nitrogen
(d) sulfur
(e) air
(f) sucrose
(g) a substance composed of molecules each of which contains two iodine atoms
(h) gasoline
17.
Classify each of the following as an element, a compound, or a mixture:
(a) iron
(b) oxygen
(c) mercury oxide
(d) pancake syrup
(e) carbon dioxide
(f) a substance composed of molecules each of which contains one hydrogen atom and one chlorine atom
(g) baking soda
(h) baking powder
18.
A sulfur atom and a sulfur molecule are not identical. What is the difference?
19.
How are the molecules in oxygen gas, the molecules in hydrogen gas, and water molecules similar? How do they differ?
20.

Why are astronauts in space said to be “weightless,” but not “massless”?
21.
Prepare a list of the principal chemicals consumed and produced during the operation of an automobile.
22.
Matter is everywhere around us. Make a list by name of fifteen different kinds of matter that you encounter every day. Your list
should include (and label at least one example of each) the following: a solid, a liquid, a gas, an element, a compound, a
homogenous mixture, a heterogeneous mixture, and a pure substance.
23.
When elemental iron corrodes it combines with oxygen in the air to ultimately form red brown iron(III) oxide called rust. (a) If a
shiny iron nail with an initial mass of 23.2 g is weighed after being coated in a layer of rust, would you expect the mass to have
increased, decreased, or remained the same? Explain. (b) If the mass of the iron nail increases to 24.1 g, what mass of oxygen
combined with the iron?
24.
As stated in the text, convincing examples that demonstrate the law of conservation of matter outside of the laboratory are few and
far between. Indicate whether the mass would increase, decrease, or stay the same for the following scenarios where chemical
reactions take place:
(a) Exactly one pound of bread dough is placed in a baking tin. The dough is cooked in an oven at 350 °F releasing a wonderful
aroma of freshly baked bread during the cooking process. Is the mass of the baked loaf less than, greater than, or the same as the
one pound of original dough? Explain.
(b) When magnesium burns in air a white flaky ash of magnesium oxide is produced. Is the mass of magnesium oxide less than,
greater than, or the same as the original piece of magnesium? Explain.
(c) Antoine Lavoisier, the French scientist credited with first stating the law of conservation of matter, heated a mixture of tin and
air in a sealed flask to produce tin oxide. Did the mass of the sealed flask and contents decrease, increase, or remain the same after
the heating?
25.
Yeast converts glucose to ethanol and carbon dioxide during anaerobic fermentation as depicted in the simple chemical equation
here:
glucose ⟶ ethanol + carbon dioxide
(a) If 200.0 g of glucose is fully converted, what will be the total mass of ethanol and carbon dioxide produced?
(b) If the fermentation is carried out in an open container, would you expect the mass of the container and contents after
fermentation to be less than, greater than, or the same as the mass of the container and contents before fermentation? Explain.
(c) If 97.7 g of carbon dioxide is produced, what mass of ethanol is produced?
1.11.0.1: 1.3 Physical and Chemical Properties

26.
Classify the six underlined properties in the following paragraph as chemical or physical:
Fluorine is a pale yellow gas that reacts with most substances. The free element melts at −220 °C and boils at −188 °C. Finely
divided metals burn in fluorine with a bright flame. Nineteen grams of fluorine will react with 1.0 gram of hydrogen.
27.
Classify each of the following changes as physical or chemical:
(a) condensation of steam
(b) burning of gasoline
(c) souring of milk
(d) dissolving of sugar in water

(e) melting of gold
28.
Classify each of the following changes as physical or chemical:
(a) coal burning
(b) ice melting
(c) mixing chocolate syrup with milk
(d) explosion of a firecracker
(e) magnetizing of a screwdriver
29.
The volume of a sample of oxygen gas changed from 10 mL to 11 mL as the temperature changed. Is this a chemical or physical
change?
30.
A 2.0-liter volume of hydrogen gas combined with 1.0 liter of oxygen gas to produce 2.0 liters of water vapor. Does oxygen
undergo a chemical or physical change?
31.
Explain the difference between extensive properties and intensive properties.
32.
Identify the following properties as either extensive or intensive.
(a) volume
(b) temperature
(c) humidity
(d) heat
(e) boiling point
33.
The density (d) of a substance is an intensive property that is defined as the ratio of its mass (m) to its volume (V).
mass m
density = d=
volume V
Considering that mass and volume are both extensive properties, explain why their ratio, density, is intensive.
1.11.0.1: 1.4 Measurements

34.
Is one liter about an ounce, a pint, a quart, or a gallon?
35.
Is a meter about an inch, a foot, a yard, or a mile?
36.
Indicate the SI base units or derived units that are appropriate for the following measurements:
(a) the length of a marathon race (26 miles 385 yards)
(b) the mass of an automobile
(c) the volume of a swimming pool
(d) the speed of an airplane
(e) the density of gold

(f) the area of a football field
(g) the maximum temperature at the South Pole on April 1, 1913
37.
Indicate the SI base units or derived units that are appropriate for the following measurements:
(a) the mass of the moon
(b) the distance from Dallas to Oklahoma City
(c) the speed of sound
(d) the density of air
(e) the temperature at which alcohol boils
(f) the area of the state of Delaware
(g) the volume of a flu shot or a measles vaccination
38.
Give the name and symbol of the prefixes used with SI units to indicate multiplication by the following exact quantities.
(a) 103
(b) 10−2
(c) 0.1
(d) 10−3
(e) 1,000,000
(f) 0.000001
39.
Give the name of the prefix and the quantity indicated by the following symbols that are used with SI base units.
(a) c
(b) d
(c) G
(d) k
(e) m
(f) n
(g) p
(h) T
40.
A large piece of jewelry has a mass of 132.6 g. A graduated cylinder initially contains 48.6 mL water. When the jewelry is
submerged in the graduated cylinder, the total volume increases to 61.2 mL.
(a) Determine the density of this piece of jewelry.
(b) Assuming that the jewelry is made from only one substance, what substance is it likely to be? Explain.
41.
Visit this density simulation and click the "turn fluid into water" button to adjust the density of liquid in the beaker to 1.00 g/mL.
(a) Use the water displacement approach to measure the mass and volume of the unknown material (select the green block with
question marks).
(b) Use the measured mass and volume data from step (a) to calculate the density of the unknown material.

(c) Link out to the link provided.
(d) Assuming this material is a copper-containing gemstone, identify its three most likely identities by comparing the measured
density to the values tabulated at this gemstone density guide.
(e) How are mass and density related for blocks of the same volume?
42.
Visit this density simulation and click the "reset" button to ensure all simulator parameters are at their default values.
(a) Use the water displacement approach to measure the mass and volume of the red block.
(b) Use the measured mass and volume data from step (a) to calculate the density of the red block.
(c) Use the vertical green slide control to adjust the fluid density to values well above, then well below, and finally nearly equal to
the density of the red block, reporting your observations.
43.
Visit this density simulation and click the “turn fluid into water” button to adjust the density of liquid in the beaker to 1.00 g/mL.
Change the block material to foam, and then wait patiently until the foam block stops bobbing up and down in the water.
(a) The foam block should be floating on the surface of the water (that is, only partially submerged). What is the volume of water
displaced?
(b) Use the water volume from part (a) and the density of water (1.00 g/mL) to calculate the mass of water displaced.
(c) Remove and weigh the foam block. How does the block’s mass compare to the mass of displaced water from part (b)?
1.11.0.1: 1.5 Measurement Uncertainty, Accuracy, and Precision

44.
Express each of the following numbers in scientific notation with correct significant figures:
(a) 711.0
(b) 0.239
(c) 90743
(d) 134.2
(e) 0.05499
(f) 10000.0
(g) 0.000000738592
45.
Express each of the following numbers in exponential notation with correct significant figures:
(a) 704
(b) 0.03344
(c) 547.9
(d) 22086
(e) 1000.00
(f) 0.0000000651
(g) 0.007157
46.
Indicate whether each of the following can be determined exactly or must be measured with some degree of uncertainty:
(a) the number of eggs in a basket
(b) the mass of a dozen eggs

(c) the number of gallons of gasoline necessary to fill an automobile gas tank
(d) the number of cm in 2 m
(e) the mass of a textbook
(f) the time required to drive from San Francisco to Kansas City at an average speed of 53 mi/h
47.
Indicate whether each of the following can be determined exactly or must be measured with some degree of uncertainty:
(a) the number of seconds in an hour
(b) the number of pages in this book
(c) the number of grams in your weight
(d) the number of grams in 3 kilograms
(e) the volume of water you drink in one day
(f) the distance from San Francisco to Kansas City
48.
How many significant figures are contained in each of the following measurements?
(a) 38.7 g
(b) 2 × 1018 m
(c) 3,486,002 kg
(d) 9.74150 × 10−4 J
(e) 0.0613 cm3
(f) 17.0 kg
(g) 0.01400 g/mL
49.
How many significant figures are contained in each of the following measurements?
(a) 53 cm
(b) 2.05 × 108 m
(c) 86,002 J
(d) 9.740 × 104 m/s
(e) 10.0613 m3
(f) 0.17 g/mL
(g) 0.88400 s
50.
The following quantities were reported on the labels of commercial products. Determine the number of significant figures in each.
(a) 0.0055 g active ingredients
(b) 12 tablets
(c) 3% hydrogen peroxide
(d) 5.5 ounces
(e) 473 mL
(f) 1.75% bismuth
(g) 0.001% phosphoric acid

(h) 99.80% inert ingredients
51.
Round off each of the following numbers to two significant figures:
(a) 0.436
(b) 9.000
(c) 27.2
(d) 135
(e) 1.497 × 10−3
(f) 0.445
52.
Round off each of the following numbers to two significant figures:
(a) 517
(b) 86.3
(c) 6.382 × 103
(d) 5.0008
(e) 22.497
(f) 0.885
53.
Perform the following calculations and report each answer with the correct number of significant figures.
(a) 628 × 342
(b) (5.63 × 102) × (7.4 × 103)
(c) 28.0
13.483
(d) 8119 × 0.000023

(e) 14.98 + 27,340 + 84.7593
(f) 42.7 + 0.259
54.
Perform the following calculations and report each answer with the correct number of significant figures.
(a) 62.8 × 34
(b) 0.147 + 0.0066 + 0.012
(c) 38 × 95 × 1.792
(d) 15 – 0.15 – 0.6155
(e) 8.78 × (
0.0500
0.478
)
(f) 140 + 7.68 + 0.014

(g) 28.7 – 0.0483
(88.5−87.57)
(h) 45.13
55.
Consider the results of the archery contest shown in this figure.
(a) Which archer is most precise?

(b) Which archer is most accurate?
(c) Who is both least precise and least accurate?
56.
Classify the following sets of measurements as accurate, precise, both, or neither.
(a) Checking for consistency in the weight of chocolate chip cookies: 17.27 g, 13.05 g, 19.46 g, 16.92 g
(b) Testing the volume of a batch of 25-mL pipettes: 27.02 mL, 26.99 mL, 26.97 mL, 27.01 mL
(c) Determining the purity of gold: 99.9999%, 99.9998%, 99.9998%, 99.9999%
1.11.0.1: 1.6 Mathematical Treatment of Measurement Results

57.
Write conversion factors (as ratios) for the number of:
(a) yards in 1 meter
(b) liters in 1 liquid quart
(c) pounds in 1 kilogram
58.
Write conversion factors (as ratios) for the number of:
(a) kilometers in 1 mile
(b) liters in 1 cubic foot
(c) grams in 1 ounce
59.
The label on a soft drink bottle gives the volume in two units: 2.0 L and 67.6 fl oz. Use this information to derive a conversion
factor between the English and metric units. How many significant figures can you justify in your conversion factor?
60.
The label on a box of cereal gives the mass of cereal in two units: 978 grams and 34.5 oz. Use this information to find a conversion
factor between the English and metric units. How many significant figures can you justify in your conversion factor?
61.
Soccer is played with a round ball having a circumference between 27 and 28 in. and a weight between 14 and 16 oz. What are
these specifications in units of centimeters and grams?
62.

A woman’s basketball has a circumference between 28.5 and 29.0 inches and a maximum weight of 20 ounces (two significant
figures). What are these specifications in units of centimeters and grams?
63.
How many milliliters of a soft drink are contained in a 12.0-oz can?
64.
A barrel of oil is exactly 42 gal. How many liters of oil are in a barrel?
65.
The diameter of a red blood cell is about 3 × 10−4 in. What is its diameter in centimeters?
66.
The distance between the centers of the two oxygen atoms in an oxygen molecule is 1.21 × 10−8 cm. What is this distance in
inches?
67.
Is a 197-lb weight lifter light enough to compete in a class limited to those weighing 90 kg or less?
68.
A very good 197-lb weight lifter lifted 192 kg in a move called the clean and jerk. What was the mass of the weight lifted in
pounds?
69.
Many medical laboratory tests are run using 5.0 μL blood serum. What is this volume in milliliters?
70.
If an aspirin tablet contains 325 mg aspirin, how many grams of aspirin does it contain?
71.
Use scientific (exponential) notation to express the following quantities in terms of the SI base units in Table 1.2:
(a) 0.13 g
(b) 232 Gg
(c) 5.23 pm
(d) 86.3 mg
(e) 37.6 cm
(f) 54 μm
(g) 1 Ts
(h) 27 ps
(i) 0.15 mK
72.
Complete the following conversions between SI units.
(a) 612 g = ________ mg
(b) 8.160 m = ________ cm
(c) 3779 μg = ________ g
(d) 781 mL = ________ L
(e) 4.18 kg = ________ g
(f) 27.8 m = ________ km
(g) 0.13 mL = ________ L

(h) 1738 km = ________ m
(i) 1.9 Gg = ________ g
73.
Gasoline is sold by the liter in many countries. How many liters are required to fill a 12.0-gal gas tank?
74.
Milk is sold by the liter in many countries. What is the volume of exactly 1/2 gal of milk in liters?
75.
A long ton is defined as exactly 2240 lb. What is this mass in kilograms?
76.
Make the conversion indicated in each of the following:
(a) the men’s world record long jump, 29 ft 4¼ in., to meters
(b) the greatest depth of the ocean, about 6.5 mi, to kilometers
(c) the area of the state of Oregon, 96,981 mi2, to square kilometers
(d) the volume of 1 gill (exactly 4 oz) to milliliters
(e) the estimated volume of the oceans, 330,000,000 mi3, to cubic kilometers.
(f) the mass of a 3525-lb car to kilograms
(g) the mass of a 2.3-oz egg to grams
77.
Make the conversion indicated in each of the following:
(a) the length of a soccer field, 120 m (three significant figures), to feet
(b) the height of Mt. Kilimanjaro, at 19,565 ft, the highest mountain in Africa, to kilometers
(c) the area of an 8.5- × 11-inch sheet of paper in cm2
(d) the displacement volume of an automobile engine, 161 in.3, to liters
(e) the estimated mass of the atmosphere, 5.6 × 1015 tons, to kilograms
(f) the mass of a bushel of rye, 32.0 lb, to kilograms
(g) the mass of a 5.00-grain aspirin tablet to milligrams (1 grain = 0.00229 oz)
78.
Many chemistry conferences have held a 50-Trillion Angstrom Run (two significant figures). How long is this run in kilometers
and in miles? (1 Å = 1 × 10−10 m)
79.
A chemist’s 50-Trillion Angstrom Run (see Exercise 1.78) would be an archeologist’s 10,900 cubit run. How long is one cubit in
meters and in feet? (1 Å = 1 × 10−8 cm)
80.
The gas tank of a certain luxury automobile holds 22.3 gallons according to the owner’s manual. If the density of gasoline is 0.8206
g/mL, determine the mass in kilograms and pounds of the fuel in a full tank.
81.
As an instructor is preparing for an experiment, he requires 225 g phosphoric acid. The only container readily available is a 150-
mL Erlenmeyer flask. Is it large enough to contain the acid, whose density is 1.83 g/mL?
82.

To prepare for a laboratory period, a student lab assistant needs 125 g of a compound. A bottle containing 1/4 lb is available. Did
the student have enough of the compound?
83.
A chemistry student is 159 cm tall and weighs 45.8 kg. What is her height in inches and weight in pounds?
84.
In a recent Grand Prix, the winner completed the race with an average speed of 229.8 km/h. What was his speed in miles per hour,
meters per second, and feet per second?
85.
Solve these problems about lumber dimensions.
(a) To describe to a European how houses are constructed in the US, the dimensions of “two-by-four” lumber must be converted
into metric units. The thickness × width × length dimensions are 1.50 in. × 3.50 in. × 8.00 ft in the US. What are the dimensions
in cm × cm × m?
(b) This lumber can be used as vertical studs, which are typically placed 16.0 in. apart. What is that distance in centimeters?
86.
The mercury content of a stream was believed to be above the minimum considered safe—1 part per billion (ppb) by weight. An
analysis indicated that the concentration was 0.68 parts per billion. What quantity of mercury in grams was present in 15.0 L of the
1 ng Hg
water, the density of which is 0.998 g/ml? (1 ppb Hg = 1 g water
)
87.
Calculate the density of aluminum if 27.6 cm3 has a mass of 74.6 g.
88.
Osmium is one of the densest elements known. What is its density if 2.72 g has a volume of 0.121 cm3?
89.
Calculate these masses.
(a) What is the mass of 6.00 cm3 of mercury, density = 13.5939 g/cm3?
(b) What is the mass of 25.0 mL octane, density = 0.702 g/cm3?
90.
Calculate these masses.
(a) What is the mass of 4.00 cm3 of sodium, density = 0.97 g/cm3 ?
(b) What is the mass of 125 mL gaseous chlorine, density = 3.16 g/L?
91.
Calculate these volumes.
(a) What is the volume of 25 g iodine, density = 4.93 g/cm3?
(b) What is the volume of 3.28 g gaseous hydrogen, density = 0.089 g/L?
92.
Calculate these volumes.
(a) What is the volume of 11.3 g graphite, density = 2.25 g/cm3?
(b) What is the volume of 39.657 g bromine, density = 2.928 g/cm3?
93.
Convert the boiling temperature of gold, 2966 °C, into degrees Fahrenheit and kelvin.
94.
Convert the temperature of scalding water, 54 °C, into degrees Fahrenheit and kelvin.

95.
Convert the temperature of the coldest area in a freezer, −10 °F, to degrees Celsius and kelvin.
96.
Convert the temperature of dry ice, −77 °C, into degrees Fahrenheit and kelvin.
97.
Convert the boiling temperature of liquid ammonia, −28.1 °F, into degrees Celsius and kelvin.
98.
The label on a pressurized can of spray disinfectant warns against heating the can above 130 °F. What are the corresponding
temperatures on the Celsius and kelvin temperature scales?
99.
The weather in Europe was unusually warm during the summer of 1995. The TV news reported temperatures as high as 45 °C.
What was the temperature on the Fahrenheit scale?
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CHAPTER OVERVIEW
2: Atoms, Molecules, and Ions

General Chemistry
This chapter will describe some of the fundamental chemical principles related to the composition of matter, including those central
to the concept of molecular identity.
2.1: Introduction
2.9: Key Terms
2.10: Key Equations
2.11: Summary
2.12: Exercises
Thumbnail: Spinning Buckminsterfullerene (C ). (CC BY-SA 3.0; unported; Sponk).

60
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1
2.1: Introduction
Figure 2.1 Analysis of molecules in an exhaled breath can provide valuable information, leading to early diagnosis of diseases or
detection of environmental exposure to harmful substances. (credit: modification of work by Paul Flowers)
2.1.0.1: Chapter Outline

2.1 Early Ideas in Atomic Theory
2.2 Evolution of Atomic Theory
2.3 Atomic Structure and Symbolism
2.4 Chemical Formulas
2.5 The Periodic Table
2.6 Ionic and Molecular Compounds
2.7 Chemical Nomenclature
Lung diseases and lung cancers are among the world's most devastating illnesses partly due to delayed detection and diagnosis.
Most noninvasive screening procedures aren't reliable, and patients often resist more accurate methods due to discomfort with the
procedures or with the potential danger that the procedures cause. But what if you could be accurately diagnosed through a simple
breath test?
Early detection of biomarkers, substances that indicate an organism’s disease or physiological state, could allow diagnosis and
treatment before a condition becomes serious or irreversible. Recent studies have shown that your exhaled breath can contain
molecules that may be biomarkers for recent exposure to environmental contaminants or for pathological conditions ranging from
asthma to lung cancer. Scientists are working to develop biomarker “fingerprints” that could be used to diagnose a specific disease
based on the amounts and identities of certain molecules in a patient’s exhaled breath. In Sangeeta Bhatia's lab at MIT, a team used
substances that react specifically inside diseased lung tissue; the products of the reactions will be present as biomarkers that can be
identified through mass spectrometry (an analytical method discussed later in the chapter). A potential application would allow
patients with early symptoms to inhale or ingest a "sensor" substance, and, minutes later, to breathe into a detector for diagnosis.
Similar research by scientists such as Laura López-Sánchez has provided similar processes for lung cancer. An essential concept
underlying this goal is that of a molecule’s identity, which is determined by the numbers and types of atoms it contains, and how
they are bonded together. This chapter will describe some of the fundamental chemical principles related to the composition of
matter, including those central to the concept of molecular identity.
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State the postulates of Dalton’s atomic theory
Use postulates of Dalton’s atomic theory to explain the laws of definite and multiple proportions
The earliest recorded discussion of the basic structure of matter comes from ancient Greek philosophers, the scientists of their day.
In the fifth century BC, Leucippus and Democritus argued that all matter was composed of small, finite particles that they called
atomos, a term derived from the Greek word for “indivisible.” They thought of atoms as moving particles that differed in shape and
size, and which could join together. Later, Aristotle and others came to the conclusion that matter consisted of various
combinations of the four “elements”—fire, earth, air, and water—and could be infinitely divided. Interestingly, these philosophers
thought about atoms and “elements” as philosophical concepts, but apparently never considered performing experiments to test
their ideas.
The Aristotelian view of the composition of matter held sway for over two thousand years, until English schoolteacher John Dalton
helped to revolutionize chemistry with his hypothesis that the behavior of matter could be explained using an atomic theory. First
published in 1807, many of Dalton’s hypotheses about the microscopic features of matter are still valid in modern atomic theory.
Here are the postulates of Dalton’s atomic theory.
1. Matter is composed of exceedingly small particles called atoms. An atom is the smallest unit of an element that can participate
in a chemical change.
2. An element consists of only one type of atom, which has a mass that is characteristic of the element and is the same for all
atoms of that element (Figure 2.2). A macroscopic sample of an element contains an incredibly large number of atoms, all of
which have identical chemical properties.
Figure 2.2 A pre-1982 copper penny (left) contains approximately 3 × 1022 copper atoms (several dozen are represented as
brown spheres at the right), each of which has the same chemical properties. (credit: modification of work by “slgckgc”/Flickr)
3. Atoms of one element differ in properties from atoms of all other elements.
4. A compound consists of atoms of two or more elements combined in a small, whole-number ratio. In a given compound, the
numbers of atoms of each of its elements are always present in the same ratio (Figure 2.3).

Figure 2.3 Copper(II) oxide, a powdery, black compound, results from the combination of two types of atoms—copper (brown
spheres) and oxygen (red spheres)—in a 1:1 ratio. (credit: modification of work by “Chemicalinterest”/Wikimedia Commons)
5. Atoms are neither created nor destroyed during a chemical change, but are instead rearranged to yield substances that are
different from those present before the change (Figure 2.4).
Figure 2.4 When the elements copper (a shiny, red-brown solid, shown here as brown spheres) and oxygen (a clear and
colorless gas, shown here as red spheres) react, their atoms rearrange to form a compound containing copper and oxygen (a
powdery, black solid). (credit copper: modification of work by http://images-of-elements.com/copper.php)
Dalton’s atomic theory provides a microscopic explanation of the many macroscopic properties of matter that you’ve learned about.
For example, if an element such as copper consists of only one kind of atom, then it cannot be broken down into simpler
substances, that is, into substances composed of fewer types of atoms. And if atoms are neither created nor destroyed during a
chemical change, then the total mass of matter present when matter changes from one type to another will remain constant (the law
of conservation of matter).
2.2.0.1: Example 2.1

2.2.0.0.1: Testing Dalton’s Atomic Theory
In the following drawing, the green spheres represent atoms of a certain element. The purple spheres represent atoms of
another element. If the spheres touch, they are part of a single unit of a compound. Does the following chemical change
represented by these symbols violate any of the ideas of Dalton’s atomic theory? If so, which one?
2.2.0.0.1: Solution
The starting materials consist of two green spheres and two purple spheres. The products consist of only one green sphere and
one purple sphere. This violates Dalton’s postulate that atoms are neither created nor destroyed during a chemical change, but
are merely redistributed. (In this case, atoms appear to have been destroyed.)
In the following drawing, the green spheres represent atoms of a certain element. The purple spheres represent atoms of
another element. If the spheres touch, they are part of a single unit of a compound. Does the following chemical change
represented by these symbols violate any of the ideas of Dalton’s atomic theory? If so, which one?

2.2.0.1: Answer:
The starting materials consist of four green spheres and two purple spheres. The products consist of four green spheres and
two purple spheres. This does not violate any of Dalton’s postulates: Atoms are neither created nor destroyed, but are
redistributed in small, whole-number ratios.
Dalton knew of the experiments of French chemist Joseph Proust, who demonstrated that all samples of a pure compound contain
the same elements in the same proportion by mass. This statement is known as the law of definite proportions or the law of constant
composition. The suggestion that the numbers of atoms of the elements in a given compound always exist in the same ratio is
consistent with these observations. For example, when different samples of isooctane (a component of gasoline and one of the
standards used in the octane rating system) are analyzed, they are found to have a carbon-to-hydrogen mass ratio of 5.33:1, as
shown in Table 2.1.
Constant Composition of Isooctane
Sample Carbon Hydrogen Mass Ratio
A 14.82 g 2.78 g 14.82 g carbon

=
5.33 g carbon
2.78 g hydrogen 1.00 g hydrogen
B 22.33 g 4.19 g 22.33 g carbon

=
5.33 g carbon
C 19.40 g 3.64 g 19.40 g carbon

=
5.33 g carbon
Table 2.1
It is worth noting that although all samples of a particular compound have the same mass ratio, the converse is not true in general.
That is, samples that have the same mass ratio are not necessarily the same substance. For example, there are many compounds
other than isooctane that also have a carbon-to-hydrogen mass ratio of 5.33:1.00.
Dalton also used data from Proust, as well as results from his own experiments, to formulate another interesting law. The law of
multiple proportions states that when two elements react to form more than one compound, a fixed mass of one element will react
with masses of the other element in a ratio of small, whole numbers. For example, copper and chlorine can form a green, crystalline
solid with a mass ratio of 0.558 g chlorine to 1 g copper, as well as a brown crystalline solid with a mass ratio of 1.116 g chlorine to
1 g copper. These ratios by themselves may not seem particularly interesting or informative; however, if we take a ratio of these
ratios, we obtain a useful and possibly surprising result: a small, whole-number ratio.
1.116 g Cl
1 g Cu 2
=
0.558 g Cl 1
1 g Cu
This 2-to-1 ratio means that the brown compound has twice the amount of chlorine per amount of copper as the green compound.
This can be explained by atomic theory if the copper-to-chlorine ratio in the brown compound is 1 copper atom to 2 chlorine atoms,
and the ratio in the green compound is 1 copper atom to 1 chlorine atom. The ratio of chlorine atoms (and thus the ratio of their
masses) is therefore 2 to 1 (Figure 2.5).

Figure 2.5 Compared to the copper chlorine compound in (a), where copper is represented by brown spheres and chlorine by green
spheres, the copper chlorine compound in (b) has twice as many chlorine atoms per copper atom. (credit a: modification of work by
“Benjah-bmm27”/Wikimedia Commons; credit b: modification of work by “Walkerma”/Wikimedia Commons)
2.2.0.1: Example 2.2

2.2.0.0.1: Laws of Definite and Multiple Proportions
A sample of compound A (a clear, colorless gas) is analyzed and found to contain 4.27 g carbon and 5.69 g oxygen. A sample
of compound B (also a clear, colorless gas) is analyzed and found to contain 5.19 g carbon and 13.84 g oxygen. Are these data
an example of the law of definite proportions, the law of multiple proportions, or neither? What do these data tell you about
substances A and B?
2.2.0.0.1: Solution
In compound A, the mass ratio of oxygen to carbon is:
1.33 g O
1 g C
In compound B, the mass ratio of oxygen to carbon is:

2.67 g O
1 g C
The ratio of these ratios is:

1.33 g O
1 g C 1
=
2.67 g O
2
1 g C
This supports the law of multiple proportions. This means that A and B are different compounds, with A having one-half as
much oxygen per amount of carbon (or twice as much carbon per amount of oxygen) as B. A possible pair of compounds that
would fit this relationship would be A = CO and B = CO2.
A sample of compound X (a clear, colorless, combustible liquid with a noticeable odor) is analyzed and found to contain 14.13
g carbon and 2.96 g hydrogen. A sample of compound Y (a clear, colorless, combustible liquid with a noticeable odor that is
slightly different from X’s odor) is analyzed and found to contain 19.91 g carbon and 3.34 g hydrogen. Are these data an
example of the law of definite proportions, the law of multiple proportions, or neither? What do these data tell you about
substances X and Y?

2.2.0.1: Answer:
14.13 g C
In compound X, the mass ratio of carbon to hydrogen is 2.96 g H
. In compound Y, the mass ratio of carbon to hydrogen is
14.13 g C
19.91 g C 4.77 g C/g H

The ratio of these ratios is 4
This small, whole-number ratio supports the
2.96 g H
. 19.91 g C
= = 0.800 = .
3.34 g H 5.96 g C/g H 5
3.34 g H
law of multiple proportions. This means that X and Y are different compounds.
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Outline milestones in the development of modern atomic theory
Summarize and interpret the results of the experiments of Thomson, Millikan, and Rutherford
Describe the three subatomic particles that compose atoms
Define isotopes and give examples for several elements
If matter is composed of atoms, what are atoms composed of? Are they the smallest particles, or is there something smaller? In the
late 1800s, a number of scientists interested in questions like these investigated the electrical discharges that could be produced in
low-pressure gases, with the most significant discovery made by English physicist J. J. Thomson using a cathode ray tube. This
apparatus consisted of a sealed glass tube from which almost all the air had been removed; the tube contained two metal electrodes.
When high voltage was applied across the electrodes, a visible beam called a cathode ray appeared between them. This beam was
deflected toward the positive charge and away from the negative charge, and was produced in the same way with identical
properties when different metals were used for the electrodes. In similar experiments, the ray was simultaneously deflected by an
applied magnetic field, and measurements of the extent of deflection and the magnetic field strength allowed Thomson to calculate
the charge-to-mass ratio of the cathode ray particles. The results of these measurements indicated that these particles were much
lighter than atoms (Figure 2.6).
Figure 2.6 (a) J. J. Thomson produced a visible beam in a cathode ray tube. (b) This is an early cathode ray tube, invented in 1897
by Ferdinand Braun. (c) In the cathode ray, the beam (shown in yellow) comes from the cathode and is accelerated past the anode
toward a fluorescent scale at the end of the tube. Simultaneous deflections by applied electric and magnetic fields permitted

Thomson to calculate the mass-to-charge ratio of the particles composing the cathode ray. (credit a: modification of work by Nobel
Foundation; credit b: modification of work by Eugen Nesper; credit c: modification of work by “Kurzon”/Wikimedia Commons)
Based on his observations, here is what Thomson proposed and why: The particles are attracted by positive (+) charges and
repelled by negative (−) charges, so they must be negatively charged (like charges repel and unlike charges attract); they are less
massive than atoms and indistinguishable, regardless of the source material, so they must be fundamental, subatomic constituents
of all atoms. Although controversial at the time, Thomson’s idea was gradually accepted, and his cathode ray particle is what we
now call an electron, a negatively charged, subatomic particle with a mass more than one thousand-times less that of an atom. The
term “electron” was coined in 1891 by Irish physicist George Stoney, from “electric ion.”

Click here to hear Thomson describe his discovery in his own voice.
In 1909, more information about the electron was uncovered by American physicist Robert A. Millikan via his “oil drop”
experiments. Millikan created microscopic oil droplets, which could be electrically charged by friction as they formed or by using
X-rays. These droplets initially fell due to gravity, but their downward progress could be slowed or even reversed by an electric
field lower in the apparatus. By adjusting the electric field strength and making careful measurements and appropriate calculations,
Millikan was able to determine the charge on individual drops (Figure 2.7).
Figure 2.7 Millikan’s experiment measured the charge of individual oil drops. The tabulated data are examples of a few possible
values.
Looking at the charge data that Millikan gathered, you may have recognized that the charge of an oil droplet is always a multiple of
a specific charge, 1.6 × 10−19 C. Millikan concluded that this value must therefore be a fundamental charge—the charge of a single
electron—with his measured charges due to an excess of one electron (1 times 1.6 × 10−19 C), two electrons (2 times 1.6 × 10−19
C), three electrons (3 times 1.6 × 10−19 C), and so on, on a given oil droplet. Since the charge of an electron was now known due
to Millikan’s research, and the charge-to-mass ratio was already known due to Thomson’s research (1.759 × 1011 C/kg), it only
required a simple calculation to determine the mass of the electron as well.
1 kg
−19 −31
Mass of electron = 1.602 × 10 C × = 9.107 × 10 kg
11
1.759 × 10 C
Scientists had now established that the atom was not indivisible as Dalton had believed, and due to the work of Thomson, Millikan,
and others, the charge and mass of the negative, subatomic particles—the electrons—were known. However, the positively charged

part of an atom was not yet well understood. In 1904, Thomson proposed the “plum pudding” model of atoms, which described a
positively charged mass with an equal amount of negative charge in the form of electrons embedded in it, since all atoms are
electrically neutral. A competing model had been proposed in 1903 by Hantaro Nagaoka, who postulated a Saturn-like atom,
consisting of a positively charged sphere surrounded by a halo of electrons (Figure 2.8).
Figure 2.8 (a) Thomson suggested that atoms resembled plum pudding, an English dessert consisting of moist cake with embedded
raisins (“plums”). (b) Nagaoka proposed that atoms resembled the planet Saturn, with a ring of electrons surrounding a positive
“planet.” (credit a: modification of work by “Man vyi”/Wikimedia Commons; credit b: modification of work by
“NASA”/Wikimedia Commons)
The next major development in understanding the atom came from Ernest Rutherford, a physicist from New Zealand who largely
spent his scientific career in Canada and England. He performed a series of experiments using a beam of high-speed, positively
charged alpha particles (α particles) that were produced by the radioactive decay of radium; α particles consist of two protons and
two neutrons (you will learn more about radioactive decay in the chapter on nuclear chemistry). Rutherford and his colleagues
Hans Geiger (later famous for the Geiger counter) and Ernest Marsden aimed a beam of α particles, the source of which was
embedded in a lead block to absorb most of the radiation, at a very thin piece of gold foil and examined the resultant scattering of
the α particles using a luminescent screen that glowed briefly where hit by an α particle.
What did they discover? Most particles passed right through the foil without being deflected at all. However, some were diverted
slightly, and a very small number were deflected almost straight back toward the source (Figure 2.9). Rutherford described finding
these results: “It was quite the most incredible event that has ever happened to me in my life. It was almost as incredible as if you
fired a 15-inch shell at a piece of tissue paper and it came back and hit you.”1
Figure 2.9 Geiger and Rutherford fired α particles at a piece of gold foil and detected where those particles went, as shown in this
schematic diagram of their experiment. Most of the particles passed straight through the foil, but a few were deflected slightly and

a very small number were significantly deflected.
Here is what Rutherford deduced: Because most of the fast-moving α particles passed through the gold atoms undeflected, they
must have traveled through essentially empty space inside the atom. Alpha particles are positively charged, so deflections arose
when they encountered another positive charge (like charges repel each other). Since like charges repel one another, the few
positively charged α particles that changed paths abruptly must have hit, or closely approached, another body that also had a highly
concentrated, positive charge. Since the deflections occurred a small fraction of the time, this charge only occupied a small amount
of the space in the gold foil. Analyzing a series of such experiments in detail, Rutherford drew two conclusions:
1. The volume occupied by an atom must consist of a large amount of empty space.
2. A small, relatively heavy, positively charged body, the nucleus, must be at the center of each atom.

View this simulation of the Rutherford gold foil experiment. Adjust the slit width to produce a narrower or broader beam of α
particles to see how that affects the scattering pattern.
This analysis led Rutherford to propose a model in which an atom consists of a very small, positively charged nucleus, in which
most of the mass of the atom is concentrated, surrounded by the negatively charged electrons, so that the atom is electrically neutral
(Figure 2.10). After many more experiments, Rutherford also discovered that the nuclei of other elements contain the hydrogen
nucleus as a “building block,” and he named this more fundamental particle the proton, the positively charged, subatomic particle
found in the nucleus. With one addition, which you will learn next, this nuclear model of the atom, proposed over a century ago, is
still used today.
Figure 2.10 The α particles are deflected only when they collide with or pass close to the much heavier, positively charged gold
nucleus. Because the nucleus is very small compared to the size of an atom, very few α particles are deflected. Most pass through
the relatively large region occupied by electrons, which are too light to deflect the rapidly moving particles.

The Rutherford Scattering simulation allows you to investigate the differences between a “plum pudding” atom and a
Rutherford atom by firing α particles at each type of atom.

Another important finding was the discovery of isotopes. During the early 1900s, scientists identified several substances that
appeared to be new elements, isolating them from radioactive ores. For example, a “new element” produced by the radioactive
decay of thorium was initially given the name mesothorium. However, a more detailed analysis showed that mesothorium was
chemically identical to radium (another decay product), despite having a different atomic mass. This result, along with similar
findings for other elements, led the English chemist Frederick Soddy to realize that an element could have types of atoms with
different masses that were chemically indistinguishable. These different types are called isotopes—atoms of the same element that
differ in mass. Soddy was awarded the Nobel Prize in Chemistry in 1921 for this discovery.
One puzzle remained: The nucleus was known to contain almost all of the mass of an atom, with the number of protons only
providing half, or less, of that mass. Different proposals were made to explain what constituted the remaining mass, including the
existence of neutral particles in the nucleus. As you might expect, detecting uncharged particles is very challenging, and it was not
until 1932 that James Chadwick found evidence of neutrons, uncharged, subatomic particles with a mass approximately the same as
that of protons. The existence of the neutron also explained isotopes: They differ in mass because they have different numbers of
neutrons, but they are chemically identical because they have the same number of protons. This will be explained in more detail
later in this chapter.
2.3.0.1: Footnotes
1Ernest Rutherford, “The Development of the Theory of Atomic Structure,” ed. J. A. Ratcliffe, in Background to Modern
Science, eds. Joseph Needham and Walter Pagel, (Cambridge, UK: Cambridge University Press, 1938), 61–74. Accessed
September 22, 2014, https://ia600508.us.archive.org/3/it...e032734mbp.pdf.
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Write and interpret symbols that depict the atomic number, mass number, and charge of an atom or ion
Define the atomic mass unit and average atomic mass
Calculate average atomic mass and isotopic abundance
The development of modern atomic theory revealed much about the inner structure of atoms. It was learned that an atom contains a
very small nucleus composed of positively charged protons and uncharged neutrons, surrounded by a much larger volume of space
containing negatively charged electrons. The nucleus contains the majority of an atom’s mass because protons and neutrons are
much heavier than electrons, whereas electrons occupy almost all of an atom’s volume. The diameter of an atom is on the order of
10−10 m, whereas the diameter of the nucleus is roughly 10−15 m—about 100,000 times smaller. For a perspective about their
relative sizes, consider this: If the nucleus were the size of a blueberry, the atom would be about the size of a football stadium
(Figure 2.11).
Figure 2.11 If an atom could be expanded to the size of a football stadium, the nucleus would be the size of a single blueberry.
(credit middle: modification of work by “babyknight”/Wikimedia Commons; credit right: modification of work by Paxson
Woelber)
Atoms—and the protons, neutrons, and electrons that compose them—are extremely small. For example, a carbon atom weighs
less than 2 × 10−23 g, and an electron has a charge of less than 2 × 10−19 C (coulomb). When describing the properties of tiny
objects such as atoms, we use appropriately small units of measure, such as the atomic mass unit (amu) and the fundamental unit of
charge (e). The amu was originally defined based on hydrogen, the lightest element, then later in terms of oxygen. Since 1961, it
has been defined with regard to the most abundant isotope of carbon, atoms of which are assigned masses of exactly 12 amu. (This
isotope is known as “carbon-12” as will be discussed later in this module.) Thus, one amu is exactly 1
of the mass of one carbon-
12
12 atom: 1 amu = 1.6605 × 10−24 g. (The Dalton (Da) and the unified atomic mass unit (u) are alternative units that are equivalent
to the amu.) The fundamental unit of charge (also called the elementary charge) equals the magnitude of the charge of an electron
(e) with e = 1.602 × 10−19 C.
A proton has a mass of 1.0073 amu and a charge of 1+. A neutron is a slightly heavier particle with a mass 1.0087 amu and a
charge of zero; as its name suggests, it is neutral. The electron has a charge of 1− and is a much lighter particle with a mass of
about 0.00055 amu (it would take about 1800 electrons to equal the mass of one proton). The properties of these fundamental
particles are summarized in Table 2.2. (An observant student might notice that the sum of an atom’s subatomic particles does not
equal the atom’s actual mass: The total mass of six protons, six neutrons, and six electrons is 12.0993 amu, slightly larger than
12.00 amu. This “missing” mass is known as the mass defect, and you will learn about it in the chapter on nuclear chemistry.)
Properties of Subatomic Particles
Name Location Charge (C) Unit Charge Mass (amu) Mass (g)

Name Location Charge (C) Unit Charge Mass (amu) Mass (g)
electron outside nucleus −1.602 × 10−19 1− 0.00055 0.00091 × 10−24
proton nucleus 1.602 × 10−19 1+ 1.00727 1.67262 × 10−24
neutron nucleus 0 0 1.00866 1.67493 × 10−24
Table 2.2
The number of protons in the nucleus of an atom is its atomic number (Z). This is the defining trait of an element: Its value
determines the identity of the atom. For example, any atom that contains six protons is the element carbon and has the atomic
number 6, regardless of how many neutrons or electrons it may have. A neutral atom must contain the same number of positive and
negative charges, so the number of protons equals the number of electrons. Therefore, the atomic number also indicates the number
of electrons in an atom. The total number of protons and neutrons in an atom is called its mass number (A). The number of
neutrons is therefore the difference between the mass number and the atomic number: A – Z = number of neutrons.
atomic number (Z) = number of protons
mass number (A) = number of protons+ number of neutrons
A− Z = number of neutrons
Atoms are electrically neutral if they contain the same number of positively charged protons and negatively charged electrons.
When the numbers of these subatomic particles are not equal, the atom is electrically charged and is called an ion. The charge of an
atom is defined as follows:
Atomic charge = number of protons − number of electrons
As will be discussed in more detail later in this chapter, atoms (and molecules) typically acquire charge by gaining or losing
electrons. An atom that gains one or more electrons will exhibit a negative charge and is called an anion. Positively charged atoms
called cations are formed when an atom loses one or more electrons. For example, a neutral sodium atom (Z = 11) has 11 electrons.
If this atom loses one electron, it will become a cation with a 1+ charge (11 − 10 = 1+). A neutral oxygen atom (Z = 8) has eight
electrons, and if it gains two electrons it will become an anion with a 2− charge (8 − 10 = 2−).
2.4.0.1: Example 2.3

2.4.0.0.1: Composition of an Atom
Iodine is an essential trace element in our diet; it is needed to produce thyroid hormone. Insufficient iodine in the diet can lead
to the development of a goiter, an enlargement of the thyroid gland (Figure 2.12).

Figure 2.12 (a) Insufficient iodine in the diet can cause an enlargement of the thyroid gland called a goiter. (b) The addition of
small amounts of iodine to salt, which prevents the formation of goiters, has helped eliminate this concern in the US where salt
consumption is high. (credit a: modification of work by “Almazi”/Wikimedia Commons; credit b: modification of work by
Mike Mozart)
The addition of small amounts of iodine to table salt (iodized salt) has essentially eliminated this health concern in the United
States, but as much as 40% of the world’s population is still at risk of iodine deficiency. The iodine atoms are added as anions,
and each has a 1− charge and a mass number of 127. Determine the numbers of protons, neutrons, and electrons in one of these
iodine anions.
2.4.0.0.1: Solution
The atomic number of iodine (53) tells us that a neutral iodine atom contains 53 protons in its nucleus and 53 electrons outside
its nucleus. Because the sum of the numbers of protons and neutrons equals the mass number, 127, the number of neutrons is
74 (127 − 53 = 74). Since the iodine is added as a 1− anion, the number of electrons is 54 [53 – (1–) = 54].
An ion of platinum has a mass number of 195 and contains 74 electrons. How many protons and neutrons does it contain, and
what is its charge?
2.4.0.1: Answer:
78 protons; 117 neutrons; charge is 4+
2.4.0.1: Chemical Symbols

A chemical symbol is an abbreviation that we use to indicate an element or an atom of an element. For example, the symbol for
mercury is Hg (Figure 2.13). We use the same symbol to indicate one atom of mercury (microscopic domain) or to label a container
of many atoms of the element mercury (macroscopic domain).
Figure 2.13 The symbol Hg represents the element mercury regardless of the amount; it could represent one atom of mercury or a
large amount of mercury.
The symbols for several common elements and their atoms are listed in Table 2.3. Some symbols are derived from the common
name of the element; others are abbreviations of the name in another language. Most symbols have one or two letters, but three-
letter symbols have been used to describe some elements that have atomic numbers greater than 112. To avoid confusion with other
notations, only the first letter of a symbol is capitalized. For example, Co is the symbol for the element cobalt, but CO is the
notation for the compound carbon monoxide, which contains atoms of the elements carbon (C) and oxygen (O). All known
elements and their symbols are in the periodic table in Figure 2.26 (also found in Appendix A).
Some Common Elements and Their Symbols

Element Symbol Element Symbol
aluminum Al iron Fe (from ferrum)
bromine Br lead Pb (from plumbum)
calcium Ca magnesium Mg
carbon C mercury Hg (from hydrargyrum)
chlorine Cl nitrogen N
chromium Cr oxygen O
cobalt Co potassium K (from kalium)
copper Cu (from cuprum) silicon Si
fluorine F silver Ag (from argentum)
gold Au (from aurum) sodium Na (from natrium)
helium He sulfur S
hydrogen H tin Sn (from stannum)
iodine I zinc Zn
Table 2.3
Traditionally, the discoverer (or discoverers) of a new element names the element. However, until the name is recognized by the
International Union of Pure and Applied Chemistry (IUPAC), the recommended name of the new element is based on the Latin
word(s) for its atomic number. For example, element 106 was called unnilhexium (Unh), element 107 was called unnilseptium
(Uns), and element 108 was called unniloctium (Uno) for several years. These elements are now named after scientists (or
occasionally locations); for example, element 106 is now known as seaborgium (Sg) in honor of Glenn Seaborg, a Nobel Prize
winner who was active in the discovery of several heavy elements. Element 109 was named in honor of Lise Meitner, who
discovered nuclear fission, a phenomenon that would have world-changing impacts; Meitner also contributed to the discovery of
some major isotopes, discussed immediately below.

Visit this site to learn more about IUPAC, the International Union of Pure and Applied Chemistry, and explore its periodic
table.
2.4.0.1: Isotopes
The symbol for a specific isotope of any element is written by placing the mass number as a superscript to the left of the element
symbol (Figure 2.14). The atomic number is sometimes written as a subscript preceding the symbol, but since this number defines
the element’s identity, as does its symbol, it is often omitted. For example, magnesium exists as a mixture of three isotopes, each
with an atomic number of 12 and with mass numbers of 24, 25, and 26, respectively. These isotopes can be identified as 24Mg,
25
Mg, and 26Mg. These isotope symbols are read as “element, mass number” and can be symbolized consistent with this reading.
For instance, 24Mg is read as “magnesium 24,” and can be written as “magnesium-24” or “Mg-24.” 25Mg is read as “magnesium
25,” and can be written as “magnesium-25” or “Mg-25.” All magnesium atoms have 12 protons in their nucleus. They differ only
because a 24Mg atom has 12 neutrons in its nucleus, a 25Mg atom has 13 neutrons, and a 26Mg has 14 neutrons.

Figure 2.14 The symbol for an atom indicates the element via its usual two-letter symbol, the mass number as a left superscript, the
atomic number as a left subscript (sometimes omitted), and the charge as a right superscript.
Information about the naturally occurring isotopes of elements with atomic numbers 1 through 10 is given in Table 2.4. Note that in
addition to standard names and symbols, the isotopes of hydrogen are often referred to using common names and accompanying
symbols. Hydrogen-2, symbolized 2H, is also called deuterium and sometimes symbolized D. Hydrogen-3, symbolized 3H, is also
called tritium and sometimes symbolized T.
Nuclear Compositions of Atoms of the Very Light Elements
Element Symbol Atomic Number of Number of Mass % Natural Abundance
Number Protons Neutrons (amu)
hydrogen 1
1
H 1 1 0 1.0078 99.989
(protium)
2
1
H 1 1 1 2.0141 0.0115
(deuterium)
3
1
H 1 1 2 3.01605 — (trace)
(tritium)
helium 3
2
He 2 2 1 3.01603 0.00013
4
2
He 2 2 2 4.0026 100
lithium 6
3
Li 3 3 3 6.0151 7.59
7
3
Li 3 3 4 7.0160 92.41
beryllium 9
4
Be 4 4 5 9.0122 100
boron 10
5
B 5 5 5 10.0129 19.9
11
5
B 5 5 6 11.0093 80.1
carbon 12
6
C 6 6 6 12.0000 98.89
13
6
C 6 6 7 13.0034 1.11
14
6
C 6 6 8 14.0032 — (trace)
nitrogen 14
7
N 7 7 7 14.0031 99.63
15
7
N 7 7 8 15.0001 0.37
oxygen 16
8
O 8 8 8 15.9949 99.757

Element Symbol Atomic Number of Number of Mass % Natural Abundance
Number Protons Neutrons (amu)
17
8
O 8 8 9 16.9991 0.038
18
8
O 8 8 10 17.9992 0.205
fluorine 19
9
F 9 9 10 18.9984 100
neon 20
10
Ne 10 10 10 19.9924 90.48
21
10
Ne 10 10 11 20.9938 0.27
22
10
Ne 10 10 12 21.9914 9.25
Table 2.4

Use this Build an Atom simulator to build atoms of the first 10 elements, see which isotopes exist, check nuclear stability, and
gain experience with isotope symbols.
2.4.0.1: Atomic Mass

Because each proton and each neutron contribute approximately one amu to the mass of an atom, and each electron contributes far
less, the atomic mass of a single atom is approximately equal to its mass number (a whole number). However, the average masses
of atoms of most elements are not whole numbers because most elements exist naturally as mixtures of two or more isotopes.
The mass of an element shown in a periodic table or listed in a table of atomic masses is a weighted, average mass of all the
isotopes present in a naturally occurring sample of that element. This is equal to the sum of each individual isotope’s mass
multiplied by its fractional abundance.
average mass = ∑ (fractional abundance × isotopic mass)

i
For example, the element boron is composed of two isotopes: About 19.9% of all boron atoms are 10B with a mass of 10.0129 amu,
and the remaining 80.1% are 11B with a mass of 11.0093 amu. The average atomic mass for boron is calculated to be:
boron average mass = (0.199 × 10.0129 amu) + (0.801 × 11.0093 amu)
= 1.99 amu + 8.82 amu
= 10.81 amu
It is important to understand that no single boron atom weighs exactly 10.8 amu; 10.8 amu is the average mass of all boron atoms,
and individual boron atoms weigh either approximately 10 amu or 11 amu.
2.4.0.1: Example 2.4

2.4.0.0.1: Calculation of Average Atomic Mass
A meteorite found in central Indiana contains traces of the noble gas neon picked up from the solar wind during the meteorite’s
trip through the solar system. Analysis of a sample of the gas showed that it consisted of 91.84% 20Ne (mass 19.9924 amu),
0.47% 21Ne (mass 20.9940 amu), and 7.69% 22Ne (mass 21.9914 amu). What is the average mass of the neon in the solar
wind?
2.4.0.0.2: Solution
average mass = (0.9184 × 19.9924 amu) + (0.0047 × 20.9940 amu) + (0.0769 × 21.9914 amu)
= (18.36 + 0.099 + 1.69) amu
= 20.15 amu

The average mass of a neon atom in the solar wind is 20.15 amu. (The average mass of a terrestrial neon atom is 20.1796 amu.
This result demonstrates that we may find slight differences in the natural abundance of isotopes, depending on their origin.)
A sample of magnesium is found to contain 78.70% of 24Mg atoms (mass 23.98 amu), 10.13% of 25Mg atoms (mass 24.99
amu), and 11.17% of 26Mg atoms (mass 25.98 amu). Calculate the average mass of a Mg atom.
2.4.0.1: Answer:
24.31 amu
We can also do variations of this type of calculation, as shown in the next example.
2.4.0.1: Example 2.5

2.4.0.0.4: Calculation of Percent Abundance
Naturally occurring chlorine consists of 35Cl (mass 34.96885 amu) and 37Cl (mass 36.96590 amu), with an average mass of
35.453 amu. What is the percent composition of Cl in terms of these two isotopes?
2.4.0.0.5: Solution
The average mass of chlorine is the fraction that is 35Cl times the mass of 35Cl plus the fraction that is 37Cl times the mass of
37
Cl.
35 35 37 37
average mass = (fraction of Cl × mass of Cl) + (fraction of Cl × mass of Cl)
If we let x represent the fraction that is 35Cl, then the fraction that is 37Cl is represented by 1.00 − x.
(The fraction that is 35Cl + the fraction that is 37Cl must add up to 1, so the fraction of 37Cl must equal 1.00 − the fraction of
35Cl.)
Substituting this into the average mass equation, we have:

35.453 amu = (x × 34.96885 amu) + [(1.00 − x) × 36.96590 amu]
35.453 = 34.96885x + 36.96590 − 36.96590x
1.99705x = 1.513
1.513
x = = 0.7576
1.99705
35
So solving yields: x = 0.7576, which means that 1.00 − 0.7576 = 0.2424. Therefore, chlorine consists of 75.76% Cl and
24.24% 37Cl.
Naturally occurring copper consists of 63Cu (mass 62.9296 amu) and 65Cu (mass 64.9278 amu), with an average mass of
63.546 amu. What is the percent composition of Cu in terms of these two isotopes?
2.4.0.1: Answer:
69.15% Cu-63 and 30.85% Cu-65

Visit this site to make mixtures of the main isotopes of the first 18 elements, gain experience with average atomic mass, and
check naturally occurring isotope ratios using the Isotopes and Atomic Mass simulation.
As you will learn, isotopes are important in nature and especially in human understanding of science and medicine. Let's consider
just one natural, stable isotope: Oxygen-18, which is noted in the table above and is referred to as one of the environmental
isotopes. It is important in paleoclimatology, for example, because scientists can use the ratio between Oxygen-18 and Oxygen-16
in an ice core to determine the temperature of precipitation over time. Oxygen-18 was also critical to the discovery of metabolic
pathways and the mechanisms of enzymes. Mildred Cohn pioneered the usage of these isotopes to act as tracers, so that researchers
could follow their path through reactions and gain a better understanding of what is happening. One of her first discoveries

provided insight into the phosphorylation of glucose that takes place in mitochondria. And the methods of using isotopes for this
research contributed to entire fields of study.
The occurrence and natural abundances of isotopes can be experimentally determined using an instrument called a mass
spectrometer. Mass spectrometry (MS) is widely used in chemistry, forensics, medicine, environmental science, and many other
fields to analyze and help identify the substances in a sample of material. In a typical mass spectrometer (Figure 2.15), the sample
is vaporized and exposed to a high-energy electron beam that causes the sample’s atoms (or molecules) to become electrically
charged, typically by losing one or more electrons. These cations then pass through a (variable) electric or magnetic field that
deflects each cation’s path to an extent that depends on both its mass and charge (similar to how the path of a large steel ball rolling
past a magnet is deflected to a lesser extent that that of a small steel ball). The ions are detected, and a plot of the relative number
of ions generated versus their mass-to-charge ratios (a mass spectrum) is made. The height of each vertical feature or peak in a
mass spectrum is proportional to the fraction of cations with the specified mass-to-charge ratio. Since its initial use during the
development of modern atomic theory, MS has evolved to become a powerful tool for chemical analysis in a wide range of
applications.
Figure 2.15 Analysis of zirconium in a mass spectrometer produces a mass spectrum with peaks showing the different isotopes of
Zr.

See an animation that explains mass spectrometry. Watch this video from the Royal Society for Chemistry for a brief
description of the rudiments of mass spectrometry.
This page titled 2.4: Atomic Structure and Symbolism is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

2.5.0.1: Learning Objectives
Symbolize the composition of molecules using molecular formulas and empirical formulas
Represent the bonding arrangement of atoms within molecules using structural formulas
A molecular formula is a representation of a molecule that uses chemical symbols to indicate the types of atoms followed by
subscripts to show the number of atoms of each type in the molecule. (A subscript is used only when more than one atom of a given
type is present.) Molecular formulas are also used as abbreviations for the names of compounds.
The structural formula for a compound gives the same information as its molecular formula (the types and numbers of atoms in the
molecule) but also shows how the atoms are connected in the molecule. The structural formula for methane contains symbols for
one C atom and four H atoms, indicating the number of atoms in the molecule (Figure 2.16). The lines represent bonds that hold
the atoms together. (A chemical bond is an attraction between atoms or ions that holds them together in a molecule or a crystal.) We
will discuss chemical bonds and see how to predict the arrangement of atoms in a molecule later. For now, simply know that the
lines are an indication of how the atoms are connected in a molecule. A ball-and-stick model shows the geometric arrangement of
the atoms with atomic sizes not to scale, and a space-filling model shows the relative sizes of the atoms.
Figure A shows C H subscript 4. Figure B shows a carbon atom that is bonded to four hydrogen atoms at right angles: one above, one to the left, one to the right, and one below. Figure C shows a 3-D, ball-and-stick
model of the carbon atom bonded to four hydrogen atoms. Figure D shows a space-filling model of a carbon atom with hydrogen atoms partially embedded into the surface of the carbon atom.
Figure 2.16 A methane molecule can be represented as (a) a molecular formula, (b) a structural formula, (c) a ball-and-stick model,
and (d) a space-filling model. Carbon and hydrogen atoms are represented by black and white spheres, respectively.
Although many elements consist of discrete, individual atoms, some exist as molecules made up of two or more atoms of the
element chemically bonded together. For example, most samples of the elements hydrogen, oxygen, and nitrogen are composed of
molecules that contain two atoms each (called diatomic molecules) and thus have the molecular formulas H2, O2, and N2,
respectively. Other elements commonly found as diatomic molecules are fluorine (F2), chlorine (Cl2), bromine (Br2), and iodine
(I2). The most common form of the element sulfur is composed of molecules that consist of eight atoms of sulfur; its molecular
formula is S8 (Figure 2.17).
Figure A shows eight sulfur atoms, symbolized with the letter S, that are bonded to each other to form an octagon. Figure B shows a 3-D, ball-and-stick model of the arrangement of the sulfur atoms. The shape is
clearly not octagonal as it is represented in the structural formula. Figure C is a space-filling model that shows each sulfur atom is partially embedded into the sulfur atom it bonds with.
Figure 2.17 A molecule of sulfur is composed of eight sulfur atoms and is therefore written as S8. It can be represented as (a) a
structural formula, (b) a ball-and-stick model, and (c) a space-filling model. Sulfur atoms are represented by yellow spheres.
It is important to note that a subscript following a symbol and a number in front of a symbol do not represent the same thing; for
example, H2 and 2H represent distinctly different species. H2 is a molecular formula; it represents a diatomic molecule of
hydrogen, consisting of two atoms of the element that are chemically bonded together. The expression 2H, on the other hand,
indicates two separate hydrogen atoms that are not combined as a unit. The expression 2H2 represents two molecules of diatomic
hydrogen (Figure 2.18).
This figure shows four diagrams. The diagram for H shows a single, white sphere and is labeled one H atom. The diagram for 2 H shows two white spheres that are not bonded together. It is labeled 2 H atoms. The
diagram for H subscript 2 shows two white spheres bonded together. It is labeled one H subscript 2 molecule. The diagram for 2 H subscript 2 shows two sets of bonded, white spheres. It is labeled 2 H subscript 2
molecules.
Figure 2.18 The symbols H, 2H, H2, and 2H2 represent very different entities.
Compounds are formed when two or more elements chemically combine, resulting in the formation of bonds. For example,
hydrogen and oxygen can react to form water, and sodium and chlorine can react to form table salt. We sometimes describe the
composition of these compounds with an empirical formula, which indicates the types of atoms present and the simplest whole-
number ratio of the number of atoms (or ions) in the compound. For example, titanium dioxide (used as pigment in white paint and
in the thick, white, blocking type of sunscreen) has an empirical formula of TiO2. This identifies the elements titanium (Ti) and
oxygen (O) as the constituents of titanium dioxide, and indicates the presence of twice as many atoms of the element oxygen as
atoms of the element titanium (Figure 2.19).
Figure A shows a photo of a person applying suntan lotion to his or her lower leg. Figure B shows a 3-D ball-and-stick model of the molecule titanium dioxide, which involves a complicated interlocking of many
titanium and oxygen atoms. The titanium atoms in the molecule are shown as silver spheres and the oxygen atoms are shown as red spheres. There are twice as many oxygen atoms as titanium atoms in the molecule.
Figure 2.19 (a) The white compound titanium dioxide provides effective protection from the sun. (b) A crystal of titanium dioxide,
TiO2, contains titanium and oxygen in a ratio of 1 to 2. The titanium atoms are gray and the oxygen atoms are red. (credit a:
modification of work by “osseous”/Flickr)

As discussed previously, we can describe a compound with a molecular formula, in which the subscripts indicate the actual
numbers of atoms of each element in a molecule of the compound. In many cases, the molecular formula of a substance is derived
from experimental determination of both its empirical formula and its molecular mass (the sum of atomic masses for all atoms
composing the molecule). For example, it can be determined experimentally that benzene contains two elements, carbon (C) and
hydrogen (H), and that for every carbon atom in benzene, there is one hydrogen atom. Thus, the empirical formula is CH. An
experimental determination of the molecular mass reveals that a molecule of benzene contains six carbon atoms and six hydrogen
atoms, so the molecular formula for benzene is C6H6 (Figure 2.20).
Figure A shows that benzene is composed of six carbons shaped like a hexagon. Every other bond between the carbon atoms is a double bond. Each carbon also has a single bonded hydrogen atom. Figure B shows a
3-D, ball-and-stick drawing of benzene. The six carbon atoms are black spheres while the six hydrogen atoms are smaller, white spheres. Figure C is a space-filling model of benzene which shows that most of the
interior space is occupied by the carbon atoms. The hydrogen atoms are embedded in the outside surface of the carbon atoms. Figure d shows a small vial filled with benzene which appears to be clear.
Figure 2.20 Benzene, C6H6, is produced during oil refining and has many industrial uses. A benzene molecule can be represented
as (a) a structural formula, (b) a ball-and-stick model, and (c) a space-filling model. (d) Benzene is a clear liquid. (credit d:
modification of work by Sahar Atwa)
If we know a compound’s formula, we can easily determine the empirical formula. (This is somewhat of an academic exercise; the
reverse chronology is generally followed in actual practice.) For example, the molecular formula for acetic acid, the component
that gives vinegar its sharp taste, is C2H4O2. This formula indicates that a molecule of acetic acid (Figure 2.21) contains two carbon
atoms, four hydrogen atoms, and two oxygen atoms. The ratio of atoms is 2:4:2. Dividing by the lowest common denominator (2)
gives the simplest, whole-number ratio of atoms, 1:2:1, so the empirical formula is CH2O. Note that a molecular formula is always
a whole-number multiple of an empirical formula.
Figure A shows a jug of distilled, white vinegar. Figure B shows a structural formula for acetic acid which contains two carbon atoms connected by a single bond. The left carbon atom forms single bonds with three
hydrogen atoms. The right carbon atom forms a double bond with an oxygen atom. The right carbon atom also forms a single bond with an oxygen atom. This oxygen forms a single bond with a hydrogen atom.
Figure C shows a 3-D ball-and-stick model of acetic acid.
Figure 2.21 (a) Vinegar contains acetic acid, C2H4O2, which has an empirical formula of CH2O. It can be represented as (b) a
structural formula and (c) as a ball-and-stick model. (credit a: modification of work by “HomeSpot HQ”/Flickr)
2.5.0.1: Example 2.6

2.5.0.0.1: Empirical and Molecular Formulas
Molecules of glucose (blood sugar) contain 6 carbon atoms, 12 hydrogen atoms, and 6 oxygen atoms. What are the molecular and
empirical formulas of glucose?
2.5.0.0.1: Solution
The molecular formula is C6H12O6 because one molecule actually contains 6 C, 12 H, and 6 O atoms. The simplest whole-number
ratio of C to H to O atoms in glucose is 1:2:1, so the empirical formula is CH2O.
A molecule of metaldehyde (a pesticide used for snails and slugs) contains 8 carbon atoms, 16 hydrogen atoms, and 4 oxygen
atoms. What are the molecular and empirical formulas of metaldehyde?
2.5.0.1: Answer:
Molecular formula, C8H16O4; empirical formula, C2H4O

You can explore molecule building using an online simulation.
2.5.0.1: Portrait of a Chemist

2.5.0.0.1: Lee Cronin
What is it that chemists do? According to Lee Cronin (Figure 2.22), chemists make very complicated molecules by “chopping up”
small molecules and “reverse engineering” them. He wonders if we could “make a really cool universal chemistry set” by what he
calls “app-ing” chemistry. Could we “app” chemistry?
In a 2012 TED talk, Lee describes one fascinating possibility: combining a collection of chemical “inks” with a 3D printer capable
of fabricating a reaction apparatus (tiny test tubes, beakers, and the like) to fashion a “universal toolkit of chemistry.” This toolkit
could be used to create custom-tailored drugs to fight a new superbug or to “print” medicine personally configured to your genetic
makeup, environment, and health situation. Says Cronin, “What Apple did for music, I’d like to do for the discovery and
distribution of prescription drugs.”2 View his full talk at the TED website.
This is a photo of chemist Lee Cronin.

Figure 2.22 Chemist Lee Cronin has been named one of the UK’s 10 most inspirational scientists. The youngest chair at the
University of Glasgow, Lee runs a large research group, collaborates with many scientists worldwide, has published over 250
papers in top scientific journals, and has given more than 150 invited talks. His research focuses on complex chemical systems and
their potential to transform technology, but also branches into nanoscience, solar fuels, synthetic biology, and even artificial life and
evolution. (credit: image courtesy of Lee Cronin)
It is important to be aware that it may be possible for the same atoms to be arranged in different ways: Compounds with the same
molecular formula may have different atom-to-atom bonding and therefore different structures. For example, could there be another
compound with the same formula as acetic acid, C2H4O2? And if so, what would be the structure of its molecules?
If you predict that another compound with the formula C2H4O2 could exist, then you demonstrated good chemical insight and are
correct. Two C atoms, four H atoms, and two O atoms can also be arranged to form a methyl formate, which is used in
manufacturing, as an insecticide, and for quick-drying finishes. Methyl formate molecules have one of the oxygen atoms between
the two carbon atoms, differing from the arrangement in acetic acid molecules. Acetic acid and methyl formate are examples of
isomers—compounds with the same chemical formula but different molecular structures (Figure 2.23). Note that this small
difference in the arrangement of the atoms has a major effect on their respective chemical properties. You would certainly not want
to use a solution of methyl formate as a substitute for a solution of acetic acid (vinegar) when you make salad dressing.
Figure A shows a structural diagram of acetic acid, C subscript 2 H subscript 4 O subscript 2. Acetic acid contains two carbon atoms connected by a single bond. The left carbon atom forms single bonds with three
hydrogen atoms. The carbon on the right forms a double bond with an oxygen atom. The right carbon atom also forms a single bond to an oxygen atom which forms a single bond with a hydrogen atom. Figure B
shows a structural diagram of methyl formate, C subscript 2 H subscript 4 O subscript 2. This molecule contains a carbon atom which forms single bonds with three hydrogen atoms, and a single bond with an oxygen
atom. The oxygen atom forms a single bond with another carbon atom which forms a double bond with another oxygen atom and a single bond with a hydrogen atom.
Figure 2.23 Molecules of (a) acetic acid and methyl formate (b) are structural isomers; they have the same formula (C2H4O2) but
different structures (and therefore different chemical properties).
Many types of isomers exist (Figure 2.24). Acetic acid and methyl formate are structural isomers, compounds in which the
molecules differ in how the atoms are connected to each other. There are also various types of spatial isomers, in which the relative
orientations of the atoms in space can be different. For example, the compound carvone (found in caraway seeds, spearmint, and
mandarin orange peels) consists of two isomers that are mirror images of each other. S-(+)-carvone smells like caraway, and R-(−)-
carvone smells like spearmint.
The top left portion of this 2 row, 4 column figure shows a structural diagram of positive carvone, C subscript 10 H subscript 14 O. This molecule has a carbon atom which forms a double bond with a C H subscript 2
group and a C H subscript 3 group. The carbon atom also forms a single bond with another carbon atom which is part of a ring. This carbon atom, being part of the ring, forms single bonds with a hydrogen atom, a C
H subscript 2 group, and a C H subscript 2 group. The first C H subscript two group forms a single bond with C H which forms a double bond with a carbon atom. This carbon atom forms a single bond with a C H
subscript 3 group. The carbon atom forming part of the ring forms a single bond with a carbon atom which forms a double bond with an oxygen atom and a single bond with a C H subscript 2 group to complete the ring.
Below the structural diagram of carvone is a photo of caraway seeds. Column 2 contains identical ball and stick representations of the structural diagram in the top left position. The top right portions of these images each
contains the letter “S” and there is an arrow pointing downward from the top image to the bottom image. Columns 3 and 4 are representations of negative carvone. The top row in column three depicts a mirrored image
of the ball and stick structure to its left, reflected across the y axis. There is a downward pointing arrow to the image below, which is the same structure rotated counter clockwise 180 degrees. Both images in column 3
have an “R” in the top right corner. The image in the first row of column 4 is the same as the lewis structure in the first row of column 1, reflected across the y axis. Below this negative carvone structural diagram is a
photo of spearmint leaves.
Figure 2.24 Molecules of carvone are spatial isomers; they only differ in the relative orientations of the atoms in space. (credit
bottom left: modification of work by “Miansari66”/Wikimedia Commons; credit bottom right: modification of work by Forest &
Kim Starr)

Select this link to view an explanation of isomers, spatial isomers, and why they have different smells (select the video titled
“Mirror Molecule: Carvone”).
2.5.0.1: Footnotes
2Lee Cronin, “Print Your Own Medicine,” Talk presented at TED Global 2012, Edinburgh, Scotland, June 2012.
This page titled 2.5: Chemical Formulas is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source


State the periodic law and explain the organization of elements in the periodic table
Predict the general properties of elements based on their location within the periodic table
Identify metals, nonmetals, and metalloids by their properties and/or location on the periodic table
As early chemists worked to purify ores and discovered more elements, they realized that various elements could be grouped
together by their similar chemical behaviors. One such grouping includes lithium (Li), sodium (Na), and potassium (K): These
elements all are shiny, conduct heat and electricity well, and have similar chemical properties. A second grouping includes calcium
(Ca), strontium (Sr), and barium (Ba), which also are shiny, good conductors of heat and electricity, and have chemical properties
in common. However, the specific properties of these two groupings are notably different from each other. For example: Li, Na,
and K are much more reactive than are Ca, Sr, and Ba; Li, Na, and K form compounds with oxygen in a ratio of two of their atoms
to one oxygen atom, whereas Ca, Sr, and Ba form compounds with one of their atoms to one oxygen atom. Fluorine (F), chlorine
(Cl), bromine (Br), and iodine (I) also exhibit similar properties to each other, but these properties are drastically different from
those of any of the elements above.
Dimitri Mendeleev in Russia (1869) and Lothar Meyer in Germany (1870) independently recognized that there was a periodic
relationship among the properties of the elements known at that time. Both published tables with the elements arranged according
to increasing atomic mass. But Mendeleev went one step further than Meyer: He used his table to predict the existence of elements
that would have the properties similar to aluminum and silicon, but were yet unknown. The discoveries of gallium (1875) and
germanium (1886) provided great support for Mendeleev’s work. Although Mendeleev and Meyer had a long dispute over priority,
Mendeleev’s contributions to the development of the periodic table are now more widely recognized (Figure 2.25).
Figure 2.25 (a) Dimitri Mendeleev is widely credited with creating (b) the first periodic table of the elements. (credit a:
modification of work by Serge Lachinov; credit b: modification of work by “Den fjättrade ankan”/Wikimedia Commons)
By the twentieth century, it became apparent that the periodic relationship involved atomic numbers rather than atomic masses. The
modern statement of this relationship, the periodic law, is as follows: the properties of the elements are periodic functions of their
atomic numbers. A modern periodic table arranges the elements in increasing order of their atomic numbers and groups atoms with
similar properties in the same vertical column (Figure 2.26). Each box represents an element and contains its atomic number,
symbol, average atomic mass, and (sometimes) name. The elements are arranged in seven horizontal rows, called periods or series,
and 18 vertical columns, called groups. Groups are labeled at the top of each column. In the United States, the labels traditionally
were numerals with capital letters. However, IUPAC recommends that the numbers 1 through 18 be used, and these labels are more
common. For the table to fit on a single page, parts of two of the rows, a total of 14 columns, are usually written below the main
body of the table.

Figure 2.26 Elements in the periodic table are organized according to their properties.
Even after the periodic nature of elements and the table itself were widely accepted, gaps remained. Mendeleev had predicted, and
others including Henry Moseley had later confirmed, that there should be elements below Manganese in Group 7. German chemists
Ida Tacke and Walter Noddack set out to find the elements, a quest being pursued by scientists around the world. Their method was
unique in that they did not only consider the properties of manganese, but also the elements horizontally adjacent to the missing
elements 43 and 75 on the table. Thus, by investigating ores containing minerals of ruthenium (Ru), tungsten (W), osmium (Os),
and so on, they were able to identify naturally occurring elements that helped complete the table. Rhenium, one of their discoveries,
was one of the last natural elements to be discovered and is the last stable element to be discovered. (Francium, the last natural
element to be discovered, was identified by Marguerite Perey in 1939.)
Many elements differ dramatically in their chemical and physical properties, but some elements are similar in their behaviors. For
example, many elements appear shiny, are malleable (able to be deformed without breaking) and ductile (can be drawn into wires),
and conduct heat and electricity well. Other elements are not shiny, malleable, or ductile, and are poor conductors of heat and
electricity. We can sort the elements into large classes with common properties: metals (elements that are shiny, malleable, good
conductors of heat and electricity—shaded yellow); nonmetals (elements that appear dull, poor conductors of heat and electricity—
shaded green); and metalloids (elements that conduct heat and electricity moderately well, and possess some properties of metals
and some properties of nonmetals—shaded purple).
The elements can also be classified into the main-group elements (or representative elements) in the columns labeled 1, 2, and 13–
18; the transition metals in the columns labeled 3–123; and inner transition metals in the two rows at the bottom of the table (the
top-row elements are called lanthanides and the bottom-row elements are actinides; Figure 2.27). The elements can be subdivided

further by more specific properties, such as the composition of the compounds they form. For example, the elements in group 1 (the
first column) form compounds that consist of one atom of the element and one atom of hydrogen. These elements (except
hydrogen) are known as alkali metals, and they all have similar chemical properties. The elements in group 2 (the second column)
form compounds consisting of one atom of the element and two atoms of hydrogen: These are called alkaline earth metals, with
similar properties among members of that group. Other groups with specific names are the pnictogens (group 15), chalcogens
(group 16), halogens (group 17), and the noble gases (group 18, also known as inert gases). The groups can also be referred to by
the first element of the group: For example, the chalcogens can be called the oxygen group or oxygen family. Hydrogen is a unique,
nonmetallic element with properties similar to both group 1 and group 17 elements. For that reason, hydrogen may be shown at the
top of both groups, or by itself.
Figure 2.27 The periodic table organizes elements with similar properties into groups.

Click on this link for an interactive periodic table, which you can use to explore the properties of the elements (includes
podcasts and videos of each element). You may also want to try this one that shows photos of all the elements.
2.6.0.1: Example 2.7

2.6.0.0.1: Naming Groups of Elements
Atoms of each of the following elements are essential for life. Give the group name for the following elements:
(a) chlorine
(b) calcium
(c) sodium
(d) sulfur
2.6.0.0.1: Solution
The family names are as follows:
(a) halogen

(b) alkaline earth metal
(c) alkali metal
(d) chalcogen
Give the group name for each of the following elements:
(a) krypton
(b) selenium
(c) barium
(d) lithium
2.6.0.1: Answer:
(a) noble gas; (b) chalcogen; (c) alkaline earth metal; (d) alkali metal
As you will learn in your further study of chemistry, elements in groups often behave in a somewhat similar manner. This is partly
due to the number of electrons in their outer shell and their similar readiness to bond. These shared properties can have far-ranging
implications in nature, science, and medicine. For example, when Gertrude Elion and George Hitchens were investigating ways to
interrupt cell and virus replication to fight diseases, they utilized the similarity between sulfur and oxygen (both in Group 16) and
their capacity to bond in similar ways. Elion focused on purines, which are key components of DNA and which contain oxygen.
She found that by introducing sulfur-based compounds (called purine analogues) that mimic the structure of purines, molecules
within DNA would bond to the analogues rather than the "regular" DNA purine. With the normal DNA bonding and structure
altered, Elion successfully interrupted cell replication. At its core, the strategy worked because of the similarity between sulfur and
oxygen. Her discovery led directly to important treatments for leukemia. Overall, Elion's work with George Hitchens not only led
to more treatments, but also changed the entire methodology of drug development. By using specific elements and compounds to
target specific aspects of tumor cells, viruses, and bacteria, they laid the groundwork for many of today's most common and
important medicines, used to help millions of people each year. They were awarded the Nobel Prize in 1988.
In studying the periodic table, you might have noticed something about the atomic masses of some of the elements. Element 43
(technetium), element 61 (promethium), and most of the elements with atomic number 84 (polonium) and higher have their atomic
mass given in square brackets. This is done for elements that consist entirely of unstable, radioactive isotopes (you will learn more
about radioactivity in the nuclear chemistry chapter). An average atomic weight cannot be determined for these elements because
their radioisotopes may vary significantly in relative abundance, depending on the source, or may not even exist in nature. The
number in square brackets is the atomic mass number (an approximate atomic mass) of the most stable isotope of that element.
2.6.0.1: Footnotes
3Per the IUPAC definition, group 12 elements are not transition metals, though they are often referred to as such. Additional
details on this group’s elements are provided in a chapter on transition metals and coordination chemistry.
This page titled 2.6: The Periodic Table is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source

Define ionic and molecular (covalent) compounds
Predict the type of compound formed from elements based on their location within the periodic table
Determine formulas for simple ionic compounds
In ordinary chemical reactions, the nucleus of each atom (and thus the identity of the element) remains unchanged. Electrons, however, can
be added to atoms by transfer from other atoms, lost by transfer to other atoms, or shared with other atoms. The transfer and sharing of
electrons among atoms govern the chemistry of the elements. During the formation of some compounds, atoms gain or lose electrons, and
form electrically charged particles called ions (Figure 2.28).
Figure A shows a sodium atom, N a, which has a nucleus containing 11 protons and 12 neutrons. The atom’s surrounding electron cloud contains 11 electrons. Figure B shows a sodium ion, N a superscript plus sign. Its nucleus
contains 11 protons and 12 neutrons. The ion’s electron cloud contains 10 electrons and is smaller than that of the sodium atom in figure A.
Figure 2.28 (a) A sodium atom (Na) has equal numbers of protons and electrons (11) and is uncharged. (b) A sodium cation (Na+) has lost
an electron, so it has one more proton (11) than electrons (10), giving it an overall positive charge, signified by a superscripted plus sign.
You can use the periodic table to predict whether an atom will form an anion or a cation, and you can often predict the charge of the
resulting ion. Atoms of many main-group metals lose enough electrons to leave them with the same number of electrons as an atom of the
preceding noble gas. To illustrate, an atom of an alkali metal (group 1) loses one electron and forms a cation with a 1+ charge; an alkaline
earth metal (group 2) loses two electrons and forms a cation with a 2+ charge, and so on. For example, a neutral calcium atom, with 20
protons and 20 electrons, readily loses two electrons. This results in a cation with 20 protons, 18 electrons, and a 2+ charge. It has the same
number of electrons as atoms of the preceding noble gas, argon, and is symbolized Ca2+. The name of a metal ion is the same as the name
of the metal atom from which it forms, so Ca2+ is called a calcium ion.
When atoms of nonmetal elements form ions, they generally gain enough electrons to give them the same number of electrons as an atom
of the next noble gas in the periodic table. Atoms of group 17 gain one electron and form anions with a 1− charge; atoms of group 16 gain
two electrons and form ions with a 2− charge, and so on. For example, the neutral bromine atom, with 35 protons and 35 electrons, can
gain one electron to provide it with 36 electrons. This results in an anion with 35 protons, 36 electrons, and a 1− charge. It has the same
number of electrons as atoms of the next noble gas, krypton, and is symbolized Br−. (A discussion of the theory supporting the favored
status of noble gas electron numbers reflected in these predictive rules for ion formation is provided in a later chapter of this text.)
Note the usefulness of the periodic table in predicting likely ion formation and charge (Figure 2.29). Moving from the far left to the right
on the periodic table, main-group elements tend to form cations with a charge equal to the group number. That is, group 1 elements form
1+ ions; group 2 elements form 2+ ions, and so on. Moving from the far right to the left on the periodic table, elements often form anions
with a negative charge equal to the number of groups moved left from the noble gases. For example, group 17 elements (one group left of
the noble gases) form 1− ions; group 16 elements (two groups left) form 2− ions, and so on. This trend can be used as a guide in many
cases, but its predictive value decreases when moving toward the center of the periodic table. In fact, transition metals and some other
metals often exhibit variable charges that are not predictable by their location in the table. For example, copper can form ions with a 1+ or
2+ charge, and iron can form ions with a 2+ or 3+ charge.
Group one of the periodic table contains L i superscript plus sign in period 2, N a superscript plus sign in period 3, K superscript plus sign in period 4, R b superscript plus sign in period 5, C s superscript plus sign in period 6, and
F r superscript plus sign in period 7. Group two contains B e superscript 2 plus sign in period 2, M g superscript 2 plus sign in period 3, C a superscript 2 plus sign in period 4, S r superscript 2 plus sign in period 5, B a superscript
2 plus sign in period 6, and R a superscript 2 plus sign in period 7. Group six contains C r superscript 3 plus sign and C r superscript 6 plus sign in period 4. Group seven contains M n superscript 2 plus sign in period 4. Group eight
contains F e superscript 2 plus sign and F e superscript 3 plus sign in period 4. Group nine contains C o superscript 2 plus sign in period 4. Group ten contains N i superscript 2 plus sign in period 4, and P t superscript 2 plus sign in
period 6. Group 11 contains C U superscript plus sign and C U superscript 2 plus sign in period 4, A g superscript plus sign in period 5, and A u superscript plus sign and A u superscript 3 plus sign in period 6. Group 12 contains Z n
superscript 2 plus sign in period 4, C d superscript 2 plus sign in period 5, and H g subscript 2 superscript 2 plus sign and H g superscript 2 plus sign in period 6. Group 13 contains A l superscript 3 plus sign in period 3. Group 14
contains C superscript 4 negative sign in period 2. Group 15 contains N superscript 3 negative sign in period 2, P superscript 3 negative sign in period 3, and A s superscript 3 negative sign in period 4. Group 16 contains O
superscript 2 negative sign in period 2, S superscript 2 negative sign in period 3, S e superscript 2 negative sign in period 4 and T e superscript 2 negative sign in period 5. Group 17 contains F superscript negative sign in period 2, C
l superscript negative sign in period 3, B r superscript negative sign in period 4, I superscript negative sign in period 5, and A t superscript negative sign in period 6. Group 18 contains H e in period 1, N e in period 2, A r in period 3,
K r in period 4, X e in period 5 and R n in period 6.
Figure 2.29 Some elements exhibit a regular pattern of ionic charge when they form ions.
2.7.0.1: Example 2.8

2.7.0.0.1: Composition of Ions
An ion found in some compounds used as antiperspirants contains 13 protons and 10 electrons. What is its symbol?
2.7.0.0.1: Solution
Because the number of protons remains unchanged when an atom forms an ion, the atomic number of the element must be 13. Knowing
this lets us use the periodic table to identify the element as Al (aluminum). The Al atom has lost three electrons and thus has three more
positive charges (13) than it has electrons (10). This is the aluminum cation, Al3+.

Give the symbol and name for the ion with 34 protons and 36 electrons.
2.7.0.1: Answer:
Se2−, the selenide ion
2.7.0.1: Example 2.9

2.7.0.0.1: Formation of Ions
Magnesium and nitrogen react to form an ionic compound. Predict which forms an anion, which forms a cation, and the charges of each
ion. Write the symbol for each ion and name them.
2.7.0.0.1: Solution
Magnesium’s position in the periodic table (group 2) tells us that it is a metal. Metals form positive ions (cations). A magnesium atom
must lose two electrons to have the same number electrons as an atom of the previous noble gas, neon. Thus, a magnesium atom will form
a cation with two fewer electrons than protons and a charge of 2+. The symbol for the ion is Mg2+, and it is called a magnesium ion.
Nitrogen’s position in the periodic table (group 15) reveals that it is a nonmetal. Nonmetals form negative ions (anions). A nitrogen atom
must gain three electrons to have the same number of electrons as an atom of the following noble gas, neon. Thus, a nitrogen atom will
form an anion with three more electrons than protons and a charge of 3−. The symbol for the ion is N3−, and it is called a nitride ion.
Aluminum and carbon react to form an ionic compound. Predict which forms an anion, which forms a cation, and the charges of each ion.
Write the symbol for each ion and name them.
2.7.0.1: Answer:
Al will form a cation with a charge of 3+: Al3+, an aluminum ion. Carbon will form an anion with a charge of 4−: C4−, a carbide ion.
The ions that we have discussed so far are called monatomic ions, that is, they are ions formed from only one atom. We also find many
polyatomic ions. These ions, which act as discrete units, are electrically charged molecules (a group of bonded atoms with an overall
charge). Some of the more important polyatomic ions are listed in Table 2.5. Oxyanions are polyatomic ions that contain one or more
oxygen atoms. At this point in your study of chemistry, you should memorize the names, formulas, and charges of the most common
polyatomic ions. Because you will use them repeatedly, they will soon become familiar.
Common Polyatomic Ions
Name Formula Related Acid Formula
ammonium NH4+NH4+" role="presentation" style="position: relative;">NH 4 + NH 4

+
hydronium H3O+H3O+" role="presentation" style="position: relative;">H3 O

+
H3 O
+
peroxide O22-O22-" role="presentation" style="position: relative;">O2 2− O 2

2−
hydroxide OH-OH-" role="presentation" style="position: relative;">OH− OH −
acetate CH3COO-CH3COO-" role="presentation" style="position: relative;">CH3 COO

−
CH3 COO
−
acetic acid CH3COOH
cyanide CN− hydrocyanic HCN

acid
azide N3-N3-" role="presentation" style="position: relative;">N3 − N

3
− hydrazoic HN3
acid
carbonate CO32-CO32-" role="presentation" style="position: relative;">CO3 2− CO 3

2− carbonic acid H2CO3
bicarbonate HCO3-HCO3-" role="presentation" style="position: relative;">HCO3 − HCO 3

−
nitrate NO3−NO3−" role="presentation" style="position: relative;">NO3 − NO 3

− nitric acid HNO3

Name Formula Related Acid Formula
nitrite NO2−NO2−" role="presentation" style="position: relative;">NO2 − NO 2

− nitrous acid HNO2
sulfate SO42−SO42−" role="presentation" style="position: relative;">SO4 2− SO 4

2− sulfuric acid H2SO4
hydrogen HSO4−HSO4−" role="presentation" style="position: relative;">HSO4 − HSO 4

−
sulfate
sulfite SO32−SO32−" role="presentation" style="position: relative;">SO3 2− SO 3

2− sulfurous H2SO3
acid
hydrogen HSO3−HSO3−" role="presentation" style="position: relative;">HSO3 − HSO 3

−
sulfite
phosphate PO43−PO43−" role="presentation" style="position: relative;">PO 4 3− PO 4

3− phosphoric H3PO4
acid
hydrogen HPO42−HPO42−" role="presentation" style="position: relative;">HPO 4 2− HPO 4

2−
phosphate
dihydrogen H2PO4−H2PO4−" role="presentation" style="position: relative;">H2 PO 4 − H 2 PO 4

−
phosphate
perchlorate ClO4−ClO4−" role="presentation" style="position: relative;">ClO4 − ClO 4

− perchloric HClO4
acid
chlorate ClO3−ClO3−" role="presentation" style="position: relative;">ClO3 − ClO 3

− chloric acid HClO3
chlorite ClO2−ClO2−" role="presentation" style="position: relative;">ClO2 − ClO 2

− chlorous acid HClO2
hypochlorite ClO− hypochlorous HClO

acid
chromate CrO42−CrO42−" role="presentation" style="position: relative;">CrO4 2− CrO 4

2− chromic acid H2CrO4
dichromate Cr2O72−Cr2O72−" role="presentation" style="position: relative;">Cr2 O7 2− Cr 2 O7

2− dichromic H2Cr2O7
acid
permanganate MnO4−MnO4−" role="presentation" style="position: relative;">MnO4 − MnO 4

− permanganic HMnO4
acid
Table 2.5
Note that there is a system for naming some polyatomic ions; -ate and -ite are suffixes designating polyatomic ions containing more or
fewer oxygen atoms. Per- (short for “hyper”) and hypo- (meaning “under”) are prefixes meaning more oxygen atoms than -ate and fewer
oxygen atoms than -ite, respectively. For example, perchlorate is
ClO4−,ClO4−," role="presentation" style="position: relative;">ClO4 − ,ClO , chlorate 4is −
ClO3−,ClO3−," role="presentation" style="position: relative;">ClO3 − ,ClO , chlorite 3is −
ClO2−ClO2−" role="presentation" style="position: relative;">ClO2 − ClO 2and hypochlorite is ClO−. Unfortunately, the
−
number of oxygen atoms corresponding to a given suffix or prefix is not consistent; for example, nitrate is
NO3−NO3−" role="presentation" style="position: relative;">NO3 − NO while 3 sulfate
−
is
SO42−.SO42−." role="presentation" style="position: relative;">SO4 .SO . This will be covered in more detail in the next
2−
4
2−
module on nomenclature.
The nature of the attractive forces that hold atoms or ions together within a compound is the basis for classifying chemical bonding. When
electrons are transferred and ions form, ionic bonds result. Ionic bonds are electrostatic forces of attraction, that is, the attractive forces

experienced between objects of opposite electrical charge (in this case, cations and anions). When electrons are “shared” and molecules
form, covalent bonds result. Covalent bonds are the attractive forces between the positively charged nuclei of the bonded atoms and one or
more pairs of electrons that are located between the atoms. Compounds are classified as ionic or molecular (covalent) on the basis of the
bonds present in them.
2.7.0.1: Ionic Compounds

When an element composed of atoms that readily lose electrons (a metal) reacts with an element composed of atoms that readily gain
electrons (a nonmetal), a transfer of electrons usually occurs, producing ions. The compound formed by this transfer is stabilized by the
electrostatic attractions (ionic bonds) between the ions of opposite charge present in the compound. For example, when each sodium atom
in a sample of sodium metal (group 1) gives up one electron to form a sodium cation, Na+, and each chlorine atom in a sample of chlorine
gas (group 17) accepts one electron to form a chloride anion, Cl−, the resulting compound, NaCl, is composed of sodium ions and chloride
ions in the ratio of one Na+ ion for each Cl− ion. Similarly, each calcium atom (group 2) can give up two electrons and transfer one to each
of two chlorine atoms to form CaCl2, which is composed of Ca2+ and Cl− ions in the ratio of one Ca2+ ion to two Cl− ions.
A compound that contains ions and is held together by ionic bonds is called an ionic compound. The periodic table can help us recognize
many of the compounds that are ionic: When a metal is combined with one or more nonmetals, the compound is usually ionic. This
guideline works well for predicting ionic compound formation for most of the compounds typically encountered in an introductory
chemistry course. However, it is not always true (for example, aluminum chloride, AlCl3, is not ionic).
You can often recognize ionic compounds because of their properties. Ionic compounds are solids that typically melt at high temperatures
and boil at even higher temperatures. For example, sodium chloride melts at 801 °C and boils at 1413 °C. (As a comparison, the molecular
compound water melts at 0 °C and boils at 100 °C.) In solid form, an ionic compound is not electrically conductive because its ions are
unable to flow (“electricity” is the flow of charged particles). When molten, however, it can conduct electricity because its ions are able to
move freely through the liquid (Figure 2.30).
This figure shows three photos connected by right-facing arrows. The first shows a light bulb as part of a complex lab equipment setup. The light bulb is not lit. The second photo shows a substances being heated or set on fire.
The third shows the light bulb again which is lit.
Figure 2.30 Sodium chloride melts at 801 °C and conducts electricity when molten. (credit: modification of work by Mark Blaser and Matt
Evans)

Watch this video to see a mixture of salts melt and conduct electricity.
In every ionic compound, the total number of positive charges of the cations equals the total number of negative charges of the anions.
Thus, ionic compounds are electrically neutral overall, even though they contain positive and negative ions. We can use this observation to
help us write the formula of an ionic compound. The formula of an ionic compound must have a ratio of ions such that the numbers of
positive and negative charges are equal.
2.7.0.1: Example 2.10

2.7.0.0.1: Predicting the Formula of an Ionic Compound
The gemstone sapphire (Figure 2.31) is mostly a compound of aluminum and oxygen that contains aluminum cations, Al3+, and oxygen
anions, O2−. What is the formula of this compound?
This is a photograph of a ring with a sapphire set in it.
Figure 2.31 Although pure aluminum oxide is colorless, trace amounts of iron and titanium give blue sapphire its characteristic color.
(credit: modification of work by Stanislav Doronenko)
2.7.0.0.1: Solution
Because the ionic compound must be electrically neutral, it must have the same number of positive and negative charges. Two aluminum
ions, each with a charge of 3+, would give us six positive charges, and three oxide ions, each with a charge of 2−, would give us six
negative charges. The formula would be Al2O3.
Predict the formula of the ionic compound formed between the sodium cation, Na+, and the sulfide anion, S2−.
2.7.0.1: Answer:
Na2S
Many ionic compounds contain polyatomic ions (Table 2.5) as the cation, the anion, or both. As with simple ionic compounds, these
compounds must also be electrically neutral, so their formulas can be predicted by treating the polyatomic ions as discrete units. We use
parentheses in a formula to indicate a group of atoms that behave as a unit. For example, the formula for calcium phosphate, one of the
minerals in our bones, is Ca3(PO4)2. This formula indicates that there are three calcium ions (Ca2+) for every two phosphate
(PO43−)(PO43−)" role="presentation" style="position: relative;">(PO 4 3− )(PO ) groups. The 4
3−

PO43−PO43−" role="presentation" style="position: relative;">PO 4 3− PO groups are discrete units, each consisting of one
4
3−
phosphorus atom and four oxygen atoms, and having an overall charge of 3−. The compound is electrically neutral, and its formula shows
a total count of three Ca, two P, and eight O atoms.
2.7.0.1: Example 2.11

2.7.0.0.1: Predicting the Formula of a Compound with a Polyatomic Anion
Baking powder contains calcium dihydrogen phosphate, an ionic compound composed of the ions Ca2+ and
H2PO4−.H2PO4−." role="presentation" style="position: relative;">H2 PO 4 − . H PO . What is the formula of this compound?
2 4
−
2.7.0.0.1: Solution
The positive and negative charges must balance, and this ionic compound must be electrically neutral. Thus, we must have two negative
charges to balance the 2+ charge of the calcium ion. This requires a ratio of one Ca2+ ion to two
H2PO4−H2PO4−" role="presentation" style="position: relative;">H2 PO 4 − H PO ions. We designate this by enclosing the
2 4
−
formula for the dihydrogen phosphate ion in parentheses and adding a subscript 2. The formula is Ca(H2PO4)2.
Predict the formula of the ionic compound formed between the lithium ion and the peroxide ion,
O22−O22−" role="presentation" style="position: relative;">O2 2− O 2(Hint: Use the periodic table to predict the sign and the
2−
charge on the lithium ion.)
2.7.0.1: Answer:
Li2O2
Because an ionic compound is not made up of single, discrete molecules, it may not be properly symbolized using a molecular formula.
Instead, ionic compounds must be symbolized by a formula indicating the relative numbers of its constituent ions. For compounds
containing only monatomic ions (such as NaCl) and for many compounds containing polyatomic ions (such as CaSO4), these formulas are
just the empirical formulas introduced earlier in this chapter. However, the formulas for some ionic compounds containing polyatomic ions
are not empirical formulas. For example, the ionic compound sodium oxalate is comprised of Na+ and
C2O42−C2O42−" role="presentation" style="position: relative;">C2 O4 2− C O 2 ions combined in a 2:1 ratio, and its formula
4
2−
is written as Na2C2O4. The subscripts in this formula are not the smallest-possible whole numbers, as each can be divided by 2 to yield the
empirical formula, NaCO2. This is not the accepted formula for sodium oxalate, however, as it does not accurately represent the
compound’s polyatomic anion, C2O42−.C2O42−." role="presentation" style="position: relative;">C2 O4 2− .C O . 2 4
2−
2.7.0.1: Molecular Compounds

Many compounds do not contain ions but instead consist solely of discrete, neutral molecules. These molecular compounds (covalent
compounds) result when atoms share, rather than transfer (gain or lose), electrons. Covalent bonding is an important and extensive concept
in chemistry, and it will be treated in considerable detail in a later chapter of this text. We can often identify molecular compounds on the
basis of their physical properties. Under normal conditions, molecular compounds often exist as gases, low-boiling liquids, and low-
melting solids, although many important exceptions exist.
Whereas ionic compounds are usually formed when a metal and a nonmetal combine, covalent compounds are usually formed by a
combination of nonmetals. Thus, the periodic table can help us recognize many of the compounds that are covalent. While we can use the
positions of a compound’s elements in the periodic table to predict whether it is ionic or covalent at this point in our study of chemistry,
you should be aware that this is a very simplistic approach that does not account for a number of interesting exceptions. Shades of gray
exist between ionic and molecular compounds, and you’ll learn more about those later.
2.7.0.1: Example 2.12

2.7.0.0.1: Predicting the Type of Bonding in Compounds
Predict whether the following compounds are ionic or molecular:
(a) KI, the compound used as a source of iodine in table salt
(b) H2O2, the bleach and disinfectant hydrogen peroxide
(c) CHCl3, the anesthetic chloroform
(d) Li2CO3, a source of lithium in antidepressants
2.7.0.0.2: Solution
(a) Potassium (group 1) is a metal, and iodine (group 17) is a nonmetal; KI is predicted to be ionic.
(b) Hydrogen (group 1) is a nonmetal, and oxygen (group 16) is a nonmetal; H2O2 is predicted to be molecular.

(c) Carbon (group 14) is a nonmetal, hydrogen (group 1) is a nonmetal, and chlorine (group 17) is a nonmetal; CHCl3 is predicted to be
molecular.
(d) Lithium (group 1) is a metal, and carbonate is a polyatomic ion; Li2CO3 is predicted to be ionic.
Using the periodic table, predict whether the following compounds are ionic or covalent:
(a) SO2
(b) CaF2
(c) N2H4
(d) Al2(SO4)3
2.7.0.1: Answer:
(a) molecular; (b) ionic; (c) molecular; (d) ionic
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Derive names for common types of inorganic compounds using a systematic approach
Nomenclature, a collection of rules for naming things, is important in science and in many other situations. This module describes
an approach that is used to name simple ionic and molecular compounds, such as NaCl, CaCO3, and N2O4. The simplest of these
are binary compounds, those containing only two elements, but we will also consider how to name ionic compounds containing
polyatomic ions, and one specific, very important class of compounds known as acids (subsequent chapters in this text will focus
on these compounds in great detail). We will limit our attention here to inorganic compounds, compounds that are composed
principally of elements other than carbon, and will follow the nomenclature guidelines proposed by IUPAC. The rules for organic
compounds, in which carbon is the principle element, will be treated in a later chapter on organic chemistry.
2.8.0.1: Ionic Compounds

To name an inorganic compound, we need to consider the answers to several questions. First, is the compound ionic or molecular?
If the compound is ionic, does the metal form ions of only one type (fixed charge) or more than one type (variable charge)? Are the
ions monatomic or polyatomic? If the compound is molecular, does it contain hydrogen? If so, does it also contain oxygen? From
the answers we derive, we place the compound in an appropriate category and then name it accordingly.
2.8.0.1: Compounds Containing Only Monatomic Ions

The name of a binary compound containing monatomic ions consists of the name of the cation (the name of the metal) followed by
the name of the anion (the name of the nonmetallic element with its ending replaced by the suffix –ide). Some examples are given
in Table 2.6.
Names of Some Ionic Compounds
NaCl, sodium chloride Na2O, sodium oxide
KBr, potassium bromide CdS, cadmium sulfide
CaI2, calcium iodide Mg3N2, magnesium nitride
CsF, cesium fluoride Ca3P2, calcium phosphide
LiCl, lithium chloride Al4C3, aluminum carbide
Table 2.6
2.8.0.1: Compounds Containing Polyatomic Ions

Compounds containing polyatomic ions are named similarly to those containing only monatomic ions, i.e. by naming first the
cation and then the anion. Examples are shown in Table 2.7.
Names of Some Polyatomic Ionic Compounds
KC2H3O2, potassium acetate NH4Cl, ammonium chloride
NaHCO3, sodium bicarbonate CaSO4, calcium sulfate
Al2(CO3)3, aluminum carbonate Mg3(PO4)2, magnesium phosphate
Table 2.7

2.8.0.0.1: Ionic Compounds in Your Cabinets
Every day you encounter and use a large number of ionic compounds. Some of these compounds, where they are found, and
what they are used for are listed in Table 2.8. Look at the label or ingredients list on the various products that you use during
the next few days, and see if you run into any of those in this table, or find other ionic compounds that you could now name or
write as a formula.
Everyday Ionic Compounds
Ionic Compound Use
NaCl, sodium chloride ordinary table salt
KI, potassium iodide added to “iodized” salt for thyroid health
NaF, sodium fluoride ingredient in toothpaste
NaHCO3, sodium bicarbonate baking soda; used in cooking (and as antacid)
Na2CO3, sodium carbonate washing soda; used in cleaning agents
NaOCl, sodium hypochlorite active ingredient in household bleach
CaCO3 calcium carbonate ingredient in antacids
Mg(OH)2, magnesium hydroxide ingredient in antacids
Al(OH)3, aluminum hydroxide ingredient in antacids
NaOH, sodium hydroxide lye; used as drain cleaner
K3PO4, potassium phosphate food additive (many purposes)
MgSO4, magnesium sulfate added to purified water
Na2HPO4, sodium hydrogen phosphate anti-caking agent; used in powdered products
Na2SO3, sodium sulfite preservative
Table 2.8
2.8.0.1: Compounds Containing a Metal Ion with a Variable Charge

Most of the transition metals and some main group metals can form two or more cations with different charges. Compounds of
these metals with nonmetals are named with the same method as compounds in the first category, except the charge of the metal ion
is specified by a Roman numeral in parentheses after the name of the metal. The charge of the metal ion is determined from the
formula of the compound and the charge of the anion. For example, consider binary ionic compounds of iron and chlorine. Iron
typically exhibits a charge of either 2+ or 3+ (see Figure 2.29), and the two corresponding compound formulas are FeCl2 and
FeCl3. The simplest name, “iron chloride,” will, in this case, be ambiguous, as it does not distinguish between these two
compounds. In cases like this, the charge of the metal ion is included as a Roman numeral in parentheses immediately following
the metal name. These two compounds are then unambiguously named iron(II) chloride and iron(III) chloride, respectively. Other
examples are provided in Table 2.9.
Some Ionic Compounds with Variably Charged Metal Ions

Compound Name
FeCl2 iron(II) chloride
FeCl3 iron(III) chloride
Hg2O mercury(I) oxide
HgO mercury(II) oxide
SnF2 tin(II) fluoride
SnF4 tin(IV) fluoride
Table 2.9
Out-of-date nomenclature used the suffixes –ic and –ous to designate metals with higher and lower charges, respectively: Iron(III)
chloride, FeCl3, was previously called ferric chloride, and iron(II) chloride, FeCl2, was known as ferrous chloride. Though this
naming convention has been largely abandoned by the scientific community, it remains in use by some segments of industry. For
example, you may see the words stannous fluoride on a tube of toothpaste. This represents the formula SnF2, which is more
properly named tin(II) fluoride. The other fluoride of tin is SnF4, which was previously called stannic fluoride but is now named
tin(IV) fluoride.
2.8.0.1: Ionic Hydrates

Ionic compounds that contain water molecules as integral components of their crystals are called hydrates. The name for an ionic
hydrate is derived by adding a term to the name for the anhydrous (meaning “not hydrated”) compound that indicates the number
of water molecules associated with each formula unit of the compound. The added word begins with a Greek prefix denoting the
number of water molecules (see Table 2.10) and ends with “hydrate.” For example, the anhydrous compound copper(II) sulfate also
exists as a hydrate containing five water molecules and named copper(II) sulfate pentahydrate. Washing soda is the common name
for a hydrate of sodium carbonate containing 10 water molecules; the systematic name is sodium carbonate decahydrate.
Formulas for ionic hydrates are written by appending a vertically centered dot, a coefficient representing the number of water
molecules, and the formula for water. The two examples mentioned in the previous paragraph are represented by the formulas
copper(II) sulfate pentahydrate CuSO 4 ∙5 H2 O
sodium carbonate decahydrate Na2 CO3 ∙10 H2 O
Nomenclature Prefixes
Number Prefix Number Prefix
1 (sometimes omitted) mono- 6 hexa-
2 di- 7 hepta-
3 tri- 8 octa-
4 tetra- 9 nona-
5 penta- 10 deca-
Table 2.10
2.8.0.1: Example 2.13

2.8.0.0.1: Naming Ionic Compounds
Name the following ionic compounds
(a) Fe2S3
(b) CuSe
(c) GaN
(d) MgSO4·7H2O
(e) Ti2(SO4)3
2.8.0.0.2: Solution
The anions in these compounds have a fixed negative charge (S2−, Se2− , N3−, and SO 4), and the compounds must be
2−
neutral. Because the total number of positive charges in each compound must equal the total number of negative charges, the
positive ions must be Fe3+, Cu2+, Ga3+, Mg2+, and Ti3+. These charges are used in the names of the metal ions:
(a) iron(III) sulfide
(b) copper(II) selenide
(c) gallium(III) nitride
(d) magnesium sulfate heptahydrate
(e) titanium(III) sulfate
Write the formulas of the following ionic compounds:
(a) chromium(III) phosphide
(b) mercury(II) sulfide
(c) manganese(II) phosphate
(d) copper(I) oxide
(e) iron(III) chloride dihydrate
2.8.0.1: Answer:
(a) CrP; (b) HgS; (c) Mn3(PO4)2; (d) Cu2O; (e) FeCl3·2H2O

2.8.0.0.4: Erin Brockovich and Chromium Contamination
In the early 1990s, legal file clerk Erin Brockovich (Figure 2.32) discovered a high rate of serious illnesses in the small town of
Hinckley, California. Her investigation eventually linked the illnesses to groundwater contaminated by Cr(VI) used by Pacific
Gas & Electric (PG&E) to fight corrosion in a nearby natural gas pipeline. As dramatized in the film Erin Brockovich (for
which Julia Roberts won an Oscar), Erin and lawyer Edward Masry sued PG&E for contaminating the water near Hinckley in
1993. The settlement they won in 1996—$333 million—was the largest amount ever awarded for a direct-action lawsuit in the
US at that time.

Figure 2.32 (a) Erin Brockovich found that Cr(VI), used by PG&E, had contaminated the Hinckley, California, water supply.
(b) The Cr(VI) ion is often present in water as the polyatomic ions chromate, CrO (left), and dichromate, Cr O
4
2−
2(right).
7
2−
Chromium compounds are widely used in industry, such as for chrome plating, in dye-making, as preservatives, and to prevent
corrosion in cooling tower water, as occurred near Hinckley. In the environment, chromium exists primarily in either the
Cr(III) or Cr(VI) forms. Cr(III), an ingredient of many vitamin and nutritional supplements, forms compounds that are not very
soluble in water, and it has low toxicity. But Cr(VI) is much more toxic and forms compounds that are reasonably soluble in
water. Exposure to small amounts of Cr(VI) can lead to damage of the respiratory, gastrointestinal, and immune systems, as
well as the kidneys, liver, blood, and skin.
Despite cleanup efforts, Cr(VI) groundwater contamination remains a problem in Hinckley and other locations across the
globe. A 2010 study by the Environmental Working Group found that of 35 US cities tested, 31 had higher levels of Cr(VI) in
their tap water than the public health goal of 0.02 parts per billion set by the California Environmental Protection Agency.
2.8.0.1: Molecular (Covalent) Compounds

The bonding characteristics of inorganic molecular compounds are different from ionic compounds, and they are named using a
different system as well. The charges of cations and anions dictate their ratios in ionic compounds, so specifying the names of the
ions provides sufficient information to determine chemical formulas. However, because covalent bonding allows for significant
variation in the combination ratios of the atoms in a molecule, the names for molecular compounds must explicitly identify these
ratios.
2.8.0.1: Compounds Composed of Two Elements

When two nonmetallic elements form a molecular compound, several combination ratios are often possible. For example, carbon
and oxygen can form the compounds CO and CO2. Since these are different substances with different properties, they cannot both
have the same name (they cannot both be called carbon oxide). To deal with this situation, we use a naming method that is
somewhat similar to that used for ionic compounds, but with added prefixes to specify the numbers of atoms of each element. The
name of the more metallic element (the one farther to the left and/or bottom of the periodic table) is first, followed by the name of

the more nonmetallic element (the one farther to the right and/or top) with its ending changed to the suffix –ide. The numbers of
atoms of each element are designated by the Greek prefixes shown in Table 2.10.
When only one atom of the first element is present, the prefix mono- is usually deleted from that part. Thus, CO is named carbon
monoxide, and CO2 is called carbon dioxide. When two vowels are adjacent, the a in the Greek prefix is usually dropped. Some
other examples are shown in Table 2.11.
Names of Some Molecular Compounds Composed of Two Elements
Compound Name Compound Name
SO2 sulfur dioxide BCl3 boron trichloride
SO3 sulfur trioxide SF6 sulfur hexafluoride
NO2 nitrogen dioxide PF5 phosphorus pentafluoride
N2O4 dinitrogen tetroxide P4O10 tetraphosphorus decaoxide
N2O5 dinitrogen pentoxide IF7 iodine heptafluoride
Table 2.11
There are a few common names that you will encounter as you continue your study of chemistry. For example, although NO is
often called nitric oxide, its proper name is nitrogen monoxide. Similarly, N2O is known as nitrous oxide even though our rules
would specify the name dinitrogen monoxide. (And H2O is usually called water, not dihydrogen monoxide.) You should commit to
memory the common names of compounds as you encounter them.
2.8.0.1: Example 2.14

2.8.0.0.1: Naming Covalent Compounds
Name the following covalent compounds:
(a) SF6
(b) N2O3
(c) Cl2O7
(d) P4O6
2.8.0.0.2: Solution
Because these compounds consist solely of nonmetals, we use prefixes to designate the number of atoms of each element:
(a) sulfur hexafluoride
(b) dinitrogen trioxide
(c) dichlorine heptoxide
(d) tetraphosphorus hexoxide
Write the formulas for the following compounds:
(a) phosphorus pentachloride
(b) dinitrogen monoxide
(c) iodine heptafluoride
(d) carbon tetrachloride
2.8.0.1: Answer:
(a) PCl5; (b) N2O; (c) IF7; (d) CCl4

The following website provides practice with naming chemical compounds and writing chemical formulas. You can choose
binary, polyatomic, and variable charge ionic compounds, as well as molecular compounds.
2.8.0.1: Binary Acids

Some compounds containing hydrogen are members of an important class of substances known as acids. The chemistry of these
compounds is explored in more detail in later chapters of this text, but for now, it will suffice to note that many acids release
hydrogen ions, H+, when dissolved in water. To denote this distinct chemical property, a mixture of water with an acid is given a
name derived from the compound’s name. If the compound is a binary acid (comprised of hydrogen and one other nonmetallic
element):
1. The word “hydrogen” is changed to the prefix hydro-
2. The other nonmetallic element name is modified by adding the suffix -ic
3. The word “acid” is added as a second word
For example, when the gas HCl (hydrogen chloride) is dissolved in water, the solution is called hydrochloric acid. Several other
examples of this nomenclature are shown in Table 2.12.
Names of Some Simple Acids
Name of Gas Name of Acid
HF(g), hydrogen fluoride HF(aq), hydrofluoric acid
HCl(g), hydrogen chloride HCl(aq), hydrochloric acid
HBr(g), hydrogen bromide HBr(aq), hydrobromic acid
HI(g), hydrogen iodide HI(aq), hydroiodic acid
H2S(g), hydrogen sulfide H2S(aq), hydrosulfuric acid
Table 2.12
2.8.0.1: Oxyacids
Many compounds containing three or more elements (such as organic compounds or coordination compounds) are subject to
specialized nomenclature rules that you will learn later. However, we will briefly discuss the important compounds known as
oxyacids, compounds that contain hydrogen, oxygen, and at least one other element, and are bonded in such a way as to impart
acidic properties to the compound (you will learn the details of this in a later chapter). Typical oxyacids consist of hydrogen
combined with a polyatomic, oxygen-containing ion. To name oxyacids:
1. Omit “hydrogen”
2. Start with the root name of the anion
3. Replace –ate with –ic, or –ite with –ous
4. Add “acid”
For example, consider H2CO3 (which you might be tempted to call “hydrogen carbonate”). To name this correctly, “hydrogen” is
omitted; the –ate of carbonate is replace with –ic; and acid is added—so its name is carbonic acid. Other examples are given in
Table 2.13. There are some exceptions to the general naming method (e.g., H2SO4 is called sulfuric acid, not sulfic acid, and H2SO3
is sulfurous, not sulfous, acid).
Names of Common Oxyacids
Formula Anion Name Acid Name

Formula Anion Name Acid Name
HC2H3O2 acetate acetic acid
HNO3 nitrate nitric acid
HNO2 nitrite nitrous acid
HClO4 perchlorate perchloric acid
H2CO3 carbonate carbonic acid
H2SO4 sulfate sulfuric acid
H2SO3 sulfite sulfurous acid
H3PO4 phosphate phosphoric acid
Table 2.13
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2.9: Key Terms
actinide
inner transition metal in the bottom of the bottom two rows of the periodic table
alkali metal
element in group 1
alkaline earth metal

element in group 2
alpha particle (α particle)

positively charged particle consisting of two protons and two neutrons
anion
negatively charged atom or molecule (contains more electrons than protons)
atomic mass
average mass of atoms of an element, expressed in amu
atomic mass unit (amu)

(also, unified atomic mass unit, u, or Dalton, Da) unit of mass equal to 1
12
of the mass of a 12C atom
atomic number (Z)

number of protons in the nucleus of an atom
binary acid
compound that contains hydrogen and one other element, bonded in a way that imparts acidic properties to the compound
(ability to release H+ ions when dissolved in water)
binary compound
compound containing two different elements.
cation
positively charged atom or molecule (contains fewer electrons than protons)
chalcogen
element in group 16
chemical symbol
one-, two-, or three-letter abbreviation used to represent an element or its atoms
covalent bond
attractive force between the nuclei of a molecule’s atoms and pairs of electrons between the atoms
covalent compound
(also, molecular compound) composed of molecules formed by atoms of two or more different elements
Dalton (Da)
alternative unit equivalent to the atomic mass unit
Dalton’s atomic theory

set of postulates that established the fundamental properties of atoms
electron
negatively charged, subatomic particle of relatively low mass located outside the nucleus
empirical formula
formula showing the composition of a compound given as the simplest whole-number ratio of atoms
fundamental unit of charge

(also called the elementary charge) equals the magnitude of the charge of an electron (e) with e = 1.602 × 10−19 C
group
vertical column of the periodic table
halogen
element in group 17
hydrate
compound containing one or more water molecules bound within its crystals
inert gas
(also, noble gas) element in group 18
inner transition metal

(also, lanthanide or actinide) element in the bottom two rows; if in the first row, also called lanthanide, or if in the second row,
also called actinide
ion
electrically charged atom or molecule (contains unequal numbers of protons and electrons)
ionic bond
electrostatic forces of attraction between the oppositely charged ions of an ionic compound
ionic compound
compound composed of cations and anions combined in ratios, yielding an electrically neutral substance
isomers
compounds with the same chemical formula but different structures
isotopes
atoms that contain the same number of protons but different numbers of neutrons
lanthanide
inner transition metal in the top of the bottom two rows of the periodic table
law of constant composition

(also, law of definite proportions) all samples of a pure compound contain the same elements in the same proportions by mass
law of definite proportions

(also, law of constant composition) all samples of a pure compound contain the same elements in the same proportions by mass
law of multiple proportions

when two elements react to form more than one compound, a fixed mass of one element will react with masses of the other
element in a ratio of small whole numbers
main-group element
(also, representative element) element in groups 1, 2, and 13–18
mass number (A)
sum of the numbers of neutrons and protons in the nucleus of an atom
metal
element that is shiny, malleable, good conductor of heat and electricity
metalloid
element that conducts heat and electricity moderately well, and possesses some properties of metals and some properties of
nonmetals
molecular compound
(also, covalent compound) composed of molecules formed by atoms of two or more different elements
molecular formula
formula indicating the composition of a molecule of a compound and giving the actual number of atoms of each element in a
molecule of the compound.
monatomic ion
ion composed of a single atom
neutron
uncharged, subatomic particle located in the nucleus
noble gas
(also, inert gas) element in group 18
nomenclature
system of rules for naming objects of interest
nonmetal
element that appears dull, poor conductor of heat and electricity
nucleus
massive, positively charged center of an atom made up of protons and neutrons
oxyacid
compound that contains hydrogen, oxygen, and one other element, bonded in a way that imparts acidic properties to the
compound (ability to release H+ ions when dissolved in water)
oxyanion
polyatomic anion composed of a central atom bonded to oxygen atoms
period
(also, series) horizontal row of the periodic table
periodic law
properties of the elements are periodic function of their atomic numbers.
periodic table
table of the elements that places elements with similar chemical properties close together
pnictogen
element in group 15
polyatomic ion
ion composed of more than one atom
proton
positively charged, subatomic particle located in the nucleus
representative element
(also, main-group element) element in columns 1, 2, and 12–18
series
(also, period) horizontal row of the period table
spatial isomers
compounds in which the relative orientations of the atoms in space differ
structural formula
shows the atoms in a molecule and how they are connected
structural isomer
one of two substances that have the same molecular formula but different physical and chemical properties because their atoms
are bonded differently
transition metal
element in groups 3–12 (more strictly defined, 3–11; see chapter on transition metals and coordination chemistry)
unified atomic mass unit (u)

alternative unit equivalent to the atomic mass unit
2.10: Key Equations
average mass = ∑ (fractional abundance × isotopic mass)
i
2.11: Summary
2.1 Early Ideas in Atomic Theory
The ancient Greeks proposed that matter consists of extremely small particles called atoms. Dalton postulated that each element has
a characteristic type of atom that differs in properties from atoms of all other elements, and that atoms of different elements can
combine in fixed, small, whole-number ratios to form compounds. Samples of a particular compound all have the same elemental
proportions by mass. When two elements form different compounds, a given mass of one element will combine with masses of the
other element in a small, whole-number ratio. During any chemical change, atoms are neither created nor destroyed.
2.2 Evolution of Atomic Theory

Although no one has actually seen the inside of an atom, experiments have demonstrated much about atomic structure. Thomson’s
cathode ray tube showed that atoms contain small, negatively charged particles called electrons. Millikan discovered that there is a
fundamental electric charge—the charge of an electron. Rutherford’s gold foil experiment showed that atoms have a small, dense,
positively charged nucleus; the positively charged particles within the nucleus are called protons. Chadwick discovered that the
nucleus also contains neutral particles called neutrons. Soddy demonstrated that atoms of the same element can differ in mass;
these are called isotopes.
2.3 Atomic Structure and Symbolism

An atom consists of a small, positively charged nucleus surrounded by electrons. The nucleus contains protons and neutrons; its
diameter is about 100,000 times smaller than that of the atom. The mass of one atom is usually expressed in atomic mass units
(amu), which is referred to as the atomic mass. An amu is defined as exactly of the mass of a carbon-12 atom and is equal to
1
12
−24
1.6605 × 10 g.
Protons are relatively heavy particles with a charge of 1+ and a mass of 1.0073 amu. Neutrons are relatively heavy particles with no
charge and a mass of 1.0087 amu. Electrons are light particles with a charge of 1− and a mass of 0.00055 amu. The number of
protons in the nucleus is called the atomic number (Z) and is the property that defines an atom’s elemental identity. The sum of the
numbers of protons and neutrons in the nucleus is called the mass number and, expressed in amu, is approximately equal to the
mass of the atom. An atom is neutral when it contains equal numbers of electrons and protons.
Isotopes of an element are atoms with the same atomic number but different mass numbers; isotopes of an element, therefore, differ
from each other only in the number of neutrons within the nucleus. When a naturally occurring element is composed of several
isotopes, the atomic mass of the element represents the average of the masses of the isotopes involved. A chemical symbol
identifies the atoms in a substance using symbols, which are one-, two-, or three-letter abbreviations for the atoms.
2.4 Chemical Formulas

A molecular formula uses chemical symbols and subscripts to indicate the exact numbers of different atoms in a molecule or
compound. An empirical formula gives the simplest, whole-number ratio of atoms in a compound. A structural formula indicates
the bonding arrangement of the atoms in the molecule. Ball-and-stick and space-filling models show the geometric arrangement of
atoms in a molecule. Isomers are compounds with the same molecular formula but different arrangements of atoms.
2.5 The Periodic Table

The discovery of the periodic recurrence of similar properties among the elements led to the formulation of the periodic table, in
which the elements are arranged in order of increasing atomic number in rows known as periods and columns known as groups.
Elements in the same group of the periodic table have similar chemical properties. Elements can be classified as metals, metalloids,
and nonmetals, or as a main-group elements, transition metals, and inner transition metals. Groups are numbered 1–18 from left to
right. The elements in group 1 are known as the alkali metals; those in group 2 are the alkaline earth metals; those in 15 are the
pnictogens; those in 16 are the chalcogens; those in 17 are the halogens; and those in 18 are the noble gases.
2.6 Ionic and Molecular Compounds

Metals (particularly those in groups 1 and 2) tend to lose the number of electrons that would leave them with the same number of
electrons as in the preceding noble gas in the periodic table. By this means, a positively charged ion is formed. Similarly, nonmetals
(especially those in groups 16 and 17, and, to a lesser extent, those in Group 15) can gain the number of electrons needed to
provide atoms with the same number of electrons as in the next noble gas in the periodic table. Thus, nonmetals tend to form
negative ions. Positively charged ions are called cations, and negatively charged ions are called anions. Ions can be either
monatomic (containing only one atom) or polyatomic (containing more than one atom).
Compounds that contain ions are called ionic compounds. Ionic compounds generally form from metals and nonmetals.
Compounds that do not contain ions, but instead consist of atoms bonded tightly together in molecules (uncharged groups of atoms
that behave as a single unit), are called covalent compounds. Covalent compounds usually form from two nonmetals.
2.7 Chemical Nomenclature

Chemists use nomenclature rules to clearly name compounds. Ionic and molecular compounds are named using somewhat-different
methods. Binary ionic compounds typically consist of a metal and a nonmetal. The name of the metal is written first, followed by
the name of the nonmetal with its ending changed to –ide. For example, K2O is called potassium oxide. If the metal can form ions
with different charges, a Roman numeral in parentheses follows the name of the metal to specify its charge. Thus, FeCl2 is iron(II)
chloride and FeCl3 is iron(III) chloride. Some compounds contain polyatomic ions; the names of common polyatomic ions should
be memorized. Molecular compounds can form compounds with different ratios of their elements, so prefixes are used to specify
the numbers of atoms of each element in a molecule of the compound. Examples include SF6, sulfur hexafluoride, and N2O4,
dinitrogen tetroxide. Acids are an important class of compounds containing hydrogen and having special nomenclature rules.
Binary acids are named using the prefix hydro-, changing the –ide suffix to –ic, and adding “acid;” HCl is hydrochloric acid.
Oxyacids are named by changing the ending of the anion (–ate to –ic and –ite to –ous), and adding “acid;” H2CO3 is carbonic acid.
2.12: Exercises
2.12.0.1: 2.1 Early Ideas in Atomic Theory
1.
In the following drawing, the green spheres represent atoms of a certain element. The purple spheres represent atoms of another
element. If the spheres of different elements touch, they are part of a single unit of a compound. The following chemical change
represented by these spheres may violate one of the ideas of Dalton’s atomic theory. Which one?
2.
Which postulate of Dalton’s theory is consistent with the following observation concerning the weights of reactants and products?
When 100 grams of solid calcium carbonate is heated, 44 grams of carbon dioxide and 56 grams of calcium oxide are produced.
3.
Identify the postulate of Dalton’s theory that is violated by the following observations: 59.95% of one sample of titanium dioxide is
titanium; 60.10% of a different sample of titanium dioxide is titanium.
4.
Samples of compound X, Y, and Z are analyzed, with results shown here.
Compound Description Mass of Carbon Mass of Hydrogen
X clear, colorless, liquid with strong odor 1.776 g 0.148 g
Y clear, colorless, liquid with strong odor 1.974 g 0.329 g
Z clear, colorless, liquid with strong odor 7.812 g 0.651 g
Do these data provide example(s) of the law of definite proportions, the law of multiple proportions, neither, or both? What do
these data tell you about compounds X, Y, and Z?
2.12.0.1: 2.2 Evolution of Atomic Theory

5.
The existence of isotopes violates one of the original ideas of Dalton’s atomic theory. Which one?
6.
How are electrons and protons similar? How are they different?
7.
How are protons and neutrons similar? How are they different?
8.
Predict and test the behavior of α particles fired at a “plum pudding” model atom.
(a) Predict the paths taken by α particles that are fired at atoms with a Thomson’s plum pudding model structure. Explain why you
expect the α particles to take these paths.
(b) If α particles of higher energy than those in (a) are fired at plum pudding atoms, predict how their paths will differ from the
lower-energy α particle paths. Explain your reasoning.
(c) Now test your predictions from (a) and (b). Open the Rutherford Scattering simulation and select the “Plum Pudding Atom” tab.
Set “Alpha Particles Energy” to “min,” and select “show traces.” Click on the gun to start firing α particles. Does this match your
prediction from (a)? If not, explain why the actual path would be that shown in the simulation. Hit the pause button, or “Reset All.”

Set “Alpha Particles Energy” to “max,” and start firing α particles. Does this match your prediction from (b)? If not, explain the
effect of increased energy on the actual paths as shown in the simulation.
9.
Predict and test the behavior of α particles fired at a Rutherford atom model.
(a) Predict the paths taken by α particles that are fired at atoms with a Rutherford atom model structure. Explain why you expect
the α particles to take these paths.
(b) If α particles of higher energy than those in (a) are fired at Rutherford atoms, predict how their paths will differ from the lower-
energy α particle paths. Explain your reasoning.
(c) Predict how the paths taken by the α particles will differ if they are fired at Rutherford atoms of elements other than gold. What
factor do you expect to cause this difference in paths, and why?
(d) Now test your predictions from (a), (b), and (c). Open the Rutherford Scattering simulation and select the “Rutherford Atom”
tab. Due to the scale of the simulation, it is best to start with a small nucleus, so select “20” for both protons and neutrons, “min”
for energy, show traces, and then start firing α particles. Does this match your prediction from (a)? If not, explain why the actual
path would be that shown in the simulation. Pause or reset, set energy to “max,” and start firing α particles. Does this match your
prediction from (b)? If not, explain the effect of increased energy on the actual path as shown in the simulation. Pause or reset,
select “40” for both protons and neutrons, “min” for energy, show traces, and fire away. Does this match your prediction from (c)?
If not, explain why the actual path would be that shown in the simulation. Repeat this with larger numbers of protons and neutrons.
What generalization can you make regarding the type of atom and effect on the path of α particles? Be clear and specific.
2.12.0.1: 2.3 Atomic Structure and Symbolism

10.
In what way are isotopes of a given element always different? In what way(s) are they always the same?
11.
Write the symbol for each of the following ions:
(a) the ion with a 1+ charge, atomic number 55, and mass number 133
(b) the ion with 54 electrons, 53 protons, and 74 neutrons
(c) the ion with atomic number 15, mass number 31, and a 3− charge
(d) the ion with 24 electrons, 30 neutrons, and a 3+ charge
12.
Write the symbol for each of the following ions:
(a) the ion with a 3+ charge, 28 electrons, and a mass number of 71
(b) the ion with 36 electrons, 35 protons, and 45 neutrons
(c) the ion with 86 electrons, 142 neutrons, and a 4+ charge
(d) the ion with a 2+ charge, atomic number 38, and mass number 87
13.
Open the Build an Atom simulation and click on the Atom icon.
(a) Pick any one of the first 10 elements that you would like to build and state its symbol.
(b) Drag protons, neutrons, and electrons onto the atom template to make an atom of your element.
State the numbers of protons, neutrons, and electrons in your atom, as well as the net charge and mass number.
(c) Click on “Net Charge” and “Mass Number,” check your answers to (b), and correct, if needed.
(d) Predict whether your atom will be stable or unstable. State your reasoning.
(e) Check the “Stable/Unstable” box. Was your answer to (d) correct? If not, first predict what you can do to make a stable atom of
your element, and then do it and see if it works. Explain your reasoning.

14.
Open the Build an Atom simulation.
(a) Drag protons, neutrons, and electrons onto the atom template to make a neutral atom of Oxygen-16 and give the isotope symbol
for this atom.
(b) Now add two more electrons to make an ion and give the symbol for the ion you have created.
15.
Open the Build an Atom simulation.
(a) Drag protons, neutrons, and electrons onto the atom template to make a neutral atom of Lithium-6 and give the isotope symbol
for this atom.
(b) Now remove one electron to make an ion and give the symbol for the ion you have created.
16.
Determine the number of protons, neutrons, and electrons in the following isotopes that are used in medical diagnoses:
(a) atomic number 9, mass number 18, charge of 1−
(b) atomic number 43, mass number 99, charge of 7+
(c) atomic number 53, atomic mass number 131, charge of 1−
(d) atomic number 81, atomic mass number 201, charge of 1+
(e) Name the elements in parts (a), (b), (c), and (d).
17.
The following are properties of isotopes of two elements that are essential in our diet. Determine the number of protons, neutrons
and electrons in each and name them.
(a) atomic number 26, mass number 58, charge of 2+
(b) atomic number 53, mass number 127, charge of 1−
18.
Give the number of protons, electrons, and neutrons in neutral atoms of each of the following isotopes:
(a) 10
5
B
(b) 199
80
Hg
(c) 63
29
Cu
(d) 13
6
C
(e) 77
34
Se
19.
Give the number of protons, electrons, and neutrons in neutral atoms of each of the following isotopes:
(a) 7
3
Li
(b) 125
52
Te
(c) 109
47
Ag
(d) 15
7
N
(e) 31
15
P
20.
Click on the site and select the “Mix Isotopes” tab, hide the “Percent Composition” and “Average Atomic Mass” boxes, and then
select the element boron.
(a) Write the symbols of the isotopes of boron that are shown as naturally occurring in significant amounts.

(b) Predict the relative amounts (percentages) of these boron isotopes found in nature. Explain the reasoning behind your choice.
(c) Add isotopes to the black box to make a mixture that matches your prediction in (b). You may drag isotopes from their bins or
click on “More” and then move the sliders to the appropriate amounts.
(d) Reveal the “Percent Composition” and “Average Atomic Mass” boxes. How well does your mixture match with your
prediction? If necessary, adjust the isotope amounts to match your prediction.
(e) Select “Nature’s” mix of isotopes and compare it to your prediction. How well does your prediction compare with the naturally
occurring mixture? Explain. If necessary, adjust your amounts to make them match “Nature’s” amounts as closely as possible.
21.
Repeat Exercise 2.20 using an element that has three naturally occurring isotopes.
22.
An element has the following natural abundances and isotopic masses: 90.92% abundance with 19.99 amu, 0.26% abundance with
20.99 amu, and 8.82% abundance with 21.99 amu. Calculate the average atomic mass of this element.
23.
Average atomic masses listed by IUPAC are based on a study of experimental results. Bromine has two isotopes, 79Br and 81Br,
whose masses (78.9183 and 80.9163 amu, respectively) and abundances (50.69% and 49.31%, respectively) were determined in
earlier experiments. Calculate the average atomic mass of bromine based on these experiments.
24.
Variations in average atomic mass may be observed for elements obtained from different sources. Lithium provides an example of
this. The isotopic composition of lithium from naturally occurring minerals is 7.5% 6Li and 92.5% 7Li, which have masses of
6.01512 amu and 7.01600 amu, respectively. A commercial source of lithium, recycled from a military source, was 3.75% 6Li (and
the rest 7Li). Calculate the average atomic mass values for each of these two sources.
25.
The average atomic masses of some elements may vary, depending upon the sources of their ores. Naturally occurring boron
consists of two isotopes with accurately known masses (10B, 10.0129 amu and 11B, 11.00931 amu). The actual atomic mass of
boron can vary from 10.807 to 10.819, depending on whether the mineral source is from Turkey or the United States. Calculate the
percent abundances leading to the two values of the average atomic masses of boron from these two countries.
26.
The 18O:16O abundance ratio in some meteorites is greater than that used to calculate the average atomic mass of oxygen on earth.
Is the average mass of an oxygen atom in these meteorites greater than, less than, or equal to that of a terrestrial oxygen atom?
2.12.0.1: 2.4 Chemical Formulas

27.
Explain why the symbol for an atom of the element oxygen and the formula for a molecule of oxygen differ.
28.
Explain why the symbol for the element sulfur and the formula for a molecule of sulfur differ.
29.
Write the molecular and empirical formulas of the following compounds:
(a)
(b)
(c)

(d)
30.
Write the molecular and empirical formulas of the following compounds:
(a)
(b)
(c)
(d)
31.
Determine the empirical formulas for the following compounds:
(a) caffeine, C8H10N4O2
(b) sucrose, C12H22O11
(c) hydrogen peroxide, H2O2

(d) glucose, C6H12O6
(e) ascorbic acid (vitamin C), C6H8O6
32.
Determine the empirical formulas for the following compounds:
(a) acetic acid, C2H4O2
(b) citric acid, C6H8O7
(c) hydrazine, N2H4
(d) nicotine, C10H14N2
(e) butane, C4H10
33.
Write the empirical formulas for the following compounds:
(a)
(b)
34.
Open the Build a Molecule simulation and select the “Larger Molecules” tab. Select an appropriate atom’s “Kit” to build a
molecule with two carbon and six hydrogen atoms. Drag atoms into the space above the “Kit” to make a molecule. A name will
appear when you have made an actual molecule that exists (even if it is not the one you want). You can use the scissors tool to
separate atoms if you would like to change the connections. Click on “3D” to see the molecule, and look at both the space-filling
and ball-and-stick possibilities.
(a) Draw the structural formula of this molecule and state its name.
(b) Can you arrange these atoms in any way to make a different compound?
35.
Use the Build a Molecule simulation to repeat Exercise 2.34, but build a molecule with two carbons, six hydrogens, and one
oxygen.
(b) Can you arrange these atoms to make a different molecule? If so, draw its structural formula and state its name.
(c) How are the molecules drawn in (a) and (b) the same? How do they differ? What are they called (the type of relationship
between these molecules, not their names).?
36.
Use the Build a Molecule simulation to repeat Exercise 2.34, but build a molecule with three carbons, seven hydrogens, and one
chlorine.

(b) Can you arrange these atoms to make a different molecule? If so, draw its structural formula and state its name.
(c) How are the molecules drawn in (a) and (b) the same? How do they differ? What are they called (the type of relationship
between these molecules, not their names)?
2.12.0.1: 2.5 The Periodic Table

37.
Using the periodic table, classify each of the following elements as a metal or a nonmetal, and then further classify each as a main-
group (representative) element, transition metal, or inner transition metal:
(a) uranium
(b) bromine
(c) strontium
(d) neon
(e) gold
(f) americium
(g) rhodium
(h) sulfur
(i) carbon
(j) potassium
38.
Using the periodic table, classify each of the following elements as a metal or a nonmetal, and then further classify each as a main-
group (representative) element, transition metal, or inner transition metal:
(a) cobalt
(b) europium
(c) iodine
(d) indium
(e) lithium
(f) oxygen
(g) cadmium
(h) terbium
(i) rhenium
39.
Using the periodic table, identify the lightest member of each of the following groups:
(a) noble gases
(b) alkaline earth metals
(c) alkali metals
(d) chalcogens
40.
Using the periodic table, identify the heaviest member of each of the following groups:
(a) alkali metals
(b) chalcogens
(c) noble gases

(d) alkaline earth metals
41.
Use the periodic table to give the name and symbol for each of the following elements:
(a) the noble gas in the same period as germanium
(b) the alkaline earth metal in the same period as selenium
(c) the halogen in the same period as lithium
(d) the chalcogen in the same period as cadmium
42.
Use the periodic table to give the name and symbol for each of the following elements:
(a) the halogen in the same period as the alkali metal with 11 protons
(b) the alkaline earth metal in the same period with the neutral noble gas with 18 electrons
(c) the noble gas in the same row as an isotope with 30 neutrons and 25 protons
(d) the noble gas in the same period as gold
43.
Write a symbol for each of the following neutral isotopes. Include the atomic number and mass number for each.
(a) the alkali metal with 11 protons and a mass number of 23
(b) the noble gas element with 75 neutrons in its nucleus and 54 electrons in the neutral atom
(c) the isotope with 33 protons and 40 neutrons in its nucleus
(d) the alkaline earth metal with 88 electrons and 138 neutrons
44.
Write a symbol for each of the following neutral isotopes. Include the atomic number and mass number for each.
(a) the chalcogen with a mass number of 125
(b) the halogen whose longest-lived isotope is radioactive
(c) the noble gas, used in lighting, with 10 electrons and 10 neutrons
(d) the lightest alkali metal with three neutrons
2.12.0.1: 2.6 Ionic and Molecular Compounds

45.
Using the periodic table, predict whether the following chlorides are ionic or covalent: KCl, NCl3, ICl, MgCl2, PCl5, and CCl4.
46.
Using the periodic table, predict whether the following chlorides are ionic or covalent: SiCl4, PCl3, CaCl2, CsCl, CuCl2, and CrCl3.
47.
For each of the following compounds, state whether it is ionic or covalent. If it is ionic, write the symbols for the ions involved:
(a) NF3
(b) BaO
(c) (NH4)2CO3
(d) Sr(H2PO4)2
(e) IBr
(f) Na2O
48.

For each of the following compounds, state whether it is ionic or covalent, and if it is ionic, write the symbols for the ions involved:
(a) KClO4
(b) Mg(C2H3O2)2
(c) H2S
(d) Ag2S
(e) N2Cl4
(f) Co(NO3)2
49.
For each of the following pairs of ions, write the formula of the compound they will form:
(a) Ca2+, S2−
(b) NH 4
+
, SO 4
2−
(c) Al3+, Br−

(d) Na+, HPO 4
2−
(e) Mg2+, PO 4
3−
50.
For each of the following pairs of ions, write the formula of the compound they will form:
(a) K+, O2−
(b) NH 4
+
, PO4
3−
(c) Al3+, O2−

(d) Na+, CO 3
2−
(e) Ba2+, PO 4
3−
2.12.0.1: 2.7 Chemical Nomenclature

51.
Name the following compounds:
(a) CsCl
(b) BaO
(c) K2S
(d) BeCl2
(e) HBr
(f) AlF3
52.
Name the following compounds:
(a) NaF
(b) Rb2O
(c) BCl3
(d) H2Se
(e) P4O6
(f) ICl3
53.

Write the formulas of the following compounds:
(a) rubidium bromide
(b) magnesium selenide
(c) sodium oxide
(d) calcium chloride
(e) hydrogen fluoride
(f) gallium phosphide
(g) aluminum bromide
(h) ammonium sulfate
54.
(a) lithium carbonate
(b) sodium perchlorate
(c) barium hydroxide
(d) ammonium carbonate
(e) sulfuric acid
(f) calcium acetate
(g) magnesium phosphate
(h) sodium sulfite
55.
(a) chlorine dioxide
(b) dinitrogen tetraoxide
(c) potassium phosphide
(d) silver(I) sulfide
(e) aluminum fluoride trihydrate
(f) silicon dioxide
56.
(a) barium chloride
(b) magnesium nitride
(c) sulfur dioxide
(d) nitrogen trichloride
(e) dinitrogen trioxide
(f) tin(IV) chloride
57.
Each of the following compounds contains a metal that can exhibit more than one ionic charge. Name these compounds:
(a) Cr2O3
(b) FeCl2

(c) CrO3
(d) TiCl4
(e) CoCl2·6H2O
(f) MoS2
58.
Each of the following compounds contains a metal that can exhibit more than one ionic charge. Name these compounds:
(a) NiCO3
(b) MoO3
(c) Co(NO3)2
(d) V2O5
(e) MnO2
(f) Fe2O3
59.
The following ionic compounds are found in common household products. Write the formulas for each compound:
(a) potassium phosphate
(b) copper(II) sulfate
(c) calcium chloride
(d) titanium(IV) oxide
(e) ammonium nitrate
(f) sodium bisulfate (the common name for sodium hydrogen sulfate)
60.
The following ionic compounds are found in common household products. Name each of the compounds:
(a) Ca(H2PO4)2
(b) FeSO4
(c) CaCO3
(d) MgO
(e) NaNO2
(f) KI
61.
What are the IUPAC names of the following compounds?
(a) manganese dioxide
(b) mercurous chloride (Hg2Cl2)
(c) ferric nitrate [Fe(NO3)3]
(d) titanium tetrachloride
(e) cupric bromide (CuBr2)

CHAPTER OVERVIEW
3: Composition of Substances and Solutions

General Chemistry
Quantitative aspects of the composition of substances and mixtures are the subject of this chapter.
3.1: Introduction
3.4: Molarity
3.6: Key Terms
3.7: Key Equations
3.8: Summary
3.9: Exercises
This page titled 3: Composition of Substances and Solutions is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by
1
3.1: Introduction
Figure 3.1 The water in a swimming pool is a complex mixture of substances whose relative amounts must be carefully maintained
to ensure the health and comfort of people using the pool. (credit: modification of work by Vic Brincat)
Chapter Outline
3.1 Formula Mass and the Mole Concept
3.2 Determining Empirical and Molecular Formulas
3.3 Molarity
3.4 Other Units for Solution Concentrations
Swimming pools have long been a popular means of recreation, exercise, and physical therapy. Since it is impractical to refill large
pools with fresh water on a frequent basis, pool water is regularly treated with chemicals to prevent the growth of harmful bacteria
and algae. Proper pool maintenance requires regular additions of various chemical compounds in carefully measured amounts. For
example, the relative amount of calcium ion, Ca2+, in the water should be maintained within certain limits to prevent eye irritation
and avoid damage to the pool bed and plumbing. To maintain proper calcium levels, calcium cations are added to the water in the
form of an ionic compound that also contains anions; thus, it is necessary to know both the relative amount of Ca2+ in the
compound and the volume of water in the pool in order to achieve the proper calcium level. Quantitative aspects of the composition
of substances (such as the calcium-containing compound) and mixtures (such as the pool water) are the subject of this chapter.

Calculate formula masses for covalent and ionic compounds
Define the amount unit mole and the related quantity Avogadro’s number Explain the relation between mass, moles, and
numbers of atoms or molecules, and perform calculations deriving these quantities from one another
Many argue that modern chemical science began when scientists started exploring the quantitative as well as the qualitative aspects
of chemistry. For example, Dalton’s atomic theory was an attempt to explain the results of measurements that allowed him to
calculate the relative masses of elements combined in various compounds. Understanding the relationship between the masses of
atoms and the chemical formulas of compounds allows us to quantitatively describe the composition of substances.
3.2.0.1: Formula Mass

An earlier chapter of this text described the development of the atomic mass unit, the concept of average atomic masses, and the
use of chemical formulas to represent the elemental makeup of substances. These ideas can be extended to calculate the formula
mass of a substance by summing the average atomic masses of all the atoms represented in the substance’s formula.
3.2.0.0.1: Formula Mass for Covalent Substances
For covalent substances, the formula represents the numbers and types of atoms composing a single molecule of the substance;
therefore, the formula mass may be correctly referred to as a molecular mass. Consider chloroform (CHCl3), a covalent compound
once used as a surgical anesthetic and now primarily used in the production of tetrafluoroethylene, the building block for the "anti-
stick" polymer, Teflon. The molecular formula of chloroform indicates that a single molecule contains one carbon atom, one
hydrogen atom, and three chlorine atoms. The average molecular mass of a chloroform molecule is therefore equal to the sum of
the average atomic masses of these atoms. Figure 3.2 outlines the calculations used to derive the molecular mass of chloroform,
which is 119.37 amu.
Figure 3.2 The average mass of a chloroform molecule, CHCl3, is 119.37 amu, which is the sum of the average atomic masses of
each of its constituent atoms. The model shows the molecular structure of chloroform.
Likewise, the molecular mass of an aspirin molecule, C9H8O4, is the sum of the atomic masses of nine carbon atoms, eight
hydrogen atoms, and four oxygen atoms, which amounts to 180.15 amu (Figure 3.3).

Figure 3.3 The average mass of an aspirin molecule is 180.15 amu. The model shows the molecular structure of aspirin, C9H8O4.
3.2.0.1: Example 3.1

3.2.0.0.2: Computing Molecular Mass for a Covalent Compound
Ibuprofen, C13H18O2, is a covalent compound and the active ingredient in several popular nonprescription pain medications,
such as Advil and Motrin. What is the molecular mass (amu) for this compound?
3.2.0.0.3: Solution
Molecules of this compound are composed of 13 carbon atoms, 18 hydrogen atoms, and 2 oxygen atoms. Following the
approach described above, the average molecular mass for this compound is therefore:

Acetaminophen, C8H9NO2, is a covalent compound and the active ingredient in several popular nonprescription pain
medications, such as Tylenol. What is the molecular mass (amu) for this compound?
3.2.0.1: Answer:
151.16 amu
3.2.0.0.5: Formula Mass for Ionic Compounds

Ionic compounds are composed of discrete cations and anions combined in ratios to yield electrically neutral bulk matter. The
formula mass for an ionic compound is calculated in the same way as the formula mass for covalent compounds: by summing the
average atomic masses of all the atoms in the compound’s formula. Keep in mind, however, that the formula for an ionic compound
does not represent the composition of a discrete molecule, so it may not correctly be referred to as the “molecular mass.”
As an example, consider sodium chloride, NaCl, the chemical name for common table salt. Sodium chloride is an ionic compound
composed of sodium cations, Na+, and chloride anions, Cl−, combined in a 1:1 ratio. The formula mass for this compound is
computed as 58.44 amu (see Figure 3.4).

Figure 3.4 Table salt, NaCl, contains an array of sodium and chloride ions combined in a 1:1 ratio. Its formula mass is 58.44 amu.
Note that the average masses of neutral sodium and chlorine atoms were used in this computation, rather than the masses for
sodium cations and chlorine anions. This approach is perfectly acceptable when computing the formula mass of an ionic
compound. Even though a sodium cation has a slightly smaller mass than a sodium atom (since it is missing an electron), this
difference will be offset by the fact that a chloride anion is slightly more massive than a chloride atom (due to the extra electron).
Moreover, the mass of an electron is negligibly small with respect to the mass of a typical atom. Even when calculating the mass of
an isolated ion, the missing or additional electrons can generally be ignored, since their contribution to the overall mass is
negligible, reflected only in the nonsignificant digits that will be lost when the computed mass is properly rounded. The few
exceptions to this guideline are very light ions derived from elements with precisely known atomic masses.
3.2.0.1: Example 3.2

3.2.0.0.6: Computing Formula Mass for an Ionic Compound
Aluminum sulfate, Al2(SO4)3, is an ionic compound that is used in the manufacture of paper and in various water purification
processes. What is the formula mass (amu) of this compound?
3.2.0.0.7: Solution
The formula for this compound indicates it contains Al3+ and SO42− ions combined in a 2:3 ratio. For purposes of computing a
formula mass, it is helpful to rewrite the formula in the simpler format, Al2S3O12. Following the approach outlined above, the
formula mass for this compound is calculated as follows:

Calcium phosphate, Ca3(PO4)2, is an ionic compound and a common anti-caking agent added to food products. What is the
formula mass (amu) of calcium phosphate?
3.2.0.1: Answer:
310.18 amu
3.2.0.1: The Mole

The identity of a substance is defined not only by the types of atoms or ions it contains, but by the quantity of each type of atom or
ion. For example, water, H2O, and hydrogen peroxide, H2O2, are alike in that their respective molecules are composed of hydrogen
and oxygen atoms. However, because a hydrogen peroxide molecule contains two oxygen atoms, as opposed to the water molecule,
which has only one, the two substances exhibit very different properties. Today, sophisticated instruments allow the direct
measurement of these defining microscopic traits; however, the same traits were originally derived from the measurement of
macroscopic properties (the masses and volumes of bulk quantities of matter) using relatively simple tools (balances and

volumetric glassware). This experimental approach required the introduction of a new unit for amount of substances, the mole,
which remains indispensable in modern chemical science.
The mole is an amount unit similar to familiar units like pair, dozen, gross, etc. It provides a specific measure of the number of
atoms or molecules in a sample of matter. One Latin connotation for the word “mole” is “large mass” or “bulk,” which is consistent
with its use as the name for this unit. The mole provides a link between an easily measured macroscopic property, bulk mass, and
an extremely important fundamental property, number of atoms, molecules, and so forth. A mole of substance is that amount in
which there are 6.02214076 × 1023 discrete entities (atoms or molecules). This large number is a fundamental constant known as
Avogadro’s number (NA) or the Avogadro constant in honor of Italian scientist Amedeo Avogadro. This constant is properly
reported with an explicit unit of “per mole,” a conveniently rounded version being 6.022 × 1023/mol.
Consistent with its definition as an amount unit, 1 mole of any element contains the same number of atoms as 1 mole of any other
element. The masses of 1 mole of different elements, however, are different, since the masses of the individual atoms are drastically
different. The molar mass of an element (or compound) is the mass in grams of 1 mole of that substance, a property expressed in
units of grams per mole (g/mol) (see Figure 3.5).
Figure 3.5 Each sample contains 6.022 × 1023 atoms —1.00 mol of atoms. From left to right (top row): 65.4 g zinc, 12.0 g carbon,
24.3 g magnesium, and 63.5 g copper. From left to right (bottom row): 32.1 g sulfur, 28.1 g silicon, 207 g lead, and 118.7 g tin.
(credit: modification of work by Mark Ott)
The molar mass of any substance is numerically equivalent to its atomic or formula weight in amu. Per the amu definition, a single
12
C atom weighs 12 amu (its atomic mass is 12 amu). A mole of 12C weighs 12 g (its molar mass is 12 g/mol). This relationship
holds for all elements, since their atomic masses are measured relative to that of the amu-reference substance, 12C. Extending this
principle, the molar mass of a compound in grams is likewise numerically equivalent to its formula mass in amu (Figure 3.6).

Figure 3.6 Each sample contains 6.02 × 1023 molecules or formula units—1.00 mol of the compound or element. Clock-wise from
the upper left: 130.2 g of C8H17OH (1-octanol, formula mass 130.2 amu), 454.4 g of HgI2 (mercury(II) iodide, formula mass 454.4
amu), 32.0 g of CH3OH (methanol, formula mass 32.0 amu) and 256.5 g of S8 (sulfur, formula mass 256.5 amu). (credit: Sahar
Atwa)
Element Average Atomic Mass (amu) Molar Mass (g/mol) Atoms/Mole
C 12.01 12.01 6.022 × 1023
H 1.008 1.008 6.022 × 1023
O 16.00 16.00 6.022 × 1023
Na 22.99 22.99 6.022 × 1023
Cl 35.45 35.45 6.022 × 1023
While atomic mass and molar mass are numerically equivalent, keep in mind that they are vastly different in terms of scale, as
represented by the vast difference in the magnitudes of their respective units (amu versus g). To appreciate the enormity of the
mole, consider a small drop of water weighing about 0.03 g (see Figure 3.7). Although this represents just a tiny fraction of 1 mole
of water (~18 g), it contains more water molecules than can be clearly imagined. If the molecules were distributed equally among
the roughly seven billion people on earth, each person would receive more than 100 billion molecules.

Figure 3.7 The number of molecules in a single droplet of water is roughly 100 billion times greater than the number of people on
earth. (credit: “tanakawho”/Wikimedia commons)

The mole is used in chemistry to represent 6.022 × 1023 of something, but it can be difficult to conceptualize such a large
number. Watch this video and then complete the “Think” questions that follow. Explore more about the mole by reviewing the
information under “Dig Deeper.”
The relationships between formula mass, the mole, and Avogadro’s number can be applied to compute various quantities that
describe the composition of substances and compounds, as demonstrated in the next several example problems.
3.2.0.1: Example 3.3

3.2.0.0.1: Deriving Moles from Grams for an Element
According to nutritional guidelines from the US Department of Agriculture, the estimated average requirement for dietary
potassium is 4.7 g. What is the estimated average requirement of potassium in moles?
3.2.0.0.2: Solution
The mass of K is provided, and the corresponding amount of K in moles is requested. Referring to the periodic table, the
atomic mass of K is 39.10 amu, and so its molar mass is 39.10 g/mol. The given mass of K (4.7 g) is a bit more than one-tenth
the molar mass (39.10 g), so a reasonable “ballpark” estimate of the number of moles would be slightly greater than 0.1 mol.
The molar amount of a substance may be calculated by dividing its mass (g) by its molar mass (g/mol):
The factor-label method supports this mathematical approach since the unit “g” cancels and the answer has units of “mol:”

⎛ mol K ⎞
4.7 g K = 0.12 mol K
⎝ 39.10 g K ⎠
The calculated magnitude (0.12 mol K) is consistent with our ballpark expectation, since it is a bit greater than 0.1 mol.
Beryllium is a light metal used to fabricate transparent X-ray windows for medical imaging instruments. How many moles of
Be are in a thin-foil window weighing 3.24 g?
3.2.0.1: Answer:
0.360 mol
3.2.0.1: Example 3.4

3.2.0.0.4: Deriving Grams from Moles for an Element
A liter of air contains 9.2 × 10−4 mol argon. What is the mass of Ar in a liter of air?
3.2.0.0.5: Solution
The molar amount of Ar is provided and must be used to derive the corresponding mass in grams. Since the amount of Ar is
less than 1 mole, the mass will be less than the mass of 1 mole of Ar, approximately 40 g. The molar amount in question is
approximately one-one thousandth (~10−3) of a mole, and so the corresponding mass should be roughly one-one thousandth of
the molar mass (~0.04 g):

In this case, logic dictates (and the factor-label method supports) multiplying the provided amount (mol) by the molar mass
(g/mol):
39.95 g Ar
−4
9.2 × 10 mol Ar ( ) = 0.037 g Ar
mol Ar
The result is in agreement with our expectations, around 0.04 g Ar.

What is the mass of 2.561 mol of gold?
3.2.0.1: Answer:
504.4 g
3.2.0.1: Example 3.5

3.2.0.0.7: Deriving Number of Atoms from Mass for an Element
Copper is commonly used to fabricate electrical wire (Figure 3.8). How many copper atoms are in 5.00 g of copper wire?

Figure 3.8 Copper wire is composed of many, many atoms of Cu. (credit: Emilian Robert Vicol)
3.2.0.0.8: Solution
The number of Cu atoms in the wire may be conveniently derived from its mass by a two-step computation: first calculating
the molar amount of Cu, and then using Avogadro’s number (NA) to convert this molar amount to number of Cu atoms:
Considering that the provided sample mass (5.00 g) is a little less than one-tenth the mass of 1 mole of Cu (~64 g), a
reasonable estimate for the number of atoms in the sample would be on the order of one-tenth NA, or approximately 1022 Cu
atoms. Carrying out the two-step computation yields:
23
⎛ mol Cu ⎞ 6.022 × 10 Cu atoms 22
5.00 g Cu ( ) = 4.74 × 10 Cu atoms
⎝ 63.55 g Cu ⎠ mol Cu
The factor-label method yields the desired cancellation of units, and the computed result is on the order of 1022 as expected.
A prospector panning for gold in a river collects 15.00 g of pure gold. How many Au atoms are in this quantity of gold?
3.2.0.1: Answer:
4.586 × 1022 Au atoms

3.2.0.1: Example 3.6
3.2.0.0.10: Deriving Moles from Grams for a Compound
Our bodies synthesize protein from amino acids. One of these amino acids is glycine, which has the molecular formula
C2H5O2N. How many moles of glycine molecules are contained in 28.35 g of glycine?
Derive the number of moles of a compound from its mass following the same procedure used for an element in Example 3.3:
The molar mass of glycine is required for this calculation, and it is computed in the same fashion as its molecular mass. One
mole of glycine, C2H5O2N, contains 2 moles of carbon, 5 moles of hydrogen, 2 moles of oxygen, and 1 mole of nitrogen:
The provided mass of glycine (~28 g) is a bit more than one-third the molar mass (~75 g/mol), so the computed result is
expected to be a bit greater than one-third of a mole (~0.33 mol). Dividing the compound’s mass by its molar mass yields:
⎛ mol glycine ⎞
28.35 g glycine = 0.378 mol glycine
⎝ 75.07 g glycine ⎠
This result is consistent with the rough estimate.

How many moles of sucrose, C12H22O11, are in a 25-g sample of sucrose?
3.2.0.1: Answer:
0.073 mol
3.2.0.1: Example 3.7

3.2.0.0.13: Deriving Grams from Moles for a Compound
Vitamin C is a covalent compound with the molecular formula C6H8O6. The recommended daily dietary allowance of vitamin
C for children aged 4–8 years is 1.42 × 10−4 mol. What is the mass of this allowance in grams?

As for elements, the mass of a compound can be derived from its molar amount as shown:
The molar mass for this compound is computed to be 176.124 g/mol. The given number of moles is a very small fraction of a
mole (~10−4 or one-ten thousandth); therefore, the corresponding mass is expected to be about one-ten thousandth of the molar
mass (~0.02 g). Performing the calculation yields:
176.124 g vitamin C
−4
1.42 × 10 mol vitamin C ( ) = 0.0250 g vitamin C
mol vitamin C
This is consistent with the anticipated result.

What is the mass of 0.443 mol of hydrazine, N2H4?
3.2.0.1: Answer:
14.2 g
3.2.0.1: Example 3.8

3.2.0.0.16: Deriving the Number of Atoms and Molecules from the Mass of a Compound
A packet of an artificial sweetener contains 40.0 mg of saccharin (C7H5NO3S), which has the structural formula:
Given that saccharin has a molar mass of 183.18 g/mol, how many saccharin molecules are in a 40.0-mg (0.0400-g) sample of
saccharin? How many carbon atoms are in the same sample?
The number of molecules in a given mass of compound is computed by first deriving the number of moles, as demonstrated in
Example 3.6, and then multiplying by Avogadro’s number:
Using the provided mass and molar mass for saccharin yields:
mol C7 H5 NO3 S 23
6.022 × 10 C7 H5 NO3 S molecules
0.0400 g C7 H5 NO3 S ( )( )
183.18 g C7 H5 NO3 S 1 mol C7 H5 NO3 S
20
= 1.31 × 10 C7 H5 NO3 S molecules

The compound’s formula shows that each molecule contains seven carbon atoms, and so the number of C atoms in the
provided sample is:
7 C atoms
20 20
1.31 × 10 C7 H5 NO3 S molecules ( ) = 9.17 × 10 C atoms
1 C7 H5 NO3 S molecule

How many C4H10 molecules are contained in 9.213 g of this compound? How many hydrogen atoms?
3.2.0.1: Answer:
9.545 × 1022 molecules C4 H10; 9.545 × 1023 atoms H
3.2.0.1: How Sciences Interconnect

3.2.0.0.19: Counting Neurotransmitter Molecules in the Brain
The brain is the control center of the central nervous system (Figure 3.9). It sends and receives signals to and from muscles and
other internal organs to monitor and control their functions; it processes stimuli detected by sensory organs to guide
interactions with the external world; and it houses the complex physiological processes that give rise to our intellect and
emotions. The broad field of neuroscience spans all aspects of the structure and function of the central nervous system,
including research on the anatomy and physiology of the brain. Great progress has been made in brain research over the past
few decades, and the BRAIN Initiative, a federal initiative announced in 2013, aims to accelerate and capitalize on these
advances through the concerted efforts of various industrial, academic, and government agencies (more details available at
www.whitehouse.gov/share/brain-initiative).
Figure 3.9 (a) A typical human brain weighs about 1.5 kg and occupies a volume of roughly 1.1 L. (b) Information is
transmitted in brain tissue and throughout the central nervous system by specialized cells called neurons (micrograph shows
cells at 1600× magnification).
Specialized cells called neurons transmit information between different parts of the central nervous system by way of electrical
and chemical signals. Chemical signaling occurs at the interface between different neurons when one of the cells releases
molecules (called neurotransmitters) that diffuse across the small gap between the cells (called the synapse) and bind to the
surface of the other cell. These neurotransmitter molecules are stored in small intracellular structures called vesicles that fuse
to the cell membrane and then break open to release their contents when the neuron is appropriately stimulated. This process is
called exocytosis (see Figure 3.10). One neurotransmitter that has been very extensively studied is dopamine, C8H11NO2.
Dopamine is involved in various neurological processes that impact a wide variety of human behaviors. Dysfunctions in the
dopamine systems of the brain underlie serious neurological diseases such as Parkinson’s and schizophrenia.

Figure 3.10 (a) Chemical signals are transmitted from neurons to other cells by the release of neurotransmitter molecules into
the small gaps (synapses) between the cells. (b) Dopamine, C8H11NO2, is a neurotransmitter involved in a number of
neurological processes.
One important aspect of the complex processes related to dopamine signaling is the number of neurotransmitter molecules
released during exocytosis. Since this number is a central factor in determining neurological response (and subsequent human
thought and action), it is important to know how this number changes with certain controlled stimulations, such as the
administration of drugs. It is also important to understand the mechanism responsible for any changes in the number of
neurotransmitter molecules released—for example, some dysfunction in exocytosis, a change in the number of vesicles in the
neuron, or a change in the number of neurotransmitter molecules in each vesicle.
Significant progress has been made recently in directly measuring the number of dopamine molecules stored in individual
vesicles and the amount actually released when the vesicle undergoes exocytosis. Using miniaturized probes that can
selectively detect dopamine molecules in very small amounts, scientists have determined that the vesicles of a certain type of
mouse brain neuron contain an average of 30,000 dopamine molecules per vesicle (about 5 × 10 mol or 50 zmol).
−20
Analysis of these neurons from mice subjected to various drug therapies shows significant changes in the average number of
dopamine molecules contained in individual vesicles, increasing or decreasing by up to three-fold, depending on the specific
drug used. These studies also indicate that not all of the dopamine in a given vesicle is released during exocytosis, suggesting
that it may be possible to regulate the fraction released using pharmaceutical therapies.1
3.2.0.1: Footnotes
1Omiatek, Donna M., Amanda J. Bressler, Ann-Sofie Cans, Anne M. Andrews, Michael L. Heien, and Andrew G. Ewing. “The
Real Catecholamine Content of Secretory Vesicles in the CNS Revealed by Electrochemical Cytometry.” Scientific Report 3
(2013): 1447, accessed January 14, 2015, doi:10.1038/srep01447.
This page titled 3.2: Formula Mass and the Mole Concept is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by


Compute the percent composition of a compound
Determine the empirical formula of a compound
Determine the molecular formula of a compound
The previous section discussed the relationship between the bulk mass of a substance and the number of atoms or molecules it
contains (moles). Given the chemical formula of the substance, one may determine the amount of the substance (moles) from its
mass, and vice versa. But what if the chemical formula of a substance is unknown? In this section, these same principles will be
applied to derive the chemical formulas of unknown substances from experimental mass measurements.
3.3.0.1: Percent Composition

The elemental makeup of a compound defines its chemical identity, and chemical formulas are the most succinct way of
representing this elemental makeup. When a compound’s formula is unknown, measuring the mass of each of its constituent
elements is often the first step in the process of determining the formula experimentally. The results of these measurements permit
the calculation of the compound’s percent composition, defined as the percentage by mass of each element in the compound. For
example, consider a gaseous compound composed solely of carbon and hydrogen. The percent composition of this compound could
be represented as follows:
mass H
% H = × 100%
mass compound
mass C
% C = × 100%
mass compound
If analysis of a 10.0-g sample of this gas showed it to contain 2.5 g H and 7.5 g C, the percent composition would be calculated to
be 25% H and 75% C:
2.5 g H
% H = × 100% = 25%
10.0 g compound
7.5 g C
% C = × 100% = 75%
10.0 g compound
3.3.0.1: Example 3.9

3.3.0.0.1: Calculation of Percent Composition
Analysis of a 12.04-g sample of a liquid compound composed of carbon, hydrogen, and nitrogen showed it to contain 7.34 g C,
1.85 g H, and 2.85 g N. What is the percent composition of this compound?
3.3.0.0.2: Solution
To calculate percent composition, divide the experimentally derived mass of each element by the overall mass of the
compound, and then convert to a percentage:
7.34 g C
% C = × 100% = 61.0%
12.04 g compound
1.85 g H
% H = × 100% = 15.4%
12.04 g compound
2.85 g N
% N = × 100% = 23.7%
12.04 g compound
The analysis results indicate that the compound is 61.0% C, 15.4% H, and 23.7% N by mass.

A 24.81-g sample of a gaseous compound containing only carbon, oxygen, and chlorine is determined to contain 3.01 g C, 4.00
g O, and 17.81 g Cl. What is this compound’s percent composition?
3.3.0.1: Answer:
12.1% C, 16.1% O, 71.79% Cl
3.3.0.0.4: Determining Percent Composition from Molecular or Empirical Formulas

Percent composition is also useful for evaluating the relative abundance of a given element in different compounds of known
formulas. As one example, consider the common nitrogen-containing fertilizers ammonia (NH3), ammonium nitrate (NH4NO3),
and urea (CH4N2O). The element nitrogen is the active ingredient for agricultural purposes, so the mass percentage of nitrogen in
the compound is a practical and economic concern for consumers choosing among these fertilizers. For these sorts of applications,
the percent composition of a compound is easily derived from its formula mass and the atomic masses of its constituent elements.
A molecule of NH3 contains one N atom weighing 14.01 amu and three H atoms weighing a total of (3 × 1.008 amu) = 3.024 amu.
The formula mass of ammonia is therefore (14.01 amu + 3.024 amu) = 17.03 amu, and its percent composition is:
14.01 amu N
% N = × 100% = 82.27%
17.03 amu NH3
3.024 amu H
% H = × 100% = 17.76%
17.03 amu NH3
This same approach may be taken considering a pair of molecules, a dozen molecules, or a mole of molecules, etc. The latter
amount is most convenient and would simply involve the use of molar masses instead of atomic and formula masses, as
demonstrated Example 3.10. As long as the molecular or empirical formula of the compound in question is known, the percent
composition may be derived from the atomic or molar masses of the compound's elements.
3.3.0.1: Example 3.10

3.3.0.0.5: Determining Percent Composition from a Molecular Formula
Aspirin is a compound with the molecular formula C9H8O4. What is its percent composition?
3.3.0.0.6: Solution
To calculate the percent composition, the masses of C, H, and O in a known mass of C9H8O4 are needed. It is convenient to
consider 1 mol of C9H8O4 and use its molar mass (180.159 g/mole, determined from the chemical formula) to calculate the
percentages of each of its elements:
9 mol C × molar mass C 9 × 12.01 g/mol 108.09 g/mol

% C = × 100 = × 100 = × 100
molar mass C9 H8 O4 180.159 g/mol 180.159 g/mol
% C = 60.00% C
8 × 1.008 g/mol 8.064 g/mol

8 mol H × molar mass H
% H = × 100 = × 100 = × 100
% H = 4.476% H
4 mol O × molar mass O 4 × 16.00 g/mol 64.00 g/mol

% O= × 100 = × 100 = × 100
% O = 35.52%
Note that these percentages sum to equal 100.00% when appropriately rounded.
To three significant digits, what is the mass percentage of iron in the compound Fe2O3?
3.3.0.1: Answer:
69.9% Fe

3.3.0.1: Determination of Empirical Formulas
As previously mentioned, the most common approach to determining a compound’s chemical formula is to first measure the
masses of its constituent elements. However, keep in mind that chemical formulas represent the relative numbers, not masses, of
atoms in the substance. Therefore, any experimentally derived data involving mass must be used to derive the corresponding
numbers of atoms in the compound. This is accomplished using molar masses to convert the mass of each element to a number of
moles. These molar amounts are used to compute whole-number ratios that can be used to derive the empirical formula of the
substance. Consider a sample of compound determined to contain 1.71 g C and 0.287 g H. The corresponding numbers of atoms (in
moles) are:
1 mol C
1.71 g C × = 0.142 mol C
12.01 g C
1 mol H
0.287 g H × = 0.284 mol H
1.008 g H
Thus, this compound may be represented by the formula C0.142H0.284. Per convention, formulas contain whole-number subscripts,
which can be achieved by dividing each subscript by the smaller subscript:
C 0 .1 4 2 H 0 .2 8 4 or CH2
0 .1 4 2 0 .1 4 2
(Recall that subscripts of “1” are not written but rather assumed if no other number is present.)
The empirical formula for this compound is thus CH2. This may or may not be the compound’s molecular formula as well;
however, additional information is needed to make that determination (as discussed later in this section).
Consider as another example a sample of compound determined to contain 5.31 g Cl and 8.40 g O. Following the same approach
yields a tentative empirical formula of:
Cl0.150O0.525 = Cl 0 .1 5 0 O 0 .5 2 5 = ClO3.5
0 .1 5 0 0 .1 5 0
In this case, dividing by the smallest subscript still leaves us with a decimal subscript in the empirical formula. To convert this into
a whole number, multiply each of the subscripts by two, retaining the same atom ratio and yielding Cl2O7 as the final empirical
formula.
In summary, empirical formulas are derived from experimentally measured element masses by:
1. Deriving the number of moles of each element from its mass
2. Dividing each element’s molar amount by the smallest molar amount to yield subscripts for a tentative empirical formula
3. Multiplying all coefficients by an integer, if necessary, to ensure that the smallest whole-number ratio of subscripts is obtained
Figure 3.11 outlines this procedure in flow chart fashion for a substance containing elements A and X.
Figure 3.11 The empirical formula of a compound can be derived from the masses of all elements in the sample.
3.3.0.1: Example 3.11

3.3.0.0.1: Determining a Compound’s Empirical Formula from the Masses of Its Elements
A sample of the black mineral hematite (Figure 3.12), an oxide of iron found in many iron ores, contains 34.97 g of iron and
15.03 g of oxygen. What is the empirical formula of hematite?

Figure 3.12 Hematite is an iron oxide that is used in jewelry. (credit: Mauro Cateb)
3.3.0.0.2: Solution
This problem provides the mass in grams of each element. Begin by finding the moles of each:
mol Fe
34.97 g Fe ( ) = 0.6261 mol Fe
55.85 g
mol O
15.03 g O ( ) = 0.9394 mol O
16.00 g
Next, derive the iron-to-oxygen molar ratio by dividing by the lesser number of moles:
0.6261
= 1.000 mol Fe
0.6261
0.9394
= 1.500 mol O
0.6261
The ratio is 1.000 mol of iron to 1.500 mol of oxygen (Fe1O1.5). Finally, multiply the ratio by two to get the smallest possible
whole number subscripts while still maintaining the correct iron-to-oxygen ratio:
2 (Fe1 O1.5 ) = Fe2 O3
The empirical formula is Fe2O3.

What is the empirical formula of a compound if a sample contains 0.130 g of nitrogen and 0.370 g of oxygen?
3.3.0.1: Answer:
N2O5

For additional worked examples illustrating the derivation of empirical formulas, watch the brief video clip.
3.3.0.0.4: Deriving Empirical Formulas from Percent Composition

Finally, with regard to deriving empirical formulas, consider instances in which a compound’s percent composition is available
rather than the absolute masses of the compound’s constituent elements. In such cases, the percent composition can be used to

calculate the masses of elements present in any convenient mass of compound; these masses can then be used to derive the
empirical formula in the usual fashion.
3.3.0.1: Example 3.12

3.3.0.0.5: Determining an Empirical Formula from Percent Composition
The bacterial fermentation of grain to produce ethanol forms a gas with a percent composition of 27.29% C and 72.71% O
(Figure 3.13). What is the empirical formula for this gas?
Figure 3.13 An oxide of carbon is removed from these fermentation tanks through the large copper pipes at the top. (credit:
“Dual Freq”/Wikimedia Commons)
3.3.0.0.6: Solution
Since the scale for percentages is 100, it is most convenient to calculate the mass of elements present in a sample weighing 100
g. The calculation is “most convenient” because, per the definition for percent composition, the mass of a given element in
grams is numerically equivalent to the element’s mass percentage. This numerical equivalence results from the definition of the
“percentage” unit, whose name is derived from the Latin phrase per centum meaning “by the hundred.” Considering this
definition, the mass percentages provided may be more conveniently expressed as fractions:
27.29 g C
27.29% C =
100 g compound
72.71 g O
72.71% O =
100 g compound
The molar amounts of carbon and oxygen in a 100-g sample are calculated by dividing each element’s mass by its molar mass:
mol C
27.29 g C ( ) = 2.272 mol C
12.01 g
mol O
72.71 g O ( ) = 4.544 mol O
16.00 g
Coefficients for the tentative empirical formula are derived by dividing each molar amount by the lesser of the two:

2.272 mol C
=1
2.272
4.544 mol O
=2
2.272
Since the resulting ratio is one carbon to two oxygen atoms, the empirical formula is CO2.
What is the empirical formula of a compound containing 40.0% C, 6.71% H, and 53.28% O?
3.3.0.1: Answer:
CH2O
3.3.0.1: Derivation of Molecular Formulas

Recall that empirical formulas are symbols representing the relative numbers of a compound’s elements. Determining the absolute
numbers of atoms that compose a single molecule of a covalent compound requires knowledge of both its empirical formula and its
molecular mass or molar mass. These quantities may be determined experimentally by various measurement techniques. Molecular
mass, for example, is often derived from the mass spectrum of the compound (see discussion of this technique in the previous
chapter on atoms and molecules). Molar mass can be measured by a number of experimental methods, many of which will be
introduced in later chapters of this text.
Molecular formulas are derived by comparing the compound’s molecular or molar mass to its empirical formula mass. As the name
suggests, an empirical formula mass is the sum of the average atomic masses of all the atoms represented in an empirical formula.
If the molecular (or molar) mass of the substance is known, it may be divided by the empirical formula mass to yield the number of
empirical formula units per molecule (n):
g
molecular or molar mass (amu or )
mol
= n formula units/molecule
g
empirical formula mass (amu or )
mol
The molecular formula is then obtained by multiplying each subscript in the empirical formula by n, as shown by the generic
empirical formula AxBy:
(Ax By ) = Anx Bny
n
For example, consider a covalent compound whose empirical formula is determined to be CH2O. The empirical formula mass for
this compound is approximately 30 amu (the sum of 12 amu for one C atom, 2 amu for two H atoms, and 16 amu for one O atom).
If the compound’s molecular mass is determined to be 180 amu, this indicates that molecules of this compound contain six times
the number of atoms represented in the empirical formula:
180 amu/molecule
= 6 formula units/molecule
amu
30
formula unit
Molecules of this compound are then represented by molecular formulas whose subscripts are six times greater than those in the
empirical formula:
(CH O) = C6 H12 O6
2 6
Note that this same approach may be used when the molar mass (g/mol) instead of the molecular mass (amu) is used. In this case,
one mole of empirical formula units and molecules is considered, as opposed to single units and molecules.
3.3.0.1: Example 3.13

3.3.0.0.1: Determination of the Molecular Formula for Nicotine
Nicotine, an alkaloid in the nightshade family of plants that is mainly responsible for the addictive nature of cigarettes,
contains 74.02% C, 8.710% H, and 17.27% N. If 40.57 g of nicotine contains 0.2500 mol nicotine, what is the molecular
formula?

3.3.0.0.2: Solution
Determining the molecular formula from the provided data will require comparison of the compound’s empirical formula mass
to its molar mass. As the first step, use the percent composition to derive the compound’s empirical formula. Assuming a
convenient, a 100-g sample of nicotine yields the following molar amounts of its elements:
1 mol C
(74.02 g C) ( ) = 6.163 mol C
12.01 g C
1 mol H
(8.710 g H) ( ) = 8.624 mol H
1.01 g H
1 mol N
(17.27 g N) ( ) = 1.233 mol N
14.01 g N
Next, calculate the molar ratios of these elements relative to the least abundant element, N.
6.163 mol C / 1.233 mol N = 5
8.264 mol H / 1.233 mol N = 7
1.233 mol N / 1.233 mol N = 1
1.233
= 1.000 mol N
1.233
6.163
= 4.998 mol C
1.233
8.624
= 6.994 mol H
1.233
The C-to-N and H-to-N molar ratios are adequately close to whole numbers, and so the empirical formula is C5H7N. The
empirical formula mass for this compound is therefore 81.13 amu/formula unit, or 81.13 g/mol formula unit.
Calculate the molar mass for nicotine from the given mass and molar amount of compound:
40.57 g nicotine 162.3 g
=
0.2500 mol nicotine mol
Comparing the molar mass and empirical formula mass indicates that each nicotine molecule contains two formula units:
162.3 g/mol
= 2 formula units/molecule
g
81.13
formula unit
Finally, derive the molecular formula for nicotine from the empirical formula by multiplying each subscript by two:
(C H7 N) = C10 H14 N2
5 2

What is the molecular formula of a compound with a percent composition of 49.47% C, 5.201% H, 28.84% N, and 16.48% O,
and a molecular mass of 194.2 amu?
3.3.0.1: Answer:
C8H10N4O2
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upon request.

3.4: Molarity

Describe the fundamental properties of solutions
Calculate solution concentrations using molarity
Perform dilution calculations using the dilution equation
Preceding sections of this chapter focused on the composition of substances: samples of matter that contain only one type of
element or compound. However, mixtures—samples of matter containing two or more substances physically combined—are more
commonly encountered in nature than are pure substances. Similar to a pure substance, the relative composition of a mixture plays
an important role in determining its properties. The relative amount of oxygen in a planet’s atmosphere determines its ability to
sustain aerobic life. The relative amounts of iron, carbon, nickel, and other elements in steel (a mixture known as an “alloy”)
determine its physical strength and resistance to corrosion. The relative amount of the active ingredient in a medicine determines its
effectiveness in achieving the desired pharmacological effect. The relative amount of sugar in a beverage determines its sweetness
(see Figure 3.14). This section will describe one of the most common ways in which the relative compositions of mixtures may be
quantified.
Figure 3.14 Sugar is one of many components in the complex mixture known as coffee. The amount of sugar in a given amount of
coffee is an important determinant of the beverage’s sweetness. (credit: Jane Whitney)
3.4.0.1: Solutions
Solutions have previously been defined as homogeneous mixtures, meaning that the composition of the mixture (and therefore its
properties) is uniform throughout its entire volume. Solutions occur frequently in nature and have also been implemented in many
forms of manmade technology. A more thorough treatment of solution properties is provided in the chapter on solutions and
colloids, but provided here is an introduction to some of the basic properties of solutions.
The relative amount of a given solution component is known as its concentration. Often, though not always, a solution contains one
component with a concentration that is significantly greater than that of all other components. This component is called the solvent
and may be viewed as the medium in which the other components are dispersed, or dissolved. Solutions in which water is the
solvent are, of course, very common on our planet. A solution in which water is the solvent is called an aqueous solution.

A solute is a component of a solution that is typically present at a much lower concentration than the solvent. Solute concentrations
are often described with qualitative terms such as dilute (of relatively low concentration) and concentrated (of relatively high
concentration).
Concentrations may be quantitatively assessed using a wide variety of measurement units, each convenient for particular
applications. Molarity (M) is a useful concentration unit for many applications in chemistry. Molarity is defined as the number of
moles of solute in exactly 1 liter (1 L) of the solution:
mol solute
M =
L solution
3.4.0.1: Example 3.14

3.4.0.0.1: Calculating Molar Concentrations
A 355-mL soft drink sample contains 0.133 mol of sucrose (table sugar). What is the molar concentration of sucrose in the
beverage?
3.4.0.0.2: Solution
Since the molar amount of solute and the volume of solution are both given, the molarity can be calculated using the definition
of molarity. Per this definition, the solution volume must be converted from mL to L:
mol solute 0.133 mol
M = = = 0.375 M
1 L
L solution 355 mL ×
1000 mL

A teaspoon of table sugar contains about 0.01 mol sucrose. What is the molarity of sucrose if a teaspoon of sugar has been
dissolved in a cup of tea with a volume of 200 mL?
3.4.0.1: Answer:
0.05 M
3.4.0.1: Example 3.15

3.4.0.0.4: Deriving Moles and Volumes from Molar Concentrations
How much sugar (mol) is contained in a modest sip (~10 mL) of the soft drink from Example 3.14?
3.4.0.0.5: Solution
Rearrange the definition of molarity to isolate the quantity sought, moles of sugar, then substitute the value for molarity
derived in Example 3.14, 0.375 M:
mol solute
M =
L solution
mol solute = M × L solution
mol sugar 1 L
mol solute = 0.375 × (10 mL × ) = 0.004 mol sugar
L 1000 mL

What volume (mL) of the sweetened tea described in Example 3.14 contains the same amount of sugar (mol) as 10 mL of the
soft drink in this example?
3.4.0.1: Answer:
80 mL
3.4.0.1: Example 3.16

3.4.0.0.7: Calculating Molar Concentrations from the Mass of Solute
Distilled white vinegar (Figure 3.15) is a solution of acetic acid, CH3CO2H, in water. A 0.500-L vinegar solution contains 25.2
g of acetic acid. What is the concentration of the acetic acid solution in units of molarity?
Figure 3.15 Distilled white vinegar is a solution of acetic acid in water.

3.4.0.0.8: Solution
As in previous examples, the definition of molarity is the primary equation used to calculate the quantity sought. Since the
mass of solute is provided instead of its molar amount, use the solute’s molar mass to obtain the amount of solute in moles:
1 mol CH3 CO2 H
25.2 g CH3 CO2 H ×
mol solute 60.052 g CH3 CO2 H
M = = = 0.839 M
L solution 0.500 L solution
mol solute
M = = 0.839 M
L solution
0.839 mol solute

M =
1.00 L solution

Calculate the molarity of 6.52 g of CoCl2 (128.9 g/mol) dissolved in an aqueous solution with a total volume of 75.0 mL.
3.4.0.1: Answer:
0.674 M
3.4.0.1: Example 3.17

3.4.0.0.10: Determining the Mass of Solute in a Given Volume of Solution
How many grams of NaCl are contained in 0.250 L of a 5.30-M solution?
The volume and molarity of the solution are specified, so the amount (mol) of solute is easily computed as demonstrated in
Example 3.15:

mol solute
M =
L solution
mol solute = M × L solution
mol NaCl
mol solute = 5.30 × 0.250 L = 1.325 mol NaCl
L
Finally, this molar amount is used to derive the mass of NaCl:

58.44 g NaCl
1.325 mol NaCl × = 77.4 g NaCl
mol NaCl

How many grams of CaCl2 (110.98 g/mol) are contained in 250.0 mL of a 0.200-M solution of calcium chloride?
3.4.0.1: Answer:
5.55 g CaCl2
When performing calculations stepwise, as in Example 3.17, it is important to refrain from rounding any intermediate calculation
results, which can lead to rounding errors in the final result. In Example 3.17, the molar amount of NaCl computed in the first step,
1.325 mol, would be properly rounded to 1.32 mol if it were to be reported; however, although the last digit (5) is not significant, it
must be retained as a guard digit in the intermediate calculation. If the guard digit had not been retained, the final calculation for
the mass of NaCl would have been 77.1 g, a difference of 0.3 g.
In addition to retaining a guard digit for intermediate calculations, rounding errors may also be avoided by performing
computations in a single step (see Example 3.18). This eliminates intermediate steps so that only the final result is rounded.
3.4.0.1: Example 3.18

3.4.0.0.13: Determining the Volume of Solution Containing a Given Mass of Solute
In Example 3.16, the concentration of acetic acid in white vinegar was determined to be 0.839 M. What volume of vinegar
contains 75.6 g of acetic acid?
First, use the molar mass to calculate moles of acetic acid from the given mass:
mol solute
g solute × = mol solute
g solute
Then, use the molarity of the solution to calculate the volume of solution containing this molar amount of solute:
L solution
mol solute × = L solution
mol solute
Combining these two steps into one yields:

mol solute L solution
g solute × × = L solution
g solute mol solute
mol CH3 CO2 H L solution

75.6 g CH3 CO2 H ( ) ( ) = 1.50 L solution
60.05 g 0.839 mol CH3 CO2 H

What volume of a 1.50-M KBr solution contains 66.0 g KBr?
3.4.0.1: Answer:
0.370 L

3.4.0.1: Dilution of Solutions
Dilution is the process whereby the concentration of a solution is lessened by the addition of solvent. For example, a glass of iced
tea becomes increasingly diluted as the ice melts. The water from the melting ice increases the volume of the solvent (water) and
the overall volume of the solution (iced tea), thereby reducing the relative concentrations of the solutes that give the beverage its
taste (Figure 3.16).
Figure 3.16 Both solutions contain the same mass of copper nitrate. The solution on the right is more dilute because the copper
nitrate is dissolved in more solvent. (credit: Mark Ott)
Dilution is also a common means of preparing solutions of a desired concentration. By adding solvent to a measured portion of a
more concentrated stock solution, a solution of lesser concentration may be prepared. For example, commercial pesticides are
typically sold as solutions in which the active ingredients are far more concentrated than is appropriate for their application. Before
they can be used on crops, the pesticides must be diluted. This is also a very common practice for the preparation of a number of
common laboratory reagents.
A simple mathematical relationship can be used to relate the volumes and concentrations of a solution before and after the dilution
process. According to the definition of molarity, the number of moles of solute in a solution (n) is equal to the product of the
solution’s molarity (M) and its volume in liters (L):
n = ML
Expressions like these may be written for a solution before and after it is diluted:
n1 = M1 L1
n2 = M2 L2
where the subscripts “1” and “2” refer to the solution before and after the dilution, respectively. Since the dilution process does not
change the amount of solute in the solution, n1 = n2. Thus, these two equations may be set equal to one another:
M1 L1 = M2 L2
This relation is commonly referred to as the dilution equation. Although this equation uses molarity as the unit of concentration and
liters as the unit of volume, other units of concentration and volume may be used as long as the units properly cancel per the factor-
label method. Reflecting this versatility, the dilution equation is often written in the more general form:
C1 V1 = C2 V2
where C and V are concentration and volume, respectively.

Use the simulation to explore the relations between solute amount, solution volume, and concentration and to confirm the
dilution equation.
3.4.0.1: Example 3.19

3.4.0.0.1: Determining the Concentration of a Diluted Solution
If 0.850 L of a 5.00-M solution of copper nitrate, Cu(NO3)2, is diluted to a volume of 1.80 L by the addition of water, what is
the molarity of the diluted solution?
3.4.0.0.2: Solution
The stock concentration, C1, and volume, V1, are provided as well as the volume of the diluted solution, V2. Rearrange the
dilution equation to isolate the unknown property, the concentration of the diluted solution, C2:
C1 V1 = C2 V2
C1 V1
C2 =
V2
Since the stock solution is being diluted by more than two-fold (volume is increased from 0.85 L to 1.80 L), the diluted
solution’s concentration is expected to be less than one-half 5 M. This ballpark estimate will be compared to the calculated
result to check for any gross errors in computation (for example, such as an improper substitution of the given quantities).
Substituting the given values for the terms on the right side of this equation yields:
mol
0.850 L × 5.00
L
C2 = = 2.36 M
1.80 L
This result compares well to our ballpark estimate (it’s a bit less than one-half the stock concentration, 5 M).
What is the concentration of the solution that results from diluting 25.0 mL of a 2.04-M solution of CH3OH to 500.0 mL?
3.4.0.1: Answer:
0.102 M CH3OH
3.4.0.1: Example 3.20

3.4.0.0.4: Volume of a Diluted Solution
What volume of 0.12 M HBr can be prepared from 11 mL (0.011 L) of 0.45 M HBr?
3.4.0.0.5: Solution
Provided are the volume and concentration of a stock solution, V1 and C1, and the concentration of the resultant diluted
solution, C2. Find the volume of the diluted solution, V2 by rearranging the dilution equation to isolate V2:
C1 V1 = C2 V2
C1 V1
V2 =
C2
Since the diluted concentration (0.12 M) is slightly more than one-fourth the original concentration (0.45 M), the volume of the
diluted solution is expected to be roughly four times the original volume, or around 44 mL. Substituting the given values and
solving for the unknown volume yields:
(0.45 M)(0.011 L)
V2 =
(0.12 M)
V2 = 0.041 L
The volume of the 0.12-M solution is 0.041 L (41 mL). The result is reasonable and compares well with the rough estimate.
A laboratory experiment calls for 0.125 M HNO3. What volume of 0.125 M HNO3 can be prepared from 0.250 L of 1.88 M
HNO3?
3.4.0.1: Answer:
3.76 L

3.4.0.1: Example 3.21
3.4.0.0.7: Volume of a Concentrated Solution Needed for Dilution
What volume of 1.59 M KOH is required to prepare 5.00 L of 0.100 M KOH?
3.4.0.0.8: Solution
Given are the concentration of a stock solution, C1, and the volume and concentration of the resultant diluted solution, V2 and
C2. Find the volume of the stock solution, V1 by rearranging the dilution equation to isolate V1:
C1 V1 = C2 V2
C2 V2
V1 =
C1
Since the concentration of the diluted solution 0.100 M is roughly one-sixteenth that of the stock solution (1.59 M), the volume
of the stock solution is expected to be about one-sixteenth that of the diluted solution, or around 0.3 liters. Substituting the
given values and solving for the unknown volume yields:
(0.100 M)(5.00 L)
V1 =
1.59 M
V1 = 0.314 L
Thus, 0.314 L of the 1.59-M solution is needed to prepare the desired solution. This result is consistent with the rough estimate.
What volume of a 0.575-M solution of glucose, C6H12O6, can be prepared from 50.00 mL of a 3.00-M glucose solution?
3.4.0.1: Answer:
0.261 L
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Define the concentration units of mass percentage, volume percentage, mass-volume percentage, parts-per-million (ppm),
and parts-per-billion (ppb)
Perform computations relating a solution’s concentration and its components’ volumes and/or masses using these units
The previous section introduced molarity, a very useful measurement unit for evaluating the concentration of solutions. However,
molarity is only one measure of concentration. This section will describe some other units of concentration that are commonly used
in various applications, either for convenience or by convention.
3.5.0.1: Mass Percentage

Earlier in this chapter, percent composition was introduced as a measure of the relative amount of a given element in a compound.
Percentages are also commonly used to express the composition of mixtures, including solutions. The mass percentage of a
solution component is defined as the ratio of the component’s mass to the solution’s mass, expressed as a percentage:
mass of component
mass percentage = × 100%
mass of solution
Mass percentage is also referred to by similar names such as percent mass, percent weight, weight/weight percent, and other
variations on this theme. The most common symbol for mass percentage is simply the percent sign, %, although more detailed
symbols are often used including %mass, %weight, and (w/w)%. Use of these more detailed symbols can prevent confusion of
mass percentages with other types of percentages, such as volume percentages (to be discussed later in this section).
Mass percentages are popular concentration units for consumer products. The label of a typical liquid bleach bottle (Figure 3.17)
cites the concentration of its active ingredient, sodium hypochlorite (NaOCl), as being 7.4%. A 100.0-g sample of bleach would
therefore contain 7.4 g of NaOCl.

Figure 3.17 Liquid bleach is an aqueous solution of sodium hypochlorite (NaOCl). This brand has a concentration of 7.4% NaOCl
by mass.
3.5.0.1: Example 3.22

3.5.0.0.1: Calculation of Percent by Mass
A 5.0-g sample of spinal fluid contains 3.75 mg (0.00375 g) of glucose. What is the percent by mass of glucose in spinal fluid?
3.5.0.0.2: Solution
The spinal fluid sample contains roughly 4 mg of glucose in 5000 mg of fluid, so the mass fraction of glucose should be a bit
less than one part in 1000, or about 0.1%. Substituting the given masses into the equation defining mass percentage yields:
1 g
3.75 mg glucose ×
1000 mg
% glucose = = 0.075%
5.0 g spinal fluid
The computed mass percentage agrees with our rough estimate (it’s a bit less than 0.1%).
Note that while any mass unit may be used to compute a mass percentage (mg, g, kg, oz, and so on), the same unit must be
used for both the solute and the solution so that the mass units cancel, yielding a dimensionless ratio. In this case, the solute
mass unit in the numerator was converted from mg to g to match the units in the denominator. Alternatively, the spinal fluid
mass unit in the denominator could have been converted from g to mg instead. As long as identical mass units are used for both
solute and solution, the computed mass percentage will be correct.
A bottle of a tile cleanser contains 135 g of HCl and 775 g of water. What is the percent by mass of HCl in this cleanser?
3.5.0.1: Answer:
14.8%
3.5.0.1: Example 3.23

3.5.0.0.4: Calculations using Mass Percentage
“Concentrated” hydrochloric acid is an aqueous solution of 37.2% HCl that is commonly used as a laboratory reagent. The
density of this solution is 1.19 g/mL. What mass of HCl is contained in 0.500 L of this solution?
3.5.0.0.5: Solution
The HCl concentration is near 40%, so a 100-g portion of this solution would contain about 40 g of HCl. Since the solution
density isn’t greatly different from that of water (1 g/mL), a reasonable estimate of the HCl mass in 500 g (0.5 L) of the
solution is about five times greater than that in a 100 g portion, or 5 × 40 = 200 g. In order to derive the mass of solute in a
solution from its mass percentage, the mass of the solution must be known. Using the solution density given, convert the
solution’s volume to mass, and then use the given mass percentage to calculate the solute mass. This mathematical approach is
outlined in this flowchart:
For proper unit cancellation, the 0.500-L volume is converted into 500 mL, and the mass percentage is expressed as a ratio,
37.2 g HCl/g solution:
1.19 g solution 37.2 g HCl
500 mL solution ( ) ( ) = 221 g HCl
mL solution 100 g solution
This mass of HCl is consistent with our rough estimate of approximately 200 g.
What volume of concentrated HCl solution contains 125 g of HCl?
3.5.0.1: Answer:
282 mL
3.5.0.1: Volume Percentage

Liquid volumes over a wide range of magnitudes are conveniently measured using common and relatively inexpensive laboratory
equipment. The concentration of a solution formed by dissolving a liquid solute in a liquid solvent is therefore often expressed as a
volume percentage, %vol or (v/v)%:
volume solute
volume percentage = × 100%
volume solution
3.5.0.1: Example 3.24

3.5.0.0.1: Calculations using Volume Percentage
Rubbing alcohol (isopropanol) is usually sold as a 70%vol aqueous solution. If the density of isopropyl alcohol is 0.785 g/mL,
how many grams of isopropyl alcohol are present in a 355 mL bottle of rubbing alcohol?
3.5.0.0.2: Solution
Per the definition of volume percentage, the isopropanol volume is 70% of the total solution volume. Multiplying the
isopropanol volume by its density yields the requested mass:
70 mL isopropyl alcohol 0.785 g isopropyl alcohol
(355 mL solution) ( ) ( ) = 195 g isopropyl alchol
100 mL solution 1 mL isopropyl alcohol

Wine is approximately 12% ethanol (CH3CH2OH) by volume. Ethanol has a molar mass of 46.06 g/mol and a density 0.789
g/mL. How many moles of ethanol are present in a 750-mL bottle of wine?
3.5.0.1: Answer:
1.5 mol ethanol

3.5.0.1: Mass-Volume Percentage
“Mixed” percentage units, derived from the mass of solute and the volume of solution, are popular for certain biochemical and
medical applications. A mass-volume percent is a ratio of a solute’s mass to the solution’s volume expressed as a percentage. The
specific units used for solute mass and solution volume may vary, depending on the solution. For example, physiological saline
solution, used to prepare intravenous fluids, has a concentration of 0.9% mass/volume (m/v), indicating that the composition is 0.9
g of solute per 100 mL of solution. The concentration of glucose in blood (commonly referred to as “blood sugar”) is also typically
expressed in terms of a mass-volume ratio. Though not expressed explicitly as a percentage, its concentration is usually given in
milligrams of glucose per deciliter (100 mL) of blood (Figure 3.18).
Figure 3.18 “Mixed” mass-volume units are commonly encountered in medical settings. (a) The NaCl concentration of
physiological saline is 0.9% (m/v). (b) This device measures glucose levels in a sample of blood. The normal range for glucose
concentration in blood (fasting) is around 70–100 mg/dL. (credit a: modification of work by “The National Guard”/Flickr; credit b:
modification of work by Biswarup Ganguly)
3.5.0.1: Parts per Million and Parts per Billion

Very low solute concentrations are often expressed using appropriately small units such as parts per million (ppm) or parts per
billion (ppb). Like percentage (“part per hundred”) units, ppm and ppb may be defined in terms of masses, volumes, or mixed

mass-volume units. There are also ppm and ppb units defined with respect to numbers of atoms and molecules.
The mass-based definitions of ppm and ppb are given here:
mass solute 6
ppm = × 10 ppm
mass solution
mass solute 9
ppb = × 10 ppb
mass solution
Both ppm and ppb are convenient units for reporting the concentrations of pollutants and other trace contaminants in water.
Concentrations of these contaminants are typically very low in treated and natural waters, and their levels cannot exceed relatively
low concentration thresholds without causing adverse effects on health and wildlife. For example, the EPA has identified the
maximum safe level of fluoride ion in tap water to be 4 ppm. Inline water filters are designed to reduce the concentration of
fluoride and several other trace-level contaminants in tap water (Figure 3.19).
Figure 3.19 (a) In some areas, trace-level concentrations of contaminants can render unfiltered tap water unsafe for drinking and
cooking. (b) Inline water filters reduce the concentration of solutes in tap water. (credit a: modification of work by Jenn Durfey;
credit b: modification of work by “vastateparkstaff”/Wikimedia commons)
3.5.0.1: Example 3.25

3.5.0.0.1: Calculation of Parts per Million and Parts per Billion Concentrations
According to the EPA, when the concentration of lead in tap water reaches 15 ppb, certain remedial actions must be taken.
What is this concentration in ppm? At this concentration, what mass of lead (μg) would be contained in a typical glass of water
(300 mL)?
3.5.0.0.2: Solution
The definitions of the ppm and ppb units may be used to convert the given concentration from ppb to ppm. Comparing these
two unit definitions shows that ppm is 1000 times greater than ppb (1 ppm = 103 ppb). Thus:
1 ppm
15 ppb × = 0.015 ppm
3
10 ppb
The definition of the ppb unit may be used to calculate the requested mass if the mass of the solution is provided. Since the
volume of solution (300 mL) is given, its density must be used to derive the corresponding mass. Assume the density of tap
water to be roughly the same as that of pure water (~1.00 g/mL), since the concentrations of any dissolved substances should
not be very large. Rearranging the equation defining the ppb unit and substituting the given quantities yields:

mass solute 9
ppb = × 10 ppb
mass solution
ppb × mass solution

mass solute =
9
10 ppb
1 .0 0 g
15 ppb × 300 mL ×
mL −6
mass solute = = 4.5 × 10 g
9
10 ppb
Finally, convert this mass to the requested unit of micrograms:

1 μg
−6
4.5 × 10 g × = 4.5 μg
−6
10 g

A 50.0-g sample of industrial wastewater was determined to contain 0.48 mg of mercury. Express the mercury concentration of
the wastewater in ppm and ppb units.
3.5.0.1: Answer:
9.6 ppm, 9600 ppb
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3.6: Key Terms
aqueous solution
solution for which water is the solvent
Avogadro’s number (NA)

experimentally determined value of the number of entities comprising 1 mole of substance, equal to 6.022 × 1023 mol−1
concentrated
qualitative term for a solution containing solute at a relatively high concentration
concentration
quantitative measure of the relative amounts of solute and solvent present in a solution
dilute
qualitative term for a solution containing solute at a relatively low concentration
dilution
process of adding solvent to a solution in order to lower the concentration of solutes
dissolved
describes the process by which solute components are dispersed in a solvent
empirical formula mass

sum of average atomic masses for all atoms represented in an empirical formula
formula mass
sum of the average masses for all atoms represented in a chemical formula; for covalent compounds, this is also the molecular
mass
mass percentage
ratio of solute-to-solution mass expressed as a percentage
mass-volume percent
ratio of solute mass to solution volume, expressed as a percentage
molar mass
mass in grams of 1 mole of a substance
molarity (M)
unit of concentration, defined as the number of moles of solute dissolved in 1 liter of solution
mole
amount of substance containing the same number of atoms, molecules, ions, or other entities as the number of atoms in exactly
12 grams of 12C
parts per billion (ppb)

ratio of solute-to-solution mass multiplied by 109
parts per million (ppm)

ratio of solute-to-solution mass multiplied by 106
percent composition
percentage by mass of the various elements in a compound
solute
solution component present in a concentration less than that of the solvent
solvent
solution component present in a concentration that is higher relative to other components
volume percentage
ratio of solute-to-solution volume expressed as a percentage
3.7: Key Equations
mass X
% X = × 100%
mass compound
mass X
% X = × 100%
mass compound
g
molecular or molar mass (amu or )
mol
= n formula units/molecule
g
empirical formula mass (amu or )
mol
(AxBy)n = AnxBny
mol solute
M =
L solution
C1V1 = C2V2
mass of solute
Percent by mass = × 100
mass of solution
mass solute 6
ppm = × 10 ppm
mass solution
mass solute 9
ppb = × 10 ppb
mass solution
3.8: Summary
3.1 Formula Mass and the Mole Concept
The formula mass of a substance is the sum of the average atomic masses of each atom represented in the chemical formula and is
expressed in atomic mass units. The formula mass of a covalent compound is also called the molecular mass. A convenient amount
unit for expressing very large numbers of atoms or molecules is the mole. Experimental measurements have determined the number
of entities composing 1 mole of substance to be 6.022 × 1023, a quantity called Avogadro’s number. The mass in grams of 1 mole
of substance is its molar mass. Due to the use of the same reference substance in defining the atomic mass unit and the mole, the
formula mass (amu) and molar mass (g/mol) for any substance are numerically equivalent (for example, one H2O molecule weighs
approximately18 amu and 1 mole of H2O molecules weighs approximately 18 g).
3.2 Determining Empirical and Molecular Formulas

The chemical identity of a substance is defined by the types and relative numbers of atoms composing its fundamental entities
(molecules in the case of covalent compounds, ions in the case of ionic compounds). A compound’s percent composition provides
the mass percentage of each element in the compound, and it is often experimentally determined and used to derive the compound’s
empirical formula. The empirical formula mass of a covalent compound may be compared to the compound’s molecular or molar
mass to derive a molecular formula.
3.3 Molarity
Solutions are homogeneous mixtures. Many solutions contain one component, called the solvent, in which other components,
called solutes, are dissolved. An aqueous solution is one for which the solvent is water. The concentration of a solution is a measure
of the relative amount of solute in a given amount of solution. Concentrations may be measured using various units, with one very
useful unit being molarity, defined as the number of moles of solute per liter of solution. The solute concentration of a solution may
be decreased by adding solvent, a process referred to as dilution. The dilution equation is a simple relation between concentrations
and volumes of a solution before and after dilution.
3.4 Other Units for Solution Concentrations

In addition to molarity, a number of other solution concentration units are used in various applications. Percentage concentrations
based on the solution components’ masses, volumes, or both are useful for expressing relatively high concentrations, whereas lower
concentrations are conveniently expressed using ppm or ppb units. These units are popular in environmental, medical, and other
fields where mole-based units such as molarity are not as commonly used.
3.9: Exercises
3.9.0.1: 3.1 Formula Mass and the Mole Concept
1.
What is the total mass (amu) of carbon in each of the following molecules?
(a) CH4
(b) CHCl3
(c) C12H10O6
(d) CH3CH2CH2CH2CH3
2.
What is the total mass of hydrogen in each of the molecules?
(a) CH4
(b) CHCl3
(c) C12H10O6
(d) CH3CH2CH2CH2CH3
3.
Calculate the molecular or formula mass of each of the following:
(a) P4
(b) H2O
(c) Ca(NO3)2
(d) CH3CO2H (acetic acid)
(e) C12H22O11 (sucrose, cane sugar)
4.
Determine the molecular mass of the following compounds:
(a)
(b)
(c)
(d)

5.
Determine the molecular mass of the following compounds:
(a)
(b)
(c)
(d)
6.
Which molecule has a molecular mass of 28.05 amu?
(a)
(b)
(c)

7.
Write a sentence that describes how to determine the number of moles of a compound in a known mass of the compound using its
molecular formula.
8.
Compare 1 mole of H2, 1 mole of O2, and 1 mole of F2.
(a) Which has the largest number of molecules? Explain why.
(b) Which has the greatest mass? Explain why.
9.
Which contains the greatest mass of oxygen: 0.75 mol of ethanol (C2H5OH), 0.60 mol of formic acid (HCO2H), or 1.0 mol of water
(H2O)? Explain why.
10.
Which contains the greatest number of moles of oxygen atoms: 1 mol of ethanol (C2H5OH), 1 mol of formic acid (HCO2H), or 1
mol of water (H2O)? Explain why.
11.
How are the molecular mass and the molar mass of a compound similar and how are they different?
12.
Calculate the molar mass of each of the following compounds:
(a) hydrogen fluoride, HF
(b) ammonia, NH3
(c) nitric acid, HNO3
(d) silver sulfate, Ag2SO4
(e) boric acid, B(OH)3
13.
Calculate the molar mass of each of the following:
(a) S8
(b) C5H12
(c) Sc2(SO4)3
(d) CH3COCH3 (acetone)
(e) C6H12O6 (glucose)
14.
Calculate the empirical or molecular formula mass and the molar mass of each of the following minerals:
(a) limestone, CaCO3
(b) halite, NaCl
(c) beryl, Be3Al2Si6O18
(d) malachite, Cu2(OH)2CO3
(e) turquoise, CuAl6(PO4)4(OH)8(H2O)4
15.
Calculate the molar mass of each of the following:
(a) the anesthetic halothane, C2HBrClF3
(b) the herbicide paraquat, C12H14N2Cl2

(c) caffeine, C8H10N4O2
(d) urea, CO(NH2)2
(e) a typical soap, C17H35CO2Na
16.
Determine the number of moles of compound and the number of moles of each type of atom in each of the following:
(a) 25.0 g of propylene, C3H6
(b) 3.06 × 10−3 g of the amino acid glycine, C2H5NO2
(c) 25 lb of the herbicide Treflan, C13H16N2O4F (1 lb = 454 g)
(d) 0.125 kg of the insecticide Paris Green, Cu4(AsO3)2(CH3CO2)2
(e) 325 mg of aspirin, C6H4(CO2H)(CO2CH3)
17.
Determine the mass of each of the following:
(a) 0.0146 mol KOH
(b) 10.2 mol ethane, C2H6
(c) 1.6 × 10−3 mol Na2 SO4
(d) 6.854 × 103 mol glucose, C6 H12 O6
(e) 2.86 mol Co(NH3)6Cl3
18.
Determine the number of moles of the compound and determine the number of moles of each type of atom in each of the following:
(a) 2.12 g of potassium bromide, KBr
(b) 0.1488 g of phosphoric acid, H3PO4
(c) 23 kg of calcium carbonate, CaCO3
(d) 78.452 g of aluminum sulfate, Al2(SO4)3
(e) 0.1250 mg of caffeine, C8H10N4O2
19.
Determine the mass of each of the following:
(a) 2.345 mol LiCl
(b) 0.0872 mol acetylene, C2H2
(c) 3.3 × 10−2 mol Na2 CO3
(d) 1.23 × 103 mol fructose, C6 H12 O6
(e) 0.5758 mol FeSO4(H2O)7
20.
The approximate minimum daily dietary requirement of the amino acid leucine, C6H13NO2, is 1.1 g. What is this requirement in
moles?
21.
Determine the mass in grams of each of the following:
(a) 0.600 mol of oxygen atoms
(b) 0.600 mol of oxygen molecules, O2
(c) 0.600 mol of ozone molecules, O3

22.
A 55-kg woman has 7.5 × 10−3 mol of hemoglobin (molar mass = 64,456 g/mol) in her blood. How many hemoglobin molecules is
this? What is this quantity in grams?
23.
Determine the number of atoms and the mass of zirconium, silicon, and oxygen found in 0.3384 mol of zircon, ZrSiO4, a
semiprecious stone.
24.
Determine which of the following contains the greatest mass of hydrogen: 1 mol of CH4, 0.6 mol of C6H6, or 0.4 mol of C3H8.
25.
Determine which of the following contains the greatest mass of aluminum: 122 g of AlPO4, 266 g of Al2Cl6, or 225 g of Al2S3.
26.
Diamond is one form of elemental carbon. An engagement ring contains a diamond weighing 1.25 carats (1 carat = 200 mg). How
many atoms are present in the diamond?
27.
The Cullinan diamond was the largest natural diamond ever found (January 25, 1905). It weighed 3104 carats (1 carat = 200 mg).
How many carbon atoms were present in the stone?
28.
One 55-gram serving of a particular cereal supplies 270 mg of sodium, 11% of the recommended daily allowance. How many
moles and atoms of sodium are in the recommended daily allowance?
29.
A certain nut crunch cereal contains 11.0 grams of sugar (sucrose, C12H22O11) per serving size of 60.0 grams. How many servings
of this cereal must be eaten to consume 0.0278 moles of sugar?
30.
A tube of toothpaste contains 0.76 g of sodium monofluorophosphate (Na2PO3F) in 100 mL.
(a) What mass of fluorine atoms in mg was present?
(b) How many fluorine atoms were present?
31.
Which of the following represents the least number of molecules?
(a) 20.0 g of H2O (18.02 g/mol)
(b) 77.0 g of CH4 (16.06 g/mol)
(c) 68.0 g of C3H6 (42.08 g/mol)
(d) 100.0 g of N2O (44.02 g/mol)
(e) 84.0 g of HF (20.01 g/mol)
3.9.0.1: 3.2 Determining Empirical and Molecular Formulas

32.
What information is needed to determine the molecular formula of a compound from the empirical formula?
33.
Calculate the following to four significant figures:
(a) the percent composition of ammonia, NH3
(b) the percent composition of photographic fixer solution (“hypo”), Na2S2O3
(c) the percent of calcium ion in Ca3(PO4)2

34.
Determine the following to four significant figures:
(a) the percent composition of hydrazoic acid, HN3
(b) the percent composition of TNT, C6H2(CH3)(NO2)3
(c) the percent of SO42– in Al2(SO4)3
35.
Determine the percent ammonia, NH3, in Co(NH3)6Cl3, to three significant figures.
36.
Determine the percent water in CuSO4·5H2O to three significant figures.
37.
Determine the empirical formulas for compounds with the following percent compositions:
(a) 15.8% carbon and 84.2% sulfur
(b) 40.0% carbon, 6.7% hydrogen, and 53.3% oxygen
38.
Determine the empirical formulas for compounds with the following percent compositions:
(a) 43.6% phosphorus and 56.4% oxygen
(b) 28.7% K, 1.5% H, 22.8% P, and 47.0% O
39.
A compound of carbon and hydrogen contains 92.3% C and has a molar mass of 78.1 g/mol. What is its molecular formula?
40.
Dichloroethane, a compound that is often used for dry cleaning, contains carbon, hydrogen, and chlorine. It has a molar mass of 99
g/mol. Analysis of a sample shows that it contains 24.3% carbon and 4.1% hydrogen. What is its molecular formula?
41.
Determine the empirical and molecular formula for chrysotile asbestos. Chrysotile has the following percent composition: 28.03%
Mg, 21.60% Si, 1.16% H, and 49.21% O. The molar mass for chrysotile is 520.8 g/mol.
42.
Polymers are large molecules composed of simple units repeated many times. Thus, they often have relatively simple empirical
formulas. Calculate the empirical formulas of the following polymers:
(a) Lucite (Plexiglas); 59.9% C, 8.06% H, 32.0% O
(b) Saran; 24.8% C, 2.0% H, 73.1% Cl
(c) polyethylene; 86% C, 14% H
(d) polystyrene; 92.3% C, 7.7% H
(e) Orlon; 67.9% C, 5.70% H, 26.4% N
43.
A major textile dye manufacturer developed a new yellow dye. The dye has a percent composition of 75.95% C, 17.72% N, and
6.33% H by mass with a molar mass of about 240 g/mol. Determine the molecular formula of the dye.
3.9.0.1: 3.3 Molarity

44.
Explain what changes and what stays the same when 1.00 L of a solution of NaCl is diluted to 1.80 L.
45.

What information is needed to calculate the molarity of a sulfuric acid solution?
46.
A 200-mL sample and a 400-mL sample of a solution of salt have the same molarity. In what ways are the two samples identical?
In what ways are these two samples different?
47.
Determine the molarity for each of the following solutions:
(a) 0.444 mol of CoCl2 in 0.654 L of solution
(b) 98.0 g of phosphoric acid, H3PO4, in 1.00 L of solution
(c) 0.2074 g of calcium hydroxide, Ca(OH)2, in 40.00 mL of solution
(d) 10.5 kg of Na2SO4·10H2O in 18.60 L of solution
(e) 7.0 × 10−3 mol of I2 in 100.0 mL of solution
(f) 1.8 × 104 mg of HCl in 0.075 L of solution
48.
Determine the molarity of each of the following solutions:
(a) 1.457 mol KCl in 1.500 L of solution
(b) 0.515 g of H2SO4 in 1.00 L of solution
(c) 20.54 g of Al(NO3)3 in 1575 mL of solution
(d) 2.76 kg of CuSO4·5H2O in 1.45 L of solution
(e) 0.005653 mol of Br2 in 10.00 mL of solution
(f) 0.000889 g of glycine, C2H5NO2, in 1.05 mL of solution
49.
Consider this question: What is the mass of the solute in 0.500 L of 0.30 M glucose, C6H12O6, used for intravenous injection?
(a) Outline the steps necessary to answer the question.
(b) Answer the question.
50.
Consider this question: What is the mass of solute in 200.0 L of a 1.556-M solution of KBr?
51.
Calculate the number of moles and the mass of the solute in each of the following solutions:
(a) 2.00 L of 18.5 M H2SO4, concentrated sulfuric acid
(b) 100.0 mL of 3.8 × 10−6 M NaCN, the minimum lethal concentration of sodium cyanide in blood serum
(c) 5.50 L of 13.3 M H2CO, the formaldehyde used to “fix” tissue samples
(d) 325 mL of 1.8 × 10−6 M FeSO4, the minimum concentration of iron sulfate detectable by taste in drinking water
52.
Calculate the number of moles and the mass of the solute in each of the following solutions:
(a) 325 mL of 8.23 × 10−5 M KI, a source of iodine in the diet
(b) 75.0 mL of 2.2 × 10−5 M H2SO4, a sample of acid rain
(c) 0.2500 L of 0.1135 M K2CrO4, an analytical reagent used in iron assays

(d) 10.5 L of 3.716 M (NH4)2SO4, a liquid fertilizer
53.
Consider this question: What is the molarity of KMnO4 in a solution of 0.0908 g of KMnO4 in 0.500 L of solution?
54.
Consider this question: What is the molarity of HCl if 35.23 mL of a solution of HCl contain 0.3366 g of HCl?
55.
Calculate the molarity of each of the following solutions:
(a) 0.195 g of cholesterol, C27H46O, in 0.100 L of serum, the average concentration of cholesterol in human serum
(b) 4.25 g of NH3 in 0.500 L of solution, the concentration of NH3 in household ammonia
(c) 1.49 kg of isopropyl alcohol, C3H7OH, in 2.50 L of solution, the concentration of isopropyl alcohol in rubbing alcohol
(d) 0.029 g of I2 in 0.100 L of solution, the solubility of I2 in water at 20 °C
56.
Calculate the molarity of each of the following solutions:
(a) 293 g HCl in 666 mL of solution, a concentrated HCl solution
(b) 2.026 g FeCl3 in 0.1250 L of a solution used as an unknown in general chemistry laboratories
(c) 0.001 mg Cd2+ in 0.100 L, the maximum permissible concentration of cadmium in drinking water
(d) 0.0079 g C7H5SNO3 in one ounce (29.6 mL), the concentration of saccharin in a diet soft drink.
57.
There is about 1.0 g of calcium, as Ca2+, in 1.0 L of milk. What is the molarity of Ca2+ in milk?
58.
What volume of a 1.00-M Fe(NO3)3 solution can be diluted to prepare 1.00 L of a solution with a concentration of 0.250 M?
59.
If 0.1718 L of a 0.3556-M C3H7OH solution is diluted to a concentration of 0.1222 M, what is the volume of the resulting solution?
60.
If 4.12 L of a 0.850 M-H3PO4 solution is be diluted to a volume of 10.00 L, what is the concentration of the resulting solution?
61.
What volume of a 0.33-M C12H22O11 solution can be diluted to prepare 25 mL of a solution with a concentration of 0.025 M?
62.
What is the concentration of the NaCl solution that results when 0.150 L of a 0.556-M solution is allowed to evaporate until the
volume is reduced to 0.105 L?
63.
What is the molarity of the diluted solution when each of the following solutions is diluted to the given final volume?
(a) 1.00 L of a 0.250-M solution of Fe(NO3)3 is diluted to a final volume of 2.00 L
(b) 0.5000 L of a 0.1222-M solution of C3H7OH is diluted to a final volume of 1.250 L
(c) 2.35 L of a 0.350-M solution of H3PO4 is diluted to a final volume of 4.00 L

(d) 22.50 mL of a 0.025-M solution of C12H22O11 is diluted to 100.0 mL
64.
What is the final concentration of the solution produced when 225.5 mL of a 0.09988-M solution of Na2CO3 is allowed to
evaporate until the solution volume is reduced to 45.00 mL?
65.
A 2.00-L bottle of a solution of concentrated HCl was purchased for the general chemistry laboratory. The solution contained 868.8
g of HCl. What is the molarity of the solution?
66.
An experiment in a general chemistry laboratory calls for a 2.00-M solution of HCl. How many mL of 11.9 M HCl would be
required to make 250 mL of 2.00 M HCl?
67.
What volume of a 0.20-M K2SO4 solution contains 57 g of K2SO4?
68.
The US Environmental Protection Agency (EPA) places limits on the quantities of toxic substances that may be discharged into the
sewer system. Limits have been established for a variety of substances, including hexavalent chromium, which is limited to 0.50
mg/L. If an industry is discharging hexavalent chromium as potassium dichromate (K2Cr2O7), what is the maximum permissible
molarity of that substance?
3.9.0.1: 3.4 Other Units for Solution Concentrations

69.
Consider this question: What mass of a concentrated solution of nitric acid (68.0% HNO3 by mass) is needed to prepare 400.0 g of
a 10.0% solution of HNO3 by mass?
70.
What mass of a 4.00% NaOH solution by mass contains 15.0 g of NaOH?
71.
What mass of solid NaOH (97.0% NaOH by mass) is required to prepare 1.00 L of a 10.0% solution of NaOH by mass? The
density of the 10.0% solution is 1.109 g/mL.
72.
What mass of HCl is contained in 45.0 mL of an aqueous HCl solution that has a density of 1.19 g cm–3 and contains 37.21% HCl
by mass?
73.
The hardness of water (hardness count) is usually expressed in parts per million (by mass) of CaCO3, which is equivalent to
milligrams of CaCO3 per liter of water. What is the molar concentration of Ca2+ ions in a water sample with a hardness count of
175 mg CaCO3/L?
74.
The level of mercury in a stream was suspected to be above the minimum considered safe (1 part per billion by weight). An
analysis indicated that the concentration was 0.68 parts per billion. Assume a density of 1.0 g/mL and calculate the molarity of
mercury in the stream.
75.
In Canada and the United Kingdom, devices that measure blood glucose levels provide a reading in millimoles per liter. If a
measurement of 5.3 mM is observed, what is the concentration of glucose (C6H12O6) in mg/dL?
76.

A throat spray is 1.40% by mass phenol, C6H5OH, in water. If the solution has a density of 0.9956 g/mL, calculate the molarity of
the solution.
77.
Copper(I) iodide (CuI) is often added to table salt as a dietary source of iodine. How many moles of CuI are contained in 1.00 lb
(454 g) of table salt containing 0.0100% CuI by mass?
78.
A cough syrup contains 5.0% ethyl alcohol, C2H5OH, by mass. If the density of the solution is 0.9928 g/mL, determine the
molarity of the alcohol in the cough syrup.
79.
D5W is a solution used as an intravenous fluid. It is a 5.0% by mass solution of dextrose (C6H12O6) in water. If the density of D5W
is 1.029 g/mL, calculate the molarity of dextrose in the solution.
80.
Find the molarity of a 40.0% by mass aqueous solution of sulfuric acid, H2SO4, for which the density is 1.3057 g/mL.

CHAPTER OVERVIEW
4: Stoichiometry of Chemical Reactions

General Chemistry
This chapter will describe how to symbolize chemical reactions using chemical equations, how to classify some common chemical
reactions by identifying patterns of reactivity, and how to determine the quantitative relations between the amounts of substances
involved in chemical reactions—that is, the reaction stoichiometry.
4.1: Introduction
4.7: Key Terms
4.8: Key Equations
4.9: Summary
4.10: Exercises
This page titled 4: Stoichiometry of Chemical Reactions is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by
1
4.1: Introduction
Figure 4.1 Many modern rocket fuels are solid mixtures of substances combined in carefully measured amounts and ignited to yield
a thrust-generating chemical reaction. (credit: modification of work by NASA)

4.1 Writing and Balancing Chemical Equations
4.2 Classifying Chemical Reactions
4.3 Reaction Stoichiometry
4.4 Reaction Yields
4.5 Quantitative Chemical Analysis
Solid-fuel rockets are a central feature in the world’s space exploration programs, including the new Space Launch System being
developed by the National Aeronautics and Space Administration (NASA) to replace the retired Space Shuttle fleet (Figure 4.1).
The engines of these rockets rely on carefully prepared solid mixtures of chemicals combined in precisely measured amounts.
Igniting the mixture initiates a vigorous chemical reaction that rapidly generates large amounts of gaseous products. These gases
are ejected from the rocket engine through its nozzle, providing the thrust needed to propel heavy payloads into space. Both the
nature of this chemical reaction and the relationships between the amounts of the substances being consumed and produced by the
reaction are critically important considerations that determine the success of the technology. This chapter will describe how to
symbolize chemical reactions using chemical equations, how to classify some common chemical reactions by identifying patterns
of reactivity, and how to determine the quantitative relations between the amounts of substances involved in chemical reactions—
that is, the reaction stoichiometry.


Derive chemical equations from narrative descriptions of chemical reactions.
Write and balance chemical equations in molecular, total ionic, and net ionic formats.
An earlier chapter of this text introduced the use of element symbols to represent individual atoms. When atoms gain or lose
electrons to yield ions, or combine with other atoms to form molecules, their symbols are modified or combined to generate
chemical formulas that appropriately represent these species. Extending this symbolism to represent both the identities and the
relative quantities of substances undergoing a chemical (or physical) change involves writing and balancing a chemical equation.
Consider as an example the reaction between one methane molecule (CH4) and two diatomic oxygen molecules (O2) to produce
one carbon dioxide molecule (CO2) and two water molecules (H2O). The chemical equation representing this process is provided in
the upper half of Figure 4.2, with space-filling molecular models shown in the lower half of the figure.
Figure 4.2 The reaction between methane and oxygen to yield carbon dioxide and water (shown at bottom) may be represented by a
chemical equation using formulas (top).
This example illustrates the fundamental aspects of any chemical equation:
1. The substances undergoing reaction are called reactants, and their formulas are placed on the left side of the equation.
2. The substances generated by the reaction are called products, and their formulas are placed on the right side of the equation.
3. Plus signs (+) separate individual reactant and product formulas, and an arrow (⟶) separates the reactant and product (left
and right) sides of the equation.
4. The relative numbers of reactant and product species are represented by coefficients (numbers placed immediately to the left of
each formula). A coefficient of 1 is typically omitted.
It is common practice to use the smallest possible whole-number coefficients in a chemical equation, as is done in this example.
Realize, however, that these coefficients represent the relative numbers of reactants and products, and, therefore, they may be
correctly interpreted as ratios. Methane and oxygen react to yield carbon dioxide and water in a 1:2:1:2 ratio. This ratio is satisfied
if the numbers of these molecules are, respectively, 1-2-1-2, or 2-4-2-4, or 3-6-3-6, and so on (Figure 4.3). Likewise, these
coefficients may be interpreted with regard to any amount (number) unit, and so this equation may be correctly read in many ways,
including:
One methane molecule and two oxygen molecules react to yield one carbon dioxide molecule and two water molecules.
One dozen methane molecules and two dozen oxygen molecules react to yield one dozen carbon dioxide molecules and two
dozen water molecules.

One mole of methane molecules and 2 moles of oxygen molecules react to yield 1 mole of carbon dioxide molecules and 2
moles of water molecules.
Figure 4.3 Regardless of the absolute numbers of molecules involved, the ratios between numbers of molecules of each species that
react (the reactants) and molecules of each species that form (the products) are the same and are given by the chemical reaction
equation.
4.2.0.1: Balancing Equations

The chemical equation described in section 4.1 is balanced, meaning that equal numbers of atoms for each element involved in the
reaction are represented on the reactant and product sides. This is a requirement the equation must satisfy to be consistent with the
law of conservation of matter. It may be confirmed by simply summing the numbers of atoms on either side of the arrow and
comparing these sums to ensure they are equal. Note that the number of atoms for a given element is calculated by multiplying the
coefficient of any formula containing that element by the element’s subscript in the formula. If an element appears in more than one
formula on a given side of the equation, the number of atoms represented in each must be computed and then added together. For
example, both product species in the example reaction, CO2 and H2O, contain the element oxygen, and so the number of oxygen
atoms on the product side of the equation is
2 O atoms 1 O atom
(1 CO2 molecule × ) + (2 H2 O molecules × ) = 4 O atoms
CO2 molecule H2 O molecule
The equation for the reaction between methane and oxygen to yield carbon dioxide and water is confirmed to be balanced per this
approach, as shown here:
CH4 + 2 O2 ⟶ CO2 + 2 H2 O
Element Reactants Products Balanced?
C 1×1=1 1×1=1 1 = 1, yes
H 4×1=4 2×2=4 4 = 4, yes
O 2×2=4 (1 × 2) + (2 × 1) = 4 4 = 4, yes
A balanced chemical equation often may be derived from a qualitative description of some chemical reaction by a fairly simple
approach known as balancing by inspection. Consider as an example the decomposition of water to yield molecular hydrogen and
oxygen. This process is represented qualitatively by an unbalanced chemical equation:
H2 O ⟶ H2 + O2 (unbalanced)
Comparing the number of H and O atoms on either side of this equation confirms its imbalance:

H 1×2=2 1×2=2 2 = 2, yes
O 1×1=1 1×2=2 1 ≠ 2, no
The numbers of H atoms on the reactant and product sides of the equation are equal, but the numbers of O atoms are not. To
achieve balance, the coefficients of the equation may be changed as needed. Keep in mind, of course, that the formula subscripts
define, in part, the identity of the substance, and so these cannot be changed without altering the qualitative meaning of the
equation. For example, changing the reactant formula from H2O to H2O2 would yield balance in the number of atoms, but doing so
also changes the reactant’s identity (it’s now hydrogen peroxide and not water). The O atom balance may be achieved by changing
the coefficient for H2O to 2.
2 H2 O ⟶ H2 + O2 (unbalanced)
H 2×2=4 1×2=2 4 ≠ 2, no
O 2×1=2 1×2=2 2 = 2, yes
The H atom balance was upset by this change, but it is easily reestablished by changing the coefficient for the H2 product to 2.
2 H2 O ⟶ 2 H2 + O2 (balanced)
H 2×2=4 2×2=4 4 = 4, yes
O 2×1=2 1×2=2 2 = 2, yes
These coefficients yield equal numbers of both H and O atoms on the reactant and product sides, and the balanced equation is,
therefore:
2 H2 O ⟶ 2 H2 + O2
4.2.0.1: Example 4.1

4.2.0.0.1: Balancing Chemical Equations
Write a balanced equation for the reaction of molecular nitrogen (N2) and oxygen (O2) to form dinitrogen pentoxide.
4.2.0.0.2: Solution
First, write the unbalanced equation.
N2 + O2 ⟶ N2 O5 (unbalanced)
Next, count the number of each type of atom present in the unbalanced equation.
N 1×2=2 1×2=2 2 = 2, yes
O 1×2=2 1×5=5 2 ≠ 5, no
Though nitrogen is balanced, changes in coefficients are needed to balance the number of oxygen atoms. To balance the
number of oxygen atoms, a reasonable first attempt would be to change the coefficients for the O2 and N2O5 to integers that
will yield 10 O atoms (the least common multiple for the O atom subscripts in these two formulas).

N2 + 5 O2 ⟶ 2 N2 O5 (unbalanced)
N 1×2=2 2×2=4 2 ≠ 4, no
O 5 × 2 = 10 2 × 5 = 10 10 = 10, yes
The N atom balance has been upset by this change; it is restored by changing the coefficient for the reactant N2 to 2.
2 N2 + 5 O2 ⟶ 2 N2 O5
N 2×2=4 2×2=4 4 = 4, yes
O 5 × 2 = 10 2 × 5 = 10 10 = 10, yes
The numbers of N and O atoms on either side of the equation are now equal, and so the equation is balanced.
Write a balanced equation for the decomposition of ammonium nitrate to form molecular nitrogen, molecular oxygen, and
water. (Hint: Balance oxygen last, since it is present in more than one molecule on the right side of the equation.)
4.2.0.1: Answer:
2 NH4 NO3 ⟶ 2 N2 + O2 + 4 H2 O
It is sometimes convenient to use fractions instead of integers as intermediate coefficients in the process of balancing a chemical
equation. When balance is achieved, all the equation’s coefficients may then be multiplied by a whole number to convert the
fractional coefficients to integers without upsetting the atom balance. For example, consider the reaction of ethane (C2H6) with
oxygen to yield H2O and CO2, represented by the unbalanced equation:
C2 H6 + O2 ⟶ H2 O + CO2 (unbalanced)
Following the usual inspection approach, one might first balance C and H atoms by changing the coefficients for the two product
species, as shown:
C2 H6 + O2 ⟶ 3 H2 O + 2 CO2 (unbalanced)
This results in seven O atoms on the product side of the equation, an odd number—no integer coefficient can be used with the O2
reactant to yield an odd number, so a fractional coefficient, , is used instead to yield a provisional balanced equation:
7
7
C2 H6 + O2 ⟶ 3 H2 O + 2 CO2
2
A conventional balanced equation with integer-only coefficients is derived by multiplying each coefficient by 2:
2 C2 H6 + 7 O2 ⟶ 6 H2 O + 4 CO2
Finally with regard to balanced equations, recall that convention dictates use of the smallest whole-number coefficients. Although
the equation for the reaction between molecular nitrogen and molecular hydrogen to produce ammonia is, indeed, balanced,
3 N2 + 9 H2 ⟶ 6 NH3
the coefficients are not the smallest possible integers representing the relative numbers of reactant and product molecules. Dividing
each coefficient by the greatest common factor, 3, gives the preferred equation:
N2 + 3 H2 ⟶ 2 NH3

Use this interactive tutorial for additional practice balancing equations.
4.2.0.1: Additional Information in Chemical Equations

The physical states of reactants and products in chemical equations very often are indicated with a parenthetical abbreviation
following the formulas. Common abbreviations include s for solids, l for liquids, g for gases, and aq for substances dissolved in
water (aqueous solutions, as introduced in the preceding chapter). These notations are illustrated in the example equation here:
2Na(s) + 2 H2 O(l) ⟶ 2NaOH(aq) + H2 (g)
This equation represents the reaction that takes place when sodium metal is placed in water. The solid sodium reacts with liquid
water to produce molecular hydrogen gas and the ionic compound sodium hydroxide (a solid in pure form, but readily dissolved in
water).
Special conditions necessary for a reaction are sometimes designated by writing a word or symbol above or below the equation’s
arrow. For example, a reaction carried out by heating may be indicated by the uppercase Greek letter delta (Δ) over the arrow.
Δ
CaCO3 (s) ⟶ CaO(s) + CO2 (g)
Other examples of these special conditions will be encountered in more depth in later chapters.
4.2.0.1: Equations for Ionic Reactions

Given the abundance of water on earth, it stands to reason that a great many chemical reactions take place in aqueous media. When
ions are involved in these reactions, the chemical equations may be written with various levels of detail appropriate to their
intended use. To illustrate this, consider a reaction between ionic compounds taking place in an aqueous solution. When aqueous
solutions of CaCl2 and AgNO3 are mixed, a reaction takes place producing aqueous Ca(NO3)2 and solid AgCl:
CaCl2 (aq) + 2 AgNO3 (aq) ⟶ Ca (NO3 ) 2 (aq) + 2AgCl(s)
This balanced equation, derived in the usual fashion, is called a molecular equation because it doesn’t explicitly represent the ionic
species that are present in solution. When ionic compounds dissolve in water, they may dissociate into their constituent ions, which
are subsequently dispersed homogenously throughout the resulting solution (a thorough discussion of this important process is
provided in the chapter on solutions). Ionic compounds dissolved in water are, therefore, more realistically represented as
dissociated ions, in this case:
2+ −
CaCl2 (aq) ⟶ Ca (aq) + 2 Cl (aq)
+ −
2 AgNO (aq) ⟶ 2 Ag (aq) + 2 NO3 (aq)
3
2+ −
Ca (NO3 ) 2 (aq) ⟶ Ca (aq) + 2 NO3 (aq)
Unlike these three ionic compounds, AgCl does not dissolve in water to a significant extent, as signified by its physical state
notation, s.
Explicitly representing all dissolved ions results in a complete ionic equation. In this particular case, the formulas for the dissolved
ionic compounds are replaced by formulas for their dissociated ions:
2+ − + − 2+ −
Ca (aq) + 2 Cl (aq) + 2 Ag (aq) + 2 NO3 (aq) ⟶ Ca (aq) + 2 NO3 (aq) + 2Ag Cl(s)
Examining this equation shows that two chemical species are present in identical form on both sides of the arrow, Ca2+(aq) and
(aq). These spectator ions—ions whose presence is required to maintain charge neutrality—are neither chemically nor
−
NO 3
physically changed by the process, and so they may be eliminated from the equation to yield a more succinct representation called a
net ionic equation:
2+ − + − 2+ −
Ca (aq) + 2 Cl (aq) + 2 Ag (aq) + 2 NO3 (aq) ⟶ Ca (aq) + 2 NO3 (aq) + 2AgCl(s)
− +
2 Cl (aq) + 2 Ag (aq) ⟶ 2AgCl(s)
Following the convention of using the smallest possible integers as coefficients, this equation is then written:

− +
Cl (aq) + Ag (aq) ⟶ AgCl(s)
This net ionic equation indicates that solid silver chloride may be produced from dissolved chloride and silver(I) ions, regardless of
the source of these ions. These molecular and complete ionic equations provide additional information, namely, the ionic
compounds used as sources of Cl− and Ag+.
4.2.0.1: Example 4.2

4.2.0.0.1: Ionic and Molecular Equations
When carbon dioxide is dissolved in an aqueous solution of sodium hydroxide, the mixture reacts to yield aqueous sodium
carbonate and liquid water. Write balanced molecular, complete ionic, and net ionic equations for this process.
4.2.0.0.2: Solution
Begin by identifying formulas for the reactants and products and arranging them properly in chemical equation form:
CO2 (aq) + NaOH(aq) ⟶ Na2 CO3 (aq) + H2 O(l) (unbalanced)
Balance is achieved easily in this case by changing the coefficient for NaOH to 2, resulting in the molecular equation for this
reaction:
CO2 (aq) + 2NaOH(aq) ⟶ Na2 CO3 (aq) + H2 O(l)
The two dissolved ionic compounds, NaOH and Na2CO3, can be represented as dissociated ions to yield the complete ionic
equation:
+ − + 2−
CO2 (aq) + 2 Na (aq) + 2 OH (aq) ⟶ 2 Na (aq) + CO3 (aq) + H2 O(l)
Finally, identify the spectator ion(s), in this case Na+(aq), and remove it from each side of the equation to generate the net ionic
equation:
+ − + 2−
CO2 (aq) + 2 Na (aq) + 2 OH (aq) ⟶ 2 Na (aq) + CO3 (aq) + H2 O(l)
− 2−
CO2 (aq) + 2 OH (aq) ⟶ CO3 (aq) + H2 O(l)

Diatomic chlorine and sodium hydroxide (lye) are commodity chemicals produced in large quantities, along with diatomic
hydrogen, via the electrolysis of brine, according to the following unbalanced equation:
electricity
NaCl(aq) + H2 O(l) −−−−−→ NaOH(aq) + H2 (g) + Cl2 (g)
Write balanced molecular, complete ionic, and net ionic equations for this process.
4.2.0.1: Answer:
2NaCl(aq) + 2 H2 O(l) ⟶ 2NaOH (aq) + H2 (g) + Cl2 (g) (molecular)
+ − + −
2 Na (aq) + 2 Cl (aq) + 2 H2 O(l) ⟶ 2 Na (aq) + 2 OH (aq) + H2 (g) + Cl2 (g) (complete ionic)
− −
2 Cl (aq) + 2 H2 O(l) ⟶ 2 OH (aq) + H2 (g) + Cl2 (g) (net ionic)
This page titled 4.2: Writing and Balancing Chemical Equations is shared under a CC BY 4.0 license and was authored, remixed, and/or curated
by OpenStax via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon
request.


Define three common types of chemical reactions (precipitation, acid-base, and oxidation-reduction)
Classify chemical reactions as one of these three types given appropriate descriptions or chemical equations
Identify common acids and bases
Predict the solubility of common inorganic compounds by using solubility rules
Compute the oxidation states for elements in compounds
Humans interact with one another in various and complex ways, and we classify these interactions according to common patterns
of behavior. When two humans exchange information, we say they are communicating. When they exchange blows with their fists
or feet, we say they are fighting. Faced with a wide range of varied interactions between chemical substances, scientists have
likewise found it convenient (or even necessary) to classify chemical interactions by identifying common patterns of reactivity.
This module will provide an introduction to three of the most prevalent types of chemical reactions: precipitation, acid-base, and
oxidation-reduction.
4.3.0.1: Precipitation Reactions and Solubility Rules

A precipitation reaction is one in which dissolved substances react to form one (or more) solid products. Many reactions of this
type involve the exchange of ions between ionic compounds in aqueous solution and are sometimes referred to as double
displacement, double replacement, or metathesis reactions. These reactions are common in nature and are responsible for the
formation of coral reefs in ocean waters and kidney stones in animals. They are used widely in industry for production of a number
of commodity and specialty chemicals. Precipitation reactions also play a central role in many chemical analysis techniques,
including spot tests used to identify metal ions and gravimetric methods for determining the composition of matter (see the last
module of this chapter).
The extent to which a substance may be dissolved in water, or any solvent, is quantitatively expressed as its solubility, defined as
the maximum concentration of a substance that can be achieved under specified conditions. Substances with relatively large
solubilities are said to be soluble. A substance will precipitate when solution conditions are such that its concentration exceeds its
solubility. Substances with relatively low solubilities are said to be insoluble, and these are the substances that readily precipitate
from solution. More information on these important concepts is provided in a later chapter on solutions. For purposes of predicting
the identities of solids formed by precipitation reactions, one may simply refer to patterns of solubility that have been observed for
many ionic compounds (Table 4.1).
Soluble Ionic Compounds contain these ions exceptions
NH4+ none
group I cations:
Li+
Na+
K+
Rb+
Cs+
Cl- compounds with Ag+, Hg22+, and Pb2+

Br-
I-
F- compounds with group 2 metal cations, Pb2+, and Fe3+
C2H3O2- none
HCO3-
NO3-
ClO3-
SO42- compounds with Ag+, Ba2+, Ca2+, Hg22+, Pb2+ and Sr2+
Insoluble Ionic Compounds contain these ions exceptions
CO32- compounds with group 1 cations and NH4+

CrO42-
PO43-
S2-
OH- compounds with group 1 cations and Ba2+
Table 4.1
A vivid example of precipitation is observed when solutions of potassium iodide and lead nitrate are mixed, resulting in the
formation of solid lead iodide:
2KI(aq) + Pb(NO3 )2 (aq) ⟶ PbI 2 (s) + 2 KNO 3 (aq)
This observation is consistent with the solubility guidelines: The only insoluble compound among all those involved is lead iodide,
one of the exceptions to the general solubility of iodide salts.
The net ionic equation representing this reaction is:
2+ −
Pb (aq) + 2 I (aq) ⟶ PbI 2 (s)
Lead iodide is a bright yellow solid that was formerly used as an artist’s pigment known as iodine yellow (Figure 4.4). The
properties of pure PbI2 crystals make them useful for fabrication of X-ray and gamma ray detectors.
Figure 4.4 A precipitate of PbI2 forms when solutions containing Pb2+ and I− are mixed. (credit: Der Kreole/Wikimedia Commons)
The solubility guidelines in Table 4.1 may be used to predict whether a precipitation reaction will occur when solutions of soluble
ionic compounds are mixed together. One merely needs to identify all the ions present in the solution and then consider if possible
cation/anion pairing could result in an insoluble compound. For example, mixing solutions of silver nitrate and sodium chloride
will yield a solution containing Ag+, NO , Na+, and Cl− ions. Aside from the two ionic compounds originally present in the
3
−
solutions, AgNO3 and NaCl, two additional ionic compounds may be derived from this collection of ions: NaNO3 and AgCl. The
solubility guidelines indicate all nitrate salts are soluble but that AgCl is one of insoluble. A precipitation reaction, therefore, is
predicted to occur, as described by the following equations:
4.3.0.1: Example 4.3

4.3.0.0.1: Predicting Precipitation Reactions
Predict the result of mixing reasonably concentrated solutions of the following ionic compounds. If precipitation is expected,
write a balanced net ionic equation for the reaction.
(a) potassium sulfate and barium nitrate
(b) lithium chloride and silver acetate
(c) lead nitrate and ammonium carbonate
4.3.0.0.2: Solution
(a) The two possible products for this combination are KNO3 and BaSO4. The solubility guidelines indicate BaSO4 is
insoluble, and so a precipitation reaction is expected. The net ionic equation for this reaction, derived in the manner detailed in
the previous module, is
2+ 2−
Ba (aq) + SO (aq) ⟶ BaSO 4 (s)
4
(b) The two possible products for this combination are LiC2H3O2 and AgCl. The solubility guidelines indicate AgCl is
+ −
Ag (aq) + Cl (aq) ⟶ AgCl(s)
(c) The two possible products for this combination are PbCO3 and NH4NO3. The solubility guidelines indicate PbCO3 is
2+ 2−
Pb (aq) + CO3 (aq) ⟶ PbCO3 (s)

Which solution could be used to precipitate the barium ion, Ba2+, in a water sample: sodium chloride, sodium hydroxide, or
sodium sulfate? What is the formula for the expected precipitate?
4.3.0.1: Answer:
sodium sulfate, BaSO4
4.3.0.1: Acid-Base Reactions

An acid-base reaction is one in which a hydrogen ion, H+, is transferred from one chemical species to another. Such reactions are of
central importance to numerous natural and technological processes, ranging from the chemical transformations that take place
within cells and the lakes and oceans, to the industrial-scale production of fertilizers, pharmaceuticals, and other substances
essential to society. The subject of acid-base chemistry, therefore, is worthy of thorough discussion, and a full chapter is devoted to
this topic later in the text.
For purposes of this brief introduction, we will consider only the more common types of acid-base reactions that take place in
aqueous solutions. In this context, an acid is a substance that will dissolve in water to yield hydronium ions, H3O+. As an example,
consider the equation shown here:
− +
HCl(aq) + H2 O(aq) ⟶ Cl (aq) + H3 O (aq)
The process represented by this equation confirms that hydrogen chloride is an acid. When dissolved in water, H3O+ ions are
produced by a chemical reaction in which H+ ions are transferred from HCl molecules to H2O molecules (Figure 4.5).
Figure 4.5 When hydrogen chloride gas dissolves in water, (a) it reacts as an acid, transferring protons to water molecules to yield
(b) hydronium ions (and solvated chloride ions).
The nature of HCl is such that its reaction with water as just described is essentially 100% efficient: Virtually every HCl molecule
that dissolves in water will undergo this reaction. Acids that completely react in this fashion are called strong acids, and HCl is one
among just a handful of common acid compounds that are classified as strong (Table 4.2). A far greater number of compounds
behave as weak acids and only partially react with water, leaving a large majority of dissolved molecules in their original form and
generating a relatively small amount of hydronium ions. Weak acids are commonly encountered in nature, being the substances
partly responsible for the tangy taste of citrus fruits, the stinging sensation of insect bites, and the unpleasant smells associated with
body odor. A familiar example of a weak acid is acetic acid, the main ingredient in food vinegars:
− +
CH3 CO2 H(aq) + H2 O(l) ⇌ CH3 CO2 (aq) + H3 O (aq)
When dissolved in water under typical conditions, only about 1% of acetic acid molecules are present in the ionized form,
CH CO
3 2 (Figure 4.6). (The use of a double-arrow in the equation above denotes the partial reaction aspect of this process, a
−
concept addressed fully in the chapters on chemical equilibrium.)
Figure 4.6 (a) Fruits such as oranges, lemons, and grapefruit contain the weak acid citric acid. (b) Vinegars contain the weak acid
acetic acid. (credit a: modification of work by Scott Bauer; credit b: modification of work by Brücke-Osteuropa/Wikimedia
Commons)
Common Strong Acids
Compound Formula Name in Aqueous Solution
HBr hydrobromic acid
HCl hydrochloric acid
HI hydroiodic acid
HNO3 nitric acid
HClO4 perchloric acid
Compound Formula Name in Aqueous Solution
H2SO4 sulfuric acid
Table 4.2
A base is a substance that will dissolve in water to yield hydroxide ions, OH−. The most common bases are ionic compounds
composed of alkali or alkaline earth metal cations (groups 1 and 2) combined with the hydroxide ion—for example, NaOH and
Ca(OH)2. Unlike the acid compounds discussed previously, these compounds do not react chemically with water; instead they
dissolve and dissociate, releasing hydroxide ions directly into the solution. For example, KOH and Ba(OH)2 dissolve in water and
dissociate completely to produce cations (K+ and Ba2+, respectively) and hydroxide ions, OH−. These bases, along with other
hydroxides that completely dissociate in water, are considered strong bases.
Consider as an example the dissolution of lye (sodium hydroxide) in water:
+ −
NaOH(s) ⟶ Na (aq) + OH (aq)
This equation confirms that sodium hydroxide is a base. When dissolved in water, NaOH dissociates to yield Na+ and OH− ions.
This is also true for any other ionic compound containing hydroxide ions. Since the dissociation process is essentially complete
when ionic compounds dissolve in water under typical conditions, NaOH and other ionic hydroxides are all classified as strong
bases.
Unlike ionic hydroxides, some compounds produce hydroxide ions when dissolved by chemically reacting with water molecules. In
all cases, these compounds react only partially and so are classified as weak bases. These types of compounds are also abundant in
nature and important commodities in various technologies. For example, global production of the weak base ammonia is typically
well over 100 metric tons annually, being widely used as an agricultural fertilizer, a raw material for chemical synthesis of other
compounds, and an active ingredient in household cleaners (Figure 4.7). When dissolved in water, ammonia reacts partially to yield
hydroxide ions, as shown here:
+ −
NH3 (aq) + H2 O(l) ⇌ NH4 (aq) + OH (aq)
This is, by definition, an acid-base reaction, in this case involving the transfer of H+ ions from water molecules to ammonia
molecules. Under typical conditions, only about 1% of the dissolved ammonia is present as NH ions. 4
+
Figure 4.7 Ammonia is a weak base used in a variety of applications. (a) Pure ammonia is commonly applied as an agricultural
fertilizer. (b) Dilute solutions of ammonia are effective household cleansers. (credit a: modification of work by National Resources
Conservation Service; credit b: modification of work by pat00139)
A neutralization reaction is a specific type of acid-base reaction in which the reactants are an acid and a base (but not water), and
the products are often a salt and water
acid + base ⟶ salt + water
To illustrate a neutralization reaction, consider what happens when a typical antacid such as milk of magnesia (an aqueous
suspension of solid Mg(OH)2) is ingested to ease symptoms associated with excess stomach acid (HCl):
Mg (OH) 2 (s) + 2HCl(aq) ⟶ MgCl2 (aq) + 2 H2 O(l).
Note that in addition to water, this reaction produces a salt, magnesium chloride.
4.3.0.1: Example 4.4

4.3.0.0.1: Writing Equations for Acid-Base Reactions
Write balanced chemical equations for the acid-base reactions described here:
(a) the weak acid hydrogen hypochlorite reacts with water
(b) a solution of barium hydroxide is neutralized with a solution of nitric acid
4.3.0.0.2: Solution
(a) The two reactants are provided, HOCl and H2O. Since the substance is reported to be an acid, its reaction with water will
involve the transfer of H+ from HOCl to H2O to generate hydronium ions, H3O+ and hypochlorite ions, OCl−.
− +
HOCl(aq) + H2 O(l) ⇌ OCl (aq) + H3 O (aq)
A double-arrow is appropriate in this equation because it indicates the HOCl is a weak acid that has not reacted completely.
(b) The two reactants are provided, Ba(OH)2 and HNO3. Since this is a neutralization reaction, the two products will be water
and a salt composed of the cation of the ionic hydroxide (Ba2+) and the anion generated when the acid transfers its hydrogen
ion (NO ).
3
−
Ba (OH) (aq) + 2 HNO3 (aq) ⟶ Ba (NO3 ) 2 (aq) + 2 H2 O(l)

2

Write the net ionic equation representing the neutralization of any strong acid with an ionic hydroxide. (Hint: Consider the ions
produced when a strong acid is dissolved in water.)
4.3.0.1: Answer:
+ −
H3 O (aq) + OH (aq) ⟶ 2 H2 O(l)

4.3.0.0.4: Stomach Antacids
Our stomachs contain a solution of roughly 0.03 M HCl, which helps us digest the food we eat. The burning sensation
associated with heartburn is a result of the acid of the stomach leaking through the muscular valve at the top of the stomach
into the lower reaches of the esophagus. The lining of the esophagus is not protected from the corrosive effects of stomach acid
the way the lining of the stomach is, and the results can be very painful. When we have heartburn, it feels better if we reduce
the excess acid in the esophagus by taking an antacid. As you may have guessed, antacids are bases. One of the most common
antacids is calcium carbonate, CaCO3. The reaction,
CaCO3 (s) + 2HCl(aq) ⇌ CaCl2 (aq) + H2 O(l) + CO2 (g)
not only neutralizes stomach acid, it also produces CO2(g), which may result in a satisfying belch.
Milk of Magnesia is a suspension of the sparingly soluble base magnesium hydroxide, Mg(OH)2. It works according to the
reaction:
2+ −
Mg (OH) 2 (s) ⇌ Mg (aq) + 2 OH (aq)
The hydroxide ions generated in this equilibrium then go on to react with the hydronium ions from the stomach acid, so that:
+ −
H3 O + OH ⇌ 2 H2 O(l)
This reaction does not produce carbon dioxide, but magnesium-containing antacids can have a laxative effect. Several antacids
have aluminum hydroxide, Al(OH)3, as an active ingredient. The aluminum hydroxide tends to cause constipation, and some
antacids use aluminum hydroxide in concert with magnesium hydroxide to balance the side effects of the two substances.
4.3.0.0.5: Culinary Aspects of Chemistry
Examples of acid-base chemistry are abundant in the culinary world. One example is the use of baking soda, or sodium
bicarbonate in baking. NaHCO3 is a base. When it reacts with an acid such as lemon juice, buttermilk, or sour cream in a
batter, bubbles of carbon dioxide gas are formed from decomposition of the resulting carbonic acid, and the batter “rises.”
Baking powder is a combination of sodium bicarbonate, and one or more acid salts that react when the two chemicals come in
contact with water in the batter.
Many people like to put lemon juice or vinegar, both of which are acids, on cooked fish (Figure 4.8). It turns out that fish have
volatile amines (bases) in their systems, which are neutralized by the acids to yield involatile ammonium salts. This reduces the
odor of the fish, and also adds a “sour” taste that we seem to enjoy.
Figure 4.8 A neutralization reaction takes place between citric acid in lemons or acetic acid in vinegar, and the bases in the
flesh of fish.
Pickling is a method used to preserve vegetables using a naturally produced acidic environment. The vegetable, such as a
cucumber, is placed in a sealed jar submerged in a brine solution. The brine solution favors the growth of beneficial bacteria
and suppresses the growth of harmful bacteria. The beneficial bacteria feed on starches in the cucumber and produce lactic acid
as a waste product in a process called fermentation. The lactic acid eventually increases the acidity of the brine to a level that
kills any harmful bacteria, which require a basic environment. Without the harmful bacteria consuming the cucumbers they are
able to last much longer than if they were unprotected. A byproduct of the pickling process changes the flavor of the vegetables
with the acid making them taste sour.

Explore the microscopic view of strong and weak acids and bases.
4.3.0.1: Oxidation-Reduction Reactions

Earth’s atmosphere contains about 20% molecular oxygen, O2, a chemically reactive gas that plays an essential role in the
metabolism of aerobic organisms and in many environmental processes that shape the world. The term oxidation was originally
used to describe chemical reactions involving O2, but its meaning has evolved to refer to a broad and important reaction class
known as oxidation-reduction (redox) reactions. A few examples of such reactions will be used to develop a clear picture of this
classification.
Some redox reactions involve the transfer of electrons between reactant species to yield ionic products, such as the reaction
between sodium and chlorine to yield sodium chloride:
2Na(s) + Cl2 (g) ⟶ 2NaCl(s)
It is helpful to view the process with regard to each individual reactant, that is, to represent the fate of each reactant in the form of
an equation called a half-reaction:
+ −
2Na(s) ⟶ 2 Na (s) + 2 e
− −
Cl2 (g) + 2 e ⟶ 2 Cl (s)
These equations show that Na atoms lose electrons while Cl atoms (in the Cl2 molecule) gain electrons, the “s” subscripts for the
resulting ions signifying they are present in the form of a solid ionic compound. For redox reactions of this sort, the loss and gain
of electrons define the complementary processes that occur:
oxidation = loss of electrons
reduction = gain of electrons
In this reaction, then, sodium is oxidized and chlorine undergoes reduction. Viewed from a more active perspective, sodium
functions as a reducing agent (reductant), since it provides electrons to (or reduces) chlorine. Likewise, chlorine functions as an
oxidizing agent (oxidant), as it effectively removes electrons from (oxidizes) sodium.
reducing agent = species that is oxidized
oxidizing agent = species that is reduced
Some redox processes, however, do not involve the transfer of electrons. Consider, for example, a reaction similar to the one
yielding NaCl:
H2 (g) + Cl2 (g) ⟶ 2HCl(g)
The product of this reaction is a covalent compound, so transfer of electrons in the explicit sense is not involved. To clarify the
similarity of this reaction to the previous one and permit an unambiguous definition of redox reactions, a property called oxidation
number has been defined. The oxidation number (or oxidation state) of an element in a compound is the charge its atoms would
possess if the compound were ionic. The following guidelines are used to assign oxidation numbers to each element in a molecule
or ion.
1. The oxidation number of an atom in an elemental substance is zero.
2. The oxidation number of a monatomic ion is equal to the ion’s charge.
3. Oxidation numbers for common nonmetals are usually assigned as follows:
Hydrogen: +1 when combined with nonmetals, −1 when combined with metals
Oxygen: −2 in most compounds, sometimes −1 (so-called peroxides, O ), very rarely − (so-called superoxides, O ),
2
2− 1
2
2
−
positive values when combined with F (values vary)

Halogens: −1 for F always, −1 for other halogens except when combined with oxygen or other halogens (positive oxidation
numbers in these cases, varying values)
4. The sum of oxidation numbers for all atoms in a molecule or polyatomic ion equals the charge on the molecule or ion.
Note: The proper convention for reporting charge is to write the number first, followed by the sign (e.g., 2+), while oxidation
number is written with the reversed sequence, sign followed by number (e.g., +2). This convention aims to emphasize the
distinction between these two related properties.
4.3.0.1: Example 4.5

4.3.0.0.1: Assigning Oxidation Numbers
Follow the guidelines in this section of the text to assign oxidation numbers to all the elements in the following species:
(a) H2S
(b) SO 3
2−
(c) Na2SO4
4.3.0.0.2: Solution
(a) According to guideline 3, the oxidation number for H is +1.
Using this oxidation number and the compound’s formula, guideline 4 may then be used to calculate the oxidation number for
sulfur:
charge on H2 S = 0 = (2 × +1) + (1 × x)
x = 0 − (2 × +1) = −2
(b) Guideline 3 suggests the oxidation number for oxygen is −2.

Using this oxidation number and the ion’s formula, guideline 4 may then be used to calculate the oxidation number for sulfur:
2−
charge on SO 3 = −2 = (3 × −2) + (1 × x)
x = −2 − (3 × −2) = +4
(c) For ionic compounds, it’s convenient to assign oxidation numbers for the cation and anion separately.
According to guideline 2, the oxidation number for sodium is +1.
Assuming the usual oxidation number for oxygen (−2 per guideline 3), the oxidation number for sulfur is calculated as directed
by guideline 4:
2−
charge on SO 4 = −2 = (4 × −2) + (1 × x)
x = −2 − (4 × −2) = +6

Assign oxidation states to the elements whose atoms are underlined in each of the following compounds or ions:
(a) KNO3
(b) AlH3
(c) –
NH
–
4
+
(d) H 2 P O4
−
–
–
4.3.0.1: Answer:
(a) N, +5; (b) Al, +3; (c) N, −3; (d) P, +5
Using the oxidation number concept, an all-inclusive definition of redox reaction has been established. Oxidation-reduction (redox)
reactions are those in which one or more elements involved undergo a change in oxidation number. (While the vast majority of
redox reactions involve changes in oxidation number for two or more elements, a few interesting exceptions to this rule do exist
Example 4.6.) Definitions for the complementary processes of this reaction class are correspondingly revised as shown here:
oxidation = increase in oxidation number
reduction = decrease in oxidation number
Returning to the reactions used to introduce this topic, they may now both be identified as redox processes. In the reaction between
sodium and chlorine to yield sodium chloride, sodium is oxidized (its oxidation number increases from 0 in Na to +1 in NaCl) and
chlorine is reduced (its oxidation number decreases from 0 in Cl2 to −1 in NaCl). In the reaction between molecular hydrogen and
chlorine, hydrogen is oxidized (its oxidation number increases from 0 in H2 to +1 in HCl) and chlorine is reduced (its oxidation
number decreases from 0 in Cl2 to −1 in HCl).
Several subclasses of redox reactions are recognized, including combustion reactions in which the reductant (also called a fuel) and
oxidant (often, but not necessarily, molecular oxygen) react vigorously and produce significant amounts of heat, and often light, in
the form of a flame. Solid rocket-fuel reactions such as the one depicted in Figure 4.1 are combustion processes. A typical
propellant reaction in which solid aluminum is oxidized by ammonium perchlorate is represented by this equation:
10Al(s) + 6 NH4 ClO4 (s) ⟶ 4 Al2 O3 (s) + 2 AlCl3 (s) + 12 H2 O(g) + 3 N2 (g)

Watch a brief video showing the test firing of a small-scale, prototype, hybrid rocket engine planned for use in the new Space
Launch System being developed by NASA. The first engines firing at
3 s (green flame) use a liquid fuel/oxidant mixture, and the second, more powerful engines firing at 4 s (yellow flame) use a
solid mixture.
Single-displacement (replacement) reactions are redox reactions in which an ion in solution is displaced (or replaced) via the
oxidation of a metallic element. One common example of this type of reaction is the acid oxidation of certain metals:
Zn(s) + 2HCl (aq) ⟶ ZnCl2 (aq) + H2 (g)
Metallic elements may also be oxidized by solutions of other metal salts; for example:
Cu(s) + 2 AgNO (aq) ⟶ Cu (NO3 ) (aq) + 2Ag(s)
3 2
This reaction may be observed by placing copper wire in a solution containing a dissolved silver salt. Silver ions in solution are
reduced to elemental silver at the surface of the copper wire, and the resulting Cu2+ ions dissolve in the solution to yield a
characteristic blue color (Figure 4.9).
Figure 4.9 (a) A copper wire is shown next to a solution containing silver(I) ions. (b) Displacement of dissolved silver ions by
copper ions results in (c) accumulation of gray-colored silver metal on the wire and development of a blue color in the solution, due
to dissolved copper ions. (credit: modification of work by Mark Ott)
4.3.0.1: Example 4.6

4.3.0.0.4: Describing Redox Reactions
Identify which equations represent redox reactions, providing a name for the reaction if appropriate. For those reactions
identified as redox, name the oxidant and reductant.
(a) ZnCO 3 (s) ⟶ ZnO(s) + CO2 (g)
(b) 2Ga (l) + 3Br 2 (l) ⟶ 2 GaBr 3 (s)
(c) 2H 2 O2 (aq) ⟶ 2 H2 O (l) + O2 (g)
(d) BaCl 2 (aq) + K2 SO 4 (aq) ⟶ BaSO 4 (s) + 2KCl (aq)
(e) C2 H4 (g) + 3 O2 (g) ⟶ 2 CO2 (g) + 2 H2 O (l)
4.3.0.0.5: Solution
Redox reactions are identified per definition if one or more elements undergo a change in oxidation number.
(a) This is not a redox reaction, since oxidation numbers remain unchanged for all elements.
(b) This is a redox reaction. Gallium is oxidized, its oxidation number increasing from 0 in Ga(l) to +3 in GaBr3(s). The
reducing agent is Ga(l). Bromine is reduced, its oxidation number decreasing from 0 in Br2(l) to −1 in GaBr3(s). The oxidizing
agent is Br2(l).
(c) This is a redox reaction. It is a particularly interesting process, as it involves the same element, oxygen, undergoing both
oxidation and reduction (a so-called disproportionation reaction). Oxygen is oxidized, its oxidation number increasing from −1
in H2O2(aq) to 0 in O2(g). Oxygen is also reduced, its oxidation number decreasing from −1 in H2O2(aq) to −2 in H2O(l). For
disproportionation reactions, the same substance functions as an oxidant and a reductant.
(d) This is not a redox reaction, since oxidation numbers remain unchanged for all elements.
(e) This is a redox reaction (combustion). Carbon is oxidized, its oxidation number increasing from −2 in C2H4(g) to +4 in
CO2(g). The reducing agent (fuel) is C2H4(g). Oxygen is reduced, its oxidation number decreasing from 0 in O2(g) to −2 in
H2O(l). The oxidizing agent is O2(g).
This equation describes the production of tin(II) chloride:
Sn(s) + 2HCl(g) ⟶ SnCl 2 (s) + H2 (g)
Is this a redox reaction? If so, provide a more specific name for the reaction if appropriate, and identify the oxidant and
reductant.
4.3.0.1: Answer:
Yes, a single-replacement reaction. Sn(s)is the reductant, HCl(g) is the oxidant.
4.3.0.0.7: Balancing Redox Reactions via the Half-Reaction Method

Redox reactions that take place in aqueous media often involve water, hydronium ions, and hydroxide ions as reactants or products.
Although these species are not oxidized or reduced, they do participate in chemical change in other ways (e.g., by providing the
elements required to form oxyanions). Equations representing these reactions are sometimes very difficult to balance by inspection,
so systematic approaches have been developed to assist in the process. One very useful approach is to use the method of half-
reactions, which involves the following steps:
1. Write the two half-reactions representing the redox process.
2. Balance all elements except oxygen and hydrogen.
3. Balance oxygen atoms by adding H2O molecules.
4. Balance hydrogen atoms by adding H+ ions.
5. Balance charge by adding electrons.
6. If necessary, multiply each half-reaction’s coefficients by the smallest possible integers to yield equal numbers of electrons in
each.
7. Add the balanced half-reactions together and simplify by removing species that appear on both sides of the equation.
8. For reactions occurring in basic media (excess hydroxide ions), carry out these additional steps:
1. Add OH− ions to both sides of the equation in numbers equal to the number of H+ ions.
2. On the side of the equation containing both H+ and OH− ions, combine these ions to yield water molecules.
3. Simplify the equation by removing any redundant water molecules.
9. Finally, check to see that both the number of atoms and the total charges1 are balanced.
4.3.0.1: Example 4.7

4.3.0.0.8: Balancing Redox Reactions in Acidic Solution
Write a balanced equation for the reaction between dichromate ion and iron(II) to yield iron(III) and chromium(III) in acidic
solution.
2− 2+ 3+ 3+
Cr2 O7 + Fe ⟶ Cr + Fe
4.3.0.0.9: Solution
1. Step 1.
Write the two half-reactions.
Each half-reaction will contain one reactant and one product with one element in common.
2+ 3+
Fe ⟶ Fe
2− 3+
Cr2 O7 ⟶ Cr
2. Step 2.
Balance all elements except oxygen and hydrogen. The iron half-reaction is already balanced, but the chromium half-
reaction shows two Cr atoms on the left and one Cr atom on the right. Changing the coefficient on the right side of the
equation to 2 achieves balance with regard to Cr atoms.
2+ 3+
Fe ⟶ Fe
2− 3+
Cr2 O7 ⟶ 2 Cr
3. Step 3.
Balance oxygen atoms by adding H2O molecules. The iron half-reaction does not contain O atoms. The chromium half-
reaction shows seven O atoms on the left and none on the right, so seven water molecules are added to the right side.
2+ 3+
Fe ⟶ Fe
2− 3+
Cr2 O7 ⟶ 2 Cr + 7 H2 O
4. Step 4.
Balance hydrogen atoms by adding H+ions. The iron half-reaction does not contain H atoms. The chromium half-reaction
shows 14 H atoms on the right and none on the left, so 14 hydrogen ions are added to the left side.
2+ 3+
Fe ⟶ Fe
2− + 3+
Cr2 O7 + 14 H ⟶ 2 Cr + 7 H2 O
5. Step 5.
Balance charge by adding electrons. The iron half-reaction shows a total charge of 2+ on the left side (1 Fe2+ ion) and 3+
on the right side (1 Fe3+ ion). Adding one electron to the right side brings that side’s total charge to (3+) + (1−) = 2+, and
charge balance is achieved.
The chromium half-reaction shows a total charge of (1 ×
2−) + (14 × 1+) = 12+ on the left side (1 Cr O
2
ion and 14 H+ ions). The total charge on the right side is (2 × 3+) = 6 +
7
2−
3+
(2 Cr ions). Adding six electrons to the left side will bring that side’s total charge to (12+ + 6−) = 6+, and charge balance
is achieved.
2+ 3+ −
Fe ⟶ Fe +e
2− + − 3+
Cr2 O7 + 14 H + 6e ⟶ 2 Cr + 7 H2 O
6. Step 6.
Multiply the two half-reactions so the number of electrons in one reaction equals the number of electrons in the other
reaction. To be consistent with mass conservation, and the idea that redox reactions involve the transfer (not creation or
destruction) of electrons, the iron half-reaction’s coefficient must be multiplied by 6.
2+ 3+ −
6Fe ⟶ 6 Fe + 6e
2− − + 3+
Cr2 O7 + 6e + 14 H ⟶ 2 Cr + 7 H2 O
7. Step 7.
Add the balanced half-reactions and cancel species that appear on both sides of the equation.
2+ 2− − + 3+ − 3+
6 Fe + Cr2 O7 + 6e + 14 H ⟶ 6 Fe + 6e + 2 Cr + 7 H2 O
Only the six electrons are redundant species. Removing them from each side of the equation yields the simplified, balanced
equation here:
2+ 2− + 3+ 3+
6 Fe + Cr2 O7 + 14 H ⟶ 6 Fe + 2 Cr + 7 H2 O
A final check of atom and charge balance confirms the equation is balanced.
Reactants Products
Fe 6 6
Cr 2 2
O 7 7
H 14 14
charge 24+ 24+

In basic solution, molecular chlorine, Cl2, reacts with hydroxide ions, OH−, to yield chloride ions, Cl−. and chlorate ions,
ClO3−. HINT: This is a disproportionation reaction in which the element chlorine is both oxidized and reduced. Write a
balanced equation for this reaction.
4.3.0.1: Answer:
− − −
3 Cl2 (aq) + 6 OH (aq) ⟶ 5 Cl (aq) + ClO3 (aq) + 3 H2 O(l)
4.3.0.1: Footnotes
1The requirement of “charge balance” is just a specific type of “mass balance” in which the species in question are electrons.
An equation must represent equal numbers of electrons on the reactant and product sides, and so both atoms and charges must
be balanced.
4.3: Classifying Chemical Reactions is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by LibreTexts.

Explain the concept of stoichiometry as it pertains to chemical reactions
Use balanced chemical equations to derive stoichiometric factors relating amounts of reactants and products
Perform stoichiometric calculations involving mass, moles, and solution molarity
A balanced chemical equation provides a great deal of information in a very succinct format. Chemical formulas provide the
identities of the reactants and products involved in the chemical change, allowing classification of the reaction. Coefficients
provide the relative numbers of these chemical species, allowing a quantitative assessment of the relationships between the
amounts of substances consumed and produced by the reaction. These quantitative relationships are known as the reaction’s
stoichiometry, a term derived from the Greek words stoicheion (meaning “element”) and metron (meaning “measure”). In this
module, the use of balanced chemical equations for various stoichiometric applications is explored.
The general approach to using stoichiometric relationships is similar in concept to the way people go about many common
activities. Food preparation, for example, offers an appropriate comparison. A recipe for making eight pancakes calls for 1 cup
pancake mix, cup milk, and one egg. The “equation” representing the preparation of pancakes per this recipe is
3
3
1 cup mix + cup milk + 1 egg ⟶ 8 pancakes
4
If two dozen pancakes are needed for a big family breakfast, the ingredient amounts must be increased proportionally according to
the amounts given in the recipe. For example, the number of eggs required to make 24 pancakes is
1 egg
24 pancakes × = 3 eggs
8 pancakes
Balanced chemical equations are used in much the same fashion to determine the amount of one reactant required to react with a
given amount of another reactant, or to yield a given amount of product, and so forth. The coefficients in the balanced equation are
used to derive stoichiometric factors that permit computation of the desired quantity. To illustrate this idea, consider the production
of ammonia by reaction of hydrogen and nitrogen:
N2 (g) + 3 H2 (g) ⟶ 2 NH3 (g)
This equation shows ammonia molecules are produced from hydrogen molecules in a 2:3 ratio, and stoichiometric factors may be
derived using any amount (number) unit:
2 NH3 molecules 2 doz NH3 molecules 2 mol NH3 molecules
or or
3 H2 molecules 3 doz H2 molecules 3 mol H2 molecules
These stoichiometric factors can be used to compute the number of ammonia molecules produced from a given number of
hydrogen molecules, or the number of hydrogen molecules required to produce a given number of ammonia molecules. Similar
factors may be derived for any pair of substances in any chemical equation.
4.4.0.1: Example 4.8

4.4.0.0.1: Moles of Reactant Required in a Reaction
How many moles of I2 are required to react with 0.429 mol of Al according to the following equation (see Figure 4.10)?
2Al + 3 I2 ⟶ 2 AlI3

Figure 4.10 Aluminum and iodine react to produce aluminum iodide. The heat of the reaction vaporizes some of the solid
iodine as a purple vapor. (credit: modification of work by Mark Ott)
4.4.0.0.1: Solution
3 mol I2
Referring to the balanced chemical equation, the stoichiometric factor relating the two substances of interest is 2 mol Al
. The
molar amount of iodine is derived by multiplying the provided molar amount of aluminum by this factor:
3 mol I2
mol I2 = 0.429 mol Al ×
2 mol Al
= 0.644 mol I2

How many moles of Ca(OH)2 are required to react with 1.36 mol of H3PO4 to produce Ca3(PO4)2 according to the equation
3Ca (OH) + 2 H3 PO4 ⟶ Ca3 (PO4 ) + 6 H2 O?
2 2
4.4.0.1: Answer:
2.04 mol
4.4.0.1: Example 4.9

4.4.0.0.1: Number of Product Molecules Generated by a Reaction
How many carbon dioxide molecules are produced when 0.75 mol of propane is combusted according to this equation?
C3 H8 + 5 O2 ⟶ 3 CO2 + 4 H2 O
4.4.0.0.1: Solution
The approach here is the same as for Example 4.8, though the absolute number of molecules is requested, not the number of
moles of molecules. This will simply require use of the moles-to-numbers conversion factor, Avogadro’s number.
The balanced equation shows that carbon dioxide is produced from propane in a 3:1 ratio:
3 mol CO2
1 mol C3 H8
Using this stoichiometric factor, the provided molar amount of propane, and Avogadro’s number,

3 mol CO2 23
6.022 × 10 CO2 molecules
24
0.75 mol C3 H8 × × = 1.4 × 10 CO2 molecules
1 mol C3 H8 mol CO2

How many NH3 molecules are produced by the reaction of 4.0 mol of Ca(OH)2 according to the following equation:
(NH4 ) SO 4 + Ca (OH) ⟶ 2 NH3 + CaSO4 + 2 H2 O
2 2
4.4.0.1: Answer:
4.8 × 1024 NH3 molecules
These examples illustrate the ease with which the amounts of substances involved in a chemical reaction of known stoichiometry
may be related. Directly measuring numbers of atoms and molecules is, however, not an easy task, and the practical application of
stoichiometry requires that we use the more readily measured property of mass.
4.4.0.1: Example 4.10

4.4.0.0.1: Relating Masses of Reactants and Products
What mass of sodium hydroxide, NaOH, would be required to produce 16 g of the antacid milk of magnesia [magnesium
hydroxide, Mg(OH)2] by the following reaction?
MgCl2 (aq) + 2NaOH (aq) ⟶ Mg (OH) (s) + 2NaCl (aq)
2
4.4.0.0.1: Solution
The approach used previously in Example 4.8 and Example 4.9 is likewise used here; that is, we must derive an appropriate
stoichiometric factor from the balanced chemical equation and use it to relate the amounts of the two substances of interest. In
this case, however, masses (not molar amounts) are provided and requested, so additional steps of the sort learned in the
previous chapter are required. The calculations required are outlined in this flowchart:
1 mol Mg(OH) 2 mol NaOH

2 40.0 g NaOH
16 g Mg(OH) × × × = 22 g NaOH
2
58.3 g Mg(OH) 1 mol Mg(OH) mol NaOH

2 2

What mass of gallium oxide, Ga2O3, can be prepared from 29.0 g of gallium metal? The equation for the reaction is
4Ga + 3 O2 ⟶ 2 Ga 2 O3 .
4.4.0.1: Answer:
39.0 g

4.4.0.1: Example 4.11
4.4.0.0.1: Relating Masses of Reactants
What mass of oxygen gas, O2, from the air is consumed in the combustion of 702 g of octane, C8H18, one of the principal
components of gasoline?
2 C8 H18 + 25 O2 ⟶ 16 CO2 + 18 H2 O
4.4.0.0.1: Solution
The approach required here is the same as for the Example 4.10, differing only in that the provided and requested masses are
both for reactant species.
1 mol C8 H18 25 mol O2 32.00 g O2

3
702 g C8 H18 × × × = 2.46 × 10 g O2
114.23 g C8 H18 2 mol C8 H18 mol O2

What mass of CO is required to react with 25.13 g of Fe2O3 according to the equation Fe 2 O3 + 3CO ⟶ 2Fe + 3 CO2 ?
4.4.0.1: Answer:
13.22 g
These examples illustrate just a few instances of reaction stoichiometry calculations. Numerous variations on the beginning and
ending computational steps are possible depending upon what particular quantities are provided and sought (volumes, solution
concentrations, and so forth). Regardless of the details, all these calculations share a common essential component: the use of
stoichiometric factors derived from balanced chemical equations. Figure 4.11 provides a general outline of the various
computational steps associated with many reaction stoichiometry calculations.

Figure 4.11 The flowchart depicts the various computational steps involved in most reaction stoichiometry calculations.

4.4.0.0.1: Airbags
Airbags (Figure 4.12) are a safety feature provided in most automobiles since the 1990s. The effective operation of an airbag
requires that it be rapidly inflated with an appropriate amount (volume) of gas when the vehicle is involved in a collision. This
requirement is satisfied in many automotive airbag systems through use of explosive chemical reactions, one common choice
being the decomposition of sodium azide, NaN3. When sensors in the vehicle detect a collision, an electrical current is passed
through a carefully measured amount of NaN3 to initiate its decomposition:
2 NaN3 (s) ⟶ 3 N2 (g) + 2Na (s)
This reaction is very rapid, generating gaseous nitrogen that can deploy and fully inflate a typical airbag in a fraction of a
second (~0.03–0.1 s). Among many engineering considerations, the amount of sodium azide used must be appropriate for
generating enough nitrogen gas to fully inflate the air bag and ensure its proper function. For example, a small mass (~100 g)
of NaN3 will generate approximately 50 L of N2.

Figure 4.12 Airbags deploy upon impact to minimize serious injuries to passengers. (credit: Jon Seidman)
This page titled 4.4: Reaction Stoichiometry is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via


Explain the concepts of theoretical yield and limiting reactants/reagents.
Derive the theoretical yield for a reaction under specified conditions.
Calculate the percent yield for a reaction.
The relative amounts of reactants and products represented in a balanced chemical equation are often referred to as stoichiometric
amounts. All the exercises of the preceding module involved stoichiometric amounts of reactants. For example, when calculating
the amount of product generated from a given amount of reactant, it was assumed that any other reactants required were available
in stoichiometric amounts (or greater). In this module, more realistic situations are considered, in which reactants are not present in
stoichiometric amounts.
4.5.0.1: Limiting Reactant

Consider another food analogy, making grilled cheese sandwiches (Figure 4.13):
1 slice of cheese + 2 slices of bread ⟶ 1 sandwich
Stoichiometric amounts of sandwich ingredients for this recipe are bread and cheese slices in a 2:1 ratio. Provided with 28 slices of
bread and 11 slices of cheese, one may prepare 11 sandwiches per the provided recipe, using all the provided cheese and having six
slices of bread left over. In this scenario, the number of sandwiches prepared has been limited by the number of cheese slices, and
the bread slices have been provided in excess.
Figure 4.13 Sandwich making can illustrate the concepts of limiting and excess reactants.
Consider this concept now with regard to a chemical process, the reaction of hydrogen with chlorine to yield hydrogen chloride:
H2 (g) + Cl2 (g) ⟶ 2HCl (g)
The balanced equation shows the hydrogen and chlorine react in a 1:1 stoichiometric ratio. If these reactants are provided in any
other amounts, one of the reactants will nearly always be entirely consumed, thus limiting the amount of product that may be

generated. This substance is the limiting reactant, and the other substance is the excess reactant. Identifying the limiting and excess
reactants for a given situation requires computing the molar amounts of each reactant provided and comparing them to the
stoichiometric amounts represented in the balanced chemical equation. For example, imagine combining 3 moles of H2 and 2 moles
of Cl2. This represents a 3:2 (or 1.5:1) ratio of hydrogen to chlorine present for reaction, which is greater than the stoichiometric
ratio of 1:1. Hydrogen, therefore, is present in excess, and chlorine is the limiting reactant. Reaction of all the provided chlorine (2
mol) will consume 2 mol of the 3 mol of hydrogen provided, leaving 1 mol of hydrogen unreacted.
An alternative approach to identifying the limiting reactant involves comparing the amount of product expected for the complete
reaction of each reactant. Each reactant amount is used to separately calculate the amount of product that would be formed per the
reaction’s stoichiometry. The reactant yielding the lesser amount of product is the limiting reactant. For the example in the previous
paragraph, complete reaction of the hydrogen would yield
2 mol HCl
mol HCl produced = 3 mol H2 × = 6 mol HCl
1 mol H2
Complete reaction of the provided chlorine would produce

2 mol HCl
mol HCl produced = 2 mol Cl2 × = 4 mol HCl
1 mol Cl2
The chlorine will be completely consumed once 4 moles of HCl have been produced. Since enough hydrogen was provided to yield
6 moles of HCl, there will be unreacted hydrogen remaining once this reaction is complete. Chlorine, therefore, is the limiting
reactant and hydrogen is the excess reactant (Figure 4.14).
Figure 4.14 When H2 and Cl2 are combined in nonstoichiometric amounts, one of these reactants will limit the amount of HCl that
can be produced. This illustration shows a reaction in which hydrogen is present in excess and chlorine is the limiting reactant.

View this interactive simulation illustrating the concepts of limiting and excess reactants.
4.5.0.1: Example 4.12

4.5.0.0.1: Identifying the Limiting Reactant
Silicon nitride is a very hard, high-temperature-resistant ceramic used as a component of turbine blades in jet engines. It is
prepared according to the following equation:
3Si (s) + 2 N2 (g) ⟶ Si 3 N4 (s)
Which is the limiting reactant when 2.00 g of Si and 1.50 g of N2 react?

4.5.0.0.2: Solution
Compute the provided molar amounts of reactants, and then compare these amounts to the balanced equation to identify the
limiting reactant.
1 mol Si
mol Si = 2.00 g Si × = 0.0712 mol Si
28.09 g Si
1 mol N2
mol N2 = 1.50 g N2 × = 0.0535 mol N2
28.02 g N2
The provided Si:N2 molar ratio is:

0.0712 mol Si 1.33 mol Si
=
0.0535 mol N2 1 mol N2
The stoichiometric Si:N2 ratio is:

3 mol Si 1.5 mol Si
=
2 mol N2 1 mol N2
Comparing these ratios shows that Si is provided in a less-than-stoichiometric amount, and so is the limiting reactant.
Alternatively, compute the amount of product expected for complete reaction of each of the provided reactants. The 0.0712
moles of silicon would yield
1 mol Si 3 N4
mol Si 3 N4 produced = 0.0712 mol Si × = 0.0237 mol Si 3 N4
3 mol Si
while the 0.0535 moles of nitrogen would produce

1 mol Si 3 N4
mol Si 3 N4 produced = 0.0535 mol N2 × = 0.0268 mol Si 3 N4
2 mol N2
Since silicon yields the lesser amount of product, it is the limiting reactant.
Which is the limiting reactant when 5.00 g of H2 and 10.0 g of O2 react and form water?
4.5.0.1: Answer:
O2
4.5.0.1: Percent Yield

The amount of product that may be produced by a reaction under specified conditions, as calculated per the stoichiometry of an
appropriate balanced chemical equation, is called the theoretical yield of the reaction. In practice, the amount of product obtained is
called the actual yield, and it is often less than the theoretical yield for a number of reasons. Some reactions are inherently
inefficient, being accompanied by side reactions that generate other products. Others are, by nature, incomplete (consider the
partial reactions of weak acids and bases discussed earlier in this chapter). Some products are difficult to collect without some loss,
and so less than perfect recovery will reduce the actual yield. The extent to which a reaction’s theoretical yield is achieved is
commonly expressed as its percent yield:
actual yield
percent yield = × 100%
theoretical yield
Actual and theoretical yields may be expressed as masses or molar amounts (or any other appropriate property; e.g., volume, if the
product is a gas). As long as both yields are expressed using the same units, these units will cancel when percent yield is calculated.
4.5.0.1: Example 4.13

4.5.0.0.1: Calculation of Percent Yield
Upon reaction of 1.274 g of copper sulfate with excess zinc metal, 0.392 g copper metal was obtained according to the
equation:
CuSO 4 (aq) + Zn (s) ⟶ Cu (s) + ZnSO 4 (aq)
What is the percent yield?

4.5.0.0.2: Solution
The provided information identifies copper sulfate as the limiting reactant, and so the theoretical yield is found by the approach
illustrated in the previous module, as shown here:
1 mol CuSO 4 1 mol Cu 63.55 g Cu

1.274 g CuSO 4 × × × = 0.5072 g Cu
159.62 g CuSO 4 1 mol CuSO 4 1 mol Cu
Using this theoretical yield and the provided value for actual yield, the percent yield is calculated to be
actual yield
percent yield = ( ) × 100
theoretical yield
0.392 g Cu
0.5072 g Cu
= 77.3%

What is the percent yield of a reaction that produces 12.5 g of the gas Freon CF2Cl2 from 32.9 g of CCl4 and excess HF?
CCl4 + 2HF ⟶ CF2 Cl2 + 2HCl
4.5.0.1: Answer:
48.3%

4.5.0.0.4: Green Chemistry and Atom Economy
The purposeful design of chemical products and processes that minimize the use of environmentally hazardous substances and
the generation of waste is known as green chemistry. Green chemistry is a philosophical approach that is being applied to many
areas of science and technology, and its practice is summarized by guidelines known as the “Twelve Principles of Green
Chemistry” (see details at this website). One of the 12 principles is aimed specifically at maximizing the efficiency of
processes for synthesizing chemical products. The atom economy of a process is a measure of this efficiency, defined as the
percentage by mass of the final product of a synthesis relative to the masses of all the reactants used:
mass of product
atom economy = × 100%
mass of reactants
Though the definition of atom economy at first glance appears very similar to that for percent yield, be aware that this property
represents a difference in the theoretical efficiencies of different chemical processes. The percent yield of a given chemical
process, on the other hand, evaluates the efficiency of a process by comparing the yield of product actually obtained to the
maximum yield predicted by stoichiometry.
The synthesis of the common nonprescription pain medication, ibuprofen, nicely illustrates the success of a green chemistry
approach (Figure 4.15). First marketed in the early 1960s, ibuprofen was produced using a six-step synthesis that required 514
g of reactants to generate each mole (206 g) of ibuprofen, an atom economy of 40%. In the 1990s, an alternative process was
developed by the BHC Company (now BASF Corporation) that requires only three steps and has an atom economy of ~80%,
nearly twice that of the original process. The BHC process generates significantly less chemical waste; uses less-hazardous and
recyclable materials; and provides significant cost-savings to the manufacturer (and, subsequently, the consumer). In
recognition of the positive environmental impact of the BHC process, the company received the Environmental Protection
Agency’s Greener Synthetic Pathways Award in 1997.

Figure 4.15 (a) Ibuprofen is a popular nonprescription pain medication commonly sold as 200 mg tablets. (b) The BHC process
for synthesizing ibuprofen requires only three steps and exhibits an impressive atom economy. (credit a: modification of work
by Derrick Coetzee)
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Describe the fundamental aspects of titrations and gravimetric analysis.
Perform stoichiometric calculations using typical titration and gravimetric data.
In the 18th century, the strength (actually the concentration) of vinegar samples was determined by noting the amount of potassium
carbonate, K2CO3, which had to be added, a little at a time, before bubbling ceased. The greater the weight of potassium carbonate
added to reach the point where the bubbling ended, the more concentrated the vinegar.
We now know that the effervescence that occurred during this process was due to reaction with acetic acid, CH3CO2H, the
compound primarily responsible for the odor and taste of vinegar. Acetic acid reacts with potassium carbonate according to the
following equation:
2 CH3 CO2 H (aq) + K2 CO3 (s) ⟶ 2CH3 CO2 K(aq) + CO2 (g) + H2 O (l)
The bubbling was due to the production of CO2.

The test of vinegar with potassium carbonate is one type of quantitative analysis—the determination of the amount or concentration
of a substance in a sample. In the analysis of vinegar, the concentration of the solute (acetic acid) was determined from the amount
of reactant that combined with the solute present in a known volume of the solution. In other types of chemical analyses, the
amount of a substance present in a sample is determined by measuring the amount of product that results.
4.6.0.1: Titration
The described approach to measuring vinegar strength was an early version of the analytical technique known as titration analysis.
A typical titration analysis involves the use of a buret (Figure 4.16) to make incremental additions of a solution containing a known
concentration of some substance (the titrant) to a sample solution containing the substance whose concentration is to be measured
(the analyte). The titrant and analyte undergo a chemical reaction of known stoichiometry, and so measuring the volume of titrant
solution required for complete reaction with the analyte (the equivalence point of the titration) allows calculation of the analyte
concentration. The equivalence point of a titration may be detected visually if a distinct change in the appearance of the sample
solution accompanies the completion of the reaction. The halt of bubble formation in the classic vinegar analysis is one such
example, though, more commonly, special dyes called indicators are added to the sample solutions to impart a change in color at or
very near the equivalence point of the titration. Equivalence points may also be detected by measuring some solution property that
changes in a predictable way during the course of the titration. Regardless of the approach taken to detect a titration’s equivalence
point, the volume of titrant actually measured is called the end point. Properly designed titration methods typically ensure that the
difference between the equivalence and end points is negligible. Though any type of chemical reaction may serve as the basis for a
titration analysis, the three described in this chapter (precipitation, acid-base, and redox) are most common. Additional details
regarding titration analysis are provided in the chapter on acid-base equilibria.

Figure 4.16 (a) A student fills a buret in preparation for a titration analysis. (b) A typical buret permits volume measurements to the
nearest 0.01 mL. (credit a: modification of work by Mark Blaser and Matt Evans; credit b: modification of work by Mark Blaser
and Matt Evans)
4.6.0.1: Example 4.14

4.6.0.0.1: Titration Analysis
The end point in a titration of a 50.00-mL sample of aqueous HCl was reached by addition of 35.23 mL of 0.250 M NaOH
titrant. The titration reaction is:
HCl (aq) + NaOH (aq) ⟶ NaCl (aq) + H2 O (l)
What is the molarity of the HCl?

4.6.0.0.2: Solution
As for all reaction stoichiometry calculations, the key issue is the relation between the molar amounts of the chemical species
of interest as depicted in the balanced chemical equation. The approach outlined in previous modules of this chapter is
followed, with additional considerations required, since the amounts of reactants provided and requested are expressed as
solution concentrations.
For this exercise, the calculation will follow the following outlined steps:
The molar amount of HCl is calculated to be:
1 L 0.250 mol NaOH 1 mol HCl

−3
35.23 mL NaOH × × × = 8.81 × 10 mol HCl
1000 mL 1 L 1 mol NaOH
Using the provided volume of HCl solution and the definition of molarity, the HCl concentration is:
mol HCl
M =
L solution
−3
8.81 × 10 mol HCl
M =
1 L
50.00 mL ×
1 0 0 0 mL
M = 0.176 M
Note: For these types of titration calculations, it is convenient to recognize that solution molarity is also equal to the number of
millimoles of solute per milliliter of solution:
3
10 mmol
mol solute mol mmol solute

M = × =
3
L solution 10 mL mL solution
L
Using this version of the molarity unit will shorten the calculation by eliminating two conversion factors:
0.250 mmol NaOH 1 mmol HCl
35.23 mL NaOH × ×
mL NaOH 1 mmol NaOH
= 0.176 M HCl
50.00 mL solution

A 20.00-mL sample of aqueous oxalic acid, H2C2O4, was titrated with a 0.09113-M solution of potassium permanganate,
KMnO4 (see net ionic equation below).
− + 2+
2MnO 4 (aq) + 5 H2 C2 O4 (aq) + 6 H (aq) ⟶ 10 CO2 (g) + 2 Mn (aq) + 8 H2 O (l)
A volume of 23.24 mL was required to reach the end point. What is the oxalic acid molarity?
4.6.0.1: Answer:

0.2648 M
4.6.0.1: Gravimetric Analysis

A gravimetric analysis is one in which a sample is subjected to some treatment that causes a change in the physical state of the
analyte that permits its separation from the other components of the sample. Mass measurements of the sample, the isolated
analyte, or some other component of the analysis system, used along with the known stoichiometry of the compounds involved,
permit calculation of the analyte concentration. Gravimetric methods were the first techniques used for quantitative chemical
analysis, and they remain important tools in the modern chemistry laboratory.
The required change of state in a gravimetric analysis may be achieved by various physical and chemical processes. For example,
the moisture (water) content of a sample is routinely determined by measuring the mass of a sample before and after it is subjected
to a controlled heating process that evaporates the water. Also common are gravimetric techniques in which the analyte is subjected
to a precipitation reaction of the sort described earlier in this chapter. The precipitate is typically isolated from the reaction mixture
by filtration, carefully dried, and then weighed (Figure 4.17). The mass of the precipitate may then be used, along with relevant
stoichiometric relationships, to calculate analyte concentration.

Figure 4.17 Precipitate may be removed from a reaction mixture by filtration.
4.6.0.1: Example 4.15

4.6.0.0.1: Gravimetric Analysis
A 0.4550-g solid mixture containing MgSO4 is dissolved in water and treated with an excess of Ba(NO3)2, resulting in the
precipitation of 0.6168 g of BaSO4.
MgSO 4 (aq) + Ba (NO3 ) (aq) ⟶ BaSO 4 (s) + Mg (NO3 ) (aq)
2 2
What is the concentration (mass percent) of MgSO4 in the mixture?

4.6.0.0.2: Solution
The plan for this calculation is similar to others used in stoichiometric calculations, the central step being the connection
between the moles of BaSO4 and MgSO4 through their stoichiometric factor. Once the mass of MgSO4 is computed, it may be
used along with the mass of the sample mixture to calculate the requested percentage concentration.
The mass of MgSO4 that would yield the provided precipitate mass is

1 mol BaSO 4 1 mol MgSO4
120.37 g MgSO 4
0.6168 g BaSO 4 × × × = 0.3181 g MgSO 4
233.43 g BaSO 4 1 mol BaSO 4 1 mol MgSO4
The concentration of MgSO4 in the sample mixture is then calculated to be
mass MgSO4
percent MgSO 4 = × 100%
mass sample
0.3181 g
× 100% = 69.91%
0.4550 g

What is the percent of chloride ion in a sample if 1.1324 g of the sample produces 1.0881 g of AgCl when treated with excess
Ag+?
+ −
Ag (aq) + Cl (aq) ⟶ AgCl (s)
4.6.0.1: Answer:
23.76%
The elemental composition of hydrocarbons and related compounds may be determined via a gravimetric method known as
combustion analysis. In a combustion analysis, a weighed sample of the compound is heated to a high temperature under a stream
of oxygen gas, resulting in its complete combustion to yield gaseous products of known identities. The complete combustion of
hydrocarbons, for example, will yield carbon dioxide and water as the only products. The gaseous combustion products are swept
through separate, preweighed collection devices containing compounds that selectively absorb each product (Figure 4.18). The
mass increase of each device corresponds to the mass of the absorbed product and may be used in an appropriate stoichiometric
calculation to derive the mass of the relevant element.
Figure 4.18 This schematic diagram illustrates the basic components of a combustion analysis device for determining the carbon
and hydrogen content of a sample.
4.6.0.1: Example 4.16

4.6.0.0.4: Combustion Analysis
Polyethylene is a hydrocarbon polymer used to produce food-storage bags and many other flexible plastic items. A combustion
analysis of a 0.00126-g sample of polyethylene yields 0.00394 g of CO2 and 0.00161 g of H2O. What is the empirical formula
of polyethylene?
4.6.0.0.5: Solution
The primary assumption in this exercise is that all the carbon in the sample combusted is converted to carbon dioxide, and all
the hydrogen in the sample is converted to water:
y
Cx Hy (s) + excess O 2 (g) ⟶ x CO2 (g) + H2 O(g)
2
Note that a balanced equation is not necessary for the task at hand. To derive the empirical formula of the compound, only the
subscripts x and y are needed.

First, calculate the molar amounts of carbon and hydrogen in the sample, using the provided masses of the carbon dioxide and
water, respectively. With these molar amounts, the empirical formula for the compound may be written as described in the
previous chapter of this text. An outline of this approach is given in the following flow chart:
1 mol CO2 1 mol C −5

mol C = 0.00394 g CO2 × × = 8.95 × 10 mol C
44.01 g 1 mol CO2
1 mol H2 O 2 mol H −4
mol H = 0.00161 g H2 O × × = 1.79 × 10 mol H
18.02 g 1 mol H2 O
The empirical formula for the compound is then derived by identifying the smallest whole-number multiples for these molar
amounts. The H-to-C molar ratio is
−4
mol H 1.79 × 10 mol H 2 mol H
= =
−5
mol C 8.95 × 10 mol C 1 mol C
and the empirical formula for polyethylene is CH2.

A 0.00215-g sample of polystyrene, a polymer composed of carbon and hydrogen, produced 0.00726 g of CO2 and 0.00148 g
of H2O in a combustion analysis. What is the empirical formula for polystyrene?
4.6.0.1: Answer:
CH
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4.7: Key Terms
acid
substance that produces H3O+ when dissolved in water
acid-base reaction
reaction involving the transfer of a hydrogen ion between reactant species
actual yield
amount of product formed in a reaction
analyte
chemical species of interest
balanced equation
chemical equation with equal numbers of atoms for each element in the reactant and product
base
substance that produces OH− when dissolved in water
buret
device used for the precise delivery of variable liquid volumes, such as in a titration analysis
chemical equation
symbolic representation of a chemical reaction
coefficient
number placed in front of symbols or formulas in a chemical equation to indicate their relative amount
combustion analysis
gravimetric technique used to determine the elemental composition of a compound via the collection and weighing of its
gaseous combustion products
combustion reaction
vigorous redox reaction producing significant amounts of energy in the form of heat and, sometimes, light
complete ionic equation

chemical equation in which all dissolved ionic reactants and products, including spectator ions, are explicitly represented by
formulas for their dissociated ions
end point
measured volume of titrant solution that yields the change in sample solution appearance or other property expected for
stoichiometric equivalence (see equivalence point)
equivalence point
volume of titrant solution required to react completely with the analyte in a titration analysis; provides a stoichiometric amount
of titrant for the sample’s analyte according to the titration reaction
excess reactant
reactant present in an amount greater than required by the reaction stoichiometry
gravimetric analysis
quantitative chemical analysis method involving the separation of an analyte from a sample by a physical or chemical process
and subsequent mass measurements of the analyte, reaction product, and/or sample
half-reaction
an equation that shows whether each reactant loses or gains electrons in a reaction.
indicator
substance added to the sample in a titration analysis to permit visual detection of the end point
insoluble
of relatively low solubility; dissolving only to a slight extent
limiting reactant
reactant present in an amount lower than required by the reaction stoichiometry, thus limiting the amount of product generated
molecular equation
chemical equation in which all reactants and products are represented as neutral substances
net ionic equation

chemical equation in which only those dissolved ionic reactants and products that undergo a chemical or physical change are
represented (excludes spectator ions)
neutralization reaction
reaction between an acid and a base to produce salt and water
oxidation
process in which an element’s oxidation number is increased by loss of electrons
oxidation number
(also, oxidation state) the charge each atom of an element would have in a compound if the compound were ionic
oxidation-reduction reaction
(also, redox reaction) reaction involving a change in oxidation number for one or more reactant elements
oxidizing agent
(also, oxidant) substance that brings about the oxidation of another substance, and in the process becomes reduced
percent yield
measure of the efficiency of a reaction, expressed as a percentage of the theoretical yield
precipitate
insoluble product that forms from reaction of soluble reactants
precipitation reaction
reaction that produces one or more insoluble products; when reactants are ionic compounds, sometimes called double-
displacement or metathesis
product
substance formed by a chemical or physical change; shown on the right side of the arrow in a chemical equation
quantitative analysis
the determination of the amount or concentration of a substance in a sample
reactant
substance undergoing a chemical or physical change; shown on the left side of the arrow in a chemical equation
reducing agent
(also, reductant) substance that brings about the reduction of another substance, and in the process becomes oxidized
reduction
process in which an element’s oxidation number is decreased by gain of electrons
salt
ionic compound that can be formed by the reaction of an acid with a base that contains a cation and an anion other than
hydroxide or oxide
single-displacement reaction
(also, replacement) redox reaction involving the oxidation of an elemental substance by an ionic species
solubility
the extent to which a substance may be dissolved in water, or any solvent
soluble
of relatively high solubility; dissolving to a relatively large extent
spectator ion
ion that does not undergo a chemical or physical change during a reaction, but its presence is required to maintain charge
neutrality
stoichiometric factor
ratio of coefficients in a balanced chemical equation, used in computations relating amounts of reactants and products
stoichiometry
relationships between the amounts of reactants and products of a chemical reaction
strong acid
acid that reacts completely when dissolved in water to yield hydronium ions
strong base
base that reacts completely when dissolved in water to yield hydroxide ions
theoretical yield
amount of product that may be produced from a given amount of reactant(s) according to the reaction stoichiometry
titrant
solution containing a known concentration of substance that will react with the analyte in a titration analysis
titration analysis
quantitative chemical analysis method that involves measuring the volume of a reactant solution required to completely react
with the analyte in a sample
weak acid
acid that reacts only to a slight extent when dissolved in water to yield hydronium ions
weak base
base that reacts only to a slight extent when dissolved in water to yield hydroxide ions
4.8: Key Equations
actual yield
theoretical yield
4.9: Summary
4.1 Writing and Balancing Chemical Equations
Chemical equations are symbolic representations of chemical and physical changes. Formulas for the substances undergoing the
change (reactants) and substances generated by the change (products) are separated by an arrow and preceded by integer
coefficients indicating their relative numbers. Balanced equations are those whose coefficients result in equal numbers of atoms for
each element in the reactants and products. Chemical reactions in aqueous solution that involve ionic reactants or products may be
represented more realistically by complete ionic equations and, more succinctly, by net ionic equations.
4.2 Classifying Chemical Reactions

Chemical reactions are classified according to similar patterns of behavior. A large number of important reactions are included in
three categories: precipitation, acid-base, and oxidation-reduction (redox). Precipitation reactions involve the formation of one or
more insoluble products. Acid-base reactions involve the transfer of hydrogen ions between reactants. Redox reactions involve a
change in oxidation number for one or more reactant elements. Writing balanced equations for some redox reactions that occur in
aqueous solutions is simplified by using a systematic approach called the half-reaction method.
4.3 Reaction Stoichiometry

A balanced chemical equation may be used to describe a reaction’s stoichiometry (the relationships between amounts of reactants
and products). Coefficients from the equation are used to derive stoichiometric factors that subsequently may be used for
computations relating reactant and product masses, molar amounts, and other quantitative properties.
4.4 Reaction Yields

When reactions are carried out using less-than-stoichiometric quantities of reactants, the amount of product generated will be
determined by the limiting reactant. The amount of product generated by a chemical reaction is its actual yield. This yield is often
less than the amount of product predicted by the stoichiometry of the balanced chemical equation representing the reaction (its
theoretical yield). The extent to which a reaction generates the theoretical amount of product is expressed as its percent yield.
4.5 Quantitative Chemical Analysis

The stoichiometry of chemical reactions may serve as the basis for quantitative chemical analysis methods. Titrations involve
measuring the volume of a titrant solution required to completely react with a sample solution. This volume is then used to
calculate the concentration of analyte in the sample using the stoichiometry of the titration reaction. Gravimetric analysis involves
separating the analyte from the sample by a physical or chemical process, determining its mass, and then calculating its
concentration in the sample based on the stoichiometry of the relevant process. Combustion analysis is a gravimetric method used
to determine the elemental composition of a compound by collecting and weighing the gaseous products of its combustion.
4.10: Exercises
4.10.0.1: 4.1 Writing and Balancing Chemical Equations
1.
What does it mean to say an equation is balanced? Why is it important for an equation to be balanced?
2.
Consider molecular, complete ionic, and net ionic equations.
(a) What is the difference between these types of equations?
(b) In what circumstance would the complete and net ionic equations for a reaction be identical?
3.
Balance the following equations:
(a) PCl 5 (s) + H2 O(l) ⟶ POCl3 (l) + HCl(aq)
(b) Cu(s) + HNO 3 (aq) ⟶ Cu(NO3 ) (aq) + H2 O(l) + NO(g)

2
(c) H 2 (g) + I2 (s) ⟶ HI(s)
(d) Fe(s) + O 2 (g) ⟶ Fe2 O3 (s)
(e) Na(s) + H 2 O(l) ⟶ NaOH (aq) + H2 (g)
(f) (NH 4 )2 Cr2 O7 (s) ⟶ Cr2 O3 (s) + N2 (g) + H2 O(g)
(g) P4 (s) + Cl2 (g) ⟶ PCl3 (l)
(h) PtCl 4 (s) ⟶ Pt (s) + Cl2 (g)
4.
Balance the following equations:
(a) Ag (s) + H 2S (g) + O2 (g) ⟶ Ag2 S (s) + H2 O (l)
(b) P4 (s) + O2 (g) ⟶ P4 O10 (s)
(c) Pb(s) + H 2 O(l) + O2 (g) ⟶ Pb(OH)

2
(s)
(d) Fe(s) + H 2 O(l) ⟶ Fe3 O4 (s) + H2 (g)
(e) Sc 2 O3 (s) + SO 3 (l) ⟶ Sc 2 (SO4 ) (s)

3
(f) Ca 3 (PO4 )2 (aq) + H3 PO4 (aq) ⟶ Ca (H2 PO4 ) 2 (aq)
(g) Al(s) + H 2 SO 4 (aq) ⟶ Al2 (SO4 ) (s) + H2 (g)

3
(h) TiCl 4 (s) + H2 O(g) ⟶ TiO2 (s) + HCl(g)
5.
Write a balanced molecular equation describing each of the following chemical reactions.
(a) Solid calcium carbonate is heated and decomposes to solid calcium oxide and carbon dioxide gas.
(b) Gaseous butane, C4H10, reacts with diatomic oxygen gas to yield gaseous carbon dioxide and water vapor.
(c) Aqueous solutions of magnesium chloride and sodium hydroxide react to produce solid magnesium hydroxide and aqueous
sodium chloride.
(d) Water vapor reacts with sodium metal to produce solid sodium hydroxide and hydrogen gas.
6.
Write a balanced equation describing each of the following chemical reactions.
(a) Solid potassium chlorate, KClO3, decomposes to form solid potassium chloride and diatomic oxygen gas.
(b) Solid aluminum metal reacts with solid diatomic iodine to form solid Al2I6.

(c) When solid sodium chloride is added to aqueous sulfuric acid, hydrogen chloride gas and aqueous sodium sulfate are produced.
(d) Aqueous solutions of phosphoric acid and potassium hydroxide react to produce aqueous potassium dihydrogen phosphate and
liquid water.
7.
Colorful fireworks often involve the decomposition of barium nitrate and potassium chlorate and the reaction of the metals
magnesium, aluminum, and iron with oxygen.
(a) Write the formulas of barium nitrate and potassium chlorate.
(b) The decomposition of solid potassium chlorate leads to the formation of solid potassium chloride and diatomic oxygen gas.
Write an equation for the reaction.
(c) The decomposition of solid barium nitrate leads to the formation of solid barium oxide, diatomic nitrogen gas, and diatomic
oxygen gas. Write an equation for the reaction.
(d) Write separate equations for the reactions of the solid metals magnesium, aluminum, and iron with diatomic oxygen gas to yield
the corresponding metal oxides. (Assume the iron oxide contains Fe3+ ions.)
8.
Fill in the blank with a single chemical formula for a covalent compound that will balance the equation:
9.
Aqueous hydrogen fluoride (hydrofluoric acid) is used to etch glass and to analyze minerals for their silicon content. Hydrogen
fluoride will also react with sand (silicon dioxide).
(a) Write an equation for the reaction of solid silicon dioxide with hydrofluoric acid to yield gaseous silicon tetrafluoride and liquid
water.
(b) The mineral fluorite (calcium fluoride) occurs extensively in Illinois. Solid calcium fluoride can also be prepared by the
reaction of aqueous solutions of calcium chloride and sodium fluoride, yielding aqueous sodium chloride as the other product.
Write complete and net ionic equations for this reaction.
10.
A novel process for obtaining magnesium from sea water involves several reactions. Write a balanced chemical equation for each
step of the process.
(a) The first step is the decomposition of solid calcium carbonate from seashells to form solid calcium oxide and gaseous carbon
dioxide.
(b) The second step is the formation of solid calcium hydroxide as the only product from the reaction of the solid calcium oxide
with liquid water.
(c) Solid calcium hydroxide is then added to the seawater, reacting with dissolved magnesium chloride to yield solid magnesium
hydroxide and aqueous calcium chloride.
(d) The solid magnesium hydroxide is added to a hydrochloric acid solution, producing dissolved magnesium chloride and liquid
water.
(e) Finally, the magnesium chloride is melted and electrolyzed to yield liquid magnesium metal and diatomic chlorine gas.
11.
From the balanced molecular equations, write the complete ionic and net ionic equations for the following:
(a) K 2 C2 O4 (aq) + Ba (OH) (aq) ⟶ 2KOH(aq) + BaC2 O4 (s)
2
(b) Pb(NO 3 )2 (aq) + H2 SO 4 (aq) ⟶ PbSO 4 (s) + 2 HNO3 (aq)

(c) CaCO 3 (s) + H2 SO 4 (aq) ⟶ CaSO4 (s) + CO2 (g) + H2 O(l)
4.10.0.1: 4.2 Classifying Chemical Reactions

12.
Use the following equations to answer the next four questions:
i. H 2 O(s) ⟶ H2 O(l)
ii. Na +
(aq) + Cl
−
(aq) + Ag
+
(aq) + NO3
−
(aq) ⟶ AgCl(s) + Na
+
(aq) + NO3
−
(aq)
iii. CH 3 OH(g) + O2 (g) ⟶ CO2 (g) + H2 O(g)
iv. 2H 2 O(l) ⟶ 2 H2 (g) + O2 (g)
v. H +
(aq) + OH
−
(aq) ⟶ H2 O(l)
(a) Which equation describes a physical change?

(b) Which equation identifies the reactants and products of a combustion reaction?
(c) Which equation is not balanced?
(d) Which is a net ionic equation?
13.
Indicate what type, or types, of reaction each of the following represents:
(a) Ca(s) + Br 2 (l) ⟶ CaBr2 (s)
(b) Ca (OH) 2
(aq) + 2HBr(aq) ⟶ CaBr2 (aq) + 2 H2 O(l)
(c) C 6 H12 (l) + 9 O2 (g) ⟶ 6 CO2 (g) + 6 H2 O(g)
14.
Indicate what type, or types, of reaction each of the following represents:
(a) H 2 O(g) + C(s) ⟶ CO(g) + H2 (g)
(b) 2KClO 3 (s) ⟶ 2KCl(s) + 3 O2 (g)
(c) Al(OH) 3
(aq) + 3HCl(aq) ⟶ AlCl3 (aq) + 3 H2 O (l)
(d) Pb(NO 3 ) 2 (aq) + H2 SO 4 (aq) ⟶ PbSO 4 (s) + 2 HNO3 (aq)
15.
Silver can be separated from gold because silver dissolves in nitric acid while gold does not. Is the dissolution of silver in nitric
acid an acid-base reaction or an oxidation-reduction reaction? Explain your answer.
16.
Determine the oxidation states of the elements in the following compounds:
(a) NaI
(b) GdCl3
(c) LiNO3
(d) H2Se
(e) Mg2Si
(f) RbO2, rubidium superoxide
(g) HF
17.
Determine the oxidation states of the elements in the compounds listed. None of the oxygen-containing compounds are peroxides
or superoxides.

(a) H3PO4
(b) Al(OH)3
(c) SeO2
(d) KNO2
(e) In2S3
(f) P4O6
18.
Determine the oxidation states of the elements in the compounds listed. None of the oxygen-containing compounds are peroxides
or superoxides.
(a) H2SO4
(b) Ca(OH)2
(c) BrOH
(d) ClNO2
(e) TiCl4
(f) NaH
19.
Classify the following as acid-base reactions or oxidation-reduction reactions:
(a) Na 2 S(aq) + 2HCl(aq) ⟶ 2NaCl(aq) + H2 S(g)
(b) 2Na(s) + 2HCl(aq) ⟶ 2NaCl(aq) + H2 (g)
(c) Mg(s) + Cl 2 (g) ⟶ MgCl2 (s)
(d) MgO(s) + 2HCl(aq) ⟶ MgCl (aq) + H2 O(l)

2
(e) K 3 P(s) + 2 O2 (g) ⟶ K3 PO4 (s)
(f) 3KOH(aq) + H 3 PO4 (aq) ⟶ K3 PO4 (aq) + 3 H2 O(l)
20.
Identify the atoms that are oxidized and reduced, the change in oxidation state for each, and the oxidizing and reducing agents in
each of the following equations:
(a) Mg(s) + NiCl 2 (aq) ⟶ MgCl (aq) + Ni(s)
2
(b) PCl 3 (l) + Cl2 (g) ⟶ PCl5 (s)
(c) C 2 H4 (g) + 3 O2 (g) ⟶ 2 CO2 (g) + 2 H2 O(g)
(d) Zn(s) + H 2 SO 4 (aq) ⟶ ZnSO 4 (aq) + H2 (g)
(e) 2K 2 S2 O3 (s) + I2 (s) ⟶ K2 S4 O6 (s) + 2KI(s)
(f) 3Cu(s) + 8HNO 3 (aq) ⟶ 3Cu(NO3 ) (aq) + 2NO(g) + 4 H2 O(l)

2
21.
Complete and balance the following acid-base equations:
(a) HCl gas reacts with solid Ca(OH)2(s).
(b) A solution of Sr(OH)2 is added to a solution of HNO3.
22.
Complete and balance the following acid-base equations:
(a) A solution of HClO4 is added to a solution of LiOH.

(b) Aqueous H2SO4 reacts with NaOH.
(c) Ba(OH)2 reacts with HF gas.
23.
Complete and balance the following oxidation-reduction reactions, which give the highest possible oxidation state for the oxidized
atoms.
(a) Al(s) + F 2 (g) ⟶
(b) Al(s) + CuBr 2 (aq) ⟶ (single displacement)

(c) P 4 (s) + O2 (g) ⟶
(d) Ca(s) + H 2 O(l) ⟶ (products are a strong base and a diatomic gas)
24.
Complete and balance the following oxidation-reduction reactions, which give the highest possible oxidation state for the oxidized
atoms.
(a) K(s) + H 2 O(l) ⟶
(b) Ba(s) + HBr(aq) ⟶
(c) Sn(s) + I 2 (s) ⟶
25.
Complete and balance the equations for the following acid-base neutralization reactions. If water is used as a solvent, write the
reactants and products as aqueous ions. In some cases, there may be more than one correct answer, depending on the amounts of
reactants used.
(a) Mg(OH) 2
(s) + HClO4 (aq) ⟶
(b) SO 3 (g) + H2 O(l) ⟶ (assume an excess of water and that the product dissolves)
(c) SrO(s) + H 2 SO 4 (l) ⟶
26.
When heated to 700–800 °C, diamonds, which are pure carbon, are oxidized by atmospheric oxygen. (They burn!) Write the
balanced equation for this reaction.
27.
The military has experimented with lasers that produce very intense light when fluorine combines explosively with hydrogen. What
is the balanced equation for this reaction?
28.
Write the molecular, total ionic, and net ionic equations for the following reactions:
(a) Ca(OH) 2
(aq) + HC2 H3 O2 (aq) ⟶
(b) H 3 PO4 (aq) + CaCl2 (aq) ⟶
29.
Great Lakes Chemical Company produces bromine, Br2, from bromide salts such as NaBr, in Arkansas brine by treating the brine
with chlorine gas. Write a balanced equation for the reaction of NaBr with Cl2.
30.
In a common experiment in the general chemistry laboratory, magnesium metal is heated in air to produce MgO. MgO is a white
solid, but in these experiments it often looks gray, due to small amounts of Mg3N2, a compound formed as some of the magnesium
reacts with nitrogen. Write a balanced equation for each reaction.
31.
Lithium hydroxide may be used to absorb carbon dioxide in enclosed environments, such as manned spacecraft and submarines.
Write an equation for the reaction that involves 2 mol of LiOH per 1 mol of CO2. (Hint: Water is one of the products.)

32.
Calcium propionate is sometimes added to bread to retard spoilage. This compound can be prepared by the reaction of calcium
carbonate, CaCO3, with propionic acid, C2H5CO2H, which has properties similar to those of acetic acid. Write the balanced
equation for the formation of calcium propionate.
33.
Complete and balance the equations of the following reactions, each of which could be used to remove hydrogen sulfide from
natural gas:
(a) Ca(OH) 2
(s) + H2 S(g) ⟶
(b) Na 2 CO3 (aq) + H2 S(g) ⟶
34.
Copper(II) sulfide is oxidized by molecular oxygen to produce gaseous sulfur trioxide and solid copper(II) oxide. The gaseous
product then reacts with liquid water to produce liquid dihydrogen sulfate as the only product. Write the two equations which
represent these reactions.
35.
Write balanced chemical equations for the reactions used to prepare each of the following compounds from the given starting
material(s). In some cases, additional reactants may be required.
(a) solid ammonium nitrate from gaseous molecular nitrogen via a two-step process (first reduce the nitrogen to ammonia, then
neutralize the ammonia with an appropriate acid)
(b) gaseous hydrogen bromide from liquid molecular bromine via a one-step redox reaction
(c) gaseous H2S from solid Zn and S via a two-step process (first a redox reaction between the starting materials, then reaction of
the product with a strong acid)
36.
Calcium cyclamate Ca(C6H11NHSO3)2 is an artificial sweetener used in many countries around the world but is banned in the
United States. It can be purified industrially by converting it to the barium salt through reaction of the acid C6H11NHSO3H with
barium carbonate, treatment with sulfuric acid (barium sulfate is very insoluble), and then neutralization with calcium hydroxide.
Write the balanced equations for these reactions.
37.
Complete and balance each of the following half-reactions (steps 2–5 in half-reaction method):
(a) Sn 4+
(aq) ⟶ Sn
2+
(aq)
(b) [Ag(NH 3 )2 ]
+
(aq) ⟶ Ag (s) + NH3 (aq)
(c) Hg 2
Cl2 (s) ⟶ Hg (l) + Cl
−
(aq)
(d) H 2 O(l) ⟶ O2 (g) (in acidic solution)

(e) IO 3
−
(aq) ⟶ I2 (s) (in basic solution)
(f) SO 3
2−
(aq) ⟶ SO 4
2−
(aq) (in acidic solution)
(g) MnO 4
−
(aq) ⟶ Mn
2+
(h) Cl −
(aq) ⟶ ClO3
−
(aq) (in basic solution)
38.
Complete and balance each of the following half-reactions (steps 2–5 in half-reaction method):
(a) Cr 2+
(aq) ⟶ Cr
3+
(aq)
(b) Hg(l) + Br −
(aq) ⟶ HgBr4
2−
(aq)
(c) ZnS(s) ⟶ Zn(s) + S

2−
(aq)
(d) H 2 (g) ⟶ H2 O(l (in basic solution)

(e) H 2 (g) ⟶ H3 O
+
(f) NO 3
−
(aq) ⟶ HNO2 (aq) (in acidic solution)
(g) MnO 2 (s) ⟶ MnO 4
−
(aq) (in basic solution)
(h) Cl −
(aq) ⟶ ClO3
−
39.
Balance each of the following equations according to the half-reaction method:
(a) Sn 2+
(aq) + Cu
2+
(aq) ⟶ Sn
4+
(aq) + Cu
+
(aq)
(b) H 2 S(g) + Hg2

2+
(aq) ⟶ Hg(l) + S(s) (in acid)
(c) CN −
(aq) + ClO2 (aq) ⟶ CNO
−
(aq) + Cl
−
(aq) (in acid)
(d) Fe 2+
(aq) + Ce
4+
(aq) ⟶ Fe
3+
(aq) + Ce
3+
(aq)
(e) HBrO(aq) ⟶ Br
−
(aq) + O2 (g) (in acid)
40.
(a) Zn(s) + NO 3
−
(aq) ⟶ Zn
2+
(aq) + N2 (g) (in acid)
(b) Zn(s) + NO 3
−
(aq) ⟶ Zn
2+
(aq) + NH3 (aq) (in base)
(c) CuS(s) + NO 3
−
(aq) ⟶ Cu
2+
(aq) + S(s) + NO(g) (in acid)
(d) NH 3 (aq) + O2 (g) ⟶ NO2 (g) (gas phase)
(e) H 2 O2 (aq) + MnO 4

−
(aq) ⟶ Mn
2+
(aq) + O2 (g) (in acid)
(f) NO 2 (g) ⟶ NO3

−
(aq) + NO2
−
(aq) (in base)
(g) Fe 3+
(aq) + I
−
(aq) ⟶ Fe
2+
(aq) + I2 (aq)
41.
(a) MnO 4
−
(aq) + NO2
−
(aq) ⟶ MnO 2 (s) + NO3
−
(aq) (in base)
(b) MnO 4
2−
(aq) ⟶ MnO 4
−
(aq) + MnO 2 (s) (in base)
(c) Br 2 (l) + SO 2 (g) ⟶ Br

−
(aq) + SO 4
2−
(aq) (in acid)
4.10.0.1: 4.3 Reaction Stoichiometry

42.
Write the balanced equation, then outline the steps necessary to determine the information requested in each of the following:
(a) The number of moles and the mass of chlorine, Cl2, required to react with 10.0 g of sodium metal, Na, to produce sodium
chloride, NaCl.
(b) The number of moles and the mass of oxygen formed by the decomposition of 1.252 g of mercury(II) oxide.
(c) The number of moles and the mass of sodium nitrate, NaNO3, required to produce 128 g of oxygen. (NaNO2 is the other
product.)
(d) The number of moles and the mass of carbon dioxide formed by the combustion of 20.0 kg of carbon in an excess of oxygen.
(e) The number of moles and the mass of copper(II) carbonate needed to produce 1.500 kg of copper(II) oxide. (CO2 is the other
product.)
(f)

43.
Determine the number of moles and the mass requested for each reaction in Exercise 4.42.
44.
Write the balanced equation, then outline the steps necessary to determine the information requested in each of the following:
(a) The number of moles and the mass of Mg required to react with 5.00 g of HCl and produce MgCl2 and H2.
(b) The number of moles and the mass of oxygen formed by the decomposition of 1.252 g of silver(I) oxide.
(c) The number of moles and the mass of magnesium carbonate, MgCO3, required to produce 283 g of carbon dioxide. (MgO is the
other product.)
(d) The number of moles and the mass of water formed by the combustion of 20.0 kg of acetylene, C2H2, in an excess of oxygen.
(e) The number of moles and the mass of barium peroxide, BaO2, needed to produce 2.500 kg of barium oxide, BaO (O2 is the
other product.)
(f)
45.
Determine the number of moles and the mass requested for each reaction in Exercise 4.44.
46.
H2 is produced by the reaction of 118.5 mL of a 0.8775-M solution of H3PO4 according to the following equation:
2Cr + 2 H3 PO4 ⟶ 3 H2 + 2 CrPO4 .
(a) Outline the steps necessary to determine the number of moles and mass of H2.
(b) Perform the calculations outlined.
47.
Gallium chloride is formed by the reaction of 2.6 L of a 1.44 M solution of HCl according to the following equation:
2Ga + 6HCl ⟶ 2 GaCl3 + 3 H2 .
(a) Outline the steps necessary to determine the number of moles and mass of gallium chloride.
(b) Perform the calculations outlined.
48.
I2 is produced by the reaction of 0.4235 mol of CuCl2 according to the following equation:
2 CuCl2 + 4KI ⟶ 2CuI + 4KCl + I2 .
(a) How many molecules of I2 are produced?

(b) What mass of I2 is produced?
49.
Silver is often extracted from ores such as K[Ag(CN)2] and then recovered by the reaction
2K [Ag (CN) ] (aq) + Zn (s) ⟶ 2Ag (s) + Zn(CN) (aq) + 2KCN (aq)
2 2
(a) How many molecules of Zn(CN)2 are produced by the reaction of 35.27 g of K[Ag(CN)2]?

(b) What mass of Zn(CN)2 is produced?
50.
What mass of silver oxide, Ag2O, is required to produce 25.0 g of silver sulfadiazine, AgC10H9N4SO2, from the reaction of silver
oxide and sulfadiazine?
2 C10 H10 N4 SO 2 + Ag2 O ⟶ 2 AgC10 H9 N4 SO 2 + H2 O
51.
Carborundum is silicon carbide, SiC, a very hard material used as an abrasive on sandpaper and in other applications. It is prepared
by the reaction of pure sand, SiO2, with carbon at high temperature. Carbon monoxide, CO, is the other product of this reaction.
Write the balanced equation for the reaction, and calculate how much SiO2 is required to produce 3.00 kg of SiC.
52.
Automotive air bags inflate when a sample of sodium azide, NaN3, is very rapidly decomposed.
2 NaN3 (s) ⟶ 2Na (s) + 3 N2 (g)
What mass of sodium azide is required to produce 2.6 ft3 (73.6 L) of nitrogen gas with a density of 1.25 g/L?
53.
Urea, CO(NH2)2, is manufactured on a large scale for use in producing urea-formaldehyde plastics and as a fertilizer. What is the
maximum mass of urea that can be manufactured from the CO2 produced by combustion of 1.00 × 10 kg of carbon followed by
3
the reaction?
CO2 (g) + 2 NH3 (g) ⟶ CO (NH2 ) (s) + H2 O (l)
2
54.
In an accident, a solution containing 2.5 kg of nitric acid was spilled. Two kilograms of Na2CO3 was quickly spread on the area and
CO2 was released by the reaction. Was sufficient Na2CO3 used to neutralize all of the acid?
55.
A compact car gets 37.5 miles per gallon on the highway. If gasoline contains 84.2% carbon by mass and has a density of 0.8205
g/mL, determine the mass of carbon dioxide produced during a 500-mile trip (3.785 liters per gallon).
56.
What volume of 0.750 M hydrochloric acid solution can be prepared from the HCl produced by the reaction of 25.0 g of NaCl with
excess sulfuric acid?
NaCl (s) + H2 SO 4 (l) ⟶ HCl (g) + NaHSO4 (s)
57.
What volume of a 0.2089 M KI solution contains enough KI to react exactly with the Cu(NO3)2 in 43.88 mL of a 0.3842 M
solution of Cu(NO3)2?
2Cu(NO3 ) + 4KI ⟶ 2CuI + I2 + 4 KNO 3
2
58.
A mordant is a substance that combines with a dye to produce a stable fixed color in a dyed fabric. Calcium acetate is used as a
mordant. It is prepared by the reaction of acetic acid with calcium hydroxide.
2 CH3 CO2 H + Ca (OH) ⟶ Ca (CH3 CO2 ) + 2 H2 O
2 2
What mass of Ca(OH)2 is required to react with the acetic acid in 25.0 mL of a solution having a density of 1.065 g/mL and
containing 58.0% acetic acid by mass?
59.
The toxic pigment called white lead, Pb3(OH)2(CO3)2, has been replaced in white paints by rutile, TiO2. How much rutile (g) can
be prepared from 379 g of an ore that contains 88.3% ilmenite (FeTiO3) by mass?
2 FeTiO3 + 4HCl + Cl2 ⟶ 2 FeCl3 + 2 TiO2 + 2 H2 O
4.10.0.1: 4.4 Reaction Yields

60.
The following quantities are placed in a container: 1.5 × 1024 atoms of hydrogen, 1.0 mol of sulfur, and 88.0 g of diatomic oxygen.

(a) What is the total mass in grams for the collection of all three elements?
(b) What is the total number of moles of atoms for the three elements?
(c) If the mixture of the three elements formed a compound with molecules that contain two hydrogen atoms, one sulfur atom, and
four oxygen atoms, which substance is consumed first?
(d) How many atoms of each remaining element would remain unreacted in the change described in (c)?
61.
What is the limiting reactant in a reaction that produces sodium chloride from 8 g of sodium and 8 g of diatomic chlorine?
62.
Which of the postulates of Dalton's atomic theory explains why we can calculate a theoretical yield for a chemical reaction?
63.
A student isolated 25 g of a compound following a procedure that would theoretically yield 81 g. What was his percent yield?
64.
A sample of 0.53 g of carbon dioxide was obtained by heating 1.31 g of calcium carbonate. What is the percent yield for this
reaction?
CaCO3 (s) ⟶ CaO (s) + CO2 (s)
65.
Freon-12, CCl2F2, is prepared from CCl4 by reaction with HF. The other product of this reaction is HCl. Outline the steps needed to
determine the percent yield of a reaction that produces 12.5 g of CCl2F2 from 32.9 g of CCl4. Freon-12 has been banned and is no
longer used as a refrigerant because it catalyzes the decomposition of ozone and has a very long lifetime in the atmosphere.
Determine the percent yield.
66.
Citric acid, C6H8O7, a component of jams, jellies, and fruity soft drinks, is prepared industrially via fermentation of sucrose by the
mold Aspergillus niger. The equation representing this reaction is
C12 H22 O11 + H2 O + 3 O2 ⟶ 2 C6 H8 O7 + 4 H2 O
What mass of citric acid is produced from exactly 1 metric ton (1.000 × 103 kg) of sucrose if the yield is 92.30%?
67.
Toluene, C6H5CH3, is oxidized by air under carefully controlled conditions to benzoic acid, C6H5CO2H, which is used to prepare
the food preservative sodium benzoate, C6H5CO2Na. What is the percent yield of a reaction that converts 1.000 kg of toluene to
1.21 kg of benzoic acid?
2 C6 H5 CH3 + 3 O2 ⟶ 2 C6 H5 CO2 H + 2 H2 O
68.
In a laboratory experiment, the reaction of 3.0 mol of H2 with 2.0 mol of I2 produced 1.0 mol of HI. Determine the theoretical yield
in grams and the percent yield for this reaction.
69.
Outline the steps needed to solve the following problem, then do the calculations. Ether, (C2H5)2O, which was originally used as an
anesthetic but has been replaced by safer and more effective medications, is prepared by the reaction of ethanol with sulfuric acid.
2C2H5OH + H2SO4 ⟶ (C2H5)2O + H2SO4·H2O
What is the percent yield of ether if 1.17 L (d = 0.7134 g/mL) is isolated from the reaction of 1.500 L of C2H5OH
(d = 0.7894 g/mL)?
70.
Outline the steps needed to determine the limiting reactant when 30.0 g of propane, C3H8, is burned with 75.0 g of oxygen.
Determine the limiting reactant.

71.
Outline the steps needed to determine the limiting reactant when 0.50 mol of Cr and 0.75 mol of H3PO4 react according to the
following chemical equation.
2Cr + 2 H3 PO4 ⟶ 2 CrPO4 + 3 H2
Determine the limiting reactant.

72.
What is the limiting reactant when 1.50 g of lithium and 1.50 g of nitrogen combine to form lithium nitride, a component of
advanced batteries, according to the following unbalanced equation?
Li + N2 ⟶ Li 3 N
73.
Uranium can be isolated from its ores by dissolving it as UO2(NO3)2, then separating it as solid UO2(C2O4)·3H2O. Addition of
0.4031 g of sodium oxalate, Na2C2O4, to a solution containing 1.481 g of uranyl nitrate, UO2(NO3)2, yields 1.073 g of solid
UO2(C2O4)·3H2O.
Na2C2O4 + UO2(NO3)2 + 3H2O ⟶ UO2(C2O4)·3H2O + 2NaNO3
Determine the limiting reactant and the percent yield of this reaction.
74.
How many molecules of C2H4Cl2 can be prepared from 15 C2H4 molecules and 8 Cl2 molecules?
75.
How many molecules of the sweetener saccharin can be prepared from 30 C atoms, 25 H atoms, 12 O atoms, 8 S atoms, and 14 N
atoms?
76.
The phosphorus pentoxide used to produce phosphoric acid for cola soft drinks is prepared by burning phosphorus in oxygen.
(a) What is the limiting reactant when 0.200 mol of P4 and 0.200 mol of O2 react according to P4 + 5 O2 ⟶ P4 O10
(b) Calculate the percent yield if 10.0 g of P4O10 is isolated from the reaction.
77.
Would you agree to buy 1 trillion (1,000,000,000,000) gold atoms for $5? Explain why or why not. Find the current price of gold at
http://money.cnn.com/data/commodities/ (1 troy ounce = 31.1 g)
4.10.0.1: 4.5 Quantitative Chemical Analysis

78.
What volume of 0.0105-M HBr solution is required to titrate 125 mL of a 0.0100-M Ca(OH)2 solution?
Ca (OH) (aq) + 2HBr (aq) ⟶ CaBr2 (aq) + 2 H2 O (l)
2
79.
Titration of a 20.0-mL sample of acid rain required 1.7 mL of 0.0811 M NaOH to reach the end point. If we assume that the acidity
of the rain is due to the presence of sulfuric acid, what was the concentration of sulfuric acid in this sample of rain?
80.

What is the concentration of NaCl in a solution if titration of 15.00 mL of the solution with 0.2503 M AgNO3 requires 20.22 mL of
the AgNO3 solution to reach the end point?
AgNO3 (aq) + NaCl (aq) ⟶ AgCl (s) + NaNO3 (aq)
81.
In a common medical laboratory determination of the concentration of free chloride ion in blood serum, a serum sample is titrated
with a Hg(NO3)2 solution.
− −
2 Cl (aq) + Hg (NO3 ) (aq) ⟶ 2 NO3 (aq) + HgCl2 (s)
2
What is the Cl− concentration in a 0.25-mL sample of normal serum that requires 1.46 mL of 8.25 × 10−4 M Hg(NO3)2(aq) to
reach the end point?
82.
Potatoes can be peeled commercially by soaking them in a 3-M to 6-M solution of sodium hydroxide, then removing the loosened
skins by spraying them with water. Does a sodium hydroxide solution have a suitable concentration if titration of 12.00 mL of the
solution requires 30.6 mL of 1.65 M HCI to reach the end point?
83.
A sample of gallium bromide, GaBr3, weighing 0.165 g was dissolved in water and treated with silver nitrate, AgNO3, resulting in
the precipitation of 0.299 g AgBr. Use these data to compute the %Ga (by mass) GaBr3.
84.
The principal component of mothballs is naphthalene, a compound with a molecular mass of about 130 amu, containing only
carbon and hydrogen. A 3.000-mg sample of naphthalene burns to give 10.3 mg of CO2. Determine its empirical and molecular
formulas.
85.
A 0.025-g sample of a compound composed of boron and hydrogen, with a molecular mass of ~28 amu, burns spontaneously when
exposed to air, producing 0.063 g of B2O3. What are the empirical and molecular formulas of the compound?
86.
Sodium bicarbonate (baking soda), NaHCO3, can be purified by dissolving it in hot water (60 °C), filtering to remove insoluble
impurities, cooling to 0 °C to precipitate solid NaHCO3, and then filtering to remove the solid, leaving soluble impurities in
solution. Any NaHCO3 that remains in solution is not recovered. The solubility of NaHCO3 in hot water of 60 °C is 164 g/L. Its
solubility in cold water of 0 °C is 69 g/L. What is the percent yield of NaHCO3 when it is purified by this method?
87.
What volume of 0.600 M HCl is required to react completely with 2.50 g of sodium hydrogen carbonate?
NaHCO3 (aq) + HCl (aq) ⟶ NaCl (aq) + CO2 (g) + H2 O (l)
88.
What volume of 0.08892 M HNO3 is required to react completely with 0.2352 g of potassium hydrogen phosphate?
2 HNO3 (aq) + K2 HPO4 (aq) ⟶ H3 PO4 (aq) + 2 KNO 3 (aq)
89.
What volume of a 0.3300-M solution of sodium hydroxide would be required to titrate 15.00 mL of 0.1500 M oxalic acid?
C2 O4 H2 (aq) + 2NaOH (aq) ⟶ Na2 C2 O4 (aq) + 2 H2 O(l)
90.
What volume of a 0.00945-M solution of potassium hydroxide would be required to titrate 50.00 mL of a sample of acid rain with a
H2SO4 concentration of 1.23 × 10−4 M.
H2 SO 4 (aq) + 2KOH (aq) ⟶ K2 SO 4 (aq) + 2 H2 O (l)
91.
A sample of solid calcium hydroxide, Ca(OH)2, is allowed to stand in water until a saturated solution is formed. A titration of 75.00
mL of this solution with 5.00 × 10−2 M HCl requires 36.6 mL of the acid to reach the end point.
Ca (OH) (aq) + 2HCl (aq) ⟶ CaCl2 (aq) + 2 H2 O (l)
2

What is the molarity?
92.
What mass of Ca(OH)2 will react with 25.0 g of butanoic to form the preservative calcium butanoate according to the equation?
93.
How many milliliters of a 0.1500-M solution of KOH will be required to titrate 40.00 mL of a 0.0656-M solution of H3PO4?
H3 PO4 (aq) + 2KOH (aq) ⟶ K2 HPO4 (aq) + 2 H2 O (l)
94.
Potassium hydrogen phthalate, KHC8H4O4, or KHP, is used in many laboratories, including general chemistry laboratories, to
standardize solutions of base. KHP is one of only a few stable solid acids that can be dried by warming and weighed. A 0.3420-g
sample of KHC8H4O4 reacts with 35.73 mL of a NaOH solution in a titration. What is the molar concentration of the NaOH?
KHC 8 H4 O4 (aq) + NaOH (aq) ⟶ KNaC8 H4 O4 (aq) + H2 O (aq)
95.
The reaction of WCl6 with Al at ~400 °C gives black crystals of a compound containing only tungsten and chlorine. A sample of
this compound, when reduced with hydrogen, gives 0.2232 g of tungsten metal and hydrogen chloride, which is absorbed in water.
Titration of the hydrochloric acid thus produced requires 46.2 mL of 0.1051 M NaOH to reach the end point. What is the empirical
formula of the black tungsten chloride?

CHAPTER OVERVIEW
5: Thermochemistry

General Chemistry
Useful forms of energy are also available from a variety of chemical reactions other than combustion. For example, the energy
produced by the batteries in a cell phone, car, or flashlight results from chemical reactions. This chapter introduces many of the
basic ideas necessary to explore the relationships between chemical changes and energy, with a focus on thermal energy.
5.1: Introduction
5.2: Energy Basics
5.3: Calorimetry
5.4: Enthalpy
5.5: Key Terms
5.6: Key Equations
5.7: Summary
5.8: Exercises
Thumbnail: Flames of charcoal. (CC BY-SA 3.0; Oscar via Wikipedia)
This page titled 5: Thermochemistry is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source
1
5.1: Introduction
Figure 5.1 Sliding a match head along a rough surface initiates a combustion reaction that produces energy in the form of heat and
light. (credit: modification of work by Laszlo Ilyes)

5.1 Energy Basics
5.2 Calorimetry
5.3 Enthalpy
Chemical reactions, such as those that occur when you light a match, involve changes in energy as well as matter. Societies at all
levels of development could not function without the energy released by chemical reactions. In 2012, about 85% of US energy
consumption came from the combustion of petroleum products, coal, wood, and garbage. We use this energy to produce electricity
(38%); to transport food, raw materials, manufactured goods, and people (27%); for industrial production (21%); and to heat and
power our homes and businesses (10%).1 While these combustion reactions help us meet our essential energy needs, they are also
recognized by the majority of the scientific community as a major contributor to global climate change.
Useful forms of energy are also available from a variety of chemical reactions other than combustion. For example, the energy
produced by the batteries in a cell phone, car, or flashlight results from chemical reactions. This chapter introduces many of the
basic ideas necessary to explore the relationships between chemical changes and energy, with a focus on thermal energy.
5.1.0.1: Footnotes
1US Energy Information Administration, Primary Energy Consumption by Source and Sector, 2012,
http://www.eia.gov/totalenergy/data/...012_energy.pdf. Data derived from US Energy Information Administration, Monthly
Energy Review (January 2014).

5.2: Energy Basics

Define energy, distinguish types of energy, and describe the nature of energy changes that accompany chemical and
physical changes
Distinguish the related properties of heat, thermal energy, and temperature
Define and distinguish specific heat and heat capacity, and describe the physical implications of both
Perform calculations involving heat, specific heat, and temperature change
Chemical changes and their accompanying changes in energy are important parts of our everyday world (Figure 5.2). The
macronutrients in food (proteins, fats, and carbohydrates) undergo metabolic reactions that provide the energy to keep our bodies
functioning. We burn a variety of fuels (gasoline, natural gas, coal) to produce energy for transportation, heating, and the
generation of electricity. Industrial chemical reactions use enormous amounts of energy to produce raw materials (such as iron and
aluminum). Energy is then used to manufacture those raw materials into useful products, such as cars, skyscrapers, and bridges.
Figure 5.2 The energy involved in chemical changes is important to our daily lives: (a) A cheeseburger for lunch provides the
energy you need to get through the rest of the day; (b) the combustion of gasoline provides the energy that moves your car (and
you) between home, work, and school; and (c) coke, a processed form of coal, provides the energy needed to convert iron ore into
iron, which is essential for making many of the products we use daily. (credit a: modification of work by “Pink Sherbet
Photography”/Flickr; credit b: modification of work by Jeffery Turner)
Over 90% of the energy we use comes originally from the sun. Every day, the sun provides the earth with almost 10,000 times the
amount of energy necessary to meet all of the world’s energy needs for that day. Our challenge is to find ways to convert and store
incoming solar energy so that it can be used in reactions or chemical processes that are both convenient and nonpolluting. Plants
and many bacteria capture solar energy through photosynthesis. We release the energy stored in plants when we burn wood or plant
products such as ethanol. We also use this energy to fuel our bodies by eating food that comes directly from plants or from animals
that got their energy by eating plants. Burning coal and petroleum also releases stored solar energy: These fuels are fossilized plant
and animal matter.
This chapter will introduce the basic ideas of an important area of science concerned with the amount of heat absorbed or released
during chemical and physical changes—an area called thermochemistry. The concepts introduced in this chapter are widely used in
almost all scientific and technical fields. Food scientists use them to determine the energy content of foods. Biologists study the
energetics of living organisms, such as the metabolic combustion of sugar into carbon dioxide and water. The oil, gas, and
transportation industries, renewable energy providers, and many others endeavor to find better methods to produce energy for our
commercial and personal needs. Engineers strive to improve energy efficiency, find better ways to heat and cool our homes,
refrigerate our food and drinks, and meet the energy and cooling needs of computers and electronics, among other applications.
Understanding thermochemical principles is essential for chemists, physicists, biologists, geologists, every type of engineer, and
just about anyone who studies or does any kind of science.

5.2.0.1: Energy
Energy can be defined as the capacity to supply heat or do work. One type of work (w) is the process of causing matter to move
against an opposing force. For example, we do work when we inflate a bicycle tire—we move matter (the air in the pump) against
the opposing force of the air already in the tire.
Like matter, energy comes in different types. One scheme classifies energy into two types: potential energy, the energy an object
has because of its relative position, composition, or condition, and kinetic energy, the energy that an object possesses because of its
motion. Water at the top of a waterfall or dam has potential energy because of its position; when it flows downward through
generators, it has kinetic energy that can be used to do work and produce electricity in a hydroelectric plant (Figure 5.3). A battery
has potential energy because the chemicals within it can produce electricity that can do work.
Figure 5.3 (a) Water at a higher elevation, for example, at the top of Victoria Falls, has a higher potential energy than water at a
lower elevation. As the water falls, some of its potential energy is converted into kinetic energy. (b) If the water flows through
generators at the bottom of a dam, such as the Hoover Dam shown here, its kinetic energy is converted into electrical energy.
(credit a: modification of work by Steve Jurvetson; credit b: modification of work by “curimedia”/Wikimedia commons)
Energy can be converted from one form into another, but all of the energy present before a change occurs always exists in some
form after the change is completed. This observation is expressed in the law of conservation of energy: during a chemical or
physical change, energy can be neither created nor destroyed, although it can be changed in form. (This is also one version of the
first law of thermodynamics, as you will learn later.)
When one substance is converted into another, there is always an associated conversion of one form of energy into another. Heat is
usually released or absorbed, but sometimes the conversion involves light, electrical energy, or some other form of energy. For
example, chemical energy (a type of potential energy) is stored in the molecules that compose gasoline. When gasoline is
combusted within the cylinders of a car’s engine, the rapidly expanding gaseous products of this chemical reaction generate
mechanical energy (a type of kinetic energy) when they move the cylinders’ pistons.
According to the law of conservation of matter (seen in an earlier chapter), there is no detectable change in the total amount of
matter during a chemical change. When chemical reactions occur, the energy changes are relatively modest and the mass changes
are too small to measure, so the laws of conservation of matter and energy hold well. However, in nuclear reactions, the energy
changes are much larger (by factors of a million or so), the mass changes are measurable, and matter-energy conversions are
significant. This will be examined in more detail in a later chapter on nuclear chemistry.
5.2.0.1: Thermal Energy, Temperature, and Heat

Thermal energy is kinetic energy associated with the random motion of atoms and molecules. Temperature is a quantitative
measure of “hot” or “cold.” When the atoms and molecules in an object are moving or vibrating quickly, they have a higher
average kinetic energy (KE), and we say that the object is “hot.” When the atoms and molecules are moving slowly, they have
lower average KE, and we say that the object is “cold” (Figure 5.4). Assuming that no chemical reaction or phase change (such as

melting or vaporizing) occurs, increasing the amount of thermal energy in a sample of matter will cause its temperature to increase.
And, assuming that no chemical reaction or phase change (such as condensation or freezing) occurs, decreasing the amount of
thermal energy in a sample of matter will cause its temperature to decrease.
Figure 5.4 (a) The molecules in a sample of hot water move more rapidly than (b) those in a sample of cold water.

Click on this interactive simulation to view the effects of temperature on molecular motion.
Most substances expand as their temperature increases and contract as their temperature decreases. This property can be used to
measure temperature changes, as shown in Figure 5.5. The operation of many thermometers depends on the expansion and
contraction of substances in response to temperature changes.
Figure 5.5 (a) In an alcohol or mercury thermometer, the liquid (dyed red for visibility) expands when heated and contracts when
cooled, much more so than the glass tube that contains the liquid. (b) In a bimetallic thermometer, two different metals (such as
brass and steel) form a two-layered strip. When heated or cooled, one of the metals (brass) expands or contracts more than the other
metal (steel), causing the strip to coil or uncoil. Both types of thermometers have a calibrated scale that indicates the temperature.
(credit a: modification of work by “dwstucke”/Flickr)

The following demonstration allows one to view the effects of heating and cooling a coiled bimetallic strip.

Heat (q) is the transfer of thermal energy between two bodies at different temperatures. Heat flow (a redundant term, but one
commonly used) increases the thermal energy of one body and decreases the thermal energy of the other. Suppose we initially have
a high temperature (and high thermal energy) substance (H) and a low temperature (and low thermal energy) substance (L). The
atoms and molecules in H have a higher average KE than those in L. If we place substance H in contact with substance L, the
thermal energy will flow spontaneously from substance H to substance L. The temperature of substance H will decrease, as will the
average KE of its molecules; the temperature of substance L will increase, along with the average KE of its molecules. Heat flow
will continue until the two substances are at the same temperature (Figure 5.6).
Figure 5.6 (a) Substances H and L are initially at different temperatures, and their atoms have different average kinetic energies. (b)
When they contact each other, collisions between the molecules result in the transfer of kinetic (thermal) energy from the hotter to
the cooler matter. (c) The two objects reach “thermal equilibrium” when both substances are at the same temperature and their
molecules have the same average kinetic energy.

Click on the PhET simulation to explore energy forms and changes. Visit the Energy Systems tab to create combinations of
energy sources, transformation methods, and outputs. Click on Energy Symbols to visualize the transfer of energy.
Matter undergoing chemical reactions and physical changes can release or absorb heat. A change that releases heat is called an
exothermic process. For example, the combustion reaction that occurs when using an oxyacetylene torch is an exothermic process
—this process also releases energy in the form of light as evidenced by the torch’s flame (Figure 5.7). A reaction or change that
absorbs heat is an endothermic process. A cold pack used to treat muscle strains provides an example of an endothermic process.
When the substances in the cold pack (water and a salt like ammonium nitrate) are brought together, the resulting process absorbs
heat, leading to the sensation of cold.
Figure 5.7 (a) An oxyacetylene torch produces heat by the combustion of acetylene in oxygen. The energy released by this
exothermic reaction heats and then melts the metal being cut. The sparks are tiny bits of the molten metal flying away. (b) A cold

pack uses an endothermic process to create the sensation of cold. (credit a: modification of work by “Skatebiker”/Wikimedia
commons)
Historically, energy was measured in units of calories (cal). A calorie is the amount of energy required to raise one gram of water
by 1 degree C (1 kelvin). However, this quantity depends on the atmospheric pressure and the starting temperature of the water.
The ease of measurement of energy changes in calories has meant that the calorie is still frequently used. The Calorie (with a
capital C), or large calorie, commonly used in quantifying food energy content, is a kilocalorie. The SI unit of heat, work, and
energy is the joule. A joule (J) is defined as the amount of energy used when a force of 1 newton moves an object 1 meter. It is
named in honor of the English physicist James Prescott Joule. One joule is equivalent to 1 kg m2/s2, which is also called 1 newton–
meter. A kilojoule (kJ) is 1000 joules. To standardize its definition, 1 calorie has been set to equal 4.184 joules.
We now introduce two concepts useful in describing heat flow and temperature change. The heat capacity (C) of a body of matter is
the quantity of heat (q) it absorbs or releases when it experiences a temperature change (ΔT) of 1 degree Celsius (or equivalently, 1
kelvin):
q
C =
ΔT
Heat capacity is determined by both the type and amount of substance that absorbs or releases heat. It is therefore an extensive
property—its value is proportional to the amount of the substance.
For example, consider the heat capacities of two cast iron frying pans. The heat capacity of the large pan is five times greater than
that of the small pan because, although both are made of the same material, the mass of the large pan is five times greater than the
mass of the small pan. More mass means more atoms are present in the larger pan, so it takes more energy to make all of those
atoms vibrate faster. The heat capacity of the small cast iron frying pan is found by observing that it takes 18,150 J of energy to
raise the temperature of the pan by 50.0 °C:
18,140 J
Csmall pan = = 363 J/°C
50.0 °C
The larger cast iron frying pan, while made of the same substance, requires 90,700 J of energy to raise its temperature by 50.0 °C.
The larger pan has a (proportionally) larger heat capacity because the larger amount of material requires a (proportionally) larger
amount of energy to yield the same temperature change:
90,700 J
Clarge pan = = 1814 J/°C
50.0 °C
The specific heat capacity (c) of a substance, commonly called its “specific heat,” is the quantity of heat required to raise the
temperature of 1 gram of a substance by 1 degree Celsius (or 1 kelvin):
q
c =
mΔT
Specific heat capacity depends only on the kind of substance absorbing or releasing heat. It is an intensive property—the type, but
not the amount, of the substance is all that matters. For example, the small cast iron frying pan has a mass of 808 g. The specific
heat of iron (the material used to make the pan) is therefore:
18,140 J
ciron = = 0.449 J/g °C
(808 g)(50.0 °C)
The large frying pan has a mass of 4040 g. Using the data for this pan, we can also calculate the specific heat of iron:
90,700 J
ciron = = 0.449 J/g °C
(4040 g)(50.0 °C)
Although the large pan is more massive than the small pan, since both are made of the same material, they both yield the same
value for specific heat (for the material of construction, iron). Note that specific heat is measured in units of energy per temperature
per mass and is an intensive property, being derived from a ratio of two extensive properties (heat and mass). The molar heat
capacity, also an intensive property, is the heat capacity per mole of a particular substance and has units of J/mol °C (Figure 5.8).

Figure 5.8 Because of its larger mass, a large frying pan has a larger heat capacity than a small frying pan. Because they are made
of the same material, both frying pans have the same specific heat. (credit: Mark Blaser)
Water has a relatively high specific heat (about 4.2 J/g °C for the liquid and 2.09 J/g °C for the solid); most metals have much
lower specific heats (usually less than 1 J/g °C). The specific heat of a substance varies somewhat with temperature. However, this
variation is usually small enough that we will treat specific heat as constant over the range of temperatures that will be considered
in this chapter. Specific heats of some common substances are listed in Table 5.1.
Specific Heats of Common Substances at 25 °C and 1 bar
Substance Symbol (state) Specific Heat (J/g °C)
helium He(g) 5.193
water H2O(l) 4.184
ethanol C2H6O(l) 2.376
ice H2O(s) 2.093 (at −10 °C)
water vapor H2O(g) 1.864
nitrogen N2(g) 1.040
air 1.007
oxygen O2(g) 0.918
aluminum Al(s) 0.897
carbon dioxide CO2(g) 0.853
argon Ar(g) 0.522
iron Fe(s) 0.449
copper Cu(s) 0.385
lead Pb(s) 0.130

Substance Symbol (state) Specific Heat (J/g °C)
gold Au(s) 0.129
silicon Si(s) 0.712
Table 5.1
If we know the mass of a substance and its specific heat, we can determine the amount of heat, q, entering or leaving the substance
by measuring the temperature change before and after the heat is gained or lost:
q = (specific heat) × (mass of substance) × (temperature change)
q = c × m × ΔT = c × m × (Tfinal − Tinitial)
In this equation, c is the specific heat of the substance, m is its mass, and ΔT (which is read “delta T”) is the temperature change,
Tfinal − Tinitial. If a substance gains thermal energy, its temperature increases, its final temperature is higher than its initial
temperature, Tfinal − Tinitial has a positive value, and the value of q is positive. If a substance loses thermal energy, its temperature
decreases, the final temperature is lower than the initial temperature, Tfinal − Tinitial has a negative value, and the value of q is
negative.
5.2.0.1: Example 5.1

5.2.0.0.1: Measuring Heat
A flask containing 8.0 × 102 g of water is heated, and the temperature of the water increases from 21 °C to 85 °C. How much
heat did the water absorb?
5.2.0.0.2: Solution
To answer this question, consider these factors:
the specific heat of the substance being heated (in this case, water)
the amount of substance being heated (in this case, 8.0 × 102 g)
the magnitude of the temperature change (in this case, from 21 °C to 85 °C).
The specific heat of water is 4.184 J/g °C, so to heat 1 g of water by 1 °C requires 4.184 J. We note that since 4.184 J is
required to heat 1 g of water by 1 °C, we will need 800 times as much to heat 8.0 × 102 g of water by 1 °C. Finally, we observe
that since 4.184 J are required to heat 1 g of water by 1 °C, we will need 64 times as much to heat it by 64 °C (that is, from 21
°C to 85 °C).
This can be summarized using the equation:
2
= (4.184 J/ g °C) × (8.0 x 10 g ) × (85 − 21) °C
2
= (4.184 J/ g ° C ) × (8.0 x 10 g ) × (64) ° C
2
= 210,000 J (= 2.1 × 10 kJ)
Because the temperature increased, the water absorbed heat and q is positive.
How much heat, in joules, must be added to a 502 g iron skillet to increase its temperature from 25 °C to 250 °C? The specific
heat of iron is 0.449 J/g °C.
5.2.0.1: Answer:
5.07 × 104 J
Note that the relationship between heat, specific heat, mass, and temperature change can be used to determine any of these
quantities (not just heat) if the other three are known or can be deduced.

5.2.0.1: Example 5.2
5.2.0.0.4: Determining Other Quantities
A piece of unknown metal weighs 348 g. When the metal piece absorbs 6.64 kJ of heat, its temperature increases from 22.4 °C
to 43.6 °C. Determine the specific heat of this metal (which might provide a clue to its identity).
5.2.0.0.5: Solution
Since mass, heat, and temperature change are known for this metal, we can determine its specific heat using the relationship:
Substituting the known values:

6640 J = c × (348 g) × (43.6 − 22.4) °C
Solving:
6640 J
c = = 0.900 J/g °C
(348 g) × (21.2 °C)
Comparing this value with the values in Table 5.1, this value matches the specific heat of aluminum, which suggests that the
unknown metal may be aluminum.
A piece of unknown metal weighs 217 g. When the metal piece absorbs 1.43 kJ of heat, its temperature increases from 24.5 °C
to 39.1 °C. Determine the specific heat of this metal, and predict its identity.
5.2.0.1: Answer:
c = 0.451 J/g °C; the metal is likely to be iron

5.2.0.0.7: Solar Thermal Energy Power Plants
The sunlight that reaches the earth contains thousands of times more energy than we presently capture. Solar thermal systems
provide one possible solution to the problem of converting energy from the sun into energy we can use. Large-scale solar
thermal plants have different design specifics, but all concentrate sunlight to heat some substance; the heat “stored” in that
substance is then converted into electricity.
The Solana Generating Station in Arizona’s Sonora Desert produces 280 megawatts of electrical power. It uses parabolic
mirrors that focus sunlight on pipes filled with a heat transfer fluid (HTF) (Figure 5.9). The HTF then does two things: It turns
water into steam, which spins turbines, which in turn produces electricity, and it melts and heats a mixture of salts, which
functions as a thermal energy storage system. After the sun goes down, the molten salt mixture can then release enough of its
stored heat to produce steam to run the turbines for 6 hours. Molten salts are used because they possess a number of beneficial
properties, including high heat capacities and thermal conductivities.

Figure 5.9 This solar thermal plant uses parabolic trough mirrors to concentrate sunlight. (credit a: modification of work by
Bureau of Land Management)
The 377-megawatt Ivanpah Solar Generating System, located in the Mojave Desert in California, is the largest solar thermal
power plant in the world (Figure 5.10). Its 170,000 mirrors focus huge amounts of sunlight on three water-filled towers,
producing steam at over 538 °C that drives electricity-producing turbines. It produces enough energy to power 140,000 homes.
Water is used as the working fluid because of its large heat capacity and heat of vaporization.

Figure 5.10 (a) The Ivanpah solar thermal plant uses 170,000 mirrors to concentrate sunlight on water-filled towers. (b) It
covers 4000 acres of public land near the Mojave Desert and the California-Nevada border. (credit a: modification of work by
Craig Dietrich; credit b: modification of work by “USFWS Pacific Southwest Region”/Flickr)
This page titled 5.2: Energy Basics is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source

5.3: Calorimetry

Explain the technique of calorimetry
Calculate and interpret heat and related properties using typical calorimetry data
One technique we can use to measure the amount of heat involved in a chemical or physical process is known as calorimetry.
Calorimetry is used to measure amounts of heat transferred to or from a substance. To do so, the heat is exchanged with a calibrated
object (calorimeter). The temperature change measured by the calorimeter is used to derive the amount of heat transferred by the
process under study. The measurement of heat transfer using this approach requires the definition of a system (the substance or
substances undergoing the chemical or physical change) and its surroundings (all other matter, including components of the
measurement apparatus, that serve to either provide heat to the system or absorb heat from the system).
A calorimeter is a device used to measure the amount of heat involved in a chemical or physical process. For example, when an
exothermic reaction occurs in solution in a calorimeter, the heat produced by the reaction is absorbed by the solution, which
increases its temperature. When an endothermic reaction occurs, the heat required is absorbed from the thermal energy of the
solution, which decreases its temperature (Figure 5.11). The temperature change, along with the specific heat and mass of the
solution, can then be used to calculate the amount of heat involved in either case.
Figure 5.11 In a calorimetric determination, either (a) an exothermic process occurs and heat, q, is negative, indicating that thermal
energy is transferred from the system to its surroundings, or (b) an endothermic process occurs and heat, q, is positive, indicating
that thermal energy is transferred from the surroundings to the system.
Calorimetry measurements are important in understanding the heat transferred in reactions involving everything from microscopic
proteins to massive machines. During her time at the National Bureau of Standards, research chemist Reatha Clark King performed
calorimetric experiments to understand the precise heats of various flourine compounds. Her work was important to NASA in their
quest for better rocket fuels.
Scientists use well-insulated calorimeters that all but prevent the transfer of heat between the calorimeter and its environment,
which effectively limits the “surroundings” to the nonsystem components with the calorimeter (and the calorimeter itself). This
enables the accurate determination of the heat involved in chemical processes, the energy content of foods, and so on. General

chemistry students often use simple calorimeters constructed from polystyrene cups (Figure 5.12). These easy-to-use “coffee cup”
calorimeters allow more heat exchange with the outside environment, and therefore produce less accurate energy values.
Figure 5.12 A simple calorimeter can be constructed from two polystyrene cups. A thermometer and stirrer extend through the
cover into the reaction mixture.
Commercial solution calorimeters are also available. Relatively inexpensive calorimeters often consist of two thin-walled cups that
are nested in a way that minimizes thermal contact during use, along with an insulated cover, handheld stirrer, and simple
thermometer. More expensive calorimeters used for industry and research typically have a well-insulated, fully enclosed reaction
vessel, motorized stirring mechanism, and a more accurate temperature sensor (Figure 5.13).

Figure 5.13 Commercial solution calorimeters range from (a) simple, inexpensive models for student use to (b) expensive, more
accurate models for industry and research.
Before discussing the calorimetry of chemical reactions, consider a simpler example that illustrates the core idea behind
calorimetry. Suppose we initially have a high-temperature substance, such as a hot piece of metal (M), and a low-temperature
substance, such as cool water (W). If we place the metal in the water, heat will flow from M to W. The temperature of M will
decrease, and the temperature of W will increase, until the two substances have the same temperature—that is, when they reach
thermal equilibrium (Figure 5.14). If this occurs in a calorimeter, ideally all of this heat transfer occurs between the two substances,
with no heat gained or lost by either its external environment. Under these ideal circumstances, the net heat change is zero:
qsubstance M + qsubstance W = 0
This relationship can be rearranged to show that the heat gained by substance M is equal to the heat lost by substance W:
qsubstance M = −qsubstance W
The magnitude of the heat (change) is therefore the same for both substances, and the negative sign merely shows that qsubstance M
and qsubstance W are opposite in direction of heat flow (gain or loss) but does not indicate the arithmetic sign of either q value (that is
determined by whether the matter in question gains or loses heat, per definition). In the specific situation described, qsubstance M is a
negative value and qsubstance W is positive, since heat is transferred from M to W.

Figure 5.14 In a simple calorimetry process, (a) heat, q, is transferred from the hot metal, M, to the cool water, W, until (b) both are
at the same temperature.
5.3.0.1: Example 5.3

5.3.0.0.1: Heat Transfer between Substances at Different Temperatures
A 360.0-g piece of rebar (a steel rod used for reinforcing concrete) is dropped into 425 mL of water at 24.0 °C. The final
temperature of the water was measured as 42.7 °C. Calculate the initial temperature of the piece of rebar. Assume the specific
heat of steel is approximately the same as that for iron (Table 5.1), and that all heat transfer occurs between the rebar and the
water (there is no heat exchange with the surroundings).
5.3.0.0.1: Solution
The temperature of the water increases from 24.0 °C to 42.7 °C, so the water absorbs heat. That heat came from the piece of
rebar, which initially was at a higher temperature. Assuming that all heat transfer was between the rebar and the water, with no
heat “lost” to the outside environment, then heat given off by rebar = −heat taken in by water, or:
qrebar = −qwater
Since we know how heat is related to other measurable quantities, we have:

(c × m × ΔT) rebar
= −(c × m × ΔT) water
Letting f = final and i = initial, in expanded form, this becomes:

crebar × mrebar × (Tf,rebar − Ti,rebar) = −cwater × mwater × (Tf,water − Ti,water)
The density of water is 1.0 g/mL, so 425 mL of water = 425 g. Noting that the final temperature of both the rebar and water is
42.7 °C, substituting known values yields:
(0.449 J/g °C)(360.0 g)(42.7 °C − Ti,rebar) = −(4.184 J/g °C)(425g)(42.7 °C − 24.0 °C)
(4.184 J/g °C)(425 g)(42.7 °C − 24.0 °C)

Ti,rebar = + 42.7 °C
(0.449 J/g °C)(360.0 g)

Solving this gives Ti,rebar= 248 °C, so the initial temperature of the rebar was 248 °C.
A 248-g piece of copper is dropped into 390 mL of water at 22.6 °C. The final temperature of the water was measured as 39.9
°C. Calculate the initial temperature of the piece of copper. Assume that all heat transfer occurs between the copper and the
water.
5.3.0.1: Answer:
The initial temperature of the copper was 335.6 °C.

A 248-g piece of copper initially at 314 °C is dropped into 390 mL of water initially at 22.6 °C. Assuming that all heat transfer
occurs between the copper and the water, calculate the final temperature.
5.3.0.1: Answer:
The final temperature (reached by both copper and water) is 38.7 °C.
This method can also be used to determine other quantities, such as the specific heat of an unknown metal.
5.3.0.1: Example 5.4

5.3.0.0.1: Identifying a Metal by Measuring Specific Heat
A 59.7 g piece of metal that had been submerged in boiling water was quickly transferred into 60.0 mL of water initially at
22.0 °C. The final temperature is 28.5 °C. Use these data to determine the specific heat of the metal. Use this result to identify
the metal.
5.3.0.0.1: Solution
Assuming perfect heat transfer, heat given off by metal = −heat taken in by water, or:
qmetal = −qwater
In expanded form, this is:

cmetal × mmetal × (Tf,metal − Ti, metal) = −cwater × mwater × (Tf,water − Ti,water)
Noting that since the metal was submerged in boiling water, its initial temperature was 100.0 °C; and that for water, 60.0 mL =
60.0 g; we have:
(cmetal )(59.7 g)(28.5 °C − 100.0 °C) = −(4.18 J/g °C)(60.0 g)(28.5 °C − 22.0 °C)
Solving this:
−(4.184 J/g °C)(60.0 g)(6.5 °C)
cmetal = = 0.38 J/g °C
(59.7 g)(−71.5 °C)
Comparing this with values in Table 5.1, our experimental specific heat is closest to the value for copper (0.39 J/g °C), so we
identify the metal as copper.
A 92.9-g piece of a silver/gray metal is heated to 178.0 °C, and then quickly transferred into 75.0 mL of water initially at 24.0
°C. After 5 minutes, both the metal and the water have reached the same temperature: 29.7 °C. Determine the specific heat and
the identity of the metal. (Note: You should find that the specific heat is close to that of two different metals. Explain how you
can confidently determine the identity of the metal).
5.3.0.1: Answer:
cmetal= 0.13 J/g °C
This specific heat is close to that of either gold or lead. It would be difficult to determine which metal this was based solely
on the numerical values. However, the observation that the metal is silver/gray in addition to the value for the specific heat
indicates that the metal is lead.

When we use calorimetry to determine the heat involved in a chemical reaction, the same principles we have been discussing apply.
The amount of heat absorbed by the calorimeter is often small enough that we can neglect it (though not for highly accurate
measurements, as discussed later), and the calorimeter minimizes energy exchange with the outside environment. Because energy is
neither created nor destroyed during a chemical reaction, the heat produced or consumed in the reaction (the “system”), qreaction,
plus the heat absorbed or lost by the solution (the “surroundings”), qsolution, must add up to zero:
qreaction + qsolution = 0
This means that the amount of heat produced or consumed in the reaction equals the amount of heat absorbed or lost by the
solution:
qreaction = −qsolution
This concept lies at the heart of all calorimetry problems and calculations.
5.3.0.1: Example 5.5

5.3.0.0.1: Heat Produced by an Exothermic Reaction
When 50.0 mL of 1.00 M HCl(aq) and 50.0 mL of 1.00 M NaOH(aq), both at 22.0 °C, are added to a coffee cup calorimeter,
the temperature of the mixture reaches a maximum of 28.9 °C. What is the approximate amount of heat produced by this
reaction?
HCl(aq) + NaOH(aq) ⟶ NaCl(aq) + H2 O(l)
5.3.0.0.1: Solution
To visualize what is going on, imagine that you could combine the two solutions so quickly that no reaction took place while
they mixed; then after mixing, the reaction took place. At the instant of mixing, you have 100.0 mL of a mixture of HCl and
NaOH at 22.0 °C. The HCl and NaOH then react until the solution temperature reaches 28.9 °C.
The heat given off by the reaction is equal to that taken in by the solution. Therefore:
qreaction = −qsolution
(It is important to remember that this relationship only holds if the calorimeter does not absorb any heat from the reaction, and
there is no heat exchange between the calorimeter and the outside environment.)
Next, we know that the heat absorbed by the solution depends on its specific heat, mass, and temperature change:
qsolution = (c × m × ΔT ) solution
To proceed with this calculation, we need to make a few more reasonable assumptions or approximations. Since the solution is
aqueous, we can proceed as if it were water in terms of its specific heat and mass values. The density of water is approximately
1.0 g/mL, so 100.0 mL has a mass of about 1.0 × 102 g (two significant figures). The specific heat of water is approximately
4.184 J/g °C, so we use that for the specific heat of the solution. Substituting these values gives:
2 3
qsolution = (4.184 J/g °C)(1.0 × 10 g)(28.9 °C − 22.0 °C) = 2.9 × 10 J
Finally, since we are trying to find the heat of the reaction, we have:
3
qreaction = −qsolution = −2.9 × 10 J
The negative sign indicates that the reaction is exothermic. It produces 2.9 kJ of heat.
When 100 mL of 0.200 M NaCl(aq) and 100 mL of 0.200 M AgNO3(aq), both at 21.9 °C, are mixed in a coffee cup
calorimeter, the temperature increases to 23.5 °C as solid AgCl forms. How much heat is produced by this precipitation
reaction? What assumptions did you make to determine your value?
5.3.0.1: Answer:
1.34 × 1.3 kJ; assume no heat is absorbed by the calorimeter, no heat is exchanged between the calorimeter and its
surroundings, and that the specific heat and mass of the solution are the same as those for water

5.3.0.0.1: Thermochemistry of Hand Warmers
When working or playing outdoors on a cold day, you might use a hand warmer to warm your hands (Figure 5.15). A common
reusable hand warmer contains a supersaturated solution of NaC2H3O2 (sodium acetate) and a metal disc. Bending the disk
creates nucleation sites around which the metastable NaC2H3O2 quickly crystallizes (a later chapter on solutions will
investigate saturation and supersaturation in more detail).
The process NaC H O (aq) ⟶ NaC H O (s) is exothermic, and the heat produced by this process is absorbed by your
2 3 2 2 3 2
hands, thereby warming them (at least for a while). If the hand warmer is reheated, the NaC2H3O2 redissolves and can be
reused.
Figure 5.15 Chemical hand warmers produce heat that warms your hand on a cold day. In this one, you can see the metal disc
that initiates the exothermic precipitation reaction. (credit: modification of work by Science Buddies TV/YouTube)
Another common hand warmer produces heat when it is ripped open, exposing iron and water in the hand warmer to oxygen in
the air. One simplified version of this exothermic reaction is 2Fe(s) + O (g) ⟶ Fe O (s). Salt in the hand warmer
3
2
2 2 3
catalyzes the reaction, so it produces heat more rapidly; cellulose, vermiculite, and activated carbon help distribute the heat
evenly. Other types of hand warmers use lighter fluid (a platinum catalyst helps lighter fluid oxidize exothermically), charcoal
(charcoal oxidizes in a special case), or electrical units that produce heat by passing an electrical current from a battery through
resistive wires.

This link shows the precipitation reaction that occurs when the disk in a chemical hand warmer is flexed.
5.3.0.1: Example 5.6

5.3.0.0.1: Heat Flow in an Instant Ice Pack
When solid ammonium nitrate dissolves in water, the solution becomes cold. This is the basis for an “instant ice pack” (Figure
5.16). When 3.21 g of solid NH4NO3 dissolves in 50.0 g of water at 24.9 °C in a calorimeter, the temperature decreases to 20.3
°C.
Calculate the value of q for this reaction and explain the meaning of its arithmetic sign. State any assumptions that you made.

Figure 5.16 An instant cold pack consists of a bag containing solid ammonium nitrate and a second bag of water. When the bag
of water is broken, the pack becomes cold because the dissolution of ammonium nitrate is an endothermic process that removes
thermal energy from the water. The cold pack then removes thermal energy from your body.
5.3.0.0.1: Solution
We assume that the calorimeter prevents heat transfer between the solution and its external environment (including the
calorimeter itself), in which case:
qrxn = −qsoln

with “rxn” and “soln” used as shorthand for “reaction” and “solution,” respectively.
Assuming also that the specific heat of the solution is the same as that for water, we have:
qrxn = −qsoln = −(c × m × ΔT )

soln
= −[(4.184 J/g °C) × (53.2 g) × (20.3 °C − 24.9 °C)]
= −[(4.184 J/g °C) × (53.2 g) × (−4.6 °C)]
3
+1.0 × 10 J = +1.0 kJ
The positive sign for q indicates that the dissolution is an endothermic process.
When a 3.00-g sample of KCl was added to 3.00 × 102 g of water in a coffee cup calorimeter, the temperature decreased by
1.05 °C. How much heat is involved in the dissolution of the KCl? What assumptions did you make?
5.3.0.1: Answer:
1.33 kJ; assume that the calorimeter prevents heat transfer between the solution and its external environment (including the
calorimeter itself) and that the specific heat of the solution is the same as that for water
If the amount of heat absorbed by a calorimeter is too large to neglect or if we require more accurate results, then we must take into
account the heat absorbed both by the solution and by the calorimeter.
The calorimeters described are designed to operate at constant (atmospheric) pressure and are convenient to measure heat flow
accompanying processes that occur in solution. A different type of calorimeter that operates at constant volume, colloquially
known as a bomb calorimeter, is used to measure the energy produced by reactions that yield large amounts of heat and gaseous
products, such as combustion reactions. (The term “bomb” comes from the observation that these reactions can be vigorous enough
to resemble explosions that would damage other calorimeters.) This type of calorimeter consists of a robust steel container (the
“bomb”) that contains the reactants and is itself submerged in water (Figure 5.17). The sample is placed in the bomb, which is then
filled with oxygen at high pressure. A small electrical spark is used to ignite the sample. The energy produced by the reaction is
absorbed by the steel bomb and the surrounding water. The temperature increase is measured and, along with the known heat
capacity of the calorimeter, is used to calculate the energy produced by the reaction. Bomb calorimeters require calibration to
determine the heat capacity of the calorimeter and ensure accurate results. The calibration is accomplished using a reaction with a
known q, such as a measured quantity of benzoic acid ignited by a spark from a nickel fuse wire that is weighed before and after
the reaction. The temperature change produced by the known reaction is used to determine the heat capacity of the calorimeter. The
calibration is generally performed each time before the calorimeter is used to gather research data.

Figure 5.17 (a) A bomb calorimeter is used to measure heat produced by reactions involving gaseous reactants or products, such as
combustion. (b) The reactants are contained in the gas-tight “bomb,” which is submerged in water and surrounded by insulating
materials. (credit a: modification of work by “Harbor1”/Wikimedia commons)

Click on this link to view how a bomb calorimeter is prepared for action.
This site shows calorimetric calculations using sample data.
5.3.0.1: Example 5.7

5.3.0.0.1: Bomb Calorimetry
When 3.12 g of glucose, C6H12O6, is burned in a bomb calorimeter, the temperature of the calorimeter increases from 23.8 °C
to 35.6 °C. The calorimeter contains 775 g of water, and the bomb itself has a heat capacity of 893 J/°C. How much heat was
produced by the combustion of the glucose sample?

5.3.0.0.1: Solution
The combustion produces heat that is primarily absorbed by the water and the bomb. (The amounts of heat absorbed by the
reaction products and the unreacted excess oxygen are relatively small and dealing with them is beyond the scope of this text.
We will neglect them in our calculations.)
The heat produced by the reaction is absorbed by the water and the bomb:
qrxn = −(qwater + qbomb )
= −[(4.184 J/g °C) × (775 g) × (35.6 °C − 23.8 °C) + 893 J/°C × (35.6 °C − 23.8 °C)]
= −(38,300 J + 10,500 J)
= −48,800 J = −48.8 kJ
This reaction released 48.7 kJ of heat when 3.12 g of glucose was burned.
When 0.963 g of benzene, C6H6, is burned in a bomb calorimeter, the temperature of the calorimeter increases by 8.39 °C. The
bomb has a heat capacity of 784 J/°C and is submerged in 925 mL of water. How much heat was produced by the combustion
of the benzene sample?
5.3.0.1: Answer:
qrx = –39.0 kJ (the reaction produced 39.0 kJ of heat)
Since the first one was constructed in 1899, 35 calorimeters have been built to measure the heat produced by a living person.2
These whole-body calorimeters of various designs are large enough to hold an individual human being. More recently, whole-room
calorimeters allow for relatively normal activities to be performed, and these calorimeters generate data that more closely reflect
the real world. These calorimeters are used to measure the metabolism of individuals under different environmental conditions,
different dietary regimes, and with different health conditions, such as diabetes.
For example Carla Prado's team at University of Alberta undertook whole-body calorimetry to understand the energy expenditures
of women who had recently given birth. Studies like this help develop better recommendations and regimens for nutrition, exercise,
and general wellbeing during this period of significant physiological change. In humans, metabolism is typically measured in
Calories per day. A nutritional calorie (Calorie) is the energy unit used to quantify the amount of energy derived from the
metabolism of foods; one Calorie is equal to 1000 calories (1 kcal), the amount of energy needed to heat 1 kg of water by 1 °C.

5.3.0.0.1: Measuring Nutritional Calories
In your day-to-day life, you may be more familiar with energy being given in Calories, or nutritional calories, which are used
to quantify the amount of energy in foods. One calorie (cal) = exactly 4.184 joules, and one Calorie (note the capitalization) =
1000 cal, or 1 kcal. (This is approximately the amount of energy needed to heat 1 kg of water by 1 °C.)
The macronutrients in food are proteins, carbohydrates, and fats or oils. Proteins provide about 4 Calories per gram,
carbohydrates also provide about 4 Calories per gram, and fats and oils provide about 9 Calories/g. Nutritional labels on food
packages show the caloric content of one serving of the food, as well as the breakdown into Calories from each of the three
macronutrients (Figure 5.18).

Figure 5.18 (a) Macaroni and cheese contain energy in the form of the macronutrients in the food. (b) The food’s nutritional
information is shown on the package label. In the US, the energy content is given in Calories (per serving); the rest of the
world usually uses kilojoules. (credit a: modification of work by “Rex Roof”/Flickr)
For the example shown in (b), the total energy per 228-g portion is calculated by:
(5 g protein × 4 Calories/g) + (31 g carb × 4 Calories/g) + (12 g fat × 9 Calories/g) = 252 Calories
So, you can use food labels to count your Calories. But where do the values come from? And how accurate are they? The
caloric content of foods can be determined by using bomb calorimetry; that is, by burning the food and measuring the energy it
contains. A sample of food is weighed, mixed in a blender, freeze-dried, ground into powder, and formed into a pellet. The
pellet is burned inside a bomb calorimeter, and the measured temperature change is converted into energy per gram of food.
Today, the caloric content on food labels is derived using a method called the Atwater system that uses the average caloric
content of the different chemical constituents of food, protein, carbohydrate, and fats. The average amounts are those given in
the equation and are derived from the various results given by bomb calorimetry of whole foods. The carbohydrate amount is
discounted a certain amount for the fiber content, which is indigestible carbohydrate. To determine the energy content of a
food, the quantities of carbohydrate, protein, and fat are each multiplied by the average Calories per gram for each and the
products summed to obtain the total energy.

Click on this link to access the US Department of Agriculture (USDA) National Nutrient Database, containing nutritional
information on over 8000 foods.
5.3.0.1: Footnotes
2Francis D. Reardon et al. “The Snellen human calorimeter revisited, re-engineered and upgraded: Design and performance
characteristics.” Medical and Biological Engineering and Computing 8 (2006)721–28, http://link.springer.com/article/10....517-
006-0086-5.
This page titled 5.3: Calorimetry is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content

5.4: Enthalpy

State the first law of thermodynamics
Define enthalpy and explain its classification as a state function
Write and balance thermochemical equations
Calculate enthalpy changes for various chemical reactions
Explain Hess’s law and use it to compute reaction enthalpies
Thermochemistry is a branch of chemical thermodynamics, the science that deals with the relationships between heat, work, and
other forms of energy in the context of chemical and physical processes. As we concentrate on thermochemistry in this chapter, we
need to consider some widely used concepts of thermodynamics.
Substances act as reservoirs of energy, meaning that energy can be added to them or removed from them. Energy is stored in a
substance when the kinetic energy of its atoms or molecules is raised. The greater kinetic energy may be in the form of increased
translations (travel or straight-line motions), vibrations, or rotations of the atoms or molecules. When thermal energy is lost, the
intensities of these motions decrease and the kinetic energy falls. The total of all possible kinds of energy present in a substance is
called the internal energy (U), sometimes symbolized as E.
As a system undergoes a change, its internal energy can change, and energy can be transferred from the system to the surroundings,
or from the surroundings to the system. Energy is transferred into a system when it absorbs heat (q) from the surroundings or when
the surroundings do work (w) on the system. For example, energy is transferred into room-temperature metal wire if it is immersed
in hot water (the wire absorbs heat from the water), or if you rapidly bend the wire back and forth (the wire becomes warmer
because of the work done on it). Both processes increase the internal energy of the wire, which is reflected in an increase in the
wire’s temperature. Conversely, energy is transferred out of a system when heat is lost from the system, or when the system does
work on the surroundings.
The relationship between internal energy, heat, and work can be represented by the equation:
ΔU = q + w
as shown in Figure 5.19. This is one version of the first law of thermodynamics, and it shows that the internal energy of a system
changes through heat flow into or out of the system (positive q is heat flow in; negative q is heat flow out) or work done on or by
the system. The work, w, is positive if it is done on the system and negative if it is done by the system.
0”, “System,” and “Δ U < 0.”"> 0”, “System,” and “Δ

U < 0.”" id="2">
Figure 5.19 The internal energy, U, of a system can be changed by heat flow and work. If heat flows into the system, qin, or work is
done on the system, won, its internal energy increases, ΔU > 0. If heat flows out of the system, qout, or work is done by the system,

wby, its internal energy decreases, ΔU < 0.
A type of work called expansion work (or pressure-volume work) occurs when a system pushes back the surroundings against a
restraining pressure, or when the surroundings compress the system. An example of this occurs during the operation of an internal
combustion engine. The reaction of gasoline and oxygen is exothermic. Some of this energy is given off as heat, and some does
work pushing the piston in the cylinder. The substances involved in the reaction are the system, and the engine and the rest of the
universe are the surroundings. The system loses energy by both heating and doing work on the surroundings, and its internal energy
decreases. (The engine is able to keep the car moving because this process is repeated many times per second while the engine is
running.) We will consider how to determine the amount of work involved in a chemical or physical change in the chapter on
thermodynamics.

This view of an internal combustion engine illustrates the conversion of energy produced by the exothermic combustion
reaction of a fuel such as gasoline into energy of motion.
As discussed, the relationship between internal energy, heat, and work can be represented as ΔU = q + w. Internal energy is an
example of a state function (or state variable), whereas heat and work are not state functions. The value of a state function depends
only on the state that a system is in, and not on how that state is reached. If a quantity is not a state function, then its value does
depend on how the state is reached. An example of a state function is altitude or elevation. If you stand on the summit of Mt.
Kilimanjaro, you are at an altitude of 5895 m, and it does not matter whether you hiked there or parachuted there. The distance you
traveled to the top of Kilimanjaro, however, is not a state function. You could climb to the summit by a direct route or by a more
roundabout, circuitous path (Figure 5.20). The distances traveled would differ (distance is not a state function) but the elevation
reached would be the same (altitude is a state function).
Figure 5.20 Paths X and Y represent two different routes to the summit of Mt. Kilimanjaro. Both have the same change in elevation
(altitude or elevation on a mountain is a state function; it does not depend on path), but they have very different distances traveled
(distance walked is not a state function; it depends on the path). (credit: modification of work by Paul Shaffner)
Chemists ordinarily use a property known as enthalpy (H) to describe the thermodynamics of chemical and physical processes.
Enthalpy is defined as the sum of a system’s internal energy (U) and the mathematical product of its pressure (P) and volume (V):
H = U +PV
Enthalpy is also a state function. Enthalpy values for specific substances cannot be measured directly; only enthalpy changes for
chemical or physical processes can be determined. For processes that take place at constant pressure (a common condition for many
chemical and physical changes), the enthalpy change (ΔH) is:

ΔH = ΔU + P ΔV
The mathematical product PΔV represents work (w), namely, expansion or pressure-volume work as noted. By their definitions, the
arithmetic signs of ΔV and w will always be opposite:
P ΔV = −w
Substituting this equation and the definition of internal energy into the enthalpy-change equation yields:
ΔH = ΔU + P ΔV
= qp + w − w
= qp
where qp is the heat of reaction under conditions of constant pressure.

And so, if a chemical or physical process is carried out at constant pressure with the only work done caused by expansion or
contraction, then the heat flow (qp) and enthalpy change (ΔH) for the process are equal.
The heat given off when you operate a Bunsen burner is equal to the enthalpy change of the methane combustion reaction that takes
place, since it occurs at the essentially constant pressure of the atmosphere. On the other hand, the heat produced by a reaction
measured in a bomb calorimeter (Figure 5.17) is not equal to ΔH because the closed, constant-volume metal container prevents the
pressure from remaining constant (it may increase or decrease if the reaction yields increased or decreased amounts of gaseous
species). Chemists usually perform experiments under normal atmospheric conditions, at constant external pressure with q = ΔH,
which makes enthalpy the most convenient choice for determining heat changes for chemical reactions.
The following conventions apply when using ΔH:
A negative value of an enthalpy change, ΔH < 0, indicates an exothermic reaction; a positive value, ΔH > 0, indicates an
endothermic reaction. If the direction of a chemical equation is reversed, the arithmetic sign of its ΔH is changed (a process that
is endothermic in one direction is exothermic in the opposite direction).
Chemists use a thermochemical equation to represent the changes in both matter and energy. In a thermochemical equation, the
enthalpy change of a reaction is shown as a ΔH value following the equation for the reaction. This ΔH value indicates the
amount of heat associated with the reaction involving the number of moles of reactants and products as shown in the chemical
equation. For example, consider this equation:
1
H2 (g) + O2 (g) ⟶ H2 O(l) ΔH = −286 kJ
2
This equation indicates that when 1 mole of hydrogen gas and mole of oxygen gas at some temperature and pressure change
1
to 1 mole of liquid water at the same temperature and pressure, 286 kJ of heat are released to the surroundings. If the
coefficients of the chemical equation are multiplied by some factor, the enthalpy change must be multiplied by that same factor
(ΔH is an extensive property):
(two-fold increase in amounts)
2 H2 (g) + O2 (g) ⟶ 2 H2 O(l) ΔH = 2 × (−286 kJ) = −572 kJ
(two-fold decrease in amounts)
1 1 1 1
H2 (g) + O2 (g) ⟶ H2 O(l) ΔH = × (−286 kJ) = −143 kJ
2 4 2 2
The enthalpy change of a reaction depends on the physical states of the reactants and products, so these must be shown. For
example, when 1 mole of hydrogen gas and mole of oxygen gas change to 1 mole of liquid water at the same temperature and
1
pressure, 286 kJ of heat are released. If gaseous water forms, only 242 kJ of heat are released.
1
H2 (g) + O2 (g) ⟶ H2 O(g) ΔH = −242 kJ
2
5.4.0.1: Example 5.8

5.4.0.0.1: Writing Thermochemical Equations
When 0.0500 mol of HCl(aq) reacts with 0.0500 mol of NaOH(aq) to form 0.0500 mol of NaCl(aq), 2.9 kJ of heat are
produced. Write a balanced thermochemical equation for the reaction of one mole of HCl.

5.4.0.0.1: Solution
For the reaction of 0.0500 mol acid (HCl), q = −2.9 kJ. The reactants are provided in stoichiometric amounts (same molar ratio
as in the balanced equation), and so the amount of acid may be used to calculate a molar enthalpy change. Since ΔH is an
extensive property, it is proportional to the amount of acid neutralized:
−2.9 kJ
ΔH = 1 mol HCl × = −58 kJ
0.0500 mol HCl
The thermochemical equation is then

HCl(aq) + NaOH(aq) ⟶ NaCl(aq) + H2 O(l) ΔH = −58 kJ

When 1.34 g Zn(s) reacts with 60.0 mL of 0.750 M HCl(aq), 3.14 kJ of heat are produced. Determine the enthalpy change per
mole of zinc reacting for the reaction:
Zn(s) + 2HCl(aq) ⟶ ZnCl2 (aq) + H2 (g)
5.4.0.1: Answer:
ΔH = −153 kJ
Be sure to take both stoichiometry and limiting reactants into account when determining the ΔH for a chemical reaction.
5.4.0.1: Example 5.9

5.4.0.0.1: Writing Thermochemical Equations
A gummy bear contains 2.67 g sucrose, C12H22O11. When it reacts with 7.19 g potassium chlorate, KClO3, 43.7 kJ of heat are
produced. Write a thermochemical equation for the reaction of one mole of sucrose:
C12 H22 O11 (aq) + 8 KClO3 (aq) ⟶ 12 CO2 (g) + 11 H2 O(l) + 8KCl(aq).
5.4.0.0.1: Solution
Unlike the previous example exercise, this one does not involve the reaction of stoichiometric amounts of reactants, and so the
limiting reactant must be identified (it limits the yield of the reaction and the amount of thermal energy produced or
consumed).
The provided amounts of the two reactants are
(2.67 g) (1 mol/342.3 g) = 0.00780 mol C12 H22 O11
(7.19 g) (1 mol/122.5 g) = 0.0587 mol KCIO3
The provided molar ratio of perchlorate-to-sucrose is then

0.0587 mol KCIO3 /0.00780 mol C12 H22 O11 = 7.52
The balanced equation indicates 8 mol KClO3 are required for reaction with 1 mol C12H22O11. Since the provided amount of
KClO3 is less than the stoichiometric amount, it is the limiting reactant and may be used to compute the enthalpy change:
△ H = −43.7 kJ/0.0587 mol KCIO3 = 744 kJ/mol KCIO3
Because the equation, as written, represents the reaction of 8 mol KClO3, the enthalpy change is
(744 kJ/mol KCIO3 ) (8 mol KCIO3 ) = 5960 kJ
The enthalpy change for this reaction is −5960 kJ, and the thermochemical equation is:
C12 H22 O11 + 8 KClO3 ⟶ 12 CO2 + 11 H2 O + 8KCl ΔH = −5960 kJ

When 1.42 g of iron reacts with 1.80 g of chlorine, 3.22 g of FeCl2(s) and 8.60 kJ of heat is produced. What is the enthalpy
change for the reaction when 1 mole of FeCl2(s) is produced?
5.4.0.1: Answer:

ΔH = −338 kJ
Enthalpy changes are typically tabulated for reactions in which both the reactants and products are at the same conditions. A
standard state is a commonly accepted set of conditions used as a reference point for the determination of properties under other
different conditions. For chemists, the IUPAC standard state refers to materials under a pressure of 1 bar and solutions at 1 M, and
does not specify a temperature. Many thermochemical tables list values with a standard state of 1 atm. Because the ΔH of a
reaction changes very little with such small changes in pressure (1 bar = 0.987 atm), ΔH values (except for the most precisely
measured values) are essentially the same under both sets of standard conditions. We will include a superscripted “o” in the
enthalpy change symbol to designate standard state. Since the usual (but not technically standard) temperature is 298.15 K, this
temperature will be assumed unless some other temperature is specified. Thus, the symbol (ΔH °) is used to indicate an enthalpy
change for a process occurring under these conditions. (The symbol ΔH is used to indicate an enthalpy change for a reaction
occurring under nonstandard conditions.)
The enthalpy changes for many types of chemical and physical processes are available in the reference literature, including those
for combustion reactions, phase transitions, and formation reactions. As we discuss these quantities, it is important to pay attention
to the extensive nature of enthalpy and enthalpy changes. Since the enthalpy change for a given reaction is proportional to the
amounts of substances involved, it may be reported on that basis (i.e., as the ΔH for specific amounts of reactants). However, we
often find it more useful to divide one extensive property (ΔH) by another (amount of substance), and report a per-amount intensive
value of ΔH, often “normalized” to a per-mole basis. (Note that this is similar to determining the intensive property specific heat
from the extensive property heat capacity, as seen previously.)
5.4.0.1: Standard Enthalpy of Combustion

Standard enthalpy of combustion (ΔH ) is the enthalpy change when 1 mole of a substance burns (combines vigorously with
°
C
oxygen) under standard state conditions; it is sometimes called “heat of combustion.” For example, the enthalpy of combustion of
ethanol, −1366.8 kJ/mol, is the amount of heat produced when one mole of ethanol undergoes complete combustion at 25 °C and 1
atmosphere pressure, yielding products also at 25 °C and 1 atm.
C2 H5 OH(l) + 3 O2 (g) ⟶ 2 CO2 + 3 H2 O(l) ΔH ° = −1366.8 kJ
Enthalpies of combustion for many substances have been measured; a few of these are listed in Table 5.2. Many readily available
substances with large enthalpies of combustion are used as fuels, including hydrogen, carbon (as coal or charcoal), and
hydrocarbons (compounds containing only hydrogen and carbon), such as methane, propane, and the major components of
gasoline.
Standard Molar Enthalpies of Combustion
Substance Combustion Reaction Enthalpy of Combustion, ΔH
∘
c (
kJ
at 25 °C)
mol
carbon C(s) + O2 (g) ⟶ CO2 (g) −393.5
hydrogen H2 (g) +
1
O2 (g) ⟶ H2 O(l) −285.8
2
magnesium Mg(s) +
1
O2 (g) ⟶ MgO(s) −601.6
2
sulfur S(s) + O2 (g) ⟶ SO2 (g) −296.8
carbon monoxide CO(g) +

1
O2 (g) ⟶ CO2 (g) −283.0
2
methane CH4 (g) + 2O2 (g) ⟶ CO2 (g) + 2H2 O(l) −890.8
acetylene C2 H2 (g) +
5
O2 (g) ⟶ 2CO2 (g) + H2 O(l) −1301.1
2

Substance Combustion Reaction Enthalpy of Combustion, ΔH ∘
c (
kJ
at 25 °C)
mol
ethanol C2 H5 OH(l) + 3O2 (g) ⟶ 2CO2 (g) + 3H2 O(l) −1366.8
methanol CH3 OH(l) +

3
O2 (g) ⟶ CO2 (g) + 2H2 O(l) −726.1
2
isooctane C8 H18 (l) +

25
O2 (g) ⟶ 8CO2 (g) + 9H2 O(l) −5461
2
Table 5.2
5.4.0.1: Example 5.10

5.4.0.0.1: Using Enthalpy of Combustion
As Figure 5.21 suggests, the combustion of gasoline is a highly exothermic process. Let us determine the approximate amount
of heat produced by burning 1.00 L of gasoline, assuming the enthalpy of combustion of gasoline is the same as that of
isooctane, a common component of gasoline. The density of isooctane is 0.692 g/mL.
Figure 5.21 The combustion of gasoline is very exothermic. (credit: modification of work by “AlexEagle”/Flickr)
5.4.0.0.2: Solution
Starting with a known amount (1.00 L of isooctane), we can perform conversions between units until we arrive at the desired
amount of heat or energy. The enthalpy of combustion of isooctane provides one of the necessary conversions. Table 5.2 gives
this value as −5460 kJ per 1 mole of isooctane (C8H18).
Using these data,
1000 mL C8 H18 0.692 g C8 H18 1 mol C8 H18

−5460 kJ
4
1.00 L C8 H18 × × × × = −3.31 × 10 kJ
1 L C8 H18 1 mL C8 H18 114 g C8 H18 1 mol C8 H18
The combustion of 1.00 L of isooctane produces 33,100 kJ of heat. (This amount of energy is enough to melt 99.2 kg, or about
218 lbs, of ice.)
Note: If you do this calculation one step at a time, you would find:
3
1.00 L C8 H18 ⟶ 1.00 × 10 mL C8 H18
3
1.00 × 10 mL C8 H18 ⟶ 692 g C8 H18
692 g C8 H18 ⟶ 6.07 mol C8 H18
4
6.07 mol C8 H18 ⟶ −3.31 × 10 kJ

How much heat is produced by the combustion of 125 g of acetylene?
5.4.0.1: Answer:
6.25 × 103 kJ

5.4.0.0.4: Emerging Algae-Based Energy Technologies (Biofuels)
As reserves of fossil fuels diminish and become more costly to extract, the search is ongoing for replacement fuel sources for
the future. Among the most promising biofuels are those derived from algae (Figure 5.22). The species of algae used are
nontoxic, biodegradable, and among the world’s fastest growing organisms. About 50% of algal weight is oil, which can be
readily converted into fuel such as biodiesel. Algae can yield 26,000 gallons of biofuel per hectare—much more energy per
acre than other crops. Some strains of algae can flourish in brackish water that is not usable for growing other crops. Algae can
produce biodiesel, biogasoline, ethanol, butanol, methane, and even jet fuel.
Figure 5.22 (a) Tiny algal organisms can be (b) grown in large quantities and eventually (c) turned into a useful fuel such as
biodiesel. (credit a: modification of work by Micah Sittig; credit b: modification of work by Robert Kerton; credit c:
modification of work by John F. Williams)
According to the US Department of Energy, only 39,000 square kilometers (about 0.4% of the land mass of the US or less than
1
7
of the area used to grow corn) can produce enough algal fuel to replace all the petroleum-based fuel used in the US. The cost
of algal fuels is becoming more competitive—for instance, the US Air Force is producing jet fuel from algae at a total cost of
under $5 per gallon.3 The process used to produce algal fuel is as follows: grow the algae (which use sunlight as their energy
source and CO2 as a raw material); harvest the algae; extract the fuel compounds (or precursor compounds); process as
necessary (e.g., perform a transesterification reaction to make biodiesel); purify; and distribute (Figure 5.23).
Figure 5.23 Algae convert sunlight and carbon dioxide into oil that is harvested, extracted, purified, and transformed into a
variety of renewable fuels.

Click here to learn more about the process of creating algae biofuel.

5.4.0.1: Standard Enthalpy of Formation
A standard enthalpy of formation ΔH is an enthalpy change for a reaction in which exactly 1 mole of a pure substance is formed
∘
f
from free elements in their most stable states under standard state conditions. These values are especially useful for computing or
predicting enthalpy changes for chemical reactions that are impractical or dangerous to carry out, or for processes for which it is
difficult to make measurements. If we have values for the appropriate standard enthalpies of formation, we can determine the
enthalpy change for any reaction, which we will practice in the next section on Hess’s law.
The standard enthalpy of formation of CO2(g) is −393.5 kJ/mol. This is the enthalpy change for the exothermic reaction:
∘
C(s) + O2 (g) ⟶ CO2 (g) ΔH = ΔH ° = −393.5 kJ
f
starting with the reactants at a pressure of 1 atm and 25 °C (with the carbon present as graphite, the most stable form of carbon
under these conditions) and ending with one mole of CO2, also at 1 atm and 25 °C. For nitrogen dioxide, NO2(g), ΔH is 33.2 ∘
f
kJ/mol. This is the enthalpy change for the reaction:

1
∘
N2 (g) + O2 (g) ⟶ NO2 (g) ΔH = ΔH ° = +33.2 kJ
f
2
A reaction equation with mole of N2 and 1 mole of O2 is correct in this case because the standard enthalpy of formation always
1
refers to 1 mole of product, NO2(g).

You will find a table of standard enthalpies of formation of many common substances in Appendix G. These values indicate that
formation reactions range from highly exothermic (such as −2984 kJ/mol for the formation of P4O10) to strongly endothermic (such
as +226.7 kJ/mol for the formation of acetylene, C2H2). By definition, the standard enthalpy of formation of an element in its most
stable form is equal to zero under standard conditions, which is 1 atm for gases and 1 M for solutions.
5.4.0.1: Example 5.11

5.4.0.0.1: Evaluating an Enthalpy of Formation
Ozone, O3(g), forms from oxygen, O2(g), by an endothermic process. Ultraviolet radiation is the source of the energy that
drives this reaction in the upper atmosphere. Assuming that both the reactants and products of the reaction are in their standard
states, determine the standard enthalpy of formation, ΔH of ozone from the following information:
f
∘
3 O2 (g) ⟶ 2 O3 (g) ΔH ° = +286 kJ
5.4.0.0.2: Solution
ΔH
f
∘
is the enthalpy change for the formation of one mole of a substance in its standard state from the elements in their
standard states. Thus, ΔH for O3(g) is the enthalpy change for the reaction:
f
∘
3
O2 (g) ⟶ O3 (g)
2
For the formation of 2 mol of O3(g), ΔH ° = +286 kJ. This ratio, ( 286 kJ
2 mol O3
), can be used as a conversion factor to find the
heat produced when 1 mole of O3(g) is formed, which is the enthalpy of formation for O3(g):
286 kJ
ΔH° for 1 mole of O3 (g) = 1 mol O3 × = 143 kJ
2 mol O3
Therefore, ΔH f
∘
[ O3 (g)] = +143 kJ/mol.

Hydrogen gas, H2, reacts explosively with gaseous chlorine, Cl2, to form hydrogen chloride, HCl(g). What is the enthalpy
change for the reaction of 1 mole of H2(g) with 1 mole of Cl2(g) if both the reactants and products are at standard state
conditions? The standard enthalpy of formation of HCl(g) is −92.3 kJ/mol.
5.4.0.1: Answer:
For the reaction H 2 (g) + Cl2 (g) ⟶ 2HCl(g) ΔH ° = −184.6 kJ
5.4.0.1: Example 5.12

5.4.0.0.4: Writing Reaction Equations for ΔH ∘
f
Write the heat of formation reaction equations for:

(a) C2H5OH(l)
(b) Ca3(PO4)2(s)
5.4.0.0.5: Solution
Remembering that ΔH reaction equations are for forming 1 mole of the compound from its constituent elements under
∘
f
standard conditions, we have:

(a) 2C(s, graphite) + 3 H2 (g) +
1
2
O2 (g) ⟶ C2 H5 OH(l)
(b) 3Ca(s) + 1
2
P4 (s) + 4 O2 (g) ⟶ Ca3 (PO4 ) (s)
2
Note: The standard state of carbon is graphite, and phosphorus exists as P4.
Write the heat of formation reaction equations for:
(a) C2H5OC2H5(l)
(b) Na2CO3(s)
5.4.0.1: Answer:
(a) 4C(s, graphite) + 5 H2 (g) +
1
2
O2 (g) ⟶ C2 H5 OC 2 H5 (l); (b)
3
2Na(s) + C(s, graphite) + O2 (g) ⟶ Na2 CO3 (s)
2
5.4.0.1: Hess’s Law

There are two ways to determine the amount of heat involved in a chemical change: measure it experimentally, or calculate it from
other experimentally determined enthalpy changes. Some reactions are difficult, if not impossible, to investigate and make accurate
measurements for experimentally. And even when a reaction is not hard to perform or measure, it is convenient to be able to
determine the heat involved in a reaction without having to perform an experiment.
This type of calculation usually involves the use of Hess’s law, which states: If a process can be written as the sum of several
stepwise processes, the enthalpy change of the total process equals the sum of the enthalpy changes of the various steps. Hess’s law
is valid because enthalpy is a state function: Enthalpy changes depend only on where a chemical process starts and ends, but not on
the path it takes from start to finish. For example, we can think of the reaction of carbon with oxygen to form carbon dioxide as
occurring either directly or by a two-step process. The direct process is written:
C(s) + O2 (g) ⟶ CO2 (g) ΔH ° = −394 kJ
In the two-step process, first carbon monoxide is formed:

1
C(s) + O2 (g) ⟶ CO(g) ΔH ° = −111 kJ
2
Then, carbon monoxide reacts further to form carbon dioxide:

1
CO(g) + O2 (g) ⟶ CO2 (g) ΔH ° = −283 kJ
2
The equation describing the overall reaction is the sum of these two chemical changes:
1
Step 1: C(s) + O2 (g) ⟶ CO(g)
2
1
Step 2: CO(g) + O2 (g) ⟶ CO2 (g)
2
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
1 1
Sum: C(s) + O2 (g) + CO(g) + O2 (g) ⟶ CO(g) + CO2 (g)
2 2
Because the CO produced in Step 1 is consumed in Step 2, the net change is:
C(s) + O2 (g) ⟶ CO2 (g)

According to Hess’s law, the enthalpy change of the reaction will equal the sum of the enthalpy changes of the steps.
1
C(s) + O2 (g) ⟶ CO(g) ΔH ° = −111 kJ
2
1
CO(g)+ O2 (g) ⟶ CO2 (g)
2 ΔH °=−283 kJ
C(s)+O2 (g) ⟶ CO2 (g) ΔH °=−394 kJ
The result is shown in Figure 5.24. We see that ΔH of the overall reaction is the same whether it occurs in one step or two. This
finding (overall ΔH for the reaction = sum of ΔH values for reaction “steps” in the overall reaction) is true in general for chemical
and physical processes.
Figure 5.24 The formation of CO2(g) from its elements can be thought of as occurring in two steps, which sum to the overall
reaction, as described by Hess’s law. The horizontal blue lines represent enthalpies. For an exothermic process, the products are at
lower enthalpy than are the reactants.
Before we further practice using Hess’s law, let us recall two important features of ΔH.
1. ΔH is directly proportional to the quantities of reactants or products. For example, the enthalpy change for the reaction forming
1 mole of NO2(g) is +33.2 kJ:
1
N2 (g) + O2 (g) ⟶ NO2 (g) ΔH = +33.2 kJ
2
When 2 moles of NO2 (twice as much) are formed, the ΔH will be twice as large:
N2 (g) + 2 O2 (g) ⟶ 2 NO2 (g) ΔH = +66.4 kJ
In general, if we multiply or divide an equation by a number, then the enthalpy change should also be multiplied or divided by
the same number.
2. ΔH for a reaction in one direction is equal in magnitude and opposite in sign to ΔH for the reaction in the reverse direction. For
example, given that:
H2 (g) + Cl2 (g) ⟶ 2HCl(g) ΔH = −184.6 kJ
Then, for the “reverse” reaction, the enthalpy change is also “reversed”:
2HCl(g) ⟶ H2 (g) + Cl2 (g) ΔH = +184.6 kJ
5.4.0.1: Example 5.13

5.4.0.0.1: Stepwise Calculation of ΔH Using Hess’s Law
∘
f
Determine the enthalpy of formation, ΔH ∘

f
, of FeCl3(s) from the enthalpy changes of the following two-step process that
occurs under standard state conditions:
Fe(s) + Cl2 (g) ⟶ FeCl2 (s) ΔH° = −341.8 kJ
1
FeCl2 (s) + Cl2 (g) ⟶ FeCl3 (s) ΔH° = −57.7 kJ
2
5.4.0.0.2: Solution
We are trying to find the standard enthalpy of formation of FeCl3(s), which is equal to ΔH° for the reaction:
3
∘
Fe(s) + Cl2 (g) ⟶ FeCl3 (s) ΔH =?
f
2
Looking at the reactions, we see that the reaction for which we want to find ΔH° is the sum of the two reactions with known
ΔH values, so we must sum their ΔHs:
Fe(s) + Cl2 (g) ⟶ FeCl2 (s) ΔH ° = −341.8 kJ
1
FeCl2 (s)+ Cl2 (g) ⟶ FeCl3 (s)
2 ΔH °=−57.7 kJ
3
ΔH °=−399.5 kJ
Fe(s)+ Cl2 (g) ⟶ FeCl3 (s)
2
The enthalpy of formation, ΔH ∘

f
, of FeCl3(s) is −399.5 kJ/mol.
Calculate ΔH for the process:
N2 (g) + 2 O2 (g) ⟶ 2 NO2 (g)
from the following information:

N2 (g) + O2 (g) ⟶ 2NO(g) ΔH = 180.5 kJ
1
NO(g) + O2 (g) ⟶ NO2 (g) ΔH = −57.06 kJ
2
5.4.0.1: Answer:
66.4 kJ
Here is a less straightforward example that illustrates the thought process involved in solving many Hess’s law problems. It shows
how we can find many standard enthalpies of formation (and other values of ΔH) if they are difficult to determine experimentally.
5.4.0.1: Example 5.14

5.4.0.0.4: A More Challenging Problem Using Hess’s Law
Chlorine monofluoride can react with fluorine to form chlorine trifluoride:
(i) ClF(g) + F 2 (g) ⟶ ClF3 (g) ΔH° =?
Use the reactions here to determine the ΔH° for reaction (i):
(ii) 2OF 2 (g) ⟶ O2 (g) + 2 F2 (g) ΔH
∘
(ii)
= −49.4 kJ
(iii) 2ClF(g) + O 2 (g) ⟶ Cl2 O(g) + OF 2 (g) ΔH

∘
(iii)
= +214.0 kJ
(iv) ClF 3 (g) + O2 (g) ⟶

1
2
Cl2 O(g) +
3
2
OF 2 (g) ΔH
∘
(iv)
= +236.2 kJ
5.4.0.0.5: Solution
Our goal is to manipulate and combine reactions (ii), (iii), and (iv) such that they add up to reaction (i). Going from left to right
in (i), we first see that ClF(g) is needed as a reactant. This can be obtained by multiplying reaction (iii) by , which means that 1
the ΔH° change is also multiplied by : 1
1 1 1 1
ClF(g) + O2 (g) ⟶ Cl2 O(g) + OF 2 (g) ΔH° = (214.0) = +107.0 kJ
2 2 2 2

Next, we see that F2 is also needed as a reactant. To get this, reverse and halve reaction (ii), which means that the ΔH° changes
sign and is halved:
1
O2 (g) + F2 (g) ⟶ OF 2 (g) ΔH° = +24.7 kJ
2
To get ClF3 as a product, reverse (iv), changing the sign of ΔH°:

1 3
Cl2 O(g) + OF 2 (g) ⟶ ClF3 (g) + O2 (g) ΔH° = −236.2 kJ
2 2
Now check to make sure that these reactions add up to the reaction we want:
1 1 1
ClF(g) + O2 (g) ⟶ Cl2 O(g) + OF 2 (g) ΔH ° = +107.0 kJ
2 2 2
1
O2 (g) + F2 (g) ⟶ OF 2 (g) ΔH ° = +24.7 kJ
2
1 3
Cl2 O(g)+ OF 2 (g) ⟶ ClF3 (g)+O2 (g)
2 2 ΔH °=−236.2 kJ
ClF(g)+F2 ⟶ ClF3 (g) ΔH °=−104.5 kJ
Reactants O and O cancel out product O2; product Cl O cancels reactant Cl O; and reactant OF is cancelled by
1
2
2
1
2
2
1
2
2
1
2
2
3
2
2
products OF and OF2. This leaves only reactants ClF(g) and F2(g) and product ClF3(g), which are what we want. Since
1
2
2
summing these three modified reactions yields the reaction of interest, summing the three modified ΔH° values will give the
desired ΔH°:
ΔH ° = (+107.0 kJ) + (24.7 kJ) + (−236.2 kJ) = −104.5 kJ

Aluminum chloride can be formed from its elements:
(i) 2Al(s) + 3Cl 2 (g) ⟶ 2 AlCl3 (s) ΔH ° =?
Use the reactions here to determine the ΔH° for reaction (i):
(ii) HCl(g) ⟶ HCl(aq) ΔH
∘
(ii)
= −74.8 kJ
(iii) H
2 (g) + Cl2 (g) ⟶ 2HCl(g) ΔH
∘
(iii)
= −185 kJ
(iv) AlCl 3 (aq) ⟶ AlCl3 (s) ΔH

∘
(iv)
= +323 kJ/mol
(v) 2Al(s) + 6HCl(aq) ⟶ 2 AlCl3 (aq) + 3 H2 (g) ΔH

∘
(v)
= −1049 kJ
5.4.0.1: Answer:
−1407 kJ
We also can use Hess’s law to determine the enthalpy change of any reaction if the corresponding enthalpies of formation of the
reactants and products are available. The stepwise reactions we consider are: (i) decompositions of the reactants into their
component elements (for which the enthalpy changes are proportional to the negative of the enthalpies of formation of the
reactants), followed by (ii) re-combinations of the elements to give the products (with the enthalpy changes proportional to the
enthalpies of formation of the products). The standard enthalpy change of the overall reaction is therefore equal to: (ii) the sum of
the standard enthalpies of formation of all the products plus (i) the sum of the negatives of the standard enthalpies of formation of
the reactants. This is usually rearranged slightly to be written as follows, with ∑ representing “the sum of” and n standing for the
stoichiometric coefficients:
∘ ∘ ∘
ΔH = ∑ n × ΔH (products) − ∑ n × ΔH (reactants)
reaction f f
The following example shows in detail why this equation is valid, and how to use it to calculate the enthalpy change for a reaction
of interest.
5.4.0.1: Example 5.15

5.4.0.0.7: Using Hess’s Law
What is the standard enthalpy change for the reaction:
3 NO2 (g) + H2 O(l) ⟶ 2 HNO3 (aq) + NO(g) ΔH° =?
5.4.0.0.8: Solution: Using the Equation

Use the special form of Hess’s law given previously, and values from Appendix G:
∘ ∘ ∘
reaction f f
−207.4 kJ +90.2 kJ
= [2 mol HNO3 (aq) × +1 mol NO(g) × ]
mol HNO3 (aq) mol NO(g)
+33.2 kJ −285.8 kJ
− [3 mol NO2 (g) × +1 mol H2 O(l) × ]
mol NO2 (g) mol H2 O(l)
= [2 × (−206.64) + 90.25] − [3 × 33.2+ − (−285.83)]
= –323.03 + 186.23
= −136.80 kJ
5.4.0.0.9: Solution: Supporting Why the General Equation Is Valid

Alternatively, we can write this reaction as the sum of the decompositions of 3NO2(g) and 1H2O(l) into their constituent
elements, and the formation of 2HNO3(aq) and 1NO(g) from their constituent elements. Writing out these reactions, and noting
their relationships to the ΔH values for these compounds (from Appendix G ), we have:
∘
f
∘
3 NO2 (g) ⟶ 3/2N (g) + 3O2 (g) ΔH = −99.6 kJ
2 1
1
∘ ∘
H2 O(l) ⟶ H2 (g) + O2 (g) ΔH = +285.8 kJ [−1 × ΔH (H2 O)]
2 f
2
∘ ∘
H2 (g) + N2 (g) + 3 O2 (g) ⟶ 2 HNO3 (aq) ΔH = −414.8 kJ [2 × ΔH (HNO3 )]
3 f
1 1
∘
N2 (g) + O2 (g) ⟶ NO(g) ΔH = +90.2 kJ [1 × (NO)]
4
2 2
Summing these reaction equations gives the reaction we are interested in:
3NO2 (g) + H2 O(l) ⟶ 2 HNO3 (aq) + NO(g)
Summing their enthalpy changes gives the value we want to determine:

∘ ∘ ∘ ∘ ∘
ΔHrxn = ΔH + ΔH + ΔH + ΔH = (−99.6 kJ) + (+285.8 kJ) + (−414.8 kJ) + (+90.2 kJ)
1 2 3 4
= −138.4 kJ
So the standard enthalpy change for this reaction is ΔH° = −138.4 kJ.
Note that this result was obtained by (1) multiplying the ΔH of each product by its stoichiometric coefficient and summing
∘
f
those values, (2) multiplying the ΔH of each reactant by its stoichiometric coefficient and summing those values, and then
∘
f
(3) subtracting the result found in (2) from the result found in (1). This is also the procedure in using the general equation, as
shown.
Calculate the heat of combustion of 1 mole of ethanol, C2H5OH(l), when H2O(l) and CO2(g) are formed. Use the following
enthalpies of formation: C2H5OH(l), −278 kJ/mol; H2O(l), −286 kJ/mol; and CO2(g), −394 kJ/mol.
5.4.0.1: Answer:
−1368 kJ/mol

5.4.0.1: Footnotes
3For more on algal fuel, see http://www.theguardian.com/environme...n-fuel-problem.
This page titled 5.4: Enthalpy is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content that

5.5: Key Terms
bomb calorimeter
device designed to measure the energy change for processes occurring under conditions of constant volume; commonly used for
reactions involving solid and gaseous reactants or products
calorie (cal)
unit of heat or other energy; the amount of energy required to raise 1 gram of water by 1 degree Celsius; 1 cal is defined as
4.184 J
calorimeter
device used to measure the amount of heat absorbed or released in a chemical or physical process
calorimetry
process of measuring the amount of heat involved in a chemical or physical process
chemical thermodynamics
area of science that deals with the relationships between heat, work, and all forms of energy associated with chemical and
physical processes
endothermic process
chemical reaction or physical change that absorbs heat
energy
capacity to supply heat or do work
enthalpy (H)
sum of a system’s internal energy and the mathematical product of its pressure and volume
enthalpy change (ΔH)

heat released or absorbed by a system under constant pressure during a chemical or physical process
exothermic process
chemical reaction or physical change that releases heat
expansion work (pressure-volume work)

work done as a system expands or contracts against external pressure
first law of thermodynamics

internal energy of a system changes due to heat flow in or out of the system or work done on or by the system
heat (q)
transfer of thermal energy between two bodies
heat capacity (C)

extensive property of a body of matter that represents the quantity of heat required to increase its temperature by 1 degree
Celsius (or 1 kelvin)
Hess’s law
if a process can be represented as the sum of several steps, the enthalpy change of the process equals the sum of the enthalpy
changes of the steps
hydrocarbon
compound composed only of hydrogen and carbon; the major component of fossil fuels
internal energy (U)
total of all possible kinds of energy present in a substance or substances
joule (J)
SI unit of energy; 1 joule is the kinetic energy of an object with a mass of 2 kilograms moving with a velocity of 1 meter per
second, 1 J = 1 kg m2/s and 4.184 J = 1 cal
kinetic energy
energy of a moving body, in joules, equal to 1
2
2
mv (where m = mass and v = velocity)
nutritional calorie (Calorie)

unit used for quantifying energy provided by digestion of foods, defined as 1000 cal or 1 kcal
potential energy
energy of a particle or system of particles derived from relative position, composition, or condition
specific heat capacity (c)

intensive property of a substance that represents the quantity of heat required to raise the temperature of 1 gram of the substance
by 1 degree Celsius (or 1 kelvin)
standard enthalpy of combustion (ΔH ∘

c )
heat released when one mole of a compound undergoes complete combustion under standard conditions
standard enthalpy of formation (ΔH ∘

f
)
enthalpy change of a chemical reaction in which 1 mole of a pure substance is formed from its elements in their most stable
states under standard state conditions
standard state
set of physical conditions as accepted as common reference conditions for reporting thermodynamic properties; 1 bar of
pressure, and solutions at 1 molar concentrations, usually at a temperature of 298.15 K
state function
property depending only on the state of a system, and not the path taken to reach that state
surroundings
all matter other than the system being studied
system
portion of matter undergoing a chemical or physical change being studied
temperature
intensive property of matter that is a quantitative measure of “hotness” and “coldness”
thermal energy
kinetic energy associated with the random motion of atoms and molecules
thermochemistry
study of measuring the amount of heat absorbed or released during a chemical reaction or a physical change
work (w)
energy transfer due to changes in external, macroscopic variables such as pressure and volume; or causing matter to move
against an opposing force
5.6: Key Equations
q = c × m × ΔT = c × m × ( Tfinal − Tinitial )
ΔU = q + w
∘ ∘ ∘
reaction f f
5.7: Summary
5.1 Energy Basics
Energy is the capacity to supply heat or do work (applying a force to move matter). Kinetic energy (KE) is the energy of motion;
potential energy is energy due to relative position, composition, or condition. When energy is converted from one form into
another, energy is neither created nor destroyed (law of conservation of energy or first law of thermodynamics).
The thermal energy of matter is due to the kinetic energies of its constituent atoms or molecules. Temperature is an intensive
property of matter reflecting hotness or coldness that increases as the average kinetic energy increases. Heat is the transfer of
thermal energy between objects at different temperatures. Chemical and physical processes can absorb heat (endothermic) or
release heat (exothermic). The SI unit of energy, heat, and work is the joule (J).
Specific heat and heat capacity are measures of the energy needed to change the temperature of a substance or object. The amount
of heat absorbed or released by a substance depends directly on the type of substance, its mass, and the temperature change it
undergoes.
5.2 Calorimetry
Calorimetry is used to measure the amount of thermal energy transferred in a chemical or physical process. This requires careful
measurement of the temperature change that occurs during the process and the masses of the system and surroundings. These
measured quantities are then used to compute the amount of heat produced or consumed in the process using known mathematical
relations.
Calorimeters are designed to minimize energy exchange between their contents and the external environment. They range from
simple coffee cup calorimeters used by introductory chemistry students to sophisticated bomb calorimeters used to determine the
energy content of food.
5.3 Enthalpy
If a chemical change is carried out at constant pressure and the only work done is caused by expansion or contraction, q for the
change is called the enthalpy change with the symbol ΔH, or ΔH ° for reactions occurring under standard state conditions at 298
K. The value of ΔH for a reaction in one direction is equal in magnitude, but opposite in sign, to ΔH for the reaction in the opposite
direction, and ΔH is directly proportional to the quantity of reactants and products. The standard enthalpy of formation, ΔH , is ∘
f
the enthalpy change accompanying the formation of 1 mole of a substance from the elements in their most stable states at 1 bar and
298.15 K. If the enthalpies of formation are available for the reactants and products of a reaction, the enthalpy change can be
calculated using Hess’s law: If a process can be written as the sum of several stepwise processes, the enthalpy change of the total
process equals the sum of the enthalpy changes of the various steps.
5.8: Exercises
5.1 Energy Basics
1.
A burning match and a bonfire may have the same temperature, yet you would not sit around a burning match on a fall evening to
stay warm. Why not?
2.
Prepare a table identifying several energy transitions that take place during the typical operation of an automobile.
3.
Explain the difference between heat capacity and specific heat of a substance.
4.
Calculate the heat capacity, in joules and in calories per degree, of the following:
(a) 28.4 g of water
(b) 1.00 oz of lead
5.
Calculate the heat capacity, in joules and in calories per degree, of the following:
(a) 45.8 g of nitrogen gas
(b) 1.00 pound of aluminum metal
6.
How much heat, in joules and in calories, must be added to a 75.0–g iron block with a specific heat of 0.449 J/g °C to increase its
temperature from 25 °C to its melting temperature of 1535 °C?
7.
How much heat, in joules and in calories, is required to heat a 28.4-g (1-oz) ice cube from −23.0 °C to −1.0 °C?
8.
How much would the temperature of 275 g of water increase if 36.5 kJ of heat were added?
9.
If 14.5 kJ of heat were added to 485 g of liquid water, how much would its temperature increase?
10.
A piece of unknown substance weighs 44.7 g and requires 2110 J to increase its temperature from 23.2 °C to 89.6 °C.
(a) What is the specific heat of the substance?
(b) If it is one of the substances found in Table 5.1, what is its likely identity?
11.
A piece of unknown solid substance weighs 437.2 g, and requires 8460 J to increase its temperature from 19.3 °C to 68.9 °C.
(a) What is the specific heat of the substance?
(b) If it is one of the substances found in Table 5.1, what is its likely identity?
12.
An aluminum kettle weighs 1.05 kg.
(a) What is the heat capacity of the kettle?
(b) How much heat is required to increase the temperature of this kettle from 23.0 °C to 99.0 °C?
(c) How much heat is required to heat this kettle from 23.0 °C to 99.0 °C if it contains 1.25 L of water (density of 0.997 g/mL and a
specific heat of 4.184 J/g °C)?

13.
Most people find waterbeds uncomfortable unless the water temperature is maintained at about 85 °F. Unless it is heated, a
waterbed that contains 892 L of water cools from 85 °F to 72 °F in 24 hours. Estimate the amount of electrical energy required over
24 hours, in kWh, to keep the bed from cooling. Note that 1 kilowatt-hour (kWh) = 3.6 × 106 J, and assume that the density of
water is 1.0 g/mL (independent of temperature). What other assumptions did you make? How did they affect your calculated result
(i.e., were they likely to yield “positive” or “negative” errors)?
5.2 Calorimetry
14.
A 500-mL bottle of water at room temperature and a 2-L bottle of water at the same temperature were placed in a refrigerator. After
30 minutes, the 500-mL bottle of water had cooled to the temperature of the refrigerator. An hour later, the 2-L of water had cooled
to the same temperature. When asked which sample of water lost the most heat, one student replied that both bottles lost the same
amount of heat because they started at the same temperature and finished at the same temperature. A second student thought that
the 2-L bottle of water lost more heat because there was more water. A third student believed that the 500-mL bottle of water lost
more heat because it cooled more quickly. A fourth student thought that it was not possible to tell because we do not know the
initial temperature and the final temperature of the water. Indicate which of these answers is correct and describe the error in each
of the other answers.
15.
Would the amount of heat measured for the reaction in Example 5.5 be greater, lesser, or remain the same if we used a calorimeter
that was a poorer insulator than a coffee cup calorimeter? Explain your answer.
16.
Would the amount of heat absorbed by the dissolution in Example 5.6 appear greater, lesser, or remain the same if the experimenter
used a calorimeter that was a poorer insulator than a coffee cup calorimeter? Explain your answer.
17.
Would the amount of heat absorbed by the dissolution in Example 5.6 appear greater, lesser, or remain the same if the heat capacity
of the calorimeter were taken into account? Explain your answer.
18.
How many milliliters of water at 23 °C with a density of 1.00 g/mL must be mixed with 180 mL (about 6 oz) of coffee at 95 °C so
that the resulting combination will have a temperature of 60 °C? Assume that coffee and water have the same density and the same
specific heat.
19.
How much will the temperature of a cup (180 g) of coffee at 95 °C be reduced when a 45 g silver spoon (specific heat 0.24 J/g °C)
at 25 °C is placed in the coffee and the two are allowed to reach the same temperature? Assume that the coffee has the same density
and specific heat as water.
20.
A 45-g aluminum spoon (specific heat 0.88 J/g °C) at 24 °C is placed in 180 mL (180 g) of coffee at 85 °C and the temperature of
the two become equal.
(a) What is the final temperature when the two become equal? Assume that coffee has the same specific heat as water.
(b) The first time a student solved this problem she got an answer of 88 °C. Explain why this is clearly an incorrect answer.
21.
The temperature of the cooling water as it leaves the hot engine of an automobile is 240 °F. After it passes through the radiator it
has a temperature of 175 °F. Calculate the amount of heat transferred from the engine to the surroundings by one gallon of water
with a specific heat of 4.184 J/g °C.
22.
A 70.0-g piece of metal at 80.0 °C is placed in 100 g of water at 22.0 °C contained in a calorimeter like that shown in Figure 5.12.
The metal and water come to the same temperature at 24.6 °C. How much heat did the metal give up to the water? What is the

specific heat of the metal?
23.
If a reaction produces 1.506 kJ of heat, which is trapped in 30.0 g of water initially at 26.5 °C in a calorimeter like that in Figure
5.12, what is the resulting temperature of the water?
24.
A 0.500-g sample of KCl is added to 50.0 g of water in a calorimeter (Figure 5.12). If the temperature decreases by 1.05 °C, what is
the approximate amount of heat involved in the dissolution of the KCl, assuming the specific heat of the resulting solution is 4.18
J/g °C? Is the reaction exothermic or endothermic?
25.
Dissolving 3.0 g of CaCl2(s) in 150.0 g of water in a calorimeter (Figure 5.12) at 22.4 °C causes the temperature to rise to 25.8 °C.
What is the approximate amount of heat involved in the dissolution, assuming the specific heat of the resulting solution is 4.18 J/g
°C? Is the reaction exothermic or endothermic?
26.
When 50.0 g of 0.200 M NaCl(aq) at 24.1 °C is added to 100.0 g of 0.100 M AgNO3(aq) at 24.1 °C in a calorimeter, the
temperature increases to 25.2 °C as AgCl(s) forms. Assuming the specific heat of the solution and products is 4.20 J/g °C, calculate
the approximate amount of heat in joules produced.
27.
The addition of 3.15 g of Ba(OH)2·8H2O to a solution of 1.52 g of NH4SCN in 100 g of water in a calorimeter caused the
temperature to fall by 3.1 °C. Assuming the specific heat of the solution and products is 4.20 J/g °C, calculate the approximate
amount of heat absorbed by the reaction, which can be represented by the following equation:
Ba(OH)2·8H2O(s) + 2NH4SCN(aq) ⟶ Ba(SCN)2(aq) + 2NH3(aq) + 10H2O(l)
28.
The reaction of 50 mL of acid and 50 mL of base described in Example 5.5 increased the temperature of the solution by 6.9 ºC.
How much would the temperature have increased if 100 mL of acid and 100 mL of base had been used in the same calorimeter
starting at the same temperature of 22.0 ºC? Explain your answer.
29.
If the 3.21 g of NH4NO3 in Example 5.6 were dissolved in 100.0 g of water under the same conditions, how much would the
temperature change? Explain your answer.
30.
When 1.0 g of fructose, C6H12O6(s), a sugar commonly found in fruits, is burned in oxygen in a bomb calorimeter, the temperature
of the calorimeter increases by 1.58 °C. If the heat capacity of the calorimeter and its contents is 9.90 kJ/°C, what is q for this
combustion?
31.
When a 0.740-g sample of trinitrotoluene (TNT), C7H5N2O6, is burned in a bomb calorimeter, the temperature increases from 23.4
°C to 26.9 °C. The heat capacity of the calorimeter is 534 J/°C, and it contains 675 mL of water. How much heat was produced by
the combustion of the TNT sample?
32.
One method of generating electricity is by burning coal to heat water, which produces steam that drives an electric generator. To
determine the rate at which coal is to be fed into the burner in this type of plant, the heat of combustion per ton of coal must be
determined using a bomb calorimeter. When 1.00 g of coal is burned in a bomb calorimeter (Figure 5.17), the temperature increases
by 1.48 °C. If the heat capacity of the calorimeter is 21.6 kJ/°C, determine the heat produced by combustion of a ton of coal (2.000
3
× 10 pounds).
33.
The amount of fat recommended for someone with a daily diet of 2000 Calories is 65 g. What percent of the calories in this diet
would be supplied by this amount of fat if the average number of Calories for fat is

9.1 Calories/g?
34.
A teaspoon of the carbohydrate sucrose (common sugar) contains 16 Calories (16 kcal). What is the mass of one teaspoon of
sucrose if the average number of Calories for carbohydrates is 4.1 Calories/g?
35.
What is the maximum mass of carbohydrate in a 6-oz serving of diet soda that contains less than 1 Calorie per can if the average
number of Calories for carbohydrates is 4.1 Calories/g?
36.
A pint of premium ice cream can contain 1100 Calories. What mass of fat, in grams and pounds, must be produced in the body to
store an extra 1.1 × 103 Calories if the average number of Calories for fat is
9.1 Calories/g?
37.
A serving of a breakfast cereal contains 3 g of protein, 18 g of carbohydrates, and 6 g of fat. What is the Calorie content of a
serving of this cereal if the average number of Calories for fat is 9.1 Calories/g, for carbohydrates is 4.1 Calories/g, and for protein
is 4.1 Calories/g?
38.
Which is the least expensive source of energy in kilojoules per dollar: a box of breakfast cereal that weighs 32 ounces and costs
$4.23, or a liter of isooctane (density, 0.6919 g/mL) that costs $0.45? Compare the nutritional value of the cereal with the heat
produced by combustion of the isooctane under standard conditions. A 1.0-ounce serving of the cereal provides 130 Calories.
5.3 Enthalpy
39.
Explain how the heat measured in Example 5.5 differs from the enthalpy change for the exothermic reaction described by the
following equation:
40.
Using the data in the check your learning section of Example 5.5, calculate ΔH in kJ/mol of AgNO3(aq) for the reaction:
NaCl(aq) + AgNO (aq) ⟶ AgCl(s) + NaNO3 (aq)
3
41.
Calculate the enthalpy of solution (ΔH for the dissolution) per mole of NH4NO3 under the conditions described in Example 5.6.
42.
Calculate ΔH for the reaction described by the equation. (Hint: Use the value for the approximate amount of heat absorbed by the
reaction that you calculated in a previous exercise.)
Ba (OH) ⋅8 H2 O(s) + 2 NH4 SCN(aq) ⟶ Ba (SCN) (aq) + 2 NH3 (aq) + 10 H2 O (l)
2 2
43.
Calculate the enthalpy of solution (ΔH for the dissolution) per mole of CaCl2 (refer to Exercise 5.25).
44.
Although the gas used in an oxyacetylene torch (Figure 5.7) is essentially pure acetylene, the heat produced by combustion of one
mole of acetylene in such a torch is likely not equal to the enthalpy of combustion of acetylene listed in Table 5.2. Considering the
conditions for which the tabulated data are reported, suggest an explanation.
45.
How much heat is produced by burning 4.00 moles of acetylene under standard state conditions?
46.
How much heat is produced by combustion of 125 g of methanol under standard state conditions?
47.

How many moles of isooctane must be burned to produce 100 kJ of heat under standard state conditions?
48.
What mass of carbon monoxide must be burned to produce 175 kJ of heat under standard state conditions?
49.
When 2.50 g of methane burns in oxygen, 125 kJ of heat is produced. What is the enthalpy of combustion per mole of methane
under these conditions?
50.
How much heat is produced when 100 mL of 0.250 M HCl (density, 1.00 g/mL) and 200 mL of 0.150 M NaOH (density, 1.00
g/mL) are mixed?
HCl (aq) + NaOH (aq) ⟶ NaCl (aq) + H2 O (l) ΔH ° = −58 kJ
If both solutions are at the same temperature and the specific heat of the products is 4.19 J/g °C, how much will the temperature
increase? What assumption did you make in your calculation?
51.
A sample of 0.562 g of carbon is burned in oxygen in a bomb calorimeter, producing carbon dioxide. Assume both the reactants
and products are under standard state conditions, and that the heat released is directly proportional to the enthalpy of combustion of
graphite. The temperature of the calorimeter increases from 26.74 °C to 27.93 °C. What is the heat capacity of the calorimeter and
its contents?
52.
Before the introduction of chlorofluorocarbons, sulfur dioxide (enthalpy of vaporization, 6.00 kcal/mol) was used in household
refrigerators. What mass of SO2 must be evaporated to remove as much heat as evaporation of 1.00 kg of CCl2F2 (enthalpy of
vaporization is 17.4 kJ/mol)?
The vaporization reactions for SO2 and CCl2F2 are SO 2 (l) ⟶ SO 2 (g) and CCl
2F (l) ⟶ CCl2 F2 (g), respectively.
53.
Homes may be heated by pumping hot water through radiators. What mass of water will provide the same amount of heat when
cooled from 95.0 to 35.0 °C, as the heat provided when 100 g of steam is cooled from 110 °C to 100 °C.
54.
Which of the enthalpies of combustion in Table 5.2 the table are also standard enthalpies of formation?
55.
Does the standard enthalpy of formation of H2O(g) differ from ΔH° for the reaction 2H 2 (g) + O2 (g) ⟶ 2 H2 O (g)?
56.
Joseph Priestly prepared oxygen in 1774 by heating red mercury(II) oxide with sunlight focused through a lens. How much heat is
required to decompose exactly 1 mole of red HgO(s) to Hg(l) and O2(g) under standard conditions?
57.
How many kilojoules of heat will be released when exactly 1 mole of manganese, Mn, is burned to form Mn3O4(s) at standard state
conditions?
58.
How many kilojoules of heat will be released when exactly 1 mole of iron, Fe, is burned to form Fe2O3(s) at standard state
conditions?
59.
The following sequence of reactions occurs in the commercial production of aqueous nitric acid:
4 NH3 (g) + 5 O2 (g) ⟶ 4NO (g) + 6 H2 O (l) ΔH = −907 kJ
2NO (g) + O2 (g) ⟶ 2 NO2 (g) ΔH = −113 kJ
3 NO2 + H2 O (l) ⟶ 2 HNO3 (aq) + NO(g) ΔH = −139 kJ
Determine the total energy change for the production of one mole of aqueous nitric acid by this process.

60.
Both graphite and diamond burn.
C (s, diamond) + O2 (g) ⟶ CO2 (g)
For the conversion of graphite to diamond:

C (s, graphite) ⟶ C (s, diamond) ΔH ° = 1.90 kJ
Which produces more heat, the combustion of graphite or the combustion of diamond?
61.
From the molar heats of formation in Appendix G, determine how much heat is required to evaporate one mole of water:
H2 O (l) ⟶ H2 O (g)
62.
Which produces more heat?
Os (s) ⟶ 2 O2 (g) ⟶ OsO 4 (s)
or
Os (s) ⟶ 2 O2 (g) ⟶ OsO 4 (g)
for the phase change OsO 4 (s) ⟶ OsO 4 (g) ΔH = 56.4 kJ
63.
Calculate ΔH ° for the process
5
Sb (s) + Cl2 (g) ⟶ SbCl 5 (s)
2
3
Sb (s) + Cl2 (g) ⟶ SbCl 3 (s) ΔH ° = −314 kJ
2
SbCl 3 (s) + Cl2 (g) ⟶ SbCl 5 (s) ΔH ° = −80 kJ
64.
Calculate ΔH ° for the process Zn (s) + S (s) + 2O 2 (g) ⟶ ZnSO 4 (s)

Zn(s) + S(s) ⟶ ZnS(s) ΔH ° = −206.0 kJ
ZnS(s) + 2O2 (g) ⟶ ZnSO 4 (s) ΔH ° = −776.8 kJ
65.
Calculate ΔH for the process Hg 2
Cl2 (s) ⟶ 2Hg (l) + Cl2 (g)

Hg(l) + Cl2 (g) ⟶ HgCl2 (s) ΔH = −224 kJ
Hg(l) + HgCl2 (s) ⟶ Hg2 Cl2 (s) ΔH = −41.2 kJ
66.
Calculate ΔH ° for the process Co 3 O4 (s) ⟶ 3Co (s) + 2 O2 (g)
1
Co(s) + O2 (g) ⟶ CoO(s) ΔH ° = −237.9kJ
2
1
3CoO(s) + O2 (g) ⟶ Co3 O4 (s) ΔH ° = −177.5kJ
2
67.
Calculate the standard molar enthalpy of formation of NO(g) from the following data:
N2 (g) + 2 O2 ⟶ 2 NO2 (g) ΔH ° = 66.4 kJ
2NO(g) + O2 ⟶ 2 NO2 (g) ΔH ° = −114.1 kJ
68.

Using the data in Appendix G, calculate the standard enthalpy change for each of the following reactions:
(a) N 2 (g) + O2 (g) ⟶ 2NO (g)
(b) Si (s) + 2Cl 2 (g) ⟶ SiCl4 (g)
(c) Fe 2 O3 (s) + 3 H2 (g) ⟶ 2Fe (s) + 3 H2 O (l)
(d) 2LiOH(s) + CO 2 (g) ⟶ Li 2 CO3 (s) + H2 O(g)
69.
Using the data in Appendix G, calculate the standard enthalpy change for each of the following reactions:
(a) Si (s) + 2F 2 (g) ⟶ SiF4 (g)
(b) 2C (s) + 2H 2 (g) + O2 (g) ⟶ CH3 CO2 H (l)
(c) CH 4 (g) + N2 (g) ⟶ HCN (g) + NH3 (g);
(d) CS 2 (g) + 3 Cl2 (g) ⟶ CCl4 (g) + S2 Cl2 (g)
70.
The following reactions can be used to prepare samples of metals. Determine the enthalpy change under standard state conditions
for each.
(a) 2Ag 2
O (s) ⟶ 4Ag (s) + O2 (g)
(b) SnO (s) + CO (g) ⟶ Sn (s) + CO2 (g)
(c) Cr 2 O3 (s) + 3 H2 (g) ⟶ 2Cr (s) + 3 H2 O (l)
(d) 2Al (s) + Fe 2 O3 (s) ⟶ Al2 O3 (s) + 2Fe (s)
71.
The decomposition of hydrogen peroxide, H2O2, has been used to provide thrust in the control jets of various space vehicles. Using
the data in Appendix G, determine how much heat is produced by the decomposition of exactly 1 mole of H2O2 under standard
conditions.
2 H2 O2 (l) ⟶ 2 H2 O (g) + O2 (g)
72.
Calculate the enthalpy of combustion of propane, C3H8(g), for the formation of H2O(g) and CO2(g). The enthalpy of formation of
propane is −104 kJ/mol.
73.
Calculate the enthalpy of combustion of butane, C4H10(g) for the formation of H2O(g) and CO2(g). The enthalpy of formation of
butane is −126 kJ/mol.
74.
Both propane and butane are used as gaseous fuels. Which compound produces more heat per gram when burned?
75.
The white pigment TiO2 is prepared by the reaction of titanium tetrachloride, TiCl4, with water vapor in the gas phase:
TiCl4 (g) + 2 H2 O (g) ⟶ TiO2 (s) + 4HCl (g) .
How much heat is evolved in the production of exactly 1 mole of TiO2(s) under standard state conditions?
76.
Water gas, a mixture of H2 and CO, is an important industrial fuel produced by the reaction of steam with red hot coke, essentially
pure carbon: C (s) + H O (g) ⟶ CO (g) + H (g).
2 2
(a) Assuming that coke has the same enthalpy of formation as graphite, calculate ΔH ° for this reaction.
(b) Methanol, a liquid fuel that could possibly replace gasoline, can be prepared from water gas and additional hydrogen at high
temperature and pressure in the presence of a suitable catalyst: 2H (g) + CO(g) ⟶ CH OH(g).
2 3

Under the conditions of the reaction, methanol forms as a gas. Calculate ΔH ° for this reaction and for the condensation of gaseous
methanol to liquid methanol.
(c) Calculate the heat of combustion of 1 mole of liquid methanol to H2O(g) and CO2(g).
77.
In the early days of automobiles, illumination at night was provided by burning acetylene, C2H2. Though no longer used as auto
headlamps, acetylene is still used as a source of light by some cave explorers. The acetylene is (was) prepared in the lamp by the
reaction of water with calcium carbide, CaC2:
CaC2 (s) + 2 H2 O (l) ⟶ Ca (OH) (s) + C2 H2 (g).
2
Calculate the standard enthalpy of the reaction. The ΔH of CaC2 is −15.14 kcal/mol.
∘
f
78.
From the data in Table 5.2, determine which of the following fuels produces the greatest amount of heat per gram when burned
under standard conditions: CO(g), CH4(g), or C2H2(g).
79.
The enthalpy of combustion of hard coal averages −35 kJ/g, that of gasoline, 1.28 × 105 kJ/gal. How many kilograms of hard coal
provide the same amount of heat as is available from 1.0 gallon of gasoline? Assume that the density of gasoline is 0.692 g/mL (the
same as the density of isooctane).
80.
Ethanol, C2H5OH, is used as a fuel for motor vehicles, particularly in Brazil.
(a) Write the balanced equation for the combustion of ethanol to CO2(g) and H2O(g), and, using the data in Appendix G, calculate
the enthalpy of combustion of 1 mole of ethanol.
(b) The density of ethanol is 0.7893 g/mL. Calculate the enthalpy of combustion of exactly 1 L of ethanol.
(c) Assuming that an automobile’s mileage is directly proportional to the heat of combustion of the fuel, calculate how much
farther an automobile could be expected to travel on 1 L of gasoline than on 1 L of ethanol. Assume that gasoline has the heat of
combustion and the density of n–octane, C8H18 (ΔH = −208.4 kJ/mol; density = 0.7025 g/mL).
∘
f
81.
Among the substances that react with oxygen and that have been considered as potential rocket fuels are diborane [B2H6, produces
B2O3(s) and H2O(g)], methane [CH4, produces CO2(g) and H2O(g)], and hydrazine [N2H4, produces N2(g) and H2O(g)]. On the
basis of the heat released by 1.00 g of each substance in its reaction with oxygen, which of these compounds offers the best
possibility as a rocket fuel? The ΔH of B2H6(g), CH4(g), and N2H4(l) may be found in Appendix G.
∘
f
82.
How much heat is produced when 1.25 g of chromium metal reacts with oxygen gas under standard conditions?
83.
Ethylene, C2H4, a byproduct from the fractional distillation of petroleum, is fourth among the 50 chemical compounds produced
commercially in the largest quantities. About 80% of synthetic ethanol is manufactured from ethylene by its reaction with water in
the presence of a suitable catalyst. C H (g) + H O (g) ⟶ C H OH (l)
2 4 2 2 5
Using the data in the table in Appendix G, calculate ΔH° for the reaction.
84.
The oxidation of the sugar glucose, C6H12O6, is described by the following equation:
C6 H12 O6 (s) + 6 O2 (g) ⟶ 6 CO2 (g) + 6 H2 O (l) ΔH = −2816 kJ
The metabolism of glucose gives the same products, although the glucose reacts with oxygen in a series of steps in the body.
(a) How much heat in kilojoules can be produced by the metabolism of 1.0 g of glucose?
(b) How many Calories can be produced by the metabolism of 1.0 g of glucose?
85.
Propane, C3H8, is a hydrocarbon that is commonly used as a fuel.

(a) Write a balanced equation for the complete combustion of propane gas.
(b) Calculate the volume of air at 25 °C and 1.00 atmosphere that is needed to completely combust 25.0 grams of propane. Assume
that air is 21.0 percent O2 by volume. (Hint: We will see how to do this calculation in a later chapter on gases—for now use the
information that 1.00 L of air at 25 °C and 1.00 atm contains 0.275 g of O2.)
(c) The heat of combustion of propane is −2,219.2 kJ/mol. Calculate the heat of formation, ΔH
∘
f
of propane given that ΔH
f
∘
of
H2O(l) = −285.8 kJ/mol and ΔH of CO2(g) = −393.5 kJ/mol.
∘
f
(d) Assuming that all of the heat released in burning 25.0 grams of propane is transferred to 4.00 kilograms of water, calculate the
increase in temperature of the water.
86.
During a recent winter month in Sheboygan, Wisconsin, it was necessary to obtain 3500 kWh of heat provided by a natural gas
furnace with 89% efficiency to keep a small house warm (the efficiency of a gas furnace is the percent of the heat produced by
combustion that is transferred into the house).
(a) Assume that natural gas is pure methane and determine the volume of natural gas in cubic feet that was required to heat the
house. The average temperature of the natural gas was 56 °F; at this temperature and a pressure of 1 atm, natural gas has a density
of 0.681 g/L.
(b) How many gallons of LPG (liquefied petroleum gas) would be required to replace the natural gas used? Assume the LPG is
liquid propane [C3H8: density, 0.5318 g/mL; enthalpy of combustion, 2219 kJ/mol for the formation of CO2(g) and H2O(l)] and the
furnace used to burn the LPG has the same efficiency as the gas furnace.
(c) What mass of carbon dioxide is produced by combustion of the methane used to heat the house?
(d) What mass of water is produced by combustion of the methane used to heat the house?
(e) What volume of air is required to provide the oxygen for the combustion of the methane used to heat the house? Air contains
23% oxygen by mass. The average density of air during the month was 1.22 g/L.
(f) How many kilowatt–hours (1 kWh = 3.6 × 106 J) of electricity would be required to provide the heat necessary to heat the
house? Note electricity is 100% efficient in producing heat inside a house.
(g) Although electricity is 100% efficient in producing heat inside a house, production and distribution of electricity is not 100%
efficient. The efficiency of production and distribution of electricity produced in a coal-fired power plant is about 40%. A certain
type of coal provides 2.26 kWh per pound upon combustion. What mass of this coal in kilograms will be required to produce the
electrical energy necessary to heat the house if the efficiency of generation and distribution is 40%?

CHAPTER OVERVIEW
6: Electronic Structure and Periodic Properties

General Chemistry
The study of chemistry must at some point extend to the molecular level, for the physical and chemical properties of a substance
are ultimately explained in terms of the structure and bonding of molecules. This module introduces some basic facts and principles
that are needed for a discussion of organic molecules.
6.1: Introduction
6.3: The Bohr Model
6.5: Electronic Structure of Atoms (Electron Configurations)
6.7: Key Terms
6.8: Key Equations
6.9: Summary
6.10: Exercises
This page titled 6: Electronic Structure and Periodic Properties is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by
1
6.1: Introduction
Figure 6.1 The Crab Nebula consists of remnants of a supernova (the explosion of a star). NASA’s Hubble Space Telescope
produced this composite image. Measurements of the emitted light wavelengths enabled astronomers to identify the elements in the
nebula, determining that it contains specific ions including S+ (green filaments) and O2+ (red filaments). (credit: modification of
work by NASA and ESA)
Chapter Outline
6.1 Electromagnetic Energy
6.2 The Bohr Model
6.3 Development of Quantum Theory
6.4 Electronic Structure of Atoms (Electron Configurations)
6.5 Periodic Variations in Element Properties
In 1054, Chinese astronomers recorded the appearance of a “guest star” in the sky, visible even during the day, which then
disappeared slowly over the next two years. The sudden appearance was due to a supernova explosion, which was much brighter
than the original star. Even though this supernova was observed almost a millennium ago, the remaining Crab Nebula (Figure 6.1)
continues to release energy today. It emits not only visible light but also infrared light, X-rays, and other forms of electromagnetic
radiation. The nebula emits both continuous spectra (the blue-white glow) and atomic emission spectra (the colored filaments). In
this chapter, we will discuss light and other forms of electromagnetic radiation and how they are related to the electronic structure
of atoms. We will also see how this radiation can be used to identify elements, even from thousands of light years away.

Explain the basic behavior of waves, including travelling waves and standing waves
Describe the wave nature of light
Use appropriate equations to calculate related light-wave properties such as frequency, wavelength, and energy
Distinguish between line and continuous emission spectra
Describe the particle nature of light
The nature of light has been a subject of inquiry since antiquity. In the seventeenth century, Isaac Newton performed experiments
with lenses and prisms and was able to demonstrate that white light consists of the individual colors of the rainbow combined
together. Newton explained his optics findings in terms of a "corpuscular" view of light, in which light was composed of streams of
extremely tiny particles travelling at high speeds according to Newton's laws of motion. Others in the seventeenth century, such as
Christiaan Huygens, had shown that optical phenomena such as reflection and refraction could be equally well explained in terms
of light as waves travelling at high speed through a medium called "luminiferous aether" that was thought to permeate all space.
Early in the nineteenth century, Thomas Young demonstrated that light passing through narrow, closely spaced slits produced
interference patterns that could not be explained in terms of Newtonian particles but could be easily explained in terms of waves.
Later in the nineteenth century, after James Clerk Maxwell developed his theory of electromagnetic radiation and showed that light
was the visible part of a vast spectrum of electromagnetic waves, the particle view of light became thoroughly discredited. By the
end of the nineteenth century, scientists viewed the physical universe as roughly comprising two separate domains: matter
composed of particles moving according to Newton's laws of motion, and electromagnetic radiation consisting of waves governed
by Maxwell's equations. Today, these domains are referred to as classical mechanics and classical electrodynamics (or classical
electromagnetism). Although there were a few physical phenomena that could not be explained within this framework, scientists at
that time were so confident of the overall soundness of this framework that they viewed these aberrations as puzzling paradoxes
that would ultimately be resolved somehow within this framework. As we shall see, these paradoxes led to a contemporary
framework that intimately connects particles and waves at a fundamental level called wave-particle duality, which has superseded
the classical view.
Visible light and other forms of electromagnetic radiation play important roles in chemistry, since they can be used to infer the
energies of electrons within atoms and molecules. Much of modern technology is based on electromagnetic radiation. For example,
radio waves from a mobile phone, X-rays used by dentists, the energy used to cook food in your microwave, the radiant heat from
red-hot objects, and the light from your television screen are forms of electromagnetic radiation that all exhibit wavelike behavior.
6.2.0.1: Waves
A wave is an oscillation or periodic movement that can transport energy from one point in space to another. Common examples of
waves are all around us. Shaking the end of a rope transfers energy from your hand to the other end of the rope, dropping a pebble
into a pond causes waves to ripple outward along the water's surface, and the expansion of air that accompanies a lightning strike
generates sound waves (thunder) that can travel outward for several miles. In each of these cases, kinetic energy is transferred
through matter (the rope, water, or air) while the matter remains essentially in place. An insightful example of a wave occurs in
sports stadiums when fans in a narrow region of seats rise simultaneously and stand with their arms raised up for a few seconds
before sitting down again while the fans in neighboring sections likewise stand up and sit down in sequence. While this wave can
quickly encircle a large stadium in a few seconds, none of the fans actually travel with the wave-they all stay in or above their
seats.
Waves need not be restricted to travel through matter. As Maxwell showed, electromagnetic waves consist of an electric field
oscillating in step with a perpendicular magnetic field, both of which are perpendicular to the direction of travel. These waves can
travel through a vacuum at a constant speed of 2.998 × 108 m/s, the speed of light (denoted by c).
All waves, including forms of electromagnetic radiation, are characterized by, a wavelength (denoted by λ, the lowercase Greek
letter lambda), a frequency (denoted by ν, the lowercase Greek letter nu), and an amplitude. As can be seen in Figure 6.2, the
wavelength is the distance between two consecutive peaks or troughs in a wave (measured in meters in the SI system).
Electromagnetic waves have wavelengths that fall within an enormous range-wavelengths of kilometers (103 m) to picometers

(10−12 m) have been observed. The frequency is the number of wave cycles that pass a specified point in space in a specified
amount of time (in the SI system, this is measured in seconds). A cycle corresponds to one complete wavelength. The unit for
frequency, expressed as cycles per second [s−1], is the hertz (Hz). Common multiples of this unit are megahertz, (1 MHz = 1 × 106
Hz) and gigahertz (1 GHz = 1 × 109 Hz). The amplitude corresponds to the magnitude of the wave's displacement and so, in Figure
6.2, this corresponds to one-half the height between the peaks and troughs. The amplitude is related to the intensity of the wave,
which for light is the brightness, and for sound is the loudness.
Figure 6.2 One-dimensional sinusoidal waves show the relationship among wavelength, frequency, and speed. The wave with the
shortest wavelength has the highest frequency. Amplitude is one-half the height of the wave from peak to trough.
The product of a wave's wavelength (λ) and its frequency (ν), λν, is the speed of the wave. Thus, for electromagnetic radiation in a
vacuum, speed is equal to the fundamental constant, c:
8 −1
c = 2.998 × 10 ms = λν
Wavelength and frequency are inversely proportional: As the wavelength increases, the frequency decreases. The inverse
proportionality is illustrated in Figure 6.3. This figure also shows the electromagnetic spectrum, the range of all types of
electromagnetic radiation. Each of the various colors of visible light has specific frequencies and wavelengths associated with
them, and you can see that visible light makes up only a small portion of the electromagnetic spectrum. Because the technologies
developed to work in various parts of the electromagnetic spectrum are different, for reasons of convenience and historical legacies,
different units are typically used for different parts of the spectrum. For example, radio waves are usually specified as frequencies
(typically in units of MHz), while the visible region is usually specified in wavelengths (typically in units of nm or angstroms).

Figure 6.3 Portions of the electromagnetic spectrum are shown in order of decreasing frequency and increasing wavelength. (credit
“Cosmic ray": modification of work by NASA; credit “PET scan": modification of work by the National Institute of Health; credit
“X-ray": modification of work by Dr. Jochen Lengerke; credit “Dental curing": modification of work by the Department of the
Navy; credit “Night vision": modification of work by the Department of the Army; credit “Remote": modification of work by
Emilian Robert Vicol; credit “Cell phone": modification of work by Brett Jordan; credit “Microwave oven": modification of work
by Billy Mabray; credit “Ultrasound": modification of work by Jane Whitney; credit “AM radio": modification of work by Dave
Clausen)
6.2.0.1: Example 6.1

6.2.0.0.1: Determining the Frequency and Wavelength of Radiation
A sodium streetlight gives off yellow light that has a wavelength of 589 nm (1 nm = 1 × 10−9 m). What is the frequency of this
light?

6.2.0.0.2: Solution
We can rearrange the equation c = λν to solve for the frequency:
c
ν =
λ
Since c is expressed in meters per second, we must also convert 589 nm to meters.
8 −1 9
2.998 × 10 m s 1 × 10 nm
14 −1
ν =( )( ) = 5.09 × 10 s
589 nm 1 m

One of the frequencies used to transmit and receive cellular telephone signals in the United States is 850 MHz. What is the
wavelength in meters of these radio waves?
6.2.0.1: Answer:
0.353 m = 35.3 cm

6.2.0.0.4: Wireless Communication
Figure 6.4 Radio and cell towers are typically used to transmit long-wavelength electromagnetic radiation. Increasingly, cell
towers are designed to blend in with the landscape, as with the Tucson, Arizona, cell tower (right) disguised as a palm tree.
(credit left: modification of work by Sir Mildred Pierce; credit middle: modification of work by M.O. Stevens)
Many valuable technologies operate in the radio (3 kHz-300 GHz) frequency region of the electromagnetic spectrum. At the
low frequency (low energy, long wavelength) end of this region are AM (amplitude modulation) radio signals (540-2830 kHz)
that can travel long distances. FM (frequency modulation) radio signals are used at higher frequencies (87.5-108.0 MHz). In
AM radio, the information is transmitted by varying the amplitude of the wave (Figure 6.5). In FM radio, by contrast, the
amplitude is constant and the instantaneous frequency varies.

Figure 6.5 This schematic depicts how amplitude modulation (AM) and frequency modulation (FM) can be used to transmit a
radio wave.
Other technologies also operate in the radio-wave portion of the electromagnetic spectrum. For example, 4G cellular telephone
signals are approximately 880 MHz, while Global Positioning System (GPS) signals operate at 1.228 and 1.575 GHz, local
area wireless technology (Wi-Fi) networks operate at 2.4 to 5 GHz, and highway toll sensors operate at 5.8 GHz. The
frequencies associated with these applications are convenient because such waves tend not to be absorbed much by common
building materials.
One particularly characteristic phenomenon of waves results when two or more waves come into contact: They interfere with each
other. Figure 6.6 shows the interference patterns that arise when light passes through narrow slits closely spaced about a
wavelength apart. The fringe patterns produced depend on the wavelength, with the fringes being more closely spaced for shorter
wavelength light passing through a given set of slits. When the light passes through the two slits, each slit effectively acts as a new
source, resulting in two closely spaced waves coming into contact at the detector (the camera in this case). The dark regions in
Figure 6.6 correspond to regions where the peaks for the wave from one slit happen to coincide with the troughs for the wave from
the other slit (destructive interference), while the brightest regions correspond to the regions where the peaks for the two waves (or
their two troughs) happen to coincide (constructive interference). Likewise, when two stones are tossed close together into a pond,
interference patterns are visible in the interactions between the waves produced by the stones. Such interference patterns cannot be
explained by particles moving according to the laws of classical mechanics.

Figure 6.6 Interference fringe patterns are shown for light passing through two closely spaced, narrow slits. The spacing of the
fringes depends on the wavelength, with the fringes being more closely spaced for the shorter-wavelength blue light. (credit:
PASCO)

6.2.0.0.5: Dorothy Crowfoot Hodgkin
X-rays exhibit wavelengths of approximately 0.01–10 nm. Since these wavelengths are comparable to the spaces between
atoms in a crystalline solid, X-rays are scattered when they pass through crystals. The scattered rays undergo constructive and
destructive interference that creates a specific diffraction pattern that may be measured and used to precisely determine the
positions of atoms within the crystal. This phenomenon of X-ray diffraction is the basis for very powerful techniques enabling
the determination of molecular structure. One of the pioneers who applied this powerful technology to important biochemical
substances was Dorothy Crowfoot Hodgkin.
Born in Cairo, Egypt, in 1910 to British parents, Dorothy’s fascination with chemistry was fostered early in her life. At age 11
she was enrolled in a prestigious English grammar school where she was one of just two girls allowed to study chemistry. On
her 16th birthday, her mother, Molly, gifted her a book on X-ray crystallography, which had a profound impact on the
trajectory of her career. She studied chemistry at Oxford University, graduating with first-class honors in 1932 and directly
entering Cambridge University to pursue a doctoral degree. At Cambridge, Dorothy recognized the promise of X-ray
crystallography for protein structure determinations, conducting research that earned her a PhD in 1937. Over the course of a
very productive career, Dr. Hodgkin was credited with determining structures for several important biomolecules, including
cholesterol iodide, penicillin, and vitamin B12. In recognition of her achievements in the use of X-ray techniques to elucidate
the structures of biochemical substances, she was awarded the 1964 Nobel Prize in Chemistry. In 1969, she led a team of
scientists who deduced the structure of insulin, facilitating the mass production of this hormone and greatly advancing the
treatment of diabetic patients worldwide. Dr. Hodgkin continued working with the international scientific community, earning
numerous distinctions and awards prior to her death in 1993.
Not all waves are travelling waves. Standing waves (also known as stationary waves) remain constrained within some region of
space. As we shall see, standing waves play an important role in our understanding of the electronic structure of atoms and
molecules. The simplest example of a standing wave is a one-dimensional wave associated with a vibrating string that is held fixed
at its two end points. Figure 6.7 shows the four lowest-energy standing waves (the fundamental wave and the lowest three
harmonics) for a vibrating string at a particular amplitude. Although the string's motion lies mostly within a plane, the wave itself is
considered to be one dimensional, since it lies along the length of the string. The motion of string segments in a direction
perpendicular to the string length generates the waves and so the amplitude of the waves is visible as the maximum displacement of
the curves seen in Figure 6.7. The key observation from the figure is that only those waves having an integer number, n, of half-
wavelengths between the end points can form. A system with fixed end points such as this restricts the number and type of the
possible waveforms. This is an example of quantization, in which only discrete values from a more general set of continuous values
of some property are observed. Another important observation is that the harmonic waves (those waves displaying more than one-
half wavelength) all have one or more points between the two end points that are not in motion. These special points are nodes. The
energies of the standing waves with a given amplitude in a vibrating string increase with the number of half-wavelengths n. Since
the number of nodes is n – 1, the energy can also be said to depend on the number of nodes, generally increasing as the number of
nodes increases.

Figure 6.7 A vibrating string shows some one-dimensional standing waves. Since the two end points of the string are held fixed,
only waves having an integer number of half-wavelengths can form. The points on the string between the end points that are not
moving are called the nodes.
An example of two-dimensional standing waves is shown in Figure 6.8, which shows the vibrational patterns on a flat surface.
Although the vibrational amplitudes cannot be seen like they could in the vibrating string, the nodes have been made visible by
sprinkling the drum surface with a powder that collects on the areas of the surface that have minimal displacement. For one-
dimensional standing waves, the nodes were points on the line, but for two-dimensional standing waves, the nodes are lines on the
surface (for three-dimensional standing waves, the nodes are two-dimensional surfaces within the three-dimensional volume).
Figure 6.8 Two-dimensional standing waves can be visualized on a vibrating surface. The surface has been sprinkled with a powder
that collects near the nodal lines. There are two types of nodes visible: radial nodes (circles) and angular nodes (radii).

You can watch the formation of various radial nodes here as singer Imogen Heap projects her voice across a kettle drum.

6.2.0.1: Blackbody Radiation and the Ultraviolet Catastrophe
The last few decades of the nineteenth century witnessed intense research activity in commercializing newly discovered electric
lighting. This required obtaining a better understanding of the distributions of light emitted from various sources being considered.
Artificial lighting is usually designed to mimic natural sunlight within the limitations of the underlying technology. Such lighting
consists of a range of broadly distributed frequencies that form a continuous spectrum. Figure 6.9 shows the wavelength
distribution for sunlight. The most intense radiation is in the visible region, with the intensity dropping off rapidly for shorter
wavelength ultraviolet (UV) light, and more slowly for longer wavelength infrared (IR) light.
Figure 6.9 The spectral distribution (light intensity vs. wavelength) of sunlight reaches the Earth's atmosphere as UV light, visible
light, and IR light. The unabsorbed sunlight at the top of the atmosphere has a distribution that approximately matches the
theoretical distribution of a blackbody at 5250 °C, represented by the blue curve. (credit: modification of work by American
Society for Testing and Materials (ASTM) Terrestrial Reference Spectra for Photovoltaic Performance Evaluation)
In Figure 6.9, the solar distribution is compared to a representative distribution, called a blackbody spectrum, that corresponds to a
temperature of 5250 °C. The blackbody spectrum matches the solar spectrum quite well. A blackbody is a convenient, ideal emitter
that approximates the behavior of many materials when heated. It is “ideal” in the same sense that an ideal gas is a convenient,
simple representation of real gases that works well, provided that the pressure is not too high nor the temperature too low. A good
approximation of a blackbody that can be used to observe blackbody radiation is a metal oven that can be heated to very high
temperatures. The oven has a small hole allowing for the light being emitted within the oven to be observed with a spectrometer so
that the wavelengths and their intensities can be measured. Figure 6.10 shows the resulting curves for some representative
temperatures. Each distribution depends only on a single parameter: the temperature. The maxima in the blackbody curves, λmax,
shift to shorter wavelengths as the temperature increases, reflecting the observation that metals being heated to high temperatures
begin to glow a darker red that becomes brighter as the temperature increases, eventually becoming white hot at very high
temperatures as the intensities of all of the visible wavelengths become appreciable. This common observation was at the heart of
the first paradox that showed the fundamental limitations of classical physics that we will examine.
Physicists derived mathematical expressions for the blackbody curves using well-accepted concepts from the theories of classical
mechanics and classical electromagnetism. The theoretical expressions as functions of temperature fit the observed experimental

blackbody curves well at longer wavelengths, but showed significant discrepancies at shorter wavelengths. Not only did the
theoretical curves not show a peak, they absurdly showed the intensity becoming infinitely large as the wavelength became smaller,
which would imply that everyday objects at room temperature should be emitting large amounts of UV light. This became known
as the “ultraviolet catastrophe” because no one could find any problems with the theoretical treatment that could lead to such
unrealistic short-wavelength behavior. Finally, around 1900, Max Planck derived a theoretical expression for blackbody radiation
that fit the experimental observations exactly (within experimental error). Planck developed his theoretical treatment by extending
the earlier work that had been based on the premise that the atoms composing the oven vibrated at increasing frequencies (or
decreasing wavelengths) as the temperature increased, with these vibrations being the source of the emitted electromagnetic
radiation. But where the earlier treatments had allowed the vibrating atoms to have any energy values obtained from a continuous
set of energies (perfectly reasonable, according to classical physics), Planck found that by restricting the vibrational energies to
discrete values for each frequency, he could derive an expression for blackbody radiation that correctly had the intensity dropping
rapidly for the short wavelengths in the UV region.
E = nhν , n = 1, 2, 3, . . .
The quantity h is a constant now known as Planck's constant, in his honor. Although Planck was pleased he had resolved the
blackbody radiation paradox, he was disturbed that to do so, he needed to assume the vibrating atoms required quantized energies,
which he was unable to explain. The value of Planck's constant is very small, 6.626 × 10−34 joule seconds (J s), which helps
explain why energy quantization had not been observed previously in macroscopic phenomena.
Figure 6.10 Blackbody spectral distribution curves are shown for some representative temperatures.
6.2.0.1: The Photoelectric Effect

The next paradox in the classical theory to be resolved concerned the photoelectric effect (Figure 6.11). It had been observed that
electrons could be ejected from the clean surface of a metal when light having a frequency greater than some threshold frequency
was shone on it. Surprisingly, the kinetic energy of the ejected electrons did not depend on the brightness of the light, but increased
with increasing frequency of the light. Since the electrons in the metal had a certain amount of binding energy keeping them there,
the incident light needed to have more energy to free the electrons. According to classical wave theory, a wave's energy depends on
its intensity (which depends on its amplitude), not its frequency. One part of these observations was that the number of electrons
ejected within in a given time period was seen to increase as the brightness increased. In 1905, Albert Einstein was able to resolve

the paradox by incorporating Planck's quantization findings into the discredited particle view of light (Einstein actually won his
Nobel prize for this work, and not for his theories of relativity for which he is most famous).
Einstein argued that the quantized energies that Planck had postulated in his treatment of blackbody radiation could be applied to
the light in the photoelectric effect so that the light striking the metal surface should not be viewed as a wave, but instead as a
stream of particles (later called photons) whose energy depended on their frequency, according to Planck's formula, E = hν (or, in
terms of wavelength using c = νλ, E = hc
λ
). Electrons were ejected when hit by photons having sufficient energy (a frequency
greater than the threshold). The greater the frequency, the greater the kinetic energy imparted to the escaping electrons by the
collisions. Einstein also argued that the light intensity did not depend on the amplitude of the incoming wave, but instead
corresponded to the number of photons striking the surface within a given time period. This explains why the number of ejected
electrons increased with increasing brightness, since the greater the number of incoming photons, the greater the likelihood that
they would collide with some of the electrons.
With Einstein's findings, the nature of light took on a new air of mystery. Although many light phenomena could be explained
either in terms of waves or particles, certain phenomena, such as the interference patterns obtained when light passed through a
double slit, were completely contrary to a particle view of light, while other phenomena, such as the photoelectric effect, were
completely contrary to a wave view of light. Somehow, at a deep fundamental level still not fully understood, light is both wavelike
and particle-like. This is known as wave-particle duality.
Figure 6.11 Photons with low frequencies do not have enough energy to cause electrons to be ejected via the photoelectric effect.
For any frequency of light above the threshold frequency, the kinetic energy of an ejected electron will increase linearly with the
energy of the incoming photon.
6.2.0.1: Example 6.2

6.2.0.0.1: Calculating the Energy of Radiation
When we see light from a neon sign, we are observing radiation from excited neon atoms. If this radiation has a wavelength of
640 nm, what is the energy of the photon being emitted?
6.2.0.0.2: Solution
We use the part of Planck's equation that includes the wavelength, λ, and convert units of nanometers to meters so that the units
of λ and c are the same.
hc
E =
λ
−34 8 −1
(6.626 × 10 J s )(2.998 × 10 m s )
E =
1 m
(640 nm )( )
9
10 nm
−19
E = 3.10 × 10 J

The microwaves in an oven are of a specific frequency that will heat the water molecules contained in food. (This is why most
plastics and glass do not become hot in a microwave oven-they do not contain water molecules.) This frequency is about 3 ×
109 Hz. What is the energy of one photon in these microwaves?

6.2.0.1: Answer:
2 × 10−24 J

Use this simulation program to experiment with the photoelectric effect to see how intensity, frequency, type of metal, and
other factors influence the ejected photons.
6.2.0.1: Example 6.3

6.2.0.0.4: Photoelectric Effect
Identify which of the following statements are false and, where necessary, change the italicized word or phrase to make them
true, consistent with Einstein's explanation of the photoelectric effect.
(a) Increasing the brightness of incoming light increases the kinetic energy of the ejected electrons.
(b) Increasing the wavelength of incoming light increases the kinetic energy of the ejected electrons.
(c) Increasing the brightness of incoming light increases the number of ejected electrons.
(d) Increasing the frequency of incoming light can increase the number of ejected electrons.
6.2.0.0.5: Solution
(a) False. Increasing the brightness of incoming light has no effect on the kinetic energy of the ejected electrons. Only energy,
not the number or amplitude, of the photons influences the kinetic energy of the electrons.
(b) False. Increasing the frequency of incoming light increases the kinetic energy of the ejected electrons. Frequency is
proportional to energy and inversely proportional to wavelength. Frequencies above the threshold value transfer the excess
energy into the kinetic energy of the electrons.
(c) True. Because the number of collisions with photons increases with brighter light, the number of ejected electrons
increases.
(d) True with regard to the threshold energy binding the electrons to the metal. Below this threshold, electrons are not emitted
and above it they are. Once over the threshold value, further increasing the frequency does not increase the number of ejected
electrons
Calculate the threshold energy in kJ/mol of electrons in aluminum, given that the lowest frequency photon for which the
photoelectric effect is observed is 9.87 × 1014 Hz.
6.2.0.1: Answer:
394 kJ/mol
6.2.0.1: Line Spectra

Another paradox within the classical electromagnetic theory that scientists in the late nineteenth century struggled with concerned
the light emitted from atoms and molecules. When solids, liquids, or condensed gases are heated sufficiently, they radiate some of
the excess energy as light. Photons produced in this manner have a range of energies, and thereby produce a continuous spectrum in
which an unbroken series of wavelengths is present. Most of the light generated from stars (including our sun) is produced in this
fashion. You can see all the visible wavelengths of light present in sunlight by using a prism to separate them. As can be seen in
Figure 6.9, sunlight also contains UV light (shorter wavelengths) and IR light (longer wavelengths) that can be detected using
instruments but that are invisible to the human eye. Incandescent (glowing) solids such as tungsten filaments in incandescent lights
also give off light that contains all wavelengths of visible light. These continuous spectra can often be approximated by blackbody
radiation curves at some appropriate temperature, such as those shown in Figure 6.10.
In contrast to continuous spectra, light can also occur as discrete or line spectra having very narrow line widths interspersed
throughout the spectral regions such as those shown in Figure 6.13. Exciting a gas at low partial pressure using an electrical

current, or heating it, will produce line spectra. Fluorescent light bulbs and neon signs operate in this way (Figure 6.12). Each
element displays its own characteristic set of lines, as do molecules, although their spectra are generally much more complicated.
Figure 6.12 Neon signs operate by exciting a gas at low partial pressure using an electrical current. This sign shows the elaborate
artistic effects that can be achieved. (credit: Dave Shaver)
Each emission line consists of a single wavelength of light, which implies that the light emitted by a gas consists of a set of discrete
energies. For example, when an electric discharge passes through a tube containing hydrogen gas at low pressure, the H2 molecules
are broken apart into separate H atoms and we see a blue-pink color. Passing the light through a prism produces a line spectrum,
indicating that this light is composed of photons of four visible wavelengths, as shown in Figure 6.13.

Figure 6.13 Compare the two types of emission spectra: continuous spectrum of white light (top) and the line spectra of the light
from excited sodium, hydrogen, calcium, and mercury atoms.
The origin of discrete spectra in atoms and molecules was extremely puzzling to scientists in the late nineteenth century, since
according to classical electromagnetic theory, only continuous spectra should be observed. Even more puzzling, in 1885, Johann
Balmer was able to derive an empirical equation that related the four visible wavelengths of light emitted by hydrogen atoms to
whole integers. That equation is the following one, in which k is a constant:
1 1 1
=k( − ) , n = 3, 4, 5, 6
2
λ 4 n
Other discrete lines for the hydrogen atom were found in the UV and IR regions. Johannes Rydberg generalized Balmer's work and
developed an empirical formula that predicted all of hydrogen's emission lines, not just those restricted to the visible range, where,
n1 and n2 are integers, n1 < n2, and R is the Rydberg constant (1.097 × 107 m−1).
∞
1 1 1
= R∞ ( − )
2 2
λ n n
1 2
Even in the late nineteenth century, spectroscopy was a very precise science, and so the wavelengths of hydrogen were measured to
very high accuracy, which implied that the Rydberg constant could be determined very precisely as well. That such a simple
formula as the Rydberg formula could account for such precise measurements seemed astounding at the time, but it was the
eventual explanation for emission spectra by Neils Bohr in 1913 that ultimately convinced scientists to abandon classical physics
and spurred the development of modern quantum mechanics.
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6.3: The Bohr Model

Describe the Bohr model of the hydrogen atom
Use the Rydberg equation to calculate energies of light emitted or absorbed by hydrogen atoms
Following the work of Ernest Rutherford and his colleagues in the early twentieth century, the picture of atoms consisting of tiny
dense nuclei surrounded by lighter and even tinier electrons continually moving about the nucleus was well established. This
picture was called the planetary model, since it pictured the atom as a miniature “solar system” with the electrons orbiting the
nucleus like planets orbiting the sun. The simplest atom is hydrogen, consisting of a single proton as the nucleus about which a
single electron moves. The electrostatic force attracting the electron to the proton depends only on the distance between the two
particles. This classical mechanics description of the atom is incomplete, however, since an electron moving in an elliptical orbit
would be accelerating (by changing direction) and, according to classical electromagnetism, it should continuously emit
electromagnetic radiation. This loss in orbital energy should result in the electron’s orbit getting continually smaller until it spirals
into the nucleus, implying that atoms are inherently unstable.
In 1913, Niels Bohr attempted to resolve the atomic paradox by ignoring classical electromagnetism’s prediction that the orbiting
electron in hydrogen would continuously emit light. Instead, he incorporated into the classical mechanics description of the atom
Planck’s ideas of quantization and Einstein’s finding that light consists of photons whose energy is proportional to their frequency.
Bohr assumed that the electron orbiting the nucleus would not normally emit any radiation (the stationary state hypothesis), but it
would emit or absorb a photon if it moved to a different orbit. The energy absorbed or emitted would reflect differences in the
orbital energies according to this equation:
hc
∣ΔE∣ = ∣ Ef − Ei ∣ = hν =
λ
In this equation, h is Planck’s constant and Ei and Ef are the initial and final orbital energies, respectively. The absolute value of the
energy difference is used, since frequencies and wavelengths are always positive. Instead of allowing for continuous values of
energy, Bohr assumed the energies of these electron orbitals were quantized:
k
En = − , n = 1, 2, 3, …
2
n
In this expression, k is a constant comprising fundamental constants such as the electron mass and charge and Planck’s constant.
Inserting the expression for the orbit energies into the equation for ΔE gives
1 1 hc
ΔE = k ( − ) =
2 2
n n λ
1 2
or
1 k 1 1
= ( − )
2 2
λ hc n n
1 2
which is identical to the Rydberg equation in which R = ∞ . When Bohr calculated his theoretical value for the Rydberg
k
hc
constant, R , and compared it with the experimentally accepted value, he got excellent agreement. Since the Rydberg constant
∞
was one of the most precisely measured constants at that time, this level of agreement was astonishing and meant that Bohr’s model
was taken seriously, despite the many assumptions that Bohr needed to derive it.
The lowest few energy levels are shown in Figure 6.14. One of the fundamental laws of physics is that matter is most stable with
the lowest possible energy. Thus, the electron in a hydrogen atom usually moves in the n = 1 orbit, the orbit in which it has the
lowest energy. When the electron is in this lowest energy orbit, the atom is said to be in its ground electronic state (or simply
ground state). If the atom receives energy from an outside source, it is possible for the electron to move to an orbit with a higher n
value and the atom is now in an excited electronic state (or simply an excited state) with a higher energy. When an electron

transitions from an excited state (higher energy orbit) to a less excited state, or ground state, the difference in energy is emitted as a
photon. Similarly, if a photon is absorbed by an atom, the energy of the photon moves an electron from a lower energy orbit up to a
more excited one. We can relate the energy of electrons in atoms to what we learned previously about energy. The law of
conservation of energy says that we can neither create nor destroy energy. Thus, if a certain amount of external energy is required
to excite an electron from one energy level to another, that same amount of energy will be liberated when the electron returns to its
initial state (Figure 6.15).
Since Bohr’s model involved only a single electron, it could also be applied to the single electron ions He+, Li2+, Be3+, and so
forth, which differ from hydrogen only in their nuclear charges, and so one-electron atoms and ions are collectively referred to as
hydrogen-like atoms. The energy expression for hydrogen-like atoms is a generalization of the hydrogen atom energy, in which Z is
the nuclear charge (+1 for hydrogen, +2 for He, +3 for Li, and so on) and k has a value of 2.179 × 10–18 J.
2
kZ
En = −
2
n
The sizes of the circular orbits for hydrogen-like atoms are given in terms of their radii by the following expression, in which a is 0
a constant called the Bohr radius, with a value of 5.292 × 10−11 m:

2
n
r = a0
Z
The equation also shows us that as the electron’s energy increases (as n increases), the electron is found at greater distances from
the nucleus. This is implied by the inverse dependence of electrostatic attraction on distance, since, as the electron moves away
from the nucleus, the electrostatic attraction between it and the nucleus decreases and it is held less tightly in the atom. Note that as
n gets larger and the orbits get larger, their energies get closer to zero, and so the limits n ⟶ ∞ and r ⟶ ∞ imply that E = 0
corresponds to the ionization limit where the electron is completely removed from the nucleus. Thus, for hydrogen in the ground
state n = 1, the ionization energy would be:
ΔE = En ⟶ ∞ − E1 = 0 + k = k
With three extremely puzzling paradoxes now solved (blackbody radiation, the photoelectric effect, and the hydrogen atom), and all
involving Planck’s constant in a fundamental manner, it became clear to most physicists at that time that the classical theories that
worked so well in the macroscopic world were fundamentally flawed and could not be extended down into the microscopic domain
of atoms and molecules. Unfortunately, despite Bohr’s remarkable achievement in deriving a theoretical expression for the Rydberg
constant, he was unable to extend his theory to the next simplest atom, He, which only has two electrons. Bohr’s model was
severely flawed, since it was still based on the classical mechanics notion of precise orbits, a concept that was later found to be
untenable in the microscopic domain, when a proper model of quantum mechanics was developed to supersede classical
mechanics.

Figure 6.14 Quantum numbers and energy levels in a hydrogen atom. The more negative the calculated value, the lower the energy.
6.3.0.1: Example 6.4

6.3.0.0.1: Calculating the Energy of an Electron in a Bohr Orbit
Early researchers were very excited when they were able to predict the energy of an electron at a particular distance from the
nucleus in a hydrogen atom. If a spark promotes the electron in a hydrogen atom into an orbit with n = 3, what is the calculated
energy, in joules, of the electron?
6.3.0.0.1: Solution
The energy of the electron is given by this equation:
2
−kZ
E =
2
n
The atomic number, Z, of hydrogen is 1; k = 2.179 × 10–18 J; and the electron is characterized by an n value of 3. Thus,

−18 2
−(2.179 × 10 J) × (1)
−19
E = = −2.421 × 10 J
2
(3)

The electron in Figure 6.15 is promoted even further to an orbit with n = 6. What is its new energy?
6.3.0.1: Answer:
−6.053 × 10–20 J
Figure 6.15 The horizontal lines show the relative energy of orbits in the Bohr model of the hydrogen atom, and the vertical arrows
depict the energy of photons absorbed (left) or emitted (right) as electrons move between these orbits.
6.3.0.1: Example 6.5

6.3.0.0.1: Calculating the Energy and Wavelength of Electron Transitions in a One–electron (Bohr) System
What is the energy (in joules) and the wavelength (in meters) of the line in the spectrum of hydrogen that represents the
movement of an electron from Bohr orbit with n = 4 to the orbit with n = 6? In what part of the electromagnetic spectrum do
we find this radiation?
6.3.0.0.1: Solution
In this case, the electron starts out with n = 4, so n1 = 4. It comes to rest in the n = 6 orbit, so n2 = 6. The difference in energy
between the two states is given by this expression:
1 1
−18
ΔE = E1 − E2 = 2.179 × 10 ( − )
2 2
n n
1 2

1 1
−18
ΔE = 2.179 × 10 ( − ) J
2 2
4 6
−18
1 1
ΔE = 2.179 × 10 ( − ) J
16 36
−20
ΔE = 7.566 × 10 J
This energy difference is positive, indicating a photon enters the system (is absorbed) to excite the electron from the n = 4 orbit
up to the n = 6 orbit. The wavelength of a photon with this energy is found by the expression E= . Rearrangement gives: hc
hc
λ =
E
8 −1
2.998 × 10 m s
−34
= (6.626 × 10 J s ) ×
−20
7.566 × 10 J
−6
= 2.626 × 10 m
From the illustration of the electromagnetic spectrum in Electromagnetic Energy, we can see that this wavelength is found in
the infrared portion of the electromagnetic spectrum.
What is the energy in joules and the wavelength in meters of the photon produced when an electron falls from the n = 5 to the n
= 3 level in a He+ ion (Z = 2 for He+)?
6.3.0.1: Answer:
6.198 × 10–19 J; 3.205 × 10−7 m
Bohr’s model of the hydrogen atom provides insight into the behavior of matter at the microscopic level, but it does not account for
electron–electron interactions in atoms with more than one electron. It does introduce several important features of all models used
to describe the distribution of electrons in an atom. These features include the following:
The energies of electrons (energy levels) in an atom are quantized, described by quantum numbers: integer numbers having only
specific allowed value and used to characterize the arrangement of electrons in an atom.
An electron’s energy increases with increasing distance from the nucleus.
The discrete energies (lines) in the spectra of the elements result from quantized electronic energies.
Of these features, the most important is the postulate of quantized energy levels for an electron in an atom. As a consequence, the
model laid the foundation for the quantum mechanical model of the atom. Bohr won a Nobel Prize in Physics for his contributions
to our understanding of the structure of atoms and how that is related to line spectra emissions.
This page titled 6.3: The Bohr Model is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source


Extend the concept of wave–particle duality that was observed in electromagnetic radiation to matter as well
Understand the general idea of the quantum mechanical description of electrons in an atom, and that it uses the notion of
three-dimensional wave functions, or orbitals, that define the distribution of probability to find an electron in a particular
part of space
List and describe traits of the four quantum numbers that form the basis for completely specifying the state of an electron in
an atom
Bohr’s model explained the experimental data for the hydrogen atom and was widely accepted, but it also raised many questions.
Why did electrons orbit at only fixed distances defined by a single quantum number n = 1, 2, 3, and so on, but never in between?
Why did the model work so well describing hydrogen and one-electron ions, but could not correctly predict the emission spectrum
for helium or any larger atoms? To answer these questions, scientists needed to completely revise the way they thought about
matter.
6.4.0.1: Behavior in the Microscopic World

We know how matter behaves in the macroscopic world—objects that are large enough to be seen by the naked eye follow the rules
of classical physics. A billiard ball moving on a table will behave like a particle: It will continue in a straight line unless it collides
with another ball or the table cushion, or is acted on by some other force (such as friction). The ball has a well-defined position and
velocity (or a well-defined momentum, p = mv, defined by mass m and velocity v) at any given moment. In other words, the ball is
moving in a classical trajectory. This is the typical behavior of a classical object.
When waves interact with each other, they show interference patterns that are not displayed by macroscopic particles such as the
billiard ball. For example, interacting waves on the surface of water can produce interference patterns similar to those shown on
Figure 6.16. This is a case of wave behavior on the macroscopic scale, and it is clear that particles and waves are very different
phenomena in the macroscopic realm.
Figure 6.16 An interference pattern on the water surface is formed by interacting waves. The waves are caused by reflection of
water from the rocks. (credit: modification of work by Sukanto Debnath)
As technological improvements allowed scientists to probe the microscopic world in greater detail, it became increasingly clear by
the 1920s that very small pieces of matter follow a different set of rules from those we observe for large objects. The
unquestionable separation of waves and particles was no longer the case for the microscopic world.
One of the first people to pay attention to the special behavior of the microscopic world was Louis de Broglie. He asked the
question: If electromagnetic radiation can have particle-like character, can electrons and other submicroscopic particles exhibit
wavelike character? In his 1925 doctoral dissertation, de Broglie extended the wave–particle duality of light that Einstein used to
resolve the photoelectric-effect paradox to material particles. He predicted that a particle with mass m and velocity v (that is, with
linear momentum p) should also exhibit the behavior of a wave with a wavelength value λ, given by this expression in which h is
the familiar Planck’s constant:

h h
λ = =
mv p
This is called the de Broglie wavelength. Unlike the other values of λ discussed in this chapter, the de Broglie wavelength is a
characteristic of particles and other bodies, not electromagnetic radiation (note that this equation involves velocity [v, m/s], not
frequency [ν, Hz]. Although these two symbols appear nearly identical, they mean very different things). Where Bohr had
postulated the electron as being a particle orbiting the nucleus in quantized orbits, de Broglie argued that Bohr’s assumption of
quantization can be explained if the electron is considered not as a particle, but rather as a circular standing wave such that only an
integer number of wavelengths could fit exactly within the orbit (Figure 6.17).
Figure 6.17 If an electron is viewed as a wave circling around the nucleus, an integer number of wavelengths must fit into the orbit
for this standing wave behavior to be possible.
For a circular orbit of radius r, the circumference is 2πr, and so de Broglie’s condition is:
2πr = nλ, n = 1, 2, 3, …
Shortly after de Broglie proposed the wave nature of matter, two scientists at Bell Laboratories, C. J. Davisson and L. H. Germer,
demonstrated experimentally that electrons can exhibit wavelike behavior by showing an interference pattern for electrons
travelling through a regular atomic pattern in a crystal. The regularly spaced atomic layers served as slits, as used in other
interference experiments. Since the spacing between the layers serving as slits needs to be similar in size to the wavelength of the
tested wave for an interference pattern to form, Davisson and Germer used a crystalline nickel target for their “slits,” since the
spacing of the atoms within the lattice was approximately the same as the de Broglie wavelengths of the electrons that they used.
Figure 6.18 shows an interference pattern. It is strikingly similar to the interference patterns for light shown in Electromagnetic
Energy for light passing through two closely spaced, narrow slits. The wave–particle duality of matter can be seen in Figure 6.18
by observing what happens if electron collisions are recorded over a long period of time. Initially, when only a few electrons have
been recorded, they show clear particle-like behavior, having arrived in small localized packets that appear to be random. As more
and more electrons arrived and were recorded, a clear interference pattern that is the hallmark of wavelike behavior emerged. Thus,
it appears that while electrons are small localized particles, their motion does not follow the equations of motion implied by
classical mechanics, but instead it is governed by some type of a wave equation. Thus the wave–particle duality first observed with
photons is actually a fundamental behavior intrinsic to all quantum particles.

Figure 6.18 (a) The interference pattern for electrons passing through very closely spaced slits demonstrates that quantum particles
such as electrons can exhibit wavelike behavior. (b) The experimental results illustrated here demonstrate the wave–particle duality
in electrons.

View the Dr. Quantum – Double Slit Experiment cartoon for an easy-to-understand description of wave–particle duality and
the associated experiments.
6.4.0.1: Example 6.6

6.4.0.0.1: Calculating the Wavelength of a Particle
If an electron travels at a velocity of 1.000 × 107 m s–1 and has a mass of 9.109 × 10–28 g, what is its wavelength?
6.4.0.0.2: Solution
We can use de Broglie’s equation to solve this problem, but we first must do a unit conversion of Planck’s constant. You
learned earlier that 1 J = 1 kg m2/s2. Thus, we can write h = 6.626 × 10–34 J s as 6.626 × 10–34 kg m2/s.
h
λ =
mv
−34 2
6.626 × 10 kg m /s
=
−31 7
(9.109 × 10 kg)(1.000 × 10 m/s)
−11
= 7.274 × 10 m
This is a small value, but it is significantly larger than the size of an electron in the classical (particle) view. This size is the
same order of magnitude as the size of an atom. This means that electron wavelike behavior is going to be noticeable in an
atom.
Calculate the wavelength of a softball with a mass of 100 g traveling at a velocity of 35 m s–1, assuming that it can be modeled
as a single particle.
6.4.0.1: Answer:
1.9 × 10–34 m.
We never think of a thrown softball having a wavelength, since this wavelength is so small it is impossible for our senses
or any known instrument to detect (strictly speaking, the wavelength of a real baseball would correspond to the
wavelengths of its constituent atoms and molecules, which, while much larger than this value, would still be
microscopically tiny). The de Broglie wavelength is only appreciable for matter that has a very small mass and/or a very
high velocity.
Werner Heisenberg considered the limits of how accurately we can measure properties of an electron or other microscopic particles.
He determined that there is a fundamental limit to how accurately one can measure both a particle’s position and its momentum
simultaneously. The more accurately we measure the momentum of a particle, the less accurately we can determine its position at
that time, and vice versa. This is summed up in what we now call the Heisenberg uncertainty principle: It is fundamentally
impossible to determine simultaneously and exactly both the momentum and the position of a particle. For a particle of mass m
moving with velocity vx in the x direction (or equivalently with momentum px), the product of the uncertainty in the position, Δx,
and the uncertainty in the momentum, Δpx , must be greater than or equal to (where ℏ = , the value of Planck’s constant
ℏ
2
h
2π
divided by 2π).
ℏ
Δx × Δpx = (Δx) (mΔv) ≥
2
This equation allows us to calculate the limit to how precisely we can know both the simultaneous position of an object and its
momentum. For example, if we improve our measurement of an electron’s position so that the uncertainty in the position (Δx) has a
value of, say, 1 pm (10–12 m, about 1% of the diameter of a hydrogen atom), then our determination of its momentum must have an
uncertainty with a value of at least
−34 2
ħ (1.055 × 10 kg m /s)
−23
[Δp = mΔv = ] = = 5 × 10 kg m/s.
−12
(2Δx) (2 × 1 × 1 0 m)

The value of ħ is not large, so the uncertainty in the position or momentum of a macroscopic object like a baseball is too
insignificant to observe. However, the mass of a microscopic object such as an electron is small enough that the uncertainty can be
large and significant.
It should be noted that Heisenberg’s uncertainty principle is not just limited to uncertainties in position and momentum, but it also
links other dynamical variables. For example, when an atom absorbs a photon and makes a transition from one energy state to
another, the uncertainty in the energy and the uncertainty in the time required for the transition are similarly related, as ΔE Δt ≥ .
ℏ
Heisenberg’s principle imposes ultimate limits on what is knowable in science. The uncertainty principle can be shown to be a
consequence of wave–particle duality, which lies at the heart of what distinguishes modern quantum theory from classical
mechanics.

Read this article that describes a recent macroscopic demonstration of the uncertainty principle applied to microscopic objects.
6.4.0.1: The Quantum–Mechanical Model of an Atom

Shortly after de Broglie published his ideas that the electron in a hydrogen atom could be better thought of as being a circular
standing wave instead of a particle moving in quantized circular orbits, Erwin Schrödinger extended de Broglie’s work by deriving
what is today known as the Schrödinger equation. When Schrödinger applied his equation to hydrogen-like atoms, he was able to
reproduce Bohr’s expression for the energy and, thus, the Rydberg formula governing hydrogen spectra. Schrödinger described
electrons as three-dimensional stationary waves, or wavefunctions, represented by the Greek letter psi, ψ. A few years later, Max
Born proposed an interpretation of the wavefunction ψ that is still accepted today: Electrons are still particles, and so the waves
represented by ψ are not physical waves but, instead, are complex probability amplitudes. The square of the magnitude of a
wavefunction ∣ψ∣ describes the probability of the quantum particle being present near a certain location in space. This means that
2
wavefunctions can be used to determine the distribution of the electron’s density with respect to the nucleus in an atom. In the most
general form, the Schrödinger equation can be written as:
ˆ
H ψ = Eψ
Ĥ is the Hamiltonian operator, a set of mathematical operations representing the total energy of the quantum particle (such as an
electron in an atom), ψ is the wavefunction of this particle that can be used to find the special distribution of the probability of
finding the particle, and E is the actual value of the total energy of the particle.
Schrödinger’s work, as well as that of Heisenberg and many other scientists following in their footsteps, is generally referred to as
quantum mechanics.

You may also have heard of Schrödinger because of his famous thought experiment. This story explains the concepts of
superposition and entanglement as related to a cat in a box with poison.
6.4.0.1: Understanding Quantum Theory of Electrons in Atoms

The goal of this section is to understand the electron orbitals (location of electrons in atoms), their different energies, and other
properties. The use of quantum theory provides the best understanding to these topics. This knowledge is a precursor to chemical
bonding.
As was described previously, electrons in atoms can exist only on discrete energy levels but not between them. It is said that the
energy of an electron in an atom is quantized, that is, it can be equal only to certain specific values and can jump from one energy
level to another but not transition smoothly or stay between these levels.
The energy levels are labeled with an n value, where n = 1, 2, 3, …. Generally speaking, the energy of an electron in an atom is
greater for greater values of n. This number, n, is referred to as the principal quantum number. The principal quantum number
defines the location of the energy level. It is essentially the same concept as the n in the Bohr atom description. Another name for
the principal quantum number is the shell number. The shells of an atom can be thought of concentric circles radiating out from the
nucleus. The electrons that belong to a specific shell are most likely to be found within the corresponding circular area. The further
we proceed from the nucleus, the higher the shell number, and so the higher the energy level (Figure 6.19). The positively charged

protons in the nucleus stabilize the electronic orbitals by electrostatic attraction between the positive charges of the protons and the
negative charges of the electrons. So the further away the electron is from the nucleus, the greater the energy it has.
Figure 6.19 Different shells are numbered by principal quantum numbers.

This quantum mechanical model for where electrons reside in an atom can be used to look at electronic transitions, the events when
an electron moves from one energy level to another. If the transition is to a higher energy level, energy is absorbed, and the energy
change has a positive value. To obtain the amount of energy necessary for the transition to a higher energy level, a photon is
absorbed by the atom. A transition to a lower energy level involves a release of energy, and the energy change is negative. This
process is accompanied by emission of a photon by the atom. The following equation summarizes these relationships and is based
on the hydrogen atom:
ΔE = Efinal − Einitial
−18 1 1
= −2.18 × 10 ( − ) J
2 2
n n
f i
The values nf and ni are the final and initial energy states of the electron. Example 6.5 in the previous section of the chapter
demonstrates calculations of such energy changes.
The principal quantum number is one of three quantum numbers used to characterize an orbital. An atomic orbital is a general
region in an atom within which an electron is most probable to reside. The quantum mechanical model specifies the probability of
finding an electron in the three-dimensional space around the nucleus and is based on solutions of the Schrödinger equation. In
addition, the principal quantum number defines the energy of an electron in a hydrogen or hydrogen-like atom or an ion (an atom
or an ion with only one electron) and the general region in which discrete energy levels of electrons in a multi-electron atoms and
ions are located.
Another quantum number is l, the secondary (angular momentum) quantum number. It is an integer that may take the values, l = 0,
1, 2, …, n – 1. This means that an orbital with n = 1 can have only one value of l, l = 0, whereas n = 2 permits l = 0 and l = 1, and
so on. Whereas the principal quantum number, n, defines the general size and energy of the orbital, the secondary quantum number
l specifies the shape of the orbital. Orbitals with the same value of l define a subshell.
Orbitals with l = 0 are called s orbitals and they make up the s subshells. The value l = 1 corresponds to the p orbitals. For a given
n, p orbitals constitute a p subshell (e.g., 3p if n = 3). The orbitals with l = 2 are called the d orbitals, followed by the f-, g-, and h-
orbitals for l = 3, 4, and 5.
There are certain distances from the nucleus at which the probability density of finding an electron located at a particular orbital is
zero. In other words, the value of the wavefunction ψ is zero at this distance for this orbital. Such a value of radius r is called a
radial node. The number of radial nodes in an orbital is n – l – 1.

Figure 6.20 The graphs show the probability (y axis) of finding an electron for the 1s, 2s, 3s orbitals as a function of distance from
the nucleus.
Consider the examples in Figure 6.20. The orbitals depicted are of the s type, thus l = 0 for all of them. It can be seen from the
graphs of the probability densities that there are 1 – 0 – 1 = 0 places where the density is zero (nodes) for 1s (n = 1), 2 – 0 – 1 = 1
node for 2s, and 3 – 0 – 1 = 2 nodes for the 3s orbitals.
The s subshell electron density distribution is spherical and the p subshell has a dumbbell shape. The d and f orbitals are more
complex. These shapes represent the three-dimensional regions within which the electron is likely to be found.

Figure 6.21 Shapes of s, p, d, and f orbitals.
The magnetic quantum number, ml, specifies the relative spatial orientation of a particular orbital. Generally speaking, ml can be
equal to –l, –(l – 1), …, 0, …, (l – 1), l. The total number of possible orbitals with the same value of l (that is, in the same subshell)
is 2l + 1. Thus, there is one s-orbital in an s subshell (l = 0), there are three p-orbitals in a p subshell (l = 1), five d-orbitals in a d
subshell (l = 2), seven f-orbitals in an f subshell (l = 3), and so forth. The principal quantum number defines the general value of the
electronic energy. The angular momentum quantum number determines the shape of the orbital. And the magnetic quantum number
specifies orientation of the orbital in space, as can be seen in Figure 6.21.
Figure 6.22 The chart shows the energies of electron orbitals in a multi-electron atom.
Figure 6.22 illustrates the energy levels for various orbitals. The number before the orbital name (such as 2s, 3p, and so forth)
stands for the principal quantum number, n. The letter in the orbital name defines the subshell with a specific angular momentum
quantum number l = 0 for s orbitals, 1 for p orbitals, 2 for d orbitals. Finally, there are more than one possible orbitals for l ≥ 1,
each corresponding to a specific value of ml. In the case of a hydrogen atom or a one-electron ion (such as He+, Li2+, and so on),
energies of all the orbitals with the same n are the same. This is called a degeneracy, and the energy levels for the same principal
quantum number, n, are called degenerate orbitals. However, in atoms with more than one electron, this degeneracy is eliminated
by the electron–electron interactions, and orbitals that belong to different subshells have different energies, as shown on Figure
6.22. Orbitals within the same subshell are still degenerate and have the same energy.
While the three quantum numbers discussed in the previous paragraphs work well for describing electron orbitals, some
experiments showed that they were not sufficient to explain all observed results. It was demonstrated in the 1920s that when
hydrogen-line spectra are examined at extremely high resolution, some lines are actually not single peaks but, rather, pairs of
closely spaced lines. This is the so-called fine structure of the spectrum, and it implies that there are additional small differences in
energies of electrons even when they are located in the same orbital. These observations led Samuel Goudsmit and George
Uhlenbeck to propose that electrons have a fourth quantum number. They called this the spin quantum number, or ms.
The other three quantum numbers, n, l, and ml, are properties of specific atomic orbitals that also define in what part of the space an
electron is most likely to be located. Orbitals are a result of solving the Schrödinger equation for electrons in atoms. The electron

spin is a different kind of property. It is a completely quantum phenomenon with no analogues in the classical realm. In addition, it
cannot be derived from solving the Schrödinger equation and is not related to the normal spatial coordinates (such as the Cartesian
x, y, and z). Electron spin describes an intrinsic electron "rotation" or "spinning." Each electron acts as a tiny magnet or a tiny
rotating object with an angular momentum, or as a loop with an electric current, even though this rotation or current cannot be
observed in terms of spatial coordinates.
The magnitude of the overall electron spin can only have one value, and an electron can only “spin” in one of two quantized states.
One is termed the α state, with the z component of the spin being in the positive direction of the z axis. This corresponds to the spin
quantum number m = . The other is called the β state, with the z component of the spin being negative and m = − . Any
s
1
2
s
1
electron, regardless of the atomic orbital it is located in, can only have one of those two values of the spin quantum number. The
energies of electrons having m = − and m =
s
1
2
s are different if an external magnetic field is applied.
1
Figure 6.23 Electrons with spin values ± 1
2
in an external magnetic field.
Figure 6.23 illustrates this phenomenon. An electron acts like a tiny magnet. Its moment is directed up (in the positive direction of
the z axis) for the spin quantum number and down (in the negative z direction) for the spin quantum number of − . A magnet
1
2
1
has a lower energy if its magnetic moment is aligned with the external magnetic field (the left electron on Figure 6.23) and a higher
energy for the magnetic moment being opposite to the applied field. This is why an electron with m = s
1
2
has a slightly lower
energy in an external field in the positive z direction, and an electron with m = − has a slightly higher energy in the same field.
s
1
This is true even for an electron occupying the same orbital in an atom. A spectral line corresponding to a transition for electrons
from the same orbital but with different spin quantum numbers has two possible values of energy; thus, the line in the spectrum will
show a fine structure splitting.
6.4.0.1: The Pauli Exclusion Principle

An electron in an atom is completely described by four quantum numbers: n, l, ml, and ms. The first three quantum numbers define
the orbital and the fourth quantum number describes the intrinsic electron property called spin. An Austrian physicist Wolfgang
Pauli formulated a general principle that gives the last piece of information that we need to understand the general behavior of
electrons in atoms. The Pauli exclusion principle can be formulated as follows: No two electrons in the same atom can have exactly
the same set of all the four quantum numbers. What this means is that two electrons can share the same orbital (the same set of the
quantum numbers n, l, and ml) only if their spin quantum numbers ms have different values. Since the spin quantum number can
only have two values (± ) , no more than two electrons can occupy the same orbital (and if two electrons are located in the same
1
orbital, they must have opposite spins). Therefore, any atomic orbital can be populated by only zero, one, or two electrons.
The properties and meaning of the quantum numbers of electrons in atoms are briefly summarized in Table 6.1.
Quantum Numbers, Their Properties, and Significance
Name Symbol Allowed Physical meaning

values

Quantum Numbers, Their Properties, and Significance
Name Symbol Allowed Physical meaning

values
principal quantum number n 1, 2, 3, 4, shell, the general region for the value of energy for an electron
…. on the orbital
angular momentum or azimuthal quantum l 0≤l≤n–1 subshell, the shape of the orbital
number
magnetic quantum number ml – l ≤ ml ≤ l orientation of the orbital
spin quantum number ms 1

, −
1
direction of the intrinsic quantum “spinning” of the electron
2 2
Table 6.1
6.4.0.1: Example 6.7

6.4.0.0.1: Working with Shells and Subshells
Indicate the number of subshells, the number of orbitals in each subshell, and the values of l and ml for the orbitals in the n = 4
shell of an atom.
6.4.0.0.2: Solution
For n = 4, l can have values of 0, 1, 2, and 3. Thus, s, p, d, and f subshells are found in the n = 4 shell of an atom. For l = 0 (the
s subshell), ml can only be 0. Thus, there is only one 4s orbital. For l = 1 (p-type orbitals), m can have values of –1, 0, +1, so
we find three 4p orbitals. For l = 2 (d-type orbitals), ml can have values of –2, –1, 0, +1, +2, so we have five 4d orbitals. When
l = 3 (f-type orbitals), ml can have values of –3, –2, –1, 0, +1, +2, +3, and we can have seven 4f orbitals. Thus, we find a total
of 16 orbitals in the n = 4 shell of an atom.
Identify the subshell in which electrons with the following quantum numbers are found: (a) n = 3, l = 1; (b) n = 5, l = 3; (c) n =
2, l = 0.
6.4.0.1: Answer:
(a) 3p (b) 5f (c) 2s
6.4.0.1: Example 6.8

6.4.0.0.4: Maximum Number of Electrons
Calculate the maximum number of electrons that can occupy a shell with (a) n = 2, (b) n = 5, and (c) n as a variable. Note you
are only looking at the orbitals with the specified n value, not those at lower energies.
6.4.0.0.5: Solution
(a) When n = 2, there are four orbitals (a single 2s orbital, and three orbitals labeled 2p). These four orbitals can contain eight
electrons.
(b) When n = 5, there are five subshells of orbitals that we need to sum:
1 orbital labeled 5s
3 orbitals labeled 5p
5 orbitals labeled 5d
7 orbitals labeled 5f
+9 orbitals labeled 5g
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
25 orbitals total

Again, each orbital holds two electrons, so 50 electrons can fit in this shell.
(c) The number of orbitals in any shell n will equal n2. There can be up to two electrons in each orbital, so the maximum
number of electrons will be 2 × n2.
If a shell contains a maximum of 32 electrons, what is the principal quantum number, n?
6.4.0.1: Answer:
n=4
6.4.0.1: Example 6.9

6.4.0.0.7: Working with Quantum Numbers
Complete the following table for atomic orbitals:
Orbital n l ml degeneracy Radial nodes (no.)
4f
4 1
7 7 3
5d
6.4.0.0.8: Solution
The table can be completed using the following rules:
The orbital designation is nl, where l = 0, 1, 2, 3, 4, 5, … is mapped to the letter sequence s, p, d, f, g, h, …,
The ml degeneracy is the number of orbitals within an l subshell, and so is 2l + 1 (there is one s orbital, three p orbitals, five
d orbitals, seven f orbitals, and so forth).
The number of radial nodes is equal to n – l – 1.
Orbital n l ml degeneracy Radial nodes (no.)
4f 4 3 7 0
4p 4 1 3 2
7f 7 3 7 3
5d 5 2 5 2

How many orbitals have l = 2 and n = 3?
6.4.0.1: Answer:
The five degenerate 3d orbitals
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6.5: Electronic Structure of Atoms (Electron Configurations)

Derive the predicted ground-state electron configurations of atoms
Identify and explain exceptions to predicted electron configurations for atoms and ions
Relate electron configurations to element classifications in the periodic table
Having introduced the basics of atomic structure and quantum mechanics, we can use our understanding of quantum numbers to
determine how atomic orbitals relate to one another. This allows us to determine which orbitals are occupied by electrons in each
atom. The specific arrangement of electrons in orbitals of an atom determines many of the chemical properties of that atom.
6.5.0.1: Orbital Energies and Atomic Structure

The energy of atomic orbitals increases as the principal quantum number, n, increases. In any atom with two or more electrons, the
repulsion between the electrons makes energies of subshells with different values of l differ so that the energy of the orbitals
increases within a shell in the order s < p < d < f. Figure 6.24 depicts how these two trends in increasing energy relate. The 1s
orbital at the bottom of the diagram is the orbital with electrons of lowest energy. The energy increases as we move up to the 2s and
then 2p, 3s, and 3p orbitals, showing that the increasing n value has more influence on energy than the increasing l value for small
atoms. However, this pattern does not hold for larger atoms. The 3d orbital is higher in energy than the 4s orbital. Such overlaps
continue to occur frequently as we move up the chart.
Figure 6.24 Generalized energy-level diagram for atomic orbitals in an atom with two or more electrons (not to scale).
Electrons in successive atoms on the periodic table tend to fill low-energy orbitals first. Thus, many students find it confusing that,
for example, the 5p orbitals fill immediately after the 4d, and immediately before the 6s. The filling order is based on observed
experimental results, and has been confirmed by theoretical calculations. As the principal quantum number, n, increases, the size of
the orbital increases and the electrons spend more time farther from the nucleus. Thus, the attraction to the nucleus is weaker and
the energy associated with the orbital is higher (less stabilized). But this is not the only effect we have to take into account. Within
each shell, as the value of l increases, the electrons are less penetrating (meaning there is less electron density found close to the
nucleus), in the order s > p > d > f. Electrons that are closer to the nucleus slightly repel electrons that are farther out, offsetting the
more dominant electron–nucleus attractions slightly (recall that all electrons have −1 charges, but nuclei have +Z charges). This

phenomenon is called shielding and will be discussed in more detail in the next section. Electrons in orbitals that experience more
shielding are less stabilized and thus higher in energy. For small orbitals (1s through 3p), the increase in energy due to n is more
significant than the increase due to l; however, for larger orbitals the two trends are comparable and cannot be simply predicted. We
will discuss methods for remembering the observed order.
The arrangement of electrons in the orbitals of an atom is called the electron configuration of the atom. We describe an electron
configuration with a symbol that contains three pieces of information (Figure 6.25):
1. The number of the principal quantum shell, n,
2. The letter that designates the orbital type (the subshell, l), and
3. A superscript number that designates the number of electrons in that particular subshell.
For example, the notation 2p4 (read "two–p–four") indicates four electrons in a p subshell (l = 1) with a principal quantum number
(n) of 2. The notation 3d8 (read "three–d–eight") indicates eight electrons in the d subshell (i.e., l = 2) of the principal shell for
which n = 3.
Figure 6.25 The diagram of an electron configuration specifies the subshell (n and l value, with letter symbol) and superscript
number of electrons.
6.5.0.1: The Aufbau Principle

To determine the electron configuration for any particular atom, we can “build” the structures in the order of atomic numbers.
Beginning with hydrogen, and continuing across the periods of the periodic table, we add one proton at a time to the nucleus and
one electron to the proper subshell until we have described the electron configurations of all the elements. This procedure is called
the Aufbau principle, from the German word Aufbau (“to build up”). Each added electron occupies the subshell of lowest energy
available (in the order shown in Figure 6.24), subject to the limitations imposed by the allowed quantum numbers according to the
Pauli exclusion principle. Electrons enter higher-energy subshells only after lower-energy subshells have been filled to capacity.
Figure 6.26 illustrates the traditional way to remember the filling order for atomic orbitals. Since the arrangement of the periodic
table is based on the electron configurations, Figure 6.27 provides an alternative method for determining the electron configuration.
The filling order simply begins at hydrogen and includes each subshell as you proceed in increasing Z order. For example, after
filling the 3p block up to Ar, we see the orbital will be 4s (K, Ca), followed by the 3d orbitals.

Figure 6.26 This diagram depicts the energy order for atomic orbitals and is useful for deriving ground-state electron
configurations.
Figure 6.27 This partial periodic table shows electron configurations for the valence subshells of atoms. By “building up” from
hydrogen, this table can be used to determine the electron configuration for atoms of most elements in the periodic table. (Electron
configurations of the lanthanides and actinides are not accurately predicted by this simple approach. See Figure 6.29
We will now construct the ground-state electron configuration and orbital diagram for a selection of atoms in the first and second
periods of the periodic table. Orbital diagrams are pictorial representations of the electron configuration, showing the individual
orbitals and the pairing arrangement of electrons. We start with a single hydrogen atom (atomic number 1), which consists of one
proton and one electron. Referring to Figure 6.26 or Figure 6.27, we would expect to find the electron in the 1s orbital. By
convention, the m = + value is usually filled first. The electron configuration and the orbital diagram are:
s
1
Following hydrogen is the noble gas helium, which has an atomic number of 2. The helium atom contains two protons and two
electrons. The first electron has the same four quantum numbers as the hydrogen atom electron (n = 1, l = 0, ml = 0, m = + ).
s
1
The second electron also goes into the 1s orbital and fills that orbital. The second electron has the same n, l, and ml quantum
numbers, but must have the opposite spin quantum number, m = − . This is in accord with the Pauli exclusion principle: No two
s
1
electrons in the same atom can have the same set of four quantum numbers. For orbital diagrams, this means two arrows go in each
box (representing two electrons in each orbital) and the arrows must point in opposite directions (representing paired spins). The
electron configuration and orbital diagram of helium are:

The n = 1 shell is completely filled in a helium atom.
The next atom is the alkali metal lithium with an atomic number of 3. The first two electrons in lithium fill the 1s orbital and have
the same sets of four quantum numbers as the two electrons in helium. The remaining electron must occupy the orbital of next
lowest energy, the 2s orbital (Figure 6.26 or Figure 6.27). Thus, the electron configuration and orbital diagram of lithium are:
An atom of the alkaline earth metal beryllium, with an atomic number of 4, contains four protons in the nucleus and four electrons
surrounding the nucleus. The fourth electron fills the remaining space in the 2s orbital.
An atom of boron (atomic number 5) contains five electrons. The n = 1 shell is filled with two electrons and three electrons will
occupy the n = 2 shell. Because any s subshell can contain only two electrons, the fifth electron must occupy the next energy level,
which will be a 2p orbital. There are three degenerate 2p orbitals (ml = −1, 0, +1) and the electron can occupy any one of these p
orbitals. When drawing orbital diagrams, we include empty boxes to depict any empty orbitals in the same subshell that we are
filling.
Carbon (atomic number 6) has six electrons. Four of them fill the 1s and 2s orbitals. The remaining two electrons occupy the 2p
subshell. We now have a choice of filling one of the 2p orbitals and pairing the electrons or of leaving the electrons unpaired in two
different, but degenerate, p orbitals. The orbitals are filled as described by Hund’s rule: the lowest-energy configuration for an atom
with electrons within a set of degenerate orbitals is that having the maximum number of unpaired electrons. Thus, the two electrons
in the carbon 2p orbitals have identical n, l, and ms quantum numbers and differ in their ml quantum number (in accord with the
Pauli exclusion principle). The electron configuration and orbital diagram for carbon are:
Nitrogen (atomic number 7) fills the 1s and 2s subshells and has one electron in each of the three 2p orbitals, in accordance with
Hund’s rule. These three electrons have unpaired spins. Oxygen (atomic number 8) has a pair of electrons in any one of the 2p
orbitals (the electrons have opposite spins) and a single electron in each of the other two. Fluorine (atomic number 9) has only one
2p orbital containing an unpaired electron. All of the electrons in the noble gas neon (atomic number 10) are paired, and all of the
orbitals in the n = 1 and the n = 2 shells are filled. The electron configurations and orbital diagrams of these four elements are:

The alkali metal sodium (atomic number 11) has one more electron than the neon atom. This electron must go into the lowest-
energy subshell available, the 3s orbital, giving a 1s22s22p63s1 configuration. The electrons occupying the outermost shell orbital(s)
(highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons (Figure 6.28).
Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron configurations by writing
the noble gas that matches the core electron configuration, along with the valence electrons in a condensed format. For our sodium
example, the symbol [Ne] represents core electrons, (1s22s22p6) and our abbreviated or condensed configuration is [Ne]3s1.
Figure 6.28 A core-abbreviated electron configuration (right) replaces the core electrons with the noble gas symbol whose
configuration matches the core electron configuration of the other element.
Similarly, the abbreviated configuration of lithium can be represented as [He]2s1, where [He] represents the configuration of the
helium atom, which is identical to that of the filled inner shell of lithium. Writing the configurations in this way emphasizes the
similarity of the configurations of lithium and sodium. Both atoms, which are in the alkali metal family, have only one electron in a
valence s subshell outside a filled set of inner shells.
1
Li: [He] 2s
1
Na: [Ne] 3s
The alkaline earth metal magnesium (atomic number 12), with its 12 electrons in a [Ne]3s2 configuration, is analogous to its family
member beryllium, [He]2s2. Both atoms have a filled s subshell outside their filled inner shells. Aluminum (atomic number 13),
with 13 electrons and the electron configuration [Ne]3s23p1, is analogous to its family member boron, [He]2s22p1.
The electron configurations of silicon (14 electrons), phosphorus (15 electrons), sulfur (16 electrons), chlorine (17 electrons), and
argon (18 electrons) are analogous in the electron configurations of their outer shells to their corresponding family members
carbon, nitrogen, oxygen, fluorine, and neon, respectively, except that the principal quantum number of the outer shell of the
heavier elements has increased by one to n = 3. Figure 6.29 shows the lowest energy, or ground-state, electron configuration for
these elements as well as that for atoms of each of the known elements.

Figure 6.29 This version of the periodic table shows the outer-shell electron configuration of each element. Note that down each
group, the configuration is often similar.
When we come to the next element in the periodic table, the alkali metal potassium (atomic number 19), we might expect that we
would begin to add electrons to the 3d subshell. However, all available chemical and physical evidence indicates that potassium is
like lithium and sodium, and that the next electron is not added to the 3d level but is, instead, added to the 4s level (Figure 6.29).
As discussed previously, the 3d orbital with no radial nodes is higher in energy because it is less penetrating and more shielded
from the nucleus than the 4s, which has three radial nodes. Thus, potassium has an electron configuration of [Ar]4s1. Hence,
potassium corresponds to Li and Na in its valence shell configuration. The next electron is added to complete the 4s subshell and
calcium has an electron configuration of [Ar]4s2. This gives calcium an outer-shell electron configuration corresponding to that of
beryllium and magnesium.
Beginning with the transition metal scandium (atomic number 21), additional electrons are added successively to the 3d subshell.
This subshell is filled to its capacity with 10 electrons (remember that for l = 2 [d orbitals], there are 2l + 1 = 5 values of ml,
meaning that there are five d orbitals that have a combined capacity of 10 electrons). The 4p subshell fills next. Note that for three
series of elements, scandium (Sc) through copper (Cu), yttrium (Y) through silver (Ag), and lutetium (Lu) through gold (Au), a
total of 10 d electrons are successively added to the (n – 1) shell next to the n shell to bring that (n – 1) shell from 8 to 18 electrons.
For two series, lanthanum (La) through lutetium (Lu) and actinium (Ac) through lawrencium (Lr), 14 f electrons (l = 3, 2l + 1 = 7
ml values; thus, seven orbitals with a combined capacity of 14 electrons) are successively added to the (n – 2) shell to bring that
shell from 18 electrons to a total of 32 electrons.
6.5.0.1: Example 6.10

6.5.0.0.1: Quantum Numbers and Electron Configurations
What is the electron configuration and orbital diagram for a phosphorus atom? What are the four quantum numbers for the last
electron added?
6.5.0.0.2: Solution
The atomic number of phosphorus is 15. Thus, a phosphorus atom contains 15 electrons. The order of filling of the energy
levels is 1s, 2s, 2p, 3s, 3p, 4s, . . . The 15 electrons of the phosphorus atom will fill up to the 3p orbital, which will contain
three electrons:
The last electron added is a 3p electron. Therefore, n = 3 and, for a p-type orbital, l = 1. The ml value could be –1, 0, or +1. The
three p orbitals are degenerate, so any of these ml values is correct. For unpaired electrons, convention assigns the value of
+
1
2
for the spin quantum number; thus, m = + .
s
1

Identify the atoms from the electron configurations given:
(a) [Ar]4s23d5
(b) [Kr]5s24d105p6
6.5.0.1: Answer:
(a) Mn (b) Xe
The periodic table can be a powerful tool in predicting the electron configuration of an element. However, we do find exceptions to
the order of filling of orbitals that are shown in Figure 6.26 or Figure 6.27. For instance, the electron configurations (shown in
Figure 6.29) of the transition metals chromium (Cr; atomic number 24) and copper (Cu; atomic number 29), among others, are not
those we would expect. In general, such exceptions involve subshells with very similar energy, and small effects can lead to
changes in the order of filling.
In the case of Cr and Cu, we find that half-filled and completely filled subshells apparently represent conditions of preferred
stability. This stability is such that an electron shifts from the 4s into the 3d orbital to gain the extra stability of a half-filled 3d
subshell (in Cr) or a filled 3d subshell (in Cu). Other exceptions also occur. For example, niobium (Nb, atomic number 41) is
predicted to have the electron configuration [Kr]5s24d3. Experimentally, we observe that its ground-state electron configuration is
actually [Kr]5s14d4. We can rationalize this observation by saying that the electron–electron repulsions experienced by pairing the
electrons in the 5s orbital are larger than the gap in energy between the 5s and 4d orbitals. There is no simple method to predict the
exceptions for atoms where the magnitude of the repulsions between electrons is greater than the small differences in energy
between subshells.
6.5.0.1: Electron Configurations and the Periodic Table

As described earlier, the periodic table arranges atoms based on increasing atomic number so that elements with the same chemical
properties recur periodically. When their electron configurations are added to the table (Figure 6.29), we also see a periodic
recurrence of similar electron configurations in the outer shells of these elements. Because they are in the outer shells of an atom,
valence electrons play the most important role in chemical reactions. The outer electrons have the highest energy of the electrons in
an atom and are more easily lost or shared than the core electrons. Valence electrons are also the determining factor in some
physical properties of the elements.
Elements in any one group (or column) have the same number of valence electrons; the alkali metals lithium and sodium each have
only one valence electron, the alkaline earth metals beryllium and magnesium each have two, and the halogens fluorine and
chlorine each have seven valence electrons. The similarity in chemical properties among elements of the same group occurs
because they have the same number of valence electrons. It is the loss, gain, or sharing of valence electrons that defines how
elements react.

It is important to remember that the periodic table was developed on the basis of the chemical behavior of the elements, well before
any idea of their atomic structure was available. Now we can understand why the periodic table has the arrangement it has—the
arrangement puts elements whose atoms have the same number of valence electrons in the same group. This arrangement is
emphasized in Figure 6.29, which shows in periodic-table form the electron configuration of the last subshell to be filled by the
Aufbau principle. The colored sections of Figure 6.29 show the three categories of elements classified by the orbitals being filled:
main group, transition, and inner transition elements. These classifications determine which orbitals are counted in the valence
shell, or highest energy level orbitals of an atom.
1. Main group elements (sometimes called representative elements) are those in which the last electron added enters an s or a p
orbital in the outermost shell, shown in blue and red in Figure 6.29. This category includes all the nonmetallic elements, as well
as many metals and the metalloids. The valence electrons for main group elements are those with the highest n level. For
example, gallium (Ga, atomic number 31) has the electron configuration [Ar]4s23d104p1, which contains three valence electrons
(underlined). The completely filled d orbitals count as core, not valence, electrons.
2. Transition elements or transition metals. These are metallic elements in which the last electron added enters a d orbital. The
valence electrons (those added after the last noble gas configuration) in these elements include the ns and (n – 1) d electrons.
The official IUPAC definition of transition elements specifies those with partially filled d orbitals. Thus, the elements with
completely filled orbitals (Zn, Cd, Hg, as well as Cu, Ag, and Au in Figure 6.29) are not technically transition elements.
However, the term is frequently used to refer to the entire d block (colored yellow in Figure 6.29), and we will adopt this usage
in this textbook.
3. Inner transition elements are metallic elements in which the last electron added occupies an f orbital. They are shown in green
in Figure 6.29. The valence shells of the inner transition elements consist of the (n – 2)f, the (n – 1)d, and the ns subshells.
There are two inner transition series:
1. The lanthanide series: lanthanum (La) through lutetium (Lu)
2. The actinide series: actinium (Ac) through lawrencium (Lr)
Lanthanum and actinium, because of their similarities to the other members of the series, are included and used to name the series,
even though they are transition metals with no f electrons.
6.5.0.1: Electron Configurations of Ions

Ions are formed when atoms gain or lose electrons. A cation (positively charged ion) forms when one or more electrons are
removed from a parent atom. For main group elements, the electrons that were added last are the first electrons removed. For
transition metals and inner transition metals, however, electrons in the s orbital are easier to remove than the d or f electrons, and
so the highest ns electrons are lost, and then the (n – 1)d or (n – 2)f electrons are removed. An anion (negatively charged ion)
forms when one or more electrons are added to a parent atom. The added electrons fill in the order predicted by the Aufbau
principle.
6.5.0.1: Example 6.11

6.5.0.0.1: Predicting Electron Configurations of Ions
What is the electron configuration of:
(a) Na+
(b) P3–
(c) Al2+
(d) Fe2+
(e) Sm3+
6.5.0.0.2: Solution
First, write out the electron configuration for each parent atom. We have chosen to show the full, unabbreviated configurations
to provide more practice for students who want it, but listing the core-abbreviated electron configurations is also acceptable.
Next, determine whether an electron is gained or lost. Remember electrons are negatively charged, so ions with a positive
charge have lost an electron. For main group elements, the last orbital gains or loses the electron. For transition metals, the last
s orbital loses an electron before the d orbitals.
(a) Na: 1s22s22p63s1. Sodium cation loses one electron, so Na+: 1s22s22p63s1 = Na+: 1s22s22p6.

(b) P: 1s22s22p63s23p3. Phosphorus trianion gains three electrons, so P3−: 1s22s22p63s23p6.
(c) Al: 1s22s22p63s23p1. Aluminum dication loses two electrons Al2+: 1s22s22p63s23p1 =
Al2+: 1s22s22p63s1.
(d) Fe: 1s22s22p63s23p64s23d6. Iron(II) loses two electrons and, since it is a transition metal, they are removed from the 4s
orbital Fe2+: 1s22s22p63s23p64s23d6 = 1s22s22p63s23p63d6.
(e). Sm: 1s22s22p63s23p64s23d104p65s24d105p66s24f6. Samarium trication loses three electrons. The first two will be lost from
the 6s orbital, and the final one is removed from the 4f orbital. Sm3+: 1s22s22p63s23p64s23d104p65s24d105p66s24f6 =
1s22s22p63s23p64s23d104p65s24d105p64f5.
Which ion with a +2 charge has the electron configuration 1s22s22p63s23p64s23d104p64d5? Which ion with a +3 charge has this
configuration?
6.5.0.1: Answer:
Tc2+, Ru3+
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Describe and explain the observed trends in atomic size, ionization energy, and electron affinity of the elements
The elements in groups (vertical columns) of the periodic table exhibit similar chemical behavior. This similarity occurs because
the members of a group have the same number and distribution of electrons in their valence shells. However, there are also other
patterns in chemical properties on the periodic table. For example, as we move down a group, the metallic character of the atoms
increases. Oxygen, at the top of group 16 (6A), is a colorless gas; in the middle of the group, selenium is a semiconducting solid;
and, toward the bottom, polonium is a silver-grey solid that conducts electricity.
As we go across a period from left to right, we add a proton to the nucleus and an electron to the valence shell with each successive
element. As we go down the elements in a group, the number of electrons in the valence shell remains constant, but the principal
quantum number increases by one each time. An understanding of the electronic structure of the elements allows us to examine
some of the properties that govern their chemical behavior. These properties vary periodically as the electronic structure of the
elements changes. They are (1) size (radius) of atoms and ions, (2) ionization energies, and (3) electron affinities.

Explore visualizations of the periodic trends discussed in this section (and many more trends). With just a few clicks, you can
create three-dimensional versions of the periodic table showing atomic size or graphs of ionization energies from all measured
elements.
6.6.0.1: Variation in Covalent Radius

The quantum mechanical picture makes it difficult to establish a definite size of an atom. However, there are several practical ways
to define the radius of atoms and, thus, to determine their relative sizes that give roughly similar values. We will use the covalent
radius (Figure 6.30), which is defined as one-half the distance between the nuclei of two identical atoms when they are joined by a
covalent bond (this measurement is possible because atoms within molecules still retain much of their atomic identity). We know
that as we scan down a group, the principal quantum number, n, increases by one for each element. Thus, the electrons are being
added to a region of space that is increasingly distant from the nucleus. Consequently, the size of the atom (and its covalent radius)
must increase as we increase the distance of the outermost electrons from the nucleus. This trend is illustrated for the covalent radii
of the halogens in Table 6.2 and Figure 6.30. The trends for the entire periodic table can be seen in Figure 6.30.
Covalent Radii of the Halogen Group Elements
Atom Covalent radius (pm) Nuclear charge
F 64 +9
Cl 99 +17
Br 114 +35
I 133 +53
At 148 +85
Table 6.2

Figure 6.30 (a) The radius of an atom is defined as one-half the distance between the nuclei in a molecule consisting of two
identical atoms joined by a covalent bond. The atomic radius for the halogens increases down the group as n increases. (b)
Covalent radii of the elements are shown to scale. The general trend is that radii increase down a group and decrease across a
period.

Figure 6.31 Within each period, the trend in atomic radius decreases as Z increases; for example, from K to Kr. Within each group
(e.g., the alkali metals shown in purple), the trend is that atomic radius increases as Z increases.
As shown in Figure 6.31, as we move across a period from left to right, we generally find that each element has a smaller covalent
radius than the element preceding it. This might seem counterintuitive because it implies that atoms with more electrons have a
smaller atomic radius. This can be explained with the concept of effective nuclear charge, Zeff. This is the pull exerted on a specific
electron by the nucleus, taking into account any electron–electron repulsions. For hydrogen, there is only one electron and so the
nuclear charge (Z) and the effective nuclear charge (Zeff) are equal. For all other atoms, the inner electrons partially shield the outer
electrons from the pull of the nucleus, and thus:
Zeff = Z − shielding

Shielding is determined by the probability of another electron being between the electron of interest and the nucleus, as well as by
the electron–electron repulsions the electron of interest encounters. Core electrons are adept at shielding, while electrons in the
same valence shell do not block the nuclear attraction experienced by each other as efficiently. Thus, each time we move from one
element to the next across a period, Z increases by one, but the shielding increases only slightly. Thus, Zeff increases as we move
from left to right across a period. The stronger pull (higher effective nuclear charge) experienced by electrons on the right side of
the periodic table draws them closer to the nucleus, making the covalent radii smaller.
Thus, as we would expect, the outermost or valence electrons are easiest to remove because they have the highest energies, are
shielded more, and are farthest from the nucleus. As a general rule, when the representative elements form cations, they do so by
the loss of the ns or np electrons that were added last in the Aufbau process. The transition elements, on the other hand, lose the ns
electrons before they begin to lose the (n – 1)d electrons, even though the ns electrons are added first, according to the Aufbau
principle.
6.6.0.1: Example 6.12

6.6.0.0.1: Sorting Atomic Radii
Predict the order of increasing covalent radius for Ge, Fl, Br, Kr.
6.6.0.0.2: Solution
Radius increases as we move down a group, so Ge < Fl (Note: Fl is the symbol for flerovium, element 114, NOT fluorine).
Radius decreases as we move across a period, so Kr < Br < Ge. Putting the trends together, we obtain Kr < Br < Ge < Fl.
Give an example of an atom whose size is smaller than fluorine.
6.6.0.1: Answer:
Ne or He
6.6.0.1: Variation in Ionic Radii

Ionic radius is the measure used to describe the size of an ion. A cation always has fewer electrons and the same number of protons
as the parent atom; it is smaller than the atom from which it is derived (Figure 6.32). For example, the covalent radius of an
aluminum atom (1s22s22p63s23p1) is 118 pm, whereas the ionic radius of an Al3+ (1s22s22p6) is 68 pm. As electrons are removed
from the outer valence shell, the remaining core electrons occupying smaller shells experience a greater effective nuclear charge
Zeff (as discussed) and are drawn even closer to the nucleus.
Figure 6.32 The radius for a cation is smaller than the parent atom (Al), due to the lost electrons; the radius for an anion is larger
than the parent (S), due to the gained electrons.
Cations with larger charges are smaller than cations with smaller charges (e.g., V2+ has an ionic radius of 79 pm, while that of V3+
is 64 pm). Proceeding down the groups of the periodic table, we find that cations of successive elements with the same charge
generally have larger radii, corresponding to an increase in the principal quantum number, n.
An anion (negative ion) is formed by the addition of one or more electrons to the valence shell of an atom. This results in a greater
repulsion among the electrons and a decrease in Zeff per electron. Both effects (the increased number of electrons and the decreased
Zeff) cause the radius of an anion to be larger than that of the parent atom (Figure 6.32). For example, a sulfur atom ([Ne]3s23p4)
has a covalent radius of 104 pm, whereas the ionic radius of the sulfide anion ([Ne]3s23p6) is 170 pm. For consecutive elements
proceeding down any group, anions have larger principal quantum numbers and, thus, larger radii.
Atoms and ions that have the same electron configuration are said to be isoelectronic. Examples of isoelectronic species are N3–,
O2–, F–, Ne, Na+, Mg2+, and Al3+ (1s22s22p6). Another isoelectronic series is P3–, S2–, Cl–, Ar, K+, Ca2+, and Sc3+ ([Ne]3s23p6). For
atoms or ions that are isoelectronic, the number of protons determines the size. The greater the nuclear charge, the smaller the
radius in a series of isoelectronic ions and atoms.

6.6.0.1: Variation in Ionization Energies
The amount of energy required to remove the most loosely bound electron from a gaseous atom in its ground state is called its first
ionization energy (IE1). The first ionization energy for an element, X, is the energy required to form a cation with +1 charge:
+ −
X(g) ⟶ X (g) + e IE1
The energy required to remove the second most loosely bound electron is called the second ionization energy (IE2).
+ 2+ −
X (g) ⟶ X (g) + e IE2
The energy required to remove the third electron is the third ionization energy, and so on. Energy is always required to remove
electrons from atoms or ions, so ionization processes are endothermic and IE values are always positive. For larger atoms, the most
loosely bound electron is located farther from the nucleus and so is easier to remove. Thus, as size (atomic radius) increases, the
ionization energy should decrease. Relating this logic to what we have just learned about radii, we would expect first ionization
energies to decrease down a group and to increase across a period.
Figure 6.33 graphs the relationship between the first ionization energy and the atomic number of several elements. The values of
first ionization energy for the elements are given in Figure 6.34. Within a period, the IE1 generally increases with increasing Z.
Down a group, the IE1 value generally decreases with increasing Z. There are some systematic deviations from this trend, however.
Note that the ionization energy of boron (atomic number 5) is less than that of beryllium (atomic number 4) even though the
nuclear charge of boron is greater by one proton. This can be explained because the energy of the subshells increases as l increases,
due to penetration and shielding (as discussed previously in this chapter). Within any one shell, the s electrons are lower in energy
than the p electrons. This means that an s electron is harder to remove from an atom than a p electron in the same shell. The
electron removed during the ionization of beryllium ([He]2s2) is an s electron, whereas the electron removed during the ionization
of boron ([He]2s22p1) is a p electron; this results in a lower first ionization energy for boron, even though its nuclear charge is
greater by one proton. Thus, we see a small deviation from the predicted trend occurring each time a new subshell begins.

Figure 6.33 The first ionization energy of the elements in the first five periods are plotted against their atomic number.
Figure 6.34 This version of the periodic table shows the first ionization energy (IE1), in kJ/mol, of selected elements.
Another deviation occurs as orbitals become more than one-half filled. The first ionization energy for oxygen is slightly less than
that for nitrogen, despite the trend in increasing IE1 values across a period. Looking at the orbital diagram of oxygen, we can see
that removing one electron will eliminate the electron–electron repulsion caused by pairing the electrons in the 2p orbital and will
result in a half-filled orbital (which is energetically favorable). Analogous changes occur in succeeding periods (note the dip for
sulfur after phosphorus in Figure 6.34).
Removing an electron from a cation is more difficult than removing an electron from a neutral atom because of the greater
electrostatic attraction to the cation. Likewise, removing an electron from a cation with a higher positive charge is more difficult
than removing an electron from an ion with a lower charge. Thus, successive ionization energies for one element always increase.
As seen in Table 6.3, there is a large increase in the ionization energies for each element. This jump corresponds to removal of the
core electrons, which are harder to remove than the valence electrons. For example, Sc and Ga both have three valence electrons,
so the rapid increase in ionization energy occurs after the third ionization.
Successive Ionization Energies for Selected Elements (kJ/mol)
Element IE1 IE2 IE3 IE4 IE5 IE6 IE7
K 418.8 3051.8 4419.6 5876.9 7975.5 9590.6 11343
Ca 589.8 1145.4 4912.4 6490.6 8153.0 10495.7 12272.9
Sc 633.1 1235.0 2388.7 7090.6 8842.9 10679.0 13315.0
Ga 578.8 1979.4 2964.6 6180 8298.7 10873.9 13594.8
Ge 762.2 1537.5 3302.1 4410.6 9021.4 Not available Not available

Element IE1 IE2 IE3 IE4 IE5 IE6 IE7
As 944.5 1793.6 2735.5 4836.8 6042.9 12311.5 Not available
Table 6.3
6.6.0.1: Example 6.13

6.6.0.0.1: Ranking Ionization Energies
Predict the order of increasing energy for the following processes: IE1 for Al, IE1 for Tl, IE2 for Na, IE3 for Al.
6.6.0.0.2: Solution
Removing the 6p1 electron from Tl is easier than removing the 3p1 electron from Al because the higher n orbital is farther from
the nucleus, so IE1(Tl) < IE1(Al). Ionizing the third electron from Al (Al
2+
⟶ Al + e ) requires more energy
3+ −
because the cation Al2+ exerts a stronger pull on the electron than the neutral Al atom, so IE1(Al) < IE3(Al). The second
ionization energy for sodium removes a core electron, which is a much higher energy process than removing valence electrons.
Putting this all together, we obtain: IE1(Tl) < IE1(Al) < IE3(Al) < IE2(Na).
Which has the lowest value for IE1: O, Po, Pb, or Ba?
6.6.0.1: Answer:
Ba
6.6.0.1: Variation in Electron Affinities

The electron affinity (EA) is the energy change for the process of adding an electron to a gaseous atom to form an anion (negative
ion).
− −
X(g) + e ⟶ X (g) EA1
This process can be either endothermic or exothermic, depending on the element. The EA of some of the elements is given in
Figure 6.35. You can see that many of these elements have negative values of EA, which means that energy is released when the
gaseous atom accepts an electron. However, for some elements, energy is required for the atom to become negatively charged and
the value of their EA is positive. Just as with ionization energy, subsequent EA values are associated with forming ions with more
charge. The second EA is the energy associated with adding an electron to an anion to form a –2 ion, and so on.
As we might predict, it becomes easier to add an electron across a series of atoms as the effective nuclear charge of the atoms
increases. We find, as we go from left to right across a period, EAs tend to become more negative. The exceptions found among the
elements of group 2 (2A), group 15 (5A), and group 18 (8A) can be understood based on the electronic structure of these groups.
The noble gases, group 18 (8A), have a completely filled shell and the incoming electron must be added to a higher n level, which
is more difficult to do. Group 2 (2A) has a filled ns subshell, and so the next electron added goes into the higher energy np, so,
again, the observed EA value is not as the trend would predict. Finally, group 15 (5A) has a half-filled np subshell and the next
electron must be paired with an existing np electron. In all of these cases, the initial relative stability of the electron configuration
disrupts the trend in EA.
We also might expect the atom at the top of each group to have the most negative EA; their first ionization potentials suggest that
these atoms have the largest effective nuclear charges. However, as we move down a group, we see that the second element in the
group most often has the most negative EA. This can be attributed to the small size of the n = 2 shell and the resulting large
electron–electron repulsions. For example, chlorine, with an EA value of –348 kJ/mol, has the highest value of any element in the
periodic table. The EA of fluorine is –322 kJ/mol. When we add an electron to a fluorine atom to form a fluoride anion (F–), we
add an electron to the n = 2 shell. The electron is attracted to the nucleus, but there is also significant repulsion from the other
electrons already present in this small valence shell. The chlorine atom has the same electron configuration in the valence shell, but
because the entering electron is going into the n = 3 shell, it occupies a considerably larger region of space and the electron–
electron repulsions are reduced. The entering electron does not experience as much repulsion and the chlorine atom accepts an
additional electron more readily, resulting in a more negative EA.

Figure 6.35 This version of the periodic table displays the electron affinity values (in kJ/mol) for selected elements.
The properties discussed in this section (size of atoms and ions, effective nuclear charge, ionization energies, and electron
affinities) are central to understanding chemical reactivity. For example, because fluorine has an energetically favorable EA and a
large energy barrier to ionization (IE), it is much easier to form fluorine anions than cations. Metallic properties including
conductivity and malleability (the ability to be formed into sheets) depend on having electrons that can be removed easily. Thus,
metallic character increases as we move down a group and decreases across a period in the same trend observed for atomic size
because it is easier to remove an electron that is farther away from the nucleus.
This page titled 6.6: Periodic Variations in Element Properties is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

6.7: Key Terms
amplitude
extent of the displacement caused by a wave
atomic orbital
mathematical function that describes the behavior of an electron in an atom (also called the wavefunction)
Aufbau principle
procedure in which the electron configuration of the elements is determined by “building” them in order of atomic numbers,
adding one proton to the nucleus and one electron to the proper subshell at a time
blackbody
idealized perfect absorber of all incident electromagnetic radiation; such bodies emit electromagnetic radiation in characteristic
continuous spectra called blackbody radiation
Bohr’s model of the hydrogen atom

structural model in which an electron moves around the nucleus only in circular orbits, each with a specific allowed radius
continuous spectrum
electromagnetic radiation given off in an unbroken series of wavelengths (e.g., white light from the sun)
core electron
electron in an atom that occupies the orbitals of the inner shells
covalent radius
one-half the distance between the nuclei of two identical atoms when they are joined by a covalent bond
d orbital
region of space with high electron density that is either four lobed or contains a dumbbell and torus shape; describes orbitals
with l = 2.
degenerate orbitals
orbitals that have the same energy
effective nuclear charge

charge that leads to the Coulomb force exerted by the nucleus on an electron, calculated as the nuclear charge minus shielding
electromagnetic radiation
energy transmitted by waves that have an electric-field component and a magnetic-field component
electromagnetic spectrum
range of energies that electromagnetic radiation can comprise, including radio, microwaves, infrared, visible, ultraviolet, X-
rays, and gamma rays
electron affinity
energy change associated with addition of an electron to a gaseous atom or ion
electron configuration
listing that identifies the electron occupancy of an atom’s shells and subshells
electron density
a measure of the probability of locating an electron in a particular region of space, it is equal to the squared absolute value of
the wave function ψ
excited state
state having an energy greater than the ground-state energy
f orbital
multilobed region of space with high electron density, describes orbitals with l = 3
frequency (ν)
number of wave cycles (peaks or troughs) that pass a specified point in space per unit time
ground state
state in which the electrons in an atom, ion, or molecule have the lowest energy possible
Heisenberg uncertainty principle

rule stating that it is impossible to exactly determine both certain conjugate dynamical properties such as the momentum and the
position of a particle at the same time. The uncertainty principle is a consequence of quantum particles exhibiting wave–particle
duality
hertz (Hz)
the unit of frequency, which is the number of cycles per second, s−1
Hund’s rule
every orbital in a subshell is singly occupied with one electron before any one orbital is doubly occupied, and all electrons in
singly occupied orbitals have the same spin
intensity
property of wave-propagated energy related to the amplitude of the wave, such as brightness of light or loudness of sound
interference pattern
pattern typically consisting of alternating bright and dark fringes; it results from constructive and destructive interference of
waves
ionization energy
energy required to remove an electron from a gaseous atom or ion
isoelectronic
group of ions or atoms that have identical electron configurations
line spectrum
electromagnetic radiation emitted at discrete wavelengths by a specific atom (or atoms) in an excited state
magnetic quantum number (ml)

quantum number signifying the orientation of an atomic orbital around the nucleus
node
any point of a standing wave with zero amplitude
orbital diagram
pictorial representation of the electron configuration showing each orbital as a box and each electron as an arrow
p orbital
dumbbell-shaped region of space with high electron density, describes orbitals with l = 1
Pauli exclusion principle

specifies that no two electrons in an atom can have the same value for all four quantum numbers
photon
smallest possible packet of electromagnetic radiation, a particle of light
principal quantum number (n)

quantum number specifying the shell an electron occupies in an atom
quantization
limitation of some property to specific discrete values, not continuous
quantum mechanics
field of study that includes quantization of energy, wave-particle duality, and the Heisenberg uncertainty principle to describe
matter
quantum number
number having only specific allowed values and used to characterize the arrangement of electrons in an atom
s orbital
spherical region of space with high electron density, describes orbitals with l = 0
secondary (angular momentum) quantum number (l)

quantum number distinguishing the different shapes of orbitals; it is also a measure of the orbital angular momentum
shell
atomic orbitals with the same principal quantum number, n
spin quantum number (ms)

number specifying the electron spin direction, either + 1
2
or − 1
standing wave
(also, stationary wave) localized wave phenomenon characterized by discrete wavelengths determined by the boundary
conditions used to generate the waves; standing waves are inherently quantized
subshell
atomic orbitals with the same values of n and l
valence electrons
electrons in the high energy outer shell(s) of an atom
valence shell
high energy outer shell(s) of an atom
wave
oscillation of a property over time or space; can transport energy from one point to another
wave-particle duality
observation that elementary particles can exhibit both wave-like and particle-like properties
wavefunction (ψ)
mathematical description of an atomic orbital that describes the shape of the orbital; it can be used to calculate the probability of
finding the electron at any given location in the orbital, as well as dynamical variables such as the energy and the angular
momentum
wavelength (λ)
distance between two consecutive peaks or troughs in a wave
6.8: Key Equations
c = λν
E = hν =
hc
λ
, where h = 6.626 × 10−34 J s
1 1 1
= R∞ ( − )
2 2
λ n n
1 2
2
kZ
En = − , n = 1, 2, 3, …
n2
2 1 1
ΔE = kZ ( − )
2 2
n1 n2
2
n
r = a0
Z
6.9: Summary
6.1 Electromagnetic Energy
Light and other forms of electromagnetic radiation move through a vacuum with a constant speed, c, of 2.998 × 108 m s−1. This
radiation shows wavelike behavior, which can be characterized by a frequency, ν, and a wavelength, λ, such that c = λν. Light is an
example of a travelling wave. Other important wave phenomena include standing waves, periodic oscillations, and vibrations.
Standing waves exhibit quantization, since their wavelengths are limited to discrete integer multiples of some characteristic lengths.
Electromagnetic radiation that passes through two closely spaced narrow slits having dimensions roughly similar to the wavelength
will show an interference pattern that is a result of constructive and destructive interference of the waves. Electromagnetic radiation
also demonstrates properties of particles called photons. The energy of a photon is related to the frequency (or alternatively, the
wavelength) of the radiation as E = hν (or E = hc
λ
), where h is Planck's constant. That light demonstrates both wavelike and
particle-like behavior is known as wave-particle duality. All forms of electromagnetic radiation share these properties, although
various forms including X-rays, visible light, microwaves, and radio waves interact differently with matter and have very different
practical applications. Electromagnetic radiation can be generated by exciting matter to higher energies, such as by heating it. The
emitted light can be either continuous (incandescent sources like the sun) or discrete (from specific types of excited atoms).
Continuous spectra often have distributions that can be approximated as blackbody radiation at some appropriate temperature. The
line spectrum of hydrogen can be obtained by passing the light from an electrified tube of hydrogen gas through a prism. This line
spectrum was simple enough that an empirical formula called the Rydberg formula could be derived from the spectrum. Three
historically important paradoxes from the late 19th and early 20th centuries that could not be explained within the existing
framework of classical mechanics and classical electromagnetism were the blackbody problem, the photoelectric effect, and the
discrete spectra of atoms. The resolution of these paradoxes ultimately led to quantum theories that superseded the classical
theories.
6.2 The Bohr Model

Bohr incorporated Planck’s and Einstein’s quantization ideas into a model of the hydrogen atom that resolved the paradox of atom
stability and discrete spectra. The Bohr model of the hydrogen atom explains the connection between the quantization of photons
and the quantized emission from atoms. Bohr described the hydrogen atom in terms of an electron moving in a circular orbit about
a nucleus. He postulated that the electron was restricted to certain orbits characterized by discrete energies. Transitions between
these allowed orbits result in the absorption or emission of photons. When an electron moves from a higher-energy orbit to a more
stable one, energy is emitted in the form of a photon. To move an electron from a stable orbit to a more excited one, a photon of
energy must be absorbed. Using the Bohr model, we can calculate the energy of an electron and the radius of its orbit in any one-
electron system.
6.3 Development of Quantum Theory

Macroscopic objects act as particles. Microscopic objects (such as electrons) have properties of both a particle and a wave. Their
exact trajectories cannot be determined. The quantum mechanical model of atoms describes the three-dimensional position of the
electron in a probabilistic manner according to a mathematical function called a wavefunction, often denoted as ψ. Atomic
wavefunctions are also called orbitals. The squared magnitude of the wavefunction describes the distribution of the probability of
finding the electron in a particular region in space. Therefore, atomic orbitals describe the areas in an atom where electrons are
most likely to be found.
An atomic orbital is characterized by three quantum numbers. The principal quantum number, n, can be any positive integer. The
general region for value of energy of the orbital and the average distance of an electron from the nucleus are related to n. Orbitals
having the same value of n are said to be in the same shell. The secondary (angular momentum) quantum number, l, can have any
integer value from 0 to n – 1. This quantum number describes the shape or type of the orbital. Orbitals with the same principal
quantum number and the same l value belong to the same subshell. The magnetic quantum number, ml, with 2l + 1 values ranging
from –l to +l, describes the orientation of the orbital in space. In addition, each electron has a spin quantum number, ms, that can be
equal to ± . No two electrons in the same atom can have the same set of values for all the four quantum numbers.
1
6.4 Electronic Structure of Atoms (Electron Configurations)

The relative energy of the subshells determine the order in which atomic orbitals are filled (1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, and so on).
Electron configurations and orbital diagrams can be determined by applying the Pauli exclusion principle (no two electrons can
have the same set of four quantum numbers) and Hund’s rule (whenever possible, electrons retain unpaired spins in degenerate
orbitals).
Electrons in the outermost orbitals, called valence electrons, are responsible for most of the chemical behavior of elements. In the
periodic table, elements with analogous valence electron configurations usually occur within the same group. There are some
exceptions to the predicted filling order, particularly when half-filled or completely filled orbitals can be formed. The periodic table
can be divided into three categories based on the orbital in which the last electron to be added is placed: main group elements (s
and p orbitals), transition elements (d orbitals), and inner transition elements (f orbitals).
6.5 Periodic Variations in Element Properties

Electron configurations allow us to understand many periodic trends. Covalent radius increases as we move down a group because
the n level (orbital size) increases. Covalent radius mostly decreases as we move left to right across a period because the effective
nuclear charge experienced by the electrons increases, and the electrons are pulled in tighter to the nucleus. Anionic radii are larger
than the parent atom, while cationic radii are smaller, because the number of valence electrons has changed while the nuclear
charge has remained constant. Ionization energy (the energy associated with forming a cation) decreases down a group and mostly
increases across a period because it is easier to remove an electron from a larger, higher energy orbital. Electron affinity (the energy
associated with forming an anion) is more favorable (exothermic) when electrons are placed into lower energy orbitals, closer to
the nucleus. Therefore, electron affinity becomes increasingly negative as we move left to right across the periodic table and
decreases as we move down a group. For both IE and electron affinity data, there are exceptions to the trends when dealing with
completely filled or half-filled subshells.
6.10: Exercises
6.10.0.1: 6.1 Electromagnetic Energy
1.
The light produced by a red neon sign is due to the emission of light by excited neon atoms. Qualitatively describe the spectrum
produced by passing light from a neon lamp through a prism.
2.
An FM radio station found at 103.1 on the FM dial broadcasts at a frequency of 1.031 × 108 s−1 (103.1 MHz). What is the
wavelength of these radio waves in meters?
3.
FM-95, an FM radio station, broadcasts at a frequency of 9.51 × 107 s−1 (95.1 MHz). What is the wavelength of these radio waves
in meters?
4.
A bright violet line occurs at 435.8 nm in the emission spectrum of mercury vapor. What amount of energy, in joules, must be
released by an electron in a mercury atom to produce a photon of this light?
5.
Light with a wavelength of 614.5 nm looks orange. What is the energy, in joules, per photon of this orange light? What is the
energy in eV (1 eV = 1.602 × 10−19 J)?
6.
Heated lithium atoms emit photons of light with an energy of 2.961 × 10−19 J. Calculate the frequency and wavelength of one of
these photons. What is the total energy in 1 mole of these photons? What is the color of the emitted light?
7.
A photon of light produced by a surgical laser has an energy of 3.027 × 10−19 J. Calculate the frequency and wavelength of the
photon. What is the total energy in 1 mole of photons? What is the color of the emitted light?
8.
When rubidium ions are heated to a high temperature, two lines are observed in its line spectrum at wavelengths (a) 7.9 × 10−7 m
and (b) 4.2 × 10−7 m. What are the frequencies of the two lines? What color do we see when we heat a rubidium compound?
9.
The emission spectrum of cesium contains two lines whose frequencies are (a) 3.45 × 1014 Hz and (b) 6.53 × 1014 Hz. What are
the wavelengths and energies per photon of the two lines? What color are the lines?
10.
Photons of infrared radiation are responsible for much of the warmth we feel when holding our hands before a fire. These photons
will also warm other objects. How many infrared photons with a wavelength of 1.5 × 10−6 m must be absorbed by the water to
warm a cup of water (175 g) from 25.0 °C to 40 °C?
11.
One of the radiographic devices used in a dentist's office emits an X-ray of wavelength 2.090 × 10−11 m. What is the energy, in
joules, and frequency of this X-ray?
12.
The eyes of certain reptiles pass a single visual signal to the brain when the visual receptors are struck by photons of a wavelength
of 850 nm. If a total energy of 3.15 × 10−14 J is required to trip the signal, what is the minimum number of photons that must strike
the receptor?
13.
RGB color television and computer displays use cathode ray tubes that produce colors by mixing red, green, and blue light. If we
look at the screen with a magnifying glass, we can see individual dots turn on and off as the colors change. Using a spectrum of

visible light, determine the approximate wavelength of each of these colors. What is the frequency and energy of a photon of each
of these colors?
14.
Answer the following questions about a Blu-ray laser:
(a) The laser on a Blu-ray player has a wavelength of 405 nm. In what region of the electromagnetic spectrum is this radiation?
What is its frequency?
(b) A Blu-ray laser has a power of 5 milliwatts (1 watt = 1 J s−1). How many photons of light are produced by the laser in 1 hour?
(c) The ideal resolution of a player using a laser (such as a Blu-ray player), which determines how close together data can be stored
on a compact disk, is determined using the following formula: Resolution = 0.60(λ/NA), where λ is the wavelength of the laser and
NA is the numerical aperture. Numerical aperture is a measure of the size of the spot of light on the disk; the larger the NA, the
smaller the spot. In a typical Blu-ray system, NA = 0.95. If the 405-nm laser is used in a Blu-ray player, what is the closest that
information can be stored on a Blu-ray disk?
(d) The data density of a Blu-ray disk using a 405-nm laser is 1.5 × 107 bits mm−2. Disks have an outside diameter of 120 mm and
a hole of 15-mm diameter. How many data bits can be contained on the disk? If a Blu-ray disk can hold 9,400,000 pages of text,
how many data bits are needed for a typed page? (Hint: Determine the area of the disk that is available to hold data. The area inside
a circle is given by A = πr2, where the radius r is one-half of the diameter.)
15.
What is the threshold frequency for sodium metal if a photon with frequency 6.66 × 1014 s−1 ejects an electron with 7.74 × 10−20 J
kinetic energy? Will the photoelectric effect be observed if sodium is exposed to orange light?
6.10.0.1: 6.2 The Bohr Model

16.
Why is the electron in a Bohr hydrogen atom bound less tightly when it has a quantum number of 3 than when it has a quantum
number of 1?
17.
What does it mean to say that the energy of the electrons in an atom is quantized?
18.
Using the Bohr model, determine the energy, in joules, necessary to ionize a ground-state hydrogen atom. Show your calculations.
19.
The electron volt (eV) is a convenient unit of energy for expressing atomic-scale energies. It is the amount of energy that an
electron gains when subjected to a potential of 1 volt; 1 eV = 1.602 × 10–19 J. Using the Bohr model, determine the energy, in
electron volts, of the photon produced when an electron in a hydrogen atom moves from the orbit with n = 5 to the orbit with n = 2.
Show your calculations.
20.
Using the Bohr model, determine the lowest possible energy, in joules, for the electron in the Li2+ ion.
21.
Using the Bohr model, determine the lowest possible energy for the electron in the He+ ion.
22.
Using the Bohr model, determine the energy of an electron with n = 6 in a hydrogen atom.
23.
Using the Bohr model, determine the energy of an electron with n = 8 in a hydrogen atom.
24.
How far from the nucleus in angstroms (1 angstrom = 1 × 10–10 m) is the electron in a hydrogen atom if it has an energy of –8.72
–20
× 10 J?

25.
What is the radius, in angstroms, of the orbital of an electron with n = 8 in a hydrogen atom?
26.
Using the Bohr model, determine the energy in joules of the photon produced when an electron in a He+ ion moves from the orbit
with n = 5 to the orbit with n = 2.
27.
Using the Bohr model, determine the energy in joules of the photon produced when an electron in a Li2+ ion moves from the orbit
with n = 2 to the orbit with n = 1.
28.
Consider a large number of hydrogen atoms with electrons randomly distributed in the n = 1, 2, 3, and 4 orbits.
(a) How many different wavelengths of light are emitted by these atoms as the electrons fall into lower-energy orbits?
(b) Calculate the lowest and highest energies of light produced by the transitions described in part (a).
(c) Calculate the frequencies and wavelengths of the light produced by the transitions described in part (b).
29.
How are the Bohr model and the Rutherford model of the atom similar? How are they different?
30.
The spectra of hydrogen and of calcium are shown here.
What causes the lines in these spectra? Why are the colors of the lines different? Suggest a reason for the observation that the
spectrum of calcium is more complicated than the spectrum of hydrogen.

6.10.0.1: 6.3 Development of Quantum Theory
31.
How are the Bohr model and the quantum mechanical model of the hydrogen atom similar? How are they different?
32.
What are the allowed values for each of the four quantum numbers: n, l, ml, and ms?
33.
Describe the properties of an electron associated with each of the following four quantum numbers: n, l, ml, and ms.
34.
Answer the following questions:
(a) Without using quantum numbers, describe the differences between the shells, subshells, and orbitals of an atom.
(b) How do the quantum numbers of the shells, subshells, and orbitals of an atom differ?
35.
Identify the subshell in which electrons with the following quantum numbers are found:
(a) n = 2, l = 1
(b) n = 4, l = 2
(c) n = 6, l = 0
36.
Which of the subshells described in the previous question contain degenerate orbitals? How many degenerate orbitals are in each?
37.
Identify the subshell in which electrons with the following quantum numbers are found:
(a) n = 3, l = 2
(b) n = 1, l = 0
(c) n = 4, l = 3
38.
Which of the subshells described in the previous question contain degenerate orbitals? How many degenerate orbitals are in each?
39.
Sketch the boundary surface of a d x2 −y 2 and a py orbital. Be sure to show and label the axes.
40.
Sketch the px and dxz orbitals. Be sure to show and label the coordinates.
41.
Consider the orbitals shown here in outline.
(a) What is the maximum number of electrons contained in an orbital of type (x)? Of type (y)? Of type (z)?
(b) How many orbitals of type (x) are found in a shell with n = 2? How many of type (y)? How many of type (z)?

(c) Write a set of quantum numbers for an electron in an orbital of type (x) in a shell with n = 4. Of an orbital of type (y) in a shell
with n = 2. Of an orbital of type (z) in a shell with n = 3.
(d) What is the smallest possible n value for an orbital of type (x)? Of type (y)? Of type (z)?
(e) What are the possible l and ml values for an orbital of type (x)? Of type (y)? Of type (z)?
42.
State the Heisenberg uncertainty principle. Describe briefly what the principle implies.
43.
How many electrons could be held in the second shell of an atom if the spin quantum number ms could have three values instead of
just two? (Hint: Consider the Pauli exclusion principle.)
44.
Which of the following equations describe particle-like behavior? Which describe wavelike behavior? Do any involve both types of
behavior? Describe the reasons for your choices.
(a) c = λν
2
(b) E = mν
2
n a0
(c) r = Z
(d) E = hν
(e) λ = mν
h
45.
Write a set of quantum numbers for each of the electrons with an n of 4 in a Se atom.
6.10.0.1: 6.4 Electronic Structure of Atoms (Electron Configurations)

46.
Read the labels of several commercial products and identify monatomic ions of at least four transition elements contained in the
products. Write the complete electron configurations of these cations.
47.
Read the labels of several commercial products and identify monatomic ions of at least six main group elements contained in the
products. Write the complete electron configurations of these cations and anions.
48.
Using complete subshell notation (not abbreviations, 1s22s22p6, and so forth), predict the electron configuration of each of the
following atoms:
(a) C
(b) P
(c) V
(d) Sb
(e) Sm
49.
Using complete subshell notation (1s22s22p6, and so forth), predict the electron configuration of each of the following atoms:
(a) N
(b) Si
(c) Fe
(d) Te

(e) Tb
50.
Is 1s22s22p6 the symbol for a macroscopic property or a microscopic property of an element? Explain your answer.
51.
What additional information do we need to answer the question “Which ion has the electron configuration 1s22s22p63s23p6”?
52.
Draw the orbital diagram for the valence shell of each of the following atoms:
(a) C
(b) P
(c) V
(d) Sb
(e) Ru
53.
Use an orbital diagram to describe the electron configuration of the valence shell of each of the following atoms:
(a) N
(b) Si
(c) Fe
(d) Te
(e) Mo
54.
Using complete subshell notation (1s22s22p6, and so forth), predict the electron configurations of the following ions.
(a) N3–
(b) Ca2+
(c) S–
(d) Cs2+
(e) Cr2+
(f) Gd3+
55.
Which atom has the electron configuration 1s22s22p63s23p64s23d104p65s24d2?
56.
Which atom has the electron configuration 1s22s22p63s23p63d74s2?
57.
Which ion with a +1 charge has the electron configuration 1s22s22p63s23p63d104s24p6? Which ion with a –2 charge has this
configuration?
58.
Which of the following atoms contains only three valence electrons: Li, B, N, F, Ne?
59.
Which of the following has two unpaired electrons?
(a) Mg

(b) Si
(c) S
(d) Both Mg and S
(e) Both Si and S.
60.
Which atom would be expected to have a half-filled 6p subshell?
61.
Which atom would be expected to have a half-filled 4s subshell?
62.
In one area of Australia, the cattle did not thrive despite the presence of suitable forage. An investigation showed the cause to be
the absence of sufficient cobalt in the soil. Cobalt forms cations in two oxidation states, Co2+ and Co3+. Write the electron structure
of the two cations.
63.
Thallium was used as a poison in the Agatha Christie mystery story “The Pale Horse.” Thallium has two possible cationic forms,
+1 and +3. The +1 compounds are the more stable. Write the electron structure of the +1 cation of thallium.
64.
Write the electron configurations for the following atoms or ions:
(a) B3+
(b) O–
(c) Cl3+
(d) Ca2+
(e) Ti
65.
Cobalt–60 and iodine–131 are radioactive isotopes commonly used in nuclear medicine. How many protons, neutrons, and
electrons are in atoms of these isotopes? Write the complete electron configuration for each isotope.
66.
Write a set of quantum numbers for each of the electrons with an n of 3 in a Sc atom.
6.10.0.1: 6.5 Periodic Variations in Element Properties

67.
Based on their positions in the periodic table, predict which has the smallest atomic radius: Mg, Sr, Si, Cl, I.
68.
Based on their positions in the periodic table, predict which has the largest atomic radius: Li, Rb, N, F, I.
69.
Based on their positions in the periodic table, predict which has the largest first ionization energy: Mg, Ba, B, O, Te.
70.
Based on their positions in the periodic table, predict which has the smallest first ionization energy: Li, Cs, N, F, I.
71.
Based on their positions in the periodic table, rank the following atoms in order of increasing first ionization energy: F, Li, N, Rb
72.
Based on their positions in the periodic table, rank the following atoms in order of increasing first ionization energy: Mg, O, S, Si
73.

Atoms of which group in the periodic table have a valence shell electron configuration of ns2np3?
74.
Atoms of which group in the periodic table have a valence shell electron configuration of ns2?
75.
Based on their positions in the periodic table, list the following atoms in order of increasing radius: Mg, Ca, Rb, Cs.
76.
Based on their positions in the periodic table, list the following atoms in order of increasing radius: Sr, Ca, Si, Cl.
77.
Based on their positions in the periodic table, list the following ions in order of increasing radius: K+, Ca2+, Al3+, Si4+.
78.
List the following ions in order of increasing radius: Li+, Mg2+, Br–, Te2–.
79.
Which atom and/or ion is (are) isoelectronic with Br+: Se2+, Se, As–, Kr, Ga3+, Cl–?
80.
Which of the following atoms and ions is (are) isoelectronic with S2+: Si4+, Cl3+, Ar, As3+, Si, Al3+?
81.
Compare both the numbers of protons and electrons present in each to rank the following ions in order of increasing radius: As3–,
Br–, K+, Mg2+.
82.
Of the five elements Al, Cl, I, Na, Rb, which has the most exothermic reaction? (E represents an atom.) What name is given to the
energy for the reaction? Hint: Note the process depicted does not correspond to electron affinity.)
+ −
E (g) + e ⟶ E(g)
83.
Of the five elements Sn, Si, Sb, O, Te, which has the most endothermic reaction? (E represents an atom.) What name is given to the
energy for the reaction?
+ −
E(g) ⟶ E (g) + e
84.
The ionic radii of the ions S2–, Cl–, and K+ are 184, 181, 138 pm respectively. Explain why these ions have different sizes even
though they contain the same number of electrons.
85.
Which main group atom would be expected to have the lowest second ionization energy?
86.
Explain why Al is a member of group 13 rather than group 3?

CHAPTER OVERVIEW
7: Chemical Bonding and Molecular Geometry

General Chemistry
A chemical bond is an attraction between atoms that allows the formation of chemical substances that contain two or more atoms.
The bond is caused by the electrostatic force of attraction between opposite charges, either between electrons and nuclei, or as the
result of a dipole attraction. All bonds can be explained by quantum theory, but, in practice, simplification rules allow chemists to
predict the strength, directionality, and polarity of bonds. The octet rule and VSEPR theory are two examples. More sophisticated
theories are valence bond theory which includes orbital hybridization and resonance, and the linear combination of atomic orbitals
molecular orbital method. Electrostatics are used to describe bond polarities and the effects they have on chemical substances.
7.1: Introduction
7.2: Ionic Bonding
7.8: Key Terms
7.9: Key Equations
7.10: Summary
7.11: Exercises
Thumbnail: Covalently bonded hydrogen and carbon in a w:molecule of methane. (CC BY-SA 2.5; DynaBlast via Wikipedia)
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1
7.1: Introduction
Figure 7.1 Nicknamed “buckyballs,” buckminsterfullerene molecules (C60) contain only carbon atoms (left) arranged to form a
geometric framework of hexagons and pentagons, similar to the pattern on a soccer ball (center). This molecular structure is named
after architect R. Buckminster Fuller, whose innovative designs combined simple geometric shapes to create large, strong structures
such as this weather radar dome near Tucson, Arizona (right). (credit middle: modification of work by “Petey21”/Wikimedia
Commons; credit right: modification of work by Bill Morrow)

7.1 Ionic Bonding
7.2 Covalent Bonding
7.3 Lewis Symbols and Structures
7.4 Formal Charges and Resonance
7.5 Strengths of Ionic and Covalent Bonds
7.6 Molecular Structure and Polarity
It has long been known that pure carbon occurs in different forms (allotropes) including graphite and diamonds. But it was not until
1985 that a new form of carbon was recognized: buckminsterfullerene. This molecule was named after the architect and inventor R.
Buckminster Fuller (1895–1983), whose signature architectural design was the geodesic dome, characterized by a lattice shell
structure supporting a spherical surface. Experimental evidence revealed the formula, C60, and then scientists determined how 60
carbon atoms could form one symmetric, stable molecule. They were guided by bonding theory—the topic of this chapter—which
explains how individual atoms connect to form more complex structures.

7.2: Ionic Bonding

Explain the formation of cations, anions, and ionic compounds
Predict the charge of common metallic and nonmetallic elements, and write their electron configurations
As you have learned, ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom
loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more
electrons in its valence shell.
Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds:
electrostatic forces of attraction between oppositely charged cations and anions. The properties of ionic compounds shed some light
on the nature of ionic bonds. Ionic solids exhibit a crystalline structure and tend to be rigid and brittle; they also tend to have high
melting and boiling points, which suggests that ionic bonds are very strong. Ionic solids are also poor conductors of electricity for
the same reason—the strength of ionic bonds prevents ions from moving freely in the solid state. Most ionic solids, however,
dissolve readily in water. Once dissolved or melted, ionic compounds are excellent conductors of electricity and heat because the
ions can move about freely.
Neutral atoms and their associated ions have very different physical and chemical properties. Sodium atoms form sodium metal, a
soft, silvery-white metal that burns vigorously in air and reacts explosively with water. Chlorine atoms form chlorine gas, Cl2, a
yellow-green gas that is extremely corrosive to most metals and very poisonous to animals and plants. The vigorous reaction
between the elements sodium and chlorine forms the white, crystalline compound sodium chloride, common table salt, which
contains sodium cations and chloride anions (Figure 7.2). The compound composed of these ions exhibits properties entirely
different from the properties of the elements sodium and chlorine. Chlorine is poisonous, but sodium chloride is essential to life;
sodium atoms react vigorously with water, but sodium chloride simply dissolves in water.
Figure 7.2 (a) Sodium is a soft metal that must be stored in mineral oil to prevent reaction with air or water. (b) Chlorine is a pale
yellow-green gas. (c) When combined, they form white crystals of sodium chloride (table salt). (credit a: modification of work by
“Jurii”/Wikimedia Commons)
7.2.0.1: The Formation of Ionic Compounds

Binary ionic compounds are composed of just two elements: a metal (which forms the cations) and a nonmetal (which forms the
anions). For example, NaCl is a binary ionic compound. We can think about the formation of such compounds in terms of the
periodic properties of the elements. Many metallic elements have relatively low ionization potentials and lose electrons easily.
These elements lie to the left in a period or near the bottom of a group on the periodic table. Nonmetal atoms have relatively high
electron affinities and thus readily gain electrons lost by metal atoms, thereby filling their valence shells. Nonmetallic elements are
found in the upper-right corner of the periodic table.

As all substances must be electrically neutral, the total number of positive charges on the cations of an ionic compound must equal
the total number of negative charges on its anions. The formula of an ionic compound represents the simplest ratio of the numbers
of ions necessary to give identical numbers of positive and negative charges. For example, the formula for aluminum oxide, Al2O3,
indicates that this ionic compound contains two aluminum cations, Al3+, for every three oxide anions, O2− [thus, (2 × +3) + (3 × –
2) = 0].
It is important to note, however, that the formula for an ionic compound does not represent the physical arrangement of its ions. It
is incorrect to refer to a sodium chloride (NaCl) “molecule” because there is not a single ionic bond, per se, between any specific
pair of sodium and chloride ions. The attractive forces between ions are isotropic—the same in all directions—meaning that any
particular ion is equally attracted to all of the nearby ions of opposite charge. This results in the ions arranging themselves into a
tightly bound, three-dimensional lattice structure. Sodium chloride, for example, consists of a regular arrangement of equal
numbers of Na+ cations and Cl– anions (Figure 7.3).
Figure 7.3 The atoms in sodium chloride (common table salt) are arranged to (a) maximize opposite charges interacting. The
smaller spheres represent sodium ions, the larger ones represent chloride ions. In the expanded view (b), the geometry can be seen
more clearly. Note that each ion is “bonded” to all of the surrounding ions—six in this case.
The strong electrostatic attraction between Na+ and Cl– ions holds them tightly together in solid NaCl. It requires 769 kJ of energy
to dissociate one mole of solid NaCl into separate gaseous Na+ and Cl– ions:
+ –
NaCl(s) ⟶ Na (g) + Cl (g) ΔH = 769 kJ
7.2.0.1: Electronic Structures of Cations

When forming a cation, an atom of a main group element tends to lose all of its valence electrons, thus assuming the electronic
structure of the noble gas that precedes it in the periodic table. For groups 1 (the alkali metals) and 2 (the alkaline earth metals), the
group numbers are equal to the numbers of valence shell electrons and, consequently, to the charges of the cations formed from
atoms of these elements when all valence shell electrons are removed. For example, calcium is a group 2 element whose neutral
atoms have 20 electrons and a ground state electron configuration of 1s22s22p63s23p64s2. When a Ca atom loses both of its valence
electrons, the result is a cation with 18 electrons, a 2+ charge, and an electron configuration of 1s22s22p63s23p6. The Ca2+ ion is
therefore isoelectronic with the noble gas Ar.
For groups 13–17, the group numbers exceed the number of valence electrons by 10 (accounting for the possibility of full d
subshells in atoms of elements in the fourth and greater periods). Thus, the charge of a cation formed by the loss of all valence
electrons is equal to the group number minus 10. For example, aluminum (in group 13) forms 3+ ions (Al3+).
Exceptions to the expected behavior involve elements toward the bottom of the groups. In addition to the expected ions Tl3+, Sn4+,
Pb4+, and Bi5+, a partial loss of these atoms’ valence shell electrons can also lead to the formation of Tl+, Sn2+, Pb2+, and Bi3+ ions.
The formation of these 1+, 2+, and 3+ cations is ascribed to the inert pair effect, which reflects the relatively low energy of the
valence s-electron pair for atoms of the heavy elements of groups 13, 14, and 15. Mercury (group 12) also exhibits an unexpected
behavior: it forms a diatomic ion, Hg 2
(an ion formed from two mercury atoms, with an Hg-Hg bond), in addition to the
2+
expected monatomic ion Hg2+ (formed from only one mercury atom).

Transition and inner transition metal elements behave differently than main group elements. Most transition metal cations have 2+
or 3+ charges that result from the loss of their outermost s electron(s) first, sometimes followed by the loss of one or two d
electrons from the next-to-outermost shell. For example, iron (1s22s22p63s23p63d64s2) forms the ion Fe2+ (1s22s22p63s23p63d6) by
the loss of the 4s electrons and the ion Fe3+ (1s22s22p63s23p63d5) by the loss of the 4s electrons and one of the 3d electrons.
Although the d orbitals of the transition elements are—according to the Aufbau principle—the last to fill when building up electron
configurations, the outermost s electrons are the first to be lost when these atoms ionize. When the inner transition metals form
ions, they usually have a 3+ charge, resulting from the loss of their outermost s electrons and a d or f electron.
7.2.0.1: Example 7.1

7.2.0.0.1: Determining the Electronic Structures of Cations
There are at least 14 elements categorized as “essential trace elements” for the human body. They are called “essential”
because they are required for healthy bodily functions, “trace” because they are required only in small amounts, and
“elements” in spite of the fact that they are really ions. Two of these essential trace elements, chromium and zinc, are required
as Cr3+ and Zn2+. Write the electron configurations of these cations.
7.2.0.0.2: Solution
First, write the electron configuration for the neutral atoms:
Zn: [Ar]3d104s2
Cr: [Ar]3d54s1
Next, remove electrons from the highest energy orbital. For the transition metals, electrons are removed from the s orbital first
and then from the d orbital. For the p-block elements, electrons are removed from the p orbitals and then from the s orbital.
Zinc is a member of group 12, so it should have a charge of 2+, and thus loses only the two electrons in its s orbital. Chromium
is a transition element and should lose its s electrons and then its d electrons when forming a cation. Thus, we find the
following electron configurations of the ions:
Zn2+: [Ar]3d10
Cr3+: [Ar]3d3
Potassium and magnesium are required in our diet. Write the electron configurations of the ions expected from these elements.
7.2.0.1: Answer:
K+: [Ar], Mg2+: [Ne]
7.2.0.1: Electronic Structures of Anions

Most monatomic anions form when a neutral nonmetal atom gains enough electrons to completely fill its outer s and p orbitals,
thereby reaching the electron configuration of the next noble gas. Thus, it is simple to determine the charge on such a negative ion:
The charge is equal to the number of electrons that must be gained to fill the s and p orbitals of the parent atom. Oxygen, for
example, has the electron configuration 1s22s22p4, whereas the oxygen anion has the electron configuration of the noble gas neon
(Ne), 1s22s22p6. The two additional electrons required to fill the valence orbitals give the oxide ion the charge of 2– (O2–).
7.2.0.1: Example 7.2

7.2.0.0.1: Determining the Electronic Structure of Anions
Selenium and iodine are two essential trace elements that form anions. Write the electron configurations of the anions.
7.2.0.0.2: Solution
Se2–: [Ar]3d104s24p6
I–: [Kr]4d105s25p6
Write the electron configurations of a phosphorus atom and its negative ion. Give the charge on the anion.
7.2.0.1: Answer:
P: [Ne]3s23p3; P3–: [Ne]3s23p6

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Describe the formation of covalent bonds
Define electronegativity and assess the polarity of covalent bonds
Ionic bonding results from the electrostatic attraction of oppositely charged ions that are typically produced by the transfer of
electrons between metallic and nonmetallic atoms. A different type of bonding results from the mutual attraction of atoms for a
“shared” pair of electrons. Such bonds are called covalent bonds. Covalent bonds are formed between two atoms when both have
similar tendencies to attract electrons to themselves (i.e., when both atoms have identical or fairly similar ionization energies and
electron affinities). For example, two hydrogen atoms bond covalently to form an H2 molecule; each hydrogen atom in the H2
molecule has two electrons stabilizing it, giving each atom the same number of valence electrons as the noble gas He.
Compounds that contain covalent bonds exhibit different physical properties than ionic compounds. Because the attraction between
molecules, which are electrically neutral, is weaker than that between electrically charged ions, covalent compounds generally have
much lower melting and boiling points than ionic compounds. In fact, many covalent compounds are liquids or gases at room
temperature, and, in their solid states, they are typically much softer than ionic solids. Furthermore, whereas ionic compounds are
good conductors of electricity when dissolved in water, most covalent compounds are insoluble in water; since they are electrically
neutral, they are poor conductors of electricity in any state.
7.3.0.1: Formation of Covalent Bonds

Nonmetal atoms frequently form covalent bonds with other nonmetal atoms. For example, the hydrogen molecule, H2, contains a
covalent bond between its two hydrogen atoms. Figure 7.4 illustrates why this bond is formed. Starting on the far right, we have
two separate hydrogen atoms with a particular potential energy, indicated by the red line. Along the x-axis is the distance between
the two atoms. As the two atoms approach each other (moving left along the x-axis), their valence orbitals (1s) begin to overlap.
The single electrons on each hydrogen atom then interact with both atomic nuclei, occupying the space around both atoms. The
strong attraction of each shared electron to both nuclei stabilizes the system, and the potential energy decreases as the bond
distance decreases. If the atoms continue to approach each other, the positive charges in the two nuclei begin to repel each other,
and the potential energy increases. The bond length is determined by the distance at which the lowest potential energy is achieved.

Figure 7.4 The potential energy of two separate hydrogen atoms (right) decreases as they approach each other, and the single
electrons on each atom are shared to form a covalent bond. The bond length is the internuclear distance at which the lowest
potential energy is achieved.
It is essential to remember that energy must be added to break chemical bonds (an endothermic process), whereas forming chemical
bonds releases energy (an exothermic process). In the case of H2, the covalent bond is very strong; a large amount of energy, 436
kJ, must be added to break the bonds in one mole of hydrogen molecules and cause the atoms to separate:
H2 (g) ⟶ 2H(g) ΔH = 436 kJ
Conversely, the same amount of energy is released when one mole of H2 molecules forms from two moles of H atoms:
2H(g) ⟶ H2 (g) ΔH = −436 kJ
7.3.0.1: Pure vs. Polar Covalent Bonds

If the atoms that form a covalent bond are identical, as in H2, Cl2, and other diatomic molecules, then the electrons in the bond
must be shared equally. We refer to this as a pure covalent bond. Electrons shared in pure covalent bonds have an equal probability
of being near each nucleus.
In the case of Cl2, each atom starts off with seven valence electrons, and each Cl shares one electron with the other, forming one
covalent bond:
Cl + Cl ⟶ Cl2
The total number of electrons around each individual atom consists of six nonbonding electrons and two shared (i.e., bonding)
electrons for eight total electrons, matching the number of valence electrons in the noble gas argon. Since the bonding atoms are
identical, Cl2 also features a pure covalent bond.
When the atoms linked by a covalent bond are different, the bonding electrons are shared, but no longer equally. Instead, the
bonding electrons are more attracted to one atom than the other, giving rise to a shift of electron density toward that atom. This
unequal distribution of electrons is known as a polar covalent bond, characterized by a partial positive charge on one atom and a
partial negative charge on the other. The atom that attracts the electrons more strongly acquires the partial negative charge and vice
versa. For example, the electrons in the H–Cl bond of a hydrogen chloride molecule spend more time near the chlorine atom than
near the hydrogen atom. Thus, in an HCl molecule, the chlorine atom carries a partial negative charge and the hydrogen atom has a
partial positive charge. Figure 7.5 shows the distribution of electrons in the H–Cl bond. Note that the shaded area around Cl is
much larger than it is around H. Compare this to Figure 7.4, which shows the even distribution of electrons in the H2 nonpolar
bond.
We sometimes designate the positive and negative atoms in a polar covalent bond using a lowercase Greek letter “delta,” δ, with a
plus sign or minus sign to indicate whether the atom has a partial positive charge (δ+) or a partial negative charge (δ–). This
symbolism is shown for the H–Cl molecule in Figure 7.5.

Figure 7.5 (a) The distribution of electron density in the HCl molecule is uneven. The electron density is greater around the
chlorine nucleus. The small, black dots indicate the location of the hydrogen and chlorine nuclei in the molecule. (b) Symbols δ+
and δ– indicate the polarity of the H–Cl bond.
7.3.0.1: Electronegativity
Whether a bond is nonpolar or polar covalent is determined by a property of the bonding atoms called electronegativity.
Electronegativity is a measure of the tendency of an atom to attract electrons (or electron density) towards itself. It determines how
the shared electrons are distributed between the two atoms in a bond. The more strongly an atom attracts the electrons in its bonds,
the larger its electronegativity. Electrons in a polar covalent bond are shifted toward the more electronegative atom; thus, the more
electronegative atom is the one with the partial negative charge. The greater the difference in electronegativity, the more polarized
the electron distribution and the larger the partial charges of the atoms.
Figure 7.6 shows the electronegativity values of the elements as proposed by one of the most famous chemists of the twentieth
century: Linus Pauling (Figure 7.7). In general, electronegativity increases from left to right across a period in the periodic table
and decreases down a group. Thus, the nonmetals, which lie in the upper right, tend to have the highest electronegativities, with
fluorine the most electronegative element of all (EN = 4.0). Metals tend to be less electronegative elements, and the group 1 metals
have the lowest electronegativities. Note that noble gases are excluded from this figure because these atoms usually do not share
electrons with others atoms since they have a full valence shell. (While noble gas compounds such as XeO2 do exist, they can only
be formed under extreme conditions, and thus they do not fit neatly into the general model of electronegativity.)
Figure 7.6 The electronegativity values derived by Pauling follow predictable periodic trends, with the higher electronegativities
toward the upper right of the periodic table.
7.3.0.0.1: Electronegativity versus Electron Affinity
We must be careful not to confuse electronegativity and electron affinity. The electron affinity of an element is a measurable
physical quantity, namely, the energy released or absorbed when an isolated gas-phase atom acquires an electron, measured in
kJ/mol. Electronegativity, on the other hand, describes how tightly an atom attracts electrons in a bond. It is a dimensionless
quantity that is calculated, not measured. Pauling derived the first electronegativity values by comparing the amounts of energy
required to break different types of bonds. He chose an arbitrary relative scale ranging from 0 to 4.

7.3.0.0.2: Linus Pauling
Linus Pauling, shown in Figure 7.7, is the only person to have received two unshared (individual) Nobel Prizes: one for
chemistry in 1954 for his work on the nature of chemical bonds and one for peace in 1962 for his opposition to weapons of
mass destruction. He developed many of the theories and concepts that are foundational to our current understanding of
chemistry, including electronegativity and resonance structures.

Figure 7.7 Linus Pauling (1901–1994) made many important contributions to the field of chemistry. He was also a prominent
activist, publicizing issues related to health and nuclear weapons.
Pauling also contributed to many other fields besides chemistry. His research on sickle cell anemia revealed the cause of the
disease—the presence of a genetically inherited abnormal protein in the blood—and paved the way for the field of molecular
genetics. His work was also pivotal in curbing the testing of nuclear weapons; he proved that radioactive fallout from nuclear
testing posed a public health risk.
7.3.0.0.3: Electronegativity and Bond Type

The absolute value of the difference in electronegativity (ΔEN) of two bonded atoms provides a rough measure of the polarity to be
expected in the bond and, thus, the bond type. When the difference is very small or zero, the bond is covalent and nonpolar. When
it is large, the bond is polar covalent or ionic. The absolute values of the electronegativity differences between the atoms in the
bonds H–H, H–Cl, and Na–Cl are 0 (nonpolar), 0.9 (polar covalent), and 2.1 (ionic), respectively. The degree to which electrons are
shared between atoms varies from completely equal (pure covalent bonding) to not at all (ionic bonding). Figure 7.8 shows the
relationship between electronegativity difference and bond type.
Figure 7.8 As the electronegativity difference increases between two atoms, the bond becomes more ionic.
A rough approximation of the electronegativity differences associated with covalent, polar covalent, and ionic bonds is shown in
Figure 7.8. This table is just a general guide, however, with many exceptions. For example, the H and F atoms in HF have an
electronegativity difference of 1.9, and the N and H atoms in NH3 a difference of 0.9, yet both of these compounds form bonds that
are considered polar covalent. Likewise, the Na and Cl atoms in NaCl have an electronegativity difference of 2.1, and the Mn and I
atoms in MnI2 have a difference of 1.0, yet both of these substances form ionic compounds.

The best guide to the covalent or ionic character of a bond is to consider the types of atoms involved and their relative positions in
the periodic table. Bonds between two nonmetals are generally covalent; bonding between a metal and a nonmetal is often ionic.
Some compounds contain both covalent and ionic bonds. The atoms in polyatomic ions, such as OH–, NO , and NH , are held
3
−
4
+
together by polar covalent bonds. However, these polyatomic ions form ionic compounds by combining with ions of opposite
charge. For example, potassium nitrate, KNO3, contains the K+ cation and the polyatomic NO anion. Thus, bonding in
3
−
potassium nitrate is ionic, resulting from the electrostatic attraction between the ions K+ and NO , as well as covalent between
3
−
the nitrogen and oxygen atoms in NO . 3

−
7.3.0.1: Example 7.3

7.3.0.0.4: Electronegativity and Bond Polarity
Bond polarities play an important role in determining the structure of proteins. Using the electronegativity values in Figure 7.6,
arrange the following covalent bonds—all commonly found in amino acids—in order of increasing polarity. Then designate the
positive and negative atoms using the symbols δ+ and δ–:
C–H, C–N, C–O, N–H, O–H, S–H
7.3.0.0.5: Solution
The polarity of these bonds increases as the absolute value of the electronegativity difference increases. The atom with the δ–
designation is the more electronegative of the two. Table 7.1 shows these bonds in order of increasing polarity.
Bond Polarity and Electronegativity Difference
Bond ΔEN Polarity
C–H 0.4 δ− δ+
C −H
S–H 0.4 δ− δ+
S −H
C–N 0.5 δ+ δ−
C −N
N–H 0.9 δ− δ+
N −H
C–O 1.0 δ+ δ−
C −O
O–H 1.4 δ− δ+
O −H
Table 7.1
Silicones are polymeric compounds containing, among others, the following types of covalent bonds: Si–O, Si–C, C–H, and
C–C. Using the electronegativity values in Figure 7.6, arrange the bonds in order of increasing polarity and designate the
positive and negative atoms using the symbols δ+ and δ–.
7.3.0.1: Answer:
Bond Electronegativity Difference Polarity
C–C 0.0 nonpolar
C–H 0.4 δ− δ+
C −H
Si–C 0.7 δ+ δ−
Si− C

Bond Electronegativity Difference Polarity
Si–O 1.7 δ+ δ−
Si− O
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Write Lewis symbols for neutral atoms and ions
Draw Lewis structures depicting the bonding in simple molecules
Thus far in this chapter, we have discussed the various types of bonds that form between atoms and/or ions. In all cases, these
bonds involve the sharing or transfer of valence shell electrons between atoms. In this section, we will explore the typical method
for depicting valence shell electrons and chemical bonds, namely Lewis symbols and Lewis structures.
7.4.0.1: Lewis Symbols

We use Lewis symbols to describe valence electron configurations of atoms and monatomic ions. A Lewis symbol consists of an
elemental symbol surrounded by one dot for each of its valence electrons:
Figure 7.9 shows the Lewis symbols for the elements of the third period of the periodic table.
Figure 7.9 Lewis symbols illustrating the number of valence electrons for each element in the third period of the periodic table.
Lewis symbols can also be used to illustrate the formation of cations from atoms, as shown here for sodium and calcium:
Likewise, they can be used to show the formation of anions from atoms, as shown here for chlorine and sulfur:
Figure 7.10 demonstrates the use of Lewis symbols to show the transfer of electrons during the formation of ionic compounds.

Figure 7.10 Cations are formed when atoms lose electrons, represented by fewer Lewis dots, whereas anions are formed by atoms
gaining electrons. The total number of electrons does not change.
7.4.0.1: Lewis Structures

We also use Lewis symbols to indicate the formation of covalent bonds, which are shown in Lewis structures, drawings that
describe the bonding in molecules and polyatomic ions. For example, when two chlorine atoms form a chlorine molecule, they
share one pair of electrons:
The Lewis structure indicates that each Cl atom has three pairs of electrons that are not used in bonding (called lone pairs) and one
shared pair of electrons (written between the atoms). A dash (or line) is sometimes used to indicate a shared pair of electrons:
A single shared pair of electrons is called a single bond. Each Cl atom interacts with eight valence electrons: the six in the lone
pairs and the two in the single bond.
7.4.0.0.1: The Octet Rule
The other halogen molecules (F2, Br2, I2, and At2) form bonds like those in the chlorine molecule: one single bond between atoms
and three lone pairs of electrons per atom. This allows each halogen atom to have a noble gas electron configuration. The tendency
of main group atoms to form enough bonds to obtain eight valence electrons is known as the octet rule.
The number of bonds that an atom can form can often be predicted from the number of electrons needed to reach an octet (eight
valence electrons); this is especially true of the nonmetals of the second period of the periodic table (C, N, O, and F). For example,
each atom of a group 14 element has four electrons in its outermost shell and therefore requires four more electrons to reach an
octet. These four electrons can be gained by forming four covalent bonds, as illustrated here for carbon in CCl4 (carbon
tetrachloride) and silicon in SiH4 (silane). Because hydrogen only needs two electrons to fill its valence shell, it is an exception to
the octet rule. The transition elements and inner transition elements also do not follow the octet rule:

Group 15 elements such as nitrogen have five valence electrons in the atomic Lewis symbol: one lone pair and three unpaired
electrons. To obtain an octet, these atoms form three covalent bonds, as in NH3 (ammonia). Oxygen and other atoms in group 16
obtain an octet by forming two covalent bonds:
7.4.0.0.2: Double and Triple Bonds

As previously mentioned, when a pair of atoms shares one pair of electrons, we call this a single bond. However, a pair of atoms
may need to share more than one pair of electrons in order to achieve the requisite octet. A double bond forms when two pairs of
electrons are shared between a pair of atoms, as between the carbon and oxygen atoms in CH2O (formaldehyde) and between the
two carbon atoms in C2H4 (ethylene):
A triple bond forms when three electron pairs are shared by a pair of atoms, as in carbon monoxide (CO) and the cyanide ion
(CN–):
7.4.0.1: Writing Lewis Structures with the Octet Rule

For very simple molecules and molecular ions, we can write the Lewis structures by merely pairing up the unpaired electrons on
the constituent atoms. See these examples:
For more complicated molecules and molecular ions, it is helpful to follow the step-by-step procedure outlined here:

1. Determine the total number of valence (outer shell) electrons. For cations, subtract one electron for each positive charge. For
anions, add one electron for each negative charge.
2. Draw a skeleton structure of the molecule or ion, arranging the atoms around a central atom. (Generally, the least
electronegative element should be placed in the center.) Connect each atom to the central atom with a single bond (one electron
pair).
3. Distribute the remaining electrons as lone pairs on the terminal atoms (except hydrogen), completing an octet around each
atom.
4. Place all remaining electrons on the central atom.
5. Rearrange the electrons of the outer atoms to make multiple bonds with the central atom in order to obtain octets wherever
possible.
Let us determine the Lewis structures of SiH4, CHO 2
−
, NO+, and OF2 as examples in following this procedure:
1. Determine the total number of valence (outer shell) electrons in the molecule or ion.
For a molecule, we add the number of valence electrons on each atom in the molecule:
SiH4
Si: 4 valence electrons/atom × 1 atom = 4
+ H: 1 valence electron/atom × 4 atoms = 4
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
= 8 valence electrons
For a negative ion, such as CHO , we add the number of valence electrons on the atoms to the number of negative charges
2
−
on the ion (one electron is gained for each single negative charge):
−
CHO2
C: 4 valence electrons/atom × 1 atom = 4
H: 1 valence electron/atom × 1 atom = 1
O: 6 valence electrons/atom × 2 atoms = 12
+ 1 additional electron = 1
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
For a positive ion, such as NO+, we add the number of valence electrons on the atoms in the ion and then subtract the
number of positive charges on the ion (one electron is lost for each single positive charge) from the total number of valence
electrons:
+
NO
N: 5 valence electrons/atom × 1 atom = 5
O: 6 valence electron/atom × 1 atom = 6
+ −1 electron (positive charge) = −1
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
Since OF2 is a neutral molecule, we simply add the number of valence electrons:

OF 2
O: 6 valence electrons/atom × 1 atom = 6
+ F: 7 valence electrons/atom × 2 atoms = 14
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
2. Draw a skeleton structure of the molecule or ion, arranging the atoms around a central atom and connecting each atom to the
central atom with a single (one electron pair) bond. (Note that we denote ions with brackets around the structure, indicating the
charge outside the brackets:)
When several arrangements of atoms are possible, as for CHO , we must use experimental evidence to choose the correct
2
−
one. In general, the less electronegative elements are more likely to be central atoms. In CHO , the less electronegative
2
−
carbon atom occupies the central position with the oxygen and hydrogen atoms surrounding it. Other examples include P in
POCl3, S in SO2, and Cl in ClO . An exception is that hydrogen is almost never a central atom. As the most electronegative
4
−
element, fluorine also cannot be a central atom.

3. Distribute the remaining electrons as lone pairs on the terminal atoms (except hydrogen) to complete their valence shells with
an octet of electrons.
There are no remaining electrons on SiH4, so it is unchanged:
4. Place all remaining electrons on the central atom.

For SiH4, CHO , and NO+, there are no remaining electrons; we already placed all of the electrons determined in Step 1.
2
−
For OF2, we had 16 electrons remaining in Step 3, and we placed 12, leaving 4 to be placed on the central atom:
5. Rearrange the electrons of the outer atoms to make multiple bonds with the central atom in order to obtain octets wherever
possible.
SiH4: Si already has an octet, so nothing needs to be done.
: We have distributed the valence electrons as lone pairs on the oxygen atoms, but the carbon atom lacks an octet:
−
CHO 2
NO+: For this ion, we added eight valence electrons, but neither atom has an octet. We cannot add any more electrons since
we have already used the total that we found in Step 1, so we must move electrons to form a multiple bond:

This still does not produce an octet, so we must move another pair, forming a triple bond:
In OF2, each atom has an octet as drawn, so nothing changes.
7.4.0.1: Example 7.4

7.4.0.0.1: Writing Lewis Structures
NASA’s Cassini-Huygens mission detected a large cloud of toxic hydrogen cyanide (HCN) on Titan, one of Saturn’s moons.
Titan also contains ethane (H3CCH3), acetylene (HCCH), and ammonia (NH3). What are the Lewis structures of these
molecules?
7.4.0.0.2: Solution
1. Step 1. Calculate the number of valence electrons.
HCN: (1 × 1) + (4 × 1) + (5 × 1) = 10
H3CCH3: (1 × 3) + (2 × 4) + (1 × 3) = 14
HCCH: (1 × 1) + (2 × 4) + (1 × 1) = 10
NH3: (5 × 1) + (3 × 1) = 8
2. Step 2. Draw a skeleton and connect the atoms with single bonds. Remember that H is never a central atom:
3. Step 3. Where needed, distribute electrons to the terminal atoms:
HCN: six electrons placed on N

H3CCH3: no electrons remain
HCCH: no terminal atoms capable of accepting electrons
NH3: no terminal atoms capable of accepting electrons
4. Step 4. Where needed, place remaining electrons on the central atom:
HCN: no electrons remain

H3CCH3: no electrons remain
HCCH: four electrons placed on carbon
NH3: two electrons placed on nitrogen
5. Step 5. Where needed, rearrange electrons to form multiple bonds in order to obtain an octet on each atom:
HCN: form two more C–N bonds
H3CCH3: all atoms have the correct number of electrons
HCCH: form a triple bond between the two carbon atoms

NH3: all atoms have the correct number of electrons

Both carbon monoxide, CO, and carbon dioxide, CO2, are products of the combustion of fossil fuels. Both of these gases also
cause problems: CO is toxic and CO2 has been implicated in global climate change. What are the Lewis structures of these two
molecules?
7.4.0.1: Answer:

7.4.0.0.4: Fullerene Chemistry
Carbon, in various forms and compounds, has been known since prehistoric times, . Soot has been used as a pigment (often
called carbon black) for thousands of years. Charcoal, high in carbon content, has likewise been critical to human development.
Carbon is the key additive to iron in the steelmaking process, and diamonds have a unique place in both culture and industry.
With all this usage came significant study, particularly with the emergence of organic chemistry. And even with all the known
forms and functions of the element, scientists began to uncover the potential for even more varied and extensive carbon
structures.
As early as the 1960s, chemists began to observe complex carbon structures, but they had little evidence to support their
concepts, or their work did not make it into the mainstream. Eiji Osawa predicted a spherical form based on observations of a
similar structure, but his work was not widely known outside Japan. In a similar manner, the most comprehensive advance was
likely computational chemist Elena Galpern's, who in 1973 predicted a highly stable, 60-carbon molecule; her work was also
isolated to her native Russia. Still later, Harold Kroto, working with Canadian radio astronomers, sought to uncover the nature
of long carbon chains that had been discovered in interstellar space.
Kroto sought to use a machine developed by Richard Smalley's team at Rice University to learn more about these structures.
Together with Robert Curl, who had introduced them, and three graduate students—James Heath, Sean O’Brien, and Yuan Liu
—they performed an intensive series of experiments that led to a major discovery.
In 1996, the Nobel Prize in Chemistry was awarded to Richard Smalley (Figure 7.11), Robert Curl, and Harold Kroto for their
work in discovering a new form of carbon, the C60 buckminsterfullerene molecule (Figure 7.1). An entire class of compounds,
including spheres and tubes of various shapes, were discovered based on C60. This type of molecule, called a fullerene, shows
promise in a variety of applications. Because of their size and shape, fullerenes can encapsulate other molecules, so they have
shown potential in various applications from hydrogen storage to targeted drug delivery systems. They also possess unique
electronic and optical properties that have been put to good use in solar powered devices and chemical sensors.

Figure 7.11 Richard Smalley (1943–2005), a professor of physics, chemistry, and astronomy at Rice University, was one of the
leading advocates for fullerene chemistry. Upon his death in 2005, the US Senate honored him as the “Father of
Nanotechnology.” (credit: United States Department of Energy)
7.4.0.1: Exceptions to the Octet Rule

Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into
three categories:
Odd-electron molecules have an odd number of valence electrons, and therefore have an unpaired electron.
Electron-deficient molecules have a central atom that has fewer electrons than needed for a noble gas configuration.
Hypervalent molecules have a central atom that has more electrons than needed for a noble gas configuration.
7.4.0.0.1: Odd-electron Molecules
We call molecules that contain an odd number of electrons free radicals. Nitric oxide, NO, is an example of an odd-electron
molecule; it is produced in internal combustion engines when oxygen and nitrogen react at high temperatures.
To draw the Lewis structure for an odd-electron molecule like NO, we follow the same five steps we would for other molecules,
but with a few minor changes:
1. Determine the total number of valence (outer shell) electrons. The sum of the valence electrons is 5 (from N) + 6 (from O) = 11.
The odd number immediately tells us that we have a free radical, so we know that not every atom can have eight electrons in its
valence shell.
2. Draw a skeleton structure of the molecule. We can easily draw a skeleton with an N–O single bond:
N–O
3. Distribute the remaining electrons as lone pairs on the terminal atoms. In this case, there is no central atom, so we distribute the
electrons around both atoms. We give eight electrons to the more electronegative atom in these situations; thus oxygen has the

filled valence shell:
4. Place all remaining electrons on the central atom. Since there are no remaining electrons, this step does not apply.
5. Rearrange the electrons to make multiple bonds with the central atom in order to obtain octets wherever possible. We know that
an odd-electron molecule cannot have an octet for every atom, but we want to get each atom as close to an octet as possible. In
this case, nitrogen has only five electrons around it. To move closer to an octet for nitrogen, we take one of the lone pairs from
oxygen and use it to form a NO double bond. (We cannot take another lone pair of electrons on oxygen and form a triple bond
because nitrogen would then have nine electrons:)
7.4.0.0.2: Electron-deficient Molecules

We will also encounter a few molecules that contain central atoms that do not have a filled valence shell. Generally, these are
molecules with central atoms from groups 2 and 13, outer atoms that are hydrogen, or other atoms that do not form multiple bonds.
For example, in the Lewis structures of beryllium dihydride, BeH2, and boron trifluoride, BF3, the beryllium and boron atoms each
have only four and six electrons, respectively. It is possible to draw a structure with a double bond between a boron atom and a
fluorine atom in BF3, satisfying the octet rule, but experimental evidence indicates the bond lengths are closer to that expected for
B–F single bonds. This suggests the best Lewis structure has three B–F single bonds and an electron deficient boron. The reactivity
of the compound is also consistent with an electron deficient boron. However, the B–F bonds are slightly shorter than what is
actually expected for B–F single bonds, indicating that some double bond character is found in the actual molecule.
An atom like the boron atom in BF3, which does not have eight electrons, is very reactive. It readily combines with a molecule
containing an atom with a lone pair of electrons. For example, NH3 reacts with BF3 because the lone pair on nitrogen can be shared
with the boron atom:
7.4.0.0.3: Hypervalent Molecules

Elements in the second period of the periodic table (n = 2) can accommodate only eight electrons in their valence shell orbitals
because they have only four valence orbitals (one 2s and three 2p orbitals). Elements in the third and higher periods (n ≥ 3) have
more than four valence orbitals and can share more than four pairs of electrons with other atoms because they have empty d orbitals
in the same shell. Molecules formed from these elements are sometimes called hypervalent molecules. Figure 7.12 shows the Lewis
structures for two hypervalent molecules, PCl5 and SF6.
Figure 7.12 In PCl5, the central atom phosphorus shares five pairs of electrons. In SF6, sulfur shares six pairs of electrons.
In some hypervalent molecules, such as IF5 and XeF4, some of the electrons in the outer shell of the central atom are lone pairs:

When we write the Lewis structures for these molecules, we find that we have electrons left over after filling the valence shells of
the outer atoms with eight electrons. These additional electrons must be assigned to the central atom.
7.4.0.1: Example 7.5

7.4.0.0.4: Writing Lewis Structures: Octet Rule Violations
Xenon is a noble gas, but it forms a number of stable compounds. We examined XeF4 earlier. What are the Lewis structures of
XeF2 and XeF6?
7.4.0.0.5: Solution
We can draw the Lewis structure of any covalent molecule by following the six steps discussed earlier. In this case, we can
condense the last few steps, since not all of them apply.
1. Step 1. Calculate the number of valence electrons:
XeF2: 8 + (2 × 7) = 22
XeF6: 8 + (6 × 7) = 50
2. Step 2. Draw a skeleton joining the atoms by single bonds. Xenon will be the central atom because fluorine cannot be a
central atom:
3. Step 3. Distribute the remaining electrons.

XeF2: We place three lone pairs of electrons around each F atom, accounting for 12 electrons and giving each F atom 8
electrons. Thus, six electrons (three lone pairs) remain. These lone pairs must be placed on the Xe atom. This is acceptable
because Xe atoms have empty valence shell d orbitals and can accommodate more than eight electrons. The Lewis structure
of XeF2 shows two bonding pairs and three lone pairs of electrons around the Xe atom:
XeF6: We place three lone pairs of electrons around each F atom, accounting for 36 electrons. Two electrons remain, and
this lone pair is placed on the Xe atom:

The halogens form a class of compounds called the interhalogens, in which halogen atoms covalently bond to each other. Write
the Lewis structures for the interhalogens BrCl3 and ICl . 4
−
7.4.0.1: Answer:

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Compute formal charges for atoms in any Lewis structure
Use formal charges to identify the most reasonable Lewis structure for a given molecule
Explain the concept of resonance and draw Lewis structures representing resonance forms for a given molecule
In the previous section, we discussed how to write Lewis structures for molecules and polyatomic ions. As we have seen, however,
in some cases, there is seemingly more than one valid structure for a molecule. We can use the concept of formal charges to help us
predict the most appropriate Lewis structure when more than one is reasonable.
7.5.0.1: Calculating Formal Charge

The formal charge of an atom in a molecule is the hypothetical charge the atom would have if we could redistribute the electrons in
the bonds evenly between the atoms. Another way of saying this is that formal charge results when we take the number of valence
electrons of a neutral atom, subtract the nonbonding electrons, and then subtract the number of bonds connected to that atom in the
Lewis structure.
Thus, we calculate formal charge as follows:
1
formal charge = # valence shell electrons (free atom) − # lone pair electrons − # bonding electrons
2
We can double-check formal charge calculations by determining the sum of the formal charges for the whole structure. The sum of
the formal charges of all atoms in a molecule must be zero; the sum of the formal charges in an ion should equal the charge of the
ion.
We must remember that the formal charge calculated for an atom is not the actual charge of the atom in the molecule. Formal
charge is only a useful bookkeeping procedure; it does not indicate the presence of actual charges.
7.5.0.1: Example 7.6

7.5.0.0.1: Calculating Formal Charge from Lewis Structures
Assign formal charges to each atom in the interhalogen ion ICl 4
−
.
7.5.0.0.2: Solution
1. Step 1. We divide the bonding electron pairs equally for all I–Cl bonds:
2. Step 2. We assign lone pairs of electrons to their atoms. Each Cl atom now has seven electrons assigned to it, and the I
atom has eight.
3. Step 3. Subtract this number from the number of valence electrons for the neutral atom:
I: 7 – 8 = –1
Cl: 7 – 7 = 0
The sum of the formal charges of all the atoms equals –1, which is identical to the charge of the ion (–1).
Calculate the formal charge for each atom in the carbon monoxide molecule:
7.5.0.1: Answer:

C −1, O +1
7.5.0.1: Example 7.7

7.5.0.0.4: Calculating Formal Charge from Lewis Structures
Assign formal charges to each atom in the interhalogen molecule BrCl3.
7.5.0.0.5: Solution
1. Step 1. Assign one of the electrons in each Br–Cl bond to the Br atom and one to the Cl atom in that bond:
2. Step 2. Assign the lone pairs to their atom. Now each Cl atom has seven electrons and the Br atom has seven electrons.
3. Step 3. Subtract this number from the number of valence electrons for the neutral atom. This gives the formal charge:
Br: 7 – 7 = 0
Cl: 7 – 7 = 0
All atoms in BrCl3 have a formal charge of zero, and the sum of the formal charges totals zero, as it must in a neutral
molecule.
Determine the formal charge for each atom in NCl3.
7.5.0.1: Answer:
N: 0; all three Cl atoms: 0
7.5.0.1: Using Formal Charge to Predict Molecular Structure

The arrangement of atoms in a molecule or ion is called its molecular structure. In many cases, following the steps for writing
Lewis structures may lead to more than one possible molecular structure—different multiple bond and lone-pair electron
placements or different arrangements of atoms, for instance. A few guidelines involving formal charge can be helpful in deciding
which of the possible structures is most likely for a particular molecule or ion:
1. A molecular structure in which all formal charges are zero is preferable to one in which some formal charges are not zero.
2. If the Lewis structure must have nonzero formal charges, the arrangement with the smallest nonzero formal charges is
preferable.
3. Lewis structures are preferable when adjacent formal charges are zero or of the opposite sign.
4. When we must choose among several Lewis structures with similar distributions of formal charges, the structure with the
negative formal charges on the more electronegative atoms is preferable.
To see how these guidelines apply, let us consider some possible structures for carbon dioxide, CO2. We know from our previous
discussion that the less electronegative atom typically occupies the central position, but formal charges allow us to understand why
this occurs. We can draw three possibilities for the structure: carbon in the center and double bonds, carbon in the center with a
single and triple bond, and oxygen in the center with double bonds:

Comparing the three formal charges, we can definitively identify the structure on the left as preferable because it has only formal
charges of zero (Guideline 1).
As another example, the thiocyanate ion, an ion formed from a carbon atom, a nitrogen atom, and a sulfur atom, could have three
different molecular structures: NCS–, CNS–, or CSN–. The formal charges present in each of these molecular structures can help us
pick the most likely arrangement of atoms. Possible Lewis structures and the formal charges for each of the three possible
structures for the thiocyanate ion are shown here:
Note that the sum of the formal charges in each case is equal to the charge of the ion (–1). However, the first arrangement of atoms
is preferred because it has the lowest number of atoms with nonzero formal charges (Guideline 2). Also, it places the least
electronegative atom in the center, and the negative charge on the more electronegative element (Guideline 4).
7.5.0.1: Example 7.8

7.5.0.0.1: Using Formal Charge to Determine Molecular Structure
Nitrous oxide, N2O, commonly known as laughing gas, is used as an anesthetic in minor surgeries, such as the routine
extraction of wisdom teeth. Which is the more likely structure for nitrous oxide?
7.5.0.0.2: Solution
Determining formal charge yields the following:

The structure with a terminal oxygen atom best satisfies the criteria for the most stable distribution of formal charge:
The number of atoms with formal charges are minimized (Guideline 2), there is no formal charge with a magnitude greater
than one (Guideline 2), the negative formal charge is on the more electronegative element (Guideline 4), and the less
electronegative atom is in the center position.
Which is the most likely molecular structure for the nitrite (NO 2
−
) ion?
7.5.0.1: Answer:
ONO–
7.5.0.1: Resonance
Notice that the more likely structure for the nitrite anion in Example 7.8 may actually be drawn in two different ways, distinguished
by the locations of the N-O and N=O bonds:

If nitrite ions do indeed contain a single and a double bond, we would expect for the two bond lengths to be different. A double
bond between two atoms is shorter (and stronger) than a single bond between the same two atoms. Experiments show, however,
that both N–O bonds in NO have the same strength and length, and are identical in all other properties.
2
−
It is not possible to write a single Lewis structure for NO in which nitrogen has an octet and both bonds are equivalent. Instead,
2
−
we use the concept of resonance: if two or more Lewis structures with the same arrangement of atoms can be written for a molecule
or ion, the actual distribution of electrons is an average of that shown by the various Lewis structures. The actual distribution of
electrons in each of the nitrogen-oxygen bonds in NO is the average of a double bond and a single bond. We call the individual
2
−
Lewis structures resonance forms. The actual electronic structure of the molecule (the average of the resonance forms) is called a
resonance hybrid of the individual resonance forms. A double-headed arrow between Lewis structures indicates that they are
resonance forms.
We should remember that a molecule described as a resonance hybrid never possesses an electronic structure described by either
resonance form. It does not fluctuate between resonance forms; rather, the actual electronic structure is always the average of that
shown by all resonance forms. George Wheland, one of the pioneers of resonance theory, used a historical analogy to describe the
relationship between resonance forms and resonance hybrids. A medieval traveler, having never before seen a rhinoceros, described
it as a hybrid of a dragon and a unicorn because it had many properties in common with both. Just as a rhinoceros is neither a
dragon sometimes nor a unicorn at other times, a resonance hybrid is neither of its resonance forms at any given time. Like a
rhinoceros, it is a real entity that experimental evidence has shown to exist. It has some characteristics in common with its
resonance forms, but the resonance forms themselves are convenient, imaginary images (like the unicorn and the dragon).
The carbonate anion, CO 3
2−
, provides a second example of resonance:
One oxygen atom must have a double bond to carbon to complete the octet on the central atom. All oxygen atoms, however, are
equivalent, and the double bond could form from any one of the three atoms. This gives rise to three resonance forms of the
carbonate ion. Because we can write three identical resonance structures, we know that the actual arrangement of electrons in the
carbonate ion is the average of the three structures. Again, experiments show that all three C–O bonds are exactly the same.

Use this online quiz to practice your skills in drawing resonance structures and estimating formal charges.
This page titled 7.5: Formal Charges and Resonance is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax


Describe the energetics of covalent and ionic bond formation and breakage
Use the Born-Haber cycle to compute lattice energies for ionic compounds
Use average covalent bond energies to estimate enthalpies of reaction
A bond’s strength describes how strongly each atom is joined to another atom, and therefore how much energy is required to break
the bond between the two atoms. In this section, you will learn about the bond strength of covalent bonds, and then compare that to
the strength of ionic bonds, which is related to the lattice energy of a compound.
7.6.0.1: Bond Strength: Covalent Bonds

Stable molecules exist because covalent bonds hold the atoms together. We measure the strength of a covalent bond by the energy
required to break it, that is, the energy necessary to separate the bonded atoms. Separating any pair of bonded atoms requires
energy (see Figure 7.4). The stronger a bond, the greater the energy required to break it.
The energy required to break a specific covalent bond in one mole of gaseous molecules is called the bond energy or the bond
dissociation energy. The bond energy for a diatomic molecule, DX–Y, is defined as the standard enthalpy change for the
endothermic reaction:
XY (g) ⟶ X (g) + Y (g) DX−Y = ΔH °
For example, the bond energy of the pure covalent H–H bond, DH–H, is 436 kJ per mole of H–H bonds broken:
H2 (g) ⟶ 2H (g) DH−H = ΔH ° = 436 kJ
Molecules with three or more atoms have two or more bonds. The sum of all bond energies in such a molecule is equal to the
standard enthalpy change for the endothermic reaction that breaks all the bonds in the molecule. For example, the sum of the four
C–H bond energies in CH4, 1660 kJ, is equal to the standard enthalpy change of the reaction:
The average C–H bond energy, DC–H, is 1660/4 = 415 kJ/mol because there are four moles of C–H bonds broken per mole of the
reaction. Although the four C–H bonds are equivalent in the original molecule, they do not each require the same energy to break;
once the first bond is broken (which requires 439 kJ/mol), the remaining bonds are easier to break. The 415 kJ/mol value is the
average, not the exact value required to break any one bond.
The strength of a bond between two atoms increases as the number of electron pairs in the bond increases. Generally, as the bond
strength increases, the bond length decreases. Thus, we find that triple bonds are stronger and shorter than double bonds between
the same two atoms; likewise, double bonds are stronger and shorter than single bonds between the same two atoms. Average bond
energies for some common bonds appear in Table 7.2, and a comparison of bond lengths and bond strengths for some common
bonds appears in Table 7.3. When one atom bonds to various atoms in a group, the bond strength typically decreases as we move
down the group. For example, C–F is 439 kJ/mol, C–Cl is 330 kJ/mol, and C–Br is 275 kJ/mol.
Bond Energies (kJ/mol)
Bond Bond Energy Bond Bond Energy Bond Bond Energy
H–H 436 C–S 260 F–Cl 255
H–C 415 C–Cl 330 F–Br 235

Bond Energies (kJ/mol)
Bond Bond Energy Bond Bond Energy Bond Bond Energy
H–N 390 C–Br 275 Si–Si 230
H–O 464 C–I 240 Si–P 215
H–F 569 N–N 160 Si–S 225
H–Si 395 N = N 418 Si–Cl 359
H–P 320 N ≡ N 946 Si–Br 290
H–S 340 N–O 200 Si–I 215
H–Cl 432 N–F 270 P–P 215
H–Br 370 N–P 210 P–S 230
H–I 295 N–Cl 200 P–Cl 330
C–C 345 N–Br 245 P–Br 270
C = C 611 O–O 140 P–I 215
C ≡ C 837 O = O 498 S–S 215
C–N 290 O–F 160 S–Cl 250
C = N 615 O–Si 370 S–Br 215
C ≡ N 891 O–P 350 Cl–Cl 243
C–O 350 O–Cl 205 Cl–Br 220
C = O 741 O–I 200 Cl–I 210
C ≡ O 1080 F–F 160 Br–Br 190
C–F 439 F–Si 540 Br–I 180
C–Si 360 F–P 489 I–I 150
C–P 265 F–S 285
Table 7.2
Average Bond Lengths and Bond Energies for Some Common Bonds
Bond Bond Length (Å) Bond Energy (kJ/mol)
C–C 1.54 345

Bond Bond Length (Å) Bond Energy (kJ/mol)
C = C 1.34 611
C ≡ C 1.20 837
C–N 1.43 290
C = N 1.38 615
C ≡ N 1.16 891
C–O 1.43 350
C = O 1.23 741
C ≡ O 1.13 1080
Table 7.3
We can use bond energies to calculate approximate enthalpy changes for reactions where enthalpies of formation are not available.
Calculations of this type will also tell us whether a reaction is exothermic or endothermic. An exothermic reaction (ΔH negative,
heat produced) results when the bonds in the products are stronger than the bonds in the reactants. An endothermic reaction (ΔH
positive, heat absorbed) results when the bonds in the products are weaker than those in the reactants.
The enthalpy change, ΔH, for a chemical reaction is approximately equal to the sum of the energy required to break all bonds in the
reactants (energy “in”, positive sign) plus the energy released when all bonds are formed in the products (energy “out,” negative
sign). This can be expressed mathematically in the following way:
ΔH = ƩDbonds broken − ƩDbonds formed
In this expression, the symbol Ʃ means “the sum of” and D represents the bond energy in kilojoules per mole, which is always a
positive number. The bond energy is obtained from a table (like Table 7.3) and will depend on whether the particular bond is a
single, double, or triple bond. Thus, in calculating enthalpies in this manner, it is important that we consider the bonding in all
reactants and products. Because D values are typically averages for one type of bond in many different molecules, this calculation
provides a rough estimate, not an exact value, for the enthalpy of reaction.
Consider the following reaction:
H2 (g) + Cl2 (g) ⟶ 2HCl (g)
or
H–H (g) + Cl–Cl (g) ⟶ 2H–Cl (g)
To form two moles of HCl, one mole of H–H bonds and one mole of Cl–Cl bonds must be broken. The energy required to break
these bonds is the sum of the bond energy of the H–H bond (436 kJ/mol) and the Cl–Cl bond (243 kJ/mol). During the reaction,
two moles of H–Cl bonds are formed (bond energy = 432 kJ/mol), releasing 2 × 432 kJ; or 864 kJ. Because the bonds in the
products are stronger than those in the reactants, the reaction releases more energy than it consumes:

ΔH = [ DH−H + DCl−Cl ] − 2 DH−Cl
= [436 + 243] − 2 (432) = −185 kJ
This excess energy is released as heat, so the reaction is exothermic. Appendix G gives a value for the standard molar enthalpy of
formation of HCl(g), ΔH , of –92.307 kJ/mol. Twice that value is –184.6 kJ, which agrees well with the answer obtained earlier
∘
f
for the formation of two moles of HCl.

7.6.0.1: Example 7.9
7.6.0.0.1: Using Bond Energies to Calculate Approximate Enthalpy Changes
Methanol, CH3OH, may be an excellent alternative fuel. The high-temperature reaction of steam and carbon produces a
mixture of the gases carbon monoxide, CO, and hydrogen, H2, from which methanol can be produced. Using the bond energies
in Table 7.3, calculate the approximate enthalpy change, ΔH, for the reaction here:
CO (g) + 2 H2 (g) ⟶ CH3 OH (g)
7.6.0.0.2: Solution
First, we need to write the Lewis structures of the reactants and the products:
From this, we see that ΔH for this reaction involves the energy required to break a C–O triple bond and two H–H single bonds,
as well as the energy produced by the formation of three C–H single bonds, a C–O single bond, and an O–H single bond. We
can express this as follows:
ΔH = [ DC≡O + 2 (DH−H )] − [3 (DC−H ) + DC−O + DO−H ]
Using the bond energy values in Table 7.3, we obtain:

ΔH = [1080 + 2 (436)] − [3 (415) + 350 + 464]
= −107 kJ
We can compare this value to the value calculated based on ΔH data from Appendix G:
∘
f
∘ ∘ ∘
ΔH = [ΔH CH3 OH (g)] − [ΔH CO (g) + 2 × ΔH H2 ]
f f f
= [−201.0] − [−110.52 + 2 × 0]
= −90.5 kJ
Note that there is a fairly significant gap between the values calculated using the two different methods. This occurs because D
values are the average of different bond strengths; therefore, they often give only rough agreement with other data.
Ethyl alcohol, CH3CH2OH, was one of the first organic chemicals deliberately synthesized by humans. It has many uses in
industry, and it is the alcohol contained in alcoholic beverages. It can be obtained by the fermentation of sugar or synthesized
by the hydration of ethylene in the following reaction:
Using the bond energies in Table 7.3, calculate an approximate enthalpy change, ΔH, for this reaction.
7.6.0.1: Answer:
–35 kJ
7.6.0.1: Ionic Bond Strength and Lattice Energy

An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a
compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy
required to separate one mole of the solid into its component gaseous ions. For the ionic solid MX, the lattice energy is the enthalpy
change of the process:

n+ n−
MX (s) ⟶ M (g) + X (g) ΔHlattice
Note that we are using the convention where the ionic solid is separated into ions, so our lattice energies will be endothermic
(positive values). Some texts use the equivalent but opposite convention, defining lattice energy as the energy released when
separate ions combine to form a lattice and giving negative (exothermic) values. Thus, if you are looking up lattice energies in
another reference, be certain to check which definition is being used. In both cases, a larger magnitude for lattice energy indicates a
more stable ionic compound. For sodium chloride, ΔHlattice = 769 kJ. Thus, it requires 769 kJ to separate one mole of solid NaCl
into gaseous Na+ and Cl– ions. When one mole each of gaseous Na+ and Cl– ions form solid NaCl, 769 kJ of heat is released.
The lattice energy ΔHlattice of an ionic crystal can be expressed by the following equation (derived from Coulomb’s law, governing
the forces between electric charges):
+ −
C (Z ) (Z )
ΔHlattice =
Ro
in which C is a constant that depends on the type of crystal structure; Z+ and Z– are the charges on the ions; and Ro is the interionic
distance (the sum of the radii of the positive and negative ions). Thus, the lattice energy of an ionic crystal increases rapidly as the
charges of the ions increase and the sizes of the ions decrease. When all other parameters are kept constant, doubling the charge of
both the cation and anion quadruples the lattice energy. For example, the lattice energy of LiF (Z+ and Z– = 1) is 1023 kJ/mol,
whereas that of MgO (Z+ and Z– = 2) is 3900 kJ/mol (Ro is nearly the same—about 200 pm for both compounds).
Different interatomic distances produce different lattice energies. For example, we can compare the lattice energy of MgF2 (2957
kJ/mol) to that of MgI2 (2327 kJ/mol) to observe the effect on lattice energy of the smaller ionic size of F– as compared to I–.
7.6.0.1: Example 7.10

7.6.0.0.1: Lattice Energy Comparisons
The precious gem ruby is aluminum oxide, Al2O3, containing traces of Cr3+. The compound Al2Se3 is used in the fabrication of
some semiconductor devices. Which has the larger lattice energy, Al2O3 or Al2Se3?
7.6.0.0.2: Solution
In these two ionic compounds, the charges Z+ and Z– are the same, so the difference in lattice energy will depend upon Ro. The
O2– ion is smaller than the Se2– ion. Thus, Al2O3 would have a shorter interionic distance than Al2Se3, and Al2O3 would have
the larger lattice energy.
Zinc oxide, ZnO, is a very effective sunscreen. How would the lattice energy of ZnO compare to that of NaCl?
7.6.0.1: Answer:
ZnO would have the larger lattice energy because the Z values of both the cation and the anion in ZnO are greater, and the
interionic distance of ZnO is smaller than that of NaCl.
7.6.0.1: The Born-Haber Cycle

It is not possible to measure lattice energies directly. However, the lattice energy can be calculated using the equation given in the
previous section or by using a thermochemical cycle. The Born-Haber cycle is an application of Hess’s law that breaks down the
formation of an ionic solid into a series of individual steps:
, the standard enthalpy of formation of the compound
∘
ΔH
f
IE, the ionization energy of the metal

EA, the electron affinity of the nonmetal
ΔH , the enthalpy of sublimation of the metal
∘
s
D, the bond dissociation energy of the nonmetal

ΔHlattice, the lattice energy of the compound
Figure 7.13 diagrams the Born-Haber cycle for the formation of solid cesium fluoride.

Figure 7.13 The Born-Haber cycle shows the relative energies of each step involved in the formation of an ionic solid from the
necessary elements in their reference states.
We begin with the elements in their most common states, Cs(s) and F2(g). The ΔH represents the conversion of solid cesium into
∘
s
a gas, and then the ionization energy converts the gaseous cesium atoms into cations. In the next step, we account for the energy
required to break the F–F bond to produce fluorine atoms. Converting one mole of fluorine atoms into fluoride ions is an
exothermic process, so this step gives off energy (the electron affinity) and is shown as decreasing along the y-axis. We now have
one mole of Cs cations and one mole of F anions. These ions combine to produce solid cesium fluoride. The enthalpy change in
this step is the negative of the lattice energy, so it is also an exothermic quantity. The total energy involved in this conversion is
equal to the experimentally determined enthalpy of formation, ΔH , of the compound from its elements. In this case, the overall
∘
f
change is exothermic.
Hess’s law can also be used to show the relationship between the enthalpies of the individual steps and the enthalpy of formation.
Table 7.4 shows this for fluoride, CsF.
Enthalpy of sublimation of Cs(s) Cs (s) ⟶ Cs (g)

∘
ΔH = ΔHs = 76.5kJ/mol
One-half of the bond energy of F2 1

F2 (g) ⟶ F (g) ΔH =
1
D = 79.4kJ/mol
2 2
Ionization energy of Cs(g) Cs (g) ⟶ Cs

+
(g) + e
−
ΔH = IE = 375.7kJ/mol
Electron affinity of F F (g) + e

−
⟶ F
−
(g) ΔH = EA = −328.2kJ/mol
Negative of the lattice energy of Cs

+
(g) + F
−
(g) ⟶ CsF (s) ΔH = −ΔHlattice =?
CsF(s)
Enthalpy of formation of CsF(s), ΔH = ΔH

∘
= ΔHs +
∘ 1
D + IE + (EA) + (−ΔHlattice ) ΔH = −553.5kJ/mol
f 2
add steps 1–5 1
Cs (s) + F2 (g) ⟶ CsF (s)
2
Table 7.4

Thus, the lattice energy can be calculated from other values. For cesium fluoride, using this data, the lattice energy is:
ΔHlattice = 76.5 + 79.4 + 375.7 + (–328.2)– (–553.5) = 756.9 kJ/mol
The Born-Haber cycle may also be used to calculate any one of the other quantities in the equation for lattice energy, provided that
the remainder is known. For example, if the relevant enthalpy of sublimation ΔH , ionization energy (IE), bond dissociation
∘
s
enthalpy (D), lattice energy ΔHlattice, and standard enthalpy of formation ΔH are known, the Born-Haber cycle can be used to
f
∘
determine the electron affinity of an atom.

Lattice energies calculated for ionic compounds are typically much higher than bond dissociation energies measured for covalent
bonds. Whereas lattice energies typically fall in the range of 600–4000 kJ/mol (some even higher), covalent bond dissociation
energies are typically between 150–400 kJ/mol for single bonds. Keep in mind, however, that these are not directly comparable
values. For ionic compounds, lattice energies are associated with many interactions, as cations and anions pack together in an
extended lattice. For covalent bonds, the bond dissociation energy is associated with the interaction of just two atoms.
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Predict the structures of small molecules using valence shell electron pair repulsion (VSEPR) theory
Explain the concepts of polar covalent bonds and molecular polarity
Assess the polarity of a molecule based on its bonding and structure
Thus far, we have used two-dimensional Lewis structures to represent molecules. However, molecular structure is actually three-
dimensional, and it is important to be able to describe molecular bonds in terms of their distances, angles, and relative
arrangements in space (Figure 7.14). A bond angle is the angle between any two bonds that include a common atom, usually
measured in degrees. A bond distance (or bond length) is the distance between the nuclei of two bonded atoms along the straight
line joining the nuclei. Bond distances are measured in Ångstroms (1 Å = 10–10 m) or picometers (1 pm = 10–12 m, 100 pm = 1 Å).
Figure 7.14 Bond distances (lengths) and angles are shown for the formaldehyde molecule, H2CO.
7.7.0.1: VSEPR Theory

Valence shell electron-pair repulsion theory (VSEPR theory) enables us to predict the molecular structure, including approximate
bond angles around a central atom, of a molecule from an examination of the number of bonds and lone electron pairs in its Lewis
structure. The VSEPR model assumes that electron pairs in the valence shell of a central atom will adopt an arrangement that
minimizes repulsions between these electron pairs by maximizing the distance between them. The electrons in the valence shell of
a central atom form either bonding pairs of electrons, located primarily between bonded atoms, or lone pairs. The electrostatic
repulsion of these electrons is reduced when the various regions of high electron density assume positions as far from each other as
possible.
VSEPR theory predicts the arrangement of electron pairs around each central atom and, usually, the correct arrangement of atoms
in a molecule. We should understand, however, that the theory only considers electron-pair repulsions. Other interactions, such as
nuclear-nuclear repulsions and nuclear-electron attractions, are also involved in the final arrangement that atoms adopt in a
particular molecular structure.
As a simple example of VSEPR theory, let us predict the structure of a gaseous BeF2 molecule. The Lewis structure of BeF2
(Figure 7.15) shows only two electron pairs around the central beryllium atom. With two bonds and no lone pairs of electrons on
the central atom, the bonds are as far apart as possible, and the electrostatic repulsion between these regions of high electron
density is reduced to a minimum when they are on opposite sides of the central atom. The bond angle is 180° (Figure 7.15).
Figure 7.15 The BeF2 molecule adopts a linear structure in which the two bonds are as far apart as possible, on opposite sides of the
Be atom.

Figure 7.16 illustrates this and other electron-pair geometries that minimize the repulsions among regions of high electron density
(bonds and/or lone pairs). Two regions of electron density around a central atom in a molecule form a linear geometry; three
regions form a trigonal planar geometry; four regions form a tetrahedral geometry; five regions form a trigonal bipyramidal
geometry; and six regions form an octahedral geometry.
Figure 7.16 The basic electron-pair geometries predicted by VSEPR theory maximize the space around any region of electron
density (bonds or lone pairs).
7.7.0.0.1: Electron-pair Geometry versus Molecular Structure
It is important to note that electron-pair geometry around a central atom is not the same thing as its molecular structure. The
electron-pair geometries shown in Figure 7.16 describe all regions where electrons are located, bonds as well as lone pairs.
Molecular structure describes the location of the atoms, not the electrons.
We differentiate between these two situations by naming the geometry that includes all electron pairs the electron-pair geometry.
The structure that includes only the placement of the atoms in the molecule is called the molecular structure. The electron-pair
geometries will be the same as the molecular structures when there are no lone electron pairs around the central atom, but they will
be different when there are lone pairs present on the central atom.

For example, the methane molecule, CH4, which is the major component of natural gas, has four bonding pairs of electrons around
the central carbon atom; the electron-pair geometry is tetrahedral, as is the molecular structure (Figure 7.17). On the other hand, the
ammonia molecule, NH3, also has four electron pairs associated with the nitrogen atom, and thus has a tetrahedral electron-pair
geometry. One of these regions, however, is a lone pair, which is not included in the molecular structure, and this lone pair
influences the shape of the molecule (Figure 7.18).
Figure 7.17 The molecular structure of the methane molecule, CH4, is shown with a tetrahedral arrangement of the hydrogen
atoms. VSEPR structures like this one are often drawn using the wedge and dash notation, in which solid lines represent bonds in
the plane of the page, solid wedges represent bonds coming up out of the plane, and dashed lines represent bonds going down into
the plane.
Figure 7.18 (a) The electron-pair geometry for the ammonia molecule is tetrahedral with one lone pair and three single bonds. (b)
The trigonal pyramidal molecular structure is determined from the electron-pair geometry. (c) The actual bond angles deviate
slightly from the idealized angles because the lone pair takes up a larger region of space than do the single bonds, causing the HNH
angle to be slightly smaller than 109.5°.
As seen in Figure 7.18, small distortions from the ideal angles in Figure 7.16 can result from differences in repulsion between
various regions of electron density. VSEPR theory predicts these distortions by establishing an order of repulsions and an order of
the amount of space occupied by different kinds of electron pairs. The order of electron-pair repulsions from greatest to least
repulsion is:
lone pair-lone pair > lone pair-bonding pair > bonding pair-bonding pair
This order of repulsions determines the amount of space occupied by different regions of electrons. A lone pair of electrons
occupies a larger region of space than the electrons in a triple bond; in turn, electrons in a triple bond occupy more space than those
in a double bond, and so on. The order of sizes from largest to smallest is:
lone pair > triple bond > double bond > single bond
Consider formaldehyde, H2CO, which is used as a preservative for biological and anatomical specimens (Figure 7.14). This
molecule has regions of high electron density that consist of two single bonds and one double bond. The basic geometry is trigonal
planar with 120° bond angles, but we see that the double bond causes slightly larger angles (121°), and the angle between the single
bonds is slightly smaller (118°).
In the ammonia molecule, the three hydrogen atoms attached to the central nitrogen are not arranged in a flat, trigonal planar
molecular structure, but rather in a three-dimensional trigonal pyramid (Figure 7.18) with the nitrogen atom at the apex and the
three hydrogen atoms forming the base. The ideal bond angles in a trigonal pyramid are based on the tetrahedral electron pair
geometry. Again, there are slight deviations from the ideal because lone pairs occupy larger regions of space than do bonding
electrons. The H–N–H bond angles in NH3 are slightly smaller than the 109.5° angle in a regular tetrahedron (Figure 7.16) because
the lone pair-bonding pair repulsion is greater than the bonding pair-bonding pair repulsion (Figure 7.18). Figure 7.19 illustrates the
ideal molecular structures, which are predicted based on the electron-pair geometries for various combinations of lone pairs and
bonding pairs.

Figure 7.19 The molecular structures are identical to the electron-pair geometries when there are no lone pairs present (first
column). For a particular number of electron pairs (row), the molecular structures for one or more lone pairs are determined based
on modifications of the corresponding electron-pair geometry.
According to VSEPR theory, the terminal atom locations (Xs in Figure 7.19) are equivalent within the linear, trigonal planar, and
tetrahedral electron-pair geometries (the first three rows of the table). It does not matter which X is replaced with a lone pair
because the molecules can be rotated to convert positions. For trigonal bipyramidal electron-pair geometries, however, there are
two distinct X positions, as shown in Figure 7.20: an axial position (if we hold a model of a trigonal bipyramid by the two axial
positions, we have an axis around which we can rotate the model) and an equatorial position (three positions form an equator
around the middle of the molecule). As shown in Figure 7.19, the axial position is surrounded by bond angles of 90°, whereas the
equatorial position has more space available because of the 120° bond angles. In a trigonal bipyramidal electron-pair geometry,
lone pairs always occupy equatorial positions because these more spacious positions can more easily accommodate the larger lone
pairs.
Theoretically, we can come up with three possible arrangements for the three bonds and two lone pairs for the ClF3 molecule
(Figure 7.20). The stable structure is the one that puts the lone pairs in equatorial locations, giving a T-shaped molecular structure.

Figure 7.20 (a) In a trigonal bipyramid, the two axial positions are located directly across from one another, whereas the three
equatorial positions are located in a triangular arrangement. (b–d) The two lone pairs (red lines) in ClF3 have several possible
arrangements, but the T-shaped molecular structure (b) is the one actually observed, consistent with the larger lone pairs both
occupying equatorial positions.
When a central atom has two lone electron pairs and four bonding regions, we have an octahedral electron-pair geometry. The two
lone pairs are on opposite sides of the octahedron (180° apart), giving a square planar molecular structure that minimizes lone pair-
lone pair repulsions (Figure 7.19).
7.7.0.0.2: Predicting Electron Pair Geometry and Molecular Structure
The following procedure uses VSEPR theory to determine the electron pair geometries and the molecular structures:
1. Write the Lewis structure of the molecule or polyatomic ion.
2. Count the number of regions of electron density (lone pairs and bonds) around the central atom. A single, double, or triple bond
counts as one region of electron density.
3. Identify the electron-pair geometry based on the number of regions of electron density: linear, trigonal planar, tetrahedral,
trigonal bipyramidal, or octahedral (Figure 7.19, first column).
4. Use the number of lone pairs to determine the molecular structure (Figure 7.19). If more than one arrangement of lone pairs and
chemical bonds is possible, choose the one that will minimize repulsions, remembering that lone pairs occupy more space than
multiple bonds, which occupy more space than single bonds. In trigonal bipyramidal arrangements, repulsion is minimized
when every lone pair is in an equatorial position. In an octahedral arrangement with two lone pairs, repulsion is minimized
when the lone pairs are on opposite sides of the central atom.
The following examples illustrate the use of VSEPR theory to predict the molecular structure of molecules or ions that have no
lone pairs of electrons. In this case, the molecular structure is identical to the electron pair geometry.
7.7.0.1: Example 7.11

7.7.0.0.3: Predicting Electron-pair Geometry and Molecular Structure: CO2 and BCl3
Predict the electron-pair geometry and molecular structure for each of the following:
(a) carbon dioxide, CO2, a molecule produced by the combustion of fossil fuels
(b) boron trichloride, BCl3, an important industrial chemical
7.7.0.0.4: Solution
(a) We write the Lewis structure of CO2 as:

This shows us two regions of high electron density around the carbon atom—each double bond counts as one region, and there
are no lone pairs on the carbon atom. Using VSEPR theory, we predict that the two regions of electron density arrange
themselves on opposite sides of the central atom with a bond angle of 180°. The electron-pair geometry and molecular
structure are identical, and CO2 molecules are linear.
(b) We write the Lewis structure of BCl3 as:

Thus we see that BCl3 contains three bonds, and there are no lone pairs of electrons on boron. The arrangement of three
regions of high electron density gives a trigonal planar electron-pair geometry. The B–Cl bonds lie in a plane with 120° angles
between them. BCl3 also has a trigonal planar molecular structure (Figure 7.21).
Figure 7.21
The electron-pair geometry and molecular structure of BCl3 are both trigonal planar. Note that the VSEPR geometry indicates
the correct bond angles (120°), unlike the Lewis structure shown above.
Carbonate, CO , is a common polyatomic ion found in various materials from eggshells to antacids. What are the electron-
3
2−
pair geometry and molecular structure of this polyatomic ion?
7.7.0.1: Answer:
The electron-pair geometry is trigonal planar and the molecular structure is trigonal planar. Due to resonance, all three C–
O bonds are identical. Whether they are single, double, or an average of the two, each bond counts as one region of
electron density.
7.7.0.1: Example 7.12

7.7.0.0.6: Predicting Electron-pair Geometry and Molecular Structure: Ammonium
Two of the top 50 chemicals produced in the United States, ammonium nitrate and ammonium sulfate, both used as fertilizers,
contain the ammonium ion. Predict the electron-pair geometry and molecular structure of the NH cation.
4
+
7.7.0.0.7: Solution
We write the Lewis structure of NH 4

+
as:
We can see that NH contains four bonds from the nitrogen atom to hydrogen atoms and no lone pairs. We expect the four
4
+
regions of high electron density to arrange themselves so that they point to the corners of a tetrahedron with the central
nitrogen atom in the middle (Figure 7.19). Therefore, the electron pair geometry of NH is tetrahedral, and the molecular
4
+
structure is also tetrahedral (Figure 7.22).
Figure 7.22 The ammonium ion displays a tetrahedral electron-pair geometry as well as a tetrahedral molecular structure.

Identify a molecule with trigonal bipyramidal molecular structure.
7.7.0.1: Answer:
Any molecule with five electron pairs around the central atoms including no lone pairs will be trigonal bipyramidal. PF5 is
a common example.
The next several examples illustrate the effect of lone pairs of electrons on molecular structure.
7.7.0.1: Example 7.13

7.7.0.0.9: Predicting Electron-pair Geometry and Molecular Structure: Lone Pairs on the Central Atom
Predict the electron-pair geometry and molecular structure of a water molecule.
The Lewis structure of H2O indicates that there are four regions of high electron density around the oxygen atom: two lone
pairs and two chemical bonds:

We predict that these four regions are arranged in a tetrahedral fashion (Figure 7.23), as indicated in Figure 7.19. Thus, the
electron-pair geometry is tetrahedral and the molecular structure is bent with an angle slightly less than 109.5°. In fact, the
bond angle is 104.5°.
Figure 7.23 (a) H2O has four regions of electron density around the central atom, so it has a tetrahedral electron-pair geometry.
(b) Two of the electron regions are lone pairs, so the molecular structure is bent.
The hydronium ion, H3O+, forms when acids are dissolved in water. Predict the electron-pair geometry and molecular structure
of this cation.
7.7.0.1: Answer:
electron pair geometry: tetrahedral; molecular structure: trigonal pyramidal
7.7.0.1: Example 7.14

7.7.0.0.12: Predicting Electron-pair Geometry and Molecular Structure: SF4
Sulfur tetrafluoride, SF4, is extremely valuable for the preparation of fluorine-containing compounds used as herbicides (i.e.,
SF4 is used as a fluorinating agent). Predict the electron-pair geometry and molecular structure of a SF4 molecule.

The Lewis structure of SF4 indicates five regions of electron density around the sulfur atom: one lone pair and four bonding
pairs:
We expect these five regions to adopt a trigonal bipyramidal electron-pair geometry. To minimize lone pair repulsions, the lone
pair occupies one of the equatorial positions. The molecular structure (Figure 7.24) is that of a seesaw (Figure 7.19).
Figure 7.24 (a) SF4 has a trigonal bipyramidal arrangement of the five regions of electron density. (b) One of the regions is a
lone pair, which results in a seesaw-shaped molecular structure.
Predict the electron pair geometry and molecular structure for molecules of XeF2.
7.7.0.1: Answer:
The electron-pair geometry is trigonal bipyramidal. The molecular structure is linear.
7.7.0.1: Example 7.15

7.7.0.0.15: Predicting Electron-pair Geometry and Molecular Structure: XeF4
Of all the noble gases, xenon is the most reactive, frequently reacting with elements such as oxygen and fluorine. Predict the
electron-pair geometry and molecular structure of the XeF4 molecule.
The Lewis structure of XeF4 indicates six regions of high electron density around the xenon atom: two lone pairs and four
bonds:
These six regions adopt an octahedral arrangement (Figure 7.19), which is the electron-pair geometry. To minimize repulsions,
the lone pairs should be on opposite sides of the central atom (Figure 7.25). The five atoms are all in the same plane and have a
square planar molecular structure.

Figure 7.25 (a) XeF4 adopts an octahedral arrangement with two lone pairs (red lines) and four bonds in the electron-pair
geometry. (b) The molecular structure is square planar with the lone pairs directly across from one another.
In a certain molecule, the central atom has three lone pairs and two bonds. What will the electron pair geometry and molecular
structure be?
7.7.0.1: Answer:
electron pair geometry: trigonal bipyramidal; molecular structure: linear
7.7.0.0.18: Molecular Structure for Multicenter Molecules

When a molecule or polyatomic ion has only one central atom, the molecular structure completely describes the shape of the
molecule. Larger molecules do not have a single central atom, but are connected by a chain of interior atoms that each possess a
“local” geometry. The way these local structures are oriented with respect to each other also influences the molecular shape, but
such considerations are largely beyond the scope of this introductory discussion. For our purposes, we will only focus on
determining the local structures.
7.7.0.1: Example 7.16

7.7.0.0.19: Predicting Structure in Multicenter Molecules
The Lewis structure for the simplest amino acid, glycine, H2NCH2CO2H, is shown here. Predict the local geometry for the
nitrogen atom, the two carbon atoms, and the oxygen atom with a hydrogen atom attached:
Consider each central atom independently. The electron-pair geometries:

nitrogen––four regions of electron density; tetrahedral
carbon (CH2)––four regions of electron density; tetrahedral

carbon (CO2)—three regions of electron density; trigonal planar
oxygen (OH)—four regions of electron density; tetrahedral
The local structures:
nitrogen––three bonds, one lone pair; trigonal pyramidal
carbon (CH2)—four bonds, no lone pairs; tetrahedral
carbon (CO2)—three bonds (double bond counts as one bond), no lone pairs; trigonal planar
oxygen (OH)—two bonds, two lone pairs; bent (109°)
Another amino acid is alanine, which has the Lewis structure shown here. Predict the electron-pair geometry and local
structure of the nitrogen atom, the three carbon atoms, and the oxygen atom with hydrogen attached:
7.7.0.1: Answer:
electron-pair geometries: nitrogen––tetrahedral; carbon (CH)—tetrahedral; carbon (CH3)—tetrahedral; carbon (CO2)—
trigonal planar; oxygen (OH)—tetrahedral; local structures: nitrogen—trigonal pyramidal; carbon (CH)—tetrahedral;
carbon (CH3)—tetrahedral; carbon (CO2)—trigonal planar; oxygen (OH)—bent (109°)

The molecular shape simulator lets you build various molecules and practice naming their electron-pair geometries and
molecular structures.
7.7.0.1: Example 7.17

7.7.0.0.22: Molecular Simulation
Using molecular shape simulator allows us to control whether bond angles and/or lone pairs are displayed by checking or
unchecking the boxes under “Options” on the right. We can also use the “Name” checkboxes at bottom-left to display or hide
the electron pair geometry (called “electron geometry” in the simulator) and/or molecular structure (called “molecular shape”
in the simulator).
Build the molecule HCN in the simulator based on the following Lewis structure:
H–C ≡ N
Click on each bond type or lone pair at right to add that group to the central atom. Once you have the complete molecule, rotate
it to examine the predicted molecular structure. What molecular structure is this?
The molecular structure is linear.
Build a more complex molecule in the simulator. Identify the electron-group geometry, molecular structure, and bond angles.
Then try to find a chemical formula that would match the structure you have drawn.
7.7.0.1: Answer:
Answers will vary. For example, an atom with four single bonds, a double bond, and a lone pair has an octahedral electron-
group geometry and a square pyramidal molecular structure. XeOF4 is a molecule that adopts this structure.

7.7.0.1: Molecular Polarity and Dipole Moment
As discussed previously, polar covalent bonds connect two atoms with differing electronegativities, leaving one atom with a partial
positive charge (δ+) and the other atom with a partial negative charge (δ–), as the electrons are pulled toward the more
electronegative atom. This separation of charge gives rise to a bond dipole moment. The magnitude of a bond dipole moment is
represented by the Greek letter mu (µ) and is given by the formula shown here, where Q is the magnitude of the partial charges
(determined by the electronegativity difference) and r is the distance between the charges:
μ = Qr
This bond moment can be represented as a vector, a quantity having both direction and magnitude (Figure 7.26). Dipole vectors are
shown as arrows pointing along the bond from the less electronegative atom toward the more electronegative atom. A small plus
sign is drawn on the less electronegative end to indicate the partially positive end of the bond. The length of the arrow is
proportional to the magnitude of the electronegativity difference between the two atoms.
Figure 7.26 (a) There is a small difference in electronegativity between C and H, represented as a short vector. (b) The
electronegativity difference between B and F is much larger, so the vector representing the bond moment is much longer.
A whole molecule may also have a separation of charge, depending on its molecular structure and the polarity of each of its bonds.
If such a charge separation exists, the molecule is said to be a polar molecule (or dipole); otherwise the molecule is said to be
nonpolar. The dipole moment measures the extent of net charge separation in the molecule as a whole. We determine the dipole
moment by adding the bond moments in three-dimensional space, taking into account the molecular structure.
For diatomic molecules, there is only one bond, so its bond dipole moment determines the molecular polarity. Homonuclear
diatomic molecules such as Br2 and N2 have no difference in electronegativity, so their dipole moment is zero. For heteronuclear
molecules such as CO, there is a small dipole moment. For HF, there is a larger dipole moment because there is a larger difference
in electronegativity.
When a molecule contains more than one bond, the geometry must be taken into account. If the bonds in a molecule are arranged
such that their bond moments cancel (vector sum equals zero), then the molecule is nonpolar. This is the situation in CO2 (Figure
7.27). Each of the bonds is polar, but the molecule as a whole is nonpolar. From the Lewis structure, and using VSEPR theory, we
determine that the CO2 molecule is linear with polar C=O bonds on opposite sides of the carbon atom. The bond moments cancel
because they are pointed in opposite directions. In the case of the water molecule (Figure 7.27), the Lewis structure again shows
that there are two bonds to a central atom, and the electronegativity difference again shows that each of these bonds has a nonzero
bond moment. In this case, however, the molecular structure is bent because of the lone pairs on O, and the two bond moments do
not cancel. Therefore, water does have a net dipole moment and is a polar molecule (dipole).

Figure 7.27 The overall dipole moment of a molecule depends on the individual bond dipole moments and how they are arranged.
(a) Each CO bond has a bond dipole moment, but they point in opposite directions so that the net CO2 molecule is nonpolar. (b) In
contrast, water is polar because the OH bond moments do not cancel out.
The OCS molecule has a structure similar to CO2, but a sulfur atom has replaced one of the oxygen atoms. To determine if this
molecule is polar, we draw the molecular structure. VSEPR theory predicts a linear molecule:
The C-O bond is considerably polar. Although C and S have very similar electronegativity values, S is slightly more
electronegative than C, and so the C-S bond is just slightly polar. Because oxygen is more electronegative than sulfur, the oxygen
end of the molecule is the negative end.
Chloromethane, CH3Cl, is a tetrahedral molecule with three slightly polar C-H bonds and a more polar C-Cl bond. The relative
electronegativities of the bonded atoms is H < C < Cl, and so the bond moments all point toward the Cl end of the molecule and
sum to yield a considerable dipole moment (the molecules are relatively polar).
For molecules of high symmetry such as BF3 (trigonal planar), CH4 (tetrahedral), PF5 (trigonal bipyramidal), and SF6 (octahedral),
all the bonds are of identical polarity (same bond moment) and they are oriented in geometries that yield nonpolar molecules
(dipole moment is zero). Molecules of less geometric symmetry, however, may be polar even when all bond moments are identical.
For these molecules, the directions of the equal bond moments are such that they sum to give a nonzero dipole moment and a polar
molecule. Examples of such molecules include hydrogen sulfide, H2S (nonlinear), and ammonia, NH3 (trigonal pyramidal).
To summarize, to be polar, a molecule must:

1. Contain at least one polar covalent bond.
2. Have a molecular structure such that the sum of the vectors of each bond dipole moment does not cancel.
7.7.0.0.1: Properties of Polar Molecules
Polar molecules tend to align when placed in an electric field with the positive end of the molecule oriented toward the negative
plate and the negative end toward the positive plate (Figure 7.28). We can use an electrically charged object to attract polar
molecules, but nonpolar molecules are not attracted. Also, polar solvents are better at dissolving polar substances, and nonpolar
solvents are better at dissolving nonpolar substances.

Figure 7.28 (a) Molecules are always randomly distributed in the liquid state in the absence of an electric field. (b) When an
electric field is applied, polar molecules like HF will align to the dipoles with the field direction.

The molecule polarity simulation provides many ways to explore dipole moments of bonds and molecules.
7.7.0.1: Example 7.18

7.7.0.0.2: Polarity Simulations
Open the molecule polarity simulation and select the “Three Atoms” tab at the top. This should display a molecule ABC with
three electronegativity adjustors. You can display or hide the bond moments, molecular dipoles, and partial charges at the right.
Turning on the Electric Field will show whether the molecule moves when exposed to a field, similar to Figure 7.28.
Use the electronegativity controls to determine how the molecular dipole will look for the starting bent molecule if:
(a) A and C are very electronegative and B is in the middle of the range.
(b) A is very electronegative, and B and C are not.
7.7.0.0.3: Solution
(a) Molecular dipole moment points immediately between A and C.
(b) Molecular dipole moment points along the A–B bond, toward A.

Determine the partial charges that will give the largest possible bond dipoles.
7.7.0.1: Answer:
The largest bond moments will occur with the largest partial charges. The two solutions above represent how unevenly the
electrons are shared in the bond. The bond moments will be maximized when the electronegativity difference is greatest.
The controls for A and C should be set to one extreme, and B should be set to the opposite extreme. Although the
magnitude of the bond moment will not change based on whether B is the most electronegative or the least, the direction of
the bond moment will.
This page titled 7.7: Molecular Structure and Polarity is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

7.8: Key Terms
axial position
location in a trigonal bipyramidal geometry in which there is another atom at a 180° angle and the equatorial positions are at a
90° angle
bond angle
angle between any two covalent bonds that share a common atom
bond dipole moment

separation of charge in a bond that depends on the difference in electronegativity and the bond distance represented by partial
charges or a vector
bond distance
(also, bond length) distance between the nuclei of two bonded atoms
bond energy
(also, bond dissociation energy) energy required to break a covalent bond in a gaseous substance
bond length
distance between the nuclei of two bonded atoms at which the lowest potential energy is achieved
Born-Haber cycle
thermochemical cycle relating the various energetic steps involved in the formation of an ionic solid from the relevant elements
covalent bond
bond formed when electrons are shared between atoms
dipole moment
property of a molecule that describes the separation of charge determined by the sum of the individual bond moments based on
the molecular structure
double bond
covalent bond in which two pairs of electrons are shared between two atoms
electron-pair geometry
arrangement around a central atom of all regions of electron density (bonds, lone pairs, or unpaired electrons)
electronegativity
tendency of an atom to attract electrons in a bond to itself
equatorial position
one of the three positions in a trigonal bipyramidal geometry with 120° angles between them; the axial positions are located at a
90° angle
formal charge
charge that would result on an atom by taking the number of valence electrons on the neutral atom and subtracting the
nonbonding electrons and the number of bonds (one-half of the bonding electrons)
free radical
molecule that contains an odd number of electrons
hypervalent molecule
molecule containing at least one main group element that has more than eight electrons in its valence shell
inert pair effect
tendency of heavy atoms to form ions in which their valence s electrons are not lost
ionic bond
strong electrostatic force of attraction between cations and anions in an ionic compound
lattice energy (ΔHlattice)

energy required to separate one mole of an ionic solid into its component gaseous ions
Lewis structure
diagram showing lone pairs and bonding pairs of electrons in a molecule or an ion
Lewis symbol
symbol for an element or monatomic ion that uses a dot to represent each valence electron in the element or ion
linear
shape in which two outside groups are placed on opposite sides of a central atom
lone pair
two (a pair of) valence electrons that are not used to form a covalent bond
molecular structure
arrangement of atoms in a molecule or ion
molecular structure
structure that includes only the placement of the atoms in the molecule
octahedral
shape in which six outside groups are placed around a central atom such that a three-dimensional shape is generated with four
groups forming a square and the other two forming the apex of two pyramids, one above and one below the square plane
octet rule
guideline that states main group atoms will form structures in which eight valence electrons interact with each nucleus, counting
bonding electrons as interacting with both atoms connected by the bond
polar covalent bond

covalent bond between atoms of different electronegativities; a covalent bond with a positive end and a negative end
polar molecule
(also, dipole) molecule with an overall dipole moment
pure covalent bond

(also, nonpolar covalent bond) covalent bond between atoms of identical electronegativities
resonance
situation in which one Lewis structure is insufficient to describe the bonding in a molecule and the average of multiple
structures is observed
resonance forms
two or more Lewis structures that have the same arrangement of atoms but different arrangements of electrons
resonance hybrid
average of the resonance forms shown by the individual Lewis structures
single bond
bond in which a single pair of electrons is shared between two atoms
tetrahedral
shape in which four outside groups are placed around a central atom such that a three-dimensional shape is generated with four
corners and 109.5° angles between each pair and the central atom
trigonal bipyramidal
shape in which five outside groups are placed around a central atom such that three form a flat triangle with 120° angles
between each pair and the central atom, and the other two form the apex of two pyramids, one above and one below the
triangular plane
trigonal planar
shape in which three outside groups are placed in a flat triangle around a central atom with 120° angles between each pair and
the central atom
triple bond
bond in which three pairs of electrons are shared between two atoms
valence shell electron-pair repulsion theory (VSEPR)

theory used to predict the bond angles in a molecule based on positioning regions of high electron density as far apart as
possible to minimize electrostatic repulsion
vector
quantity having magnitude and direction
7.9: Key Equations
1
formal charge = # valence shell electrons (free atom) − # lone pair electrons − # bonding electrons
2
Bond energy for a diatomic molecule: XY (g) ⟶ X (g) + Y (g) DX–Y = ΔH °
Enthalpy change: ΔH = ƩDbonds broken – ƩDbonds formed
Lattice energy for a solid MX: MX (s) ⟶ M

n+
(g) + X
n−
(g) ΔHlattice
+ −
C(Z )(Z )
Lattice energy for an ionic crystal: ΔH lattice =
Ro
7.10: Summary
7.1 Ionic Bonding
Atoms gain or lose electrons to form ions with particularly stable electron configurations. The charges of cations formed by the
representative metals may be determined readily because, with few exceptions, the electronic structures of these ions have either a
noble gas configuration or a completely filled electron shell. The charges of anions formed by the nonmetals may also be readily
determined because these ions form when nonmetal atoms gain enough electrons to fill their valence shells.
7.2 Covalent Bonding

Covalent bonds form when electrons are shared between atoms and are attracted by the nuclei of both atoms. In pure covalent
bonds, the electrons are shared equally. In polar covalent bonds, the electrons are shared unequally, as one atom exerts a stronger
force of attraction on the electrons than the other. The ability of an atom to attract a pair of electrons in a chemical bond is called its
electronegativity. The difference in electronegativity between two atoms determines how polar a bond will be. In a diatomic
molecule with two identical atoms, there is no difference in electronegativity, so the bond is nonpolar or pure covalent. When the
electronegativity difference is very large, as is the case between metals and nonmetals, the bonding is characterized as ionic.
7.3 Lewis Symbols and Structures

Valence electronic structures can be visualized by drawing Lewis symbols (for atoms and monatomic ions) and Lewis structures
(for molecules and polyatomic ions). Lone pairs, unpaired electrons, and single, double, or triple bonds are used to indicate where
the valence electrons are located around each atom in a Lewis structure. Most structures—especially those containing second row
elements—obey the octet rule, in which every atom (except H) is surrounded by eight electrons. Exceptions to the octet rule occur
for odd-electron molecules (free radicals), electron-deficient molecules, and hypervalent molecules.
7.4 Formal Charges and Resonance

In a Lewis structure, formal charges can be assigned to each atom by treating each bond as if one-half of the electrons are assigned
to each atom. These hypothetical formal charges are a guide to determining the most appropriate Lewis structure. A structure in
which the formal charges are as close to zero as possible is preferred. Resonance occurs in cases where two or more Lewis
structures with identical arrangements of atoms but different distributions of electrons can be written. The actual distribution of
electrons (the resonance hybrid) is an average of the distribution indicated by the individual Lewis structures (the resonance forms).
7.5 Strengths of Ionic and Covalent Bonds

The strength of a covalent bond is measured by its bond dissociation energy, that is, the amount of energy required to break that
particular bond in a mole of molecules. Multiple bonds are stronger than single bonds between the same atoms. The enthalpy of a
reaction can be estimated based on the energy input required to break bonds and the energy released when new bonds are formed.
For ionic bonds, the lattice energy is the energy required to separate one mole of a compound into its gas phase ions. Lattice energy
increases for ions with higher charges and shorter distances between ions. Lattice energies are often calculated using the Born-
Haber cycle, a thermochemical cycle including all of the energetic steps involved in converting elements into an ionic compound.
7.6 Molecular Structure and Polarity

VSEPR theory predicts the three-dimensional arrangement of atoms in a molecule. It states that valence electrons will assume an
electron-pair geometry that minimizes repulsions between areas of high electron density (bonds and/or lone pairs). Molecular
structure, which refers only to the placement of atoms in a molecule and not the electrons, is equivalent to electron-pair geometry
only when there are no lone electron pairs around the central atom. A dipole moment measures a separation of charge. For one
bond, the bond dipole moment is determined by the difference in electronegativity between the two atoms. For a molecule, the
overall dipole moment is determined by both the individual bond moments and how these dipoles are arranged in the molecular
structure. Polar molecules (those with an appreciable dipole moment) interact with electric fields, whereas nonpolar molecules do
not.
7.11: Exercises
7.11.0.1: 7.1 Ionic Bonding
1.
Does a cation gain protons to form a positive charge or does it lose electrons?
2.
Iron(III) sulfate [Fe2(SO4)3] is composed of Fe3+ and SO 4
2−
ions. Explain why a sample of iron(III) sulfate is uncharged.
3.
Which of the following atoms would be expected to form negative ions in binary ionic compounds and which would be expected to
form positive ions: P, I, Mg, Cl, In, Cs, O, Pb, Co?
4.
Which of the following atoms would be expected to form negative ions in binary ionic compounds and which would be expected to
form positive ions: Br, Ca, Na, N, F, Al, Sn, S, Cd?
5.
Predict the charge on the monatomic ions formed from the following atoms in binary ionic compounds:
(a) P
(b) Mg
(c) Al
(d) O
(e) Cl
(f) Cs
6.
Predict the charge on the monatomic ions formed from the following atoms in binary ionic compounds:
(a) I
(b) Sr
(c) K
(d) N
(e) S
(f) In
7.
Write the electron configuration for each of the following ions:
(a) As3–
(b) I–
(c) Be2+
(d) Cd2+
(e) O2–
(f) Ga3+
(g) Li+
(h) N3–
(i) Sn2+

(j) Co2+
(k) Fe2+
(l) As3+
8.
Write the electron configuration for the monatomic ions formed from the following elements (which form the greatest
concentration of monatomic ions in seawater):
(a) Cl
(b) Na
(c) Mg
(d) Ca
(e) K
(f) Br
(g) Sr
(h) F
9.
Write out the full electron configuration for each of the following atoms and for the monatomic ion found in binary ionic
compounds containing the element:
(a) Al
(b) Br
(c) Sr
(d) Li
(e) As
(f) S
10.
From the labels of several commercial products, prepare a list of six ionic compounds in the products. For each compound, write
the formula. (You may need to look up some formulas in a suitable reference.)
7.11.0.1: 7.2 Covalent Bonding

11.
Why is it incorrect to speak of a molecule of solid NaCl?
12.
What information can you use to predict whether a bond between two atoms is covalent or ionic?
13.
Predict which of the following compounds are ionic and which are covalent, based on the location of their constituent atoms in the
periodic table:
(a) Cl2CO
(b) MnO
(c) NCl3
(d) CoBr2
(e) K2S
(f) CO

(g) CaF2
(h) HI
(i) CaO
(j) IBr
(k) CO2
14.
Explain the difference between a nonpolar covalent bond, a polar covalent bond, and an ionic bond.
15.
From its position in the periodic table, determine which atom in each pair is more electronegative:
(a) Br or Cl
(b) N or O
(c) S or O
(d) P or S
(e) Si or N
(f) Ba or P
(g) N or K
16.
From its position in the periodic table, determine which atom in each pair is more electronegative:
(a) N or P
(b) N or Ge
(c) S or F
(d) Cl or S
(e) H or C
(f) Se or P
(g) C or Si
17.
From their positions in the periodic table, arrange the atoms in each of the following series in order of increasing electronegativity:
(a) C, F, H, N, O
(b) Br, Cl, F, H, I
(c) F, H, O, P, S
(d) Al, H, Na, O, P
(e) Ba, H, N, O, As
18.
From their positions in the periodic table, arrange the atoms in each of the following series in order of increasing electronegativity:
(a) As, H, N, P, Sb
(b) Cl, H, P, S, Si
(c) Br, Cl, Ge, H, Sr
(d) Ca, H, K, N, Si
(e) Cl, Cs, Ge, H, Sr

19.
Which atoms can bond to sulfur so as to produce a positive partial charge on the sulfur atom?
20.
Which is the most polar bond?
(a) C–C
(b) C–H
(c) N–H
(d) O–H
(e) Se–H
21.
Identify the more polar bond in each of the following pairs of bonds:
(a) HF or HCl
(b) NO or CO
(c) SH or OH
(d) PCl or SCl
(e) CH or NH
(f) SO or PO
(g) CN or NN
22.
Which of the following molecules or ions contain polar bonds?
(a) O3
(b) S8
(c) O 2
2−
(d) NO 3
−
(e) CO2
(f) H2S
(g) BH 4
−
7.11.0.1: 7.3 Lewis Symbols and Structures

23.
Write the Lewis symbols for each of the following ions:
(a) As3–
(b) I–
(c) Be2+
(d) O2–
(e) Ga3+
(f) Li+
(g) N3–
24.

Many monatomic ions are found in seawater, including the ions formed from the following list of elements. Write the Lewis
symbols for the monatomic ions formed from the following elements:
(a) Cl
(b) Na
(c) Mg
(d) Ca
(e) K
(f) Br
(g) Sr
(h) F
25.
Write the Lewis symbols of the ions in each of the following ionic compounds and the Lewis symbols of the atom from which they
are formed:
(a) MgS
(b) Al2O3
(c) GaCl3
(d) K2O
(e) Li3N
(f) KF
26.
In the Lewis structures listed here, M and X represent various elements in the third period of the periodic table. Write the formula
of each compound using the chemical symbols of each element:
(a)
(b)
(c)
(d)
27.
Write the Lewis structure for the diatomic molecule P2, an unstable form of phosphorus found in high-temperature phosphorus
vapor.
28.

Write Lewis structures for the following:
(a) H2
(b) HBr
(c) PCl3
(d) SF2
(e) H2CCH2
(f) HNNH
(g) H2CNH
(h) NO–
(i) N2
(j) CO
(k) CN–
29.
(a) O2
(b) H2CO
(c) AsF3
(d) ClNO
(e) SiCl4
(f) H3O+
(g) NH 4
+
(h) BF 4
−
(i) HCCH
(j) ClCN
(k) C 2
2+
30.
(a) ClF3
(b) PCl5
(c) BF3
(d) PF 6
−
31.
(a) SeF6
(b) XeF4
(c) SeCl 3
+
(d) Cl2BBCl2 (contains a B–B bond)

32.
Write Lewis structures for:

(a) PO 4
3−
(b) ICl 4
−
(c) SO 3
2−
(d) HONO
33.
Correct the following statement: “The bonds in solid PbCl2 are ionic; the bond in a HCl molecule is covalent. Thus, all of the
valence electrons in PbCl2 are located on the Cl– ions, and all of the valence electrons in a HCl molecule are shared between the H
and Cl atoms.”
34.
Write Lewis structures for the following molecules or ions:
(a) SbH3
(b) XeF2
(c) Se8 (a cyclic molecule with a ring of eight Se atoms)
35.
Methanol, H3COH, is used as the fuel in some race cars. Ethanol, C2H5OH, is used extensively as motor fuel in Brazil. Both
methanol and ethanol produce CO2 and H2O when they burn. Write the chemical equations for these combustion reactions using
Lewis structures instead of chemical formulas.
36.
Many planets in our solar system contain organic chemicals including methane (CH4) and traces of ethylene (C2H4), ethane (C2H6),
propyne (H3CCCH), and diacetylene (HCCCCH). Write the Lewis structures for each of these molecules.
37.
Carbon tetrachloride was formerly used in fire extinguishers for electrical fires. It is no longer used for this purpose because of the
formation of the toxic gas phosgene, Cl2CO. Write the Lewis structures for carbon tetrachloride and phosgene.
38.
Identify the atoms that correspond to each of the following electron configurations. Then, write the Lewis symbol for the common
ion formed from each atom:
(a) 1s22s22p5
(b) 1s22s22p63s2
(c) 1s22s22p63s23p64s23d10
(d) 1s22s22p63s23p64s23d104p4
(e) 1s22s22p63s23p64s23d104p1
39.
The arrangement of atoms in several biologically important molecules is given here. Complete the Lewis structures of these
molecules by adding multiple bonds and lone pairs. Do not add any more atoms.
(a) the amino acid serine:

(b) urea:
(c) pyruvic acid:
(d) uracil:
(e) carbonic acid:
40.
A compound with a molar mass of about 28 g/mol contains 85.7% carbon and 14.3% hydrogen by mass. Write the Lewis structure
for a molecule of the compound.
41.
A compound with a molar mass of about 42 g/mol contains 85.7% carbon and 14.3% hydrogen by mass. Write the Lewis structure
for a molecule of the compound.
42.
Two arrangements of atoms are possible for a compound with a molar mass of about 45 g/mol that contains 52.2% C, 13.1% H, and
34.7% O by mass. Write the Lewis structures for the two molecules.
43.
How are single, double, and triple bonds similar? How do they differ?

7.11.0.1: 7.4 Formal Charges and Resonance
44.
Write resonance forms that describe the distribution of electrons in each of these molecules or ions.
(a) selenium dioxide, OSeO
(b) nitrate ion, NO 3
−
(c) nitric acid, HNO3 (N is bonded to an OH group and two O atoms)

(d) benzene, C6H6:
(e) the formate ion:
45.
Write resonance forms that describe the distribution of electrons in each of these molecules or ions.
(a) sulfur dioxide, SO2
(b) carbonate ion, CO 3
2−
(c) hydrogen carbonate ion, HCO 3

−
(C is bonded to an OH group and two O atoms)
(d) pyridine:
(e) the allyl ion:
46.
Write the resonance forms of ozone, O3, the component of the upper atmosphere that protects the Earth from ultraviolet radiation.
47.
Sodium nitrite, which has been used to preserve bacon and other meats, is an ionic compound. Write the resonance forms of the
nitrite ion, NO .
2
–

48.
In terms of the bonds present, explain why acetic acid, CH3CO2H, contains two distinct types of carbon-oxygen bonds, whereas the
acetate ion, formed by loss of a hydrogen ion from acetic acid, only contains one type of carbon-oxygen bond. The skeleton
structures of these species are shown:
49.
Write the Lewis structures for the following, and include resonance structures where appropriate. Indicate which has the strongest
carbon-oxygen bond.
(a) CO2
(b) CO
50.
Toothpastes containing sodium hydrogen carbonate (sodium bicarbonate) and hydrogen peroxide are widely used. Write Lewis
structures for the hydrogen carbonate ion and hydrogen peroxide molecule, with resonance forms where appropriate.
51.
Determine the formal charge of each element in the following:
(a) HCl
(b) CF4
(c) PCl3
(d) PF5
52.
Determine the formal charge of each element in the following:
(a) H3O+
(b) SO 4
2−
(c) NH3
(d) O 2
2−
(e) H2O2
53.
Calculate the formal charge of chlorine in the molecules Cl2, BeCl2, and ClF5.
54.
Calculate the formal charge of each element in the following compounds and ions:
(a) F2CO
(b) NO–
(c) BF 4
−
(d) SnCl 3
−
(e) H2CCH2
(f) ClF3

(g) SeF6
(h) PO 4
3−
55.
Draw all possible resonance structures for each of these compounds. Determine the formal charge on each atom in each of the
resonance structures:
(a) O3
(b) SO2
(c) NO 2
−
(d) NO 3
−
56.
Based on formal charge considerations, which of the following would likely be the correct arrangement of atoms in nitrosyl
chloride: ClNO or ClON?
57.
Based on formal charge considerations, which of the following would likely be the correct arrangement of atoms in hypochlorous
acid: HOCl or OClH?
58.
Based on formal charge considerations, which of the following would likely be the correct arrangement of atoms in sulfur dioxide:
OSO or SOO?
59.
Draw the structure of hydroxylamine, H3NO, and assign formal charges; look up the structure. Is the actual structure consistent
with the formal charges?
60.
Iodine forms a series of fluorides (listed here). Write Lewis structures for each of the four compounds and determine the formal
charge of the iodine atom in each molecule:
(a) IF
(b) IF3
(c) IF5
(d) IF7
61.
Write the Lewis structure and chemical formula of the compound with a molar mass of about 70 g/mol that contains 19.7%
nitrogen and 80.3% fluorine by mass, and determine the formal charge of the atoms in this compound.
62.
Which of the following structures would we expect for nitrous acid? Determine the formal charges:
63.
Sulfuric acid is the industrial chemical produced in greatest quantity worldwide. About 90 billion pounds are produced each year in
the United States alone. Write the Lewis structure for sulfuric acid, H2SO4, which has two oxygen atoms and two OH groups
bonded to the sulfur.

7.11.0.1: 7.5 Strengths of Ionic and Covalent Bonds
64.
Which bond in each of the following pairs of bonds is the strongest?
(a) C–C or C = C
(b) C–N or C ≡ N
(c)C ≡ O or C = O
(d) H–F or H–Cl
(e) C–H or O–H
(f) C–N or C–O
65.
Using the bond energies in Table 7.2, determine the approximate enthalpy change for each of the following reactions:
(a) H 2 (g) + Br 2 (g) ⟶ 2HBr (g)
(b) CH 4 (g) + I2 (g) ⟶ CH3 I (g) + HI (g)
(c) C 2 H4 (g) + 3 O2 (g) ⟶ 2 CO2 (g) + 2 H2 O (g)
66.
Using the bond energies in Table 7.2, determine the approximate enthalpy change for each of the following reactions:
(a) Cl 2 (g) + 3 F2 (g) ⟶ 2 ClF3 (g)
(b) H 2C = CH2 (g) + H2 (g) ⟶ H3 CCH3 (g)
(c) 2C 2 H6 (g) + 7 O2 (g) ⟶ 4 CO2 (g) + 6 H2 O (g)
67.
When a molecule can form two different structures, the structure with the stronger bonds is usually the more stable form. Use bond
energies to predict the correct structure of the hydroxylamine molecule:
68.
How does the bond energy of HCl(g) differ from the standard enthalpy of formation of HCl(g)?
69.
Using the standard enthalpy of formation data in Appendix G, show how the standard enthalpy of formation of HCl(g) can be used
to determine the bond energy.
70.
Using the standard enthalpy of formation data in Appendix G, calculate the bond energy of the carbon-sulfur double bond in CS2.
71.
Using the standard enthalpy of formation data in Appendix G, determine which bond is stronger: the S–F bond in SF4(g) or in
SF6(g)?
72.
Using the standard enthalpy of formation data in Appendix G, determine which bond is stronger: the P–Cl bond in PCl3(g) or in
PCl5(g)?
73.
Complete the following Lewis structure by adding bonds (not atoms), and then indicate the longest bond:

74.
Use the bond energy to calculate an approximate value of ΔH for the following reaction. Which is the more stable form of FNO2?
75.
Use principles of atomic structure to answer each of the following:1
(a) The radius of the Ca atom is 197 pm; the radius of the Ca2+ ion is 99 pm. Account for the difference.
(b) The lattice energy of CaO(s) is –3460 kJ/mol; the lattice energy of K2O is –2240 kJ/mol. Account for the difference.
(c) Given these ionization values, explain the difference between Ca and K with regard to their first and second ionization energies.
Element First Ionization Energy (kJ/mol) Second Ionization Energy (kJ/mol)
K 419 3050
Ca 590 1140
(d) The first ionization energy of Mg is 738 kJ/mol and that of Al is 578 kJ/mol. Account for this difference.
76.
The lattice energy of LiF is 1023 kJ/mol, and the Li–F distance is 200.8 pm. NaF crystallizes in the same structure as LiF but with a
Na–F distance of 231 pm. Which of the following values most closely approximates the lattice energy of NaF: 510, 890, 1023,
1175, or 4090 kJ/mol? Explain your choice.
77.
For which of the following substances is the least energy required to convert one mole of the solid into separate ions?
(a) MgO
(b) SrO
(c) KF
(d) CsF
(e) MgF2
78.
The reaction of a metal, M, with a halogen, X2, proceeds by an exothermic reaction as indicated by this equation:
M (s) + X (g) ⟶ MX (s).
2 For each of the following, indicate which option will make the reaction more exothermic. Explain
2
your answers.
(a) a large radius vs. a small radius for M+2
(b) a high ionization energy vs. a low ionization energy for M
(c) an increasing bond energy for the halogen
(d) a decreasing electron affinity for the halogen
(e) an increasing size of the anion formed by the halogen

79.
The lattice energy of LiF is 1023 kJ/mol, and the Li–F distance is 201 pm. MgO crystallizes in the same structure as LiF but with a
Mg–O distance of 205 pm. Which of the following values most closely approximates the lattice energy of MgO: 256 kJ/mol, 512
kJ/mol, 1023 kJ/mol, 2046 kJ/mol, or 4008 kJ/mol? Explain your choice.
80.
Which compound in each of the following pairs has the larger lattice energy? Note: Mg2+ and Li+ have similar radii; O2– and F–
have similar radii. Explain your choices.
(a) MgO or MgSe
(b) LiF or MgO
(c) Li2O or LiCl
(d) Li2Se or MgO
81.
Which compound in each of the following pairs has the larger lattice energy? Note: Ba2+ and
K+ have similar radii; S2– and Cl– have similar radii. Explain your choices.
(a) K2O or Na2O
(b) K2S or BaS
(c) KCl or BaS
(d) BaS or BaCl2
82.
Which of the following compounds requires the most energy to convert one mole of the solid into separate ions?
(a) MgO
(b) SrO
(c) KF
(d) CsF
(e) MgF2
83.
Which of the following compounds requires the most energy to convert one mole of the solid into separate ions?
(a) K2S
(b) K2O
(c) CaS
(d) Cs2S
(e) CaO
84.
The lattice energy of KF is 794 kJ/mol, and the interionic distance is 269 pm. The Na–F
distance in NaF, which has the same structure as KF, is 231 pm. Which of the following values is the closest approximation of the
lattice energy of NaF: 682 kJ/mol, 794 kJ/mol, 924 kJ/mol, 1588 kJ/mol, or 3175 kJ/mol? Explain your answer.
7.11.0.1: 7.6 Molecular Structure and Polarity

85.
Explain why the HOH molecule is bent, whereas the HBeH molecule is linear.
86.

What feature of a Lewis structure can be used to tell if a molecule’s (or ion’s) electron-pair geometry and molecular structure will
be identical?
87.
Explain the difference between electron-pair geometry and molecular structure.
88.
Why is the H–N–H angle in NH3 smaller than the H–C–H bond angle in CH4? Why is the H–N–H angle in NH 4
+
identical to the
H–C–H bond angle in CH4?
89.
Explain how a molecule that contains polar bonds can be nonpolar.
90.
As a general rule, MXn molecules (where M represents a central atom and X represents terminal atoms; n = 2 – 5) are polar if there
is one or more lone pairs of electrons on M. NH3 (M = N, X = H, n = 3) is an example. There are two molecular structures with
lone pairs that are exceptions to this rule. What are they?
91.
Predict the electron pair geometry and the molecular structure of each of the following molecules or ions:
(a) SF6
(b) PCl5
(c) BeH2
(d) CH 3
+
92.
Identify the electron pair geometry and the molecular structure of each of the following molecules or ions:
(a) IF6
+
(b) CF4
(c) BF3
(d) SiF 5
−
(e) BeCl2
93.
What are the electron-pair geometry and the molecular structure of each of the following molecules or ions?
(a) ClF5
(b) ClO 2
−
(c) TeCl 4
2−
(d) PCl3
(e) SeF4
(f) PH 2
−
94.
Predict the electron pair geometry and the molecular structure of each of the following ions:
(a) H3O+
(b) PCl 4
−
(c) SnCl 3
+
(d) BrCl 4
−

(e) ICl3
(f) XeF4
(g) SF2
95.
Identify the electron pair geometry and the molecular structure of each of the following molecules:
(a) ClNO (N is the central atom)
(b) CS2
(c) Cl2CO (C is the central atom)
(d) Cl2SO (S is the central atom)
(e) SO2F2 (S is the central atom)
(f) XeO2F2 (Xe is the central atom)
(g) ClOF 2
+
(Cl is the central atom)
96.
Predict the electron pair geometry and the molecular structure of each of the following:
(a) IOF5 (I is the central atom)
(b) POCl3 (P is the central atom)
(c) Cl2SeO (Se is the central atom)
(d) ClSO+ (S is the central atom)
(e) F2SO (S is the central atom)
(f) NO 2
−
(g) SiO 4
4−
97.
Which of the following molecules and ions contain polar bonds? Which of these molecules and ions have dipole moments?
(a) ClF5
(b) ClO 2
−
(c) TeCl 4
2−
(d) PCl3
(e) SeF4
(f) PH 2
−
(g) XeF2
98.
Which of these molecules and ions contain polar bonds? Which of these molecules and ions have dipole moments?
(a) H3O+
(b) PCl 4
−
(c) SnCl 3
−
(d) BrCl 4
−
(e) ICl3
(f) XeF4
(g) SF2

99.
Which of the following molecules have dipole moments?
(a) CS2
(b) SeS2
(c) CCl2F2
(d) PCl3 (P is the central atom)
(e) ClNO (N is the central atom)
100.
Identify the molecules with a dipole moment:
(a) SF4
(b) CF4
(c) Cl2CCBr2
(d) CH3Cl
(e) H2CO
101.
The molecule XF3 has a dipole moment. Is X boron or phosphorus?
102.
The molecule XCl2 has a dipole moment. Is X beryllium or sulfur?
103.
Is the Cl2BBCl2 molecule polar or nonpolar?
104.
There are three possible structures for PCl2F3 with phosphorus as the central atom. Draw them and discuss how measurements of
dipole moments could help distinguish among them.
105.
Describe the molecular structure around the indicated atom or atoms:
(a) the sulfur atom in sulfuric acid, H2SO4 [(HO)2SO2]
(b) the chlorine atom in chloric acid, HClO3 [HOClO2]
(c) the oxygen atom in hydrogen peroxide, HOOH
(d) the nitrogen atom in nitric acid, HNO3 [HONO2]
(e) the oxygen atom in the OH group in nitric acid, HNO3 [HONO2]
(f) the central oxygen atom in the ozone molecule, O3
(g) each of the carbon atoms in propyne, CH3CCH
(h) the carbon atom in Freon, CCl2F2
(i) each of the carbon atoms in allene, H2CCCH2
106.
Draw the Lewis structures and predict the shape of each compound or ion:
(a) CO2
(b) NO 2
−
(c) SO3

(d) SO 3
2−
107.
A molecule with the formula AB2, in which A and B represent different atoms, could have one of three different shapes. Sketch and
name the three different shapes that this molecule might have. Give an example of a molecule or ion for each shape.
108.
A molecule with the formula AB3, in which A and B represent different atoms, could have one of three different shapes. Sketch and
name the three different shapes that this molecule might have. Give an example of a molecule or ion that has each shape.
109.
Draw the Lewis electron dot structures for these molecules, including resonance structures where appropriate:
(a) CS 3
2−
(b) CS2
(c) CS
(d) predict the molecular shapes for CS 3
2−
and CS2 and explain how you arrived at your predictions
110.
What is the molecular structure of the stable form of FNO2? (N is the central atom.)
111.
A compound with a molar mass of about 42 g/mol contains 85.7% carbon and 14.3% hydrogen. What is its molecular structure?
112.
Use the simulation to perform the following exercises for a two-atom molecule:
(a) Adjust the electronegativity value so the bond dipole is pointing toward B. Then determine what the electronegativity values
must be to switch the dipole so that it points toward A.
(b) With a partial positive charge on A, turn on the electric field and describe what happens.
(c) With a small partial negative charge on A, turn on the electric field and describe what happens.
(d) Reset all, and then with a large partial negative charge on A, turn on the electric field and describe what happens.
113.
Use the simulation to perform the following exercises for a real molecule. You may need to rotate the molecules in three
dimensions to see certain dipoles.
(a) Sketch the bond dipoles and molecular dipole (if any) for O3. Explain your observations.
(b) Look at the bond dipoles for NH3. Use these dipoles to predict whether N or H is more electronegative.
(c) Predict whether there should be a molecular dipole for NH3 and, if so, in which direction it will point. Check the molecular
dipole box to test your hypothesis.
114.
Use the Molecule Shape simulator to build a molecule. Starting with the central atom, click on the double bond to add one double
bond. Then add one single bond and one lone pair. Rotate the molecule to observe the complete geometry. Name the electron group
geometry and molecular structure and predict the bond angle. Then click the check boxes at the bottom and right of the simulator to
check your answers.
115.
Use the Molecule Shape simulator to explore real molecules. On the Real Molecules tab, select H2O. Switch between the “real”
and “model” modes. Explain the difference observed.
116.
Use the Molecule Shape simulator to explore real molecules. On the Real Molecules tab, select “model” mode and S2O. What is
the model bond angle? Explain whether the “real” bond angle should be larger or smaller than the ideal model angle.

7.11.0.1: Footnotes
1This question is taken from the Chemistry Advanced Placement Examination and is used with the permission of the
Educational Testing Service.

CHAPTER OVERVIEW
8: Advanced Theories of Covalent Bonding

General Chemistry
We have examined the basic ideas of bonding, showing that atoms share electrons to form molecules with stable Lewis structures
and that we can predict the shapes of those molecules by valence shell electron pair repulsion (VSEPR) theory. These ideas provide
an important starting point for understanding chemical bonding. But these models sometimes fall short in their abilities to predict
the behavior of real substances. How can we reconcile the geometries of s, p, and d atomic orbitals with molecular shapes that
show angles like 120° and 109.5°? Furthermore, we know that electrons and magnetic behavior are related through electromagnetic
fields.
8.1: Introduction
8.4: Multiple Bonds
8.6: Key Terms
8.7: Key Equations
8.8: Summary
8.9: Exercises
This page titled 8: Advanced Theories of Covalent Bonding is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by
1
8.1: Introduction
Figure 8.1 Oxygen molecules orient randomly most of the time, as shown in the top magnified view. However, when we pour
liquid oxygen through a magnet, the molecules line up with the magnetic field, and the attraction allows them to stay suspended
between the poles of the magnet where the magnetic field is strongest. Other diatomic molecules (like N2) flow past the magnet.
The detailed explanation of bonding described in this chapter allows us to understand this phenomenon. (credit: modification of
work by Jefferson Lab)

8.1 Valence Bond Theory
8.2 Hybrid Atomic Orbitals
8.3 Multiple Bonds
8.4 Molecular Orbital Theory
We have examined the basic ideas of bonding, showing that atoms share electrons to form molecules with stable Lewis structures
and that we can predict the shapes of those molecules by valence shell electron pair repulsion (VSEPR) theory. These ideas provide
an important starting point for understanding chemical bonding. But these models sometimes fall short in their abilities to predict
the behavior of real substances. How can we reconcile the geometries of s, p, and d atomic orbitals with molecular shapes that
show angles like 120° and 109.5°? Furthermore, we know that electrons and magnetic behavior are related through electromagnetic
fields. Both N2 and O2 have fairly similar Lewis structures that contain lone pairs of electrons.
Yet oxygen demonstrates very different magnetic behavior than nitrogen. We can pour liquid nitrogen through a magnetic field with
no visible interactions, while liquid oxygen (shown in Figure 8.1) is attracted to the magnet and floats in the magnetic field. We
need to understand the additional concepts of valence bond theory, orbital hybridization, and molecular orbital theory to understand
these observations.


Describe the formation of covalent bonds in terms of atomic orbital overlap
Define and give examples of σ and π bonds
As we know, a scientific theory is a strongly supported explanation for observed natural laws or large bodies of experimental data.
For a theory to be accepted, it must explain experimental data and be able to predict behavior. For example, VSEPR theory has
gained widespread acceptance because it predicts three-dimensional molecular shapes that are consistent with experimental data
collected for thousands of different molecules. However, VSEPR theory does not provide an explanation of chemical bonding.
There are successful theories that describe the electronic structure of atoms. We can use quantum mechanics to predict the specific
regions around an atom where electrons are likely to be located: A spherical shape for an s orbital, a dumbbell shape for a p orbital,
and so forth. However, these predictions only describe the orbitals around free atoms. When atoms bond to form molecules, atomic
orbitals are not sufficient to describe the regions where electrons will be located in the molecule. A more complete understanding
of electron distributions requires a model that can account for the electronic structure of molecules. One popular theory holds that a
covalent bond forms when a pair of electrons is shared by two atoms and is simultaneously attracted by the nuclei of both atoms. In
the following sections, we will discuss how such bonds are described by valence bond theory and hybridization.
Valence bond theory describes a covalent bond as the overlap of half-filled atomic orbitals (each containing a single electron) that
yield a pair of electrons shared between the two bonded atoms. We say that orbitals on two different atoms overlap when a portion
of one orbital and a portion of a second orbital occupy the same region of space. According to valence bond theory, a covalent bond
results when two conditions are met: (1) an orbital on one atom overlaps an orbital on a second atom and (2) the single electrons in
each orbital combine to form an electron pair. The mutual attraction between this negatively charged electron pair and the two
atoms’ positively charged nuclei serves to physically link the two atoms through a force we define as a covalent bond. The strength
of a covalent bond depends on the extent of overlap of the orbitals involved. Orbitals that overlap extensively form bonds that are
stronger than those that have less overlap.
The energy of the system depends on how much the orbitals overlap. Figure 8.2 illustrates how the sum of the energies of two
hydrogen atoms (the colored curve) changes as they approach each other. When the atoms are far apart there is no overlap, and by
convention we set the sum of the energies at zero. As the atoms move together, their orbitals begin to overlap. Each electron begins
to feel the attraction of the nucleus in the other atom. In addition, the electrons begin to repel each other, as do the nuclei. While the
atoms are still widely separated, the attractions are slightly stronger than the repulsions, and the energy of the system decreases. (A
bond begins to form.) As the atoms move closer together, the overlap increases, so the attraction of the nuclei for the electrons
continues to increase (as do the repulsions among electrons and between the nuclei). At some specific distance between the atoms,
which varies depending on the atoms involved, the energy reaches its lowest (most stable) value. This optimum distance between
the two bonded nuclei is the bond distance between the two atoms. The bond is stable because at this point, the attractive and
repulsive forces combine to create the lowest possible energy configuration. If the distance between the nuclei were to decrease
further, the repulsions between nuclei and the repulsions as electrons are confined in closer proximity to each other would become
stronger than the attractive forces. The energy of the system would then rise (making the system destabilized), as shown at the far
left of Figure 8.2.

Figure 8.2 (a) The interaction of two hydrogen atoms changes as a function of distance. (b) The energy of the system changes as
the atoms interact. The lowest (most stable) energy occurs at a distance of 74 pm, which is the bond length observed for the H2
molecule.
The bond energy is the difference between the energy minimum (which occurs at the bond distance) and the energy of the two
separated atoms. This is the quantity of energy released when the bond is formed. Conversely, the same amount of energy is
required to break the bond. For the H2 molecule shown in Figure 8.2, at the bond distance of 74 pm the system is 7.24 × 10−19 J
lower in energy than the two separated hydrogen atoms. This may seem like a small number. However, we know from our earlier
description of thermochemistry that bond energies are often discussed on a per-mole basis. For example, it requires 7.24 × 10−19 J
to break one H–H bond, but it takes 4.36 × 105 J to break 1 mole of H–H bonds. A comparison of some bond lengths and energies
is shown in Table 8.1. We can find many of these bonds in a variety of molecules, and this table provides average values. For
example, breaking the first C–H bond in CH4 requires 439.3 kJ/mol, while breaking the first C–H bond in H–CH2C6H5 (a common
paint thinner) requires 375.5 kJ/mol.

Representative Bond Energies and Lengths
Bond Length (pm) Energy (kJ/mol) Bond Length (pm) Energy (kJ/mol)
H–H 74 436 C–O 140.1 358
H–C 106.8 413 C = O 119.7 745
H–N 101.5 391 C ≡ O 113.7 1072
H–O 97.5 467 H–Cl 127.5 431
C–C 150.6 347 H–Br 141.4 366
C = C 133.5 614 H–I 160.9 298
C ≡ C 120.8 839 O–O 148 146
C–N 142.1 305 O = O 120.8 498
C = N 130.0 615 F–F 141.2 159
C ≡ N 116.1 891 Cl–Cl 198.8 243
Table 8.1
In addition to the distance between two orbitals, the orientation of orbitals also affects their overlap (other than for two s orbitals,
which are spherically symmetric). Greater overlap is possible when orbitals are oriented such that they overlap on a direct line
between the two nuclei. Figure 8.3 illustrates this for two p orbitals from different atoms; the overlap is greater when the orbitals
overlap end to end rather than at an angle.
Figure 8.3 (a) The overlap of two p orbitals is greatest when the orbitals are directed end to end. (b) Any other arrangement results
in less overlap. The dots indicate the locations of the nuclei.
The overlap of two s orbitals (as in H2), the overlap of an s orbital and a p orbital (as in HCl), and the end-to-end overlap of two p
orbitals (as in Cl2) all produce sigma bonds (σ bonds), as illustrated in Figure 8.4. A σ bond is a covalent bond in which the
electron density is concentrated in the region along the internuclear axis; that is, a line between the nuclei would pass through the
center of the overlap region. Single bonds in Lewis structures are described as σ bonds in valence bond theory.
Figure 8.4 Sigma (σ) bonds form from the overlap of the following: (a) two s orbitals, (b) an s orbital and a p orbital, and (c) two p
orbitals. The dots indicate the locations of the nuclei.
A pi bond (π bond) is a type of covalent bond that results from the side-by-side overlap of two p orbitals, as illustrated in Figure
8.5. In a π bond, the regions of orbital overlap lie on opposite sides of the internuclear axis. Along the axis itself, there is a node,
that is, a plane with no probability of finding an electron.

Figure 8.5 Pi (π) bonds form from the side-by-side overlap of two p orbitals. The dots indicate the location of the nuclei.
While all single bonds are σ bonds, multiple bonds consist of both σ and π bonds. As the Lewis structures below suggest, O2
contains a double bond, and N2 contains a triple bond. The double bond consists of one σ bond and one π bond, and the triple bond
consists of one σ bond and two π bonds. Between any two atoms, the first bond formed will always be a σ bond, but there can only
be one σ bond in any one location. In any multiple bond, there will be one σ bond, and the remaining one or two bonds will be π
bonds. These bonds are described in more detail later in this chapter.
As seen in Table 8.1, an average carbon-carbon single bond is 347 kJ/mol, while in a carbon-carbon double bond, the π bond
increases the bond strength by 267 kJ/mol. Adding an additional π bond causes a further increase of 225 kJ/mol. We can see a
similar pattern when we compare other σ and π bonds. Thus, each individual π bond is generally weaker than a corresponding σ
bond between the same two atoms. In a σ bond, there is a greater degree of orbital overlap than in a π bond.
8.2.0.1: Example 8.1

8.2.0.0.1: Counting σ and π Bonds
Butadiene, C4H6, is used to make synthetic rubber. Identify the number of σ and π bonds contained in this molecule.
8.2.0.0.1: Solution
There are six σ C–H bonds and one σ C–C bond, for a total of seven from the single bonds. There are two double bonds that
each have a π bond in addition to the σ bond. This gives a total nine σ and two π bonds overall.
Identify each illustration as depicting a σ or π bond:
(a) side-by-side overlap of a 4p and a 2p orbital
(b) end-to-end overlap of a 4p and 4p orbital
(c) end-to-end overlap of a 4p and a 2p orbital
8.2.0.1: Answer:
(a) is a π bond with a node along the axis connecting the nuclei while (b) and (c) are σ bonds that overlap along the axis.

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Explain the concept of atomic orbital hybridization
Determine the hybrid orbitals associated with various molecular geometries
Thinking in terms of overlapping atomic orbitals is one way for us to explain how chemical bonds form in diatomic molecules.
However, to understand how molecules with more than two atoms form stable bonds, we require a more detailed model. As an
example, let us consider the water molecule, in which we have one oxygen atom bonding to two hydrogen atoms. Oxygen has the
electron configuration 1s22s22p4, with two unpaired electrons (one in each of the two 2p orbitals). Valence bond theory would
predict that the two O–H bonds form from the overlap of these two 2p orbitals with the 1s orbitals of the hydrogen atoms. If this
were the case, the bond angle would be 90°, as shown in Figure 8.6, because p orbitals are perpendicular to each other.
Experimental evidence shows that the bond angle is 104.5°, not 90°. The prediction of the valence bond theory model does not
match the real-world observations of a water molecule; a different model is needed.
Figure 8.6 The hypothetical overlap of two of the 2p orbitals on an oxygen atom (red) with the 1s orbitals of two hydrogen atoms
(blue) would produce a bond angle of 90°. This is not consistent with experimental evidence.1
Quantum-mechanical calculations suggest why the observed bond angles in H2O differ from those predicted by the overlap of the
1s orbital of the hydrogen atoms with the 2p orbitals of the oxygen atom. The mathematical expression known as the wave
function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are
bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes.
This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the
linear combination of atomic orbitals, LCAO, (a technique that we will encounter again later). The new orbitals that result are
called hybrid orbitals. The valence orbitals in an isolated oxygen atom are a 2s orbital and three 2p orbitals. The valence orbitals in
an oxygen atom in a water molecule differ; they consist of four equivalent hybrid orbitals that point approximately toward the
corners of a tetrahedron (Figure 8.7). Consequently, the overlap of the O and H orbitals should result in a tetrahedral bond angle
(109.5°). The observed angle of 104.5° is experimental evidence for which quantum-mechanical calculations give a useful
explanation: Valence bond theory must include a hybridization component to give accurate predictions.
Figure 8.7 (a) A water molecule has four regions of electron density, so VSEPR theory predicts a tetrahedral arrangement of hybrid
orbitals. (b) Two of the hybrid orbitals on oxygen contain lone pairs, and the other two overlap with the 1s orbitals of hydrogen
atoms to form the O–H bonds in H2O. This description is more consistent with the experimental structure.

The following ideas are important in understanding hybridization:
1. Hybrid orbitals do not exist in isolated atoms. They are formed only in covalently bonded atoms.
2. Hybrid orbitals have shapes and orientations that are very different from those of the atomic orbitals in isolated atoms.
3. A set of hybrid orbitals is generated by combining atomic orbitals. The number of hybrid orbitals in a set is equal to the number
of atomic orbitals that were combined to produce the set.
4. All orbitals in a set of hybrid orbitals are equivalent in shape and energy.
5. The type of hybrid orbitals formed in a bonded atom depends on its electron-pair geometry as predicted by the VSEPR theory.
6. Hybrid orbitals overlap to form σ bonds. Unhybridized orbitals overlap to form π bonds.
In the following sections, we shall discuss the common types of hybrid orbitals.
8.3.0.1: sp Hybridization
The beryllium atom in a gaseous BeCl2 molecule is an example of a central atom with no lone pairs of electrons in a linear
arrangement of three atoms. There are two regions of valence electron density in the BeCl2 molecule that correspond to the two
covalent Be–Cl bonds. To accommodate these two electron domains, two of the Be atom’s four valence orbitals will mix to yield
two hybrid orbitals. This hybridization process involves mixing of the valence s orbital with one of the valence p orbitals to yield
two equivalent sp hybrid orbitals that are oriented in a linear geometry (Figure 8.8). In this figure, the set of sp orbitals appears
similar in shape to the original p orbital, but there is an important difference. The number of atomic orbitals combined always
equals the number of hybrid orbitals formed. The p orbital is one orbital that can hold up to two electrons. The sp set is two
equivalent orbitals that point 180° from each other. The two electrons that were originally in the s orbital are now distributed to the
two sp orbitals, which are half filled. In gaseous BeCl2, these half-filled hybrid orbitals will overlap with orbitals from the chlorine
atoms to form two identical σ bonds.
Figure 8.8 Hybridization of an s orbital (blue) and a p orbital (red) of the same atom produces two sp hybrid orbitals (yellow). Each
hybrid orbital is oriented primarily in just one direction. Note that each sp orbital contains one lobe that is significantly larger than
the other. The set of two sp orbitals are oriented at 180°, which is consistent with the geometry for two domains.
We illustrate the electronic differences in an isolated Be atom and in the bonded Be atom in the orbital energy-level diagram in
Figure 8.9. These diagrams represent each orbital by a horizontal line (indicating its energy) and each electron by an arrow. Energy
increases toward the top of the diagram. We use one upward arrow to indicate one electron in an orbital and two arrows (up and
down) to indicate two electrons of opposite spin.

Figure 8.9 This orbital energy-level diagram shows the sp hybridized orbitals on Be in the linear BeCl2 molecule. Each of the two
sp hybrid orbitals holds one electron and is thus half filled and available for bonding via overlap with a Cl 3p orbital.
When atomic orbitals hybridize, the valence electrons occupy the newly created orbitals. The Be atom had two valence electrons,
so each of the sp orbitals gets one of these electrons. Each of these electrons pairs up with the unpaired electron on a chlorine atom
when a hybrid orbital and a chlorine orbital overlap during the formation of the Be–Cl bonds.
Any central atom surrounded by just two regions of valence electron density in a molecule will exhibit sp hybridization. Other
examples include the mercury atom in the linear HgCl2 molecule, the zinc atom in Zn(CH3)2, which contains a linear C–Zn–C
arrangement, and the carbon atoms in HCCH and CO2.

Check out the University of Wisconsin-Oshkosh website to learn about visualizing hybrid orbitals in three dimensions.
8.3.0.1: sp2 Hybridization

The valence orbitals of a central atom surrounded by three regions of electron density consist of a set of three sp2 hybrid orbitals
and one unhybridized p orbital. This arrangement results from sp2 hybridization, the mixing of one s orbital and two p orbitals to
produce three identical hybrid orbitals oriented in a trigonal planar geometry (Figure 8.10).

Figure 8.10 The hybridization of an s orbital (blue) and two p orbitals (red) produces three equivalent sp2 hybridized orbitals
(yellow) oriented at 120° with respect to each other. The remaining unhybridized p orbital is not shown here, but is located along
the z axis.
Although quantum mechanics yields the “plump” orbital lobes as depicted in Figure 8.10, sometimes for clarity these orbitals are
drawn thinner and without the minor lobes, as in Figure 8.11, to avoid obscuring other features of a given illustration. We will use
these “thinner” representations whenever the true view is too crowded to easily visualize.

Figure 8.11 This alternate way of drawing the trigonal planar sp2 hybrid orbitals is sometimes used in more crowded figures.
The observed structure of the borane molecule, BH3, suggests sp2 hybridization for boron in this compound. The molecule is
trigonal planar, and the boron atom is involved in three bonds to hydrogen atoms (Figure 8.12). We can illustrate the comparison of
orbitals and electron distribution in an isolated boron atom and in the bonded atom in BH3 as shown in the orbital energy level
diagram in Figure 8.13. We redistribute the three valence electrons of the boron atom in the three sp2 hybrid orbitals, and each
boron electron pairs with a hydrogen electron when B–H bonds form.
Figure 8.12 BH3 is an electron-deficient molecule with a trigonal planar structure.
Figure 8.13 In an isolated B atom, there are one 2s and three 2p valence orbitals. When boron is in a molecule with three regions of
electron density, three of the orbitals hybridize and create a set of three sp2 orbitals and one unhybridized 2p orbital. The three half-
filled hybrid orbitals each overlap with an orbital from a hydrogen atom to form three σ bonds in BH3.
Any central atom surrounded by three regions of electron density will exhibit sp2 hybridization. This includes molecules with a
lone pair on the central atom, such as ClNO (Figure 8.14), or molecules with two single bonds and a double bond connected to the
central atom, as in formaldehyde, CH2O, and ethene, H2CCH2.
Figure 8.14 The central atom(s) in each of the structures shown contain three regions of electron density and are sp2 hybridized. As
we know from the discussion of VSEPR theory, a region of electron density contains all of the electrons that point in one direction.
A lone pair, an unpaired electron, a single bond, or a multiple bond would each count as one region of electron density.
8.3.0.1: sp3 Hybridization

The valence orbitals of an atom surrounded by a tetrahedral arrangement of bonding pairs and lone pairs consist of a set of four sp3
hybrid orbitals. The hybrids result from the mixing of one s orbital and all three p orbitals that produces four identical sp3 hybrid

orbitals (Figure 8.15). Each of these hybrid orbitals points toward a different corner of a tetrahedron.
Figure 8.15 The hybridization of an s orbital (blue) and three p orbitals (red) produces four equivalent sp3 hybridized orbitals
(yellow) oriented at 109.5° with respect to each other.
A molecule of methane, CH4, consists of a carbon atom surrounded by four hydrogen atoms at the corners of a tetrahedron. The
carbon atom in methane exhibits sp3 hybridization. We illustrate the orbitals and electron distribution in an isolated carbon atom
and in the bonded atom in CH4 in Figure 8.16. The four valence electrons of the carbon atom are distributed equally in the hybrid
orbitals, and each carbon electron pairs with a hydrogen electron when the C–H bonds form.

Figure 8.16 The four valence atomic orbitals from an isolated carbon atom all hybridize when the carbon bonds in a molecule like
CH4 with four regions of electron density. This creates four equivalent sp3 hybridized orbitals. Overlap of each of the hybrid
orbitals with a hydrogen orbital creates a C–H σ bond.
In a methane molecule, the 1s orbital of each of the four hydrogen atoms overlaps with one of the four sp3 orbitals of the carbon
atom to form a sigma (σ) bond. This results in the formation of four strong, equivalent covalent bonds between the carbon atom and
each of the hydrogen atoms to produce the methane molecule, CH4.
The structure of ethane, C2H6, is similar to that of methane in that each carbon in ethane has four neighboring atoms arranged at the
corners of a tetrahedron—three hydrogen atoms and one carbon atom (Figure 8.17). However, in ethane an sp3 orbital of one
carbon atom overlaps end to end with an sp3 orbital of a second carbon atom to form a σ bond between the two carbon atoms. Each
of the remaining sp3 hybrid orbitals overlaps with an s orbital of a hydrogen atom to form carbon–hydrogen σ bonds. The structure
and overall outline of the bonding orbitals of ethane are shown in Figure 8.17. The orientation of the two CH3 groups is not fixed
relative to each other. Experimental evidence shows that rotation around σ bonds occurs easily.
Figure 8.17 (a) In the ethane molecule, C2H6, each carbon has four sp3 orbitals. (b) These four orbitals overlap to form seven σ
bonds.

An sp3 hybrid orbital can also hold a lone pair of electrons. For example, the nitrogen atom in ammonia is surrounded by three
bonding pairs and a lone pair of electrons directed to the four corners of a tetrahedron. The nitrogen atom is sp3 hybridized with
one hybrid orbital occupied by the lone pair.
The molecular structure of water is consistent with a tetrahedral arrangement of two lone pairs and two bonding pairs of electrons.
Thus we say that the oxygen atom is sp3 hybridized, with two of the hybrid orbitals occupied by lone pairs and two by bonding
pairs. Since lone pairs occupy more space than bonding pairs, structures that contain lone pairs have bond angles slightly distorted
from the ideal. Perfect tetrahedra have angles of 109.5°, but the observed angles in ammonia (107.3°) and water (104.5°) are
slightly smaller. Other examples of sp3 hybridization include CCl4, PCl3, and NCl3.
8.3.0.1: sp3d and sp3d2 Hybridization

To describe the five bonding orbitals in a trigonal bipyramidal arrangement, we must use five of the valence shell atomic orbitals
(the s orbital, the three p orbitals, and one of the d orbitals), which gives five sp3d hybrid orbitals. With an octahedral arrangement
of six hybrid orbitals, we must use six valence shell atomic orbitals (the s orbital, the three p orbitals, and two of the d orbitals in its
valence shell), which gives six sp3d2 hybrid orbitals. These hybridizations are only possible for atoms that have d orbitals in their
valence subshells (that is, not those in the first or second period).
In a molecule of phosphorus pentachloride, PCl5, there are five P–Cl bonds (thus five pairs of valence electrons around the
phosphorus atom) directed toward the corners of a trigonal bipyramid. We use the 3s orbital, the three 3p orbitals, and one of the 3d
orbitals to form the set of five sp3d hybrid orbitals (Figure 8.19) that are involved in the P–Cl bonds. Other atoms that exhibit sp3d
hybridization include the sulfur atom in SF4 and the chlorine atoms in ClF3 and in ClF . (The electrons on fluorine atoms are
4
+
omitted for clarity.)
Figure 8.18 The three compounds pictured exhibit sp3d hybridization in the central atom and a trigonal bipyramid form. SF4 and
ClF 4 have one lone pair of electrons on the central atom, and ClF3 has two lone pairs giving it the T-shape shown.
+
Figure 8.19 (a) The five regions of electron density around phosphorus in PCl5 require five hybrid sp3d orbitals. (b) These orbitals
combine to form a trigonal bipyramidal structure with each large lobe of the hybrid orbital pointing at a vertex. As before, there are
also small lobes pointing in the opposite direction for each orbital (not shown for clarity).
The sulfur atom in sulfur hexafluoride, SF6, exhibits sp3d2 hybridization. A molecule of sulfur hexafluoride has six bonding pairs
of electrons connecting six fluorine atoms to a single sulfur atom. There are no lone pairs of electrons on the central atom. To bond
six fluorine atoms, the 3s orbital, the three 3p orbitals, and two of the 3d orbitals form six equivalent sp3d2 hybrid orbitals, each
directed toward a different corner of an octahedron. Other atoms that exhibit sp3d2 hybridization include the phosphorus atom in
, the iodine atom in the interhalogens IF , IF5, ICl and the xenon atom in XeF4.
− + − −
PCl 6 6 4, IF 4

Figure 8.20 (a) Sulfur hexafluoride, SF6, has an octahedral structure that requires sp3d2 hybridization. (b) The six sp3d2 orbitals
form an octahedral structure around sulfur. Again, the minor lobe of each orbital is not shown for clarity.
8.3.0.1: Assignment of Hybrid Orbitals to Central Atoms

The hybridization of an atom is determined based on the number of regions of electron density that surround it. The geometrical
arrangements characteristic of the various sets of hybrid orbitals are shown in Figure 8.21. These arrangements are identical to
those of the electron-pair geometries predicted by VSEPR theory. VSEPR theory predicts the shapes of molecules, and hybrid
orbital theory provides an explanation for how those shapes are formed. To find the hybridization of a central atom, we can use the
following guidelines:
1. Determine the Lewis structure of the molecule.
2. Determine the number of regions of electron density around an atom using VSEPR theory, in which single bonds, multiple
bonds, radicals, and lone pairs each count as one region.
3. Assign the set of hybridized orbitals from Figure 8.21 that corresponds to this geometry.

Figure 8.21 The shapes of hybridized orbital sets are consistent with the electron-pair geometries. For example, an atom surrounded
by three regions of electron density is sp2 hybridized, and the three sp2 orbitals are arranged in a trigonal planar fashion.
It is important to remember that hybridization was devised to rationalize experimentally observed molecular geometries. The model
works well for molecules containing small central atoms, in which the valence electron pairs are close together in space. However,
for larger central atoms, the valence-shell electron pairs are farther from the nucleus, and there are fewer repulsions. Their
compounds exhibit structures that are often not consistent with VSEPR theory, and hybridized orbitals are not necessary to explain
the observed data. For example, we have discussed the H–O–H bond angle in H2O, 104.5°, which is more consistent with sp3
hybrid orbitals (109.5°) on the central atom than with 2p orbitals (90°). Sulfur is in the same group as oxygen, and H2S has a
similar Lewis structure. However, it has a much smaller bond angle (92.1°), which indicates much less hybridization on sulfur than
oxygen. Continuing down the group, tellurium is even larger than sulfur, and for H2Te, the observed bond angle (90°) is consistent
with overlap of the 5p orbitals, without invoking hybridization. We invoke hybridization where it is necessary to explain the
observed structures.
8.3.0.1: Example 8.2

8.3.0.0.1: Assigning Hybridization
Ammonium sulfate is important as a fertilizer. What is the hybridization of the sulfur atom in the sulfate ion, SO 4
2−
?
8.3.0.0.2: Solution

The Lewis structure of sulfate shows there are four regions of electron density. The hybridization is sp3.
What is the hybridization of the selenium atom in SeF4?
8.3.0.1: Answer:
The selenium atom is sp3d hybridized.
8.3.0.1: Example 8.3

8.3.0.0.4: Assigning Hybridization
Urea, NH2C(O)NH2, is sometimes used as a source of nitrogen in fertilizers. What is the hybridization of the carbon atom in
urea?
8.3.0.0.5: Solution
The Lewis structure of urea is

The carbon atom is surrounded by three regions of electron density, positioned in a trigonal planar arrangement. The
hybridization in a trigonal planar electron pair geometry is sp2 (Figure 8.21), which is the hybridization of the carbon atom in
urea.
Acetic acid, H3CC(O)OH, is the molecule that gives vinegar its odor and sour taste. What is the hybridization of the two
carbon atoms in acetic acid?
8.3.0.1: Answer:
H3C, sp3; C(O)OH, sp2

8.3.0.1: Footnotes
1Note that orbitals may sometimes be drawn in an elongated “balloon” shape rather than in a more realistic “plump” shape in
order to make the geometry easier to visualize.
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8.4: Multiple Bonds

Describe multiple covalent bonding in terms of atomic orbital overlap
Relate the concept of resonance to π-bonding and electron delocalization
The hybrid orbital model appears to account well for the geometry of molecules involving single covalent bonds. Is it also capable
of describing molecules containing double and triple bonds? We have already discussed that multiple bonds consist of σ and π
bonds. Next we can consider how we visualize these components and how they relate to hybrid orbitals. The Lewis structure of
ethene, C2H4, shows us that each carbon atom is surrounded by one other carbon atom and two hydrogen atoms.
The three bonding regions form a trigonal planar electron-pair geometry. Thus we expect the σ bonds from each carbon atom are
formed using a set of sp2 hybrid orbitals that result from hybridization of two of the 2p orbitals and the 2s orbital (Figure 8.22).
These orbitals form the C–H single bonds and the σ bond in the C = C double bond (Figure 8.23). The π bond in the C = C
double bond results from the overlap of the third (remaining) 2p orbital on each carbon atom that is not involved in hybridization.
This unhybridized p orbital (lobes shown in red and blue in Figure 8.23) is perpendicular to the plane of the sp2 hybrid orbitals.
Thus the unhybridized 2p orbitals overlap in a side-by-side fashion, above and below the internuclear axis (Figure 8.23) and form a
π bond.
Figure 8.22 In ethene, each carbon atom is sp2 hybridized, and the sp2 orbitals and the p orbital are singly occupied. The hybrid
orbitals overlap to form σ bonds, while the p orbitals on each carbon atom overlap to form a π bond.

Figure 8.23 In the ethene molecule, C2H4, there are (a) five σ bonds. One C–C σ bond results from overlap of sp2 hybrid orbitals on
the carbon atom with one sp2 hybrid orbital on the other carbon atom. Four C–H bonds result from the overlap between the C
atoms' sp2 orbitals with s orbitals on the hydrogen atoms. (b) The π bond is formed by the side-by-side overlap of the two
unhybridized p orbitals in the two carbon atoms. The two lobes of the π bond are above and below the plane of the σ system.
In an ethene molecule, the four hydrogen atoms and the two carbon atoms are all in the same plane. If the two planes of sp2 hybrid
orbitals tilted relative to each other, the p orbitals would not be oriented to overlap efficiently to create the π bond. The planar
configuration for the ethene molecule occurs because it is the most stable bonding arrangement. This is a significant difference
between σ and π bonds; rotation around single (σ) bonds occurs easily because the end-to-end orbital overlap does not depend on
the relative orientation of the orbitals on each atom in the bond. In other words, rotation around the internuclear axis does not
change the extent to which the σ bonding orbitals overlap because the bonding electron density is symmetric about the axis.
Rotation about the internuclear axis is much more difficult for multiple bonds; however, this would drastically alter the off-axis
overlap of the π bonding orbitals, essentially breaking the π bond.
In molecules with sp hybrid orbitals, two unhybridized p orbitals remain on the atom (Figure 8.24). We find this situation in
acetylene, H−C≡C−H, which is a linear molecule. The sp hybrid orbitals of the two carbon atoms overlap end to end to form a σ
bond between the carbon atoms (Figure 8.25). The remaining sp orbitals form σ bonds with hydrogen atoms. The two unhybridized
p orbitals per carbon are positioned such that they overlap side by side and, hence, form two π bonds. The two carbon atoms of
acetylene are thus bound together by one σ bond and two π bonds, giving a triple bond.
Figure 8.24 Diagram of the two linear sp hybrid orbitals of a carbon atom, which lie in a straight line, and the two unhybridized p
orbitals at perpendicular angles.
Figure 8.25 (a) In the acetylene molecule, C2H2, there are two C–H σ bonds and a C ≡ C triple bond involving one C–C σ bond
and two C–C π bonds. The dashed lines, each connecting two lobes, indicate the side-by-side overlap of the four unhybridized p
orbitals. (b) This shows the overall outline of the bonds in C2H2. The two lobes of each of the π bonds are positioned across from
each other around the line of the C–C σ bond.
Hybridization involves only σ bonds, lone pairs of electrons, and single unpaired electrons (radicals). Structures that account for
these features describe the correct hybridization of the atoms. However, many structures also include resonance forms. Remember
that resonance forms occur when various arrangements of π bonds are possible. Since the arrangement of π bonds involves only the
unhybridized orbitals, resonance does not influence the assignment of hybridization.
For example, molecule benzene has two resonance forms (Figure 8.26). We can use either of these forms to determine that each of
the carbon atoms is bonded to three other atoms with no lone pairs, so the correct hybridization is sp2. The electrons in the

unhybridized p orbitals form π bonds. Neither resonance structure completely describes the electrons in the π bonds. They are not
located in one position or the other, but in reality are delocalized throughout the ring. Valence bond theory does not easily address
delocalization. Bonding in molecules with resonance forms is better described by molecular orbital theory. (See the next module.)
Figure 8.26 Each carbon atom in benzene, C6H6, is sp2 hybridized, independently of which resonance form is considered. The
electrons in the π bonds are not located in one set of p orbitals or the other, but rather delocalized throughout the molecule.
8.4.0.1: Example 8.4

8.4.0.0.1: Assignment of Hybridization Involving Resonance
Some acid rain results from the reaction of sulfur dioxide with atmospheric water vapor, followed by the formation of sulfuric
acid. Sulfur dioxide, SO2, is a major component of volcanic gases as well as a product of the combustion of sulfur-containing
coal. What is the hybridization of the S atom in SO2?
8.4.0.0.1: Solution
The resonance structures of SO2 are

The sulfur atom is surrounded by two bonds and one lone pair of electrons in either resonance structure. Therefore, the
electron-pair geometry is trigonal planar, and the hybridization of the sulfur atom is sp2.
Another acid in acid rain is nitric acid, HNO3, which is produced by the reaction of nitrogen dioxide, NO2, with atmospheric
water vapor. What is the hybridization of the nitrogen atom in NO2? (Note: the lone electron on nitrogen occupies a hybridized
orbital just as a lone pair would.)
8.4.0.1: Answer:
sp2
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Outline the basic quantum-mechanical approach to deriving molecular orbitals from atomic orbitals
Describe traits of bonding and antibonding molecular orbitals
Calculate bond orders based on molecular electron configurations
Write molecular electron configurations for first- and second-row diatomic molecules
Relate these electron configurations to the molecules’ stabilities and magnetic properties
For almost every covalent molecule that exists, we can now draw the Lewis structure, predict the electron-pair geometry, predict
the molecular geometry, and come close to predicting bond angles. However, one of the most important molecules we know, the
oxygen molecule O2, presents a problem with respect to its Lewis structure. We would write the following Lewis structure for O2:
This electronic structure adheres to all the rules governing Lewis theory. There is an O=O double bond, and each oxygen atom has
eight electrons around it. However, this picture is at odds with the magnetic behavior of oxygen. By itself, O2 is not magnetic, but it
is attracted to magnetic fields. Thus, when we pour liquid oxygen past a strong magnet, it collects between the poles of the magnet
and defies gravity, as in Figure 8.1. Such attraction to a magnetic field is called paramagnetism, and it arises in molecules that have
unpaired electrons. And yet, the Lewis structure of O2 indicates that all electrons are paired. How do we account for this
discrepancy?
Magnetic susceptibility measures the force experienced by a substance in a magnetic field. When we compare the weight of a
sample to the weight measured in a magnetic field (Figure 8.27), paramagnetic samples that are attracted to the magnet will appear
heavier because of the force exerted by the magnetic field. We can calculate the number of unpaired electrons based on the increase
in weight.

Figure 8.27 A Gouy balance compares the mass of a sample in the presence of a magnetic field with the mass with the
electromagnet turned off to determine the number of unpaired electrons in a sample.
Experiments show that each O2 molecule has two unpaired electrons. The Lewis-structure model does not predict the presence of
these two unpaired electrons. Unlike oxygen, the apparent weight of most molecules decreases slightly in the presence of an
inhomogeneous magnetic field. Materials in which all of the electrons are paired are diamagnetic and weakly repel a magnetic
field. Paramagnetic and diamagnetic materials do not act as permanent magnets. Only in the presence of an applied magnetic field
do they demonstrate attraction or repulsion.

Water, like most molecules, contains all paired electrons. Living things contain a large percentage of water, so they
demonstrate diamagnetic behavior. If you place a frog near a sufficiently large magnet, it will levitate. You can see videos of
diamagnetic floating frogs, strawberries, and more.
Molecular orbital theory (MO theory) provides an explanation of chemical bonding that accounts for the paramagnetism of the
oxygen molecule. It also explains the bonding in a number of other molecules, such as violations of the octet rule and more
molecules with more complicated bonding (beyond the scope of this text) that are difficult to describe with Lewis structures.
Additionally, it provides a model for describing the energies of electrons in a molecule and the probable location of these electrons.
Unlike valence bond theory, which uses hybrid orbitals that are assigned to one specific atom, MO theory uses the combination of
atomic orbitals to yield molecular orbitals that are delocalized over the entire molecule rather than being localized on its constituent
atoms. MO theory also helps us understand why some substances are electrical conductors, others are semiconductors, and still
others are insulators. Table 8.2 summarizes the main points of the two complementary bonding theories. Both theories provide
different, useful ways of describing molecular structure.
Comparison of Bonding Theories
Valence Bond Theory Molecular Orbital Theory
considers bonds as localized between one pair of atoms considers electrons delocalized throughout the entire molecule
creates bonds from overlap of atomic orbitals (s, p, d…) and hybrid combines atomic orbitals to form molecular orbitals (σ, σ*, π,
orbitals (sp, sp2, sp3…) π*)
forms σ or π bonds creates bonding and antibonding interactions based on which

orbitals are filled
predicts molecular shape based on the number of regions of electron predicts the arrangement of electrons in molecules
density
needs multiple structures to describe resonance
Table 8.2
Molecular orbital theory describes the distribution of electrons in molecules in much the same way that the distribution of electrons
in atoms is described using atomic orbitals. Using quantum mechanics, the behavior of an electron in a molecule is still described
by a wave function, Ψ, analogous to the behavior in an atom. Just like electrons around isolated atoms, electrons around atoms in
molecules are limited to discrete (quantized) energies. The region of space in which a valence electron in a molecule is likely to be
found is called a molecular orbital (Ψ2). Like an atomic orbital, a molecular orbital is full when it contains two electrons with
opposite spin.
We will consider the molecular orbitals in molecules composed of two identical atoms (H2 or Cl2, for example). Such molecules
are called homonuclear diatomic molecules. In these diatomic molecules, several types of molecular orbitals occur.
The mathematical process of combining atomic orbitals to generate molecular orbitals is called the linear combination of atomic
orbitals (LCAO). The wave function describes the wavelike properties of an electron. Molecular orbitals are combinations of
atomic orbital wave functions. Combining waves can lead to constructive interference, in which peaks line up with peaks, or
destructive interference, in which peaks line up with troughs (Figure 8.28). In orbitals, the waves are three dimensional, and they

combine with in-phase waves producing regions with a higher probability of electron density and out-of-phase waves producing
nodes, or regions of no electron density.
Figure 8.28 (a) When in-phase waves combine, constructive interference produces a wave with greater amplitude. (b) When out-of-
phase waves combine, destructive interference produces a wave with less (or no) amplitude.
There are two types of molecular orbitals that can form from the overlap of two atomic s orbitals on adjacent atoms. The two types
are illustrated in Figure 8.29. The in-phase combination produces a lower energy σs molecular orbital (read as "sigma-s") in which
most of the electron density is directly between the nuclei. The out-of-phase addition (which can also be thought of as subtracting
the wave functions) produces a higher energy σ molecular orbital (read as "sigma-s-star") molecular orbital in which there is a
∗
s
node between the nuclei. The asterisk signifies that the orbital is an antibonding orbital. Electrons in a σs orbital are attracted by
both nuclei at the same time and are more stable (of lower energy) than they would be in the isolated atoms. Adding electrons to
these orbitals creates a force that holds the two nuclei together, so we call these orbitals bonding orbitals. Electrons in the σ ∗
s
orbitals are located well away from the region between the two nuclei. The attractive force between the nuclei and these electrons
pulls the two nuclei apart. Hence, these orbitals are called antibonding orbitals. Electrons fill the lower-energy bonding orbital
before the higher-energy antibonding orbital, just as they fill lower-energy atomic orbitals before they fill higher-energy atomic
orbitals.
Figure 8.29 Sigma (σ) and sigma-star (σ*) molecular orbitals are formed by the combination of two s atomic orbitals. The dots (·)
indicate the locations of nuclei.

You can watch animations visualizing the calculated atomic orbitals combining to form various molecular orbitals at the
Orbitron website.
In p orbitals, the wave function gives rise to two lobes with opposite phases, analogous to how a two-dimensional wave has both
parts above and below the average. We indicate the phases by shading the orbital lobes different colors. When orbital lobes of the
same phase overlap, constructive wave interference increases the electron density. When regions of opposite phase overlap, the
destructive wave interference decreases electron density and creates nodes. When p orbitals overlap end to end, they create σ and
σ* orbitals (Figure 8.30). If two atoms are located along the x-axis in a Cartesian coordinate system, the two px orbitals overlap end

to end and form σpx (bonding) and σ (antibonding) (read as "sigma-p-x" and "sigma-p-x star," respectively). Just as with s-orbital
∗
px
overlap, the asterisk indicates the orbital with a node between the nuclei, which is a higher-energy, antibonding orbital.
Figure 8.30 Combining wave functions of two p atomic orbitals along the internuclear axis creates two molecular orbitals, σ p and
∗
σp .
The side-by-side overlap of two p orbitals gives rise to a pi (π) bonding molecular orbital and a π* antibonding molecular orbital, as
shown in Figure 8.31. In valence bond theory, we describe π bonds as containing a nodal plane containing the internuclear axis and
perpendicular to the lobes of the p orbitals, with electron density on either side of the node. In molecular orbital theory, we describe
the π orbital by this same shape, and a π bond exists when this orbital contains electrons. Electrons in this orbital interact with both
nuclei and help hold the two atoms together, making it a bonding orbital. For the out-of-phase combination, there are two nodal
planes created, one along the internuclear axis and a perpendicular one between the nuclei.
Figure 8.31 Side-by-side overlap of each two p orbitals results in the formation of two π molecular orbitals. Combining the out-of-
phase orbitals results in an antibonding molecular orbital with two nodes. One contains the internuclear axis, and one is
perpendicular to the axis. Combining the in-phase orbitals results in a bonding orbital. There is a node (blue) containing the
internuclear axis with the two lobes of the orbital located above and below this node.
In the molecular orbitals of diatomic molecules, each atom also has two sets of p orbitals oriented side by side (py and pz), so these
four atomic orbitals combine pairwise to create two π orbitals and two π* orbitals. The πpy and π orbitals are oriented at right
∗
py
angles to the πpz and π orbitals. Except for their orientation, the πpy and πpz orbitals are identical and have the same energy; they
∗
pz
are degenerate orbitals. The π and π antibonding orbitals are also degenerate and identical except for their orientation. A total
∗
py
∗
pz
of six molecular orbitals results from the combination of the six atomic p orbitals in two atoms: σpx and σ , πpy and π , πpz and
∗
px
∗
py
∗
πpz .
8.5.0.1: Example 8.5

8.5.0.0.1: Molecular Orbitals
Predict what type (if any) of molecular orbital would result from adding the wave functions so each pair of orbitals shown
overlap. The orbitals are all similar in energy.
8.5.0.0.1: Solution
(a) is an in-phase combination, resulting in a σ3p orbital
(b) will not result in a new orbital because the in-phase component (bottom) and out-of-phase component (top) cancel out.
Only orbitals with the correct alignment can combine.
(c) is an out-of-phase combination, resulting in a π ∗
3p
orbital.
Label the molecular orbital shown as σ or π, bonding or antibonding and indicate where the node occurs.
8.5.0.1: Answer:
The orbital is located along the internuclear axis, so it is a σ orbital. There is a node bisecting the internuclear axis, so it is
an antibonding orbital.

8.5.0.0.1: Walter Kohn: Nobel Laureate
Walter Kohn (Figure 8.32) is a theoretical physicist who studies the electronic structure of solids. His work combines the
principles of quantum mechanics with advanced mathematical techniques. This technique, called density functional theory,
makes it possible to compute properties of molecular orbitals, including their shape and energies. Kohn and mathematician
John Pople were awarded the Nobel Prize in Chemistry in 1998 for their contributions to our understanding of electronic
structure. Kohn also made significant contributions to the physics of semiconductors.

Figure 8.32 Walter Kohn developed methods to describe molecular orbitals. (credit: image courtesy of Walter Kohn)
Kohn’s biography has been remarkable outside the realm of physical chemistry as well. He was born in Austria, and during
World War II he was part of the Kindertransport program that rescued 10,000 children from the Nazi regime. His summer jobs
included discovering gold deposits in Canada and helping Polaroid explain how its instant film worked. Dr. Kohn passed away
in 2016 at the age of 93.

8.5.0.0.1: Computational Chemistry in Drug Design
While the descriptions of bonding described in this chapter involve many theoretical concepts, they also have many practical,
real-world applications. For example, drug design is an important field that uses our understanding of chemical bonding to
develop pharmaceuticals. This interdisciplinary area of study uses biology (understanding diseases and how they operate) to
identify specific targets, such as a binding site that is involved in a disease pathway. By modeling the structures of the binding

site and potential drugs, computational chemists can predict which structures can fit together and how effectively they will
bind (see Figure 8.33). Thousands of potential candidates can be narrowed down to a few of the most promising candidates.
These candidate molecules are then carefully tested to determine side effects, how effectively they can be transported through
the body, and other factors. Dozens of important new pharmaceuticals have been discovered with the aid of computational
chemistry, and new research projects are underway.
Figure 8.33 The molecule shown, HIV-1 protease, is an important target for pharmaceutical research. By designing molecules
that bind to this protein, scientists are able to drastically inhibit the progress of the disease.
8.5.0.1: Molecular Orbital Energy Diagrams

The relative energy levels of atomic and molecular orbitals are typically shown in a molecular orbital diagram (Figure 8.34). For a
diatomic molecule, the atomic orbitals of one atom are shown on the left, and those of the other atom are shown on the right. Each
horizontal line represents one orbital that can hold two electrons. The molecular orbitals formed by the combination of the atomic
orbitals are shown in the center. Dashed lines show which of the atomic orbitals combine to form the molecular orbitals. For each
pair of atomic orbitals that combine, one lower-energy (bonding) molecular orbital and one higher-energy (antibonding) orbital
result. Thus we can see that combining the six 2p atomic orbitals results in three bonding orbitals (one σ and two π) and three
antibonding orbitals (one σ* and two π*).
We predict the distribution of electrons in these molecular orbitals by filling the orbitals in the same way that we fill atomic
orbitals, by the Aufbau principle. Lower-energy orbitals fill first, electrons spread out among degenerate orbitals before pairing,
and each orbital can hold a maximum of two electrons with opposite spins (Figure 8.34). Just as we write electron configurations
for atoms, we can write the molecular electronic configuration by listing the orbitals with superscripts indicating the number of
electrons present. For clarity, we place parentheses around molecular orbitals with the same energy. In this case, each orbital is at a
different energy, so parentheses separate each orbital. Thus we would expect a diatomic molecule or ion containing seven electrons
(such as Be ) would have the molecular electron configuration (σ ) (σ ) (σ ) (σ ) . It is common to omit the core
2
+
1s
2 ∗
1s
2
2s
2 ∗
2s
1
electrons from molecular orbital diagrams and configurations and include only the valence electrons.
Figure 8.34 This is the molecular orbital diagram for the homonuclear diatomic Be , showing the molecular orbitals of the
2
+
valence shell only. The molecular orbitals are filled in the same manner as atomic orbitals, using the Aufbau principle and Hund’s
rule.

8.5.0.1: Bond Order
The filled molecular orbital diagram shows the number of electrons in both bonding and antibonding molecular orbitals. The net
contribution of the electrons to the bond strength of a molecule is identified by determining the bond order that results from the
filling of the molecular orbitals by electrons.
When using Lewis structures to describe the distribution of electrons in molecules, we define bond order as the number of bonding
pairs of electrons between two atoms. Thus a single bond has a bond order of 1, a double bond has a bond order of 2, and a triple
bond has a bond order of 3. We define bond order differently when we use the molecular orbital description of the distribution of
electrons, but the resulting bond order is usually the same. The MO technique is more accurate and can handle cases when the
Lewis structure method fails, but both methods describe the same phenomenon.
In the molecular orbital model, an electron contributes to a bonding interaction if it occupies a bonding orbital and it contributes to
an antibonding interaction if it occupies an antibonding orbital. The bond order is calculated by subtracting the destabilizing
(antibonding) electrons from the stabilizing (bonding) electrons. Since a bond consists of two electrons, we divide by two to get the
bond order. We can determine bond order with the following equation:
(number of bonding electrons) − (number of antibonding electrons)
bond order =
2
The order of a covalent bond is a guide to its strength; a bond between two given atoms becomes stronger as the bond order
increases (Table 8.1). If the distribution of electrons in the molecular orbitals between two atoms is such that the resulting bond
would have a bond order of zero, a stable bond does not form. We next look at some specific examples of MO diagrams and bond
orders.
8.5.0.1: Bonding in Diatomic Molecules

A dihydrogen molecule (H2) forms from two hydrogen atoms. When the atomic orbitals of the two atoms combine, the electrons
occupy the molecular orbital of lowest energy, the σ1s bonding orbital. A dihydrogen molecule, H2, readily forms because the
energy of a H2 molecule is lower than that of two H atoms. The σ1s orbital that contains both electrons is lower in energy than
either of the two 1s atomic orbitals.
A molecular orbital can hold two electrons, so both electrons in the H2 molecule are in the σ1s bonding orbital; the electron
configuration is (σ ) . We represent this configuration by a molecular orbital energy diagram (Figure 8.35) in which a single
1s
2
upward arrow indicates one electron in an orbital, and two (upward and downward) arrows indicate two electrons of opposite spin.
Figure 8.35 The molecular orbital energy diagram predicts that H2 will be a stable molecule with lower energy than the separated
atoms.
A dihydrogen molecule contains two bonding electrons and no antibonding electrons so we have
(2 − 0)
bond order in H 2 = =1
2
Because the bond order for the H–H bond is equal to 1, the bond is a single bond.
A helium atom has two electrons, both of which are in its 1s orbital. Two helium atoms do not combine to form a dihelium
molecule, He2, with four electrons, because the stabilizing effect of the two electrons in the lower-energy bonding orbital would be

offset by the destabilizing effect of the two electrons in the higher-energy antibonding molecular orbital. We would write the
hypothetical electron configuration of He2 as (σ ) (σ ) as in Figure 8.36. The net energy change would be zero, so there is no
1s
2 ∗
1s
2
driving force for helium atoms to form the diatomic molecule. In fact, helium exists as discrete atoms rather than as diatomic
molecules. The bond order in a hypothetical dihelium molecule would be zero.
(2 − 2)
bond order in He 2 = =0
2
A bond order of zero indicates that no bond is formed between two atoms.
Figure 8.36 The molecular orbital energy diagram predicts that He2 will not be a stable molecule, since it has equal numbers of
bonding and antibonding electrons.
8.5.0.0.1: The Diatomic Molecules of the Second Period
Eight possible homonuclear diatomic molecules might be formed by the atoms of the second period of the periodic table: Li2, Be2,
B2, C2, N2, O2, F2, and Ne2. However, we can predict that the Be2 molecule and the Ne2 molecule would not be stable. We can see
this by a consideration of the molecular electron configurations (Table 8.3).
We predict valence molecular orbital electron configurations just as we predict electron configurations of atoms. Valence electrons
are assigned to valence molecular orbitals with the lowest possible energies. Consistent with Hund’s rule, whenever there are two
or more degenerate molecular orbitals, electrons fill each orbital of that type singly before any pairing of electrons takes place.
As we saw in valence bond theory, σ bonds are generally more stable than π bonds formed from degenerate atomic orbitals.
Similarly, in molecular orbital theory, σ orbitals are usually more stable than π orbitals. However, this is not always the case. The
MOs for the valence orbitals of the second period are shown in Figure 8.37. Looking at Ne2 molecular orbitals, we see that the
order is consistent with the generic diagram shown in the previous section. However, for atoms with three or fewer electrons in the
p orbitals (Li through N) we observe a different pattern, in which the σp orbital is higher in energy than the πp set. Obtain the
molecular orbital diagram for a homonuclear diatomic ion by adding or subtracting electrons from the diagram for the neutral
molecule.

Figure 8.37 This shows the MO diagrams for each homonuclear diatomic molecule in the second period. The orbital energies
decrease across the period as the effective nuclear charge increases and atomic radius decreases. Between N2 and O2, the order of
the orbitals changes.
This switch in orbital ordering occurs because of a phenomenon called s-p mixing. s-p mixing does not create new orbitals; it
merely influences the energies of the existing molecular orbitals. The σs wavefunction mathematically combines with the σp
wavefunction, with the result that the σs orbital becomes more stable, and the σp orbital becomes less stable (Figure 8.38).
Similarly, the antibonding orbitals also undergo s-p mixing, with the σs* becoming more stable and the σp* becoming less stable.

Figure 8.38 Without mixing, the MO pattern occurs as expected, with the σp orbital lower in energy than the πp orbitals. When s-p
mixing occurs, the orbitals shift as shown, with the σp orbital higher in energy than the πp orbitals.
s-p mixing occurs when the s and p orbitals have similar energies. The energy difference between 2s and 2p orbitals in O, F, and Ne
is greater than that in Li, Be, B, C, and N. Because of this, O2, F2, and Ne2 exhibit negligible s-p mixing (not sufficient to change
the energy ordering), and their MO diagrams follow the normal pattern, as shown in Figure 8.37. All of the other period 2 diatomic
molecules do have s-p mixing, which leads to the pattern where the σp orbital is raised above the πp set.
Using the MO diagrams shown in Figure 8.37, we can add in the electrons and determine the molecular electron configuration and
bond order for each of the diatomic molecules. As shown in Table 8.3, Be2 and Ne2 molecules would have a bond order of 0, and
these molecules do not exist.
Electron Configuration and Bond Order for Molecular Orbitals in Homonuclear Diatomic Molecules of Period Two Elements

Molecule Electron Configuration Bond Order
Li2 ( σ2s )
2
1
Be2 (unstable) 2
( σ2s ) ( σ
∗
)
2
0
2s
B2 2
( σ2s ) ( σ
∗ 2 2
) ( π2py , π2pz ) 1
2s
C2 2
( σ2s ) ( σ
∗ 2 4
) ( π2py , π2pz ) 2
2s
N2 2
( σ2s ) ( σ
∗ 2 4 2
) ( π2py , π2pz ) ( σ2px ) 3
2s
O2 2
( σ2s ) ( σ
∗ 2 2 4 ∗
) ( σ2px ) ( π2py , π2pz ) ( π
∗
, π
2
) 2
2s 2py 2pz
F2 2
( σ2s ) ( σ
∗ 2 2 4 ∗
) ( σ2px ) ( π2py , π2pz ) ( π
∗
, π
4
) 1
2s 2py 2pz
Ne2 (unstable) 2
( σ2s ) ( σ
∗ 2 2 4 ∗
) ( σ2px ) ( π2py , π2pz ) ( π
∗
, π
4
) (σ
∗
)
2
0
2s 2py 2pz 2px
Table 8.3
The combination of two lithium atoms to form a lithium molecule, Li2, is analogous to the formation of H2, but the atomic orbitals
involved are the valence 2s orbitals. Each of the two lithium atoms has one valence electron. Hence, we have two valence electrons
available for the σ2s bonding molecular orbital. Because both valence electrons would be in a bonding orbital, we would predict the
Li2 molecule to be stable. The molecule is, in fact, present in appreciable concentration in lithium vapor at temperatures near the
boiling point of the element. All of the other molecules in Table 8.3 with a bond order greater than zero are also known.
The O2 molecule has enough electrons to half fill the (π

∗
2py
, π
∗
2pz
) level. We expect the two electrons that occupy these two
degenerate orbitals to be unpaired, and this molecular electronic configuration for O2 is in accord with the fact that the oxygen
molecule has two unpaired electrons (Figure 8.40). The presence of two unpaired electrons has proved to be difficult to explain
using Lewis structures, but the molecular orbital theory explains it quite well. In fact, the unpaired electrons of the oxygen
molecule provide a strong piece of support for the molecular orbital theory.

8.5.0.0.2: Band Theory
When two identical atomic orbitals on different atoms combine, two molecular orbitals result (see Figure 8.29). The bonding
orbital is lower in energy than the original atomic orbitals because the atomic orbitals are in-phase in the molecular orbital. The
antibonding orbital is higher in energy than the original atomic orbitals because the atomic orbitals are out-of-phase.
In a solid, similar things happen, but on a much larger scale. Remember that even in a small sample there are a huge number of
atoms (typically > 1023 atoms), and therefore a huge number of atomic orbitals that may be combined into molecular orbitals.
When N valence atomic orbitals, all of the same energy and each containing one (1) electron, are combined, N/2 (filled)
bonding orbitals and N/2 (empty) antibonding orbitals will result. Each bonding orbital will show an energy lowering as the
atomic orbitals are mostly in-phase, but each of the bonding orbitals will be a little different and have slightly different
energies. The antibonding orbitals will show an increase in energy as the atomic orbitals are mostly out-of-phase, but each of
the antibonding orbitals will also be a little different and have slightly different energies. The allowed energy levels for all the
bonding orbitals are so close together that they form a band, called the valence band. Likewise, all the antibonding orbitals are
very close together and form a band, called the conduction band. Figure 8.39 shows the bands for three important classes of
materials: insulators, semiconductors, and conductors.

Figure 8.39 Molecular orbitals in solids are so closely spaced that they are described as bands. The valence band is lower in
energy and the conduction band is higher in energy. The type of solid is determined by the size of the “band gap” between the
valence and conduction bands. Only a very small amount of energy is required to move electrons from the valence band to the
conduction band in a conductor, and so they conduct electricity well. In an insulator, the band gap is large, so that very few
electrons move, and they are poor conductors of electricity. Semiconductors are in between: they conduct electricity better than
insulators, but not as well as conductors.
In order to conduct electricity, electrons must move from the filled valence band to the empty conduction band where they can
move throughout the solid. The size of the band gap, or the energy difference between the top of the valence band and the
bottom of the conduction band, determines how easy it is to move electrons between the bands. Only a small amount of energy
is required in a conductor because the band gap is very small. This small energy difference is “easy” to overcome, so they are
good conductors of electricity. In an insulator, the band gap is so “large” that very few electrons move into the conduction
band; as a result, insulators are poor conductors of electricity. Semiconductors conduct electricity when “moderate” amounts of
energy are provided to move electrons out of the valence band and into the conduction band. Semiconductors, such as silicon,
are found in many electronics.
Semiconductors are used in devices such as computers, smartphones, and solar cells. Solar cells produce electricity when light
provides the energy to move electrons out of the valence band. The electricity that is generated may then be used to power a
light or tool, or it can be stored for later use by charging a battery. As of December 2014, up to 46% of the energy in sunlight
could be converted into electricity using solar cells.
8.5.0.1: Example 8.6

8.5.0.0.3: Molecular Orbital Diagrams, Bond Order, and Number of Unpaired Electrons
Draw the molecular orbital diagram for the oxygen molecule, O2. From this diagram, calculate the bond order for O2. How
does this diagram account for the paramagnetism of O2?
8.5.0.0.4: Solution
We draw a molecular orbital energy diagram similar to that shown in Figure 8.37. Each oxygen atom contributes six electrons,
so the diagram appears as shown in Figure 8.40.

Figure 8.40 The molecular orbital energy diagram for O2 predicts two unpaired electrons.
We calculate the bond order as
(8 − 4)
O2 = =2
2
Oxygen's paramagnetism is explained by the presence of two unpaired electrons in the (π2py, π2pz)* molecular orbitals.
The main component of air is N2. From the molecular orbital diagram of N2, predict its bond order and whether it is
diamagnetic or paramagnetic.
8.5.0.1: Answer:
N2 has a bond order of 3 and is diamagnetic.

8.5.0.1: Example 8.7
8.5.0.0.6: Ion Predictions with MO Diagrams
Give the molecular orbital configuration for the valence electrons in C 2
2−
. Will this ion be stable?
8.5.0.0.7: Solution
Looking at the appropriate MO diagram, we see that the π orbitals are lower in energy than the σp orbital. The valence electron
configuration for C2 is (σ ) (σ ) (π , π ) . Adding two more electrons to generate the C
2s
2 ∗
2s
2
2py 2pz
4
anion will give a valence 2
2−
electron configuration of (σ ) (σ ) (π , π ) (σ ) . Since this has six more bonding electrons than antibonding, the
2s
2 ∗
2s
2
2py 2pz
4
2px
2
bond order will be 3, and the ion should be stable.

How many unpaired electrons would be present on a Be 2
2−
ion? Would it be paramagnetic or diamagnetic?
8.5.0.1: Answer:
two, paramagnetic

Creating molecular orbital diagrams for molecules with more than two atoms relies on the same basic ideas as the diatomic
examples presented here. However, with more atoms, computers are required to calculate how the atomic orbitals combine. See
three-dimensional drawings of the molecular orbitals for C6H6.
This page titled 8.5: Molecular Orbital Theory is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via

8.6: Key Terms
antibonding orbital
molecular orbital located outside of the region between two nuclei; electrons in an antibonding orbital destabilize the molecule
bond order
number of pairs of electrons between two atoms; it can be found by the number of bonds in a Lewis structure or by the
difference between the number of bonding and antibonding electrons divided by two
bonding orbital
molecular orbital located between two nuclei; electrons in a bonding orbital stabilize a molecule
degenerate orbitals
orbitals that have the same energy
diamagnetism
phenomenon in which a material is not magnetic itself but is repelled by a magnetic field; it occurs when there are only paired
electrons present
homonuclear diatomic molecule

molecule consisting of two identical atoms
hybrid orbital
orbital created by combining atomic orbitals on a central atom
hybridization
model that describes the changes in the atomic orbitals of an atom when it forms a covalent compound
linear combination of atomic orbitals

technique for combining atomic orbitals to create molecular orbitals
molecular orbital
region of space in which an electron has a high probability of being found in a molecule
molecular orbital diagram

visual representation of the relative energy levels of molecular orbitals
molecular orbital theory

model that describes the behavior of electrons delocalized throughout a molecule in terms of the combination of atomic wave
functions
node
plane separating different lobes of orbitals, where the probability of finding an electron is zero
overlap
coexistence of orbitals from two different atoms sharing the same region of space, leading to the formation of a covalent bond
paramagnetism
phenomenon in which a material is not magnetic itself but is attracted to a magnetic field; it occurs when there are unpaired
electrons present
pi bond (π bond)
covalent bond formed by side-by-side overlap of atomic orbitals; the electron density is found on opposite sides of the
internuclear axis
s-p mixing
change that causes σp orbitals to be less stable than πp orbitals due to the mixing of s and p-based molecular orbitals of similar
energies.
sigma bond (σ bond)

covalent bond formed by overlap of atomic orbitals along the internuclear axis
sp hybrid orbital
one of a set of two orbitals with a linear arrangement that results from combining one s and one p orbital
sp2 hybrid orbital

one of a set of three orbitals with a trigonal planar arrangement that results from combining one s and two p orbitals
sp3 hybrid orbital

one of a set of four orbitals with a tetrahedral arrangement that results from combining one s and three p orbitals
sp3d hybrid orbital

one of a set of five orbitals with a trigonal bipyramidal arrangement that results from combining one s, three p, and one d orbital
sp3d2 hybrid orbital

one of a set of six orbitals with an octahedral arrangement that results from combining one s, three p, and two d orbitals
valence bond theory

description of bonding that involves atomic orbitals overlapping to form σ or π bonds, within which pairs of electrons are
shared
π bonding orbital
molecular orbital formed by side-by-side overlap of atomic orbitals, in which the electron density is found on opposite sides of
the internuclear axis
π* bonding orbital
antibonding molecular orbital formed by out of phase side-by-side overlap of atomic orbitals, in which the electron density is
found on both sides of the internuclear axis, and there is a node between the nuclei
σ bonding orbital
molecular orbital in which the electron density is found along the axis of the bond
σ* bonding orbital
antibonding molecular orbital formed by out-of-phase overlap of atomic orbital along the axis of the bond, generating a node
between the nuclei
8.7: Key Equations
(number of bonding electron)−(number of antibonding electrons)
bond order =
2
8.8: Summary
8.1 Valence Bond Theory
Valence bond theory describes bonding as a consequence of the overlap of two separate atomic orbitals on different atoms that
creates a region with one pair of electrons shared between the two atoms. When the orbitals overlap along an axis containing the
nuclei, they form a σ bond. When they overlap in a fashion that creates a node along this axis, they form a π bond.
8.2 Hybrid Atomic Orbitals

We can use hybrid orbitals, which are mathematical combinations of some or all of the valence atomic orbitals, to describe the
electron density around covalently bonded atoms. These hybrid orbitals either form sigma (σ) bonds directed toward other atoms of
the molecule or contain lone pairs of electrons. We can determine the type of hybridization around a central atom from the
geometry of the regions of electron density about it. Two such regions imply sp hybridization; three, sp2 hybridization; four, sp3
hybridization; five, sp3d hybridization; and six, sp3d2 hybridization. Pi (π) bonds are formed from unhybridized atomic orbitals (p
or d orbitals).
8.3 Multiple Bonds

Multiple bonds consist of a σ bond located along the axis between two atoms and one or two π bonds. The σ bonds are usually
formed by the overlap of hybridized atomic orbitals, while the π bonds are formed by the side-by-side overlap of unhybridized
orbitals. Resonance occurs when there are multiple unhybridized orbitals with the appropriate alignment to overlap, so the
placement of π bonds can vary.
8.4 Molecular Orbital Theory

Molecular orbital (MO) theory describes the behavior of electrons in a molecule in terms of combinations of the atomic wave
functions. The resulting molecular orbitals may extend over all the atoms in the molecule. Bonding molecular orbitals are formed
by in-phase combinations of atomic wave functions, and electrons in these orbitals stabilize a molecule. Antibonding molecular
orbitals result from out-of-phase combinations of atomic wave functions and electrons in these orbitals make a molecule less stable.
Molecular orbitals located along an internuclear axis are called σ MOs. They can be formed from s orbitals or from p orbitals
oriented in an end-to-end fashion. Molecular orbitals formed from p orbitals oriented in a side-by-side fashion have electron
density on opposite sides of the internuclear axis and are called π orbitals.
We can describe the electronic structure of diatomic molecules by applying molecular orbital theory to the valence electrons of the
atoms. Electrons fill molecular orbitals following the same rules that apply to filling atomic orbitals; Hund’s rule and the Aufbau
principle tell us that lower-energy orbitals will fill first, electrons will spread out before they pair up, and each orbital can hold a
maximum of two electrons with opposite spins. Materials with unpaired electrons are paramagnetic and attracted to a magnetic
field, while those with all-paired electrons are diamagnetic and repelled by a magnetic field. Correctly predicting the magnetic
properties of molecules is in advantage of molecular orbital theory over Lewis structures and valence bond theory.
8.9: Exercises
8.9.0.1: 8.1 Valence Bond Theory
1.
Explain how σ and π bonds are similar and how they are different.
2.
Draw a curve that describes the energy of a system with H and Cl atoms at varying distances. Then, find the minimum energy of
this curve two ways.
(a) Use the bond energy found in Table 8.1 to calculate the energy for one single HCl bond (Hint: How many bonds are in a mole?)
(b) Use the enthalpy of reaction and the bond energies for H2 and Cl2 to solve for the energy of one mole of HCl bonds.
∘
H2 (g) + Cl2 (g) ⇌ 2HCl(g) ΔHrxn = −184.7 kJ/mol
3.
Explain why bonds occur at specific average bond distances instead of the atoms approaching each other infinitely close.
4.
Use valence bond theory to explain the bonding in F2, HF, and ClBr. Sketch the overlap of the atomic orbitals involved in the
bonds.
5.
Use valence bond theory to explain the bonding in O2. Sketch the overlap of the atomic orbitals involved in the bonds in O2.
6.
How many σ and π bonds are present in the molecule HCN?
7.
A friend tells you N2 has three π bonds due to overlap of the three p-orbitals on each N atom. Do you agree?
8.
Draw the Lewis structures for CO2 and CO, and predict the number of σ and π bonds for each molecule.
(a) CO2
(b) CO
8.9.0.1: 8.2 Hybrid Atomic Orbitals

9.
Why is the concept of hybridization required in valence bond theory?
10.
Give the shape that describes each hybrid orbital set:
(a) sp2
(b) sp3d
(c) sp
(d) sp3d2
11.
Explain why a carbon atom cannot form five bonds using sp3d hybrid orbitals.
12.
What is the hybridization of the central atom in each of the following?
(a) BeH2

(b) SF6
(c) PO 4
3−
(d) PCl5
13.
A molecule with the formula AB3 could have one of four different shapes. Give the shape and the hybridization of the central A
atom for each.
14.
Methionine, CH3SCH2CH2CH(NH2)CO2H, is an amino acid found in proteins. The Lewis structure of this compound is shown
below. What is the hybridization type of each carbon, oxygen, the nitrogen, and the sulfur?
15.
Sulfuric acid is manufactured by a series of reactions represented by the following equations:
S8 (s) + 8 O2 (g) ⟶ 8 SO 2 (g)
2SO2 (g) + O2 (g) ⟶ 2 SO 3 (g)
SO 3 (g) + H2 O(l) ⟶ H2 SO 4 (l)
Draw a Lewis structure, predict the molecular geometry by VSEPR, and determine the hybridization of sulfur for the following:
(a) circular S8 molecule
(b) SO2 molecule
(c) SO3 molecule
(d) H2SO4 molecule (the hydrogen atoms are bonded to oxygen atoms)
16.
Two important industrial chemicals, ethene, C2H4, and propene, C3H6, are produced by the steam (or thermal) cracking process:
2 C3 H8 (g) ⟶ C2 H4 (g) + C3 H6 (g) + CH4 (g) + H2 (g)
For each of the four carbon compounds, do the following:

(a) Draw a Lewis structure.
(b) Predict the geometry about the carbon atom.
(c) Determine the hybridization of each type of carbon atom.
17.
Analysis of a compound indicates that it contains 77.55% Xe and 22.45% F by mass.
(a) What is the empirical formula for this compound? (Assume this is also the molecular formula in responding to the remaining
parts of this exercise).
(b) Write a Lewis structure for the compound.
(c) Predict the shape of the molecules of the compound.
(d) What hybridization is consistent with the shape you predicted?
18.
Consider nitrous acid, HNO2 (HONO).

(a) Write a Lewis structure.
(b) What are the electron pair and molecular geometries of the internal oxygen and nitrogen atoms in the HNO2 molecule?
(c) What is the hybridization on the internal oxygen and nitrogen atoms in HNO2?
19.
Strike-anywhere matches contain a layer of KClO3 and a layer of P4S3. The heat produced by the friction of striking the match
causes these two compounds to react vigorously, which sets fire to the wooden stem of the match. KClO3 contains the ClO ion. 3
−
P4S3 is an unusual molecule with the skeletal structure.
(a) Write Lewis structures for P4S3 and the ClO 3

–
ion.
(b) Describe the geometry about the P atoms, the S atom, and the Cl atom in these species.
(c) Assign a hybridization to the P atoms, the S atom, and the Cl atom in these species.
(d) Determine the oxidation states and formal charge of the atoms in P4S3 and the ClO 3
–
ion.
20.
Identify the hybridization of each carbon atom in the following molecule. (The arrangement of atoms is given; you need to
determine how many bonds connect each pair of atoms.)
21.
Write Lewis structures for NF3 and PF5. On the basis of hybrid orbitals, explain the fact that NF3, PF3, and PF5 are stable
molecules, but NF5 does not exist.
22.
In addition to NF3, two other fluoro derivatives of nitrogen are known: N2F4 and N2F2. What shapes do you predict for these two
molecules? What is the hybridization for the nitrogen in each molecule?
8.9.0.1: 8.3 Multiple Bonds

23.
The bond energy of a C–C single bond averages 347 kJ mol−1; that of a C ≡ C triple bond averages 839 kJ mol−1. Explain why the
triple bond is not three times as strong as a single bond.
24.
For the carbonate ion, CO 3
2−
, draw all of the resonance structures. Identify which orbitals overlap to create each bond.
25.
A useful solvent that will dissolve salts as well as organic compounds is the compound acetonitrile, H3CCN. It is present in paint
strippers.
(a) Write the Lewis structure for acetonitrile, and indicate the direction of the dipole moment in the molecule.
(b) Identify the hybrid orbitals used by the carbon atoms in the molecule to form σ bonds.
(c) Describe the atomic orbitals that form the π bonds in the molecule. Note that it is not necessary to hybridize the nitrogen atom.

26.
For the molecule allene, H C = C = CH
2 2, give the hybridization of each carbon atom. Will the hydrogen atoms be in the same
plane or perpendicular planes?
27.
Identify the hybridization of the central atom in each of the following molecules and ions that contain multiple bonds:
(a) ClNO (N is the central atom)
(b) CS2
(c) Cl2CO (C is the central atom)
(d) Cl2SO (S is the central atom)
(e) SO2F2 (S is the central atom)
(f) XeO2F2 (Xe is the central atom)
(g) ClOF 2
+
(Cl is the central atom)
28.
Describe the molecular geometry and hybridization of the N, P, or S atoms in each of the following compounds.
(a) H3PO4, phosphoric acid, used in cola soft drinks
(b) NH4NO3, ammonium nitrate, a fertilizer and explosive
(c) S2Cl2, disulfur dichloride, used in vulcanizing rubber
(d) K4[O3POPO3], potassium pyrophosphate, an ingredient in some toothpastes
29.
For each of the following molecules, indicate the hybridization requested and whether or not the electrons will be delocalized:
(a) ozone (O3) central O hybridization
(b) carbon dioxide (CO2) central C hybridization
(c) nitrogen dioxide (NO2) central N hybridization
(d) phosphate ion (PO 4
3−
) central P hybridization
30.
For each of the following structures, determine the hybridization requested and whether the electrons will be delocalized:
(a) Hybridization of each carbon
(b) Hybridization of sulfur
(c) All atoms

31.
Draw the orbital diagram for carbon in CO2 showing how many carbon atom electrons are in each orbital.
8.9.0.1: 8.4 Molecular Orbital Theory

32.
Sketch the distribution of electron density in the bonding and antibonding molecular orbitals formed from two s orbitals and from
two p orbitals.
33.
How are the following similar, and how do they differ?
(a) σ molecular orbitals and π molecular orbitals
(b) ψ for an atomic orbital and ψ for a molecular orbital
(c) bonding orbitals and antibonding orbitals
34.
If molecular orbitals are created by combining five atomic orbitals from atom A and five atomic orbitals from atom B combine,
how many molecular orbitals will result?
35.
Can a molecule with an odd number of electrons ever be diamagnetic? Explain why or why not.
36.
Can a molecule with an even number of electrons ever be paramagnetic? Explain why or why not.
37.
Why are bonding molecular orbitals lower in energy than the parent atomic orbitals?
38.
Calculate the bond order for an ion with this configuration:
2 2 2 4 3
∗ ∗ ∗
(σ2s ) (σ ) (σ2px ) (π2py , π2pz ) (π , π )
2s 2py 2pz
39.
Explain why an electron in the bonding molecular orbital in the H2 molecule has a lower energy than an electron in the 1s atomic
orbital of either of the separated hydrogen atoms.
40.
Predict the valence electron molecular orbital configurations for the following, and state whether they will be stable or unstable
ions.
(a) Na 2
2+
(b) Mg 2
2+
(c) Al 2
2+
(d) Si 2
2+

(e) P 2
2+
(f) S 2
2+
(g) F 2
2+
(h) Ar 2
2+
41.
Determine the bond order of each member of the following groups, and determine which member of each group is predicted by the
molecular orbital model to have the strongest bond.
(a) H2, H 2
+
, H2
−
(b) O2, O 2
2+
, O2
2−
(c) Li2, Be 2
+
, Be2
(d) F2, F 2
+
, F2
−
(e) N2, N 2
+
, N2
−
42.
For the first ionization energy for an N2 molecule, what molecular orbital is the electron removed from?
43.
Compare the atomic and molecular orbital diagrams to identify the member of each of the following pairs that has the highest first
ionization energy (the most tightly bound electron) in the gas phase:
(a) H and H2
(b) N and N2
(c) O and O2
(d) C and C2
(e) B and B2
44.
Which of the period 2 homonuclear diatomic molecules are predicted to be paramagnetic?
45.
A friend tells you that the 2s orbital for fluorine starts off at a much lower energy than the 2s orbital for lithium, so the resulting σ2s
molecular orbital in F2 is more stable than in Li2. Do you agree?
46.
True or false: Boron contains 2s22p1 valence electrons, so only one p orbital is needed to form molecular orbitals.
47.
What charge would be needed on F2 to generate an ion with a bond order of 2?
48.
Predict whether the MO diagram for S2 would show s-p mixing or not.
49.
Explain why N 2
2+
is diamagnetic, while O
2
4+
, which has the same number of valence electrons, is paramagnetic.
50.
Using the MO diagrams, predict the bond order for the stronger bond in each pair:
(a) B2 or B 2
+
(b) F2 or F 2
+
(c) O2 or O 2
2+

(d) C2
+
or C
2
−

CHAPTER OVERVIEW
9: Gases

General Chemistry
In this chapter, we examine the relationships between gas temperature, pressure, amount, and volume. We will study a simple
theoretical model and use it to analyze the experimental behavior of gases. The results of these analyses will show us the
limitations of the theory and how to improve on it.
9.1: Introduction
9.2: Gas Pressure
9.8: Key Terms
9.9: Key Equations
9.10: Summary
9.11: Exercises
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
[email protected]).
Thumbnail: As long as black-body radiation (not shown) doesn't escape a system, atoms in thermal agitation undergo essentially
elastic collisions. On average, two atoms rebound from each other with the same kinetic energy as before a collision. Five
atoms are colored red so their paths of motion are easier to see. (Public Domain; Greg L via Wikipedia)
This page titled 9: Gases is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content that was
edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request.
1
9.1: Introduction
Figure 9.1 The hot air inside these balloons is less dense than the surrounding cool air. This results in a buoyant force that causes
the balloons to rise when their guy lines are untied. (credit: modification of work by Anthony Quintano)
Chapter Outline
9.1 Gas Pressure
9.2 Relating Pressure, Volume, Amount, and Temperature: The Ideal Gas Law
9.3 Stoichiometry of Gaseous Substances, Mixtures, and Reactions
9.4 Effusion and Diffusion of Gases
9.5 The Kinetic-Molecular Theory
9.6 Non-Ideal Gas Behavior
We are surrounded by an ocean of gas—the atmosphere—and many of the properties of gases are familiar to us from our daily
activities. Heated gases expand, which can make a hot air balloon rise (Figure 9.1) or cause a blowout in a bicycle tire left in the
sun on a hot day.
Gases have played an important part in the development of chemistry. In the seventeenth and eighteenth centuries, many scientists
investigated gas behavior, providing the first mathematical descriptions of the behavior of matter.
In this chapter, we will examine the relationships between gas temperature, pressure, amount, and volume. We will study a simple
theoretical model and use it to analyze the experimental behavior of gases. The results of these analyses will show us the
limitations of the theory and how to improve on it.
9.2: Gas Pressure

Define the property of pressure
Define and convert among the units of pressure measurements
Describe the operation of common tools for measuring gas pressure
Calculate pressure from manometer data
The earth’s atmosphere exerts a pressure, as does any other gas. Although we do not normally notice atmospheric pressure, we are
sensitive to pressure changes—for example, when your ears “pop” during take-off and landing while flying, or when you dive
underwater. Gas pressure is caused by the force exerted by gas molecules colliding with the surfaces of objects (Figure 9.2).
Although the force of each collision is very small, any surface of appreciable area experiences a large number of collisions in a
short time, which can result in a high pressure. In fact, normal air pressure is strong enough to crush a metal container when not
balanced by equal pressure from inside the container.
Figure 9.2 The atmosphere above us exerts a large pressure on objects at the surface of the earth, roughly equal to the weight of a
bowling ball pressing on an area the size of a human thumbnail.

A dramatic illustration of atmospheric pressure is provided in this brief video, which shows a railway tanker car imploding
when its internal pressure is decreased.
A smaller scale demonstration of this phenomenon is briefly explained.
Atmospheric pressure is caused by the weight of the column of air molecules in the atmosphere above an object, such as the tanker
car. At sea level, this pressure is roughly the same as that exerted by a full-grown African elephant standing on a doormat, or a
typical bowling ball resting on your thumbnail. These may seem like huge amounts, and they are, but life on earth has evolved
under such atmospheric pressure. If you actually perch a bowling ball on your thumbnail, the pressure experienced is twice the
usual pressure, and the sensation is unpleasant.
In general, pressure is defined as the force exerted on a given area: P = . Note that pressure is directly proportional to force and
F
inversely proportional to area. Thus, pressure can be increased either by increasing the amount of force or by decreasing the area
over which it is applied; pressure can be decreased by decreasing the force or increasing the area.

Let’s apply this concept to determine which exerts a greater pressure in Figure 9.3—the elephant or the figure skater? A large
African elephant can weigh 7 tons, supported on four feet, each with a diameter of about 1.5 ft (footprint area of 250 in2), so the
pressure exerted by each foot is about 14 lb/in2:
lb 1 elephant 1 foot 2
pressure per elephant foot = 14,000 × × = 14 lb/in
2
elephant 4 feet 250 in
The figure skater weighs about 120 lbs, supported on two skate blades, each with an area of about 2 in2, so the pressure exerted by
each blade is about 30 lb/in2:
lb 1 skater 1 blade 2
pressure per skate blade = 120 × × = 30 lb/in
2
skater 2 blades 2 in
Even though the elephant is more than one hundred-times heavier than the skater, it exerts less than one-half of the pressure. On the
other hand, if the skater removes their skates and stands with bare feet (or regular footwear) on the ice, the larger area over which
their weight is applied greatly reduces the pressure exerted:
lb 1 skater 1 foot 2
pressure per human foot = 120 × × = 2 lb/in
2
skater 2 feet 30 in
Figure 9.3 Although (a) an elephant’s weight is large, creating a very large force on the ground, (b) the figure skater exerts a much
higher pressure on the ice due to the small surface area of the skates. (credit a: modification of work by Guido da Rozze; credit b:
modification of work by Ryosuke Yagi)
The SI unit of pressure is the pascal (Pa), with 1 Pa = 1 N/m2, where N is the newton, a unit of force defined as 1 kg m/s2. One
pascal is a small pressure; in many cases, it is more convenient to use units of kilopascal (1 kPa = 1000 Pa) or bar (1 bar = 100,000
Pa). In the United States, pressure is often measured in pounds of force on an area of one square inch—pounds per square inch (psi)
—for example, in car tires. Pressure can also be measured using the unit atmosphere (atm), which originally represented the
average sea level air pressure at the approximate latitude of Paris (45°). Table 9.1 provides some information on these and a few
other common units for pressure measurements
Pressure Units
Unit Name and Abbreviation Definition or Relation to Other Unit
pascal (Pa) 1 Pa = 1 N/m2

recommended IUPAC unit
kilopascal (kPa) 1 kPa = 1000 Pa
pounds per square inch (psi) air pressure at sea level is ~14.7 psi
atmosphere (atm) 1 atm = 101,325 Pa = 760 torr

air pressure at sea level is ~1 atm

Unit Name and Abbreviation Definition or Relation to Other Unit
bar (bar, or b) 1 bar = 100,000 Pa (exactly)

commonly used in meteorology
millibar (mbar, or mb) 1000 mbar = 1 bar
inches of mercury (in. Hg) 1 in. Hg = 3386 Pa

used by aviation industry, also some weather reports
torr 1 torr =
1
atm
760
named after Evangelista Torricelli, inventor of the barometer
millimeters of mercury (mm Hg) 1 mm Hg ~1 torr
Table 9.1
9.2.0.1: Example 9.1

9.2.0.0.1: Conversion of Pressure Units
The United States National Weather Service reports pressure in both inches of Hg and millibars. Convert a pressure of 29.2 in.
Hg into:
(a) torr
(b) atm
(c) kPa
(d) mbar
9.2.0.0.1: Solution
This is a unit conversion problem. The relationships between the various pressure units are given in Table 9.1.
25.4 mm
(a) 29.2 in Hg × ×
1 torr
= 742 torr
1 in 1 mm Hg
(b) 742 torr ×

1 atm
= 0.976 atm
760 torr
(c) 742 torr ×

101.325 kPa
= 98.9 kPa
760 torr
1000 Pa 1 bar
(d) 98.9 kPa × × ×
1000 mbar
= 989 mbar
1 kPa 100,000 Pa 1 bar

A typical barometric pressure in Kansas City is 740 torr. What is this pressure in atmospheres, in millimeters of mercury, in
kilopascals, and in bar?
9.2.0.1: Answer:
0.974 atm; 740 mm Hg; 98.7 kPa; 0.987 bar
We can measure atmospheric pressure, the force exerted by the atmosphere on the earth’s surface, with a barometer (Figure 9.4). A
barometer is a glass tube that is closed at one end, filled with a nonvolatile liquid such as mercury, and then inverted and immersed
in a container of that liquid. The atmosphere exerts pressure on the liquid outside the tube, the column of liquid exerts pressure
inside the tube, and the pressure at the liquid surface is the same inside and outside the tube. The height of the liquid in the tube is
therefore proportional to the pressure exerted by the atmosphere.

Figure 9.4 In a barometer, the height, h, of the column of liquid is used as a measurement of the air pressure. Using very dense
liquid mercury (left) permits the construction of reasonably sized barometers, whereas using water (right) would require a
barometer more than 30 feet tall.
If the liquid is water, normal atmospheric pressure will support a column of water over 10 meters high, which is rather inconvenient
for making (and reading) a barometer. Because mercury (Hg) is about 13.6-times denser than water, a mercury barometer only
needs to be 1
13.6
as tall as a water barometer—a more suitable size. Standard atmospheric pressure of 1 atm at sea level (101,325
Pa) corresponds to a column of mercury that is about 760 mm (29.92 in.) high. The torr was originally intended to be a unit equal
to one millimeter of mercury, but it no longer corresponds exactly. The pressure exerted by a fluid due to gravity is known as
hydrostatic pressure, p:
p = hρg
where h is the height of the fluid, ρ (lowercase Greek letter rho) is the density of the fluid, and g is acceleration due to gravity.
9.2.0.1: Example 9.2

9.2.0.0.1: Calculation of Barometric Pressure
Show the calculation supporting the claim that atmospheric pressure near sea level corresponds to the pressure exerted by a
column of mercury that is about 760 mm high. The density of mercury = 13.6 g/cm3.
9.2.0.0.1: Solution
The hydrostatic pressure is given by p = hρg, with h = 760 mm, ρ = 13.6 g/cm3, and g = 9.81 m/s2. Plugging these values into
the equation and doing the necessary unit conversions will give us the value we seek. (Note: We are expecting to find a
pressure of ~101,325 Pa.)
2
kg⋅m/s kg
2
101,325 N /m = 101,325 = 101,325
2 2
m m⋅s

3
1 m 13.6 g 1 kg (100 cm) 9.81 m
p = (760 mm × ) × ( × × ) × ( )
1000 mm 1 cm3 1000 g
(1 m)
3
1 s2
3 2 5 2 5 2
= (0.760 m) (13,600 kg/m ) (9.81 m/s ) = 1.01 × 10 kg/ms = 1.01 × 10 N /m
5
= 1.01 × 10 Pa

Calculate the height of a column of water at 25 °C that corresponds to normal atmospheric pressure. The density of water at
this temperature is 1.0 g/cm3.
9.2.0.1: Answer:
10.3 m
A manometer is a device similar to a barometer that can be used to measure the pressure of a gas trapped in a container. A closed-
end manometer is a U-shaped tube with one closed arm, one arm that connects to the gas to be measured, and a nonvolatile liquid
(usually mercury) in between. As with a barometer, the distance between the liquid levels in the two arms of the tube (h in the
diagram) is proportional to the pressure of the gas in the container. An open-end manometer (Figure 9.5) is the same as a closed-
end manometer, but one of its arms is open to the atmosphere. In this case, the distance between the liquid levels corresponds to the
difference in pressure between the gas in the container and the atmosphere.
Figure 9.5 A manometer can be used to measure the pressure of a gas. The (difference in) height between the liquid levels (h) is a
measure of the pressure. Mercury is usually used because of its large density.
9.2.0.1: Example 9.3

9.2.0.0.1: Calculation of Pressure Using a Closed-End Manometer
The pressure of a sample of gas is measured with a closed-end manometer, as shown to the right. The liquid in the manometer
is mercury. Determine the pressure of the gas in:
(a) torr
(b) Pa
(c) bar

9.2.0.0.1: Solution
The pressure of the gas is equal to a column of mercury of height 26.4 cm. (The pressure at the bottom horizontal line is equal
on both sides of the tube. The pressure on the left is due to the gas and the pressure on the right is due to 26.4 cm Hg, or
mercury.) We could use the equation p = hρg as in Example 9.2, but it is simpler to just convert between units using Table 9.1.
10 mm Hg
(a) 26.4 cm Hg × ×
1 torr
= 264 torr
1 cm Hg 1 mm Hg
1 atm 101,325 Pa
(b) 264 torr × × = 35,200 Pa
760 torr 1 atm
(c) 35,200 Pa ×
1 bar
= 0.352 bar
100,000 Pa

The pressure of a sample of gas is measured with a closed-end manometer. The liquid in the manometer is mercury. Determine
the pressure of the gas in:
(a) torr
(b) Pa
(c) bar
9.2.0.1: Answer:
(a) ~150 torr; (b) ~20,000 Pa; (c) ~0.20 bar
9.2.0.1: Example 9.4

9.2.0.0.1: Calculation of Pressure Using an Open-End Manometer
The pressure of a sample of gas is measured at sea level with an open-end Hg (mercury) manometer, as shown to the right.
Determine the pressure of the gas in:
(a) mm Hg
(b) atm
(c) kPa
9.2.0.0.1: Solution
The pressure of the gas equals the hydrostatic pressure due to a column of mercury of height 13.7 cm plus the pressure of the
atmosphere at sea level. (The pressure at the bottom horizontal line is equal on both sides of the tube. The pressure on the left
is due to the gas and the pressure on the right is due to 13.7 cm of Hg plus atmospheric pressure.)
(a) In mm Hg, this is: 137 mm Hg + 760 mm Hg = 897 mm Hg
(b) 897 mm Hg ×
1 atm
= 1.18 atm
760 mm Hg
(c) 1.18 atm ×

101.325 kPa
= 1.20 × 10
2
kPa
1 atm

The pressure of a sample of gas is measured at sea level with an open-end Hg manometer, as shown to the right. Determine the
pressure of the gas in:
(a) mm Hg
(b) atm
(c) kPa

9.2.0.1: Answer:
(a) 642 mm Hg; (b) 0.845 atm; (c) 85.6 kPa

9.2.0.0.1: Measuring Blood Pressure
Blood pressure is measured using a device called a sphygmomanometer (Greek sphygmos = “pulse”). It consists of an
inflatable cuff to restrict blood flow, a manometer to measure the pressure, and a method of determining when blood flow
begins and when it becomes impeded (Figure 9.6). Since its invention in 1881, it has been an essential medical device. There
are many types of sphygmomanometers: manual ones that require a stethoscope and are used by medical professionals;
mercury ones, used when the most accuracy is required; less accurate mechanical ones; and digital ones that can be used with
little training but that have limitations. When using a sphygmomanometer, the cuff is placed around the upper arm and inflated
until blood flow is completely blocked, then slowly released. As the heart beats, blood forced through the arteries causes a rise
in pressure. This rise in pressure at which blood flow begins is the systolic pressure—the peak pressure in the cardiac cycle.
When the cuff’s pressure equals the arterial systolic pressure, blood flows past the cuff, creating audible sounds that can be
heard using a stethoscope. This is followed by a decrease in pressure as the heart’s ventricles prepare for another beat. As cuff
pressure continues to decrease, eventually sound is no longer heard; this is the diastolic pressure—the lowest pressure (resting
phase) in the cardiac cycle. Blood pressure units from a sphygmomanometer are in terms of millimeters of mercury (mm Hg).
Figure 9.6 (a) A medical technician prepares to measure a patient’s blood pressure with a sphygmomanometer. (b) A typical
sphygmomanometer uses a valved rubber bulb to inflate the cuff and a diaphragm gauge to measure pressure. (credit a:
modification of work by Master Sgt. Jeffrey Allen)

9.2.0.0.1: Meteorology, Climatology, and Atmospheric Science
Throughout the ages, people have observed clouds, winds, and precipitation, trying to discern patterns and make predictions:
when it is best to plant and harvest; whether it is safe to set out on a sea voyage; and much more. We now face complex
weather and atmosphere-related challenges that will have a major impact on our civilization and the ecosystem. Several
different scientific disciplines use chemical principles to help us better understand weather, the atmosphere, and climate. These
are meteorology, climatology, and atmospheric science. Meteorology is the study of the atmosphere, atmospheric phenomena,
and atmospheric effects on earth’s weather. Meteorologists seek to understand and predict the weather in the short term, which
can save lives and benefit the economy. Weather forecasts (Figure 9.7) are the result of thousands of measurements of air
pressure, temperature, and the like, which are compiled, modeled, and analyzed in weather centers worldwide.

Figure 9.7 Meteorologists use weather maps to describe and predict weather. Regions of high (H) and low (L) pressure have
large effects on weather conditions. The gray lines represent locations of constant pressure known as isobars. (credit:
modification of work by National Oceanic and Atmospheric Administration)
In terms of weather, low-pressure systems occur when the earth’s surface atmospheric pressure is lower than the surrounding
environment: Moist air rises and condenses, producing clouds. Movement of moisture and air within various weather fronts
instigates most weather events.
The atmosphere is the gaseous layer that surrounds a planet. Earth’s atmosphere, which is roughly 100–125 km thick, consists
of roughly 78.1% nitrogen and 21.0% oxygen, and can be subdivided further into the regions shown in Figure 9.8: the
exosphere (furthest from earth, > 700 km above sea level), the thermosphere (80–700 km), the mesosphere (50–80 km), the
stratosphere (second lowest level of our atmosphere, 12–50 km above sea level), and the troposphere (up to 12 km above sea
level, roughly 80% of the earth’s atmosphere by mass and the layer where most weather events originate). As you go higher in
the troposphere, air density and temperature both decrease.

Figure 9.8 Earth’s atmosphere has five layers: the troposphere, the stratosphere, the mesosphere, the thermosphere, and the
exosphere.
Climatology is the study of the climate, averaged weather conditions over long time periods, using atmospheric data. However,
climatologists study patterns and effects that occur over decades, centuries, and millennia, rather than shorter time frames of
hours, days, and weeks like meteorologists. Atmospheric science is an even broader field, combining meteorology,
climatology, and other scientific disciplines that study the atmosphere.
This page titled 9.2: Gas Pressure is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content


Identify the mathematical relationships between the various properties of gases
Use the ideal gas law, and related gas laws, to compute the values of various gas properties under specified conditions
During the seventeenth and especially eighteenth centuries, driven both by a desire to understand nature and a quest to make
balloons in which they could fly (Figure 9.9), a number of scientists established the relationships between the macroscopic physical
properties of gases, that is, pressure, volume, temperature, and amount of gas. Although their measurements were not precise by
today’s standards, they were able to determine the mathematical relationships between pairs of these variables (e.g., pressure and
temperature, pressure and volume) that hold for an ideal gas—a hypothetical construct that real gases approximate under certain
conditions. Eventually, these individual laws were combined into a single equation—the ideal gas law—that relates gas quantities
for gases and is quite accurate for low pressures and moderate temperatures. We will consider the key developments in individual
relationships (for pedagogical reasons not quite in historical order), then put them together in the ideal gas law.
Figure 9.9 In 1783, the first (a) hydrogen-filled balloon flight, (b) manned hot air balloon flight, and (c) manned hydrogen-filled
balloon flight occurred. When the hydrogen-filled balloon depicted in (a) landed, the frightened villagers of Gonesse reportedly
destroyed it with pitchforks and knives. The launch of the latter was reportedly viewed by 400,000 people in Paris.
9.3.0.1: Pressure and Temperature: Amontons’s Law

Imagine filling a rigid container attached to a pressure gauge with gas and then sealing the container so that no gas may escape. If
the container is cooled, the gas inside likewise gets colder and its pressure is observed to decrease. Since the container is rigid and
tightly sealed, both the volume and number of moles of gas remain constant. If we heat the sphere, the gas inside gets hotter (Figure
9.10) and the pressure increases.

Figure 9.10 The effect of temperature on gas pressure: When the hot plate is off, the pressure of the gas in the sphere is relatively
low. As the gas is heated, the pressure of the gas in the sphere increases.
This relationship between temperature and pressure is observed for any sample of gas confined to a constant volume. An example
of experimental pressure-temperature data is shown for a sample of air under these conditions in Figure 9.11. We find that
temperature and pressure are linearly related, and if the temperature is on the kelvin scale, then P and T are directly proportional
(again, when volume and moles of gas are held constant); if the temperature on the kelvin scale increases by a certain factor, the
gas pressure increases by the same factor.

Figure 9.11 For a constant volume and amount of air, the pressure and temperature are directly proportional, provided the
temperature is in kelvin. (Measurements cannot be made at lower temperatures because of the condensation of the gas.) When this
line is extrapolated to lower pressures, it reaches a pressure of 0 at –273 °C, which is 0 on the kelvin scale and the lowest possible
temperature, called absolute zero.
Guillaume Amontons was the first to empirically establish the relationship between the pressure and the temperature of a gas
(~1700), and Joseph Louis Gay-Lussac determined the relationship more precisely (~1800). Because of this, the P-T relationship
for gases is known as either Amontons’s law or Gay-Lussac’s law. Under either name, it states that the pressure of a given amount
of gas is directly proportional to its temperature on the kelvin scale when the volume is held constant. Mathematically, this can be
written:
P ∝ T or P = constant × T or P = k × T
where ∝ means “is proportional to,” and k is a proportionality constant that depends on the identity, amount, and volume of the gas.
For a confined, constant volume of gas, the ratio P
T
is therefore constant (i.e., P
T
=k ). If the gas is initially in “Condition 1” (with
P1 P2
P = P1 and T = T1), and then changes to “Condition 2” (with P = P2 and T = T2), we have that T1
=k and T2
= k, which reduces
P1 P2
to T1
=
T2
. This equation is useful for pressure-temperature calculations for a confined gas at constant volume. Note that
temperatures must be on the kelvin scale for any gas law calculations (0 on the kelvin scale and the lowest possible temperature is
called absolute zero). (Also note that there are at least three ways we can describe how the pressure of a gas changes as its
temperature changes: We can use a table of values, a graph, or a mathematical equation.)
9.3.0.1: Example 9.5

9.3.0.0.1: Predicting Change in Pressure with Temperature
A can of hair spray is used until it is empty except for the propellant, isobutane gas.
(a) On the can is the warning “Store only at temperatures below 120 °F (48.8 °C). Do not incinerate.” Why?
(b) The gas in the can is initially at 24 °C and 360 kPa, and the can has a volume of 350 mL. If the can is left in a car that
reaches 50 °C on a hot day, what is the new pressure in the can?

9.3.0.0.2: Solution
(a) The can contains an amount of isobutane gas at a constant volume, so if the temperature is increased by heating, the
pressure will increase proportionately. High temperature could lead to high pressure, causing the can to burst. (Also, isobutane
is combustible, so incineration could cause the can to explode.)
(b) We are looking for a pressure change due to a temperature change at constant volume, so we will use Amontons’s/Gay-
Lussac’s law. Taking P1 and T1 as the initial values, T2 as the temperature where the pressure is unknown and P2 as the
unknown pressure, and converting °C to K, we have:
P1 P2 360 kPa P2
= which means that =
T1 T2 297 K 323 K
360 kPa × 323 K

Rearranging and solving gives: P 2 = = 390 kPa
297 K

A sample of nitrogen, N2, occupies 45.0 mL at 27 °C and 600 torr. What pressure will it have if cooled to –73 °C while the
volume remains constant?
9.3.0.1: Answer:
400 torr
9.3.0.1: Volume and Temperature: Charles’s Law

If we fill a balloon with air and seal it, the balloon contains a specific amount of air at atmospheric pressure, let’s say 1 atm. If we
put the balloon in a refrigerator, the gas inside gets cold and the balloon shrinks (although both the amount of gas and its pressure
remain constant). If we make the balloon very cold, it will shrink a great deal, and it expands again when it warms up.

This video shows how cooling and heating a gas causes its volume to decrease or increase, respectively.
These examples of the effect of temperature on the volume of a given amount of a confined gas at constant pressure are true in
general: The volume increases as the temperature increases, and decreases as the temperature decreases. Volume-temperature data
for a 1-mole sample of methane gas at 1 atm are listed and graphed in Figure 9.12.
Figure 9.12 The volume and temperature are linearly related for 1 mole of methane gas at a constant pressure of 1 atm. If the
temperature is in kelvin, volume and temperature are directly proportional. The line stops at 111 K because methane liquefies at
this temperature; when extrapolated, it intersects the graph’s origin, representing a temperature of absolute zero.
The relationship between the volume and temperature of a given amount of gas at constant pressure is known as Charles’s law in
recognition of the French scientist and balloon flight pioneer Jacques Alexandre César Charles. Charles’s law states that the volume
of a given amount of gas is directly proportional to its temperature on the kelvin scale when the pressure is held constant.

Mathematically, this can be written as:
V α T or V = constant⋅T or V = k⋅T or V1 / T1 = V2 / T2
with k being a proportionality constant that depends on the amount and pressure of the gas.
For a confined, constant pressure gas sample, V
T
is constant (i.e., the ratio = k), and as seen with the P-T relationship, this leads to
V1 V2
another form of Charles’s law: T1
=
T2
.
9.3.0.1: Example 9.6

9.3.0.0.1: Predicting Change in Volume with Temperature
A sample of carbon dioxide, CO2, occupies 0.300 L at 10 °C and 750 torr. What volume will the gas have at 30 °C and 750
torr?
9.3.0.0.2: Solution
Because we are looking for the volume change caused by a temperature change at constant pressure, this is a job for Charles’s
law. Taking V1 and T1 as the initial values, T2 as the temperature at which the volume is unknown and V2 as the unknown
volume, and converting °C into K we have:
V1 V2 0.300 L V2
T1 T2 283 K 303 K
0.300 L × 303 K
Rearranging and solving gives: V 2 = = 0.321 L
283 K
This answer supports our expectation from Charles’s law, namely, that raising the gas temperature (from 283 K to 303 K) at a
constant pressure will yield an increase in its volume (from 0.300 L to 0.321 L).
A sample of oxygen, O2, occupies 32.2 mL at 30 °C and 452 torr. What volume will it occupy at –70 °C and the same
pressure?
9.3.0.1: Answer:
21.6 mL
9.3.0.1: Example 9.7

9.3.0.0.4: Measuring Temperature with a Volume Change
Temperature is sometimes measured with a gas thermometer by observing the change in the volume of the gas as the
temperature changes at constant pressure. The hydrogen in a particular hydrogen gas thermometer has a volume of 150.0 cm3
when immersed in a mixture of ice and water (0.00 °C). When immersed in boiling liquid ammonia, the volume of the
hydrogen, at the same pressure, is 131.7 cm3. Find the temperature of boiling ammonia on the kelvin and Celsius scales.
9.3.0.0.5: Solution
A volume change caused by a temperature change at constant pressure means we should use Charles’s law. Taking V1 and T1 as
the initial values, T2 as the temperature at which the volume is unknown and V2 as the unknown volume, and converting °C
into K we have:
3 3
V1 V2 150.0 cm 131.7 cm
T1 T2 273.15 K T2
3
131.7 cm × 273.15 K
Rearrangement gives T 2 =
3
= 239.8 K
150.0 cm
Subtracting 273.15 from 239.8 K, we find that the temperature of the boiling ammonia on the Celsius scale is –33.4 °C.
What is the volume of a sample of ethane at 467 K and 1.1 atm if it occupies 405 mL at 298 K and 1.1 atm?
9.3.0.1: Answer:
635 mL

9.3.0.1: Volume and Pressure: Boyle’s Law
If we partially fill an airtight syringe with air, the syringe contains a specific amount of air at constant temperature, say 25 °C. If we
slowly push in the plunger while keeping temperature constant, the gas in the syringe is compressed into a smaller volume and its
pressure increases; if we pull out the plunger, the volume increases and the pressure decreases. This example of the effect of
volume on the pressure of a given amount of a confined gas is true in general. Decreasing the volume of a contained gas will
increase its pressure, and increasing its volume will decrease its pressure. In fact, if the volume increases by a certain factor, the
pressure decreases by the same factor, and vice versa. Volume-pressure data for an air sample at room temperature are graphed in
Figure 9.13.
Figure 9.13 When a gas occupies a smaller volume, it exerts a higher pressure; when it occupies a larger volume, it exerts a lower
pressure (assuming the amount of gas and the temperature do not change). Since P and V are inversely proportional, a graph of 1
vs. V is linear.
Unlike the P-T and V-T relationships, pressure and volume are not directly proportional to each other. Instead, P and V exhibit
inverse proportionality: Increasing the pressure results in a decrease of the volume of the gas. Mathematically this can be written:
P α 1/V or P = k⋅1/V or P ⋅V = k or P1 V1 = P2 V2

with k being a constant. Graphically, this relationship is shown by the straight line that results when plotting the inverse of the
pressure ( ) versus the volume (V), or the inverse of volume ( ) versus the pressure (P). Graphs with curved lines are difficult
P
1
V
1
to read accurately at low or high values of the variables, and they are more difficult to use in fitting theoretical equations and
parameters to experimental data. For those reasons, scientists often try to find a way to “linearize” their data. If we plot P versus V,
we obtain a hyperbola (see Figure 9.14).
Figure 9.14 The relationship between pressure and volume is inversely proportional. (a) The graph of P vs. V is a hyperbola,
whereas (b) the graph of ( ) vs. V is linear.
1
The relationship between the volume and pressure of a given amount of gas at constant temperature was first published by the
English natural philosopher Robert Boyle over 300 years ago. It is summarized in the statement now known as Boyle’s law: The
volume of a given amount of gas held at constant temperature is inversely proportional to the pressure under which it is measured.
9.3.0.1: Example 9.8

9.3.0.0.1: Volume of a Gas Sample
The sample of gas in Figure 9.13 has a volume of 15.0 mL at a pressure of 13.0 psi. Determine the pressure of the gas at a
volume of 7.5 mL, using:
(a) the P-V graph in Figure 9.13
(b) the 1
P
vs. V graph in Figure 9.13
(c) the Boyle’s law equation
Comment on the likely accuracy of each method.
9.3.0.0.2: Solution
(a) Estimating from the P-V graph gives a value for P somewhere around 27 psi.
(b) Estimating from the 1
P
versus V graph give a value of about 26 psi.
(c) From Boyle’s law, we know that the product of pressure and volume (PV) for a given sample of gas at a constant
temperature is always equal to the same value. Therefore we have P1V1 = k and P2V2 = k which means that P1V1 = P2V2.
Using P1 and V1 as the known values 13.0 psi and 15.0 mL, P2 as the pressure at which the volume is unknown, and V2 as the
unknown volume, we have:
P1 V1 = P2 V2 or 13.0 psi × 15.0 mL = P2 × 7.5 mL
Solving:
13.0 psi × 15.0 mL

P2 = = 26 psi
7.5 mL
It was more difficult to estimate well from the P-V graph, so (a) is likely more inaccurate than (b) or (c). The calculation will
be as accurate as the equation and measurements allow.

The sample of gas in Figure 9.13 has a volume of 30.0 mL at a pressure of 6.5 psi. Determine the volume of the gas at a
pressure of 11.0 psi, using:
(a) the P-V graph in Figure 9.13
(b) the 1
P
vs. V graph in Figure 9.13
(c) the Boyle’s law equation
Comment on the likely accuracy of each method.
9.3.0.1: Answer:
(a) about 17–18 mL; (b) ~18 mL; (c) 17.7 mL; it was more difficult to estimate well from the P-V graph, so (a) is likely
more inaccurate than (b); the calculation will be as accurate as the equation and measurements allow

9.3.0.0.4: Breathing and Boyle’s Law
What do you do about 20 times per minute for your whole life, without break, and often without even being aware of it? The
answer, of course, is respiration, or breathing. How does it work? It turns out that the gas laws apply here. Your lungs take in
gas that your body needs (oxygen) and get rid of waste gas (carbon dioxide). Lungs are made of spongy, stretchy tissue that
expands and contracts while you breathe. When you inhale, your diaphragm and intercostal muscles (the muscles between your
ribs) contract, expanding your chest cavity and making your lung volume larger. The increase in volume leads to a decrease in
pressure (Boyle’s law). This causes air to flow into the lungs (from high pressure to low pressure). When you exhale, the
process reverses: Your diaphragm and rib muscles relax, your chest cavity contracts, and your lung volume decreases, causing
the pressure to increase (Boyle’s law again), and air flows out of the lungs (from high pressure to low pressure). You then
breathe in and out again, and again, repeating this Boyle’s law cycle for the rest of your life (Figure 9.15).

Figure 9.15 Breathing occurs because expanding and contracting lung volume creates small pressure differences between your
lungs and your surroundings, causing air to be drawn into and forced out of your lungs.
9.3.0.1: Moles of Gas and Volume: Avogadro’s Law

The Italian scientist Amedeo Avogadro advanced a hypothesis in 1811 to account for the behavior of gases, stating that equal
volumes of all gases, measured under the same conditions of temperature and pressure, contain the same number of molecules.
Over time, this relationship was supported by many experimental observations as expressed by Avogadro’s law: For a confined
gas, the volume (V) and number of moles (n) are directly proportional if the pressure and temperature both remain constant.
In equation form, this is written as:
V1 V2
V ∝n or V =k × n or =
n1 n2
Mathematical relationships can also be determined for the other variable pairs, such as P versus n, and n versus T.

Visit this interactive PhET simulation to investigate the relationships between pressure, volume, temperature, and amount of
gas. Use the simulation to examine the effect of changing one parameter on another while holding the other parameters
constant (as described in the preceding sections on the various gas laws).
9.3.0.1: The Ideal Gas Law

To this point, four separate laws have been discussed that relate pressure, volume, temperature, and the number of moles of the gas:
Boyle’s law: PV = constant at constant T and n
Amontons’s law: = constant at constant V and n
P
Charles’s law: = constant at constant P and n

V
Avogadro’s law: = constant at constant P and T

V
Combining these four laws yields the ideal gas law, a relation between the pressure, volume, temperature, and number of moles of
a gas:
P V = nRT
where P is the pressure of a gas, V is its volume, n is the number of moles of the gas, T is its temperature on the kelvin scale, and R
is a constant called the ideal gas constant or the universal gas constant. The units used to express pressure, volume, and temperature
will determine the proper form of the gas constant as required by dimensional analysis, the most commonly encountered values
being 0.08206 L atm mol–1 K–1 and 8.314 kPa L mol–1 K–1.
Gases whose properties of P, V, and T are accurately described by the ideal gas law (or the other gas laws) are said to exhibit ideal
behavior or to approximate the traits of an ideal gas. An ideal gas is a hypothetical construct that may be used along with kinetic
molecular theory to effectively explain the gas laws as will be described in a later module of this chapter. Although all the
calculations presented in this module assume ideal behavior, this assumption is only reasonable for gases under conditions of
relatively low pressure and high temperature. In the final module of this chapter, a modified gas law will be introduced that
accounts for the non-ideal behavior observed for many gases at relatively high pressures and low temperatures.
The ideal gas equation contains five terms, the gas constant R and the variable properties P, V, n, and T. Specifying any four of
these terms will permit use of the ideal gas law to calculate the fifth term as demonstrated in the following example exercises.
9.3.0.1: Example 9.9

9.3.0.0.1: Using the Ideal Gas Law
Methane, CH4, is being considered for use as an alternative automotive fuel to replace gasoline. One gallon of gasoline could
be replaced by 655 g of CH4. What is the volume of this much methane at 25 °C and 745 torr?

9.3.0.0.2: Solution
We must rearrange PV = nRT to solve for V: V =
nRT
–1 –1
If we choose to use R = 0.08206 L atm mol K , then the amount must be in moles, temperature must be in kelvin, and
pressure must be in atm.
Converting into the “right” units:
1 mol
n = 6 55 g CH4 × = 40.8 mol
16.043 g CH
4
T = 25 °C + 273 = 298 K
1 atm
P = 745 torr × = 0.980 atm
760 torr
–1 –1
nRT (40.8 mol )(0.08206 L atm mol K )(298 K )
3
V = = = 1.02 × 10 L
P 0.980 atm
It would require 1020 L (269 gal) of gaseous methane at about 1 atm of pressure to replace 1 gal of gasoline. It requires a large
container to hold enough methane at 1 atm to replace several gallons of gasoline.
Calculate the pressure in bar of 2520 moles of hydrogen gas stored at 27 °C in the 180-L storage tank of a modern hydrogen-
powered car.
9.3.0.1: Answer:
350 bar
If the number of moles of an ideal gas are kept constant under two different sets of conditions, a useful mathematical relationship
P1 V1 P2 V2
called the combined gas law is obtained: =
T1
using units of atm, L, and K. Both sets of conditions are equal to the
T2
product of n × R (where n = the number of moles of the gas and R is the ideal gas law constant).
9.3.0.1: Example 9.10

9.3.0.0.4: Using the Combined Gas Law
When filled with air, a typical scuba tank with a volume of 13.2 L has a pressure of 153 atm (Figure 9.16). If the water
temperature is 27 °C, how many liters of air will such a tank provide to a diver’s lungs at a depth of approximately 70 feet in
the ocean where the pressure is 3.13 atm?

Figure 9.16 Scuba divers use compressed air to breathe while underwater. (credit: modification of work by Mark Goodchild)
Letting 1 represent the air in the scuba tank and 2 represent the air in the lungs, and noting that body temperature (the
temperature the air will be in the lungs) is 37 °C, we have:
P1 V1 P2 V2 (153 atm) (13.2 L) (3.13 atm) (V2 )

= ⟶ =
T1 T2 (300 K) (310 K)
Solving for V2:
(153 atm ) (13.2 L) (310 K )
V2 = = 667 L
(300 K ) (3.13 atm )
(Note: Be advised that this particular example is one in which the assumption of ideal gas behavior is not very reasonable,
since it involves gases at relatively high pressures and low temperatures. Despite this limitation, the calculated volume can be
viewed as a good “ballpark” estimate.)
A sample of ammonia is found to occupy 0.250 L under laboratory conditions of 27 °C and 0.850 atm. Find the volume of this
sample at 0 °C and 1.00 atm.
9.3.0.1: Answer:
0.193 L

9.3.0.0.6: The Interdependence between Ocean Depth and Pressure in Scuba Diving
Whether scuba diving at the Great Barrier Reef in Australia (shown in Figure 9.17) or in the Caribbean, divers must understand
how pressure affects a number of issues related to their comfort and safety.
Figure 9.17 Scuba divers, whether at the Great Barrier Reef or in the Caribbean, must be aware of buoyancy, pressure
equalization, and the amount of time they spend underwater, to avoid the risks associated with pressurized gases in the body.
(credit: Kyle Taylor)
Pressure increases with ocean depth, and the pressure changes most rapidly as divers reach the surface. The pressure a diver
experiences is the sum of all pressures above the diver (from the water and the air). Most pressure measurements are given in
units of atmospheres, expressed as “atmospheres absolute” or ATA in the diving community: Every 33 feet of salt water
represents 1 ATA of pressure in addition to 1 ATA of pressure from the atmosphere at sea level. As a diver descends, the

increase in pressure causes the body’s air pockets in the ears and lungs to compress; on the ascent, the decrease in pressure
causes these air pockets to expand, potentially rupturing eardrums or bursting the lungs. Divers must therefore undergo
equalization by adding air to body airspaces on the descent by breathing normally and adding air to the mask by breathing out
of the nose or adding air to the ears and sinuses by equalization techniques; the corollary is also true on ascent, divers must
release air from the body to maintain equalization. Buoyancy, or the ability to control whether a diver sinks or floats, is
controlled by the buoyancy compensator (BCD). If a diver is ascending, the air in their BCD expands because of lower
pressure according to Boyle’s law (decreasing the pressure of gases increases the volume). The expanding air increases the
buoyancy of the diver, and they begin to ascend. The diver must vent air from the BCD or risk an uncontrolled ascent that
could rupture the lungs. In descending, the increased pressure causes the air in the BCD to compress and the diver sinks much
more quickly; the diver must add air to the BCD or risk an uncontrolled descent, facing much higher pressures near the ocean
floor. The pressure also impacts how long a diver can stay underwater before ascending. The deeper a diver dives, the more
compressed the air that is breathed because of increased pressure: If a diver dives 33 feet, the pressure is 2 ATA and the air
would be compressed to one-half of its original volume. The diver uses up available air twice as fast as at the surface.
9.3.0.1: Standard Conditions of Temperature and Pressure

We have seen that the volume of a given quantity of gas and the number of molecules (moles) in a given volume of gas vary with
changes in pressure and temperature. Chemists sometimes make comparisons against a standard temperature and pressure (STP)
for reporting properties of gases: 273.15 K and 1 atm (101.325 kPa).1 At STP, one mole of an ideal gas has a volume of about 22.4
L—this is referred to as the standard molar volume (Figure 9.18).
Figure 9.18 Regardless of its chemical identity, one mole of gas behaving ideally occupies a volume of ~22.4 L at STP.
9.3.0.1: Footnotes
1The IUPAC definition of standard pressure was changed from 1 atm to 1 bar (100 kPa) in 1982, but the prior definition
remains in use by many literature resources and will be used in this text.
This page titled 9.3: Relating Pressure, Volume, Amount, and Temperature - The Ideal Gas Law is shared under a CC BY 4.0 license and was
authored, remixed, and/or curated by OpenStax via source content that was edited to the style and standards of the LibreTexts platform; a detailed
edit history is available upon request.


Use the ideal gas law to compute gas densities and molar masses
Perform stoichiometric calculations involving gaseous substances
State Dalton’s law of partial pressures and use it in calculations involving gaseous mixtures
The study of the chemical behavior of gases was part of the basis of perhaps the most fundamental chemical revolution in history.
French nobleman Antoine Lavoisier, widely regarded as the “father of modern chemistry,” changed chemistry from a qualitative to
a quantitative science through his work with gases. He discovered the law of conservation of matter, discovered the role of oxygen
in combustion reactions, determined the composition of air, explained respiration in terms of chemical reactions, and more. He was
a casualty of the French Revolution, guillotined in 1794. Of his death, mathematician and astronomer Joseph-Louis Lagrange said,
“It took the mob only a moment to remove his head; a century will not suffice to reproduce it.”2 Much of the knowledge we do
have about Lavoisier's contributions is due to his wife, Marie-Anne Paulze Lavoisier, who worked with him in his lab. A trained
artist fluent in several languages, she created detailed illustrations of the equipment in his lab, and translated texts from foreign
scientists to complement his knowledge. After his execution, she was instrumental in publishing Lavoisier's major treatise, which
unified many concepts of chemistry and laid the groundwork for significant further study.
As described in an earlier chapter of this text, we can turn to chemical stoichiometry for answers to many of the questions that ask
“How much?” The essential property involved in such use of stoichiometry is the amount of substance, typically measured in moles
(n). For gases, molar amount can be derived from convenient experimental measurements of pressure, temperature, and volume.
Therefore, these measurements are useful in assessing the stoichiometry of pure gases, gas mixtures, and chemical reactions
involving gases. This section will not introduce any new material or ideas, but will provide examples of applications and ways to
integrate concepts already discussed.
9.4.0.1: Gas Density and Molar Mass

The ideal gas law described previously in this chapter relates the properties of pressure P, volume V, temperature T, and molar
amount n. This law is universal, relating these properties in identical fashion regardless of the chemical identity of the gas:
P V = nRT
The density d of a gas, on the other hand, is determined by its identity. As described in another chapter of this text, the density of a
substance is a characteristic property that may be used to identify the substance.
m
d =
V
Rearranging the ideal gas equation to isolate V and substituting into the density equation yields
mP m P
d = =( )
nRT n RT
The ratio m/n is the definition of molar mass, ℳ:

m
M =
n
The density equation can then be written

MP
d =
RT
This relation may be used for calculating the densities of gases of known identities at specified values of pressure and temperature
as demonstrated in Example 9.11.
9.4.0.1: Example 9.11

9.4.0.0.1: Measuring Gas Density
What is the density of molecular nitrogen gas at STP?
9.4.0.0.2: Solution
The molar mass of molecular nitrogen, N2, is 28.01 g/mol. Substituting this value along with standard temperature and pressure
into the gas density equation yields
MP (28.01 g/mol)(1.00 atm)

d = = = 1.25 g/L
−1 −1
RT (0.0821 L⋅atm⋅mol K )(273 K)

What is the density of molecular hydrogen gas at 17.0 °C and a pressure of 760 torr?
9.4.0.1: Answer:
d = 0.0847 g/L
When the identity of a gas is unknown, measurements of the mass, pressure, volume, and temperature of a sample can be used to
calculate the molar mass of the gas (a useful property for identification purposes). Combining the ideal gas equation
P V = nRT
and the definition of molar mass

m
M =
n
yields the following equation:

mRT
M =
PV
Determining the molar mass of a gas via this approach is demonstrated in Example 9.12.
9.4.0.1: Example 9.12

9.4.0.0.4: Determining the Molecular Formula of a Gas from its Molar Mass and Empirical Formula
Cyclopropane, a gas once used with oxygen as a general anesthetic, is composed of 85.7% carbon and 14.3% hydrogen by
mass. Find the empirical formula. If 1.56 g of cyclopropane occupies a volume of 1.00 L at 0.984 atm and 50 °C, what is the
molecular formula for cyclopropane?
9.4.0.0.5: Solution
First determine the empirical formula of the gas. Assume 100 g and convert the percentage of each element into grams.
Determine the number of moles of carbon and hydrogen in the 100-g sample of cyclopropane. Divide by the smallest number
of moles to relate the number of moles of carbon to the number of moles of hydrogen. In the last step, realize that the smallest
whole number ratio is the empirical formula:
1 mol C 7.136
85.7 g C × = 7.136 mol C = 1.00 mol C
12.01 g C 7.136
1 mol H 14.158
14.3 g H × = 14.158 mol H = 1.98 mol H
1.01 g H 7.136
Empirical formula is CH2 [empirical mass (EM) of 14.03 g/empirical unit].

Next, use the provided values for mass, pressure, temperature and volume to compute the molar mass of the gas:
−1 −1
mRT (1.56 g)(0.0821 L⋅atm⋅mol K )(323 K)
M = = = 42.0 g/mol
PV (0.984 atm)(1.00 L)
Comparing the molar mass to the empirical formula mass shows how many empirical formula units make up a molecule:
M 42.0 g/mol
= =3
EM 14.0 g/mol

The molecular formula is thus derived from the empirical formula by multiplying each of its subscripts by three:
(CH2 ) = C3 H6
3

Acetylene, a fuel used welding torches, is composed of 92.3% C and 7.7% H by mass. Find the empirical formula. If 1.10 g of
acetylene occupies of volume of 1.00 L at 1.15 atm and 59.5 °C, what is the molecular formula for acetylene?
9.4.0.1: Answer:
Empirical formula, CH; Molecular formula, C2H2
9.4.0.1: Example 9.13

9.4.0.0.7: Determining the Molar Mass of a Volatile Liquid
The approximate molar mass of a volatile liquid can be determined by:
1. Heating a sample of the liquid in a flask with a tiny hole at the top, which converts the liquid into gas that may escape
through the hole
2. Removing the flask from heat at the instant when the last bit of liquid becomes gas, at which time the flask will be filled
with only gaseous sample at ambient pressure
3. Sealing the flask and permitting the gaseous sample to condense to liquid, and then weighing the flask to determine the
sample’s mass (see Figure 9.19)
Figure 9.19 When the volatile liquid in the flask is heated past its boiling point, it becomes gas and drives air out of the flask.
At tl ⟶ g , the flask is filled with volatile liquid gas at the same pressure as the atmosphere. If the flask is then cooled to room
temperature, the gas condenses and the mass of the gas that filled the flask, and is now liquid, can be measured. (credit:
modification of work by Mark Ott)
Using this procedure, a sample of chloroform gas weighing 0.494 g is collected in a flask with a volume of 129 cm3 at 99.6 °C
when the atmospheric pressure is 742.1 mm Hg. What is the approximate molar mass of chloroform?
9.4.0.0.8: Solution
Since M = m
n
and n = PV
RT
, substituting and rearranging gives M = mRT
PV
,
then
mRT (0.494 g) × 0.08206 L⋅atm/mol K × 372.8 K

M= = = 120 g/mol.
PV 0.976 atm × 0.129 L

A sample of phosphorus that weighs 3.243 × 10−2 g exerts a pressure of 31.89 kPa in a 56.0-mL bulb at 550 °C. What are the
molar mass and molecular formula of phosphorus vapor?
9.4.0.1: Answer:
124 g/mol P4
9.4.0.1: The Pressure of a Mixture of Gases: Dalton’s Law

Unless they chemically react with each other, the individual gases in a mixture of gases do not affect each other’s pressure. Each
individual gas in a mixture exerts the same pressure that it would exert if it were present alone in the container (Figure 9.20). The

pressure exerted by each individual gas in a mixture is called its partial pressure. This observation is summarized by Dalton’s law
of partial pressures: The total pressure of a mixture of ideal gases is equal to the sum of the partial pressures of the component
gases:
PT otal = PA + PB + PC + ... = Σi Pi
In the equation PTotal is the total pressure of a mixture of gases, PA is the partial pressure of gas A; PB is the partial pressure of gas
B; PC is the partial pressure of gas C; and so on.
Figure 9.20 If equal-volume cylinders containing gasses at pressures of 300 kPa, 450 kPa, and 600 kPa are all combined in the
same-size cylinder, the total pressure of the gas mixture is 1350 kPa.
The partial pressure of gas A is related to the total pressure of the gas mixture via its mole fraction (X), a unit of concentration
defined as the number of moles of a component of a solution divided by the total number of moles of all components:
nA
PA = XA × PT otal where XA =
nT otal
where PA, XA, and nA are the partial pressure, mole fraction, and number of moles of gas A, respectively, and nTotal is the number of
moles of all components in the mixture.
9.4.0.1: Example 9.14

9.4.0.0.1: The Pressure of a Mixture of Gases
A 10.0-L vessel contains 2.50 × 10−3 mol of H2, 1.00 × 10−3 mol of He, and 3.00 × 10−4 mol of Ne at 35 °C.
(a) What are the partial pressures of each of the gases?
(b) What is the total pressure in atmospheres?
9.4.0.0.2: Solution
The gases behave independently, so the partial pressure of each gas can be determined from the ideal gas equation, using
P =
nRT
V
:
−3 −1 −1
(2.50 × 10 mol ) (0.08206 L atm mol K ) (308 K )
−3
PH = = 6.32 × 10 atm
2
10.0 L
−3 −1 −1
(1.00 × 10 mol ) (0.08206 L atm mol K ) (308 K )
−3
PHe = = 2.53 × 10 atm
10.0 L

−4 −1 −1
(3.00 × 10 mol ) (0.08206 L atm mol K ) (308 K )
−4
PNe = = 7.58 × 10 atm
10.0 L
The total pressure is given by the sum of the partial pressures:

−3
PT = PH2 + PHe + PNe = (0.00632 + 0.00253 + 0.00076) atm = 9.61 × 10 atm

A 5.73-L flask at 25 °C contains 0.0388 mol of N2, 0.147 mol of CO, and 0.0803 mol of H2. What is the total pressure in the
flask in atmospheres?
9.4.0.1: Answer:
1.137 atm
Here is another example of this concept, but dealing with mole fraction calculations.
9.4.0.1: Example 9.15

9.4.0.0.4: The Pressure of a Mixture of Gases
A gas mixture used for anesthesia contains 2.83 mol oxygen, O2, and 8.41 mol nitrous oxide, N2O. The total pressure of the
mixture is 192 kPa.
(a) What are the mole fractions of O2 and N2O?
(b) What are the partial pressures of O2 and N2O?
9.4.0.0.5: Solution
nA
The mole fraction is given by X A =
nTot al
and the partial pressure is PA = XA × PTotal.
For O2,
nO 2.83 mol
2
XO2 = = = 0.252
nT otal (2.83 + 8.41) mol
and P O2 = XO2 × PT otal = 0.252 × 192 kPa = 48.4 kPa
For N2O,
nN2 O 8.41 mol
XN O = = = 0.748
2
nTotal (2.83 + 8.41) mol
and
PN2 O = XN2 O × PTotal = 0.748 × 192 kPa = 144 kPa

What is the pressure of a mixture of 0.200 g of H2, 1.00 g of N2, and 0.820 g of Ar in a container with a volume of 2.00 L at 20
°C?
9.4.0.1: Answer:
1.87 atm
9.4.0.1: Collection of Gases over Water

A simple way to collect gases that do not react with water is to capture them in a bottle that has been filled with water and inverted
into a dish filled with water. The pressure of the gas inside the bottle can be made equal to the air pressure outside by raising or
lowering the bottle. When the water level is the same both inside and outside the bottle (Figure 9.21), the pressure of the gas is
equal to the atmospheric pressure, which can be measured with a barometer.

Figure 9.21 When a reaction produces a gas that is collected above water, the trapped gas is a mixture of the gas produced by the
reaction and water vapor. If the collection flask is appropriately positioned to equalize the water levels both within and outside the
flask, the pressure of the trapped gas mixture will equal the atmospheric pressure outside the flask (see the earlier discussion of
manometers).
However, there is another factor we must consider when we measure the pressure of the gas by this method. Water evaporates and
there is always gaseous water (water vapor) above a sample of liquid water. As a gas is collected over water, it becomes saturated
with water vapor and the total pressure of the mixture equals the partial pressure of the gas plus the partial pressure of the water
vapor. The pressure of the pure gas is therefore equal to the total pressure minus the pressure of the water vapor—this is referred to
as the “dry” gas pressure, that is, the pressure of the gas only, without water vapor. The vapor pressure of water, which is the
pressure exerted by water vapor in equilibrium with liquid water in a closed container, depends on the temperature (Figure 9.22);
more detailed information on the temperature dependence of water vapor can be found in Table 9.2, and vapor pressure will be
discussed in more detail in the next chapter on liquids.

Figure 9.22 This graph shows the vapor pressure of water at sea level as a function of temperature.
Vapor Pressure of Ice and Water in Various Temperatures at Sea Level
Temperature (°C) Pressure (torr) Temperature (°C) Pressure (torr) Temperature (°C) Pressure (torr)
–10 1.95 18 15.5 30 31.8
–5 3.0 19 16.5 35 42.2
–2 3.9 20 17.5 40 55.3
0 4.6 21 18.7 50 92.5
2 5.3 22 19.8 60 149.4
4 6.1 23 21.1 70 233.7
6 7.0 24 22.4 80 355.1
8 8.0 25 23.8 90 525.8
10 9.2 26 25.2 95 633.9
12 10.5 27 26.7 99 733.2
14 12.0 28 28.3 100.0 760.0
16 13.6 29 30.0 101.0 787.6
Table 9.2
9.4.0.1: Example 9.16

9.4.0.0.1: Pressure of a Gas Collected Over Water
If 0.200 L of argon is collected over water at a temperature of 26 °C and a pressure of 750 torr in a system like that shown in
Figure 9.21, what is the partial pressure of argon?
9.4.0.0.2: Solution
According to Dalton’s law, the total pressure in the bottle (750 torr) is the sum of the partial pressure of argon and the partial
pressure of gaseous water:
PT = PAr + PH O
2
Rearranging this equation to solve for the pressure of argon gives:

PAr = PT − PH O
2
The pressure of water vapor above a sample of liquid water at 26 °C is 25.2 torr (Appendix E), so:
PAr = 750 torr − 25.2 torr = 725 torr

A sample of oxygen collected over water at a temperature of 29.0 °C and a pressure of 764 torr has a volume of 0.560 L. What
volume would the dry oxygen from this sample have under the same conditions of temperature and pressure?
9.4.0.1: Answer:
0.537 L

9.4.0.1: Chemical Stoichiometry and Gases
Chemical stoichiometry describes the quantitative relationships between reactants and products in chemical reactions.
We have previously measured quantities of reactants and products using masses for solids and volumes in conjunction with the
molarity for solutions; now we can also use gas volumes to indicate quantities. If we know the volume, pressure, and temperature
of a gas, we can use the ideal gas equation to calculate how many moles of the gas are present. If we know how many moles of a
gas are involved, we can calculate the volume of a gas at any temperature and pressure.
9.4.0.1: Avogadro’s Law Revisited

Sometimes we can take advantage of a simplifying feature of the stoichiometry of gases that solids and solutions do not exhibit: All
gases that show ideal behavior contain the same number of molecules in the same volume (at the same temperature and pressure).
Thus, the ratios of volumes of gases involved in a chemical reaction are given by the coefficients in the equation for the reaction,
provided that the gas volumes are measured at the same temperature and pressure.
We can extend Avogadro’s law (that the volume of a gas is directly proportional to the number of moles of the gas) to chemical
reactions with gases: Gases combine, or react, in definite and simple proportions by volume, provided that all gas volumes are
measured at the same temperature and pressure. For example, since nitrogen and hydrogen gases react to produce ammonia gas
according to N (g) + 3H (g) ⟶ 2NH (g), a given volume of nitrogen gas reacts with three times that volume of hydrogen
2 2 3
gas to produce two times that volume of ammonia gas, if pressure and temperature remain constant.
The explanation for this is illustrated in Figure 9.23. According to Avogadro’s law, equal volumes of gaseous N2, H2, and NH3, at
the same temperature and pressure, contain the same number of molecules. Because one molecule of N2 reacts with three
molecules of H2 to produce two molecules of NH3, the volume of H2 required is three times the volume of N2, and the volume of
NH3 produced is two times the volume of N2.
Figure 9.23 One volume of N2 combines with three volumes of H2 to form two volumes of NH3.
9.4.0.1: Example 9.17

9.4.0.0.1: Reaction of Gases
Propane, C3H8(g), is used in gas grills to provide the heat for cooking. What volume of O2(g) measured at 25 °C and 760 torr is
required to react with 2.7 L of propane measured under the same conditions of temperature and pressure? Assume that the
propane undergoes complete combustion.

9.4.0.0.2: Solution
The ratio of the volumes of C3H8 and O2 will be equal to the ratio of their coefficients in the balanced equation for the reaction:
C3 H8 (g) + 5 O2 (g) ⟶ 3 CO2 (g) + 4 H2 O (l)
1 volume + 5 volumes 3 volumes + 4 volumes
From the equation, we see that one volume of C3H8 will react with five volumes of O2:
5 L O2
2.7 L C3 H8 × = 13.5 L O2
1 L C3 H8
A volume of 13.5 L of O2 will be required to react with 2.7 L of C3H8.

An acetylene tank for an oxyacetylene welding torch provides 9340 L of acetylene gas, C2H2, at 0 °C and 1 atm. How many
tanks of oxygen, each providing 7.00 × 103 L of O2 at 0 °C and 1 atm, will be required to burn the acetylene?
2 C2 H2 + 5 O2 ⟶ 4 CO2 + 2 H2 O
9.4.0.1: Answer:
3.34 tanks (2.34 × 104 L)
9.4.0.1: Example 9.18

9.4.0.0.4: Volumes of Reacting Gases
Ammonia is an important fertilizer and industrial chemical. Suppose that a volume of 683 billion cubic feet of gaseous
ammonia, measured at 25 °C and 1 atm, was manufactured. What volume of H2(g), measured under the same conditions, was
required to prepare this amount of ammonia by reaction with N2?
N2 (g) + 3 H2 (g) ⟶ 2 NH3 (g)
9.4.0.0.5: Solution
Because equal volumes of H2 and NH3 contain equal numbers of molecules and each three molecules of H2 that react produce
two molecules of NH3, the ratio of the volumes of H2 and NH3 will be equal to 3:2. Two volumes of NH3, in this case in units
of billion ft3, will be formed from three volumes of H2:
3
3
3 billion ft H2 3 3
683 billion ft NH3 × = 1.02 × 10 billion ft H2
3
2 billion ft NH3
The manufacture of 683 billion ft3 of NH3 required 1020 billion ft3 of H2. (At 25 °C and 1 atm, this is the volume of a cube
with an edge length of approximately 1.9 miles.)
What volume of O2(g) measured at 25 °C and 760 torr is required to react with 17.0 L of ethylene, C2H4(g), measured under
the same conditions of temperature and pressure? The products are CO2 and water vapor.
9.4.0.1: Answer:
51.0 L
9.4.0.1: Example 9.19

9.4.0.0.7: Volume of Gaseous Product
What volume of hydrogen at 27 °C and 723 torr may be prepared by the reaction of 8.88 g of gallium with an excess of
hydrochloric acid?
2Ga (s) + 6HCl (aq) ⟶ 2 GaCl3 (aq) + 3 H2 (g)
9.4.0.0.8: Solution
Convert the provided mass of the limiting reactant, Ga, to moles of hydrogen produced:

1 mol Ga 3 mol H2
8.88 g Ga × × = 0.191 mol H2
69.723 g Ga 2 mol Ga
Convert the provided temperature and pressure values to appropriate units (K and atm, respectively), and then use the molar
amount of hydrogen gas and the ideal gas equation to calculate the volume of gas:
−1 −1
nRT 0.191 mol × 0.08206 L atm mol K × 300 K
V =( ) = = 4.94 L
P 0.951 atm

Sulfur dioxide is an intermediate in the preparation of sulfuric acid. What volume of SO2 at 343 °C and 1.21 atm is produced
by burning l.00 kg of sulfur in excess oxygen?
9.4.0.1: Answer:
1.30 × 103 L

9.4.0.0.10: Greenhouse Gases and Climate Change
The thin skin of our atmosphere keeps the earth from being an ice planet and makes it habitable. In fact, this is due to less than
0.5% of the air molecules. Of the energy from the sun that reaches the earth, almost is reflected back into space, with the rest
1
absorbed by the atmosphere and the surface of the earth. Some of the energy that the earth absorbs is re-emitted as infrared (IR)
radiation, a portion of which passes back out through the atmosphere into space. Most if this IR radiation, however, is absorbed
by certain atmospheric gases, effectively trapping heat within the atmosphere in a phenomenon known as the greenhouse
effect. This effect maintains global temperatures within the range needed to sustain life on earth. Without our atmosphere, the
earth's average temperature would be lower by more than 30 °C (nearly 60 °F). The major greenhouse gases (GHGs) are water
vapor, carbon dioxide, methane, and ozone. Since the Industrial Revolution, human activity has been increasing the
concentrations of GHGs, which have changed the energy balance and are significantly altering the earth’s climate (Figure
9.24).
Figure 9.24 Greenhouse gases trap enough of the sun’s energy to make the planet habitable—this is known as the greenhouse
effect. Human activities are increasing greenhouse gas levels, warming the planet and causing more extreme weather events.
There is strong evidence from multiple sources that higher atmospheric levels of CO2 are caused by human activity, with fossil
fuel burning accounting for about of the recent increase in CO2. Reliable data from ice cores reveals that CO2 concentration
3
in the atmosphere is at the highest level in the past 800,000 years; other evidence indicates that it may be at its highest level in
20 million years. In recent years, the CO2 concentration has increased preindustrial levels of ~280 ppm to more than 400 ppm
today (Figure 9.25).

Figure 9.25 CO2 levels over the past 700,000 years were typically from 200–300 ppm, with a steep, unprecedented increase
over the past 50 years.

Click here to see a 2-minute video explaining greenhouse gases and global warming.

9.4.0.0.11: Susan Solomon
Atmospheric and climate scientist Susan Solomon (Figure 9.26) is the author of one of The New York Times books of the year
(The Coldest March, 2001), one of Time magazine’s 100 most influential people in the world (2008), and a working group
leader of the Intergovernmental Panel on Climate Change (IPCC), which was the recipient of the 2007 Nobel Peace Prize. She
helped determine and explain the cause of the formation of the ozone hole over Antarctica, and has authored many important
papers on climate change. She has been awarded the top scientific honors in the US and France (the National Medal of Science
and the Grande Medaille, respectively), and is a member of the National Academy of Sciences, the Royal Society, the French
Academy of Sciences, and the European Academy of Sciences. Formerly a professor at the University of Colorado, she is now
at MIT, and continues to work at NOAA.
For more information, watch this video about Susan Solomon.
Figure 9.26 Susan Solomon’s research focuses on climate change and has been instrumental in determining the cause of the
ozone hole over Antarctica. (credit: National Oceanic and Atmospheric Administration)
9.4.0.1: Footnotes
2“Quotations by Joseph-Louis Lagrange,” last modified February 2006, accessed February 10, 2015, http://www-history.mcs.st-
andrews.ac.../Lagrange.html
This page titled 9.4: Stoichiometry of Gaseous Substances, Mixtures, and Reactions is shared under a CC BY 4.0 license and was authored,
remixed, and/or curated by OpenStax via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit
history is available upon request.


Define and explain effusion and diffusion
State Graham’s law and use it to compute relevant gas properties
If you have ever been in a room when a piping hot pizza was delivered, you have been made aware of the fact that gaseous
molecules can quickly spread throughout a room, as evidenced by the pleasant aroma that soon reaches your nose. Although
gaseous molecules travel at tremendous speeds (hundreds of meters per second), they collide with other gaseous molecules and
travel in many different directions before reaching the desired target. At room temperature, a gaseous molecule will experience
billions of collisions per second. The mean free path is the average distance a molecule travels between collisions. The mean free
path increases with decreasing pressure; in general, the mean free path for a gaseous molecule will be hundreds of times the
diameter of the molecule
In general, we know that when a sample of gas is introduced to one part of a closed container, its molecules very quickly disperse
throughout the container; this process by which molecules disperse in space in response to differences in concentration is called
diffusion (shown in Figure 9.27). The gaseous atoms or molecules are, of course, unaware of any concentration gradient, they
simply move randomly—regions of higher concentration have more particles than regions of lower concentrations, and so a net
movement of species from high to low concentration areas takes place. In a closed environment, diffusion will ultimately result in
equal concentrations of gas throughout, as depicted in Figure 9.27. The gaseous atoms and molecules continue to move, but since
their concentrations are the same in both bulbs, the rates of transfer between the bulbs are equal (no net transfer of molecules
occurs).
Figure 9.27 (a) Two gases, H2 and O2, are initially separated. (b) When the stopcock is opened, they mix together. The lighter gas,
H2, passes through the opening faster than O2, so just after the stopcock is opened, more H2 molecules move to the O2 side than O2
molecules move to the H2 side. (c) After a short time, both the slower-moving O2 molecules and the faster-moving H2 molecules
have distributed themselves evenly on both sides of the vessel.
We are often interested in the rate of diffusion, the amount of gas passing through some area per unit time:
amount of gas passing through an area
rate of diffusion =
unit of time
The diffusion rate depends on several factors: temperature; the mass of the atoms or molecules; the concentration gradient (the
increase or decrease in concentration from one point to another); the amount of surface area available for diffusion; and the
distance the gas particles must travel. Note also that the time required for diffusion to occur is inversely proportional to the rate of
diffusion, as shown in the rate of diffusion equation.
A process involving movement of gaseous species similar to diffusion is effusion, the escape of gas molecules through a tiny hole
such as a pinhole in a balloon into a vacuum (Figure 9.28). Although diffusion and effusion rates both depend on the molar mass of
the gas involved, their rates are not equal; however, the ratios of their rates are the same.

Figure 9.28 Diffusion involves the unrestricted dispersal of molecules throughout space due to their random motion. When this
process is restricted to passage of molecules through very small openings in a physical barrier, the process is called effusion.
If a mixture of gases is placed in a container with porous walls, the gases effuse through the small openings in the walls. The lighter
gases pass through the small openings more rapidly (at a higher rate) than the heavier ones (Figure 9.29). In 1832, Thomas Graham
studied the rates of effusion of different gases and formulated Graham’s law of effusion: The rate of effusion of a gas is inversely
proportional to the square root of the mass of its particles:
1
rate of effusion ∝
−−
√M
This means that if two gases A and B are at the same temperature and pressure, the ratio of their effusion rates is inversely
proportional to the ratio of the square roots of the masses of their particles:
−−−
rate of effusion of A √MB
=
−−−
rate of effusion of B √MA
Figure 9.29 The left photograph shows two balloons inflated with different gases, helium (orange) and argon (blue).The right-side
photograph shows the balloons approximately 12 hours after being filled, at which time the helium balloon has become noticeably
more deflated than the argon balloon, due to the greater effusion rate of the lighter helium gas. (credit: modification of work by
Paul Flowers)
9.5.0.1: Example 9.20

9.5.0.0.1: Applying Graham’s Law to Rates of Effusion
Calculate the ratio of the rate of effusion of hydrogen to the rate of effusion of oxygen.
9.5.0.0.1: Solution
From Graham’s law, we have:

−−−−−−−−−
−1
√32 g mol −−
rate of effusion of hydrogen √16 4
= = =
−−−−−−−−− –
rate of effusion of oxygen √1 1
−1
√2 g mol
Hydrogen effuses four times as rapidly as oxygen.

At a particular pressure and temperature, nitrogen gas effuses at the rate of 79 mL/s. Under the same conditions, at what rate
will sulfur dioxide effuse?
9.5.0.1: Answer:
52 mL/s
9.5.0.1: Example 9.21

9.5.0.0.1: Effusion Time Calculations
It takes 243 s for 4.46 × 10−5 mol Xe to effuse through a tiny hole. Under the same conditions, how long will it take 4.46 ×
10−5 mol Ne to effuse?
9.5.0.0.1: Solution
It is important to resist the temptation to use the times directly, and to remember how rate relates to time as well as how it
relates to mass. Recall the definition of rate of effusion:
amount of gas transferred
rate of effusion =
time
and combine it with Graham’s law:

−−−−
rate of effusion of gas Xe √MNe
=
−−−−
rate of effusion of gas Ne √MXe
To get:
amount of Xe transferred −−−−
√MNe
time for Xe
=
amount of Ne transferred
−−−−
√MXe
time for Ne
Noting that amount of A = amount of B, and solving for time for Ne:
amount of Xe −−−− −−−−
time for Ne √MNe √MNe
time for Xe
= = =
−−−− −−−−
amount of Ne time for Xe √MXe √MXe
time for Ne
and substitute values:

−−−−−−− −−−−

 20.2 g mol
time for Ne 
= = 0.392
243 s
⎷ 131.3 g mol
Finally, solve for the desired quantity:

time for Ne = 0.392 × 243 s = 95.3 s
Note that this answer is reasonable: Since Ne is lighter than Xe, the effusion rate for Ne will be larger than that for Xe, which
means the time of effusion for Ne will be smaller than that for Xe.
A party balloon filled with helium deflates to of its original volume in 8.0 hours. How long will it take an identical balloon
2
filled with the same number of moles of air (ℳ = 28.2 g/mol) to deflate to of its original volume?
1

9.5.0.1: Answer:
32 h
9.5.0.1: Example 9.22

9.5.0.0.1: Determining Molar Mass Using Graham’s Law
An unknown gas effuses 1.66 times more rapidly than CO2. What is the molar mass of the unknown gas? Can you make a
reasonable guess as to its identity?
9.5.0.0.1: Solution
From Graham’s law, we have:
−−−−−
rate of effusion of Unknown √MCO2
= −−−−−−−−
rate of effusion of CO 2 √MUnknown
Plug in known data:

−−−−− −−−−
1.66 √44.0 g/mol
=
−−−−−−−−
1 √MUnknown
Solve:
44.0 g/mol
MUnknown = = 16.0 g/mol
2
(1.66)
The gas could well be CH4, the only gas with this molar mass.
Hydrogen gas effuses through a porous container 8.97-times faster than an unknown gas. Estimate the molar mass of the
unknown gas.
9.5.0.1: Answer:
163 g/mol

9.5.0.0.1: Use of Diffusion for Nuclear Energy Applications: Uranium Enrichment
Gaseous diffusion has been used to produce enriched uranium for use in nuclear power plants and weapons. Naturally
occurring uranium contains only 0.72% of 235U, the kind of uranium that is “fissile,” that is, capable of sustaining a nuclear
fission chain reaction. Nuclear reactors require fuel that is 2–5% 235U, and nuclear bombs need even higher concentrations.
One way to enrich uranium to the desired levels is to take advantage of Graham’s law. In a gaseous diffusion enrichment plant,
uranium hexafluoride (UF6, the only uranium compound that is volatile enough to work) is slowly pumped through large
cylindrical vessels called diffusers, which contain porous barriers with microscopic openings. The process is one of diffusion
because the other side of the barrier is not evacuated. The 235UF6 molecules have a higher average speed and diffuse through
the barrier a little faster than the heavier 238UF6 molecules. The gas that has passed through the barrier is slightly enriched in
235
UF6 and the residual gas is slightly depleted. The small difference in molecular weights between 235UF6 and 238UF6 only
about 0.4% enrichment, is achieved in one diffuser (Figure 9.30). But by connecting many diffusers in a sequence of stages
(called a cascade), the desired level of enrichment can be attained.

Figure 9.30 In a diffuser, gaseous UF6 is pumped through a porous barrier, which partially separates 235UF6 from 238UF6 The
UF6 must pass through many large diffuser units to achieve sufficient enrichment in 235U.
The large scale separation of gaseous 235UF6 from 238UF6 was first done during the World War II, at the atomic energy
installation in Oak Ridge, Tennessee, as part of the Manhattan Project (the development of the first atomic bomb). Although
the theory is simple, this required surmounting many daunting technical challenges to make it work in practice. The barrier
must have tiny, uniform holes (about 10–6 cm in diameter) and be porous enough to produce high flow rates. All materials (the
barrier, tubing, surface coatings, lubricants, and gaskets) need to be able to contain, but not react with, the highly reactive and
corrosive UF6.
Because gaseous diffusion plants require very large amounts of energy (to compress the gas to the high pressures required and
drive it through the diffuser cascade, to remove the heat produced during compression, and so on), it is now being replaced by
gas centrifuge technology, which requires far less energy. A current hot political issue is how to deny this technology to Iran, to
prevent it from producing enough enriched uranium for them to use to make nuclear weapons.
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State the postulates of the kinetic-molecular theory
Use this theory’s postulates to explain the gas laws
The gas laws that we have seen to this point, as well as the ideal gas equation, are empirical, that is, they have been derived from
experimental observations. The mathematical forms of these laws closely describe the macroscopic behavior of most gases at
pressures less than about 1 or 2 atm. Although the gas laws describe relationships that have been verified by many experiments,
they do not tell us why gases follow these relationships.
The kinetic molecular theory (KMT) is a simple microscopic model that effectively explains the gas laws described in previous
modules of this chapter. This theory is based on the following five postulates described here. (Note: The term “molecule” will be
used to refer to the individual chemical species that compose the gas, although some gases are composed of atomic species, for
example, the noble gases.)
1. Gases are composed of molecules that are in continuous motion, travelling in straight lines and changing direction only when
they collide with other molecules or with the walls of a container.
2. The molecules composing the gas are negligibly small compared to the distances between them.
3. The pressure exerted by a gas in a container results from collisions between the gas molecules and the container walls.
4. Gas molecules exert no attractive or repulsive forces on each other or the container walls; therefore, their collisions are elastic
(do not involve a loss of energy).
5. The average kinetic energy of the gas molecules is proportional to the kelvin temperature of the gas.
The test of the KMT and its postulates is its ability to explain and describe the behavior of a gas. The various gas laws can be
derived from the assumptions of the KMT, which have led chemists to believe that the assumptions of the theory accurately
represent the properties of gas molecules. We will first look at the individual gas laws (Boyle’s, Charles’s, Amontons’s,
Avogadro’s, and Dalton’s laws) conceptually to see how the KMT explains them. Then, we will more carefully consider the
relationships between molecular masses, speeds, and kinetic energies with temperature, and explain Graham’s law.
9.6.0.1: The Kinetic-Molecular Theory Explains the Behavior of Gases, Part I

Recalling that gas pressure is exerted by rapidly moving gas molecules and depends directly on the number of molecules hitting a
unit area of the wall per unit of time, we see that the KMT conceptually explains the behavior of a gas as follows:
Amontons’s law. If the temperature is increased, the average speed and kinetic energy of the gas molecules increase. If the
volume is held constant, the increased speed of the gas molecules results in more frequent and more forceful collisions with the
walls of the container, therefore increasing the pressure (Figure 9.31).
Charles’s law. If the temperature of a gas is increased, a constant pressure may be maintained only if the volume occupied by
the gas increases. This will result in greater average distances traveled by the molecules to reach the container walls, as well as
increased wall surface area. These conditions will decrease the both the frequency of molecule-wall collisions and the number
of collisions per unit area, the combined effects of which balance the effect of increased collision forces due to the greater
kinetic energy at the higher temperature.
Boyle’s law. If the gas volume volume of a given amount of gas at a given temperature is decreased (that is, if the gas is
compressed), the molecules will be exposed to a decreased container wall area. Collisions with the container wall will therefore
occur more frequently and the pressure exerted by the gas will increase (Figure 9.31).
Avogadro’s law. At constant pressure and temperature, the frequency and force of molecule-wall collisions are constant. Under
such conditions, increasing the number of gaseous molecules will require a proportional increase in the container volume in
order to yield a decrease in the number of collisions per unit area to compensate for the increased frequency of collisions
(Figure 9.31).
Dalton’s Law. Because of the large distances between them, the molecules of one gas in a mixture bombard the container walls
with the same frequency whether other gases are present or not, and the total pressure of a gas mixture equals the sum of the
(partial) pressures of the individual gases.

Figure 9.31 (a) When gas temperature increases, gas pressure increases due to increased force and frequency of molecular
collisions. (b) When volume decreases, gas pressure increases due to increased frequency of molecular collisions. (c) When the
amount of gas increases at a constant pressure, volume increases to yield a constant number of collisions per unit wall area per unit
time.
9.6.0.1: molecular speeds and Kinetic Energy

The previous discussion showed that the KMT qualitatively explains the behaviors described by the various gas laws. The
postulates of this theory may be applied in a more quantitative fashion to derive these individual laws. To do this, we must first
look at speeds and kinetic energies of gas molecules, and the temperature of a gas sample.
In a gas sample, individual molecules have widely varying speeds; however, because of the vast number of molecules and
collisions involved, the molecular speed distribution and average speed are constant. This molecular speed distribution is known as
a Maxwell-Boltzmann distribution, and it depicts the relative numbers of molecules in a bulk sample of gas that possesses a given
speed (Figure 9.32).

Figure 9.32 The molecular speed distribution for oxygen gas at 300 K is shown here. Very few molecules move at either very low
or very high speeds. The number of molecules with intermediate speeds increases rapidly up to a maximum, which is the most
probable speed, then drops off rapidly. Note that the most probable speed, νp, is a little less than 400 m/s, while the root mean
square speed, urms, is closer to 500 m/s.
The kinetic energy (KE) of a particle of mass (m) and speed (u) is given by:
1
2
KE = mu
2
Expressing mass in kilograms and speed in meters per second will yield energy values in units of joules (J = kg m2 s–2). To deal
with a large number of gas molecules, we use averages for both speed and kinetic energy. In the KMT, the root mean square speed
of a particle, urms, is defined as the square root of the average of the squares of the speeds with n = the number of particles:
−−−−−−−−−−−−−−−−−−−
−− 2 2 2 2
u +u +u +u +…
√¯¯
¯¯
2 1 2 3 4
urms = u = √
n
The average kinetic energy for a mole of particles, KEavg, is then equal to:

1 2
KE avg = M urms
2
where M is the molar mass expressed in units of kg/mol. The KEavg of a mole of gas molecules is also directly proportional to the
temperature of the gas and may be described by the equation:
3
KE avg = RT
2
where R is the gas constant and T is the kelvin temperature. When used in this equation, the appropriate form of the gas constant is
8.314 J/mol⋅K (8.314 kg m2s–2mol–1K–1). These two separate equations for KEavg may be combined and rearranged to yield a
relation between molecular speed and temperature:
9.6.0.1: Example 9.23

9.6.0.0.1: Calculation of urms
Calculate the root-mean-square speed for a nitrogen molecule at 30 °C.
9.6.0.0.2: Solution
Convert the temperature into Kelvin:
30 °C + 273 = 303 K
Determine the molar mass of nitrogen in kilograms:

28.0 g 1 kg
× = 0.028 kg/mol
1 mol 1000 g
Replace the variables and constants in the root-mean-square speed equation, replacing Joules with the equivalent kg m2s–2:
−−−−−
3RT
urms = √
M
9.6.0.1: Answer:
441 m/s
If the temperature of a gas increases, its KEavg increases, more molecules have higher speeds and fewer molecules have lower
speeds, and the distribution shifts toward higher speeds overall, that is, to the right. If temperature decreases, KEavg decreases, more
molecules have lower speeds and fewer molecules have higher speeds, and the distribution shifts toward lower speeds overall, that
is, to the left. This behavior is illustrated for nitrogen gas in Figure 9.33.

Figure 9.33 The molecular speed distribution for nitrogen gas (N2) shifts to the right and flattens as the temperature increases; it
shifts to the left and heightens as the temperature decreases.
At a given temperature, all gases have the same KEavg for their molecules. Gases composed of lighter molecules have more high-
speed particles and a higher urms, with a speed distribution that peaks at relatively higher speeds. Gases consisting of heavier
molecules have more low-speed particles, a lower urms, and a speed distribution that peaks at relatively lower speeds. This trend is
demonstrated by the data for a series of noble gases shown in Figure 9.34.

Figure 9.34 molecular speed is directly related to molecular mass. At a given temperature, lighter molecules move faster on average
than heavier molecules.

The gas simulator may be used to examine the effect of temperature on molecular speeds. Examine the simulator’s “energy
histograms” (molecular speed distributions) and “species information” (which gives average speed values) for molecules of
different masses at various temperatures.
9.6.0.1: The Kinetic-Molecular Theory Explains the Behavior of Gases, Part II

According to Graham’s law, the molecules of a gas are in rapid motion and the molecules themselves are small. The average
distance between the molecules of a gas is large compared to the size of the molecules. As a consequence, gas molecules can move
past each other easily and diffuse at relatively fast rates.
The rate of effusion of a gas depends directly on the (average) speed of its molecules:
effusion rate ∝ urms
Using this relation, and the equation relating molecular speed to mass, Graham’s law may be easily derived as shown here:
−−−−−
3RT
urms = √
M
3RT 3RT
M = =
2 2
urms ū
−
−−−
3RT
−−−−
√
effusion rate A urms MA MB
A
= = −
−−− = √
effusion rate B urms B 3RT MA
√
MB
The ratio of the rates of effusion is thus derived to be inversely proportional to the ratio of the square roots of their masses. This is
the same relation observed experimentally and expressed as Graham’s law.

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Describe the physical factors that lead to deviations from ideal gas behavior
Explain how these factors are represented in the van der Waals equation
Define compressibility (Z) and describe how its variation with pressure reflects non-ideal behavior
Quantify non-ideal behavior by comparing computations of gas properties using the ideal gas law and the van der Waals
equation
Thus far, the ideal gas law, PV = nRT, has been applied to a variety of different types of problems, ranging from reaction
stoichiometry and empirical and molecular formula problems to determining the density and molar mass of a gas. As mentioned in
the previous modules of this chapter, however, the behavior of a gas is often non-ideal, meaning that the observed relationships
between its pressure, volume, and temperature are not accurately described by the gas laws. In this section, the reasons for these
deviations from ideal gas behavior are considered.
One way in which the accuracy of PV = nRT can be judged is by comparing the actual volume of 1 mole of gas (its molar volume,
Vm) to the molar volume of an ideal gas at the same temperature and pressure. This ratio is called the compressibility factor (Z)
with:
molar volume of gas at same T and P P Vm
Z = =( )
molar volume of ideal gas at same T and P RT measured
Ideal gas behavior is therefore indicated when this ratio is equal to 1, and any deviation from 1 is an indication of non-ideal
behavior. Figure 9.35 shows plots of Z over a large pressure range for several common gases.
Figure 9.35 A graph of the compressibility factor (Z) vs. pressure shows that gases can exhibit significant deviations from the
behavior predicted by the ideal gas law.

As is apparent from Figure 9.35, the ideal gas law does not describe gas behavior well at relatively high pressures. To determine
why this is, consider the differences between real gas properties and what is expected of a hypothetical ideal gas.
Particles of a hypothetical ideal gas have no significant volume and do not attract or repel each other. In general, real gases
approximate this behavior at relatively low pressures and high temperatures. However, at high pressures, the molecules of a gas are
crowded closer together, and the amount of empty space between the molecules is reduced. At these higher pressures, the volume
of the gas molecules themselves becomes appreciable relative to the total volume occupied by the gas. The gas therefore becomes
less compressible at these high pressures, and although its volume continues to decrease with increasing pressure, this decrease is
not proportional as predicted by Boyle’s law.
At relatively low pressures, gas molecules have practically no attraction for one another because they are (on average) so far apart,
and they behave almost like particles of an ideal gas. At higher pressures, however, the force of attraction is also no longer
insignificant. This force pulls the molecules a little closer together, slightly decreasing the pressure (if the volume is constant) or
decreasing the volume (at constant pressure) (Figure 9.36). This change is more pronounced at low temperatures because the
molecules have lower KE relative to the attractive forces, and so they are less effective in overcoming these attractions after
colliding with one another.
Figure 9.36 (a) Attractions between gas molecules serve to decrease the gas volume at constant pressure compared to an ideal gas
whose molecules experience no attractive forces. (b) These attractive forces will decrease the force of collisions between the
molecules and container walls, therefore reducing the pressure exerted at constant volume compared to an ideal gas.
There are several different equations that better approximate gas behavior than does the ideal gas law. The first, and simplest, of
these was developed by the Dutch scientist Johannes van der Waals in 1879. The van der Waals equation improves upon the ideal
gas law by adding two terms: one to account for the volume of the gas molecules and another for the attractive forces between
them.
The constant a corresponds to the strength of the attraction between molecules of a particular gas, and the constant b corresponds to
2
the size of the molecules of a particular gas. The “correction” to the pressure term in the ideal gas law is , and the “correction”
n a
2
V
to the volume is nb. Note that when V is relatively large and n is relatively small, both of these correction terms become negligible,
and the van der Waals equation reduces to the ideal gas law, PV = nRT. Such a condition corresponds to a gas in which a relatively
low number of molecules is occupying a relatively large volume, that is, a gas at a relatively low pressure. Experimental values for
the van der Waals constants of some common gases are given in Table 9.3.
Values of van der Waals Constants for Some Common Gases

Gas a (L2 atm/mol2) b (L/mol)
N2 1.39 0.0391
O2 1.36 0.0318
CO2 3.59 0.0427
H2O 5.46 0.0305
He 0.0342 0.0237
CCl4 20.4 0.1383
Table 9.3
At low pressures, the correction for intermolecular attraction, a, is more important than the one for molecular volume, b. At high
pressures and small volumes, the correction for the volume of the molecules becomes important because the molecules themselves
are incompressible and constitute an appreciable fraction of the total volume. At some intermediate pressure, the two corrections
have opposing influences and the gas appears to follow the relationship given by PV = nRT over a small range of pressures. This
behavior is reflected by the “dips” in several of the compressibility curves shown in Figure 9.35. The attractive force between
molecules initially makes the gas more compressible than an ideal gas, as pressure is raised (Z decreases with increasing P). At
very high pressures, the gas becomes less compressible (Z increases with P), as the gas molecules begin to occupy an increasingly
significant fraction of the total gas volume.
Strictly speaking, the ideal gas equation functions well when intermolecular attractions between gas molecules are negligible and
the gas molecules themselves do not occupy an appreciable part of the whole volume. These criteria are satisfied under conditions
of low pressure and high temperature. Under such conditions, the gas is said to behave ideally, and deviations from the gas laws are
small enough that they may be disregarded—this is, however, very often not the case.
9.7.0.1: Example 9.24

9.7.0.0.1: Comparison of Ideal Gas Law and van der Waals Equation
A 4.25-L flask contains 3.46 mol CO2 at 229 °C. Calculate the pressure of this sample of CO2:
(a) from the ideal gas law
(b) from the van der Waals equation
(c) Explain the reason(s) for the difference.
9.7.0.0.1: Solution
(a) From the ideal gas law:
−1 −1
nRT 3.46 mol × 0.08206 L atm mol K × 502 K
P = = = 33.5 atm
V
4.25 L
(b) From the van der Waals equation:

2 2
n a nRT n a
(P + ) × (V − nb) = nRT ⟶ P = −
2 2
V (V − nb) V
−1 −1 2 2 2
3.46 mol × 0.08206 L atm mol K × 502 K (3.46 mol) × 3.59 L atm mol
P = −
−1 2
(4.25 L − 3.46 mol × 0.0427 L mol ) (4.25 L)
This finally yields P = 32.4 atm.

(c) This is not very different from the value from the ideal gas law because the pressure is not very high and the temperature is
not very low. The value is somewhat different because CO2 molecules do have some volume and attractions between

molecules, and the ideal gas law assumes they do not have volume or attractions.
9.7.0.0.1: Check your Learning
A 560-mL flask contains 21.3 g N2 at 145 °C. Calculate the pressure of N2:
(a) from the ideal gas law
(b) from the van der Waals equation
(c) Explain the reason(s) for the difference.
9.7.0.1: Answer:
(a) 46.562 atm; (b) 46.594 atm; (c) The van der Waals equation takes into account the volume of the gas molecules
themselves as well as intermolecular attractions.
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9.8: Key Terms
absolute zero
temperature at which the volume of a gas would be zero according to Charles’s law.
Amontons’s law
(also, Gay-Lussac’s law) pressure of a given number of moles of gas is directly proportional to its kelvin temperature when the
volume is held constant
atmosphere (atm)
unit of pressure; 1 atm = 101,325 Pa
Avogadro’s law
volume of a gas at constant temperature and pressure is proportional to the number of gas molecules
bar
(bar or b) unit of pressure; 1 bar = 100,000 Pa
barometer
device used to measure atmospheric pressure
Boyle’s law
volume of a given number of moles of gas held at constant temperature is inversely proportional to the pressure under which it
is measured
Charles’s law
volume of a given number of moles of gas is directly proportional to its kelvin temperature when the pressure is held constant
compressibility factor (Z)

ratio of the experimentally measured molar volume for a gas to its molar volume as computed from the ideal gas equation
Dalton’s law of partial pressures

total pressure of a mixture of ideal gases is equal to the sum of the partial pressures of the component gases
diffusion
movement of an atom or molecule from a region of relatively high concentration to one of relatively low concentration
(discussed in this chapter with regard to gaseous species, but applicable to species in any phase)
effusion
transfer of gaseous atoms or molecules from a container to a vacuum through very small openings
Graham’s law of effusion

rates of diffusion and effusion of gases are inversely proportional to the square roots of their molecular masses
hydrostatic pressure
pressure exerted by a fluid due to gravity
ideal gas
hypothetical gas whose physical properties are perfectly described by the gas laws
ideal gas constant (R)

constant derived from the ideal gas equation R = 0.08206 L atm mol–1 K–1 or 8.314 L kPa mol–1 K–1
ideal gas law
relation between the pressure, volume, amount, and temperature of a gas under conditions derived by combination of the simple
gas laws
kinetic molecular theory

theory based on simple principles and assumptions that effectively explains ideal gas behavior
manometer
device used to measure the pressure of a gas trapped in a container
mean free path

average distance a molecule travels between collisions
mole fraction (X)

concentration unit defined as the ratio of the molar amount of a mixture component to the total number of moles of all mixture
components
partial pressure
pressure exerted by an individual gas in a mixture
pascal (Pa)
SI unit of pressure; 1 Pa = 1 N/m2
pounds per square inch (psi)

unit of pressure common in the US
pressure
force exerted per unit area
rate of diffusion
amount of gas diffusing through a given area over a given time
root mean square speed (urms)

measure of average speed for a group of particles calculated as the square root of the average squared speed
standard conditions of temperature and pressure (STP)

273.15 K (0 °C) and 1 atm (101.325 kPa)
standard molar volume

volume of 1 mole of gas at STP, approximately 22.4 L for gases behaving ideally
torr
unit of pressure; 1 torr = 1
760
atm
van der Waals equation

modified version of the ideal gas equation containing additional terms to account for non-ideal gas behavior
vapor pressure of water

pressure exerted by water vapor in equilibrium with liquid water in a closed container at a specific temperature
9.9: Key Equations
F
P =
A
p = hρg
PV = nRT
PTotal = PA + PB + PC + … = Ʃ iPi
PA = XA PTotal
nA
XA =
nT otal
amount of gas passing through an area

rate of diffusion =
unit of time
rate of effusion of gas A √mB √MB

= =
rate of effusion of gas B √mA √MA
− − −− − − − −− − −−
−− 2 2 2 2
u1 + u2 + u3 + u4 +…
√¯
¯¯¯
2 √
urms = u =
n
3
KE avg = RT
2
−
−−−
3RT
urms = √
M
molar volume of gas at same T and P P × Vm

Z = = ( )
molar volume of ideal gas at same T and P R × T
measured
2
n a
(P + ) × (V − nb) = nRT
2
V
9.10: Summary
9.1 Gas Pressure
Gases exert pressure, which is force per unit area. The pressure of a gas may be expressed in the SI unit of pascal or kilopascal, as
well as in many other units including torr, atmosphere, and bar. Atmospheric pressure is measured using a barometer; other gas
pressures can be measured using one of several types of manometers.
The behavior of gases can be described by several laws based on experimental observations of their properties. The pressure of a
given amount of gas is directly proportional to its absolute temperature, provided that the volume does not change (Amontons’s
law). The volume of a given gas sample is directly proportional to its absolute temperature at constant pressure (Charles’s law). The
volume of a given amount of gas is inversely proportional to its pressure when temperature is held constant (Boyle’s law). Under
the same conditions of temperature and pressure, equal volumes of all gases contain the same number of molecules (Avogadro’s
law).
The equations describing these laws are special cases of the ideal gas law, PV = nRT, where P is the pressure of the gas, V is its
volume, n is the number of moles of the gas, T is its kelvin temperature, and R is the ideal (universal) gas constant.

The ideal gas law can be used to derive a number of convenient equations relating directly measured quantities to properties of
interest for gaseous substances and mixtures. Appropriate rearrangement of the ideal gas equation may be made to permit the
calculation of gas densities and molar masses. Dalton’s law of partial pressures may be used to relate measured gas pressures for
gaseous mixtures to their compositions. Avogadro’s law may be used in stoichiometric computations for chemical reactions
involving gaseous reactants or products.

Gaseous atoms and molecules move freely and randomly through space. Diffusion is the process whereby gaseous atoms and
molecules are transferred from regions of relatively high concentration to regions of relatively low concentration. Effusion is a
similar process in which gaseous species pass from a container to a vacuum through very small orifices. The rates of effusion of
gases are inversely proportional to the square roots of their densities or to the square roots of their atoms/molecules’ masses
(Graham’s law).

The kinetic molecular theory is a simple but very effective model that effectively explains ideal gas behavior. The theory assumes
that gases consist of widely separated molecules of negligible volume that are in constant motion, colliding elastically with one
another and the walls of their container with average speeds determined by their absolute temperatures. The individual molecules
of a gas exhibit a range of speeds, the distribution of these speeds being dependent on the temperature of the gas and the mass of its
molecules.

Gas molecules possess a finite volume and experience forces of attraction for one another. Consequently, gas behavior is not
necessarily described well by the ideal gas law. Under conditions of low pressure and high temperature, these factors are negligible,
the ideal gas equation is an accurate description of gas behavior, and the gas is said to exhibit ideal behavior. However, at lower
temperatures and higher pressures, corrections for molecular volume and molecular attractions are required to account for finite
molecular size and attractive forces. The van der Waals equation is a modified version of the ideal gas law that can be used to
account for the non-ideal behavior of gases under these conditions.
9.11: Exercises
9.1 Gas Pressure
1.
Why are sharp knives more effective than dull knives? (Hint: Think about the definition of pressure.)
2.
Why do some small bridges have weight limits that depend on how many wheels or axles the crossing vehicle has?
3.
Why should you roll or belly-crawl rather than walk across a thinly-frozen pond?
4.
A typical barometric pressure in Redding, California, is about 750 mm Hg. Calculate this pressure in atm and kPa.
5.
A typical barometric pressure in Denver, Colorado, is 615 mm Hg. What is this pressure in atmospheres and kilopascals?
6.
A typical barometric pressure in Kansas City is 740 torr. What is this pressure in atmospheres, in millimeters of mercury, and in
kilopascals?
7.
Canadian tire pressure gauges are marked in units of kilopascals. What reading on such a gauge corresponds to 32 psi?
8.
During the Viking landings on Mars, the atmospheric pressure was determined to be on the average about 6.50 millibars (1 bar =
0.987 atm). What is that pressure in torr and kPa?
9.
The pressure of the atmosphere on the surface of the planet Venus is about 88.8 atm. Compare that pressure in psi to the normal
pressure on earth at sea level in psi.
10.
A medical laboratory catalog describes the pressure in a cylinder of a gas as 14.82 MPa. What is the pressure of this gas in
atmospheres and torr?
11.
Consider this scenario and answer the following questions: On a mid-August day in the northeastern United States, the following
information appeared in the local newspaper: atmospheric pressure at sea level 29.97 in. Hg, 1013.9 mbar.
(a) What was the pressure in kPa?
(b) The pressure near the seacoast in the northeastern United States is usually reported near 30.0 in. Hg. During a hurricane, the
pressure may fall to near 28.0 in. Hg. Calculate the drop in pressure in torr.
12.
Why is it necessary to use a nonvolatile liquid in a barometer or manometer?
13.
The pressure of a sample of gas is measured at sea level with a closed-end manometer. The liquid in the manometer is mercury.
Determine the pressure of the gas in:
(a) torr
(b) Pa
(c) bar

14.
The pressure of a sample of gas is measured with an open-end manometer, partially shown to the right. The liquid in the
manometer is mercury. Assuming atmospheric pressure is 29.92 in. Hg, determine the pressure of the gas in:
(a) torr
(b) Pa
(c) bar
15.
The pressure of a sample of gas is measured at sea level with an open-end mercury manometer. Assuming atmospheric pressure is
760.0 mm Hg, determine the pressure of the gas in:
(a) mm Hg
(b) atm
(c) kPa

16.
The pressure of a sample of gas is measured at sea level with an open-end mercury manometer. Assuming atmospheric pressure is
760 mm Hg, determine the pressure of the gas in:
(a) mm Hg
(b) atm
(c) kPa
17.
How would the use of a volatile liquid affect the measurement of a gas using open-ended manometers vs. closed-end manometers?
18.
Sometimes leaving a bicycle in the sun on a hot day will cause a blowout. Why?
19.
Explain how the volume of the bubbles exhausted by a scuba diver (Figure 9.16) change as they rise to the surface, assuming that
they remain intact.
20.
One way to state Boyle’s law is “All other things being equal, the pressure of a gas is inversely proportional to its volume.” (a)
What is the meaning of the term “inversely proportional?” (b) What are the “other things” that must be equal?
21.
An alternate way to state Avogadro’s law is “All other things being equal, the number of molecules in a gas is directly proportional
to the volume of the gas.” (a) What is the meaning of the term “directly proportional?” (b) What are the “other things” that must be
equal?
22.

How would the graph in Figure 9.12 change if the number of moles of gas in the sample used to determine the curve were doubled?
23.
How would the graph in Figure 9.13 change if the number of moles of gas in the sample used to determine the curve were doubled?
24.
In addition to the data found in Figure 9.13, what other information do we need to find the mass of the sample of air used to
determine the graph?
25.
Determine the volume of 1 mol of CH4 gas at 150 K and 1 atm, using Figure 9.12.
26.
Determine the pressure of the gas in the syringe shown in Figure 9.13 when its volume is 12.5 mL, using:
(a) the appropriate graph
(b) Boyle’s law
27.
A spray can is used until it is empty except for the propellant gas, which has a pressure of 1344 torr at 23 °C. If the can is thrown
into a fire (T = 475 °C), what will be the pressure in the hot can?
28.
What is the temperature of an 11.2-L sample of carbon monoxide, CO, at 744 torr if it occupies 13.3 L at 55 °C and 744 torr?
29.
A 2.50-L volume of hydrogen measured at –196 °C is warmed to 100 °C. Calculate the volume of the gas at the higher
temperature, assuming no change in pressure.
30.
A balloon inflated with three breaths of air has a volume of 1.7 L. At the same temperature and pressure, what is the volume of the
balloon if five more same-sized breaths are added to the balloon?
31.
A weather balloon contains 8.80 moles of helium at a pressure of 0.992 atm and a temperature of 25 °C at ground level. What is the
volume of the balloon under these conditions?
32.
The volume of an automobile air bag was 66.8 L when inflated at 25 °C with 77.8 g of nitrogen gas. What was the pressure in the
bag in kPa?
33.
How many moles of gaseous boron trifluoride, BF3, are contained in a 4.3410-L bulb at 788.0 K if the pressure is 1.220 atm? How
many grams of BF3?
34.
Iodine, I2, is a solid at room temperature but sublimes (converts from a solid into a gas) when warmed. What is the temperature in a
73.3-mL bulb that contains 0.292 g of I2 vapor at a pressure of 0.462 atm?

35.
How many grams of gas are present in each of the following cases?
(a) 0.100 L of CO2 at 307 torr and 26 °C
(b) 8.75 L of C2H4, at 378.3 kPa and 483 K
(c) 221 mL of Ar at 0.23 torr and –54 °C
36.
A high altitude balloon is filled with 1.41 × 104 L of hydrogen at a temperature of 21 °C and a pressure of 745 torr. What is the
volume of the balloon at a height of 20 km, where the temperature is –48 °C and the pressure is 63.1 torr?
37.
A cylinder of medical oxygen has a volume of 35.4 L, and contains O2 at a pressure of 151 atm and a temperature of 25 °C. What
volume of O2 does this correspond to at normal body conditions, that is, 1 atm and 37 °C?
38.
A large scuba tank (Figure 9.16) with a volume of 18 L is rated for a pressure of 220 bar. The tank is filled at 20 °C and contains
enough air to supply 1860 L of air to a diver at a pressure of 2.37 atm (a depth of 45 feet). Was the tank filled to capacity at 20 °C?
39.
A 20.0-L cylinder containing 11.34 kg of butane, C4H10, was opened to the atmosphere. Calculate the mass of the gas remaining in
the cylinder if it were opened and the gas escaped until the pressure in the cylinder was equal to the atmospheric pressure, 0.983
atm, and a temperature of 27 °C.
40.
While resting, the average 70-kg human male consumes 14 L of pure O2 per hour at 25 °C and 100 kPa. How many moles of O2
are consumed by a 70 kg man while resting for 1.0 h?
41.
For a given amount of gas showing ideal behavior, draw labeled graphs of:
(a) the variation of P with V
(b) the variation of V with T
(c) the variation of P with T
(d) the variation of 1
P
with V
42.
A liter of methane gas, CH4, at STP contains more atoms of hydrogen than does a liter of pure hydrogen gas, H2, at STP. Using
Avogadro’s law as a starting point, explain why.
43.
The effect of chlorofluorocarbons (such as CCl2F2) on the depletion of the ozone layer is well known. The use of substitutes, such
as CH3CH2F(g), for the chlorofluorocarbons, has largely corrected the problem. Calculate the volume occupied by 10.0 g of each
of these compounds at STP:
(a) CCl2F2(g)
(b) CH3CH2F(g)
44.
As 1 g of the radioactive element radium decays over 1 year, it produces 1.16 × 1018 alpha particles (helium nuclei). Each alpha
particle becomes an atom of helium gas. What is the pressure in pascal of the helium gas produced if it occupies a volume of 125
mL at a temperature of 25 °C?
45.

A balloon with a volume of 100.21 L at 21 °C and 0.981 atm is released and just barely clears the top of Mount Crumpit in British
Columbia. If the final volume of the balloon is 144.53 L at a temperature of 5.24 °C, what is the pressure experienced by the
balloon as it clears Mount Crumpet?
46.
If the temperature of a fixed amount of a gas is doubled at constant volume, what happens to the pressure?
47.
If the volume of a fixed amount of a gas is tripled at constant temperature, what happens to the pressure?

48.
What is the density of laughing gas, dinitrogen monoxide, N2O, at a temperature of 325 K and a pressure of 113.0 kPa?
49.
Calculate the density of Freon 12, CF2Cl2, at 30.0 °C and 0.954 atm.
50.
Which is denser at the same temperature and pressure, dry air or air saturated with water vapor? Explain.
51.
A cylinder of O2(g) used in breathing by patients with emphysema has a volume of 3.00 L at a pressure of 10.0 atm. If the
temperature of the cylinder is 28.0 °C, what mass of oxygen is in the cylinder?
52.
What is the molar mass of a gas if 0.0494 g of the gas occupies a volume of 0.100 L at a temperature 26 °C and a pressure of 307
torr?
53.
What is the molar mass of a gas if 0.281 g of the gas occupies a volume of 125 mL at a temperature 126 °C and a pressure of 777
torr?
54.
How could you show experimentally that the molecular formula of propene is C3H6, not CH2?
55.
The density of a certain gaseous fluoride of phosphorus is 3.93 g/L at STP. Calculate the molar mass of this fluoride and determine
its molecular formula.
56.
Consider this question: What is the molecular formula of a compound that contains 39% C, 45% N, and 16% H if 0.157 g of the
compound occupies l25 mL with a pressure of 99.5 kPa at 22 °C?
57.
A 36.0–L cylinder of a gas used for calibration of blood gas analyzers in medical laboratories contains 350 g CO2, 805 g O2, and
4,880 g N2. At 25 degrees C, what is the pressure in the cylinder in atmospheres?
58.
A cylinder of a gas mixture used for calibration of blood gas analyzers in medical laboratories contains 5.0% CO2, 12.0% O2, and
the remainder N2 at a total pressure of 146 atm. What is the partial pressure of each component of this gas? (The percentages given
indicate the percent of the total pressure that is due to each component.)
59.
A sample of gas isolated from unrefined petroleum contains 90.0% CH4, 8.9% C2H6, and 1.1% C3H8 at a total pressure of 307.2
kPa. What is the partial pressure of each component of this gas? (The percentages given indicate the percent of the total pressure

that is due to each component.)
60.
A mixture of 0.200 g of H2, 1.00 g of N2, and 0.820 g of Ar is stored in a closed container at STP. Find the volume of the container,
assuming that the gases exhibit ideal behavior.
61.
Most mixtures of hydrogen gas with oxygen gas are explosive. However, a mixture that contains less than 3.0 % O2 is not. If
enough O2 is added to a cylinder of H2 at 33.2 atm to bring the total pressure to 34.5 atm, is the mixture explosive?
62.
A commercial mercury vapor analyzer can detect, in air, concentrations of gaseous Hg atoms (which are poisonous) as low as 2 ×
10−6 mg/L of air. At this concentration, what is the partial pressure of gaseous mercury if the atmospheric pressure is 733 torr at 26
°C?
63.
A sample of carbon monoxide was collected over water at a total pressure of 756 torr and a temperature of 18 °C. What is the
pressure of the carbon monoxide? (See Table 9.2 for the vapor pressure of water.)
64.
In an experiment in a general chemistry laboratory, a student collected a sample of a gas over water. The volume of the gas was 265
mL at a pressure of 753 torr and a temperature of 27 °C. The mass of the gas was 0.472 g. What was the molar mass of the gas?
65.
Joseph Priestley first prepared pure oxygen by heating mercuric oxide, HgO:
2HgO (s) ⟶ 2Hg (l) + O2 (g)
(a) Outline the steps necessary to answer the following question: What volume of O2 at 23 °C and 0.975 atm is produced by the
decomposition of 5.36 g of HgO?
66.
Cavendish prepared hydrogen in 1766 by the novel method of passing steam through a red-hot gun barrel:
4 H2 O (g) + 3Fe (s) ⟶ Fe3 O4 (s) + 4 H2 (g)
(a) Outline the steps necessary to answer the following question: What volume of H2 at a pressure of 745 torr and a temperature of
20 °C can be prepared from the reaction of 15.O g of H2O?
67.
The chlorofluorocarbon CCl2F2 can be recycled into a different compound by reaction with hydrogen to produce CH2F2(g), a
compound useful in chemical manufacturing:
CCl2 F2 (g) + 4 H2 (g) ⟶ CH2 F2 (g) + 2HCl (g)
(a) Outline the steps necessary to answer the following question: What volume of hydrogen at 225 atm and 35.5 °C would be
required to react with 1 ton (1.000 × 103 kg) of CCl2F2?
68.
Automobile air bags are inflated with nitrogen gas, which is formed by the decomposition of solid sodium azide (NaN3). The other
product is sodium metal. Calculate the volume of nitrogen gas at 27 °C and 756 torr formed by the decomposition of 125 g of
sodium azide.
69.
Lime, CaO, is produced by heating calcium carbonate, CaCO3; carbon dioxide is the other product.

(a) Outline the steps necessary to answer the following question: What volume of carbon dioxide at 875 K and 0.966 atm is
produced by the decomposition of 1 ton (1.000 × 103 kg) of calcium carbonate?
70.
Before small batteries were available, carbide lamps were used for bicycle lights. Acetylene gas, C2H2, and solid calcium
hydroxide were formed by the reaction of calcium carbide, CaC2, with water. The ignition of the acetylene gas provided the light.
Currently, the same lamps are used by some cavers, and calcium carbide is used to produce acetylene for carbide cannons.
(a) Outline the steps necessary to answer the following question: What volume of C2H2 at 1.005 atm and 12.2 °C is formed by the
reaction of 15.48 g of CaC2 with water?
71.
Calculate the volume of oxygen required to burn 12.00 L of ethane gas, C2H6, to produce carbon dioxide and water, if the volumes
of C2H6 and O2 are measured under the same conditions of temperature and pressure.
72.
What volume of O2 at STP is required to oxidize 8.0 L of NO at STP to NO2? What volume of NO2 is produced at STP?
73.
Consider the following questions:
(a) What is the total volume of the CO2(g) and H2O(g) at 600 °C and 0.888 atm produced by the combustion of 1.00 L of C2H6(g)
measured at STP?
(b) What is the partial pressure of H2O in the product gases?
74.
Methanol, CH3OH, is produced industrially by the following reaction:
copper catalyst 300 °C, 300 atm
CO (g) + 2 H2 (g) −−−−−−−−−−−−−−−−−−−−−−−→ CH3 OH (g)
Assuming that the gases behave as ideal gases, find the ratio of the total volume of the reactants to the final volume.
75.
What volume of oxygen at 423.0 K and a pressure of 127.4 kPa is produced by the decomposition of 129.7 g of BaO2 to BaO and
O2?
76.
A 2.50-L sample of a colorless gas at STP decomposed to give 2.50 L of N2 and 1.25 L of O2 at STP. What is the colorless gas?
77.
Ethanol, C2H5OH, is produced industrially from ethylene, C2H4, by the following sequence of reactions:
3 C2 H4 + 2 H2 SO 4 ⟶ C2 H5 HSO 4 + (C2 H5 )2 SO 4
C2 H5 HSO 4 + (C2 H5 )2 SO 4 + 3 H2 O ⟶ 3 C2 H5 OH + 2 H2 SO 4
What volume of ethylene at STP is required to produce 1.000 metric ton (1000 kg) of ethanol if the overall yield of ethanol is
90.1%?
78.
One molecule of hemoglobin will combine with four molecules of oxygen. If 1.0 g of hemoglobin combines with 1.53 mL of
oxygen at body temperature (37 °C) and a pressure of 743 torr, what is the molar mass of hemoglobin?
79.
A sample of a compound of xenon and fluorine was confined in a bulb with a pressure of 18 torr. Hydrogen was added to the bulb
until the pressure was 72 torr. Passage of an electric spark through the mixture produced Xe and HF. After the HF was removed by
reaction with solid KOH, the final pressure of xenon and unreacted hydrogen in the bulb was 36 torr. What is the empirical formula
of the xenon fluoride in the original sample? (Note: Xenon fluorides contain only one xenon atom per molecule.)

80.
One method of analyzing amino acids is the van Slyke method. The characteristic amino groups (−NH2) in protein material are
allowed to react with nitrous acid, HNO2, to form N2 gas. From the volume of the gas, the amount of amino acid can be
determined. A 0.0604-g sample of a biological sample containing glycine, CH2(NH2)COOH, was analyzed by the van Slyke
method and yielded 3.70 mL of N2 collected over water at a pressure of 735 torr and 29 °C. What was the percentage of glycine in
the sample?
CH2 (NH2 ) CO2 H + HNO2 ⟶ CH2 (OH) CO2 H + H2 O + N2

81.
A balloon filled with helium gas takes 6 hours to deflate to 50% of its original volume. How long will it take for an identical
balloon filled with the same volume of hydrogen gas (instead of helium) to decrease its volume by 50%?
82.
Explain why the numbers of molecules are not identical in the left- and right-hand bulbs shown in the center illustration of Figure
9.27.
83.
Starting with the definition of rate of effusion and Graham’s finding relating rate and molar mass, show how to derive the Graham’s
law equation, relating the relative rates of effusion for two gases to their molecular masses.
84.
Heavy water, D2O (molar mass = 20.03 g mol–1), can be separated from ordinary water, H2O (molar mass = 18.01), as a result of
the difference in the relative rates of diffusion of the molecules in the gas phase. Calculate the relative rates of diffusion of H2O and
D2O.
85.
Which of the following gases diffuse more slowly than oxygen? F2, Ne, N2O, C2H2, NO, Cl2, H2S
86.
During the discussion of gaseous diffusion for enriching uranium, it was claimed that 235UF6 diffuses 0.4% faster than 238UF6.
Show the calculation that supports this value. The molar mass of 235UF6 = 235.043930 + 6 × 18.998403 = 349.034348 g/mol, and
the molar mass of 238UF6 = 238.050788 + 6 × 18.998403 = 352.041206 g/mol.
87.
Calculate the relative rate of diffusion of 1H2 (molar mass 2.0 g/mol) compared with 2H2 (molar mass 4.0 g/mol) and the relative
rate of diffusion of O2 (molar mass 32 g/mol) compared with O3 (molar mass 48 g/mol).
88.
A gas of unknown identity diffuses at a rate of 83.3 mL/s in a diffusion apparatus in which carbon dioxide diffuses at the rate of
102 mL/s. Calculate the molecular mass of the unknown gas.
89.
When two cotton plugs, one moistened with ammonia and the other with hydrochloric acid, are simultaneously inserted into
opposite ends of a glass tube that is 87.0 cm long, a white ring of NH4Cl forms where gaseous NH3 and gaseous HCl first come
into contact. NH (g) + HCl (g) ⟶ NH Cl (s) At approximately what distance from the ammonia moistened plug does this
3 4
occur? (Hint: Calculate the rates of diffusion for both NH3 and HCl, and find out how much faster NH3 diffuses than HCl.)

90.
Using the postulates of the kinetic molecular theory, explain why a gas uniformly fills a container of any shape.
91.
Can the speed of a given molecule in a gas double at constant temperature? Explain your answer.
92.

Describe what happens to the average kinetic energy of ideal gas molecules when the conditions are changed as follows:
(a) The pressure of the gas is increased by reducing the volume at constant temperature.
(b) The pressure of the gas is increased by increasing the temperature at constant volume.
(c) The average speed of the molecules is increased by a factor of 2.
93.
The distribution of molecular speeds in a sample of helium is shown in Figure 9.34. If the sample is cooled, will the distribution of
speeds look more like that of H2 or of H2O? Explain your answer.
94.
What is the ratio of the average kinetic energy of a SO2 molecule to that of an O2 molecule in a mixture of two gases? What is the
ratio of the root mean square speeds, urms, of the two gases?
95.
A 1-L sample of CO initially at STP is heated to 546 K, and its volume is increased to 2 L.
(a) What effect do these changes have on the number of collisions of the molecules of the gas per unit area of the container wall?
(b) What is the effect on the average kinetic energy of the molecules?
(c) What is the effect on the root mean square speed of the molecules?
96.
The root mean square speed of H2 molecules at 25 °C is about 1.6 km/s. What is the root mean square speed of a N2 molecule at 25
°C?
97.
(a) Is the pressure of the gas in the hot-air balloon shown at the opening of this chapter greater than, less than, or equal to that of the
atmosphere outside the balloon?
(b) Is the density of the gas in the hot-air balloon shown at the opening of this chapter greater than, less than, or equal to that of the
atmosphere outside the balloon?
(c) At a pressure of 1 atm and a temperature of 20 °C, dry air has a density of 1.2256 g/L. What is the (average) molar mass of dry
air?
(d) The average temperature of the gas in a hot-air balloon is 1.30 × 102 °F. Calculate its density, assuming the molar mass equals
that of dry air.
(e) The lifting capacity of a hot-air balloon is equal to the difference in the mass of the cool air displaced by the balloon and the
mass of the gas in the balloon. What is the difference in the mass of 1.00 L of the cool air in part (c) and the hot air in part (d)?
(f) An average balloon has a diameter of 60 feet and a volume of 1.1 × 105 ft3. What is the lifting power of such a balloon? If the
weight of the balloon and its rigging is 500 pounds, what is its capacity for carrying passengers and cargo?
(g) A balloon carries 40.0 gallons of liquid propane (density 0.5005 g/L). What volume of CO2 and H2O gas is produced by the
combustion of this propane?
(h) A balloon flight can last about 90 minutes. If all of the fuel is burned during this time, what is the approximate rate of heat loss
(in kJ/min) from the hot air in the bag during the flight?
98.
R1
Show that the ratio of the rate of diffusion of Gas 1 to the rate of diffusion of Gas 2, R2
, is the same at 0 °C and 100 °C.

99.
Graphs showing the behavior of several different gases follow. Which of these gases exhibit behavior significantly different from
that expected for ideal gases?

100.
Explain why the plot of PV for CO2 differs from that of an ideal gas.

101.
Under which of the following sets of conditions does a real gas behave most like an ideal gas, and for which conditions is a real gas
expected to deviate from ideal behavior? Explain.
(a) high pressure, small volume
(b) high temperature, low pressure
(c) low temperature, high pressure
102.
Describe the factors responsible for the deviation of the behavior of real gases from that of an
ideal gas.
103.
For which of the following gases should the correction for the molecular volume be largest:
CO, CO2, H2, He, NH3, SF6?
104.
A 0.245-L flask contains 0.467 mol CO2 at 159 °C. Calculate the pressure:
(a) using the ideal gas law
(b) using the van der Waals equation
(c) Explain the reason for the difference.
(d) Identify which correction (that for P or V) is dominant and why.
105.
(a) If XX behaved as an ideal gas, what would its graph of Z vs. P look like?
(b) For most of this chapter, we performed calculations treating gases as ideal. Was this justified?
(c) What is the effect of the volume of gas molecules on Z? Under what conditions is this effect small? When is it large? Explain
using an appropriate diagram.

(d) What is the effect of intermolecular attractions on the value of Z? Under what conditions is this effect small? When is it large?
Explain using an appropriate diagram.
(e) In general, under what temperature conditions would you expect Z to have the largest deviations from the Z for an ideal gas?

CHAPTER OVERVIEW
10: Liquids and Solids

General Chemistry
The great distances between atoms and molecules in a gaseous phase, and the corresponding absence of any significant interactions
between them, allows for simple descriptions of many physical properties that are the same for all gases, regardless of their
chemical identities. As described in the final module of the chapter on gases, this situation changes at high pressures and low
temperatures—conditions that permit the atoms and molecules to interact to a much greater extent. In the liquid and solid states,
these interactions are of considerable strength and play an important role in determining a number of physical properties that do
depend on the chemical identity of the substance. In this chapter, the nature of these interactions and their effects on various
physical properties of liquid and solid phases will be examined.
10.1: Introduction
10.8: Key Terms
10.9: Key Equations
10.10: Summary
10.11: Exercises
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1
10.1: Introduction
Figure 10.1 Solid carbon dioxide (“dry ice”, left) sublimes vigorously when placed in a liquid (right), cooling the liquid and
generating a dense mist of water above the cylinder. (credit: modification of work by Paul Flowers)

10.1 Intermolecular Forces
10.2 Properties of Liquids
10.3 Phase Transitions
10.4 Phase Diagrams
10.5 The Solid State of Matter
10.6 Lattice Structures in Crystalline Solids
Leprosy has been a devastating disease throughout much of human history. Aside from the symptoms and complications of the
illness, its social stigma led sufferers to be cast out of communities and isolated in colonies; in some regions this practice lasted
well into the twentieth century. At that time, the best potential treatment for leprosy was oil from the chaulmoogra tree, but the oil
was extremely thick, causing blisters and making usage painful and ineffective. Healthcare professionals seeking a better
application contacted Alice Ball, a young chemist at the University of Hawaii, who had focused her masters thesis on a similar
plant. Ball initiated a sequence of procedures (repeated acidification and purification to change the characteristics of the oil and
isolate the active substances (esters, discussed later in this text). The "Ball Method" as it later came to be called, became the
standard treatment for leprosy for decades. In the liquid and solid states, atomic and molecular interactions are of considerable
strength and play an important role in determining a number of physical properties of the substance. For example, the thickness, or
viscosity, of the chaulmoogra oil was due to its intermolecular forces. In this chapter, the nature of these interactions and their
effects on various physical properties of liquid and solid phases will be examined.
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Describe the types of intermolecular forces possible between atoms or molecules in condensed phases (dispersion forces,
dipole-dipole attractions, and hydrogen bonding)
Identify the types of intermolecular forces experienced by specific molecules based on their structures
Explain the relation between the intermolecular forces present within a substance and the temperatures associated with
changes in its physical state
As was the case for gaseous substances, the kinetic molecular theory may be used to explain the behavior of solids and liquids. In
the following description, the term particle will be used to refer to an atom, molecule, or ion. Note that we will use the popular
phrase “intermolecular attraction” to refer to attractive forces between the particles of a substance, regardless of whether these
particles are molecules, atoms, or ions.
Consider these two aspects of the molecular-level environments in solid, liquid, and gaseous matter:
Particles in a solid are tightly packed together and often arranged in a regular pattern; in a liquid, they are close together with no
regular arrangement; in a gas, they are far apart with no regular arrangement.
Particles in a solid vibrate about fixed positions and do not generally move in relation to one another; in a liquid, they move
past each other but remain in essentially constant contact; in a gas, they move independently of one another except when they
collide.
The differences in the properties of a solid, liquid, or gas reflect the strengths of the attractive forces between the atoms, molecules,
or ions that make up each phase. The phase in which a substance exists depends on the relative extents of its intermolecular forces
(IMFs) and the kinetic energies (KE) of its molecules. IMFs are the various forces of attraction that may exist between the atoms
and molecules of a substance due to electrostatic phenomena, as will be detailed in this module. These forces serve to hold particles
close together, whereas the particles’ KE provides the energy required to overcome the attractive forces and thus increase the
distance between particles. Figure 10.2 illustrates how changes in physical state may be induced by changing the temperature,
hence, the average KE, of a given substance.
Figure 10.2 Transitions between solid, liquid, and gaseous states of a substance occur when conditions of temperature or pressure
favor the associated changes in intermolecular forces. (Note: The space between particles in the gas phase is much greater than

shown.)
As an example of the processes depicted in this figure, consider a sample of water. When gaseous water is cooled sufficiently, the
attractions between H2O molecules will be capable of holding them together when they come into contact with each other; the gas
condenses, forming liquid H2O. For example, liquid water forms on the outside of a cold glass as the water vapor in the air is
cooled by the cold glass, as seen in Figure 10.3.
Figure 10.3 Condensation forms when water vapor in the air is cooled enough to form liquid water, such as (a) on the outside of a
cold beverage glass or (b) in the form of fog. (credit a: modification of work by Jenny Downing; credit b: modification of work by
Cory Zanker)
We can also liquefy many gases by compressing them, if the temperature is not too high. The increased pressure brings the
molecules of a gas closer together, such that the attractions between the molecules become strong relative to their KE.
Consequently, they form liquids. Butane, C4H10, is the fuel used in disposable lighters and is a gas at standard temperature and
pressure. Inside the lighter’s fuel compartment, the butane is compressed to a pressure that results in its condensation to the liquid
state, as shown in Figure 10.4.

Figure 10.4 Gaseous butane is compressed within the storage compartment of a disposable lighter, resulting in its condensation to
the liquid state. (credit: modification of work by “Sam-Cat”/Flickr)
Finally, if the temperature of a liquid becomes sufficiently low, or the pressure on the liquid becomes sufficiently high, the
molecules of the liquid no longer have enough KE to overcome the IMF between them, and a solid forms. A more thorough

discussion of these and other changes of state, or phase transitions, is provided in a later module of this chapter.

Access this interactive simulation on states of matter, phase transitions, and intermolecular forces. This simulation is useful for
visualizing concepts introduced throughout this chapter.
10.2.0.1: Forces between Molecules

Under appropriate conditions, the attractions between all gas molecules will cause them to form liquids or solids. This is due to
intermolecular forces, not intramolecular forces. Intramolecular forces are those within the molecule that keep the molecule
together, for example, the bonds between the atoms. Intermolecular forces are the attractions between molecules, which determine
many of the physical properties of a substance. Figure 10.5 illustrates these different molecular forces. The strengths of these
attractive forces vary widely, though usually the IMFs between small molecules are weak compared to the intramolecular forces
that bond atoms together within a molecule. For example, to overcome the IMFs in one mole of liquid HCl and convert it into
gaseous HCl requires only about 17 kilojoules. However, to break the covalent bonds between the hydrogen and chlorine atoms in
one mole of HCl requires about 25 times more energy—430 kilojoules.
Figure 10.5 Intramolecular forces keep a molecule intact. Intermolecular forces hold multiple molecules together and determine
many of a substance’s properties.
All of the attractive forces between neutral atoms and molecules are known as van der Waals forces, although they are usually
referred to more informally as intermolecular attraction. We will consider the various types of IMFs in the next three sections of
this module.
10.2.0.1: Dispersion Forces

One of the three van der Waals forces is present in all condensed phases, regardless of the nature of the atoms or molecules
composing the substance. This attractive force is called the London dispersion force in honor of German-born American physicist
Fritz London who, in 1928, first explained it. This force is often referred to as simply the dispersion force. Because the electrons of
an atom or molecule are in constant motion (or, alternatively, the electron’s location is subject to quantum-mechanical variability),
at any moment in time, an atom or molecule can develop a temporary, instantaneous dipole if its electrons are distributed
asymmetrically. The presence of this dipole can, in turn, distort the electrons of a neighboring atom or molecule, producing an
induced dipole. These two rapidly fluctuating, temporary dipoles thus result in a relatively weak electrostatic attraction between the
species—a so-called dispersion force like that illustrated in Figure 10.6.

Figure 10.6 Dispersion forces result from the formation of temporary dipoles, as illustrated here for two nonpolar diatomic
molecules.
Dispersion forces that develop between atoms in different molecules can attract the two molecules to each other. The forces are
relatively weak, however, and become significant only when the molecules are very close. Larger and heavier atoms and molecules
exhibit stronger dispersion forces than do smaller and lighter atoms and molecules. F2 and Cl2 are gases at room temperature
(reflecting weaker attractive forces); Br2 is a liquid, and I2 is a solid (reflecting stronger attractive forces). Trends in observed
melting and boiling points for the halogens clearly demonstrate this effect, as seen in Table 10.1.
Melting and Boiling Points of the Halogens
Halogen Molar Mass Atomic Radius Melting Point Boiling Point
fluorine, F2 38 g/mol 72 pm 53 K 85 K
chlorine, Cl2 71 g/mol 99 pm 172 K 238 K
bromine, Br2 160 g/mol 114 pm 266 K 332 K
iodine, I2 254 g/mol 133 pm 387 K 457 K
astatine, At2 420 g/mol 150 pm 575 K 610 K
Table 10.1
The increase in melting and boiling points with increasing atomic/molecular size may be rationalized by considering how the
strength of dispersion forces is affected by the electronic structure of the atoms or molecules in the substance. In a larger atom, the

valence electrons are, on average, farther from the nuclei than in a smaller atom. Thus, they are less tightly held and can more
easily form the temporary dipoles that produce the attraction. The measure of how easy or difficult it is for another electrostatic
charge (for example, a nearby ion or polar molecule) to distort a molecule’s charge distribution (its electron cloud) is known as
polarizability. A molecule that has a charge cloud that is easily distorted is said to be very polarizable and will have large
dispersion forces; one with a charge cloud that is difficult to distort is not very polarizable and will have small dispersion forces.
10.2.0.1: Example 10.1

10.2.0.0.1: London Forces and Their Effects
Order the following compounds of a group 14 element and hydrogen from lowest to highest boiling point: CH4, SiH4, GeH4,
and SnH4. Explain your reasoning.
Applying the skills acquired in the chapter on chemical bonding and molecular geometry, all of these compounds are predicted
to be nonpolar, so they may experience only dispersion forces: the smaller the molecule, the less polarizable and the weaker the
dispersion forces; the larger the molecule, the larger the dispersion forces. The molar masses of CH4, SiH4, GeH4, and SnH4
are approximately 16 g/mol, 32 g/mol, 77 g/mol, and 123 g/mol, respectively. Therefore, CH4 is expected to have the lowest
boiling point and SnH4 the highest boiling point. The ordering from lowest to highest boiling point is expected to be CH4 <
SiH4 < GeH4 < SnH4.
A graph of the actual boiling points of these compounds versus the period of the group 14 element shows this prediction to be
correct:

Order the following hydrocarbons from lowest to highest boiling point: C2H6, C3H8, and C4H10.
10.2.0.1: Answer:
C2H6 < C3H8 < C4H10. All of these compounds are nonpolar and only have London dispersion forces: the larger the
molecule, the larger the dispersion forces and the higher the boiling point. The ordering from lowest to highest boiling
point is therefore C2H6 < C3H8 < C4H10.

The shapes of molecules also affect the magnitudes of the dispersion forces between them. For example, boiling points for the
isomers n-pentane, isopentane, and neopentane (shown in Figure 10.7) are 36 °C, 27 °C, and 9.5 °C, respectively. Even though
these compounds are composed of molecules with the same chemical formula, C5H12, the difference in boiling points suggests that
dispersion forces in the liquid phase are different, being greatest for n-pentane and least for neopentane. The elongated shape of n-
pentane provides a greater surface area available for contact between molecules, resulting in correspondingly stronger dispersion
forces. The more compact shape of isopentane offers a smaller surface area available for intermolecular contact and, therefore,
weaker dispersion forces. Neopentane molecules are the most compact of the three, offering the least available surface area for
intermolecular contact and, hence, the weakest dispersion forces. This behavior is analogous to the connections that may be formed
between strips of VELCRO brand fasteners: the greater the area of the strip’s contact, the stronger the connection.
Figure 10.7 The strength of the dispersion forces increases with the contact area between molecules, as demonstrated by the boiling
points of these pentane isomers.

10.2.0.0.4: Geckos and Intermolecular Forces
Geckos have an amazing ability to adhere to most surfaces. They can quickly run up smooth walls and across ceilings that have
no toe-holds, and they do this without having suction cups or a sticky substance on their toes. And while a gecko can lift its
feet easily as it walks along a surface, if you attempt to pick it up, it sticks to the surface. How are geckos (as well as spiders
and some other insects) able to do this? Although this phenomenon has been investigated for hundreds of years, scientists only
recently uncovered the details of the process that allows geckos’ feet to behave this way.
Geckos’ toes are covered with hundreds of thousands of tiny hairs known as setae, with each seta, in turn, branching into
hundreds of tiny, flat, triangular tips called spatulae. The huge numbers of spatulae on its setae provide a gecko, shown in
Figure 10.8, with a large total surface area for sticking to a surface. In 2000, Kellar Autumn, who leads a multi-institutional
gecko research team, found that geckos adhered equally well to both polar silicon dioxide and nonpolar gallium arsenide. This
proved that geckos stick to surfaces because of dispersion forces—weak intermolecular attractions arising from temporary,
synchronized charge distributions between adjacent molecules. Although dispersion forces are very weak, the total attraction
over millions of spatulae is large enough to support many times the gecko’s weight.

In 2014, two scientists developed a model to explain how geckos can rapidly transition from “sticky” to “non-sticky.” Alex
Greaney and Congcong Hu at Oregon State University described how geckos can achieve this by changing the angle between
their spatulae and the surface. Geckos’ feet, which are normally nonsticky, become sticky when a small shear force is applied.
By curling and uncurling their toes, geckos can alternate between sticking and unsticking from a surface, and thus easily move
across it. Later research led by Alyssa Stark at University of Akron showed that geckos can maintain their hold on hydrophobic
surfaces (similar to the leaves in their habitats) equally well whether the surfaces were wet or dry. Stark's experiment used a
ribbon to gently pull the geckos until they slipped, so that the researchers could determine the geckos' ability to hold various
surfaces under wet and dry conditions. Further investigations may eventually lead to the development of better adhesives and
other applications.
Figure 10.8 Geckos’ toes contain large numbers of tiny hairs (setae), which branch into many triangular tips (spatulae). Geckos
adhere to surfaces because of van der Waals attractions between the surface and a gecko’s millions of spatulae. By changing
how the spatulae contact the surface, geckos can turn their stickiness “on” and “off.” (credit photo: modification of work by
“JC*+A!”/Flickr)

Watch this video to learn more about Kellar Autumn’s research that determined that van der Waals forces are responsible for a
gecko’s ability to cling and climb.
10.2.0.1: Dipole-Dipole Attractions

Recall from the chapter on chemical bonding and molecular geometry that polar molecules have a partial positive charge on one
side and a partial negative charge on the other side of the molecule—a separation of charge called a dipole. Consider a polar
molecule such as hydrogen chloride, HCl. In the HCl molecule, the more electronegative Cl atom bears the partial negative charge,
whereas the less electronegative H atom bears the partial positive charge. An attractive force between HCl molecules results from
the attraction between the positive end of one HCl molecule and the negative end of another. This attractive force is called a dipole-
dipole attraction—the electrostatic force between the partially positive end of one polar molecule and the partially negative end of
another, as illustrated in Figure 10.9.
Figure 10.9 This image shows two arrangements of polar molecules, such as HCl, that allow an attraction between the partial
negative end of one molecule and the partial positive end of another.

The effect of a dipole-dipole attraction is apparent when we compare the properties of HCl molecules to nonpolar F2 molecules.
Both HCl and F2 consist of the same number of atoms and have approximately the same molecular mass. At a temperature of 150
K, molecules of both substances would have the same average KE. However, the dipole-dipole attractions between HCl molecules
are sufficient to cause them to “stick together” to form a liquid, whereas the relatively weaker dispersion forces between nonpolar
F2 molecules are not, and so this substance is gaseous at this temperature. The higher normal boiling point of HCl (188 K)
compared to F2 (85 K) is a reflection of the greater strength of dipole-dipole attractions between HCl molecules, compared to the
attractions between nonpolar F2 molecules. We will often use values such as boiling or freezing points, or enthalpies of
vaporization or fusion, as indicators of the relative strengths of IMFs of attraction present within different substances.
10.2.0.1: Example 10.2

10.2.0.0.1: Dipole-Dipole Forces and Their Effects
Predict which will have the higher boiling point: N2 or CO. Explain your reasoning.
CO and N2 are both diatomic molecules with masses of about 28 amu, so they experience similar London dispersion forces.
Because CO is a polar molecule, it experiences dipole-dipole attractions. Because N2 is nonpolar, its molecules cannot exhibit
dipole-dipole attractions. The dipole-dipole attractions between CO molecules are comparably stronger than the dispersion
forces between nonpolar N2 molecules, so CO is expected to have the higher boiling point.
Predict which will have the higher boiling point: ICl or Br2. Explain your reasoning.
10.2.0.1: Answer:
ICl. ICl and Br2 have similar masses (~160 amu) and therefore experience similar London dispersion forces. ICl is polar
and thus also exhibits dipole-dipole attractions; Br2 is nonpolar and does not. The relatively stronger dipole-dipole
attractions require more energy to overcome, so ICl will have the higher boiling point.
10.2.0.1: Hydrogen Bonding

Nitrosyl fluoride (ONF, molecular mass 49 amu) is a gas at room temperature. Water (H2O, molecular mass 18 amu) is a liquid,
even though it has a lower molecular mass. We clearly cannot attribute this difference between the two compounds to dispersion
forces. Both molecules have about the same shape and ONF is the heavier and larger molecule. It is, therefore, expected to
experience more significant dispersion forces. Additionally, we cannot attribute this difference in boiling points to differences in
the dipole moments of the molecules. Both molecules are polar and exhibit comparable dipole moments. The large difference
between the boiling points is due to a particularly strong dipole-dipole attraction that may occur when a molecule contains a
hydrogen atom bonded to a fluorine, oxygen, or nitrogen atom (the three most electronegative elements). The very large difference
in electronegativity between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for a
N atom), combined with the very small size of a H atom and the relatively small sizes of F, O, or N atoms, leads to highly
concentrated partial charges with these atoms. Molecules with F-H, O-H, or N-H moieties are very strongly attracted to similar
moieties in nearby molecules, a particularly strong type of dipole-dipole attraction called hydrogen bonding. Examples of hydrogen
bonds include HF⋯HF, H2O⋯HOH, and H3N⋯HNH2, in which the hydrogen bonds are denoted by dots. Figure 10.10 illustrates
hydrogen bonding between water molecules.

Figure 10.10 Water molecules participate in multiple hydrogen-bonding interactions with nearby water molecules.
Despite use of the word “bond,” keep in mind that hydrogen bonds are intermolecular attractive forces, not intramolecular
attractive forces (covalent bonds). Hydrogen bonds are much weaker than covalent bonds, only about 5 to 10% as strong, but are
generally much stronger than other dipole-dipole attractions and dispersion forces.
Hydrogen bonds have a pronounced effect on the properties of condensed phases (liquids and solids). For example, consider the
trends in boiling points for the binary hydrides of group 15 (NH3, PH3, AsH3, and SbH3), group 16 hydrides (H2O, H2S, H2Se, and
H2Te), and group 17 hydrides (HF, HCl, HBr, and HI). The boiling points of the heaviest three hydrides for each group are plotted
in Figure 10.11. As we progress down any of these groups, the polarities of the molecules decrease slightly, whereas the sizes of the
molecules increase substantially. The effect of increasingly stronger dispersion forces dominates that of increasingly weaker dipole-
dipole attractions, and the boiling points are observed to increase steadily.

Figure 10.11 For the group 15, 16, and 17 hydrides, the boiling points for each class of compounds increase with increasing
molecular mass for elements in periods 3, 4, and 5.
If we use this trend to predict the boiling points for the lightest hydride for each group, we would expect NH3 to boil at about −120
°C, H2O to boil at about −80 °C, and HF to boil at about −110 °C. However, when we measure the boiling points for these
compounds, we find that they are dramatically higher than the trends would predict, as shown in Figure 10.12. The stark contrast
between our naïve predictions and reality provides compelling evidence for the strength of hydrogen bonding.

Figure 10.12 In comparison to periods 3−5, the binary hydrides of period 2 elements in groups 17, 16 and 15 (F, O and N,
respectively) exhibit anomalously high boiling points due to hydrogen bonding.
10.2.0.1: Example 10.3

10.2.0.0.1: Effect of Hydrogen Bonding on Boiling Points
Consider the compounds dimethylether (CH3OCH3), ethanol (CH3CH2OH), and propane (CH3CH2CH3). Their boiling points,
not necessarily in order, are −42.1 °C, −24.8 °C, and 78.4 °C. Match each compound with its boiling point. Explain your
reasoning.
The VSEPR-predicted shapes of CH3OCH3, CH3CH2OH, and CH3CH2CH3 are similar, as are their molar masses (46 g/mol,
46 g/mol, and 44 g/mol, respectively), so they will exhibit similar dispersion forces. Since CH3CH2CH3 is nonpolar, it may
exhibit only dispersion forces. Because CH3OCH3 is polar, it will also experience dipole-dipole attractions. Finally,
CH3CH2OH has an −OH group, and so it will experience the uniquely strong dipole-dipole attraction known as hydrogen
bonding. So the ordering in terms of strength of IMFs, and thus boiling points, is CH3CH2CH3 < CH3OCH3 < CH3CH2OH.
The boiling point of propane is −42.1 °C, the boiling point of dimethylether is −24.8 °C, and the boiling point of ethanol is
78.5 °C.
Ethane (CH3CH3) has a melting point of −183 °C and a boiling point of −89 °C. Predict the melting and boiling points for
methylamine (CH3NH2). Explain your reasoning.

10.2.0.1: Answer:
The melting point and boiling point for methylamine are predicted to be significantly greater than those of ethane.
CH3CH3 and CH3NH2 are similar in size and mass, but methylamine possesses an −NH group and therefore may exhibit
hydrogen bonding. This greatly increases its IMFs, and therefore its melting and boiling points. It is difficult to predict
values, but the known values are a melting point of −93 °C and a boiling point of −6 °C.

10.2.0.0.4: Hydrogen Bonding and DNA
Deoxyribonucleic acid (DNA) is found in every living organism and contains the genetic information that determines the
organism’s characteristics, provides the blueprint for making the proteins necessary for life, and serves as a template to pass
this information on to the organism’s offspring. A DNA molecule consists of two (anti-)parallel chains of repeating
nucleotides, which form its well-known double helical structure, as shown in Figure 10.13.
Figure 10.13 Two separate DNA molecules form a double-stranded helix in which the molecules are held together via
hydrogen bonding. (credit: modification of work by Jerome Walker, Dennis Myts)
Each nucleotide contains a (deoxyribose) sugar bound to a phosphate group on one side, and one of four nitrogenous bases on
the other. Two of the bases, cytosine (C) and thymine (T), are single-ringed structures known as pyrimidines. The other two,
adenine (A) and guanine (G), are double-ringed structures called purines. These bases form complementary base pairs
consisting of one purine and one pyrimidine, with adenine pairing with thymine, and cytosine with guanine. Each base pair is
held together by hydrogen bonding. A and T share two hydrogen bonds, C and G share three, and both pairings have a similar
shape and structure Figure 10.14.

Figure 10.14 The geometries of the base molecules result in maximum hydrogen bonding between adenine and thymine (AT)
and between guanine and cytosine (GC), so-called “complementary base pairs.”
The cumulative effect of millions of hydrogen bonds effectively holds the two strands of DNA together. Importantly, the two
strands of DNA can relatively easily “unzip” down the middle since hydrogen bonds are relatively weak compared to the
covalent bonds that hold the atoms of the individual DNA molecules together. This allows both strands to function as a
template for replication.
This page titled 10.2: Intermolecular Forces is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via


Distinguish between adhesive and cohesive forces
Define viscosity, surface tension, and capillary rise
Describe the roles of intermolecular attractive forces in each of these properties/phenomena
When you pour a glass of water, or fill a car with gasoline, you observe that water and gasoline flow freely. But when you pour
syrup on pancakes or add oil to a car engine, you note that syrup and motor oil do not flow as readily. The viscosity of a liquid is a
measure of its resistance to flow. Water, gasoline, and other liquids that flow freely have a low viscosity. Honey, syrup, motor oil,
and other liquids that do not flow freely, like those shown in Figure 10.15, have higher viscosities. We can measure viscosity by
measuring the rate at which a metal ball falls through a liquid (the ball falls more slowly through a more viscous liquid) or by
measuring the rate at which a liquid flows through a narrow tube (more viscous liquids flow more slowly).
Figure 10.15 (a) Honey and (b) motor oil are examples of liquids with high viscosities; they flow slowly. (credit a: modification of
work by Scott Bauer; credit b: modification of work by David Nagy)
The IMFs between the molecules of a liquid, the size and shape of the molecules, and the temperature determine how easily a
liquid flows. As Table 10.2 shows, the more structurally complex are the molecules in a liquid and the stronger the IMFs between
them, the more difficult it is for them to move past each other and the greater is the viscosity of the liquid. As the temperature
increases, the molecules move more rapidly and their kinetic energies are better able to overcome the forces that hold them
together; thus, the viscosity of the liquid decreases.
Viscosities of Common Substances at 25 °C
Substance Formula Viscosity (mPa·s)
water H2O 0.890
mercury Hg 1.526
ethanol C2H5OH 1.074
octane C8H18 0.508

Substance Formula Viscosity (mPa·s)
ethylene glycol CH2(OH)CH2(OH) 16.1
honey variable ~2,000–10,000
motor oil variable ~50–500
Table 10.2
The various IMFs between identical molecules of a substance are examples of cohesive forces. The molecules within a liquid are
surrounded by other molecules and are attracted equally in all directions by the cohesive forces within the liquid. However, the
molecules on the surface of a liquid are attracted only by about one-half as many molecules. Because of the unbalanced molecular
attractions on the surface molecules, liquids contract to form a shape that minimizes the number of molecules on the surface—that
is, the shape with the minimum surface area. A small drop of liquid tends to assume a spherical shape, as shown in Figure 10.16,
because in a sphere, the ratio of surface area to volume is at a minimum. Larger drops are more greatly affected by gravity, air
resistance, surface interactions, and so on, and as a result, are less spherical.
Figure 10.16 Attractive forces result in a spherical water drop that minimizes surface area; cohesive forces hold the sphere together;
adhesive forces keep the drop attached to the web. (credit photo: modification of work by “OliBac”/Flickr)
Surface tension is defined as the energy required to increase the surface area of a liquid, or the force required to increase the length
of a liquid surface by a given amount. This property results from the cohesive forces between molecules at the surface of a liquid,
and it causes the surface of a liquid to behave like a stretched rubber membrane. Surface tensions of several liquids are presented in
Table 10.3. Among common liquids, water exhibits a distinctly high surface tension due to strong hydrogen bonding between its
molecules. As a result of this high surface tension, the surface of water represents a relatively “tough skin” that can withstand
considerable force without breaking. A steel needle carefully placed on water will float. Some insects, like the one shown in Figure
10.17, even though they are denser than water, move on its surface because they are supported by the surface tension.
Surface Tensions of Common Substances at 25 °C
Substance Formula Surface Tension (mN/m)
water H2O 71.99
mercury Hg 458.48
ethanol C2H5OH 21.97

Substance Formula Surface Tension (mN/m)
octane C8H18 21.14
ethylene glycol CH2(OH)CH2(OH) 47.99
Table 10.3
Figure 10.17 Surface tension (right) prevents this insect, a “water strider,” from sinking into the water.
Surface tension is affected by a variety of variables, including the introduction of additional substances on the surface. In the late
1800s, Agnes Pockels, who was initially blocked from pursuing a scientific career but studied on her own, began investigating the
impact and characteristics of soapy and greasy films in water. Using homemade materials, she developed an instrument known as a
trough for measuring surface contaminants and their effects. With the support of renowned scientist Lord Rayleigh, her 1891 paper
showed that surface contamination significantly reduces surface tension, and also that changing the characteristics of the surface
(compressing or expanding it) also affects surface tension. Decades later, Irving Langmuir and Katharine Blodgett built on Pockels'
work in their own trough and important advances in surface chemistry. Langmuir pioneered methods for producing single-molecule
layers of film; Blodgett applied these to the development of non-reflective glass (critical for film-making and other applications),
and also studied methods related to cleaning surfaces, which are important in semiconductor fabrication.
The IMFs of attraction between two different molecules are called adhesive forces. Consider what happens when water comes into
contact with some surface. If the adhesive forces between water molecules and the molecules of the surface are weak compared to
the cohesive forces between the water molecules, the water does not “wet” the surface. For example, water does not wet waxed
surfaces or many plastics such as polyethylene. Water forms drops on these surfaces because the cohesive forces within the drops
are greater than the adhesive forces between the water and the plastic. Water spreads out on glass because the adhesive force
between water and glass is greater than the cohesive forces within the water. When water is confined in a glass tube, its meniscus
(surface) has a concave shape because the water wets the glass and creeps up the side of the tube. On the other hand, the cohesive
forces between mercury atoms are much greater than the adhesive forces between mercury and glass. Mercury therefore does not
wet glass, and it forms a convex meniscus when confined in a tube because the cohesive forces within the mercury tend to draw it
into a drop (Figure 10.18).

Figure 10.18 Differences in the relative strengths of cohesive and adhesive forces result in different meniscus shapes for mercury
(left) and water (right) in glass tubes. (credit: Mark Ott)
If you place one end of a paper towel in spilled wine, as shown in Figure 10.19, the liquid wicks up the paper towel. A similar
process occurs in a cloth towel when you use it to dry off after a shower. These are examples of capillary action—when a liquid
flows within a porous material due to the attraction of the liquid molecules to the surface of the material and to other liquid
molecules. The adhesive forces between the liquid and the porous material, combined with the cohesive forces within the liquid,
may be strong enough to move the liquid upward against gravity.
Figure 10.19 Wine wicks up a paper towel (left) because of the strong attractions of water (and ethanol) molecules to the −OH
groups on the towel’s cellulose fibers and the strong attractions of water molecules to other water (and ethanol) molecules (right).
(credit photo: modification of work by Mark Blaser)
Towels soak up liquids like water because the fibers of a towel are made of molecules that are attracted to water molecules. Most
cloth towels are made of cotton, and paper towels are generally made from paper pulp. Both consist of long molecules of cellulose
that contain many −OH groups. Water molecules are attracted to these −OH groups and form hydrogen bonds with them, which
draws the H2O molecules up the cellulose molecules. The water molecules are also attracted to each other, so large amounts of
water are drawn up the cellulose fibers.
Capillary action can also occur when one end of a small diameter tube is immersed in a liquid, as illustrated in Figure 10.20. If the
liquid molecules are strongly attracted to the tube molecules, the liquid creeps up the inside of the tube until the weight of the liquid
and the adhesive forces are in balance. The smaller the diameter of the tube is, the higher the liquid climbs. It is partly by capillary
action occurring in plant cells called xylem that water and dissolved nutrients are brought from the soil up through the roots and
into a plant. Capillary action is the basis for thin layer chromatography, a laboratory technique commonly used to separate small
quantities of mixtures. You depend on a constant supply of tears to keep your eyes lubricated and on capillary action to pump tear
fluid away.

Figure 10.20 Depending upon the relative strengths of adhesive and cohesive forces, a liquid may rise (such as water) or fall (such
as mercury) in a glass capillary tube. The extent of the rise (or fall) is directly proportional to the surface tension of the liquid and
inversely proportional to the density of the liquid and the radius of the tube.
The height to which a liquid will rise in a capillary tube is determined by several factors as shown in the following equation:
2T cos θ
h =
rρg
In this equation, h is the height of the liquid inside the capillary tube relative to the surface of the liquid outside the tube, T is the
surface tension of the liquid, θ is the contact angle between the liquid and the tube, r is the radius of the tube, ρ is the density of the
liquid, and g is the acceleration due to gravity, 9.8 m/s2. When the tube is made of a material to which the liquid molecules are
strongly attracted, they will spread out completely on the surface, which corresponds to a contact angle of 0°. This is the situation
for water rising in a glass tube.
10.3.0.1: Example 10.4

10.3.0.0.1: Capillary Rise
At 25 °C, how high will water rise in a glass capillary tube with an inner diameter of 0.25 mm?
For water, T = 71.99 mN/m and ρ = 1.0 g/cm3.
The liquid will rise to a height h given by: h = 2T cos θ
rρg
The Newton is defined as a kg m/s , and so the provided surface tension is equivalent to 0.07199 kg/s2. The provided density
2
must be converted into units that will cancel appropriately: ρ = 1000 kg/m3. The diameter of the tube in meters is 0.00025 m,
so the radius is 0.000125 m. For a glass tube immersed in water, the contact angle is θ = 0°, so cos θ = 1. Finally, acceleration
due to gravity on the earth is g = 9.8 m/s2. Substituting these values into the equation, and cancelling units, we have:

2
2 (0.07199 kg/s )
h = = 0.12 m = 12 cm
3 2
(0.000125 m) (1000 kg/m ) (9.8 m/s )

Water rises in a glass capillary tube to a height of 8.4 cm. What is the diameter of the capillary tube?
10.3.0.1: Answer:
diameter = 0.36 mm

10.3.0.0.1: Biomedical Applications of Capillary Action
Many medical tests require drawing a small amount of blood, for example to determine the amount of glucose in someone with
diabetes or the hematocrit level in an athlete. This procedure can be easily done because of capillary action, the ability of a
liquid to flow up a small tube against gravity, as shown in Figure 10.21. When your finger is pricked, a drop of blood forms
and holds together due to surface tension—the unbalanced intermolecular attractions at the surface of the drop. Then, when the
open end of a narrow-diameter glass tube touches the drop of blood, the adhesive forces between the molecules in the blood
and those at the glass surface draw the blood up the tube. How far the blood goes up the tube depends on the diameter of the
tube (and the type of fluid). A small tube has a relatively large surface area for a given volume of blood, which results in larger
(relative) attractive forces, allowing the blood to be drawn farther up the tube. The liquid itself is held together by its own
cohesive forces. When the weight of the liquid in the tube generates a downward force equal to the upward force associated
with capillary action, the liquid stops rising.
Figure 10.21 Blood is collected for medical analysis by capillary action, which draws blood into a small diameter glass tube.
(credit: modification of work by Centers for Disease Control and Prevention)
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Define phase transitions and phase transition temperatures
Explain the relation between phase transition temperatures and intermolecular attractive forces
Describe the processes represented by typical heating and cooling curves, and compute heat flows and enthalpy changes
accompanying these processes
We witness and utilize changes of physical state, or phase transitions, in a great number of ways. As one example of global
significance, consider the evaporation, condensation, freezing, and melting of water. These changes of state are essential aspects of
our earth’s water cycle as well as many other natural phenomena and technological processes of central importance to our lives. In
this module, the essential aspects of phase transitions are explored.
10.4.0.1: Vaporization and Condensation

When a liquid vaporizes in a closed container, gas molecules cannot escape. As these gas phase molecules move randomly about,
they will occasionally collide with the surface of the condensed phase, and in some cases, these collisions will result in the
molecules re-entering the condensed phase. The change from the gas phase to the liquid is called condensation. When the rate of
condensation becomes equal to the rate of vaporization, neither the amount of the liquid nor the amount of the vapor in the
container changes. The vapor in the container is then said to be in equilibrium with the liquid. Keep in mind that this is not a static
situation, as molecules are continually exchanged between the condensed and gaseous phases. Such is an example of a dynamic
equilibrium, the status of a system in which reciprocal processes (for example, vaporization and condensation) occur at equal rates.
The pressure exerted by the vapor in equilibrium with a liquid in a closed container at a given temperature is called the liquid’s
vapor pressure (or equilibrium vapor pressure). The area of the surface of the liquid in contact with a vapor and the size of the
vessel have no effect on the vapor pressure, although they do affect the time required for the equilibrium to be reached. We can
measure the vapor pressure of a liquid by placing a sample in a closed container, like that illustrated in Figure 10.22, and using a
manometer to measure the increase in pressure that is due to the vapor in equilibrium with the condensed phase.
Figure 10.22 In a closed container, dynamic equilibrium is reached when (a) the rate of molecules escaping from the liquid to
become the gas (b) increases and eventually (c) equals the rate of gas molecules entering the liquid. When this equilibrium is
reached, the vapor pressure of the gas is constant, although the vaporization and condensation processes continue.
The chemical identities of the molecules in a liquid determine the types (and strengths) of intermolecular attractions possible;
consequently, different substances will exhibit different equilibrium vapor pressures. Relatively strong intermolecular attractive
forces will serve to impede vaporization as well as favoring “recapture” of gas-phase molecules when they collide with the liquid
surface, resulting in a relatively low vapor pressure. Weak intermolecular attractions present less of a barrier to vaporization, and a
reduced likelihood of gas recapture, yielding relatively high vapor pressures. The following example illustrates this dependence of
vapor pressure on intermolecular attractive forces.
10.4.0.1: Example 10.5

10.4.0.0.1: Explaining Vapor Pressure in Terms of IMFs
Given the shown structural formulas for these four compounds, explain their relative vapor pressures in terms of types and
extents of IMFs:
Diethyl ether has a very small dipole and most of its intermolecular attractions are London forces. Although this molecule is
the largest of the four under consideration, its IMFs are the weakest and, as a result, its molecules most readily escape from the
liquid. It also has the highest vapor pressure. Due to its smaller size, ethanol exhibits weaker dispersion forces than diethyl
ether. However, ethanol is capable of hydrogen bonding and, therefore, exhibits stronger overall IMFs, which means that fewer
molecules escape from the liquid at any given temperature, and so ethanol has a lower vapor pressure than diethyl ether. Water
is much smaller than either of the previous substances and exhibits weaker dispersion forces, but its extensive hydrogen
bonding provides stronger intermolecular attractions, fewer molecules escaping the liquid, and a lower vapor pressure than for
either diethyl ether or ethanol. Ethylene glycol has two −OH groups, so, like water, it exhibits extensive hydrogen bonding. It
is much larger than water and thus experiences larger London forces. Its overall IMFs are the largest of these four substances,
which means its vaporization rate will be the slowest and, consequently, its vapor pressure the lowest.
At 20 °C, the vapor pressures of several alcohols are given in this table. Explain these vapor pressures in terms of types and
extents of IMFs for these alcohols:
Compound methanol CH3OH ethanol C2H5OH propanol C3H7OH butanol C4H9OH
Vapor Pressure at 20 °C 11.9 kPa 5.95 kPa 2.67 kPa 0.56 kPa
10.4.0.1: Answer:
All these compounds exhibit hydrogen bonding; these strong IMFs are difficult for the molecules to overcome, so the
vapor pressures are relatively low. As the size of molecule increases from methanol to butanol, dispersion forces increase,
which means that the vapor pressures decrease as observed:
Pmethanol > Pethanol > Ppropanol > Pbutanol.
As temperature increases, the vapor pressure of a liquid also increases due to the increased average KE of its molecules. Recall that
at any given temperature, the molecules of a substance experience a range of kinetic energies, with a certain fraction of molecules
having a sufficient energy to overcome IMF and escape the liquid (vaporize). At a higher temperature, a greater fraction of
molecules have enough energy to escape from the liquid, as shown in Figure 10.23. The escape of more molecules per unit of time
and the greater average speed of the molecules that escape both contribute to the higher vapor pressure.

Figure 10.23 Temperature affects the distribution of kinetic energies for the molecules in a liquid. At the higher temperature, more
molecules have the necessary kinetic energy, KE, to escape from the liquid into the gas phase.
10.4.0.1: Boiling Points

When the vapor pressure increases enough to equal the external atmospheric pressure, the liquid reaches its boiling point. The
boiling point of a liquid is the temperature at which its equilibrium vapor pressure is equal to the pressure exerted on the liquid by
its gaseous surroundings. For liquids in open containers, this pressure is that due to the earth’s atmosphere. The normal boiling
point of a liquid is defined as its boiling point when surrounding pressure is equal to 1 atm (101.3 kPa). Figure 10.24 shows the
variation in vapor pressure with temperature for several different substances. Considering the definition of boiling point, these
curves may be seen as depicting the dependence of a liquid’s boiling point on surrounding pressure.

Figure 10.24 The boiling points of liquids are the temperatures at which their equilibrium vapor pressures equal the pressure of the
surrounding atmosphere. Normal boiling points are those corresponding to a pressure of 1 atm (101.3 kPa.)
10.4.0.1: Example 10.6

10.4.0.0.1: A Boiling Point at Reduced Pressure
A typical atmospheric pressure in Leadville, Colorado (elevation 10,200 feet) is 68 kPa. Use the graph in Figure 10.24 to
determine the boiling point of water at this elevation.
The graph of the vapor pressure of water versus temperature in Figure 10.24 indicates that the vapor pressure of water is 68
kPa at about 90 °C. Thus, at about 90 °C, the vapor pressure of water will equal the atmospheric pressure in Leadville, and
water will boil.

The boiling point of ethyl ether was measured to be 10 °C at a base camp on the slopes of Mount Everest. Use Figure 10.24 to
determine the approximate atmospheric pressure at the camp.
10.4.0.1: Answer:
Approximately 40 kPa (0.4 atm)
The quantitative relation between a substance’s vapor pressure and its temperature is described by the Clausius-Clapeyron
equation:
−Δ Hva p/RT
P = Ae
where ΔHvap is the enthalpy of vaporization for the liquid, R is the gas constant, and A is a constant whose value depends on the
chemical identity of the substance. Temperature T must be in Kelvin in this equation. This equation is often rearranged into
logarithmic form to yield the linear equation:
ΔHvap
ln P = − + ln A
RT
This linear equation may be expressed in a two-point format that is convenient for use in various computations, as demonstrated in
the example exercises that follow. If at temperature T1, the vapor pressure is P1, and at temperature T2, the vapor pressure is P2, the
corresponding linear equations are:
ΔHvap ΔHvap
ln P1 = − + ln A and ln P2 = − + ln A
RT1 RT2
Since the constant, A, is the same, these two equations may be rearranged to isolate ln A and then set them equal to one another:
ΔHvap ΔHvap
ln P1 + = ln P2 +
RT1 RT2
which can be combined into:
P2 ΔHvap 1 1
ln ( ) = ( − )
P1 R T1 T2
10.4.0.1: Example 10.7

10.4.0.0.4: Estimating Enthalpy of Vaporization
Isooctane (2,2,4-trimethylpentane) has an octane rating of 100. It is used as one of the standards for the octane-rating system
for gasoline. At 34.0 °C, the vapor pressure of isooctane is 10.0 kPa, and at 98.8 °C, its vapor pressure is 100.0 kPa. Use this
information to estimate the enthalpy of vaporization for isooctane.
The enthalpy of vaporization, ΔHvap, can be determined by using the Clausius-Clapeyron equation:
P2 ΔHvap 1 1
ln ( ) = ( − )
P1 R T1 T2
Since we have two vapor pressure-temperature values (T1 = 34.0 °C = 307.2 K, P1 = 10.0 kPa and T2 = 98.8 °C = 372.0 K, P2
= 100 kPa), we can substitute them into this equation and solve for ΔHvap. Rearranging the Clausius-Clapeyron equation and
solving for ΔHvap yields:
P2 100 kPa
R⋅ln ( ) (8.3145 J/mol⋅K) ⋅ln ( )
P1 10.0 kPa
ΔHvap = = = 33,800 J/mol = 33.8 kJ/mol

1 1 1 1
( − ) ( − )
T1 T2 307.2 K 372.0 K
Note that the pressure can be in any units, so long as they agree for both P values, but the temperature must be in kelvin for the
Clausius-Clapeyron equation to be valid.

At 20.0 °C, the vapor pressure of ethanol is 5.95 kPa, and at 63.5 °C, its vapor pressure is 53.3 kPa. Use this information to
estimate the enthalpy of vaporization for ethanol.
10.4.0.1: Answer:
41,360 J/mol or 41.4 kJ/mol
10.4.0.1: Example 10.8

10.4.0.0.7: Estimating Temperature (or Vapor Pressure)
For benzene (C6H6), the normal boiling point is 80.1 °C and the enthalpy of vaporization is 30.8 kJ/mol. What is the boiling
point of benzene in Denver, where atmospheric pressure = 83.4 kPa?
If the temperature and vapor pressure are known at one point, along with the enthalpy of vaporization, ΔHvap, then the
temperature that corresponds to a different vapor pressure (or the vapor pressure that corresponds to a different temperature)
can be determined by using the Clausius-Clapeyron equation:
P2 ΔHvap 1 1
ln ( ) = ( − )
P1 R T1 T2
Since the normal boiling point is the temperature at which the vapor pressure equals atmospheric pressure at sea level, we
know one vapor pressure-temperature value (T1 = 80.1 °C = 353.3 K, P1 = 101.3 kPa, ΔHvap = 30.8 kJ/mol) and want to find
the temperature (T2) that corresponds to vapor pressure P2 = 83.4 kPa. We can substitute these values into the Clausius-
Clapeyron equation and then solve for T2. Rearranging the Clausius-Clapeyron equation and solving for T2 yields:
−1 −1
P2 83.4 kPa
⎛ −R⋅ln ( ) ⎞ ⎛ − (8.3145 J/mol⋅K) ⋅ln ( ) ⎞
P1 1 101.3 kPa 1 ∘
T2 = ⎜ + ⎟ = ⎜ + ⎟ = 346.9 K or 73.8 C
ΔHvap T1 30,800 J/mol 353.3 K
⎝ ⎠ ⎝ ⎠

For acetone (CH3)2CO, the normal boiling point is 56.5 °C and the enthalpy of vaporization is 31.3 kJ/mol. What is the vapor
pressure of acetone at 25.0 °C?
10.4.0.1: Answer:
30.1 kPa
10.4.0.1: Enthalpy of Vaporization

Vaporization is an endothermic process. The cooling effect can be evident when you leave a swimming pool or a shower. When the
water on your skin evaporates, it removes heat from your skin and causes you to feel cold. The energy change associated with the
vaporization process is the enthalpy of vaporization, ΔHvap. For example, the vaporization of water at standard temperature is
represented by:
H2 O(l) ⟶ H2 O(g) ΔHvap = 44.01 kJ/mol
As described in the chapter on thermochemistry, the reverse of an endothermic process is exothermic. And so, the condensation of
a gas releases heat:
H2 O(g) ⟶ H2 O(l) ΔHcon = −ΔHvap = −44.01 kJ/mol
10.4.0.1: Example 10.9

10.4.0.0.1: Using Enthalpy of Vaporization
One way our body is cooled is by evaporation of the water in sweat (Figure 10.25). In very hot climates, we can lose as much
as 1.5 L of sweat per day. Although sweat is not pure water, we can get an approximate value of the amount of heat removed
by evaporation by assuming that it is. How much heat is required to evaporate 1.5 L of water (1.5 kg) at T = 37 °C (normal
body temperature); ΔHvap = 43.46 kJ/mol at 37 °C.

Figure 10.25 Evaporation of sweat helps cool the body. (credit: “Kullez”/Flickr)
We start with the known volume of sweat (approximated as just water) and use the given information to convert to the amount
of heat needed:
1000 g 1 mol 43.46 kJ
3
1.5 L × × × = 3.6 × 10 kJ
1 L 18 g 1 mol
Thus, 3600 kJ of heat are removed by the evaporation of 1.5 L of water.

How much heat is required to evaporate 100.0 g of liquid ammonia, NH3, at its boiling point if its enthalpy of vaporization is
4.8 kJ/mol?
10.4.0.1: Answer:
28 kJ
10.4.0.1: Melting and Freezing

When we heat a crystalline solid, we increase the average energy of its atoms, molecules, or ions and the solid gets hotter. At some
point, the added energy becomes large enough to partially overcome the forces holding the molecules or ions of the solid in their
fixed positions, and the solid begins the process of transitioning to the liquid state, or melting. At this point, the temperature of the
solid stops rising, despite the continual input of heat, and it remains constant until all of the solid is melted. Only after all of the
solid has melted will continued heating increase the temperature of the liquid (Figure 10.26).
Figure 10.26 (a) This beaker of ice has a temperature of −12.0 °C. (b) After 10 minutes the ice has absorbed enough heat from the
air to warm to 0 °C. A small amount has melted. (c) Thirty minutes later, the ice has absorbed more heat, but its temperature is still
0 °C. The ice melts without changing its temperature. (d) Only after all the ice has melted does the heat absorbed cause the
temperature to increase to 22.2 °C. (credit: modification of work by Mark Ott)

If we stop heating during melting and place the mixture of solid and liquid in a perfectly insulated container so no heat can enter or
escape, the solid and liquid phases remain in equilibrium. This is almost the situation with a mixture of ice and water in a very good
thermos bottle; almost no heat gets in or out, and the mixture of solid ice and liquid water remains for hours. In a mixture of solid
and liquid at equilibrium, the reciprocal processes of melting and freezing occur at equal rates, and the quantities of solid and liquid
therefore remain constant. The temperature at which the solid and liquid phases of a given substance are in equilibrium is called the
melting point of the solid or the freezing point of the liquid. Use of one term or the other is normally dictated by the direction of the
phase transition being considered, for example, solid to liquid (melting) or liquid to solid (freezing).
The enthalpy of fusion and the melting point of a crystalline solid depend on the strength of the attractive forces between the units
present in the crystal. Molecules with weak attractive forces form crystals with low melting points. Crystals consisting of particles
with stronger attractive forces melt at higher temperatures.
The amount of heat required to change one mole of a substance from the solid state to the liquid state is the enthalpy of fusion,
ΔHfus of the substance. The enthalpy of fusion of ice is 6.0 kJ/mol at 0 °C. Fusion (melting) is an endothermic process:
H2 O(s) ⟶ H2 O(l) ΔHfus = 6.01 kJ/mol
The reciprocal process, freezing, is an exothermic process whose enthalpy change is −6.0 kJ/mol at 0 °C:
H2 O(l) ⟶ H2 O(s) ΔHfrz = −ΔHfus = −6.01 kJ/mol
10.4.0.1: Sublimation and Deposition

Some solids can transition directly into the gaseous state, bypassing the liquid state, via a process known as sublimation. At room
temperature and standard pressure, a piece of dry ice (solid CO2) sublimes, appearing to gradually disappear without ever forming
any liquid. Snow and ice sublime at temperatures below the melting point of water, a slow process that may be accelerated by
winds and the reduced atmospheric pressures at high altitudes. When solid iodine is warmed, the solid sublimes and a vivid purple
vapor forms (Figure 10.27). The reverse of sublimation is called deposition, a process in which gaseous substances condense
directly into the solid state, bypassing the liquid state. The formation of frost is an example of deposition.

Figure 10.27 Sublimation of solid iodine in the bottom of the tube produces a purple gas that subsequently deposits as solid iodine
on the colder part of the tube above. (credit: modification of work by Mark Ott)
Like vaporization, the process of sublimation requires an input of energy to overcome intermolecular attractions. The enthalpy of
sublimation, ΔHsub, is the energy required to convert one mole of a substance from the solid to the gaseous state. For example, the
sublimation of carbon dioxide is represented by:
CO2 (s) ⟶ CO2 (g) ΔHsub = 26.1 kJ/mol
Likewise, the enthalpy change for the reverse process of deposition is equal in magnitude but opposite in sign to that for
sublimation:
CO2 (g) ⟶ CO2 (s) ΔHdep = −ΔHsub = −26.1 kJ/mol
Consider the extent to which intermolecular attractions must be overcome to achieve a given phase transition. Converting a solid
into a liquid requires that these attractions be only partially overcome; transition to the gaseous state requires that they be
completely overcome. As a result, the enthalpy of fusion for a substance is less than its enthalpy of vaporization. This same logic
can be used to derive an approximate relation between the enthalpies of all phase changes for a given substance. Though not an
entirely accurate description, sublimation may be conveniently modeled as a sequential two-step process of melting followed by
vaporization in order to apply Hess’s Law. Viewed in this manner, the enthalpy of sublimation for a substance may be estimated as
the sum of its enthalpies of fusion and vaporization, as illustrated in Figure 10.28. For example:
solid ⟶ liquid ΔHfus
liquid ⟶ gas ΔHvap
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
solid ⟶ gas ΔHsub = ΔHfus + ΔHvap

Figure 10.28 For a given substance, the sum of its enthalpy of fusion and enthalpy of vaporization is approximately equal to its
enthalpy of sublimation.
10.4.0.1: Heating and Cooling Curves

In the chapter on thermochemistry, the relation between the amount of heat absorbed or released by a substance, q, and its
accompanying temperature change, ΔT, was introduced:
q = mcΔT
where m is the mass of the substance and c is its specific heat. The relation applies to matter being heated or cooled, but not
undergoing a change in state. When a substance being heated or cooled reaches a temperature corresponding to one of its phase
transitions, further gain or loss of heat is a result of diminishing or enhancing intermolecular attractions, instead of increasing or
decreasing molecular kinetic energies. While a substance is undergoing a change in state, its temperature remains constant. Figure
10.29 shows a typical heating curve.
Consider the example of heating a pot of water to boiling. A stove burner will supply heat at a roughly constant rate; initially, this
heat serves to increase the water’s temperature. When the water reaches its boiling point, the temperature remains constant despite
the continued input of heat from the stove burner. This same temperature is maintained by the water as long as it is boiling. If the
burner setting is increased to provide heat at a greater rate, the water temperature does not rise, but instead the boiling becomes

more vigorous (rapid). This behavior is observed for other phase transitions as well: For example, temperature remains constant
while the change of state is in progress.
Figure 10.29 A typical heating curve for a substance depicts changes in temperature that result as the substance absorbs increasing
amounts of heat. Plateaus in the curve (regions of constant temperature) are exhibited when the substance undergoes phase
transitions.
10.4.0.1: Example 10.10

10.4.0.0.1: Total Heat Needed to Change Temperature and Phase for a Substance
How much heat is required to convert 135 g of ice at −15 °C into water vapor at 120 °C?
The transition described involves the following steps:
1. Heat ice from −15 °C to 0 °C
2. Melt ice
3. Heat water from 0 °C to 100 °C
4. Boil water
5. Heat steam from 100 °C to 120 °C
The heat needed to change the temperature of a given substance (with no change in phase) is: q = m × c × ΔT (see previous
chapter on thermochemistry). The heat needed to induce a given change in phase is given by q = n × ΔH.
Using these equations with the appropriate values for specific heat of ice, water, and steam, and enthalpies of fusion and
vaporization, we have:
qtotal = (m⋅c⋅ΔT ) + n⋅ΔHfus + (m⋅c⋅ΔT ) + n⋅ΔHvap + (m⋅c⋅ΔT )
ice water steam

1 mol
= (135 g⋅2.09 J/g⋅°C⋅15°C) + (135⋅ ⋅6.01 kJ/mol)
18.02 g
1 mol
+ (135 g⋅4.18 J/g⋅°C⋅100°C) + (135 g⋅ ⋅40.67 kJ/mol)
18.02 g
+ (135 g⋅1.84 J/g⋅°C⋅20°C)
= 4230 J + 45.0 kJ + 56,500 J + 305 kJ + 4970 J
Converting the quantities in J to kJ permits them to be summed, yielding the total heat required:
= 4.23 kJ + 45.0 kJ + 56.5 kJ + 305 kJ + 4.97 kJ = 416 kJ
NOTE: The value of ΔHvap at the boiling point of water (40.67 kJ/mol) is used here instead of the value at standard
temperature (44.01 kJ/mol).
What is the total amount of heat released when 94.0 g water at 80.0 °C cools to form ice at −30.0 °C?
10.4.0.1: Answer:
68.7 kJ
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Explain the construction and use of a typical phase diagram
Use phase diagrams to identify stable phases at given temperatures and pressures, and to describe phase transitions
resulting from changes in these properties
Describe the supercritical fluid phase of matter
In the previous module, the variation of a liquid’s equilibrium vapor pressure with temperature was described. Considering the
definition of boiling point, plots of vapor pressure versus temperature represent how the boiling point of the liquid varies with
pressure. Also described was the use of heating and cooling curves to determine a substance’s melting (or freezing) point. Making
such measurements over a wide range of pressures yields data that may be presented graphically as a phase diagram. A phase
diagram combines plots of pressure versus temperature for the liquid-gas, solid-liquid, and solid-gas phase-transition equilibria of a
substance. These diagrams indicate the physical states that exist under specific conditions of pressure and temperature, and also
provide the pressure dependence of the phase-transition temperatures (melting points, sublimation points, boiling points). A typical
phase diagram for a pure substance is shown in Figure 10.30.
Figure 10.30 The physical state of a substance and its phase-transition temperatures are represented graphically in a phase diagram.
To illustrate the utility of these plots, consider the phase diagram for water shown in Figure 10.31.

Figure 10.31 The pressure and temperature axes on this phase diagram of water are not drawn to constant scale in order to illustrate
several important properties.
We can use the phase diagram to identify the physical state of a sample of water under specified conditions of pressure and
temperature. For example, a pressure of 50 kPa and a temperature of −10 °C correspond to the region of the diagram labeled “ice.”
Under these conditions, water exists only as a solid (ice). A pressure of 50 kPa and a temperature of 50 °C correspond to the
“water” region—here, water exists only as a liquid. At 25 kPa and 200 °C, water exists only in the gaseous state. Note that on the
H2O phase diagram, the pressure and temperature axes are not drawn to a constant scale in order to permit the illustration of several
important features as described here.
The curve BC in Figure 10.31 is the plot of vapor pressure versus temperature as described in the previous module of this chapter.
This “liquid-vapor” curve separates the liquid and gaseous regions of the phase diagram and provides the boiling point for water at
any pressure. For example, at 1 atm, the boiling point is 100 °C. Notice that the liquid-vapor curve terminates at a temperature of
374 °C and a pressure of 218 atm, indicating that water cannot exist as a liquid above this temperature, regardless of the pressure.
The physical properties of water under these conditions are intermediate between those of its liquid and gaseous phases. This
unique state of matter is called a supercritical fluid, a topic that will be described in the next section of this module.
The solid-vapor curve, labeled AB in Figure 10.31, indicates the temperatures and pressures at which ice and water vapor are in
equilibrium. These temperature-pressure data pairs correspond to the sublimation, or deposition, points for water. If we could zoom
in on the solid-gas line in Figure 10.31, we would see that ice has a vapor pressure of about 0.20 kPa at −10 °C. Thus, if we place a
frozen sample in a vacuum with a pressure less than 0.20 kPa, ice will sublime. This is the basis for the “freeze-drying” process
often used to preserve foods, such as the ice cream shown in Figure 10.32.

Figure 10.32 Freeze-dried foods, like this ice cream, are dehydrated by sublimation at pressures below the triple point for water.
(credit: ʺlwaoʺ/Flickr)
The solid-liquid curve labeled BD shows the temperatures and pressures at which ice and liquid water are in equilibrium,
representing the melting/freezing points for water. Note that this curve exhibits a slight negative slope (greatly exaggerated for
clarity), indicating that the melting point for water decreases slightly as pressure increases. Water is an unusual substance in this
regard, as most substances exhibit an increase in melting point with increasing pressure. This behavior is partly responsible for the
movement of glaciers, like the one shown in Figure 10.33. The bottom of a glacier experiences an immense pressure due to its
weight that can melt some of the ice, forming a layer of liquid water on which the glacier may more easily slide.
Figure 10.33 The immense pressures beneath glaciers result in partial melting to produce a layer of water that provides lubrication
to assist glacial movement. This satellite photograph shows the advancing edge of the Perito Moreno glacier in Argentina. (credit:
NASA)
The point of intersection of all three curves is labeled B in Figure 10.31. At the pressure and temperature represented by this point,
three phases of water coexist in equilibrium. This temperature-pressure data pair is called the triple point. At pressures lower than
the triple point, water cannot exist as a liquid, regardless of the temperature.
10.5.0.1: Example 10.11

10.5.0.0.1: Determining the State of Water
Using the phase diagram for water given in Figure 10.31, determine the state of water at the following temperatures and
pressures:
(a) −10 °C and 50 kPa
(b) 25 °C and 90 kPa
(c) 50 °C and 40 kPa
(d) 80 °C and 5 kPa
(e) −10 °C and 0.3 kPa
(f) 50 °C and 0.3 kPa
Using the phase diagram for water, we can determine that the state of water at each temperature and pressure given are as
follows: (a) solid; (b) liquid; (c) liquid; (d) gas; (e) solid; (f) gas.
What phase changes can water undergo as the temperature changes if the pressure is held at 0.3 kPa? If the pressure is held at
50 kPa?
10.5.0.1: Answer:
At 0.3 kPa: s ⟶ g at −58 °C. At 50 kPa: s ⟶ l at 0 °C, l ⟶ g at 78 °C
Consider the phase diagram for carbon dioxide shown in Figure 10.34 as another example. The solid-liquid curve exhibits a
positive slope, indicating that the melting point for CO2 increases with pressure as it does for most substances (water being a
notable exception as described previously). Notice that the triple point is well above 1 atm, indicating that carbon dioxide cannot
exist as a liquid under ambient pressure conditions. Instead, cooling gaseous carbon dioxide at 1 atm results in its deposition into
the solid state. Likewise, solid carbon dioxide does not melt at 1 atm pressure but instead sublimes to yield gaseous CO2. Finally,
notice that the critical point for carbon dioxide is observed at a relatively modest temperature and pressure in comparison to water.
Figure 10.34 A phase diagram for carbon dioxide is shown. The pressure axis is plotted on a logarithmic scale to accommodate the
large range of values.

10.5.0.1: Example 10.12
10.5.0.0.1: Determining the State of Carbon Dioxide
Using the phase diagram for carbon dioxide shown in Figure 10.34, determine the state of CO2 at the following temperatures
and pressures:
(a) −30 °C and 2000 kPa
(b) −90 °C and 1000 kPa
(c) −60 °C and 100 kPa
(d) −40 °C and 1500 kPa
(e) 0 °C and 100 kPa
(f) 20 °C and 100 kPa
Using the phase diagram for carbon dioxide provided, we can determine that the state of CO2 at each temperature and pressure
given are as follows: (a) liquid; (b) solid; (c) gas; (d) liquid; (e) gas; (f) gas.
Identify the phase changes that carbon dioxide will undergo as its temperature is increased from −100 °C while holding its
pressure constant at 1500 kPa. At 50 kPa. At what approximate temperatures do these phase changes occur?
10.5.0.1: Answer:
at 1500 kPa: s ⟶ l at −55 °C, l ⟶ g at −10 °C;
at 50 kPa: s ⟶ g at −60 °C
10.5.0.1: Supercritical Fluids

If we place a sample of water in a sealed container at 25 °C, remove the air, and let the vaporization-condensation equilibrium
establish itself, we are left with a mixture of liquid water and water vapor at a pressure of 0.03 atm. A distinct boundary between
the more dense liquid and the less dense gas is clearly observed. As we increase the temperature, the pressure of the water vapor
increases, as described by the liquid-gas curve in the phase diagram for water (Figure 10.31), and a two-phase equilibrium of liquid
and gaseous phases remains. At a temperature of 374 °C, the vapor pressure has risen to 218 atm, and any further increase in
temperature results in the disappearance of the boundary between liquid and vapor phases. All of the water in the container is now
present in a single phase whose physical properties are intermediate between those of the gaseous and liquid states. This phase of
matter is called a supercritical fluid, and the temperature and pressure above which this phase exists is the critical point (Figure
10.35). Above its critical temperature, a gas cannot be liquefied no matter how much pressure is applied. The pressure required to
liquefy a gas at its critical temperature is called the critical pressure. The critical temperatures and critical pressures of some
common substances are given in the following table.
Substance Critical Temperature (°C) Critical Pressure (kPa)
hydrogen −240.0 1300
nitrogen −147.2 3400
oxygen −118.9 5000
carbon dioxide 31.1 7400
ammonia 132.4 11,300
sulfur dioxide 157.2 7800

Substance Critical Temperature (°C) Critical Pressure (kPa)
water 374.0 22,000
Figure 10.35 (a) A sealed container of liquid carbon dioxide slightly below its critical point is heated, resulting in (b) the formation
of the supercritical fluid phase. Cooling the supercritical fluid lowers its temperature and pressure below the critical point, resulting
in the reestablishment of separate liquid and gaseous phases (c and d). Colored floats illustrate differences in density between the
liquid, gaseous, and supercritical fluid states. (credit: modification of work by “mrmrobin”/YouTube)

Observe the liquid-to-supercritical fluid transition for carbon dioxide.
Like a gas, a supercritical fluid will expand and fill a container, but its density is much greater than typical gas densities, typically
being close to those for liquids. Similar to liquids, these fluids are capable of dissolving nonvolatile solutes. They exhibit
essentially no surface tension and very low viscosities, however, so they can more effectively penetrate very small openings in a
solid mixture and remove soluble components. These properties make supercritical fluids extremely useful solvents for a wide
range of applications. For example, supercritical carbon dioxide has become a very popular solvent in the food industry, being used
to decaffeinate coffee, remove fats from potato chips, and extract flavor and fragrance compounds from citrus oils. It is nontoxic,
relatively inexpensive, and not considered to be a pollutant. After use, the CO2 can be easily recovered by reducing the pressure
and collecting the resulting gas.
10.5.0.1: Example 10.13

10.5.0.0.1: The Critical Temperature of Carbon Dioxide
If we shake a carbon dioxide fire extinguisher on a cool day (18 °C), we can hear liquid CO2 sloshing around inside the
cylinder. However, the same cylinder appears to contain no liquid on a hot summer day (35 °C). Explain these observations.
On the cool day, the temperature of the CO2 is below the critical temperature of CO2, 304 K or 31 °C, so liquid CO2 is present
in the cylinder. On the hot day, the temperature of the CO2 is greater than its critical temperature of 31 °C. Above this
temperature no amount of pressure can liquefy CO2 so no liquid CO2 exists in the fire extinguisher.
Ammonia can be liquefied by compression at room temperature; oxygen cannot be liquefied under these conditions. Why do
the two gases exhibit different behavior?
10.5.0.1: Answer:
The critical temperature of ammonia is 405.5 K, which is higher than room temperature. The critical temperature of
oxygen is below room temperature; thus oxygen cannot be liquefied at room temperature.

10.5.0.0.4: Decaffeinating Coffee Using Supercritical CO2
Coffee is the world’s second most widely traded commodity, following only petroleum. Across the globe, people love coffee’s
aroma and taste. Many of us also depend on one component of coffee—caffeine—to help us get going in the morning or stay

alert in the afternoon. But late in the day, coffee’s stimulant effect can keep you from sleeping, so you may choose to drink
decaffeinated coffee in the evening.
Since the early 1900s, many methods have been used to decaffeinate coffee. All have advantages and disadvantages, and all
depend on the physical and chemical properties of caffeine. Because caffeine is a somewhat polar molecule, it dissolves well in
water, a polar liquid. However, since many of the other 400-plus compounds that contribute to coffee’s taste and aroma also
dissolve in H2O, hot water decaffeination processes can also remove some of these compounds, adversely affecting the smell
and taste of the decaffeinated coffee. Dichloromethane (CH2Cl2) and ethyl acetate (CH3CO2C2H5) have similar polarity to
caffeine, and are therefore very effective solvents for caffeine extraction, but both also remove some flavor and aroma
components, and their use requires long extraction and cleanup times. Because both of these solvents are toxic, health concerns
have been raised regarding the effect of residual solvent remaining in the decaffeinated coffee.
Supercritical fluid extraction using carbon dioxide is now being widely used as a more effective and environmentally friendly
decaffeination method (Figure 10.36). At temperatures above 304.2 K and pressures above 7376 kPa, CO2 is a supercritical
fluid, with properties of both gas and liquid. Like a gas, it penetrates deep into the coffee beans; like a liquid, it effectively
dissolves certain substances. Supercritical carbon dioxide extraction of steamed coffee beans removes 97−99% of the caffeine,
leaving coffee’s flavor and aroma compounds intact. Because CO2 is a gas under standard conditions, its removal from the
extracted coffee beans is easily accomplished, as is the recovery of the caffeine from the extract. The caffeine recovered from
coffee beans via this process is a valuable product that can be used subsequently as an additive to other foods or drugs.
Figure 10.36 (a) Caffeine molecules have both polar and nonpolar regions, making it soluble in solvents of varying polarities.
(b) The schematic shows a typical decaffeination process involving supercritical carbon dioxide.
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Define and describe the bonding and properties of ionic, molecular, metallic, and covalent network crystalline solids
Describe the main types of crystalline solids: ionic solids, metallic solids, covalent network solids, and molecular solids
Explain the ways in which crystal defects can occur in a solid
When most liquids are cooled, they eventually freeze and form crystalline solids, solids in which the atoms, ions, or molecules are
arranged in a definite repeating pattern. It is also possible for a liquid to freeze before its molecules become arranged in an orderly
pattern. The resulting materials are called amorphous solids or noncrystalline solids (or, sometimes, glasses). The particles of such
solids lack an ordered internal structure and are randomly arranged (Figure 10.37).
Figure 10.37 The entities of a solid phase may be arranged in a regular, repeating pattern (crystalline solids) or randomly
(amorphous).
Metals and ionic compounds typically form ordered, crystalline solids. Substances that consist of large molecules, or a mixture of
molecules whose movements are more restricted, often form amorphous solids. For examples, candle waxes are amorphous solids
composed of large hydrocarbon molecules. Some substances, such as silicon dioxide (shown in Figure 10.38), can form either
crystalline or amorphous solids, depending on the conditions under which it is produced. Also, amorphous solids may undergo a
transition to the crystalline state under appropriate conditions.
Figure 10.38 (a) Silicon dioxide, SiO2, is abundant in nature as one of several crystalline forms of the mineral quartz. (b) Rapid
cooling of molten SiO2 yields an amorphous solid known as “fused silica”.
Crystalline solids are generally classified according to the nature of the forces that hold its particles together. These forces are
primarily responsible for the physical properties exhibited by the bulk solids. The following sections provide descriptions of the

major types of crystalline solids: ionic, metallic, covalent network, and molecular.
10.6.0.1: Ionic Solids

Ionic solids, such as sodium chloride and nickel oxide, are composed of positive and negative ions that are held together by
electrostatic attractions, which can be quite strong (Figure 10.39). Many ionic crystals also have high melting points. This is due to
the very strong attractions between the ions—in ionic compounds, the attractions between full charges are (much) larger than those
between the partial charges in polar molecular compounds. This will be looked at in more detail in a later discussion of lattice
energies. Although they are hard, they also tend to be brittle, and they shatter rather than bend. Ionic solids do not conduct
electricity; however, they do conduct when molten or dissolved because their ions are free to move. Many simple compounds
formed by the reaction of a metallic element with a nonmetallic element are ionic.
Figure 10.39 Sodium chloride is an ionic solid.
10.6.0.1: Metallic Solids

Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms Figure 10.40. The structure of metallic
crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such
a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk
properties. All exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many are very hard and quite
strong. Because of their malleability (the ability to deform under pressure or hammering), they do not shatter and, therefore, make
useful construction materials. The melting points of the metals vary widely. Mercury is a liquid at room temperature, and the alkali
metals melt below 200 °C. Several post-transition metals also have low melting points, whereas the transition metals melt at
temperatures above 1000 °C. These differences reflect differences in strengths of metallic bonding among the metals.
Figure 10.40 Copper is a metallic solid.
10.6.0.1: Covalent Network Solid

Covalent network solids include crystals of diamond, silicon, some other nonmetals, and some covalent compounds such as silicon
dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of covalent bonds. The
atoms in these solids are held together by a network of covalent bonds, as shown in Figure 10.41. To break or to melt a covalent
network solid, covalent bonds must be broken. Because covalent bonds are relatively strong, covalent network solids are typically
characterized by hardness, strength, and high melting points. For example, diamond is one of the hardest substances known and
melts above 3500 °C.

Figure 10.41 A covalent crystal contains a three-dimensional network of covalent bonds, as illustrated by the structures of
diamond, silicon dioxide, silicon carbide, and graphite. Graphite is an exceptional example, composed of planar sheets of covalent
crystals that are held together in layers by noncovalent forces. Unlike typical covalent solids, graphite is very soft and electrically
conductive.
10.6.0.1: Molecular Solid

Molecular solids, such as ice, sucrose (table sugar), and iodine, as shown in Figure 10.42, are composed of neutral molecules. The
strengths of the attractive forces between the units present in different crystals vary widely, as indicated by the melting points of the
crystals. Small symmetrical molecules (nonpolar molecules), such as H2, N2, O2, and F2, have weak attractive forces and form
molecular solids with very low melting points (below −200 °C). Substances consisting of larger, nonpolar molecules have larger
attractive forces and melt at higher temperatures. Molecular solids composed of molecules with permanent dipole moments (polar
molecules) melt at still higher temperatures. Examples include ice (melting point, 0 °C) and table sugar (melting point, 185 °C).
Figure 10.42 Carbon dioxide (CO2) consists of small, nonpolar molecules and forms a molecular solid with a melting point of −78
°C. Iodine (I2) consists of larger, nonpolar molecules and forms a molecular solid that melts at 114 °C.

10.6.0.1: Properties of Solids
A crystalline solid, like those listed in Table 10.4, has a precise melting temperature because each atom or molecule of the same
type is held in place with the same forces or energy. Thus, the attractions between the units that make up the crystal all have the
same strength and all require the same amount of energy to be broken. The gradual softening of an amorphous material differs
dramatically from the distinct melting of a crystalline solid. This results from the structural nonequivalence of the molecules in the
amorphous solid. Some forces are weaker than others, and when an amorphous material is heated, the weakest intermolecular
attractions break first. As the temperature is increased further, the stronger attractions are broken. Thus amorphous materials soften
over a range of temperatures.
Types of Crystalline Solids and Their Properties
Type of Type of Particles Type of Properties Examples
Solid Attractions
ionic ions ionic hard, brittle, conducts electricity as a liquid but not as a solid, NaCl, Al2O3
bonds high to very high melting points
metallic atoms of metallic shiny, malleable, ductile, conducts heat and electricity well, Cu, Fe, Ti, Pb,
electropositive bonds variable hardness and melting temperature U
elements
covalent atoms of covalent very hard, not conductive, very high melting points C (diamond),
network electronegative bonds SiO2, SiC
elements
molecular molecules (or IMFs variable hardness, variable brittleness, not conductive, low H2O, CO2, I2,
atoms) melting points C12H22O11
Table 10.4

10.6.0.0.1: Graphene: Material of the Future
Carbon is an essential element in our world. The unique properties of carbon atoms allow the existence of carbon-based life
forms such as ourselves. Carbon forms a huge variety of substances that we use on a daily basis, including those shown in
Figure 10.43. You may be familiar with diamond and graphite, the two most common allotropes of carbon. (Allotropes are
different structural forms of the same element.) Diamond is one of the hardest-known substances, whereas graphite is soft
enough to be used as pencil lead. These very different properties stem from the different arrangements of the carbon atoms in
the different allotropes.

Figure 10.43 Diamond is extremely hard because of the strong bonding between carbon atoms in all directions. Graphite (in
pencil lead) rubs off onto paper due to the weak attractions between the carbon layers. An image of a graphite surface shows
the distance between the centers of adjacent carbon atoms. (credit left photo: modification of work by Steve Jurvetson; credit
middle photo: modification of work by United States Geological Survey)
You may be less familiar with a recently discovered form of carbon: graphene. Graphene was first isolated in 2004 by using
tape to peel off thinner and thinner layers from graphite. It is essentially a single sheet (one atom thick) of graphite. Graphene,
illustrated in Figure 10.44, is not only strong and lightweight, but it is also an excellent conductor of electricity and heat. These
properties may prove very useful in a wide range of applications, such as vastly improved computer chips and circuits, better
batteries and solar cells, and stronger and lighter structural materials. The 2010 Nobel Prize in Physics was awarded to Andre
Geim and Konstantin Novoselov for their pioneering work with graphene.

Figure 10.44 Graphene sheets can be formed into buckyballs, nanotubes, and stacked layers.

10.6.0.1: Crystal Defects
In a crystalline solid, the atoms, ions, or molecules are arranged in a definite repeating pattern, but occasional defects may occur in
the pattern. Several types of defects are known, as illustrated in Figure 10.45. Vacancies are defects that occur when positions that
should contain atoms or ions are vacant. Less commonly, some atoms or ions in a crystal may occupy positions, called interstitial
sites, located between the regular positions for atoms. Other distortions are found in impure crystals, as, for example, when the
cations, anions, or molecules of the impurity are too large to fit into the regular positions without distorting the structure. Trace
amounts of impurities are sometimes added to a crystal (a process known as doping) in order to create defects in the structure that
yield desirable changes in its properties. For example, silicon crystals are doped with varying amounts of different elements to
yield suitable electrical properties for their use in the manufacture of semiconductors and computer chips.
Figure 10.45 Types of crystal defects include vacancies, interstitial atoms, and substitutions impurities.
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Describe the arrangement of atoms and ions in crystalline structures
Compute ionic radii using unit cell dimensions
Explain the use of X-ray diffraction measurements in determining crystalline structures
Over 90% of naturally occurring and man-made solids are crystalline. Most solids form with a regular arrangement of their
particles because the overall attractive interactions between particles are maximized, and the total intermolecular energy is
minimized, when the particles pack in the most efficient manner. The regular arrangement at an atomic level is often reflected at a
macroscopic level. In this module, we will explore some of the details about the structures of metallic and ionic crystalline solids,
and learn how these structures are determined experimentally.
10.7.0.1: The Structures of Metals

We will begin our discussion of crystalline solids by considering elemental metals, which are relatively simple because each
contains only one type of atom. A pure metal is a crystalline solid with metal atoms packed closely together in a repeating pattern.
Some of the properties of metals in general, such as their malleability and ductility, are largely due to having identical atoms
arranged in a regular pattern. The different properties of one metal compared to another partially depend on the sizes of their atoms
and the specifics of their spatial arrangements. We will explore the similarities and differences of four of the most common metal
crystal geometries in the sections that follow.
10.7.0.1: Unit Cells of Metals

The structure of a crystalline solid, whether a metal or not, is best described by considering its simplest repeating unit, which is
referred to as its unit cell. The unit cell consists of lattice points that represent the locations of atoms or ions. The entire structure
then consists of this unit cell repeating in three dimensions, as illustrated in Figure 10.46.
Figure 10.46 A unit cell shows the locations of lattice points repeating in all directions.
Let us begin our investigation of crystal lattice structure and unit cells with the most straightforward structure and the most basic
unit cell. To visualize this, imagine taking a large number of identical spheres, such as tennis balls, and arranging them uniformly in
a container. The simplest way to do this would be to make layers in which the spheres in one layer are directly above those in the
layer below, as illustrated in Figure 10.47. This arrangement is called simple cubic structure, and the unit cell is called the simple
cubic unit cell or primitive cubic unit cell.

Figure 10.47 When metal atoms are arranged with spheres in one layer directly above or below spheres in another layer, the lattice
structure is called simple cubic. Note that the spheres are in contact.
In a simple cubic structure, the spheres are not packed as closely as they could be, and they only “fill” about 52% of the volume of
the container. This is a relatively inefficient arrangement, and only one metal (polonium, Po) crystallizes in a simple cubic
structure. As shown in Figure 10.48, a solid with this type of arrangement consists of planes (or layers) in which each atom
contacts only the four nearest neighbors in its layer; one atom directly above it in the layer above; and one atom directly below it in
the layer below. The number of other particles that each particle in a crystalline solid contacts is known as its coordination number.
For a polonium atom in a simple cubic array, the coordination number is, therefore, six.
Figure 10.48 An atom in a simple cubic lattice structure contacts six other atoms, so it has a coordination number of six.
In a simple cubic lattice, the unit cell that repeats in all directions is a cube defined by the centers of eight atoms, as shown in
Figure 10.49. Atoms at adjacent corners of this unit cell contact each other, so the edge length of this cell is equal to two atomic
radii, or one atomic diameter. A cubic unit cell contains only the parts of these atoms that are within it. Since an atom at a corner of
a simple cubic unit cell is contained by a total of eight unit cells, only one-eighth of that atom is within a specific unit cell. And
since each simple cubic unit cell has one atom at each of its eight “corners,” there is 8 × 1
8
= 1 atom within one simple cubic unit
cell.

Figure 10.49 A simple cubic lattice unit cell contains one-eighth of an atom at each of its eight corners, so it contains one atom
total.
10.7.0.1: Example 10.14

10.7.0.0.1: Calculation of Atomic Radius and Density for Metals, Part 1
The edge length of the unit cell of alpha polonium is 336 pm.
(a) Determine the radius of a polonium atom.
(b) Determine the density of alpha polonium.
Alpha polonium crystallizes in a simple cubic unit cell:

(a) Two adjacent Po atoms contact each other, so the edge length of this cell is equal to two Po atomic radii: l = 2r. Therefore,
336 pm
the radius of Po is r = =
2
l
2
= 168 pm.
(b) Density is given by density = mass

. The density of polonium can be found by determining the density of its unit cell
volume
(the mass contained within a unit cell divided by the volume of the unit cell). Since a Po unit cell contains one-eighth of a Po
atom at each of its eight corners, a unit cell contains one Po atom.
The mass of a Po unit cell can be found by:

1 Po atom 1 mol Po 208.998 g
−22
1 Po unit cell × × × = 3.47 × 10 g
23
1 Po unit cell 6.022 × 10 Po atoms 1 mol Po
The volume of a Po unit cell can be found by:

3
3 −10 −23 3
V =l = (336 × 10 cm) = 3.79 × 10 cm
(Note that the edge length was converted from pm to cm to get the usual volume units for density.)
−22
3.471 × 10 g
Therefore, the density of Po = −23
= 9.16 g/cm
3
3.79 × 10 cm 3

The edge length of the unit cell for nickel is 0.3524 nm. The density of Ni is 8.90 g/cm3. Does nickel crystallize in a simple
cubic structure? Explain.
10.7.0.1: Answer:
No. If Ni was simple cubic, its density would be given by:
1 mol Ni 58.693 g −23
1 Ni atom × 23
× = 9.746 × 10 g
6.022 × 10 Ni atoms 1 mol Ni
3
3 −8 −23 3
V =l = (3.524 × 10 cm) = 4.376 × 10 cm
−23
9.746 × 10 g 3
Then the density of Ni would be = 4.376 × 10
= 2.23 g/cm
−23
cm 3
Since the actual density of Ni is not close to this, Ni does not form a simple cubic structure.
Most metal crystals are one of the four major types of unit cells. For now, we will focus on the three cubic unit cells: simple cubic
(which we have already seen), body-centered cubic unit cell, and face-centered cubic unit cell—all of which are illustrated in
Figure 10.50. (Note that there are actually seven different lattice systems, some of which have more than one type of lattice, for a
total of 14 different types of unit cells. We leave the more complicated geometries for later in this module.)
Figure 10.50 Cubic unit cells of metals show (in the upper figures) the locations of lattice points and (in the lower figures) metal
atoms located in the unit cell.

Some metals crystallize in an arrangement that has a cubic unit cell with atoms at all of the corners and an atom in the center, as
shown in Figure 10.51. This is called a body-centered cubic (BCC) solid. Atoms in the corners of a BCC unit cell do not contact
each other but contact the atom in the center. A BCC unit cell contains two atoms: one-eighth of an atom at each of the eight
corners (8 × 1
8
= 1 atom from the corners) plus one atom from the center. Any atom in this structure touches four atoms in the
layer above it and four atoms in the layer below it. Thus, an atom in a BCC structure has a coordination number of eight.
Figure 10.51 In a body-centered cubic structure, atoms in a specific layer do not touch each other. Each atom touches four atoms in
the layer above it and four atoms in the layer below it.
Atoms in BCC arrangements are much more efficiently packed than in a simple cubic structure, occupying about 68% of the total
volume. Isomorphous metals with a BCC structure include K, Ba, Cr, Mo, W, and Fe at room temperature. (Elements or
compounds that crystallize with the same structure are said to be isomorphous.)
Many other metals, such as aluminum, copper, and lead, crystallize in an arrangement that has a cubic unit cell with atoms at all of
the corners and at the centers of each face, as illustrated in Figure 10.52. This arrangement is called a face-centered cubic (FCC)
solid. A FCC unit cell contains four atoms: one-eighth of an atom at each of the eight corners (8 × 1
8
= 1 atom from the corners)
and one-half of an atom on each of the six faces (6 × 1
2
= 3 atoms from the faces). The atoms at the corners touch the atoms in
the centers of the adjacent faces along the face diagonals of the cube. Because the atoms are on identical lattice points, they have
identical environments.
Figure 10.52 A face-centered cubic solid has atoms at the corners and, as the name implies, at the centers of the faces of its unit
cells.
Atoms in an FCC arrangement are packed as closely together as possible, with atoms occupying 74% of the volume. This structure
is also called cubic closest packing (CCP). In CCP, there are three repeating layers of hexagonally arranged atoms. Each atom
contacts six atoms in its own layer, three in the layer above, and three in the layer below. In this arrangement, each atom touches 12
near neighbors, and therefore has a coordination number of 12. The fact that FCC and CCP arrangements are equivalent may not be
immediately obvious, but why they are actually the same structure is illustrated in Figure 10.53.

Figure 10.53 A CCP arrangement consists of three repeating layers (ABCABC…) of hexagonally arranged atoms. Atoms in a CCP
structure have a coordination number of 12 because they contact six atoms in their layer, plus three atoms in the layer above and
three atoms in the layer below. By rotating our perspective, we can see that a CCP structure has a unit cell with a face containing an
atom from layer A at one corner, atoms from layer B across a diagonal (at two corners and in the middle of the face), and an atom
from layer C at the remaining corner. This is the same as a face-centered cubic arrangement.
Because closer packing maximizes the overall attractions between atoms and minimizes the total intermolecular energy, the atoms
in most metals pack in this manner. We find two types of closest packing in simple metallic crystalline structures: CCP, which we
have already encountered, and hexagonal closest packing (HCP) shown in Figure 10.54. Both consist of repeating layers of
hexagonally arranged atoms. In both types, a second layer (B) is placed on the first layer (A) so that each atom in the second layer
is in contact with three atoms in the first layer. The third layer is positioned in one of two ways. In HCP, atoms in the third layer are
directly above atoms in the first layer (i.e., the third layer is also type A), and the stacking consists of alternating type A and type B
close-packed layers (i.e., ABABAB⋯). In CCP, atoms in the third layer are not above atoms in either of the first two layers (i.e.,
the third layer is type C), and the stacking consists of alternating type A, type B, and type C close-packed layers (i.e.,
ABCABCABC⋯). About two–thirds of all metals crystallize in closest-packed arrays with coordination numbers of 12. Metals
that crystallize in an HCP structure include Cd, Co, Li, Mg, Na, and Zn, and metals that crystallize in a CCP structure include Ag,
Al, Ca, Cu, Ni, Pb, and Pt.
Figure 10.54 In both types of closest packing, atoms are packed as compactly as possible. Hexagonal closest packing consists of
two alternating layers (ABABAB…). Cubic closest packing consists of three alternating layers (ABCABCABC…).

10.7.0.1: Example 10.15
10.7.0.0.4: Calculation of Atomic Radius and Density for Metals, Part 2
Calcium crystallizes in a face-centered cubic structure. The edge length of its unit cell is 558.8 pm.
(a) What is the atomic radius of Ca in this structure?
(b) Calculate the density of Ca.
(a) In an FCC structure, Ca atoms contact each other across the diagonal of the face, so the length of the diagonal is equal to
four Ca atomic radii (d = 4r). Two adjacent edges and the diagonal of the face form a right triangle, with the length of each side
equal to 558.8 pm and the length of the hypotenuse equal to four Ca atomic radii:
2 2 2 2 2 2
a +a =d ⟶ (558.8 pm) + (558.5 pm) = (4r)
−−−−−−−−−−−−−−−
2 2
(558.8 pm) +(558.5 pm)
Solving this gives r = √
16
= 197.6 pm for a Ca radius.
(b) Density is given by density = . The density of calcium can be found by determining the density of its unit cell: for
mass
volume
example, the mass contained within a unit cell divided by the volume of the unit cell. A face-centered Ca unit cell has one-
eighth of an atom at each of the eight corners (8 × = 1 atom) and one-half of an atom on each of the six faces 6 ×
1
8
=3
1
atoms), for a total of four atoms in the unit cell.

The mass of the unit cell can be found by:
4 Ca atoms 1 mol Ca 40.078 g
−22
1 Ca unit cell × × × = 2.662 × 10 g
23
1 Ca unit cell 6.022 × 10 Ca atoms 1 mol Ca
The volume of a Ca unit cell can be found by:

3
3 −10 −22 3
V =a = (558.8 × 10 cm) = 1.745 × 10 cm
(Note that the edge length was converted from pm to cm to get the usual volume units for density.)
−22
2.662 × 10 g
Then, the density of Ca =
−22
= 1.53 g/cm
3
1.745 × 10 cm 3

Silver crystallizes in an FCC structure. The edge length of its unit cell is 409 pm.
(a) What is the atomic radius of Ag in this structure?
(b) Calculate the density of Ag.
10.7.0.1: Answer:
(a) 144 pm; (b) 10.5 g/cm3

In general, a unit cell is defined by the lengths of three axes (a, b, and c) and the angles (α, β, and γ) between them, as illustrated in
Figure 10.55. The axes are defined as being the lengths between points in the space lattice. Consequently, unit cell axes join points
with identical environments.
Figure 10.55 A unit cell is defined by the lengths of its three axes (a, b, and c) and the angles (α, β, and γ) between the axes.
There are seven different lattice systems, some of which have more than one type of lattice, for a total of fourteen different unit
cells, which have the shapes shown in Figure 10.56.

Figure 10.56 There are seven different lattice systems and 14 different unit cells.
10.7.0.1: The Structures of Ionic Crystals

Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a
crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction.
Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible
of the opposite charge and (2) when the cations and anions are in contact with each other. Structures are determined by two
principal factors: the relative sizes of the ions and the ratio of the numbers of positive and negative ions in the compound.
In simple ionic structures, we usually find the anions, which are normally larger than the cations, arranged in a closest-packed
array. (As seen previously, additional electrons attracted to the same nucleus make anions larger and fewer electrons attracted to the
same nucleus make cations smaller when compared to the atoms from which they are formed.) The smaller cations commonly
occupy one of two types of holes (or interstices) remaining between the anions. The smaller of the holes is found between three
anions in one plane and one anion in an adjacent plane. The four anions surrounding this hole are arranged at the corners of a
tetrahedron, so the hole is called a tetrahedral hole. The larger type of hole is found at the center of six anions (three in one layer
and three in an adjacent layer) located at the corners of an octahedron; this is called an octahedral hole. Figure 10.57 illustrates both
of these types of holes.

Figure 10.57 Cations may occupy two types of holes between anions: octahedral holes or tetrahedral holes.
Depending on the relative sizes of the cations and anions, the cations of an ionic compound may occupy tetrahedral or octahedral
holes, as illustrated in Figure 10.58. Relatively small cations occupy tetrahedral holes, and larger cations occupy octahedral holes.
If the cations are too large to fit into the octahedral holes, the anions may adopt a more open structure, such as a simple cubic array.
The larger cations can then occupy the larger cubic holes made possible by the more open spacing.
Figure 10.58 A cation’s size and the shape of the hole occupied by the compound are directly related.
There are two tetrahedral holes for each anion in either an HCP or CCP array of anions. A compound that crystallizes in a closest-
packed array of anions with cations in the tetrahedral holes can have a maximum cation:anion ratio of 2:1; all of the tetrahedral
holes are filled at this ratio. Examples include Li2O, Na2O, Li2S, and Na2S. Compounds with a ratio of less than 2:1 may also
crystallize in a closest-packed array of anions with cations in the tetrahedral holes, if the ionic sizes fit. In these compounds,
however, some of the tetrahedral holes remain vacant.
10.7.0.1: Example 10.16

10.7.0.0.1: Occupancy of Tetrahedral Holes
Zinc sulfide is an important industrial source of zinc and is also used as a white pigment in paint. Zinc sulfide crystallizes with
zinc ions occupying one-half of the tetrahedral holes in a closest-packed array of sulfide ions. What is the formula of zinc
sulfide?
Because there are two tetrahedral holes per anion (sulfide ion) and one-half of these holes are occupied by zinc ions, there must
be 1
2
× 2, or 1, zinc ion per sulfide ion. Thus, the formula is ZnS.

Lithium selenide can be described as a closest-packed array of selenide ions with lithium ions in all of the tetrahedral holes.
What it the formula of lithium selenide?
10.7.0.1: Answer:
Li2Se
The ratio of octahedral holes to anions in either an HCP or CCP structure is 1:1. Thus, compounds with cations in octahedral holes
in a closest-packed array of anions can have a maximum cation:anion ratio of 1:1. In NiO, MnS, NaCl, and KH, for example, all of
the octahedral holes are filled. Ratios of less than 1:1 are observed when some of the octahedral holes remain empty.
10.7.0.1: Example 10.17

10.7.0.0.4: Stoichiometry of Ionic Compounds
Sapphire is aluminum oxide. Aluminum oxide crystallizes with aluminum ions in two-thirds of the octahedral holes in a
closest-packed array of oxide ions. What is the formula of aluminum oxide?
Because there is one octahedral hole per anion (oxide ion) and only two-thirds of these holes are occupied, the ratio of
aluminum to oxygen must be :1, which would give Al O. The simplest whole number ratio is 2:3, so the formula is Al2O3.
2
3
2/3

The white pigment titanium oxide crystallizes with titanium ions in one-half of the octahedral holes in a closest-packed array
of oxide ions. What is the formula of titanium oxide?
10.7.0.1: Answer:
TiO2
In a simple cubic array of anions, there is one cubic hole that can be occupied by a cation for each anion in the array. In CsCl, and
in other compounds with the same structure, all of the cubic holes are occupied. Half of the cubic holes are occupied in SrH2, UO2,
SrCl2, and CaF2.
Different types of ionic compounds often crystallize in the same structure when the relative sizes of their ions and their
stoichiometries (the two principal features that determine structure) are similar.
10.7.0.1: Unit Cells of Ionic Compounds

Many ionic compounds crystallize with cubic unit cells, and we will use these compounds to describe the general features of ionic
structures.
When an ionic compound is composed of cations and anions of similar size in a 1:1 ratio, it typically forms a simple cubic
structure. Cesium chloride, CsCl, (illustrated in Figure 10.59) is an example of this, with Cs+ and Cl− having radii of 174 pm and
181 pm, respectively. We can think of this as chloride ions forming a simple cubic unit cell, with a cesium ion in the center; or as
cesium ions forming a unit cell with a chloride ion in the center; or as simple cubic unit cells formed by Cs+ ions overlapping unit
cells formed by Cl− ions. Cesium ions and chloride ions touch along the body diagonals of the unit cells. One cesium ion and one
chloride ion are present per unit cell, giving the l:l stoichiometry required by the formula for cesium chloride. Note that there is no
lattice point in the center of the cell, and CsCl is not a BCC structure because a cesium ion is not identical to a chloride ion.

Figure 10.59 Ionic compounds with similar-sized cations and anions, such as CsCl, usually form a simple cubic structure. They can
be described by unit cells with either cations at the corners or anions at the corners.
We have said that the location of lattice points is arbitrary. This is illustrated by an alternate description of the CsCl structure in
which the lattice points are located in the centers of the cesium ions. In this description, the cesium ions are located on the lattice
points at the corners of the cell, and the chloride ion is located at the center of the cell. The two unit cells are different, but they
describe identical structures.
When an ionic compound is composed of a 1:1 ratio of cations and anions that differ significantly in size, it typically crystallizes
with an FCC unit cell, like that shown in Figure 10.60. Sodium chloride, NaCl, is an example of this, with Na+ and Cl− having radii
of 102 pm and 181 pm, respectively. We can think of this as chloride ions forming an FCC cell, with sodium ions located in the
octahedral holes in the middle of the cell edges and in the center of the cell. The sodium and chloride ions touch each other along
the cell edges. The unit cell contains four sodium ions and four chloride ions, giving the 1:1 stoichiometry required by the formula,
NaCl.
Figure 10.60 Ionic compounds with anions that are much larger than cations, such as NaCl, usually form an FCC structure. They
can be described by FCC unit cells with cations in the octahedral holes.
The cubic form of zinc sulfide, zinc blende, also crystallizes in an FCC unit cell, as illustrated in Figure 10.61. This structure
contains sulfide ions on the lattice points of an FCC lattice. (The arrangement of sulfide ions is identical to the arrangement of
chloride ions in sodium chloride.) The radius of a zinc ion is only about 40% of the radius of a sulfide ion, so these small Zn2+ ions
are located in alternating tetrahedral holes, that is, in one half of the tetrahedral holes. There are four zinc ions and four sulfide ions
in the unit cell, giving the empirical formula ZnS.

Figure 10.61 ZnS, zinc sulfide (or zinc blende) forms an FCC unit cell with sulfide ions at the lattice points and much smaller zinc
ions occupying half of the tetrahedral holes in the structure.
A calcium fluoride unit cell, like that shown in Figure 10.62, is also an FCC unit cell, but in this case, the cations are located on the
lattice points; equivalent calcium ions are located on the lattice points of an FCC lattice. All of the tetrahedral sites in the FCC
array of calcium ions are occupied by fluoride ions. There are four calcium ions and eight fluoride ions in a unit cell, giving a
calcium:fluorine ratio of 1:2, as required by the chemical formula, CaF2. Close examination of Figure 10.62 will reveal a simple
cubic array of fluoride ions with calcium ions in one half of the cubic holes. The structure cannot be described in terms of a space
lattice of points on the fluoride ions because the fluoride ions do not all have identical environments. The orientation of the four
calcium ions about the fluoride ions differs.
Figure 10.62 Calcium fluoride, CaF2, forms an FCC unit cell with calcium ions (green) at the lattice points and fluoride ions (red)
occupying all of the tetrahedral sites between them.
10.7.0.1: Calculation of Ionic Radii

If we know the edge length of a unit cell of an ionic compound and the position of the ions in the cell, we can calculate ionic radii
for the ions in the compound if we make assumptions about individual ionic shapes and contacts.
10.7.0.1: Example 10.18

10.7.0.0.1: Calculation of Ionic Radii
The edge length of the unit cell of LiCl (NaCl-like structure, FCC) is 0.514 nm or 5.14 Å. Assuming that the lithium ion is
small enough so that the chloride ions are in contact, as in Figure 10.60, calculate the ionic radius for the chloride ion.
Note: The length unit angstrom, Å, is often used to represent atomic-scale dimensions and is equivalent to 10−10 m.

On the face of a LiCl unit cell, chloride ions contact each other across the diagonal of the face:
Drawing a right triangle on the face of the unit cell, we see that the length of the diagonal is equal to four chloride radii (one
radius from each corner chloride and one diameter—which equals two radii—from the chloride ion in the center of the face),
so d = 4r. From the Pythagorean theorem, we have:
2 2 2
a +a =d
which yields:
2 2 2 2
(0.514 nm) + (0.514 nm) = (4r) = 16 r
Solving this gives:

−−−−−−−−−−−−−−−−−−−−−
2 2
(0.514 nm) + (0.514 nm)
−
r = √ = 0.182 nm (1.82 Å) for a Cl radius.
16

The edge length of the unit cell of KCl (NaCl-like structure, FCC) is 6.28 Å. Assuming anion-cation contact along the cell
edge, calculate the radius of the potassium ion. The radius of the chloride ion is 1.82 Å.
10.7.0.1: Answer:
The radius of the potassium ion is 1.33 Å.
It is important to realize that values for ionic radii calculated from the edge lengths of unit cells depend on numerous assumptions,
such as a perfect spherical shape for ions, which are approximations at best. Hence, such calculated values are themselves
approximate and comparisons cannot be pushed too far. Nevertheless, this method has proved useful for calculating ionic radii from
experimental measurements such as X-ray crystallographic determinations.
10.7.0.1: X-Ray Crystallography

The size of the unit cell and the arrangement of atoms in a crystal may be determined from measurements of the diffraction of X-
rays by the crystal, termed X-ray crystallography. Diffraction is the change in the direction of travel experienced by an
electromagnetic wave when it encounters a physical barrier whose dimensions are comparable to those of the wavelength of the
light. X-rays are electromagnetic radiation with wavelengths about as long as the distance between neighboring atoms in crystals
(on the order of a few Å).
When a beam of monochromatic X-rays strikes a crystal, its rays are scattered in all directions by the atoms within the crystal.
When scattered waves traveling in the same direction encounter one another, they undergo interference, a process by which the
waves combine to yield either an increase or a decrease in amplitude (intensity) depending upon the extent to which the combining
waves’ maxima are separated (see Figure 10.63).

Figure 10.63 Light waves occupying the same space experience interference, combining to yield waves of greater (a) or lesser (b)
intensity, depending upon the separation of their maxima and minima.
When X-rays of a certain wavelength, λ, are scattered by atoms in adjacent crystal planes separated by a distance, d, they may
undergo constructive interference when the difference between the distances traveled by the two waves prior to their combination is
an integer factor, n, of the wavelength. This condition is satisfied when the angle of the diffracted beam, θ, is related to the
wavelength and interatomic distance by the equation:
nλ = 2d sin θ
This relation is known as the Bragg equation in honor of W. H. Bragg, the English physicist who first explained this phenomenon.
Figure 10.64 illustrates two examples of diffracted waves from the same two crystal planes. The figure on the left depicts waves
diffracted at the Bragg angle, resulting in constructive interference, while that on the right shows diffraction and a different angle
that does not satisfy the Bragg condition, resulting in destructive interference.

Figure 10.64 The diffraction of X-rays scattered by the atoms within a crystal permits the determination of the distance between the
atoms. The top image depicts constructive interference between two scattered waves and a resultant diffracted wave of high
intensity. The bottom image depicts destructive interference and a low intensity diffracted wave.

Visit this site for more details on the Bragg equation and a simulator that allows you to explore the effect of each variable on
the intensity of the diffracted wave.
An X-ray diffractometer, such as the one illustrated in Figure 10.65, may be used to measure the angles at which X-rays are
diffracted when interacting with a crystal as described earlier. From such measurements, the Bragg equation may be used to
compute distances between atoms as demonstrated in the following example exercise.
Figure 10.65 (a) In a diffractometer, a beam of X-rays strikes a crystalline material, producing (b) an X-ray diffraction pattern that
can be analyzed to determine the crystal structure.
10.7.0.1: Example 10.19

10.7.0.0.1: Using the Bragg Equation
In a diffractometer, X-rays with a wavelength of 0.1315 nm were used to produce a diffraction pattern for copper. The first
order diffraction (n = 1) occurred at an angle θ = 25.25°. Determine the spacing between the diffracting planes in copper.
The distance between the planes is found by solving the Bragg equation, nλ = 2d sin θ, for d.
1(0.1315 nm)
This gives: d =
nλ
2 sin θ
=
2 sin (25.25°)
= 0.154 nm

A crystal with spacing between planes equal to 0.394 nm diffracts X-rays with a wavelength of 0.147 nm. What is the angle for
the first order diffraction?

10.7.0.1: Answer:
10.8°

10.7.0.0.4: X-ray Crystallographer Rosalind Franklin
The discovery of the structure of DNA in 1953 by Francis Crick and James Watson is one of the great achievements in the
history of science. They were awarded the 1962 Nobel Prize in Physiology or Medicine, along with Maurice Wilkins, who
provided experimental proof of DNA’s structure. British chemist Rosalind Franklin made invaluable contributions to this
monumental achievement through her work in measuring X-ray diffraction images of DNA. Early in her career, Franklin’s
research on the structure of coals proved helpful to the British war effort. After shifting her focus to biological systems in the
early 1950s, Franklin and doctoral student Raymond Gosling discovered that DNA consists of two forms: a long, thin fiber
formed when wet (type “B”) and a short, wide fiber formed when dried (type “A”). Her X-ray diffraction images of DNA
(Figure 10.66) provided the crucial information that allowed Watson and Crick to confirm that DNA forms a double helix, and
to determine details of its size and structure. Franklin also conducted pioneering research on viruses and the RNA that contains
their genetic information, uncovering new information that radically changed the body of knowledge in the field. After
developing ovarian cancer, Franklin continued to work until her death in 1958 at age 37. Among many posthumous
recognitions of her work, the Chicago Medical School of Finch University of Health Sciences changed its name to the Rosalind
Franklin University of Medicine and Science in 2004, and adopted an image of her famous X-ray diffraction image of DNA as
its official university logo.
Figure 10.66 This illustration shows an X-ray diffraction image similar to the one Franklin found in her research. (credit:
National Institutes of Health)
This page titled 10.7: Lattice Structures in Crystalline Solids is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

10.8: Key Terms
adhesive force
force of attraction between molecules of different chemical identities
amorphous solid
(also, noncrystalline solid) solid in which the particles lack an ordered internal structure
body-centered cubic (BCC) solid

crystalline structure that has a cubic unit cell with lattice points at the corners and in the center of the cell
body-centered cubic unit cell

simplest repeating unit of a body-centered cubic crystal; it is a cube containing lattice points at each corner and in the center of
the cube
boiling point
temperature at which the vapor pressure of a liquid equals the pressure of the gas above it
Bragg equation
equation that relates the angles at which X-rays are diffracted by the atoms within a crystal
capillary action
flow of liquid within a porous material due to the attraction of the liquid molecules to the surface of the material and to other
liquid molecules
Clausius-Clapeyron equation
mathematical relationship between the temperature, vapor pressure, and enthalpy of vaporization for a substance
cohesive force
force of attraction between identical molecules
condensation
change from a gaseous to a liquid state
coordination number
number of atoms closest to any given atom in a crystal or to the central metal atom in a complex
covalent network solid

solid whose particles are held together by covalent bonds
critical point
temperature and pressure above which a gas cannot be condensed into a liquid
crystalline solid
solid in which the particles are arranged in a definite repeating pattern
cubic closest packing (CCP)

crystalline structure in which planes of closely packed atoms or ions are stacked as a series of three alternating layers of
different relative orientations (ABC)
deposition
change from a gaseous state directly to a solid state
diffraction
redirection of electromagnetic radiation that occurs when it encounters a physical barrier of appropriate dimensions
dipole-dipole attraction
intermolecular attraction between two permanent dipoles
dispersion force
(also, London dispersion force) attraction between two rapidly fluctuating, temporary dipoles; significant only when particles
are very close together
dynamic equilibrium
state of a system in which reciprocal processes are occurring at equal rates
face-centered cubic (FCC) solid

crystalline structure consisting of a cubic unit cell with lattice points on the corners and in the center of each face
face-centered cubic unit cell

simplest repeating unit of a face-centered cubic crystal; it is a cube containing lattice points at each corner and in the center of
each face
freezing
change from a liquid state to a solid state
freezing point
temperature at which the solid and liquid phases of a substance are in equilibrium; see also melting point
hexagonal closest packing (HCP)

crystalline structure in which close packed layers of atoms or ions are stacked as a series of two alternating layers of different
relative orientations (AB)
hole
(also, interstice) space between atoms within a crystal
hydrogen bonding
occurs when exceptionally strong dipoles attract; bonding that exists when hydrogen is bonded to one of the three most
electronegative elements: F, O, or N
induced dipole
temporary dipole formed when the electrons of an atom or molecule are distorted by the instantaneous dipole of a neighboring
atom or molecule
instantaneous dipole
temporary dipole that occurs for a brief moment in time when the electrons of an atom or molecule are distributed
asymmetrically
intermolecular force
noncovalent attractive force between atoms, molecules, and/or ions
interstitial sites
spaces between the regular particle positions in any array of atoms or ions
ionic solid
solid composed of positive and negative ions held together by strong electrostatic attractions
isomorphous
possessing the same crystalline structure
melting
change from a solid state to a liquid state
melting point
temperature at which the solid and liquid phases of a substance are in equilibrium; see also freezing point
metallic solid
solid composed of metal atoms
molecular solid
solid composed of neutral molecules held together by intermolecular forces of attraction
normal boiling point

temperature at which a liquid’s vapor pressure equals 1 atm (760 torr)
octahedral hole
open space in a crystal at the center of six particles located at the corners of an octahedron
phase diagram
pressure-temperature graph summarizing conditions under which the phases of a substance can exist
polarizability
measure of the ability of a charge to distort a molecule’s charge distribution (electron cloud)
simple cubic structure

crystalline structure with a cubic unit cell with lattice points only at the corners
simple cubic unit cell

(also, primitive cubic unit cell) unit cell in the simple cubic structure
space lattice
all points within a crystal that have identical environments
sublimation
change from solid state directly to gaseous state
supercritical fluid
substance at a temperature and pressure higher than its critical point; exhibits properties intermediate between those of gaseous
and liquid states
surface tension
energy required to increase the area, or length, of a liquid surface by a given amount
tetrahedral hole
tetrahedral space formed by four atoms or ions in a crystal
triple point
temperature and pressure at which three phases of a substance are in equilibrium
unit cell
smallest portion of a space lattice that is repeated in three dimensions to form the entire lattice
vacancy
defect that occurs when a position that should contain an atom or ion is vacant
van der Waals force
attractive or repulsive force between molecules, including dipole-dipole, dipole-induced dipole, and London dispersion forces;
does not include forces due to covalent or ionic bonding, or the attraction between ions and molecules
vapor pressure
(also, equilibrium vapor pressure) pressure exerted by a vapor in equilibrium with a solid or a liquid at a given temperature
vaporization
change from liquid state to gaseous state
viscosity
measure of a liquid’s resistance to flow
X-ray crystallography
experimental technique for determining distances between atoms in a crystal by measuring the angles at which X-rays are
diffracted when passing through the crystal
10.9: Key Equations
2T cos θ
h =
rρg
−ΔHvap /RT
P = Ae
ΔHvap
ln P = − + ln A
RT
P2 ΔHvap
1 1
ln ( ) = ( − )
P1 R T1 T2
nλ = 2d sin θ
10.10: Summary
10.1 Intermolecular Forces
The physical properties of condensed matter (liquids and solids) can be explained in terms of the kinetic molecular theory. In a
liquid, intermolecular attractive forces hold the molecules in contact, although they still have sufficient KE to move past each other.
Intermolecular attractive forces, collectively referred to as van der Waals forces, are responsible for the behavior of liquids and
solids and are electrostatic in nature. Dipole-dipole attractions result from the electrostatic attraction of the partial negative end of
one polar molecule for the partial positive end of another. The temporary dipole that results from the motion of the electrons in an
atom can induce a dipole in an adjacent atom and give rise to the London dispersion force. London forces increase with increasing
molecular size. Hydrogen bonds are a special type of dipole-dipole attraction that results when hydrogen is bonded to one of the
three most electronegative elements: F, O, or N.
10.2 Properties of Liquids

The intermolecular forces between molecules in the liquid state vary depending upon their chemical identities and result in
corresponding variations in various physical properties. Cohesive forces between like molecules are responsible for a liquid’s
viscosity (resistance to flow) and surface tension (elasticity of a liquid surface). Adhesive forces between the molecules of a liquid
and different molecules composing a surface in contact with the liquid are responsible for phenomena such as surface wetting and
capillary rise.
10.3 Phase Transitions

Phase transitions are processes that convert matter from one physical state into another. There are six phase transitions between the
three phases of matter. Melting, vaporization, and sublimation are all endothermic processes, requiring an input of heat to overcome
intermolecular attractions. The reciprocal transitions of freezing, condensation, and deposition are all exothermic processes,
involving heat as intermolecular attractive forces are established or strengthened. The temperatures at which phase transitions occur
are determined by the relative strengths of intermolecular attractions and are, therefore, dependent on the chemical identity of the
substance.
10.4 Phase Diagrams

The temperature and pressure conditions at which a substance exists in solid, liquid, and gaseous states are summarized in a phase
diagram for that substance. Phase diagrams are combined plots of pressure-temperature equilibrium curves representing the
relationships between phase transition temperatures and pressures. The point of intersection of any three curves in a phase diagram
represents a substance’s triple point—the temperature and pressure at which three different phases are in equilibrium. At pressures
below a solid-liquid-gas triple point, a substance cannot exist in the liquid state, regardless of its temperature. The terminus of the
liquid-gas curve represents the substance’s critical point, the pressure and temperature above which a liquid phase cannot exist.
10.5 The Solid State of Matter

Some substances form crystalline solids consisting of particles in a very organized structure; others form amorphous
(noncrystalline) solids with an internal structure that is not ordered. The main types of crystalline solids are ionic solids, metallic
solids, covalent network solids, and molecular solids. The properties of the different kinds of crystalline solids are due to the types
of particles of which they consist, the arrangements of the particles, and the strengths of the attractions between them. Because
their particles experience identical attractions, crystalline solids have distinct melting temperatures; the particles in amorphous
solids experience a range of interactions, so they soften gradually and melt over a range of temperatures. Some crystalline solids
have defects in the definite repeating pattern of their particles. These defects (which include vacancies, atoms or ions not in the
regular positions, and impurities) change physical properties such as electrical conductivity, which is exploited in the silicon
crystals used to manufacture computer chips.
10.6 Lattice Structures in Crystalline Solids

The structures of crystalline metals and simple ionic compounds can be described in terms of packing of spheres. Metal atoms can
pack in hexagonal closest-packed structures, cubic closest-packed structures, body-centered structures, and simple cubic structures.
The anions in simple ionic structures commonly adopt one of these structures, and the cations occupy the spaces remaining
between the anions. Small cations usually occupy tetrahedral holes in a closest-packed array of anions. Larger cations usually
occupy octahedral holes. Still larger cations can occupy cubic holes in a simple cubic array of anions. The structure of a solid can
be described by indicating the size and shape of a unit cell and the contents of the cell. The type of structure and dimensions of the
unit cell can be determined by X-ray diffraction measurements.
10.11: Exercises
10.11.0.1: 10.1 Intermolecular Forces
1.
In terms of their bulk properties, how do liquids and solids differ? How are they similar?
2.
In terms of the kinetic molecular theory, in what ways are liquids similar to solids? In what ways are liquids different from solids?
3.
In terms of the kinetic molecular theory, in what ways are liquids similar to gases? In what ways are liquids different from gases?
4.
Explain why liquids assume the shape of any container into which they are poured, whereas solids are rigid and retain their shape.
5.
What is the evidence that all neutral atoms and molecules exert attractive forces on each other?
6.
Open the PhET States of Matter Simulation to answer the following questions:
(a) Select the Solid, Liquid, Gas tab. Explore by selecting different substances, heating and cooling the systems, and changing the
state. What similarities do you notice between the four substances for each phase (solid, liquid, gas)? What differences do you
notice?
(b) For each substance, select each of the states and record the given temperatures. How do the given temperatures for each state
correlate with the strengths of their intermolecular attractions? Explain.
(c) Select the Interaction Potential tab, and use the default neon atoms. Move the Ne atom on the right and observe how the
potential energy changes. Select the Total Force button, and move the Ne atom as before. When is the total force on each atom
attractive and large enough to matter? Then select the Component Forces button, and move the Ne atom. When do the attractive
(van der Waals) and repulsive (electron overlap) forces balance? How does this relate to the potential energy versus the distance
between atoms graph? Explain.
7.
Define the following and give an example of each:
(a) dispersion force
(b) dipole-dipole attraction
(c) hydrogen bond
8.
The types of intermolecular forces in a substance are identical whether it is a solid, a liquid, or a gas. Why then does a substance
change phase from a gas to a liquid or to a solid?
9.
Why do the boiling points of the noble gases increase in the order He < Ne < Ar < Kr < Xe?
10.
Neon and HF have approximately the same molecular masses.
(a) Explain why the boiling points of Neon and HF differ.
(b) Compare the change in the boiling points of Ne, Ar, Kr, and Xe with the change of the boiling points of HF, HCl, HBr, and HI,
and explain the difference between the changes with increasing atomic or molecular mass.
11.
Arrange each of the following sets of compounds in order of increasing boiling point temperature:

(a) HCl, H2O, SiH4
(b) F2, Cl2, Br2
(c) CH4, C2H6, C3H8
(d) O2, NO, N2
12.
The molecular mass of butanol, C4H9OH, is 74.14; that of ethylene glycol, CH2(OH)CH2OH, is 62.08, yet their boiling points are
117.2 °C and 174 °C, respectively. Explain the reason for the difference.
13.
On the basis of intermolecular attractions, explain the differences in the boiling points of n–butane (−1 °C) and chloroethane (12
°C), which have similar molar masses.
14.
On the basis of dipole moments and/or hydrogen bonding, explain in a qualitative way the differences in the boiling points of
acetone (56.2 °C) and 1-propanol (97.4 °C), which have similar molar masses.
15.
The melting point of H2O(s) is 0 °C. Would you expect the melting point of H2S(s) to be −85 °C, 0 °C, or 185 °C? Explain your
answer.
16.
Silane (SiH4), phosphine (PH3), and hydrogen sulfide (H2S) melt at −185 °C, −133 °C, and −85 °C, respectively. What does this
suggest about the polar character and intermolecular attractions of the three compounds?
17.
Explain why a hydrogen bond between two water molecules is weaker than a hydrogen bond between two hydrogen fluoride
molecules.
18.
Under certain conditions, molecules of acetic acid, CH3COOH, form “dimers,” pairs of acetic acid molecules held together by
strong intermolecular attractions:
Draw a dimer of acetic acid, showing how two CH3COOH molecules are held together, and stating the type of IMF that is
responsible.
19.
Proteins are chains of amino acids that can form in a variety of arrangements, one of which is a helix. What kind of IMF is
responsible for holding the protein strand in this shape? On the protein image, show the locations of the IMFs that hold the protein
together:
20.
The density of liquid NH3 is 0.64 g/mL; the density of gaseous NH3 at STP is 0.0007 g/mL. Explain the difference between the
densities of these two phases.

21.
Identify the intermolecular forces present in the following solids:
(a) CH3CH2OH
(b) CH3CH2CH3
(c) CH3CH2Cl
10.11.0.1: 10.2 Properties of Liquids

22.
The test tubes shown here contain equal amounts of the specified motor oils. Identical metal spheres were dropped at the same time
into each of the tubes, and a brief moment later, the spheres had fallen to the heights indicated in the illustration.
Rank the motor oils in order of increasing viscosity, and explain your reasoning:
23.
Although steel is denser than water, a steel needle or paper clip placed carefully lengthwise on the surface of still water can be
made to float. Explain at a molecular level how this is possible.

Figure 10.67 (credit: Cory Zanker)
24.
The surface tension and viscosity values for diethyl ether, acetone, ethanol, and ethylene glycol are shown here.
(a) Explain their differences in viscosity in terms of the size and shape of their molecules and their IMFs.
(b) Explain their differences in surface tension in terms of the size and shape of their molecules and their IMFs:
25.
You may have heard someone use the figure of speech “slower than molasses in winter” to describe a process that occurs slowly.
Explain why this is an apt idiom, using concepts of molecular size and shape, molecular interactions, and the effect of changing
temperature.
26.
It is often recommended that you let your car engine run idle to warm up before driving, especially on cold winter days. While the
benefit of prolonged idling is dubious, it is certainly true that a warm engine is more fuel efficient than a cold one. Explain the
reason for this.
27.
The surface tension and viscosity of water at several different temperatures are given in this table.
Water Surface Tension (mN/m) Viscosity (mPa s)
0 °C 75.6 1.79
20 °C 72.8 1.00
60 °C 66.2 0.47
100 °C 58.9 0.28
(a) As temperature increases, what happens to the surface tension of water? Explain why this occurs, in terms of molecular
interactions and the effect of changing temperature.
(b) As temperature increases, what happens to the viscosity of water? Explain why this occurs, in terms of molecular interactions
and the effect of changing temperature.
28.

At 25 °C, how high will water rise in a glass capillary tube with an inner diameter of 0.63 mm? Refer to Example 10.4 for the
required information.
29.
Water rises in a glass capillary tube to a height of 17 cm. What is the diameter of the capillary tube?
10.11.0.1: 10.3 Phase Transitions

30.
Heat is added to boiling water. Explain why the temperature of the boiling water does not change. What does change?
31.
Heat is added to ice at 0 °C. Explain why the temperature of the ice does not change. What does change?
32.
What feature characterizes the dynamic equilibrium between a liquid and its vapor in a closed container?
33.
Identify two common observations indicating some liquids have sufficient vapor pressures to noticeably evaporate?
34.
Identify two common observations indicating some solids, such as dry ice and mothballs, have vapor pressures sufficient to
sublime?
35.
What is the relationship between the intermolecular forces in a liquid and its vapor pressure?
36.
What is the relationship between the intermolecular forces in a solid and its melting temperature?
37.
Why does spilled gasoline evaporate more rapidly on a hot day than on a cold day?
38.
Carbon tetrachloride, CCl4, was once used as a dry cleaning solvent, but is no longer used because it is carcinogenic. At 57.8 °C,
the vapor pressure of CCl4 is 54.0 kPa, and its enthalpy of vaporization is 33.05 kJ/mol. Use this information to estimate the normal
boiling point for CCl4.
39.
When is the boiling point of a liquid equal to its normal boiling point?
40.
How does the boiling of a liquid differ from its evaporation?
41.
Use the information in Figure 10.24 to estimate the boiling point of water in Denver when the atmospheric pressure is 83.3 kPa.
42.
A syringe at a temperature of 20 °C is filled with liquid ether in such a way that there is no space for any vapor. If the temperature
is kept constant and the plunger is withdrawn to create a volume that can be occupied by vapor, what would be the approximate
pressure of the vapor produced?
43.
Explain the following observations:
(a) It takes longer to cook an egg in Ft. Davis, Texas (altitude, 5000 feet above sea level) than it does in Boston (at sea level).
(b) Perspiring is a mechanism for cooling the body.
44.

The enthalpy of vaporization of water is larger than its enthalpy of fusion. Explain why.
45.
Explain why the molar enthalpies of vaporization of the following substances increase in the order CH4 < C2H6 < C3H8, even
though the type of IMF (dispersion) is the same.
46.
Explain why the enthalpies of vaporization of the following substances increase in the order CH4 < NH3 < H2O, even though all
three substances have approximately the same molar mass.
47.
The enthalpy of vaporization of CO2(l) is 9.8 kJ/mol. Would you expect the enthalpy of vaporization of CS2(l) to be 28 kJ/mol, 9.8
kJ/mol, or −8.4 kJ/mol? Discuss the plausibility of each of these answers.
48.
The hydrogen fluoride molecule, HF, is more polar than a water molecule, H2O (for example, has a greater dipole moment), yet the
molar enthalpy of vaporization for liquid hydrogen fluoride is lesser than that for water. Explain.
49.
Ethyl chloride (boiling point, 13 °C) is used as a local anesthetic. When the liquid is sprayed on the skin, it cools the skin enough to
freeze and numb it. Explain the cooling effect of liquid ethyl chloride.
50.
Which contains the compounds listed correctly in order of increasing boiling points?
(a) N2 < CS2 < H2O < KCl
(b) H2O < N2 < CS2 < KCl
(c) N2 < KCl < CS2 < H2O
(d) CS2 < N2 < KCl < H2O
(e) KCl < H2O < CS2 < N2
51.
How much heat is required to convert 422 g of liquid H2O at 23.5 °C into steam at 150 °C?
52.
Evaporation of sweat requires energy and thus take excess heat away from the body. Some of the water that you drink may
eventually be converted into sweat and evaporate. If you drink a 20-ounce bottle of water that had been in the refrigerator at 3.8 °C,
how much heat is needed to convert all of that water into sweat and then to vapor? (Note: Your body temperature is 36.6 °C. For
the purpose of solving this problem, assume that the thermal properties of sweat are the same as for water.)
53.
Titanium tetrachloride, TiCl4, has a melting point of −23.2 °C and has a ΔH fusion = 9.37 kJ/mol.
(a) How much energy is required to melt 263.1 g TiCl4?
(b) For TiCl4, which will likely have the larger magnitude: ΔH fusion or ΔH vaporization? Explain your reasoning.
10.11.0.1: 10.4 Phase Diagrams

54.
From the phase diagram for water (Figure 10.31), determine the state of water at:
(a) 35 °C and 85 kPa
(b) −15 °C and 40 kPa
(c) −15 °C and 0.1 kPa
(d) 75 °C and 3 kPa

(e) 40 °C and 0.1 kPa
(f) 60 °C and 50 kPa
55.
What phase changes will take place when water is subjected to varying pressure at a constant temperature of 0.005 °C? At 40 °C?
At −40 °C?
56.
Pressure cookers allow food to cook faster because the higher pressure inside the pressure cooker increases the boiling temperature
of water. A particular pressure cooker has a safety valve that is set to vent steam if the pressure exceeds 3.4 atm. What is the
approximate maximum temperature that can be reached inside this pressure cooker? Explain your reasoning.
57.
From the phase diagram for carbon dioxide in Figure 10.34, determine the state of CO2 at:
(a) 20 °C and 1000 kPa
(b) 10 °C and 2000 kPa
(c) 10 °C and 100 kPa
(d) −40 °C and 500 kPa
(e) −80 °C and 1500 kPa
(f) −80 °C and 10 kPa
58.
Determine the phase changes that carbon dioxide undergoes as pressure is increased at a constant temperature of (a) −50 °C and (b)
50 °C. If the temperature is held at −40 °C? At 20 °C? (See the phase diagram in Figure 10.34.)
59.
Consider a cylinder containing a mixture of liquid carbon dioxide in equilibrium with gaseous carbon dioxide at an initial pressure
of 65 atm and a temperature of 20 °C. Sketch a plot depicting the change in the cylinder pressure with time as gaseous carbon
dioxide is released at constant temperature.
60.
Dry ice, CO2(s), does not melt at atmospheric pressure. It sublimes at a temperature of −78 °C. What is the lowest pressure at
which CO2(s) will melt to give CO2(l)? At approximately what temperature will this occur? (See Figure 10.34 for the phase
diagram.)
61.
If a severe storm results in the loss of electricity, it may be necessary to use a clothesline to dry laundry. In many parts of the
country in the dead of winter, the clothes will quickly freeze when they are hung on the line. If it does not snow, will they dry
anyway? Explain your answer.
62.
Is it possible to liquefy nitrogen at room temperature (about 25 °C)? Is it possible to liquefy sulfur dioxide at room temperature?
Explain your answers.
63.
Elemental carbon has one gas phase, one liquid phase, and two different solid phases, as shown in the phase diagram:

(a) On the phase diagram, label the gas and liquid regions.
(b) Graphite is the most stable phase of carbon at normal conditions. On the phase diagram, label the graphite phase.
(c) If graphite at normal conditions is heated to 2500 K while the pressure is increased to 1010 Pa, it is converted into diamond.
Label the diamond phase.
(d) Circle each triple point on the phase diagram.
(e) In what phase does carbon exist at 5000 K and 108 Pa?
(f) If the temperature of a sample of carbon increases from 3000 K to 5000 K at a constant pressure of 106 Pa, which phase
transition occurs, if any?
10.11.0.1: 10.5 The Solid State of Matter

64.
What types of liquids typically form amorphous solids?
65.
At very low temperatures oxygen, O2, freezes and forms a crystalline solid. Which best describes these crystals?
(a) ionic
(b) covalent network
(c) metallic
(d) amorphous
(e) molecular crystals
66.
As it cools, olive oil slowly solidifies and forms a solid over a range of temperatures. Which best describes the solid?

(a) ionic
(b) covalent network
(c) metallic
(d) amorphous
67.
Explain why ice, which is a crystalline solid, has a melting temperature of 0 °C, whereas butter, which is an amorphous solid,
softens over a range of temperatures.
68.
Identify the type of crystalline solid (metallic, network covalent, ionic, or molecular) formed by each of the following substances:
(a) SiO2
(b) KCl
(c) Cu
(d) CO2
(e) C (diamond)
(f) BaSO4
(g) NH3
(h) NH4F
(i) C2H5OH
69.
Identify the type of crystalline solid (metallic, network covalent, ionic, or molecular) formed by each of the following substances:
(a) CaCl2
(b) SiC
(c) N2
(d) Fe
(e) C (graphite)
(f) CH3CH2CH2CH3
(g) HCl
(h) NH4NO3
(i) K3PO4
70.
Classify each substance in the table as either a metallic, ionic, molecular, or covalent network solid:
Substance Appearance Melting Point Electrical Conductivity Solubility in Water
X lustrous, malleable 1500 °C high insoluble
Y soft, yellow 113 °C none insoluble
Z hard, white 800 °C only if melted/dissolved soluble
71.

Classify each substance in the table as either a metallic, ionic, molecular, or covalent network solid:
Substance Appearance Melting Point Electrical Conductivity Solubility in Water
X brittle, white 800 °C only if melted/dissolved soluble
Y shiny, malleable 1100 °C high insoluble
Z hard, colorless 3550 °C none insoluble
72.
Identify the following substances as ionic, metallic, covalent network, or molecular solids:
Substance A is malleable, ductile, conducts electricity well, and has a melting point of 1135 °C. Substance B is brittle, does not
conduct electricity as a solid but does when molten, and has a melting point of 2072 °C. Substance C is very hard, does not conduct
electricity, and has a melting point of 3440 °C. Substance D is soft, does not conduct electricity, and has a melting point of 185 °C.
73.
Substance A is shiny, conducts electricity well, and melts at 975 °C. Substance A is likely a(n):
(a) ionic solid
(b) metallic solid
(c) molecular solid
(d) covalent network solid
74.
Substance B is hard, does not conduct electricity, and melts at 1200 °C. Substance B is likely a(n):
(a) ionic solid
(b) metallic solid
(c) molecular solid
(d) covalent network solid
10.11.0.1: 10.6 Lattice Structures in Crystalline Solids

75.
Describe the crystal structure of iron, which crystallizes with two equivalent metal atoms in a cubic unit cell.
76.
Describe the crystal structure of Pt, which crystallizes with four equivalent metal atoms in a cubic unit cell.
77.
What is the coordination number of a chromium atom in the body-centered cubic structure of chromium?
78.
What is the coordination number of an aluminum atom in the face-centered cubic structure of aluminum?
79.
Cobalt metal crystallizes in a hexagonal closest packed structure. What is the coordination number of a cobalt atom?
80.
Nickel metal crystallizes in a cubic closest packed structure. What is the coordination number of a nickel atom?
81.
Tungsten crystallizes in a body-centered cubic unit cell with an edge length of 3.165 Å.
(a) What is the atomic radius of tungsten in this structure?

(b) Calculate the density of tungsten.
82.
Platinum (atomic radius = 1.38 Å) crystallizes in a cubic closely packed structure. Calculate the edge length of the face-centered
cubic unit cell and the density of platinum.
83.
Barium crystallizes in a body-centered cubic unit cell with an edge length of 5.025 Å
(a) What is the atomic radius of barium in this structure?
(b) Calculate the density of barium.
84.
Aluminum (atomic radius = 1.43 Å) crystallizes in a cubic closely packed structure. Calculate the edge length of the face-centered
cubic unit cell and the density of aluminum.
85.
The density of aluminum is 2.7 g/cm3; that of silicon is 2.3 g/cm3. Explain why Si has the lower density even though it has heavier
atoms.
86.
The free space in a metal may be found by subtracting the volume of the atoms in a unit cell from the volume of the cell. Calculate
the percentage of free space in each of the three cubic lattices if all atoms in each are of equal size and touch their nearest
neighbors. Which of these structures represents the most efficient packing? That is, which packs with the least amount of unused
space?
87.
Cadmium sulfide, sometimes used as a yellow pigment by artists, crystallizes with cadmium, occupying one-half of the tetrahedral
holes in a closest packed array of sulfide ions. What is the formula of cadmium sulfide? Explain your answer.
88.
A compound of cadmium, tin, and phosphorus is used in the fabrication of some semiconductors. It crystallizes with cadmium
occupying one-fourth of the tetrahedral holes and tin occupying one-fourth of the tetrahedral holes in a closest packed array of
phosphide ions. What is the formula of the compound? Explain your answer.
89.
What is the formula of the magnetic oxide of cobalt, used in recording tapes, that crystallizes with cobalt atoms occupying one-
eighth of the tetrahedral holes and one-half of the octahedral holes in a closely packed array of oxide ions?
90.
A compound containing zinc, aluminum, and sulfur crystallizes with a closest-packed array of sulfide ions. Zinc ions are found in
one-eighth of the tetrahedral holes and aluminum ions in one-half of the octahedral holes. What is the empirical formula of the
compound?
91.
A compound of thallium and iodine crystallizes in a simple cubic array of iodide ions with thallium ions in all of the cubic holes.
What is the formula of this iodide? Explain your answer.
92.
Which of the following elements reacts with sulfur to form a solid in which the sulfur atoms form a closest-packed array with all of
the octahedral holes occupied: Li, Na, Be, Ca, or Al?
93.
What is the percent by mass of titanium in rutile, a mineral that contains titanium and oxygen, if structure can be described as a
closest packed array of oxide ions with titanium ions in one-half of the octahedral holes? What is the oxidation number of titanium?
94.

Explain why the chemically similar alkali metal chlorides NaCl and CsCl have different structures, whereas the chemically
different NaCl and MnS have the same structure.
95.
As minerals were formed from the molten magma, different ions occupied the same cites in the crystals. Lithium often occurs along
with magnesium in minerals despite the difference in the charge on their ions. Suggest an explanation.
96.
Rubidium iodide crystallizes with a cubic unit cell that contains iodide ions at the corners and a rubidium ion in the center. What is
the formula of the compound?
97.
One of the various manganese oxides crystallizes with a cubic unit cell that contains manganese ions at the corners and in the
center. Oxide ions are located at the center of each edge of the unit cell. What is the formula of the compound?
98.
NaH crystallizes with the same crystal structure as NaCl. The edge length of the cubic unit cell of NaH is 4.880 Å.
(a) Calculate the ionic radius of H−. (The ionic radius of Li+ is 0.0.95 Å.)
(b) Calculate the density of NaH.
99.
Thallium(I) iodide crystallizes with the same structure as CsCl. The edge length of the unit cell of TlI is 4.20 Å. Calculate the ionic
radius of TI+. (The ionic radius of I− is 2.16 Å.)
100.
A cubic unit cell contains manganese ions at the corners and fluoride ions at the center of each edge.
(a) What is the empirical formula of this compound? Explain your answer.
(b) What is the coordination number of the Mn3+ ion?
(c) Calculate the edge length of the unit cell if the radius of a Mn3+ ion is 0.65 A.
(d) Calculate the density of the compound.
101.
What is the spacing between crystal planes that diffract X-rays with a wavelength of 1.541 nm at an angle θ of 15.55° (first order
reflection)?
102.
A diffractometer using X-rays with a wavelength of 0.2287 nm produced first order diffraction peak for a crystal angle θ = 16.21°.
Determine the spacing between the diffracting planes in this crystal.
103.
A metal with spacing between planes equal to 0.4164 nm diffracts X-rays with a wavelength of 0.2879 nm. What is the diffraction
angle for the first order diffraction peak?
104.
Gold crystallizes in a face-centered cubic unit cell. The second-order reflection (n = 2) of X-rays for the planes that make up the
tops and bottoms of the unit cells is at θ = 22.20°. The wavelength of the X-rays is 1.54 Å. What is the density of metallic gold?
105.
When an electron in an excited molybdenum atom falls from the L to the K shell, an X-ray is emitted. These X-rays are diffracted
at an angle of 7.75° by planes with a separation of 2.64 Å. What is the difference in energy between the K shell and the L shell in
molybdenum assuming a first order diffraction?

CHAPTER OVERVIEW
11: Solutions and Colloids

General Chemistry
In this chapter, we will consider the nature of solutions, and examine factors that determine whether a solution will form and what
properties it may have. In addition, we will discuss colloids—systems that resemble solutions but consist of dispersions of particles
somewhat larger than ordinary molecules or ions.
11.1: Introduction
11.3: Electrolytes
11.4: Solubility
11.6: Colloids
11.7: Key Terms
11.8: Key Equations
11.9: Summary
11.10: Exercises
Thumbnail: Nile red solution. (CC BY-SA 3.0; Armin Kübelbeck).
This page titled 11: Solutions and Colloids is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via
1
11.1: Introduction
Figure 11.1 Coral reefs, such as this one at the Palmyra Atoll National Wildlife Refuge, are vital to the ecosystem of earth’s oceans.
The health of coral reefs and all marine life depends on the specific chemical composition of the complex mixture known as
seawater. (credit: modification of work by “USFWS – Pacific Region”/Wikimedia Commons)

11.1 The Dissolution Process
11.2 Electrolytes
11.3 Solubility
11.4 Colligative Properties
11.5 Colloids
Coral reefs are home to about 25% of all marine species. They are being threatened by climate change, oceanic acidification, and
water pollution, all of which change the composition of the solution known as seawater. Dissolved oxygen in seawater is critical for
sea creatures, but as the oceans warm, oxygen becomes less soluble. As the concentration of carbon dioxide in the atmosphere
increases, the concentration of carbon dioxide in the oceans increases, contributing to oceanic acidification. Coral reefs are
particularly sensitive to the acidification of the ocean, since the exoskeletons of the coral polyps are soluble in acidic solutions.
Humans contribute to the changing of seawater composition by allowing agricultural runoff and other forms of pollution to affect
our oceans.
Solutions are crucial to the processes that sustain life and to many other processes involving chemical reactions. This chapter
considers the nature of solutions and examines factors that determine whether a solution will form and what properties it may have.
The properties of colloids—mixtures containing dispersed particles larger than the molecules and ions of typical solutions—are
also discussed.


Describe the basic properties of solutions and how they form
Predict whether a given mixture will yield a solution based on molecular properties of its components
Explain why some solutions either produce or absorb heat when they form
An earlier chapter of this text introduced solutions, defined as homogeneous mixtures of two or more substances. Often, one
component of a solution is present at a significantly greater concentration, in which case it is called the solvent. The other
components of the solution present in relatively lesser concentrations are called solutes. Sugar is a covalent solid composed of
sucrose molecules, C12H22O11. When this compound dissolves in water, its molecules become uniformly distributed among the
molecules of water:
C12 H22 O11 (s) ⟶ C12 H22 O11 (aq)
The subscript “aq” in the equation signifies that the sucrose molecules are solutes and are therefore individually dispersed
throughout the aqueous solution (water is the solvent). Although sucrose molecules are heavier than water molecules, they remain
dispersed throughout the solution; gravity does not cause them to “settle out” over time.
Potassium dichromate, K2Cr2O7, is an ionic compound composed of colorless potassium ions, K+, and orange dichromate ions,
. When a small amount of solid potassium dichromate is added to water, the compound dissolves and dissociates to yield
2−
Cr O
2 7
potassium ions and dichromate ions uniformly distributed throughout the mixture (Figure 11.2), as indicated in this equation:
+ 2−
K2 C r2 O7 (s) ⟶ 2 K (aq) + C r2 O7 (aq)
As with the mixture of sugar and water, this mixture is also an aqueous solution. Its solutes, potassium and dichromate ions, remain
individually dispersed among the solvent (water) molecules.
Figure 11.2 When potassium dichromate (K2Cr2O7) is mixed with water, it forms a homogeneous orange solution. (credit:
modification of work by Mark Ott)

Visit this virtual lab to view simulations of the dissolution of common covalent and ionic substances (sugar and salt) in water.
Water is used so often as a solvent that the word solution has come to imply an aqueous solution to many people. However, almost
any gas, liquid, or solid can act as a solvent. Many alloys are solid solutions of one metal dissolved in another; for example, US
five-cent coins contain nickel dissolved in copper. Air is a gaseous solution, a homogeneous mixture of nitrogen, oxygen, and
several other gases. Oxygen (a gas), alcohol (a liquid), and sugar (a solid) all dissolve in water (a liquid) to form liquid solutions.
Table 11.1 gives examples of several different solutions and the phases of the solutes and solvents.
Different Types of Solutions
Solution Solute Solvent
air O2(g) N2(g)
soft drinks1 CO2(g) H2O(l)

Solution Solute Solvent
hydrogen in palladium H2(g) Pd(s)
rubbing alcohol H2O(l) C3H8O(l) (2-propanol)
saltwater NaCl(s) H2O(l)
brass Zn(s) Cu(s)
Table 11.1
Solutions exhibit these defining traits:
They are homogeneous; after a solution is mixed, it has the same composition at all points throughout (its composition is
uniform).
The physical state of a solution—solid, liquid, or gas—is typically the same as that of the solvent, as demonstrated by the
examples in Table 11.1.
The components of a solution are dispersed on a molecular scale; they consist of a mixture of separated solute particles
(molecules, atoms, and/or ions) each closely surrounded by solvent species.
The dissolved solute in a solution will not settle out or separate from the solvent.
The composition of a solution, or the concentrations of its components, can be varied continuously (within limits determined by
the solubility of the components, discussed in detail later in this chapter).
11.2.0.1: The Formation of Solutions

The formation of a solution is an example of a spontaneous process, a process that occurs under specified conditions without the
requirement of energy from some external source. Sometimes a mixture is stirred to speed up the dissolution process, but this is not
necessary; a homogeneous solution will form eventually. The topic of spontaneity is critically important to the study of chemical
thermodynamics and is treated more thoroughly in a later chapter of this text. For purposes of this chapter’s discussion, it will
suffice to consider two criteria that favor, but do not guarantee, the spontaneous formation of a solution:
1. a decrease in the internal energy of the system (an exothermic change, as discussed in the previous chapter on thermochemistry)
2. an increased dispersal of matter in the system (which indicates an increase in the entropy of the system, as you will learn about
in the later chapter on thermodynamics)
In the process of dissolution, an internal energy change often, but not always, occurs as heat is absorbed or evolved. An increase in
matter dispersal always results when a solution forms from the uniform distribution of solute molecules throughout a solvent.
When the strengths of the intermolecular forces of attraction between solute and solvent species in a solution are no different than
those present in the separated components, the solution is formed with no accompanying energy change. Such a solution is called
an ideal solution. A mixture of ideal gases (or gases such as helium and argon, which closely approach ideal behavior) is an
example of an ideal solution, since the entities comprising these gases experience no significant intermolecular attractions.
When containers of helium and argon are connected, the gases spontaneously mix due to diffusion and form a solution (Figure
11.3). The formation of this solution clearly involves an increase in matter dispersal, since the helium and argon atoms occupy a
volume twice as large as that which each occupied before mixing.

Figure 11.3 Samples of helium and argon spontaneously mix to give a solution.
Ideal solutions may also form when structurally similar liquids are mixed. For example, mixtures of the alcohols methanol
(CH3OH) and ethanol (C2H5OH) form ideal solutions, as do mixtures of the hydrocarbons pentane, C5H12, and hexane, C6H14.
Placing methanol and ethanol, or pentane and hexane, in the bulbs shown in Figure 11.3 will result in the same diffusion and
subsequent mixing of these liquids as is observed for the He and Ar gases (although at a much slower rate), yielding solutions with
no significant change in energy. Unlike a mixture of gases, however, the components of these liquid-liquid solutions do, indeed,
experience intermolecular attractive forces. But since the molecules of the two substances being mixed are structurally very similar,
the intermolecular attractive forces between like and unlike molecules are essentially the same, and the dissolution process,
therefore, does not entail any appreciable increase or decrease in energy. These examples illustrate how increased matter dispersal
alone can provide the driving force required to cause the spontaneous formation of a solution. In some cases, however, the relative
magnitudes of intermolecular forces of attraction between solute and solvent species may prevent dissolution.
Three types of intermolecular attractive forces are relevant to the dissolution process: solute-solute, solvent-solvent, and solute-
solvent. As illustrated in Figure 11.4, the formation of a solution may be viewed as a stepwise process in which energy is consumed
to overcome solute-solute and solvent-solvent attractions (endothermic processes) and released when solute-solvent attractions are
established (an exothermic process referred to as solvation). The relative magnitudes of the energy changes associated with these
stepwise processes determine whether the dissolution process overall will release or absorb energy. In some cases, solutions do not
form because the energy required to separate solute and solvent species is so much greater than the energy released by solvation.

Figure 11.4 This schematic representation of dissolution shows a stepwise process involving the endothermic separation of solute
and solvent species (Steps 1 and 2) and exothermic solvation (Step 3).
Consider the example of an ionic compound dissolving in water. Formation of the solution requires the electrostatic forces between
the cations and anions of the compound (solute–solute) be overcome completely as attractive forces are established between these
ions and water molecules (solute–solvent). Hydrogen bonding between a relatively small fraction of the water molecules must also
be overcome to accommodate any dissolved solute. If the solute’s electrostatic forces are significantly greater than the solvation
forces, the dissolution process is significantly endothermic and the compound may not dissolve to an appreciable extent. Calcium
carbonate, the major component of coral reefs, is one example of such an “insoluble” ionic compound (see Figure 11.1). On the
other hand, if the solvation forces are much stronger than the compound’s electrostatic forces, the dissolution is significantly
exothermic and the compound may be highly soluble. common example of this type of ionic compound is sodium hydroxide,
commonly known as lye.

As noted at the beginning of this module, spontaneous solution formation is favored, but not guaranteed, by exothermic dissolution
processes. While many soluble compounds do, indeed, dissolve with the release of heat, some dissolve endothermically.
Ammonium nitrate (NH4NO3) is one such example and is used to make instant cold packs, like the one pictured in Figure 11.5,
which are used for treating injuries. A thin-walled plastic bag of water is sealed inside a larger bag with solid NH4NO3. When the
smaller bag is broken, a solution of NH4NO3 forms, absorbing heat from the surroundings (the injured area to which the pack is
applied) and providing a cold compress that decreases swelling. Endothermic dissolutions such as this one require a greater energy
input to separate the solute species than is recovered when the solutes are solvated, but they are spontaneous nonetheless due to the
increase in disorder that accompanies formation of the solution.
Figure 11.5 An instant cold pack gets cold when certain salts, such as ammonium nitrate, dissolve in water—an endothermic
process.

Watch this brief video illustrating endothermic and exothermic dissolution processes.
11.2.0.1: Footnotes
1If bubbles of gas are observed within the liquid, the mixture is not homogeneous and, thus, not a solution.
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11.3: Electrolytes

Define and give examples of electrolytes
Distinguish between the physical and chemical changes that accompany dissolution of ionic and covalent electrolytes
Relate electrolyte strength to solute-solvent attractive forces
When some substances are dissolved in water, they undergo either a physical or a chemical change that yields ions in solution.
These substances constitute an important class of compounds called electrolytes. Substances that do not yield ions when dissolved
are called nonelectrolytes. If the physical or chemical process that generates the ions is essentially 100% efficient (all of the
dissolved compound yields ions), then the substance is known as a strong electrolyte. If only a relatively small fraction of the
dissolved substance undergoes the ion-producing process, it is called a weak electrolyte.
Substances may be identified as strong, weak, or nonelectrolytes by measuring the electrical conductance of an aqueous solution
containing the substance. To conduct electricity, a substance must contain freely mobile, charged species. Most familiar is the
conduction of electricity through metallic wires, in which case the mobile, charged entities are electrons. Solutions may also
conduct electricity if they contain dissolved ions, with conductivity increasing as ion concentration increases. Applying a voltage to
electrodes immersed in a solution permits assessment of the relative concentration of dissolved ions, either quantitatively, by
measuring the electrical current flow, or qualitatively, by observing the brightness of a light bulb included in the circuit (Figure
11.6).
Figure 11.6 Solutions of nonelectrolytes such as ethanol do not contain dissolved ions and cannot conduct electricity. Solutions of
electrolytes contain ions that permit the passage of electricity. The conductivity of an electrolyte solution is related to the strength
of the electrolyte.
11.3.0.1: Ionic Electrolytes

Water and other polar molecules are attracted to ions, as shown in Figure 11.7. The electrostatic attraction between an ion and a
molecule with a dipole is called an ion-dipole attraction. These attractions play an important role in the dissolution of ionic
compounds in water.

Figure 11.7 As potassium chloride (KCl) dissolves in water, the ions are hydrated. The polar water molecules are attracted by the
charges on the K+ and Cl− ions. Water molecules in front of and behind the ions are not shown.
When ionic compounds dissolve in water, the ions in the solid separate and disperse uniformly throughout the solution because
water molecules surround and solvate the ions, reducing the strong electrostatic forces between them. This process represents a
physical change known as dissociation. Under most conditions, ionic compounds will dissociate nearly completely when dissolved,
and so they are classified as strong electrolytes. Even sparingly, soluble ionic compounds are strong electrolytes, since the small
amount that does dissolve will dissociate completely.
Consider what happens at the microscopic level when solid KCl is added to water. Ion-dipole forces attract the positive (hydrogen)
end of the polar water molecules to the negative chloride ions at the surface of the solid, and they attract the negative (oxygen) ends
to the positive potassium ions. The water molecules surround individual K+ and Cl− ions, reducing the strong interionic forces that
bind the ions together and letting them move off into solution as solvated ions, as Figure 11.7 shows. Overcoming the electrostatic
attraction permits the independent motion of each hydrated ion in a dilute solution as the ions transition from fixed positions in the
undissolved compound to widely dispersed, solvated ions in solution.
11.3.0.1: Covalent Electrolytes

Pure water is an extremely poor conductor of electricity because it is only very slightly ionized—only about two out of every 1
billion molecules ionize at 25 °C. Water ionizes when one molecule of water gives up a proton (H+ ion) to another molecule of
water, yielding hydronium and hydroxide ions.

+ −
H2 O (l) + H2 O (l) ⇌ H3 O (aq) + OH (aq)
In some cases, solutions prepared from covalent compounds conduct electricity because the solute molecules react chemically with
the solvent to produce ions. For example, pure hydrogen chloride is a gas consisting of covalent HCl molecules. This gas contains
no ions. However, an aqueous solution of HCl is a very good conductor, indicating that an appreciable concentration of ions exists
within the solution.
Because HCl is an acid, its molecules react with water, transferring H+ ions to form hydronium ions (H3O+) and chloride ions (Cl−):
This reaction is essentially 100% complete for HCl (i.e., it is a strong acid and, consequently, a strong electrolyte). Likewise, weak
acids and bases that only react partially generate relatively low concentrations of ions when dissolved in water and are classified as
weak electrolytes. The reader may wish to review the discussion of strong and weak acids provided in the earlier chapter of this
text on reaction classes and stoichiometry.
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11.4: Solubility

Describe the effects of temperature and pressure on solubility
State Henry’s law and use it in calculations involving the solubility of a gas in a liquid
Explain the degrees of solubility possible for liquid-liquid solutions
Imagine adding a small amount of sugar to a glass of water, stirring until all the sugar has dissolved, and then adding a bit more.
You can repeat this process until the sugar concentration of the solution reaches its natural limit, a limit determined primarily by the
relative strengths of the solute-solute, solute-solvent, and solvent-solvent attractive forces discussed in the previous two modules of
this chapter. You can be certain that you have reached this limit because, no matter how long you stir the solution, undissolved
sugar remains. The concentration of sugar in the solution at this point is known as its solubility.
The solubility of a solute in a particular solvent is the maximum concentration that may be achieved under given conditions when
the dissolution process is at equilibrium.
When a solute’s concentration is equal to its solubility, the solution is said to be saturated with that solute. If the solute’s
concentration is less than its solubility, the solution is said to be unsaturated. A solution that contains a relatively low concentration
of solute is called dilute, and one with a relatively high concentration is called concentrated.

Use this interactive simulation to prepare various saturated solutions.
Solutions may be prepared in which a solute concentration exceeds its solubility. Such solutions are said to be supersaturated, and
they are interesting examples of nonequilibrium states (a detailed treatment of this important concept is provided in the text
chapters on equilibrium). For example, the carbonated beverage in an open container that has not yet “gone flat” is supersaturated
with carbon dioxide gas; given time, the CO2 concentration will decrease until it reaches its solubility.

Watch this impressive video showing the precipitation of sodium acetate from a supersaturated solution.
11.4.0.1: Solutions of Gases in Liquids

As for any solution, the solubility of a gas in a liquid is affected by the intermolecular attractive forces between solute and solvent
species. Unlike solid and liquid solutes, however, there is no solute-solute intermolecular attraction to overcome when a gaseous
solute dissolves in a liquid solvent (see Figure 11.4) since the atoms or molecules comprising a gas are far separated and experience
negligible interactions. Consequently, solute-solvent interactions are the sole energetic factor affecting solubility. For example, the
water solubility of oxygen is approximately three times greater than that of helium (there are greater dispersion forces between
water and the larger oxygen molecules) but 100 times less than the solubility of chloromethane, CHCl3 (polar chloromethane
molecules experience dipole–dipole attraction to polar water molecules). Likewise note the solubility of oxygen in hexane, C6H14,
is approximately 20 times greater than it is in water because greater dispersion forces exist between oxygen and the larger hexane
molecules.
Temperature is another factor affecting solubility, with gas solubility typically decreasing as temperature increases (Figure 11.8).
This inverse relation between temperature and dissolved gas concentration is responsible for one of the major impacts of thermal
pollution in natural waters.

Figure 11.8 The solubilities of these gases in water decrease as the temperature increases. All solubilities were measured with a
constant pressure of 101.3 kPa (1 atm) of gas above the solutions.
When the temperature of a river, lake, or stream is raised, the solubility of oxygen in the water is decreased. Decreased levels of
dissolved oxygen may have serious consequences for the health of the water’s ecosystems and, in severe cases, can result in large-
scale fish kills (Figure 11.9).
Figure 11.9 (a) The small bubbles of air in this glass of chilled water formed when the water warmed to room temperature and the
solubility of its dissolved air decreased. (b) The decreased solubility of oxygen in natural waters subjected to thermal pollution can

result in large-scale fish kills. (credit a: modification of work by Liz West; credit b: modification of work by U.S. Fish and Wildlife
Service)
The solubility of a gaseous solute is also affected by the partial pressure of solute in the gas to which the solution is exposed. Gas
solubility increases as the pressure of the gas increases. Carbonated beverages provide a nice illustration of this relationship. The
carbonation process involves exposing the beverage to a relatively high pressure of carbon dioxide gas and then sealing the
beverage container, thus saturating the beverage with CO2 at this pressure. When the beverage container is opened, a familiar hiss
is heard as the carbon dioxide gas pressure is released, and some of the dissolved carbon dioxide is typically seen leaving solution
in the form of small bubbles (Figure 11.10). At this point, the beverage is supersaturated with carbon dioxide and, with time, the
dissolved carbon dioxide concentration will decrease to its equilibrium value and the beverage will become “flat.”
Figure 11.10 Opening the bottle of carbonated beverage reduces the pressure of the gaseous carbon dioxide above the beverage.
The solubility of CO2 is thus lowered, and some dissolved carbon dioxide may be seen leaving the solution as small gas bubbles.
(credit: modification of work by Derrick Coetzee)
For many gaseous solutes, the relation between solubility, Cg, and partial pressure, Pg, is a proportional one:
Cg = kPg
where k is a proportionality constant that depends on the identity of the gaseous solute, the identity of the solvent, and the solution
temperature. This is a mathematical statement of Henry’s law: The quantity of an ideal gas that dissolves in a definite volume of
liquid is directly proportional to the pressure of the gas.
11.4.0.1: Example 11.1

11.4.0.0.1: Application of Henry’s Law
At 20 °C, the concentration of dissolved oxygen in water exposed to gaseous oxygen at a partial pressure of 101.3 kPa is 1.38
−3
× 10 mol L−1. Use Henry’s law to determine the solubility of oxygen when its partial pressure is 20.7 kPa, the approximate
pressure of oxygen in earth’s atmosphere.
According to Henry’s law, for an ideal solution the solubility, Cg, of a gas (1.38 × 10−3 mol L−1, in this case) is directly
proportional to the pressure, Pg, of the undissolved gas above the solution (101.3 kPa in this case). Because both Cg and Pg are
known, this relation can be rearranged and used to solve for k.

Cg = kPg
Cg
k =
Pg
−3 −1
1.38 × 10 mol L
=
101.3 kPa
−5 −1 −1
= 1.36 × 10 mol L kPa
Now, use k to find the solubility at the lower pressure.
Cg = kPg
−5 −1 −1
1.36 × 10 mol L kPa × 20.7 kPa
−4 −1
= 2.82 × 10 mol L
Note that various units may be used to express the quantities involved in these sorts of computations. Any combination of units
that yield to the constraints of dimensional analysis are acceptable.
Exposing a 100.0 mL sample of water at 0 °C to an atmosphere containing a gaseous solute at 152 torr resulted in the
dissolution of 1.45 × 10−3 g of the solute. Use Henry’s law to determine the solubility of this gaseous solute when its pressure
is 760 torr.
11.4.0.1: Answer:
7.25 × 10−3 in 100.0 mL or 0.0725 g/L
11.4.0.1: Example 11.2

11.4.0.0.4: Thermal Pollution and Oxygen Solubility
A certain species of freshwater trout requires a dissolved oxygen concentration of 7.5 mg/L. Could these fish thrive in a
thermally polluted mountain stream (water temperature is 30.0 °C, partial pressure of atmospheric oxygen is 0.17 atm)? Use
the data in Figure 11.8 to estimate a value for the Henry's law constant at this temperature.
First, estimate the Henry’s law constant for oxygen in water at the specified temperature of 30.0 °C (Figure 11.8 indicates the
solubility at this temperature is approximately ~1.2 mol/L).
Cg
−3 −3
k = = 1.2 × 10 mol/L/1.00 atm = 1.2 × 10 mol/L atm
Pg
Then, use this k value to compute the oxygen solubility at the specified oxygen partial pressure, 0.17 atm.
−3 −4
Cg = kPg = (1.2 × 10 mol/L atm) (0.17 atm) = 2.0 × 10 mol/L
Finally, convert this dissolved oxygen concentration from mol/L to mg/L.

−4
(2.0 × 10 mol/L) (32.0 g/1 mol) (1000 mg/g) = 6.4 mg/L.
This concentration is lesser than the required minimum value of 7.5 mg/L, and so these trout would likely not thrive in the
polluted stream.
What dissolved oxygen concentration is expected for the stream above when it returns to a normal summer time temperature of
15 °C?
11.4.0.1: Answer:
8.2 mg/L

11.4.0.0.7: Decompression Sickness or “The Bends”
Decompression sickness (DCS), or “the bends,” is an effect of the increased pressure of the air inhaled by scuba divers when
swimming underwater at considerable depths. In addition to the pressure exerted by the atmosphere, divers are subjected to
additional pressure due to the water above them, experiencing an increase of approximately 1 atm for each 10 m of depth.
Therefore, the air inhaled by a diver while submerged contains gases at the corresponding higher ambient pressure, and the
concentrations of the gases dissolved in the diver’s blood are proportionally higher per Henry’s law.
As the diver ascends to the surface of the water, the ambient pressure decreases and the dissolved gases becomes less soluble.
If the ascent is too rapid, the gases escaping from the diver’s blood may form bubbles that can cause a variety of symptoms
ranging from rashes and joint pain to paralysis and death. To avoid DCS, divers must ascend from depths at relatively slow
speeds (10 or 20 m/min) or otherwise make several decompression stops, pausing for several minutes at given depths during
the ascent. When these preventive measures are unsuccessful, divers with DCS are often provided hyperbaric oxygen therapy
in pressurized vessels called decompression (or recompression) chambers (Figure 11.11). Researchers are also investigating
related body reactions and defenses in order to develop better testing and treatment for decompression sicknetss. For example,
Ingrid Eftedal, a barophysiologist specializing in bodily reactions to diving, has shown that white blood cells undergo chemical
and genetic changes as a result of the condition; these can potentially be used to create biomarker tests and other methods to
manage decompression sickness.
Figure 11.11 (a) US Navy divers undergo training in a recompression chamber. (b) Divers receive hyperbaric oxygen therapy.
Deviations from Henry’s law are observed when a chemical reaction takes place between the gaseous solute and the solvent. Thus,
for example, the solubility of ammonia in water increases more rapidly with increasing pressure than predicted by the law because
ammonia, being a base, reacts to some extent with water to form ammonium ions and hydroxide ions.
Gases can form supersaturated solutions. If a solution of a gas in a liquid is prepared either at low temperature or under pressure (or
both), then as the solution warms or as the gas pressure is reduced, the solution may become supersaturated. In 1986, more than
1700 people in Cameroon were killed when a cloud of gas, almost certainly carbon dioxide, bubbled from Lake Nyos (Figure
11.12), a deep lake in a volcanic crater. The water at the bottom of Lake Nyos is saturated with carbon dioxide by volcanic activity
beneath the lake. It is believed that the lake underwent a turnover due to gradual heating from below the lake, and the warmer, less-
dense water saturated with carbon dioxide reached the surface. Consequently, tremendous quantities of dissolved CO2 were
released, and the colorless gas, which is denser than air, flowed down the valley below the lake and suffocated humans and animals
living in the valley.

Figure 11.12 (a) It is believed that the 1986 disaster that killed more than 1700 people near Lake Nyos in Cameroon resulted when
a large volume of carbon dioxide gas was released from the lake. (b) A CO2 vent has since been installed to help outgas the lake in
a slow, controlled fashion and prevent a similar catastrophe from happening in the future. (credit a: modification of work by Jack
Lockwood; credit b: modification of work by Bill Evans)
11.4.0.1: Solutions of Liquids in Liquids

Some liquids may be mixed in any proportions to yield solutions; in other words, they have infinite mutual solubility and are said
to be miscible. Ethanol, sulfuric acid, and ethylene glycol (popular for use as antifreeze, pictured in Figure 11.13) are examples of
liquids that are completely miscible with water. Two-cycle motor oil is miscible with gasoline, mixtures of which are used as
lubricating fuels for various types of outdoor power equipment (chainsaws, leaf blowers, and so on).

Figure 11.13 Water and antifreeze are miscible; mixtures of the two are homogeneous in all proportions. (credit:
“dno1967”/Wikimedia commons)
Miscible liquids are typically those with very similar polarities. Consider, for example, liquids that are polar or capable of hydrogen
bonding. For such liquids, the dipole-dipole attractions (or hydrogen bonding) of the solute molecules with the solvent molecules
are at least as strong as those between molecules in the pure solute or in the pure solvent. Hence, the two kinds of molecules mix
easily. Likewise, nonpolar liquids are miscible with each other because there is no appreciable difference in the strengths of solute-
solute, solvent-solvent, and solute-solvent intermolecular attractions. The solubility of polar molecules in polar solvents and of
nonpolar molecules in nonpolar solvents is, again, an illustration of the chemical axiom “like dissolves like.”
Two liquids that do not mix to an appreciable extent are called immiscible. Separate layers are formed when immiscible liquids are
poured into the same container. Gasoline, oil (Figure 11.14), benzene, carbon tetrachloride, some paints, and many other nonpolar
liquids are immiscible with water. Relatively weak attractive forces between the polar water molecules and the nonpolar liquid
molecules are not adequate to overcome much stronger hydrogen bonding between water molecules. The distinction between
immiscibility and miscibility is really one of extent, so that miscible liquids are of infinite mutual solubility, while liquids said to be
immiscible are of very low (though not zero) mutual solubility.
Figure 11.14 Water and oil are immiscible. Mixtures of these two substances will form two separate layers with the less dense oil
floating on top of the water. (credit: “Yortw”/Flickr)
Two liquids, such as bromine and water, that are of moderate mutual solubility are said to be partially miscible. Two partially
miscible liquids usually form two layers when mixed. In the case of the bromine and water mixture, the upper layer is water,

saturated with bromine, and the lower layer is bromine saturated with water. Since bromine is nonpolar, and, thus, not very soluble
in water, the water layer is only slightly discolored by the bright orange bromine dissolved in it. Since the solubility of water in
bromine is very low, there is no noticeable effect on the dark color of the bromine layer (Figure 11.15).
Figure 11.15 Bromine (the deep orange liquid on the left) and water (the clear liquid in the middle) are partially miscible. The top
layer in the mixture on the right is a saturated solution of bromine in water; the bottom layer is a saturated solution of water in
bromine. (credit: Paul Flowers)
11.4.0.1: Solutions of Solids in Liquids

The dependence of solubility on temperature for a number of solids in water is shown by the solubility curves in Figure 11.16.
Reviewing these data indicates a general trend of increasing solubility with temperature, although there are exceptions, as
illustrated by the ionic compound cerium sulfate.

Figure 11.16 This graph shows how the solubility of several solids changes with temperature.
The temperature dependence of solubility can be exploited to prepare supersaturated solutions of certain compounds. A solution
may be saturated with the compound at an elevated temperature (where the solute is more soluble) and subsequently cooled to a
lower temperature without precipitating the solute. The resultant solution contains solute at a concentration greater than its
equilibrium solubility at the lower temperature (i.e., it is supersaturated) and is relatively stable. Precipitation of the excess solute

can be initiated by adding a seed crystal (see the video in the Link to Learning earlier in this module) or by mechanically agitating
the solution. Some hand warmers, such as the one pictured in Figure 11.17, take advantage of this behavior.
Figure 11.17 This hand warmer produces heat when the sodium acetate in a supersaturated solution precipitates. Precipitation of the
solute is initiated by a mechanical shockwave generated when the flexible metal disk within the solution is “clicked.” (credit:
modification of work by “Velela”/Wikimedia Commons)

This video shows the crystallization process occurring in a hand warmer.
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Express concentrations of solution components using mole fraction and molality
Describe the effect of solute concentration on various solution properties (vapor pressure, boiling point, freezing point, and
osmotic pressure)
Perform calculations using the mathematical equations that describe these various colligative effects
Describe the process of distillation and its practical applications
Explain the process of osmosis and describe how it is applied industrially and in nature
The properties of a solution are different from those of either the pure solute(s) or solvent. Many solution properties are dependent
upon the chemical identity of the solute. Compared to pure water, a solution of hydrogen chloride is more acidic, a solution of
ammonia is more basic, a solution of sodium chloride is more dense, and a solution of sucrose is more viscous. There are a few
solution properties, however, that depend only upon the total concentration of solute species, regardless of their identities. These
colligative properties include vapor pressure lowering, boiling point elevation, freezing point depression, and osmotic pressure.
This small set of properties is of central importance to many natural phenomena and technological applications, as will be
described in this module.
11.5.0.1: Mole Fraction and Molality

Several units commonly used to express the concentrations of solution components were introduced in an earlier chapter of this
text, each providing certain benefits for use in different applications. For example, molarity (M) is a convenient unit for use in
stoichiometric calculations, since it is defined in terms of the molar amounts of solute species:
mol solute
M =
L solution
Because solution volumes vary with temperature, molar concentrations will likewise vary. When expressed as molarity, the
concentration of a solution with identical numbers of solute and solvent species will be different at different temperatures, due to
the contraction/expansion of the solution. More appropriate for calculations involving many colligative properties are mole-based
concentration units whose values are not dependent on temperature. Two such units are mole fraction (introduced in the previous
chapter on gases) and molality.
The mole fraction, X, of a component is the ratio of its molar amount to the total number of moles of all solution components:
mol A
XA =
total mol of all components
By this definition, the sum of mole fractions for all solution components (the solvent and all solutes) is equal to one.
Molality is a concentration unit defined as the ratio of the numbers of moles of solute to the mass of the solvent in kilograms:
mol solute
m =
kg solvent
Since these units are computed using only masses and molar amounts, they do not vary with temperature and, thus, are better suited
for applications requiring temperature-independent concentrations, including several colligative properties, as will be described in
this chapter module.
11.5.0.1: Example 11.3

11.5.0.0.1: Calculating Mole Fraction and Molality
The antifreeze in most automobile radiators is a mixture of equal volumes of ethylene glycol and water, with minor amounts of
other additives that prevent corrosion. What are the (a) mole fraction and (b) molality of ethylene glycol, C2H4(OH)2, in a
solution prepared from 2.22 × 103 g of ethylene glycol and 2.00 × 103 g of water (approximately 2 L of glycol and 2 L of
water)?

(a) The mole fraction of ethylene glycol may be computed by first deriving molar amounts of both solution components and
then substituting these amounts into the definition of mole fraction.
1 mol C2 H4 (OH)
3 2
mol C2 H4 (OH)2 = 2.22 × 10 g × = 35.8 mol C2 H4 (OH)2
62.07 g C2 H4 (OH)2
3 1 mol H2 O
mol H2 O = 2.00 × 10 g × = 111 mol H2 O
18.02 g H2 O
35.8 mol C2 H4 (OH)2

Xethylene glycol = = 0.244
(35.8+111) mol total
Notice that mole fraction is a dimensionless property, being the ratio of properties with identical units (moles).
(b) Derive moles of solute and mass of solvent (in kg).
First, use the given mass of ethylene glycol and its molar mass to find the moles of solute:
mol C2 H2 (OH)2
3
2.22 × 10 g C2 H4 (OH)2 ( ) = 35.8 mol C2 H4 (OH)2
62.07 g
Then, convert the mass of the water from grams to kilograms:

1 kg
3
2.00 × 10 g H2 O ( ) = 2.00 kg H2 O
1000 g
Finally, calculate molality per its definition:
mol solute
molality =
kg solvent
35.8 mol C2 H4 (OH)

2
molality =
2 kg H2 O
molality = 17.9 m

What are the mole fraction and molality of a solution that contains 0.850 g of ammonia, NH3, dissolved in 125 g of water?
11.5.0.1: Answer:
7.14 × 10−3; 0.399 m
11.5.0.1: Example 11.4

11.5.0.0.4: Converting Mole Fraction and Molal Concentrations
Calculate the mole fraction of solute and solvent in a 3.0 m solution of sodium chloride.
Converting from one concentration unit to another is accomplished by first comparing the two unit definitions. In this case,
both units have the same numerator (moles of solute) but different denominators. The provided molal concentration may be
written as:
3.0 mol NaCl
1 kg H2 O
The numerator for this solution’s mole fraction is, therefore, 3.0 mol NaCl. The denominator may be computed by deriving the
molar amount of water corresponding to 1.0 kg
1000 g mol H2 O
1.0 kg H2 O ( )( ) = 55 mol H2 O
1 kg 18.02 g
and then substituting these molar amounts into the definition for mole fraction.

mol H2 O
XH2 O =
mol NaCl+mol H2 O
55 mol H2 O
XH2 O =
3.0 mol NaCl+55 mol H2 O
XH O = 0.95
2
mol NaCl
XNaCl =
mol NaCl+mol H2 O
3.0 mol NaCl

XNaCl =
3.0 mol NaCl+55 mol H2 O
XNaCl = 0.052

The mole fraction of iodine, I2, dissolved in dichloromethane, CH2Cl2, is 0.115. What is the molal concentration, m, of iodine
in this solution?
11.5.0.1: Answer:
1.50 m
11.5.0.1: Example 11.5

11.5.0.0.7: Molality and Molarity Conversions
Intravenous infusion of a 0.556 M aqueous solution of glucose (density of 1.04 g/mL) is part of some post-operative recovery
therapies. What is the molal concentration of glucose in this solution?
The provided molal concentration may be explicitly written as:
M = 0.556 mol glucose/1 L solution
Consider the definition of molality:

m = mol solute/kg solvent
The amount of glucose in 1-L of this solution is 0.556 mol, so the mass of water in this volume of solution is needed.
First, compute the mass of 1.00 L of the solution:
(1.0 L soln) (1.04 g/mL) (1000 mL/1L) (1 kg/1000 g) = 1.04 kg soln
This is the mass of both the water and its solute, glucose, and so the mass of glucose must be subtracted. Compute the mass of
glucose from its molar amount:
(0.556 mol glucose) (180.2 g/1 mol) = 100.2 g or 0.1002 kg
Subtracting the mass of glucose yields the mass of water in the solution:
1.04 kg solution − 0.1002 kg glucose = 0.94 kg water
Finally, the molality of glucose in this solution is computed as:

m = 0.556 mol glucose/0.94 kg water = 0.59 m

Nitric acid, HNO3(aq), is commercially available as a 33.7 m aqueous solution (density = 1.35 g/mL). What is the molarity of
this solution?
11.5.0.1: Answer:
14.6 M
11.5.0.1: Vapor Pressure Lowering

As described in the chapter on liquids and solids, the equilibrium vapor pressure of a liquid is the pressure exerted by its gaseous
phase when vaporization and condensation are occurring at equal rates:

liquid ⇌ gas
Dissolving a nonvolatile substance in a volatile liquid results in a lowering of the liquid’s vapor pressure. This phenomenon can be
rationalized by considering the effect of added solute molecules on the liquid's vaporization and condensation processes. To
vaporize, solvent molecules must be present at the surface of the solution. The presence of solute decreases the surface area
available to solvent molecules and thereby reduces the rate of solvent vaporization. Since the rate of condensation is unaffected by
the presence of solute, the net result is that the vaporization-condensation equilibrium is achieved with fewer solvent molecules in
the vapor phase (i.e., at a lower vapor pressure) (Figure 11.18). While this interpretation is useful, it does not account for several
important aspects of the colligative nature of vapor pressure lowering. A more rigorous explanation involves the property of
entropy, a topic of discussion in a later text chapter on thermodynamics. For purposes of understanding the lowering of a liquid's
vapor pressure, it is adequate to note that the more dispersed nature of matter in a solution, compared to separate solvent and solute
phases, serves to effectively stabilize the solvent molecules and hinder their vaporization. A lower vapor pressure results, and a
correspondingly higher boiling point as described in the next section of this module.
Figure 11.18 The presence of nonvolatile solutes lowers the vapor pressure of a solution by impeding the evaporation of solvent
molecules.
The relationship between the vapor pressures of solution components and the concentrations of those components is described by
Raoult’s law: The partial pressure exerted by any component of an ideal solution is equal to the vapor pressure of the pure
component multiplied by its mole fraction in the solution.
∗
PA = XA P
A
where PA is the partial pressure exerted by component A in the solution, P

A
∗
is the vapor pressure of pure A, and XA is the mole
fraction of A in the solution.
Recalling that the total pressure of a gaseous mixture is equal to the sum of partial pressures for all its components (Dalton’s law of
partial pressures), the total vapor pressure exerted by a solution containing i components is

∗
Psolution = ∑ Pi = ∑ Xi P
i
i i
A nonvolatile substance is one whose vapor pressure is negligible (P* ≈ 0), and so the vapor pressure above a solution containing
only nonvolatile solutes is due only to the solvent:
∗
Psolution = Xsolvent P
solvent
11.5.0.1: Example 11.6

11.5.0.0.1: Calculation of a Vapor Pressure
Compute the vapor pressure of an ideal solution containing 92.1 g of glycerin, C3H5(OH)3, and 184.4 g of ethanol, C2H5OH, at
40 °C. The vapor pressure of pure ethanol is 0.178 atm at 40 °C. Glycerin is essentially nonvolatile at this temperature.
Since the solvent is the only volatile component of this solution, its vapor pressure may be computed per Raoult’s law as:
∗
solvent
First, calculate the molar amounts of each solution component using the provided mass data.
1 mol C3 H5 (OH)3
92.1 g C3 H5 (OH)3 × = 1.00 mol C3 H5 (OH)3
92.094 g C3 H5 (OH)
3
1 mol C2 H5 OH
184.4 g C2 H5 OH × = 4.000 mol C2 H5 OH
46.069 g C2 H5 OH
Next, calculate the mole fraction of the solvent (ethanol) and use Raoult’s law to compute the solution’s vapor pressure.
4.000 mol
XC H5 OH = = 0.800
2
(1.00 mol+4.000 mol)
∗
Psolv = XsolvP = 0.800 × 0.178 atm = 0.142 atm
solv

A solution contains 5.00 g of urea, CO(NH2)2 (a nonvolatile solute) and 0.100 kg of water. If the vapor pressure of pure water
at 25 °C is 23.7 torr, what is the vapor pressure of the solution assuming ideal behavior?
11.5.0.1: Answer:
23.4 torr
11.5.0.1: Distillation of Solutions

Solutions whose components have significantly different vapor pressures may be separated by a selective vaporization process
known as distillation. Consider the simple case of a mixture of two volatile liquids, A and B, with A being the more volatile liquid.
Raoult’s law can be used to show that the vapor above the solution is enriched in component A, that is, the mole fraction of A in the
vapor is greater than the mole fraction of A in the liquid (see end-of-chapter Exercise 65). By appropriately heating the mixture,
component A may be vaporized, condensed, and collected—effectively separating it from component B.
Distillation is widely applied in both laboratory and industrial settings, being used to refine petroleum, to isolate fermentation
products, and to purify water. A typical apparatus for laboratory-scale distillations is shown in Figure 11.19.

Figure 11.19 A typical laboratory distillation unit is shown in (a) a photograph and (b) a schematic diagram of the components.
(credit a: modification of work by “Rifleman82”/Wikimedia commons; credit b: modification of work by “Slashme”/Wikimedia
Commons)
Oil refineries use large-scale fractional distillation to separate the components of crude oil. The crude oil is heated to high
temperatures at the base of a tall fractionating column, vaporizing many of the components that rise within the column. As
vaporized components reach adequately cool zones during their ascent, they condense and are collected. The collected liquids are
simpler mixtures of hydrocarbons and other petroleum compounds that are of appropriate composition for various applications
(e.g., diesel fuel, kerosene, gasoline), as depicted in Figure 11.20.

Figure 11.20 Crude oil is a complex mixture that is separated by large-scale fractional distillation to isolate various simpler
mixtures.
11.5.0.1: Boiling Point Elevation

As described in the chapter on liquids and solids, the boiling point of a liquid is the temperature at which its vapor pressure is equal
to ambient atmospheric pressure. Since the vapor pressure of a solution is lowered due to the presence of nonvolatile solutes, it
stands to reason that the solution’s boiling point will subsequently be increased. Vapor pressure increases with temperature, and so
a solution will require a higher temperature than will pure solvent to achieve any given vapor pressure, including one equivalent to
that of the surrounding atmosphere. The increase in boiling point observed when nonvolatile solute is dissolved in a solvent, ΔTb, is
called boiling point elevation and is directly proportional to the molal concentration of solute species:
ΔTb = Kb m
where Kb is the boiling point elevation constant, or the ebullioscopic constant and m is the molal concentration (molality) of all
solute species.

Boiling point elevation constants are characteristic properties that depend on the identity of the solvent. Values of Kb for several
solvents are listed in Table 11.2.
Boiling Point Elevation and Freezing Point Depression Constants for Several Solvents
Solvent Boiling Point (°C at 1 atm) Kb (ºCm−1) Freezing Point (°C at 1 atm) Kf (ºCm−1)
water 100.0 0.512 0.0 1.86
hydrogen acetate 118.1 3.07 16.6 3.9
benzene 80.1 2.53 5.5 5.12
chloroform 61.26 3.63 −63.5 4.68
nitrobenzene 210.9 5.24 5.67 8.1
Table 11.2
The extent to which the vapor pressure of a solvent is lowered and the boiling point is elevated depends on the total number of
solute particles present in a given amount of solvent, not on the mass or size or chemical identities of the particles. A 1 m aqueous
solution of sucrose (342 g/mol) and a 1 m aqueous solution of ethylene glycol (62 g/mol) will exhibit the same boiling point
because each solution has one mole of solute particles (molecules) per kilogram of solvent.
11.5.0.1: Example 11.7

11.5.0.0.1: Calculating the Boiling Point of a Solution
Assuming ideal solution behavior, what is the boiling point of a 0.33 m solution of a nonvolatile solute in benzene?
Use the equation relating boiling point elevation to solute molality to solve this problem in two steps.
1. Step 1. Calculate the change in boiling point.

−1
ΔTb = Kb m = 2.53 °C m × 0.33 m = 0.83 °C
2. Step 2. Add the boiling point elevation to the pure solvent’s boiling point.
Boiling temperature = 80.1 °C + 0.83 °C = 80.9 °C

Assuming ideal solution behavior, what is the boiling point of the antifreeze described in Example 11.3?
11.5.0.1: Answer:
109.2 °C
11.5.0.1: Example 11.8

11.5.0.0.4: The Boiling Point of an Iodine Solution
Find the boiling point of a solution of 92.1 g of iodine, I2, in 800.0 g of chloroform, CHCl3, assuming that the iodine is
nonvolatile and that the solution is ideal.

A four-step approach to solving this problem is outlined below.
1. Step 1. Convert from grams to moles of I2 using the molar mass of I2 in the unit conversion factor.
Result: 0.363 mol
2. Step 2. Determine the molality of the solution from the number of moles of solute and the mass of solvent, in kilograms.
Result: 0.454 m
3. Step 3. Use the direct proportionality between the change in boiling point and molal concentration to determine how much
the boiling point changes.
Result: 1.65 °C
4. Step 4. Determine the new boiling point from the boiling point of the pure solvent and the change.
Result: 62.91 °C
Check each result as a self-assessment.
What is the boiling point of a solution of 1.0 g of glycerin, C3H5(OH)3, in 47.8 g of water? Assume an ideal solution.
11.5.0.1: Answer:
100.12 °C
11.5.0.1: Freezing Point Depression

Solutions freeze at lower temperatures than pure liquids. This phenomenon is exploited in “de-icing” schemes that use salt (Figure
11.21), calcium chloride, or urea to melt ice on roads and sidewalks, and in the use of ethylene glycol as an “antifreeze” in
automobile radiators. Seawater freezes at a lower temperature than fresh water, and so the Arctic and Antarctic oceans remain
unfrozen even at temperatures below 0 °C (as do the body fluids of fish and other cold-blooded sea animals that live in these
oceans).
Figure 11.21 Rock salt (NaCl), calcium chloride (CaCl2), or a mixture of the two are used to melt ice. (credit: modification of work
by Eddie Welker)

The decrease in freezing point of a dilute solution compared to that of the pure solvent, ΔTf, is called the freezing point depression
and is directly proportional to the molal concentration of the solute
ΔTf = Kf m
where m is the molal concentration of the solute and Kf is called the freezing point depression constant (or cryoscopic constant).
Just as for boiling point elevation constants, these are characteristic properties whose values depend on the chemical identity of the
solvent. Values of Kf for several solvents are listed in Table 11.2.
11.5.0.1: Example 11.9

11.5.0.0.1: Calculation of the Freezing Point of a Solution
Assuming ideal solution behavior, what is the freezing point of the 0.33 m solution of a nonvolatile nonelectrolyte solute in
benzene described in Example 11.4?
Use the equation relating freezing point depression to solute molality to solve this problem in two steps.
1. Step 1. Calculate the change in freezing point.

−1
ΔTf = Kf m = 5.12 °C m × 0.33 m = 1.7 °C
2. Step 2. Subtract the freezing point change observed from the pure solvent’s freezing point.
Freezing Temperature = 5.5 °C − 1.7 °C = 3.8 °C

Assuming ideal solution behavior, what is the freezing point of a 1.85 m solution of a nonvolatile nonelectrolyte solute in
nitrobenzene?
11.5.0.1: Answer:
−9.3 °C

11.5.0.0.4: Colligative Properties and De-Icing
Sodium chloride and its group 2 analogs calcium and magnesium chloride are often used to de-ice roadways and sidewalks,
due to the fact that a solution of any one of these salts will have a freezing point lower than 0 °C, the freezing point of pure
water. The group 2 metal salts are frequently mixed with the cheaper and more readily available sodium chloride (“rock salt”)
for use on roads, since they tend to be somewhat less corrosive than the NaCl, and they provide a larger depression of the
freezing point, since they dissociate to yield three particles per formula unit, rather than two particles like the sodium chloride.
Because these ionic compounds tend to hasten the corrosion of metal, they would not be a wise choice to use in antifreeze for
the radiator in your car or to de-ice a plane prior to takeoff. For these applications, covalent compounds, such as ethylene or
propylene glycol, are often used. The glycols used in radiator fluid not only lower the freezing point of the liquid, but they
elevate the boiling point, making the fluid useful in both winter and summer. Heated glycols are often sprayed onto the surface
of airplanes prior to takeoff in inclement weather in the winter to remove ice that has already formed and prevent the formation
of more ice, which would be particularly dangerous if formed on the control surfaces of the aircraft (Figure 11.22).

Figure 11.22 Freezing point depression is exploited to remove ice from (a) roadways and (b) the control surfaces of aircraft.
11.5.0.1: Phase Diagram for a Solution

The colligative effects on vapor pressure, boiling point, and freezing point described in the previous section are conveniently
summarized by comparing the phase diagrams for a pure liquid and a solution derived from that liquid (Figure 11.23).
Figure 11.23 Phase diagrams for a pure solvent (solid curves) and a solution formed by dissolving nonvolatile solute in the solvent
(dashed curves).
The liquid-vapor curve for the solution is located beneath the corresponding curve for the solvent, depicting the vapor pressure
lowering, ΔP, that results from the dissolution of nonvolatile solute. Consequently, at any given pressure, the solution’s boiling
point is observed at a higher temperature than that for the pure solvent, reflecting the boiling point elevation, ΔTb, associated with

the presence of nonvolatile solute. The solid-liquid curve for the solution is displaced left of that for the pure solvent, representing
the freezing point depression, ΔTf, that accompanies solution formation. Finally, notice that the solid-gas curves for the solvent and
its solution are identical. This is the case for many solutions comprising liquid solvents and nonvolatile solutes. Just as for
vaporization, when a solution of this sort is frozen, it is actually just the solvent molecules that undergo the liquid-to-solid
transition, forming pure solid solvent that excludes solute species. The solid and gaseous phases, therefore, are composed of solvent
only, and so transitions between these phases are not subject to colligative effects.
11.5.0.1: Osmosis and Osmotic Pressure of Solutions

A number of natural and synthetic materials exhibit selective permeation, meaning that only molecules or ions of a certain size,
shape, polarity, charge, and so forth, are capable of passing through (permeating) the material. Biological cell membranes provide
elegant examples of selective permeation in nature, while dialysis tubing used to remove metabolic wastes from blood is a more
simplistic technological example. Regardless of how they may be fabricated, these materials are generally referred to as
semipermeable membranes.
Consider the apparatus illustrated in Figure 11.24, in which samples of pure solvent and a solution are separated by a membrane
that only solvent molecules may permeate. Solvent molecules will diffuse across the membrane in both directions. Since the
concentration of solvent is greater in the pure solvent than the solution, these molecules will diffuse from the solvent side of the
membrane to the solution side at a faster rate than they will in the reverse direction. The result is a net transfer of solvent molecules
from the pure solvent to the solution. Diffusion-driven transfer of solvent molecules through a semipermeable membrane is a
process known as osmosis.
Figure 11.24 (a) A solution and pure solvent are initially separated by an osmotic membrane. (b) Net transfer of solvent molecules
to the solution occurs until its osmotic pressure yields equal rates of transfer in both directions.
When osmosis is carried out in an apparatus like that shown in Figure 11.24, the volume of the solution increases as it becomes
diluted by accumulation of solvent. This causes the level of the solution to rise, increasing its hydrostatic pressure (due to the
weight of the column of solution in the tube) and resulting in a faster transfer of solvent molecules back to the pure solvent side.
When the pressure reaches a value that yields a reverse solvent transfer rate equal to the osmosis rate, bulk transfer of solvent

ceases. This pressure is called the osmotic pressure (Π) of the solution. The osmotic pressure of a dilute solution is related to its
solute molarity, M, and absolute temperature, T, according to the equation
Π = M RT
where R is the universal gas constant.
11.5.0.1: Example 11.10

11.5.0.0.1: Calculation of Osmotic Pressure
Assuming ideal solution behavior, what is the osmotic pressure (atm) of a 0.30 M solution of glucose in water that is used for
intravenous infusion at body temperature, 37 °C?
Find the osmotic pressure, Π, using the formula Π = MRT, where T is on the Kelvin scale (310 K) and the value of R is
expressed in appropriate units (0.08206 L atm/mol K).
Π = M RT
= 0.30 mol/L × 0.08206 L atm/mol K × 310 K
= 7.6 atm

Assuming ideal solution behavior, what is the osmotic pressure (atm) a solution with a volume of 0.750 L that contains 5.0 g of
methanol, CH3OH, in water at 37 °C?
11.5.0.1: Answer:
5.3 atm
If a solution is placed in an apparatus like the one shown in Figure 11.25, applying pressure greater than the osmotic pressure of the
solution reverses the osmosis and pushes solvent molecules from the solution into the pure solvent. This technique of reverse
osmosis is used for large-scale desalination of seawater and on smaller scales to produce high-purity tap water for drinking.

Figure 11.25 Applying a pressure greater than the osmotic pressure of a solution will reverse osmosis. Solvent molecules from the
solution are pushed into the pure solvent.

11.5.0.0.4: Reverse Osmosis Water Purification
In the process of osmosis, diffusion serves to move water through a semipermeable membrane from a less concentrated
solution to a more concentrated solution. Osmotic pressure is the amount of pressure that must be applied to the more
concentrated solution to cause osmosis to stop. If greater pressure is applied, the water will go from the more concentrated
solution to a less concentrated (more pure) solution. This is called reverse osmosis. Reverse osmosis (RO) is used to purify
water in many applications, from desalination plants in coastal cities, to water-purifying machines in grocery stores (Figure
11.26), and smaller reverse-osmosis household units. With a hand-operated pump, small RO units can be used in third-world
countries, disaster areas, and in lifeboats. Our military forces have a variety of generator-operated RO units that can be
transported in vehicles to remote locations.
Figure 11.26 Reverse osmosis systems for purifying drinking water are shown here on (a) small and (b) large scales. (credit a:
modification of work by Jerry Kirkhart; credit b: modification of work by Willard J. Lathrop)
Examples of osmosis are evident in many biological systems because cells are surrounded by semipermeable membranes. Carrots
and celery that have become limp because they have lost water can be made crisp again by placing them in water. Water moves into
the carrot or celery cells by osmosis. A cucumber placed in a concentrated salt solution loses water by osmosis and absorbs some
salt to become a pickle. Osmosis can also affect animal cells. Solute concentrations are particularly important when solutions are
injected into the body. Solutes in body cell fluids and blood serum give these solutions an osmotic pressure of approximately 7.7
atm. Solutions injected into the body must have the same osmotic pressure as blood serum; that is, they should be isotonic with
blood serum. If a less concentrated solution, a hypotonic solution, is injected in sufficient quantity to dilute the blood serum, water
from the diluted serum passes into the blood cells by osmosis, causing the cells to expand and rupture. This process is called
hemolysis. When a more concentrated solution, a hypertonic solution, is injected, the cells lose water to the more concentrated
solution, shrivel, and possibly die in a process called crenation. These effects are illustrated in Figure 11.27.

Figure 11.27 Red blood cell membranes are water permeable and will (a) swell and possibly rupture in a hypotonic solution; (b)
maintain normal volume and shape in an isotonic solution; and (c) shrivel and possibly die in a hypertonic solution. (credit a/b/c:
modifications of work by “LadyofHats”/Wikimedia commons)
11.5.0.1: Determination of Molar Masses

Osmotic pressure and changes in freezing point, boiling point, and vapor pressure are directly proportional to the number of solute
species present in a given amount of solution. Consequently, measuring one of these properties for a solution prepared using a
known mass of solute permits determination of the solute’s molar mass.
11.5.0.1: Example 11.11

11.5.0.0.1: Determination of a Molar Mass from a Freezing Point Depression
A solution of 4.00 g of a nonelectrolyte dissolved in 55.0 g of benzene is found to freeze at 2.32 °C. Assuming ideal solution
behavior, what is the molar mass of this compound?

Solve this problem using the following steps.
1. Step 1. Determine the change in freezing point from the observed freezing point and the freezing point of pure benzene
(Table 11.2).
ΔTf = 5.5 °C − 2.32 °C = 3.2 °C
2. Step 2. Determine the molal concentration from Kf, the freezing point depression constant for benzene (Table 11.2), and
ΔTf.
ΔTf = Kf m
ΔTf 3.2 °C
m = = −1
= 0.63 m
Kf 5.12 °C m
3. Step 3. Determine the number of moles of compound in the solution from the molal concentration and the mass of solvent
used to make the solution.
0.63 mol solute
Moles of solute = × 0.0550 kg solvent = 0.035 mol
1.00 kg solvent
4. Step 4. Determine the molar mass from the mass of the solute and the number of moles in that mass.
4.00 g
2
Molar mass = = 1.1 × 10 g/mol
0.035 mol

A solution of 35.7 g of a nonelectrolyte in 220.0 g of chloroform has a boiling point of 64.5 °C. Assuming ideal solution
behavior, what is the molar mass of this compound?
11.5.0.1: Answer:
1.8 × 102 g/mol
11.5.0.1: Example 11.12

11.5.0.0.4: Determination of a Molar Mass from Osmotic Pressure
A 0.500 L sample of an aqueous solution containing 10.0 g of hemoglobin has an osmotic pressure of 5.9 torr at 22 °C.
Assuming ideal solution behavior, what is the molar mass of hemoglobin?

Here is one set of steps that can be used to solve the problem:
1. Step 1. Convert the osmotic pressure to atmospheres, then determine the molar concentration from the osmotic pressure.
5.9 torr × 1 atm −3

Π = = 7.8 × 10 atm
760 torr
Π = MRT
−3
Π 7.8 × 10 atm −4
M = = = 3.2 × 10 M
RT (0.08206 L atm/mol K)(295 K)
2. Step 2. Determine the number of moles of hemoglobin in the solution from the concentration and the volume of the solution.
−4
3.2 × 10 mol −4
moles of hemoglobin = × 0.500 L solution = 1.6 × 10 mol
1 L solution
3. Step 3. Determine the molar mass from the mass of hemoglobin and the number of moles in that mass.
10.0 g
4
molar mass = = 6.2 × 10 g/mol
−4
1.6 × 10 mol

Assuming ideal solution behavior, what is the molar mass of a protein if a solution of 0.02 g of the protein in 25.0 mL of
solution has an osmotic pressure of 0.56 torr at 25 °C?
11.5.0.1: Answer:
3 × 104 g/mol
11.5.0.1: Colligative Properties of Electrolytes

As noted previously in this module, the colligative properties of a solution depend only on the number, not on the identity, of solute
species dissolved. The concentration terms in the equations for various colligative properties (freezing point depression, boiling
point elevation, osmotic pressure) pertain to all solute species present in the solution. For the solutions considered thus far in this
chapter, the solutes have been nonelectrolytes that dissolve physically without dissociation or any other accompanying process.
Each molecule that dissolves yields one dissolved solute molecule. The dissolution of an electroyte, however, is not this simple, as
illustrated by the two common examples below:
+ −
dissociation NaCl(s) ⟶ Na (aq) + Cl (aq)
− +
ionization HCl(aq) + H2 O(l) ⟶ Cl (aq) + H3 O (aq)
Considering the first of these examples, and assuming complete dissociation, a 1.0 m aqueous solution of NaCl contains 2.0 mole
of ions (1.0 mol Na+ and 1.0 mol Cl−) per each kilogram of water, and its freezing point depression is expected to be
ΔTf = 2.0 mol ions/kg water × 1.86 °C kg water/mol ion = 3.7 °C.
When this solution is actually prepared and its freezing point depression measured, however, a value of 3.4 °C is obtained. Similar
discrepancies are observed for other ionic compounds, and the differences between the measured and expected colligative property
values typically become more significant as solute concentrations increase. These observations suggest that the ions of sodium
chloride (and other strong electrolytes) are not completely dissociated in solution.
To account for this and avoid the errors accompanying the assumption of total dissociation, an experimentally measured parameter
named in honor of Nobel Prize-winning German chemist Jacobus Henricus van’t Hoff is used. The van’t Hoff factor (i) is defined

as the ratio of solute particles in solution to the number of formula units dissolved:
moles of particles in solution
i =
moles of formula units dissolved
Values for measured van’t Hoff factors for several solutes, along with predicted values assuming complete dissociation, are shown
in Table 11.3.
Predicated and Measured van’t Hoff Factors for Several 0.050 m Aqueous Solutions
Formula unit Classification Dissolution products i (predicted) i (measured)
C12H22O11 (glucose) Nonelectrolyte C12H22O11 1 1.0
NaCl Strong electrolyte Na+, Cl− 2 1.9
HCl Strong electrolyte (acid) H3O+, Cl− 2 1.9
MgSO4 Strong electrolyte Mg2+, SO42−, 2 1.3
MgCl2 Strong electrolyte Mg2+, 2Cl− 3 2.7
FeCl3 Strong electrolyte Fe3+, 3Cl− 4 3.4
Table 11.3
In 1923, the chemists Peter Debye and Erich Hückel proposed a theory to explain the apparent incomplete ionization of strong
electrolytes. They suggested that although interionic attraction in an aqueous solution is very greatly reduced by solvation of the
ions and the insulating action of the polar solvent, it is not completely nullified. The residual attractions prevent the ions from
behaving as totally independent particles (Figure 11.28). In some cases, a positive and negative ion may actually touch, giving a
solvated unit called an ion pair. Thus, the activity, or the effective concentration, of any particular kind of ion is less than that
indicated by the actual concentration. Ions become more and more widely separated the more dilute the solution, and the residual
interionic attractions become less and less. Thus, in extremely dilute solutions, the effective concentrations of the ions (their
activities) are essentially equal to the actual concentrations. Note that the van’t Hoff factors for the electrolytes in Table 11.3 are for
0.05 m solutions, at which concentration the value of i for NaCl is 1.9, as opposed to an ideal value of 2.

Figure 11.28 Dissociation of ionic compounds in water is not always complete due to the formation of ion pairs.

11.5.0.1: Example 11.13
11.5.0.0.1: The Freezing Point of a Solution of an Electrolyte
The concentration of ions in seawater is approximately the same as that in a solution containing 4.2 g of NaCl dissolved in 125
g of water. Use this information and a predicted value for the van’t Hoff factor (Table 11.3) to determine the freezing
temperature the solution (assume ideal solution behavior).
Solve this problem using the following series of steps.
1. Step 1. Convert from grams to moles of NaCl using the molar mass of NaCl in the unit conversion factor.
Result: 0.072 mol NaCl
2. Step 2. Determine the number of moles of ions present in the solution using the number of moles of ions in 1 mole of NaCl
as the conversion factor (2 mol ions/1 mol NaCl).
Result: 0.14 mol ions
3. Step 3. Determine the molality of the ions in the solution from the number of moles of ions and the mass of solvent, in
kilograms.
Result: 1.2 m
4. Step 4. Use the direct proportionality between the change in freezing point and molal concentration to determine how much
the freezing point changes.
Result: 2.1 °C
5. Step 5. Determine the new freezing point from the freezing point of the pure solvent and the change.
Result: −2.1 °C
Check each result as a self-assessment, taking care to avoid rounding errors by retaining guard digits in each step’s result
for computing the next step’s result.
Assuming complete dissociation and ideal solution behavior, calculate the freezing point of a solution of 0.724 g of CaCl2 in
175 g of water.
11.5.0.1: Answer:
−0.208 °C
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11.6: Colloids

Describe the composition and properties of colloidal dispersions
List and explain several technological applications of colloids
As a child, you may have made suspensions such as mixtures of mud and water, flour and water, or a suspension of solid pigments
in water, known as tempera paint. These suspensions are heterogeneous mixtures composed of relatively large particles that are
visible (or that can be seen with a magnifying glass). They are cloudy, and the suspended particles settle out after mixing. On the
other hand, a solution is a homogeneous mixture in which no settling occurs and in which the dissolved species are molecules or
ions. Solutions exhibit completely different behavior from suspensions. A solution may be colored, but it is transparent, the
molecules or ions are invisible, and they do not settle out on standing. Another class of mixtures called colloids (or colloidal
dispersions) exhibit properties intermediate between those of suspensions and solutions (Figure 11.29). The particles in a colloid
are larger than most simple molecules; however, colloidal particles are small enough that they do not settle out upon standing.
Figure 11.29 (a) A solution is a homogeneous mixture that appears clear, such as the saltwater in this aquarium. (b) In a colloid,
such as milk, the particles are much larger but remain dispersed and do not settle. (c) A suspension, such as mud, is a
heterogeneous mixture of suspended particles that appears cloudy and in which the particles can settle. (credit a photo:
modification of work by Adam Wimsatt; credit b photo: modification of work by Melissa Wiese; credit c photo: modification of
work by Peter Burgess)
The particles in a colloid are large enough to scatter light, a phenomenon called the Tyndall effect. This can make colloidal
mixtures appear cloudy or opaque, such as the searchlight beams shown in Figure 11.30. Clouds are colloidal mixtures. They are
composed of water droplets that are much larger than molecules, but that are small enough that they do not settle out.

Figure 11.30 The paths of searchlight beams are made visible when light is scattered by colloidal-size particles in the air (fog,
smoke, etc.). (credit: “Bahman”/Wikimedia Commons)
The term “colloid”—from the Greek words kolla, meaning “glue,” and eidos, meaning “like”—was first used in 1861 by Thomas
Graham to classify mixtures such as starch in water and gelatin. Many colloidal particles are aggregates of hundreds or thousands
of molecules, but others (such as proteins and polymer molecules) consist of a single extremely large molecule. The protein and
synthetic polymer molecules that form colloids may have molecular masses ranging from a few thousand to many million atomic
mass units.
Analogous to the identification of solution components as “solute” and “solvent,” the components of a colloid are likewise
classified according to their relative amounts. The particulate component typically present in a relatively minor amount is called the
dispersed phase and the substance or solution throughout which the particulate is dispersed is called the dispersion medium.
Colloids may involve virtually any combination of physical states (gas in liquid, liquid in solid, solid in gas, etc.), as illustrated by
the examples of colloidal systems given in Table 11.4.
Examples of Colloidal Systems
Dispersed Phase Dispersion Medium Common Examples Name
solid gas smoke, dust —
solid liquid starch in water, some inks, paints, milk of magnesia sol
solid solid some colored gems, some alloys —

Dispersed Phase Dispersion Medium Common Examples Name
liquid gas clouds, fogs, mists, sprays aerosol
liquid liquid milk, mayonnaise, butter emulsion
liquid solid jellies, gels, pearl, opal (H2O in SiO2) gel
gas liquid foams, whipped cream, beaten egg whites foam
gas solid pumice, floating soaps —
Table 11.4
11.6.0.1: Preparation of Colloidal Systems

Colloids are prepared by producing particles of colloidal dimensions and distributing these particles throughout a dispersion
medium. Particles of colloidal size are formed by two methods:
1. Dispersion methods: breaking down larger particles. For example, paint pigments are produced by dispersing large particles by
grinding in special mills.
2. Condensation methods: growth from smaller units, such as molecules or ions. For example, clouds form when water molecules
condense and form very small droplets.
A few solid substances, when brought into contact with water, disperse spontaneously and form colloidal systems. Gelatin, glue,
starch, and dehydrated milk powder behave in this manner. The particles are already of colloidal size; the water simply disperses
them. Powdered milk particles of colloidal size are produced by dehydrating milk spray. Some atomizers produce colloidal
dispersions of a liquid in air.
An emulsion may be prepared by shaking together or blending two immiscible liquids. This breaks one liquid into droplets of
colloidal size, which then disperse throughout the other liquid. Oil spills in the ocean may be difficult to clean up, partly because
wave action can cause the oil and water to form an emulsion. In many emulsions, however, the dispersed phase tends to coalesce,
form large drops, and separate. Therefore, emulsions are usually stabilized by an emulsifying agent, a substance that inhibits the
coalescence of the dispersed liquid. For example, a little soap will stabilize an emulsion of kerosene in water. Milk is an emulsion
of butterfat in water, with the protein casein serving as the emulsifying agent. Mayonnaise is an emulsion of oil in vinegar, with egg
yolk components as the emulsifying agents.
Condensation methods form colloidal particles by aggregation of molecules or ions. If the particles grow beyond the colloidal size
range, drops or precipitates form, and no colloidal system results. Clouds form when water molecules aggregate and form colloid-
sized particles. If these water particles coalesce to form adequately large water drops of liquid water or crystals of solid water, they
settle from the sky as rain, sleet, or snow. Many condensation methods involve chemical reactions. A red colloidal suspension of
iron(III) hydroxide may be prepared by mixing a concentrated solution of iron(III) chloride with hot water:
3+ − + −
Fe (aq) + 3 Cl (aq) + 6 H2 O (l) ⟶ Fe(OH) (s) + H3 O (aq) + 3 Cl (aq).
3
A colloidal gold sol results from the reduction of a very dilute solution of gold(III) chloride by a reducing agent such as
formaldehyde, tin(II) chloride, or iron(II) sulfate:
3+ −
Au + 3e ⟶ Au
Some gold sols prepared in 1857 are still intact (the particles have not coalesced and settled), illustrating the long-term stability of
many colloids.
11.6.0.1: Soaps and Detergents

Pioneers made soap by boiling fats with a strongly basic solution made by leaching potassium carbonate, K2CO3, from wood ashes
with hot water. Animal fats contain polyesters of fatty acids (long-chain carboxylic acids). When animal fats are treated with a base
like potassium carbonate or sodium hydroxide, glycerol and salts of fatty acids such as palmitic, oleic, and stearic acid are formed.

The salts of fatty acids are called soaps. The sodium salt of stearic acid, sodium stearate, has the formula C17H35CO2Na and
contains an uncharged nonpolar hydrocarbon chain, the C17H35— unit, and an ionic carboxylate group, the —CO unit (Figure
2
−
11.31).
Figure 11.31 Soaps contain a nonpolar hydrocarbon end (blue) and an ionic end (red). The ionic end is a carboxylate group. The
length of the hydrocarbon end can vary from soap to soap.
Detergents (soap substitutes) also contain nonpolar hydrocarbon chains, such as C12H25—, and an ionic group, such as a sulfate—
, or a sulfonate—SO (Figure 11.32). Soaps form insoluble calcium and magnesium compounds in hard water;
− −
OSO 3 3
detergents form water-soluble products—a definite advantage for detergents.
Figure 11.32 Detergents contain a nonpolar hydrocarbon end (blue) and an ionic end (red). The ionic end can be either a sulfate or a
sulfonate. The length of the hydrocarbon end can vary from detergent to detergent.
The cleaning action of soaps and detergents can be explained in terms of the structures of the molecules involved. The hydrocarbon
(nonpolar) end of a soap or detergent molecule dissolves in, or is attracted to, nonpolar substances such as oil, grease, or dirt
particles. The ionic end is attracted by water (polar), illustrated in Figure 11.33. As a result, the soap or detergent molecules
become oriented at the interface between the dirt particles and the water so they act as a kind of bridge between two different kinds
of matter, nonpolar and polar. Molecules such as this are termed amphiphilic since they have both a hydrophobic (“water-fearing”)
part and a hydrophilic (“water-loving”) part. As a consequence, dirt particles become suspended as colloidal particles and are
readily washed away.
Figure 11.33 This diagrammatic cross section of an emulsified drop of oil in water shows how soap or detergent acts as an
emulsifier.

11.6.0.0.1: Deepwater Horizon Oil Spill
The blowout of the Deepwater Horizon oil drilling rig on April 20, 2010, in the Gulf of Mexico near Mississippi began the
largest marine oil spill in the history of the petroleum industry. In the 87 days following the blowout, an estimated 4.9 million
barrels (210 million gallons) of oil flowed from the ruptured well 5000 feet below the water’s surface. The well was finally
declared sealed on September 19, 2010.
Crude oil is immiscible with and less dense than water, so the spilled oil rose to the surface of the water. Floating booms,
skimmer ships, and controlled burns were used to remove oil from the water’s surface in an attempt to protect beaches and
wetlands along the Gulf coast. In addition to removal of the oil, attempts were also made to lessen its environmental impact by
rendering it “soluble” (in the loose sense of the term) and thus allowing it to be diluted to hopefully less harmful levels by the
vast volume of ocean water. This approach used 1.84 million gallons of the oil dispersant Corexit 9527, most of which was
injected underwater at the site of the leak, with small amounts being sprayed on top of the spill. Corexit 9527 contains 2-
butoxyethanol (C6H14O2), an amphiphilic molecule whose polar and nonpolar ends are useful for emulsifying oil into small
droplets, increasing the surface area of the oil and making it more available to marine bacteria for digestion (Figure 11.34).
While this approach avoids many of the immediate hazards that bulk oil poses to marine and coastal ecosystems, it introduces
the possibility of long-term effects resulting from the introduction of the complex and potential toxic components of petroleum
into the ocean’s food chain. A number of organizations are involved in monitoring the extended impact of this oil spill,
including the National Oceanic and Atmospheric Administration (visit this website for additional details).
Figure 11.34 (a) This NASA satellite image shows the oil slick from the Deepwater Horizon spill. (b) A US Air Force plane
sprays Corexit, a dispersant. (c) The molecular structure of 2-butoxyethanol is shown. (credit a: modification of work by
“NASA, FT2, demis.nl”/Wikimedia Commons; credit b: modification of work by “NASA/MODIS Rapid Response
Team”/Wikimedia Commons)
11.6.0.1: Electrical Properties of Colloidal Particles

Dispersed colloidal particles are often electrically charged. A colloidal particle of iron(III) hydroxide, for example, does not contain
enough hydroxide ions to compensate exactly for the positive charges on the iron(III) ions. Thus, each individual colloidal particle
bears a positive charge, and the colloidal dispersion consists of charged colloidal particles and some free hydroxide ions, which
keep the dispersion electrically neutral. Most metal hydroxide colloids have positive charges, whereas most metals and metal
sulfides form negatively charged dispersions. All colloidal particles in any one system have charges of the same sign. This helps
keep them dispersed because particles containing like charges repel each other.
The charged nature of some colloidal particles may be exploited to remove them from a variety of mixtures. For example, the
particles comprising smoke are often colloidally dispersed and electrically charged. Frederick Cottrell, an American chemist,
developed a process to remove these particles. The charged particles are attracted to highly charged electrodes, where they are
neutralized and deposited as dust (Figure 11.36). This is one of the important methods used to clean up the smoke from a variety of
industrial processes. The process is also important in the recovery of valuable products from the smoke and flue dust of smelters,
furnaces, and kilns. There are also similar electrostatic air filters designed for home use to improve indoor air quality.

11.6.0.0.1: Frederick Gardner Cottrell

Figure 11.35 (a) Frederick Cottrell developed (b) the electrostatic precipitator, a device designed to curb air pollution by
removing colloidal particles from air. (credit b: modification of work by “SpLot”/Wikimedia Commons)
Born in Oakland, CA, in 1877, Frederick Cottrell devoured textbooks as if they were novels and graduated from high school at
the age of 16. He then entered the University of California (UC), Berkeley, completing a Bachelor’s degree in three years. He
saved money from his $1200 annual salary as a chemistry teacher at Oakland High School to fund his studies in chemistry in
Berlin with Nobel prize winner Jacobus Henricus van’t Hoff, and in Leipzig with Wilhelm Ostwald, another Nobel awardee.
After earning his PhD in physical chemistry, he returned to the United States to teach at UC Berkeley. He also consulted for the
DuPont Company, where he developed the electrostatic precipitator, a device designed to curb air pollution by removing
colloidal particles from air. Cottrell used the proceeds from his invention to fund a nonprofit research corporation to finance
scientific research.

Figure 11.36 In a Cottrell precipitator, positively and negatively charged particles are attracted to highly charged electrodes, where
they are neutralized and deposited as dust.
11.6.0.1: Gels
Gelatin desserts, such as Jell-O, are a type of colloid (Figure 11.37). Gelatin sets on cooling because the hot aqueous mixture of
gelatin coagulates as it cools, yielding an extremely viscous body known as a gel. A gel is a colloidal dispersion of a liquid phase
throughout a solid phase. It appears that the fibers of the dispersing medium form a complex three-dimensional network, the
interstices being filled with the liquid medium or a dilute solution of the dispersing medium.
Figure 11.37 Gelatin desserts are colloids in which an aqueous solution of sweeteners and flavors is dispersed throughout a medium
of solid proteins. (credit photo: modification of work by Steven Depolo)
Pectin, a carbohydrate from fruit juices, is a gel-forming substance important in jelly making. Silica gel, a colloidal dispersion of
hydrated silicon dioxide, is formed when dilute hydrochloric acid is added to a dilute solution of sodium silicate. Canned Heat is a
flammable gel made by mixing alcohol and a saturated aqueous solution of calcium acetate.
This page titled 11.6: Colloids is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content

11.7: Key Terms
alloy
solid mixture of a metallic element and one or more additional elements
amphiphilic
molecules possessing both hydrophobic (nonpolar) and a hydrophilic (polar) parts
boiling point elevation

elevation of the boiling point of a liquid by addition of a solute
boiling point elevation constant

the proportionality constant in the equation relating boiling point elevation to solute molality; also known as the ebullioscopic
constant
colligative property
property of a solution that depends only on the concentration of a solute species
colloid
(also, colloidal dispersion) mixture in which relatively large solid or liquid particles are dispersed uniformly throughout a gas,
liquid, or solid
crenation
process whereby biological cells become shriveled due to loss of water by osmosis
dispersed phase
substance present as relatively large solid or liquid particles in a colloid
dispersion medium
solid, liquid, or gas in which colloidal particles are dispersed
dissociation
physical process accompanying the dissolution of an ionic compound in which the compound’s constituent ions are solvated
and dispersed throughout the solution
electrolyte
substance that produces ions when dissolved in water
emulsifying agent
amphiphilic substance used to stabilize the particles of some emulsions
emulsion
colloid formed from immiscible liquids
freezing point depression

lowering of the freezing point of a liquid by addition of a solute
freezing point depression constant

(also, cryoscopic constant) proportionality constant in the equation relating freezing point depression to solute molality
gel
colloidal dispersion of a liquid in a solid
hemolysis
rupture of red blood cells due to the accumulation of excess water by osmosis
Henry’s law
the proportional relationship between the concentration of dissolved gas in a solution and the partial pressure of the gas in
contact with the solution
hypertonic
of greater osmotic pressure
hypotonic
of less osmotic pressure
ideal solution
solution that forms with no accompanying energy change
immiscible
of negligible mutual solubility; typically refers to liquid substances
ion pair
solvated anion/cation pair held together by moderate electrostatic attraction
ion-dipole attraction
electrostatic attraction between an ion and a polar molecule
isotonic
of equal osmotic pressure
miscible
mutually soluble in all proportions; typically refers to liquid substances
molality (m)
a concentration unit defined as the ratio of the numbers of moles of solute to the mass of the solvent in kilograms
nonelectrolyte
substance that does not produce ions when dissolved in water
osmosis
diffusion of solvent molecules through a semipermeable membrane
osmotic pressure (Π)

opposing pressure required to prevent bulk transfer of solvent molecules through a semipermeable membrane
partially miscible
of moderate mutual solubility; typically refers to liquid substances
Raoult’s law
the relationship between a solution’s vapor pressure and the vapor pressures and concentrations of its components
saturated
of concentration equal to solubility; containing the maximum concentration of solute possible for a given temperature and
pressure
semipermeable membrane
a membrane that selectively permits passage of certain ions or molecules
solubility
extent to which a solute may be dissolved in water, or any solvent
solvation
exothermic process in which intermolecular attractive forces between the solute and solvent in a solution are established
spontaneous process
physical or chemical change that occurs without the addition of energy from an external source
strong electrolyte
substance that dissociates or ionizes completely when dissolved in water
supersaturated
of concentration that exceeds solubility; a nonequilibrium state
suspension
heterogeneous mixture in which relatively large component particles are temporarily dispersed but settle out over time
Tyndall effect
scattering of visible light by a colloidal dispersion
unsaturated
of concentration less than solubility
van’t Hoff factor (i)

the ratio of the number of moles of particles in a solution to the number of moles of formula units dissolved in the solution
weak electrolyte
substance that ionizes only partially when dissolved in water
11.8: Key Equations
Cg = kPg
∗
(PA = XA P )
A
∗
Psolution = ∑ Pi = ∑ Xi P
i
i i
∗
solvent
ΔTb = Kbm
ΔTf = Kfm
Π = MRT
11.9: Summary
11.1 The Dissolution Process
A solution forms when two or more substances combine physically to yield a mixture that is homogeneous at the molecular level.
The solvent is the most concentrated component and determines the physical state of the solution. The solutes are the other
components typically present at concentrations less than that of the solvent. Solutions may form endothermically or exothermically,
depending upon the relative magnitudes of solute and solvent intermolecular attractive forces. Ideal solutions form with no
appreciable change in energy.
11.2 Electrolytes
Substances that dissolve in water to yield ions are called electrolytes. Electrolytes may be covalent compounds that chemically
react with water to produce ions (for example, acids and bases), or they may be ionic compounds that dissociate to yield their
constituent cations and anions, when dissolved. Dissolution of an ionic compound is facilitated by ion-dipole attractions between
the ions of the compound and the polar water molecules. Soluble ionic substances and strong acids ionize completely and are
strong electrolytes, while weak acids and bases ionize to only a small extent and are weak electrolytes. Nonelectrolytes are
substances that do not produce ions when dissolved in water.
11.3 Solubility
The extent to which one substance will dissolve in another is determined by several factors, including the types and relative
strengths of intermolecular attractive forces that may exist between the substances’ atoms, ions, or molecules. This tendency to
dissolve is quantified as a substance’s solubility, its maximum concentration in a solution at equilibrium under specified conditions.
A saturated solution contains solute at a concentration equal to its solubility. A supersaturated solution is one in which a solute’s
concentration exceeds its solubility—a nonequilibrium (unstable) condition that will result in solute precipitation when the solution
is appropriately perturbed. Miscible liquids are soluble in all proportions, and immiscible liquids exhibit very low mutual solubility.
Solubilities for gaseous solutes decrease with increasing temperature, while those for most, but not all, solid solutes increase with
temperature. The concentration of a gaseous solute in a solution is proportional to the partial pressure of the gas to which the
solution is exposed, a relation known as Henry’s law.
11.4 Colligative Properties

Properties of a solution that depend only on the concentration of solute particles are called colligative properties. They include
changes in the vapor pressure, boiling point, and freezing point of the solvent in the solution. The magnitudes of these properties
depend only on the total concentration of solute particles in solution, not on the type of particles. The total concentration of solute
particles in a solution also determines its osmotic pressure. This is the pressure that must be applied to the solution to prevent
diffusion of molecules of pure solvent through a semipermeable membrane into the solution. Ionic compounds may not completely
dissociate in solution due to activity effects, in which case observed colligative effects may be less than predicted.
11.5 Colloids
Colloids are mixtures in which one or more substances are dispersed as relatively large solid particles or liquid droplets throughout
a solid, liquid, or gaseous medium. The particles of a colloid remain dispersed and do not settle due to gravity, and they are often
electrically charged. Colloids are widespread in nature and are involved in many technological applications.
11.10: Exercises
11.10.0.1: 11.1 The Dissolution Process
1.
How do solutions differ from compounds? From other mixtures?
2.
Which of the principal characteristics of solutions are evident in the solutions of K2Cr2O7 shown in Figure 11.2?
3.
When KNO3 is dissolved in water, the resulting solution is significantly colder than the water was originally.
(a) Is the dissolution of KNO3 an endothermic or an exothermic process?
(b) What conclusions can you draw about the intermolecular attractions involved in the process?
(c) Is the resulting solution an ideal solution?
4.
Give an example of each of the following types of solutions:
(a) a gas in a liquid
(b) a gas in a gas
(c) a solid in a solid
5.
Indicate the most important types of intermolecular attractions in each of the following solutions:
(a) The solution in Figure 11.2.
(b) NO(l) in CO(l)
(c) Cl2(g) in Br2(l)
(d) HCl(g) in benzene C6H6(l)
(e) Methanol CH3OH(l) in H2O(l)
6.
Predict whether each of the following substances would be more soluble in water (polar solvent) or in a hydrocarbon such as
heptane (C7H16, nonpolar solvent):
(a) vegetable oil (nonpolar)
(b) isopropyl alcohol (polar)
(c) potassium bromide (ionic)
7.
Heat is released when some solutions form; heat is absorbed when other solutions form. Provide a molecular explanation for the
difference between these two types of spontaneous processes.
8.
Solutions of hydrogen in palladium may be formed by exposing Pd metal to H2 gas. The concentration of hydrogen in the
palladium depends on the pressure of H2 gas applied, but in a more complex fashion than can be described by Henry’s law. Under
certain conditions, 0.94 g of hydrogen gas is dissolved in 215 g of palladium metal (solution density = 10.8 g cm3).
(a) Determine the molarity of this solution.
(b) Determine the molality of this solution.
(c) Determine the percent by mass of hydrogen atoms in this solution.

11.10.0.1: 11.2 Electrolytes
9.
Explain why the ions Na+ and Cl− are strongly solvated in water but not in hexane, a solvent composed of nonpolar molecules.
10.
Explain why solutions of HBr in benzene (a nonpolar solvent) are nonconductive, while solutions in water (a polar solvent) are
conductive.
11.
Consider the solutions presented:
(a) Which of the following sketches best represents the ions in a solution of Fe(NO3)3(aq)?
(b) Write a balanced chemical equation showing the products of the dissolution of Fe(NO3)3.
12.
Compare the processes that occur when methanol (CH3OH), hydrogen chloride (HCl), and sodium hydroxide (NaOH) dissolve in
water. Write equations and prepare sketches showing the form in which each of these compounds is present in its respective
solution.
13.
What is the expected electrical conductivity of the following solutions?
(a) NaOH(aq)
(b) HCl(aq)
(c) C6H12O6(aq) (glucose)
(d) NH3(aq)
14.
Why are most solid ionic compounds electrically nonconductive, whereas aqueous solutions of ionic compounds are good
conductors? Would you expect a liquid (molten) ionic compound to be electrically conductive or nonconductive? Explain.
15.
Indicate the most important type of intermolecular attraction responsible for solvation in each of the following solutions:
(a) the solutions in Figure 11.7
(b) methanol, CH3OH, dissolved in ethanol, C2H5OH
(c) methane, CH4, dissolved in benzene, C6H6
(d) the polar halocarbon CF2Cl2 dissolved in the polar halocarbon CF2ClCFCl2
(e) O2(l) in N2(l)

11.10.0.1: 11.3 Solubility
16.
Suppose you are presented with a clear solution of sodium thiosulfate, Na2S2O3. How could you determine whether the solution is
unsaturated, saturated, or supersaturated?
17.
Supersaturated solutions of most solids in water are prepared by cooling saturated solutions. Supersaturated solutions of most gases
in water are prepared by heating saturated solutions. Explain the reasons for the difference in the two procedures.
18.
Suggest an explanation for the observations that ethanol, C2H5OH, is completely miscible with water and that ethanethiol,
C2H5SH, is soluble only to the extent of 1.5 g per 100 mL of water.
19.
Calculate the percent by mass of KBr in a saturated solution of KBr in water at 10 °C. See Figure 11.16 for useful data, and report
the computed percentage to one significant digit.
20.
Which of the following gases is expected to be most soluble in water? Explain your reasoning.
(a) CH4
(b) CCl4
(c) CHCl3
21.
At 0 °C and 1.00 atm, as much as 0.70 g of O2 can dissolve in 1 L of water. At 0 °C and 4.00 atm, how many grams of O2 dissolve
in 1 L of water?
22.
Refer to Figure 11.10.
(a) How did the concentration of dissolved CO2 in the beverage change when the bottle was opened?
(b) What caused this change?
(c) Is the beverage unsaturated, saturated, or supersaturated with CO2?
23.
The Henry’s law constant for CO2 is 3.4 × 10−2 M/atm at 25 °C. Assuming ideal solution behavior, what pressure of carbon
dioxide is needed to maintain a CO2 concentration of 0.10 M in a can of lemon-lime soda?
24.
The Henry’s law constant for O2 is 1.3 × 10−3 M/atm at 25 °C. Assuming ideal solution behavior, what mass of oxygen would be
dissolved in a 40-L aquarium at 25 °C, assuming an atmospheric pressure of 1.00 atm, and that the partial pressure of O2 is 0.21
atm?
25.
Assuming ideal solution behavior, how many liters of HCl gas, measured at 30.0 °C and 745 torr, are required to prepare 1.25 L of
a 3.20-M solution of hydrochloric acid?
11.10.0.1: 11.4 Colligative Properties

26.
Which is/are part of the macroscopic domain of solutions and which is/are part of the microscopic domain: boiling point elevation,
Henry’s law, hydrogen bond, ion-dipole attraction, molarity, nonelectrolyte, nonstoichiometric compound, osmosis, solvated ion?
27.
What is the microscopic explanation for the macroscopic behavior illustrated in Figure 11.14?
28.

Sketch a qualitative graph of the pressure versus time for water vapor above a sample of pure water and a sugar solution, as the
liquids evaporate to half their original volume.
29.
A solution of potassium nitrate, an electrolyte, and a solution of glycerin (C3H5(OH)3), a nonelectrolyte, both boil at 100.3 °C.
What other physical properties of the two solutions are identical?
30.
What are the mole fractions of H3PO4 and water in a solution of 14.5 g of H3PO4 in 125 g of water?
31.
What are the mole fractions of HNO3 and water in a concentrated solution of nitric acid (68.0% HNO3 by mass)?
32.
Calculate the mole fraction of each solute and solvent:
(a) 583 g of H2SO4 in 1.50 kg of water—the acid solution used in an automobile battery
(b) 0.86 g of NaCl in 1.00 × 102 g of water—a solution of sodium chloride for intravenous injection
(c) 46.85 g of codeine, C18H21NO3, in 125.5 g of ethanol, C2H5OH
(d) 25 g of I2 in 125 g of ethanol, C2H5OH
33.
Calculate the mole fraction of each solute and solvent:
(a) 0.710 kg of sodium carbonate (washing soda), Na2CO3, in 10.0 kg of water—a saturated solution at 0 °C
(b) 125 g of NH4NO3 in 275 g of water—a mixture used to make an instant ice pack
(c) 25 g of Cl2 in 125 g of dichloromethane, CH2Cl2
(d) 0.372 g of tetrahydropyridine, C5H9N, in 125 g of chloroform, CHCl3
34.
Calculate the mole fractions of methanol, CH3OH; ethanol, C2H5OH; and water in a solution that is 40% methanol, 40% ethanol,
and 20% water by mass. (Assume the data are good to two significant figures.)
35.
What is the difference between a 1 M solution and a 1 m solution?
36.
What is the molality of phosphoric acid, H3PO4, in a solution of 14.5 g of H3PO4 in 125 g of water?
37.
What is the molality of nitric acid in a concentrated solution of nitric acid (68.0% HNO3 by mass)?
38.
Calculate the molality of each of the following solutions:

(a) 583 g of H2SO4 in 1.50 kg of water—the acid solution used in an automobile battery
(b) 0.86 g of NaCl in 1.00 × 102 g of water—a solution of sodium chloride for intravenous injection
(c) 46.85 g of codeine, C18H21NO3, in 125.5 g of ethanol, C2H5OH
(d) 25 g of I2 in 125 g of ethanol, C2H5OH
39.
Calculate the molality of each of the following solutions:
(a) 0.710 kg of sodium carbonate (washing soda), Na2CO3, in 10.0 kg of water—a saturated solution at 0°C
(b) 125 g of NH4NO3 in 275 g of water—a mixture used to make an instant ice pack
(c) 25 g of Cl2 in 125 g of dichloromethane, CH2Cl2
(d) 0.372 g of tetrahydropyridine, C5H9N, in 125 g of chloroform, CHCl3
40.
75 mg
The concentration of glucose, C6H12O6, in normal spinal fluid is 100 g
. What is the molality of the solution?
41.
A 13.0% solution of K2CO3 by mass has a density of 1.09 g/cm3. Calculate the molality of the solution.
42.
Why does 1 mol of sodium chloride depress the freezing point of 1 kg of water almost twice as much as 1 mol of glycerin?
43.
Assuming ideal solution behavior, what is the boiling point of a solution of 115.0 g of nonvolatile sucrose, C12H22O11, in 350.0 g of
water?
(a) Outline the steps necessary to answer the question
(b) Answer the question
44.
Assuming ideal solution behavior, what is the boiling point of a solution of 9.04 g of I2 in 75.5 g of benzene, assuming the I2 is
nonvolatile?
45.
Assuming ideal solution behavior, what is the freezing temperature of a solution of 115.0 g of sucrose, C12H22O11, in 350.0 g of
water?
46.
Assuming ideal solution behavior, what is the freezing point of a solution of 9.04 g of I2 in 75.5 g of benzene?
(a) Outline the steps necessary to answer the following question.
47.
Assuming ideal solution behavior, what is the osmotic pressure of an aqueous solution of 1.64 g of Ca(NO3)2 in water at 25 °C?
The volume of the solution is 275 mL.

48.
Assuming ideal solution behavior, what is osmotic pressure of a solution of bovine insulin (molar mass, 5700 g mol−1) at 18 °C if
100.0 mL of the solution contains 0.103 g of the insulin?
49.
Assuming ideal solution behavior, what is the molar mass of a solution of 5.00 g of a compound in 25.00 g of carbon tetrachloride
(bp 76.8 °C; Kb = 5.02 °C/m) that boils at 81.5 °C at 1 atm?
(b) Solve the problem.
50.
A sample of an organic compound (a nonelectrolyte) weighing 1.35 g lowered the freezing point of 10.0 g of benzene by 3.66 °C.
Assuming ideal solution behavior, calculate the molar mass of the compound.
51.
A 1.0 m solution of HCl in benzene has a freezing point of 0.4 °C. Is HCl an electrolyte in benzene? Explain.
52.
A solution contains 5.00 g of urea, CO(NH2)2, a nonvolatile compound, dissolved in 0.100 kg of water. If the vapor pressure of
pure water at 25 °C is 23.7 torr, what is the vapor pressure of the solution (assuming ideal solution behavior)?
53.
A 12.0-g sample of a nonelectrolyte is dissolved in 80.0 g of water. The solution freezes at −1.94 °C. Assuming ideal solution
behavior, calculate the molar mass of the substance.
54.
Arrange the following solutions in order by their decreasing freezing points: 0.1 m Na3PO4, 0.1 m C2H5OH, 0.01 m CO2, 0.15 m
NaCl, and 0.2 m CaCl2.
55.
Calculate the boiling point elevation of 0.100 kg of water containing 0.010 mol of NaCl, 0.020 mol of Na2SO4, and 0.030 mol of
MgCl2, assuming complete dissociation of these electrolytes and ideal solution behavior.
56.
How could you prepare a 3.08 m aqueous solution of glycerin, C3H8O3? Assuming ideal solution behavior, what is the freezing
point of this solution?
57.
A sample of sulfur weighing 0.210 g was dissolved in 17.8 g of carbon disulfide, CS2 (Kb = 2.34 °C/m). If the boiling point
elevation was 0.107 °C, what is the formula of a sulfur molecule in carbon disulfide (assuming ideal solution behavior)?
58.
In a significant experiment performed many years ago, 5.6977 g of cadmium iodide in 44.69 g of water raised the boiling point
0.181 °C. What does this suggest about the nature of a solution of CdI2?
59.
Lysozyme is an enzyme that cleaves cell walls. A 0.100-L sample of a solution of lysozyme that contains 0.0750 g of the enzyme
exhibits an osmotic pressure of 1.32 × 10−3 atm at 25 °C. Assuming ideal solution behavior, what is the molar mass of lysozyme?
60.
The osmotic pressure of a solution containing 7.0 g of insulin per liter is 23 torr at 25 °C. Assuming ideal solution behavior, what is
the molar mass of insulin?
61.

The osmotic pressure of human blood is 7.6 atm at 37 °C. What mass of glucose, C6H12O6, is required to make 1.00 L of aqueous
solution for intravenous feeding if the solution must have the same osmotic pressure as blood at body temperature, 37 °C (assuming
ideal solution behavior)?
62.
Assuming ideal solution behavior, what is the freezing point of a solution of dibromobenzene, C6H4Br2, in 0.250 kg of benzene, if
the solution boils at 83.5 °C?
63.
Assuming ideal solution behavior, what is the boiling point of a solution of NaCl in water if the solution freezes at −0.93 °C?
64.
The sugar fructose contains 40.0% C, 6.7% H, and 53.3% O by mass. A solution of 11.7 g of fructose in 325 g of ethanol has a
boiling point of 78.59 °C. The boiling point of ethanol is 78.35 °C, and Kb for ethanol is 1.20 °C/m. Assuming ideal solution
behavior, what is the molecular formula of fructose?
65.
The vapor pressure of methanol, CH3OH, is 94 torr at 20 °C. The vapor pressure of ethanol, C2H5OH, is 44 torr at the same
temperature.
(a) Calculate the mole fraction of methanol and of ethanol in a solution of 50.0 g of methanol and 50.0 g of ethanol.
(b) Ethanol and methanol form a solution that behaves like an ideal solution. Calculate the vapor pressure of methanol and of
ethanol above the solution at 20 °C.
(c) Calculate the mole fraction of methanol and of ethanol in the vapor above the solution.
66.
The triple point of air-free water is defined as 273.16 K. Why is it important that the water be free of air?
67.
Meat can be classified as fresh (not frozen) even though it is stored at −1 °C. Why wouldn’t meat freeze at this temperature?
68.
An organic compound has a composition of 93.46% C and 6.54% H by mass. A solution of 0.090 g of this compound in 1.10 g of
camphor melts at 158.4 °C. The melting point of pure camphor is 178.4 °C. Kf for camphor is 37.7 °C/m. Assuming ideal solution
behavior, what is the molecular formula of the solute? Show your calculations.
69.
A sample of HgCl2 weighing 9.41 g is dissolved in 32.75 g of ethanol, C2H5OH (Kb = 1.20 °C/m). The boiling point elevation of
the solution is 1.27 °C. Is HgCl2 an electrolyte in ethanol? Show your calculations.
70.
A salt is known to be an alkali metal fluoride. A quick approximate determination of freezing point indicates that 4 g of the salt
dissolved in 100 g of water produces a solution that freezes at about −1.4 °C. Assuming ideal solution behavior, what is the formula
of the salt? Show your calculations.
11.10.0.1: 11.5 Colloids

71.
Identify the dispersed phase and the dispersion medium in each of the following colloidal systems: starch dispersion, smoke, fog,
pearl, whipped cream, floating soap, jelly, milk, and ruby.
72.
Distinguish between dispersion methods and condensation methods for preparing colloidal systems.
73.
How do colloids differ from solutions with regard to dispersed particle size and homogeneity?
74.

Explain the cleansing action of soap.
75.
How can it be demonstrated that colloidal particles are electrically charged?

CHAPTER OVERVIEW
12: Kinetics

General Chemistry
Chemical kinetics is the study of rates of chemical processes and includes investigations of how different experimental conditions
can influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as
the construction of mathematical models that can describe the characteristics of a chemical reaction.
12.1: Introduction
12.4: Rate Laws
12.8: Catalysis
12.9: Key Terms
12.11: Summary
12.12: Exercises
Thumbnail: Molecular collisions frequency. (Public Domain; Sadi Carnot via Wikipedia)
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1
12.1: Introduction
Figure 12.1 An agama lizard basks in the sun. As its body warms, the chemical reactions of its metabolism speed up.

12.1 Chemical Reaction Rates
12.2 Factors Affecting Reaction Rates
12.3 Rate Laws
12.4 Integrated Rate Laws
12.5 Collision Theory
12.6 Reaction Mechanisms
12.7 Catalysis
The lizard in the photograph is not simply enjoying the sunshine or working on its tan. The heat from the sun’s rays is critical to the
lizard’s survival. A warm lizard can move faster than a cold one because the chemical reactions that allow its muscles to move
occur more rapidly at higher temperatures. A cold lizard is a slower lizard and an easier meal for predators.
From baking a cake to determining the useful lifespan of a bridge, rates of chemical reactions play important roles in our
understanding of processes that involve chemical changes. Two questions are typically posed when planning to carry out a
chemical reaction. The first is: “Will the reaction produce the desired products in useful quantities?” The second question is: “How
rapidly will the reaction occur?” A third question is often asked when investigating reactions in greater detail: “What specific
molecular-level processes take place as the reaction occurs?” Knowing the answer to this question is of practical importance when
the yield or rate of a reaction needs to be controlled.
The study of chemical kinetics concerns the second and third questions—that is, the rate at which a reaction yields products and the
molecular-scale means by which a reaction occurs. This chapter examines the factors that influence the rates of chemical reactions,
the mechanisms by which reactions proceed, and the quantitative techniques used to describe the rates at which reactions occur.


Define chemical reaction rate
Derive rate expressions from the balanced equation for a given chemical reaction
Calculate reaction rates from experimental data
A rate is a measure of how some property varies with time. Speed is a familiar rate that expresses the distance traveled by an object
in a given amount of time. Wage is a rate that represents the amount of money earned by a person working for a given amount of
time. Likewise, the rate of a chemical reaction is a measure of how much reactant is consumed, or how much product is produced,
by the reaction in a given amount of time.
The rate of reaction is the change in the amount of a reactant or product per unit time. Reaction rates are therefore determined by
measuring the time dependence of some property that can be related to reactant or product amounts. Rates of reactions that
consume or produce gaseous substances, for example, are conveniently determined by measuring changes in volume or pressure.
For reactions involving one or more colored substances, rates may be monitored via measurements of light absorption. For
reactions involving aqueous electrolytes, rates may be measured via changes in a solution’s conductivity.
For reactants and products in solution, their relative amounts (concentrations) are conveniently used for purposes of expressing
reaction rates. For example, the concentration of hydrogen peroxide, H2O2, in an aqueous solution changes slowly over time as it
decomposes according to the equation:
2H2 O2 (aq) ⟶ 2H2 O(l) + O2 (g)
The rate at which the hydrogen peroxide decomposes can be expressed in terms of the rate of change of its concentration, as shown
here:
change in concentration of reactant
rate of decomposition of H2 O2 =−
time interval
[ H2 O2 ] − [ H2 O2 ]
t t
2 1
=−
t2 − t1
Δ[ H2 O2 ]
=−
Δt
This mathematical representation of the change in species concentration over time is the rate expression for the reaction. The
brackets indicate molar concentrations, and the symbol delta (Δ) indicates “change in.” Thus, [H O ] represents the molar
2 2 t
1
concentration of hydrogen peroxide at some time t1; likewise,[H O ] represents the molar concentration of hydrogen peroxide at
2 2 t
2
a later time t2; and Δ[H2O2] represents the change in molar concentration of hydrogen peroxide during the time interval Δt (that is,
t2 − t1). Since the reactant concentration decreases as the reaction proceeds, Δ[H2O2] is a negative quantity. Reaction rates are, by
convention, positive quantities, and so this negative change in concentration is multiplied by −1. Figure 12.2 provides an example
of data collected during the decomposition of H2O2.

Figure 12.2 The rate of decomposition of H2O2 in an aqueous solution decreases as the concentration of H2O2 decreases.
To obtain the tabulated results for this decomposition, the concentration of hydrogen peroxide was measured every 6 hours over the
course of a day at a constant temperature of 40 °C. Reaction rates were computed for each time interval by dividing the change in
concentration by the corresponding time increment, as shown here for the first 6-hour period:
−Δ[ H2 O2 ] −(0.500 mol/L − 1.000 mol/L)
−1 −1
= = 0.0833 mol L h
Δt (6.00 h − 0.00 h)
Notice that the reaction rates vary with time, decreasing as the reaction proceeds. Results for the last 6-hour period yield a reaction
rate of:
−Δ[ H2 O2 ] −(0.0625 mol/L − 0.125 mol/L)
−1 −1
= = 0.010 mol L h
Δt (24.00 h − 18.00 h)
This behavior indicates the reaction continually slows with time. Using the concentrations at the beginning and end of a time period
over which the reaction rate is changing results in the calculation of an average rate for the reaction over this time interval. At any
specific time, the rate at which a reaction is proceeding is known as its instantaneous rate. The instantaneous rate of a reaction at
“time zero,” when the reaction commences, is its initial rate. Consider the analogy of a car slowing down as it approaches a stop
sign. The vehicle’s initial rate—analogous to the beginning of a chemical reaction—would be the speedometer reading at the
moment the driver begins pressing the brakes (t0). A few moments later, the instantaneous rate at a specific moment—call it t1—
would be somewhat slower, as indicated by the speedometer reading at that point in time. As time passes, the instantaneous rate
will continue to fall until it reaches zero, when the car (or reaction) stops. Unlike instantaneous speed, the car’s average speed is
not indicated by the speedometer; but it can be calculated as the ratio of the distance traveled to the time required to bring the
vehicle to a complete stop (Δt). Like the decelerating car, the average rate of a chemical reaction will fall somewhere between its
initial and final rates.
The instantaneous rate of a reaction may be determined one of two ways. If experimental conditions permit the measurement of
concentration changes over very short time intervals, then average rates computed as described earlier provide reasonably good
approximations of instantaneous rates. Alternatively, a graphical procedure may be used that, in effect, yields the results that would
be obtained if short time interval measurements were possible. In a plot of the concentration of hydrogen peroxide against time, the
instantaneous rate of decomposition of H2O2 at any time t is given by the slope of a straight line that is tangent to the curve at that
time (Figure 12.3). These tangent line slopes may be evaluated using calculus, but the procedure for doing so is beyond the scope
of this chapter.
Figure 12.3 This graph shows a plot of concentration versus time for a 1.000 M solution of H2O2. The rate at any time is equal to
the negative of the slope of a line tangent to the curve at that time. Tangents are shown at t = 0 h (“initial rate”) and at t = 12 h
(“instantaneous rate” at 12 h).

12.2.0.0.1: Reaction Rates in Analysis: Test Strips for Urinalysis
Physicians often use disposable test strips to measure the amounts of various substances in a patient’s urine (Figure 12.4).
These test strips contain various chemical reagents, embedded in small pads at various locations along the strip, which undergo
changes in color upon exposure to sufficient concentrations of specific substances. The usage instructions for test strips often
stress that proper read time is critical for optimal results. This emphasis on read time suggests that kinetic aspects of the
chemical reactions occurring on the test strip are important considerations.
The test for urinary glucose relies on a two-step process represented by the chemical equations shown here:
catalyst
C6 H12 O6 + O2 −−−−→ C6 H10 O6 + H2 O2
catalyst
−
2H2 O2 + 2 I −−−−→ I2 + 2H2 O + O2
The first equation depicts the oxidation of glucose in the urine to yield glucolactone and hydrogen peroxide. The hydrogen
peroxide produced subsequently oxidizes colorless iodide ion to yield brown iodine, which may be visually detected. Some
strips include an additional substance that reacts with iodine to produce a more distinct color change.
The two test reactions shown above are inherently very slow, but their rates are increased by special enzymes embedded in the
test strip pad. This is an example of catalysis, a topic discussed later in this chapter. A typical glucose test strip for use with
urine requires approximately 30 seconds for completion of the color-forming reactions. Reading the result too soon might lead
one to conclude that the glucose concentration of the urine sample is lower than it actually is (a false-negative result). Waiting
too long to assess the color change can lead to a false positive due to the slower (not catalyzed) oxidation of iodide ion by other
substances found in urine.
Figure 12.4 Test strips are commonly used to detect the presence of specific substances in a person’s urine. Many test strips
have several pads containing various reagents to permit the detection of multiple substances on a single strip. (credit: Iqbal
Osman)
12.2.0.1: Relative Rates of Reaction

The rate of a reaction may be expressed as the change in concentration of any reactant or product. For any given reaction, these rate
expressions are all related simply to one another according to the reaction stoichiometry. The rate of the general reaction
aA ⟶ bB
can be expressed in terms of the decrease in the concentration of A or the increase in the concentration of B. These two rate
expressions are related by the stoichiometry of the reaction:
1 ΔA 1 ΔB
rate = −( )( ) =( )( )
a Δt b Δt
Consider the reaction represented by the following equation:

2NH3 (g) ⟶ N2 (g) + 3H2 (g)
The relation between the reaction rates expressed in terms of nitrogen production and ammonia consumption, for example, is:
Δmol NH3 1 mol N2 Δmol N2
− × =
Δt 2 mol NH3 Δt
This may be represented in an abbreviated format by omitting the units of the stoichiometric factor:
1 Δmol NH3 Δmol N2
− =
2 Δt Δt
Note that a negative sign has been included as a factor to account for the opposite signs of the two amount changes (the reactant
amount is decreasing while the product amount is increasing). For homogeneous reactions, both the reactants and products are
present in the same solution and thus occupy the same volume, so the molar amounts may be replaced with molar concentrations:
1 Δ[ NH3 ] Δ[ N2 ]
− =
2 Δt Δt
Similarly, the rate of formation of H2 is three times the rate of formation of N2 because three moles of H2 are produced for each
mole of N2 produced.
1 Δ[ H2 ] Δ[ N2 ]
=
3 Δt Δt
Figure 12.5 illustrates the change in concentrations over time for the decomposition of ammonia into nitrogen and hydrogen at
1100 °C. Slopes of the tangent lines at t = 500 s show that the instantaneous rates derived from all three species involved in the
reaction are related by their stoichiometric factors. The rate of hydrogen production, for example, is observed to be three times
greater than that for nitrogen production:
−6
2.91 × 10 M /s
≈3
−7
9.70 × 10 M /s

Figure 12.5 Changes in concentrations of the reactant and products for the reaction 2NH ⟶ N + 3H . The rates of change of 3 2 2
the three concentrations are related by the reaction stoichiometry, as shown by the different slopes of the tangents at t = 500 s.
12.2.0.1: Example 12.1

12.2.0.0.1: Expressions for Relative Reaction Rates
The first step in the production of nitric acid is the combustion of ammonia:
4 NH3 (g) + 5 O2 (g) ⟶ 4NO(g) + 6 H2 O(g)
Write the equations that relate the rates of consumption of the reactants and the rates of formation of the products.
Considering the stoichiometry of this homogeneous reaction, the rates for the consumption of reactants and formation of
products are:
1 Δ[ NH3 ] 1 Δ [ O2 ] 1 Δ [NO] 1 Δ [ H2 O]
− =− = =
4 Δt 5 Δt 4 Δt 6 Δt

The rate of formation of Br2 is 6.0 × 10−6 mol/L/s in a reaction described by the following net ionic equation:
− − +
5Br + BrO 3 + 6H ⟶ 3Br2 + 3H2 O
Write the equations that relate the rates of consumption of the reactants and the rates of formation of the products.
12.2.0.1: Answer:
− − +
Δ[ Br ] Δ[ BrO3 ] Δ[ H ] Δ[ Br2 ] Δ[ H2 O]
1 1 1 1
− =− =− = =
5 Δt Δt 6 Δt 3 Δt 3 Δt
12.2.0.1: Example 12.2

12.2.0.0.4: Reaction Rate Expressions for Decomposition of H2O2
The graph in Figure 12.3 shows the rate of the decomposition of H2O2 over time:
2H2 O2 ⟶ 2H2 O + O2
Based on these data, the instantaneous rate of decomposition of H2O2 at t = 11.1 h is determined to be
3.20 × 10−2 mol/L/h, that is:
Δ [ H2 O2 ]
−2 −1 −1
− = 3.20 × 10 mol L h
Δt
What is the instantaneous rate of production of H2O and O2?

The reaction stoichiometry shows that
1 Δ [ H2 O2 ] 1 Δ [ H2 O] Δ[ O2 ]
− = =
2 Δt 2 Δt Δt
Therefore:
1 Δ [ O2 ]
−2 −1 −1
× 3.20 × 10 mol L h =
2 Δt
and
Δ [ O2 ]
−2 −1 −1
= 1.60 × 10 mol L h
Δt

If the rate of decomposition of ammonia, NH3, at 1150 K is 2.10 × 10−6 mol/L/s, what is the rate of production of nitrogen and
hydrogen?

12.2.0.1: Answer:
1.05 × 10−6 mol/L/s, N2 and 3.15 × 10−6 mol/L/s, H2.
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Describe the effects of chemical nature, physical state, temperature, concentration, and catalysis on reaction rates
The rates at which reactants are consumed and products are formed during chemical reactions vary greatly. Five factors typically
affecting the rates of chemical reactions will be explored in this section: the chemical nature of the reacting substances, the state of
subdivision (one large lump versus many small particles) of the reactants, the temperature of the reactants, the concentration of the
reactants, and the presence of a catalyst.
12.3.0.1: The Chemical Nature of the Reacting Substances

The rate of a reaction depends on the nature of the participating substances. Reactions that appear similar may have different rates
under the same conditions, depending on the identity of the reactants. For example, when small pieces of the metals iron and
sodium are exposed to air, the sodium reacts completely with air overnight, whereas the iron is barely affected. The active metals
calcium and sodium both react with water to form hydrogen gas and a base. Yet calcium reacts at a moderate rate, whereas sodium
reacts so rapidly that the reaction is almost explosive.
12.3.0.1: The Physical States of the Reactants

A chemical reaction between two or more substances requires intimate contact between the reactants. When reactants are in
different physical states, or phases (solid, liquid, gaseous, dissolved), the reaction takes place only at the interface between the
phases. Consider the heterogeneous reaction between a solid phase and either a liquid or gaseous phase. Compared with the
reaction rate for large solid particles, the rate for smaller particles will be greater because the surface area in contact with the other
reactant phase is greater. For example, large pieces of iron react more slowly with acids than they do with finely divided iron
powder (Figure 12.6). Large pieces of wood smolder, smaller pieces burn rapidly, and saw dust burns explosively.
Figure 12.6 (a) Iron powder reacts rapidly with dilute hydrochloric acid and produces bubbles of hydrogen gas: 2Fe(s) + 6HCl(aq)
⟶ 2FeCl3(aq) + 3H2(g). (b) An iron nail reacts more slowly because the surface area exposed to the acid is much less.

Watch this video to see the reaction of cesium with water in slow motion and a discussion of how the state of reactants and
particle size affect reaction rates.
12.3.0.1: Temperature of the Reactants

Chemical reactions typically occur faster at higher temperatures. Food can spoil quickly when left on the kitchen counter. However,
the lower temperature inside of a refrigerator slows that process so that the same food remains fresh for days. Gas burners, hot
plates, and ovens are often used in the laboratory to increase the speed of reactions that proceed slowly at ordinary temperatures.
For many chemical processes, reaction rates are approximately doubled when the temperature is raised by 10 °C.

12.3.0.1: Concentrations of the Reactants
The rates of many reactions depend on the concentrations of the reactants. Rates usually increase when the concentration of one or
more of the reactants increases. For example, calcium carbonate (CaCO3) deteriorates as a result of its reaction with the pollutant
sulfur dioxide. The rate of this reaction depends on the amount of sulfur dioxide in the air (Figure 12.7). An acidic oxide, sulfur
dioxide combines with water vapor in the air to produce sulfurous acid in the following reaction:
SO 2 (g) + H2 O(g) ⟶ H2 SO 3 (aq)
Calcium carbonate reacts with sulfurous acid as follows:

CaCO3 (s) + H2 SO 3 (aq) ⟶ CaSO3 (aq) + CO2 (g) + H2 O(l)
In a polluted atmosphere where the concentration of sulfur dioxide is high, calcium carbonate deteriorates more rapidly than in less
polluted air. Similarly, phosphorus burns much more rapidly in an atmosphere of pure oxygen than in air, which is only about 20%
oxygen.
Figure 12.7 Statues made from carbonate compounds such as limestone and marble typically weather slowly over time due to the
actions of water, and thermal expansion and contraction. However, pollutants like sulfur dioxide can accelerate weathering. As the
concentration of air pollutants increases, deterioration of limestone occurs more rapidly. (credit: James P Fisher III)

Phosphorus burns rapidly in air, but it will burn even more rapidly if the concentration of oxygen is higher. Watch this video to
see an example.
12.3.0.1: The Presence of a Catalyst

Relatively dilute aqueous solutions of hydrogen peroxide, H2O2, are commonly used as topical antiseptics. Hydrogen peroxide
decomposes to yield water and oxygen gas according to the equation:
2 H2 O2 (aq) ⟶ 2 H2 O(l) + O2 (g)
Under typical conditions, this decomposition occurs very slowly. When dilute H2O2(aq) is poured onto an open wound, however,
the reaction occurs rapidly and the solution foams because of the vigorous production of oxygen gas. This dramatic difference is
caused by the presence of substances within the wound’s exposed tissues that accelerate the decomposition process. Substances that
function to increase the rate of a reaction are called catalysts, a topic treated in greater detail later in this chapter.

Chemical reactions occur when molecules collide with each other and undergo a chemical transformation. Before physically
performing a reaction in a laboratory, scientists can use molecular modeling simulations to predict how the parameters
discussed earlier will influence the rate of a reaction. Use the PhET Reactions & Rates interactive to explore how temperature,
concentration, and the nature of the reactants affect reaction rates.

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12.4: Rate Laws

Explain the form and function of a rate law
Use rate laws to calculate reaction rates
Use rate and concentration data to identify reaction orders and derive rate laws
As described in the previous module, the rate of a reaction is often affected by the concentrations of reactants. Rate laws
(sometimes called differential rate laws) or rate equations are mathematical expressions that describe the relationship between the
rate of a chemical reaction and the concentration of its reactants. As an example, consider the reaction described by the chemical
equation
aA + bB ⟶ products
where a and b are stoichiometric coefficients. The rate law for this reaction is written as:
m n
rate = k[A] [B]
in which [A] and [B] represent the molar concentrations of reactants, and k is the rate constant, which is specific for a particular
reaction at a particular temperature. The exponents m and n are the reaction orders and are typically positive integers, though they
can be fractions, negative, or zero. The rate constant k and the reaction orders m and n must be determined experimentally by
observing how the rate of a reaction changes as the concentrations of the reactants are changed. The rate constant k is independent
of the reactant concentrations, but it does vary with temperature.
The reaction orders in a rate law describe the mathematical dependence of the rate on reactant concentrations. Referring to the
generic rate law above, the reaction is m order with respect to A and n order with respect to B. For example, if m = 1 and n = 2, the
reaction is first order in A and second order in B. The overall reaction order is simply the sum of orders for each reactant. For the
example rate law here, the reaction is third order overall (1 + 2 = 3). A few specific examples are shown below to further illustrate
this concept.
The rate law:
rate = k [ H2 O2 ]
describes a reaction that is first order in hydrogen peroxide and first order overall. The rate law:
2
rate = k[ C4 H6 ]
describes a reaction that is second order in C4H6 and second order overall. The rate law:
+ −
rate = k [ H ] [ OH ]
describes a reaction that is first order in H+, first order in OH−, and second order overall.
12.4.0.1: Example 12.3

12.4.0.0.1: Writing Rate Laws from Reaction Orders
An experiment shows that the reaction of nitrogen dioxide with carbon monoxide:
NO2 (g) + CO(g) ⟶ NO(g) + CO2 (g)
is second order in NO2 and zero order in CO at 100 °C. What is the rate law for the reaction?
The reaction will have the form:
m n
rate = k[NO2 ] [CO]
The reaction is second order in NO2; thus m = 2. The reaction is zero order in CO; thus n = 0. The rate law is:

2 0 2
rate = k[ NO2 ] [CO] = k[ NO2 ]
Remember that a number raised to the zero power is equal to 1, thus [CO]0 = 1, which is why the CO concentration term may
be omitted from the rate law: the rate of reaction is solely dependent on the concentration of NO2. A later chapter section on
reaction mechanisms will explain how a reactant’s concentration can have no effect on a reaction rate despite being involved in
the reaction.
The rate law for the reaction:
H2 (g) + 2NO(g) ⟶ N2 O(g) + H2 O(g)
has been determined to be rate = k[NO]2[H2]. What are the orders with respect to each reactant, and what is the overall order of
the reaction?
12.4.0.1: Answer:
order in NO = 2; order in H2 = 1; overall order = 3

In a transesterification reaction, a triglyceride reacts with an alcohol to form an ester and glycerol. Many students learn about
the reaction between methanol (CH3OH) and ethyl acetate (CH3CH2OCOCH3) as a sample reaction before studying the
chemical reactions that produce biodiesel:
CH3 OH + CH3 CH2 OCOCH3 ⟶ CH3 OCOCH3 + CH3 CH2 OH
The rate law for the reaction between methanol and ethyl acetate is, under certain conditions, determined to be:
rate = k [ CH3 OH]
What is the order of reaction with respect to methanol and ethyl acetate, and what is the overall order of reaction?
12.4.0.1: Answer:
order in CH3OH = 1; order in CH3CH2OCOCH3 = 0; overall order = 1
A common experimental approach to the determination of rate laws is the method of initial rates. This method involves measuring
reaction rates for multiple experimental trials carried out using different initial reactant concentrations. Comparing the measured
rates for these trials permits determination of the reaction orders and, subsequently, the rate constant, which together are used to
formulate a rate law. This approach is illustrated in the next two example exercises.
12.4.0.1: Example 12.4

12.4.0.0.1: Determining a Rate Law from Initial Rates
Ozone in the upper atmosphere is depleted when it reacts with nitrogen oxides. The rates of the reactions of nitrogen oxides
with ozone are important factors in deciding how significant these reactions are in the formation of the ozone hole over
Antarctica (Figure 12.8). One such reaction is the combination of nitric oxide, NO, with ozone, O3:

Figure 12.8 A contour map showing stratospheric ozone concentration and the “ozone hole” that occurs over Antarctica during
its spring months. (credit: modification of work by NASA)
NO(g) + O3 (g) ⟶ NO2 (g) + O2 (g)

This reaction has been studied in the laboratory, and the following rate data were determined at 25 °C.
Trial [NO] (mol/L) [O3] (mol/L) Δ[NO 2 ]

(mol L
−1
s
−1
)
Δt
1 1.00 × 10−6 3.00 × 10−6 6.60 × 10−5
2 1.00 × 10−6 6.00 × 10−6 1.32 × 10−4
3 1.00 × 10−6 9.00 × 10−6 1.98 × 10−4
4 2.00 × 10−6 9.00 × 10−6 3.96 × 10−4
5 3.00 × 10−6 9.00 × 10−6 5.94 × 10−4
Determine the rate law and the rate constant for the reaction at 25 °C.
The rate law will have the form:
m n
rate = k[NO] [ O3 ]
Determine the values of m, n, and k from the experimental data using the following three-part process:
1. Step 1.
Determine the value of m from the data in which [NO] varies and [O3] is constant. In the last three experiments, [NO]
varies while [O3] remains constant. When [NO] doubles from trial 3 to 4, the rate doubles, and when [NO] triples from trial
3 to 5, the rate also triples. Thus, the rate is also directly proportional to [NO], and m in the rate law is equal to 1.
2. Step 2.
Determine the value of n from data in which [O3] varies and [NO] is constant. In the first three experiments, [NO] is
constant and [O3] varies. The reaction rate changes in direct proportion to the change in [O3]. When [O3] doubles from trial
1 to 2, the rate doubles; when [O3] triples from trial 1 to 3, the rate increases also triples. Thus, the rate is directly
proportional to [O3], and n is equal to 1.The rate law is thus:
1 1
rate = k[NO] [ O3 ] = k [NO] [ O3 ]
3. Step 3.
Determine the value of k from one set of concentrations and the corresponding rate. The data from trial 1 are used below:
rate
k =
[NO][ O3 ]
−5 −1 −1
6.60 × 10 mol L s
=
−6 −1 −6 −1
(1.00 × 10 mol L ) (3.00 × 10 mol L )
7 −1 −1
= 2. 20 × 10 L mol s

Acetaldehyde decomposes when heated to yield methane and carbon monoxide according to the equation:
CH3 CHO(g) ⟶ CH4 (g) + CO(g)
Determine the rate law and the rate constant for the reaction from the following experimental data:
Trial [CH3CHO] (mol/L) −

Δ[CH CHO]
3
(mol L
−1 −1
s )
Δt
1 1.75 × 10−3 2.06 × 10−11
2 3.50 × 10−3 8.24 × 10−11

Trial [CH3CHO] (mol/L) −
Δ[CH CHO]
3
(mol L
−1 −1
s )
Δt
3 7.00 × 10−3 3.30 × 10−10
12.4.0.1: Answer:
rate = k[ CH3 CHO]
2
with k = 6.73 × 10−6 L/mol/s
12.4.0.1: Example 12.5

12.4.0.0.1: Determining Rate Laws from Initial Rates
Using the initial rates method and the experimental data, determine the rate law and the value of the rate constant for this
reaction:
2NO(g) + Cl2 (g) ⟶ 2NOCl(g)
Trial [NO] (mol/L) [Cl2] (mol/L) −

Δ[NO]
(mol L
−1 −1
s )
Δt
1 0.10 0.10 0.00300
2 0.10 0.15 0.00450
3 0.15 0.10 0.00675
The rate law for this reaction will have the form:
m n
rate = k[NO] [ Cl2 ]
As in Example 12.4, approach this problem in a stepwise fashion, determining the values of m and n from the experimental
data and then using these values to determine the value of k. In this example, however, an explicit algebraic approach (vs. the
implicit approach of the previous example) will be used to determine the values of m and n:
1. Step 1.
Determine the value of m from the data in which [NO] varies and [Cl2] is constant. Write the ratios with the subscripts x
and y to indicate data from two different trials:
m n
ratex k[NO] [ Cl2 ]
x x
=
m n
ratey k[NO]y [ Cl2 ]y
Using the third trial and the first trial, in which [Cl2] does not vary, gives:
m n
rate 3 0.00675 k(0.15 ) (0.10 )
= =
m n
rate 1 0.00300 k(0.10) (0.10 )
Canceling equivalent terms in the numerator and denominator leaves:

m
0.00675 (0.15)
=
m
0.00300 (0.10)
which simplifies to:

m
2.25 = (1.5)
Use logarithms to determine the value of the exponent m:

ln (2.25) = mln (1.5)
ln(2.25)
= m
ln(1.5)
2 = m
Confirm the result

2
1.5 = 2.25
2. Step 2.
Determine the value of n from data in which [Cl2] varies and [NO] is constant.
m n
rate 2 0.00450 k(0.10 ) (0.15 )
= =
m n
rate 1 0.00300 k(0.10 ) (0.10 )
Cancelation gives:
n
0.0045 (0.15)
=
n
0.0030 (0.10)
which simplifies to:

n
1.5 = (1.5)
Thus n must be 1, and the form of the rate law is:

m n 2
rate = k[NO] [ Cl2 ] = k[NO] [ Cl2 ]
3. Step 3.
Determine the numerical value of the rate constant k with appropriate units. The units for the rate of a reaction are mol/L/s.
The units for k are whatever is needed so that substituting into the rate law expression affords the appropriate units for the
rate. In this example, the concentration units are mol3/L3. The units for k should be mol−2 L2/s so that the rate is in terms of
mol/L/s.
To determine the value of k once the rate law expression has been solved, simply plug in values from the first experimental
trial and solve for k:
2 1
−1 −1 −1 −1
0.00300 mol L s = k(0.10 mol L ) (0.10 mol L )
−2 2 −1
k = 3.0 mol L s

Use the provided initial rate data to derive the rate law for the reaction whose equation is:
− − − −
OCl (aq) + I (aq) ⟶ OI (aq) + Cl (aq)
Trial [OCl−] (mol/L) [I−] (mol/L) Initial Rate (mol/L/s)
1 0.0040 0.0020 0.00184
2 0.0020 0.0040 0.00092
3 0.0020 0.0020 0.00046
Determine the rate law expression and the value of the rate constant k with appropriate units for this reaction.
12.4.0.1: Answer:
x y
0.00092 k(0.0020 ) (0.0040 )
rate 2
= = x y
rate 3 0.00046 k(0.0020 ) (0.0020 )
y
2.00 = 2.00

y=1
x y
rate 1 0.00184 k(0.0040 ) (0.0020 )
= = x y
rate 2 0.00092 k(0.0020 ) (0.0040 )
x
2
2.00 = y
2
x
2
2.00 = 1
2
x
4.00 = 2
x = 2
Substituting the concentration data from trial 1 and solving for k yields:
− 2 1
−
rate = k[ OCl ] [I ]
2 1
0.00184 = k(0.0040) (0.0020)
4 −2 2 −1
k = 5.75 × 10 mol L s
12.4.0.1: Reaction Order and Rate Constant Units

In some of our examples, the reaction orders in the rate law happen to be the same as the coefficients in the chemical equation for
the reaction. This is merely a coincidence and very often not the case.
Rate laws may exhibit fractional orders for some reactants, and negative reaction orders are sometimes observed when an increase
in the concentration of one reactant causes a decrease in reaction rate. A few examples illustrating these points are provided:
2
NO2 + CO ⟶ NO + CO2 rate = k[ NO2 ]
2
CH3 CHO ⟶ CH4 + CO rate = k[ CH3 CHO]
2N2 O5 ⟶ NO2 + O2 rate = k [ N2 O5 ]
2NO2 + F2 ⟶ 2NO2 F rate = k [ NO2 ] [ F2 ]
2NO2 Cl ⟶ 2NO2 + Cl2 rate = k [ NO2 Cl]
It is important to note that rate laws are determined by experiment only and are not reliably predicted by reaction stoichiometry.
The units for a rate constant will vary as appropriate to accommodate the overall order of the reaction. The unit of the rate constant
for the second-order reaction described in Example 12.4 was determined to be L mol s . For the third-order reaction described
−1 −1
in Example 12.5, the unit for k was derived to be L mol s . Dimensional analysis requires the rate constant unit for a reaction
2 −2 −1
whose overall order is x to be L mol s . Table 12.1 summarizes the rate constant units for common reaction orders.
x−1 1−x −1
Rate Constant Units for Common Reaction Orders

Overall Reaction Order (x) Rate Constant Unit (Lx−1 mol1−x s−1)
0 (zero) mol L−1 s−1
1 (first) s−1
2 (second) L mol−1 s−1
3 (third) L2 mol−2 s−1
Table 12.1
Note that the units in this table were derived using specific units for concentration (mol/L) and time (s), though any valid units for
these two properties may be used.
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Explain the form and function of an integrated rate law
Perform integrated rate law calculations for zero-, first-, and second-order reactions
Define half-life and carry out related calculations
Identify the order of a reaction from concentration/time data
The rate laws discussed thus far relate the rate and the concentrations of reactants. We can also determine a second form of each
rate law that relates the concentrations of reactants and time. These are called integrated rate laws. We can use an integrated rate
law to determine the amount of reactant or product present after a period of time or to estimate the time required for a reaction to
proceed to a certain extent. For example, an integrated rate law is used to determine the length of time a radioactive material must
be stored for its radioactivity to decay to a safe level.
Using calculus, the differential rate law for a chemical reaction can be integrated with respect to time to give an equation that
relates the amount of reactant or product present in a reaction mixture to the elapsed time of the reaction. This process can either be
very straightforward or very complex, depending on the complexity of the differential rate law. For purposes of discussion, we will
focus on the resulting integrated rate laws for first-, second-, and zero-order reactions.
12.5.0.1: First-Order Reactions

Integration of the rate law for a simple first-order reaction (rate = k[A]) results in an equation describing how the reactant
concentration varies with time:
−kt
[A]t = [A]0 e
where [A]t is the concentration of A at any time t, [A]0 is the initial concentration of A, and k is the first-order rate constant.
For mathematical convenience, this equation may be rearranged to other formats, including direct and indirect proportionalities:
[A]t [A]0
ln ( ) = −kt or ln ( ) = kt
[A] [A]
0 t
and a format showing a linear dependence of concentration in time:

ln[A]t = ln[A]0 −kt
12.5.0.1: Example 12.6

12.5.0.0.1: The Integrated Rate Law for a First-Order Reaction
The rate constant for the first-order decomposition of cyclobutane, C4H8 at 500 °C is 9.2 × 10−3 s−1:
C4 H8 ⟶ 2C2 H4
How long will it take for 80.0% of a sample of C4H8 to decompose?

Since the relative change in reactant concentration is provided, a convenient format for the integrated rate law is:
[A]
0
ln ( ) = kt
[A]t
The initial concentration of C4H8, [A]0, is not provided, but the provision that 80.0% of the sample has decomposed is enough
information to solve this problem. Let x be the initial concentration, in which case the concentration after 80.0% decomposition
is 20.0% of x or 0.200x. Rearranging the rate law to isolate t and substituting the provided quantities yields:

[x] 1
t = ln ×
[0.200x] k
1
= ln 5 ×
−3 −1
9.2 × 10 s
1
= 1.609 ×
−3 −1
9.2 × 10 s
2
= 1.7 × 10 s

Iodine-131 is a radioactive isotope that is used to diagnose and treat some forms of thyroid cancer. Iodine-131 decays to xenon-
131 according to the equation:
I-131 ⟶ Xe-131 + electron
The decay is first-order with a rate constant of 0.138 d−1. How many days will it take for 90% of the iodine−131 in a 0.500 M
solution of this substance to decay to Xe-131?
12.5.0.1: Answer:
16.7 days
In the next example exercise, a linear format for the integrated rate law will be convenient:
ln[A]t = (−k)(t) + ln[A]
0
y = mx + b
A plot of ln[A]t versus t for a first-order reaction is a straight line with a slope of −k and a y-intercept of ln[A]0. If a set of rate data
are plotted in this fashion but do not result in a straight line, the reaction is not first order in A.
12.5.0.1: Example 12.7

12.5.0.0.4: Graphical Determination of Reaction Order and Rate Constant
Show that the data in Figure 12.2 can be represented by a first-order rate law by graphing ln[H2O2] versus time. Determine the
rate constant for the decomposition of H2O2 from these data.
The data from Figure 12.2 are tabulated below, and a plot of ln[H2O2] is shown in Figure 12.9.
Time (h) [H2O2] (M) ln[H2O2]
0.00 1.000 0.000
6.00 0.500 −0.693
12.00 0.250 −1.386
18.00 0.125 −2.079
24.00 0.0625 −2.772

Figure 12.9 A linear relationship between ln[H2O2] and time suggests the decomposition of hydrogen peroxide is a first-order
reaction.
The plot of ln[H2O2] versus time is linear, indicating that the reaction may be described by a first-order rate law.
According to the linear format of the first-order integrated rate law, the rate constant is given by the negative of this plot’s
slope.
change in y Δy Δln [ H2 O2 ]
slope = = =
change in x Δx Δt
The slope of this line may be derived from two values of ln[H2O2] at different values of t (one near each end of the line is
preferable). For example, the value of ln[H2O2] when t is 0.00 h is 0.000; the value when t = 24.00 h is −2.772
−2.772−0.000
slope =
24.00−0.00 h
−2.772
=
24.00 h
−1
= −0.116 h
−1 −1
k = −slope = − (−0.116 h ) = 0.116 h

Graph the following data to determine whether the reaction A ⟶ B+C is first order.
Time (s) [A]
4.0 0.220
8.0 0.144

Time (s) [A]
12.0 0.110
16.0 0.088
20.0 0.074
12.5.0.1: Answer:
The plot of ln[A]t vs. t is not linear, indicating the reaction is not first order:
12.5.0.1: Second-Order Reactions

The equations that relate the concentrations of reactants and the rate constant of second-order reactions can be fairly complicated.
To illustrate the point with minimal complexity, only the simplest second-order reactions will be described here, namely, those
whose rates depend on the concentration of just one reactant. For these types of reactions, the differential rate law is written as:
2
rate = k[A]
For these second-order reactions, the integrated rate law is:

1 1
= kt +
[A]t [A]0
where the terms in the equation have their usual meanings as defined earlier.
12.5.0.1: Example 12.8

12.5.0.0.1: The Integrated Rate Law for a Second-Order Reaction
The reaction of butadiene gas (C4H6) to yield C8H12 gas is described by the equation:
2C4 H6 (g) ⟶ C8 H12 (g)
This “dimerization” reaction is second order with a rate constant equal to 5.76 × 10−2 L mol−1 min−1 under certain conditions.
If the initial concentration of butadiene is 0.200 M, what is the concentration after 10.0 min?
For a second-order reaction, the integrated rate law is written
1 1
= kt +
[A]t [A]
0
We know three variables in this equation: [A]0 = 0.200 mol/L, k = 5.76 × 10−2 L/mol/min, and t = 10.0 min. Therefore, we can
solve for [A], the fourth variable:

1 −2 −1 −1 1
= (5.76 × 10 L mol min ) (10 min) +
−1
[A] 0.200 mol
t
1 −1 −1 −1
= (5.76 × 10 L mol ) + 5.00 L mol
[A]
t
1 −1
= 5.58 L mol
[A]t
−1 −1
[A]t = 1.79 × 10 mol L
Therefore 0.179 mol/L of butadiene remain at the end of 10.0 min, compared to the 0.200 mol/L that was originally present.
If the initial concentration of butadiene is 0.0200 M, what is the concentration remaining after 20.0 min?
12.5.0.1: Answer:
0.0195 mol/L
The integrated rate law for second-order reactions has the form of the equation of a straight line:
1 1
= kt +
[A]t [A]0
y = mx + b
A plot of 1
[A]
versus t for a second-order reaction is a straight line with a slope of k and a y-intercept of 1
[A]
. If the plot is not a
t 0
straight line, then the reaction is not second order.
12.5.0.1: Example 12.9

12.5.0.0.4: Graphical Determination of Reaction Order and Rate Constant
The data below are for the same reaction described in Example 12.8. Prepare and compare two appropriate data plots to
identify the reaction as being either first or second order. After identifying the reaction order, estimate a value for the rate
constant.
Time (s) [C4H6] (M)
0 1.00 × 10−2
1600 5.04 × 10−3
3200 3.37 × 10−3
4800 2.53 × 10−3
6200 2.08 × 10−3
In order to distinguish a first-order reaction from a second-order reaction, prepare a plot of ln[C4H6]t versus t and compare it to
a plot of versus t. The values needed for these plots follow.
[C4 H6 ]
1
Time (s) 1
(M
−1
) ln[C4H6]
[C4 H6 ]
0 100 −4.605
1600 198 −5.289
3200 296 −5.692

Time (s) 1
(M
−1
) ln[C4H6]
[C4 H6 ]
4800 395 −5.978
6200 481 −6.175
The plots are shown in Figure 12.10, which clearly shows the plot of ln[C4H6]t versus t is not linear, therefore the reaction is
not first order. The plot of versus t is linear, indicating that the reaction is second order.
1
[C4 H6 ]t
Figure 12.10 These two graphs show first- and second-order plots for the dimerization of C4H6. The linear trend in the second-
order plot (right) indicates that the reaction follows second-order kinetics.
According to the second-order integrated rate law, the rate constant is equal to the slope of the 1
[A]
versus t plot. Using the data
t
for t = 0 s and t = 6200 s, the rate constant is estimated as follows:

−1 −1
(481 M − 100 M )
−1 −1
k = slope = = 0.0614 M s
(6200 s − 0 s)

Do the following data fit a second-order rate law?
Time (s) [A] (M)
5 0.952
10 0.625
15 0.465
20 0.370
25 0.308
35 0.230
12.5.0.1: Answer:
Yes. The plot of [A]
1
vs. t is linear:
t

12.5.0.1: Zero-Order Reactions
For zero-order reactions, the differential rate law is:
rate = k
A zero-order reaction thus exhibits a constant reaction rate, regardless of the concentration of its reactant(s). This may seem
counterintuitive, since the reaction rate certainly can’t be finite when the reactant concentration is zero. For purposes of this
introductory text, it will suffice to note that zero-order kinetics are observed for some reactions only under certain specific
conditions. These same reactions exhibit different kinetic behaviors when the specific conditions aren’t met, and for this reason the
more prudent term pseudo-zero-order is sometimes used.
The integrated rate law for a zero-order reaction is a linear function:
[A]t = −kt + [A]

0
y = mx + b
A plot of [A] versus t for a zero-order reaction is a straight line with a slope of −k and a y-intercept of [A]0. Figure 12.11 shows a
plot of [NH3] versus t for the thermal decomposition of ammonia at the surface of two different heated solids. The decomposition
reaction exhibits first-order behavior at a quartz (SiO2) surface, as suggested by the exponentially decaying plot of concentration
versus time. On a tungsten surface, however, the plot is linear, indicating zero-order kinetics.
12.5.0.1: Example 12.10

12.5.0.0.1: Graphical Determination of Zero-Order Rate Constant
Use the data plot in Figure 12.11 to graphically estimate the zero-order rate constant for ammonia decomposition at a tungsten
surface.
The integrated rate law for zero-order kinetics describes a linear plot of reactant concentration, [A]t, versus time, t, with a slope
equal to the negative of the rate constant, −k. Following the mathematical approach of previous examples, the slope of the
linear data plot (for decomposition on W) is estimated from the graph. Using the ammonia concentrations at t = 0 and t = 1000
s:
−1 −1
(0.0015 mol L − 0.0028 mol L )
−6 −1 −1
k = −slope = − = 1.3 × 10 mol L s
(1000 s − 0 s)

The zero-order plot in Figure 12.11 shows an initial ammonia concentration of 0.0028 mol L−1 decreasing linearly with time
for 1000 s. Assuming no change in this zero-order behavior, at what time (min) will the concentration reach 0.0001 mol L−1?
12.5.0.1: Answer:

35 min
Figure 12.11 The decomposition of NH3 on a tungsten (W) surface is a zero-order reaction, whereas on a quartz (SiO2) surface, the
reaction is first order.
12.5.0.1: The Half-Life of a Reaction

The half-life of a reaction (t1/2) is the time required for one-half of a given amount of reactant to be consumed. In each succeeding
half-life, half of the remaining concentration of the reactant is consumed. Using the decomposition of hydrogen peroxide (Figure
12.2) as an example, we find that during the first half-life (from 0.00 hours to 6.00 hours), the concentration of H2O2 decreases
from 1.000 M to 0.500 M. During the second half-life (from 6.00 hours to 12.00 hours), it decreases from 0.500 M to 0.250 M;
during the third half-life, it decreases from 0.250 M to 0.125 M. The concentration of H2O2 decreases by half during each
successive period of 6.00 hours. The decomposition of hydrogen peroxide is a first-order reaction, and, as can be shown, the half-
life of a first-order reaction is independent of the concentration of the reactant. However, half-lives of reactions with other orders
depend on the concentrations of the reactants.

12.5.0.0.1: First-Order Reactions
An equation relating the half-life of a first-order reaction to its rate constant may be derived from the integrated rate law as follows:
[A]0
ln = kt
[A]t
[A]
0 1
t = ln ×
[A] k
t
Invoking the definition of half-life, symbolized t1/2 , requires that the concentration of A at this point is one-half its initial
concentration: t = t , [A] = [A] .
1/2 t
1
2 0
Substituting these terms into the rearranged integrated rate law and simplifying yields the equation for half-life:
[A]0
1
t1/2 = ln ×
1
k
[A]
0
2
1 1
= ln 2 × = 0.693 ×
k k
0.693
t1/2 =
k
This equation describes an expected inverse relation between the half-life of the reaction and its rate constant, k. Faster reactions
exhibit larger rate constants and correspondingly shorter half-lives. Slower reactions exhibit smaller rate constants and longer half-
lives.
12.5.0.1: Example 12.11

12.5.0.0.2: Calculation of a First-order Rate Constant using Half-Life
Calculate the rate constant for the first-order decomposition of hydrogen peroxide in water at 40 °C, using the data given in
Figure 12.12.
Figure 12.12 The decomposition of H2O2 (2H O ⟶ 2H O + O ) at 40 °C is illustrated. The intensity of the color
2 2 2 2
symbolizes the concentration of H2O2 at the indicated times; H2O2 is actually colorless.
Inspecting the concentration/time data in Figure 12.12 shows the half-life for the decomposition of H2O2 is 2.16 × 104 s:
0.693
t1/2 =
k
0.693 0.693 −5 −1
k = = = 3.21 × 10 s
t1 / 2 2.16 × 10
4
s

The first-order radioactive decay of iodine-131 exhibits a rate constant of 0.138 d−1. What is the half-life for this decay?
12.5.0.1: Answer:
5.02 d.

12.5.0.0.5: Second-Order Reactions
Following the same approach as used for first-order reactions, an equation relating the half-life of a second-order reaction to its rate
constant and initial concentration may be derived from its integrated rate law:
1 1
= kt +
[A]t [A]0
or
1 1
− = kt
[A] [A]
0
Restrict t to t1/2
t = t1/2
define [A]t as one-half [A]0

1
[A]t = [A]
0
2
and then substitute into the integrated rate law and simplify:
1 1
− = kt1/2
1
[A]
[A] 0
0
2
2 1
− = kt1/2
[A]0 [A]0
1
= kt1/2
[A]0
1
t1/2 =
k[A]0
For a second-order reaction, t 1/2

is inversely proportional to the concentration of the reactant, and the half-life increases as the
reaction proceeds because the concentration of reactant decreases. Unlike with first-order reactions, the rate constant of a second-
order reaction cannot be calculated directly from the half-life unless the initial concentration is known.
12.5.0.0.6: Zero-Order Reactions
As for other reaction orders, an equation for zero-order half-life may be derived from the integrated rate law:
[A] = −kt + [A]
0
[A]
Restricting the time and concentrations to those defined by half-life: t = t1/2 and [A] =
2
0
. Substituting these terms into the
zero-order integrated rate law yields:
[A]
0
= −kt1/2 + [A]0
2
[A]
0
kt1/2 =
2
[A]0
t1/2 =
2k
As for all reaction orders, the half-life for a zero-order reaction is inversely proportional to its rate constant. However, the half-life
of a zero-order reaction increases as the initial concentration increases.
Equations for both differential and integrated rate laws and the corresponding half-lives for zero-, first-, and second-order reactions
are summarized in Table 12.2.
Summary of Rate Laws for Zero-, First-, and Second-Order Reactions
Zero-Order First-Order Second-Order
rate law rate = k rate = k[A] rate = k[A]2
units of rate constant M s−1 s−1 M−1 s−1

Zero-Order First-Order Second-Order
integrated rate law [A] = −kt + [A]0 ln[A] = −kt + ln[A]0 1

= kt + (
1
)
[A] [A]
0
plot needed for linear fit of rate data [A] vs. t ln[A] vs. t 1
vs. t
[A]
relationship between slope of linear plot and rate constant k = −slope k = −slope k = slope
half-life t1/2 =
[A] 0
t1/2 =
0.693
t1/2 =
1
k [A] k
2k 0
Table 12.2
12.5.0.1: Example 12.12

12.5.0.0.7: Half-Life for Zero-Order and Second-Order Reactions
What is the half-life for the butadiene dimerization reaction described in Example 12.8?
The reaction in question is second order, is initiated with a 0.200 mol L−1 reactant solution, and exhibits a rate constant of
0.0576 L mol−1 min−1. Substituting these quantities into the second-order half-life equation:
1
t1/2 = = 18 min
−1 −1 −1
[(0.0576 L mol min )(0.200 mol L )]

What is the half-life (min) for the thermal decomposition of ammonia on tungsten (see Figure 12.11)?
12.5.0.1: Answer:
87 min
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Use the postulates of collision theory to explain the effects of physical state, temperature, and concentration on reaction
rates
Define the concepts of activation energy and transition state
Use the Arrhenius equation in calculations relating rate constants to temperature
We should not be surprised that atoms, molecules, or ions must collide before they can react with each other. Atoms must be close
together to form chemical bonds. This simple premise is the basis for a very powerful theory that explains many observations
regarding chemical kinetics, including factors affecting reaction rates.
Collision theory is based on the following postulates:
1. The rate of a reaction is proportional to the rate of reactant collisions:
# collisions
reaction rate ∝
time
2. The reacting species must collide in an orientation that allows contact between the atoms that will become bonded together in
the product.
3. The collision must occur with adequate energy to permit mutual penetration of the reacting species’ valence shells so that the
electrons can rearrange and form new bonds (and new chemical species).
We can see the importance of the two physical factors noted in postulates 2 and 3, the orientation and energy of collisions, when we
consider the reaction of carbon monoxide with oxygen:
2 CO(g) + O2 (g) ⟶ 2 CO2 (g)
Carbon monoxide is a pollutant produced by the combustion of hydrocarbon fuels. To reduce this pollutant, automobiles have
catalytic converters that use a catalyst to carry out this reaction. It is also a side reaction of the combustion of gunpowder that
results in muzzle flash for many firearms. If carbon monoxide and oxygen are present in sufficient amounts, the reaction will occur
at high temperature and pressure.
The first step in the gas-phase reaction between carbon monoxide and oxygen is a collision between the two molecules:
CO(g) + O2 (g) ⟶ CO2 (g) + O(g)
Although there are many different possible orientations the two molecules can have relative to each other, consider the two
presented in Figure 12.13. In the first case, the oxygen side of the carbon monoxide molecule collides with the oxygen molecule. In
the second case, the carbon side of the carbon monoxide molecule collides with the oxygen molecule. The second case is clearly
more likely to result in the formation of carbon dioxide, which has a central carbon atom bonded to two oxygen atoms
(O = C = O). This is a rather simple example of how important the orientation of the collision is in terms of creating the desired
product of the reaction.

Figure 12.13 Illustrated are two collisions that might take place between carbon monoxide and oxygen molecules. The orientation
of the colliding molecules partially determines whether a reaction between the two molecules will occur.
If the collision does take place with the correct orientation, there is still no guarantee that the reaction will proceed to form carbon
dioxide. In addition to a proper orientation, the collision must also occur with sufficient energy to result in product formation.
When reactant species collide with both proper orientation and adequate energy, they combine to form an unstable species called an
activated complex or a transition state. These species are very short lived and usually undetectable by most analytical instruments.
In some cases, sophisticated spectral measurements have been used to observe transition states.
Collision theory explains why most reaction rates increase as concentrations increase. With an increase in the concentration of any
reacting substance, the chances for collisions between molecules are increased because there are more molecules per unit of
volume. More collisions mean a faster reaction rate, assuming the energy of the collisions is adequate.
12.6.0.1: Activation Energy and the Arrhenius Equation

The minimum energy necessary to form a product during a collision between reactants is called the activation energy (Ea). How
this energy compares to the kinetic energy provided by colliding reactant molecules is a primary factor affecting the rate of a
chemical reaction. If the activation energy is much larger than the average kinetic energy of the molecules, the reaction will occur
slowly since only a few fast-moving molecules will have enough energy to react. If the activation energy is much smaller than the
average kinetic energy of the molecules, a large fraction of molecules will be adequately energetic and the reaction will proceed
rapidly.
Figure 12.14 shows how the energy of a chemical system changes as it undergoes a reaction converting reactants to products
according to the equation
A+B ⟶ C +D
These reaction diagrams are widely used in chemical kinetics to illustrate various properties of the reaction of interest. Viewing the
diagram from left to right, the system initially comprises reactants only, A + B. Reactant molecules with sufficient energy can
collide to form a high-energy activated complex or transition state. The unstable transition state can then subsequently decay to
yield stable products, C + D. The diagram depicts the reaction's activation energy, Ea, as the energy difference between the
reactants and the transition state. Using a specific energy, the enthalpy (see chapter on thermochemistry), the enthalpy change of
the reaction, ΔH, is estimated as the energy difference between the reactants and products. In this case, the reaction is exothermic
(ΔH < 0) since it yields a decrease in system enthalpy.
Figure 12.14 Reaction diagram for the exothermic reaction A + B ⟶ C + D.
The Arrhenius equation relates the activation energy and the rate constant, k, for many chemical reactions:
−Ea /RT
k = Ae

In this equation, R is the ideal gas constant, which has a value 8.314 J/mol/K, T is temperature on the Kelvin scale, Ea is the
activation energy in joules per mole, e is the constant 2.7183, and A is a constant called the frequency factor, which is related to the
frequency of collisions and the orientation of the reacting molecules.
Postulates of collision theory are nicely accommodated by the Arrhenius equation. The frequency factor, A, reflects how well the
reaction conditions favor properly oriented collisions between reactant molecules. An increased probability of effectively oriented
collisions results in larger values for A and faster reaction rates.
The exponential term, e−Ea/RT, describes the effect of activation energy on reaction rate. According to kinetic molecular theory (see
chapter on gases), the temperature of matter is a measure of the average kinetic energy of its constituent atoms or molecules. The
distribution of energies among the molecules composing a sample of matter at any given temperature is described by the plot
shown in Figure 12.15(a). Two shaded areas under the curve represent the numbers of molecules possessing adequate energy (RT)
to overcome the activation barriers (Ea). A lower activation energy results in a greater fraction of adequately energized molecules
and a faster reaction.
The exponential term also describes the effect of temperature on reaction rate. A higher temperature represents a correspondingly
greater fraction of molecules possessing sufficient energy (RT) to overcome the activation barrier (Ea), as shown in Figure
12.15(b). This yields a greater value for the rate constant and a correspondingly faster reaction rate.
Figure 12.15 Molecular energy distributions showing numbers of molecules with energies exceeding (a) two different activation
energies at a given temperature, and (b) a given activation energy at two different temperatures.
A convenient approach for determining Ea for a reaction involves the measurement of k at two or more different temperatures and
using an alternate version of the Arrhenius equation that takes the form of a linear equation
−Ea 1
ln k = ( )( ) + ln A
R T
y = mx + b
−Ea
A plot of ln k versus 1
T
is linear with a slope equal to R
and a y-intercept equal to ln A.
12.6.0.1: Example 12.13

12.6.0.0.1: Determination of Ea
The variation of the rate constant with temperature for the decomposition of HI(g) to H2(g) and I2(g) is given here. What is the
activation energy for the reaction?
2HI(g) ⟶ H2 (g) + I2 (g)
T (K) k (L/mol/s)
555 3.52 × 10−7
575 1.22 × 10−6

T (K) k (L/mol/s)
645 8.59 × 10−5
700 1.16 × 10−3
781 3.95 × 10−2
Use the provided data to derive values of 1
T
and ln k:
1
(K
−1
) ln k
T
1.80 × 10−3 −14.860
1.74 × 10−3 −13.617
1.55 × 10−3 −9.362
1.43 × 10−3 −6.759
1.28 × 10−3 −3.231
Figure 12.16 is a graph of ln k versus . In practice, the equation of the line (slope and y-intercept) that best fits these plotted
T
1
data points would be derived using a statistical process called regression. This is helpful for most experimental data because a
perfect fit of each data point with the line is rarely encountered. For the data here, the fit is nearly perfect and the slope may be
estimated using any two of the provided data pairs. Using the first and last data points permits estimation of the slope.
Figure 12.16 This graph shows the linear relationship between ln k and 1
T
for the reaction 2HI ⟶ H2 + I2 according to the
Arrhenius equation.

Δ(ln k)
Slope =
1
Δ( )
T
(−14.860) − (−3.231)
=
−3 −1 −3 −1
(1.80 × 10 K ) − (1.28 × 10 K )
−11.629 4
= −1
= –2.2 × 10 K
−3
0.52 × 10 K
Ea
= −
R
4 −1 −1
Ea = −slope × R = −(−2.2 × 10 K × 8.314 J mol K )
5 −1 −1
1.8 × 10 J mol or 180 kJ mol
Alternative approach: A more expedient approach involves deriving activation energy from measurements of the rate constant
at just two temperatures. In this approach, the Arrhenius equation is rearranged to a convenient two-point form:
k1 Ea 1 1
ln = ( − )
k2 R T2 T1
Rearranging this equation to isolate activation energy yields:
⎛ ⎞
ln k2 − ln k1
Ea = −R ⎜ ⎟
1 1
⎝ ( ) − ( ) ⎠
T2 T1
Any two data pairs may be substituted into this equation—for example, the first and last entries from the above data table:
−3.231 − (−14.860)
−1 −1
Ea = −8.314 J mol K ( )
−3 −1 −3 −1
1.28 × 10 K − 1.80 × 10 K
and the result is Ea = 1.8 × 105 J mol−1 or 180 kJ mol−1

This approach yields the same result as the more rigorous graphical approach used above, as expected. In practice, the
graphical approach typically provides more reliable results when working with actual experimental data.
The rate constant for the rate of decomposition of N2O5 to NO and O2 in the gas phase is 1.66 L/mol/s at 650 K and 7.39
L/mol/s at 700 K:
2N2 O5 (g) ⟶ 4NO(g) + 3O2 (g)
Assuming the kinetics of this reaction are consistent with the Arrhenius equation, calculate the activation energy for this
decomposition.
12.6.0.1: Answer:
1.1 × 105 J mol−1 or 110 kJ mol−1
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Distinguish net reactions from elementary reactions (steps)
Identify the molecularity of elementary reactions
Write a balanced chemical equation for a process given its reaction mechanism
Derive the rate law consistent with a given reaction mechanism
Chemical reactions very often occur in a step-wise fashion, involving two or more distinct reactions taking place in sequence. A
balanced equation indicates what is reacting and what is produced, but it reveals no details about how the reaction actually takes
place. The reaction mechanism (or reaction path) provides details regarding the precise, step-by-step process by which a reaction
occurs.
The decomposition of ozone, for example, appears to follow a mechanism with two steps:
O3 (g) ⟶ O2 (g) + O
O + O3 (g) ⟶ 2 O2 (g)
Each of the steps in a reaction mechanism is an elementary reaction. These elementary reactions occur precisely as represented in
the step equations, and they must sum to yield the balanced chemical equation representing the overall reaction:
2 O3 (g) ⟶ 3 O2 (g)
Notice that the oxygen atom produced in the first step of this mechanism is consumed in the second step and therefore does not
appear as a product in the overall reaction. Species that are produced in one step and consumed in a subsequent step are called
intermediates.
While the overall reaction equation for the decomposition of ozone indicates that two molecules of ozone react to give three
molecules of oxygen, the mechanism of the reaction does not involve the direct collision and reaction of two ozone molecules.
Instead, one O3 decomposes to yield O2 and an oxygen atom, and a second O3 molecule subsequently reacts with the oxygen atom
to yield two additional O2 molecules.
Unlike balanced equations representing an overall reaction, the equations for elementary reactions are explicit representations of
the chemical change taking place. The reactant(s) in an elementary reaction’s equation undergo only the bond-breaking and/or
making events depicted to yield the product(s). For this reason, the rate law for an elementary reaction may be derived directly
from the balanced chemical equation describing the reaction. This is not the case for typical chemical reactions, for which rate
laws may be reliably determined only via experimentation.
12.7.0.1: Unimolecular Elementary Reactions

The molecularity of an elementary reaction is the number of reactant species (atoms, molecules, or ions). For example, a
unimolecular reaction involves the reaction of a single reactant species to produce one or more molecules of product:
A ⟶ products
The rate law for a unimolecular reaction is first order:

rate = k[A]
A unimolecular reaction may be one of several elementary reactions in a complex mechanism. For example, the reaction:
O3 ⟶ O2 + O
illustrates a unimolecular elementary reaction that occurs as one part of a two-step reaction mechanism as described above.
However, some unimolecular reactions may be the only step of a single-step reaction mechanism. (In other words, an “overall”
reaction may also be an elementary reaction in some cases.) For example, the gas-phase decomposition of cyclobutane, C4H8, to
ethylene, C2H4, is represented by the following chemical equation:

This equation represents the overall reaction observed, and it might also represent a legitimate unimolecular elementary reaction.
The rate law predicted from this equation, assuming it is an elementary reaction, turns out to be the same as the rate law derived
experimentally for the overall reaction, namely, one showing first-order behavior:
Δ[ C4 H8 ]
rate = − = k[ C4 H8 ]
Δt
This agreement between observed and predicted rate laws is interpreted to mean that the proposed unimolecular, single-step
process is a reasonable mechanism for the butadiene reaction.
12.7.0.1: Bimolecular Elementary Reactions

A bimolecular reaction involves two reactant species, for example:
A + B ⟶ products
and
2A ⟶ products
For the first type, in which the two reactant molecules are different, the rate law is first-order in A and first order in B (second-order
overall):
rate = k[A][B]
For the second type, in which two identical molecules collide and react, the rate law is second order in A:
2
rate = k[A][A] = k[A]
Some chemical reactions occur by mechanisms that consist of a single bimolecular elementary reaction. One example is the
reaction of nitrogen dioxide with carbon monoxide:
NO2 (g) + CO(g) ⟶ NO(g) + CO2 (g)
(see Figure 12.17)
Figure 12.17 The probable mechanism for the reaction between NO2 and CO to yield NO and CO2.
Bimolecular elementary reactions may also be involved as steps in a multistep reaction mechanism. The reaction of atomic oxygen
with ozone is the second step of the two-step ozone decomposition mechanism discussed earlier in this section:
O(g) + O3 (g) ⟶ 2O2 (g)
12.7.0.1: Termolecular Elementary Reactions

An elementary termolecular reaction involves the simultaneous collision of three atoms, molecules, or ions. Termolecular
elementary reactions are uncommon because the probability of three particles colliding simultaneously is less than one one-
thousandth of the probability of two particles colliding. There are, however, a few established termolecular elementary reactions.
The reaction of nitric oxide with oxygen appears to involve termolecular steps:

2NO + O2 ⟶ 2 NO2
2
rate = k[NO] [ O2 ]
Likewise, the reaction of nitric oxide with chlorine appears to involve termolecular steps:
2NO + Cl2 ⟶ 2NOCl
2
rate = k[NO] [ Cl2 ]
12.7.0.1: Relating Reaction Mechanisms to Rate Laws

It’s often the case that one step in a multistep reaction mechanism is significantly slower than the others. Because a reaction cannot
proceed faster than its slowest step, this step will limit the rate at which the overall reaction occurs. The slowest step is therefore
called the rate-limiting step (or rate-determining step) of the reaction Figure 12.18.
Figure 12.18 A cattle chute is a nonchemical example of a rate-determining step. Cattle can only be moved from one holding pen to
another as quickly as one animal can make its way through the chute. (credit: Loren Kerns)
As described earlier, rate laws may be derived directly from the chemical equations for elementary reactions. This is not the case,
however, for ordinary chemical reactions. The balanced equations most often encountered represent the overall change for some
chemical system, and very often this is the result of some multistep reaction mechanisms. In every case, the rate law must be
determined from experimental data and the reaction mechanism subsequently deduced from the rate law (and sometimes from other
data). The reaction of NO2 and CO provides an illustrative example:
NO2 (g) + CO(g) ⟶ CO2 (g) + NO(g)
For temperatures above 225 °C, the rate law has been found to be:
rate = k [ NO2 ] [CO]
The reaction is first order with respect to NO2 and first-order with respect to CO. This is consistent with a single-step bimolecular
mechanism and it is possible that this is the mechanism for this reaction at high temperatures.
At temperatures below 225 °C, the reaction is described by a rate law that is second order with respect to NO2:
2
rate = k[ NO2 ]
This rate law is not consistent with the single-step mechanism, but is consistent with the following two-step mechanism:
NO2 (g) + NO2 (g) ⟶ NO3 (g) + NO(g) (slow)
NO3 (g) + CO(g) ⟶ NO2 (g) + CO2 (g) (fast)
The rate-determining (slower) step gives a rate law showing second-order dependence on the NO2 concentration, and the sum of
the two equations gives the net overall reaction.

In general, when the rate-determining (slower) step is the first step in a mechanism, the rate law for the overall reaction is the same
as the rate law for this step. However, when the rate-determining step is preceded by a step involving a rapidly reversible reaction
the rate law for the overall reaction may be more difficult to derive.
As discussed in several chapters of this text, a reversible reaction is at equilibrium when the rates of the forward and reverse
processes are equal. Consider the reversible elementary reaction in which NO dimerizes to yield an intermediate species N2O2.
When this reaction is at equilibrium:
NO + NO ⇌ N2 O2
rateforward = ratereverse
2
k1 [NO] = k−1 [ N2 O2 ]
This expression may be rearranged to express the concentration of the intermediate in terms of the reactant NO:
2
k1 [NO]
( ) = [ N2 O2 ]
k−1
Since intermediate species concentrations are not used in formulating rate laws for overall reactions, this approach is sometimes
necessary, as illustrated in the following example exercise.
12.7.0.1: Example 12.14

12.7.0.0.1: Deriving a Rate Law from a Reaction Mechanism
The two-step mechanism below has been proposed for a reaction between nitrogen monoxide and molecular chlorine:
Step 1: NO(g) + Cl2 (g) ⇌ NOCl2 (g) fast
Step 2: NOCl2 (g) + NO(g) ⟶ 2NOCl(g) slow
Use this mechanism to derive the equation and predicted rate law for the overall reaction.
The equation for the overall reaction is obtained by adding the two elementary reactions:
To derive a rate law from this mechanism, first write rates laws for each of the two steps.
rate1 = k1 [NO][ Cl2 ] for the forward reaction of step 1
rate−1 = k−1 [ NOCl2 ] for the reverse reaction of step 1
rate2 = k2 [ NOCl2 ][NO] for step 2
Step 2 is the rate-determining step, and so the rate law for the overall reaction should be the same as for this step. However, the
step 2 rate law, as written, contains an intermediate species concentration, [NOCl2]. To remedy this, use the first step’s rate
laws to derive an expression for the intermediate concentration in terms of the reactant concentrations.
Assuming step 1 is at equilibrium:
rate1 = rate−1
k1 [NO] [ Cl2 ] = k−1 [ NOCl2 ]
k1
[ NOCl2 ] = ( ) [NO] [ Cl2 ]
k− 1
Substituting this expression into the rate law for step 2 yields:
k2 k1 2
rate2 = rateoverall = ( )[NO] [ Cl2 ]
k−1

The first step of a proposed multistep mechanism is:
F2 (g) ⇌ 2F(g) fast
Derive the equation relating atomic fluorine concentration to molecular fluorine concentration.

12.7.0.1: Answer:
1/2
k1 [ F2 ]
[F] = ( )
k−1
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12.8: Catalysis

Explain the function of a catalyst in terms of reaction mechanisms and potential energy diagrams
List examples of catalysis in natural and industrial processes
Among the factors affecting chemical reaction rates discussed earlier in this chapter was the presence of a catalyst, a substance that
can increase the reaction rate without being consumed in the reaction. The concepts introduced in the previous section on reaction
mechanisms provide the basis for understanding how catalysts are able to accomplish this very important function.
Figure 12.19 shows reaction diagrams for a chemical process in the absence and presence of a catalyst. Inspection of the diagrams
reveals several traits of these reactions. Consistent with the fact that the two diagrams represent the same overall reaction, both
curves begin and end at the same energies (in this case, because products are more energetic than reactants, the reaction is
endothermic). The reaction mechanisms, however, are clearly different. The uncatalyzed reaction proceeds via a one-step
mechanism (one transition state observed), whereas the catalyzed reaction follows a two-step mechanism (two transition states
observed) with a notably lesser activation energy. This difference illustrates the means by which a catalyst functions to accelerate
reactions, namely, by providing an alternative reaction mechanism with a lower activation energy. Although the catalyzed reaction
mechanism for a reaction needn’t necessarily involve a different number of steps than the uncatalyzed mechanism, it must provide
a reaction path whose rate determining step is faster (lower Ea).
Figure 12.19 Reaction diagrams for an endothermic process in the absence (red curve) and presence (blue curve) of a catalyst. The
catalyzed pathway involves a two-step mechanism (note the presence of two transition states) and an intermediate species
(represented by the valley between the two transitions states).
12.8.0.1: Example 12.15

12.8.0.0.1: Reaction Diagrams for Catalyzed Reactions

The two reaction diagrams here represent the same reaction: one without a catalyst and one with a catalyst. Estimate the
activation energy for each process, and identify which one involves a catalyst.
Activation energies are calculated by subtracting the reactant energy from the transition state energy.
diagram (a): Ea = 32 kJ − 6 kJ = 26 kJ
diagram (b): Ea = 20 kJ − 6 kJ = 14 kJ
The catalyzed reaction is the one with lesser activation energy, in this case represented by diagram b.
Reaction diagrams for a chemical process with and without a catalyst are shown below. Both reactions involve a two-step
mechanism with a rate-determining first step. Compute activation energies for the first step of each mechanism, and identify
which corresponds to the catalyzed reaction. How do the second steps of these two mechanisms compare?
12.8.0.1: Answer:
For the first step, Ea = 80 kJ for (a) and 70 kJ for (b), so diagram (b) depicts the catalyzed reaction. Activation energies for
the second steps of both mechanisms are the same, 20 kJ.
12.8.0.1: Homogeneous Catalysts

A homogeneous catalyst is present in the same phase as the reactants. It interacts with a reactant to form an intermediate substance,
which then decomposes or reacts with another reactant in one or more steps to regenerate the original catalyst and form product.
As an important illustration of homogeneous catalysis, consider the earth’s ozone layer. Ozone in the upper atmosphere, which
protects the earth from ultraviolet radiation, is formed when oxygen molecules absorb ultraviolet light and undergo the reaction:

hv
3 O2 (g) −−−→ 2 O3 (g)
Ozone is a relatively unstable molecule that decomposes to yield diatomic oxygen by the reverse of this equation. This
decomposition reaction is consistent with the following two-step mechanism:
O3 ⟶ O2 + O
O + O3 ⟶ 2 O2
A number of substances can catalyze the decomposition of ozone. For example, the nitric oxide–catalyzed decomposition of ozone
is believed to occur via the following three-step mechanism:
NO(g) + O3 (g) ⟶ NO2 (g) + O2 (g)
O3 (g) ⟶ O2 (g) + O(g)
NO2 (g) + O(g) ⟶ NO(g) + O2 (g)
As required, the overall reaction is the same for both the two-step uncatalyzed mechanism and the three-step NO-catalyzed
mechanism:
2 O3 (g) ⟶ 3 O2 (g)
Notice that NO is a reactant in the first step of the mechanism and a product in the last step. This is another characteristic trait of a
catalyst: Though it participates in the chemical reaction, it is not consumed by the reaction.

12.8.0.0.1: Mario J. Molina
The 1995 Nobel Prize in Chemistry was shared by Paul J. Crutzen, Mario J. Molina (Figure 12.20), and F. Sherwood Rowland
“for their work in atmospheric chemistry, particularly concerning the formation and decomposition of ozone.”1 Molina, a
Mexican citizen, carried out the majority of his work at the Massachusetts Institute of Technology (MIT).
Figure 12.20 (a) Mexican chemist Mario Molina (1943 –) shared the Nobel Prize in Chemistry in 1995 for his research on (b)
the Antarctic ozone hole. (credit a: courtesy of Mario Molina; credit b: modification of work by NASA)
In 1974, Molina and Rowland published a paper in the journal Nature detailing the threat of chlorofluorocarbon gases to the
stability of the ozone layer in earth’s upper atmosphere. The ozone layer protects earth from solar radiation by absorbing
ultraviolet light. As chemical reactions deplete the amount of ozone in the upper atmosphere, a measurable “hole” forms above
Antarctica, and an increase in the amount of solar ultraviolet radiation— strongly linked to the prevalence of skin cancers—

reaches earth’s surface. The work of Molina and Rowland was instrumental in the adoption of the Montreal Protocol, an
international treaty signed in 1987 that successfully began phasing out production of chemicals linked to ozone destruction.
Molina and Rowland demonstrated that chlorine atoms from human-made chemicals can catalyze ozone destruction in a
process similar to that by which NO accelerates the depletion of ozone. Chlorine atoms are generated when chlorocarbons or
chlorofluorocarbons—once widely used as refrigerants and propellants—are photochemically decomposed by ultraviolet light
or react with hydroxyl radicals. A sample mechanism is shown here using methyl chloride:
CH3 Cl + OH ⟶ Cl + other products
Chlorine radicals break down ozone and are regenerated by the following catalytic cycle:
Cl + O3 ⟶ ClO + O2
ClO + O ⟶ Cl + O2
overall Reaction: O3 + O ⟶ 2 O2
A single monatomic chlorine can break down thousands of ozone molecules. Luckily, the majority of atmospheric chlorine
exists as the catalytically inactive forms Cl2 and ClONO2.
Since receiving his portion of the Nobel Prize, Molina has continued his work in atmospheric chemistry at MIT.

12.8.0.0.2: Glucose-6-Phosphate Dehydrogenase Deficiency
Enzymes in the human body act as catalysts for important chemical reactions in cellular metabolism. As such, a deficiency of a
particular enzyme can translate to a life-threatening disease. G6PD (glucose-6-phosphate dehydrogenase) deficiency, a genetic
condition that results in a shortage of the enzyme glucose-6-phosphate dehydrogenase, is the most common enzyme deficiency
in humans. This enzyme, shown in Figure 12.21, is the rate-limiting enzyme for the metabolic pathway that supplies NADPH
to cells (Figure 12.22).
Figure 12.21 Glucose-6-phosphate dehydrogenase is a rate-limiting enzyme for the metabolic pathway that supplies NADPH to
cells.
A disruption in this pathway can lead to reduced glutathione in red blood cells; once all glutathione is consumed, enzymes and
other proteins such as hemoglobin are susceptible to damage. For example, hemoglobin can be metabolized to bilirubin, which
leads to jaundice, a condition that can become severe. People who suffer from G6PD deficiency must avoid certain foods and
medicines containing chemicals that can trigger damage their glutathione-deficient red blood cells.

Figure 12.22 In the mechanism for the pentose phosphate pathway, G6PD catalyzes the reaction that regulates NADPH, a co-
enzyme that regulates glutathione, an antioxidant that protects red blood cells and other cells from oxidative damage.
12.8.0.1: Heterogeneous Catalysts

A heterogeneous catalyst is a catalyst that is present in a different phase (usually a solid) than the reactants. Such catalysts
generally function by furnishing an active surface upon which a reaction can occur. Gas and liquid phase reactions catalyzed by
heterogeneous catalysts occur on the surface of the catalyst rather than within the gas or liquid phase.
Heterogeneous catalysis typically involves the following processes:
1. Adsorption of the reactant(s) onto the surface of the catalyst
2. Activation of the adsorbed reactant(s)
3. Reaction of the adsorbed reactant(s)
4. Desorption of product(s) from the surface of the catalyst
Figure 12.23 illustrates the steps of a mechanism for the reaction of compounds containing a carbon–carbon double bond with
hydrogen on a nickel catalyst. Nickel is the catalyst used in the hydrogenation of polyunsaturated fats and oils (which contain
several carbon–carbon double bonds) to produce saturated fats and oils (which contain only carbon–carbon single bonds).

Figure 12.23 Mechanism for the Ni-catalyzed reaction C H + H ⟶ C H . (a) Hydrogen is adsorbed on the surface, breaking
2 4 2 2 6
the H–H bonds and forming Ni–H bonds. (b) Ethylene is adsorbed on the surface, breaking the C–C π-bond and forming Ni–C
bonds. (c) Atoms diffuse across the surface and form new C–H bonds when they collide. (d) C2H6 molecules desorb from the Ni
surface.
Many important chemical products are prepared via industrial processes that use heterogeneous catalysts, including ammonia, nitric
acid, sulfuric acid, and methanol. Heterogeneous catalysts are also used in the catalytic converters found on most gasoline-powered
automobiles (Figure 12.24).

12.8.0.0.1: Automobile Catalytic Converters
Scientists developed catalytic converters to reduce the amount of toxic emissions produced by burning gasoline in internal
combustion engines. By utilizing a carefully selected blend of catalytically active metals, it is possible to effect complete
combustion of all carbon-containing compounds to carbon dioxide while also reducing the output of nitrogen oxides. This is
particularly impressive when we consider that one step involves adding more oxygen to the molecule and the other involves
removing the oxygen (Figure 12.24).

Figure 12.24 A catalytic converter allows for the combustion of all carbon-containing compounds to carbon dioxide, while at
the same time reducing the output of nitrogen oxide and other pollutants in emissions from gasoline-burning engines.
Most modern, three-way catalytic converters possess a surface impregnated with a platinum-rhodium catalyst, which catalyzes
the conversion of nitric oxide into dinitrogen and oxygen as well as the conversion of carbon monoxide and hydrocarbons such
as octane into carbon dioxide and water vapor:
2 NO2 (g) ⟶ N2 (g) + 2 O2 (g)
2CO(g) + O2 (g) ⟶ 2 CO2 (g)
2 C8 H18 (g) + 25 O2 (g) ⟶ 16 CO2 (g) + 18 H2 O(g)
In order to be as efficient as possible, most catalytic converters are preheated by an electric heater. This ensures that the metals
in the catalyst are fully active even before the automobile exhaust is hot enough to maintain appropriate reaction temperatures.

The University of California at Davis’ “ChemWiki” provides a thorough explanation of how catalytic converters work.

12.8.0.0.2: Enzyme Structure and Function
The study of enzymes is an important interconnection between biology and chemistry. Enzymes are usually proteins
(polypeptides) that help to control the rate of chemical reactions between biologically important compounds, particularly those
that are involved in cellular metabolism. Different classes of enzymes perform a variety of functions, as shown in Table 12.3.
Classes of Enzymes and Their Functions

Class Function
oxidoreductases redox reactions
transferases transfer of functional groups
hydrolases hydrolysis reactions
lyases group elimination to form double bonds
isomerases isomerization
ligases bond formation with ATP hydrolysis
Table 12.3
Enzyme molecules possess an active site, a part of the molecule with a shape that allows it to bond to a specific substrate (a
reactant molecule), forming an enzyme-substrate complex as a reaction intermediate. There are two models that attempt to
explain how this active site works. The most simplistic model is referred to as the lock-and-key hypothesis, which suggests that
the molecular shapes of the active site and substrate are complementary, fitting together like a key in a lock. The induced fit
hypothesis, on the other hand, suggests that the enzyme molecule is flexible and changes shape to accommodate a bond with
the substrate. This is not to suggest that an enzyme’s active site is completely malleable, however. Both the lock-and-key
model and the induced fit model account for the fact that enzymes can only bind with specific substrates, since in general a
particular enzyme only catalyzes a particular reaction (Figure 12.25).
Figure 12.25 (a) According to the lock-and-key model, the shape of an enzyme’s active site is a perfect fit for the substrate. (b)
According to the induced fit model, the active site is somewhat flexible, and can change shape in order to bond with the
substrate.

The Royal Society of Chemistry provides an excellent introduction to enzymes for students and teachers.
12.8.0.1: Footnotes
1“The Nobel Prize in Chemistry 1995,” Nobel Prize.org, accessed February 18, 2015,
http://www.nobelprize.org/nobel_priz...aureates/1995/.
This page titled 12.8: Catalysis is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content

12.9: Key Terms
activated complex
(also, transition state) unstable combination of reactant species formed during a chemical reaction
activation energy (Ea)

minimum energy necessary in order for a reaction to take place
Arrhenius equation
mathematical relationship between a reaction’s rate constant, activation energy, and temperature
average rate
rate of a chemical reaction computed as the ratio of a measured change in amount or concentration of substance to the time
interval over which the change occurred
bimolecular reaction
elementary reaction involving two reactant species
catalyst
substance that increases the rate of a reaction without itself being consumed by the reaction
collision theory
model that emphasizes the energy and orientation of molecular collisions to explain and predict reaction kinetics
elementary reaction
reaction that takes place in a single step, precisely as depicted in its chemical equation
frequency factor (A)

proportionality constant in the Arrhenius equation, related to the relative number of collisions having an orientation capable of
leading to product formation
half-life of a reaction (tl/2)

time required for half of a given amount of reactant to be consumed
heterogeneous catalyst
catalyst present in a different phase from the reactants, furnishing a surface at which a reaction can occur
homogeneous catalyst
catalyst present in the same phase as the reactants
initial rate
instantaneous rate of a chemical reaction at t = 0 s (immediately after the reaction has begun)
instantaneous rate
rate of a chemical reaction at any instant in time, determined by the slope of the line tangential to a graph of concentration as a
function of time
integrated rate law

equation that relates the concentration of a reactant to elapsed time of reaction
intermediate
species produced in one step of a reaction mechanism and consumed in a subsequent step
method of initial rates
common experimental approach to determining rate laws that involves measuring reaction rates at varying initial reactant
concentrations
molecularity
number of reactant species involved in an elementary reaction
overall reaction order

sum of the reaction orders for each substance represented in the rate law
rate constant (k)

proportionality constant in a rate law
rate expression
mathematical representation defining reaction rate as change in amount, concentration, or pressure of reactant or product
species per unit time
rate law
(also, rate equation) (also, differential rate laws) mathematical equation showing the dependence of reaction rate on the rate
constant and the concentration of one or more reactants
rate of reaction
measure of the speed at which a chemical reaction takes place
rate-determining step
(also, rate-limiting step) slowest elementary reaction in a reaction mechanism; determines the rate of the overall reaction
reaction diagram
used in chemical kinetics to illustrate various properties of a reaction
reaction mechanism
stepwise sequence of elementary reactions by which a chemical change takes place
reaction order
value of an exponent in a rate law (for example, zero order for 0, first order for 1, second order for 2, and so on)
termolecular reaction
elementary reaction involving three reactant species
unimolecular reaction
elementary reaction involving a single reactant species
1 Δ[A] 1 Δ[B]
relative reaction rates for aA ⟶ bB = − =
a Δt b Δt
integrated rate law for zero-order reactions: [A] t = −kt + [A] ,

0
[A]
half-life for a zero-order reaction t 1/2 =
2k
0
integrated rate law for first-order reactions: ln[A] t = −kt + ln [A] ,

0
half-life for a first-order reaction t

0.693
1/2 =
k
integrated rate law for second-order reactions:

1 1
= kt + ,
[A]t [A] 0
half-life for a second-order reaction t

1
1/2 =
[A] 0 k
− Ea /RT
k = Ae
−Ea 1
ln k = ( ) ( ) + ln A
R T
k1 Ea 1 1
ln = ( − )
k2 R T2 T1
12.11: Summary
12.1 Chemical Reaction Rates
The rate of a reaction can be expressed either in terms of the decrease in the amount of a reactant or the increase in the amount of a
product per unit time. Relations between different rate expressions for a given reaction are derived directly from the stoichiometric
coefficients of the equation representing the reaction.
12.2 Factors Affecting Reaction Rates

The rate of a chemical reaction is affected by several parameters. Reactions involving two phases proceed more rapidly when there
is greater surface area contact. If temperature or reactant concentration is increased, the rate of a given reaction generally increases
as well. A catalyst can increase the rate of a reaction by providing an alternative pathway with a lower activation energy.
12.3 Rate Laws

Rate laws (differential rate laws) provide a mathematical description of how changes in the concentration of a substance affect the
rate of a chemical reaction. Rate laws are determined experimentally and cannot be predicted by reaction stoichiometry. The order
of reaction describes how much a change in the concentration of each substance affects the overall rate, and the overall order of a
reaction is the sum of the orders for each substance present in the reaction. Reaction orders are typically first order, second order, or
zero order, but fractional and even negative orders are possible.
12.4 Integrated Rate Laws

Integrated rate laws are mathematically derived from differential rate laws, and they describe the time dependence of reactant and
product concentrations.
The half-life of a reaction is the time required to decrease the amount of a given reactant by one-half. A reaction’s half-life varies
with rate constant and, for some reaction orders, reactant concentration. The half-life of a zero-order reaction decreases as the
initial concentration of the reactant in the reaction decreases. The half-life of a first-order reaction is independent of concentration,
and the half-life of a second-order reaction decreases as the concentration increases.
12.5 Collision Theory

Chemical reactions typically require collisions between reactant species. These reactant collisions must be of proper orientation and
sufficient energy in order to result in product formation. Collision theory provides a simple but effective explanation for the effect
of many experimental parameters on reaction rates. The Arrhenius equation describes the relation between a reaction’s rate
constant, activation energy, temperature, and dependence on collision orientation.
12.6 Reaction Mechanisms

The sequence of individual steps, or elementary reactions, by which reactants are converted into products during the course of a
reaction is called the reaction mechanism. The molecularity of an elementary reaction is the number of reactant species involved,
typically one (unimolecular), two (bimolecular), or, less commonly, three (termolecular). The overall rate of a reaction is
determined by the rate of the slowest in its mechanism, called the rate-determining step. Unimolecular elementary reactions have
first-order rate laws, while bimolecular elementary reactions have second-order rate laws. By comparing the rate laws derived from
a reaction mechanism to that determined experimentally, the mechanism may be deemed either incorrect or plausible.
12.7 Catalysis
Catalysts affect the rate of a chemical reaction by altering its mechanism to provide a lower activation energy. Catalysts can be
homogenous (in the same phase as the reactants) or heterogeneous (a different phase than the reactants).
12.12: Exercises
12.12.0.1: 12.1 Chemical Reaction Rates
1.
What is the difference between average rate, initial rate, and instantaneous rate?
2.
Ozone decomposes to oxygen according to the equation 2O (g) ⟶ 3O (g). Write the equation that relates the rate expressions
3 2
for this reaction in terms of the disappearance of O3 and the formation of oxygen.
3.
In the nuclear industry, chlorine trifluoride is used to prepare uranium hexafluoride, a volatile compound of uranium used in the
separation of uranium isotopes. Chlorine trifluoride is prepared by the reaction Cl (g) + 3F (g) ⟶ 2ClF (g). Write the
2 2 3
equation that relates the rate expressions for this reaction in terms of the disappearance of Cl2 and F2 and the formation of ClF3.
4.
A study of the rate of dimerization of C4H6 gave the data shown in the table:
2C4 H6 ⟶ C8 H12
Time (s) 0 1600 3200 4800 6200
[C4H6] (M) 1.00 × 10−2 5.04 × 10−3 3.37 × 10−3 2.53 × 10−3 2.08 × 10−3
(a) Determine the average rate of dimerization between 0 s and 1600 s, and between 1600 s and 3200 s.
(b) Estimate the instantaneous rate of dimerization at 3200 s from a graph of time versus [C4H6]. What are the units of this rate?
(c) Determine the average rate of formation of C8H12 at 1600 s and the instantaneous rate of formation at 3200 s from the rates
found in parts (a) and (b).
5.
A study of the rate of the reaction represented as 2A ⟶ B gave the following data:
Time (s) 0.0 5.0 10.0 15.0 20.0 25.0 35.0
[A] (M) 1.00 0.775 0.625 0.465 0.360 0.285 0.230
(a) Determine the average rate of disappearance of A between 0.0 s and 10.0 s, and between 10.0 s and 20.0 s.
(b) Estimate the instantaneous rate of disappearance of A at 15.0 s from a graph of time versus [A]. What are the units of this rate?
(c) Use the rates found in parts (a) and (b) to determine the average rate of formation of B between 0.00 s and 10.0 s, and the
instantaneous rate of formation of B at 15.0 s.
6.
Consider the following reaction in aqueous solution:
− − +
5Br (aq) + BrO 3 (aq) + 6H (aq) ⟶ 3Br2 (aq) + 3H2 O(l)
If the rate of disappearance of Br–(aq) at a particular moment during the reaction is 3.5 × 10−4 mol L−1 s−1, what is the rate of
appearance of Br2(aq) at that moment?
12.12.0.1: 12.2 Factors Affecting Reaction Rates

7.
Describe the effect of each of the following on the rate of the reaction of magnesium metal with a solution of hydrochloric acid: the
molarity of the hydrochloric acid, the temperature of the solution, and the size of the pieces of magnesium.
8.

Explain why an egg cooks more slowly in boiling water in Denver than in New York City. (Hint: Consider the effect of temperature
on reaction rate and the effect of pressure on boiling point.)
9.
Go to the PhET Reactions & Rates interactive. Use the Single Collision tab to represent how the collision between monatomic
oxygen (O) and carbon monoxide (CO) results in the breaking of one bond and the formation of another. Pull back on the red
plunger to release the atom and observe the results. Then, click on “Reload Launcher” and change to “Angled shot” to see the
difference.
(a) What happens when the angle of the collision is changed?
(b) Explain how this is relevant to rate of reaction.
10.
In the PhET Reactions & Rates interactive, use the “Many Collisions” tab to observe how multiple atoms and molecules interact
under varying conditions. Select a molecule to pump into the chamber. Set the initial temperature and select the current amounts of
each reactant. Select “Show bonds” under Options. How is the rate of the reaction affected by concentration and temperature?
11.
In the PhET Reactions & Rates interactive, on the Many Collisions tab, set up a simulation with 15 molecules of A and 10
molecules of BC. Select “Show Bonds” under Options.
(a) Leave the Initial Temperature at the default setting. Observe the reaction. Is the rate of reaction fast or slow?
(b) Click “Pause” and then “Reset All,” and then enter 15 molecules of A and 10 molecules of BC once again. Select “Show
Bonds” under Options. This time, increase the initial temperature until, on the graph, the total average energy line is completely
above the potential energy curve. Describe what happens to the reaction.
12.12.0.1: 12.3 Rate Laws

12.
How do the rate of a reaction and its rate constant differ?
13.
Doubling the concentration of a reactant increases the rate of a reaction four times. With this knowledge, answer the following
questions:
(a) What is the order of the reaction with respect to that reactant?
(b) Tripling the concentration of a different reactant increases the rate of a reaction three times. What is the order of the reaction
with respect to that reactant?
14.
Tripling the concentration of a reactant increases the rate of a reaction nine-fold. With this knowledge, answer the following
questions:
(a) What is the order of the reaction with respect to that reactant?
(b) Increasing the concentration of a reactant by a factor of four increases the rate of a reaction four-fold. What is the order of the
reaction with respect to that reactant?
15.
How will the rate of reaction change for the process: CO(g) + NO 2 (g) ⟶ CO2 (g) + NO(g) if the rate law for the reaction is
2
rate = k[ NO2 ] ?
(a) Decreasing the pressure of NO2 from 0.50 atm to 0.250 atm.
(b) Increasing the concentration of CO from 0.01 M to 0.03 M.
16.
How will each of the following affect the rate of the reaction: CO(g) + NO2 (g) ⟶ CO2 (g) + NO(g) if the rate law for the
reaction is rate = k [NO ] [CO]?
2

(a) Increasing the pressure of NO2 from 0.1 atm to 0.3 atm
(b) Increasing the concentration of CO from 0.02 M to 0.06 M.
17.
Regular flights of supersonic aircraft in the stratosphere are of concern because such aircraft produce nitric oxide, NO, as a
byproduct in the exhaust of their engines. Nitric oxide reacts with ozone, and it has been suggested that this could contribute to
depletion of the ozone layer. The reaction NO + O ⟶ NO + O is first order with respect to both NO and O3 with a rate
3 2 2
constant of 2.20 × 107 L/mol/s. What is the instantaneous rate of disappearance of NO when [NO] = 3.3 × 10−6 M and [O3] = 5.9
−7
× 10 M?
18.
Radioactive phosphorus is used in the study of biochemical reaction mechanisms because phosphorus atoms are components of
many biochemical molecules. The location of the phosphorus (and the location of the molecule it is bound in) can be detected from
the electrons (beta particles) it produces:
32 32 −
P ⟶ S+e
15 16
−2
rate = 4.85 × 10 day
−1
[
32
P]
What is the instantaneous rate of production of electrons in a sample with a phosphorus concentration of 0.0033 M?
19.
The rate constant for the radioactive decay of 14C is 1.21 × 10−4 year−1. The products of the decay are nitrogen atoms and electrons
(beta particles):
14 14 −
C ⟶ N+e
6 7
14
rate = k[ C]
6
What is the instantaneous rate of production of N atoms in a sample with a carbon-14 content of 6.5 × 10−9 M?
20.
The decomposition of acetaldehyde is a second order reaction with a rate constant of 4.71 × 10−8 L mol−1 s−1. What is the
instantaneous rate of decomposition of acetaldehyde in a solution with a concentration of 5.55 × 10−4 M?
21.
Alcohol is removed from the bloodstream by a series of metabolic reactions. The first reaction produces acetaldehyde; then other
products are formed. The following data have been determined for the rate at which alcohol is removed from the blood of an
average male, although individual rates can vary by 25–30%. Women metabolize alcohol a little more slowly than men:
[C2H5OH] (M) 4.4 × 10−2 3.3 × 10−2 2.2 × 10−2
Rate (mol L−1 h−1) 2.0 × 10−2 2.0 × 10−2 2.0 × 10−2
Determine the rate law, the rate constant, and the overall order for this reaction.
22.
Under certain conditions the decomposition of ammonia on a metal surface gives the following data:
[NH3] (M) 1.0 × 10−3 2.0 × 10−3 3.0 × 10−3
Rate (mol L−1 h−1) 1.5 × 10−6 1.5 × 10−6 1.5 × 10−6
Determine the rate law, the rate constant, and the overall order for this reaction.
23.
Nitrosyl chloride, NOCl, decomposes to NO and Cl2.
2NOCl(g) ⟶ 2NO(g) + Cl2 (g)
Determine the rate law, the rate constant, and the overall order for this reaction from the following data:

[NOCl] (M) 0.10 0.20 0.30
Rate (mol L−1 h−1) 8.0 × 10−10 3.2 × 10−9 7.2 × 10−9
24.
From the following data, determine the rate law, the rate constant, and the order with respect to A for the reaction A ⟶ 2C .
[A] (M) 1.33 × 10−2 2.66 × 10−2 3.99 × 10−2
Rate (mol L−1 h−1) 3.80 × 10−7 1.52 × 10−6 3.42 × 10−6
25.
Nitrogen monoxide reacts with chlorine according to the equation:
The following initial rates of reaction have been observed for certain reactant concentrations:
[NO] (mol/L) [Cl2] (mol/L) Rate (mol L−1 h−1)
0.50 0.50 1.14
1.00 0.50 4.56
1.00 1.00 9.12
What is the rate law that describes the rate’s dependence on the concentrations of NO and Cl2? What is the rate constant? What are
the orders with respect to each reactant?
26.
Hydrogen reacts with nitrogen monoxide to form dinitrogen monoxide (laughing gas) according to the equation:
H2 (g) + 2NO(g) ⟶ N2 O(g) + H2 O(g)
Determine the rate law, the rate constant, and the orders with respect to each reactant from the following data:
[NO] (M) 0.30 0.60 0.60
[H2] (M) 0.35 0.35 0.70
Rate (mol L−1 s−1) 2.835 × 10−3 1.134 × 10−2 2.268 × 10−2
27.
For the reaction A ⟶ B + C, the following data were obtained at 30 °C:
[A] (M) 0.230 0.356 0.557
Rate (mol L−1 s−1) 4.17 × 10−4 9.99 × 10−4 2.44 × 10−3
(a) What is the order of the reaction with respect to [A], and what is the rate law?
(b) What is the rate constant?
28.
For the reaction Q ⟶ W + X, the following data were obtained at 30 °C:

[Q]initial (M) 0.170 0.212 0.357
Rate (mol L−1 s−1) 6.68 × 10−3 1.04 × 10−2 2.94 × 10−2
(a) What is the order of the reaction with respect to [Q], and what is the rate law?
(b) What is the rate constant?
29.
The rate constant for the first-order decomposition at 45 °C of dinitrogen pentoxide, N2O5, dissolved in chloroform, CHCl3, is 6.2
−4
× 10 min−1.
2N2 O5 ⟶ 4NO2 + O2
What is the rate of the reaction when [N2O5] = 0.40 M?

30.
The annual production of HNO3 in 2013 was 60 million metric tons Most of that was prepared by the following sequence of
reactions, each run in a separate reaction vessel.
(a) 4NH 3 (g) + 5O2 (g) ⟶ 4NO(g) + 6H2 O(g)
(b) 2NO(g) + O 2 (g) ⟶ 2NO2 (g)
(c) 3NO 2 (g) + H2 O(l) ⟶ 2HNO3 (aq) + NO(g)
The first reaction is run by burning ammonia in air over a platinum catalyst. This reaction is fast. The reaction in equation (c) is
also fast. The second reaction limits the rate at which nitric acid can be prepared from ammonia. If equation (b) is second order in
NO and first order in O2, what is the rate of formation of NO2 when the oxygen concentration is 0.50 M and the nitric oxide
concentration is 0.75 M? The rate constant for the reaction is 5.8 × 10−6 L2 mol−2 s−1.
31.
The following data have been determined for the reaction:
− − − −
I + OCl ⟶ IO + Cl
1 2 3
[I
−
]
initial
(M) 0.10 0.20 0.30
[OCl
−
]
initial
(M) 0.050 0.050 0.010
Rate (mol L−1 s−1) 3.05 × 10−4 6.20 × 10−4 1.83 × 10−4
Determine the rate law and the rate constant for this reaction.
12.12.0.1: 12.4 Integrated Rate Laws

32.
Describe how graphical methods can be used to determine the order of a reaction and its rate constant from a series of data that
includes the concentration of A at varying times.
33.
Use the data provided to graphically determine the order and rate constant of the following reaction: SO 2 Cl2 ⟶ SO 2 + Cl2
Time (s) 0 5.00 × 103 1.00 × 104 1.50 × 104
[SO2Cl2] (M) 0.100 0.0896 0.0802 0.0719
Time (s) 2.50 × 104 3.00 × 104 4.00 × 104

[SO2Cl2] (M) 0.0577 0.0517 0.0415
34.
Pure ozone decomposes slowly to oxygen, 2O3 (g) ⟶ 3O2 (g). Use the data provided in a graphical method and determine the
order and rate constant of the reaction.
Time (h) 0 2.0 × 103 7.6 × 103 1.00 × 104
[O3] (M) 1.00 × 10−5 4.98 × 10−6 2.07 × 10−6 1.66 × 10−6
Time (h) 1.23 × 104 1.43 × 104 1.70 × 104
[O3] (M) 1.39 × 10−6 1.22 × 10−6 1.05 × 10−6
35.
From the given data, use a graphical method to determine the order and rate constant of the following reaction:
2X ⟶ Y + Z
Time (s) 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0
[X] (M) 0.0990 0.0497 0.0332 0.0249 0.0200 0.0166 0.0143 0.0125
36.
What is the half-life for the first-order decay of phosphorus-32? (
32
15
P ⟶
32
16
S+e
−
) The rate constant for the decay is 4.85 ×
10−2 day−1.
37.
What is the half-life for the first-order decay of carbon-14? (
14
6
C ⟶
14
7
N+e
−
) The rate constant for the decay is 1.21 × 10−4
year−1.
38.
What is the half-life for the decomposition of NOCl when the concentration of NOCl is 0.15 M? The rate constant for this second-
order reaction is 8.0 × 10−8 L mol−1 s−1.
39.
What is the half-life for the decomposition of O3 when the concentration of O3 is 2.35 × 10−6 M? The rate constant for this second-
order reaction is 50.4 L mol−1 h−1.
40.
The reaction of compound A to give compounds C and D was found to be second-order in A. The rate constant for the reaction
was determined to be 2.42 L mol−1 s−1. If the initial concentration is 0.500 mol/L, what is the value of t1/2?
41.
The half-life of a reaction of compound A to give compounds D and E is 8.50 min when the initial concentration of A is 0.150 M.
How long will it take for the concentration to drop to 0.0300 M if the reaction is (a) first order with respect to A or (b) second order
with respect to A?
42.
Some bacteria are resistant to the antibiotic penicillin because they produce penicillinase, an enzyme with a molecular weight of 3
4
× 10 g/mol that converts penicillin into inactive molecules. Although the kinetics of enzyme-catalyzed reactions can be complex,
at low concentrations this reaction can be described by a rate law that is first order in the catalyst (penicillinase) and that also

involves the concentration of penicillin. From the following data: 1.0 L of a solution containing 0.15 µg (0.15 × 10−6 g) of
penicillinase, determine the order of the reaction with respect to penicillin and the value of the rate constant.
[Penicillin] (M) Rate (mol L−1 min−1)
2.0 × 10−6 1.0 × 10−10
3.0 × 10−6 1.5 × 10−10
4.0 × 10−6 2.0 × 10−10
43.
Both technetium-99 and thallium-201 are used to image heart muscle in patients with suspected heart problems. The half-lives are 6
h and 73 h, respectively. What percent of the radioactivity would remain for each of the isotopes after 2 days (48 h)?
44.
There are two molecules with the formula C3H6. Propene, CH CH = CH
3 2, is the monomer of the polymer polypropylene, which
is used for indoor-outdoor carpets. Cyclopropane is used as an anesthetic:
When heated to 499 °C, cyclopropane rearranges (isomerizes) and forms propene with a rate constant of
5.95 × 10−4 s−1. What is the half-life of this reaction? What fraction of the cyclopropane remains after 0.75 h at 499 °C?
45.
Fluorine-18 is a radioactive isotope that decays by positron emission to form oxygen-18 with a half-life of 109.7 min. (A positron
is a particle with the mass of an electron and a single unit of positive charge; the equation is F ⟶ O + e) Physicians use
18
9
18
8 +1
0
18
F to study the brain by injecting a quantity of fluoro-substituted glucose into the blood of a patient. The glucose accumulates in
the regions where the brain is active and needs nourishment.
(a) What is the rate constant for the decomposition of fluorine-18?
(b) If a sample of glucose containing radioactive fluorine-18 is injected into the blood, what percent of the radioactivity will remain
after 5.59 h?
(c) How long does it take for 99.99% of the 18F to decay?
46.
Suppose that the half-life of steroids taken by an athlete is 42 days. Assuming that the steroids biodegrade by a first-order process,
how long would it take for 1
64
of the initial dose to remain in the athlete’s body?
47.
Recently, the skeleton of King Richard III was found under a parking lot in England. If tissue samples from the skeleton contain
about 93.79% of the carbon-14 expected in living tissue, what year did King Richard III die? The half-life for carbon-14 is 5730
years.
48.
Nitroglycerine is an extremely sensitive explosive. In a series of carefully controlled experiments, samples of the explosive were
heated to 160 °C and their first-order decomposition studied. Determine the average rate constants for each experiment using the
following data:
Initial [C3H5N3O9] (M) 4.88 3.52 2.29 1.81 5.33 4.05 2.95 1.72

t (s) 300 300 300 300 180 180 180 180
% Decomposed 52.0 52.9 53.2 53.9 34.6 35.9 36.0 35.4
49.
For the past 10 years, the unsaturated hydrocarbon 1,3-butadiene (CH = CH– CH = CH ) has ranked 38th among the top 50
2 2
industrial chemicals. It is used primarily for the manufacture of synthetic rubber. An isomer exists also as cyclobutene:
The isomerization of cyclobutene to butadiene is first-order and the rate constant has been measured as 2.0 × 10−4 s−1 at 150 °C in
a 0.53-L flask. Determine the partial pressure of cyclobutene and its concentration after 30.0 minutes if an isomerization reaction is
carried out at 150 °C with an initial pressure of 55 torr.
12.12.0.1: 12.5 Collision Theory

50.
Chemical reactions occur when reactants collide. What are two factors that may prevent a collision from producing a chemical
reaction?
51.
When every collision between reactants leads to a reaction, what determines the rate at which the reaction occurs?
52.
What is the activation energy of a reaction, and how is this energy related to the activated complex of the reaction?
53.
Account for the relationship between the rate of a reaction and its activation energy.
54.
Describe how graphical methods can be used to determine the activation energy of a reaction from a series of data that includes the
rate of reaction at varying temperatures.
55.
How does an increase in temperature affect rate of reaction? Explain this effect in terms of the collision theory of the reaction rate.
56.
The rate of a certain reaction doubles for every 10 °C rise in temperature.
(a) How much faster does the reaction proceed at 45 °C than at 25 °C?
(b) How much faster does the reaction proceed at 95 °C than at 25 °C?
57.
In an experiment, a sample of NaClO3 was 90% decomposed in 48 min. Approximately how long would this decomposition have
taken if the sample had been heated 20 °C higher? (Hint: Assume the rate doubles for each 10 °C rise in temperature.)
58.
The rate constant at 325 °C for the decomposition reaction C H ⟶ 4 8 2C2 H4 is 6.1 × 10−8 s−1, and the activation energy is 261
kJ per mole of C4H8. Determine the frequency factor for the reaction.
59.

The rate constant for the decomposition of acetaldehyde, CH3CHO, to methane, CH4, and carbon monoxide, CO, in the gas phase
is 1.1 × 10−2 L mol−1 s−1 at 703 K and 4.95 L mol−1 s−1 at 865 K. Determine the activation energy for this decomposition.
60.
An elevated level of the enzyme alkaline phosphatase (ALP) in human serum is an indication of possible liver or bone disorder.
The level of serum ALP is so low that it is very difficult to measure directly. However, ALP catalyzes a number of reactions, and
its relative concentration can be determined by measuring the rate of one of these reactions under controlled conditions. One such
reaction is the conversion of p-nitrophenyl phosphate (PNPP) to p-nitrophenoxide ion (PNP) and phosphate ion. Control of
temperature during the test is very important; the rate of the reaction increases 1.47 times if the temperature changes from 30 °C to
37 °C. What is the activation energy for the ALP–catalyzed conversion of PNPP to PNP and phosphate?
61.
In terms of collision theory, to which of the following is the rate of a chemical reaction proportional?
(a) the change in free energy per second
(b) the change in temperature per second
(c) the number of collisions per second
(d) the number of product molecules
62.
Hydrogen iodide, HI, decomposes in the gas phase to produce hydrogen, H2, and iodine, I2. The value of the rate constant, k, for the
reaction was measured at several different temperatures and the data are shown here:
Temperature (K) k (L mol−1 s−1)
555 6.23 × 10−7
575 2.42 × 10−6
645 1.44 × 10−4
700 2.01 × 10−3
What is the value of the activation energy (in kJ/mol) for this reaction?
63.
The element Co exists in two oxidation states, Co(II) and Co(III), and the ions form many complexes. The rate at which one of the
complexes of Co(III) was reduced by Fe(II) in water was measured. Determine the activation energy of the reaction from the
following data:
T (K) k (s−1)
293 0.054
298 0.100
64.
The hydrolysis of the sugar sucrose to the sugars glucose and fructose,
C12 H22 O11 + H2 O ⟶ C6 H12 O6 + C6 H12 O6
follows a first-order rate law for the disappearance of sucrose: rate = k[C12H22O11] (The products of the reaction, glucose and
fructose, have the same molecular formulas but differ in the arrangement of the atoms in their molecules.)
(a) In neutral solution, k = 2.1 × 10−11 s−1 at 27 °C and 8.5 × 10−11 s−1 at 37 °C. Determine the activation energy, the frequency
factor, and the rate constant for this equation at 47 °C (assuming the kinetics remain consistent with the Arrhenius equation at this

temperature).
(b) When a solution of sucrose with an initial concentration of 0.150 M reaches equilibrium, the concentration of sucrose is 1.65 ×
10−7 M. How long will it take the solution to reach equilibrium at 27 °C in the absence of a catalyst? Because the concentration of
sucrose at equilibrium is so low, assume that the reaction is irreversible.
(c) Why does assuming that the reaction is irreversible simplify the calculation in part (b)?
65.
Use the PhET Reactions & Rates interactive simulation to simulate a system. On the “Single collision” tab of the simulation applet,
enable the “Energy view” by clicking the “+” icon. Select the first A + BC ⟶ AB + C reaction (A is yellow, B is purple, and
C is navy blue). Using the “straight shot” default option, try launching the A atom with varying amounts of energy. What changes
when the Total Energy line at launch is below the transition state of the Potential Energy line? Why? What happens when it is
above the transition state? Why?
66.
Use the PhET Reactions & Rates interactive simulation to simulate a system. On the “Single collision” tab of the simulation applet,
enable the “Energy view” by clicking the “+” icon. Select the first A + BC ⟶ AB + C reaction (A is yellow, B is purple, and
C is navy blue). Using the “angled shot” option, try launching the A atom with varying angles, but with more Total energy than the
transition state. What happens when the A atom hits the BC molecule from different directions? Why?
12.12.0.1: 12.6 Reaction Mechanisms

67.
Why are elementary reactions involving three or more reactants very uncommon?
68.
In general, can we predict the effect of doubling the concentration of A on the rate of the overall reaction A + B ⟶ C ? Can we
predict the effect if the reaction is known to be an elementary reaction?
69.
Define these terms:
(a) unimolecular reaction
(b) bimolecular reaction
(c) elementary reaction
(d) overall reaction
70.
What is the rate law for the elementary termolecular reaction A + 2B ⟶ products? For 3A ⟶ products?
71.
Given the following reactions and the corresponding rate laws, in which of the reactions might the elementary reaction and the
overall reaction be the same?
(a) Cl2 + CO ⟶ Cl2 CO
3/2
rate = k[ Cl2 ] [CO]
(b) PCl3 + Cl2 ⟶ PCl5
rate = k [ PCl3 ] [ Cl2 ]
(c) 2NO + H2 ⟶ N2 + H2 O2
rate = k [NO] [ H2 ]
(d) 2NO + O2 ⟶ 2 NO2
2
rate = k[NO] [ O2 ]
(e) NO + O3 ⟶ NO2 + O2
rate = k [NO] [ O3 ]

72.
Write the rate law for each of the following elementary reactions:
sunlight
(a) O 3 −−−−→ O2 + O
(b) O 3 + Cl ⟶ O2 + ClO
(c) ClO + O ⟶ Cl + O2
(d) O 3 + NO ⟶ NO2 + O2
(e) NO 2 + O ⟶ NO + O2
73.
Nitrogen monoxide, NO, reacts with hydrogen, H2, according to the following equation:
2NO + 2 H2 ⟶ N2 + 2 H2 O
What would the rate law be if the mechanism for this reaction were:
2NO + H2 ⟶ N2 + H2 O2 (slow)
H2 O2 + H2 ⟶ 2 H2 O (fast)
74.
Experiments were conducted to study the rate of the reaction represented by this equation.2
2NO(g) + 2 H2 (g) ⟶ N2 (g) + 2 H2 O(g)
Initial concentrations and rates of reaction are given here.
Experiment Initial Concentration [NO] (mol Initial Concentration, [H2] (mol L−1 Initial Rate of Formation of N2 (mol L−1
L−1) min−1) min−1)
1 0.0060 0.0010 1.8 × 10−4
2 0.0060 0.0020 3.6 × 10−4
3 0.0010 0.0060 0.30 × 10−4
4 0.0020 0.0060 1.2 × 10−4
Consider the following questions:

(a) Determine the order for each of the reactants, NO and H2, from the data given and show your reasoning.
(b) Write the overall rate law for the reaction.
(c) Calculate the value of the rate constant, k, for the reaction. Include units.
(d) For experiment 2, calculate the concentration of NO remaining when exactly one-half of the original amount of H2 had been
consumed.
(e) The following sequence of elementary steps is a proposed mechanism for the reaction.
Step 1: NO + NO ⇌ N2 O2
Step 2: N 2 O2 + H2 ⇌ H2 O + N2 O
Step 3: N 2O + H2 ⇌ N2 + H2 O
Based on the data presented, which of these is the rate determining step? Show that the mechanism is consistent with the observed
rate law for the reaction and the overall stoichiometry of the reaction.
75.
The reaction of CO with Cl2 gives phosgene (COCl2), a nerve gas that was used in World War I. Use the mechanism shown here to
complete the following exercises:

Cl2 (g) ⇌ 2Cl(g) (fast, k1 represents the forward rate constant, k−1 the reverse rate constant)
CO(g) + Cl(g) ⟶ COCl(g) (slow, k2 the rate constant)
COCl(g) + Cl(g) ⟶ COCl (g) (fast, k3 the rate constant)
2
(a) Write the overall reaction.

(b) Identify all intermediates.
(c) Write the rate law for each elementary reaction.
(d) Write the overall rate law expression.
12.12.0.1: 12.7 Catalysis

76.
Account for the increase in reaction rate brought about by a catalyst.
77.
Compare the functions of homogeneous and heterogeneous catalysts.
78.
Consider this scenario and answer the following questions: Chlorine atoms resulting from decomposition of chlorofluoromethanes,
such as CCl2F2, catalyze the decomposition of ozone in the atmosphere. One simplified mechanism for the decomposition is:
sunlight
O3 −−−−→ O2 + O
O3 + Cl ⟶ O2 + ClO
ClO + O ⟶ Cl + O2
(a) Explain why chlorine atoms are catalysts in the gas-phase transformation:
2 O3 ⟶ 3 O2
(b) Nitric oxide is also involved in the decomposition of ozone by the mechanism:
sunlight
O3 −−−−→ O2 + O
O3 + NO ⟶ NO2 + O2
NO2 + O ⟶ NO + O2
Is NO a catalyst for the decomposition? Explain your answer.

79.
For each of the following pairs of reaction diagrams, identify which of the pair is catalyzed:
(a)

(b)
80.
For each of the following pairs of reaction diagrams, identify which of the pairs is catalyzed:
(a)
(b)
81.
For each of the following reaction diagrams, estimate the activation energy (Ea) of the reaction:

(a)
(b)
82.
For each of the following reaction diagrams, estimate the activation energy (Ea) of the reaction:
(a)
(b)

83.
Assuming the diagrams in Exercise 12.81 represent different mechanisms for the same reaction, which of the reactions has the
faster rate?
84.
Consider the similarities and differences in the two reaction diagrams shown in Exercise 12.82. Do these diagrams represent two
different overall reactions, or do they represent the same overall reaction taking place by two different mechanisms? Explain your
answer.
12.12.0.1: Footnotes
2This question is taken from the Chemistry Advanced Placement Examination and is used with the permission of the

CHAPTER OVERVIEW
13: Fundamental Equilibrium Concepts

General Chemistry
In this chapter, you will learn how to predict the position of the balance and the yield of a product of a reaction under specific
conditions, how to change a reaction's conditions to increase or reduce yield, and how to evaluate an equilibrium system's reaction
to disturbances.
13.1: Introduction
13.6: Key Terms
13.7: Key Equations
13.8: Summary
13.9: Exercises
This page titled 13: Fundamental Equilibrium Concepts is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by
1
13.1: Introduction
Figure 13.1 Transport of carbon dioxide in the body involves several reversible chemical reactions, including hydrolysis and acid
ionization (among others).

13.1 Chemical Equilibria
13.2 Equilibrium Constants
13.3 Shifting Equilibria: Le Châtelier’s Principle
13.4 Equilibrium Calculations
Imagine a beach populated with sunbathers and swimmers. As those basking in the sun get too hot, they enter the surf to swim and
cool off. As the swimmers tire, they return to the beach to rest. If the rate at which sunbathers enter the surf were to equal the rate at
which swimmers return to the sand, then the numbers (though not the identities) of sunbathers and swimmers would remain
constant. This scenario illustrates a dynamic phenomenon known as equilibrium, in which opposing processes occur at equal rates.
Chemical and physical processes are subject to this phenomenon; these processes are at equilibrium when the forward and reverse
reaction rates are equal. Equilibrium systems are pervasive in nature; the various reactions involving carbon dioxide dissolved in
blood are examples (see Figure 13.1). This chapter provides a thorough introduction to the essential aspects of chemical equilibria.


Describe the nature of equilibrium systems
Explain the dynamic nature of a chemical equilibrium
The convention for writing chemical equations involves placing reactant formulas on the left side of a reaction arrow and product
formulas on the right side. By this convention, and the definitions of “reactant” and “product,” a chemical equation represents the
reaction in question as proceeding from left to right. Reversible reactions, however, may proceed in both forward (left to right) and
reverse (right to left) directions. When the rates of the forward and reverse reactions are equal, the concentrations of the reactant
and product species remain constant over time and the system is at equilibrium. The relative concentrations of reactants and
products in equilibrium systems vary greatly; some systems contain mostly products at equilibrium, some contain mostly reactants,
and some contain appreciable amounts of both.
Figure 13.2 illustrates fundamental equilibrium concepts using the reversible decomposition of colorless dinitrogen tetroxide to
yield brown nitrogen dioxide, an elementary reaction described by the equation:
N2 O4 (g) ⇌ 2 NO2 (g)
Note that a special double arrow is used to emphasize the reversible nature of the reaction.

Figure 13.2 (a) A sealed tube containing colorless N2O4 darkens as it decomposes to yield brown NO2. (b) Changes in
concentration over time as the decomposition reaction achieves equilibrium. (c) At equilibrium, the forward and reverse reaction
rates are equal.
For this elementary process, rate laws for the forward and reverse reactions may be derived directly from the reaction
stoichiometry:
ratef = kf [ N2 O4 ]
2
rater = kr [ NO2 ]
As the reaction begins (t = 0), the concentration of the N2O4 reactant is finite and that of the NO2 product is zero, so the forward
reaction proceeds at a finite rate while the reverse reaction rate is zero. As time passes, N2O4 is consumed and its concentration
falls, while NO2 is produced and its concentration increases (Figure 13.2b). The decreasing concentration of the reactant slows the
forward reaction rate, and the increasing product concentration speeds the reverse reaction rate (Figure 13.2c). This process
continues until the forward and reverse reaction rates become equal, at which time the reaction has reached equilibrium, as
characterized by constant concentrations of its reactants and products (shaded areas of Figure 13.2b and Figure 13.2c). It’s
important to emphasize that chemical equilibria are dynamic; a reaction at equilibrium has not “stopped,” but is proceeding in the
forward and reverse directions at the same rate. This dynamic nature is essential to understanding equilibrium behavior as
discussed in this and subsequent chapters of the text.

Figure 13.3 A two-person juggling act illustrates the dynamic aspect of chemical equilibria. Each person is throwing and catching
clubs at the same rate, and each holds a (approximately) constant number of clubs.
Physical changes, such as phase transitions, are also reversible and may establish equilibria. This concept was introduced in another
chapter of this text through discussion of the vapor pressure of a condensed phase (liquid or solid). As one example, consider the
vaporization of bromine:
Br 2 (l) ⇌ Br 2 (g)
When liquid bromine is added to an otherwise empty container and the container is sealed, the forward process depicted above
(vaporization) will commence and continue at a roughly constant rate as long as the exposed surface area of the liquid and its
temperature remain constant. As increasing amounts of gaseous bromine are produced, the rate of the reverse process
(condensation) will increase until it equals the rate of vaporization and equilibrium is established. A photograph showing this phase
transition equilibrium is provided in Figure 13.4.

Figure 13.4 A sealed tube containing an equilibrium mixture of liquid and gaseous bromine. (credit: http://images-of-
elements.com/bromine.php)
This page titled 13.2: Chemical Equilibria is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source


Derive reaction quotients from chemical equations representing homogeneous and heterogeneous reactions
Calculate values of reaction quotients and equilibrium constants, using concentrations and pressures
Relate the magnitude of an equilibrium constant to properties of the chemical system
The status of a reversible reaction is conveniently assessed by evaluating its reaction quotient (Q). For a reversible reaction
described by
mA + nB+ ⇌ xC + yD
the reaction quotient is derived directly from the stoichiometry of the balanced equation as
x y
[C] [D]
Qc =
m n
[A] [B]
where the subscript c denotes the use of molar concentrations in the expression. If the reactants and products are gaseous, a reaction
quotient may be similarly derived using partial pressures:
x y
PC PD
Qp =
m n
PA PB
Note that the reaction quotient equations above are a simplification of more rigorous expressions that use relative values for
concentrations and pressures rather than absolute values. These relative concentration and pressure values are dimensionless (they
have no units); consequently, so are the reaction quotients. For purposes of this introductory text, it will suffice to use the simplified
equations and to disregard units when computing Q. In most cases, this will introduce only modest errors in calculations involving
reaction quotients.
13.3.0.1: Example 13.1

13.3.0.0.1: Writing Reaction Quotient Expressions
Write the concentration-based reaction quotient expression for each of the following reactions:
(a) 3O 2 (g) ⇌ 2 O3 (g)
(b) N 2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)
(c) 4NH 3 (g) + 7 O2 (g) ⇌ 4 NO2 (g) + 6 H2 O(g)
2
[ O3 ]
(a) Q c =
3
[ O2 ]
2
[ NH3 ]
(b) Q c =
3
[ N2 ] [ H2 ]
4 6
[ NO2 ] [ H2 O]
(c) Q c =
4 7
[ NH3 ] [ O2 ]

Write the concentration-based reaction quotient expression for each of the following reactions:
(a) 2SO 2 (g) + O2 (g) ⇌ 2 SO 3 (g)
(b) C 4 H8 (g) ⇌ 2 C2 H4 (g)
(c) 2C 4 H10 (g) + 13 O2 (g) ⇌ 8 CO2 (g) + 10 H2 O(g)
13.3.0.1: Answer:

2 2 8 10
[ SO 3 ] [ C2 H4 ] [ CO2 ] [ H2 O]
(a) Q c = 2
; (b) Q
c =
[ C4 H8 ]
; (c) Q
c = 2 13
[ SO 2 ] [ O2 ] [ C4 H10 ] [ O2 ]
Figure 13.5 Changes in concentrations and Qc for a chemical equilibrium achieved beginning with (a) a mixture of reactants only
and (b) products only.
The numerical value of Q varies as a reaction proceeds towards equilibrium; therefore, it can serve as a useful indicator of the
reaction’s status. To illustrate this point, consider the oxidation of sulfur dioxide:
2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
Two different experimental scenarios are depicted in Figure 13.5, one in which this reaction is initiated with a mixture of reactants
only, SO2 and O2, and another that begins with only product, SO3. For the reaction that begins with a mixture of reactants only, Q is
initially equal to zero:
2 2
[SO 3 ] 0
Qc = = =0
2 2
[ SO 2 ] [ O2 ] [ SO 2 ] [ O2 ]
As the reaction proceeds toward equilibrium in the forward direction, reactant concentrations decrease (as does the denominator of
Qc), product concentration increases (as does the numerator of Qc), and the reaction quotient consequently increases. When

equilibrium is achieved, the concentrations of reactants and product remain constant, as does the value of Qc.
If the reaction begins with only product present, the value of Qc is initially undefined (immeasurably large, or infinite):
2 2
[SO 3 ] [SO 3 ]
Qc = = → ∞
2
0
[ SO 2 ] [ O2 ]
In this case, the reaction proceeds toward equilibrium in the reverse direction. The product concentration and the numerator of Qc
decrease with time, the reactant concentrations and the denominator of Qc increase, and the reaction quotient consequently
decreases until it becomes constant at equilibrium.
The constant value of Q exhibited by a system at equilibrium is called the equilibrium constant, K:
K ≡ Q at equilibrium
Comparison of the data plots in Figure 13.5 shows that both experimental scenarios resulted in the same value for the equilibrium
constant. This is a general observation for all equilibrium systems, known as the law of mass action: At a given temperature, the
reaction quotient for a system at equilibrium is constant.
13.3.0.1: Example 13.2

13.3.0.0.1: Evaluating a Reaction Quotient
Gaseous nitrogen dioxide forms dinitrogen tetroxide according to this equation:
2 NO2 (g) ⇌ N2 O4 (g)
When 0.10 mol NO2 is added to a 1.0-L flask at 25 °C, the concentration changes so that at equilibrium, [NO2] = 0.016 M and
[N2O4] = 0.042 M.
(a) What is the value of the reaction quotient before any reaction occurs?
(b) What is the value of the equilibrium constant for the reaction?
As for all equilibrium calculations in this text, use the simplified equations for Q and K and disregard any concentration or
pressure units, as noted previously in this section.
(a) Before any product is formed, [NO 2] =
0.10 mol
1.0 L
= 0.10 M , and [N2O4] = 0 M. Thus,
[ N2 O4 ] 0
Qc = = =0
2 2
[ NO2 ] 0.10
The equilibrium constant is 1.6 × 102.

[ N2 O4 ]
(b) At equilibrium, K c = Qc = 2
=
0.042
2
= 1.6 × 10 .
2
[ NO2 ] 0.016

For the reaction 2SO (g) + O (g) ⇌ 2SO (g), the concentrations at equilibrium are [SO2] = 0.90 M, [O2] = 0.35 M, and
2 2 3
[SO3] = 1.1 M. What is the value of the equilibrium constant, Kc?
13.3.0.1: Answer:
Kc = 4.3
By its definition, the magnitude of an equilibrium constant explicitly reflects the composition of a reaction mixture at equilibrium,
and it may be interpreted with regard to the extent of the forward reaction. A reaction exhibiting a large K will reach equilibrium
when most of the reactant has been converted to product, whereas a small K indicates the reaction achieves equilibrium after very
little reactant has been converted. It’s important to keep in mind that the magnitude of K does not indicate how rapidly or slowly
equilibrium will be reached. Some equilibria are established so quickly as to be nearly instantaneous, and others so slowly that no
perceptible change is observed over the course of days, years, or longer.
The equilibrium constant for a reaction can be used to predict the behavior of mixtures containing its reactants and/or products. As
demonstrated by the sulfur dioxide oxidation process described above, a chemical reaction will proceed in whatever direction is

necessary to achieve equilibrium. Comparing Q to K for an equilibrium system of interest allows prediction of what reaction
(forward or reverse), if any, will occur.
To further illustrate this important point, consider the reversible reaction shown below:
CO(g) + H2 O(g) ⇌ CO2 (g) + H2 (g) Kc = 0.640 T = 800 °C
The bar charts in Figure 13.6 represent changes in reactant and product concentrations for three different reaction mixtures. The
reaction quotients for mixtures 1 and 3 are initially lesser than the reaction’s equilibrium constant, so each of these mixtures will
experience a net forward reaction to achieve equilibrium. The reaction quotient for mixture 2 is initially greater than the
equilibrium constant, so this mixture will proceed in the reverse direction until equilibrium is established.
Figure 13.6 Compositions of three mixtures before (Qc ≠ Kc) and after (Qc = Kc) equilibrium is established for the reaction
CO(g) + H2 O(g) ⇌ CO2 (g) + H2 (g).
13.3.0.1: Example 13.3

13.3.0.0.1: Predicting the Direction of Reaction
Given here are the starting concentrations of reactants and products for three experiments involving this reaction:
CO(g) + H2 O(g) ⇌ CO2 (g) + H2 (g)
Kc = 0.64
Determine in which direction the reaction proceeds as it goes to equilibrium in each of the three experiments shown.
Reactants/Products Experiment 1 Experiment 2 Experiment 3
[CO]i 0.020 M 0.011 M 0.0094 M
[H2O]i 0.020 M 0.0011 M 0.0025 M
[CO2]i 0.0040 M 0.037 M 0.0015 M
[H2]i 0.0040 M 0.046 M 0.0076 M

Experiment 1:
[ CO2 ] [ H2 ] (0.0040) (0.0040)
Qc = = = 0.040.
[CO] [ H2 O] (0.020) (0.020)
Qc < Kc (0.040 < 0.64)

The reaction will proceed in the forward direction.
Experiment 2:
[ CO2 ] [ H2 ] (0.037) (0.046)
2
Qc = = = 1.4 × 10
[CO] [ H2 O] (0.011) (0.0011)
Qc > Kc (140 > 0.64)

The reaction will proceed in the reverse direction.
Experiment 3:
[ CO2 ] [ H2 ] (0.0015) (0.0076)
Qc = = = 0.48
[CO] [ H2 O] (0.0094) (0.0025)
Qc < Kc (0.48 < 0.64)

The reaction will proceed in the forward direction.
Calculate the reaction quotient and determine the direction in which each of the following reactions will proceed to reach
equilibrium.
(a) A 1.00-L flask containing 0.0500 mol of NO(g), 0.0155 mol of Cl2(g), and 0.500 mol of NOCl:
4
2NO(g) + Cl2 (g) ⇌ 2NOCl(g) Kc = 4.6 × 10
(b) A 5.0-L flask containing 17 g of NH3, 14 g of N2, and 12 g of H2:

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) Kc = 0.060
(c) A 2.00-L flask containing 230 g of SO3(g):

2 SO 3 (g) ⇌ 2 SO 2 (g) + O2 (g) Kc = 0.230
13.3.0.1: Answer:
(a) Qc = 6.45 × 103, forward. (b) Qc = 0.23, reverse. (c) Qc = 0, forward.
13.3.0.1: Homogeneous Equilibria

A homogeneous equilibrium is one in which all reactants and products (and any catalysts, if applicable) are present in the same
phase. By this definition, homogeneous equilibria take place in solutions. These solutions are most commonly either liquid or
gaseous phases, as shown by the examples below:
[ C2 H2 Br4 ]
C2 H2 (aq) + 2 Br 2 (aq) ⇌ C2 H2 Br 4 (aq) Kc =
2
[ C2 H2 ] [ Br2 ]
−
[ I3 ]
− −
I2 (aq) + I (aq) ⇌ I3 (aq) Kc = −
[ I2 ][ I ]
+ −
[ H3 O ][F ]
+ −
HF(aq) + H2 O(l) ⇌ H3 O (aq) + F (aq) Kc =
[HF]
+ −
[ NH4 ][OH ]
+ −
NH3 (aq) + H2 O(l) ⇌ NH4 (aq) + OH (aq) Kc =
[ NH3 ]
These examples all involve aqueous solutions, those in which water functions as the solvent. In the last two examples, water also
functions as a reactant, but its concentration is not included in the reaction quotient. The reason for this omission is related to the

more rigorous form of the Q (or K) expression mentioned previously in this chapter, in which relative concentrations for liquids
and solids are equal to 1 and needn’t be included. Consequently, reaction quotients include concentration or pressure terms only for
gaseous and solute species.
The equilibria below all involve gas-phase solutions:
[ C2 H4 ] [ H2 ]
C2 H6 (g) ⇌ C2 H4 (g) + H2 (g) Kc =
[ C2 H6 ]
2
[ O3 ]
3 O2 (g) ⇌ 2 O3 (g) Kc =
3
[ O2 ]
2
[ NH3 ]
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) Kc =
3
[ N2 ] [ H2 ]
3 4
[ CO2 ] [ H2 O]
C3 H8 (g) + 5 O2 (g) ⇌ 3 CO2 (g) + 4 H2 O(g) Kc =
5
[ C3 H8 ] [ O2 ]
For gas-phase solutions, the equilibrium constant may be expressed in terms of either the molar concentrations (Kc) or partial
pressures (Kp) of the reactants and products. A relation between these two K values may be simply derived from the ideal gas
equation and the definition of molarity:
P V = nRT
n
P =( ) RT
V
= M RT
where P is partial pressure, V is volume, n is molar amount, R is the gas constant, T is temperature, and M is molar concentration.
For the gas-phase reaction mA + nB ⇌ xC + yD:
x y
(PC ) (PD )
KP =
m n
(PA ) (PB )
x y
([C] × RT ) ([D] × RT )
=
m n
([A] × RT ) ([B] × RT )
x y x+y
[C] [D] (RT )
= ×
m n m+n
[A] [B] (RT )
(x+y)−(m+n)
= Kc (RT )
Δn
= Kc (RT )
And so, the relationship between Kc and KP is

Δn
KP = Kc (RT )
where Δn is the difference in the molar amounts of product and reactant gases, in this case:
Δn = (x+y) − (m+n)
13.3.0.1: Example 13.4

13.3.0.0.1: Calculation of KP
Write the equations relating Kc to KP for each of the following reactions:
(a) C2 H6 (g) ⇌ C2 H4 (g) + H2 (g)
(b) CO(g) + H 2 O(g) ⇌ CO2 (g) + H2 (g)
(c) N 2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)
(d) Kc is equal to 0.28 for the following reaction at 900 °C:

CS2 (g) + 4 H2 (g) ⇌ CH4 (g) + 2 H2 S(g)

What is KP at this temperature?
(a) Δn = (2) − (1) = 1
KP = Kc (RT)Δn = Kc (RT)1 = Kc (RT)
(b) Δn = (2) − (2) = 0
KP = Kc (RT)Δn = Kc (RT)0 = Kc
(c) Δn = (2) − (1 + 3) = −2
KP = Kc (RT)Δn = Kc (RT)−2 =
Kc
2
(RT )
(d) KP = Kc (RT)Δn = (0.28)[(0.0821)(1173)]−2 = 3.0 × 10−5

Write the equations relating Kc to KP for each of the following reactions:
(a) 2SO 2 (g) + O2 (g) ⇌ 2 SO 3 (g)
(b) N 2 O4 (g) ⇌ 2 NO2 (g)
(c) C3 H8 (g) + 5 O2 (g) ⇌ 3 CO2 (g) + 4 H2 O(g)
(d) At 227 °C, the following reaction has Kc = 0.0952:

CH3 OH(g) ⇌ CO(g) + 2 H2 (g)
What would be the value of KP at this temperature?
13.3.0.1: Answer:
(a) KP = Kc (RT)−1; (b) KP = Kc (RT); (c) KP = Kc (RT); (d) 160 or 1.6 × 102
13.3.0.1: Heterogeneous Equilibria

A heterogeneous equilibrium involves reactants and products in two or more different phases, as illustrated by the following
examples:
2+ − 2+ − 2
PbCl2 (s) ⇌ Pb (aq) + 2 Cl (aq) Kc = [ Pb ] [ Cl ]
1
CaO(s) + CO2 (g) ⇌ CaCO3 (s) Kc =
[CO ]
2
[CS2 ]
C(s) + 2S(g) ⇌ CS2 (g) Kc =
2
[S]
Br 2 (l) ⇌ Br 2 (g) Kc = [ Br 2 (g)]
Again, note that concentration terms are only included for gaseous and solute species, as discussed previously.
Two of the above examples include terms for gaseous species only in their equilibrium constants, and so Kp expressions may also
be written:
1
CaO(s) + CO2 (g) ⇌ CaCO3 (s) KP =
PCO
2
PCS
2
C(s) + 2S(g) ⇌ CS2 (g) KP =
2
( PS )
13.3.0.1: Coupled Equilibria

The equilibrium systems discussed so far have all been relatively simple, involving just single reversible reactions. Many systems,
however, involve two or more coupled equilibrium reactions, those which have in common one or more reactant or product species.
Since the law of mass action allows for a straightforward derivation of equilibrium constant expressions from balanced chemical
equations, the K value for a system involving coupled equilibria can be related to the K values of the individual reactions. Three
basic manipulations are involved in this approach, as described below.
1. Changing the direction of a chemical equation essentially swaps the identities of “reactants” and “products,” and so the
equilibrium constant for the reversed equation is simply the reciprocal of that for the forward equation.

[B]
A ⇌ B Kc =
[A]
[A]
B⇌ A Kc' =
[B]
1
Kc' =
Kc
2. Changing the stoichiometric coefficients in an equation by some factor x results in an exponential change in the equilibrium
constant by that same factor:
[B]
A ⇌ B Kc =
[A]
x
[B]
xA ⇌ xB Kc' = x
[A]
x
Kc' = Kc
3. Adding two or more equilibrium equations together yields an overall equation whose equilibrium constant is the mathematical
product of the individual reaction’s K values:
[B]
A ⇌ B Kc1 =
[A]
[C]
B⇌ C Kc2 =
[B]
The net reaction for these coupled equilibria is obtained by summing the two equilibrium equations and canceling any
redundancies:
A+B ⇌ B+C
A+ B ⇌ B +C
[C]
A ⇌ C Kc' =
[A]
Comparing the equilibrium constant for the net reaction to those for the two coupled equilibrium reactions reveals the following
relationship:
[B] [C] [B] [C] [C]

Kc1 Kc2 = × = = = Kc'
[A] [B] [A] [B] [A]
Kc' = Kc1 Kc2
Example 13.5 demonstrates the use of this strategy in describing coupled equilibrium processes.
13.3.0.1: Example 13.5

13.3.0.0.1: Equilibrium Constants for Coupled Reactions
A mixture containing nitrogen, hydrogen, and iodine established the following equilibrium at 400 °C:
2NH3 (g) + 3I2 (g) ⇌ N2 (g) + 6HI(g)
Use the information below to calculate Kc for this reaction.

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) Kc1 = 0.50 at 400 °C
H2 (g) + I2 (g) ⇌ 2HI(g) Kc2 = 50 at 400 °C
The equilibrium equation of interest and its K value may be derived from the equations for the two coupled reactions as
follows.
Reverse the first coupled reaction equation:
1 1
2NH3 (g) ⇌ N2 (g) + 3 H2 (g) Kc1' = = = 2.0
Kc1 0.50
Multiply the second coupled reaction by 3:

3 3 5
3H2 (g) + 3 I2 (g) ⇌ 6HI(g) Kc2' = K = 50 = 1.2 × 10
c2
Finally, add the two revised equations:
2NH3 (g) + 3 H2 (g) + 3 I2 (g) ⇌ N2 (g) + 3 H2 (g) + 6HI(g)
2NH3 (g) + 3 I2 (g) ⇌ N2 (g) + 6HI(g)
5 5
Kc = Kc1' Kc2' = (2.0)(1.2 × 10 ) = 2.5 × 10

Use the provided information to calculate Kc for the following reaction at 550 °C:
H2 (g) + CO2 (g) ⇌ CO(g) + H2 O(g) Kc =?
CoO(s) + CO(g) ⇌ Co(s) + CO2 (g) Kc1 = 490
CoO(s) + H2 (g) ⇌ Co(s) + H2 O(g) Kc1 = 67
13.3.0.1: Answer:
Kc = 0.14
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Describe the ways in which an equilibrium system can be stressed
Predict the response of a stressed equilibrium using Le Châtelier’s principle
A system at equilibrium is in a state of dynamic balance, with forward and reverse reactions taking place at equal rates. If an equilibrium system is subjected to a change in conditions that affects these
reaction rates differently (a stress), then the rates are no longer equal and the system is not at equilibrium. The system will subsequently experience a net reaction in the direction of greater rate (a
shift) that will re-establish the equilibrium. This phenomenon is summarized by Le Châtelier’s principle: if an equilibrium system is stressed, the system will experience a shift in response to the stress
that re-establishes equilibrium.
Reaction rates are affected primarily by concentrations, as described by the reaction’s rate law, and temperature, as described by the Arrhenius equation. Consequently, changes in concentration and
temperature are the two stresses that can shift an equilibrium.
13.4.0.1: Effect of a Change in Concentration

If an equilibrium system is subjected to a change in the concentration of a reactant or product species, the rate of either the forward or the reverse reaction will change. As an example, consider the
equilibrium reaction
H2(g)+I2(g)⇌2HI(g)Kc=50.0at400°CH2(g)+I2(g)⇌2HI(g)Kc=50.0at400°C" role="presentation">H2 (g) + I2 (g) ⇌ 2HI(g) Kc = 50.0 at 400 °C
H2 (g) + I2 (g) ⇌ 2HI(g) Kc = 50.0 at 400 °C
The rate laws for the forward and reverse reactions are
forwardH2(g)+I2(g)→2HI(g)ratef=kf[H2]m[I2]nreverse2HI(g)→H2(g)+I2(g)rater=kr[HI]xforwardH2(g)+I2(g)→2HI(g)ratef=kf[H2]m[I2]nreverse2HI(g)→H2(g)+I2(g)rater=kr[HI]x" ro
m n
f orward H2 (g) + I2 (g) → 2HI(g) ratef = kf [ H2 ] [ I2 ]
x
reverse 2HI(g) → H2 (g) + I2 (g) rater = kr [HI]
When this system is at equilibrium, the forward and reverse reaction rates are equal.
ratef=raterratef=rater" role="presentation">ratef = rater
ratef = rater
If the system is stressed by adding reactant, either H2 or I2, the resulting increase in concentration causes the rate of the forward reaction to increase, exceeding that of the reverse reaction:
ratef>raterratef>rater" role="presentation">ratef > rater
ratef > rater
The system will experience a temporary net reaction in the forward direction to re-establish equilibrium (the equilibrium will shift right). This same shift will result if some product HI is removed
from the system, which decreases the rate of the reverse reaction, again resulting in the same imbalance in rates.
The same logic can be used to explain the left shift that results from either removing reactant or adding product to an equilibrium system. These stresses both result in an increased rate for the reverse
reaction
ratef<raterratef<rater" role="presentation">ratef < rater
ratef < rater
and a temporary net reaction in the reverse direction to re-establish equilibrium.

As an alternative to this kinetic interpretation, the effect of changes in concentration on equilibria can be rationalized in terms of reaction quotients. When the system is at equilibrium,
2
[HI]
Qc=[HI]2[H2][I2]=KcQc=[HI]2[H2][I2]=Kc" role="presentation">Qc = = Kc
[H2 ][I2 ]
2
[HI]
Qc = = Kc
[ H2 ][ I2 ]
If reactant is added (increasing the denominator of the reaction quotient) or product is removed (decreasing the numerator), then Qc < Kc and the equilibrium will shift right. Note that the three
different ways of inducing this stress result in three different changes in the composition of the equilibrium mixture. If H2 is added, the right shift will consume I2 and produce HI as equilibrium is re-
established, yielding a mixture with a greater concentrations of H2 and HI and a lesser concentration of I2 than was present before. If I2 is added, the new equilibrium mixture will have greater
concentrations of I2 and HI and a lesser concentration of H2. Finally, if HI is removed, the concentrations of all three species will be lower when equilibrium is reestablished. Despite these differences
in composition, the value of the equilibrium constant will be the same after the stress as it was before (per the law of mass action). The same logic may be applied for stresses involving removing
reactants or adding product, in which case Qc > Kc and the equilibrium will shift left.
For gas-phase equilibria such as this one, some additional perspectives on changing the concentrations of reactants and products are worthy of mention. The partial pressure P of an ideal gas is
proportional to its molar concentration M,
n P
M=nV=PRTM=nV=PRT" role="presentation">M = =
V RT
n P
M = =
V RT
and so changes in the partial pressures of any reactant or product are essentially changes in concentrations and thus yield the same effects on equilibria. Aside from adding or removing reactant or
product, the pressures (concentrations) of species in a gas-phase equilibrium can also be changed by changing the volume occupied by the system. Since all species of a gas-phase equilibrium occupy
the same volume, a given change in volume will cause the same change in concentration for both reactants and products. In order to discern what shift, if any, this type of stress will induce the
stoichiometry of the reaction must be considered.
At equilibrium, the reaction H2(g) + I2(g) ⇌ 2HI(g) is described by the reaction quotient
2
PHI
QP=PHI2PH2PI2=KpQP=PHI2PH2PI2=Kp" role="presentation">QP = = Kp
PH PI
2 2

2
PHI
QP = = Kp
PH PI
2 2
If the volume occupied by an equilibrium mixture of these species is decreased by a factor of 3, the partial pressures of all three species will be increased by a factor of 3:
Qp'=(3PHI)23PH23PI2=9PHI29PH2PI2=PHI2PH2PI2=QP=KPQP'=QP=KPQp'=(3PHI)23PH23PI2=9PHI29PH2PI2=PHI2PH2PI2=QP=KPQP'=QP=KP" role="presentation">
2
(3P HI)
′
Qp = =
3P H 3P I 9P
2 2
′
QP = QP = KP
2
(3 PHI ) 9P 2
P 2
′ HI HI
Qp = = = = QP = KP
3 PH 3 PI 9PH PI PH PI
2 2 2 2 2 2
′
QP = QP = KP
And so, changing the volume of this gas-phase equilibrium mixture does not result in a shift of the equilibrium.
A similar treatment of a different system, 2NO2(g) ⇌ 2 NO(g) + O2(g), however, yields a different result:
QP=PNO2PO2PNO22QP'=(3PNO)23PO2(3PNO2)2=9PNO23PO29PNO22=27PNO2PO29PNO22=3QP>KPQP'=3QP>KPQP=PNO2PO2PNO22QP'=(3PNO)23PO2(3PNO2)2=9PNO23PO29PN
2
PNO PO
2
QP =
2
PNO
2
2 2 2
(3 PNO ) 3 PO 9 PNO 3 PO 27PNO PO
′ 2 2 2
QP = = = = 3 QP > KP
2 9P 9PNO
2
(3 PNO ) NO
2
2 2 2
′
QP = 3 QP > KP
In this case, the change in volume results in a reaction quotient greater than the equilibrium constant, and so the equilibrium will shift left.
These results illustrate the relationship between the stoichiometry of a gas-phase equilibrium and the effect of a volume-induced pressure (concentration) change. If the total molar amounts of
reactants and products are equal, as in the first example, a change in volume does not shift the equilibrium. If the molar amounts of reactants and products are different, a change in volume will shift
the equilibrium in a direction that better “accommodates” the volume change. In the second example, two moles of reactant (NO2) yield three moles of product (2NO + O2), and so decreasing the
system volume causes the equilibrium to shift left since the reverse reaction produces less gas (2 mol) than the forward reaction (3 mol). Conversely, increasing the volume of this equilibrium system
would result in a shift towards products.

Check out this link to see a dramatic visual demonstration of how equilibrium changes with pressure changes.

13.4.0.0.1: Equilibrium and Soft Drinks
The connection between chemistry and carbonated soft drinks goes back to 1767, when Joseph Priestley (1733–1804) developed a method of infusing water with carbon dioxide to make carbonated
water. Priestley’s approach involved production of carbon dioxide by reacting oil of vitriol (sulfuric acid) with chalk (calcium carbonate).
The carbon dioxide was then dissolved in water, reacting to produce hydrogen carbonate, a weak acid that subsequently ionized to yield bicarbonate and hydrogen ions:
dissolutionCO2(g)⇌CO2(aq)hydrolysisCO2(aq)+H2O(l)⇌H2CO3(aq)ionizationH2CO3(aq)⇌HCO3−(aq)+H+(aq)dissolutionCO2(g)⇌CO2(aq)hydrolysisCO2(aq)+H
dissolution CO2 (g) ⇌ CO2 (aq)
hydrolysis CO2 (aq) + H2 O(l) ⇌ H2 CO3 (aq)
− +
ionization H2 CO3 (aq) ⇌ HCO3 (aq) + H (aq)
These same equilibrium reactions are the basis of today’s soft-drink carbonation process. Beverages are exposed to a high pressure of gaseous carbon dioxide during the process to shift the first
equilibrium above to the right, resulting in desirably high concentrations of dissolved carbon dioxide and, per similar shifts in the other two equilibria, its hydrolysis and ionization products. A bottle
or can is then nearly filled with the carbonated beverage, leaving a relatively small volume of air in the container above the beverage surface (the headspace) before it is sealed. The pressure of carbon
dioxide in the container headspace is very low immediately after sealing, but it rises as the dissolution equilibrium is re-established by shifting to the left. Since the volume of the beverage is
significantly greater than the volume of the headspace, only a relatively small amount of dissolved carbon dioxide is lost to the headspace.
When a carbonated beverage container is opened, a hissing sound is heard as pressurized CO2 escapes from the headspace. This causes the dissolution equilibrium to shift left, resulting in a decrease
in the concentration of dissolved CO2 and subsequent left-shifts of the hydrolysis and ionization equilibria. Fortunately for the consumer, the dissolution equilibrium is usually re-established slowly,
and so the beverage may be enjoyed while its dissolved carbon dioxide concentration remains palatably high. Once the equilibria are re-established, the CO2(aq) concentration will be significantly
lowered, and the beverage acquires a characteristic taste referred to as “flat.”
A bottle of soda sitting on the ground is shown with a large amount of fizz-filled liquid spewing out of the top.
Figure 13.7 Opening a soft-drink bottle lowers the CO2 pressure above the beverage, shifting the dissolution equilibrium and releasing dissolved CO2 from the beverage. (credit: modification of work
by “D Coetzee”/Flickr)
13.4.0.1: Effect of a Change in Temperature

Consistent with the law of mass action, an equilibrium stressed by a change in concentration will shift to re-establish equilibrium without any change in the value of the equilibrium constant, K. When
an equilibrium shifts in response to a temperature change, however, it is re-established with a different relative composition that exhibits a different value for the equilibrium constant.
To understand this phenomenon, consider the elementary reaction
A⇌BA⇌B" role="presentation" style="text-align: center; position: relative;">A ⇌ B
A ⇌ B

Since this is an elementary reaction, the rates laws for the forward and reverse may be derived directly from the balanced equation’s stoichiometry:
ratef = kf [A]
ratef=kf[A]rater=kr[B]ratef=kf[A]rater=kr[B]" role="presentation" style="text-align: center; position: relative;">
rater = kr [B]
ratef = kf [A]
rater = kr [B]
When the system is at equilibrium,

rater=ratefrater=ratef" role="presentation" style="text-align: center; position: relative;">rater = ratef
rater = ratef
Substituting the rate laws into this equality and rearranging gives
kf [A] = kr [B]
kf[A]=kr[B][B][A]=kfkr=Kckf[A]=kr[B][B][A]=kfkr=Kc" role="presentation" style="text-align: center; position: relative;"> [B] kf

= = Kc
[A] kr
kf [A] = kr [B]
[B] kf
= = Kc
[A] kr
The equilibrium constant is seen to be a mathematical function of the rate constants for the forward and reverse reactions. Since the rate constants vary with temperature as described by the Arrhenius
equation, is stands to reason that the equilibrium constant will likewise vary with temperature (assuming the rate constants are affected to different extents by the temperature change). For more
complex reactions involving multistep reaction mechanisms, a similar but more complex mathematical relation exists between the equilibrium constant and the rate constants of the steps in the
mechanism. Regardless of how complex the reaction may be, the temperature-dependence of its equilibrium constant persists.
Predicting the shift an equilibrium will experience in response to a change in temperature is most conveniently accomplished by considering the enthalpy change of the reaction. For example, the
decomposition of dinitrogen tetroxide is an endothermic (heat-consuming) process:
N2O4(g)⇌2NO2(g)ΔH=+57.20kJN2O4(g)⇌2NO2(g)ΔH=+57.20kJ" role="presentation">N2 O4 (g) ⇌ 2 NO2 (g) ΔH = +57.20 kJ
N2 O4 (g) ⇌ 2 NO2 (g) ΔH = +57.20 kJ
For purposes of applying Le Chatelier’s principle, heat (q) may be viewed as a reactant:
heat+N2O4(g)⇌2NO2(g)heat+N2O4(g)⇌2NO2(g)" role="presentation"> heat + N2 O4 (g) ⇌ 2 NO2 (g)
heat + N2 O4 (g) ⇌ 2 NO2 (g)
Raising the temperature of the system is akin to increasing the amount of a reactant, and so the equilibrium will shift to the right. Lowering the system temperature will likewise cause the equilibrium
to shift left. For exothermic processes, heat is viewed as a product of the reaction and so the opposite temperature dependence is observed.
13.4.0.1: Effect of a Catalyst

The kinetics chapter of this text identifies a catalyst as a substance that enables a reaction to proceed via a different mechanism with an accelerated rate. The catalyzed reaction mechanism involves a
lower energy transition state than the uncatalyzed reaction, resulting in a lower activation energy, Ea, and a correspondingly greater rate constant.
To discern the effect of catalysis on an equilibrium system, consider the reaction diagram for a simple one-step (elementary) reaction shown in Figure 13.8. The lowered transition state energy of the
catalyzed reaction results in lowered activation energies for both the forward and the reverse reactions. Consequently, both forward and reverse reactions are accelerated, and equilibrium is achieved
more quickly but without a change in the equilibrium constant.
A graph is shown labeled “Transition state.” The y-axis on the graph is labeled “Energy” and the x-axis is labeled “Extent of Reaction.” Two curves are plotted on the graph. Both start mid-way up the y-axis. The red curve has a steep initial slope as it increases, then reaches its peak where it meets a horizontal dotted line, then
has a steep decline before leveling out. From the initial point to the horizontal line, there is a vertical line with arrows on each end labeled “E subscript a forward.” From the end point to the horizontal line, there is a vertical line with arrows on each end labeled “E subscript a reverse.” The second curve is less steep than the first
and does not reach as high of a peak on the y-axis. It meets a separate horizontal dotted line at its peak, then declines at a similar rate to the first curve before leveling out with the first curve. From the initial point where the slope begins to increase to the horizontal line, there is a vertical line with arrows on each end labeled “E
subscript a forward.” From the end point right as it levels out to the horizontal line, there is a vertical line with arrows on each end labeled “E subscript a reverse.”
Figure 13.8 Reaction diagrams for an elementary process in the absence (red) and presence (blue) of a catalyst. The presence of catalyst lowers the activation energies of both the forward and reverse
reactions but does not affect the value of the equilibrium constant.
An interesting case study highlighting these equilibrium concepts is the industrial production of ammonia, NH3. This substance is among the “top 10” industrial chemicals with regard to production,
with roughly two billion pounds produced annually in the US. Ammonia is used as a chemical feedstock to synthesize a wide range of commercially useful compounds, including fertilizers, plastics,
dyes, and explosives.
Most industrial production of ammonia uses the Haber-Bosch process based on the following equilibrium reaction:
N2(g)+3H2(g)⇌2NH3(g)ΔH=−92.2kJN2(g)+3H2(g)⇌2NH3(g)ΔH=−92.2kJ" role="presentation"> N2 (g) + 3H2 (g) ⇌ 2 NH3 (g) ΔH = −92.2 kJ
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) ΔH = −92.2 kJ
The traits of this reaction present challenges to its use in an efficient industrial process. The equilibrium constant is relatively small (Kp on the order of 10−5 at 25 °C), meaning very little ammonia is
present in an equilibrium mixture. Also, the rate of this reaction is relatively slow at low temperatures. To raise the yield of ammonia, the industrial process is designed to operate under conditions
favoring product formation:
High pressures (concentrations) of reactants are used, ~150−250 atm, to shift the equilibrium right, favoring product formation.
Ammonia is continually removed (collected) from the equilibrium mixture during the process, lowering its concentration and also shifting the equilibrium right.
Although low temperatures favor product formation for this exothermic process, the reaction rate at low temperatures is inefficiently slow. A catalyst is used to accelerate the reaction to reasonable
rates at relatively moderate temperatures (400−500 °C).
A diagram illustrating a typical industrial setup for production of ammonia via the Haber-Bosch process is shown in Figure 13.9.
A diagram is shown that is composed of three main sections. The first section shows an intake pipe labeled with blue arrows and the terms, “N subscript 2, H subscript 2, feed gases,” and “Compressor.” This pipe leads to a large chamber with a turbine in the top section and a coil in the bottom section. From top to bottom, the
sections of this chamber are labeled, “Heat exchanger,” “Catalyst chamber 400 to 500 degrees C,” “Catalyst,” “Heater,” and “Preheated feed gases.” One pipe leads from the top of this chamber with red arrows and is labeled, “N H subscript 3 and unreacted N subscript 2, H subscript 2,” while another pipe leads to the bottom of
the chamber and reads, “Compressor,” and has orange arrows going through it. These two pipes are connected to a square container that is labeled, “Heat exchanger,” and has red arrows going into it from the upper pipe, orange arrows going away from it to the lower pipe and into a third system. The pipes leading into and out of the
heat exchanger are labeled, “Recycled N subscript 2, H subscript 2.” The third system shows a container with an interior zig-zag-shaped pipe that sits on a base that contains a curled pipe on a storage tank. From the top of the image to the bottom are the terms, “N H subscript 3 and unreacted N subscript 2, H subscript 2,”
“Condenser,” “Cold water in,” “Refrigeration,” “N H subscript 3 ( l ),” and “Storage” Blue arrows lead away from the base of this system and into the second system while other blue arrows lead into the system from the right side of the diagram and back out of the same chamber.
Figure 13.9 The figure shows a typical industrial setup for the commercial production of ammonia by the Haber-Bosch process. The process operates under conditions that stress the chemical
equilibrium to favor product formation.
This page titled 13.4: Shifting Equilibria- Le Châtelier’s Principle is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content that was edited to the style and standards
of the LibreTexts platform; a detailed edit history is available upon request.


Identify the changes in concentration or pressure that occur for chemical species in equilibrium systems
Calculate equilibrium concentrations or pressures and equilibrium constants, using various algebraic approaches
Having covered the essential concepts of chemical equilibria in the preceding sections of this chapter, this final section will
demonstrate the more practical aspect of using these concepts and appropriate mathematical strategies to perform various
equilibrium calculations. These types of computations are essential to many areas of science and technology—for example, in the
formulation and dosing of pharmaceutical products. After a drug is ingested or injected, it is typically involved in several chemical
equilibria that affect its ultimate concentration in the body system of interest. Knowledge of the quantitative aspects of these
equilibria is required to compute a dosage amount that will solicit the desired therapeutic effect.
Many of the useful equilibrium calculations that will be demonstrated here require terms representing changes in reactant and
product concentrations. These terms are derived from the stoichiometry of the reaction, as illustrated by decomposition of
ammonia:
2 NH3 (g) ⇌ N2 (g) + 3 H2 (g)
As shown earlier in this chapter, this equilibrium may be established within a sealed container that initially contains either NH3
only, or a mixture of any two of the three chemical species involved in the equilibrium. Regardless of its initial composition, a
reaction mixture will show the same relationships between changes in the concentrations of the three species involved, as dictated
by the reaction stoichiometry (see also the related content on expressing reaction rates in the chapter on kinetics). For example, if
the nitrogen concentration increases by an amount x:
Δ[ N2 ] = + x
the corresponding changes in the other species concentrations are

3 mol H2
Δ[ H2 ] = Δ[ N2 ]( ) = +3x
1 mol N2
2 mol NH3
Δ[ NH3 ] = −Δ[ N2 ]( ) = −2x
1 mol N2
where the negative sign indicates a decrease in concentration.
13.5.0.1: Example 13.6

13.5.0.0.1: Determining Relative Changes in Concentration
Derive the missing terms representing concentration changes for each of the following reactions.
C2 H2 (g)+ 2 Br 2 (g) ⇌ C2 H2 Br 4 (g)
(a)
x _____ _____
− −
I2 (aq)+ I (aq) ⇌ I3 (aq)
(b)
_____ _____ x
C3 H8 (g)+ 5 O2 (g) ⇌ 3 CO2 (g)+ 4 H2 O(g)

(c)
x _____ _____ _____
C2 H2 (g)+ 2 Br 2 (g) ⇌ C2 H2 Br 4 (g)
(a)
x 2x −x
− −
I2 (aq)+ I (aq) ⇌ I3 (aq)
(b)
−x −x x

C3 H8 (g)+ 5 O2 (g) ⇌ 3 CO2 (g)+ 4 H2 O(g)
(c)
x 5x −3x −4x

Complete the changes in concentrations for each of the following reactions:
2 SO 2 (g)+ O2 (g) ⇌ 2 SO 3 (g)
(a)
_____ x _____
C4 H8 (g) ⇌ 2 C2 H4 (g)
(b)
_____ −2x
4 NH3 (g)+ 7 O2 (g) ⇌ 4 NO2 (g)+ 6 H2 O(g)
(c)
_____ _____ _____ _____
13.5.0.1: Answer:
(a) 2x, x, −2x; (b) x, −2x; (c) 4x, 7x, −4x, −6x or −4x, −7x, 4x, 6x
13.5.0.1: Calculation of an Equilibrium Constant

The equilibrium constant for a reaction is calculated from the equilibrium concentrations (or pressures) of its reactants and
products. If these concentrations are known, the calculation simply involves their substitution into the K expression, as was
illustrated by Example 13.2. A slightly more challenging example is provided next, in which the reaction stoichiometry is used to
derive equilibrium concentrations from the information provided. The basic strategy of this computation is helpful for many types
of equilibrium computations and relies on the use of terms for the reactant and product concentrations initially present, for how
they change as the reaction proceeds, and for what they are when the system reaches equilibrium. The acronym ICE is commonly
used to refer to this mathematical approach, and the concentrations terms are usually gathered in a tabular format called an ICE
table.
13.5.0.1: Example 13.7

13.5.0.0.1: Calculation of an Equilibrium Constant
Iodine molecules react reversibly with iodide ions to produce triiodide ions.
− −
I2 (aq) + I (aq) ⇌ I3 (aq)
If a solution with the concentrations of I2 and I− both equal to 1.000 × 10−3 M before reaction gives an equilibrium
concentration of I2 of 6.61 × 10−4 M, what is the equilibrium constant for the reaction?
To calculate the equilibrium constants, equilibrium concentrations are needed for all the reactants and products:
–
[ I3 ]
KC =
−
[ I2 ][ I ]
Provided are the initial concentrations of the reactants and the equilibrium concentration of the product. Use this information to
derive terms for the equilibrium concentrations of the reactants, presenting all the information in an ICE table.

At equilibrium the concentration of I2 is 6.61 × 10−4 M so that
−3 −4
1.000 × 10 − x = 6.61 × 10
−3 −4
x = 1.000 × 10 − 6.61 × 10
−4
= 3.39 × 10 M
The ICE table may now be updated with numerical values for all its concentrations:
Finally, substitute the equilibrium concentrations into the K expression and solve:
−
[ I3 ]
Kc =
−
[ I2 ] [ I ]
−4
3.39 × 10 M
= = 776
−4 −4
(6.61 × 10 M )(6.61 × 10 M)

Ethanol and acetic acid react and form water and ethyl acetate, the solvent responsible for the odor of some nail polish
removers.
C2 H5 OH + CH3 CO2 H ⇌ CH3 CO2 C2 H5 + H2 O
When 1 mol each of C2H5OH and CH3CO2H are allowed to react in 1 L of the solvent dioxane, equilibrium is established
when mol of each of the reactants remains. Calculate the equilibrium constant for the reaction. (Note: Water is a solute in
1
this reaction.)
13.5.0.1: Answer:
Kc = 4
13.5.0.1: Calculation of a Missing Equilibrium Concentration

When the equilibrium constant and all but one equilibrium concentration are provided, the other equilibrium concentration(s) may
be calculated. A computation of this sort is illustrated in the next example exercise.

13.5.0.1: Example 13.8
13.5.0.0.1: Calculation of a Missing Equilibrium Concentration
Nitrogen oxides are air pollutants produced by the reaction of nitrogen and oxygen at high temperatures. At 2000 °C, the value
of the Kc for the reaction, N (g) + O (g) ⇌ 2NO(g), is 4.1 × 10−4. Calculate the equilibrium concentration of NO(g) in air
2 2
at 1 atm pressure and 2000 °C. The equilibrium concentrations of N2 and O2 at this pressure and temperature are 0.036 M and
0.0089 M, respectively.
Substitute the provided quantities into the equilibrium constant expression and solve for [NO]:
2
[NO]
Kc =
[ N2 ] [ O2 ]
2
[NO] = Kc [ N2 ] [ O2 ]
−−−−−−−−−−
[NO] = √ Kc [ N2 ] [ O2 ]
−−−−−−−−−−−−−−−−−−−−−−−
−4
= √ (4.1 × 10 ) (0.036) (0.0089)
− −−−−−−−− −
−7
= √ 1.31 × 10
−4
= 3.6 × 10
Thus [NO] is 3.6 × 10−4 mol/L at equilibrium under these conditions.

To confirm this result, it may be used along with the provided equilibrium concentrations to calculate a value for K:
2
[NO]
Kc =
[ N2 ] [ O2 ]
2
−4
(3.6 × 10 )
=
(0.036) (0.0089)
−4
= 4.0 × 10
This result is consistent with the provided value for K within nominal uncertainty, differing by just 1 in the least significant
digit’s place.
The equilibrium constant Kc for the reaction of nitrogen and hydrogen to produce ammonia at a certain temperature is 6.00 ×
10−2. Calculate the equilibrium concentration of ammonia if the equilibrium concentrations of nitrogen and hydrogen are 4.26
M and 2.09 M, respectively.
13.5.0.1: Answer:
1.53 mol/L
13.5.0.1: Calculation of Equilibrium Concentrations from Initial Concentrations

Perhaps the most challenging type of equilibrium calculation can be one in which equilibrium concentrations are derived from
initial concentrations and an equilibrium constant. For these calculations, a four-step approach is typically useful:
1. Identify the direction in which the reaction will proceed to reach equilibrium.
2. Develop an ICE table.
3. Calculate the concentration changes and, subsequently, the equilibrium concentrations.
4. Confirm the calculated equilibrium concentrations.
The last two example exercises of this chapter demonstrate the application of this strategy.
13.5.0.1: Example 13.9

13.5.0.0.1: Calculation of Equilibrium Concentrations
Under certain conditions, the equilibrium constant Kc for the decomposition of PCl5(g) into PCl3(g) and Cl2(g) is 0.0211. What
are the equilibrium concentrations of PCl5, PCl3, and Cl2 in a mixture that initially contained only PCl5 at a concentration of
1.00 M?
Use the stepwise process described earlier.
1. Step 1.
Determine the direction the reaction proceeds.
The balanced equation for the decomposition of PCl5 is
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
Because only the reactant is present initially Qc = 0 and the reaction will proceed to the right.
2. Step 2.
Develop an ICE table.
3. Step 3.
Solve for the change and the equilibrium concentrations.
Substituting the equilibrium concentrations into the equilibrium constant equation gives
[ PCl3 ] [ Cl2 ]
Kc = = 0.0211
[ PCl5 ]
(x) (x)
=
(1.00 − x)
(x) (x)
0.0211 =
(1.00 − x)
2
0.0211 (1.00 − x) = x
2
x + 0.0211x − 0.0211 = 0
Appendix B shows an equation of the form ax2 + bx + c = 0 can be rearranged to solve for x:
− − −−−−−
2
−b ± √ b − 4ac
x =
2a
In this case, a = 1, b = 0.0211, and c = −0.0211. Substituting the appropriate values for a, b, and c yields:
−−−−−−−−−−−−−−−−−−−−−
2
−0.0211 ± √ (0.0211) − 4(1)(−0.0211)
x =
2(1)
−−−−−−−−−−−−−−−−−−−−−−−−−
−4 −2
−0.0211 ± √ (4.45 × 10 ) + (8.44 × 10 )
=
2

−0.0211 ± 0.291
=
2
The two roots of the quadratic are, therefore,

−0.0211 + 0.291
x = = 0.135
2
and
−0.0211 − 0.291
x = = −0.156
2
For this scenario, only the positive root is physically meaningful (concentrations are either zero or positive), and so x =
0.135 M.
The equilibrium concentrations are
[ PCl5 ] = 1.00 − 0.135 = 0.87 M
[ PCl3 ] = x = 0.135 M
[ Cl2 ] = x = 0.135 M
4. Step 4.
Confirm the calculated equilibrium concentrations.
Substitution into the expression for Kc (to check the calculation) gives
[ PCl3 ] [ Cl2 ] (0.135) (0.135)
Kc = = = 0.021
[ PCl5 ] 0.87
The equilibrium constant calculated from the equilibrium concentrations is equal to the value of Kc given in the problem
(when rounded to the proper number of significant figures).
Acetic acid, CH3CO2H, reacts with ethanol, C2H5OH, to form water and ethyl acetate, CH3CO2C2H5.
CH3 CO2 H + C2 H5 OH ⇌ CH3 CO2 C2 H5 + H2 O
The equilibrium constant for this reaction with dioxane as a solvent is 4.0. What are the equilibrium concentrations for a
mixture that is initially 0.15 M in CH3CO2H, 0.15 M in C2H5OH, 0.40 M in CH3CO2C2H5, and 0.40 M in H2O?
13.5.0.1: Answer:
[CH3CO2H] = 0.18 M, [C2H5OH] = 0.18 M, [CH3CO2C2H5] = 0.37 M, [H2O] = 0.37 M

A 1.00-L flask is filled with 1.00 mole of H2 and 2.00 moles of I2. The value of the equilibrium constant for the reaction of
hydrogen and iodine reacting to form hydrogen iodide is 50.5 under the given conditions. What are the equilibrium
concentrations of H2, I2, and HI in moles/L?
H2 (g) + I2 (g) ⇌ 2HI(g)
13.5.0.1: Answer:
[H2] = 0.06 M, [I2] = 1.06 M, [HI] = 1.88 M
13.5.0.1: Example 13.10

13.5.0.0.5: Calculation of Equilibrium Concentrations Using an Algebra-Simplifying Assumption
What are the concentrations at equilibrium of a 0.15 M solution of HCN?
+ − −10
HCN(aq) ⇌ H (aq) + CN (aq) Kc = 4.9 × 10

Using “x” to represent the concentration of each product at equilibrium gives this ICE table.
Substitute the equilibrium concentration terms into the Kc expression

(x)(x)
Kc =
0.15 − x
rearrange to the quadratic form and solve for x

2 −10 −11
x + 4.9 × 10 − 7.35 × 10 =0
−6 −6
x = 8.56 × 10 M (3 sig. figs.) = 8.6 × 10 M (2 sig. figs.)
Thus [H+] = [CN–] = x = 8.6 × 10–6 M and [HCN] = 0.15 – x = 0.15 M.

Note in this case that the change in concentration is significantly less than the initial concentration (a consequence of the small
K), and so the initial concentration experiences a negligible change:
if x ≪ 0.15 M, then (0.15– x) ≈ 0.15
This approximation allows for a more expedient mathematical approach to the calculation that avoids the need to solve for the
roots of a quadratic equation:
2
(x)(x) x
Kc = ≈
0.15 − x 0.15
2
x
−10
4.9 × 10 =
0.15
2 −10 −11
x = (0.15)(4.9 × 10 ) = 7.4 × 10
− −−−−−−− −−
−11 −6
x = √ 7.4 × 10 = 8.6 × 10 M
The value of x calculated is, indeed, much less than the initial concentration
−6
8.6 × 10 ≪ 0.15
and so the approximation was justified. If this simplified approach were to yield a value for x that did not justify the
approximation, the calculation would need to be repeated without making the approximation.
What are the equilibrium concentrations in a 0.25 M NH3 solution?
+ − −5
NH3 (aq) + H2 O(l) ⇌ NH4 (aq) + OH (aq) Kc = 1.8 × 10
13.5.0.1: Answer:
[ OH
−
] = [ NH4
+
] = 0.0021 M ; [NH3] = 0.25 M
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13.6: Key Terms
equilibrium
state of a reversible reaction in which the forward and reverse processes occur at equal rates
equilibrium constant (K)

value of the reaction quotient for a system at equilibrium; may be expressed using concentrations (Kc) or partial pressures (Kp)
heterogeneous equilibria
equilibria in which reactants and products occupy two or more different phases
homogeneous equilibria
equilibria in which all reactants and products occupy the same phase
law of mass action

when a reversible reaction has attained equilibrium at a given temperature, the reaction quotient remains constant
Le Châtelier’s principle
an equilibrium subjected to stress will shift in a way to counter the stress and re-establish equilibrium
reaction quotient (Q)

mathematical function describing the relative amounts of reactants and products in a reaction mixture; may be expressed in
terms of concentrations (Qc) or pressures (Qp)
reversible reaction
chemical reaction that can proceed in both the forward and reverse directions under given conditions
13.7: Key Equations
x y
[C] [D]
Qc = m n
for the reaction mA + nB ⇌ xC + yD
[A] [B]
x y
(PC ) (PD )
QP = m n
for the reaction mA + nB ⇌ xC + yD
(PA ) (PB )
P = MRT
Kc = Qc at equilibrium
Kp = Qp at equilibrium
KP = Kc (RT)Δn
13.8: Summary
13.1 Chemical Equilibria
A reversible reaction is at equilibrium when the forward and reverse processes occur at equal rates. Chemical equilibria are
dynamic processes characterized by constant amounts of reactant and product species.
13.2 Equilibrium Constants

The composition of a reaction mixture may be represented by a mathematical function known as the reaction quotient, Q. For a
reaction at equilibrium, the composition is constant, and Q is called the equilibrium constant, K.
A homogeneous equilibrium is an equilibrium in which all components are in the same phase. A heterogeneous equilibrium is an
equilibrium in which components are in two or more phases.
13.3 Shifting Equilibria: Le Châtelier’s Principle

Systems at equilibrium can be disturbed by changes to temperature, concentration, and, in some cases, volume and pressure. The
system’s response to these disturbances is described by Le Châtelier’s principle: An equilibrium system subjected to a disturbance
will shift in a way that counters the disturbance and re-establishes equilibrium. A catalyst will increase the rate of both the forward
and reverse reactions of a reversible process, increasing the rate at which equilibrium is reached but not altering the equilibrium
mixture’s composition (K does not change).
13.4 Equilibrium Calculations

Calculating values for equilibrium constants and/or equilibrium concentrations is of practical benefit to many applications. A
mathematical strategy that uses initial concentrations, changes in concentrations, and equilibrium concentrations (and goes by the
acronym ICE) is useful for several types of equilibrium calculations.
13.9: Exercises
13.9.0.1: 13.1 Chemical Equilibria
1.
What does it mean to describe a reaction as “reversible”?
2.
When writing an equation, how is a reversible reaction distinguished from a nonreversible reaction?
3.
If a reaction is reversible, when can it be said to have reached equilibrium?
4.
Is a system at equilibrium if the rate constants of the forward and reverse reactions are equal?
5.
If the concentrations of products and reactants are equal, is the system at equilibrium?
13.9.0.1: 13.2 Equilibrium Constants

6.
Explain why there may be an infinite number of values for the reaction quotient of a reaction at a given temperature but there can
be only one value for the equilibrium constant at that temperature.
7.
Explain why an equilibrium between Br2(l) and Br2(g) would not be established if the container were not a closed vessel shown in
Figure 13.4.
8.
If you observe the following reaction at equilibrium, is it possible to tell whether the reaction started with pure NO2 or with pure
N2O4?
2 NO2 (g) ⇌ N2 O4 (g)
9.
Among the solubility rules previously discussed is the statement: All chlorides are soluble except Hg2Cl2, AgCl, PbCl2, and CuCl.
(a) Write the expression for the equilibrium constant for the reaction represented by the equation
AgCl(s) ⇌ Ag
+
(aq) + Cl
−
(aq). Is Kc > 1, < 1, or ≈ 1? Explain your answer.
(b) Write the expression for the equilibrium constant for the reaction represented by the equation
Pb
2+ −
(aq) + 2 Cl (aq) ⇌ PbCl2 (s). Is Kc > 1, < 1, or ≈ 1? Explain your answer.
10.
Among the solubility rules previously discussed is the statement: Carbonates, phosphates, borates, and arsenates—except those of
the ammonium ion and the alkali metals—are insoluble.
(a) Write the expression for the equilibrium constant for the reaction represented by the equation
CaCO3 (s) ⇌ Ca
2+
(aq) + CO3
2−
(aq). Is Kc > 1, < 1, or ≈ 1? Explain your answer.
(b) Write the expression for the equilibrium constant for the reaction represented by the equation
3 Ba
2+
(aq) + 2 PO4
3−
(aq) ⇌ Ba 3 (PO4 ) (s).
2
Is Kc > 1, < 1, or ≈ 1? Explain your answer.
11.
Benzene is one of the compounds used as octane enhancers in unleaded gasoline. It is manufactured by the catalytic conversion of
acetylene to benzene: 3C H (g) ⇌ C H (g). Which value of Kc would make this reaction most useful commercially? Kc ≈ 0.01,
2 2 6 6
Kc ≈ 1, or Kc ≈ 10. Explain your answer.

12.

Show that the complete chemical equation, the total ionic equation, and the net ionic equation for the reaction represented by the
equation KI(aq) + I (aq) ⇌ KI (aq) give the same expression for the reaction quotient. KI3 is composed of the ions K+ and I .
2 3 3
−
13.
For a titration to be effective, the reaction must be rapid and the yield of the reaction must essentially be 100%. Is Kc > 1, < 1, or ≈
1 for a titration reaction?
14.
For a precipitation reaction to be useful in a gravimetric analysis, the product of the reaction must be insoluble. Is Kc > 1, < 1, or ≈
1 for a useful precipitation reaction?
15.
Write the mathematical expression for the reaction quotient, Qc, for each of the following reactions:
(a) CH 4 (g) + Cl2 (g) ⇌ CH3 Cl(g) + HCl(g)
(b) N 2 (g) + O2 (g) ⇌ 2NO(g)
(c) 2SO 2 (g) + O2 (g) ⇌ 2 SO 3 (g)
(d) BaSO 3 (s) ⇌ BaO(s) + SO 2 (g)
(e) P 4 (g) + 5 O2 (g) ⇌ P4 O10 (s)
(f) Br 2 (g) ⇌ 2Br(g)
(g) CH 4 (g) + 2 O2 (g) ⇌ CO2 (g) + 2 H2 O(l)
(h) CuSO 4 ⋅5 H2 O(s) ⇌ CuSO 4 (s) + 5 H2 O(g)
16.
Write the mathematical expression for the reaction quotient, Qc, for each of the following reactions:
(a) N 2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)
(b) 4NH 3 (g) + 5 O2 (g) ⇌ 4NO(g) + 6 H2 O(g)
(c) N 2 O4 (g) ⇌ 2 NO2 (g)
(d) CO 2 (g) + H2 (g) ⇌ CO(g) + H2 O(g)
(e) NH 4 Cl(s) ⇌ NH3 (g) + HCl(g)
(f) 2Pb(NO 3 ) 2 (s) ⇌ 2PbO(s) + 4 NO2 (g) + O2 (g)
(g) 2H 2 (g) + O2 (g) ⇌ 2 H2 O(l)
(h) S 8 (g) ⇌ 8S(g)
17.
The initial concentrations or pressures of reactants and products are given for each of the following systems. Calculate the reaction
quotient and determine the direction in which each system will proceed to reach equilibrium.
(a) 2NH 3 (g) ⇌ N2 (g) + 3 H2 (g) Kc = 17; [NH3] = 0.20 M, [N2] = 1.00 M, [H2] = 1.00 M
(b) 2NH 3 (g) ⇌ N2 (g) + 3 H2 (g) KP = 6.8 × 10 ;
4
NH3 = 3.0 atm, N2 = 2.0 atm, H2 = 1.0 atm
(c) 2SO 3 (g) ⇌ 2 SO 2 (g) + O2 (g) Kc = 0.230; [SO3] = 0.00 M, [SO2] = 1.00 M, [O2] = 1.00 M
(d) 2SO 3 (g) ⇌ 2 SO 2 (g) + O2 (g) KP = 16.5; SO3 = 1.00 atm, SO2 = 1.00 atm, O2 = 1.00 atm
(e) 2NO(g) + Cl 2 (g) ⇌ 2NOCl(g) Kc = 4.6 × 10 ;
4
[NO] = 1.00 M, [Cl2] = 1.00 M, [NOCl] = 0 M
(f) N 2 (g) + O2 (g) ⇌ 2NO(g) KP = 0.050; NO = 10.0 atm, N2 = O2 = 5 atm
18.
The initial concentrations or pressures of reactants and products are given for each of the following systems. Calculate the reaction
quotient and determine the direction in which each system will proceed to reach equilibrium.

(a) 2NH 3 (g) ⇌ N2 (g) + 3 H2 (g) Kc = 17; [NH3] = 0.50 M, [N2] = 0.15 M, [H2] = 0.12 M
(b) 2NH 3 (g) ⇌ N2 (g) + 3 H2 (g) KP = 6.8 × 10 ;
4
NH3 = 2.00 atm, N2 = 10.00 atm, H2 = 10.00 atm
(c) 2SO 3 (g) ⇌ 2 SO 2 (g) + O2 (g) Kc = 0.230; [SO3] = 2.00 M, [SO2] = 2.00 M, [O2] = 2.00 M
(d) 2SO 3 (g) ⇌ 2 SO 2 (g) + O2 (g) KP = 6.5 atm; SO2 = 1.00 atm, O2 = 1.130 atm, SO3 = 0 atm
(e) 2NO(g) + Cl 2 (g) ⇌ 2NOCl(g) KP = 2.5 × 10 ;
3
NO = 1.00 atm, Cl2 = 1.00 atm, NOCl = 0 atm
(f) N 2 (g) + O2 (g) ⇌ 2NO(g) Kc = 0.050; [N2] = 0.100 M, [O2] = 0.200 M, [NO] = 1.00 M
19.
The following reaction has KP = 4.50 × 10−5 at 720 K.
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)
If a reaction vessel is filled with each gas to the partial pressures listed, in which direction will it shift to reach equilibrium? P(NH3)
= 93 atm, P(N2) = 48 atm, and P(H2) = 52 atm
20.
Determine if the following system is at equilibrium. If not, in which direction will the system need to shift to reach equilibrium?
SO 2 Cl2 (g) ⇌ SO 2 (g) + Cl2 (g)
[SO2Cl2] = 0.12 M, [Cl2] = 0.16 M and [SO2] = 0.050 M. Kc for the reaction is 0.078.
21.
Which of the systems described in Exercise 13.15 are homogeneous equilibria? Which are heterogeneous equilibria?
22.
Which of the systems described in Exercise 13.16 are homogeneous equilibria? Which are heterogeneous equilibria?
23.
For which of the reactions in Exercise 13.15 does Kc (calculated using concentrations) equal KP (calculated using pressures)?
24.
For which of the reactions in Exercise 13.16 does Kc (calculated using concentrations) equal KP (calculated using pressures)?
25.
Convert the values of Kc to values of KP or the values of KP to values of Kc.
(a) N 2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) Kc = 0.50 at 400 °C
(b) H 2 (g) + I2 (g) ⇌ 2HI(g) Kc = 50.2 at 448 °C
(c) Na 2 SO 4 ⋅10 H2 O(s) ⇌ Na2 SO 4 (s) + 10 H2 O(g) KP = 4.08 × 10

−25
at 25 °C
(d) H 2 O(l) ⇌ H2 O(g) KP = 0.122 at 50 °C
26.
Convert the values of Kc to values of KP or the values of KP to values of Kc.
(a) Cl 2 (g) + Br 2 (g) ⇌ 2BrCl(g) Kc = 4.7 × 10
−2
at 25 °C
(b) 2SO 2 (g) + O2 (g) ⇌ 2 SO 3 (g) KP = 48.2 at 500 °C
(c) CaCl 2 ⋅6 H2 O(s) ⇌ CaCl2 (s) + 6 H2 O(g) KP = 5.09 × 10

−44
at 25 °C
(d) H 2 O(l) ⇌ H2 O(g) KP = 0.196 at 60 °C
27.
What is the value of the equilibrium constant expression for the change H 2 O(l) ⇌ H2 O(g) at 30 °C? (See Appendix E.)
28.
Write the expression of the reaction quotient for the ionization of HOCN in water.
29.

Write the reaction quotient expression for the ionization of NH3 in water.
30.
What is the approximate value of the equilibrium constant KP for the change C 2 H5 OC 2 H5 (l) ⇌ C2 H5 OC 2 H5 (g) at 25 °C. (The
equilibrium vapor pressure for this substance is 570 torr at 25 °C.)
13.9.0.1: 13.3 Shifting Equilibria: Le Châtelier’s Principle

31.
The following equation represents a reversible decomposition:
CaCO3 (s) ⇌ CaO(s) + CO2 (g)
Under what conditions will decomposition in a closed container proceed to completion so that no CaCO3 remains?
32.
Explain how to recognize the conditions under which changes in volume will affect gas-phase systems at equilibrium.
33.
What property of a reaction can we use to predict the effect of a change in temperature on the value of an equilibrium constant?
34.
The following reaction occurs when a burner on a gas stove is lit:
CH4 (g) + 2 O2 (g) ⇌ CO2 (g) + 2 H2 O(g)
Is an equilibrium among CH4, O2, CO2, and H2O established under these conditions? Explain your answer.
35.
A necessary step in the manufacture of sulfuric acid is the formation of sulfur trioxide, SO3, from sulfur dioxide, SO2, and oxygen,
O2, shown here. At high temperatures, the rate of formation of SO3 is higher, but the equilibrium amount (concentration or partial
pressure) of SO3 is lower than it would be at lower temperatures.
2 SO 2 (g) + O2 (g) ⇌ 2 SO 3 (g)
(a) Does the equilibrium constant for the reaction increase, decrease, or remain about the same as the temperature increases?
(b) Is the reaction endothermic or exothermic?
36.
Suggest four ways in which the concentration of hydrazine, N2H4, could be increased in an equilibrium described by the following
equation:
N2 (g) + 2 H2 (g) ⇌ N2 H4 (g) ΔH = 95 kJ
37.
Suggest four ways in which the concentration of PH3 could be increased in an equilibrium described by the following equation:
P4 (g) + 6 H2 (g) ⇌ 4 PH3 (g) ΔH = 110.5 kJ
38.
How will an increase in temperature affect each of the following equilibria? How will a decrease in the volume of the reaction
vessel affect each?
(a) 2NH 3 (g) ⇌ N2 (g) + 3 H2 (g) ΔH = 92 kJ
(b) N 2 (g) + O2 (g) ⇌ 2NO(g) ΔH = 181 kJ
(c) 2O 3 (g) ⇌ 3 O2 (g) ΔH = −285 kJ
(d) CaO(s) + CO 2 (g) ⇌ CaCO3 (s) ΔH = −176 kJ
39.
How will an increase in temperature affect each of the following equilibria? How will a decrease in the volume of the reaction
vessel affect each?
(a) 2H 2 O(g) ⇌ 2 H2 (g) + O2 (g) ΔH = 484 kJ

(b) N 2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) ΔH = −92.2 kJ
(c) 2Br(g) ⇌ Br 2 (g) ΔH = −224 kJ
(d) H 2 (g) + I2 (s) ⇌ 2HI(g) ΔH = 53 kJ
40.
Methanol can be prepared from carbon monoxide and hydrogen at high temperature and pressure in the presence of a suitable
catalyst.
(a) Write the expression for the equilibrium constant (Kc) for the reversible reaction
2 H2 (g) + CO(g) ⇌ CH3 OH(g) ΔH = −90.2 kJ
(b) What will happen to the concentrations of H2, CO, and CH3OH at equilibrium if more H2 is added?
(c) What will happen to the concentrations of H2, CO, and CH3OH at equilibrium if CO is removed?
(d) What will happen to the concentrations of H2, CO, and CH3OH at equilibrium if CH3OH is added?
(e) What will happen to the concentrations of H2, CO, and CH3OH at equilibrium if the temperature of the system is increased?
(f) What will happen to the concentrations of H2, CO, and CH3OH at equilibrium if more catalyst is added?
41.
Nitrogen and oxygen react at high temperatures.
N2 (g) + O2 (g) ⇌ 2NO(g) ΔH = 181 kJ
(b) What will happen to the concentrations of N2, O2, and NO at equilibrium if more O2 is added?
(c) What will happen to the concentrations of N2, O2, and NO at equilibrium if N2 is removed?
(d) What will happen to the concentrations of N2, O2, and NO at equilibrium if NO is added?
(e) What will happen to the concentrations of N2, O2, and NO at equilibrium if the volume of the reaction vessel is decreased?
(f) What will happen to the concentrations of N2, O2, and NO at equilibrium if the temperature of the system is increased?
(g) What will happen to the concentrations of N2, O2, and NO at equilibrium if a catalyst is added?
42.
Water gas, a mixture of H2 and CO, is an important industrial fuel produced by the reaction of steam with red hot coke, essentially
pure carbon.
(a) Write the expression for the equilibrium constant for the reversible reaction
C(s) + H2 O(g) ⇌ CO(g) + H2 (g) ΔH = 131.30 kJ
(b) What will happen to the concentration of each reactant and product at equilibrium if more C is added?
(c) What will happen to the concentration of each reactant and product at equilibrium if H2O is removed?
(d) What will happen to the concentration of each reactant and product at equilibrium if CO is added?
(e) What will happen to the concentration of each reactant and product at equilibrium if the temperature of the system is increased?
43.
Pure iron metal can be produced by the reduction of iron(III) oxide with hydrogen gas.
Fe2 O3 (s) + 3 H2 (g) ⇌ 2Fe(s) + 3 H2 O(g) ΔH = 98.7 kJ
(b) What will happen to the concentration of each reactant and product at equilibrium if more Fe is added?
(c) What will happen to the concentration of each reactant and product at equilibrium if H2O is removed?
(d) What will happen to the concentration of each reactant and product at equilibrium if H2 is added?

(e) What will happen to the concentration of each reactant and product at equilibrium if the volume of the reaction vessel is
decreased?
(f) What will happen to the concentration of each reactant and product at equilibrium if the temperature of the system is increased?
44.
Ammonia is a weak base that reacts with water according to this equation:
+ −
NH3 (aq) + H2 O(l) ⇌ NH4 (aq) + OH (aq)
Will any of the following increase the percent of ammonia that is converted to the ammonium ion in water?
(a) Addition of NaOH
(b) Addition of HCl
(c) Addition of NH4Cl
45.
Acetic acid is a weak acid that reacts with water according to this equation:
+ −
CH3 CO2 H(aq) + H2 O(aq) ⇌ H3 O (aq) + CH3 CO2 (aq)
Will any of the following increase the percent of acetic acid that reacts and produces CH 3 CO2
−
ion?
(a) Addition of HCl
(b) Addition of NaOH
(c) Addition of NaCH3CO2
46.
Suggest two ways in which the equilibrium concentration of Ag+ can be reduced in a solution of Na+, Cl−, Ag+, and NO3
−
, in
contact with solid AgCl.
+ − + − + −
Na (aq) + Cl (aq) + Ag (aq) + NO3 (aq) ⇌ AgCl(s) + Na (aq) + NO3 (aq)
ΔH = −65.9 kJ
47.
How can the pressure of water vapor be increased in the following equilibrium?
H2 O(l) ⇌ H2 O(g) ΔH = 41 kJ
48.
A solution is saturated with silver sulfate and contains excess solid silver sulfate:
+ 2−
Ag2 SO 4 (s) ⇌ 2 Ag (aq) + SO 4 (aq)
A small amount of solid silver sulfate containing a radioactive isotope of silver is added to this solution. Within a few minutes, a
portion of the solution phase is sampled and tests positive for radioactive Ag+ ions. Explain this observation.
49.
When equal molar amounts of HCl and HOCl are dissolved separately in equal amounts of water, the solution of HCl freezes at a
lower temperature. Which compound has the larger equilibrium constant for acid ionization?
(a) HCl
(b) H+ + Cl–
(c) HOCl
(d) H+ + OCl–
13.9.0.1: 13.4 Equilibrium Calculations

50.
A reaction is represented by this equation: A(aq) + 2B(aq) ⇌ 2C(aq) Kc = 1 × 10
3
(a) Write the mathematical expression for the equilibrium constant.

(b) Using concentrations ≤1 M, identify two sets of concentrations that describe a mixture of A, B, and C at equilibrium.

51.
A reaction is represented by this equation: 2W(aq) ⇌ X(aq) + 2Y(aq) Kc = 5 × 10
−4
(a) Write the mathematical expression for the equilibrium constant.

(b) Using concentrations of ≤1 M, identify two sets of concentrations that describe a mixture of W, X, and Y at equilibrium.
52.
What is the value of the equilibrium constant at 500 °C for the formation of NH3 according to the following equation?
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)
An equilibrium mixture of NH3(g), H2(g), and N2(g) at 500 °C was found to contain 1.35 M H2, 1.15 M N2, and 4.12 × 10−1 M
NH3.
53.
Hydrogen is prepared commercially by the reaction of methane and water vapor at elevated temperatures.
CH4 (g) + H2 O(g) ⇌ 3 H2 (g) + CO(g)
What is the equilibrium constant for the reaction if a mixture at equilibrium contains gases with the following concentrations: CH4,
0.126 M; H2O, 0.242 M; CO, 0.126 M; H2 1.15 M, at a temperature of 760 °C?
54.
A 0.72-mol sample of PCl5 is put into a 1.00-L vessel and heated. At equilibrium, the vessel contains 0.40 mol of PCl3(g) and 0.40
mol of Cl2(g). Calculate the value of the equilibrium constant for the decomposition of PCl5 to PCl3 and Cl2 at this temperature.
55.
At 1 atm and 25 °C, NO2 with an initial concentration of 1.00 M is 0.0033% decomposed into NO and O2. Calculate the value of
the equilibrium constant for the reaction.
2 NO2 (g) ⇌ 2NO(g) + O2 (g)
56.
Calculate the value of the equilibrium constant KP for the reaction 2NO(g) + Cl2 (g) ⇌ 2NOCl(g) from these equilibrium
pressures: NO, 0.050 atm; Cl2, 0.30 atm; NOCl, 1.2 atm.
57.
When heated, iodine vapor dissociates according to this equation:
I2 (g) ⇌ 2I(g)
At 1274 K, a sample exhibits a partial pressure of I2 of 0.1122 atm and a partial pressure due to I atoms of 0.1378 atm. Determine
the value of the equilibrium constant, KP, for the decomposition at 1274 K.
58.
A sample of ammonium chloride was heated in a closed container.
NH4 Cl(s) ⇌ NH3 (g) + HCl(g)
At equilibrium, the pressure of NH3(g) was found to be 1.75 atm. What is the value of the equilibrium constant KP for the
decomposition at this temperature?
59.
At a temperature of 60 °C, the vapor pressure of water is 0.196 atm. What is the value of the equilibrium constant KP for the
vaporization equilibrium at 60 °C?
H2 O(l) ⇌ H2 O(g)
60.
Complete the following partial ICE tables.
(a)

2 SO 3 (g) ⇌ 2 SO 2 (g)+ O2 (g)
change ___ ___ +x
(b)
4 NH3 (g) + 3 O2 (g) ⇌ 2 N2 (g)+ 6 H2 O(g)
change ___ +x ___ ___
(c)
2 CH4 (g) ⇌ C2 H2 (g)+ 3 H2 (g)
change ___ +x ___
(d)
CH4 (g)+ H2 O(g) ⇌ CO(g)+ 3 H2 (g)
change ___ +x ___ ___
(e)
NH4 Cl(s) ⇌ NH3 (g)+ HCl(g)
change +x ___
(f)
Ni(s)+ 4CO(g) ⇌ Ni (CO) (g)
4
change +x ___
61.
Complete the following partial ICE tables.
(a)
2 H2 (g)+ O2 (g) ⇌ 2 H2 O(g)
change ___ ___ +x
(b)
CS2 (g)+ 4 H2 (g) ⇌ CH4 (g)+ 2 H2 S(g)
change +x ___ ___ ___
(c)
H2 (g)+ Cl2 (g) ⇌ 2HCl(g)
change +x ___ ___
(d)
2 NH3 (g) + 2 O2 (g) ⇌ N2 O(g)+ 3 H2 O(g)
change ___ ___ ___ +x
(e)
NH4 HS(s) ⇌ NH3 (g)+ H2 S(g)
change +x ___
(f)
Fe(s)+ 5CO(g) ⇌ Fe(CO) (g)
5
change ___ +x
62.
Why are there no changes specified for Ni in Exercise 13.60, part (f)? What property of Ni does change?
63.
Why are there no changes specified for NH4HS in Exercise 13.61, part (e)? What property of NH4HS does change?

64.
Analysis of the gases in a sealed reaction vessel containing NH3, N2, and H2 at equilibrium at 400 °C established the concentration
of N2 to be 1.2 M and the concentration of H2 to be 0.24 M.
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) Kc = 0.50 at 400 °C
Calculate the equilibrium molar concentration of NH3.

65.
Calculate the number of moles of HI that are at equilibrium with 1.25 mol of H2 and 1.25 mol of I2 in a 5.00−L flask at 448 °C.
H2 + I2 ⇌ 2HI Kc = 50.2 at 448 °C
66.
What is the pressure of BrCl in an equilibrium mixture of Cl2, Br2, and BrCl if the pressure of Cl2 in the mixture is 0.115 atm and
the pressure of Br2 in the mixture is 0.450 atm?
−2
Cl2 (g) + Br 2 (g) ⇌ 2BrCl(g) KP = 4.7 × 10
67.
What is the pressure of CO2 in a mixture at equilibrium that contains 0.50 atm H2, 2.0 atm of H2O, and 1.0 atm of CO at 990 °C?
H2 (g) + CO2 (g) ⇌ H2 O(g) + CO(g) KP = 1.6 at 990 °C
68.
Cobalt metal can be prepared by reducing cobalt(II) oxide with carbon monoxide.
2
CoO(s) + CO(g) ⇌ Co(s) + CO2 (g) Kc = 4.90 × 10 at 550 °C
What concentration of CO remains in an equilibrium mixture with [CO2] = 0.100 M?

69.
Carbon reacts with water vapor at elevated temperatures.
C(s) + H2 O(g) ⇌ CO(g) + H2 (g) Kc = 0.2 at 1000 °C
Assuming a reaction mixture initially contains only reactants, what is the concentration of CO in an equilibrium mixture with
[H2O] = 0.500 M at 1000 °C?
70.
Sodium sulfate 10−hydrate, Na2SO4·10H2O, dehydrates according to the equation
−25
Na2 SO 4 ⋅10 H2 O(s) ⇌ Na2 SO 4 (s) + 10 H2 O(g) KP = 4.08 × 10 at 25 °C
What is the pressure of water vapor at equilibrium with a mixture of Na2SO4·10H2O and NaSO4?
71.
Calcium chloride 6−hydrate, CaCl2·6H2O, dehydrates according to the equation
−44
CaCl2 ⋅6 H2 O(s) ⇌ CaCl2 (s) + 6 H2 O(g) KP = 5.09 × 10 at 25 °C
What is the pressure of water vapor at equilibrium with a mixture of CaCl2·6H2O and CaCl2 at 25 °C?
72.
A student solved the following problem and found the equilibrium concentrations to be [SO2] = 0.590 M, [O2] = 0.0450 M, and
[SO3] = 0.260 M. How could this student check the work without reworking the problem? The problem was: For the following
reaction at 600 °C:
2 SO 2 (g) + O2 (g) ⇌ 2 SO 3 (g) Kc = 4.32
73.
A student solved the following problem and found [N2O4] = 0.16 M at equilibrium. How could this student recognize that the
answer was wrong without reworking the problem? The problem was: What is the equilibrium concentration of N2O4 in a mixture
formed from a sample of NO2 with a concentration of 0.10 M?

2 NO2 (g) ⇌ N2 O4 (g) Kc = 160
74.
Assume that the change in concentration of N2O4 is small enough to be neglected in the following problem.
(a) Calculate the equilibrium concentration of both species in 1.00 L of a solution prepared from 0.129 mol of N2O4 with
chloroform as the solvent.
N2 O4 (g) ⇌ 2 NO2 (g) Kc = 1.07 × 10
−5
in chloroform
(b) Confirm that the change is small enough to be neglected.
75.
Assume that the change in concentration of COCl2 is small enough to be neglected in the following problem.
(a) Calculate the equilibrium concentration of all species in an equilibrium mixture that results from the decomposition of COCl2
with an initial concentration of 0.3166 M.
−10
COCl2 (g) ⇌ CO(g) + Cl2 (g) Kc = 2.2 × 10

76.
Assume that the change in pressure of H2S is small enough to be neglected in the following problem.
(a) Calculate the equilibrium pressures of all species in an equilibrium mixture that results from the decomposition of H2S with an
initial pressure of 0.824 atm.
−6
2 H2 S(g) ⇌ 2 H2 (g) + S2 (g) KP = 2.2 × 10

77.
What are all concentrations after a mixture that contains [H2O] = 1.00 M and [Cl2O] = 1.00 M comes to equilibrium at 25 °C?
H2 O(g) + Cl2 O(g) ⇌ 2HOCl(g) Kc = 0.0900
78.
What are the concentrations of PCl5, PCl3, and Cl2 in an equilibrium mixture produced by the decomposition of a sample of pure
PCl5 with [PCl5] = 2.00 M?
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) Kc = 0.0211
79.
Calculate the number of grams of HI that are at equilibrium with 1.25 mol of H2 and 63.5 g of iodine at 448 °C.
H2 + I2 ⇌ 2HI Kc = 50.2 at 448 °C
80.
Butane exists as two isomers, n−butane and isobutane.
KP = 2.5 at 25 °C
What is the pressure of isobutane in a container of the two isomers at equilibrium with a total pressure of 1.22 atm?
81.

What is the minimum mass of CaCO3 required to establish equilibrium at a certain temperature in a 6.50-L container if the
equilibrium constant (Kc) is 0.50 for the decomposition reaction of CaCO3 at that temperature?
CaCO3 (s) ⇌ CaO(s) + CO2 (g)
82.
The equilibrium constant (Kc) for this reaction is 1.60 at 990 °C:
H2 (g) + CO2 (g) ⇌ H2 O(g) + CO(g)
Calculate the number of moles of each component in the final equilibrium mixture obtained from adding 1.00 mol of H2, 2.00 mol
of CO2, 0.750 mol of H2O, and 1.00 mol of CO to a 5.00-L container at 990 °C.
83.
In a 3.0-L vessel, the following equilibrium partial pressures are measured: N2, 190 torr; H2, 317 torr; NH3, 1.00 × 103 torr.
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)
(a) How will the partial pressures of H2, N2, and NH3 change if H2 is removed from the system? Will they increase, decrease, or
remain the same?
(b) Hydrogen is removed from the vessel until the partial pressure of nitrogen, at equilibrium, is 250 torr. Calculate the partial
pressures of the other substances under the new conditions.
84.
The equilibrium constant (Kc) for this reaction is 5.0 at a given temperature.
CO(g) + H2 O(g) ⇌ CO2 (g) + H2 (g)
(a) On analysis, an equilibrium mixture of the substances present at the given temperature was found to contain 0.20 mol of CO,
0.30 mol of water vapor, and 0.90 mol of H2 in a liter. How many moles of CO2 were there in the equilibrium mixture?
(b) Maintaining the same temperature, additional H2 was added to the system, and some water vapor was removed by drying. A
new equilibrium mixture was thereby established containing 0.40 mol of CO, 0.30 mol of water vapor, and 1.2 mol of H2 in a liter.
How many moles of CO2 were in the new equilibrium mixture? Compare this with the quantity in part (a), and discuss whether the
second value is reasonable. Explain how it is possible for the water vapor concentration to be the same in the two equilibrium
solutions even though some vapor was removed before the second equilibrium was established.
85.
Antimony pentachloride decomposes according to this equation:
SbCl 5 (g) ⇌ SbCl 3 (g) + Cl2 (g)
An equilibrium mixture in a 5.00-L flask at 448 °C contains 3.85 g of SbCl5, 9.14 g of SbCl3, and 2.84 g of Cl2. How many grams
of each will be found if the mixture is transferred into a 2.00-L flask at the same temperature?
86.
Consider the equilibrium
4 NO2 (g) + 6 H2 O(g) ⇌ 4 NH3 (g) + 7 O2 (g)
(a) What is the expression for the equilibrium constant (Kc) of the reaction?
(b) How must the concentration of NH3 change to reach equilibrium if the reaction quotient is less than the equilibrium constant?
(c) If the reaction were at equilibrium, how would an increase in the volume of the reaction vessel affect the pressure of NO2?
(d) If the change in the pressure of NO2 is 28 torr as a mixture of the four gases reaches equilibrium, how much will the pressure of
O2 change?
87.
The binding of oxygen by hemoglobin (Hb), giving oxyhemoglobin (HbO2), is partially regulated by the concentration of H3O+
and dissolved CO2 in the blood. Although the equilibrium is complicated, it can be summarized as
+ +
HbO 2 (aq) + H3 O (aq) + CO2 (g) ⇌ CO2 −Hb−H + O2 (g) + H2 O(l)

(a) Write the equilibrium constant expression for this reaction.
(b) Explain why the production of lactic acid and CO2 in a muscle during exertion stimulates release of O2 from the
oxyhemoglobin in the blood passing through the muscle.
88.
Liquid N2O3 is dark blue at low temperatures, but the color fades and becomes greenish at higher temperatures as the compound
decomposes to NO and NO2. At 25 °C, a value of KP = 1.91 has been established for this decomposition. If 0.236 moles of N2O3
are placed in a 1.52-L vessel at 25 °C, calculate the equilibrium partial pressures of N2O3(g), NO2(g), and NO(g).
89.
A 1.00-L vessel at 400 °C contains the following equilibrium concentrations: N2, 1.00 M; H2, 0.50 M; and NH3, 0.25 M. How
many moles of hydrogen must be removed from the vessel to increase the concentration of nitrogen to 1.1 M? The equilibrium
reaction is
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

CHAPTER OVERVIEW
14: Acid-Base Equilibria

General Chemistry
This chapter will illustrate the chemistry of acid-base reactions and equilibria, and provide you with tools for quantifying the
concentrations of acids and bases in solutions.
14.1: Introduction
14.3: pH and pOH
14.7: Buffers
14.9: Key Terms
14.11: Summary
14.12: Exercises
This page titled 14: Acid-Base Equilibria is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source
1
14.1: Introduction
Figure 14.1 Sinkholes such as this are the result of reactions between acidic groundwaters and basic rock formations, like
limestone. (credit: modification of work by Emil Kehnel)
Chapter Outline
14.1 Brønsted-Lowry Acids and Bases
14.2 pH and pOH
14.3 Relative Strengths of Acids and Bases
14.4 Hydrolysis of Salts
14.5 Polyprotic Acids
14.6 Buffers
14.7 Acid-Base Titrations
Liquid water is essential to life on our planet, and chemistry involving the characteristic ions of water, H+ and OH–, is widely
encountered in nature and society. As introduced in another chapter of this text, acid-base chemistry involves the transfer of
hydrogen ions from donors (acids) to acceptors (bases). These H+ transfer reactions are reversible, and the equilibria established by
acid-base systems are essential aspects of phenomena ranging from sinkhole formation (Figure 14.1) to oxygen transport in the
human body. This chapter will further explore acid-base chemistry with an emphasis on the equilibrium aspects of this important
reaction class.

Identify acids, bases, and conjugate acid-base pairs according to the Brønsted-Lowry definition
Write equations for acid and base ionization reactions
Use the ion-product constant for water to calculate hydronium and hydroxide ion concentrations
Describe the acid-base behavior of amphiprotic substances
The acid-base reaction class has been studied for quite some time. In 1680, Robert Boyle reported traits of acid solutions that
included their ability to dissolve many substances, to change the colors of certain natural dyes, and to lose these traits after coming
in contact with alkali (base) solutions. In the eighteenth century, it was recognized that acids have a sour taste, react with limestone
to liberate a gaseous substance (now known to be CO2), and interact with alkalis to form neutral substances. In 1815, Humphry
Davy contributed greatly to the development of the modern acid-base concept by demonstrating that hydrogen is the essential
constituent of acids. Around that same time, Joseph Louis Gay-Lussac concluded that acids are substances that can neutralize bases
and that these two classes of substances can be defined only in terms of each other. The significance of hydrogen was reemphasized
in 1884 when Svante Arrhenius defined an acid as a compound that dissolves in water to yield hydrogen cations (now recognized
to be hydronium ions) and a base as a compound that dissolves in water to yield hydroxide anions.
Johannes Brønsted and Thomas Lowry proposed a more general description in 1923 in which acids and bases were defined in terms
of the transfer of hydrogen ions, H+. (Note that these hydrogen ions are often referred to simply as protons, since that subatomic
particle is the only component of cations derived from the most abundant hydrogen isotope, 1H.) A compound that donates a proton
to another compound is called a Brønsted-Lowry acid, and a compound that accepts a proton is called a Brønsted-Lowry base. An
acid-base reaction is, thus, the transfer of a proton from a donor (acid) to an acceptor (base).
The concept of conjugate pairs is useful in describing Brønsted-Lowry acid-base reactions (and other reversible reactions, as well).
When an acid donates H+, the species that remains is called the conjugate base of the acid because it reacts as a proton acceptor in
the reverse reaction. Likewise, when a base accepts H+, it is converted to its conjugate acid. The reaction between water and
ammonia illustrates this idea. In the forward direction, water acts as an acid by donating a proton to ammonia and subsequently
becoming a hydroxide ion, OH−, the conjugate base of water. The ammonia acts as a base in accepting this proton, becoming an
ammonium ion, NH , the conjugate acid of ammonia. In the reverse direction, a hydroxide ion acts as a base in accepting a
4
+
proton from ammonium ion, which acts as an acid.
The reaction between a Brønsted-Lowry acid and water is called acid ionization. For example, when hydrogen fluoride dissolves in
water and ionizes, protons are transferred from hydrogen fluoride molecules to water molecules, yielding hydronium ions and
fluoride ions:

Base ionization of a species occurs when it accepts protons from water molecules. In the example below, pyridine molecules,
C5NH5, undergo base ionization when dissolved in water, yielding hydroxide and pyridinium ions:
The preceding ionization reactions suggest that water may function as both a base (as in its reaction with hydrogen fluoride) and an
acid (as in its reaction with ammonia). Species capable of either donating or accepting protons are called amphiprotic, or more
generally, amphoteric, a term that may be used for acids and bases per definitions other than the Brønsted-Lowry one. The
equations below show the two possible acid-base reactions for two amphiprotic species, bicarbonate ion and water:
– 2– +
HCO3 (aq) + H2 O(l) CO3 (aq) + H3 O (aq)
– –
HCO3 (aq) + H2 O(l) H2 CO3 (aq) + OH (aq)
The first equation represents the reaction of bicarbonate as an acid with water as a base, whereas the second represents reaction of
bicarbonate as a base with water as an acid. When bicarbonate is added to water, both these equilibria are established
simultaneously and the composition of the resulting solution may be determined through appropriate equilibrium calculations, as
described later in this chapter.
In the liquid state, molecules of an amphiprotic substance can react with one another as illustrated for water in the equations below:
The process in which like molecules react to yield ions is called autoionization. Liquid water undergoes autoionization to a very
slight extent; at 25 °C, approximately two out of every billion water molecules are ionized. The extent of the water autoionization
process is reflected in the value of its equilibrium constant, the ion-product constant for water, Kw:
+ − + −
H2 O(l) + H2 O(l) ⇌ H3 O (aq) + OH (aq) Kw = [ H3 O ][ OH ]

The slight ionization of pure water is reflected in the small value of the equilibrium constant; at 25 °C, Kw has a value of 1.0 ×
10−14. The process is endothermic, and so the extent of ionization and the resulting concentrations of hydronium ion and hydroxide
ion increase with temperature. For example, at 100 °C, the value for Kw is about 5.6 × 10−13, roughly 50 times larger than the
value at 25 °C.
14.2.0.1: Example 14.1

14.2.0.0.1: Ion Concentrations in Pure Water
What are the hydronium ion concentration and the hydroxide ion concentration in pure water at 25 °C?
The autoionization of water yields the same number of hydronium and hydroxide ions. Therefore, in pure water, [H3O+] =
[OH−] = x. At 25 °C:
+ − 2 −14
Kw = [ H3 O ][ OH ] = (x)(x) = x = 1.0 × 10
So:
− −−−−−−− −−
+ − −14 −7
x = [ H3 O ] = [ OH ] = √ 1.0 × 10 = 1.0 × 10 M
The hydronium ion concentration and the hydroxide ion concentration are the same, 1.0 × 10−7 M.
The ion product of water at 80 °C is 2.4 × 10−13. What are the concentrations of hydronium and hydroxide ions in pure water
at 80 °C?
14.2.0.1: Answer:
[H3O+] = [OH−] = 4.9 × 10−7 M
14.2.0.1: Example 14.2

14.2.0.0.1: The Inverse Relation between [H3O+] and [OH−]
A solution of an acid in water has a hydronium ion concentration of 2.0 × 10−6 M. What is the concentration of hydroxide ion
at 25 °C?
Use the value of the ion-product constant for water at 25 °C
+ − + − −14
2 H2 O(l) ⇌ H3 O (aq) + OH (aq) Kw = [ H3 O ][ OH ] = 1.0 × 10
to calculate the missing equilibrium concentration.

Rearrangement of the Kw expression shows that [OH−] is inversely proportional to [H3O+]:
−14
−
Kw 1.0 × 10
−9
[ OH ] = = = 5.0 × 10
+ −6
[ H3 O ] 2.0 × 10
Compared with pure water, a solution of acid exhibits a higher concentration of hydronium ions (due to ionization of the acid)
and a proportionally lower concentration of hydroxide ions. This may be explained via Le Châtelier’s principle as a left shift in
the water autoionization equilibrium resulting from the stress of increased hydronium ion concentration.
Substituting the ion concentrations into the Kw expression confirms this calculation, resulting in the expected value:
+ − −6 −9 −14
Kw = [ H3 O ][ OH ] = (2.0 × 10 )(5.0 × 10 ) = 1.0 × 10

What is the hydronium ion concentration in an aqueous solution with a hydroxide ion concentration of 0.001 M at 25 °C?
14.2.0.1: Answer:
[H3O+] = 1 × 10−11 M

14.2.0.1: Example 14.3
14.2.0.0.1: Representing the Acid-Base Behavior of an Amphoteric Substance
Write separate equations representing the reaction of HSO 3
−
(a) as an acid with OH−

(b) as a base with HI
(a) HSO 3
−
(aq) + OH
−
(aq) ⇌ SO 3
2−
(aq) + H2 O(l)
(b) HSO 3
−
(aq) + HI(aq) ⇌ H2 SO 3 (aq) + I
−
(aq)

Write separate equations representing the reaction of H 2 PO4
−
(a) as a base with HBr

(b) as an acid with OH−
14.2.0.1: Answer:
(a) H 2 PO4
−
(aq) + HBr(aq) ⇌ H3 PO4 (aq) + Br
−
(aq); (b) H
2 PO4
−
(aq) + OH
−
(aq) ⇌ HPO4
2−
(aq) + H2 O(l)
This page titled 14.2: Brønsted-Lowry Acids and Bases is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

14.3: pH and pOH

Explain the characterization of aqueous solutions as acidic, basic, or neutral
Express hydronium and hydroxide ion concentrations on the pH and pOH scales
Perform calculations relating pH and pOH
As discussed earlier, hydronium and hydroxide ions are present both in pure water and in all aqueous solutions, and their
concentrations are inversely proportional as determined by the ion product of water (Kw). The concentrations of these ions in a
solution are often critical determinants of the solution’s properties and the chemical behaviors of its other solutes, and specific
vocabulary has been developed to describe these concentrations in relative terms. A solution is neutral if it contains equal
concentrations of hydronium and hydroxide ions; acidic if it contains a greater concentration of hydronium ions than hydroxide
ions; and basic if it contains a lesser concentration of hydronium ions than hydroxide ions.
A common means of expressing quantities that may span many orders of magnitude is to use a logarithmic scale. One such scale
that is very popular for chemical concentrations and equilibrium constants is based on the p-function, defined as shown where “X”
is the quantity of interest and “log” is the base-10 logarithm:
pX = −log X
The pH of a solution is therefore defined as shown here, where [H3O+] is the molar concentration of hydronium ion in the solution:
+
pH = −log [ H3 O ]
Rearranging this equation to isolate the hydronium ion molarity yields the equivalent expression:
+ −pH
[ H3 O ] = 10
Likewise, the hydroxide ion molarity may be expressed as a p-function, or pOH:

−
pOH = −log [ OH ]
or
− −pOH
[ OH ] = 10
Finally, the relation between these two ion concentration expressed as p-functions is easily derived from the Kw expression:
+ −
Kw = [ H3 O ] [ OH ]
+ − + −
−log Kw = −log ([ H3 O ] [ OH ]) = −log [ H3 O ] + −log [ OH ]
pKw = pH + pOH
At 25 °C, the value of Kw is 1.0 × 10−14, and so:

14.00 = pH + pOH
As was shown in Example 14.1, the hydronium ion molarity in pure water (or any neutral solution) is 1.0 × 10−7 M at 25 °C. The
pH and pOH of a neutral solution at this temperature are therefore:
+ −7
pH = −log [ H3 O ] = −log (1.0 × 1 0 ) = 7.00
− −7
pOH = −log [ OH ] = −log (1.0 × 1 0 ) = 7.00
And so, at this temperature, acidic solutions are those with hydronium ion molarities greater than 1.0 × 10−7 M and hydroxide ion
molarities less than 1.0 × 10−7 M (corresponding to pH values less than 7.00 and pOH values greater than 7.00). Basic solutions
are those with hydronium ion molarities less than 1.0 × 10−7 M and hydroxide ion molarities greater than 1.0 × 10−7 M
(corresponding to pH values greater than 7.00 and pOH values less than 7.00).

Since the autoionization constant Kw is temperature dependent, these correlations between pH values and the acidic/neutral/basic
adjectives will be different at temperatures other than 25 °C. For example, the “Check Your Learning” exercise accompanying
Example 14.1 showed the hydronium molarity of pure water at 80 °C is 4.9 × 10−7 M, which corresponds to pH and pOH values
of:
+ −7
pH = −log [ H3 O ] = −log (4.9 × 10 ) = 6.31
− −7
pOH = −log [ OH ] = −log (4.9 × 10 ) = 6.31
At this temperature, then, neutral solutions exhibit pH = pOH = 6.31, acidic solutions exhibit pH less than 6.31 and pOH greater
than 6.31, whereas basic solutions exhibit pH greater than 6.31 and pOH less than 6.31. This distinction can be important when
studying certain processes that occur at other temperatures, such as enzyme reactions in warm-blooded organisms at a temperature
around 36–40 °C. Unless otherwise noted, references to pH values are presumed to be those at 25 °C (Table 14.1).
Summary of Relations for Acidic, Basic and Neutral Solutions
Classification Relative Ion Concentrations pH at 25 °C
acidic [H3O+] > [OH−] pH < 7
neutral [H3O+] = [OH−] pH = 7
basic [H3O+] < [OH−] pH > 7
Table 14.1
Figure 14.2 shows the relationships between [H3O+], [OH−], pH, and pOH for solutions classified as acidic, basic, and neutral.

Figure 14.2 The pH and pOH scales represent concentrations of H3O+ and OH−, respectively. The pH and pOH values of some
common substances at 25 °C are shown in this chart.
14.3.0.1: Example 14.4

14.3.0.0.1: Calculation of pH from [H3O+]
What is the pH of stomach acid, a solution of HCl with a hydronium ion concentration of 1.2 × 10−3 M?
+
pH = −log [ H3 O ]
−3
= −log(1.2 × 10 )
= − (−2.92) = 2.92
(The use of logarithms is explained in Appendix B. When taking the log of a value, keep as many decimal places in the result
as there are significant figures in the value.)
Water exposed to air contains carbonic acid, H2CO3, due to the reaction between carbon dioxide and water:
CO2 (aq) + H2 O(l) ⇌ H2 CO3 (aq)
Air-saturated water has a hydronium ion concentration caused by the dissolved CO2 of 2.0 × 10−6 M, about 20-times larger
than that of pure water. Calculate the pH of the solution at 25 °C.
14.3.0.1: Answer:
5.70
14.3.0.1: Example 14.5

14.3.0.0.1: Calculation of Hydronium Ion Concentration from pH
Calculate the hydronium ion concentration of blood, the pH of which is 7.3.
+
pH = −log [ H3 O ] = 7.3
+
log [ H3 O ] = −7.3
+ −7.3 +
[ H3 O ] = 10 or [ H3 O ] = antilog of −7.3
+ −8
[ H3 O ] = 5 × 10 M
(On a calculator take the antilog, or the “inverse” log, of −7.3, or calculate 10−7.3.)

Calculate the hydronium ion concentration of a solution with a pH of −1.07.
14.3.0.1: Answer:
12 M

14.3.0.0.1: Environmental Science
Normal rainwater has a pH between 5 and 6 due to the presence of dissolved CO2 which forms carbonic acid:
H2 O(l) + CO2 (g) ⟶ H2 CO3 (aq)
+ −
H2 CO3 (aq) ⇌ H (aq) + HCO3 (aq)
Acid rain is rainwater that has a pH of less than 5, due to a variety of nonmetal oxides, including CO2, SO2, SO3, NO, and NO2
being dissolved in the water and reacting with it to form not only carbonic acid, but sulfuric acid and nitric acid. The formation
and subsequent ionization of sulfuric acid are shown here:
H2 O(l) + SO 3 (g) ⟶ H2 SO 4 (aq)
+ −
H2 SO 4 (aq) ⟶ H (aq) + HSO 4 (aq)
Carbon dioxide is naturally present in the atmosphere because most organisms produce it as a waste product of metabolism.
Carbon dioxide is also formed when fires release carbon stored in vegetation or fossil fuels. Sulfur trioxide in the atmosphere is
naturally produced by volcanic activity, but it also originates from burning fossil fuels, which have traces of sulfur, and from
the process of “roasting” ores of metal sulfides in metal-refining processes. Oxides of nitrogen are formed in internal
combustion engines where the high temperatures make it possible for the nitrogen and oxygen in air to chemically combine.
Acid rain is a particular problem in industrial areas where the products of combustion and smelting are released into the air
without being stripped of sulfur and nitrogen oxides. In North America and Europe until the 1980s, it was responsible for the
destruction of forests and freshwater lakes, when the acidity of the rain actually killed trees, damaged soil, and made lakes
uninhabitable for all but the most acid-tolerant species. Acid rain also corrodes statuary and building facades that are made of
marble and limestone (Figure 14.3). Regulations limiting the amount of sulfur and nitrogen oxides that can be released into the
atmosphere by industry and automobiles have reduced the severity of acid damage to both natural and manmade environments
in North America and Europe. It is now a growing problem in industrial areas of China and India.
For further information on acid rain, visit this website hosted by the US Environmental Protection Agency.
Figure 14.3 (a) Acid rain makes trees more susceptible to drought and insect infestation, and depletes nutrients in the soil. (b) It
also is corrodes statues that are carved from marble or limestone. (credit a: modification of work by Chris M Morris; credit b:
modification of work by “Eden, Janine and Jim”/Flickr)

14.3.0.1: Example 14.6
14.3.0.0.1: Calculation of pOH
What are the pOH and the pH of a 0.0125-M solution of potassium hydroxide, KOH?
Potassium hydroxide is a highly soluble ionic compound and completely dissociates when dissolved in dilute solution, yielding
[OH−] = 0.0125 M:
−
pOH = −log [ OH ] = −log 0.0125
= −(−1.903) = 1.903
The pH can be found from the pOH:

pH + pOH = 14.00
pH = 14.00 − pOH = 14.00 − 1.903 = 12.10

The hydronium ion concentration of vinegar is approximately 4 × 10−3 M. What are the corresponding values of pOH and pH?
14.3.0.1: Answer:
pOH = 11.6, pH = 2.4
The acidity of a solution is typically assessed experimentally by measurement of its pH. The pOH of a solution is not usually
measured, as it is easily calculated from an experimentally determined pH value. The pH of a solution can be directly measured
using a pH meter (Figure 14.4).
Figure 14.4 (a) A research-grade pH meter used in a laboratory can have a resolution of 0.001 pH units, an accuracy of ± 0.002 pH
units, and may cost in excess of $1000. (b) A portable pH meter has lower resolution (0.01 pH units), lower accuracy (± 0.2 pH
units), and a far lower price tag. (credit b: modification of work by Jacopo Werther)
The pH of a solution may also be visually estimated using colored indicators (Figure 14.5). The acid-base equilibria that enable use
of these indicator dyes for pH measurements are described in a later section of this chapter.

Figure 14.5 (a) A solution containing a dye mixture, called universal indicator, takes on different colors depending upon its pH. (b)
Convenient test strips, called pH paper, contain embedded indicator dyes that yield pH-dependent color changes on contact with
aqueous solutions.(credit: modification of work by Sahar Atwa)
This page titled 14.3: pH and pOH is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source


Assess the relative strengths of acids and bases according to their ionization constants
Rationalize trends in acid–base strength in relation to molecular structure
Carry out equilibrium calculations for weak acid–base systems
14.4.0.1: Acid and Base Ionization Constants

The relative strength of an acid or base is the extent to which it ionizes when dissolved in water. If the ionization reaction is
essentially complete, the acid or base is termed strong; if relatively little ionization occurs, the acid or base is weak. As will be
evident throughout the remainder of this chapter, there are many more weak acids and bases than strong ones. The most common
strong acids and bases are listed in Figure 14.6.
Figure 14.6 Some of the common strong acids and bases are listed here.
The relative strengths of acids may be quantified by measuring their equilibrium constants in aqueous solutions. In solutions of the
same concentration, stronger acids ionize to a greater extent, and so yield higher concentrations of hydronium ions than do weaker
acids. The equilibrium constant for an acid is called the acid-ionization constant, Ka. For the reaction of an acid HA:
+ −
HA(aq) + H2 O(l) ⇌ H3 O (aq) + A (aq),
the acid ionization constant is written

+ −
[ H3 O ][ A ]
Ka =
[HA]
where the concentrations are those at equilibrium. Although water is a reactant in the reaction, it is the solvent as well, so we do not
include [H2O] in the equation. The larger the Ka of an acid, the larger the concentration of H O and A− relative to the
3
+
concentration of the nonionized acid, HA, in an equilibrium mixture, and the stronger the acid. An acid is classified as “strong”
when it undergoes complete ionization, in which case the concentration of HA is zero and the acid ionization constant is
immeasurably large (Ka ≈ ∞). Acids that are partially ionized are called “weak,” and their acid ionization constants may be
experimentally measured. A table of ionization constants for weak acids is provided in Appendix H.
To illustrate this idea, three acid ionization equations and Ka values are shown below. The ionization constants increase from first to
last of the listed equations, indicating the relative acid strength increases in the order CH3CO2H < HNO2 < HSO : 4
−
+ − −5
CH3 CO2 H(aq) + H2 O(l) ⇌ H3 O (aq) + CH3 CO2 (aq) Ka = 1.8 × 10

+ − −4
HNO2 (aq) + H2 O(l) ⇌ H3 O (aq) + NO2 (aq) Ka = 4.6 × 10
− + 2− −2
HSO 4 (aq) + H2 O(aq) ⇌ H3 O (aq) + SO 4 (aq) Ka = 1.2 × 10
Another measure of the strength of an acid is its percent ionization. The percent ionization of a weak acid is defined in terms of the
composition of an equilibrium mixture:
+
[ H3 O ]
eq
% ionization = × 100
[HA]
0
where the numerator is equivalent to the concentration of the acid's conjugate base (per stoichiometry, [A−] = [H3O+]). Unlike the
Ka value, the percent ionization of a weak acid varies with the initial concentration of acid, typically decreasing as concentration
increases. Equilibrium calculations of the sort described later in this chapter can be used to confirm this behavior.
14.4.0.1: Example 14.7

14.4.0.0.1: Calculation of Percent Ionization from pH
Calculate the percent ionization of a 0.125-M solution of nitrous acid (a weak acid), with a pH of 2.09.
The percent ionization for an acid is:
+
[ H3 O ]
eq
× 100
[ HNO2 ]
0
Converting the provided pH to hydronium ion molarity yields

+ −2.09
[ H3 O ] = 10 = 0.0081 M
Substituting this value and the provided initial acid concentration into the percent ionization equation gives
−3
8.1 × 10
× 100 = 6.5%
0.125
(Recall the provided pH value of 2.09 is logarithmic, and so it contains just two significant digits, limiting the certainty of the
computed percent ionization.)
Calculate the percent ionization of a 0.10-M solution of acetic acid with a pH of 2.89.
14.4.0.1: Answer:
1.3% ionized

View the simulation of strong and weak acids and bases at the molecular level.
Just as for acids, the relative strength of a base is reflected in the magnitude of its base-ionization constant (Kb) in aqueous
solutions. In solutions of the same concentration, stronger bases ionize to a greater extent, and so yield higher hydroxide ion
concentrations than do weaker bases. A stronger base has a larger ionization constant than does a weaker base. For the reaction of a
base, B:
+ −
B(aq) + H2 O(l) ⇌ HB (aq) + OH (aq),
the ionization constant is written as

+ −
[ HB ] [ OH ]
Kb =
[B]
Inspection of the data for three weak bases presented below shows the base strength increases in the order
− −
NO2 < CH2 CO2 < NH3 .

− − −11
NO2 (aq) + H2 O(l) ⇌ HNO2 (aq) + OH (aq) Kb = 2.17 × 10
− − −10
CH3 CO2 (aq) + H2 O(l) ⇌ CH3 CO2 H(aq) + OH (aq) Kb = 5.6 × 10
+ − −5
NH3 (aq) + H2 O(l) ⇌ NH4 (aq) + OH (aq) Kb = 1.8 × 10
A table of ionization constants for weak bases appears in Appendix I. As for acids, the relative strength of a base is also reflected in
its percent ionization, computed as
−
% ionization = [ OH ] / [B] ×100%
eq 0
but will vary depending on the base ionization constant and the initial concentration of the solution.
14.4.0.1: Relative Strengths of Conjugate Acid-Base Pairs

Brønsted-Lowry acid-base chemistry is the transfer of protons; thus, logic suggests a relation between the relative strengths of
conjugate acid-base pairs. The strength of an acid or base is quantified in its ionization constant, Ka or Kb, which represents the
extent of the acid or base ionization reaction. For the conjugate acid-base pair HA / A−, ionization equilibrium equations and
ionization constant expressions are
+ −
[ H3 O ] [A ]
+ −
HA(aq) + H2 O(l) ⇌ H3 O (aq) + A (aq) Ka =
[HA]
–
[HA] [ OH ]
− −
A (aq) + H2 O(l) ⇌ OH (aq) + HA(aq) Kb =
−
[A ]
Adding these two chemical equations yields the equation for the autoionization for water:
− + − −
HA(aq) + H2 O(l) + A (aq) + H2 O(l) ⇌ H3 O (aq) + A (aq) + OH (aq) + HA(aq)
+ −
2H2 O(l) ⇌ H3 O (aq) + OH (aq)
As discussed in another chapter on equilibrium, the equilibrium constant for a summed reaction is equal to the mathematical
product of the equilibrium constants for the added reactions, and so
+ − −
[ H3 O ][ A ] [HA] [ OH ]
+ −
Ka × Kb = × = [ H3 O ] [ OH ] = Kw
−
[HA] [A ]
This equation states the relation between ionization constants for any conjugate acid-base pair, namely, their mathematical product
is equal to the ion product of water, Kw. By rearranging this equation, a reciprocal relation between the strengths of a conjugate
acid-base pair becomes evident:
Ka = Kw / Kb or Kb = Kw / Ka
The inverse proportional relation between Ka and Kb means the stronger the acid or base, the weaker its conjugate partner. Figure
14.7 illustrates this relation for several conjugate acid-base pairs.

Figure 14.7 Relative strengths of several conjugate acid-base pairs are shown.
Figure 14.8 This figure shows strengths of conjugate acid-base pairs relative to the strength of water as the reference substance.
The listing of conjugate acid–base pairs shown in Figure 14.8 is arranged to show the relative strength of each species as compared
with water, whose entries are highlighted in each of the table’s columns. In the acid column, those species listed below water are
weaker acids than water. These species do not undergo acid ionization in water; they are not Bronsted-Lowry acids. All the species
listed above water are stronger acids, transferring protons to water to some extent when dissolved in an aqueous solution to
generate hydronium ions. Species above water but below hydronium ion are weak acids, undergoing partial acid ionization, wheres
those above hydronium ion are strong acids that are completely ionized in aqueous solution.
If all these strong acids are completely ionized in water, why does the column indicate they vary in strength, with nitric acid being
the weakest and perchloric acid the strongest? Notice that the sole acid species present in an aqueous solution of any strong acid is
H3O+(aq), meaning that hydronium ion is the strongest acid that may exist in water; any stronger acid will react completely with
water to generate hydronium ions. This limit on the acid strength of solutes in a solution is called a leveling effect. To measure the
differences in acid strength for “strong” acids, the acids must be dissolved in a solvent that is less basic than water. In such
solvents, the acids will be “weak,” and so any differences in the extent of their ionization can be determined. For example, the
binary hydrogen halides HCl, HBr, and HI are strong acids in water but weak acids in ethanol (strength increasing HCl < HBr <
HI).

The right column of Figure 14.8 lists a number of substances in order of increasing base strength from top to bottom. Following the
same logic as for the left column, species listed above water are weaker bases and so they don’t undergo base ionization when
dissolved in water. Species listed between water and its conjugate base, hydroxide ion, are weak bases that partially ionize. Species
listed below hydroxide ion are strong bases that completely ionize in water to yield hydroxide ions (i.e., they are leveled to
hydroxide). A comparison of the acid and base columns in this table supports the reciprocal relation between the strengths of
conjugate acid-base pairs. For example, the conjugate bases of the strong acids (top of table) are all of negligible strength. A strong
acid exhibits an immeasurably large Ka, and so its conjugate base will exhibit a Kb that is essentially zero:
strong acid : Ka ≈ ∞
conjugate base : Kb = Kw / Ka = Kw /∞ ≈ 0
A similar approach can be used to support the observation that conjugate acids of strong bases (Kb ≈ ∞) are of negligible strength
(Ka ≈ 0).
14.4.0.1: Example 14.8

14.4.0.0.1: Calculating Ionization Constants for Conjugate Acid-Base Pairs
Use the Kb for the nitrite ion, NO 2
−
, to calculate the Ka for its conjugate acid.
Kb for NO is given in this section as 2.17 × 10−11. The conjugate acid of NO
2
−
2
−
is HNO2; Ka for HNO2 can be calculated
using the relationship:
−14
Ka × Kb = 1.0 × 10 = Kw
Solving for Ka yields

−14
Kw 1.0 × 10 −4
Ka = = = 4.6 × 10
−11
Kb 2.17 × 10
This answer can be verified by finding the Ka for HNO2 in Appendix H.

Determine the relative acid strengths of NH and HCN by comparing their ionization constants. The ionization constant of
4
+
HCN is given in Appendix H as 4.9 × 10−10. The ionization constant of NH is not listed, but the ionization constant of its
4
+
conjugate base, NH3, is listed as 1.8 × 10−5.
14.4.0.1: Answer:
NH4
+
is the slightly stronger acid (Ka for NH 4
+
= 5.6 × 10−10).
14.4.0.1: Acid-Base Equilibrium Calculations

The chapter on chemical equilibria introduced several types of equilibrium calculations and the various mathematical strategies that
are helpful in performing them. These strategies are generally useful for equilibrium systems regardless of chemical reaction class,
and so they may be effectively applied to acid-base equilibrium problems. This section presents several example exercises
involving equilibrium calculations for acid-base systems.

14.4.0.1: Example 14.9
14.4.0.0.1: Determination of Ka from Equilibrium Concentrations
Acetic acid is the principal ingredient in vinegar (Figure 14.9) that provides its sour taste. At equilibrium, a solution contains
[CH3CO2H] = 0.0787 M and [H O ] = [CH CO ] = 0.00118 M . What is the value of Ka for acetic acid?
3
+
3 2
−

Figure 14.9 Vinegar contains acetic acid, a weak acid. (credit: modification of work by “HomeSpot HQ”/Flickr)
The relevant equilibrium equation and its equilibrium constant expression are shown below. Substitution of the provided
equilibrium concentrations permits a straightforward calculation of the Ka for acetic acid.
+ −
CH3 CO2 H(aq) + H2 O(l) ⇌ H3 O (aq) + CH3 CO2 (aq)
+ −
[ H3 O ] [ CH3 CO2 ] (0.00118)(0.00118)
−5
Ka = = = 1.77 × 10
[ CH3 CO2 H] 0.0787

The HSO 4
−
ion, weak acid used in some household cleansers:
− + 2−
HSO 4 (aq) + H2 O(l) ⇌ H3 O (aq) + SO 4 (aq)
What is the acid ionization constant for this weak acid if an equilibrium mixture has the following composition: [ H3 O
+
] =
0.027 M; [HSO ] = 0.29 M ; and [SO ] = 0.13 M ?
4
−
4
2−
14.4.0.1: Answer:
Ka for HSO 4
−
= 1.2 × 10−2
14.4.0.1: Example 14.10

14.4.0.0.4: Determination of Kb from Equilibrium Concentrations
Caffeine, C8H10N4O2 is a weak base. What is the value of Kb for caffeine if a solution at equilibrium has [C8H10N4O2] = 0.050
M, [C H N O H ] = 5.0 × 10−3 M, and [OH−] = 2.5 × 10−3 M?
8 10 4 2
+
The relevant equilibrium equation and its equilibrium constant expression are shown below. Substitution of the provided
equilibrium concentrations permits a straightforward calculation of the Kb for caffeine.
+ −
C8 H10 N4 O2 (aq) + H2 O(l) ⇌ C8 H10 N4 O2 H (aq) + OH (aq)
+ − −3 −3
[ C8 H10 N4 O2 H ][ OH ] (5.0 × 10 )(2.5 × 10 )
−4
Kb = = = 2.5 × 10
[ C8 H10 N4 O2 ] 0.050

What is the equilibrium constant for the ionization of the HPO 4
2−
ion, a weak base
2− − −
HPO4 (aq) + H2 O(l) ⇌ H2 PO4 (aq) + OH (aq)
if the composition of an equilibrium mixture is as follows: [OH−] = 1.3 × 10−6 M; [ H2 PO4

−
] = 0.042 M ; and
2−
[ HPO4 ] = 0.341 M ?
14.4.0.1: Answer:
Kb for HPO 4
2−
= 1.6 × 10
−7
14.4.0.1: Example 14.11

14.4.0.0.7: Determination of Ka or Kb from pH
The pH of a 0.0516-M solution of nitrous acid, HNO2, is 2.34. What is its Ka?
+ −
HNO2 (aq) + H2 O(l) ⇌ H3 O (aq) + NO2 (aq)
The nitrous acid concentration provided is a formal concentration, one that does not account for any chemical equilibria that
may be established in solution. Such concentrations are treated as “initial” values for equilibrium calculations using the ICE
table approach. Notice the initial value of hydronium ion is listed as approximately zero because a small concentration of H3O+
is present (1 × 10−7 M) due to the autoprotolysis of water. In many cases, such as all the ones presented in this chapter, this
concentration is much less than that generated by ionization of the acid (or base) in question and may be neglected.
The pH provided is a logarithmic measure of the hydronium ion concentration resulting from the acid ionization of the nitrous
acid, and so it represents an “equilibrium” value for the ICE table:
+ −2.34
[ H3 O ] = 10 = 0.0046 M
The ICE table for this system is then
Finally, calculate the value of the equilibrium constant using the data in the table:
+ −
[ H3 O ] [ NO2 ] (0.0046)(0.0046)
−4
Ka = = = 4.6 × 10
[ HNO2 ] (0.0470)

14.4.0.0.9: Check Your Learning.
The pH of a solution of household ammonia, a 0.950-M solution of NH3, is 11.612. What is Kb for NH3.
14.4.0.1: Answer:
Kb = 1.8 × 10−5
14.4.0.1: Example 14.12

14.4.0.0.10: Calculating Equilibrium Concentrations in a Weak Acid Solution
Formic acid, HCO2H, is one irritant that causes the body’s reaction to some ant bites and stings (Figure 14.10).
Figure 14.10 The pain of some ant bites and stings is caused by formic acid. (credit: John Tann)
What is the concentration of hydronium ion and the pH of a 0.534-M solution of formic acid?
+ − −4
HCO2 H(aq) + H2 O(l) ⇌ H3 O (aq) + HCO2 (aq) Ka = 1.8 × 10
14.4.0.0.11: Solution
The ICE table for this system is
Substituting the equilibrium concentration terms into the Ka expression gives

+ −
[ H3 O ] [ HCO2 ]
−4
Ka = 1.8 × 10 =
[ HCO2 H]
(x) (x)
−4
= = 1.8 × 10
0.534 − x
The relatively large initial concentration and small equilibrium constant permits the simplifying assumption that x will be much
lesser than 0.534, and so the equation becomes

2
−4
x
Ka = 1.8 × 10 =
0.534
Solving the equation for x yields

2 −4 −5
x = 0.534 × (1.8 × 10 ) = 9.6 × 10
− −−−−−−− −
−5
x = √ 9.6 × 10
−3
= 9.8 × 10 M
To check the assumption that x is small compared to 0.534, its relative magnitude can be estimated:
−3
x 9.8 × 10 −2
= = 1.8 × 10 (1.8% of 0.534)
0.534 0.534
Because x is less than 5% of the initial concentration, the assumption is valid.

As defined in the ICE table, x is equal to the equilibrium concentration of hydronium ion:
+
x = [ H3 O ] = 0.0098 M
Finally, the pH is calculated to be

+
pH = −log[ H3 O ] = −log(0.0098) = 2.01

Only a small fraction of a weak acid ionizes in aqueous solution. What is the percent ionization of a 0.100-M solution of acetic
acid, CH3CO2H?
+ − −5
14.4.0.1: Answer:
percent ionization = 1.3%
14.4.0.1: Example 14.13

14.4.0.0.13: Calculating Equilibrium Concentrations in a Weak Base Solution
Find the concentration of hydroxide ion, the pOH, and the pH of a 0.25-M solution of trimethylamine, a weak base:
+ − −5
(CH3 )3 N(aq) + H2 O(l) ⇌ (CH3 )3 NH (aq) + OH (aq) Kb = 6.3 × 10
14.4.0.0.14: Solution
Substituting the equilibrium concentration terms into the Kb expression gives

+ −
[ (CH3 ) NH ] [ OH ] (x) (x)
3 −5
Kb = = = 6.3 × 10
[ (CH3 )3 N] 0.25 − x
Assuming x << 0.25 and solving for x yields

−3
x = 4.0 × 10 M
This value is less than 5% of the initial concentration (0.25), so the assumption is justified.
As defined in the ICE table, x is equal to the equilibrium concentration of hydroxide ion:
− −3
[ OH ] = ~0 + x = x = 4.0 × 10 M
−3
= 4.0 × 10 M
The pOH is calculated to be

−3
pOH = −log (4.0 × 10 ) = 2.40
Using the relation introduced in the previous section of this chapter:

pH + pOH = pKw = 14.00
permits the computation of pH:

pH = 14.00 − pOH = 14.00 − 2.40 = 11.60

Calculate the hydroxide ion concentration and the percent ionization of a 0.0325-M solution of ammonia, a weak base with a
Kb of 1.76 × 10−5.
14.4.0.1: Answer:
7.56 × 10−4 M, 2.33%
In some cases, the strength of the weak acid or base and its formal (initial) concentration result in an appreciable ionization.
Though the ICE strategy remains effective for these systems, the algebra is a bit more involved because the simplifying assumption
that x is negligible cannot be made. Calculations of this sort are demonstrated in Example 14.14 below.
14.4.0.1: Example 14.14

14.4.0.0.16: Calculating Equilibrium Concentrations without Simplifying Assumptions
Sodium bisulfate, NaHSO4, is used in some household cleansers as a source of the HSO 4
−
ion, a weak acid. What is the pH of
a 0.50-M solution of HSO ? 4
−
− + 2− −2
HSO 4 (aq) + H2 O(l) ⇌ H3 O (aq) + SO 4 (aq) Ka = 1.2 × 10
14.4.0.0.17: Solution

Substituting the equilibrium concentration terms into the Ka expression gives

+ 2−
[ H3 O ] [ SO 4 ] (x) (x)
−2
Ka = 1.2 × 10 = =
−
[ HSO 4 ] 0.50 − x
If the assumption that x << 0.5 is made, simplifying and solving the above equation yields
x = 0.077 M
This value of x is clearly not significantly less than 0.50 M; rather, it is approximately 15% of the initial concentration:
When we check the assumption, we calculate:
x
[ HSO 4 − ]
i
−2
x 7.7 × 10
= = 0.15 (15%)
0.50 0.50
Because the simplifying assumption is not valid for this system, the equilibrium constant expression is solved as follows:
(x) (x)
−2
Ka = 1.2 × 10 =
0.50 − x
Rearranging this equation yields

−3 −2 2
6.0 × 10 − 1.2 × 10 x =x
Writing the equation in quadratic form gives

2 −2 −3
x + 1.2 × 10 x − 6.0 × 10 =0
Solving for the two roots of this quadratic equation results in a negative value that may be discarded as physically irrelevant
and a positive value equal to x. As defined in the ICE table, x is equal to the hydronium concentration.
+
x = [ H3 O ] = 0.072 M
+
pH = −log[ H3 O ] = −log(0.072) = 1.14

Calculate the pH in a 0.010-M solution of caffeine, a weak base:
+ − −4
C8 H10 N4 O2 (aq) + H2 O(l) ⇌ C8 H10 N4 O2 H (aq) + OH (aq) Kb = 2.5 × 10
14.4.0.1: Answer:
pH 11.16
14.4.0.1: Effect of Molecular Structure on Acid-Base Strength

14.4.0.0.1: Binary Acids and Bases
In the absence of any leveling effect, the acid strength of binary compounds of hydrogen with nonmetals (A) increases as the H-A
bond strength decreases down a group in the periodic table. For group 17, the order of increasing acidity is HF < HCl < HBr < HI.
Likewise, for group 16, the order of increasing acid strength is H2O < H2S < H2Se < H2Te.
Across a row in the periodic table, the acid strength of binary hydrogen compounds increases with increasing electronegativity of
the nonmetal atom because the polarity of the H-A bond increases. Thus, the order of increasing acidity (for removal of one proton)
across the second row is CH4 < NH3 < H2O < HF; across the third row, it is SiH4 < PH3 < H2S < HCl (see Figure 14.11).
Figure 14.11 The figure shows trends in the strengths of binary acids and bases.
14.4.0.1: Ternary Acids and Bases

Ternary compounds composed of hydrogen, oxygen, and some third element (“E”) may be structured as depicted in the image
below. In these compounds, the central E atom is bonded to one or more O atoms, and at least one of the O atoms is also bonded to
an H atom, corresponding to the general molecular formula OmE(OH)n. These compounds may be acidic, basic, or amphoteric
depending on the properties of the central E atom. Examples of such compounds include sulfuric acid, O2S(OH)2, sulfurous acid,
OS(OH)2, nitric acid, O2NOH, perchloric acid, O3ClOH, aluminum hydroxide, Al(OH)3, calcium hydroxide, Ca(OH)2, and
potassium hydroxide, KOH:

If the central atom, E, has a low electronegativity, its attraction for electrons is low. Little tendency exists for the central atom to
form a strong covalent bond with the oxygen atom, and bond a between the element and oxygen is more readily broken than bond b
between oxygen and hydrogen. Hence bond a is ionic, hydroxide ions are released to the solution, and the material behaves as a
base—this is the case with Ca(OH)2 and KOH. Lower electronegativity is characteristic of the more metallic elements; hence, the
metallic elements form ionic hydroxides that are by definition basic compounds.
If, on the other hand, the atom E has a relatively high electronegativity, it strongly attracts the electrons it shares with the oxygen
atom, making bond a relatively strongly covalent. The oxygen-hydrogen bond, bond b, is thereby weakened because electrons are
displaced toward E. Bond b is polar and readily releases hydrogen ions to the solution, so the material behaves as an acid. High
electronegativities are characteristic of the more nonmetallic elements. Thus, nonmetallic elements form covalent compounds
containing acidic −OH groups that are called oxyacids.
Increasing the oxidation number of the central atom E also increases the acidity of an oxyacid because this increases the attraction
of E for the electrons it shares with oxygen and thereby weakens the O-H bond. Sulfuric acid, H2SO4, or O2S(OH)2 (with a sulfur
oxidation number of +6), is more acidic than sulfurous acid, H2SO3, or OS(OH)2 (with a sulfur oxidation number of +4). Likewise
nitric acid, HNO3, or O2NOH (N oxidation number = +5), is more acidic than nitrous acid, HNO2, or ONOH (N oxidation number
= +3). In each of these pairs, the oxidation number of the central atom is larger for the stronger acid (Figure 14.12).
Figure 14.12 As the oxidation number of the central atom E increases, the acidity also increases.
Hydroxy compounds of elements with intermediate electronegativities and relatively high oxidation numbers (for example,
elements near the diagonal line separating the metals from the nonmetals in the periodic table) are usually amphoteric. This means
that the hydroxy compounds act as acids when they react with strong bases and as bases when they react with strong acids. The
amphoterism of aluminum hydroxide, which commonly exists as the hydrate Al(H2O)3(OH)3, is reflected in its solubility in both
strong acids and strong bases. In strong bases, the relatively insoluble hydrated aluminum hydroxide, Al(H2O)3(OH)3, is converted
into the soluble ion, [Al(H O) (OH) ] , by reaction with hydroxide ion:
2 2 4
−
− −
Al (H2 O) (OH) (aq) + OH (aq) ⇌ H2 O(l) + [Al (H2 O) (OH) ] (aq)
3 3 2 4

In this reaction, a proton is transferred from one of the aluminum-bound H2O molecules to a hydroxide ion in solution. The
Al(H2O)3(OH)3 compound thus acts as an acid under these conditions. On the other hand, when dissolved in strong acids, it is
converted to the soluble ion [Al(H O) ] by reaction with hydronium ion:
2 6
3+
+ 3+
3H3 O (aq) + Al (H2 O) (OH) (aq) ⇌ Al (H2 O) (aq) + 3H2 O(l)
3 3 6
In this case, protons are transferred from hydronium ions in solution to Al(H2O)3(OH)3, and the compound functions as a base.
This page titled 14.4: Relative Strengths of Acids and Bases is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by


Predict whether a salt solution will be acidic, basic, or neutral
Calculate the concentrations of the various species in a salt solution
Describe the acid ionization of hydrated metal ions
14.5.0.1: Salts with Acidic Ions

Salts are ionic compounds composed of cations and anions, either of which may be capable of undergoing an acid or base
ionization reaction with water. Aqueous salt solutions, therefore, may be acidic, basic, or neutral, depending on the relative acid-
base strengths of the salt's constituent ions. For example, dissolving ammonium chloride in water results in its dissociation, as
described by the equation
+ −
NH4 Cl(s) ⇌ NH4 (aq) + Cl (aq)
The ammonium ion is the conjugate acid of the base ammonia, NH3; its acid ionization (or acid hydrolysis) reaction is represented
by
+ +
NH4 (aq) + H2 O(l) ⇌ H3 O (aq) + NH3 (aq) Ka = Kw / Kb
Since ammonia is a weak base, Kb is measurable and Ka > 0 (ammonium ion is a weak acid).
The chloride ion is the conjugate base of hydrochloric acid, and so its base ionization (or base hydrolysis) reaction is represented by
− −
Cl (aq) + H2 O(l) ⇌ HCl(aq) + OH (aq) Kb = Kw / Ka
Since HCl is a strong acid, Ka is immeasurably large and Kb ≈ 0 (chloride ions don’t undergo appreciable hydrolysis).
Thus, dissolving ammonium chloride in water yields a solution of weak acid cations (NH 4
+
) and inert anions (Cl−), resulting in an
acidic solution.
14.5.0.1: Example 14.15

14.5.0.0.1: Calculating the pH of an Acidic Salt Solution
Aniline is an amine that is used to manufacture dyes. It is isolated as anilinium chloride, [C H NH ]Cl, a salt prepared by the
6 5 3
reaction of the weak base aniline and hydrochloric acid. What is the pH of a 0.233 M solution of anilinium chloride
+ +
C6 H5 NH3 (aq) + H2 O(l) ⇌ H3 O (aq) + C6 H5 NH2 (aq)
The Ka for anilinium ion is derived from the Kb for its conjugate base, aniline (see Appendix H):
−14
Kw 1.0 × 10
−5
Ka = = = 2.3 × 10
Kb −10
4.3 × 10
Using the provided information, an ICE table for this system is prepared:
Substituting these equilibrium concentration terms into the Ka expression gives

+ +
Ka = [ C6 H5 NH2 ][ H3 O ]/[ C6 H5 NH3 ]
−5
2.3 × 10 = (x)(x)/0.233 − x)
Assuming x << 0.233, the equation is simplified and solved for x:
−5 2
2.3 × 10 = x /0.233
x = 0.0023 M
The ICE table defines x as the hydronium ion molarity, and so the pH is computed as
+
pH = −log[ H3 O ] = −log(0.0023) = 2.64

What is the hydronium ion concentration in a 0.100-M solution of ammonium nitrate, NH4NO3, a salt composed of the ions
NH 4 and NO . Which is the stronger acid C H NH or NH ?
+
3
−
6 5 3
+
4
+
14.5.0.1: Answer:
[H3O+] = 7.5 × 10−6 M; C 6 H5 NH3
+
is the stronger acid.
14.5.0.1: Salts with Basic Ions

As another example, consider dissolving sodium acetate in water:
+ −
NaCH3 CO2 (s) ⇋ Na (aq) + CH3 CO2 (aq)
The sodium ion does not undergo appreciable acid or base ionization and has no effect on the solution pH. This may seem obvious
from the ion's formula, which indicates no hydrogen or oxygen atoms, but some dissolved metal ions function as weak acids, as
addressed later in this section.
The acetate ion, CH 3 CO2
−
, is the conjugate base of acetic acid, CH3CO2H, and so its base ionization (or base hydrolysis) reaction
is represented by
−
CH3 CO2 (aq) + H2 O(l) ⇌ CH3 CO2 H(aq) + OH − (aq) Kb = Kw / Ka
Because acetic acid is a weak acid, its Ka is measurable and Kb > 0 (acetate ion is a weak base).
Dissolving sodium acetate in water yields a solution of inert cations (Na+) and weak base anions (CH 3
CO2
−
), resulting in a basic
solution.
14.5.0.1: Example 14.16

14.5.0.0.1: Equilibrium in a Solution of a Salt of a Weak Acid and a Strong Base
Determine the acetic acid concentration in a solution with [CH 3 CO2
−
] = 0.050 M and [OH−] = 2.5 × 10−6 M at equilibrium.
The reaction is:
− −
CH3 CO2 (aq) + H2 O(l) ⇌ CH3 CO2 H(aq) + OH (aq)
The provided equilibrium concentrations and a value for the equilibrium constant will permit calculation of the missing
equilibrium concentration. The process in question is the base ionization of acetate ion, for which
−14
Kw 1.0 × 10
− −10
Kb (for CH3 CO2 ) = = = 5.6 × 10
−5
Ka (for CH3 CO2 H) 1.8 × 10
Substituting the available values into the Kb expression gives

−
[ CH3 CO2 H][ OH ]
−10
Kb = = 5.6 × 10
−
[ CH3 CO2 ]

−6
[ CH3 CO2 H](2.5 × 10 )
−10
= = 5.6 × 10
(0.050)
Solving the above equation for the acetic acid molarity yields [CH3CO2H] = 1.1 × 10−5 M.
What is the pH of a 0.083-M solution of NaCN?
14.5.0.1: Answer:
11.11
14.5.0.1: Salts with Acidic and Basic Ions

Some salts are composed of both acidic and basic ions, and so the pH of their solutions will depend on the relative strengths of
these two species. Likewise, some salts contain a single ion that is amphiprotic, and so the relative strengths of this ion’s acid and
base character will determine its effect on solution pH. For both types of salts, a comparison of the Ka and Kb values allows
prediction of the solution’s acid-base status, as illustrated in the following example exercise.
14.5.0.1: Example 14.17

14.5.0.0.1: Determining the Acidic or Basic Nature of Salts
Determine whether aqueous solutions of the following salts are acidic, basic, or neutral:
(a) KBr
(b) NaHCO3
(c) Na2HPO4
(d) NH4F
Consider each of the ions separately in terms of its effect on the pH of the solution, as shown here:
(a) The K+ cation is inert and will not affect pH. The bromide ion is the conjugate base of a strong acid, and so it is of
negligible base strength (no appreciable base ionization). The solution is neutral.
(b) The Na+ cation is inert and will not affect the pH of the solution; while the HCO3
−
anion is amphiprotic. The Ka of
−11
−14
HCO3
−
is 4.7 × 10 ,and its Kb is 1.0 × 10
−7
= 2.3 × 10
−8
.
4.3 × 10
Since Kb >> Ka, the solution is basic.

(c) The Na+ cation is inert and will not affect the pH of the solution, while the HPO4
2−
anion is amphiprotic. The Ka of
HPO 4 is 4.2 × 10−13,
2−
−14
and its Kb is 1.0 × 10

−8
= 1.6 × 10
−7
. Because Kb >> Ka, the solution is basic.
6.2 × 10
(d) The NH ion is acidic (see above discussion) and the F− ion is basic (conjugate base of the weak acid HF). Comparing the
4
+
two ionization constants: Ka of NH is 5.6 × 10−10 and the Kb of F− is 1.6 × 10−11, so the solution is acidic, since Ka > Kb.
4
+

(a) K2CO3
(b) CaCl2
(c) KH2PO4
(d) (NH4)2CO3
14.5.0.1: Answer:
(a) basic; (b) neutral; (c) acidic; (d) basic

14.5.0.1: The Ionization of Hydrated Metal Ions
Unlike the group 1 and 2 metal ions of the preceding examples (Na+, Ca2+, etc.), some metal ions function as acids in aqueous
solutions. These ions are not just loosely solvated by water molecules when dissolved, instead they are covalently bonded to a fixed
number of water molecules to yield a complex ion (see chapter on coordination chemistry). As an example, the dissolution of
aluminum nitrate in water is typically represented as
3 −
Al(NO3 )(s) ⇌ Al + (aq) + 3 NO3 (aq)
However, the aluminum(III) ion actually reacts with six water molecules to form a stable complex ion, and so the more explicit
representation of the dissolution process is
3+ −
Al (NO3 )3 (s) + 6 H2 O(l) ⇌ Al (H2 O) 6 (aq) + 3 NO3 (aq)
As shown in Figure 14.13, the Al(H O) ions involve bonds between a central Al atom and the O atoms of the six water
2 6
3+
molecules. Consequently, the bonded water molecules' O–H bonds are more polar than in nonbonded water molecules, making the
bonded molecules more prone to donation of a hydrogen ion:
3+ + 2+ −5
Al (H2 O) (aq) + H2 O(l) ⇌ H3 O (aq) + Al (H2 O) (OH) (aq) Ka = 1.4 × 10
6 5
The conjugate base produced by this process contains five other bonded water molecules capable of acting as acids, and so the
sequential or step-wise transfer of protons is possible as depicted in few equations below:
3+ + 2+
Al (H2 O) (aq) + H2 O(l) ⇌ H3 O (aq) + Al (H2 O) (OH) (aq)
6 5
2+ + +
Al (H2 O) 5 (OH) (aq) + H2 O(l) ⇌ H3 O (aq) + Al (H2 O) 4 (OH) 2 (aq)
+ +
Al (H2 O) (OH) (aq) + H2 O(l) ⇌ H3 O (aq) + Al (H2 O) (OH) (aq)
4 2 3 3
This is an example of a polyprotic acid, the topic of discussion in a later section of this chapter.
Figure 14.13 When an aluminum ion reacts with water, the hydrated aluminum ion becomes a weak acid.
Aside from the alkali metals (group 1) and some alkaline earth metals (group 2), most other metal ions will undergo acid ionization
to some extent when dissolved in water. The acid strength of these complex ions typically increases with increasing charge and
decreasing size of the metal ions. The first-step acid ionization equations for a few other acidic metal ions are shown below:
14.5.0.1: Example 14.18

14.5.0.0.1: Hydrolysis of [Al(H2O)6]3+
Calculate the pH of a 0.10-M solution of aluminum chloride, which dissolves completely to give the hydrated aluminum ion
3+
[Al (H O) ]
2 6
in solution.
The equation for the reaction and Ka are:
3+ + 2+ −5
Al (H2 O) (aq) + H2 O(l) ⇌ H3 O (aq) + Al (H2 O) (OH) (aq) Ka = 1.4 × 10
6 5

An ICE table with the provided information is
Substituting the expressions for the equilibrium concentrations into the equation for the ionization constant yields:
+ 2+
[ H3 O ][Al (H2 O) 5 (OH) ]
Ka =
3+
[Al (H2 O) 6 ]
(x)(x)
−5
= = 1.4 × 10
0.10 − x
Assuming x << 0.10 and solving the simplified equation gives:

−3
x = 1.2 × 10 M
The ICE table defined x as equal to the hydronium ion concentration, and so the pH is calculated to be
+ −3
[ H3 O ] = 0 + x = 1.2 × 10 M
+
pH = −log[ H3 O ] = 2.92 (an acidic solution)

What is [Al(H 2 O) 5 (OH)
2+
] in a 0.15-M solution of Al(NO3)3 that contains enough of the strong acid HNO3 to bring [H3O+]
to 0.10 M?
14.5.0.1: Answer:
2.1 × 10−5 M
This page titled 14.5: Hydrolysis of Salt Solutions is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax


Extend previously introduced equilibrium concepts to acids and bases that may donate or accept more than one proton
Acids are classified by the number of protons per molecule that they can give up in a reaction. Acids such as HCl, HNO3, and HCN
that contain one ionizable hydrogen atom in each molecule are called monoprotic acids. Their reactions with water are:
+ −
HCl(aq) + H2 O(l) ⟶ H3 O (aq) + Cl (aq)
+ −
HNO3 (aq) + H2 O(l) ⟶ H3 O (aq) + NO3 (aq)
+ −
HCN(aq) + H2 O(l) ⇌ H3 O (aq) + CN (aq)
Even though it contains four hydrogen atoms, acetic acid, CH3CO2H, is also monoprotic because only the hydrogen atom from the
carboxyl group (COOH) reacts with bases:
Similarly, monoprotic bases are bases that will accept a single proton.
Diprotic acids contain two ionizable hydrogen atoms per molecule; ionization of such acids occurs in two steps. The first ionization
always takes place to a greater extent than the second ionization. For example, sulfuric acid, a strong acid, ionizes as follows:
+ − 2
First ionization: H2 SO 4 (aq) + H2 O(l) ⇌ H3 O (aq) + HSO 4 (aq) Ka1 = more than 10 ; complete dissociation
− + 2− −2
Second ionization: HSO 4 (aq) + H2 O(l) ⇌ H3 O (aq) + SO 4 (aq) Ka2 = 1.2 × 10
This stepwise ionization process occurs for all polyprotic acids. Carbonic acid, H2CO3, is an example of a weak diprotic acid. The
first ionization of carbonic acid yields hydronium ions and bicarbonate ions in small amounts.
First ionization:
+ −
+ [ H3 O ][ HCO3 ]
− −7
H2 CO3 (aq) + H2 O(l) ⇌ H3 O (aq) + HCO3 (aq) KH2 CO3 = = 4.3 × 10
[ H2 CO3 ]
The bicarbonate ion can also act as an acid. It ionizes and forms hydronium ions and carbonate ions in even smaller quantities.
Second ionization:
+ 2−
[ H3 O ][ CO3 ]
− + 2− −11
HCO3 (aq) + H2 O(l) ⇌ H3 O (aq) + CO3 (aq) KHCO − = = 4.7 × 10
3 −
[ HCO3 ]
KH2 CO3 is larger than K by a factor of 104, so H2CO3 is the dominant producer of hydronium ion in the solution. This means
HCO3
−
that little of the HCO formed by the ionization of H2CO3 ionizes to give hydronium ions (and carbonate ions), and the
3
−
concentrations of H3O+ and HCO are practically equal in a pure aqueous solution of H2CO3.
3
−
If the first ionization constant of a weak diprotic acid is larger than the second by a factor of at least 20, it is appropriate to treat the
first ionization separately and calculate concentrations resulting from it before calculating concentrations of species resulting from
subsequent ionization. This approach is demonstrated in the following example exercise.
14.6.0.1: Example 14.19

14.6.0.0.1: Ionization of a Diprotic Acid
“Carbonated water” contains a palatable amount of dissolved carbon dioxide. The solution is acidic because CO2 reacts with
water to form carbonic acid, H2CO3. What are [H O ], [HCO ], and [CO ] in a saturated solution of CO2 with an initial
3
+
3
−
3
2−
[H2CO3] = 0.033 M?
+ − −7
H2 CO3 (aq) + H2 O(l) ⇌ H3 O (aq) + HCO3 (aq) Ka1 = 4.3 × 10
− + 2− −11
HCO3 (aq) + H2 O(l) ⇌ H3 O (aq) + CO3 (aq) Ka2 = 4.7 × 10
As indicated by the ionization constants, H2CO3 is a much stronger acid than HCO 3
−
, so the stepwise ionization reactions may
be treated separately.
The first ionization reaction is
+ − −7
H2 CO3 (aq) + H2 O(l) ⇌ H3 O (aq) + HCO3 (aq) Ka1 = 4.3 × 10
Using provided information, an ICE table for this first step is prepared:
Substituting the equilibrium concentrations into the equilibrium equation gives

+ −
[ H3 O ][ HCO3 ] (x)(x)
−7
KH CO3 = = = 4.3 × 10
2
[ H2 CO3 ] 0.033 − x
Assuming x << 0.033 and solving the simplified equation yields

−4
x = 1.2 × 10
The ICE table defined x as equal to the bicarbonate ion molarity and the hydronium ion molarity:
[ H2 CO3 ] = 0.033 M
+ − −4
[ H3 O ] = [ HCO3 ] = 1.2 × 10 M
Using the bicarbonate ion concentration computed above, the second ionization is subjected to a similar equilibrium calculation:
− + 2−
HCO3 (aq) + H2 O(l) ⇌ H3 O (aq) + CO3 (aq)
+ 2− −4 2−
[ H3 O ][ CO3 ] (1.2 × 10 )[ CO3 ]
KHCO − = =
3
[ HCO3 − ] 1.2 × 10
−4
−11 −4
(4.7 × 10 )(1.2 × 10 )
2− −11
[ CO3 ] = = 4.7 × 10 M
−4
1.2 × 10
To summarize: at equilibrium [H2CO3] = 0.033 M; [ H3 O

+
] = 1.2 × 10−4; [ HCO3
− −4
] = 1.2 × 10 M;
2− −11
[ CO3 ] = 4.7 × 10 M.

The concentration of H2S in a saturated aqueous solution at room temperature is approximately 0.1 M. Calculate [H 3O
+
], [HS−],
and [S2−] in the solution:
+ − −8
H2 S(aq) + H2 O(l) ⇌ H3 O (aq) + HS (aq) Ka1 = 8.9 × 10
− + 2− −19
HS (aq) + H2 O(l) ⇌ H3 O (aq) + S (aq) Ka2 = 1.0 × 10
14.6.0.1: Answer:
[H2S] = 0.1 M; [H 3O
+
] = [HS−] = 0.000094 M; [S2−] = 1 × 10−19 M
A triprotic acid is an acid that has three ionizable H atoms. Phosphoric acid is one example:
+ − −3
First ionization: H3 PO4 (aq) + H2 O(l) ⇌ H3 O (aq) + H2 PO4 (aq) Ka1 = 7.5 × 10
− + 2− −8
Second ionization: H2 PO4 (aq) + H2 O(l) ⇌ H3 O (aq) + HPO4 (aq) Ka2 = 6.2 × 10
2− + 3− −13
Third ionization: HPO4 (aq) + H2 O(l) ⇌ H3 O (aq) + PO4 (aq) Ka3 = 4.2 × 10
As for the diprotic acid examples, each successive ionization reaction is less extensive than the former, reflected in decreasing values
for the stepwise acid ionization constants. This is a general characteristic of polyprotic acids and successive ionization constants
often differ by a factor of about 105 to 106.
This set of three dissociation reactions may appear to make calculations of equilibrium concentrations in a solution of H3PO4
complicated. However, because the successive ionization constants differ by a factor of 105 to 106, large differences exist in the small
changes in concentration accompanying the ionization reactions. This allows the use of math-simplifying assumptions and processes,
as demonstrated in the examples above.
Polyprotic bases are capable of accepting more than one hydrogen ion. The carbonate ion is an example of a diprotic base, because it
can accept two protons, as shown below. Similar to the case for polyprotic acids, note the ionization constants decrease with
ionization step. Likewise, equilibrium calculations involving polyprotic bases follow the same approaches as those for polyprotic
acids.
2− − − −4
H2 O(l) + CO3 (aq) ⇌ HCO3 (aq) + OH (aq) Kb1 = 2.1 × 10
− − −8
H2 O(l) + H CO3 (aq) ⇌ H2 CO3 (aq) + OH (aq) Kb2 = 2.3 × 10
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14.7: Buffers

Describe the composition and function of acid–base buffers
Calculate the pH of a buffer before and after the addition of added acid or base
A solution containing appreciable amounts of a weak conjugate acid-base pair is called a buffer solution, or a buffer. Buffer
solutions resist a change in pH when small amounts of a strong acid or a strong base are added (Figure 14.14). A solution of acetic
acid and sodium acetate (CH3COOH + CH3COONa) is an example of a buffer that consists of a weak acid and its salt. An example
of a buffer that consists of a weak base and its salt is a solution of ammonia and ammonium chloride (NH3(aq) + NH4Cl(aq)).
Figure 14.14 (a) The unbuffered solution on the left and the buffered solution on the right have the same pH (pH 8); they are basic,
showing the yellow color of the indicator methyl orange at this pH. (b) After the addition of 1 mL of a 0.01-M HCl solution, the
buffered solution has not detectably changed its pH but the unbuffered solution has become acidic, as indicated by the change in
color of the methyl orange, which turns red at a pH of about 4. (credit: modification of work by Mark Ott)
14.7.0.1: How Buffers Work

To illustrate the function of a buffer solution, consider a mixture of roughly equal amounts of acetic acid and sodium acetate. The
presence of a weak conjugate acid-base pair in the solution imparts the ability to neutralize modest amounts of added strong acid or
base. For example, strong base added to this solution will neutralize hydronium ion, causing the acetic acid ionization equilibrium
to shift to the right and generate additional amounts of the weak conjugate base (acetate ion):
+ −
CH3 CO2 H(aq) + H2 O(l) ⇌ H3 O (aq) + CH3 CO2 (aq)
Likewise, strong acid added to this buffer solution will shift the above ionization equilibrium left, producing additional amounts of
the weak conjugate acid (acetic acid). Figure 14.15 provides a graphical illustration of the changes in conjugate-partner
concentration that occur in this buffer solution when strong acid and base are added. The buffering action of the solution is
essentially a result of the added strong acid and base being converted to the weak acid and base that make up the buffer's conjugate
pair. The weaker acid and base undergo only slight ionization, as compared with the complete ionization of the strong acid and
base, and the solution pH, therefore, changes much less drastically than it would in an unbuffered solution.

Figure 14.15 Buffering action in a mixture of acetic acid and acetate salt.
14.7.0.1: Example 14.20

14.7.0.0.1: pH Changes in Buffered and Unbuffered Solutions
Acetate buffers are used in biochemical studies of enzymes and other chemical components of cells to prevent pH changes that
might affect the biochemical activity of these compounds.
(a) Calculate the pH of an acetate buffer that is a mixture with 0.10 M acetic acid and 0.10 M sodium acetate.
(b) Calculate the pH after 1.0 mL of 0.10 NaOH is added to 100 mL of this buffer.
(c) For comparison, calculate the pH after 1.0 mL of 0.10 M NaOH is added to 100 mL of a solution of an unbuffered solution
with a pH of 4.74.
(a) Following the ICE approach to this equilibrium calculation yields the following:
Substituting the equilibrium concentration terms into the Ka expression, assuming x << 0.10, and solving the simplified
equation for x yields

−5
x = 1.8 × 10 M
+ −5
[ H3 O ] = 0 + x = 1.8 × 10 M
+ −5
pH = −log [ H3 O ] = −log (1.8 × 10 )
= 4.74
(b) Calculate the pH after 1.0 mL of 0.10 M NaOH is added to 100 mL of this buffer.
Adding strong base will neutralize some of the acetic acid, yielding the conjugate base acetate ion. Compute the new
concentrations of these two buffer components, then repeat the equilibrium calculation of part (a) using these new
concentrations.
0.10 mol NaOH −4

0.0010 L × ( ) = 1.0 × 10 mol NaOH
1 L
The initial molar amount of acetic acid is
0.100 mol CH3 CO2 H

−2
0.100 L × ( ) = 1.00 × 10 mol CH3 CO2 H
1 L
The amount of acetic acid remaining after some is neutralized by the added base is
−2 −2 −2
(1.0 × 10 ) − (0.01 × 10 ) = 0.99 × 10 mol CH3 CO2 H
The newly formed acetate ion, along with the initially present acetate, gives a final acetate concentration of
−2 −2 −2
(1.0 × 10 ) + (0.01 × 10 ) = 1.01 × 10 mol NaCH3 CO2
Compute molar concentrations for the two buffer components:

−3
9.9 × 10 mol
[ CH3 CO2 H] = = 0.098 M
0.101 L
−2
1.01 × 10 mol
[ NaCH3 CO2 ] = = 0.100 M
0.101 L
Using these concentrations, the pH of the solution may be computed as in part (a) above, yielding pH = 4.75 (only slightly
different from that prior to adding the strong base).
(c) For comparison, calculate the pH after 1.0 mL of 0.10 M NaOH is added to 100 mL of a solution of an unbuffered solution
with a pH of 4.74.
The amount of hydronium ion initially present in the solution is
+ −4.74 −5
[ H3 O ] = 10 = 1.8 × 10 M
+ −5 −6 +
mol H3 O = (0.100 L)(1.8 × 10 M ) = 1.8 × 10 mol H3 O
The amount of hydroxide ion added to the solution is

− −4 −
mol OH = (0.0010 L)(0.10 M ) = 1.0 × 10 mol OH
The added hydroxide will neutralize hydronium ion via the reaction
+ −
H3 O (aq) + OH (aq) ⇋ 2 H2 O(l)
The 1:1 stoichiometry of this reaction shows that an excess of hydroxide has been added (greater molar amount than the
initially present hydronium ion).
The amount of hydroxide ion remaining is
−4 −6 −5 −
1.0 × 10 mol − 1.8 × 10 mol = 9.8 × 10 mol OH
corresponding to a hydroxide molarity of

−5 − −4
9.8 × 10 mol OH /0.101 L = 9.7 × 10 M
The pH of the solution is then calculated to be

−4
pH = 14.00 − pOH = 14.00 − −log(9.7 × 10 ) = 10.99
In this unbuffered solution, addition of the base results in a significant rise in pH (from 4.74 to 10.99) compared with the very
slight increase observed for the buffer solution in part (b) (from 4.74 to 4.75).
Show that adding 1.0 mL of 0.10 M HCl changes the pH of 100 mL of a 1.8 × 10−5 M HCl solution from 4.74 to 3.00.
14.7.0.1: Answer:
Initial pH of 1.8 × 10−5 M HCl; pH = −log[H3O+] = −log[1.8 × 10−5] = 4.74
Moles of H3O+ in 100 mL 1.8 × 10−5 M HCl; 1.8 × 10−5 moles/L × 0.100 L = 1.8 × 10−6
Moles of H3O+ added by addition of 1.0 mL of 0.10 M HCl: 0.10 moles/L × 0.0010 L = 1.0 × 10−4 moles; final pH after
addition of 1.0 mL of 0.10 M HCl:
+ ⎛ −4 −6 ⎞
+
total moles H3 O 1.0 × 10 mol + 1.8 × 10 mol
pH = −log[ H3 O ] = −log( ) = −log ⎜ ⎟ = 3.00
total volume 1 L
⎝ 101 mL( ) ⎠
1000 mL
14.7.0.1: Buffer Capacity

Buffer solutions do not have an unlimited capacity to keep the pH relatively constant (Figure 14.16). Instead, the ability of a buffer
solution to resist changes in pH relies on the presence of appreciable amounts of its conjugate weak acid-base pair. When enough
strong acid or base is added to substantially lower the concentration of either member of the buffer pair, the buffering action within
the solution is compromised.
Figure 14.16 The indicator color (methyl orange) shows that a small amount of acid added to a buffered solution of pH 8 (beaker
on the left) has little affect on the buffered system (middle beaker). However, a large amount of acid exhausts the buffering
capacity of the solution and the pH changes dramatically (beaker on the right). (credit: modification of work by Mark Ott)
The buffer capacity is the amount of acid or base that can be added to a given volume of a buffer solution before the pH changes
significantly, usually by one unit. Buffer capacity depends on the amounts of the weak acid and its conjugate base that are in a
buffer mixture. For example, 1 L of a solution that is 1.0 M in acetic acid and 1.0 M in sodium acetate has a greater buffer capacity
than 1 L of a solution that is 0.10 M in acetic acid and 0.10 M in sodium acetate even though both solutions have the same pH. The
first solution has more buffer capacity because it contains more acetic acid and acetate ion.
14.7.0.1: Selection of Suitable Buffer Mixtures

There are two useful rules of thumb for selecting buffer mixtures:
1. A good buffer mixture should have about equal concentrations of both of its components. A buffer solution has generally lost its
usefulness when one component of the buffer pair is less than about 10% of the other. Figure 14.17 shows how pH changes for

an acetic acid-acetate ion buffer as base is added. The initial pH is 4.74. A change of 1 pH unit occurs when the acetic acid
concentration is reduced to 11% of the acetate ion concentration.
Figure 14.17 Change in pH as an increasing amount of a 0.10-M NaOH solution is added to 100 mL of a buffer solution in
which, initially, [CH3CO2H] = 0.10 M and [CH CO ] = 0.10 M . Note the greatly diminished buffering action occurring
3 2
−
after the buffer capacity has been reached, resulting in drastic rises in pH on adding more strong base.
2. Weak acids and their salts are better as buffers for pHs less than 7; weak bases and their salts are better as buffers for pHs
greater than 7.
Blood is an important example of a buffered solution, with the principal acid and ion responsible for the buffering action being
carbonic acid, H2CO3, and the bicarbonate ion, HCO . When a hydronium ion is introduced to the blood stream, it is removed
3
−
primarily by the reaction:

+ −
H3 O (aq) + HCO3 (aq) ⟶ H2 CO3 (aq) + H2 O(l)
An added hydroxide ion is removed by the reaction:

− −
OH (aq) + H2 CO3 (aq) ⟶ HCO3 (aq) + H2 O(l)
The added strong acid or base is thus effectively converted to the much weaker acid or base of the buffer pair (H3O+ is converted to
H2CO3 and OH- is converted to HCO3-). The pH of human blood thus remains very near the value determined by the buffer pairs
pKa, in this case, 7.35. Normal variations in blood pH are usually less than 0.1, and pH changes of 0.4 or greater are likely to be
fatal.
14.7.0.1: The Henderson-Hasselbalch Equation

The ionization-constant expression for a solution of a weak acid can be written as:
+ −
[ H3 O ] [A ]
Ka =
[HA]
Rearranging to solve for [H3O+] yields:

[HA]
+
[ H3 O ] = Ka ×
−
[A ]
Taking the negative logarithm of both sides of this equation gives

[HA]
+
−log [ H3 O ] = −log Ka − log ,
−
[A ]
which can be written as

−
[A ]
pH = pKa + log
[HA]
where pKa is the negative of the logarithm of the ionization constant of the weak acid (pKa = −log Ka). This equation relates the pH,
the ionization constant of a weak acid, and the concentrations of the weak conjugate acid-base pair in a buffered solution. Scientists
often use this expression, called the Henderson-Hasselbalch equation, to calculate the pH of buffer solutions. It is important to note
that the “x is small” assumption must be valid to use this equation.

14.7.0.0.1: Lawrence Joseph Henderson and Karl Albert Hasselbalch
Lawrence Joseph Henderson (1878–1942) was an American physician, biochemist and physiologist, to name only a few of his
many pursuits. He obtained a medical degree from Harvard and then spent 2 years studying in Strasbourg, then a part of
Germany, before returning to take a lecturer position at Harvard. He eventually became a professor at Harvard and worked
there his entire life. He discovered that the acid-base balance in human blood is regulated by a buffer system formed by the
dissolved carbon dioxide in blood. He wrote an equation in 1908 to describe the carbonic acid-carbonate buffer system in
blood. Henderson was broadly knowledgeable; in addition to his important research on the physiology of blood, he also wrote
on the adaptations of organisms and their fit with their environments, on sociology and on university education. He also
founded the Fatigue Laboratory, at the Harvard Business School, which examined human physiology with specific focus on
work in industry, exercise, and nutrition.
In 1916, Karl Albert Hasselbalch (1874–1962), a Danish physician and chemist, shared authorship in a paper with Christian
Bohr in 1904 that described the Bohr effect, which showed that the ability of hemoglobin in the blood to bind with oxygen was
inversely related to the acidity of the blood and the concentration of carbon dioxide. The pH scale was introduced in 1909 by
another Dane, Sørensen, and in 1912, Hasselbalch published measurements of the pH of blood. In 1916, Hasselbalch expressed
Henderson’s equation in logarithmic terms, consistent with the logarithmic scale of pH, and thus the Henderson-Hasselbalch
equation was born.

14.7.0.0.2: Medicine: The Buffer System in Blood
The normal pH of human blood is about 7.4. The carbonate buffer system in the blood uses the following equilibrium reaction:
− +
CO2 (g) + 2 H2 O(l) ⇌ H2 CO3 (aq) ⇌ HCO3 (aq) + H3 O (aq)
The concentration of carbonic acid, H2CO3 is approximately 0.0012 M, and the concentration of the hydrogen carbonate ion,
, is around 0.024 M. Using the Henderson-Hasselbalch equation and the pKa of carbonic acid at body temperature, we
−
HCO 3
can calculate the pH of blood:

[base] 0.024
pH = pKa + log = 6.4 + log = 7.7
[acid] 0.0012
The fact that the H2CO3 concentration is significantly lower than that of the HCO ion may seem unusual, but this imbalance
3
−
is due to the fact that most of the by-products of our metabolism that enter our bloodstream are acidic. Therefore, there must be
a larger proportion of base than acid, so that the capacity of the buffer will not be exceeded.
Lactic acid is produced in our muscles when we exercise. As the lactic acid enters the bloodstream, it is neutralized by the
HCO 3 ion, producing H2CO3. An enzyme then accelerates the breakdown of the excess carbonic acid to carbon dioxide and
−

water, which can be eliminated by breathing. In fact, in addition to the regulating effects of the carbonate buffering system on
the pH of blood, the body uses breathing to regulate blood pH. If the pH of the blood decreases too far, an increase in breathing
removes CO2 from the blood through the lungs driving the equilibrium reaction such that [H3O+] is lowered. If the blood is too
alkaline, a lower breath rate increases CO2 concentration in the blood, driving the equilibrium reaction the other way,
increasing [H+] and restoring an appropriate pH.

View information on the buffer system encountered in natural waters.
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Interpret titration curves for strong and weak acid-base systems
Compute sample pH at important stages of a titration
Explain the function of acid-base indicators
As seen in the chapter on the stoichiometry of chemical reactions, titrations can be used to quantitatively analyze solutions for their
acid or base concentrations. In this section, we will explore the underlying chemical equilibria that make acid-base titrimetry a
useful analytical technique.
14.8.0.1: Titration Curves

A titration curve is a plot of some solution property versus the amount of added titrant. For acid-base titrations, solution pH is a
useful property to monitor because it varies predictably with the solution composition and, therefore, may be used to monitor the
titration’s progress and detect its end point. The following example exercise demonstrates the computation of pH for a titration
solution after additions of several specified titrant volumes. The first example involves a strong acid titration that requires only
stoichiometric calculations to derive the solution pH. The second example addresses a weak acid titration requiring equilibrium
calculations.
14.8.0.1: Example 14.21

14.8.0.0.1: Calculating pH for Titration Solutions: Strong Acid/Strong Base
A titration is carried out for 25.00 mL of 0.100 M HCl (strong acid) with 0.100 M of a strong base NaOH (the titration curve is
shown in Figure 14.18). Calculate the pH at these volumes of added base solution:
(a) 0.00 mL
(b) 12.50 mL
(c) 25.00 mL
(d) 37.50 mL
(a) Titrant volume = 0 mL. The solution pH is due to the acid ionization of HCl. Because this is a strong acid, the ionization is
complete and the hydronium ion molarity is 0.100 M. The pH of the solution is then
pH = −log (0.100) = 1.000
(b) Titrant volume = 12.50 mL. Since the acid sample and the base titrant are both monoprotic and equally concentrated, this
titrant addition involves less than a stoichiometric amount of base, and so it is completely consumed by reaction with the
excess acid in the sample. The concentration of acid remaining is computed by subtracting the consumed amount from the
intial amount and then dividing by the solution volume:
1000 mL
+ 0.002500 mol × ( ) − 0.100 M × 12.50 mL
n(H ) 1 L
+
[ H3 O ] = = = 0.0333 M
V 25.00 mL + 12.50 mL
(c) Titrant volume = 25.00 mL. This titrant addition involves a stoichiometric amount of base (the equivalence point), and so
only products of the neutralization reaction are in solution (water and NaCl). Neither the cation nor the anion of this salt
undergo acid-base ionization; the only process generating hydronium ions is the autoprotolysis of water. The solution is
neutral, having a pH = 7.00.
(d) Titrant volume = 37.50 mL. This involves the addition of titrant in excess of the equivalence point. The solution pH is then
calculated using the concentration of hydroxide ion:
− +
n(OH )0 > n(H )0

1000 mL
− 0.100 M × 37.50 mL − 0.002500 mol × ( )
n(OH ) 1 L
−
[ OH ] = = = 0.0200 M
V 25.00 mL + 37.50 mL
pH = 14 − pOH = 14 + log([OH−]) = 14 + log(0.0200) = 12.30

Calculate the pH for the strong acid/strong base titration between 50.0 mL of 0.100 M HNO3(aq) and 0.200 M NaOH (titrant)
at the listed volumes of added base: 0.00 mL, 15.0 mL, 25.0 mL, and 40.0 mL.
14.8.0.1: Answer:
0.00: 1.000; 15.0: 1.5111; 25.0: 7; 40.0: 12.523
14.8.0.1: Example 14.22

14.8.0.0.4: Titration of a Weak Acid with a Strong Base
Consider the titration of 25.00 mL of 0.100 M CH3CO2H with 0.100 M NaOH. The reaction can be represented as:
− −
CH3 CO2 H + OH ⟶ CH3 CO2 + H2 O
Calculate the pH of the titration solution after the addition of the following volumes of NaOH titrant:
(a) 0.00 mL
(b) 25.00 mL
(c) 12.50 mL
(d) 37.50 mL
(a) The initial pH is computed for the acetic acid solution in the usual ICE approach:
+
[ H3 O ][ CH3 CO2
−
] [ H3 O
+ 2
] −−−−−−−−−−−−−− − −−−−−−−−−−−−−−− −
Ka =
[ CH3 CO2 H]
≈
[ CH3 CO2 H]
, and [H 3O
+
] = √Ka × [ CH3 CO2 H] = √1.8 × 10
−5
× 0.100 = 1.3 × 10
−3
−3
pH = −log(1.3 × 10 ) = 2.87
(b) The acid and titrant are both monoprotic and the sample and titrant solutions are equally concentrated; thus, this volume of
titrant represents the equivalence point. Unlike the strong-acid example above, however, the reaction mixture in this case
contains a weak conjugate base (acetate ion). The solution pH is computed considering the base ionization of acetate, which is
present at a concentration of
0.00250 mol
−
= 0.0500 MCH3 CO2
0.0500 L
Base ionization of acetate is represented by the equation

− −
CH3 CO2 (aq) + H2 O(l) ⇌ CH3 CO2 H(aq) + OH (aq)
+ − −14
[H ][ OH ] Kw 1.0 × 10
−10
Kb = = = = 5.6 × 10
−5
Ka Ka 1.8 × 10
Assuming x << 0.0500, the pH may be calculated via the usual ICE approach: K b =
x
0.0500 M
− −6
x = [ OH ] = 5.3 × 10
−6
pOH = −log(5.3 × 10 ) = 5.28
pH = 14.00 − 5.28 = 8.72
Note that the pH at the equivalence point of this titration is significantly greater than 7, as expected when titrating a weak acid
with a strong base.

(c) Titrant volume = 12.50 mL. This volume represents one-half of the stoichiometric amount of titrant, and so one-half of the
acetic acid has been neutralized to yield an equivalent amount of acetate ion. The concentrations of these conjugate acid-base
partners, therefore, are equal. A convenient approach to computing the pH is use of the Henderson-Hasselbalch equation:
−
[Base] [ CH3 CO2 ]
−5
pH = p Ka + log = −log(Ka ) + log = −log(1.8 × 10 ) + log(1)
[Acid] [ CH3 CO2 H]
−5
pH = −log(1.8 × 10 ) = 4.74
(pH = pKa at the half-equivalence point in a titration of a weak acid)

(d) Titrant volume = 37.50 mL. This volume represents a stoichiometric excess of titrant, and a reaction solution containing
both the titration product, acetate ion, and the excess strong titrant. In such solutions, the solution pH is determined primarily
by the amount of excess strong base:
(0.003750 mol − 0.00250 mol)
− −2
[ OH ] = = 2.00 × 10 M
0.06250 L
−2
pOH = −log (2.00 × 10 ) = 1.70, and pH = 14.00 − 1.70 = 12.30

Calculate the pH for the weak acid/strong base titration between 50.0 mL of 0.100 M HCOOH(aq) (formic acid) and 0.200 M
NaOH (titrant) at the listed volumes of added base: 0.00 mL, 15.0 mL, 25.0 mL, and 30.0 mL.
14.8.0.1: Answer:
0.00 mL: 2.37; 15.0 mL: 3.92; 25.00 mL: 8.29; 30.0 mL: 12.097
Performing additional calculations similar to those in the preceding example permits a more full assessment of titration curves. A
summary of pH/volume data pairs for the strong and weak acid titrations is provided in Table 14.2 and plotted as titration curves in
Figure 14.18. A comparison of these two curves illustrates several important concepts that are best addressed by identifying the
four stages of a titration:
initial state (added titrant volume = 0 mL): pH is determined by the acid being titrated; because the two acid samples are equally
concentrated, the weak acid will exhibit a greater initial pH
pre-equivalence point (0 mL < V < 25 mL): solution pH increases gradually and the acid is consumed by reaction with added
titrant; composition includes unreacted acid and the reaction product, its conjugate base
equivalence point (V = 25 mL): a drastic rise in pH is observed as the solution composition transitions from acidic to either neutral
(for the strong acid sample) or basic (for the weak acid sample), with pH determined by ionization of the conjugate base of the acid
postequivalence point (V > 25 mL): pH is determined by the amount of excess strong base titrant added; since both samples are
titrated with the same titrant, both titration curves appear similar at this stage.
pH Values in the Titrations of a Strong Acid and of a Weak Acid
Volume of 0.100 M NaOH Added (mL) Moles of NaOH Added pH Values 0.100 M HCl1 pH Values 0.100 M CH3CO2H2
0.0 0.0 1.00 2.87
5.0 0.00050 1.18 4.14
10.0 0.00100 1.37 4.57
15.0 0.00150 1.60 4.92
20.0 0.00200 1.95 5.35

Volume of 0.100 M NaOH Added (mL) Moles of NaOH Added pH Values 0.100 M HCl1 pH Values 0.100 M CH3CO2H2
22.0 0.00220 2.20 5.61
24.0 0.00240 2.69 6.13
24.5 0.00245 3.00 6.44
24.9 0.00249 3.70 7.14
25.0 0.00250 7.00 8.72
25.1 0.00251 10.30 10.30
25.5 0.00255 11.00 11.00
26.0 0.00260 11.29 11.29
28.0 0.00280 11.75 11.75
30.0 0.00300 11.96 11.96
35.0 0.00350 12.22 12.22
40.0 0.00400 12.36 12.36
45.0 0.00450 12.46 12.46
50.0 0.00500 12.52 12.52
Table 14.2

Figure 14.18 (a) The titration curve for the titration of 25.00 mL of 0.100 M HCl (strong acid) with 0.100 M NaOH (strong base)
has an equivalence point of 7.00 pH. (b) The titration curve for the titration of 25.00 mL of 0.100 M acetic acid (weak acid) with
0.100 M NaOH (strong base) has an equivalence point of 8.72 pH.
14.8.0.1: Acid-Base Indicators

Certain organic substances change color in dilute solution when the hydronium ion concentration reaches a particular value. For
example, phenolphthalein is a colorless substance in any aqueous solution with a hydronium ion concentration greater than 5.0 ×
10−9 M (pH < 8.3). In more basic solutions where the hydronium ion concentration is less than 5.0 × 10−9 M (pH > 8.3), it is red or

pink. Substances such as phenolphthalein, which can be used to determine the pH of a solution, are called acid-base indicators.
Acid-base indicators are either weak organic acids or weak organic bases.
The equilibrium in a solution of the acid-base indicator methyl orange, a weak acid, can be represented by an equation in which we
use HIn as a simple representation for the complex methyl orange molecule:
+ −
HIn(aq) + H2 O(l) ⇌ H3 O (aq) + In (aq)
red yellow
+ −
[ H3 O ] [ In ]
−4
Ka = = 4.0 × 10
[HIn]
The anion of methyl orange, In−, is yellow, and the nonionized form, HIn, is red. When we add acid to a solution of methyl orange,
the increased hydronium ion concentration shifts the equilibrium toward the nonionized red form, in accordance with Le
Châtelier’s principle. If we add base, we shift the equilibrium towards the yellow form. This behavior is completely analogous to
the action of buffers.
The perceived color of an indicator solution is determined by the ratio of the concentrations of the two species In− and HIn. If most
of the indicator (typically about 60−90% or more) is present as In−, the perceived color of the solution is yellow. If most is present
as HIn, then the solution color appears red. The Henderson-Hasselbalch equation is useful for understanding the relationship
between the pH of an indicator solution and its composition (thus, perceived color):
−
[ In ]
pH = pKa + log ( )
[HIn]
In solutions where pH > pKa, the logarithmic term must be positive, indicating an excess of the conjugate base form of the indicator
(yellow solution). When pH < pKa, the log term must be negative, indicating an excess of the conjugate acid (red solution). When
the solution pH is close to the indicator pKa, appreciable amounts of both conjugate partners are present, and the solution color is
that of an additive combination of each (yellow and red, yielding orange). The color change interval (or pH interval) for an acid-
base indicator is defined as the range of pH values over which a change in color is observed, and for most indicators this range is
approximately pKa ± 1.
There are many different acid-base indicators that cover a wide range of pH values and can be used to determine the approximate
pH of an unknown solution by a process of elimination. Universal indicators and pH paper contain a mixture of indicators and
exhibit different colors at different pHs. Figure 14.19 presents several indicators, their colors, and their color-change intervals.

Figure 14.19 This chart illustrates the color change intervals for several acid-base indicators.
Figure 14.20 Titration curves for strong and weak acids illustrating the proper choice of acid-base indicator. Any of the three
indicators will exhibit a reasonably sharp color change at the equivalence point of the strong acid titration, but only phenolphthalein
is suitable for use in the weak acid titration.
The titration curves shown in Figure 14.20 illustrate the choice of a suitable indicator for specific titrations. In the strong acid
titration, use of any of the three indicators should yield reasonably sharp color changes and accurate end point determinations. For
this titration, the solution pH reaches the lower limit of the methyl orange color change interval after addition of ~24 mL of titrant,
at which point the initially red solution would begin to appear orange. When 25 mL of titrant has been added (the equivalence
point), the pH is well above the upper limit and the solution will appear yellow. The titration's end point may then be estimated as
the volume of titrant that yields a distinct orange-to-yellow color change. This color change would be challenging for most human
eyes to precisely discern. More-accurate estimates of the titration end point are possible using either litmus or phenolphthalein,
both of which exhibit color change intervals that are encompassed by the steep rise in pH that occurs around the 25.00 mL
equivalence point.
The weak acid titration curve in Figure 14.20 shows that only one of the three indicators is suitable for end point detection. If
methyl orange is used in this titration, the solution will undergo a gradual red-to-orange-to-yellow color change over a relatively
large volume interval (0–6 mL), completing the color change well before the equivalence point (25 mL) has been reached. Use of
litmus would show a color change that begins after adding 7–8 mL of titrant and ends just before the equivalence point.
Phenolphthalein, on the other hand, exhibits a color change interval that nicely brackets the abrupt change in pH occurring at the

titration's equivalence point. A sharp color change from colorless to pink will be observed within a very small volume interval
around the equivalence point.
14.8.0.1: Footnotes
1Titration of 25.00 mL of 0.100 M HCl (0.00250 mol of HCI) with 0.100 M NaOH.
2Titration of 25.00 mL of 0.100 M CH3CO2H (0.00250 mol of CH3CO2H) with 0.100 M NaOH.
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14.9: Key Terms
acid ionization
reaction involving the transfer of a proton from an acid to water, yielding hydronium ions and the conjugate base of the acid
acid ionization constant (Ka)

equilibrium constant for an acid ionization reaction
acid-base indicator
weak acid or base whose conjugate partner imparts a different solution color; used in visual assessments of solution pH
acidic
a solution in which [H3O+] > [OH−]
amphiprotic
species that may either donate or accept a proton in a Bronsted-Lowry acid-base reaction
amphoteric
species that can act as either an acid or a base
autoionization
reaction between identical species yielding ionic products; for water, this reaction involves transfer of protons to yield
hydronium and hydroxide ions
base ionization
reaction involving the transfer of a proton from water to a base, yielding hydroxide ions and the conjugate acid of the base
base ionization constant (Kb)

equilibrium constant for a base ionization reaction
basic
a solution in which [H3O+] < [OH−]
Brønsted-Lowry acid
proton donor
Brønsted-Lowry base
proton acceptor
buffer
mixture of appreciable amounts of a weak acid-base pair the pH of a buffer resists change when small amounts of acid or base
are added
buffer capacity
amount of an acid or base that can be added to a volume of a buffer solution before its pH changes significantly (usually by one
pH unit)
color-change interval
range in pH over which the color change of an indicator is observed
conjugate acid
substance formed when a base gains a proton
conjugate base
substance formed when an acid loses a proton
diprotic acid
acid containing two ionizable hydrogen atoms per molecule
diprotic base
base capable of accepting two protons
Henderson-Hasselbalch equation
logarithmic version of the acid ionization constant expression, conveniently formatted for calculating the pH of buffer solutions
ion-product constant for water (Kw)

equilibrium constant for the autoionization of water
leveling effect
observation that acid-base strength of solutes in a given solvent is limited to that of the solvent’s characteristic acid and base
species (in water, hydronium and hydroxide ions, respectively)
monoprotic acid
acid containing one ionizable hydrogen atom per molecule
neutral
describes a solution in which [H3O+] = [OH−]
oxyacid
ternary compound with acidic properties, molecules of which contain a central nonmetallic atom bonded to one or more O
atoms, at least one of which is bonded to an ionizable H atom
percent ionization
ratio of the concentration of ionized acid to initial acid concentration expressed as a percentage
pH
logarithmic measure of the concentration of hydronium ions in a solution
pOH
logarithmic measure of the concentration of hydroxide ions in a solution
stepwise ionization
process in which a polyprotic acid is ionized by losing protons sequentially
titration curve
plot of some sample property (such as pH) versus volume of added titrant
triprotic acid
acid that contains three ionizable hydrogen atoms per molecule
Kw = [H3O+][OH−] = 1.0 × 10−14 (at 25 °C)
+
pH = −log[H3 O ]
pOH = −log[OH−]
[H3O+] = 10−pH
[OH−] = 10−pOH
pH + pOH = pKw = 14.00 at 25 °C
+ −
[H3 O ][ A ]
Ka =
[HA]
+ −
[HB ][ OH ]
Kb =
[B]
Ka × Kb = 1.0 × 10−14 = Kw
+
[H3 O ]
eq
Percent ionization = × 100
[HA] 0
pKa = −log Ka
pKb = −log Kb
−
[A ]
pH = p Ka + log
[HA]
14.11: Summary
14.1 Brønsted-Lowry Acids and Bases
A compound that can donate a proton (a hydrogen ion) to another compound is called a Brønsted-Lowry acid. The compound that
accepts the proton is called a Brønsted-Lowry base. The species remaining after a Brønsted-Lowry acid has lost a proton is the
conjugate base of the acid. The species formed when a Brønsted-Lowry base gains a proton is the conjugate acid of the base. Thus,
an acid-base reaction occurs when a proton is transferred from an acid to a base, with formation of the conjugate base of the
reactant acid and formation of the conjugate acid of the reactant base. Amphiprotic species can act as both proton donors and
proton acceptors. Water is the most important amphiprotic species. It can form both the hydronium ion, H3O+, and the hydroxide
ion, OH− when it undergoes autoionization:
+ −
2H2 O(l) ⇌ H3 O (aq) + OH (aq)
The ion product of water, Kw is the equilibrium constant for the autoionization reaction:
+ − −14
Kw = [ H3 O ] [ OH ] = 1.0 × 1 0 at 25 °C
14.2 pH and pOH

Concentrations of hydronium and hydroxide ions in aqueous media are often represented as logarithmic pH and pOH values,
respectively. At 25 °C, the autoprotolysis equilibrium for water requires the sum of pH and pOH to equal 14 for any aqueous
solution. The relative concentrations of hydronium and hydroxide ion in a solution define its status as acidic ([H3O+] > [OH−]),
basic ([H3O+] < [OH−]), or neutral ([H3O+] = [OH−]). At 25 °C, a pH < 7 indicates an acidic solution, a pH > 7 a basic solution,
and a pH = 7 a neutral solution.
14.3 Relative Strengths of Acids and Bases

The relative strengths of acids and bases are reflected in the magnitudes of their ionization constants; the stronger the acid or base,
the larger its ionization constant. A reciprocal relation exists between the strengths of a conjugate acid-base pair: the stronger the
acid, the weaker its conjugate base. Water exerts a leveling effect on dissolved acids or bases, reacting completely to generate its
characteristic hydronium and hydroxide ions (the strongest acid and base that may exist in water). The strengths of the binary acids
increase from left to right across a period of the periodic table (CH4 < NH3 < H2O < HF), and they increase down a group (HF <
HCl < HBr < HI). The strengths of oxyacids that contain the same central element increase as the oxidation number of the element
increases (H2SO3 < H2SO4). The strengths of oxyacids also increase as the electronegativity of the central element increases
[H2SeO4 < H2SO4].
14.4 Hydrolysis of Salts

The ions composing salts may possess acidic or basic character, ionizing when dissolved in water to yield acidic or basic solutions.
Acidic cations are typically the conjugate partners of weak bases, and basic anions are the conjugate partners of weak acids. Many
metal ions bond to water molecules when dissolved to yield complex ions that may function as acids.
14.5 Polyprotic Acids

An acid that contains more than one ionizable proton is a polyprotic acid. These acids undergo stepwise ionization reactions
involving the transfer of single protons. The ionization constants for polyprotic acids decrease with each subsequent step; these
decreases typically are large enough to permit simple equilibrium calculations that treat each step separately.
14.6 Buffers
Solutions that contain appreciable amounts of a weak conjugate acid-base pair are called buffers. A buffered solution will
experience only slight changes in pH when small amounts of acid or base are added. Addition of large amounts of acid or base can
exceed the buffer capacity, consuming most of one conjugate partner and preventing further buffering action.
14.7 Acid-Base Titrations

The titration curve for an acid-base titration is typically a plot of pH versus volume of added titrant. These curves are useful in
selecting appropriate acid-base indicators that will permit accurate determinations of titration end points.
14.12: Exercises
14.12.0.1: 14.1 Brønsted-Lowry Acids and Bases
1.
Write equations that show NH3 as both a conjugate acid and a conjugate base.
2.
Write equations that show H 2 PO4
−
acting both as an acid and as a base.
3.
Show by suitable net ionic equations that each of the following species can act as a Brønsted-Lowry acid:
(a) H 3O
+
(b) HCl
(c) NH3
(d) CH3CO2H
(e) NH 4
+
(f) HSO 4
−
4.
Show by suitable net ionic equations that each of the following species can act as a Brønsted-Lowry acid:
(a) HNO3
(b) PH 4
+
(c) H2S
(d) CH3CH2COOH
(e) H 2 PO4
−
(f) HS−
5.
Show by suitable net ionic equations that each of the following species can act as a Brønsted-Lowry base:
(a) H2O
(b) OH−
(c) NH3
(d) CN−
(e) S2−
(f) H2 PO4
−
6.
Show by suitable net ionic equations that each of the following species can act as a Brønsted-Lowry base:
(a) HS−
(b) PO 4
3−
(c) NH 2
−
(d) C2H5OH
(e) O2−
(f) H2 PO4
−

7.
What is the conjugate acid of each of the following? What is the conjugate base of each?
(a) OH−
(b) H2O
(c) HCO 3
−
(d) NH3
(e) HSO 4
−
(f) H2O2
(g) HS−
(h) H 5 N2
+
8.
What is the conjugate acid of each of the following? What is the conjugate base of each?
(a) H2S
(b) H 2 PO4
−
(c) PH3
(d) HS−
(e) HSO 3
−
(f) H 3 O2
+
(g) H4N2
(h) CH3OH
9.
Identify and label the Brønsted-Lowry acid, its conjugate base, the Brønsted-Lowry base, and its conjugate acid in each of the
following equations:
(a) HNO 3 + H2 O ⟶ H3 O
+
+ NO3
−
(b) CN −
+ H2 O ⟶ HCN + OH
−
(c) H 2 SO 4 + Cl
−
⟶ HCl + HSO 4
−
(d) HSO 4
−
+ OH
−
⟶ SO 4
2−
+ H2 O
(e) O 2−
+ H2 O ⟶ 2 OH
−
+ 3+ 2+ 2+
(f) [Cu(H 2 O) 3 (OH)] + [Al (H2 O) 6 ] ⟶ [Cu(H2 O) 4 ] + [Al (H2 O) 5 (OH)]
(g) H 2S + NH2
−
⟶ HS
−
+ NH3
10.
Identify and label the Brønsted-Lowry acid, its conjugate base, the Brønsted-Lowry base, and its conjugate acid in each of the
following equations:
(a) NO 2
−
+ H2 O ⟶ HNO2 + OH
−
(b) HBr + H 2O ⟶ H3 O
+
+ Br
−
(c) HS −
+ H2 O ⟶ H2 S + OH
−
(d) H 2 PO4
−
+ OH
−
⟶ HPO4
2−
+ H2 O
(e) H 2 PO4
−
+ HCl ⟶ H3 PO4 + Cl
−
(f) [Fe(H 2 O) 5 (OH)]

2+
+ [Al (H2 O) ]
6
3+
⟶ [Fe(H2 O) ]
6
3+
+ [Al (H2 O) (OH)]
5
2+

(g) CH 3 OH +H
− −
⟶ CH3 O + H2
11.
What are amphiprotic species? Illustrate with suitable equations.
12.
State which of the following species are amphiprotic and write chemical equations illustrating the amphiprotic character of these
species:
(a) H2O
(b) H 2 PO4
−
(c) S2−
(d) CO 3
2−
(e) HSO 4
−
13.
State which of the following species are amphiprotic and write chemical equations illustrating the amphiprotic character of these
species.
(a) NH3
(b) HPO 4
−
(c) Br−
(d) NH 4
+
(e) ASO 4
3−
14.
Is the self-ionization of water endothermic or exothermic? The ionization constant for water (Kw) is 2.9 × 10−14 at 40 °C and 9.3 ×
10−14 at 60 °C.
14.12.0.1: 14.2 pH and pOH

15.
Explain why a sample of pure water at 40 °C is neutral even though [H3O+] = 1.7 × 10−7 M. Kw is 2.9 × 10−14 at 40 °C.
16.
The ionization constant for water (Kw) is 2.9 × 10−14 at 40 °C. Calculate [H3O+], [OH−], pH, and pOH for pure water at 40 °C.
17.
The ionization constant for water (Kw) is 9.311 × 10−14 at 60 °C. Calculate [H3O+], [OH−], pH, and pOH for pure water at 60 °C.
18.
Calculate the pH and the pOH of each of the following solutions at 25 °C for which the substances ionize completely:
(a) 0.200 M HCl
(b) 0.0143 M NaOH
(c) 3.0 M HNO3
(d) 0.0031 M Ca(OH)2
19.
Calculate the pH and the pOH of each of the following solutions at 25 °C for which the substances ionize completely:
(a) 0.000259 M HClO4
(b) 0.21 M NaOH
(c) 0.000071 M Ba(OH)2

(d) 2.5 M KOH
20.
What are the pH and pOH of a solution of 2.0 M HCl, which ionizes completely?
21.
What are the hydronium and hydroxide ion concentrations in a solution whose pH is 6.52?
22.
Calculate the hydrogen ion concentration and the hydroxide ion concentration in wine from its pH. See Figure 14.2 for useful
information.
23.
Calculate the hydronium ion concentration and the hydroxide ion concentration in lime juice from its pH. See Figure 14.2 for
useful information.
24.
The hydronium ion concentration in a sample of rainwater is found to be 1.7 × 10−6 M at 25 °C. What is the concentration of
hydroxide ions in the rainwater?
25.
The hydroxide ion concentration in household ammonia is 3.2 × 10−3 M at 25 °C. What is the concentration of hydronium ions in
the solution?
14.12.0.1: 14.3 Relative Strengths of Acids and Bases

26.
Explain why the neutralization reaction of a strong acid and a weak base gives a weakly acidic solution.
27.
Explain why the neutralization reaction of a weak acid and a strong base gives a weakly basic solution.
28.
Use this list of important industrial compounds (and Figure 14.8) to answer the following questions regarding: Ca(OH)2,
CH3CO2H, HCl, H2CO3, HF, HNO2, HNO3, H3PO4, H2SO4, NH3, NaOH, Na2CO3.
(a) Identify the strong Brønsted-Lowry acids and strong Brønsted-Lowry bases.
(b) Identify the compounds that can behave as Brønsted-Lowry acids with strengths lying between those of H3O+ and H2O.
(c) Identify the compounds that can behave as Brønsted-Lowry bases with strengths lying between those of H2O and OH−.
29.
The odor of vinegar is due to the presence of acetic acid, CH3CO2H, a weak acid. List, in order of descending concentration, all of
the ionic and molecular species present in a 1-M aqueous solution of this acid.
30.
Household ammonia is a solution of the weak base NH3 in water. List, in order of descending concentration, all of the ionic and
molecular species present in a 1-M aqueous solution of this base.
31.
Explain why the ionization constant, Ka, for H2SO4 is larger than the ionization constant for H2SO3.
32.
Explain why the ionization constant, Ka, for HI is larger than the ionization constant for HF.
33.
Gastric juice, the digestive fluid produced in the stomach, contains hydrochloric acid, HCl. Milk of Magnesia, a suspension of solid
Mg(OH)2 in an aqueous medium, is sometimes used to neutralize excess stomach acid. Write a complete balanced equation for the
neutralization reaction, and identify the conjugate acid-base pairs.

34.
Nitric acid reacts with insoluble copper(II) oxide to form soluble copper(II) nitrate, Cu(NO3)2, a compound that has been used to
prevent the growth of algae in swimming pools. Write the balanced chemical equation for the reaction of an aqueous solution of
HNO3 with CuO.
35.
What is the ionization constant at 25 °C for the weak acid CH 3 NH3
+
, the conjugate acid of the weak base CH3NH2, Kb = 4.4 ×
10−4.
36.
What is the ionization constant at 25 °C for the weak acid (CH 3 ) 2 NH2
+
, the conjugate acid of the weak base (CH3)2NH, Kb = 5.9
−4
× 10 ?
37.
Which base, CH3NH2 or (CH3)2NH, is the stronger base? Which conjugate acid, (CH3 ) NH2
2
+
or CH3 NH3
+
, is the stronger
acid?
38.
Which is the stronger acid, NH 4
+
or HBrO?
39.
Which is the stronger base, (CH3)3N or H 2 BO 3
−
?
40.
Predict which acid in each of the following pairs is the stronger and explain your reasoning for each.
(a) H2O or HF
(b) B(OH)3 or Al(OH)3
(c) HSO 3
−
or HSO 4
−
(d) NH3 or H2S

(e) H2O or H2Te
41.
Predict which compound in each of the following pairs of compounds is more acidic and explain your reasoning for each.
(a) HSO 4
−
or HSeO 4
−
(b) NH3 or H2O

(c) PH3 or HI
(d) NH3 or PH3
(e) H2S or HBr
42.
Rank the compounds in each of the following groups in order of increasing acidity or basicity, as indicated, and explain the order
you assign.
(a) acidity: HCl, HBr, HI
(b) basicity: H2O, OH−, H−, Cl−
(c) basicity: Mg(OH)2, Si(OH)4, ClO3(OH) (Hint: Formula could also be written as HClO4.)
(d) acidity: HF, H2O, NH3, CH4
43.
Rank the compounds in each of the following groups in order of increasing acidity or basicity, as indicated, and explain the order
you assign.

(a) acidity: NaHSO3, NaHSeO3, NaHSO4
(b) basicity: BrO 2
−
, ClO2
−
, IO2
−
(c) acidity: HOCl, HOBr, HOI

(d) acidity: HOCl, HOClO, HOClO2, HOClO3
(e) basicity: NH2
−
, HS−, HTe−, PH 2
−
(f) basicity: BrO−, BrO 2

−
, BrO 3
−
, BrO 4
−
44.
Both HF and HCN ionize in water to a limited extent. Which of the conjugate bases, F− or CN−, is the stronger base?
45.
The active ingredient formed by aspirin in the body is salicylic acid, C6H4OH(CO2H). The carboxyl group (−CO2H) acts as a weak
acid. The phenol group (an OH group bonded to an aromatic ring) also acts as an acid but a much weaker acid. List, in order of
descending concentration, all of the ionic and molecular species present in a 0.001-M aqueous solution of C6H4OH(CO2H).
46.
Are the concentrations of hydronium ion and hydroxide ion in a solution of an acid or a base in water directly proportional or
inversely proportional? Explain your answer.
47.
What two common assumptions can simplify calculation of equilibrium concentrations in a solution of a weak acid or base?
48.
Which of the following will increase the percent of NH3 that is converted to the ammonium ion in water?
(a) addition of NaOH
(b) addition of HCl
(c) addition of NH4Cl
49.
Which of the following will increase the percentage of HF that is converted to the fluoride ion in water?
(a) addition of NaOH
(b) addition of HCl
(c) addition of NaF
50.
What is the effect on the concentrations of NO 2
−
, HNO2, and OH− when the following are added to a solution of KNO2 in water:
(a) HCl
(b) HNO2
(c) NaOH
(d) NaCl
(e) KNO
51.
What is the effect on the concentration of hydrofluoric acid, hydronium ion, and fluoride ion when the following are added to
separate solutions of hydrofluoric acid?
(a) HCl
(b) KF
(c) NaCl

(d) KOH
(e) HF
52.
Why is the hydronium ion concentration in a solution that is 0.10 M in HCl and 0.10 M in HCOOH determined by the
concentration of HCl?
53.
From the equilibrium concentrations given, calculate Ka for each of the weak acids and Kb for each of the weak bases.
(a) CH3CO2H: [H O ] = 1.34 × 10−3 M;
3
+
[ CH CO ] = 1.34 × 10
−−3 M;
3 2
[CH3CO2H] = 9.866 × 10−2 M;

(b) ClO−: [OH−] = 4.0 × 10−4 M;
[HClO] = 2.38 × 10−4 M;
[ClO−] = 0.273 M;
(c) HCO2H: [HCO2H] = 0.524 M;
[ H O ] = 9.8 × 10
+ −3 M;
3
[ HCO ] = 9.8 × 10
− −3 M;
2
(d) C 6 H5 NH3
+
: [ C6 H5 NH3
+
] = 0.233 M;
−3
[C6H5NH2] = 2.3 × 10 M;
−3
[ H O ] = 2.3 × 10 M
+
3
54.
From the equilibrium concentrations given, calculate Ka for each of the weak acids and Kb for each of the weak bases.
(a) NH3: [OH−] = 3.1 × 10−3 M;
−3
] = 3.1 × 10 M;
+
[ NH 4
[NH3] = 0.533 M;
(b) HNO2: [H O ] = 0.011 M;
3
+
] = 0.0438 M;
−
[ NO 2
[HNO2] = 1.07 M;
(c) (CH3)3N: [(CH3)3N] = 0.25 M;
[(CH3)3NH+] = 4.3 × 10−3 M;
[OH−] = 3.7 × 10−3 M;
(d) NH 4
+
: [ NH4
+
] = 0.100 M;
[NH3] = 7.5 × 10−6 M;
[H3O+] = 7.5 × 10−6 M
55.
Determine Kb for the nitrite ion, NO 2
−
. In a 0.10-M solution this base is 0.0015% ionized.
56.
Determine Ka for hydrogen sulfate ion, HSO 4
−
. In a 0.10-M solution the acid is 29% ionized.
57.
Calculate the ionization constant for each of the following acids or bases from the ionization constant of its conjugate base or
conjugate acid:
(a) F−

(b) NH 4
+
(c) AsO 4
3−
(d) (CH 3 ) 2 NH2

+
(e) NO 2
−
(f) HC 2 O4
−
(as a base)
58.
Calculate the ionization constant for each of the following acids or bases from the ionization constant of its conjugate base or
conjugate acid:
(a) HTe− (as a base)
(b) (CH 3 ) 3 NH
+
(c) HAsO 4
2–
(as a base)
(d) HO 2
−
(as a base)
(e) C 6 H5 NH3
+
(f) HSO 3
−
(as a base)
59.
Using the Ka value of 1.4 × 10−5, place Al(H 2 O) 6
3+
in the correct location in Figure 14.7.
60.
Calculate the concentration of all solute species in each of the following solutions of acids or bases. Assume that the ionization of
water can be neglected, and show that the change in the initial concentrations can be neglected.
(a) 0.0092 M HClO, a weak acid
(b) 0.0784 M C6H5NH2, a weak base
(c) 0.0810 M HCN, a weak acid
(d) 0.11 M (CH3)3N, a weak base
(e) 0.120 M Fe(H 2 O) 6
2+
a weak acid, Ka = 1.6 × 10−7
61.
Propionic acid, C2H5CO2H (Ka = 1.34 × 10−5), is used in the manufacture of calcium propionate, a food preservative. What is the
pH of a 0.698-M solution of C2H5CO2H?
62.
White vinegar is a 5.0% by mass solution of acetic acid in water. If the density of white vinegar is 1.007 g/cm3, what is the pH?
63.
The ionization constant of lactic acid, CH3CH(OH)CO2H, an acid found in the blood after strenuous exercise, is 1.36 × 10−4. If
20.0 g of lactic acid is used to make a solution with a volume of 1.00 L, what is the concentration of hydronium ion in the solution?
64.
Nicotine, C10H14N2, is a base that will accept two protons (Kb1 = 7 × 10−7, Kb2 = 1.4 × 10−11). What is the concentration of each
species present in a 0.050-M solution of nicotine?
65.
The pH of a 0.23-M solution of HF is 1.92. Determine Ka for HF from these data.
66.
The pH of a 0.15-M solution of HSO 4
−
is 1.43. Determine Ka for HSO 4
−
from these data.
67.

The pH of a 0.10-M solution of caffeine is 11.70. Determine Kb for caffeine from these data:
+ −
C8 H10 N4 O2 (aq) + H2 O(l) ⇌ C8 H10 N4 O2 H (aq) + OH (aq)
68.
The pH of a solution of household ammonia, a 0.950 M solution of NH3, is 11.612. Determine Kb for NH3 from these data.
14.12.0.1: 14.4 Hydrolysis of Salts

69.
(a) Al(NO3)3
(b) RbI
(c) KHCO2
(d) CH3NH3Br
70.
(a) FeCl3
(b) K2CO3
(c) NH4Br
(d) KClO4
71.
Novocaine, C13H21O2N2Cl, is the salt of the base procaine and hydrochloric acid. The ionization constant for procaine is 7 × 10−6.
Is a solution of novocaine acidic or basic? What are [H3O+], [OH−], and pH of a 2.0% solution by mass of novocaine, assuming
that the density of the solution is 1.0 g/mL.
14.12.0.1: 14.5 Polyprotic Acids

72.
Which of the following concentrations would be practically equal in a calculation of the equilibrium concentrations in a 0.134-M
solution of H2CO3, a diprotic acid: [H O ], [OH−], [H2CO3], [HCO ] , [CO ]? No calculations are needed to answer this
3
+
3
−
3
2−
question.
73.
Calculate the concentration of each species present in a 0.050-M solution of H2S.
74.
Calculate the concentration of each species present in a 0.010-M solution of phthalic acid, C6H4(CO2H)2.
+ − −3
C6 H4 (CO2 H) (aq) + H2 O(l) ⇌ H3 O (aq) + C6 H4 (CO2 H) (CO2 ) (aq) Ka = 1.1 × 10
2
+ 2− −6
C6 H4 (CO2 H)(CO2 ) (aq) + H2 O(l) ⇌ H3 O (aq) + C6 H4 (CO2 ) (aq) Ka = 3.9 × 10
2
75.
Salicylic acid, HOC6H4CO2H, and its derivatives have been used as pain relievers for a long time. Salicylic acid occurs in small
amounts in the leaves, bark, and roots of some vegetation (most notably historically in the bark of the willow tree). Extracts of
these plants have been used as medications for centuries. The acid was first isolated in the laboratory in 1838.
(a) Both functional groups of salicylic acid ionize in water, with Ka = 1.0 × 10−3 for the—CO2H group and 4.2 × 10−13 for the
−OH group. What is the pH of a saturated solution of the acid (solubility = 1.8 g/L).
(b) Aspirin was discovered as a result of efforts to produce a derivative of salicylic acid that would not be irritating to the stomach
lining. Aspirin is acetylsalicylic acid, CH3CO2C6H4CO2H. The −CO2H functional group is still present, but its acidity is reduced,

Ka = 3.0 × 10−4. What is the pH of a solution of aspirin with the same concentration as a saturated solution of salicylic acid (See
Part a).
76.
The ion HTe− is an amphiprotic species; it can act as either an acid or a base.
(a) What is Ka for the acid reaction of HTe− with H2O?
(b) What is Kb for the reaction in which HTe− functions as a base in water?
(c) Demonstrate whether or not the second ionization of H2Te can be neglected in the calculation of [HTe−] in a 0.10 M solution of
H2Te.
14.12.0.1: 14.6 Buffers

77.
Explain why a buffer can be prepared from a mixture of NH4Cl and NaOH but not from NH3 and NaOH.
78.
Explain why the pH does not change significantly when a small amount of an acid or a base is added to a solution that contains
equal amounts of the acid H3PO4 and a salt of its conjugate base NaH2PO4.
79.
Explain why the pH does not change significantly when a small amount of an acid or a base is added to a solution that contains
equal amounts of the base NH3 and a salt of its conjugate acid NH4Cl.
80.
What is [H3O+] in a solution of 0.25 M CH3CO2H and 0.030 M NaCH3CO2?
+ − −5
81.
What is [H3O+] in a solution of 0.075 M HNO2 and 0.030 M NaNO2?
+ − −5
HNO2 (aq) + H2 O(l) ⇌ H3 O (aq) + NO2 (aq) Ka = 4.5 × 10
82.
What is [OH−] in a solution of 0.125 M CH3NH2 and 0.130 M CH3NH3Cl?
+ − −4
CH3 NH2 (aq) + H2 O(l) ⇌ CH3 NH3 (aq) + OH (aq) Kb = 4.4 × 10
83.
What is [OH−] in a solution of 1.25 M NH3 and 0.78 M NH4NO3?
+ − −5
NH3 (aq) + H2 O(l) ⇌ NH4 (aq) + OH (aq) Kb = 1.8 × 10
84.
What is the effect on the concentration of acetic acid, hydronium ion, and acetate ion when the following are added to an acidic
buffer solution of equal concentrations of acetic acid and sodium acetate:
(a) HCl
(b) KCH3CO2
(c) NaCl
(d) KOH
(e) CH3CO2H
85.
What is the effect on the concentration of ammonia, hydroxide ion, and ammonium ion when the following are added to a basic
buffer solution of equal concentrations of ammonia and ammonium nitrate:
(a) KI
(b) NH3

(c) HI
(d) NaOH
(e) NH4Cl
86.
What will be the pH of a buffer solution prepared from 0.20 mol NH3, 0.40 mol NH4NO3, and just enough water to give 1.00 L of
solution?
87.
Calculate the pH of a buffer solution prepared from 0.155 mol of phosphoric acid, 0.250 mole of KH2PO4, and enough water to
make 0.500 L of solution.
88.
How much solid NaCH3CO2•3H2O must be added to 0.300 L of a 0.50-M acetic acid solution to give a buffer with a pH of 5.00?
(Hint: Assume a negligible change in volume as the solid is added.)
89.
What mass of NH4Cl must be added to 0.750 L of a 0.100-M solution of NH3 to give a buffer solution with a pH of 9.26? (Hint:
Assume a negligible change in volume as the solid is added.)
90.
A buffer solution is prepared from equal volumes of 0.200 M acetic acid and 0.600 M sodium acetate. Use 1.80 × 10−5 as Ka for
acetic acid.
(a) What is the pH of the solution?
(b) Is the solution acidic or basic?
(c) What is the pH of a solution that results when 3.00 mL of 0.034 M HCl is added to 0.200 L of the original buffer?
91.
A 5.36–g sample of NH4Cl was added to 25.0 mL of 1.00 M NaOH and the resulting solution
diluted to 0.100 L.
(a) What is the pH of this buffer solution?
(b) Is the solution acidic or basic?
(c) What is the pH of a solution that results when 3.00 mL of 0.034 M HCl is added to the solution?
14.12.0.1: 14.7 Acid-Base Titrations

92.
Explain how to choose the appropriate acid-base indicator for the titration of a weak base with a strong acid.
93.
Explain why an acid-base indicator changes color over a range of pH values rather than at a specific pH.
94.
Calculate the pH at the following points in a titration of 40 mL (0.040 L) of 0.100 M barbituric acid (Ka = 9.8 × 10−5) with 0.100
M KOH.
(a) no KOH added
(b) 20 mL of KOH solution added
(c) 39 mL of KOH solution added
(d) 40 mL of KOH solution added
(e) 41 mL of KOH solution added
95.

The indicator dinitrophenol is an acid with a Ka of 1.1 × 10−4. In a 1.0 × 10−4-M solution, it is colorless in acid and yellow in base.
Calculate the pH range over which it goes from 10% ionized (colorless) to 90% ionized (yellow).

CHAPTER OVERVIEW
15: Equilibria of Other Reaction Classes

General Chemistry
We previously learned about aqueous solutions and their importance, as well as about solubility rules. While this gives us a picture
of solubility, that picture is not complete if we look at the rules alone. Solubility equilibrium, which we will explore in this chapter,
is a more complex topic that allows us to determine the extent to which a slightly soluble ionic solid will dissolve, and the
conditions under which precipitation.
15.1: Introduction
15.5: Key Terms
15.6: Key Equations
15.7: Summary
15.8: Exercises
Thumbnail: Lead (II) iodide precipitates when potassium iodide is mixed with lead (II) nitrate. (CC BY-SA 3.0
Unported; PRHaney via Wikipedia)
This page titled 15: Equilibria of Other Reaction Classes is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by
1
15.1: Introduction
Figure 15.1 The mineral fluorite (CaF2) is formed when dissolved calcium and fluoride ions precipitate from groundwater within
the Earth’s crust. Note that pure fluorite is colorless, and that the color in this sample is due to the presence of other metal ions in
the crystal.
Chapter Outline
15.1 Precipitation and Dissolution
15.2 Lewis Acids and Bases
15.3 Coupled Equilibria
The mineral fluorite, CaF2 Figure 15.1, is commonly used as a semiprecious stone in many types of jewelry because of its striking
appearance. Deposits of fluorite are formed through a process called hydrothermal precipitation in which calcium and fluoride ions
dissolved in groundwater combine to produce insoluble CaF2 in response to some change in solution conditions. For example, a
decrease in temperature may trigger fluorite precipitation if its solubility is exceeded at the lower temperature. Because fluoride ion
is a weak base, its solubility is also affected by solution pH, and so geologic or other processes that change groundwater pH will
also affect the precipitation of fluorite. This chapter extends the equilibrium discussion of other chapters by addressing some
additional reaction classes (including precipitation) and systems involving coupled equilibrium reactions.

Write chemical equations and equilibrium expressions representing solubility equilibria
Carry out equilibrium computations involving solubility, equilibrium expressions, and solute concentrations
Solubility equilibria are established when the dissolution and precipitation of a solute species occur at equal rates. These equilibria
underlie many natural and technological processes, ranging from tooth decay to water purification. An understanding of the factors
affecting compound solubility is, therefore, essential to the effective management of these processes. This section applies
previously introduced equilibrium concepts and tools to systems involving dissolution and precipitation.
15.2.0.1: The Solubility Product

Recall from the chapter on solutions that the solubility of a substance can vary from essentially zero (insoluble or sparingly
soluble) to infinity (miscible). A solute with finite solubility can yield a saturated solution when it is added to a solvent in an
amount exceeding its solubility, resulting in a heterogeneous mixture of the saturated solution and the excess, undissolved solute.
For example, a saturated solution of silver chloride is one in which the equilibrium shown below has been established.
dissolution
+ −
AgCl(s) ⇌ Ag (aq) + Cl (aq)
precipitation
In this solution, an excess of solid AgCl dissolves and dissociates to produce aqueous Ag+ and Cl– ions at the same rate that these
aqueous ions combine and precipitate to form solid AgCl (Figure 15.2). Because silver chloride is a sparingly soluble salt, the
equilibrium concentration of its dissolved ions in the solution is relatively low.
Figure 15.2 Silver chloride is a sparingly soluble ionic solid. When it is added to water, it dissolves slightly and produces a mixture
consisting of a very dilute solution of Ag+ and Cl– ions in equilibrium with undissolved silver chloride.
The equilibrium constant for solubility equilibria such as this one is called the solubility product constant, Ksp, in this case
+ − + −
AgCl(s) ⇌ Ag (aq) + Cl (aq) Ksp = [ Ag (aq)][ Cl (aq)]
Recall that only gases and solutes are represented in equilibrium constant expressions, so the Ksp does not include a term for the
undissolved AgCl. A listing of solubility product constants for several sparingly soluble compounds is provided in Appendix J.
15.2.0.1: Example 15.1

15.2.0.0.1: Writing Equations and Solubility Products
Write the dissolution equation and the solubility product expression for each of the following slightly soluble ionic compounds:
(a) AgI, silver iodide, a solid with antiseptic properties

(b) CaCO3, calcium carbonate, the active ingredient in many over-the-counter chewable antacids
(c) Mg(OH)2, magnesium hydroxide, the active ingredient in Milk of Magnesia
(d) Mg(NH4)PO4, magnesium ammonium phosphate, an essentially insoluble substance used in tests for magnesium
(e) Ca5(PO4)3OH, the mineral apatite, a source of phosphate for fertilizers
+ − + −
(a) AgI(s) ⇌ Ag (aq) + I (aq) Ksp = [Ag ][ I ]
2+ 2− 2+ 2−
(b) CaCO3 (s) ⇌ Ca (aq) + CO3 (aq) Ksp = [ Ca ][CO ]
3
2+ − 2+ − 2
(c) Mg(OH) (s) ⇌ Mg (aq) + 2OH (aq) Ksp = [ Mg ] [ OH ]
2
2+ + 3− 2+ + 3−
(d) Mg(NH4 )PO4 (s) ⇌ Mg (aq) + NH4 (aq) + PO4 (aq) Ksp = [ Mg ][NH ] [PO ]
4 4
5
2+ 3− − 2+ 3− 3 −
(e) Ca5 (PO4 )3OH(s) ⇌ 5Ca (aq) + 3PO4 (aq) + OH (aq) Ksp = [Ca ] [PO4 ] [ OH ]

Write the dissolution equation and the solubility product for each of the following slightly soluble compounds:
(a) BaSO4
(b) Ag2SO4
(c) Al(OH)3
(d) Pb(OH)Cl
15.2.0.1: Answer:
2+ 2+ −
2− 2
(a) BaSO 4 (s) ⇌ Ba (aq) + SO 4 (aq) Ksp = [ Ba ][SO ];
4
+ 2− + 2 2−
(b) Ag2 SO 4 (s) ⇌ 2Ag (aq) + SO 4 (aq) Ksp = [ Ag ] [ SO 4 ];
3+ − 3+ − 3
(c) Al(OH)3 (s) ⇌ Al (aq) + 3OH (aq) Ksp = [ Al ] [OH ] ;
2+ − − 2+ − −
(d) Pb(OH)Cl(s) ⇌ Pb (aq) + OH (aq) + Cl (aq) Ksp = [ Pb ] [OH ][ Cl ]
15.2.0.1: Ksp and Solubility

The Ksp of a slightly soluble ionic compound may be simply related to its measured solubility provided the dissolution process
involves only dissociation and solvation, for example:
m+ n−
Mp Xq (s) ⇌ p M (aq) + q X (aq)
For cases such as these, one may derive Ksp values from provided solubilities, or vice-versa. Calculations of this sort are most
conveniently performed using a compound’s molar solubility, measured as moles of dissolved solute per liter of saturated solution.
15.2.0.1: Example 15.2

15.2.0.0.1: Calculation of Ksp from Equilibrium Concentrations
Fluorite, CaF2, is a slightly soluble solid that dissolves according to the equation:
2+ −
CaF2 (s) ⇌ Ca (aq) + 2F (aq)
The concentration of Ca2+ in a saturated solution of CaF2 is 2.15 × 10–4 M. What is the solubility product of fluorite?
According to the stoichiometry of the dissolution equation, the fluoride ion molarity of a CaF2 solution is equal to twice its
calcium ion molarity:
− − 2+ −4 −4
[F ] = (2 mol F / 1 mol Ca ) = (2) (2.15 × 10 M ) = 4.30 × 10 M
Substituting the ion concentrations into the Ksp expression gives

2
2+ − 2 −4 −4 −11
Ksp = [ Ca ][F ] = (2.15 × 10 ) (4.30 × 10 ) = 3.98 × 10

In a saturated solution of Mg(OH)2, the concentration of Mg2+ is 1.31 × 10–4 M. What is the solubility product for Mg(OH)2?
2+ −
Mg(OH) 2 (s) ⇌ Mg (aq) + 2OH (aq)
15.2.0.1: Answer:
8.99 × 10–12
15.2.0.1: Example 15.3

15.2.0.0.4: Determination of Molar Solubility from Ksp
The Ksp of copper(I) bromide, CuBr, is 6.3 × 10–9. Calculate the molar solubility of copper bromide.
The dissolution equation and solubility product expression are
+ −
CuBr(s) ⇌ Cu (aq) + Br (aq)
+ −
Ksp = [ Cu ][ Br ]
Following the ICE approach to this calculation yields the table
Substituting the equilibrium concentration terms into the solubility product expression and solving for x yields
+ −
Ksp = [Cu ][ Br ]
−9 2
6.3 × 10 = (x)(x) = x
−−−−−−−−−−−
−9 −5
x = √ (6.3 × 10 ) = 7.9 × 10 M
Since the dissolution stoichiometry shows one mole of copper(I) ion and one mole of bromide ion are produced for each moles
of Br dissolved, the molar solubility of CuBr is 7.9 × 10–5 M.
The Ksp of AgI is 1.5 × 10–16. Calculate the molar solubility of silver iodide.
15.2.0.1: Answer:
1.2 × 10–8 M
15.2.0.1: Example 15.4

15.2.0.0.7: Determination of Molar Solubility from Ksp
The Ksp of calcium hydroxide, Ca(OH)2, is 1.3 × 10–6. Calculate the molar solubility of calcium hydroxide.
The dissolution equation and solubility product expression are
2+ −
Ca(OH)2 (s) ⇌ Ca (aq) + 2OH (aq)

2+ − 2
Ksp = [ Ca ] [ OH ]
Substituting terms for the equilibrium concentrations into the solubility product expression and solving for x gives
2+ − 2
Ksp = [ Ca ] [ OH ]
−6 2 2 3
1.3 × 10 = (x)(2x ) = (x)(4 x ) = 4 x
−−−−−−−−−−
−6
3
1.3 × 10 −3
x =√ = 6.9 × 10 M
4
As defined in the ICE table, x is the molarity of calcium ion in the saturated solution. The dissolution stoichiometry shows a
1:1 relation between moles of calcium ion in solution and moles of compound dissolved, and so, the molar solubility of
Ca(OH)2 is 6.9 × 10–3 M.
The Ksp of PbI2 is 1.4 × 10–8. Calculate the molar solubility of lead(II) iodide.
15.2.0.1: Answer:
1.5 × 10–3 M
15.2.0.1: Example 15.5

15.2.0.0.10: Determination of Ksp from Gram Solubility
Many of the pigments used by artists in oil-based paints (Figure 15.3) are sparingly soluble in water. For example, the
solubility of the artist’s pigment chrome yellow, PbCrO4, is 4.6 × 10–6 g/L. Determine the solubility product for PbCrO4.

Figure 15.3 Oil paints contain pigments that are very slightly soluble in water. In addition to chrome yellow (PbCrO4),
examples include Prussian blue (Fe7(CN)18), the reddish-orange color vermilion (HgS), and green color veridian (Cr2O3).
(credit: Sonny Abesamis)
15.2.0.0.11: Solution
Before calculating the solubility product, the provided solubility must be converted to molarity:
−6
4.6 × 10 g PbCrO 1 mol PbCrO4
4
[ PbCrO 4 ] = ×
1 L 323.2 g PbCrO 4
−8
1.4 × 10 mol PbCrO4
=
1 L
−8
= 1.4 × 10 M
The dissolution equation for this compound is

2+ 2−
PbCrO 4 (s) ⇌ Pb (aq) + CrO4 (aq)
The dissolution stoichiometry shows a 1:1 relation between the molar amounts of compound and its two ions, and so both
[Pb2+] and [CrO ] are equal to the molar solubility of PbCrO4:
4
2−
2+ 2− −8
[ Pb ] = [ CrO4 ] = 1.4 × 10 M
Ksp = [Pb2+][CrO 4
2−
] = (1.4 × 10–8)(1.4 × 10–8) = 2.0 × 10–16
The solubility of TlCl [thallium(I) chloride], an intermediate formed when thallium is being isolated from ores, is 3.12 grams
per liter at 20 °C. What is its solubility product?
15.2.0.1: Answer:
1.69 × 10–4
15.2.0.1: Example 15.6

15.2.0.0.13: Calculating the Solubility of Hg2Cl2
Calomel, Hg2Cl2, is a compound composed of the diatomic ion of mercury(I), Hg , and chloride ions, Cl–. Although most
2
2+
mercury compounds are now known to be poisonous, eighteenth-century physicians used calomel as a medication. Their
patients rarely suffered any mercury poisoning from the treatments because calomel has a very low solubility, as suggested by
its very small Ksp:
2+ − −18
Hg2 Cl2 (s) ⇌ Hg2 (aq) + 2Cl (aq) Ksp = 1.1 × 10
Calculate the molar solubility of Hg2Cl2.

15.2.0.0.14: Solution
The dissolution stoichiometry shows a 1:1 relation between the amount of compound dissolved and the amount of mercury(I)
ions, and so the molar solubility of Hg2Cl2 is equal to the concentration of Hg ions 2
2+
Following the ICE approach results in

Substituting the equilibrium concentration terms into the solubility product expression and solving for x gives
2+ − 2
Ksp = [ Hg2 ] [ Cl ]
−18 2
1.1 × 10 = (x)(2x )
3 −18
4x = 1.1 × 10
−−−−−−−−−−−−−
−18
1.1 × 10 −7
3
x = √( ) = 6.5 × 10 M
4
2+ −7 −7
[ Hg ] = 6.5 × 10 M = 6.5 × 10 M
2
− −7 −6
[ Cl ] = 2x = 2(6.5 × 10 ) = 1.3 × 10 M
The dissolution stoichiometry shows the molar solubility of Hg2Cl2 is equal to [Hg 2
2+
], or 6.5 × 10–7 M.
Determine the molar solubility of MgF2 from its solubility product: Ksp = 6.4 × 10–9.
15.2.0.1: Answer:
1.2 × 10–3 M

15.2.0.0.16: Using Barium Sulfate for Medical Imaging
Various types of medical imaging techniques are used to aid diagnoses of illnesses in a noninvasive manner. One such
technique utilizes the ingestion of a barium compound before taking an X-ray image. A suspension of barium sulfate, a chalky
powder, is ingested by the patient. Since the Ksp of barium sulfate is 2.3 × 10–8, very little of it dissolves as it coats the lining
of the patient’s intestinal tract. Barium-coated areas of the digestive tract then appear on an X-ray as white, allowing for greater
visual detail than a traditional X-ray (Figure 15.4).

Figure 15.4 A suspension of barium sulfate coats the intestinal tract, permitting greater visual detail than a traditional X-ray.
(credit modification of work by “glitzy queen00”/Wikimedia Commons)
Medical imaging using barium sulfate can be used to diagnose acid reflux disease, Crohn’s disease, and ulcers in addition to
other conditions.
Visit this website for more information on how barium is used in medical diagnoses and which conditions it is used to
diagnose.
15.2.0.1: Predicting Precipitation

The equation that describes the equilibrium between solid calcium carbonate and its solvated ions is:
2+ 2− 2+ 2− −9
CaCO3 (s) ⇌ Ca (aq) + CO3 (aq) Ksp = [ Ca ] [ CO3 ] = 8.7 × 10
It is important to realize that this equilibrium is established in any aqueous solution containing Ca2+ and CO32– ions, not just in a
solution formed by saturating water with calcium carbonate. Consider, for example, mixing aqueous solutions of the soluble
compounds sodium carbonate and calcium nitrate. If the concentrations of calcium and carbonate ions in the mixture do not yield a
reaction quotient, Qsp, that exceeds the solubility product, Ksp, then no precipitation will occur. If the ion concentrations yield a
reaction quotient greater than the solubility product, then precipitation will occur, lowering those concentrations until equilibrium is
established (Qsp = Ksp). The comparison of Qsp to Ksp to predict precipitation is an example of the general approach to predicting
the direction of a reaction first introduced in the chapter on equilibrium. For the specific case of solubility equilibria:
Qsp < Ksp: the reaction proceeds in the forward direction (solution is not saturated; no precipitation observed)
Qsp > Ksp: the reaction proceeds in the reverse direction (solution is supersaturated; precipitation will occur)
This predictive strategy and related calculations are demonstrated in the next few example exercises.
15.2.0.1: Example 15.7

15.2.0.0.1: Precipitation of Mg(OH)2
The first step in the preparation of magnesium metal is the precipitation of Mg(OH)2 from sea water by the addition of lime,
Ca(OH)2, a readily available inexpensive source of OH– ion:
2+ − −12
Mg(OH) (s) ⇌ Mg (aq) + 2OH (aq) Ksp = 8.9 × 10
2
The concentration of Mg2+(aq) in sea water is 0.0537 M. Will Mg(OH)2 precipitate when enough Ca(OH)2 is added to give a
[OH–] of 0.0010 M?
Calculation of the reaction quotient under these conditions is shown here:
2+ − 2 2 −8
Q = [ Mg ] [ OH ] = (0.0537)(0.0010) = 5.4 × 10
Because Q is greater than Ksp (Q = 5.4 × 10–8 is larger than Ksp = 8.9 × 10–12), the reverse reaction will proceed, precipitating
magnesium hydroxide until the dissolved ion concentrations have been sufficiently lowered, so that Qsp = Ksp.
Predict whether CaHPO4 will precipitate from a solution with [Ca2+] = 0.0001 M and [HPO 4
2−
] = 0.001 M.
15.2.0.1: Answer:
No precipitation of CaHPO4; Q = 1 × 10–7, which is less than Ksp (7 × 10–7)
15.2.0.1: Example 15.8

15.2.0.0.4: Precipitation of AgCl
Does silver chloride precipitate when equal volumes of a 2.0 × 10–4-M solution of AgNO3 and a 2.0 × 10–4-M solution of
NaCl are mixed?
The equation for the equilibrium between solid silver chloride, silver ion, and chloride ion is:
+ −
The solubility product is 1.6 × 10–10 (see Appendix J).

AgCl will precipitate if the reaction quotient calculated from the concentrations in the mixture of AgNO3 and NaCl is greater
than Ksp. Because the volume doubles when equal volumes of AgNO3 and NaCl solutions are mixed, each concentration is
reduced to half its initial value
1
−4 −4
(2.0 × 10 ) M = 1.0 × 10 M
2
The reaction quotient, Q, is greater than Ksp for AgCl, so a supersaturated solution is formed:
+ − −4 −4 −8
Q = [ Ag ] [Cl ] = (1.0 × 10 )(1.0 × 10 ) = 1.0 × 10 > Ksp
AgCl will precipitate from the mixture until the dissolution equilibrium is established, with Q equal to Ksp.
Will KClO4 precipitate when 20 mL of a 0.050-M solution of K+ is added to 80 mL of a 0.50-M solution of ClO 4
−
? (Hint: Use
the dilution equation to calculate the concentrations of potassium and perchlorate ions in the mixture.)
15.2.0.1: Answer:
No, Q = 4.0 × 10–3, which is less than Ksp = 1.05 × 10–2
15.2.0.1: Example 15.9

15.2.0.0.7: Precipitation of Calcium Oxalate
Blood will not clot if calcium ions are removed from its plasma. Some blood collection tubes contain salts of the oxalate ion,
, for this purpose (Figure 15.5). At sufficiently high concentrations, the calcium and oxalate ions form solid,
2−
C O
2 4
CaC2O4·H2O (calcium oxalate monohydrate). The concentration of Ca2+ in a sample of blood serum is 2.2 × 10–3 M. What
concentration of C O 2 4ion must be established before CaC2O4·H2O begins to precipitate?
2−

Figure 15.5 Anticoagulants can be added to blood that will combine with the Ca2+ ions in blood serum and prevent the blood
from clotting. (credit: modification of work by Neeta Lind)
The equilibrium expression is:
2+ 2−
CaC2 O4 (s) ⇌ Ca (aq) + C2 O4 (aq)
For this reaction:

2+ 2− −8
Ksp = [ Ca ][ C2 O4 ] = 1.96 × 10
(see Appendix J)
Substitute the provided calcium ion concentration into the solubility product expression and solve for oxalate concentration:
2+ 2− −8
Q = Ksp = [ Ca ] [C2 O4 ] = 1.96 × 10
−3 2− −8
(2.2 × 10 )[ C2 O4 ] = 1.96 × 10
−8
1.96 × 10
2− −6
[ C2 O4 ] = = 8.9 × 10 M
−3
2.2 × 10
A concentration of [C 2 O4
2−
] = 8.9 × 10–6 M is necessary to initiate the precipitation of CaC2O4 under these conditions.
If a solution contains 0.0020 mol of CrO per liter, what concentration of Ag+ ion must be reached by adding solid AgNO3
4
2−
before Ag2CrO4 begins to precipitate? Neglect any increase in volume upon adding the solid silver nitrate.
15.2.0.1: Answer:
6.7 × 10–5 M
15.2.0.1: Example 15.10

15.2.0.0.10: Concentrations Following Precipitation
Clothing washed in water that has a manganese [Mn2+(aq)] concentration exceeding 0.1 mg/L (1.8 × 10–6 M) may be stained
by the manganese upon oxidation, but the amount of Mn2+ in the water can be decreased by adding a base to precipitate
Mn(OH)2. What pH is required to keep [Mn2+] equal to 1.8 × 10–6 M?
15.2.0.0.11: Solution
The dissolution of Mn(OH)2 is described by the equation:
2+ − −13
Mn(OH) 2 (s) ⇌ Mn (aq) + 2OH (aq) Ksp = 2 × 10
At equilibrium:
2+ − 2
Ksp = [ Mn ] [ OH ]
or
−6 − 2 −13
(1.8 × 10 )[ OH ] = 2 × 10
so
− −4
[ OH ] = 3.3 × 10 M
Calculate the pH from the pOH:

−
pOH = −log[ OH ] = −log(3.3 × 10 − 4) = 3.48
pH = 14.00 − pOH = 14.00 − 3.48 = 10.52
(final result rounded to one significant digit, limited by the certainty of the Ksp)

The first step in the preparation of magnesium metal is the precipitation of Mg(OH)2 from sea water by the addition of
Ca(OH)2. The concentration of Mg2+(aq) in sea water is 5.37 × 10–2 M. Calculate the pH at which [Mg2+] is decreased to 1.0
–5
× 10 M
15.2.0.1: Answer:
10.97
In solutions containing two or more ions that may form insoluble compounds with the same counter ion, an experimental strategy
called selective precipitation may be used to remove individual ions from solution. By increasing the counter ion concentration in a
controlled manner, ions in solution may be precipitated individually, assuming their compound solubilities are adequately different.
In solutions with equal concentrations of target ions, the ion forming the least soluble compound will precipitate first (at the lowest
concentration of counter ion), with the other ions subsequently precipitating as their compound’s solubilities are reached. As an
illustration of this technique, the next example exercise describes separation of a two halide ions via precipitation of one as a silver
salt.

15.2.0.0.13: The Role of Precipitation in Wastewater Treatment
Solubility equilibria are useful tools in the treatment of wastewater carried out in facilities that may treat the municipal water in
your city or town (Figure 15.6). Specifically, selective precipitation is used to remove contaminants from wastewater before it
is released back into natural bodies of water. For example, phosphate ions (PO ) are often present in the water discharged
4
3−
from manufacturing facilities. An abundance of phosphate causes excess algae to grow, which impacts the amount of oxygen
available for marine life as well as making water unsuitable for human consumption.
Figure 15.6 Wastewater treatment facilities, such as this one, remove contaminants from wastewater before the water is
released back into the natural environment. (credit: “eutrophication&hypoxia”/Wikimedia Commons)
One common way to remove phosphates from water is by the addition of calcium hydroxide, or lime, Ca(OH)2. As the water is
made more basic, the calcium ions react with phosphate ions to produce hydroxylapatite, Ca5(PO4)3OH, which then
precipitates out of the solution:
2+ 3− −
5 Ca + 3PO4 + OH ⇌ Ca5 (PO ) ⋅OH(s)
4 3
Because the amount of calcium ion added does not result in exceeding the solubility products for other calcium salts, the
anions of those salts remain behind in the wastewater. The precipitate is then removed by filtration and the water is brought
back to a neutral pH by the addition of CO2 in a recarbonation process. Other chemicals can also be used for the removal of
phosphates by precipitation, including iron(III) chloride and aluminum sulfate.
View this site for more information on how phosphorus is removed from wastewater.

15.2.0.1: Example 15.11
15.2.0.0.14: Precipitation of Silver Halides
A solution contains 0.00010 mol of KBr and 0.10 mol of KCl per liter. AgNO3 is gradually added to this solution. Which forms
first, solid AgBr or solid AgCl?
15.2.0.0.15: Solution
The two equilibria involved are:
+ − −10
AgCl(s) ⇌ Ag (aq) + Cl (aq) Ksp = 1.6 × 10
+ − −13
AgBr(s) ⇌ Ag (aq) + Br (aq) Ksp = 5.0 × 10
If the solution contained about equal concentrations of Cl– and Br–, then the silver salt with the smaller Ksp (AgBr) would
precipitate first. The concentrations are not equal, however, so the [Ag+] at which AgCl begins to precipitate and the [Ag+] at
which AgBr begins to precipitate must be calculated. The salt that forms at the lower [Ag+] precipitates first.
AgBr precipitates when Q equals Ksp for AgBr
+ − + −13
Qsp = Ksp = [ Ag ] [Br ] = [ Ag ](0.00010) = 5.0 × 10
−13
+
5.0 × 10 −9
[ Ag ] = = 5.0 × 10 M
0.00010
AgBr begins to precipitate when [Ag+] is 5.0 × 10–9 M.

For AgCl: AgCl precipitates when Q equals Ksp for AgCl (1.6 × 10–10). When [Cl–] = 0.10 M:
+ − + −10
Qsp = Ksp = [ Ag ] [Cl ] = [ Ag ](0.10) = 1.6 × 10
−10
+
1.6 × 10
−9
[ Ag ] = = 1.6 × 10 M
0.10
AgCl begins to precipitate when [Ag+] is 1.6 × 10–9 M.

AgCl begins to precipitate at a lower [Ag+] than AgBr, so AgCl begins to precipitate first. Note the chloride ion concentration
of the initial mixture was significantly greater than the bromide ion concentration, and so silver chloride precipitated first
despite having a Ksp greater than that of silver bromide.
If silver nitrate solution is added to a solution which is 0.050 M in both Cl– and Br– ions, at what [Ag+] would precipitation
begin, and what would be the formula of the precipitate?
15.2.0.1: Answer:
[Ag+] = 1.0 × 10–11 M; AgBr precipitates first
15.2.0.1: Common Ion Effect

Compared with pure water, the solubility of an ionic compound is less in aqueous solutions containing a common ion (one also
produced by dissolution of the ionic compound). This is an example of a phenomenon known as the common ion effect, which is a
consequence of the law of mass action that may be explained using Le ChÂtelier’s principle. Consider the dissolution of silver
iodide:
+ −
AgI(s) ⇌ Ag (aq) + I (aq)
This solubility equilibrium may be shifted left by the addition of either silver(I) or iodide ions, resulting in the precipitation of AgI
and lowered concentrations of dissolved Ag+ and I–. In solutions that already contain either of these ions, less AgI may be
dissolved than in solutions without these ions.
This effect may also be explained in terms of mass action as represented in the solubility product expression:
+ −
Ksp = [ Ag ][ I ]

The mathematical product of silver(I) and iodide ion molarities is constant in an equilibrium mixture regardless of the source of the
ions, and so an increase in one ion’s concentration must be balanced by a proportional decrease in the other.

View this simulation to explore various aspects of the common ion effect.
15.2.0.1: Example 15.12

15.2.0.0.1: Common Ion Effect on Solubility
What is the effect on the amount of solid Mg(OH)2 and the concentrations of Mg2+ and OH– when each of the following are
added to a saturated solution of Mg(OH)2?
(a) MgCl2
(b) KOH
(c) NaNO3
(d) Mg(OH)2
The solubility equilibrium is
2+ −
Mg (OH) (s) ⇌ Mg (aq) + 2 OH (aq)
2
(a) Adding a common ion, Mg2+, will increase the concentration of this ion and shift the solubility equilibrium to the left,
decreasing the concentration of hydroxide ion and increasing the amount of undissolved magnesium hydroxide.
(b) Adding a common ion, OH–, will increase the concentration of this ion and shift the solubility equilibrium to the left,
decreasing the concentration of magnesium ion and increasing the amount of undissolved magnesium hydroxide.
(c) The added compound does not contain a common ion, and no effect on the magnesium hydroxide solubility equilibrium is
expected.
(d) Adding more solid magnesium hydroxide will increase the amount of undissolved compound in the mixture. The solution is
already saturated, though, so the concentrations of dissolved magnesium and hydroxide ions will remain the same.
2+ − 2
Q = [ Mg ] [ OH ]
Thus, changing the amount of solid magnesium hydroxide in the mixture has no effect on the value of Q, and no shift is
required to restore Q to the value of the equilibrium constant.
What is the effect on the amount of solid NiCO3 and the concentrations of Ni2+ and CO 3
2−
when each of the following are
added to a saturated solution of NiCO3
(a) Ni(NO3)2
(b) KClO4
(c) NiCO3
(d) K2CO3
15.2.0.1: Answer:
(a) mass of NiCO3(s) increases, [Ni2+] increases, [CO ] decreases; (b) no appreciable effect; (c) no effect except to
3
2−
increase the amount of solid NiCO3; (d) mass of NiCO3(s) increases, [Ni2+] decreases, [CO ] increases; 3
2−
15.2.0.1: Example 15.13

15.2.0.0.4: Common Ion Effect
Calculate the molar solubility of cadmium sulfide (CdS) in a 0.010-M solution of cadmium bromide (CdBr2). The Ksp of CdS
is 1.0 × 10–28.

This calculation can be performed using the ICE approach:
2+ 2−
CdS(s) ⇌ Cd (aq) + S (aq)
2+ 2− −28
Ksp = [ Cd ][ S ] = 1.0 × 10
−28
(0.010 + x)(x) = 1.0 × 10
Because Ksp is very small, assume x << 0.010 and solve the simplified equation for x:
−28
(0.010)(x) = 1.0 × 10
−26
x = 1.0 × 10 M
The molar solubility of CdS in this solution is 1.0 × 10–26 M.

Calculate the molar solubility of aluminum hydroxide, Al(OH)3, in a 0.015-M solution of aluminum nitrate, Al(NO3)3. The Ksp
of Al(OH)3 is 2 × 10–32.
15.2.0.1: Answer:
4 × 10–11 M
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Explain the Lewis model of acid-base chemistry
Write equations for the formation of adducts and complex ions
Perform equilibrium calculations involving formation constants
In 1923, G. N. Lewis proposed a generalized definition of acid-base behavior in which acids and bases are identified by their ability
to accept or to donate a pair of electrons and form a coordinate covalent bond.
A coordinate covalent bond (or dative bond) occurs when one of the atoms in the bond provides both bonding electrons. For
example, a coordinate covalent bond occurs when a water molecule combines with a hydrogen ion to form a hydronium ion. A
coordinate covalent bond also results when an ammonia molecule combines with a hydrogen ion to form an ammonium ion. Both
of these equations are shown here.
Reactions involving the formation of coordinate covalent bonds are classified as Lewis acid-base chemistry. The species donating
the electron pair that compose the bond is a Lewis base, the species accepting the electron pair is a Lewis acid, and the product of
the reaction is a Lewis acid-base adduct. As the two examples above illustrate, Brønsted-Lowry acid-base reactions represent a
subcategory of Lewis acid reactions, specifically, those in which the acid species is H+. A few examples involving other Lewis
acids and bases are described below.
The boron atom in boron trifluoride, BF3, has only six electrons in its valence shell. Being short of the preferred octet, BF3 is a very
good Lewis acid and reacts with many Lewis bases; a fluoride ion is the Lewis base in this reaction, donating one of its lone pairs:
In the following reaction, each of two ammonia molecules, Lewis bases, donates a pair of electrons to a silver ion, the Lewis acid:

Nonmetal oxides act as Lewis acids and react with oxide ions, Lewis bases, to form oxyanions:
Many Lewis acid-base reactions are displacement reactions in which one Lewis base displaces another Lewis base from an acid-
base adduct, or in which one Lewis acid displaces another Lewis acid:
Another type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a
central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral
molecules like H2O or NH3, or ions such as CN– or OH–. Often, the ligands act as Lewis bases, donating a pair of electrons to the
central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination chemistry—the
topic of another chapter in this text.
The equilibrium constant for the reaction of a metal ion with one or more ligands to form a coordination complex is called a
formation constant (Kf) (sometimes called a stability constant). For example, the complex ion Cu(CN) 2
−
is produced by the reaction

+ − −
Cu (aq) + 2 CN (aq) ⇌ Cu(CN) (aq)
2

The formation constant for this reaction is
−
[Cu(CN) ]
2
Kf =
+ − 2
[ Cu ] [ CN ]
Alternatively, the reverse reaction (decomposition of the complex ion) can be considered, in which case the equilibrium constant is
a dissociation constant (Kd). Per the relation between equilibrium constants for reciprocal reactions described, the dissociation
constant is the mathematical inverse of the formation constant, Kd = Kf–1. A tabulation of formation constants is provided in
Appendix K.
As an example of dissolution by complex ion formation, let us consider what happens when we add aqueous ammonia to a mixture
of silver chloride and water. Silver chloride dissolves slightly in water, giving a small concentration of Ag+ ([Ag+] = 1.3 × 10–5
M):
+ −
However, if NH3 is present in the water, the complex ion, Ag(NH 3 )2

+
, can form according to the equation:
+ +
Ag (aq) + 2 NH3 (aq) ⇌ Ag (NH3 ) (aq)
2
with
+
[Ag (NH3 )2 ]
7
Kf = = 1.7 × 10
+ 2
[ Ag ] [ NH3 ]
The large size of this formation constant indicates that most of the free silver ions produced by the dissolution of AgCl combine
with NH 3 to form Ag(NH ) . As a consequence, the concentration of silver ions, [Ag + ], is reduced, and the reaction quotient
3 2
+
for the dissolution of silver chloride, [Ag + ][Cl – ], falls below the solubility product of AgCl:
+ −
Q = [ Ag ] [ Cl ] < Ksp
More silver chloride then dissolves. If the concentration of ammonia is great enough, all of the silver chloride dissolves.
15.3.0.1: Example 15.14

15.3.0.0.1: Dissociation of a Complex Ion
Calculate the concentration of the silver ion in a solution that initially is 0.10 M with respect to Ag(NH 3 )2
+
.
Applying the standard ICE approach to this reaction yields the following:
Substituting these equilibrium concentration terms into the Kf expression gives

+
[Ag (NH3 ) ]
2
Kf =
+ 2
[ Ag ] [ NH3 ]
7
0.10 − x
1.7 × 10 =
2
(x)(2x)
The very large equilibrium constant means the amount of the complex ion that will dissociate, x, will be very small. Assuming
x << 0.1 permits simplifying the above equation:

7
0.10
1.7 × 10 =
2
(x)(2x)
0.10
3 −9
x = = 1.5 × 10
7
4(1.7 × 10 )
3
−−−−−−−− −
−9 −3
x = √ 1.5 × 10 = 1.1 × 10
Because only 1.1% of the Ag(NH 3 )2

+
dissociates into Ag+ and NH3, the assumption that x is small is justified.
Using this value of x and the relations in the above ICE table allows calculation of all species’ equilibrium concentrations:
+ −3
[ Ag ] = 0 + x = 1.1 × 10 M
−3
[ NH3 ] = 0 + 2x = 2.2 × 10 M
+
[Ag (NH3 ) ] = 0.10 − x = 0.10 − 0.0011 = 0.099
2
The concentration of free silver ion in the solution is 0.0011 M.

Calculate the silver ion concentration, [Ag+], of a solution prepared by dissolving 1.00 g of AgNO3 and 10.0 g of KCN in
sufficient water to make 1.00 L of solution. (Hint: Because Kf is very large, assume the reaction goes to completion then
calculate the [Ag+] produced by dissociation of the complex.)
15.3.0.1: Answer:
2.9 × 10–22 M
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Describe examples of systems involving two (or more) coupled chemical equilibria
Calculate reactant and product concentrations for coupled equilibrium systems
As discussed in preceding chapters on equilibrium, coupled equilibria involve two or more separate chemical reactions that share
one or more reactants or products. This section of this chapter will address solubility equilibria coupled with acid-base and
complex-formation reactions.
An environmentally relevant example illustrating the coupling of solubility and acid-base equilibria is the impact of ocean
acidification on the health of the ocean’s coral reefs. These reefs are built upon skeletons of sparingly soluble calcium carbonate
excreted by colonies of corals (small marine invertebrates). The relevant dissolution equilibrium is
2+ −2 −9
CaCO3 (s) ⇌ Ca (aq) + CO3 (aq) Ksp = 8.7 × 10
Rising concentrations of atmospheric carbon dioxide contribute to an increased acidity of ocean waters due to the dissolution,
hydrolysis, and acid ionization of carbon dioxide:
CO2 (g) ⇌ CO2 (aq)
CO2 (aq) + H2 O(l) ⇌ H2 CO3 (aq)
− + −7
H2 CO3 (aq) + H2 O(l) ⇌ HCO3 (aq) + H3 O (aq) Ka1 = 4.3 × 10
− 2− + −11
HCO3 (aq) + H2 O(l) ⇌ CO3 (aq) + H3 O (aq) Ka2 = 4.7 × 10
Inspection of these equilibria shows the carbonate ion is involved in the calcium carbonate dissolution and the acid hydrolysis of
bicarbonate ion. Combining the dissolution equation with the reverse of the acid hydrolysis equation yields
+ 2+ −
CaCO3 (s) + H3 O (aq) ⇌ Ca (aq) + HCO3 (aq) + H2 O(l) K = Ksp / Ka2 = 180
The equilibrium constant for this net reaction is much greater than the Ksp for calcium carbonate, indicating its solubility is
markedly increased in acidic solutions. As rising carbon dioxide levels in the atmosphere increase the acidity of ocean waters, the
calcium carbonate skeletons of coral reefs become more prone to dissolution and subsequently less healthy (Figure 15.7).
Figure 15.7 Healthy coral reefs (a) support a dense and diverse array of sea life across the ocean food chain. But when coral are
unable to adequately build and maintain their calcium carbonate skeletons because of excess ocean acidification, the unhealthy reef
(b) is only capable of hosting a small fraction of the species as before, and the local food chain starts to collapse. (credit a:
modification of work by NOAA Photo Library; credit b: modification of work by “prilfish”/Flickr)

Learn more about ocean acidification and how it affects other marine creatures.
This site has detailed information about how ocean acidification specifically affects coral reefs.
The dramatic increase in solubility with increasing acidity described above for calcium carbonate is typical of salts containing basic
anions (e.g., carbonate, fluoride, hydroxide, sulfide). Another familiar example is the formation of dental cavities in tooth enamel.
The major mineral component of enamel is calcium hydroxyapatite (Figure 15.8), a sparingly soluble ionic compound whose
dissolution equilibrium is
2+ 3− −
Ca5 (PO4 ) OH(s) ⇌ 5 Ca (aq) + 3 PO4 (aq) + OH (aq)
3
Figure 15.8 Crystal of the mineral hydroxyapatite, Ca5(PO4)3OH, is shown here. The pure compound is white, but like many other
minerals, this sample is colored because of the presence of impurities.
This compound dissolved to yield two different basic ions: triprotic phosphate ions
3− + 2−
PO4 (aq) + H3 O (aq) ⟶ H2 PO4 (aq) + H2 O(l)
2− + −
H2 PO4 (aq) + H3 O (aq) ⟶ H2 PO4 (aq) + H2 O(l)
− +
H2 PO4 (aq) + H3 O (aq) ⟶ H3 PO4 (aq) + H2 O(l)
and monoprotic hydroxide ions:

− +
OH (aq) + H3 O ⟶ 2 H2 O
Of the two basic productions, the hydroxide is, of course, by far the stronger base (it’s the strongest base that can exist in aqueous
solution), and so it is the dominant factor providing the compound an acid-dependent solubility. Dental cavities form when the acid
waste of bacteria growing on the surface of teeth hastens the dissolution of tooth enamel by reacting completely with the strong
base hydroxide, shifting the hydroxyapatite solubility equilibrium to the right. Some toothpastes and mouth rinses contain added
NaF or SnF2 that make enamel more acid resistant by replacing the strong base hydroxide with the weak base fluoride:
+ −
NaF + Ca5 (PO4 ) OH ⇌ Ca5 (PO4 ) F + Na + OH
3 3
The weak base fluoride ion reacts only partially with the bacterial acid waste, resulting in a less extensive shift in the solubility
equilibrium and an increased resistance to acid dissolution. See the Chemistry in Everyday Life feature on the role of fluoride in
preventing tooth decay for more information.

15.4.0.0.1: Role of Fluoride in Preventing Tooth Decay
As we saw previously, fluoride ions help protect our teeth by reacting with hydroxylapatite to form fluorapatite, Ca5(PO4)3F.
Since it lacks a hydroxide ion, fluorapatite is more resistant to attacks by acids in our mouths and is thus less soluble,
protecting our teeth. Scientists discovered that naturally fluorinated water could be beneficial to your teeth, and so it became

common practice to add fluoride to drinking water. Toothpastes and mouthwashes also contain amounts of fluoride (Figure
15.9).
Figure 15.9 Fluoride, found in many toothpastes, helps prevent tooth decay (credit: Kerry Ceszyk).
Unfortunately, excess fluoride can negate its advantages. Natural sources of drinking water in various parts of the world have
varying concentrations of fluoride, and places where that concentration is high are prone to certain health risks when there is
no other source of drinking water. The most serious side effect of excess fluoride is the bone disease, skeletal fluorosis. When
excess fluoride is in the body, it can cause the joints to stiffen and the bones to thicken. It can severely impact mobility and can
negatively affect the thyroid gland. Skeletal fluorosis is a condition that over 2.7 million people suffer from across the world.
So while fluoride can protect our teeth from decay, the US Environmental Protection Agency sets a maximum level of 4
ppm (4 mg/L) of fluoride in drinking water in the US. Fluoride levels in water are not regulated in all countries, so fluorosis is
a problem in areas with high levels of fluoride in the groundwater.
The solubility of ionic compounds may also be increased when dissolution is coupled to the formation of a complex ion. For
example, aluminum hydroxide dissolves in a solution of sodium hydroxide or another strong base because of the formation of the
complex ion Al(OH) . 4
−
The equations for the dissolution of aluminum hydroxide, the formation of the complex ion, and the combined (net) equation are
shown below. As indicated by the relatively large value of K for the net reaction, coupling complex formation with dissolution
drastically increases the solubility of Al(OH)3.
3+ − −32
Al (OH) (s) ⇌ Al (aq) + 3 OH (aq) Ksp = 2 × 10
3
3+ − − 33
Al (aq) + 4 OH (aq) ⇌ Al (OH) 4 (aq) Kf = 1.1 × 10
− −
Net: Al (OH) (s) + OH (aq) ⇌ Al (OH) (aq) K = Ksp Kf = 22
3 4
15.4.0.1: Example 15.15

15.4.0.0.1: Increased Solubility in Acidic Solutions
Compute and compare the molar solublities for aluminum hydroxide, Al(OH)3, dissolved in (a) pure water and (b) a buffer
containing 0.100 M acetic acid and 0.100 M sodium acetate.
(a) The molar solubility of aluminum hydroxide in water is computed considering the dissolution equilibrium only as
demonstrated in several previous examples:

3+ − −32
Al(OH) (s) ⇌ Al (aq) + 3OH (aq) Ksp = 2 × 10
3
3+ 1 / 4
−32 −9
molar solubility in water = [ Al ] = (2 × 10 / 27) = 5 × 10 M
(b) The concentration of hydroxide ion of the buffered solution is conveniently calculated by the Henderson-Hasselbalch
equation:
−
pH = pK a + log [ CH3 COO ] / [ CH3 COOH]
pH = 4.74 + log (0.100 / 0.100) = 4.74
At this pH, the concentration of hydroxide ion is
pOH = 14.00 – 4.74 = 9.26
− −9.26 −10
[ OH ] = 10 = 5.5 × 10
The solubility of Al(OH)3 in this buffer is then calculated from its solubility product expressions:
3+ − 3
Ksp = [ Al ] [ OH ]
3+ − 3 −32 −10
3
−4
molar solubility in buffer = [ Al ] = Ksp / [ OH ] = (2 × 10 ) / (5.5 × 10 ) = 1.2 × 10 M
Compared to pure water, the solubility of aluminum hydroxide in this mildly acidic buffer is approximately ten million times
greater (though still relatively low).
What is the solubility of aluminum hydroxide in a buffer comprised of 0.100 M formic acid and 0.100 M sodium formate?
15.4.0.1: Answer:
0.1 M
15.4.0.1: Example 15.16

15.4.0.0.1: Multiple Equilibria
Unexposed silver halides are removed from photographic film when they react with sodium thiosulfate (Na2S2O3, called hypo)
to form the complex ion Ag(S O ) (Kf = 4.7 × 1013).
2 3 2
3−
What mass of Na2S2O3 is required to prepare 1.00 L of a solution that will dissolve 1.00 g of AgBr by the formation of
3−
Ag (S2 O3 ) ?
2
Two equilibria are involved when silver bromide dissolves in an aqueous thiosulfate solution containing the S 2 O3
2−
ion:
dissolution: AgBr(s) ⇌ Ag +
(aq) + Br
−
(aq) Ksp = 5.0 × 10
−13
complexation: Ag +
(aq) + 2S2 O3
2−
(aq) ⇌ Ag (S2 O3 )
2
3−
(aq) Kf = 4.7 × 10
13
Combining these two equilibrium equations yields

2– 3–
AgBr(s) + 2 S2 O3 (aq) Ag(S2 O3 )2 (aq)
3– –
K=[Ag( S2 O3 )2 ][ Br ]
2– 2
= Ksp Kf = 24
[ S2 O3 ]

The concentration of bromide resulting from dissolution of 1.00 g of AgBr in 1.00 L of solution is
–
1 mol AgBr 1 mol Br
1.00 g AgBr × ×
187.77 g/mol 1 mol AgBr
–
[ Br ] = = 0.00532 M
1.00 L
The stoichiometry of the dissolution equilibrium indicates the same concentration of aqueous silver ion will result, 0.00532 M,
and the very large value of K ensures that essentially all the dissolved silver ion will be complexed by thiosulfate ion:
f
3–
[Ag(S2 O3 )2 ] = 0.00532 M
Rearranging the K expression for the combined equilibrium equations and solving for the concentration of thiosulfate ion
yields
3– –
[Ag(S2 O3 )2 ][ Br ] (0.00532 M )(0.00532 M )
2–
[ S2 O3 ] = = = 0.0011 M
K 24
Finally, the total mass of Na2 S2 O3 required to provide enough thiosulfate to yield the concentrations cited above can be
calculated.
Mass of Na 2 S2 O3 required to yield 0.00532 M Ag(S 2 O2 )
2
3–
3– 2–
mol Ag(S2 O3 )2 2 mol S2 O3 1 mol NaS2 O3 158.1 g NaS2 O3
0.00532 × × × = 1.68 g
3– 2–
1.00 L 1 mol Ag(S2 O3 )2 1 mol S2 O3 1 mol NaS2 O3
Mass of Na 2 S2 O3 required to yield 0.00110 M S 2 O3

2–
2– 2–
mol S2 O3 1 mol S2 O3 158.1 g Na2 S2 O3
0.0011 × × = 0.17 g
1.00 L 1 mol Na2 S2 O3 1 mol Na2 S2 O3
The mass of Na 2 S2 O3 required to dissolve 1.00 g of AgBr in 1.00 L of water is thus 1.68 g + 0.17 g = 1.85 g
AgCl(s), silver chloride, has a very low solubility: AgCl(s) ⇌ Ag (aq) + Cl (aq), Ksp = 1.6 × 10–10. Adding ammonia
+ −
significantly increases the solubility of AgCl because a complex ion is formed: Ag (aq) + 2NH (aq) ⇌ Ag(NH ) (aq), +
3 3 2
+
Kf = 1.7 × 107. What mass of NH3 is required to prepare 1.00 L of solution that will dissolve 2.00 g of AgCl by formation of
+
Ag (NH3 ) ?
2
15.4.0.1: Answer:
1.00 L of a solution prepared with 4.81 g NH3 dissolves 2.0 g of AgCl.
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15.5: Key Terms
common ion effect
effect on equilibrium when a substance with an ion in common with the dissolved species is added to the solution; causes a
decrease in the solubility of an ionic species, or a decrease in the ionization of a weak acid or base
complex ion
ion consisting of a central atom surrounding molecules or ions called ligands via coordinate covalent bonds
coordinate covalent bond

(also, dative bond) covalent bond in which both electrons originated from the same atom
coupled equilibria
system characterized the simultaneous establishment of two or more equilibrium reactions sharing one or more reactant or
product
dissociation constant
(Kd) equilibrium constant for the decomposition of a complex ion into its components
formation constant
(Kf) (also, stability constant) equilibrium constant for the formation of a complex ion from its components
Lewis acid
any species that can accept a pair of electrons and form a coordinate covalent bond
Lewis acid-base adduct

compound or ion that contains a coordinate covalent bond between a Lewis acid and a Lewis base
Lewis acid-base chemistry

reactions involving the formation of coordinate covalent bonds
Lewis base
any species that can donate a pair of electrons and form a coordinate covalent bond
ligand
molecule or ion acting as a Lewis base in complex ion formation; bonds to the central atom of the complex
molar solubility
solubility of a compound expressed in units of moles per liter (mol/L)
selective precipitation
process in which ions are separated using differences in their solubility with a given precipitating reagent
solubility product constant (Ksp)

equilibrium constant for the dissolution of an ionic compound
15.6: Key Equations
m+ n− m+ p n− q
Mp Xq (s) ⇌ pM (aq) + qX (aq) Ksp = [M ] [X ]
15.7: Summary
15.1 Precipitation and Dissolution
The equilibrium constant for an equilibrium involving the precipitation or dissolution of a slightly soluble ionic solid is called the
solubility product, Ksp, of the solid. For a heterogeneous equilibrium involving the slightly soluble solid MpXq and its ions Mm+
and Xn–:
m+ n−
Mp Xq (s) ⇌ p M (aq) + q X (aq)
the solubility product expression is:

m+ p n− q
Ksp = [M ] [X ]
The solubility product of a slightly soluble electrolyte can be calculated from its solubility; conversely, its solubility can be
calculated from its Ksp, provided the only significant reaction that occurs when the solid dissolves is the formation of its ions.
A slightly soluble electrolyte begins to precipitate when the magnitude of the reaction quotient for the dissolution reaction exceeds
the magnitude of the solubility product. Precipitation continues until the reaction quotient equals the solubility product.
15.2 Lewis Acids and Bases

A Lewis acid is a species that can accept an electron pair, whereas a Lewis base has an electron pair available for donation to a
Lewis acid. Complex ions are examples of Lewis acid-base adducts and comprise central metal atoms or ions acting as Lewis acids
bonded to molecules or ions called ligands that act as Lewis bases. The equilibrium constant for the reaction between a metal ion
and ligands produces a complex ion called a formation constant; for the reverse reaction, it is called a dissociation constant.
15.3 Coupled Equilibria

Systems involving two or more chemical equilibria that share one or more reactant or product are called coupled equilibria.
Common examples of coupled equilibria include the increased solubility of some compounds in acidic solutions (coupled
dissolution and neutralization equilibria) and in solutions containing ligands (coupled dissolution and complex formation). The
equilibrium tools from other chapters may be applied to describe and perform calculations on these systems.
15.8: Exercises
15.8.0.1: 15.1 Precipitation and Dissolution
1.
(a)
+ −
AgI(s) ⟶ Ag (aq) +I (aq)
x _____
(b)
2+ 2−
CaCO3 (s) ⟶ Ca (aq)+ CO3 (aq)
____ x
(c)
2+ −
Mg (OH) (s) ⟶ Mg (aq)+ 2 OH (aq)
2
x _____
(d)
2+ 3−
Mg 3 (PO4 ) (s) ⟶ 3 Mg (aq)+ 2 PO4 (aq)
2
x _____
(e)
2+ 3− −
Ca5 (PO4 ) OH(s) ⟶ 5 Ca (aq)+ 3 PO4 (aq)+ OH (aq)
3
_____ _____ x
2.
(a)
2+ 2−
BaSO 4 (s) ⟶ Ba (aq)+ SO 4 (aq)
x _____
(b
+ 2−
Ag2 SO 4 (s) ⟶ 2 Ag (aq)+ SO 4 (aq)
_____ x
(c)
3+ −
Al (OH) (s) ⟶ Al (aq)+ 3 OH (aq)
3
x _____
(d)
2+ − −
Pb(OH)Cl(s) ⟶ Pb (aq)+ OH (aq)+ Cl (aq)
_____ x _____

(e)
2+ 3−
Ca3 (AsO 4 ) (s) ⟶ 3 Ca (aq)+ 2 AsO 4 (aq)
2
3x _____
3.
How do the concentrations of Ag+ and CrO 4
2−
in a saturated solution above 1.0 g of solid Ag2CrO4 change when 100 g of solid
Ag2CrO4 is added to the system? Explain.
4.
How do the concentrations of Pb2+ and S2– change when K2S is added to a saturated solution of PbS?
5.
What additional information do we need to answer the following question: How is the equilibrium of solid silver bromide with a
saturated solution of its ions affected when the temperature is raised?
6.
Which of the following slightly soluble compounds has a solubility greater than that calculated from its solubility product because
of hydrolysis of the anion present: CoSO3, CuI, PbCO3, PbCl2, Tl2S, KClO4?
7.
Which of the following slightly soluble compounds has a solubility greater than that calculated from its solubility product because
of hydrolysis of the anion present: AgCl, BaSO4, CaF2, Hg2I2, MnCO3, and ZnS?
8.
Write the ionic equation for dissolution and the solubility product (Ksp) expression for each of the following slightly soluble ionic
compounds:
(a) PbCl2
(b) Ag2S
(c) Sr3(PO4)2
(d) SrSO4
9.
Write the ionic equation for the dissolution and the Ksp expression for each of the following slightly soluble ionic compounds:
(a) LaF3
(b) CaCO3
(c) Ag2SO4
(d) Pb(OH)2
10.
The Handbook of Chemistry and Physics gives solubilities of the following compounds in grams per 100 mL of water. Because
these compounds are only slightly soluble, assume that the volume does not change on dissolution and calculate the solubility
product for each.
(a) BaSiF6, 0.026 g/100 mL (contains SiF 6
2−
ions)
–2
(b) Ce(IO3)4, 1.5 × 10 g/100 mL
(c) Gd2(SO4)3, 3.98 g/100 mL
(d) (NH4)2PtBr6, 0.59 g/100 mL (contains PtBr 6
2−
ions)
11.
The Handbook of Chemistry and Physics gives solubilities of the following compounds in grams per 100 mL of water. Because
these compounds are only slightly soluble, assume that the volume does not change on dissolution and calculate the solubility

product for each.
(a) BaSeO4, 0.0118 g/100 mL
(b) Ba(BrO3)2·H2O, 0.30 g/100 mL
(c) NH4MgAsO4·6H2O, 0.038 g/100 mL
(d) La2(MoO4)3, 0.00179 g/100 mL
12.
Use solubility products and predict which of the following salts is the most soluble, in terms of moles per liter, in pure water: CaF2,
Hg2Cl2, PbI2, or Sn(OH)2.
13.
Assuming that no equilibria other than dissolution are involved, calculate the molar solubility of each of the following from its
solubility product:
(a) KHC4H4O6
(b) PbI2
(c) Ag4[Fe(CN)6], a salt containing the Fe(CN) 6
4–
ion
(d) Hg2I2
14.
Assuming that no equilibria other than dissolution are involved, calculate the molar solubility of each of the following from its
solubility product:
(a) Ag2SO4
(b) PbBr2
(c) AgI
(d) CaC2O4·H2O
15.
Assuming that no equilibria other than dissolution are involved, calculate the concentration of all solute species in each of the
following solutions of salts in contact with a solution containing a common ion. Show that changes in the initial concentrations of
the common ions can be neglected.
(a) AgCl(s) in 0.025 M NaCl
(b) CaF2(s) in 0.00133 M KF
(c) Ag2SO4(s) in 0.500 L of a solution containing 19.50 g of K2SO4
(d) Zn(OH)2(s) in a solution buffered at a pH of 11.45
16.
following solutions of salts in contact with a solution containing a common ion. Show that changes in the initial concentrations of
the common ions can be neglected.
(a) TlCl(s) in 1.250 M HCl
(b) PbI2(s) in 0.0355 M CaI2
(c) Ag2CrO4(s) in 0.225 L of a solution containing 0.856 g of K2CrO4
(d) Cd(OH)2(s) in a solution buffered at a pH of 10.995
17.
following solutions of salts in contact with a solution containing a common ion. Show that it is not appropriate to neglect the

changes in the initial concentrations of the common ions.
(a) TlCl(s) in 0.025 M TlNO3
(b) BaF2(s) in 0.0313 M KF
(c) MgC2O4 in 2.250 L of a solution containing 8.156 g of Mg(NO3)2
(d) Ca(OH)2(s) in an unbuffered solution initially with a pH of 12.700
18.
Explain why the changes in concentrations of the common ions in Exercise 15.17 can be neglected.
19.
Explain why the changes in concentrations of the common ions in Exercise 15.18 cannot be neglected.
20.
Calculate the solubility of aluminum hydroxide, Al(OH)3, in a solution buffered at pH 11.00.
21.
Refer to Appendix J for solubility products for calcium salts. Determine which of the calcium salts listed is most soluble in moles
per liter and which is most soluble in grams per liter.
22.
Most barium compounds are very poisonous; however, barium sulfate is often administered internally as an aid in the X-ray
examination of the lower intestinal tract (Figure 15.4). This use of BaSO4 is possible because of its low solubility. Calculate the
molar solubility of BaSO4 and the mass of barium present in 1.00 L of water saturated with BaSO4.
23.
Public Health Service standards for drinking water set a maximum of 250 mg/L (2.60 × 10–3 M) of SO 4 because of its cathartic
2−
action (it is a laxative). Does natural water that is saturated with CaSO4 (“gyp” water) as a result or passing through soil containing
gypsum, CaSO4·2H2O, meet these standards? What is the concentration of SO 4 in such water?
2−
24.
Perform the following calculations:
(a) Calculate [Ag+] in a saturated aqueous solution of AgBr.
(b) What will [Ag+] be when enough KBr has been added to make [Br–] = 0.050 M?
(c) What will [Br–] be when enough AgNO3 has been added to make [Ag+] = 0.020 M?
25.
The solubility product of CaSO4·2H2O is 2.4 × 10–5. What mass of this salt will dissolve in 1.0 L of 0.010 M SO 4
2−
?
26.
Assuming that no equilibria other than dissolution are involved, calculate the concentrations of ions in a saturated solution of each
of the following (see Appendix J for solubility products).
(a) TlCl
(b) BaF2
(c) Ag2CrO4
(d) CaC2O4·H2O
(e) the mineral anglesite, PbSO4
27.
Assuming that no equilibria other than dissolution are involved, calculate the concentrations of ions in a saturated solution of each
of the following (see Appendix J for solubility products):
(a) AgI

(b) Ag2SO4
(c) Mn(OH)2
(d) Sr(OH)2·8H2O
(e) the mineral brucite, Mg(OH)2
28.
The following concentrations are found in mixtures of ions in equilibrium with slightly soluble solids. From the concentrations
given, calculate Ksp for each of the slightly soluble solids indicated:
(a) AgBr: [Ag+] = 5.7 × 10–7 M, [Br–] = 5.7 × 10–7 M
(b) CaCO3: [Ca2+] = 5.3 × 10–3 M, [CO 3
2−
] = 9.0 × 10–7 M
(c) PbF2: [Pb2+] = 2.1 × 10–3 M, [F–] = 4.2 × 10–3 M
(d) Ag2CrO4: [Ag+] = 5.3 × 10–5 M, 3.2 × 10–3 M
(e) InF3: [In3+] = 2.3 × 10–3 M, [F–] = 7.0 × 10–3 M
29.
The following concentrations are found in mixtures of ions in equilibrium with slightly soluble solids. From the concentrations
given, calculate Ksp for each of the slightly soluble solids indicated:
(a) TlCl: [Tl+] = 1.21 × 10–2 M, [Cl–] = 1.2 × 10–2 M
(b) Ce(IO3)4: [Ce4+] = 1.8 × 10–4 M, [IO 3
−
] = 2.6 × 10–13 M
(c) Gd2(SO4)3: [Gd3+] = 0.132 M, [SO 4
2−
] = 0.198 M
+ –2
(d) Ag2SO4: [Ag ] = 2.40 × 10 M, [SO 4
2−
] = 2.05 × 10–2 M
(e) BaSO4: [Ba2+] = 0.500 M, [SO 4
2−
] = 4.6 × 10−8 M
30.
Which of the following compounds precipitates from a solution that has the concentrations indicated? (See Appendix J for Ksp
values.)
(a) KClO4: [K+] = 0.01 M, [ClO 4
−
] = 0.01 M
(b) K2PtCl6: [K+] = 0.01 M, [PtCl 6
2−
] = 0.01 M
(c) PbI2: [Pb ] = 0.003 M, [I ] = 1.3 × 10–3 M
2+ –
(d) Ag2S: [Ag+] = 1 × 10–10 M, [S2–] = 1 × 10–13 M

31.
Which of the following compounds precipitates from a solution that has the concentrations indicated? (See Appendix J for Ksp
values.)
(a) CaCO3: [Ca2+] = 0.003 M, [CO 3
2−
] = 0.003 M
(b) Co(OH)2: [Co2+] = 0.01 M, [OH–] = 1 × 10–7 M
(c) CaHPO4: [Ca2+] = 0.01 M, [HPO 4
2−
] = 2 × 10–6 M
(d) Pb3(PO4)2: [Pb2+] = 0.01 M, [PO 4
3−
]= 1 × 10–13 M
32.
Calculate the concentration of Tl+ when TlCl just begins to precipitate from a solution that is 0.0250 M in Cl–.
33.
Calculate the concentration of sulfate ion when BaSO4 just begins to precipitate from a solution that is 0.0758 M in Ba2+.
34.
Calculate the concentration of Sr2+ when SrCrO4 starts to precipitate from a solution that is 0.0025 M in CrO42–.

35.
Calculate the concentration of PO 4
3−
when Ag3PO4 starts to precipitate from a solution that is 0.0125 M in Ag+.
36.
Calculate the concentration of F– required to begin precipitation of CaF2 in a solution that is 0.010 M in Ca2+.
37.
Calculate the concentration of Ag+ required to begin precipitation of Ag2CO3 in a solution that is 2.50 × 10–6 M in CO 3
2−
.
38.
What [Ag+] is required to reduce [CO 3
2−
] to 8.2 × 10–4 M by precipitation of Ag2CO3?
39.
What [F–] is required to reduce [Ca2+] to 1.0 × 10–4 M by precipitation of CaF2?
40.
A volume of 0.800 L of a 2 × 10–4-M Ba(NO3)2 solution is added to 0.200 L of 5 × 10–4 M Li2SO4. Does BaSO4 precipitate?
Explain your answer.
41.
Perform these calculations for nickel(II) carbonate. (a) With what volume of water must a precipitate containing NiCO3 be washed
to dissolve 0.100 g of this compound? Assume that the wash water becomes saturated with NiCO3 (Ksp = 1.36 × 10–7).
(b) If the NiCO3 were a contaminant in a sample of CoCO3 (Ksp = 1.0 × 10–12), what mass of CoCO3 would have been lost? Keep
in mind that both NiCO3 and CoCO3 dissolve in the same solution.
42.
Iron concentrations greater than 5.4 × 10–6 M in water used for laundry purposes can cause staining. What [OH–] is required to
reduce [Fe2+] to this level by precipitation of Fe(OH)2?
43.
A solution is 0.010 M in both Cu2+ and Cd2+. What percentage of Cd2+ remains in the solution when 99.9% of the Cu2+ has been
precipitated as CuS by adding sulfide?
44.
A solution is 0.15 M in both Pb2+ and Ag+. If Cl– is added to this solution, what is [Ag+] when PbCl2 begins to precipitate?
45.
What reagent might be used to separate the ions in each of the following mixtures, which are 0.1 M with respect to each ion? In
some cases it may be necessary to control the pH. (Hint: Consider the Ksp values given in Appendix J.)
(a) Hg2
2+
and Cu2+
(b) SO 4
2−
and Cl–
(c) Hg2+ and Co2+
(d) Zn2+ and Sr2+
(e) Ba2+ and Mg2+
(f) CO 3
2−
and OH–
46.
A solution contains 1.0 × 10–5 mol of KBr and 0.10 mol of KCl per liter. AgNO3 is gradually added to this solution. Which forms
first, solid AgBr or solid AgCl?
47.
A solution contains 1.0 × 10–2 mol of KI and 0.10 mol of KCl per liter. AgNO3 is gradually added to this solution. Which forms
first, solid AgI or solid AgCl?
48.

The calcium ions in human blood serum are necessary for coagulation (Figure 15.5). Potassium oxalate, K2C2O4, is used as an
anticoagulant when a blood sample is drawn for laboratory tests because it removes the calcium as a precipitate of CaC2O4·H2O. It
is necessary to remove all but 1.0% of the Ca2+ in serum in order to prevent coagulation. If normal blood serum with a buffered pH
of 7.40 contains 9.5 mg of Ca2+ per 100 mL of serum, what mass of K2C2O4 is required to prevent the coagulation of a 10 mL
blood sample that is 55% serum by volume? (All volumes are accurate to two significant figures. Note that the volume of serum in
a 10-mL blood sample is 5.5 mL. Assume that the Ksp value for CaC2O4 in serum is the same as in water.)
49.
About 50% of urinary calculi (kidney stones) consist of calcium phosphate, Ca3(PO4)2. The normal mid range calcium content
excreted in the urine is 0.10 g of Ca2+ per day. The normal mid range amount of urine passed may be taken as 1.4 L per day. What
is the maximum concentration of phosphate ion that urine can contain before a calculus begins to form?
50.
The pH of normal urine is 6.30, and the total phosphate concentration ([PO ] + [HPO ] + [H PO ] + [H3PO4]) is 0.020 M.
4
3−
4
2−
2 4
−
What is the minimum concentration of Ca2+ necessary to induce kidney stone formation? (See Exercise 15.49 for additional
information.)
51.
Magnesium metal (a component of alloys used in aircraft and a reducing agent used in the production of uranium, titanium, and
other active metals) is isolated from sea water by the following sequence of reactions:
2+ 2+
Mg (aq) + Ca(OH) (aq) ⟶ Mg(OH) (s) + Ca (aq)
2 2
Mg(OH) (s) + 2HCl(aq) ⟶ MgCl2 (s) + 2H2 O(l)

2
electrolysis
MgCl2 (l) −−−−−−−→ Mg(s) + Cl2 (g)
Sea water has a density of 1.026 g/cm3 and contains 1272 parts per million of magnesium as Mg2+(aq) by mass. What mass, in
kilograms, of Ca(OH)2 is required to precipitate 99.9% of the magnesium in 1.00 × 103 L of sea water?
52.
Hydrogen sulfide is bubbled into a solution that is 0.10 M in both Pb2+ and Fe2+ and 0.30 M in HCl. After the solution has come to
equilibrium it is saturated with H2S ([H2S] = 0.10 M). What concentrations of Pb2+ and Fe2+ remain in the solution? For a saturated
solution of H2S we can use the equilibrium:
+ 2− −26
H2 S(aq) + 2H2 O(l) ⇌ 2H3 O (aq) + S (aq) K = 1.0 × 1 0
(Hint: The [H 3O
+
] changes as metal sulfides precipitate.)
53.
Perform the following calculations involving concentrations of iodate ions:
(a) The iodate ion concentration of a saturated solution of La(IO3)3 was found to be 3.1 × 10–3 mol/L. Find the Ksp.
(b) Find the concentration of iodate ions in a saturated solution of Cu(IO3)2 (Ksp = 7.4 × 10–8).
54.
Calculate the molar solubility of AgBr in 0.035 M NaBr (Ksp = 5 × 10–13).
55.
How many grams of Pb(OH)2 will dissolve in 500 mL of a 0.050-M PbCl2 solution (Ksp = 1.2 × 10–15)?
56.
Use the simulation from the earlier Link to Learning to complete the following exercise. Using 0.01 g CaF2, give the Ksp values
found in a 0.2-M solution of each of the salts. Discuss why the values change as you change soluble salts.
57.
How many grams of Milk of Magnesia, Mg(OH)2 (s) (58.3 g/mol), would be soluble in 200 mL of water. Ksp = 7.1 × 10–12.
Include the ionic reaction and the expression for Ksp in your answer. (Kw = 1 × 10–14 = [H3O+][OH–])
58.

Two hypothetical salts, LM2 and LQ, have the same molar solubility in H2O. If Ksp for LM2 is 3.20 × 10–5, what is the Ksp value
for LQ?
59.
The carbonate ion concentration is gradually increased in a solution containing equal concentrations of the divalent cations of
magnesium, calcium, strontium, barium, and manganese. Which of the following carbonates will precipitate first? Which will
precipitate last? Explain.
(a) MgCO 3
∙ 3 H2 O Ksp = 1 × 1 0
−5
(b) CaCO 3 Ksp = 8.7 × 1 0

−9
(c) SrCO 3 Ksp = 7 × 1 0

−10
(d) BaCO 3 Ksp = 1.6 × 1 0

−9
(e) MnCO 3 Ksp = 8.8 × 1 0

−11
60.
How many grams of Zn(CN)2(s) (117.44 g/mol) would be soluble in 100 mL of H2O? Include the balanced reaction and the
expression for Ksp in your answer. The Ksp value for Zn(CN)2(s) is 3.0 × 10–16.
15.8.0.1: 15.2 Lewis Acids and Bases

61.
Even though Ca(OH)2 is an inexpensive base, its limited solubility restricts its use. What is the pH of a saturated solution of
Ca(OH)2?
62.
Under what circumstances, if any, does a sample of solid AgCl completely dissolve in pure water?
63.
Explain why the addition of NH3 or HNO3 to a saturated solution of Ag2CO3 in contact with solid Ag2CO3 increases the solubility
of the solid.
64.
Calculate the cadmium ion concentration, [Cd2+], in a solution prepared by mixing 0.100 L of 0.0100 M Cd(NO3)2 with 0.150 L of
0.100 NH3(aq).
65.
Explain why addition of NH3 or HNO3 to a saturated solution of Cu(OH)2 in contact with solid Cu(OH)2 increases the solubility of
the solid.
66.
Sometimes equilibria for complex ions are described in terms of dissociation constants, Kd. For the complex ion AlF6
3−
the
dissociation reaction is:
3+ − 6
[ Al ][F ]
AlF6
3−
⇌ Al
3+
+ 6F
−
and K
d =
[ AlF6
3−
]
−24
= 2 × 10
Calculate the value of the formation constant, Kf, for AlF 6

3−
.
67.
Using the value of the formation constant for the complex ion Co(NH 3 )6
2+
, calculate the dissociation constant.
68.
Using the dissociation constant, Kd = 7.8 × 10–18, calculate the equilibrium concentrations of Cd2+ and CN– in a 0.250-M solution
of Cd(CN) . 4
2−
69.
Using the dissociation constant, Kd = 3.4 × 10–15, calculate the equilibrium concentrations of Zn2+ and OH– in a 0.0465-M solution
of Zn(OH) . 4
2−

70.
Using the dissociation constant, Kd = 2.2 × 10–34, calculate the equilibrium concentrations of Co3+ and NH3 in a 0.500-M solution
of Co(NH ) . 3 6
3+
71.
Using the dissociation constant, Kd = 1 × 10–44, calculate the equilibrium concentrations of Fe3+ and CN– in a 0.333 M solution of
3−
Fe(CN) .
6
72.
Calculate the mass of potassium cyanide ion that must be added to 100 mL of solution to dissolve 2.0 × 10–2 mol of silver cyanide,
AgCN.
73.
Calculate the minimum concentration of ammonia needed in 1.0 L of solution to dissolve 3.0 × 10–3 mol of silver bromide.
74.
A roll of 35-mm black and white photographic film contains about 0.27 g of unexposed AgBr before developing. What mass of
Na2S2O3·5H2O (sodium thiosulfate pentahydrate or hypo) in 1.0 L of developer is required to dissolve the AgBr as Ag(S O ) 2 3 2
3−
(Kf = 4.7 × 1013)?

75.
We have seen an introductory definition of an acid: An acid is a compound that reacts with water and increases the amount of
hydronium ion present. In the chapter on acids and bases, we saw two more definitions of acids: a compound that donates a proton
(a hydrogen ion, H+) to another compound is called a Brønsted-Lowry acid, and a Lewis acid is any species that can accept a pair
of electrons. Explain why the introductory definition is a macroscopic definition, while the Brønsted-Lowry definition and the
Lewis definition are microscopic definitions.
76.
Write the Lewis structures of the reactants and product of each of the following equations, and identify the Lewis acid and the
Lewis base in each:
(a) CO 2 + OH
−
⟶ HCO3
−
(b) B(OH) 3
+ OH
−
⟶ B(OH)
4
−
(c) I −
+ I2 ⟶ I3
−
(d) AlCl 3 + Cl
−
⟶ AlCl4
−
(use Al-Cl single bonds)
(e) O 2−
+ SO 3 ⟶ SO 4
2−
77.
Write the Lewis structures of the reactants and product of each of the following equations, and identify the Lewis acid and the
Lewis base in each:
(a) CS 2 + SH
−
⟶ HCS3
−
(b) BF 3 +F
−
⟶ BF 4
−
(c) I −
+ SnI 2 ⟶ SnI 3
−
(d) Al(OH) 3
+ OH
−
⟶ Al (OH)
4
−
(e) F −
+ SO 3 ⟶ SFO3
−
78.
Using Lewis structures, write balanced equations for the following reactions:
(a) HCl(g) + PH 3 (g) ⟶
(b) H 3O
+
+ CH3
−
⟶
(c) CaO + SO 3 ⟶

(d) NH 4
+
+ C2 H5 O
−
⟶
79.
Calculate [HgCl 4
2−
] in a solution prepared by adding 0.0200 mol of NaCl to 0.250 L of a 0.100-M HgCl2 solution.
80.
In a titration of cyanide ion, 28.72 mL of 0.0100 M AgNO3 is added before precipitation begins. [The reaction of Ag+ with CN–
goes to completion, producing the Ag(CN) complex.] Precipitation of solid AgCN takes place when excess Ag+ is added to the
2
−
solution, above the amount needed to complete the formation of Ag(CN) . How many grams of NaCN were in the original
2
−
sample?
81.
What are the concentrations of Ag+, CN–, and Ag(CN) 2
−
in a saturated solution of AgCN?
82.
In dilute aqueous solution HF acts as a weak acid. However, pure liquid HF (boiling point = 19.5 °C) is a strong acid. In liquid HF,
HNO3 acts like a base and accepts protons. The acidity of liquid HF can be increased by adding one of several inorganic fluorides
that are Lewis acids and accept F– ion (for example, BF3 or SbF5). Write balanced chemical equations for the reaction of pure
HNO3 with pure HF and of pure HF with BF3.
83.
The simplest amino acid is glycine, H2NCH2CO2H. The common feature of amino acids is that they contain the functional groups:
an amine group, –NH2, and a carboxylic acid group, –CO2H. An amino acid can function as either an acid or a base. For glycine,
the acid strength of the carboxyl group is about the same as that of acetic acid, CH3CO2H, and the base strength of the amino group
is slightly greater than that of ammonia, NH3.
(a) Write the Lewis structures of the ions that form when glycine is dissolved in 1 M HCl and in 1 M KOH.
(b) Write the Lewis structure of glycine when this amino acid is dissolved in water. (Hint: Consider the relative base strengths of
the –NH2 and −CO groups.)2
−
84.
Boric acid, H3BO3, is not a Brønsted-Lowry acid but a Lewis acid.
(a) Write an equation for its reaction with water.
(b) Predict the shape of the anion thus formed.
(c) What is the hybridization on the boron consistent with the shape you have predicted?
15.8.0.1: 15.3 Coupled Equilibria

85.
A saturated solution of a slightly soluble electrolyte in contact with some of the solid electrolyte is said to be a system in
equilibrium. Explain. Why is such a system called a heterogeneous equilibrium?
86.
Calculate the equilibrium concentration of Ni2+ in a 1.0-M solution [Ni(NH3)6](NO3)2.
87.
Calculate the equilibrium concentration of Zn2+ in a 0.30-M solution of Zn(CN) 4
2−
.
88.
Calculate the equilibrium concentration of Cu2+ in a solution initially with 0.050 M Cu2+ and 1.00 M NH3.
89.
Calculate the equilibrium concentration of Zn2+ in a solution initially with 0.150 M Zn2+ and 2.50 M CN–.
90.
Calculate the Fe3+ equilibrium concentration when 0.0888 mole of K3[Fe(CN)6] is added to a solution with 0.0.00010 M CN–.

91.
Calculate the Co2+ equilibrium concentration when 0.010 mole of [Co(NH3)6](NO3)2 is added to a solution with 0.25 M NH3.
Assume the volume is 1.00 L.
92.
Calculate the molar solubility of Sn(OH)2 in a buffer solution containing equal concentrations of NH3 and NH 4
+
.
93.
Calculate the molar solubility of Al(OH)3 in a buffer solution with 0.100 M NH3 and 0.400 M NH 4
+
.
94.
What is the molar solubility of CaF2 in a 0.100-M solution of HF? Ka for HF = 6.4 × 10–4.
95.
What is the molar solubility of BaSO4 in a 0.250-M solution of NaHSO4? Ka for HSO 4
−
= 1.2 × 10–2.
96.
What is the molar solubility of Tl(OH)3 in a 0.10-M solution of NH3?
97.
What is the molar solubility of Pb(OH)2 in a 0.138-M solution of CH3NH2?
98.
A solution of 0.075 M CoBr2 is saturated with H2S ([H2S] = 0.10 M). What is the minimum pH at which CoS begins to precipitate?
2+ 2− 27
CoS(s) ⇌ Co (aq) + S (aq) Ksp = 2.3 × 10
+ 2− −27
H2 S(aq) + 2 H2 O(l) ⇌ 2 H3 O (aq) + S (aq) K = 8.9 × 10
99.
A 0.125-M solution of Mn(NO3)2 is saturated with H2S ([H2S] = 0.10 M). At what pH does MnS begin to precipitate?
2+ 2− −13
MnS(s) ⇌ Mn (aq) + S (aq) Ksp = 2.3 × 10
+ 2− −26
H2 S(aq) + 2 H2 O(l) ⇌ 2 H3 O (aq) + S (aq) K = 1.0 × 10
100.
Both AgCl and AgI dissolve in NH3.
(a) What mass of AgI dissolves in 1.0 L of 1.0 M NH3?
(b) What mass of AgCl dissolves in 1.0 L of 1.0 M NH3?
101.
The following question is taken from a Chemistry Advanced Placement Examination and is used with the permission of the
Solve the following problem:
2+ −
MgF2 (s) ⇌ Mg (aq) + 2 F (aq)
In a saturated solution of MgF2 at 18 °C, the concentration of Mg2+ is 1.21 × 10–3 M. The equilibrium is represented by the
preceding equation.
(a) Write the expression for the solubility-product constant, Ksp, and calculate its value at 18 °C.
(b) Calculate the equilibrium concentration of Mg2+ in 1.000 L of saturated MgF2 solution at 18 °C to which 0.100 mol of solid KF
has been added. The KF dissolves completely. Assume the volume change is negligible.
(c) Predict whether a precipitate of MgF2 will form when 100.0 mL of a 3.00 × 10–3-M solution of Mg(NO3)2 is mixed with 200.0
mL of a 2.00 × 10–3-M solution of NaF at 18 °C. Show the calculations to support your prediction.
(d) At 27 °C the concentration of Mg2+ in a saturated solution of MgF2 is 1.17 × 10–3 M. Is the dissolving of MgF2 in water an
endothermic or an exothermic process? Give an explanation to support your conclusion.

102.
Which of the following compounds, when dissolved in a 0.01-M solution of HClO4, has a solubility greater than in pure water:
CuCl, CaCO3, MnS, PbBr2, CaF2? Explain your answer.
103.
Which of the following compounds, when dissolved in a 0.01-M solution of HClO4, has a solubility greater than in pure water:
AgBr, BaF2, Ca3(PO4)2, ZnS, PbI2? Explain your answer.
104.
What is the effect on the amount of solid Mg(OH)2 that dissolves and the concentrations of Mg2+ and OH– when each of the
following are added to a mixture of solid Mg(OH)2 and water at equilibrium?
(a) MgCl2
(b) KOH
(c) HClO4
(d) NaNO3
(e) Mg(OH)2
105.
What is the effect on the amount of CaHPO4 that dissolves and the concentrations of Ca2+ and HPO4
2−
when each of the
following are added to a mixture of solid CaHPO4 and water at equilibrium?
(a) CaCl2
(b) HCl
(c) KClO4
(d) NaOH
(e) CaHPO4
106.
Identify all chemical species present in an aqueous solution of Ca3(PO4)2 and list these species in decreasing order of their
concentrations. (Hint: Remember that the PO ion is a weak base.)
4
3−

CHAPTER OVERVIEW
16: Thermodynamics

General Chemistry
Among the many capabilities of chemistry is its ability to predict if a process will occur under specified conditions.
Thermodynamics, the study of relationships between the energy and work associated with chemical and physical processes,
provides this predictive ability. Previous chapters in this text have described various applications of thermochemistry, an important
aspect of thermodynamics concerned with the heat flow accompanying chemical reactions and phase transitions. This chapter will
introduce additional thermodynamic concepts, including those that enable the prediction of any chemical or physical changes under
a given set of conditions.
16.1: Introduction
16.2: Spontaneity
16.3: Entropy
16.5: Free Energy
16.6: Key Terms
16.7: Key Equations
16.8: Summary
16.9: Exercises
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1
16.1: Introduction
Figure 16.1 Geysers are a dramatic display of thermodynamic principles in nature. Water deep within the underground channels of
the geyser is under high pressure and heated to high temperature by magma. When a pocket of water near the surface reaches
boiling point and is expelled, the resulting drop in pressure causes larger volumes of water to flash boil, forcefully ejecting steam
and water in an impressive eruption. (credit: modification of work by Yellowstone National Park)
Chapter Outline
16.1 Spontaneity
16.2 Entropy
16.3 The Second and Third Laws of Thermodynamics
16.4 Free Energy
Among the many capabilities of chemistry is its ability to predict if a process will occur under specified conditions.
Thermodynamics, the study of relationships between the energy and work associated with chemical and physical processes,
provides this predictive ability. Previous chapters in this text have described various applications of thermochemistry, an important
aspect of thermodynamics concerned with the heat flow accompanying chemical reactions and phase transitions. This chapter will
introduce additional thermodynamic concepts, including those that enable the prediction of any chemical or physical changes under
a given set of conditions.
16.2: Spontaneity

Distinguish between spontaneous and nonspontaneous processes
Describe the dispersal of matter and energy that accompanies certain spontaneous processes
Processes have a natural tendency to occur in one direction under a given set of conditions. Water will naturally flow downhill, but
uphill flow requires outside intervention such as the use of a pump. Iron exposed to the earth’s atmosphere will corrode, but rust is
not converted to iron without intentional chemical treatment. A spontaneous process is one that occurs naturally under certain
conditions. A nonspontaneous process, on the other hand, will not take place unless it is “driven” by the continual input of energy
from an external source. A process that is spontaneous in one direction under a particular set of conditions is nonspontaneous in the
reverse direction. At room temperature and typical atmospheric pressure, for example, ice will spontaneously melt, but water will
not spontaneously freeze.
The spontaneity of a process is not correlated to the speed of the process. A spontaneous change may be so rapid that it is
essentially instantaneous or so slow that it cannot be observed over any practical period of time. To illustrate this concept, consider
the decay of radioactive isotopes, a topic more thoroughly treated in the chapter on nuclear chemistry. Radioactive decay is by
definition a spontaneous process in which the nuclei of unstable isotopes emit radiation as they are converted to more stable nuclei.
All the decay processes occur spontaneously, but the rates at which different isotopes decay vary widely. Technetium-99m is a
popular radioisotope for medical imaging studies that undergoes relatively rapid decay and exhibits a half-life of about six hours.
Uranium-238 is the most abundant isotope of uranium, and its decay occurs much more slowly, exhibiting a half-life of more than
four billion years (Figure 16.2).
Figure 16.2 Both U-238 and Tc-99m undergo spontaneous radioactive decay, but at drastically different rates. Over the course of
one week, essentially all of a Tc-99m sample and none of a U-238 sample will have decayed.
As another example, consider the conversion of diamond into graphite (Figure 16.3).
C(s, diamond) ⟶ C(s, graphite)
The phase diagram for carbon indicates that graphite is the stable form of this element under ambient atmospheric pressure, while
diamond is the stable allotrope at very high pressures, such as those present during its geologic formation. Thermodynamic

calculations of the sort described in the last section of this chapter indicate that the conversion of diamond to graphite at ambient
pressure occurs spontaneously, yet diamonds are observed to exist, and persist, under these conditions. Though the process is
spontaneous under typical ambient conditions, its rate is extremely slow; so, for all practical purposes diamonds are indeed
“forever.” Situations such as these emphasize the important distinction between the thermodynamic and the kinetic aspects of a
process. In this particular case, diamonds are said to be thermodynamically unstable but kinetically stable under ambient
conditions.
Figure 16.3 The conversion of carbon from the diamond allotrope to the graphite allotrope is spontaneous at ambient pressure, but
its rate is immeasurably slow at low to moderate temperatures. This process is known as graphitization, and its rate can be
increased to easily measurable values at temperatures in the 1000–2000 K range. (credit "diamond" photo: modification of work by
"Fancy Diamonds"/Flickr; credit "graphite" photo: modification of work by images-of-elements.com/carbon.php)
16.2.0.1: Dispersal of Matter and Energy

Extending the discussion of thermodynamic concepts toward the objective of predicting spontaneity, consider now an isolated
system consisting of two flasks connected with a closed valve. Initially there is an ideal gas in one flask and the other flask is
empty (P = 0). (Figure 16.4). When the valve is opened, the gas spontaneously expands to fill both flasks equally. Recalling the
definition of pressure-volume work from the chapter on thermochemistry, note that no work has been done because the pressure in
a vacuum is zero.
w = −P ΔV = 0 (P = 0 in a vacuum)
Note as well that since the system is isolated, no heat has been exchanged with the surroundings (q = 0). The first law of
thermodynamics confirms that there has been no change in the system’s internal energy as a result of this process.
ΔU = q + w = 0 + 0 = 0
The spontaneity of this process is therefore not a consequence of any change in energy that accompanies the process. Instead, the
driving force appears to be related to the greater, more uniform dispersal of matter that results when the gas is allowed to expand.
Initially, the system was comprised of one flask containing matter and another flask containing nothing. After the spontaneous
expansion took place, the matter was distributed both more widely (occupying twice its original volume) and more uniformly
(present in equal amounts in each flask).

Figure 16.4 An isolated system consists of an ideal gas in one flask that is connected by a closed valve to a second flask containing
a vacuum. Once the valve is opened, the gas spontaneously becomes evenly distributed between the flasks.
Now consider two objects at different temperatures: object X at temperature TX and object Y at temperature TY, with TX > TY
(Figure 16.5). When these objects come into contact, heat spontaneously flows from the hotter object (X) to the colder one (Y).
This corresponds to a loss of thermal energy by X and a gain of thermal energy by Y.
qX < 0 and qY = −qX > 0
From the perspective of this two-object system, there was no net gain or loss of thermal energy, rather the available thermal energy
was redistributed among the two objects. This spontaneous process resulted in a more uniform dispersal of energy.
Figure 16.5 When two objects at different temperatures come in contact, heat spontaneously flows from the hotter to the colder
object.
As illustrated by the two processes described, an important factor in determining the spontaneity of a process is the extent to which
it changes the dispersal or distribution of matter and/or energy. In each case, a spontaneous process took place that resulted in a
more uniform distribution of matter or energy.
16.2.0.1: Example 16.1

16.2.0.0.1: Redistribution of Matter during a Spontaneous Process
Describe how matter is redistributed when the following spontaneous processes take place:
(a) A solid sublimes.
(b) A gas condenses.
(c) A drop of food coloring added to a glass of water forms a solution with uniform color.

Figure 16.6 (credit a: modification of work by Jenny Downing; credit b: modification of work by “Fuzzy Gerdes”/Flickr; credit
c: modification of work by Paul A. Flowers)
(a) Sublimation is the conversion of a solid (relatively high density) to a gas (much lesser density). This process yields a much
greater dispersal of matter, since the molecules will occupy a much greater volume after the solid-to-gas transition.
(b) Condensation is the conversion of a gas (relatively low density) to a liquid (much greater density). This process yields a
much lesser dispersal of matter, since the molecules will occupy a much lesser volume after the gas-to-liquid transition.
(c) The process in question is diffusion. This process yields a more uniform dispersal of matter, since the initial state of the
system involves two regions of different dye concentrations (high in the drop of dye, zero in the water), and the final state of
the system contains a single dye concentration throughout.
Describe how energy is redistributed when a spoon at room temperature is placed in a cup of hot coffee.
16.2.0.1: Answer:
Heat will spontaneously flow from the hotter object (coffee) to the colder object (spoon), resulting in a more uniform
distribution of thermal energy as the spoon warms and the coffee cools.
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16.3: Entropy

Define entropy
Explain the relationship between entropy and the number of microstates
Predict the sign of the entropy change for chemical and physical processes
In 1824, at the age of 28, Nicolas Léonard Sadi Carnot (Figure 16.7) published the results of an extensive study regarding the
efficiency of steam heat engines. A later review of Carnot’s findings by Rudolf Clausius introduced a new thermodynamic property
that relates the spontaneous heat flow accompanying a process to the temperature at which the process takes place. This new
property was expressed as the ratio of the reversible heat (qrev) and the kelvin temperature (T). In thermodynamics, a reversible
process is one that takes place at such a slow rate that it is always at equilibrium and its direction can be changed (it can be
“reversed”) by an infinitesimally small change in some condition. Note that the idea of a reversible process is a formalism required
to support the development of various thermodynamic concepts; no real processes are truly reversible, rather they are classified as
irreversible.
Figure 16.7 (a) Nicholas Léonard Sadi Carnot’s research into steam-powered machinery and (b) Rudolf Clausius’s later study of
those findings led to groundbreaking discoveries about spontaneous heat flow processes.
Similar to other thermodynamic properties, this new quantity is a state function, so its change depends only upon the initial and
final states of a system. In 1865, Clausius named this property entropy (S) and defined its change for any process as the following:
qrev
ΔS =
T
The entropy change for a real, irreversible process is then equal to that for the theoretical reversible process that involves the same
initial and final states.

16.3.0.1: Entropy and Microstates
Following the work of Carnot and Clausius, Ludwig Boltzmann developed a molecular-scale statistical model that related the
entropy of a system to the number of microstates (W) possible for the system. A microstate is a specific configuration of all the
locations and energies of the atoms or molecules that make up a system. The relation between a system’s entropy and the number
of possible microstates is
S = k ln W
−23
where k is the Boltzmann constant, 1.38 × 10 J/K.
As for other state functions, the change in entropy for a process is the difference between its final (Sf) and initial (Si) values:
Wf
ΔS = Sf − Si = k ln Wf − k ln Wi = k ln
Wi
For processes involving an increase in the number of microstates, Wf > Wi, the entropy of the system increases and ΔS > 0.
Conversely, processes that reduce the number of microstates, Wf < Wi, yield a decrease in system entropy, ΔS < 0. This molecular-
scale interpretation of entropy provides a link to the probability that a process will occur as illustrated in the next paragraphs.
Consider the general case of a system comprised of N particles distributed among n boxes. The number of microstates possible for
such a system is nN. For example, distributing four particles among two boxes will result in 24 = 16 different microstates as
illustrated in Figure 16.8. Microstates with equivalent particle arrangements (not considering individual particle identities) are
grouped together and are called distributions. The probability that a system will exist with its components in a given distribution is
proportional to the number of microstates within the distribution. Since entropy increases logarithmically with the number of
microstates, the most probable distribution is therefore the one of greatest entropy.
Figure 16.8 The sixteen microstates associated with placing four particles in two boxes are shown. The microstates are collected
into five distributions—(a), (b), (c), (d), and (e)—based on the numbers of particles in each box.
For this system, the most probable configuration is one of the six microstates associated with distribution (c) where the particles are
evenly distributed between the boxes, that is, a configuration of two particles in each box. The probability of finding the system in
this configuration is 6
16
or . The least probable configuration of the system is one in which all four particles are in one box,
3
corresponding to distributions (a) and (e), each with a probability of . The probability of finding all particles in only one box
16
1
(either the left box or right box) is then ( + ) =

1
16
1
16
or .
2
16
1
As you add more particles to the system, the number of possible microstates increases exponentially (2N). A macroscopic
(laboratory-sized) system would typically consist of moles of particles (N ~ 1023), and the corresponding number of microstates
would be staggeringly huge. Regardless of the number of particles in the system, however, the distributions in which roughly equal
numbers of particles are found in each box are always the most probable configurations.

This matter dispersal model of entropy is often described qualitatively in terms of the disorder of the system. By this description,
microstates in which all the particles are in a single box are the most ordered, thus possessing the least entropy. Microstates in
which the particles are more evenly distributed among the boxes are more disordered, possessing greater entropy.
The previous description of an ideal gas expanding into a vacuum (Figure 16.4) is a macroscopic example of this particle-in-a-box
model. For this system, the most probable distribution is confirmed to be the one in which the matter is most uniformly dispersed
or distributed between the two flasks. Initially, the gas molecules are confined to just one of the two flasks. Opening the valve
between the flasks increases the volume available to the gas molecules and, correspondingly, the number of microstates possible for
the system. Since Wf > Wi, the expansion process involves an increase in entropy (ΔS > 0) and is spontaneous.
A similar approach may be used to describe the spontaneous flow of heat. Consider a system consisting of two objects, each
containing two particles, and two units of thermal energy (represented as “*”) in Figure 16.9. The hot object is comprised of
particles A and B and initially contains both energy units. The cold object is comprised of particles C and D, which initially has no
energy units. Distribution (a) shows the three microstates possible for the initial state of the system, with both units of energy
contained within the hot object. If one of the two energy units is transferred, the result is distribution (b) consisting of four
microstates. If both energy units are transferred, the result is distribution (c) consisting of three microstates. Thus, we may describe
this system by a total of ten microstates. The probability that the heat does not flow when the two objects are brought into contact,
that is, that the system remains in distribution (a), is . More likely is the flow of heat to yield one of the other two distribution,
3
10
the combined probability being . The most likely result is the flow of heat to yield the uniform dispersal of energy represented
7
10
by distribution (b), the probability of this configuration being . This supports the common observation that placing hot and cold
4
10
objects in contact results in spontaneous heat flow that ultimately equalizes the objects’ temperatures. And, again, this spontaneous
process is also characterized by an increase in system entropy.
Figure 16.9 This shows a microstate model describing the flow of heat from a hot object to a cold object. (a) Before the heat flow
occurs, the object comprised of particles A and B contains both units of energy and as represented by a distribution of three
microstates. (b) If the heat flow results in an even dispersal of energy (one energy unit transferred), a distribution of four
microstates results. (c) If both energy units are transferred, the resulting distribution has three microstates.
16.3.0.1: Example 16.2

16.3.0.0.1: Determination of ΔS
Calculate the change in entropy for the process depicted below.
The initial number of microstates is one, the final six:
Wc 6
−23 −23
ΔS = k ln = 1.38 × 10 J/K × ln = 2.47 × 10 J/K
Wa 1

The sign of this result is consistent with expectation; since there are more microstates possible for the final state than for the
initial state, the change in entropy should be positive.
Consider the system shown in Figure 16.9. What is the change in entropy for the process where all the energy is transferred
from the hot object (AB) to the cold object (CD)?
16.3.0.1: Answer:
0 J/K
16.3.0.1: Predicting the Sign of ΔS

The relationships between entropy, microstates, and matter/energy dispersal described previously allow us to make generalizations
regarding the relative entropies of substances and to predict the sign of entropy changes for chemical and physical processes.
Consider the phase changes illustrated in Figure 16.10. In the solid phase, the atoms or molecules are restricted to nearly fixed
positions with respect to each other and are capable of only modest oscillations about these positions. With essentially fixed
locations for the system’s component particles, the number of microstates is relatively small. In the liquid phase, the atoms or
molecules are free to move over and around each other, though they remain in relatively close proximity to one another. This
increased freedom of motion results in a greater variation in possible particle locations, so the number of microstates is
correspondingly greater than for the solid. As a result, Sliquid > Ssolid and the process of converting a substance from solid to liquid
(melting) is characterized by an increase in entropy, ΔS > 0. By the same logic, the reciprocal process (freezing) exhibits a decrease
in entropy, ΔS < 0.
Figure 16.10 The entropy of a substance increases (ΔS > 0) as it transforms from a relatively ordered solid, to a less-ordered liquid,
and then to a still less-ordered gas. The entropy decreases (ΔS < 0) as the substance transforms from a gas to a liquid and then to a
solid.
Now consider the gaseous phase, in which a given number of atoms or molecules occupy a much greater volume than in the liquid
phase. Each atom or molecule can be found in many more locations, corresponding to a much greater number of microstates.
Consequently, for any substance, Sgas > Sliquid > Ssolid, and the processes of vaporization and sublimation likewise involve increases
in entropy, ΔS > 0. Likewise, the reciprocal phase transitions, condensation and deposition, involve decreases in entropy, ΔS < 0.
According to kinetic-molecular theory, the temperature of a substance is proportional to the average kinetic energy of its particles.
Raising the temperature of a substance will result in more extensive vibrations of the particles in solids and more rapid translations
of the particles in liquids and gases. At higher temperatures, the distribution of kinetic energies among the atoms or molecules of
the substance is also broader (more dispersed) than at lower temperatures. Thus, the entropy for any substance increases with
temperature (Figure 16.11).

Figure 16.11 Entropy increases as the temperature of a substance is raised, which corresponds to the greater spread of kinetic
energies. When a substance undergoes a phase transition, its entropy changes significantly.

Try this simulator with interactive visualization of the dependence of particle location and freedom of motion on physical state
and temperature.
The entropy of a substance is influenced by the structure of the particles (atoms or molecules) that comprise the substance. With
regard to atomic substances, heavier atoms possess greater entropy at a given temperature than lighter atoms, which is a
consequence of the relation between a particle’s mass and the spacing of quantized translational energy levels (a topic beyond the
scope of this text). For molecules, greater numbers of atoms increase the number of ways in which the molecules can vibrate and
thus the number of possible microstates and the entropy of the system.
Finally, variations in the types of particles affects the entropy of a system. Compared to a pure substance, in which all particles are
identical, the entropy of a mixture of two or more different particle types is greater. This is because of the additional orientations
and interactions that are possible in a system comprised of nonidentical components. For example, when a solid dissolves in a
liquid, the particles of the solid experience both a greater freedom of motion and additional interactions with the solvent particles.
This corresponds to a more uniform dispersal of matter and energy and a greater number of microstates. The process of dissolution
therefore involves an increase in entropy, ΔS > 0.
Considering the various factors that affect entropy allows us to make informed predictions of the sign of ΔS for various chemical
and physical processes as illustrated in Example 16.3.
16.3.0.1: Example 16.3

16.3.0.0.1: Predicting the Sign of ∆S
Predict the sign of the entropy change for the following processes. Indicate the reason for each of your predictions.
(a) One mole liquid water at room temperature ⟶ one mole liquid water at 50 °C
(b) Ag +
(aq) + Cl
−
(aq) ⟶ AgCl(s)
(c) C6 H6 (l) +
15
2
O2 (g) ⟶ 6 CO2 (g) + 3 H2 O(l)
(d) NH 3 (s) ⟶ NH3 (l)
(a) positive, temperature increases
(b) negative, reduction in the number of ions (particles) in solution, decreased dispersal of matter

(c) negative, net decrease in the amount of gaseous species
(d) positive, phase transition from solid to liquid, net increase in dispersal of matter
Predict the sign of the entropy change for the following processes. Give a reason for your prediction.
(a) NaNO 3 (s) ⟶ Na
+
(aq) + NO3
−
(aq)
(b) the freezing of liquid water

(c) CO 2 (s) ⟶ CO2 (g)
(d) CaCO 3 (s) ⟶ CaO(s) + CO2 (g)
16.3.0.1: Answer:
(a) Positive; The solid dissolves to give an increase of mobile ions in solution. (b) Negative; The liquid becomes a more
ordered solid. (c) Positive; The relatively ordered solid becomes a gas. (d) Positive; There is a net increase in the amount
of gaseous species.
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State and explain the second and third laws of thermodynamics
Calculate entropy changes for phase transitions and chemical reactions under standard conditions
16.4.0.1: The Second Law of Thermodynamics

In the quest to identify a property that may reliably predict the spontaneity of a process, a promising candidate has been identified:
entropy. Processes that involve an increase in entropy of the system (ΔS > 0) are very often spontaneous; however, examples to the
contrary are plentiful. By expanding consideration of entropy changes to include the surroundings, we may reach a significant
conclusion regarding the relation between this property and spontaneity. In thermodynamic models, the system and surroundings
comprise everything, that is, the universe, and so the following is true:
ΔSuniv = ΔSsys + ΔSsurr
To illustrate this relation, consider again the process of heat flow between two objects, one identified as the system and the other as
the surroundings. There are three possibilities for such a process:
1. The objects are at different temperatures, and heat flows from the hotter to the cooler object. This is always observed to occur
spontaneously. Designating the hotter object as the system and invoking the definition of entropy yields the following:
−qrev qrev
ΔSsys = and ΔSsurr =
Tsys Tsurr
The magnitudes of −qrev and qrev are equal, their opposite arithmetic signs denoting loss of heat by the system and gain of heat
by the surroundings. Since Tsys > Tsurr in this scenario, the entropy decrease of the system will be less than the entropy increase
of the surroundings, and so the entropy of the universe will increase:
|ΔSsys | < |ΔSsurr |
ΔSuniv = ΔSsys + ΔSsurr > 0
2. The objects are at different temperatures, and heat flows from the cooler to the hotter object. This is never observed to occur
spontaneously. Again designating the hotter object as the system and invoking the definition of entropy yields the following:
qrev −qrev
ΔSsys = and ΔSsurr =
Tsys Tsurr
The arithmetic signs of qrev denote the gain of heat by the system and the loss of heat by the surroundings. The magnitude of the
entropy change for the surroundings will again be greater than that for the system, but in this case, the signs of the heat changes
(that is, the direction of the heat flow) will yield a negative value for ΔSuniv. This process involves a decrease in the entropy of
the universe.
3. The objects are at essentially the same temperature, Tsys ≈ Tsurr, and so the magnitudes of the entropy changes are essentially the
same for both the system and the surroundings. In this case, the entropy change of the universe is zero, and the system is at
equilibrium.
|ΔSsys | ≈ |ΔSsurr |
ΔSuniv = ΔSsys + ΔSsurr = 0
These results lead to a profound statement regarding the relation between entropy and spontaneity known as the second law of
thermodynamics: all spontaneous changes cause an increase in the entropy of the universe. A summary of these three relations is
provided in Table 16.1.
The Second Law of Thermodynamics
ΔSuniv > 0 spontaneous

ΔSuniv < 0 nonspontaneous (spontaneous in opposite direction)
ΔSuniv = 0 at equilibrium
Table 16.1
For many realistic applications, the surroundings are vast in comparison to the system. In such cases, the heat gained or lost by the
surroundings as a result of some process represents a very small, nearly infinitesimal, fraction of its total thermal energy. For
example, combustion of a fuel in air involves transfer of heat from a system (the fuel and oxygen molecules undergoing reaction) to
surroundings that are infinitely more massive (the earth’s atmosphere). As a result, qsurr is a good approximation of qrev, and the
second law may be stated as the following:
qsurr
ΔSuniv = ΔSsys + ΔSsurr = ΔSsys +
T
We may use this equation to predict the spontaneity of a process as illustrated in Example 16.4.
16.4.0.1: Example 16.4

16.4.0.0.1: Will Ice Spontaneously Melt?
The entropy change for the process
H2 O(s) ⟶ H2 O(l)
is 22.1 J/K and requires that the surroundings transfer 6.00 kJ of heat to the system. Is the process spontaneous at −10.00 °C? Is
it spontaneous at +10.00 °C?
We can assess the spontaneity of the process by calculating the entropy change of the universe. If ΔSuniv is positive, then the
process is spontaneous. At both temperatures, ΔSsys = 22.1 J/K and qsurr = −6.00 kJ.
At −10.00 °C (263.15 K), the following is true:
qsurr
T
3
−6.00 × 10 J
= 22.1 J/K + = −0.7 J/K
263.15 K
Suniv < 0, so melting is nonspontaneous (not spontaneous) at −10.0 °C.

At 10.00 °C (283.15 K), the following is true:
qsurr
ΔSuniv = ΔSsys +
T
3
−6.00 × 10 J
= 22.1 J/K + = +0.9 J/K
283.15 K
Suniv > 0, so melting is spontaneous at 10.00 °C.

Using this information, determine if liquid water will spontaneously freeze at the same temperatures. What can you say about
the values of Suniv?
16.4.0.1: Answer:
Entropy is a state function, so ΔSfreezing = −ΔSmelting = −22.1 J/K and qsurr = +6.00 kJ. At −10.00 °C spontaneous, +0.7 J/K;
at +10.00 °C nonspontaneous, −0.9 J/K.
16.4.0.1: The Third Law of Thermodynamics

The previous section described the various contributions of matter and energy dispersal that contribute to the entropy of a system.
With these contributions in mind, consider the entropy of a pure, perfectly crystalline solid possessing no kinetic energy (that is, at

a temperature of absolute zero, 0 K). This system may be described by a single microstate, as its purity, perfect crystallinity and
complete lack of motion means there is but one possible location for each identical atom or molecule comprising the crystal (W =
1). According to the Boltzmann equation, the entropy of this system is zero.
S = k ln W = k ln (1) = 0
This limiting condition for a system’s entropy represents the third law of thermodynamics: the entropy of a pure, perfect crystalline
substance at 0 K is zero.
Careful calorimetric measurements can be made to determine the temperature dependence of a substance’s entropy and to derive
absolute entropy values under specific conditions. Standard entropies (S°) are for one mole of substance under standard conditions
(a pressure of 1 bar and a temperature of 298.15 K; see details regarding standard conditions in the thermochemistry chapter of this
text). The standard entropy change (ΔS°) for a reaction may be computed using standard entropies as shown below:
ΔS° = ∑ ν S°(products) − ∑ ν S°(reactants)
where ν represents stoichiometric coefficients in the balanced equation representing the process. For example, ΔS° for the
following reaction at room temperature
mA + nB ⟶ xC + yD,
is computed as:
= [xS°(C) + yS°(D)] − [mS°(A) + nS°(B)]
A partial listing of standard entropies is provided in Table 16.2, and additional values are provided in Appendix G. The example
exercises that follow demonstrate the use of S° values in calculating standard entropy changes for physical and chemical processes.
Substance S° (J mol−1 K−1)
carbon
C(s, graphite) 5.740
C(s, diamond) 2.38
CO(g) 197.7
CO2(g) 213.8
CH4(g) 186.3
C2H4(g) 219.5
C2H6(g) 229.5
CH3OH(l) 126.8
C2H5OH(l) 160.7
hydrogen
H2(g) 130.57
H(g) 114.6

H2O(g) 188.71
H2O(l) 69.91
HCI(g) 186.8
H2S(g) 205.7
oxygen
O2(g) 205.03
Table 16.2 Standard entropies for selected substances measured at 1 atm and 298.15 K. (Values are approximately equal to those
measured at 1 bar, the currently accepted standard state pressure.)
16.4.0.1: Example 16.5

16.4.0.0.1: Determination of ΔS°
Calculate the standard entropy change for the following process:
H2 O(g) ⟶ H2 O(l)
Calculate the entropy change using standard entropies as shown above:
−1 −1 −1 −1
ΔS° = (1 mol)(70.0 J mol K ) − (1 mol)(188.8 J mol K ) = −118.8 J/K
The value for ΔS° is negative, as expected for this phase transition (condensation), which the previous section discussed.
Calculate the standard entropy change for the following process:
H2 (g) + C2 H4 (g) ⟶ C2 H6 (g)
16.4.0.1: Answer:
−120.6 J K–1 mol–1
16.4.0.1: Example 16.6

16.4.0.0.4: Determination of ΔS°
Calculate the standard entropy change for the combustion of methanol, CH3OH:
2 CH3 OH(l) + 3 O2 (g) ⟶ 2 CO2 (g) + 4 H2 O(l)
Calculate the entropy change using standard entropies as shown above:
ΔS° = ∑ ν S°(products) − ∑ ν S°(reactants)
[2 mol × S° (CO2 (g)) + 4 mol × S° (H2 O(l))] − [2 mol × S° (CH3 OH(l)) + 3 mol × S° (O2 (g))]
= { [2(213.8) + 4 × 70.0] − [2 (126.8) + 3 (205.03)] } = −161.1 J/K

Calculate the standard entropy change for the following reaction:
Ca (OH) (s) ⟶ CaO(s) + H2 O(l)
2
16.4.0.1: Answer:
24.7 J/K

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upon request.

16.5: Free Energy

Define Gibbs free energy, and describe its relation to spontaneity
Calculate free energy change for a process using free energies of formation for its reactants and products
Calculate free energy change for a process using enthalpies of formation and the entropies for its reactants and products
Explain how temperature affects the spontaneity of some processes
Relate standard free energy changes to equilibrium constants
One of the challenges of using the second law of thermodynamics to determine if a process is spontaneous is that it requires
measurements of the entropy change for the system and the entropy change for the surroundings. An alternative approach involving
a new thermodynamic property defined in terms of system properties only was introduced in the late nineteenth century by
American mathematician Josiah Willard Gibbs. This new property is called the Gibbs free energy (G) (or simply the free energy),
and it is defined in terms of a system’s enthalpy and entropy as the following:
G = H −TS
Free energy is a state function, and at constant temperature and pressure, the free energy change (ΔG) may be expressed as the
following:
ΔG = ΔH − T ΔS
(For simplicity’s sake, the subscript “sys” will be omitted henceforth.)

The relationship between this system property and the spontaneity of a process may be understood by recalling the previously
derived second law expression:
qsurr
ΔSuniv = ΔS +
T
The first law requires that qsurr = −qsys, and at constant pressure qsys = ΔH, so this expression may be rewritten as:
ΔH
ΔSuniv = ΔS −
T
Multiplying both sides of this equation by −T, and rearranging yields the following:
−T ΔSuniv = ΔH − T ΔS
Comparing this equation to the previous one for free energy change shows the following relation:
ΔG = −T ΔSuniv
The free energy change is therefore a reliable indicator of the spontaneity of a process, being directly related to the previously
identified spontaneity indicator, ΔSuniv. Table 16.3 summarizes the relation between the spontaneity of a process and the arithmetic
signs of these indicators.
Relation between Process Spontaneity and Signs of Thermodynamic Properties
ΔSuniv > 0 ΔG < 0 spontaneous
ΔSuniv < 0 ΔG > 0 nonspontaneous
ΔSuniv = 0 ΔG = 0 at equilibrium
Table 16.3

16.5.0.1: What’s “Free” about ΔG?
In addition to indicating spontaneity, the free energy change also provides information regarding the amount of useful work (w) that
may be accomplished by a spontaneous process. Although a rigorous treatment of this subject is beyond the scope of an
introductory chemistry text, a brief discussion is helpful for gaining a better perspective on this important thermodynamic property.
For this purpose, consider a spontaneous, exothermic process that involves a decrease in entropy. The free energy, as defined by
ΔG = ΔH − T ΔS
may be interpreted as representing the difference between the energy produced by the process, ΔH, and the energy lost to the
surroundings, TΔS. The difference between the energy produced and the energy lost is the energy available (or “free”) to do useful
work by the process, ΔG. If the process somehow could be made to take place under conditions of thermodynamic reversibility, the
amount of work that could be done would be maximal:
ΔG = wmax
where w max refers to all types of work except expansion (pressure-volume) work.
However, as noted previously in this chapter, such conditions are not realistic. In addition, the technologies used to extract work
from a spontaneous process (e.g., batteries) are never 100% efficient, and so the work done by these processes is always less than
the theoretical maximum. Similar reasoning may be applied to a nonspontaneous process, for which the free energy change
represents the minimum amount of work that must be done on the system to carry out the process.
16.5.0.1: Calculating Free Energy Change

Free energy is a state function, so its value depends only on the conditions of the initial and final states of the system. A convenient
and common approach to the calculation of free energy changes for physical and chemical reactions is by use of widely available
compilations of standard state thermodynamic data. One method involves the use of standard enthalpies and entropies to compute
standard free energy changes, ΔG°, according to the following relation.
ΔG° = ΔH ° − T ΔS°
16.5.0.1: Example 16.7

16.5.0.0.1: Using Standard Enthalpy and Entropy Changes to Calculate ΔG°
Use standard enthalpy and entropy data from Appendix G to calculate the standard free energy change for the vaporization of
water at room temperature (298 K). What does the computed value for ΔG° say about the spontaneity of this process?
The process of interest is the following:
H2 O(l) ⟶ H2 O(g)
The standard change in free energy may be calculated using the following equation:
ΔG° = ΔH ° − T ΔS°
From Appendix G:
Substance ΔH
f
∘
(kJ/mol) S°(J/K⋅mol)
H2O(l) −285.83 70.0
H2O(g) −241.82 188.8
Using the appendix data to calculate the standard enthalpy and entropy changes yields:
∘ ∘
ΔH ° = ΔH (H2 O(g)) − ΔH (H2 O(l))
f f
= [−241.82 kJ/mol − (−285.83)] kJ/mol = 44.01 kJ
ΔS° = 1 mol × S° (H2 O(g)) − 1 mol × S° (H2 O(l))
= (1 mol)188.8 J/mol⋅K − (1 mol)70.0 J/mol K = 118.8 J/K

ΔG° = ΔH ° − T ΔS°
Substitution into the standard free energy equation yields:

ΔG° = ΔH ° − T ΔS°
1 kJ
= 44.01 kJ − (298 K × 118.8 J/K) ×
1000 J
44.01 kJ − 35.4 kJ = 8.6 kJ
At 298 K (25 °C) ΔG° > 0, so boiling is nonspontaneous (not spontaneous).

Use standard enthalpy and entropy data from Appendix G to calculate the standard free energy change for the reaction shown
here (298 K). What does the computed value for ΔG° say about the spontaneity of this process?
C2 H6 (g) ⟶ H2 (g) + C2 H4 (g)
16.5.0.1: Answer:
ΔG° = 102.0 kJ/mol; the reaction is nonspontaneous (not spontaneous) at 25 °C.
The standard free energy change for a reaction may also be calculated from standard free energy of formation ΔGf° values of the
reactants and products involved in the reaction. The standard free energy of formation is the free energy change that accompanies
the formation of one mole of a substance from its elements in their standard states. Similar to the standard enthalpy of formation,
ΔG is by definition zero for elemental substances in their standard states. The approach used to calculate ΔG for a reaction from
∘ °
f
ΔG values is the same as that demonstrated previously for enthalpy and entropy changes. For the reaction
∘
f
mA + nB ⟶ xC + yD,
the standard free energy change at room temperature may be calculated as
ΔG° = ∑ νΔG°(products) − ∑ νΔG°(reactants)
∘ ∘ ∘ ∘
= [xΔG (C) + yΔG (D)] − [mΔG (A) + nΔG (B)] .
f f f f
16.5.0.1: Example 16.8

16.5.0.0.4: Using Standard Free Energies of Formation to Calculate ΔG°
Consider the decomposition of yellow mercury(II) oxide.
1
HgO(s, yellow) ⟶ Hg(l) + O2 (g)
2
Calculate the standard free energy change at room temperature, ΔG°, using (a) standard free energies of formation and (b)
standard enthalpies of formation and standard entropies. Do the results indicate the reaction to be spontaneous or
nonspontaneous under standard conditions?
The required data are available in Appendix G and are shown here.
Compound ΔG
∘
f
(kJ/mol) ΔH
∘
f
(kJ/mol) S° (J/K⋅mol)
HgO (s, yellow) −58.43 −90.46 71.13
Hg(l) 0 0 75.9

Compound ΔG
∘
f
(kJ/mol) ΔH
f
∘
(kJ/mol) S° (J/K⋅mol)
O2(g) 0 0 205.2
(a) Using free energies of formation:

∘ ∘
ΔG° = ∑ ν G (products) − ∑ ν ΔG (reactants)
f f
1
∘ ∘ ∘
= [1ΔG Hg(l) + ΔG O2 (g)] − 1ΔG HgO(s, yellow)
f f f
2
1
= [1 mol(0 kJ/mol) + mol(0 kJ/mol)] − 1 mol(−58.43 kJ/mol) = 58.43 kJ/mol
2
(b) Using enthalpies and entropies of formation:

∘ ∘
ΔH ° = ∑ ν ΔH (products) − ∑ ν ΔH (reactants)
f f
1
∘ ∘ ∘
= [1ΔH Hg(l) + ΔH O2 (g)] − 1ΔH HgO(s, yellow)
f f f
2
1
= [1 mol(0 kJ/mol) + mol(0 kJ/mol)] − 1 mol(−90.46 kJ/mol) = 90.46 kJ/mol
2
ΔS° = ∑ νΔS°(products) − ∑ νΔS°(reactants)
1
= [1ΔS°Hg(l) + ΔS° O2 (g)] − 1ΔS°HgO(s, yellow)
2
1
= [1 mol (75.9 J/mol K) + mol(205.2 J/mol K)] − 1 mol(71.13 J/mol K) = 107.4 J/mol K
2
1 kJ
ΔG° = ΔH ° − T ΔS° = 90.46 kJ − 298.15 K × 107.4 J/K⋅mol ×
1000 J
ΔG° = (90.46 − 32.01) kJ/mol = 58.45 kJ/mol
Both ways to calculate the standard free energy change at 25 °C give the same numerical value (to three significant figures),
and both predict that the process is nonspontaneous (not spontaneous) at room temperature.
Calculate ΔG° using (a) free energies of formation and (b) enthalpies of formation and entropies (Appendix G). Do the results
indicate the reaction to be spontaneous or nonspontaneous at 25 °C?
C2 H4 (g) ⟶ H2 (g) + C2 H2 (g)
16.5.0.1: Answer:
(a) 140.8 kJ/mol, nonspontaneous
(b) 141.5 kJ/mol, nonspontaneous
16.5.0.1: Free Energy Changes for Coupled Reactions

The use of free energies of formation to compute free energy changes for reactions as described above is possible because ΔG is a
state function, and the approach is analogous to the use of Hess’ Law in computing enthalpy changes (see the chapter on
thermochemistry). Consider the vaporization of water as an example:
H2 O(l) → H2 O(g)
An equation representing this process may be derived by adding the formation reactions for the two phases of water (necessarily
reversing the reaction for the liquid phase). The free energy change for the sum reaction is the sum of free energy changes for the

two added reactions:
1 ∘
H2 (g) + O2 (g) → H2 O(g) ΔG gas
2 f
1 ∘
H2 O(l) → H2 (g) + O2 (g) − ΔG liquid
2 f
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
∘ ∘
H2 O(l) → H2 O(g) ΔG° = ΔG gas − ΔG liquid
f f
This approach may also be used in cases where a nonspontaneous reaction is enabled by coupling it to a spontaneous reaction. For
example, the production of elemental zinc from zinc sulfide is thermodynamically unfavorable, as indicated by a positive value for
ΔG°:
∘
ZnS(s) → Zn(s) + S(s) ΔG = 201.3 kJ
1
The industrial process for production of zinc from sulfidic ores involves coupling this decomposition reaction to the
thermodynamically favorable oxidation of sulfur:
∘
S(s) + O2 (g) → SO 2 (g) ΔG = −300.1 kJ
2
The coupled reaction exhibits a negative free energy change and is spontaneous:
ZnS(s) + O2 (g) → Zn(s) + SO2 (g) ΔG° = 201.3 kJ + −300.1 kJ = –98.8 kJ
This process is typically carried out at elevated temperatures, so this result obtained using standard free energy values is just an
estimate. The gist of the calculation, however, holds true.
16.5.0.1: Example 16.9

16.5.0.0.1: Calculating Free Energy Change for a Coupled Reaction
Is a reaction coupling the decomposition of ZnS to the formation of H2S expected to be spontaneous under standard
conditions?
Following the approach outlined above and using free energy values from Appendix G:
∘
Decomposition of zinc sulfide: ZnS(s) → Zn(s) + S(s) ΔG = 201.3 kJ
1
∘
Formation of hydrogen sulfide: S(s) + H2 (g) → H2 S(g) ΔG = −33.4 kJ
2
Coupled reaction: ZnS(s) + H2 (g) → Zn(s) + H2 S(g) ΔG° = 201.3 kJ + −33.4 kJ = 167.9 kJ
The coupled reaction exhibits a positive free energy change and is thus nonspontaneous.
What is the standard free energy change for the reaction below? Is the reaction expected to be spontaneous under standard
conditions?
FeS(s) + O2 (g) → Fe(s) + SO 2 (g)
16.5.0.1: Answer:
−199.7 kJ; spontaneous
16.5.0.1: Temperature Dependence of Spontaneity

As was previously demonstrated in this chapter’s section on entropy, the spontaneity of a process may depend upon the temperature
of the system. Phase transitions, for example, will proceed spontaneously in one direction or the other depending upon the
temperature of the substance in question. Likewise, some chemical reactions can also exhibit temperature dependent spontaneities.
To illustrate this concept, the equation relating free energy change to the enthalpy and entropy changes for the process is
considered:
ΔG = ΔH − T ΔS

The spontaneity of a process, as reflected in the arithmetic sign of its free energy change, is then determined by the signs of the
enthalpy and entropy changes and, in some cases, the absolute temperature. Since T is the absolute (kelvin) temperature, it can only
have positive values. Four possibilities therefore exist with regard to the signs of the enthalpy and entropy changes:
1. Both ΔH and ΔS are positive. This condition describes an endothermic process that involves an increase in system entropy. In
this case, ΔG will be negative if the magnitude of the TΔS term is greater than ΔH. If the TΔS term is less than ΔH, the free
energy change will be positive. Such a process is spontaneous at high temperatures and nonspontaneous at low temperatures.
2. Both ΔH and ΔS are negative. This condition describes an exothermic process that involves a decrease in system entropy. In
this case, ΔG will be negative if the magnitude of the TΔS term is less than ΔH. If the TΔS term’s magnitude is greater than ΔH,
the free energy change will be positive. Such a process is spontaneous at low temperatures and nonspontaneous at high
temperatures.
3. ΔH is positive and ΔS is negative. This condition describes an endothermic process that involves a decrease in system entropy.
In this case, ΔG will be positive regardless of the temperature. Such a process is nonspontaneous at all temperatures.
4. ΔH is negative and ΔS is positive. This condition describes an exothermic process that involves an increase in system entropy.
In this case, ΔG will be negative regardless of the temperature. Such a process is spontaneous at all temperatures.
These four scenarios are summarized in Figure 16.12.
Figure 16.12 There are four possibilities regarding the signs of enthalpy and entropy changes.
16.5.0.1: Example 16.10

16.5.0.0.1: Predicting the Temperature Dependence of Spontaneity
The incomplete combustion of carbon is described by the following equation:
2C(s) + O2 (g) ⟶ 2CO(g)
How does the spontaneity of this process depend upon temperature?

Combustion processes are exothermic (ΔH < 0). This particular reaction involves an increase in entropy due to the
accompanying increase in the amount of gaseous species (net gain of one mole of gas, ΔS > 0). The reaction is therefore
spontaneous (ΔG < 0) at all temperatures.
Popular chemical hand warmers generate heat by the air-oxidation of iron:
4Fe(s) + 3O2 (g) ⟶ 2Fe2 O3 (s)
How does the spontaneity of this process depend upon temperature?
16.5.0.1: Answer:
ΔH and ΔS are negative; the reaction is spontaneous at low temperatures.

When considering the conclusions drawn regarding the temperature dependence of spontaneity, it is important to keep in mind what
the terms “high” and “low” mean. Since these terms are adjectives, the temperatures in question are deemed high or low relative to
some reference temperature. A process that is nonspontaneous at one temperature but spontaneous at another will necessarily
undergo a change in “spontaneity” (as reflected by its ΔG) as temperature varies. This is clearly illustrated by a graphical
presentation of the free energy change equation, in which ΔG is plotted on the y axis versus T on the x axis:
ΔG = ΔH − T ΔS
y = b + mx
Such a plot is shown in Figure 16.13. A process whose enthalpy and entropy changes are of the same arithmetic sign will exhibit a
temperature-dependent spontaneity as depicted by the two yellow lines in the plot. Each line crosses from one spontaneity domain
(positive or negative ΔG) to the other at a temperature that is characteristic of the process in question. This temperature is
represented by the x-intercept of the line, that is, the value of T for which ΔG is zero:
ΔG = 0 = ΔH − T ΔS
ΔH
T =
ΔS
So, saying a process is spontaneous at “high” or “low” temperatures means the temperature is above or below, respectively, that
temperature at which ΔG for the process is zero. As noted earlier, the condition of ΔG = 0 describes a system at equilibrium.
Figure 16.13 These plots show the variation in ΔG with temperature for the four possible combinations of arithmetic sign for ΔH
and ΔS.

16.5.0.1: Example 16.11
16.5.0.0.4: Equilibrium Temperature for a Phase Transition
As defined in the chapter on liquids and solids, the boiling point of a liquid is the temperature at which its liquid and gaseous
phases are in equilibrium (that is, when vaporization and condensation occur at equal rates). Use the information in Appendix
G to estimate the boiling point of water.
The process of interest is the following phase change:
H2 O(l) ⟶ H2 O(g)
When this process is at equilibrium, ΔG = 0, so the following is true:

ΔH °
0 = ΔH ° − T ΔS° or T =
ΔS°
Using the standard thermodynamic data from Appendix G,

∘ ∘
ΔH ° = 1 mol × ΔH (H2 O(g)) − 1 mol × ΔH (H2 O(l))
f f
= (1 mol) − 241.82 kJ/mol − (1 mol) (−286.83 kJ/mol) = 44.01 kJ
ΔS° = 1 mol × ΔS° (H2 O(g)) − 1 mol × ΔS° (H2 O(l))
= (1 mol) 188.8 J/K⋅mol − (1 mol) 70.0 J/K⋅mol = 118.8 J/K
3
ΔH ° 44.01 × 10 J
T = = = 370.5 K = 97.3 °C
ΔS° 118.8 J/K
The accepted value for water’s normal boiling point is 373.2 K (100.0 °C), and so this calculation is in reasonable agreement.
Note that the values for enthalpy and entropy changes data used were derived from standard data at 298 K (Appendix G). If
desired, you could obtain more accurate results by using enthalpy and entropy changes determined at (or at least closer to) the
actual boiling point.
Use the information in Appendix G to estimate the boiling point of CS2.
16.5.0.1: Answer:
313 K (accepted value 319 K)
16.5.0.1: Free Energy and Equilibrium

The free energy change for a process may be viewed as a measure of its driving force. A negative value for ΔG represents a driving
force for the process in the forward direction, while a positive value represents a driving force for the process in the reverse
direction. When ΔG is zero, the forward and reverse driving forces are equal, and the process occurs in both directions at the same
rate (the system is at equilibrium).
In the chapter on equilibrium the reaction quotient, Q, was introduced as a convenient measure of the status of an equilibrium
system. Recall that Q is the numerical value of the mass action expression for the system, and that you may use its value to identify
the direction in which a reaction will proceed in order to achieve equilibrium. When Q is lesser than the equilibrium constant, K,
the reaction will proceed in the forward direction until equilibrium is reached and Q = K. Conversely, if Q > K, the process will
proceed in the reverse direction until equilibrium is achieved.
The free energy change for a process taking place with reactants and products present under nonstandard conditions (pressures
other than 1 bar; concentrations other than 1 M) is related to the standard free energy change according to this equation:
ΔG = ΔG° + RT ln Q
R is the gas constant (8.314 J/K mol), T is the kelvin or absolute temperature, and Q is the reaction quotient. For gas phase
equilibria, the pressure-based reaction quotient, QP, is used. The concentration-based reaction quotient, QC, is used for condensed
phase equilibria. This equation may be used to predict the spontaneity for a process under any given set of conditions as illustrated
in Example 16.12.

16.5.0.1: Example 16.12
16.5.0.0.1: Calculating ΔG under Nonstandard Conditions
What is the free energy change for the process shown here under the specified conditions?
T = 25 °C, P N2 = 0.870 atm, PH
2
= 0.250 atm, and P NH3 = 12.9 atm
2NH3 (g) ⟶ 3H2 (g) + N2 (g) ΔG° = 33.0 kJ/mol
The equation relating free energy change to standard free energy change and reaction quotient may be used directly:
3
(0.250 ) × 0.870
kJ J
ΔG = ΔG° + RT ln Q = 33.0 + (8.314 × 298 K × ln )
2
mol mol K 12.9
J
= 9680 or 9.68 kJ/mol
mol
Since the computed value for ΔG is positive, the reaction is nonspontaneous under these conditions.
Calculate the free energy change for this same reaction at 875 °C in a 5.00 L mixture containing 0.100 mol of each gas. Is the
reaction spontaneous under these conditions?
16.5.0.1: Answer:
ΔG = –123.5 kJ/mol; yes
For a system at equilibrium, Q = K and ΔG = 0, and the previous equation may be written as
0 = ΔG° + RT ln K (at equilibrium)
ΔG °
−
ΔG° = −RT ln K or K =e RT
This form of the equation provides a useful link between these two essential thermodynamic properties, and it can be used to derive
equilibrium constants from standard free energy changes and vice versa. The relations between standard free energy changes and
equilibrium constants are summarized in Table 16.4.
Relations between Standard Free Energy Changes and Equilibrium Constants
K ΔG° Composition of an Equilibrium Mixture
>1 <0 Products are more abundant
<1 >0 Reactants are more abundant
=1 =0 Reactants and products are comparably abundant
Table 16.4
16.5.0.1: Example 16.13

16.5.0.0.4: Calculating an Equilibrium Constant using Standard Free Energy Change
Given that the standard free energies of formation of Ag+(aq), Cl−(aq), and AgCl(s) are 77.1 kJ/mol, −131.2 kJ/mol, and
−109.8 kJ/mol, respectively, calculate the solubility product, Ksp, for AgCl.
The reaction of interest is the following:
+ − + −
AgCl(s) ⇌ Ag (aq) + Cl (aq) Ksp = [ Ag ][ Cl ]
The standard free energy change for this reaction is first computed using standard free energies of formation for its reactants
and products:

∘ + ∘ − ∘
ΔG° = [ΔG (Ag (aq)) + ΔG (Cl (aq))] − [ΔG (AgCl(s))]
f f f
= [77.1 kJ/mol − 131.2 kJ/mol] − [−109.8 kJ/mol] = 55.7 kJ/mol
The equilibrium constant for the reaction may then be derived from its standard free energy change:
3
−
ΔG °
ΔG° 55.7 × 10 J/mol
−22.470 −10
Ksp = e RT
= exp (− ) = exp (− ) = exp (−22.470) = e = 1.74 × 10
RT 8.314 J/mol⋅K × 298.15 K
This result is in reasonable agreement with the value provided in Appendix J.

Use the thermodynamic data provided in Appendix G to calculate the equilibrium constant for the dissociation of dinitrogen
tetroxide at 25 °C.
2NO2 (g) ⇌ N2 O4 (g)
16.5.0.1: Answer:
K = 6.9
To further illustrate the relation between these two essential thermodynamic concepts, consider the observation that reactions
spontaneously proceed in a direction that ultimately establishes equilibrium. As may be shown by plotting the free energy versus
the extent of the reaction (for example, as reflected in the value of Q), equilibrium is established when the system’s free energy is
minimized (Figure 16.14). If a system consists of reactants and products in nonequilibrium amounts (Q ≠ K), the reaction will
proceed spontaneously in the direction necessary to establish equilibrium.

Figure 16.14 These plots show the free energy versus reaction progress for systems whose standard free energy changes are (a)
negative, (b) positive, and (c) zero. Nonequilibrium systems will proceed spontaneously in whatever direction is necessary to
minimize free energy and establish equilibrium.
This page titled 16.5: Free Energy is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source content

16.6: Key Terms
entropy (S)
state function that is a measure of the matter and/or energy dispersal within a system, determined by the number of system
microstates; often described as a measure of the disorder of the system
Gibbs free energy change (G)

thermodynamic property defined in terms of system enthalpy and entropy; all spontaneous processes involve a decrease in G
microstate
possible configuration or arrangement of matter and energy within a system
nonspontaneous process
process that requires continual input of energy from an external source
reversible process
process that takes place so slowly as to be capable of reversing direction in response to an infinitesimally small change in
conditions; hypothetical construct that can only be approximated by real processes
second law of thermodynamics

all spontaneous processes involve an increase in the entropy of the universe
spontaneous change
process that takes place without a continuous input of energy from an external source
standard entropy (S°)

entropy for one mole of a substance at 1 bar pressure; tabulated values are usually determined at 298.15 K
standard entropy change (ΔS°)

change in entropy for a reaction calculated using the standard entropies
standard free energy change (ΔG°)

change in free energy for a process occurring under standard conditions (1 bar pressure for gases, 1 M concentration for
solutions)
standard free energy of formation (ΔG ∘

f
)
change in free energy accompanying the formation of one mole of substance from its elements in their standard states
third law of thermodynamics

entropy of a perfect crystal at absolute zero (0 K) is zero
16.7: Key Equations
qre v
ΔS =
T
S = k ln W
Wf
ΔS = k ln
Wi
ΔS° = ∑ νS°(products) − ∑ νS°(reactants)
qre v
ΔS =
T
ΔSuniv = ΔSsys + ΔSsurr
qsurr
T
ΔG = ΔH − TΔS
16.8: Summary
16.1 Spontaneity
Chemical and physical processes have a natural tendency to occur in one direction under certain conditions. A spontaneous process
occurs without the need for a continual input of energy from some external source, while a nonspontaneous process requires such.
Systems undergoing a spontaneous process may or may not experience a gain or loss of energy, but they will experience a change
in the way matter and/or energy is distributed within the system.
16.2 Entropy
Entropy (S) is a state function that can be related to the number of microstates for a system (the number of ways the system can be
arranged) and to the ratio of reversible heat to kelvin temperature. It may be interpreted as a measure of the dispersal or distribution
of matter and/or energy in a system, and it is often described as representing the “disorder” of the system.
For a given substance, entropy depends on phase with Ssolid < Sliquid < Sgas. For different substances in the same physical state at a
given temperature, entropy is typically greater for heavier atoms or more complex molecules. Entropy increases when a system is
heated and when solutions form. Using these guidelines, the sign of entropy changes for some chemical reactions and physical
changes may be reliably predicted.
16.3 The Second and Third Laws of Thermodynamics

The second law of thermodynamics states that a spontaneous process increases the entropy of the universe, Suniv > 0. If ΔSuniv < 0,
the process is nonspontaneous, and if ΔSuniv = 0, the system is at equilibrium. The third law of thermodynamics establishes the zero
for entropy as that of a perfect, pure crystalline solid at 0 K. With only one possible microstate, the entropy is zero. We may
compute the standard entropy change for a process by using standard entropy values for the reactants and products involved in the
process.
16.4 Free Energy

Gibbs free energy (G) is a state function defined with regard to system quantities only and may be used to predict the spontaneity
of a process. A negative value for ΔG indicates a spontaneous process; a positive ΔG indicates a nonspontaneous process; and a ΔG
of zero indicates that the system is at equilibrium. A number of approaches to the computation of free energy changes are possible.
16.9: Exercises
16.9.0.1: 16.1 Spontaneity
1.
What is a spontaneous reaction?
2.
What is a nonspontaneous reaction?
3.
Indicate whether the following processes are spontaneous or nonspontaneous.
(a) Liquid water freezing at a temperature below its freezing point
(b) Liquid water freezing at a temperature above its freezing point
(c) The combustion of gasoline
(d) A ball thrown into the air
(e) A raindrop falling to the ground
(f) Iron rusting in a moist atmosphere
4.
A helium-filled balloon spontaneously deflates overnight as He atoms diffuse through the wall of the balloon. Describe the
redistribution of matter and/or energy that accompanies this process.
5.
Many plastic materials are organic polymers that contain carbon and hydrogen. The oxidation of these plastics in air to form carbon
dioxide and water is a spontaneous process; however, plastic materials tend to persist in the environment. Explain.
16.9.0.1: 16.2 Entropy

6.
In Figure 16.8 all possible distributions and microstates are shown for four different particles shared between two boxes. Determine
the entropy change, ΔS, if the particles are initially evenly distributed between the two boxes, but upon redistribution all end up in
Box (b).
7.
In Figure 16.8 all of the possible distributions and microstates are shown for four different particles shared between two boxes.
Determine the entropy change, ΔS, for the system when it is converted from distribution (b) to distribution (d).
8.
How does the process described in the previous item relate to the system shown in Figure 16.4?
9.
Consider a system similar to the one in Figure 16.8, except that it contains six particles instead of four. What is the probability of
having all the particles in only one of the two boxes in the case? Compare this with the similar probability for the system of four
particles that we have derived to be equal to . What does this comparison tell us about even larger systems?
1
10.
Consider the system shown in Figure 16.9. What is the change in entropy for the process where the energy is initially associated
only with particle A, but in the final state the energy is distributed between two different particles?
11.
Consider the system shown in Figure 16.9. What is the change in entropy for the process where the energy is initially associated
with particles A and B, and the energy is distributed between two particles in different boxes (one in A-B, the other in C-D)?
12.

Arrange the following sets of systems in order of increasing entropy. Assume one mole of each substance and the same temperature
for each member of a set.
(a) H2(g), HBrO4(g), HBr(g)
(b) H2O(l), H2O(g), H2O(s)
(c) He(g), Cl2(g), P4(g)
13.
At room temperature, the entropy of the halogens increases from I2 to Br2 to Cl2. Explain.
14.
Consider two processes: sublimation of I2(s) and melting of I2(s) (Note: the latter process can occur at the same temperature but
somewhat higher pressure).
I2 (s) ⟶ I2 (g)
I2 (s) ⟶ I2 (l)
Is ΔS positive or negative in these processes? In which of the processes will the magnitude of the entropy change be greater?
15.
Indicate which substance in the given pairs has the higher entropy value. Explain your choices.
(a) C2H5OH(l) or C3H7OH(l)
(b) C2H5OH(l) or C2H5OH(g)
(c) 2H(g) or H(g)
16.
Predict the sign of the entropy change for the following processes.
(a) An ice cube is warmed to near its melting point.
(b) Exhaled breath forms fog on a cold morning.
(c) Snow melts.
17.
Predict the sign of the entropy change for the following processes. Give a reason for your prediction.
(a) Na +
(aq) + Cl
−
(aq) ⟶ NaCl(s)
(b) 2Fe(s) + 3
2
O2 (g) ⟶ Fe2 O2 (s)
(c) 2C6 H14 (l) + 19 O2 (g) ⟶ 14 H2 O(g) + 12 CO2 (g)
18.
Write the balanced chemical equation for the combustion of methane, CH4(g), to give carbon dioxide and water vapor. Explain why
it is difficult to predict whether ΔS is positive or negative for this chemical reaction.
19.
Write the balanced chemical equation for the combustion of benzene, C6H6(l), to give carbon dioxide and water vapor. Would you
expect ΔS to be positive or negative in this process?
16.9.0.1: 16.3 The Second and Third Laws of Thermodynamics

20.
What is the difference between ΔS and ΔS° for a chemical change?
21.
Calculate ΔS° for the following changes.
(a) SnCl 4 (l) ⟶ SnCl 4 (g)

(b) CS 2 (g) ⟶ CS2 (l)
(c) Cu(s) ⟶ Cu(g)
(d) H 2 O(l) ⟶ H2 O(g)
(e) 2H 2 (g) + O2 (g) ⟶ 2 H2 O(l)
(f) 2HCl(g) + Pb(s) ⟶ PbCl2 (s) + H2 (g)
(g) Zn(s) + CuSO 4 (s) ⟶ Cu(s) + ZnSO 4 (s)
22.
Determine the entropy change for the combustion of liquid ethanol, C2H5OH, under the standard conditions to give gaseous carbon
dioxide and liquid water.
23.
Determine the entropy change for the combustion of gaseous propane, C3H8, under the standard conditions to give gaseous carbon
dioxide and water.
24.
“Thermite” reactions have been used for welding metal parts such as railway rails and in metal refining. One such thermite reaction
is Fe O (s) + 2Al(s) ⟶ Al O (s) + 2Fe(s). Is the reaction spontaneous at room temperature under standard conditions?
2 3 2 3
During the reaction, the surroundings absorb 851.8 kJ/mol of heat.

25.
Using the relevant S° values listed in Appendix G, calculate ΔS° 298 for the following changes:
(a) N 2 (g) + 3 H2 (g) ⟶ 2 NH3 (g)
(b) N 2 (g) +
5
2
O2 (g) ⟶ N2 O5 (g)
26.
From the following information, determine ΔS° for the following:
N(g) + O(g) ⟶ NO(g) ΔS° =?
N2 (g) + O2 (g) ⟶ 2NO(g) ΔS° = 24.8 J/K
N2 (g) ⟶ 2N(g) ΔS° = 115.0 J/K
O2 (g) ⟶ 2O(g) ΔS° = 117.0 J/K
27.
By calculating ΔSuniv at each temperature, determine if the melting of 1 mole of NaCl(s) is spontaneous at 500 °C and at 700 °C.
∘ J ∘ J ∘
S = 72.11 S = 95.06 ΔH = 27.95 kJ/mol
NaCl(s) mol⋅K NaCl(l) mol⋅K fusion
What assumptions are made about the thermodynamic information (entropy and enthalpy values) used to solve this problem?
28.
Use the standard entropy data in Appendix G to determine the change in entropy for each of the following reactions. All the
processes occur at the standard conditions and 25 °C.
(a) MnO 2 (s) ⟶ Mn(s) + O2 (g)
(b) H 2 (g) + Br 2 (l) ⟶ 2HBr(g)
(c) Cu(s) + S(g) ⟶ CuS(s)
(e) CH 4 (g) + O2 (g) ⟶ C(s, graphite) + 2H2 O(g)
(f) CS 2 (g) + 3Cl2 (g) ⟶ CCl4 (g) + S2 Cl2 (g)
29.

Use the standard entropy data in Appendix G to determine the change in entropy for each of the following reactions. All the
processes occur at the standard conditions and 25 °C.
(a) C(s, graphite) + O 2 (g) ⟶ CO2 (g)
(b) O 2 (g) + N2 (g) ⟶ 2NO(g)
(c) 2Cu(s) + S(g) ⟶ Cu2 S(s)
(d) CaO(s) + H 2 O(l) ⟶ Ca (OH) 2 (s)
(e) Fe 2 O3 (s) + 3CO(g) ⟶ 2Fe(s) + 3CO2 (g)
(f) CaSO 4 ⋅ 2H2 O(s) ⟶ CaSO4 (s) + 2H2 O(g)
16.9.0.1: 16.4 Free Energy

30.
What is the difference between ΔG and ΔG° for a chemical change?
31.
A reaction has ΔH ° = 100 kJ/mol and ΔS° = 250 J/mol⋅K. Is the reaction spontaneous at room temperature? If not, under what
temperature conditions will it become spontaneous?
32.
Explain what happens as a reaction starts with ΔG < 0 (negative) and reaches the point where ΔG = 0.
33.
Use the standard free energy of formation data in Appendix G to determine the free energy change for each of the following
reactions, which are run under standard state conditions and 25 °C. Identify each as either spontaneous or nonspontaneous at these
conditions.
(a) MnO 2 (s) ⟶ Mn(s) + O2 (g)
(b) H 2 (g) + Br 2 (l) ⟶ 2HBr(g)
(c) Cu(s) + S(g) ⟶ CuS(s)
(e) CH 4 (g) + O2 (g) ⟶ C(s, graphite) + 2H2 O(g)
(f) CS 2 (g) + 3Cl2 (g) ⟶ CCl4 (g) + S2 Cl2 (g)
34.
Use the standard free energy data in Appendix G to determine the free energy change for each of the following reactions, which are
run under standard state conditions and 25 °C. Identify each as either spontaneous or nonspontaneous at these conditions.
(a) C(s, graphite) + O 2 (g) ⟶ CO2 (g)
(b) O 2 (g) + N2 (g) ⟶ 2NO(g)
(c) 2Cu(s) + S(g) ⟶ Cu2 S(s)
(d) CaO(s) + H 2 O(l) ⟶ Ca (OH) (s)

2
(e) Fe 2 O3 (s) + 3CO(g) ⟶ 2Fe(s) + 3CO2 (g)
(f) CaSO 4 ⋅ 2H2 O(s) ⟶ CaSO4 (s) + 2H2 O(g)
35.
Given:
P4 (s) + 5O2 (g) ⟶ P4 O10 (s) ΔG° = −2697.0 kJ/mol
2H2 (g) + O2 (g) ⟶ 2H2 O(g) ΔG° = −457.18 kJ/mol
6H2 O(g) + P4 O10 (s) ⟶ 4H3 PO4 (l) ΔG° = −428.66 kJ/mol
(a) Determine the standard free energy of formation, ΔG , for phosphoric acid.
∘
f

(b) How does your calculated result compare to the value in Appendix G? Explain.
36.
Is the formation of ozone (O3(g)) from oxygen (O2(g)) spontaneous at room temperature under standard state conditions?
37.
Consider the decomposition of red mercury(II) oxide under standard state conditions.
2HgO(s, red) ⟶ 2Hg(l) + O2 (g)
(a) Is the decomposition spontaneous under standard state conditions?

(b) Above what temperature does the reaction become spontaneous?
38.
Among other things, an ideal fuel for the control thrusters of a space vehicle should decompose in a spontaneous exothermic
reaction when exposed to the appropriate catalyst. Evaluate the following substances under standard state conditions as suitable
candidates for fuels.
(a) Ammonia: 2NH 3 (g) ⟶ N2 (g) + 3H2 (g)
(b) Diborane: B 2 H6 (g) ⟶ 2B(g) + 3H2 (g)
(c) Hydrazine: N 2 H4 (g) ⟶ N2 (g) + 2H2 (g)
(d) Hydrogen peroxide: H 2 O2 (l) ⟶ H2 O(g) +

1
2
O2 (g)
39.
Calculate ΔG° for each of the following reactions from the equilibrium constant at the temperature given.
(a) N 2 (g) + O2 (g) ⟶ 2NO(g) T = 2000 °C Kp = 4.1 × 10
−4
(b) H 2 (g) + I2 (g) ⟶ 2HI(g) T = 400 °C Kp = 50.0
(c) CO 2 (g) + H2 (g) ⟶ CO(g) + H2 O(g) T = 980 °C Kp = 1.67
(d) CaCO 3 (s) ⟶ CaO(s) + CO2 (g) T = 900 °C Kp = 1.04
(e) HF(aq) + H 2 O(l) ⟶ H3 O

+
(aq) + F
−
(aq) T = 25 °C Kp = 7.2 × 10
−4
(f) AgBr(s) ⟶ Ag
+
(aq) + Br
−
(aq) T = 25 °C Kp = 3.3 × 10
−13
40.
Calculate ΔG° for each of the following reactions from the equilibrium constant at the temperature given.
(a) Cl 2 (g) + Br 2 (g) ⟶ 2BrCl(g) T = 25 °C Kp = 4.7 × 10
−2
(b) 2SO 2 (g) + O2 (g) ⇌ 2SO3 (g) T = 500 °C Kp = 48.2
(c) H 2 O(l) ⇌ H2 O(g) T = 60 °C Kp = 0.196
(d) CoO(s) + CO(g) ⇌ Co(s) + CO2 (g) T = 550 °C Kp = 4.90 × 10

2
(e) CH 3 NH2 (aq) + H2 O(l) ⟶ CH3 NH3

+
(aq) + OH
−
(aq) T = 25 °C Kp = 4.4 × 10
−4
(f) PbI 2 (s) ⟶ Pb

2+
(aq) + 2I
−
(aq) T = 25 °C Kp = 8.7 × 10
−9
41.
Calculate the equilibrium constant at 25 °C for each of the following reactions from the value of ΔG° given.
(a) O 2 (g) + 2F2 (g) ⟶ 2OF2 (g) ΔG° = −9.2 kJ
(b) I 2 (s) + Br 2 (l) ⟶ 2IBr(g) ΔG° = 7.3 kJ
(c) 2LiOH(s) + CO 2 (g) ⟶ Li 2 CO3 (s) + H2 O(g) ΔG° = −79 kJ
(d) N 2 O3 (g) ⟶ NO(g) + NO2 (g) ΔG° = −1.6 kJ
(e) SnCl 4 (l) ⟶ SnCl 4 (l) ΔG° = 8.0 kJ

42.
Calculate the equilibrium constant at 25 °C for each of the following reactions from the value of ΔG° given.
(a) I 2 (s) + Cl2 (g) ⟶ 2ICl(g) ΔG° = −10.88 kJ
(b) H 2 (g) + I2 (s) ⟶ 2HI(g) ΔG° = 3.4 kJ
(c) CS 2 (g) + 3Cl2 (g) ⟶ CCl4 (g) + S2 Cl2 (g) ΔG° = −39 kJ
(d) 2SO 2 (g) + O2 (g) ⟶ 2SO3 (g) ΔG° = −141.82 kJ
(e) CS 2 (g) ⟶ CS2 (l) ΔG° = −1.88 kJ
43.
Calculate the equilibrium constant at the temperature given.
(a) O 2 (g) + 2F2 (g) ⟶ 2F2 O(g) (T = 100 °C)
(b) I 2 (s) + Br 2 (l) ⟶ 2IBr(g) (T = 0.0 °C)
(c) 2LiOH(s) + CO 2 (g) ⟶ Li 2 CO3 (s) + H2 O(g) (T = 575 °C)
(d) N 2 O3 (g) ⟶ NO(g) + NO2 (g) (T = −10.0 °C)
(e) SnCl 4 (l) ⟶ SnCl 4 (g) (T = 200 °C)
44.
Calculate the equilibrium constant at the temperature given.
(a) I 2 (s) + Cl2 (g) ⟶ 2ICl(g) (T = 100 °C)
(b) H 2 (g) + I2 (s) ⟶ 2HI(g) (T = 0.0 °C)
(c) CS 2 (g) + 3Cl2 (g) ⟶ CCl4 (g) + S2 Cl2 (g) (T = 125 °C)
(d) 2SO 2 (g) + O2 (g) ⟶ 2SO3 (g) (T = 675 °C)
(e) CS 2 (g) ⟶ CS2 (l) (T = 90 °C)
45.
Consider the following reaction at 298 K:
N2 O4 (g) ⇌ 2NO2 (g) KP = 0.142
What is the standard free energy change at this temperature? Describe what happens to the initial system, where the reactants and
products are in standard states, as it approaches equilibrium.
46.
Determine the normal boiling point (in kelvin) of dichloromethane, CH2Cl2. Find the actual boiling point using the Internet or
some other source, and calculate the percent error in the temperature. Explain the differences, if any, between the two values.
47.
Under what conditions is N 2 O3 (g) ⟶ NO(g) + NO2 (g) spontaneous?
48.
At room temperature, the equilibrium constant (Kw) for the self-ionization of water is 1.00 × 10−14. Using this information,
calculate the standard free energy change for the aqueous reaction of hydrogen ion with hydroxide ion to produce water. (Hint: The
reaction is the reverse of the self-ionization reaction.)
49.
Hydrogen sulfide is a pollutant found in natural gas. Following its removal, it is converted to sulfur by the reaction
2H S(g) + SO (g) ⇌
2 2
3
S (s, rhombic) + 2H O(l).
8
8 What is the equilibrium constant for this reaction? Is the reaction
2
endothermic or exothermic?
50.

Consider the decomposition of CaCO3(s) into CaO(s) and CO2(g). What is the equilibrium partial pressure of CO2 at room
temperature?
51.
In the laboratory, hydrogen chloride (HCl(g)) and ammonia (NH3(g)) often escape from bottles of their solutions and react to form
the ammonium chloride (NH4Cl(s)), the white glaze often seen on glassware. Assuming that the number of moles of each gas that
escapes into the room is the same, what is the maximum partial pressure of HCl and NH3 in the laboratory at room temperature?
(Hint: The partial pressures will be equal and are at their maximum value when at equilibrium.)
52.
Benzene can be prepared from acetylene. 3C H (g) ⇌ C H (g). Determine the equilibrium constant at 25 °C and at 850 °C. Is
2 2 6 6
the reaction spontaneous at either of these temperatures? Why is all acetylene not found as benzene?
53.
Carbon dioxide decomposes into CO and O2 at elevated temperatures. What is the equilibrium partial pressure of oxygen in a
sample at 1000 °C for which the initial pressure of CO2 was 1.15 atm?
54.
Carbon tetrachloride, an important industrial solvent, is prepared by the chlorination of methane at 850 K.
CH4 (g) + 4Cl2 (g) ⟶ CCl4 (g) + 4HCl(g)
What is the equilibrium constant for the reaction at 850 K? Would the reaction vessel need to be heated or cooled to keep the
temperature of the reaction constant?
55.
Acetic acid, CH3CO2H, can form a dimer, (CH3CO2H)2, in the gas phase.
2CH3 CO2 H(g) ⟶ (CH3 CO2 H) (g)
2
The dimer is held together by two hydrogen bonds with a total strength of 66.5 kJ per mole of dimer.
At 25 °C, the equilibrium constant for the dimerization is 1.3 × 103 (pressure in atm). What is ΔS° for the reaction?
56.
Determine ΔGº for the following reactions.
(a) Antimony pentachloride decomposes at 448 °C. The reaction is:
SbCl 5 (g) ⟶ SbCl 3 (g) + Cl2 (g)
An equilibrium mixture in a 5.00 L flask at 448 °C contains 3.85 g of SbCl5, 9.14 g of SbCl3, and 2.84 g of Cl2.
(b) Chlorine molecules dissociate according to this reaction:
Cl2 (g) ⟶ 2Cl(g)
1.00% of Cl2 molecules dissociate at 975 K and a pressure of 1.00 atm.

57.
Given that the ΔG for Pb2+(aq) and Cl−(aq) is −24.3 kJ/mole and −131.2 kJ/mole respectively, determine the solubility product,
∘
f
Ksp, for PbCl2(s).

58.
Determine the standard free energy change, ΔG , for the formation of S2−(aq) given that the ΔG for Ag+(aq) and Ag2S(s) are
∘
f
∘
f
77.1 kJ/mole and −39.5 kJ/mole respectively, and the solubility product for Ag2S(s) is 8 × 10−51.
59.

Determine the standard enthalpy change, entropy change, and free energy change for the conversion of diamond to graphite.
Discuss the spontaneity of the conversion with respect to the enthalpy and entropy changes. Explain why diamond spontaneously
changing into graphite is not observed.
60.
The evaporation of one mole of water at 298 K has a standard free energy change of 8.58 kJ.
H2 O(l) ⇌ H2 O(g) ΔG° = 8.58 kJ
(a) Is the evaporation of water under standard thermodynamic conditions spontaneous?

(b) Determine the equilibrium constant, KP, for this physical process.
(c) By calculating ∆G, determine if the evaporation of water at 298 K is spontaneous when the partial pressure of water, PH2 O , is
0.011 atm.
(d) If the evaporation of water were always nonspontaneous at room temperature, wet laundry would never dry when placed
outside. In order for laundry to dry, what must be the value of P in the air?
H2 O
61.
In glycolysis, the reaction of glucose (Glu) to form glucose-6-phosphate (G6P) requires ATP to be present as described by the
following equation:
Glu + ATP ⟶ G6P + ADP ΔG° = −17 kJ
In this process, ATP becomes ADP summarized by the following equation:

ATP ⟶ ADP ΔG° = −30 kJ
Determine the standard free energy change for the following reaction, and explain why ATP is necessary to drive this process:
Glu ⟶ G6P ΔG° =?
62.
One of the important reactions in the biochemical pathway glycolysis is the reaction of glucose-6-phosphate (G6P) to form
fructose-6-phosphate (F6P):
G6P ⇌ F6P ΔG° = 1.7 kJ
(a) Is the reaction spontaneous or nonspontaneous under standard thermodynamic conditions?

(b) Standard thermodynamic conditions imply the concentrations of G6P and F6P to be 1 M, however, in a typical cell, they are not
even close to these values. Calculate ΔG when the concentrations of G6P and F6P are 120 μM and 28 μM respectively, and discuss
the spontaneity of the forward reaction under these conditions. Assume the temperature is 37 °C.
63.
Without doing a numerical calculation, determine which of the following will reduce the free energy change for the reaction, that
is, make it less positive or more negative, when the temperature is increased. Explain.
(a) N 2 (g) + 3H2 (g) ⟶ 2NH3 (g)
(b) HCl(g) + NH 3 (g) ⟶ NH4 Cl(s)
(c) (NH 4 ) 2 Cr2 O7 (s) ⟶ Cr2 O3 (s) + 4H2 O(g) + N2 (g)
(d) 2Fe(s) + 3O 2 (g) ⟶ Fe2 O3 (s)
64.
When ammonium chloride is added to water and stirred, it dissolves spontaneously and the resulting solution feels cold. Without
doing any calculations, deduce the signs of ΔG, ΔH, and ΔS for this process, and justify your choices.
65.
An important source of copper is from the copper ore, chalcocite, a form of copper(I) sulfide. When heated, the Cu2S decomposes
to form copper and sulfur described by the following equation:
Cu2 S(s) ⟶ Cu(s) + S(s)
(a) Determine ΔG° for the decomposition of Cu2S(s).

(b) The reaction of sulfur with oxygen yields sulfur dioxide as the only product. Write an equation that describes this reaction, and
determine ΔG° for the process.
(c) The production of copper from chalcocite is performed by roasting the Cu2S in air to produce the Cu. By combining the
equations from Parts (a) and (b), write the equation that describes the roasting of the chalcocite, and explain why coupling these
reactions together makes for a more efficient process for the production of the copper.
66.
What happens to ΔG (becomes more negative or more positive) for the following chemical reactions when the partial pressure of
oxygen is increased?
(a) S(s) + O 2 (g) ⟶ SO 2 (g)
(b) 2SO 2 (g) + O2 (g) ⟶ 2SO3 (g)
(c) HgO(s) ⟶ Hg(l) + O2 (g)

CHAPTER OVERVIEW
17: Electrochemistry

General Chemistry
Electrochemistry deals with chemical reactions that produce electricity and the changes associated with the passage of electrical
current through matter. The reactions involve electron transfer, and so they are oxidation-reduction (or redox) reactions. Many
metals may be purified or electroplated using electrochemical methods. Devices such as automobiles, smartphones, electronic
tablets, watches, pacemakers, and many others use batteries for power. Batteries use chemical reactions that produce electricity
spontaneously and that can be converted into useful work. All electrochemical systems involve the transfer of electrons in a
reacting system. In many systems, the reactions occur in a region known as the cell, where the transfer of electrons occurs at
electrodes.
17.1: Introduction
17.7: Corrosion
17.8: Electrolysis
17.9: Key Terms
17.11: Summary
17.12: Exercises
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1
17.1: Introduction
Figure 17.1 Electric vehicles are powered by batteries, devices that harness the energy of spontaneous redox reactions. (credit:
modification of work by Robert Couse-Baker)
Chapter Outline
17.1 Review of Redox Chemistry
17.2 Galvanic Cells
17.3 Electrode and Cell Potentials
17.4 Potential, Free Energy, and Equilibrium
17.5 Batteries and Fuel Cells
17.6 Corrosion
17.7 Electrolysis
Another chapter in this text introduced the chemistry of reduction-oxidation (redox) reactions. This important reaction class is
defined by changes in oxidation states for one or more reactant elements, and it includes a subset of reactions involving the transfer
of electrons between reactant species. Around the turn of the nineteenth century, chemists began exploring ways these electrons
could be transferred indirectly via an external circuit rather than directly via intimate contact of redox reactants. In the two
centuries since, the field of electrochemistry has evolved to yield significant insights on the fundamental aspects of redox chemistry
as well as a wealth of technologies ranging from industrial-scale metallurgical processes to robust, rechargeable batteries for
electric vehicles (Figure 17.1). In this chapter, the essential concepts of electrochemistry will be addressed.

Describe defining traits of redox chemistry
Identify the oxidant and reductant of a redox reaction
Balance chemical equations for redox reactions using the half-reaction method
Since reactions involving electron transfer are essential to the topic of electrochemistry, a brief review of redox chemistry is
provided here that summarizes and extends the content of an earlier text chapter (see chapter on reaction stoichiometry). Readers
wishing additional review are referred to the text chapter on reaction stoichiometry.
17.2.0.1: Oxidation Numbers

By definition, a redox reaction is one that entails changes in oxidation number (or oxidation state) for one or more of the elements
involved. The oxidation number of an element in a compound is essentially an assessment of how the electronic environment of its
atoms is different in comparison to atoms of the pure element. By this description, the oxidation number of an atom in an element
is equal to zero. For an atom in a compound, the oxidation number is equal to the charge the atom would have in the compound if
the compound were ionic. Consequential to these rules, the sum of oxidation numbers for all atoms in a molecule is equal to the
charge on the molecule. To illustrate this formalism, examples from the two compound classes, ionic and covalent, will be
considered.
Simple ionic compounds present the simplest examples to illustrate this formalism, since by definition the elements’ oxidation
numbers are numerically equivalent to ionic charges. Sodium chloride, NaCl, is comprised of Na+ cations and Cl− anions, and so
oxidation numbers for sodium and chlorine are, +1 and −1, respectively. Calcium fluoride, CaF2, is comprised of Ca2+ cations and
F− anions, and so oxidation numbers for calcium and fluorine are, +2 and −1, respectively.
Covalent compounds require a more challenging use of the formalism. Water is a covalent compound whose molecules consist of
two H atoms bonded separately to a central O atom via polar covalent O−H bonds. The shared electrons comprising an O−H bond
are more strongly attracted to the more electronegative O atom, and so it acquires a partial negative charge in the water molecule
(relative to an O atom in elemental oxygen). Consequently, H atoms in a water molecule exhibit partial positive charges compared
to H atoms in elemental hydrogen. The sum of the partial negative and partial positive charges for each water molecule is zero, and
the water molecule is neutral.
Imagine that the polarization of shared electrons within the O−H bonds of water were 100% complete—the result would be
transfer of electrons from H to O, and water would be an ionic compound comprised of O2− anions and H+ cations. And so, the
oxidations numbers for oxygen and hydrogen in water are −2 and +1, respectively. Applying this same logic to carbon
tetrachloride, CCl4, yields oxidation numbers of +4 for carbon and −1 for chlorine. In the nitrate ion, NO , the oxidation number
−
for nitrogen is +5 and that for oxygen is −2, summing to equal the 1− charge on the molecule:
+5 −2
(1N atom)( ) + (3 O atoms)( ) = +5 + −6 = −1
N atom O atom
17.2.0.1: Balancing Redox Equations

The unbalanced equation below describes the decomposition of molten sodium chloride:
NaCl(l) ⟶ Na(l) + Cl2 (g) unbalanced
This reaction satisfies the criterion for redox classification, since the oxidation number for Na is decreased from +1 to 0 (it
undergoes reduction) and that for Cl is increased from −1 to 0 (it undergoes oxidation). The equation in this case is easily balanced
by inspection, requiring stoichiometric coefficients of 2 for the NaCl and Na:
2NaCl(l) ⟶ 2Na(l) + Cl2 (g) balanced
Redox reactions that take place in aqueous solutions are commonly encountered in electrochemistry, and many involve water or its
characteristic ions, H+(aq) and OH−(aq), as reactants or products. In these cases, equations representing the redox reaction can be

very challenging to balance by inspection, and the use of a systematic approach called the half-reaction method is helpful. This
approach involves the following steps:
1. Write skeletal equations for the oxidation and reduction half-reactions.
2. Balance each half-reaction for all elements except H and O.
3. Balance each half-reaction for O by adding H2O.
4. Balance each half-reaction for H by adding H+.
5. Balance each half-reaction for charge by adding electrons.
6. If necessary, multiply one or both half-reactions so that the number of electrons consumed in one is equal to the number
produced in the other.
7. Add the two half-reactions and simplify.
8. If the reaction takes place in a basic medium, add OH− ions the equation obtained in step 7 to neutralize the H+ ions (add in
equal numbers to both sides of the equation) and simplify.
The examples below demonstrate the application of this method to balancing equations for aqueous redox reactions.
17.2.0.1: Example 17.1

17.2.0.0.1: Balancing Equations for Redox Reactions in Acidic Solutions
Write the balanced equation representing reaction between solid copper and nitric acid to yield aqueous copper(II) ions and
nitrogen monoxide gas.
Following the steps of the half-reaction method:
2+
oxidation: Cu(s) ⟶ Cu (aq)
reduction: HNO3 (aq) ⟶ NO(g)

2+
reduction: HNO3 (aq) ⟶ NO(g)

2+
reduction: HNO3 (aq) ⟶ NO(g) + 2H2 O(l)

2+
+
reduction: 3H (aq)+HNO3 (aq) ⟶ NO(g) + 2H2 O(l)

2+ −
oxidation: Cu(s) ⟶ Cu (aq) + 2 e
− +
reduction: 3e +3 H (aq) + HNO3 (aq) ⟶ NO(g) + 2H2 O(l)
2+ −
oxidation (×3): 3Cu(s) ⟶ 3 Cu (aq) + 6 2 e
− +
reduction (×2): 6 3 e +6 3 H (aq) + 2 HNO3 (aq) ⟶ 2NO(g) + 4 2 H2 O(l)

− + 2+ −
3Cu(s) + 6 e + 6H (aq) + 2 HNO3 (aq) ⟶ 3 Cu (aq) + 6 e + 2NO(g) + 4 H2 O(l)
+ 2+
3Cu(s) + 6 H (aq) + 2 HNO3 (aq) ⟶ 3 Cu (aq) + 2NO(g) + 4 H2 O(l)
8. If the reaction takes place in a basic medium, add OH− ions the equation obtained in step 7 to neutralize the H+ ions (add
in equal numbers to both sides of the equation) and simplify.
This step not necessary since the solution is stipulated to be acidic.
The balanced equation for the reaction in an acidic solution is then
+ 2+
3Cu(s) + 6 H (aq) + 2 HNO3 (aq) ⟶ 3 Cu (aq) + 2NO(g) + 4 H2 O(l)

The reaction above results when using relatively diluted nitric acid. If concentrated nitric acid is used, nitrogen dioxide is
produced instead of nitrogen monoxide. Write a balanced equation for this reaction.
17.2.0.1: Answer:
+ 2+
Cu(s) + 2 H (aq) + 2 HNO3 (aq) ⟶ Cu (aq) + 2 NO2 (g) + 2 H2 O(l)
17.2.0.1: Example 17.2

17.2.0.0.4: Balancing Equations for Redox Reactions in Basic Solutions
Write the balanced equation representing reaction between aqueous permanganate ion, MnO , and solid chromium(III) 4
−
hydroxide, Cr(OH)3, to yield solid manganese(IV) oxide, MnO2, and aqueous chromate ion, CrO The reaction takes place 4
2−
in a basic solution.
Following the steps of the half-reaction method:
2−
oxidation: Cr(OH) (s) ⟶ CrO4 (aq)
3
−
reduction: MnO 4 (aq) ⟶ MnO 2 (s)

2−
oxidation: Cr(OH) (s) ⟶ CrO4 (aq)
3
−
reduction: MnO 4 (aq) ⟶ MnO 2 (s)

2−
oxidation: H2 O(l)+Cr(OH)3 (s) ⟶ CrO4 (aq)
−
reduction: MnO 4 (aq) ⟶ MnO 2 (s) + 2 H2 O(l)

2− +
oxidation: H2 O(l) + Cr(OH)3 (s) ⟶ CrO4 (aq) + 5 H (aq)
+ −
reduction: 4H (aq)+MnO 4 (aq) ⟶ MnO 2 (s) + 2 H2 O(l)

2− + −
oxidation: H2 O(l) + Cr(OH)3 (s) ⟶ CrO4 (aq) + 5 H (aq) + 3 e
− + −
reduction: 3e +4 H (aq) + MnO 4 (aq) ⟶ MnO 2 (s) + 2 H2 O(l)
This step is not necessary since the number of electrons is already in balance.
− + − 2− +
H2 O(l) + Cr(OH) (s) + 3e + 4H (aq) + MnO 4 (aq) ⟶ CrO4 (aq) + 5 H (aq)
3
−
+ 3e + MnO 2 (s) + 2 H2 O(l)
− 2− +
Cr(OH) 3 (s) + MnO 4 (aq) ⟶ CrO4 (aq) + H (aq) + MnO 2 (s) + H2 O(l)
8. If the reaction takes place in a basic medium, add OH− ions the equation obtained in step 7 to neutralize the H+ ions (add
in equal numbers to both sides of the equation) and simplify.
− − 2− + −
OH (aq)+Cr(OH) 3 (s) + MnO 4 (aq) ⟶ CrO4 (aq) + H (aq) + OH (aq) + MnO 2 (s) + H2 O(l)
− − 2−
OH (aq) + Cr(OH) 3 (s) + MnO 4 (aq) ⟶ CrO4 (aq) + MnO 2 (s) + 2 H2 O(l)

Aqueous permanganate ion may also be reduced using aqueous bromide ion, Br−, the products of this reaction being solid
manganese(IV) oxide and aqueous bromate ion, BrO3−. Write the balanced equation for this reaction occurring in a basic
medium.
17.2.0.1: Answer:
− − − −
H2 O(l) + 2MnO 4 (aq) + Br (aq) ⟶ 2 MnO 2 (s) + BrO 3 (aq) + 2 OH (aq)
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Describe the function of a galvanic cell and its components
Use cell notation to symbolize the composition and construction of galvanic cells
As demonstration of spontaneous chemical change, Figure 17.2 shows the result of immersing a coiled wire of copper into an
aqueous solution of silver nitrate. A gradual but visually impressive change spontaneously occurs as the initially colorless solution
becomes increasingly blue, and the initially smooth copper wire becomes covered with a porous gray solid.
Figure 17.2 A copper wire and an aqueous solution of silver nitrate (left) are brought into contact (center) and a spontaneous
transfer of electrons occurs, creating blue Cu2+(aq) and gray Ag(s) (right).
These observations are consistent with (i) the oxidation of elemental copper to yield copper(II) ions, Cu2+(aq), which impart a blue
color to the solution, and (ii) the reduction of silver(I) ions to yield elemental silver, which deposits as a fluffy solid on the copper
wire surface. And so, the direct transfer of electrons from the copper wire to the aqueous silver ions is spontaneous under the
employed conditions. A summary of this redox system is provided by these equations:
+ 2+
overall reaction: Cu(s) + 2 Ag (aq) ⟶ Cu (aq) + 2Ag(s)
2+ −
oxidation half-reaction: Cu(s) ⟶ Cu (aq) + 2 e
+ −
reduction half-reaction: 2 Ag (aq) + 2 e ⟶ 2Ag(s)
Consider the construction of a device that contains all the reactants and products of a redox system like the one here, but prevents
physical contact between the reactants. Direct transfer of electrons is, therefore, prevented; transfer, instead, takes place indirectly
through an external circuit that contacts the separated reactants. Devices of this sort are generally referred to as electrochemical
cells, and those in which a spontaneous redox reaction takes place are called galvanic cells (or voltaic cells).
A galvanic cell based on the spontaneous reaction between copper and silver(I) is depicted in Figure 17.3. The cell is comprised of
two half-cells, each containing the redox conjugate pair (“couple”) of a single reactant. The half-cell shown at the left contains the
Cu(0)/Cu(II) couple in the form of a solid copper foil and an aqueous solution of copper nitrate. The right half-cell contains the
Ag(I)/Ag(0) couple as solid silver foil and an aqueous silver nitrate solution. An external circuit is connected to each half-cell at its
solid foil, meaning the Cu and Ag foil each function as an electrode. By definition, the anode of an electrochemical cell is the
electrode at which oxidation occurs (in this case, the Cu foil) and the cathode is the electrode where reduction occurs (the Ag foil).
The redox reactions in a galvanic cell occur only at the interface between each half-cell’s reaction mixture and its electrode. To
keep the reactants separate while maintaining charge-balance, the two half-cell solutions are connected by a tube filled with inert
electrolyte solution called a salt bridge. The spontaneous reaction in this cell produces Cu2+ cations in the anode half-cell and
consumes Ag+ ions in the cathode half-cell, resulting in a compensatory flow of inert ions from the salt bridge that maintains
charge balance. Increasing concentrations of Cu2+ in the anode half-cell are balanced by an influx of NO3− from the salt bridge,
while a flow of Na+ into the cathode half-cell compensates for the decreasing Ag+ concentration.

Figure 17.3 A galvanic cell based on the spontaneous reaction between copper and silver(I) ions.
17.3.0.1: Cell Notation

Abbreviated symbolism is commonly used to represent a galvanic cell by providing essential information on its composition and
structure. These symbolic representations are called cell notations or cell schematics, and they are written following a few
guidelines:
The relevant components of each half-cell are represented by their chemical formulas or element symbols
All interfaces between component phases are represented by vertical parallel lines; if two or more components are present in the
same phase, their formulas are separated by commas
By convention, the schematic begins with the anode and proceeds left-to-right identifying phases and interfaces encountered
within the cell, ending with the cathode
A verbal description of the cell as viewed from anode-to-cathode is often a useful first-step in writing its schematic. For example,
the galvanic cell shown in Figure 17.3 consists of a solid copper anode immersed in an aqueous solution of copper(II) nitrate that is

connected via a salt bridge to an aqueous silver(I) nitrate solution, immersed in which is a solid silver cathode. Converting this
statement to symbolism following the above guidelines results in the cell schematic:
Cu(s) │1 M Cu(NO3 )2 (aq) ║1 M AgNO3 (aq) │Ag(s)
Consider a different galvanic cell (see Figure 17.4) based on the spontaneous reaction between solid magnesium and aqueous
iron(III) ions:
3+ 2+ 2+
net cell reaction: Mg(s) + 2Fe (aq) ⟶ Mg (aq) + 2 Fe (aq)
2+ −
oxidation half-reaction: Mg(s) ⟶ Mg (aq) + 2 e
3+ − 2+
reduction half-reaction: 2Fe (aq) + 2e ⟶ 2 Fe (aq)
In this cell, a solid magnesium anode is immersed in an aqueous solution of magnesium chloride that is connected via a salt bridge
to an aqueous solution containing a mixture of iron(III) chloride and iron(II) chloride, immersed in which is a platinum cathode.
The cell schematic is then written as
Mg(s) │0.1 M MgCl2 (aq)║0.2 M FeCl3 (aq), 0.3 M FeCl2 (aq) │Pt(s)
Notice the cathode half-cell is different from the others considered thus far in that its electrode is comprised of a substance (Pt) that
is neither a reactant nor a product of the cell reaction. This is required when neither member of the half-cell’s redox couple can
reasonably function as an electrode, which must be electrically conductive and in a phase separate from the half-cell solution. In
this case, both members of the redox couple are solute species, and so Pt is used as an inert electrode that can simply provide or
accept electrons to redox species in solution. Electrodes constructed from a member of the redox couple, such as the Mg anode in
this cell, are called active electrodes.
Figure 17.4 A galvanic cell based on the spontaneous reaction between magnesium and iron(III) ions.
17.3.0.1: Example 17.3

17.3.0.0.1: Writing Galvanic Cell Schematics
A galvanic cell is fabricated by connecting two half-cells with a salt bridge, one in which a chromium wire is immersed in a 1
M CrCl3 solution and another in which a copper wire is immersed in 1 M CuCl2. Assuming the chromium wire functions as an
anode, write the schematic for this cell along with equations for the anode half-reaction, the cathode half-reaction, and the
overall cell reaction.
Since the chromium wire is stipulated to be the anode, the schematic begins with it and proceeds left-to-right, symbolizing the
other cell components until ending with the copper wire cathode:
Cr(s) │1 M CrCl3 (aq)║1 M CuCl2 (aq) │Cu(s)
The half-reactions for this cell are

3+ −
anode (oxidation): Cr(s) ⟶ Cr (aq) + 3 e
2+ −
cathode (reduction): Cu (aq) + 2 e ⟶ Cu(s)
Multiplying to make the number of electrons lost by Cr and gained by Cu2+ equal yields
3+ −
anode (oxidation): 2Cr(s) ⟶ 2 Cr (aq) + 6 e
2+ −
cathode (reduction): 3 Cu (aq) + 6 e ⟶ 3Cu(s)
Adding the half-reaction equations and simplifying yields an equation for the cell reaction:
2+ 3+
2Cr(s) + 3 Cu (aq) ⟶ 2 Cr (aq) + 3Cu(s)

Omitting solute concentrations and spectator ion identities, write the schematic for a galvanic cell whose net cell reaction is
shown below.
4+ 2+ 2+
Sn (aq) + Zn(s) ⟶ Sn (aq) + Zn (aq)
17.3.0.1: Answer:
Zn(s) │Zn2+ (aq)║Sn 4+ (aq), Sn 2+ (aq)│Pt(s)
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Describe and relate the definitions of electrode and cell potentials
Interpret electrode potentials in terms of relative oxidant and reductant strengths
Calculate cell potentials and predict redox spontaneity using standard electrode potentials
Unlike the spontaneous oxidation of copper by aqueous silver(I) ions described in section 17.2, immersing a copper wire in an
aqueous solution of lead(II) ions yields no reaction. The two species, Ag+(aq) and Pb2+(aq), thus show a distinct difference in their
redox activity towards copper: the silver ion spontaneously oxidized copper, but the lead ion did not. Electrochemical cells permit
this relative redox activity to be quantified by an easily measured property, potential. This property is more commonly called
voltage when referenced in regard to electrical applications, and it is a measure of energy accompanying the transfer of charge.
Potentials are measured in the volt unit, defined as one joule of energy per one coulomb of charge, V = J/C.
When measured for purposes of electrochemistry, a potential reflects the driving force for a specific type of charge transfer process,
namely, the transfer of electrons between redox reactants. Considering the nature of potential in this context, it is clear that the
potential of a single half-cell or a single electrode can’t be measured; “transfer” of electrons requires both a donor and recipient, in
this case a reductant and an oxidant, respectively. Instead, a half-cell potential may only be assessed relative to that of another half-
cell. It is only the difference in potential between two half-cells that may be measured, and these measured potentials are called cell
potentials, Ecell, defined as
Ecell = Ecathode − Eanode
where Ecathode and Eanode are the potentials of two different half-cells functioning as specified in the subscripts. As for other
thermodynamic quantities, the standard cell potential, E°cell, is a cell potential measured when both half-cells are under standard-
state conditions (1 M concentrations, 1 bar pressures, 298 K):
° ° °
E cell =E cathode −E anode
To simplify the collection and sharing of potential data for half-reactions, the scientific community has designated one particular
half-cell to serve as a universal reference for cell potential measurements, assigning it a potential of exactly 0 V. This half-cell is
the standard hydrogen electrode (SHE) and it is based on half-reaction below:
+ −
2H (aq) + 2 e ⟶ H2 (g)
A typical SHE contains an inert platinum electrode immersed in precisely 1 M aqueous H+ and a stream of bubbling H2 gas at 1 bar
pressure, all maintained at a temperature of 298 K (see Figure 17.5).

Figure 17.5 A standard hydrogen electrode (SHE).
The assigned potential of the SHE permits the definition of a conveniently measured potential for a single half-cell. The electrode
potential (EX) for a half-cell X is defined as the potential measured for a cell comprised of X acting as cathode and the SHE acting
as anode:
Ecell = EX − ESHE
ESHE = 0 V (defined)
Ecell = EX
When the half-cell X is under standard-state conditions, its potential is the standard electrode potential, E°X. Since the definition of
cell potential requires the half-cells function as cathodes, these potentials are sometimes called standard reduction potentials.
This approach to measuring electrode potentials is illustrated in Figure 17.6, which depicts a cell comprised of an SHE connected
to a copper(II)/copper(0) half-cell under standard-state conditions. A voltmeter in the external circuit allows measurement of the

potential difference between the two half-cells. Since the Cu half-cell is designated as the cathode in the definition of cell potential,
it is connected to the red (positive) input of the voltmeter, while the designated SHE anode is connected to the black (negative)
input. These connections insure that the sign of the measured potential will be consistent with the sign conventions of
electrochemistry per the various definitions discussed above. A cell potential of +0.337 V is measured, and so
° °
E cell =E Cu = +0.337 V
Tabulations of E° values for other half-cells measured in a similar fashion are available as reference literature to permit calculations
of cell potentials and the prediction of the spontaneity of redox processes.
Figure 17.6 A cell permitting experimental measurement of the standard electrode potential for the half-reaction
2+ −
Cu (aq) + 2 e ⟶ Cu(s)
Table 17.1 provides a listing of standard electrode potentials for a selection of half-reactions in numerical order, and a more
extensive alphabetical listing is given in Appendix L.
Selected Standard Reduction Potentials at 25 °C
Half-Reaction E° (V)
F2 (g) + 2e
−
⟶ 2F
−
(aq) +2.866
PbO2 (s) + SO4

2−
(aq) + 4H
+ −
(aq) + 2e ⟶ PbSO4 (s) + 2H2 O(l) +1.69
MnO4
−
(aq) + 8H
+
(aq) + 5e
−
⟶ Mn
2+
(aq) + 4H2 O(l) +1.507

Au
3+
(aq) + 3e
−
⟶ Au(s) +1.498
Cl2 (g) + 2e
−
⟶ 2Cl
−
(aq) +1.35827
O2 (g) + 4H
+
(aq) + 4e
−
⟶ 2H2 O(l) +1.229
Pt
2+
(aq) + 2e
−
⟶ Pt(s) +1.20
Br 2 (aq) + 2e
−
⟶ 2Br
−
(aq) +1.0873
Ag
+
(aq) + e
−
⟶ Ag(s) +0.7996
Hg
2
2+
(aq) + 2e
−
⟶ 2Hg(l) +0.7973
Fe
3+
(aq) + e
−
⟶ Fe
2+
(aq) +0.771
MnO4
−
(aq) + 2H2 O(l) + 3e
−
⟶ MnO2 (s) + 4OH
−
(aq) +0.558
I2 (s) + 2e
−
⟶ 2I
−
(aq) +0.5355
NiO 2 (s) + 2H2 O(l) + 2e

−
⟶ Ni(OH) (s) + 2OH
2
−
(aq) +0.49
Cu
2+
(aq) + 2e
−
⟶ Cu(s) +0.34
Hg Cl2 (s) + 2e
2
−
⟶ 2Hg(l) + 2Cl
−
(aq) +0.26808
AgCl(s) + e
−
⟶ Ag(s) + Cl
−
(aq) +0.22233
Sn
4+
(aq) + 2e
−
⟶ Sn
2+
(aq) +0.151
2H
+
(aq) + 2e
−
⟶ H2 (g) 0.00
Pb
2+
(aq) + 2e
−
⟶ Pb(s) −0.1262
Sn
2+
(aq) + 2e
−
⟶ Sn(s) −0.1375
Ni
2+
(aq) + 2e
−
⟶ Ni(s) −0.257
Co
2+
(aq) + 2e
−
⟶ Co(s) −0.28
PbSO4 (s) + 2e
−
⟶ Pb(s) + SO4
2−
(aq) −0.3505
Cd
2+
(aq) + 2e
−
⟶ Cd(s) −0.4030
Fe
2+
(aq) + 2e
−
⟶ Fe(s) −0.447

Cr
3+
(aq) + 3e
−
⟶ Cr(s) −0.744
Mn
2+
(aq) + 2e
−
⟶ Mn(s) −1.185
Zn(OH) (s) + 2e
2
−
⟶ Zn(s) + 2OH
−
(aq) −1.245
Zn
2+
(aq) + 2e
−
⟶ Zn(s) −0.7618
Al
3+
(aq) + 3e
−
⟶ Al(s) −1.662
2
Mg (aq) + 2e
−
⟶ Mg(s) −2.372
Na
+
(aq) + e
−
⟶ Na(s) −2.71
Ca
2+
(aq) + 2e
−
⟶ Ca(s) −2.868
Ba
2+
(aq) + 2e
−
⟶ Ba(s) −2.912
K
+
(aq) + e
−
⟶ K(s) −2.931
Li
+
(aq) + e
−
⟶ Li(s) −3.04
Table 17.1
17.4.0.1: Example 17.4

17.4.0.0.1: Calculating Standard Cell Potentials
What is the standard potential of the galvanic cell shown in Figure 17.3?
The cell in Figure 17.3 is galvanic, the spontaneous cell reaction involving oxidation of its copper anode and reduction of
silver(I) ions at its silver cathode:
+ 2+
cell reaction: Cu(s) + 2 Ag (aq) ⟶ Cu (aq) + 2Ag(s)
2+ −
anode half-reaction: Cu(s) ⟶ Cu (aq) + 2 e
+ −
cathode half-reaction: 2 Ag (aq) + 2 e ⟶ 2Ag(s)
The standard cell potential computed as

° ° °
E cell = E cathode −E anode
° °
= E Ag −E Cu
= 0.7996 V − 0.34 V
= +0.46 V

What is the standard cell potential expected if the silver cathode half-cell in Figure 17.3 is replaced with a lead half-cell:
⟶ Pb(s) ?
2+ −
Pb (aq) + 2 e
17.4.0.1: Answer:
−0. 47 V

17.4.0.1: Intrepreting Electrode and Cell Potentials
Thinking carefully about the definitions of cell and electrode potentials and the observations of spontaneous redox change
presented thus far, a significant relation is noted. The previous section described the spontaneous oxidation of copper by aqueous
silver(I) ions, but no observed reaction with aqueous lead(II) ions. Results of the calculations in Example 17.4 have just shown the
spontaneous process is described by a positive cell potential while the nonspontaneous process exhibits a negative cell potential.
And so, with regard to the relative effectiveness (“strength”) with which aqueous Ag+ and Pb2+ ions oxidize Cu under standard
conditions, the stronger oxidant is the one exhibiting the greater standard electrode potential, E°. Since by convention electrode
potentials are for reduction processes, an increased value of E° corresponds to an increased driving force behind the reduction of
the species (hence increased effectiveness of its action as an oxidizing agent on some other species). Negative values for electrode
potentials are simply a consequence of assigning a value of 0 V to the SHE, indicating the reactant of the half-reaction is a weaker
oxidant than aqueous hydrogen ions.
Applying this logic to the numerically ordered listing of standard electrode potentials in Table 17.1 shows this listing to be likewise
in order of the oxidizing strength of the half-reaction’s reactant species, decreasing from strongest oxidant (most positive E°) to
weakest oxidant (most negative E°). Predictions regarding the spontaneity of redox reactions under standard state conditions can
then be easily made by simply comparing the relative positions of their table entries. By definition, E°cell is positive when E°cathode
> E°anode, and so any redox reaction in which the oxidant’s entry is above the reductant’s entry is predicted to be spontaneous.
Reconsideration of the two redox reactions in Example 17.4 provides support for this fact. The entry for the silver(I)/silver(0) half-
reaction is above that for the copper(II)/copper(0) half-reaction, and so the oxidation of Cu by Ag+ is predicted to be spontaneous
(E°cathode > E°anode and so E°cell > 0). Conversely, the entry for the lead(II)/lead(0) half-cell is beneath that for copper(II)/copper(0),
and the oxidation of Cu by Pb2+ is nonspontaneous (E°cathode < E°anode and so E°cell < 0).
Recalling the chapter on thermodynamics, the spontaneities of the forward and reverse reactions of a reversible process show a
reciprocal relationship: if a process is spontaneous in one direction, it is non-spontaneous in the opposite direction. As an indicator
of spontaneity for redox reactions, the potential of a cell reaction shows a consequential relationship in its arithmetic sign. The
spontaneous oxidation of copper by lead(II) ions is not observed,
2+ 2+ °
Cu(s) + Pb (aq) ⟶ Cu (aq) + Pb(s)E f orward = −0.47 V (negative, non-spontaneous)
and so the reverse reaction, the oxidation of lead by copper(II) ions, is predicted to occur spontaneously:
2+ 2+ °
Pb(s) + Cu (aq) ⟶ Pb (aq) + Cu(s)E f orward = +0.47 V (positive, spontaneous)
Note that reversing the direction of a redox reaction effectively interchanges the identities of the cathode and anode half-reactions,
and so the cell potential is calculated from electrode potentials in the reverse subtraction order than that for the forward reaction. In
practice, a voltmeter would report a potential of −0.47 V with its red and black inputs connected to the Pb and Cu electrodes,
respectively. If the inputs were swapped, the reported voltage would be +0.47 V.
17.4.0.1: Example 17.5

17.4.0.0.1: Predicting Redox Spontaneity
Are aqueous iron(II) ions predicted to spontaneously oxidize elemental chromium under standard state conditions? Assume the
half-reactions to be those available in Table 17.1.
Referring to the tabulated half-reactions, the redox reaction in question can be represented by the equations below:
2+ 3+
Cr(s) + Fe (aq) ⟶ Cr (aq) + Fe(s)
The entry for the putative oxidant, Fe2+, appears above the entry for the reductant, Cr, and so a spontaneous reaction is
predicted per the quick approach described above. Supporting this predication by calculating the standard cell potential for this
reaction gives
° ° °
E cell = E cathode −E anode
° °
= E Fe(II) −E Cr
= −0.447 V − −0.744 V = +0.297 V
The positive value for the standard cell potential indicates the process is spontaneous under standard state conditions.

Use the data in Table 17.1 to predict the spontaneity of the oxidation of bromide ion by molecular iodine under standard state
conditions, supporting the prediction by calculating the standard cell potential for the reaction. Repeat for the oxidation of
iodide ion by molecular bromine.
17.4.0.1: Answer:
− − °
I2 (s) + 2 Br (aq) ⟶ 2 I (aq) + Br 2 (l) E cell = –0.5518 V (nonspontaneous)
− − °
Br 2 (s) + 2 I (aq) ⟶ 2 Br (aq) + I2 (l) E cell = +0.5518 V (spontaneous)
This page titled 17.4: Electrode and Cell Potentials is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax


Explain the relations between potential, free energy change, and equilibrium constants
Perform calculations involving the relations between cell potentials, free energy changes, and equilibrium
Use the Nernst equation to determine cell potentials under nonstandard conditions
So far in this chapter, the relationship between the cell potential and reaction spontaneity has been described, suggesting a link to
the free energy change for the reaction (see chapter on thermodynamics). The interpretation of potentials as measures of oxidant
strength was presented, bringing to mind similar measures of acid-base strength as reflected in equilibrium constants (see the
chapter on acid-base equilibria). This section provides a summary of the relationships between potential and the related
thermodynamic properties ΔG and K.
17.5.0.1: E° and ΔG°

The standard free energy change of a process, ΔG°, was defined in a previous chapter as the maximum work that could be
performed by a system, wmax. In the case of a redox reaction taking place within a galvanic cell under standard state conditions,
essentially all the work is associated with transferring the electrons from reductant-to-oxidant, welec:
ΔG° = wmax = welec
The work associated with transferring electrons is determined by the total amount of charge (coulombs) transferred and the cell
potential:
°
ΔG° = welec = −nF E
cell
°
ΔG° = −nF E
cell
where n is the number of moles of electrons transferred, F is Faraday’s constant, and E°cell is the standard cell potential. The
relation between free energy change and standard cell potential confirms the sign conventions and spontaneity criteria previously
discussed for both of these properties: spontaneous redox reactions exhibit positive potentials and negative free energy changes.
17.5.0.1: E° and K
Combining a previously derived relation between ΔG° and K (see the chapter on thermodynamics) and the equation above relating
ΔG° and E°cell yields the following:
°
ΔG° = −RT ln K = −nF E
cell
° RT
E = ( ) ln K
cell nF
This equation indicates redox reactions with large (positive) standard cell potentials will proceed far towards completion, reaching
equilibrium when the majority of reactant has been converted to product. A summary of the relations between E°, ΔG° and K is
depicted in Figure 17.7, and a table correlating reaction spontaneity to values of these properties is provided in Table 17.2.

Figure 17.7 Graphic depicting the relation between three important thermodynamic properties.
K ΔG° E°cell
>1 <0 >0 Reaction is spontaneous under standard conditions

Products more abundant at equilibrium
<1 >0 <0 Reaction is non-spontaneous under standard conditions

Reactants more abundant at equilibrium
=1 =0 =0 Reaction is at equilibrium under standard conditions

Reactants and products equally abundant
Table 17.2
17.5.0.1: Example 17.6

17.5.0.0.1: Equilibrium Constants, Standard Cell Potentials, and Standard Free Energy Changes
Use data from Appendix L to calculate the standard cell potential, standard free energy change, and equilibrium constant for
the following reaction at 25 °C. Comment on the spontaneity of the forward reaction and the composition of an equilibrium
mixture of reactants and products.
+ 2+
2 Ag (aq) + Fe(s) ⇌ 2Ag(s) + Fe (aq)
The reaction involves an oxidation-reduction reaction, so the standard cell potential can be calculated using the data in
Appendix L.

2+ − ∘
anode (oxidation): Fe(s) ⟶ Fe (aq) + 2e E 2+
= −0.447 V
Fe /Fe
+ − ∘
cathode (reduction): 2 × (Ag (aq) + e ⟶ Ag(s)) E +
= 0.7996 V
Ag /Ag
∘ ∘ ∘ ∘ ∘
E =E −E = E +
−E 2+
= +1.247 V
cell cathode anode Ag /Ag Fe /Fe
With n = 2, the equilibrium constant is then

∘ 0.0592 V
E = log K
cell n
∘
n × E /0.0592 V
K = 10 cell
2 × 1.247 V/0.0592 V
K = 10
42.128
K = 10
42
K = 1.3 × 10
The standard free energy is then

∘ ∘
ΔG = −nF E
cell
C J kJ
ΔG° = −2 × 96,485 × 1.247 = −240.6
mol C mol
The reaction is spontaneous, as indicated by a negative free energy change and a positive cell potential. The K value is very
large, indicating the reaction proceeds to near completion to yield an equilibrium mixture containing mostly products.
What is the standard free energy change and the equilibrium constant for the following reaction at room temperature? Is the
reaction spontaneous?
2+ 2+ +
Sn(s) + 2 Cu (aq) ⇌ Sn (aq) + 2 Cu (aq)
17.5.0.1: Answer:
Spontaneous; n = 2; E ∘
cell
= +0.291 V; ΔG° = −56.2
mol
kJ
; K = 6.8 × 109.
17.5.0.1: Potentials at Nonstandard Conditions: The Nernst Equation

Most of the redox processes that interest science and society do not occur under standard state conditions, and so the potentials of
these systems under nonstandard conditions are a property worthy of attention. Having established the relationship between
potential and free energy change in this section, the previously discussed relation between free energy change and reaction mixture
composition can be used for this purpose.
ΔG = ΔG° + RT ln Q
Notice the reaction quotient, Q, appears in this equation, making the free energy change dependent upon the composition of the
reaction mixture. Substituting the equation relating free energy change to cell potential yields the Nernst equation:
∘
−nF Ecell = −nF E + RT ln Q
cell
RT
∘
Ecell = E − ln Q
cell
nF
This equation describes how the potential of a redox system (such as a galvanic cell) varies from its standard state value,
specifically, showing it to be a function of the number of electrons transferred, n, the temperature, T, and the reaction mixture
composition as reflected in Q. A convenient form of the Nernst equation for most work is one in which values for the fundamental
constants (R and F) and standard temperature (298) K), along with a factor converting from natural to base-10 logarithms, have
been included:
0.0592V
∘
Ecell = E − log Q
cell
n
17.5.0.1: Example 17.7

17.5.0.0.1: Predicting Redox Spontaneity Under Nonstandard Conditions
Use the Nernst equation to predict the spontaneity of the redox reaction shown below.
2+ 2+
Co(s) + Fe (aq, 1.94 M ) ⟶ Co (aq, 0.15 M ) + Fe(s)
Collecting information from Appendix L and the problem,
2+ − ∘
Anode (oxidation): Co(s) ⟶ Co (aq) + 2e E 2+
= −0.28 V
Co /Co
2+ − ∘
Cathode (reduction): Fe (aq) + 2e ⟶ Fe(s) E 2+
= −0.447 V
Fe /Fe
∘ ∘ ∘
E =E −E = −0.447 V − (−0.28 V) = −0.17 V
cell cathode anode
Notice the negative value of the standard cell potential indicates the process is not spontaneous under standard conditions.
Substitution of the Nernst equation terms for the nonstandard conditions yields:
2+
[Co ] 0.15 M
Q = = = 0.077
2+
1.94 M
[Fe ]
∘ 0.0592 V
Ecell = E − log Q
cell n
0.0592 V
Ecell = −0.17 V − log 0.077
2
Ecell = −0.17 V + 0.033 V = −0.14 V
The cell potential remains negative (slightly) under the specified conditions, and so the reaction remains nonspontaneous.
For the cell schematic below, identify values for n and Q, and calculate the cell potential, Ecell.
3+ 2+
Al(s) │Al (aq, 0.15 M ) ║Cu (aq, 0.025 M ) │Cu(s)
17.5.0.1: Answer:
n = 6; Q = 1440; Ecell = +1.97 V, spontaneous.
A concentration cell is constructed by connecting two nearly identical half-cells, each based on the same half-reaction and using the
same electrode, varying only in the concentration of one redox species. The potential of a concentration cell, therefore, is
determined only by the difference in concentration of the chosen redox species. The example problem below illustrates the use of
the Nernst equation in calculations involving concentration cells.
17.5.0.1: Example 17.8

17.5.0.0.4: Concentration Cells
What is the cell potential of the concentration cell described by
Zn(s) │Zn2+ (aq, 0.10 M ) ║Zn2+ (aq, 0.50 M ) │Zn(s)
From the information given:
2+ − ∘
Anode: Zn(s) ⟶ Zn (aq, 0.10 M ) + 2e E = −0.7618 V
anode
2+ − ∘
Cathode: Zn (aq, 0.50 M ) + 2e ⟶ Zn(s) E = −0.7618 V
cathode
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
2+ 2+ ∘
Overall: Zn (aq, 0.50 M ) ⟶ Zn (aq, 0.10 M ) E = 0.000 V
cell
Substituting into the Nernst equation,

0.0592 V 0.10
Ecell = 0.000 V − log = +0.021 V
2 0.50

The positive value for cell potential indicates the overall cell reaction (see above) is spontaneous. This spontaneous reaction is
one in which the zinc ion concentration in the cathode falls (it is reduced to elemental zinc) while that in the anode rises (it is
produced by oxidation of the zinc anode). A greater driving force for zinc reduction is present in the cathode, where the
zinc(II) ion concentration is greater (Ecathode > Eanode).
The concentration cell above was allowed to operate until the cell reaction reached equilibrium. What are the cell potential and
the concentrations of zinc(II) in each half-cell for the cell now?
17.5.0.1: Answer:
Ecell = 0.000 V; [Zn2+]cathode = [Zn2+]anode = 0.30 M
This page titled 17.5: Potential, Free Energy, and Equilibrium is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by


Describe the electrochemistry associated with several common batteries
Distinguish the operation of a fuel cell from that of a battery
There are many technological products associated with the past two centuries of electrochemistry research, none more immediately
obvious than the battery. A battery is a galvanic cell that has been specially designed and constructed in a way that best suits its
intended use a source of electrical power for specific applications. Among the first successful batteries was the Daniell cell, which
relied on the spontaneous oxidation of zinc by copper(II) ions (Figure 17.8):
2+ 2+
Zn(s) + Cu (aq) ⟶ Zn (aq) + Cu(s)
Figure 17.8 Illustration of a Daniell cell taken from a 1904 journal publication (left) along with a simplified illustration depicting
the electrochemistry of the cell (right). The 1904 design used a porous clay pot to both contain one of the half-cell’s content and to
serve as a salt bridge to the other half-cell.
Modern batteries exist in a multitude of forms to accommodate various applications, from tiny button batteries that provide the
modest power needs of a wristwatch to the very large batteries used to supply backup energy to municipal power grids. Some
batteries are designed for single-use applications and cannot be recharged (primary cells), while others are based on conveniently
reversible cell reactions that allow recharging by an external power source (secondary cells). This section will provide a summary
of the basic electrochemical aspects of several batteries familiar to most consumers, and will introduce a related electrochemical
device called a fuel cell that can offer improved performance in certain applications.

Visit this site to learn more about batteries.
17.6.0.1: Single-Use Batteries

A common primary battery is the dry cell, which uses a zinc can as both container and anode (“–” terminal) and a graphite rod as
the cathode (“+” terminal). The Zn can is filled with an electrolyte paste containing manganese(IV) oxide, zinc(II) chloride,

ammonium chloride, and water. A graphite rod is immersed in the electrolyte paste to complete the cell. The spontaneous cell
reaction involves the oxidation of zinc:
2+ −
anode reaction: Zn(s) ⟶ Zn (aq) + 2 e
and the reduction of manganese(IV)

− −
reduction reaction: 2 MnO 2 (s) + 2 NH4 Cl(aq) + 2 e ⟶ Mn2 O3 (s) + 2 NH3 (aq) + H2 O(l) + 2 Cl
which together yield the cell reaction:

2+ −
cell reaction: 2 MnO 2 (s) + 2 NH4 Cl(aq) + Zn(s) ⟶ Zn (aq) + Mn2 O3 (s) + 2 NH3 (aq) + H2 O(l) + 2 Cl Ecell ~1.5 V
The voltage (cell potential) of a dry cell is approximately 1.5 V. Dry cells are available in various sizes (e.g., D, C, AA, AAA). All
sizes of dry cells comprise the same components, and so they exhibit the same voltage, but larger cells contain greater amounts of
the redox reactants and therefore are capable of transferring correspondingly greater amounts of charge. Like other galvanic cells,
dry cells may be connected in series to yield batteries with greater voltage outputs, if needed.
Figure 17.9 A schematic diagram shows a typical dry cell.

Visit this site to learn more about zinc-carbon batteries.
Alkaline batteries (Figure 17.10) were developed in the 1950s to improve on the performance of the dry cell, and they were
designed around the same redox couples. As their name suggests, these types of batteries use alkaline electrolytes, often potassium
hydroxide. The reactions are
− −
anode: Zn(s) + 2 OH (aq) ⟶ ZnO(s) + H2 O(l) + 2e
− −
cathode: 2 MnO 2 (s) + H2 O(l) + 2e ⟶ Mn2 O3 (s) + 2OH (aq)
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
cell: Zn(s) + 2MnO 2 (s) ⟶ ZnO(s) + Mn2 O3 (s) Ecell = +1.43 V
An alkaline battery can deliver about three to five times the energy of a zinc-carbon dry cell of similar size. Alkaline batteries are
prone to leaking potassium hydroxide, so they should be removed from devices for long-term storage. While some alkaline

batteries are rechargeable, most are not. Attempts to recharge an alkaline battery that is not rechargeable often leads to rupture of
the battery and leakage of the potassium hydroxide electrolyte.
Figure 17.10 Alkaline batteries were designed as improved replacements for zinc-carbon (dry cell) batteries.

Visit this site to learn more about alkaline batteries.
17.6.0.1: Rechargeable (Secondary) Batteries

Nickel-cadmium, or NiCd, batteries (Figure 17.11) consist of a nickel-plated cathode, cadmium-plated anode, and a potassium
hydroxide electrode. The positive and negative plates, which are prevented from shorting by the separator, are rolled together and
put into the case. This is a “jelly-roll” design and allows the NiCd cell to deliver much more current than a similar-sized alkaline
battery. The reactions are
− −
anode: Cd(s) + 2OH (aq) ⟶ Cd(OH) 2 (s) + 2e
− −
cathode: NiO2 (s) + 2H2 O(l) + 2e ⟶ Ni(OH) (s) + 2OH (aq)
2
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
cell: Cd(s) + NiO2 (s) + 2H2 O(l) ⟶ Cd(OH) 2 (s) + Ni(OH)2 (s) Ecell ~1.2 V
When properly treated, a NiCd battery can be recharged about 1000 times. Cadmium is a toxic heavy metal so NiCd batteries
should never be ruptured or incinerated, and they should be disposed of in accordance with relevant toxic waste guidelines.

Figure 17.11 NiCd batteries use a “jelly-roll” design that significantly increases the amount of current the battery can deliver as
compared to a similar-sized alkaline battery.

Visit this site for more information about nickel cadmium rechargeable batteries.
Lithium ion batteries (Figure 17.12) are among the most popular rechargeable batteries and are used in many portable electronic
devices. The reactions are
+ −
anode: LiCoO2 ⇌ Li 1−x CoO2 + x Li +x e
+ −
cathode: x Li +x e + x C6 ⇌ x LiC6
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
cell: LiCoO2 + x C6 ⇌ Li 1−x CoO2 + x LiC6 Ecell ~3.7 V
The variable stoichiometry of the cell reaction leads to variation in cell voltages, but for typical conditions, x is usually no more
than 0.5 and the cell voltage is approximately 3.7 V. Lithium batteries are popular because they can provide a large amount current,
are lighter than comparable batteries of other types, produce a nearly constant voltage as they discharge, and only slowly lose their
charge when stored.

Figure 17.12 In a lithium ion battery, charge flows as the lithium ions are transferred between the anode and cathode.

Visit this site for more information about lithium ion batteries.
The lead acid battery (Figure 17.13) is the type of secondary battery commonly used in automobiles. It is inexpensive and capable
of producing the high current required by automobile starter motors. The reactions for a lead acid battery are
− + −
anode: Pb(s) + HSO 4 (aq) ⟶ PbSO 4 (s) + H (aq) + 2e
− + −
cathode: PbO 2 (s) + HSO 4 (aq) + 3H (aq) + 2e ⟶ PbSO 4 (s) + 2 H2 O(l)
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
cell: Pb(s) + PbO 2 (s) + 2 H2 SO 4 (aq) ⟶ 2PbSO 4 (s) + 2 H2 O(l) Ecell ~2 V
Each cell produces 2 V, so six cells are connected in series to produce a 12-V car battery. Lead acid batteries are heavy and contain
a caustic liquid electrolyte, H2SO4(aq), but are often still the battery of choice because of their high current density. Since these
batteries contain a significant amount of lead, they must always be disposed of properly.

Figure 17.13 The lead acid battery in your automobile consists of six cells connected in series to give 12 V.

Visit this site for more information about lead acid batteries.
17.6.0.1: Fuel Cells

A fuel cell is a galvanic cell that uses traditional combustive fuels, most often hydrogen or methane, that are continuously fed into
the cell along with an oxidant. (An alternative, but not very popular, name for a fuel cell is a flow battery.) Within the cell, fuel and
oxidant undergo the same redox chemistry as when they are combusted, but via a catalyzed electrochemical that is significantly
more efficient. For example, a typical hydrogen fuel cell uses graphite electrodes embedded with platinum-based catalysts to
accelerate the two half-cell reactions:
Figure 17.14 In this hydrogen fuel cell, oxygen from the air reacts with hydrogen, producing water and electricity.
+ −
Anode: 2 H2 (g) ⟶ 4 H (aq) + 4e
+ −
Cathode: O2 (g) + 4 H (aq) + 4e ⟶ 2H2 O(g)
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
Cell: 2 H2 (g) + O2 (g) ⟶ 2 H2 O(g) Ecell ~1.2 V
These types of fuel cells generally produce voltages of approximately 1.2 V. Compared to an internal combustion engine, the
energy efficiency of a fuel cell using the same redox reaction is typically more than double (~20%–25% for an engine versus
~50%–75% for a fuel cell). Hydrogen fuel cells are commonly used on extended space missions, and prototypes for personal
vehicles have been developed, though the technology remains relatively immature.

Check out this link to learn more about fuel cells.

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17.7: Corrosion

Define corrosion
List some of the methods used to prevent or slow corrosion
Corrosion is usually defined as the degradation of metals by a naturally occurring electrochemical process. The formation of rust on
iron, tarnish on silver, and the blue-green patina that develops on copper are all examples of corrosion. The total cost of corrosion
remediation in the United States is significant, with estimates in excess of half a trillion dollars a year.

17.7.0.0.1: Statue of Liberty: Changing Colors
The Statue of Liberty is a landmark every American recognizes. The Statue of Liberty is easily identified by its height, stance,
and unique blue-green color (Figure 17.15). When this statue was first delivered from France, its appearance was not green. It
was brown, the color of its copper “skin.” So how did the Statue of Liberty change colors? The change in appearance was a
direct result of corrosion. The copper that is the primary component of the statue slowly underwent oxidation from the air. The
oxidation-reduction reactions of copper metal in the environment occur in several steps. Copper metal is oxidized to copper(I)
oxide (Cu2O), which is red, and then to copper(II) oxide, which is black
1
2Cu(s) + O2 (g) ⟶ Cu2 O(s) (red)
2
1
Cu2 O(s) + O2 (g) ⟶ 2CuO(s) (black)
2
Coal, which was often high in sulfur, was burned extensively in the early part of the last century. As a result, atmospheric
sulfur trioxide, carbon dioxide, and water all reacted with the CuO
2CuO(s) + CO2 (g) + H2 O(l) ⟶ Cu2 CO3 (OH) 2 (s) (green)
3CuO(s) + 2CO2 (g) + H2 O(l) ⟶ Cu2 (CO ) (OH) (s) (blue)

3 2 2
4CuO(s) + SO 3 (g) + 3H2 O(l) ⟶ Cu4 SO 4 (OH) 6 (s) (green)
These three compounds are responsible for the characteristic blue-green patina seen on the Statue of Liberty (and other outdoor
copper structures). Fortunately, formation of patina creates a protective layer on the copper surface, preventing further
corrosion of the underlying copper. The formation of the protective layer is called passivation, a phenomenon discussed further
in another chapter of this text.

Figure 17.15 (a) The Statue of Liberty is covered with a copper skin, and was originally brown, as shown in this painting. (b)
Exposure to the elements has resulted in the formation of the blue-green patina seen today.
Perhaps the most familiar example of corrosion is the formation of rust on iron. Iron will rust when it is exposed to oxygen and
water. Rust formation involves the creation of a galvanic cell at an iron surface, as illustrated in Figure 17.15. The relevant redox
reactions are described by the following equations:
2+ − ∘
anode: Fe(s) ⟶ Fe (aq) + 2 e E 2+
= −0.44 V
Fe /Fe
+ − ∘
cathode: O2 (g) + 4 H (aq) + 4 e ⟶ 2 H2 O(l) E 2
= +1.23 V
O2 /O
+ 2+ ∘
overall: 2Fe(s) + O2 (g) + 4H (aq) ⟶ 2 Fe (aq) + 2 H2 O(l) E = +1.67 V
cell
Further reaction of the iron(II) product in humid air results in the production of an iron(III) oxide hydrate known as rust:

2+ +
4 Fe (aq) + O2 (g) + (4 + 2x) H2 O(l) ⟶ 2 Fe2 O3 ⋅x H2 O(s) + 8 H (aq)
The stoichiometry of the hydrate varies, as indicated by the use of x in the compound formula. Unlike the patina on copper, the
formation of rust does not create a protective layer and so corrosion of the iron continues as the rust flakes off and exposes fresh
iron to the atmosphere.
Figure 17.16 Corrosion can occur when a painted iron or steel surface is exposed to the environment by a scratch through the paint.
A galvanic cell results that may be approximated by the simplified cell schematic Fe(s) | Fe2+(aq) ||O2(aq), H2O(l) | Fe(s).
One way to keep iron from corroding is to keep it painted. The layer of paint prevents the water and oxygen necessary for rust
formation from coming into contact with the iron. As long as the paint remains intact, the iron is protected from corrosion.
Other strategies include alloying the iron with other metals. For example, stainless steel is an alloy of iron containing a small
amount of chromium. The chromium tends to collect near the surface, where it corrodes and forms a passivating an oxide layer that
protects the iron.
Iron and other metals may also be protected from corrosion by galvanization, a process in which the metal to be protected is coated
with a layer of a more readily oxidized metal, usually zinc. When the zinc layer is intact, it prevents air from contacting the
underlying iron and thus prevents corrosion. If the zinc layer is breached by either corrosion or mechanical abrasion, the iron may
still be protected from corrosion by a cathodic protection process, which is described in the next paragraph.
Another important way to protect metal is to make it the cathode in a galvanic cell. This is cathodic protection and can be used for
metals other than just iron. For example, the rusting of underground iron storage tanks and pipes can be prevented or greatly
reduced by connecting them to a more active metal such as zinc or magnesium (Figure 17.17). This is also used to protect the metal
parts in water heaters. The more active metals (lower reduction potential) are called sacrificial anodes because as they get used up
as they corrode (oxidize) at the anode. The metal being protected serves as the cathode for the reduction of oxygen in air, and so it
simply serves to conduct (not react with) the electrons being transferred. When the anodes are properly monitored and periodically
replaced, the useful lifetime of the iron storage tank can be greatly extended.

Figure 17.17 Cathodic protection is a useful approach to electrochemically preventing corrosion of underground storage tanks.
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17.8: Electrolysis

Describe the process of electrolysis
Compare the operation of electrolytic cells with that of galvanic cells
Perform stoichiometric calculations for electrolytic processes
Electrochemical cells in which spontaneous redox reactions take place (galvanic cells) have been the topic of discussion so far in
this chapter. In these cells, electrical work is done by a redox system on its surroundings as electrons produced by the redox
reaction are transferred through an external circuit. This final section of the chapter will address an alternative scenario in which an
external circuit does work on a redox system by imposing a voltage sufficient to drive an otherwise nonspontaneous reaction, a
process known as electrolysis. A familiar example of electrolysis is recharging a battery, which involves use of an external power
source to drive the spontaneous (discharge) cell reaction in the reverse direction, restoring to some extent the composition of the
half-cells and the voltage of the battery. Perhaps less familiar is the use of electrolysis in the refinement of metallic ores, the
manufacture of commodity chemicals, and the electroplating of metallic coatings on various products (e.g., jewelry, utensils, auto
parts). To illustrate the essential concepts of electrolysis, a few specific processes will be considered.
17.8.0.1: The Electrolysis of Molten Sodium Chloride

Metallic sodium, Na, and chlorine gas, Cl2, are used in numerous applications, and their industrial production relies on the large-
scale electrolysis of molten sodium chloride, NaCl(l). The industrial process typically uses a Downs cell similar to the simplified
illustration shown in Figure 17.18. The reactions associated with this process are:
− −
anode: 2 Cl (l) ⟶ Cl2 (g) + 2e
+ −
cathode: Na (l) + e ⟶ Na(l)
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
+ −
cell: 2 Na (l) + 2Cl (l) ⟶ 2Na(l) + Cl2 (g)
The cell potential for the above process is negative, indicating the reaction as written (decomposition of liquid NaCl) is not
spontaneous. To force this reaction, a positive potential of magnitude greater than the negative cell potential must be applied to the
cell.

Figure 17.18 Cells of this sort (a cell for the electrolysis of molten sodium chloride) are used in the Downs process for production
of sodium and chlorine, and they typically use iron cathodes and carbon anodes.
17.8.0.1: The Electrolysis of Water

Water may be electrolytically decomposed in a cell similar to the one illustrated in Figure 17.19. To improve electrical conductivity
without introducing a different redox species, the hydrogen ion concentration of the water is typically increased by addition of a

strong acid. The redox processes associated with this cell are
+ − ∘
anode: 2 H2 O(l) ⟶ O2 (g) + 4H (aq) + 4e E = +1.229 V
anode
+ − ∘
cathode: 2 H (aq) + 2e ⟶ H2 (g) E = 0 V
cathode
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
∘
cell: 2 H2 O(l) ⟶ 2H2 (g) + O2 (g) E = −1.229 V
cell
Again, the cell potential as written is negative, indicating a nonspontaneous cell reaction that must be driven by imposing a cell
voltage greater than +1.229 V. Keep in mind that standard electrode potentials are used to inform thermodynamic predictions here,
though the cell is not operating under standard state conditions. Therefore, at best, calculated cell potentials should be considered
ballpark estimates.
Figure 17.19 The electrolysis of water produces stoichiometric amounts of oxygen gas at the anode and hydrogen at the anode.
17.8.0.1: The Electrolysis of Aqueous Sodium Chloride

When aqueous solutions of ionic compounds are electrolyzed, the anode and cathode half-reactions may involve the electrolysis of
either water species (H2O, H+, OH-) or solute species (the cations and anions of the compound). As an example, the electrolysis of

aqueous sodium chloride could involve either of these two anode reactions:
− − ∘
(i) 2 Cl (aq) ⟶ Cl2 (g) + 2 e E = +1.35827 V
anode
+ − ∘
(ii) 2 H2 O(l) ⟶ O2 (g) + 4 H (aq) + 4 e E = +1.229 V
anode
The standard electrode (reduction) potentials of these two half-reactions indicate water may be oxidized at a less negative/more
positive potential (–1.229 V) than chloride ion (–1.358 V). Thermodynamics thus predicts that water would be more readily
oxidized, though in practice it is observed that both water and chloride ion are oxidized under typical conditions, producing a
mixture of oxygen and chlorine gas.
Turning attention to the cathode, the possibilities for reduction are:
+ − ∘
(iii) 2H (aq) + 2 e ⟶ H2 (g) E = 0 V
cathode
− − ∘
(iv) 2H2 O(l) + 2 e ⟶ H2 (g) + 2 OH (aq) E = −0.8277 V
cathode
+ − ∘
(v) Na (aq) + e ⟶ Na(s) E = −2.71 V
cathode
Comparison of these standard half-reaction potentials suggests the reduction of hydrogen ion is thermodynamically favored.
However, in a neutral aqueous sodium chloride solution, the concentration of hydrogen ion is far below the standard state value of
1 M (approximately 10-7 M), and so the observed cathode reaction is actually reduction of water. The net cell reaction in this case is
then
− − ∘
cell: 2 H2 O(l) + 2 Cl (aq) ⟶ H2 (g) + Cl2 (g) + 2 OH (aq) E = −2.186 V
cell
This electrolysis reaction is part of the chlor-alkali process used by industry to produce chlorine and sodium hydroxide (lye).

17.8.0.0.1: Electroplating
An important use for electrolytic cells is in electroplating. Electroplating results in a thin coating of one metal on top of a
conducting surface. Reasons for electroplating include making the object more corrosion resistant, strengthening the surface,
producing a more attractive finish, or for purifying metal. The metals commonly used in electroplating include cadmium,
chromium, copper, gold, nickel, silver, and tin. Common consumer products include silver-plated or gold-plated tableware,
chrome-plated automobile parts, and jewelry. The silver plating of eating utensils is used here to illustrate the process. (Figure
17.20).
Figure 17.20 This schematic shows an electrolytic cell for silver plating eating utensils.

In the figure, the anode consists of a silver electrode, shown on the left. The cathode is located on the right and is the spoon,
which is made from inexpensive metal. Both electrodes are immersed in a solution of silver nitrate. Applying a sufficient
potential results in the oxidation of the silver anode
+ −
anode: Ag(s) ⟶ Ag (aq) + e
and reduction of silver ion at the (spoon) cathode:

+ −
cathode: Ag (aq) + e ⟶ Ag(s)
The net result is the transfer of silver metal from the anode to the cathode. Several experimental factors must be carefully
controlled to obtain high-quality silver coatings, including the exact composition of the electrolyte solution, the cell voltage
applied, and the rate of the electrolysis reaction (electrical current).
17.8.0.1: Quantitative Aspects of Electrolysis

Electrical current is defined as the rate of flow for any charged species. Most relevant to this discussion is the flow of electrons.
Current is measured in a composite unit called an ampere, defined as one coulomb per second (A = 1 C/s). The charge transferred,
Q, by passage of a constant current, I, over a specified time interval, t, is then given by the simple mathematical product
Q = It
When electrons are transferred during a redox process, the stoichiometry of the reaction may be used to derive the total amount of
(electronic) charge involved. For example, the generic reduction process
n+ −
M (aq) + ne ⟶ M(s)
involves the transfer of n mole of electrons. The charge transferred is, therefore,
Q = nF
where F is Faraday’s constant, the charge in coulombs for one mole of electrons. If the reaction takes place in an electrochemical
cell, the current flow is conveniently measured, and it may be used to assist in stoichiometric calculations related to the cell
reaction.
17.8.0.1: Example 17.9

17.8.0.0.1: Converting Current to Moles of Electrons
In one process used for electroplating silver, a current of 10.23 A was passed through an electrolytic cell for exactly 1 hour.
How many moles of electrons passed through the cell? What mass of silver was deposited at the cathode from the silver nitrate
solution?
Faraday’s constant can be used to convert the charge (Q) into moles of electrons (n). The charge is the current (I) multiplied by
the time
10.23 C 60 min 60 s
Q × 1 hr × × 36,830 C
s hr min −
n = = = = 0.381 7 mol e
− −
F 96,485 C/mol e 96,485 C/mol e
From the problem, the solution contains AgNO3, so the reaction at the cathode involves 1 mole of electrons for each mole of
silver
+ −
cathode: Ag (aq) + e ⟶ Ag(s)
The atomic mass of silver is 107.9 g/mol, so

1 mol Ag 107.9 g Ag
−
mass Ag = 0.3817 mol e × × = 41.19 g Ag
−
1 mol e 1 mol Ag

Aluminum metal can be made from aluminum(III) ions by electrolysis. What is the half-reaction at the cathode? What mass of
aluminum metal would be recovered if a current of 25.0 A passed through the solution for 15.0 minutes?

17.8.0.1: Answer:
Al
3+ −
(aq) + 3 e ⟶ Al(s); 0.0777 mol Al = 2.10 g Al.
17.8.0.1: Example 17.10

17.8.0.0.4: Time Required for Deposition
In one application, a 0.010-mm layer of chromium must be deposited on a part with a total surface area of 3.3 m2 from a
solution of containing chromium(III) ions. How long would it take to deposit the layer of chromium if the current was 33.46
A? The density of chromium (metal) is 7.19 g/cm3.
First, compute the volume of chromium that must be produced (equal to the product of surface area and thickness):
2
1 cm 10,000 cm
2 3
volume = (0.010 mm × ) × (3.3 m × ( )) = 33 cm
2
10 mm 1 m
Use the computed volume and the provided density to calculate the molar amount of chromium required:
7.19 g
3
mass = volume × density = 33 cm × = 237 g Cr
3
cm
1 mol Cr
mol Cr = 237 g Cr × = 4.56 mol Cr
52.00 g Cr
The stoichiometry of the chromium(III) reduction process requires three moles of electrons for each mole of chromium(0)
produced, and so the total charge required is:
−
3 mol e 96485 C 6
Q = 4.56 mol Cr × × = 1.32 × 10 C
−
1 mol Cr mol e
Finally, if this charge is passed at a rate of 33.46 C/s, the required time is:
6
Q 1.32 × 10 C
4
t = = = 3.95 × 10 s = 11.0 hr
I 33.46 C/s

What mass of zinc is required to galvanize the top of a 3.00 m × 5.50 m sheet of iron to a thickness of 0.100 mm of zinc? If
the zinc comes from a solution of Zn(NO3)2 and the current is 25.5 A, how long will it take to galvanize the top of the iron?
The density of zinc is 7.140 g/cm3.
17.8.0.1: Answer:
11.8 kg Zn requires 382 hours.
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17.9: Key Terms
active electrode
electrode that participates as a reactant or product in the oxidation-reduction reaction of an electrochemical cell; the mass of an
active electrode changes during the oxidation-reduction reaction
alkaline battery
primary battery similar to a dry cell that uses an alkaline (often potassium hydroxide) electrolyte; designed to be an improved
replacement for the dry cell, but with more energy storage and less electrolyte leakage than typical dry cell
anode
electrode in an electrochemical cell at which oxidation occurs
battery
single or series of galvanic cells designed for use as a source of electrical power
cathode
electrode in an electrochemical cell at which reduction occurs
cathodic protection
approach to preventing corrosion of a metal object by connecting it to a sacrificial anode composed of a more readily oxidized
metal
cell notation (schematic)

symbolic representation of the components and reactions in an electrochemical cell
cell potential (Ecell)

difference in potential of the cathode and anode half-cells
concentration cell
galvanic cell comprising half-cells of identical composition but for the concentration of one redox reactant or product
corrosion
degradation of metal via a natural electrochemical process
dry cell
primary battery, also called a zinc-carbon battery, based on the spontaneous oxidation of zinc by manganese(IV)
electrode potential (EX)

the potential of a cell in which the half-cell of interest acts as a cathode when connected to the standard hydrogen electrode
electrolysis
process using electrical energy to cause a nonspontaneous process to occur
electrolytic cell
electrochemical cell in which an external source of electrical power is used to drive an otherwise nonspontaneous process
Faraday’s constant (F)

charge on 1 mol of electrons; F = 96,485 C/mol e−
fuel cell
devices similar to galvanic cells that require a continuous feed of redox reactants; also called a flow battery
galvanic (voltaic) cell

electrochemical cell in which a spontaneous redox reaction takes place; also called a voltaic cell
galvanization
method of protecting iron or similar metals from corrosion by coating with a thin layer of more easily oxidized zinc.
half cell
component of a cell that contains the redox conjugate pair (“couple”) of a single reactant
inert electrode
electrode that conducts electrons to and from the reactants in a half-cell but that is not itself oxidized or reduced
lead acid battery

rechargeable battery commonly used in automobiles; it typically comprises six galvanic cells based on Pb half-reactions in
acidic solution
lithium ion battery

widely used rechargeable battery commonly used in portable electronic devices, based on lithium ion transfer between the
anode and cathode
Nernst equation
relating the potential of a redox system to its composition
nickel-cadmium battery
rechargeable battery based on Ni/Cd half-cells with applications similar to those of lithium ion batteries
primary cell
nonrechargeable battery, suitable for single use only
sacrificial anode
electrode constructed from an easily oxidized metal, often magnesium or zinc, used to prevent corrosion of metal objects via
cathodic protection
salt bridge
tube filled with inert electrolyte solution
secondary cell
battery designed to allow recharging
standard cell potential (E ∘

cell
)
the cell potential when all reactants and products are in their standard states (1 bar or 1 atm or gases; 1 M for solutes), usually at
298.15 K
standard electrode potential ((E ∘

X
) )
electrode potential measured under standard conditions (1 bar or 1 atm for gases; 1 M for solutes) usually at 298.15 K
standard hydrogen electrode (SHE)

half-cell based on hydrogen ion production, assigned a potential of exactly 0 V under standard state conditions, used as the
universal reference for measuring electrode potential
∘ ∘ ∘
E = E −E
cell cathode anode
∘ RT
E = ln K
cell nF
∘ 0.0257 V 0.0592 V
E = ln K = log K (at 298.15 K)
cell n n
∘ RT
Ecell = E − ln Q (Nernst equation)
cell nF
0.0592 V
Ecell = E°cell − log Q (at 298.15 K)
n
ΔG = −nFEcell
∘ ∘
ΔG = −nF E
cell
wele = wmax = −nF Ecell
Q=I×t=n×F
17.11: Summary
17.1 Review of Redox Chemistry
Redox reactions are defined by changes in reactant oxidation numbers, and those most relevant to electrochemistry involve actual
transfer of electrons. Aqueous phase redox processes often involve water or its characteristic ions, H+ and OH−, as reactants in
addition to the oxidant and reductant, and equations representing these reactions can be challenging to balance. The half-reaction
method is a systematic approach to balancing such equations that involves separate treatment of the oxidation and reduction half-
reactions.
17.2 Galvanic Cells

Galvanic cells are devices in which a spontaneous redox reaction occurs indirectly, with the oxidant and reductant redox couples
contained in separate half-cells. Electrons are transferred from the reductant (in the anode half-cell) to the oxidant (in the cathode
half-cell) through an external circuit, and inert solution phase ions are transferred between half-cells, through a salt bridge, to
maintain charge neutrality. The construction and composition of a galvanic cell may be succinctly represented using chemical
formulas and others symbols in the form of a cell schematic (cell notation).
17.3 Electrode and Cell Potentials

The property of potential, E, is the energy associated with the separation/transfer of charge. In electrochemistry, the potentials of
cells and half-cells are thermodynamic quantities that reflect the driving force or the spontaneity of their redox processes. The cell
potential of an electrochemical cell is the difference in between its cathode and anode. To permit easy sharing of half-cell potential
data, the standard hydrogen electrode (SHE) is assigned a potential of exactly 0 V and used to define a single electrode potential for
any given half-cell. The electrode potential of a half-cell, EX, is the cell potential of said half-cell acting as a cathode when
connected to a SHE acting as an anode. When the half-cell is operating under standard state conditions, its potential is the standard
electrode potential, E°X. Standard electrode potentials reflect the relative oxidizing strength of the half-reaction’s reactant, with
stronger oxidants exhibiting larger (more positive) E°X values. Tabulations of standard electrode potentials may be used to compute
standard cell potentials, E°cell, for many redox reactions. The arithmetic sign of a cell potential indicates the spontaneity of the cell
reaction, with positive values for spontaneous reactions and negative values for nonspontaneous reactions (spontaneous in the
reverse direction).
17.4 Potential, Free Energy, and Equilibrium

Potential is a thermodynamic quantity reflecting the intrinsic driving force of a redox process, and it is directly related to the free
energy change and equilibrium constant for the process. For redox processes taking place in electrochemical cells, the maximum
(electrical) work done by the system is easily computed from the cell potential and the reaction stoichiometry and is equal to the
free energy change for the process. The equilibrium constant for a redox reaction is logarithmically related to the reaction’s cell
potential, with larger (more positive) potentials indicating reactions with greater driving force that equilibrate when the reaction has
proceeded far towards completion (large value of K). Finally, the potential of a redox process varies with the composition of the
reaction mixture, being related to the reactions standard potential and the value of its reaction quotient, Q, as described by the
Nernst equation.
17.5 Batteries and Fuel Cells

Galvanic cells designed specifically to function as electrical power supplies are called batteries. A variety of both single-use
batteries (primary cells) and rechargeable batteries (secondary cells) are commercially available to serve a variety of applications,
with important specifications including voltage, size, and lifetime. Fuel cells, sometimes called flow batteries, are devices that
harness the energy of spontaneous redox reactions normally associated with combustion processes. Like batteries, fuel cells enable
the reaction’s electron transfer via an external circuit, but they require continuous input of the redox reactants (fuel and oxidant)
from an external reservoir. Fuel cells are typically much more efficient in converting the energy released by the reaction to useful
work in comparison to internal combustion engines.
17.6 Corrosion
Spontaneous oxidation of metals by natural electrochemical processes is called corrosion, familiar examples including the rusting
of iron and the tarnishing of silver. Corrosion process involve the creation of a galvanic cell in which different sites on the metal
object function as anode and cathode, with the corrosion taking place at the anodic site. Approaches to preventing corrosion of
metals include use of a protective coating of zinc (galvanization) and the use of sacrificial anodes connected to the metal object
(cathodic protection).
17.7 Electrolysis
Nonspontaneous redox processes may be forced to occur in electrochemical cells by the application of an appropriate potential
using an external power source—a process known as electrolysis. Electrolysis is the basis for certain ore refining processes, the
industrial production of many chemical commodities, and the electroplating of metal coatings on various products. Measurement of
the current flow during electrolysis permits stoichiometric calculations.
17.12: Exercises
17.12.0.1: 17.1 Review of Redox Chemistry
1.
Identify each half-reaction below as either oxidation or reduction.
(a) Fe 3+
+ 3e
−
⟶ Fe
(b) Cr ⟶ Cr
3+
+ 3e
−
(c) MnO 4
2−
⟶ MnO 4
−
+e
−
(d) Li +
+e
−
⟶ Li
2.
Identify each half-reaction below as either oxidation or reduction.
(a) Cl −
⟶ Cl2
(b) Mn 2+
⟶ MnO 2
(c) H 2 ⟶ H
+
(d) NO 3
−
⟶ NO
3.
Assuming each pair of half-reactions below takes place in an acidic solution, write a balanced equation for the overall reaction.
(a) Ca ⟶ Ca
2+
+ 2e
−
, F2 + 2e
−
⟶ 2F
−
(b) Li ⟶ Li
+
+e
−
, Cl2 + 2e
−
⟶ 2Cl
−
(c) Fe ⟶ Fe
3+
+ 3e
−
, Br 2 + 2e
−
⟶ 2Br
−
(d) Ag ⟶ Ag
+
+e
−
, MnO 4
−
+ 4H
+
+ 3e
−
⟶ MnO 2 + 2H2 O
4.
Balance the equations below assuming they occur in an acidic solution.
(a) H 2 O2 + Sn
2+
⟶ H2 O + Sn
4+
(b) PbO 2 + Hg ⟶ Hg2

2+
+ Pb
2+
(c) Al + Cr2 O7
2−
⟶ Al
3+
+ Cr
3+
5.
Identify the oxidant and reductant of each reaction of the previous exercise.
6.
Balance the equations below assuming they occur in a basic solution.
(a) SO 3
2−
(aq) + Cu(OH) (s) ⟶ SO 4
2
2−
(aq) + Cu(OH)(s)
(b) O 2 (g) + Mn(OH) 2 (s) ⟶ MnO 2 (s)
(c) NO 3
−
(aq) + H2 (g) ⟶ NO(g)
(d) Al(s) + CrO 4

2−
(aq) ⟶ Al(OH) (s) + Cr(OH)
3 4
−
(aq)
7.
Identify the oxidant and reductant of each reaction of the previous exercise.
8.
Why don’t hydroxide ions appear in equations for half-reactions occurring in acidic solution?
9.

Why don’t hydrogen ions appear in equations for half-reactions occurring in basic solution?
10.
Why must the charge balance in oxidation-reduction reactions?
17.12.0.1: 17.2 Galvanic Cells

11.
Write cell schematics for the following cell reactions, using platinum as an inert electrode as needed.
(a) Mg(s) + Ni 2+
(aq) ⟶ Mg
2+
(aq) + Ni(s)
(b) 2Ag +
(aq) + Cu(s) ⟶ Cu
2+
(aq) + 2Ag(s)
(c) Mn(s) + Sn(NO 3

)2 (aq) ⟶ Mn(NO )2 (aq) + Sn(s)
3
(d) 3CuNO 3 (aq) + Au(NO )3 (aq) ⟶ 3Cu(NO )2 (aq) + Au(s)

3 3
12.
Assuming the schematics below represent galvanic cells as written, identify the half-cell reactions occurring in each.
(a) Mg(s)│Mg 2+
(aq) ║Cu2+ (aq)│Cu(s)
(b) Ni(s)│ Ni 2+
║Ag
(aq)
+
(aq) │ Ag(s)
13.
Write a balanced equation for the cell reaction of each cell in the previous exercise.
14.
Balance each reaction below, and write a cell schematic representing the reaction as it would occur in a galvanic cell.
(a) Al(s) + Zr 4+
(aq) ⟶ Al
3+
(aq) + Zr(s)
(b) Ag +
(aq) + NO(g) ⟶ Ag(s) + NO3
−
(aq) (acidic solution)
(c) SiO 3
2−
(aq) + Mg(s) ⟶ Si(s) + Mg (OH) (s)
2
(basic solution)
(d) ClO 3
−
(aq) + MnO 2 (s) ⟶ Cl
−
(aq) + MnO 4
−
(aq) (basic solution)
15.
Identify the oxidant and reductant in each reaction of the previous exercise.
16.
From the information provided, use cell notation to describe the following systems:
(a) In one half-cell, a solution of Pt(NO3)2 forms Pt metal, while in the other half-cell, Cu metal goes into a Cu(NO3)2 solution with
all solute concentrations 1 M.
(b) The cathode consists of a gold electrode in a 0.55 M Au(NO3)3 solution and the anode is a magnesium electrode in 0.75 M
Mg(NO3)2 solution.
(c) One half-cell consists of a silver electrode in a 1 M AgNO3 solution, and in the other half-cell, a copper electrode in 1 M
Cu(NO3)2 is oxidized.
17.
Why is a salt bridge necessary in galvanic cells like the one in Figure 17.3?
18.
An active (metal) electrode was found to gain mass as the oxidation-reduction reaction was allowed to proceed. Was the electrode
an anode or a cathode? Explain.
19.
An active (metal) electrode was found to lose mass as the oxidation-reduction reaction was allowed to proceed. Was the electrode
an anode or a cathode? Explain.
20.

The masses of three electrodes (A, B, and C), each from three different galvanic cells, were measured before and after the cells
were allowed to pass current for a while. The mass of electrode A increased, that of electrode B was unchanged, and that of
electrode C decreased. Identify each electrode as active or inert, and note (if possible) whether it functioned as anode or cathode.
17.12.0.1: 17.3 Electrode and Cell Potentials

21.
Calculate the standard cell potential for each reaction below, and note whether the reaction is spontaneous under standard state
conditions.
(a) Mg(s) + Ni 2+
(aq) ⟶ Mg
2+
(aq) + Ni(s)
(b) 2Ag +
(aq) + Cu(s) ⟶ Cu
2+
(aq) + 2Ag(s)
(c) Mn(s) + Sn(NO 3

)2 (aq) ⟶ Mn(NO )2 (aq) + Sn(s)
3
(d) 3Fe(NO 3
)2 (aq) + Au(NO 3 )3 (aq) ⟶ 3Fe(NO3 )3 (aq) + Au(s)
22.
Calculate the standard cell potential for each reaction below, and note whether the reaction is spontaneous under standard state
conditions.
(a) Mn(s) + Ni 2+
(aq) ⟶ Mn
2+
(aq) + Ni(s)
(b) 3Cu 2+
(aq) + 2Al(s) ⟶ 2Al
3+
(aq) + 3Cu(s)
(c) Na(s) + LiNO 3 (aq) ⟶ NaNO3 (aq) + Li(s)
(d) Ca(NO 3
)2 (aq) + Ba(s) ⟶ Ba(NO )2 (aq) + Ca(s)
3
23.
Write the balanced cell reaction for the cell schematic below, calculate the standard cell potential, and note whether the reaction is
spontaneous under standard state conditions.
3+
Cu(s) │Cu2+ (aq)║Au │Au(s)
(aq)
24.
Determine the cell reaction and standard cell potential at 25 °C for a cell made from a cathode half-cell consisting of a silver
electrode in 1 M silver nitrate solution and an anode half-cell consisting of a zinc electrode in 1 M zinc nitrate. Is the reaction
spontaneous at standard conditions?
25.
Determine the cell reaction and standard cell potential at 25 °C for a cell made from an anode half-cell containing a cadmium
electrode in 1 M cadmium nitrate and a cathode half-cell consisting of an aluminum electrode in 1 M aluminum nitrate solution. Is
the reaction spontaneous at standard conditions?
26.
Write the balanced cell reaction for the cell schematic below, calculate the standard cell potential, and note whether the reaction is
spontaneous under standard state conditions.
+ −
Pt(s) │H2 (g)│H (aq) ║Br 2 (aq), Br │Pt(s)
(aq)
17.12.0.1: 17.4 Potential, Free Energy, and Equilibrium

27.
For each pair of standard cell potential and electron stoichiometry values below, calculate a corresponding standard free energy
change (kJ).
(a) 0.000 V, n = 2
(b) +0.434 V, n = 2
(c) −2.439 V, n = 1
28.

For each pair of standard free energy change and electron stoichiometry values below, calculate a corresponding standard cell
potential.
(a) 12 kJ/mol, n = 3
(b) −45 kJ/mol, n = 1
29.
Determine the standard cell potential and the cell potential under the stated conditions for the electrochemical reactions described
here. State whether each is spontaneous or nonspontaneous under each set of conditions at 298.15 K.
(a) Hg(l) + S 2−
(aq, 0.10 M ) + 2 Ag
+
(aq, 0.25 M ) ⟶ 2Ag(s) + HgS(s)
(b) The cell made from an anode half-cell consisting of an aluminum electrode in 0.015 M aluminum nitrate solution and a cathode
half-cell consisting of a nickel electrode in 0.25 M nickel(II) nitrate solution.
(c) The cell comprised of a half-cell in which aqueous bromine (1.0 M) is being oxidized to bromide ion (0.11 M) and a half-cell in
which Al3+ (0.023 M) is being reduced to aluminum metal.
30.
Determine ΔG and ΔG° for each of the reactions in the previous problem.
31.
Use the data in Appendix L to calculate equilibrium constants for the following reactions. Assume 298.15 K if no temperature is
given.
(a) AgCl(s) ⇌ Ag +
(aq) + Cl
−
(aq)
(b) CdS(s) ⇌ Cd 2+ 2−
(aq) + S (aq) at 377 K
(c) Hg 2+
(aq) + 4 Br
−
(aq) ⇌ [ HgBr ]
4
2−
(aq)
(d) H 2 O(l) ⇌ H
+
(aq) + OH
−
(aq) at 25 °C
17.12.0.1: 17.5 Batteries and Fuel Cells

32.
Consider a battery made from one half-cell that consists of a copper electrode in 1 M CuSO4 solution and another half-cell that
consists of a lead electrode in 1 M Pb(NO3)2 solution.
(a) What is the standard cell potential for the battery?
(b) What are the reactions at the anode, cathode, and the overall reaction?
(c) Most devices designed to use dry-cell batteries can operate between 1.0 and 1.5 V. Could this cell be used to make a battery that
could replace a dry-cell battery? Why or why not.
(d) Suppose sulfuric acid is added to the half-cell with the lead electrode and some PbSO4(s) forms. Would the cell potential
increase, decrease, or remain the same?
33.
Consider a battery with the overall reaction: Cu(s) + 2Ag + 2+
(aq) ⟶ 2Ag(s) + Cu (aq).
(a) What is the reaction at the anode and cathode?

(b) A battery is “dead” when its cell potential is zero. What is the value of Q when this battery is dead?
(c) If a particular dead battery was found to have [Cu2+] = 0.11 M, what was the concentration of silver ion?
34.
Why do batteries go dead, but fuel cells do not?
35.
Use the Nernst equation to explain the drop in voltage observed for some batteries as they discharge.
36.

Using the information thus far in this chapter, explain why battery-powered electronics perform poorly in low temperatures.
17.12.0.1: 17.6 Corrosion

37.
Which member of each pair of metals is more likely to corrode (oxidize)?
(a) Mg or Ca
(b) Au or Hg
(c) Fe or Zn
(d) Ag or Pt
38.
Consider the following metals: Ag, Au, Mg, Ni, and Zn. Which of these metals could be used as a sacrificial anode in the cathodic
protection of an underground steel storage tank? Steel is an alloy composed mostly of iron, so use −0.447 V as the standard
reduction potential for steel.
39.
Aluminum (E ∘
Al
3+
/Al
= −2.07 V) is more easily oxidized than iron (E
∘
Fe
3+
/Fe
= −0.477 V ), and yet when both are exposed to
the environment, untreated aluminum has very good corrosion resistance while the corrosion resistance of untreated iron is poor.
What might explain this observation?
40.
If a sample of iron and a sample of zinc come into contact, the zinc corrodes but the iron does not. If a sample of iron comes into
contact with a sample of copper, the iron corrodes but the copper does not. Explain this phenomenon.
41.
Suppose you have three different metals, A, B, and C. When metals A and B come into contact, B corrodes and A does not corrode.
When metals A and C come into contact, A corrodes and C does not corrode. Based on this information, which metal corrodes and
which metal does not corrode when B and C come into contact?
42.
Why would a sacrificial anode made of lithium metal be a bad choice
17.12.0.1: 17.7 Electrolysis

43.
If a 2.5 A current flows through a circuit for 35 minutes, how many coulombs of charge moved through the circuit?
44.
For the scenario in the previous question, how many electrons moved through the circuit?
45.
Write the half-reactions and cell reaction occurring during electrolysis of each molten salt below.
(a) CaCl2
(b) LiH
(c) AlCl3
(d) CrBr3
46.
What mass of each product is produced in each of the electrolytic cells of the previous problem if a total charge of 3.33 × 105 C
passes through each cell?
47.
How long would it take to reduce 1 mole of each of the following ions using the current indicated?

(a) Al3+, 1.234 A
(b) Ca2+, 22.2 A
(c) Cr5+, 37.45 A
(d) Au3+, 3.57 A
48.
A current of 2.345 A passes through the cell shown in Figure 17.19 for 45 minutes. What is the volume of the hydrogen collected at
room temperature if the pressure is exactly 1 atm? (Hint: Is hydrogen the only gas present above the water?)
49.
An irregularly shaped metal part made from a particular alloy was galvanized with zinc using a Zn(NO3)2 solution. When a current
of 2.599 A was used, it took exactly 1 hour to deposit a 0.01123-mm layer of zinc on the part. What was the total surface area of
the part? The density of zinc is 7.140 g/cm3.

CHAPTER OVERVIEW
18: Representative Metals, Metalloids, and Nonmetals

General Chemistry
The development of the periodic table in the mid-1800s came from observations that there was a periodic relationship between the
properties of the elements. Chemists, who have an understanding of the variations of these properties, have been able to use this
knowledge to solve a wide variety of technical challenges. For example, silicon and other semiconductors form the backbone of
modern electronics because of our ability to fine-tune the electrical properties of these materials. This chapter explores important
properties of representative metals, metalloids, and nonmetals in the periodic table.
18.1: Introduction
18.2: Periodicity
18.14: Key Terms
18.15: Summary
18.16: Exercises
This page titled 18: Representative Metals, Metalloids, and Nonmetals is shared under a CC BY 4.0 license and was authored, remixed, and/or
upon request.
1
18.1: Introduction
Figure 18.1 Purity is extremely important when preparing silicon wafers. Technicians in a cleanroom prepare silicon without
impurities (left). The CEO of VLSI Research, Don Hutcheson, shows off a pure silicon wafer (center). A silicon wafer covered in
Pentium chips is an enlarged version of the silicon wafers found in many electronics used today (right). (credit middle:
modification of work by “Intel Free Press”/Flickr; credit right: modification of work by Naotake Murayama)
Chapter Outline
18.1 Periodicity
18.2 Occurrence and Preparation of the Representative Metals
18.3 Structure and General Properties of the Metalloids
18.4 Structure and General Properties of the Nonmetals
18.5 Occurrence, Preparation, and Compounds of Hydrogen
18.6 Occurrence, Preparation, and Properties of Carbonates
18.7 Occurrence, Preparation, and Properties of Nitrogen
18.8 Occurrence, Preparation, and Properties of Phosphorus
18.9 Occurrence, Preparation, and Compounds of Oxygen
18.10 Occurrence, Preparation, and Properties of Sulfur
18.11 Occurrence, Preparation, and Properties of Halogens
18.12 Occurrence, Preparation, and Properties of the Noble Gases
The development of the periodic table in the mid-1800s came from observations that there was a periodic relationship between the
properties of the elements. Chemists, who have an understanding of the variations of these properties, have been able to use this
knowledge to solve a wide variety of technical challenges. For example, silicon and other semiconductors form the backbone of
modern electronics because of our ability to fine-tune the electrical properties of these materials. This chapter explores important
properties of representative metals, metalloids, and nonmetals in the periodic table.
18.2: Periodicity

Classify elements
Make predictions about the periodicity properties of the representative elements
We begin this section by examining the behaviors of representative metals in relation to their positions in the periodic table. The
primary focus of this section will be the application of periodicity to the representative metals.
It is possible to divide elements into groups according to their electron configurations. The representative elements are elements
where the s and p orbitals are filling. The transition elements are elements where the d orbitals (groups 3–11 on the periodic table)
are filling, and the inner transition metals are the elements where the f orbitals are filling. The d orbitals fill with the elements in
group 11; therefore, the elements in group 12 qualify as representative elements because the last electron enters an s orbital. Metals
among the representative elements are the representative metals. Metallic character results from an element’s ability to lose its
outer valence electrons and results in high thermal and electrical conductivity, among other physical and chemical properties. There
are 20 nonradioactive representative metals in groups 1, 2, 3, 12, 13, 14, and 15 of the periodic table (the elements shaded in yellow
in Figure 18.2). The radioactive elements copernicium, flerovium, polonium, and livermorium are also metals but are beyond the
scope of this chapter.
In addition to the representative metals, some of the representative elements are metalloids. A metalloid is an element that has
properties that are between those of metals and nonmetals; these elements are typically semiconductors.
The remaining representative elements are nonmetals. Unlike metals, which typically form cations and ionic compounds
(containing ionic bonds), nonmetals tend to form anions or molecular compounds. In general, the combination of a metal and a
nonmetal produces a salt. A salt is an ionic compound consisting of cations and anions.

Figure 18.2 The location of the representative metals is shown in the periodic table. Nonmetals are shown in green, metalloids in
purple, and the transition metals and inner transition metals in blue.
Most of the representative metals do not occur naturally in an uncombined state because they readily react with water and oxygen
in the air. However, it is possible to isolate elemental beryllium, magnesium, zinc, cadmium, mercury, aluminum, tin, and lead from
their naturally occurring minerals and use them because they react very slowly with air. Part of the reason why these elements react
slowly is that these elements react with air to form a protective coating. The formation of this protective coating is passivation. The
coating is a nonreactive film of oxide or some other compound. Elemental magnesium, aluminum, zinc, and tin are important in the
fabrication of many familiar items, including wire, cookware, foil, and many household and personal objects. Although beryllium,
cadmium, mercury, and lead are readily available, there are limitations in their use because of their toxicity.
18.2.0.1: Group 1: The Alkali Metals

The alkali metals lithium, sodium, potassium, rubidium, cesium, and francium constitute group 1 of the periodic table. Although
hydrogen is in group 1 (and also in group 17), it is a nonmetal and deserves separate consideration later in this chapter. The name
alkali metal is in reference to the fact that these metals and their oxides react with water to form very basic (alkaline) solutions.
The properties of the alkali metals are similar to each other as expected for elements in the same family. The alkali metals have the
largest atomic radii and the lowest first ionization energy in their periods. This combination makes it very easy to remove the single
electron in the outermost (valence) shell of each. The easy loss of this valence electron means that these metals readily form stable
cations with a charge of 1+. Their reactivity increases with increasing atomic number due to the ease of losing the lone valence
electron (decreasing ionization energy). Since oxidation is so easy, the reverse, reduction, is difficult, which explains why it is hard
to isolate the elements. The solid alkali metals are very soft; lithium, shown in Figure 18.3, has the lowest density of any metal (0.5
g/cm3).
The alkali metals all react vigorously with water to form hydrogen gas and a basic solution of the metal hydroxide. This means they
are easier to oxidize than is hydrogen. As an example, the reaction of lithium with water is:
2Li(s) + 2H2 O(l) ⟶ 2LiOH(aq) + H2 (g)
Figure 18.3 Lithium floats in paraffin oil because its density is less than the density of paraffin oil.
Alkali metals react directly with all the nonmetals (except the noble gases) to yield binary ionic compounds containing 1+ metal
ions. These metals are so reactive that it is necessary to avoid contact with both moisture and oxygen in the air. Therefore, they are
stored in sealed containers under mineral oil, as shown in Figure 18.4, to prevent contact with air and moisture. The pure metals
never exist free (uncombined) in nature due to their high reactivity. In addition, this high reactivity makes it necessary to prepare
the metals by electrolysis of alkali metal compounds.

Figure 18.4 To prevent contact with air and water, potassium for laboratory use comes as sticks or beads stored under kerosene or
mineral oil, or in sealed containers. (credit: http://images-of-elements.com/potassium.php)
Unlike many other metals, the reactivity and softness of the alkali metals make these metals unsuitable for structural applications.
However, there are applications where the reactivity of the alkali metals is an advantage. For example, the production of metals
such as titanium and zirconium relies, in part, on the ability of sodium to reduce compounds of these metals. The manufacture of
many organic compounds, including certain dyes, drugs, and perfumes, utilizes reduction by lithium or sodium.
Sodium and its compounds impart a bright yellow color to a flame, as seen in Figure 18.5. Passing an electrical discharge through
sodium vapor also produces this color. In both cases, this is an example of an emission spectrum as discussed in the chapter on
electronic structure. Streetlights sometime employ sodium vapor lights because the sodium vapor penetrates fog better than most
other light. This is because the fog does not scatter yellow light as much as it scatters white light. The other alkali metals and their
salts also impart color to a flame. Lithium creates a bright, crimson color, whereas the others create a pale, violet color.

Figure 18.5 Dipping a wire into a solution of a sodium salt and then heating the wire causes emission of a bright yellow light,
characteristic of sodium.

This video demonstrates the reactions of the alkali metals with water.
18.2.0.1: Group 2: The Alkaline Earth Metals

The alkaline earth metals (beryllium, magnesium, calcium, strontium, barium, and radium) constitute group 2 of the periodic table.
The name alkaline metal comes from the fact that the oxides of the heavier members of the group react with water to form alkaline
solutions. The nuclear charge increases when going from group 1 to group 2. Because of this charge increase, the atoms of the
alkaline earth metals are smaller and have higher first ionization energies than the alkali metals within the same period. The higher
ionization energy makes the alkaline earth metals less reactive than the alkali metals; however, they are still very reactive elements.
Their reactivity increases, as expected, with increasing size and decreasing ionization energy. In chemical reactions, these metals
readily lose both valence electrons to form compounds in which they exhibit an oxidation state of 2+. Due to their high reactivity, it
is common to produce the alkaline earth metals, like the alkali metals, by electrolysis. Even though the ionization energies are low,
the two metals with the highest ionization energies (beryllium and magnesium) do form compounds that exhibit some covalent
characters. Like the alkali metals, the heavier alkaline earth metals impart color to a flame. As in the case of the alkali metals, this
is part of the emission spectrum of these elements. Calcium and strontium produce shades of red, whereas barium produces a green
color.
Magnesium is a silver-white metal that is malleable and ductile at high temperatures. Passivation decreases the reactivity of
magnesium metal. Upon exposure to air, a tightly adhering layer of magnesium oxycarbonate forms on the surface of the metal and
inhibits further reaction. (The carbonate comes from the reaction of carbon dioxide in the atmosphere.) Magnesium is the lightest
of the widely used structural metals, which is why most magnesium production is for lightweight alloys.
Magnesium (shown in Figure 18.6), calcium, strontium, and barium react with water and air. At room temperature, barium shows
the most vigorous reaction. The products of the reaction with water are hydrogen and the metal hydroxide. The formation of
hydrogen gas indicates that the heavier alkaline earth metals are better reducing agents (more easily oxidized) than is hydrogen. As
expected, these metals react with both acids and nonmetals to form ionic compounds. Unlike most salts of the alkali metals, many
of the common salts of the alkaline earth metals are insoluble in water because of the high lattice energies of these compounds,
containing a divalent metal ion.
Figure 18.6 From left to right: Mg(s), warm water at pH 7, and the resulting solution with a pH greater than 7, as indicated by the
pink color of the phenolphthalein indicator. (credit: modification of work by Sahar Atwa)
The potent reducing power of hot magnesium is useful in preparing some metals from their oxides. Indeed, magnesium’s affinity
for oxygen is so great that burning magnesium reacts with carbon dioxide, producing elemental carbon:

2Mg(s) + CO2 (g) ⟶ 2MgO(s) + C(s)
For this reason, a CO2 fire extinguisher will not extinguish a magnesium fire. Additionally, the brilliant white light emitted by
burning magnesium makes it useful in flares and fireworks.
18.2.0.1: Group 12
The elements in group 12 are transition elements; however, the last electron added is not a d electron, but an s electron. Since the
last electron added is an s electron, these elements qualify as representative metals, or post-transition metals. The group 12
elements behave more like the alkaline earth metals than transition metals. Group 12 contains the four elements zinc, cadmium,
mercury, and copernicium. Each of these elements has two electrons in its outer shell (ns2). When atoms of these metals form
cations with a charge of 2+, where the two outer electrons are lost, they have pseudo-noble gas electron configurations. Mercury is
sometimes an exception because it also exhibits an oxidation state of 1+ in compounds that contain a diatomic Hg 2
ion. In their
2+
elemental forms and in compounds, cadmium and mercury are both toxic.
Zinc is the most reactive in group 12, and mercury is the least reactive. (This is the reverse of the reactivity trend of the metals of
groups 1 and 2, in which reactivity increases down a group. The increase in reactivity with increasing atomic number only occurs
for the metals in groups 1 and 2.) The decreasing reactivity is due to the formation of ions with a pseudo-noble gas configuration
and to other factors that are beyond the scope of this discussion. The chemical behaviors of zinc and cadmium are quite similar to
each other but differ from that of mercury.
Zinc and cadmium have lower reduction potentials than hydrogen, and, like the alkali metals and alkaline earth metals, they will
produce hydrogen gas when they react with acids. The reaction of zinc with hydrochloric acid, shown in Figure 18.7, is:
+ − 2+ −
Zn(s) + 2H3 O (aq) + 2Cl (aq) ⟶ H2 (g) + Zn (aq) + 2Cl (aq) + 2H2 O(l)
Figure 18.7 Zinc is an active metal. It dissolves in hydrochloric acid, forming a solution of colorless Zn2+ ions, Cl– ions, and
hydrogen gas.
Zinc is a silvery metal that quickly tarnishes to a blue-gray appearance. This change in color is due to an adherent coating of a basic
carbonate, Zn2(OH)2CO3, which passivates the metal to inhibit further corrosion. Dry cell and alkaline batteries contain a zinc
anode. Brass (Cu and Zn) and some bronze (Cu, Sn, and sometimes Zn) are important zinc alloys. About half of zinc production
serves to protect iron and other metals from corrosion. This protection may take the form of a sacrificial anode (also known as a
galvanic anode, which is a means of providing cathodic protection for various metals) or as a thin coating on the protected metal.
Galvanized steel is steel with a protective coating of zinc.

18.2.0.0.1: Sacrificial Anodes
A sacrificial anode, or galvanic anode, is a means of providing cathodic protection of various metals. Cathodic protection
refers to the prevention of corrosion by converting the corroding metal into a cathode. As a cathode, the metal resists corrosion,

which is an oxidation process. Corrosion occurs at the sacrificial anode instead of at the cathode.
The construction of such a system begins with the attachment of a more active metal (more negative reduction potential) to the
metal needing protection. Attachment may be direct or via a wire. To complete the circuit, a salt bridge is necessary. This salt
bridge is often seawater or ground water. Once the circuit is complete, oxidation (corrosion) occurs at the anode and not the
cathode.
The commonly used sacrificial anodes are magnesium, aluminum, and zinc. Magnesium has the most negative reduction
potential of the three and serves best when the salt bridge is less efficient due to a low electrolyte concentration such as in
freshwater. Zinc and aluminum work better in saltwater than does magnesium. Aluminum is lighter than zinc and has a higher
capacity; however, an oxide coating may passivate the aluminum. In special cases, other materials are useful. For example, iron
will protect copper.
Mercury is very different from zinc and cadmium. Mercury is the only metal that is liquid at 25 °C. Many metals dissolve in
mercury, forming solutions called amalgams (see the feature on Amalgams), which are alloys of mercury with one or more other
metals. Mercury, shown in Figure 18.8, is a nonreactive element that is more difficult to oxidize than hydrogen. Thus, it does not
displace hydrogen from acids; however, it will react with strong oxidizing acids, such as nitric acid:
Hg(l) + HCl(aq) ⟶ no reaction
3Hg(l) + 8HNO3 (aq) ⟶ 3Hg (NO3 )2 (aq) + 4H2 O(l) + 2NO(g)
The clear NO initially formed quickly undergoes further oxidation to the reddish brown NO2.
Figure 18.8 From left to right: Hg(l), Hg + concentrated HCl, Hg + concentrated HNO3. (credit: Sahar Atwa)
Most mercury compounds decompose when heated. Most mercury compounds contain mercury with a 2+-oxidation state. When
there is a large excess of mercury, it is possible to form compounds containing the Hg ion. All mercury compounds are toxic,
2
2+
and it is necessary to exercise great care in their synthesis.

18.2.0.0.2: Amalgams
An amalgam is an alloy of mercury with one or more other metals. This is similar to considering steel to be an alloy of iron
with other metals. Most metals will form an amalgam with mercury, with the main exceptions being iron, platinum, tungsten,
and tantalum.
Due to toxicity issues with mercury, there has been a significant decrease in the use of amalgams. Historically, amalgams were
important in electrolytic cells and in the extraction of gold. Amalgams of the alkali metals still find use because they are strong
reducing agents and easier to handle than the pure alkali metals.

Prospectors had a problem when they found finely divided gold. They learned that adding mercury to their pans collected the
gold into the mercury to form an amalgam for easier collection. Unfortunately, losses of small amounts of mercury over the
years left many streams in California polluted with mercury.
Dentists use amalgams containing silver and other metals to fill cavities. There are several reasons to use an amalgam
including low cost, ease of manipulation, and longevity compared to alternate materials. Dental amalgams are approximately
50% mercury by weight, which, in recent years, has become a concern due to the toxicity of mercury.
After reviewing the best available data, the Food and Drug Administration (FDA) considers amalgam-based fillings to be safe
for adults and children over six years of age. Even with multiple fillings, the mercury levels in the patients remain far below
the lowest levels associated with harm. Clinical studies have found no link between dental amalgams and health problems.
Health issues may not be the same in cases of children under six or pregnant women. The FDA conclusions are in line with the
opinions of the Environmental Protection Agency (EPA) and Centers for Disease Control (CDC). The only health
consideration noted is that some people are allergic to the amalgam or one of its components.
18.2.0.1: Group 13
Group 13 contains the metalloid boron and the metals aluminum, gallium, indium, and thallium. The lightest element, boron, is
semiconducting, and its binary compounds tend to be covalent and not ionic. The remaining elements of the group are metals, but
their oxides and hydroxides change characters. The oxides and hydroxides of aluminum and gallium exhibit both acidic and basic
behaviors. A substance, such as these two, that will react with both acids and bases is amphoteric. This characteristic illustrates the
combination of nonmetallic and metallic behaviors of these two elements. Indium and thallium oxides and hydroxides exhibit only
basic behavior, in accordance with the clearly metallic character of these two elements. The melting point of gallium is unusually
low (about 30 °C) and will melt in your hand.
Aluminum is amphoteric because it will react with both acids and bases. A typical reaction with an acid is:
2Al(s) + 6HCl(aq) ⟶ 2AlCl3 (aq) + 3H2 (g)
The products of the reaction of aluminum with a base depend upon the reaction conditions, with the following being one
possibility:
2Al(s) + 2NaOH(aq) + 6H2 O(l) ⟶ 2Na [Al (OH) ] (aq) + 3H2 (g)
4
With both acids and bases, the reaction with aluminum generates hydrogen gas.
The group 13 elements have a valence shell electron configuration of ns2np1. Aluminum normally uses all of its valence electrons
when it reacts, giving compounds in which it has an oxidation state of 3+. Although many of these compounds are covalent, others,
such as AlF3 and Al2(SO4)3, are ionic. Aqueous solutions of aluminum salts contain the cation [Al(H O) ] , abbreviated as Al3+
2 6
3+
(aq). Gallium, indium, and thallium also form ionic compounds containing M3+ ions. These three elements exhibit not only the
expected oxidation state of 3+ from the three valence electrons but also an oxidation state (in this case, 1+) that is two below the
expected value. This phenomenon, the inert pair effect, refers to the formation of a stable ion with an oxidation state two lower than
expected for the group. The pair of electrons is the valence s orbital for those elements. In general, the inert pair effect is important
for the lower p-block elements. In an aqueous solution, the Tl+(aq) ion is more stable than is Tl3+(aq). In general, these metals will
react with air and water to form 3+ ions; however, thallium reacts to give thallium(I) derivatives. The metals of group 13 all react
directly with nonmetals such as sulfur, phosphorus, and the halogens, forming binary compounds.
The metals of group 13 (Al, Ga, In, and Tl) are all reactive. However, passivation occurs as a tough, hard, thin film of the metal
oxide forms upon exposure to air. Disruption of this film may counter the passivation, allowing the metal to react. One way to
disrupt the film is to expose the passivated metal to mercury. Some of the metal dissolves in the mercury to form an amalgam,
which sheds the protective oxide layer to expose the metal to further reaction. The formation of an amalgam allows the metal to
react with air and water.

Although easily oxidized, the passivation of aluminum makes it very useful as a strong, lightweight building material. Because
of the formation of an amalgam, mercury is corrosive to structural materials made of aluminum. This video demonstrates how
the integrity of an aluminum beam can be destroyed by the addition of a small amount of elemental mercury.

The most important uses of aluminum are in the construction and transportation industries, and in the manufacture of aluminum
cans and aluminum foil. These uses depend on the lightness, toughness, and strength of the metal, as well as its resistance to
corrosion. Because aluminum is an excellent conductor of heat and resists corrosion, it is useful in the manufacture of cooking
utensils.
Aluminum is a very good reducing agent and may replace other reducing agents in the isolation of certain metals from their oxides.
Although more expensive than reduction by carbon, aluminum is important in the isolation of Mo, W, and Cr from their oxides.
18.2.0.1: Group 14
The metallic members of group 14 are tin, lead, and flerovium. Carbon is a typical nonmetal. The remaining elements of the group,
silicon and germanium, are examples of semimetals or metalloids. Tin and lead form the stable divalent cations, Sn2+ and Pb2+,
with oxidation states two below the group oxidation state of 4+. The stability of this oxidation state is a consequence of the inert
pair effect. Tin and lead also form covalent compounds with a formal 4+-oxidation state. For example, SnCl4 and PbCl4 are low-
boiling covalent liquids.
Figure 18.9 (a) Tin(II) chloride is an ionic solid; (b) tin(IV) chloride is a covalent liquid.
Tin reacts readily with nonmetals and acids to form tin(II) compounds (indicating that it is more easily oxidized than hydrogen) and
with nonmetals to form either tin(II) or tin(IV) compounds (shown in Figure 18.9), depending on the stoichiometry and reaction
conditions. Lead is less reactive. It is only slightly easier to oxidize than hydrogen, and oxidation normally requires a hot
concentrated acid.
Many of these elements exist as allotropes. Allotropes are two or more forms of the same element in the same physical state with
different chemical and physical properties. There are two common allotropes of tin. These allotropes are grey (brittle) tin and white
tin. As with other allotropes, the difference between these forms of tin is in the arrangement of the atoms. White tin is stable above
13.2 °C and is malleable like other metals. At low temperatures, gray tin is the more stable form. Gray tin is brittle and tends to
break down to a powder. Consequently, articles made of tin will disintegrate in cold weather, particularly if the cold spell is lengthy.
The change progresses slowly from the spot of origin, and the gray tin that is first formed catalyzes further change. In a way, this
effect is similar to the spread of an infection in a plant or animal body, leading people to call this process tin disease or tin pest.
The principal use of tin is in the coating of steel to form tin plate-sheet iron, which constitutes the tin in tin cans. Important tin
alloys are bronze (Cu and Sn) and solder (Sn and Pb). Lead is important in the lead storage batteries in automobiles.
18.2.0.1: Group 15
Bismuth, the heaviest member of group 15, is a less reactive metal than the other representative metals. It readily gives up three of
its five valence electrons to active nonmetals to form the tri-positive ion, Bi3+. It forms compounds with the group oxidation state
of 5+ only when treated with strong oxidizing agents. The stability of the 3+-oxidation state is another example of the inert pair
effect.

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Identify natural sources of representative metals
Describe electrolytic and chemical reduction processes used to prepare these elements from natural sources
Because of their reactivity, we do not find most representative metals as free elements in nature. However, compounds that contain
ions of most representative metals are abundant. In this section, we will consider the two common techniques used to isolate the
metals from these compounds—electrolysis and chemical reduction.
These metals primarily occur in minerals, with lithium found in silicate or phosphate minerals, and sodium and potassium found in
salt deposits from evaporation of ancient seas and in silicates. The alkaline earth metals occur as silicates and, with the exception of
beryllium, as carbonates and sulfates. Beryllium occurs as the mineral beryl, Be3Al2Si6O18, which, with certain impurities, may be
either the gemstone emerald or aquamarine. Magnesium is in seawater and, along with the heavier alkaline earth metals, occurs as
silicates, carbonates, and sulfates. Aluminum occurs abundantly in many types of clay and in bauxite, an impure aluminum oxide
hydroxide. The principle tin ore is the oxide cassiterite, SnO2, and the principle lead and thallium ores are the sulfides or the
products of weathering of the sulfides. The remaining representative metals occur as impurities in zinc or aluminum ores.
18.3.0.1: Electrolysis
Ions of metals in of groups 1 and 2, along with aluminum, are very difficult to reduce; therefore, it is necessary to prepare these
elements by electrolysis, an important process discussed in the chapter on electrochemistry. Briefly, electrolysis involves using
electrical energy to drive unfavorable chemical reactions to completion; it is useful in the isolation of reactive metals in their pure
forms. Sodium, aluminum, and magnesium are typical examples.
18.3.0.0.1: The Preparation of Sodium
The most important method for the production of sodium is the electrolysis of molten sodium chloride; the set-up is a Downs cell,
shown in Figure 18.10. The reaction involved in this process is:
electrolysis
2NaCl(l) −−−−−−−→ 2Na(l) + Cl2 (g)

600 °C
The electrolysis cell contains molten sodium chloride (melting point 801 °C), to which calcium chloride has been added to lower
the melting point to 600 °C (a colligative effect). The passage of a direct current through the cell causes the sodium ions to migrate
to the negatively charged cathode and pick up electrons, reducing the ions to sodium metal. Chloride ions migrate to the positively
charged anode, lose electrons, and undergo oxidation to chlorine gas. The overall cell reaction comes from adding the following
reactions:
+ −
at the cathode: 2Na + 2e ⟶ 2Na(l)
− −
at the anode: 2Cl ⟶ Cl2 (g) + 2e
+ −
overall change: 2Na + 2Cl ⟶ 2Na(l) + Cl2 (g)
Separation of the molten sodium and chlorine prevents recombination. The liquid sodium, which is less dense than molten sodium
chloride, floats to the surface and flows into a collector. The gaseous chlorine goes to storage tanks. Chlorine is also a valuable
product.

Figure 18.10 Pure sodium metal is isolated by electrolysis of molten sodium chloride using a Downs cell. It is not possible to
isolate sodium by electrolysis of aqueous solutions of sodium salts because hydrogen ions are more easily reduced than are sodium
ions; as a result, hydrogen gas forms at the cathode instead of the desired sodium metal. The high temperature required to melt
NaCl means that liquid sodium metal forms.
18.3.0.0.2: The Preparation of Aluminum
The preparation of aluminum utilizes a process invented in 1886 by Charles M. Hall, who began to work on the problem while a
student at Oberlin College in Ohio. Paul L. T. Héroult discovered the process independently a month or two later in France. In
honor to the two inventors, this electrolysis cell is known as the Hall–Héroult cell. The Hall–Héroult cell is an electrolysis cell for
the production of aluminum. Figure 18.11 illustrates the Hall–Héroult cell.
The production of aluminum begins with the purification of bauxite, the most common source of aluminum. The reaction of
bauxite, AlO(OH), with hot sodium hydroxide forms soluble sodium aluminate, while clay and other impurities remain
undissolved:
AlO(OH)(s) + NaOH(aq) + H2 O(l) ⟶ Na[Al (OH) ](aq)
4
After the removal of the impurities by filtration, the addition of acid to the aluminate leads to the reprecipitation of aluminum
hydroxide:
+ +
Na[Al (OH) ](aq) + H3 O (aq) ⟶ Al (OH) (s) + Na (aq) + 2H2 O(l)
4 3
The next step is to remove the precipitated aluminum hydroxide by filtration. Heating the hydroxide produces aluminum oxide,
Al2O3, which dissolves in a molten mixture of cryolite, Na3AlF6, and calcium fluoride, CaF2. Electrolysis of this solution takes

place in a cell like that shown in Figure 18.11. Reduction of aluminum ions to the metal occurs at the cathode, while oxygen,
carbon monoxide, and carbon dioxide form at the anode.
Figure 18.11 An electrolytic cell is used for the production of aluminum. The electrolysis of a solution of cryolite and calcium
fluoride results in aluminum metal at the cathode, and oxygen, carbon monoxide, and carbon dioxide at the anode.
18.3.0.0.3: The Preparation of Magnesium
Magnesium is the other metal that is isolated in large quantities by electrolysis. Seawater, which contains approximately 0.5%
magnesium chloride, serves as the major source of magnesium. Addition of calcium hydroxide to seawater precipitates magnesium
hydroxide. The addition of hydrochloric acid to magnesium hydroxide, followed by evaporation of the resultant aqueous solution,
leaves pure magnesium chloride. The electrolysis of molten magnesium chloride forms liquid magnesium and chlorine gas:
MgCl2 (aq) + Ca (OH) (aq) ⟶ Mg (OH) (s) + CaCl2 (aq)
2 2
Mg (OH) 2 (s) + 2HCl(aq) ⟶ MgCl2 (aq) + 2H2 O(l)
MgCl2 (l) ⟶ Mg(l) + Cl2 (g)
Some production facilities have moved away from electrolysis completely. In the next section, we will see how the Pidgeon process
leads to the chemical reduction of magnesium.
18.3.0.1: Chemical Reduction

It is possible to isolate many of the representative metals by chemical reduction using other elements as reducing agents. In general,
chemical reduction is much less expensive than electrolysis, and for this reason, chemical reduction is the method of choice for the
isolation of these elements. For example, it is possible to produce potassium, rubidium, and cesium by chemical reduction, as it is
possible to reduce the molten chlorides of these metals with sodium metal. This may be surprising given that these metals are more
reactive than sodium; however, the metals formed are more volatile than sodium and can be distilled for collection. The removal of
the metal vapor leads to a shift in the equilibrium to produce more metal (see how reactions can be driven in the discussions of Le
Châtelier’s principle in the chapter on fundamental equilibrium concepts).
The production of magnesium, zinc, and tin provide additional examples of chemical reduction.

18.3.0.0.1: The Preparation of Magnesium
The Pidgeon process involves the reaction of magnesium oxide with elemental silicon at high temperatures to form pure
magnesium:
Δ
Si(s) + 2MgO(s) −→ SiO2 (s) + 2Mg(g)
Although this reaction is unfavorable in terms of thermodynamics, the removal of the magnesium vapor produced takes advantage
of Le Châtelier’s principle to continue the forward progress of the reaction. Over 75% of the world’s production of magnesium,
primarily in China, comes from this process.
18.3.0.0.2: The Preparation of Zinc
Zinc ores usually contain zinc sulfide, zinc oxide, or zinc carbonate. After separation of these compounds from the ores, heating in
air converts the ore to zinc oxide by one of the following reactions:
Δ
2ZnS(s) + 3O2 (g) −→ 2ZnO(s) + 2SO2 (g)
Δ
ZnCO3 (s) −→ ZnO(s) + CO2 (g)
Carbon, in the form of coal, reduces the zinc oxide to form zinc vapor:
ZnO(s) + C(s) ⟶ Zn(g) + CO(g)
The zinc can be distilled (boiling point 907 °C) and condensed. This zinc contains impurities of cadmium (767 °C), iron (2862 °C),
lead (1750 °C), and arsenic (613 °C). Careful redistillation produces pure zinc. Arsenic and cadmium are distilled from the zinc
because they have lower boiling points. At higher temperatures, the zinc is distilled from the other impurities, mainly lead and iron.
18.3.0.0.3: The Preparation of Tin
The ready reduction of tin(IV) oxide by the hot coals of a campfire accounts for the knowledge of tin in the ancient world. In the
modern process, the roasting of tin ores containing SnO2 removes contaminants such as arsenic and sulfur as volatile oxides.
Treatment of the remaining material with hydrochloric acid removes the oxides of other metals. Heating the purified ore with
carbon at temperature above 1000 °C produces tin:
Δ
SnO 2 (s) + 2C(s) −→ Sn(s) + 2CO(g)
The molten tin collects at the bottom of the furnace and is drawn off and cast into blocks.
This page titled 18.3: Occurrence and Preparation of the Representative Metals is shared under a CC BY 4.0 license and was authored, remixed,


Describe the general preparation, properties, and uses of the metalloids
Describe the preparation, properties, and compounds of boron and silicon
A series of six elements called the metalloids separate the metals from the nonmetals in the periodic table. The metalloids are
boron, silicon, germanium, arsenic, antimony, and tellurium. These elements look metallic; however, they do not conduct electricity
as well as metals so they are semiconductors. They are semiconductors because their electrons are more tightly bound to their
nuclei than are those of metallic conductors. Their chemical behavior falls between that of metals and nonmetals. For example, the
pure metalloids form covalent crystals like the nonmetals, but like the metals, they generally do not form monatomic anions. This
intermediate behavior is in part due to their intermediate electronegativity values. In this section, we will briefly discuss the
chemical behavior of metalloids and deal with two of these elements—boron and silicon—in more detail.
The metalloid boron exhibits many similarities to its neighbor carbon and its diagonal neighbor silicon. All three elements form
covalent compounds. However, boron has one distinct difference in that its 2s22p1 outer electron structure gives it one less valence
electron than it has valence orbitals. Although boron exhibits an oxidation state of 3+ in most of its stable compounds, this electron
deficiency provides boron with the ability to form other, sometimes fractional, oxidation states, which occur, for example, in the
boron hydrides.
Silicon has the valence shell electron configuration 3s23p2, and it commonly forms tetrahedral structures in which it is sp3
hybridized with a formal oxidation state of 4+. The major differences between the chemistry of carbon and silicon result from the
relative strength of the carbon-carbon bond, carbon’s ability to form stable bonds to itself, and the presence of the empty 3d
valence-shell orbitals in silicon. Silicon’s empty d orbitals and boron’s empty p orbital enable tetrahedral silicon compounds and
trigonal planar boron compounds to act as Lewis acids. Carbon, on the other hand, has no available valence shell orbitals;
tetrahedral carbon compounds cannot act as Lewis acids. Germanium is very similar to silicon in its chemical behavior.
Arsenic and antimony generally form compounds in which an oxidation state of 3+ or 5+ is exhibited; however, arsenic can form
arsenides with an oxidation state of 3−. These elements tarnish only slightly in dry air but readily oxidize when warmed.
Tellurium combines directly with most elements. The most stable tellurium compounds are the tellurides—salts of Te2− formed
with active metals and lanthanides—and compounds with oxygen, fluorine, and chlorine, in which tellurium normally exhibits an
oxidation state 2+ or 4+. Although tellurium(VI) compounds are known (for example, TeF6), there is a marked resistance to
oxidation to this maximum group oxidation state.
18.4.0.1: Structures of the Metalloids

Covalent bonding is the key to the crystal structures of the metalloids. In this regard, these elements resemble nonmetals in their
behavior.
Elemental silicon, germanium, arsenic, antimony, and tellurium are lustrous, metallic-looking solids. Silicon and germanium
crystallize with a diamond structure. Each atom within the crystal has covalent bonds to four neighboring atoms at the corners of a
regular tetrahedron. Single crystals of silicon and germanium are giant, three-dimensional molecules. There are several allotropes
of arsenic with the most stable being layer like and containing puckered sheets of arsenic atoms. Each arsenic atom forms covalent
bonds to three other atoms within the sheet. The crystal structure of antimony is similar to that of arsenic, both shown in Figure
18.12. The structures of arsenic and antimony are similar to the structure of graphite, covered later in this chapter. Tellurium forms
crystals that contain infinite spiral chains of tellurium atoms. Each atom in the chain bonds to two other atoms.

Explore a cubic diamond crystal structure.

Figure 18.12 (a) Arsenic and (b) antimony have a layered structure similar to that of (c) graphite, except that the layers are
puckered rather than planar. (d) Elemental tellurium forms spiral chains.
Pure crystalline boron is transparent. The crystals consist of icosahedra, as shown in Figure 18.13, with a boron atom at each
corner. In the most common form of boron, the icosahedra pack together in a manner similar to the cubic closest packing of
spheres. All boron-boron bonds within each icosahedron are identical and are approximately 176 pm in length. In the different
forms of boron, there are different arrangements and connections between the icosahedra.
Figure 18.13 An icosahedron is a symmetrical, solid shape with 20 faces, each of which is an equilateral triangle. The faces meet at
12 corners.
The name silicon is derived from the Latin word for flint, silex. The metalloid silicon readily forms compounds containing Si-O-Si
bonds, which are of prime importance in the mineral world. This bonding capability is in contrast to the nonmetal carbon, whose
ability to form carbon-carbon bonds gives it prime importance in the plant and animal worlds.
18.4.0.1: Occurrence, Preparation, and Compounds of Boron and Silicon

Boron constitutes less than 0.001% by weight of the earth’s crust. In nature, it only occurs in compounds with oxygen. Boron is
widely distributed in volcanic regions as boric acid, B(OH)3, and in dry lake regions, including the desert areas of California, as
borates and salts of boron oxyacids, such as borax, Na2B4O7⋅10H2O.
Elemental boron is chemically inert at room temperature, reacting with only fluorine and oxygen to form boron trifluoride, BF3,
and boric oxide, B2O3, respectively. At higher temperatures, boron reacts with all nonmetals, except tellurium and the noble gases,
and with nearly all metals; it oxidizes to B2O3 when heated with concentrated nitric or sulfuric acid. Boron does not react with
nonoxidizing acids. Many boron compounds react readily with water to give boric acid, B(OH)3 (sometimes written as H3BO3).
Reduction of boric oxide with magnesium powder forms boron (95–98.5% pure) as a brown, amorphous powder:
B2 O3 (s) + 3Mg(s) ⟶ 2B(s) + 3MgO(s)

An amorphous substance is a material that appears to be a solid, but does not have a long-range order like a true solid. Treatment
with hydrochloric acid removes the magnesium oxide. Further purification of the boron begins with conversion of the impure boron
into boron trichloride. The next step is to heat a mixture of boron trichloride and hydrogen:
1500 °C
2BCl3 (g) + 3H2 (g) −−−−−→ 2B(s) + 6HCl(g) ΔH ° = 253.7 kJ
Silicon makes up nearly one-fourth of the mass of the earth’s crust—second in abundance only to oxygen. The crust is composed
almost entirely of minerals in which the silicon atoms are at the center of the silicon-oxygen tetrahedron, which connect in a variety
of ways to produce, among other things, chains, layers, and three-dimensional frameworks. These minerals constitute the bulk of
most common rocks, soil, and clays. In addition, materials such as bricks, ceramics, and glasses contain silicon compounds.
It is possible to produce silicon by the high-temperature reduction of silicon dioxide with strong reducing agents, such as carbon
and magnesium:
Δ
SiO2 (s) + 2C(s) −→ Si(s) + 2CO(g)
Δ
SiO2 (s) + 2Mg(s) −→ Si(s) + 2MgO(s)
Extremely pure silicon is necessary for the manufacture of semiconductor electronic devices. This process begins with the
conversion of impure silicon into silicon tetrahalides, or silane (SiH4), followed by decomposition at high temperatures. Zone
refining, illustrated in Figure 18.14, completes the purification. In this method, a rod of silicon is heated at one end by a heat source
that produces a thin cross-section of molten silicon. Slowly lowering the rod through the heat source moves the molten zone from
one end of the rod to other. As this thin, molten region moves, impurities in the silicon dissolve in the liquid silicon and move with
the molten region. Ultimately, the impurities move to one end of the rod, which is then cut off.

Figure 18.14 A zone-refining apparatus used to purify silicon.
This highly purified silicon, containing no more than one part impurity per million parts of silicon, is the most important element in
the computer industry. Pure silicon is necessary in semiconductor electronic devices such as transistors, computer chips, and solar
cells.
Like some metals, passivation of silicon occurs due the formation of a very thin film of oxide (primarily silicon dioxide, SiO2).
Silicon dioxide is soluble in hot aqueous base; thus, strong bases destroy the passivation. Removal of the passivation layer allows
the base to dissolve the silicon, forming hydrogen gas and silicate anions. For example:
− 4−
Si(s) + 4OH (aq) ⟶ SiO4 (aq) + 2H2 (g)
Silicon reacts with halogens at high temperatures, forming volatile tetrahalides, such as SiF4.
Unlike carbon, silicon does not readily form double or triple bonds. Silicon compounds of the general formula SiX4, where X is a
highly electronegative group, can act as Lewis acids to form six-coordinate silicon. For example, silicon tetrafluoride, SiF4, reacts
with sodium fluoride to yield Na2[SiF6], which contains the octahedral [SiF ] ion in which silicon is sp3d2 hybridized:
6
2−
2NaF(s) + SiF4 (g) ⟶ Na2 SiF6 (s)
Antimony reacts readily with stoichiometric amounts of fluorine, chlorine, bromine, or iodine, yielding trihalides or, with excess
fluorine or chlorine, forming the pentahalides SbF5 and SbCl5. Depending on the stoichiometry, it forms antimony(III) sulfide,
Sb2S3, or antimony(V) sulfide when heated with sulfur. As expected, the metallic nature of the element is greater than that of
arsenic, which lies immediately above it in group 15.
18.4.0.0.1: Boron and Silicon Halides
Boron trihalides—BF3, BCl3, BBr3, and BI3—can be prepared by the direct reaction of the elements. These nonpolar molecules
contain boron with sp2 hybridization and a trigonal planar molecular geometry. The fluoride and chloride compounds are colorless
gasses, the bromide is a liquid, and the iodide is a white crystalline solid.
Except for boron trifluoride, the boron trihalides readily hydrolyze in water to form boric acid and the corresponding hydrohalic
acid. Boron trichloride reacts according to the equation:
BCl3 (g) + 3H2 O(l) ⟶ B(OH) (aq) + 3HCl(aq)
3
Boron trifluoride reacts with hydrofluoric acid, to yield a solution of fluoroboric acid, HBF4:
+ −
BF 3 (aq) + HF(aq) + H2 O(l) ⟶ H3 O (aq) + BF 4 (aq)
In this reaction, the BF3 molecule acts as the Lewis acid (electron pair acceptor) and accepts a pair of electrons from a fluoride ion:
All the tetrahalides of silicon, SiX4, have been prepared. Silicon tetrachloride can be prepared by direct chlorination at elevated
temperatures or by heating silicon dioxide with chlorine and carbon:
Δ
SiO2 (s) + 2C(s) + 2Cl2 (g) −→ SiCl4 (g) + 2CO(g)
Silicon tetrachloride is a covalent tetrahedral molecule, which is a nonpolar, low-boiling (57 °C), colorless liquid.
It is possible to prepare silicon tetrafluoride by the reaction of silicon dioxide with hydrofluoric acid:
SiO2 (s) + 4HF(g) ⟶ SiF4 (g) + 2H2 O(l) ΔH ° = −191.2 kJ
Hydrofluoric acid is the only common acid that will react with silicon dioxide or silicates. This reaction occurs because the silicon-
fluorine bond is the only bond that silicon forms that is stronger than the silicon-oxygen bond. For this reason, it is possible to store
all common acids, other than hydrofluoric acid, in glass containers.
Except for silicon tetrafluoride, silicon halides are extremely sensitive to water. Upon exposure to water, SiCl4 reacts rapidly with
hydroxide groups, replacing all four chlorine atoms to produce unstable orthosilicic acid, Si(OH)4 or H4SiO4, which slowly

decomposes into SiO2.
18.4.0.0.2: Boron and Silicon Oxides and Derivatives
Boron burns at 700 °C in oxygen, forming boric oxide, B2O3. Boric oxide is necessary for the production of heat-resistant
borosilicate glass, like that shown in Figure 18.15 and certain optical glasses. Boric oxide dissolves in hot water to form boric acid,
B(OH)3:
B2 O3 (s) + 3H2 O(l) ⟶ 2B(OH) 3 (aq)
Figure 18.15 Laboratory glassware, such as Pyrex and Kimax, is made of borosilicate glass because it does not break when heated.
The inclusion of borates in the glass helps to mediate the effects of thermal expansion and contraction. This reduces the likelihood
of thermal shock, which causes silicate glass to crack upon rapid heating or cooling. (credit: “Tweenk”/Wikimedia Commons)
The boron atom in B(OH)3 is sp2 hybridized and is located at the center of an equilateral triangle with oxygen atoms at the corners.
In solid B(OH)3, hydrogen bonding holds these triangular units together. Boric acid, shown in Figure 18.16, is a very weak acid
that does not act as a proton donor but rather as a Lewis acid, accepting an unshared pair of electrons from the Lewis base OH−:
− + −10
B(OH) (aq) + 2H2 O(l) ⇌ B(OH) (aq) + H3 O (aq) Ka = 5.8 × 10
3 4
Figure 18.16 Boric acid has a planar structure with three –OH groups spread out equally at 120° angles from each other.
Heating boric acid to 100 °C causes molecules of water to split out between pairs of adjacent –OH groups to form metaboric acid,
HBO2. At about 150 °C, additional B-O-B linkages form, connecting the BO3 groups together with shared oxygen atoms to form
tetraboric acid, H2B4O7. Complete water loss, at still higher temperatures, results in boric oxide.
Borates are salts of the oxyacids of boron. Borates result from the reactions of a base with an oxyacid or from the fusion of boric
acid or boric oxide with a metal oxide or hydroxide. Borate anions range from the simple trigonal planar BO ion to complex
3
3−
species containing chains and rings of three- and four-coordinated boron atoms. The structures of the anions found in CaB2O4,
K[B5O6(OH)4]⋅2H2O (commonly written KB5O8⋅4H2O) and Na2[B4O5(OH)4]⋅8H2O (commonly written Na2B4O7⋅10H2O) are
shown in Figure 18.17. Commercially, the most important borate is borax, Na2[B4O5(OH)4]⋅8H2O, which is an important

component of some laundry detergents. Most of the supply of borax comes directly from dry lakes, such as Searles Lake in
California, or is prepared from kernite, Na2B4O7⋅4H2O.
Figure 18.17 The borate anions are (a) CaB2O4, (b) KB5O8⋅4H2O, and (c) Na2B4O7⋅10H2O. The anion in CaB2O4 is an “infinite”
chain.
Silicon dioxide, silica, occurs in both crystalline and amorphous forms. The usual crystalline form of silicon dioxide is quartz, a
hard, brittle, clear, colorless solid. It is useful in many ways—for architectural decorations, semiprecious jewels, and frequency
control in radio transmitters. Silica takes many crystalline forms, or polymorphs, in nature. Trace amounts of Fe3+ in quartz give
amethyst its characteristic purple color. The term quartz is also used for articles such as tubing and lenses that are manufactured
from amorphous silica. Opal is a naturally occurring form of amorphous silica.
The contrast in structure and physical properties between silicon dioxide and carbon dioxide is interesting, as illustrated in Figure
18.18. Solid carbon dioxide (dry ice) contains single CO2 molecules with each of the two oxygen atoms attached to the carbon
atom by double bonds. Very weak intermolecular forces hold the molecules together in the crystal. The volatility of dry ice reflect
these weak forces between molecules. In contrast, silicon dioxide is a covalent network solid. In silicon dioxide, each silicon atom
links to four oxygen atoms by single bonds directed toward the corners of a regular tetrahedron, and SiO4 tetrahedra share oxygen
atoms. This arrangement gives a three dimensional, continuous, silicon-oxygen network. A quartz crystal is a macromolecule of
silicon dioxide. The difference between these two compounds is the ability of the group 14 elements to form strong π bonds.
Second-period elements, such as carbon, form very strong π bonds, which is why carbon dioxide forms small molecules with
strong double bonds. Elements below the second period, such as silicon, do not form π bonds as readily as second-period elements,
and when they do form, the π bonds are weaker than those formed by second-period elements. For this reason, silicon dioxide does
not contain π bonds but only σ bonds.

Figure 18.18 Because carbon tends to form double and triple bonds and silicon does not, (a) carbon dioxide is a discrete molecule
with two C=O double bonds and (b) silicon dioxide is an infinite network of oxygen atoms bridging between silicon atoms with
each silicon atom possessing four Si-O single bonds. (credit a photo: modification of work by Erica Gerdes; credit b photo:
modification of work by Didier Descouens)
At 1600 °C, quartz melts to yield a viscous liquid. When the liquid cools, it does not crystallize readily but usually supercools and
forms a glass, also called silica. The SiO4 tetrahedra in glassy silica have a random arrangement characteristic of supercooled
liquids, and the glass has some very useful properties. Silica is highly transparent to both visible and ultraviolet light. For this
reason, it is important in the manufacture of lamps that give radiation rich in ultraviolet light and in certain optical instruments that
operate with ultraviolet light. The coefficient of expansion of silica glass is very low; therefore, rapid temperature changes do not
cause it to fracture. CorningWare and other ceramic cookware contain amorphous silica.
Silicates are salts containing anions composed of silicon and oxygen. In nearly all silicates, sp3-hybridized silicon atoms occur at
the centers of tetrahedra with oxygen at the corners. There is a variation in the silicon-to-oxygen ratio that occurs because silicon-
oxygen tetrahedra may exist as discrete, independent units or may share oxygen atoms at corners in a variety of ways. In addition,
the presence of a variety of cations gives rise to the large number of silicate minerals.
Many ceramics are composed of silicates. By including small amounts of other compounds, it is possible to modify the physical
properties of the silicate materials to produce ceramics with useful characteristics.
This page titled 18.4: Structure and General Properties of the Metalloids is shared under a CC BY 4.0 license and was authored, remixed, and/or
upon request.


Describe structure and properties of nonmetals
The nonmetals are elements located in the upper right portion of the periodic table. Their properties and behavior are quite different
from those of metals on the left side. Under normal conditions, more than half of the nonmetals are gases, one is a liquid, and the
rest include some of the softest and hardest of solids. The nonmetals exhibit a rich variety of chemical behaviors. They include the
most reactive and least reactive of elements, and they form many different ionic and covalent compounds. This section presents an
overview of the properties and chemical behaviors of the nonmetals, as well as the chemistry of specific elements. Many of these
nonmetals are important in biological systems.
In many cases, trends in electronegativity enable us to predict the type of bonding and the physical states in compounds involving
the nonmetals. We know that electronegativity decreases as we move down a given group and increases as we move from left to
right across a period. The nonmetals have higher electronegativities than do metals, and compounds formed between metals and
nonmetals are generally ionic in nature because of the large differences in electronegativity between them. The metals form cations,
the nonmetals form anions, and the resulting compounds are solids under normal conditions. On the other hand, compounds formed
between two or more nonmetals have small differences in electronegativity between the atoms, and covalent bonding—sharing of
electrons—results. These substances tend to be molecular in nature and are gases, liquids, or volatile solids at room temperature
and pressure.
In normal chemical processes, nonmetals do not form monatomic positive ions (cations) because their ionization energies are too
high. All monatomic nonmetal ions are anions; examples include the chloride ion, Cl−, the nitride ion, N3−, and the selenide ion,
Se2−.
The common oxidation states that the nonmetals exhibit in their ionic and covalent compounds are shown in Figure 18.19.
Remember that an element exhibits a positive oxidation state when combined with a more electronegative element and that it
exhibits a negative oxidation state when combined with a less electronegative element.
Figure 18.19 Nonmetals exhibit these common oxidation states in ionic and covalent compounds.
The first member of each nonmetal group exhibits different behaviors, in many respects, from the other group members. The
reasons for this include smaller size, greater ionization energy, and (most important) the fact that the first member of each group
has only four valence orbitals (one 2s and three 2p) available for bonding, whereas other group members have empty d orbitals in
their valence shells, making possible five, six, or even more bonds around the central atom. For example, nitrogen forms only NF3,
whereas phosphorus forms both PF3 and PF5.
Another difference between the first group member and subsequent members is the greater ability of the first member to form π
bonds. This is primarily a function of the smaller size of the first member of each group, which allows better overlap of atomic
orbitals. Nonmetals, other than the first member of each group, rarely form π bonds to nonmetals that are the first member of a
group. For example, sulfur-oxygen π bonds are well known, whereas sulfur does not normally form stable π bonds to itself.
The variety of oxidation states displayed by most of the nonmetals means that many of their chemical reactions involve changes in
oxidation state through oxidation-reduction reactions. There are five general aspects of the oxidation-reduction chemistry:
1. Nonmetals oxidize most metals. The oxidation state of the metal becomes positive as it undergoes oxidation and that of the
nonmetal becomes negative as it undergoes reduction. For example:

4Fe(s)+ 3O2 (g) ⟶ 2Fe2 O3 (s)
0 0 +3 −2
2. With the exception of nitrogen and carbon, which are poor oxidizing agents, a more electronegative nonmetal oxidizes a less
electronegative nonmetal or the anion of the nonmetal:
S(s)+ O2 (g) ⟶ 2SO2 (s)
0 0 +4 −2
− −
Cl2 (g)+ 2I (aq) ⟶ I2 (s) + 2Cl (aq)
0 0
3. Fluorine and oxygen are the strongest oxidizing agents within their respective groups; each oxidizes all the elements that lie
below it in the group. Within any period, the strongest oxidizing agent is in group 17. A nonmetal often oxidizes an element that
lies to its left in the same period. For example:
2As(s)+ 3Br2 (l) ⟶ 2AsBr 3 (s)
0 0 +3 −1
4. The stronger a nonmetal is as an oxidizing agent, the more difficult it is to oxidize the anion formed by the nonmetal. This
means that the most stable negative ions are formed by elements at the top of the group or in group 17 of the period.
5. Fluorine and oxygen are the strongest oxidizing elements known. Fluorine does not form compounds in which it exhibits
positive oxidation states; oxygen exhibits a positive oxidation state only when combined with fluorine. For example:
− −
2F2 (g)+ 2OH (aq) ⟶ OF 2 (g) + 2F (aq) + H2 O(l)
0 +2 −1
With the exception of most of the noble gases, all nonmetals form compounds with oxygen, yielding covalent oxides. Most of these
oxides are acidic, that is, they react with water to form oxyacids. Recall from the acid-base chapter that an oxyacid is an acid
consisting of hydrogen, oxygen, and some other element. Notable exceptions are carbon monoxide, CO, nitrous oxide, N2O, and
nitric oxide, NO. There are three characteristics of these acidic oxides:
1. Oxides such as SO2 and N2O5, in which the nonmetal exhibits one of its common oxidation states, are acid anhydrides and react
with water to form acids with no change in oxidation state. The product is an oxyacid. For example:
SO 2 (g) + H2 O(l) ⟶ H2 SO 3 (aq)
N2 O5 (s) + H2 O(l) ⟶ 2HNO3 (aq)
2. Those oxides such as NO2 and ClO2, in which the nonmetal does not exhibit one of its common oxidation states, also react with
water. In these reactions, the nonmetal is both oxidized and reduced. For example:
3NO2 (g)+ H2 O(l) ⟶ 2HNO3 (aq)+ NO(g)
+4 +5 +2
Reactions in which the same element is both oxidized and reduced are called disproportionation reactions.
3. The acid strength increases as the electronegativity of the central atom increases. To learn more, see the discussion in the
chapter on acid-base chemistry.
The binary hydrogen compounds of the nonmetals also exhibit an acidic behavior in water, although only HCl, HBr, and HI are
strong acids. The acid strength of the nonmetal hydrogen compounds increases from left to right across a period and down a group.
For example, ammonia, NH3, is a weaker acid than is water, H2O, which is weaker than is hydrogen fluoride, HF. Water, H2O, is
also a weaker acid than is hydrogen sulfide, H2S, which is weaker than is hydrogen selenide, H2Se. Weaker acidic character implies
greater basic character.
18.5.0.1: Structures of the Nonmetals

The structures of the nonmetals differ dramatically from those of metals. Metals crystallize in closely packed arrays that do not
contain molecules or covalent bonds. Nonmetal structures contain covalent bonds, and many nonmetals consist of individual

molecules. The electrons in nonmetals are localized in covalent bonds, whereas in a metal, there is delocalization of the electrons
throughout the solid.
The noble gases are all monatomic, whereas the other nonmetal gases—hydrogen, nitrogen, oxygen, fluorine, and chlorine—
normally exist as the diatomic molecules H2, N2, O2, F2, and Cl2. The other halogens are also diatomic; Br2 is a liquid and I2 exists
as a solid under normal conditions. The changes in state as one moves down the halogen family offer excellent examples of the
increasing strength of intermolecular London forces with increasing molecular mass and increasing polarizability.
Oxygen has two allotropes: O2, dioxygen, and O3, ozone. Phosphorus has three common allotropes, commonly referred to by their
colors: white, red, and black. Sulfur has several allotropes. There are also many carbon allotropes. Most people know of diamond,
graphite, and charcoal, but fewer people know of the recent discovery of fullerenes, carbon nanotubes, and graphene.
Descriptions of the physical properties of three nonmetals that are characteristic of molecular solids follow.
18.5.0.1: Carbon
Carbon occurs in the uncombined (elemental) state in many forms, such as diamond, graphite, charcoal, coke, carbon black,
graphene, and fullerene.
Diamond, shown in Figure 18.20, is a very hard crystalline material that is colorless and transparent when pure. Each atom forms
four single bonds to four other atoms at the corners of a tetrahedron (sp3 hybridization); this makes the diamond a giant molecule.
Carbon-carbon single bonds are very strong, and, because they extend throughout the crystal to form a three-dimensional network,
the crystals are very hard and have high melting points (~4400 °C).
Figure 18.20 (a) Diamond and (b) graphite are two forms of carbon. (c) In the crystal structure of diamond, the covalent bonds
form three-dimensional tetrahedrons. (d) In the crystal structure of graphite, each planar layer is composed of six-membered rings.
(credit a: modification of work by “Fancy Diamonds”/Flickr; credit b: modification of work from http://images-of-
elements.com/carbon.php)
Graphite, also shown in Figure 18.20, is a soft, slippery, grayish-black solid that conducts electricity. These properties relate to its
structure, which consists of layers of carbon atoms, with each atom surrounded by three other carbon atoms in a trigonal planar
arrangement. Each carbon atom in graphite forms three σ bonds, one to each of its nearest neighbors, by means of sp2-hybrid
orbitals. The unhybridized p orbital on each carbon atom will overlap unhybridized orbitals on adjacent carbon atoms in the same
layer to form π bonds. Many resonance forms are necessary to describe the electronic structure of a graphite layer; Figure 18.21
illustrates two of these forms.

Figure 18.21 (a) Carbon atoms in graphite have unhybridized p orbitals. Each p orbital is perpendicular to the plane of carbon
atoms. (b) These are two of the many resonance forms of graphite necessary to describe its electronic structure as a resonance
hybrid.
Atoms within a graphite layer are bonded together tightly by the σ and π bonds; however, the forces between layers are weak.
London dispersion forces hold the layers together. To learn more, see the discussion of these weak forces in the chapter on liquids
and solids. The weak forces between layers give graphite the soft, flaky character that makes it useful as the so-called “lead” in
pencils and the slippery character that makes it useful as a lubricant. The loosely held electrons in the resonating π bonds can move
throughout the solid and are responsible for the electrical conductivity of graphite.
Other forms of elemental carbon include carbon black, charcoal, and coke. Carbon black is an amorphous form of carbon prepared
by the incomplete combustion of natural gas, CH4. It is possible to produce charcoal and coke by heating wood and coal,
respectively, at high temperatures in the absence of air.
Recently, new forms of elemental carbon molecules have been identified in the soot generated by a smoky flame and in the vapor
produced when graphite is heated to very high temperatures in a vacuum or in helium. One of these new forms, first isolated by
Professor Richard Smalley and coworkers at Rice University, consists of icosahedral (soccer-ball-shaped) molecules that contain 60
carbon atoms, C60. This is buckminsterfullerene (often called bucky balls) after the architect Buckminster Fuller, who designed
domed structures, which have a similar appearance (Figure 18.22).

Figure 18.22 The molecular structure of C60, buckminsterfullerene, is icosahedral.

18.5.0.0.1: Nanotubes and Graphene
Graphene and carbon nanotubes are two recently discovered allotropes of carbon. Both of the forms bear some relationship to
graphite. Graphene is a single layer of graphite (one atom thick), as illustrated in Figure 18.23, whereas carbon nanotubes roll
the layer into a small tube, as illustrated in Figure 18.23.

Figure 18.23 (a) Graphene and (b) carbon nanotubes are both allotropes of carbon.
Graphene is a very strong, lightweight, and efficient conductor of heat and electricity discovered in 2003. As in graphite, the
carbon atoms form a layer of six-membered rings with sp2-hybridized carbon atoms at the corners. Resonance stabilizes the
system and leads to its conductivity. Unlike graphite, there is no stacking of the layers to give a three-dimensional structure.
Andre Geim and Kostya Novoselov at the University of Manchester won the 2010 Nobel Prize in Physics for their pioneering
work characterizing graphene.
The simplest procedure for preparing graphene is to use a piece of adhesive tape to remove a single layer of graphene from the
surface of a piece of graphite. This method works because there are only weak London dispersion forces between the layers in
graphite. Alternative methods are to deposit a single layer of carbon atoms on the surface of some other material (ruthenium,
iridium, or copper) or to synthesize it at the surface of silicon carbide via the sublimation of silicon.
There currently are no commercial applications of graphene. However, its unusual properties, such as high electron mobility
and thermal conductivity, should make it suitable for the manufacture of many advanced electronic devices and for thermal
management applications.
Carbon nanotubes are carbon allotropes, which have a cylindrical structure. Like graphite and graphene, nanotubes consist of
rings of sp2-hybridized carbon atoms. Unlike graphite and graphene, which occur in layers, the layers wrap into a tube and
bond together to produce a stable structure. The walls of the tube may be one atom or multiple atoms thick.

Carbon nanotubes are extremely strong materials that are harder than diamond. Depending upon the shape of the nanotube, it
may be a conductor or semiconductor. For some applications, the conducting form is preferable, whereas other applications
utilize the semiconducting form.
The basis for the synthesis of carbon nanotubes is the generation of carbon atoms in a vacuum. It is possible to produce carbon
atoms by an electrical discharge through graphite, vaporization of graphite with a laser, and the decomposition of a carbon
compound.
The strength of carbon nanotubes will eventually lead to some of their most exciting applications, as a thread produced from
several nanotubes will support enormous weight. However, the current applications only employ bulk nanotubes. The addition
of nanotubes to polymers improves the mechanical, thermal, and electrical properties of the bulk material. There are currently
nanotubes in some bicycle parts, skis, baseball bats, fishing rods, and surfboards.
18.5.0.1: Phosphorus
The name phosphorus comes from the Greek words meaning light bringing. When phosphorus was first isolated, scientists noted
that it glowed in the dark and burned when exposed to air. Phosphorus is the only member of its group that does not occur in the
uncombined state in nature; it exists in many allotropic forms. We will consider two of those forms: white phosphorus and red
phosphorus.
White phosphorus is a white, waxy solid that melts at 44.2 °C and boils at 280 °C. It is insoluble in water (in which it is stored—
see Figure 18.24), is very soluble in carbon disulfide, and bursts into flame in air. As a solid, as a liquid, as a gas, and in solution,
white phosphorus exists as P4 molecules with four phosphorus atoms at the corners of a regular tetrahedron, as illustrated in Figure
18.24. Each phosphorus atom covalently bonds to the other three atoms in the molecule by single covalent bonds. White
phosphorus is the most reactive allotrope and is very toxic.
Figure 18.24 (a) Because white phosphorus bursts into flame in air, it is stored in water. (b) The structure of white phosphorus
consists of P4 molecules arranged in a tetrahedron. (c) Red phosphorus is much less reactive than is white phosphorus. (d) The
structure of red phosphorus consists of networks of P4 tetrahedra joined by P-P single bonds. (credit a: modification of work from
http://images-of-elements.com/phosphorus.php)
Heating white phosphorus to 270–300 °C in the absence of air yields red phosphorus. Red phosphorus (shown in Figure 18.24) is
denser, has a higher melting point (~600 °C), is much less reactive, is essentially nontoxic, and is easier and safer to handle than is
white phosphorus. Its structure is highly polymeric and appears to contain three-dimensional networks of P4 tetrahedra joined by P-
P single bonds. Red phosphorus is insoluble in solvents that dissolve white phosphorus. When red phosphorus is heated, P4
molecules sublime from the solid.
18.5.0.1: Sulfur
The allotropy of sulfur is far greater and more complex than that of any other element. Sulfur is the brimstone referred to in the
Bible and other places, and references to sulfur occur throughout recorded history—right up to the relatively recent discovery that it
is a component of the atmospheres of Venus and of Io, a moon of Jupiter. The most common and most stable allotrope of sulfur is
yellow, rhombic sulfur, so named because of the shape of its crystals. Rhombic sulfur is the form to which all other allotropes
revert at room temperature. Crystals of rhombic sulfur melt at 113 °C. Cooling this liquid gives long needles of monoclinic sulfur.
This form is stable from 96 °C to the melting point, 119 °C. At room temperature, it gradually reverts to the rhombic form.
Both rhombic sulfur and monoclinic sulfur contain S8 molecules in which atoms form eight-membered, puckered rings that
resemble crowns, as illustrated in Figure 18.25. Each sulfur atom is bonded to each of its two neighbors in the ring by covalent S-S

single bonds.
Figure 18.25 These four sulfur allotropes show eight-membered, puckered rings. Each sulfur atom bonds to each of its two
neighbors in the ring by covalent S-S single bonds. Here are (a) individual S8 rings, (b) S8 chains formed when the rings open, (c)
longer chains formed by adding sulfur atoms to S8 chains, and (d) part of the very long sulfur chains formed at higher temperatures.
When rhombic sulfur melts, the straw-colored liquid is quite mobile; its viscosity is low because S8 molecules are essentially
spherical and offer relatively little resistance as they move past each other. As the temperature rises, S-S bonds in the rings break,
and polymeric chains of sulfur atoms result. These chains combine end to end, forming still longer chains that tangle with one
another. The liquid gradually darkens in color and becomes so viscous that finally (at about 230 °C) it does not pour easily. The
dangling atoms at the ends of the chains of sulfur atoms are responsible for the dark red color because their electronic structure
differs from those of sulfur atoms that have bonds to two adjacent sulfur atoms. This causes them to absorb light differently and
results in a different visible color. Cooling the liquid rapidly produces a rubberlike amorphous mass, called plastic sulfur.
Sulfur boils at 445 °C and forms a vapor consisting of S2, S6, and S8 molecules; at about 1000 °C, the vapor density corresponds to
the formula S2, which is a paramagnetic molecule like O2 with a similar electronic structure and a weak sulfur-sulfur double bond.

As seen in this discussion, an important feature of the structural behavior of the nonmetals is that the elements usually occur with
eight electrons in their valence shells. If necessary, the elements form enough covalent bonds to supplement the electrons already
present to possess an octet. For example, members of group 15 have five valence electrons and require only three additional
electrons to fill their valence shells. These elements form three covalent bonds in their free state: triple bonds in the N2 molecule or
single bonds to three different atoms in arsenic and phosphorus. The elements of group 16 require only two additional electrons.
Oxygen forms a double bond in the O2 molecule, and sulfur, selenium, and tellurium form two single bonds in various rings and
chains. The halogens form diatomic molecules in which each atom is involved in only one bond. This provides the electron
required necessary to complete the octet on the halogen atom. The noble gases do not form covalent bonds to other noble gas atoms
because they already have a filled outer shell.
This page titled 18.5: Structure and General Properties of the Nonmetals is shared under a CC BY 4.0 license and was authored, remixed, and/or
upon request.


Describe the properties, preparation, and compounds of hydrogen
Hydrogen is the most abundant element in the universe. The sun and other stars are composed largely of hydrogen. Astronomers
estimate that 90% of the atoms in the universe are hydrogen atoms. Hydrogen is a component of more compounds than any other
element. Water is the most abundant compound of hydrogen found on earth. Hydrogen is an important part of petroleum, many
minerals, cellulose and starch, sugar, fats, oils, alcohols, acids, and thousands of other substances.
At ordinary temperatures, hydrogen is a colorless, odorless, tasteless, and nonpoisonous gas consisting of the diatomic molecule
H2. Hydrogen is composed of three isotopes, and unlike other elements, these isotopes have different names and chemical symbols:
protium, 1H, deuterium, 2H (or “D”), and tritium 3H (or “T”). In a naturally occurring sample of hydrogen, there is one atom of
deuterium for every 7000 H atoms and one atom of radioactive tritium for every 1018 H atoms. The chemical properties of the
different isotopes are very similar because they have identical electron structures, but they differ in some physical properties
because of their differing atomic masses. Elemental deuterium and tritium have lower vapor pressure than ordinary hydrogen.
Consequently, when liquid hydrogen evaporates, the heavier isotopes are concentrated in the last portions to evaporate. Electrolysis
of heavy water, D2O, yields deuterium. Most tritium originates from nuclear reactions.
18.6.0.1: Preparation of Hydrogen

Elemental hydrogen must be prepared from compounds by breaking chemical bonds. The most common methods of preparing
hydrogen follow.
18.6.0.0.1: From Steam and Carbon or Hydrocarbons
Water is the cheapest and most abundant source of hydrogen. Passing steam over coke (an impure form of elemental carbon) at
1000 °C produces a mixture of carbon monoxide and hydrogen known as water gas:
1000 °C
C(s) + H2 O(g) −−−−−→ CO(g) + H2 (g)
water gas
Water gas is as an industrial fuel. It is possible to produce additional hydrogen by mixing the water gas with steam in the presence
of a catalyst to convert the CO to CO2. This reaction is the water gas shift reaction.
It is also possible to prepare a mixture of hydrogen and carbon monoxide by passing hydrocarbons from natural gas or petroleum
and steam over a nickel-based catalyst. Propane is an example of a hydrocarbon reactant:
900 °C
C3 H8 (g) + 3 H2 O(g) −−−−→ 3CO(g) + 7 H2 (g)
catalyst
18.6.0.0.2: Electrolysis
Hydrogen forms when direct current electricity passes through water containing an electrolyte such as H2SO4, as illustrated in
Figure 18.26. Bubbles of hydrogen form at the cathode, and oxygen evolves at the anode. The net reaction is:
2H2 O(l) + electrical energy ⟶ 2H2 (g) + O2 (g)

Figure 18.26 The electrolysis of water produces hydrogen and oxygen. Because there are twice as many hydrogen atoms as oxygen
atoms and both elements are diatomic, there is twice the volume of hydrogen produced at the cathode as there is oxygen produced
at the anode.
18.6.0.0.3: Reaction of Metals with Acids
This is the most convenient laboratory method of producing hydrogen. Metals with lower reduction potentials reduce the hydrogen
ion in dilute acids to produce hydrogen gas and metal salts. For example, as shown in Figure 18.27, iron in dilute hydrochloric acid
produces hydrogen gas and iron(II) chloride:
+ − 2+ −
Fe(s) + 2H3 O (aq) + 2Cl (aq) ⟶ Fe (aq) + 2Cl (aq) + H2 (g) + 2H2 O(l)

Figure 18.27 The reaction of iron with an acid produces hydrogen. Here, iron reacts with hydrochloric acid. (credit: Mark Ott)
18.6.0.0.4: Reaction of Ionic Metal Hydrides with Water
It is possible to produce hydrogen from the reaction of hydrides of the active metals, which contain the very strongly basic H−
anion, with water:
2+ −
CaH2 (s) + 2H2 O(l) ⟶ Ca (aq) + 2OH (aq) + 2H2 (g)
Metal hydrides are expensive but convenient sources of hydrogen, especially where space and weight are important factors. They
are important in the inflation of life jackets, life rafts, and military balloons.
18.6.0.1: Reactions
Under normal conditions, hydrogen is relatively inactive chemically, but when heated, it enters into many chemical reactions.
Two thirds of the world’s hydrogen production is devoted to the manufacture of ammonia, which is a fertilizer and used in the
manufacture of nitric acid. Large quantities of hydrogen are also important in the process of hydrogenation, discussed in the
chapter on organic chemistry.
It is possible to use hydrogen as a nonpolluting fuel. The reaction of hydrogen with oxygen is a very exothermic reaction, releasing
286 kJ of energy per mole of water formed. Hydrogen burns without explosion under controlled conditions. The oxygen-hydrogen
torch, because of the high heat of combustion of hydrogen, can achieve temperatures up to 2800 °C. The hot flame of this torch is
useful in cutting thick sheets of many metals. Liquid hydrogen is also an important rocket fuel (Figure 18.28).

Figure 18.28 Before the fleet’s retirement in 2011, liquid hydrogen and liquid oxygen were used in the three main engines of a
space shuttle. Two compartments in the large tank held these liquids until the shuttle was launched. (credit: “reynermedia”/Flickr)
An uncombined hydrogen atom consists of a nucleus and one valence electron in the 1s orbital. The n = 1 valence shell has a
capacity for two electrons, and hydrogen can rightfully occupy two locations in the periodic table. It is possible to consider
hydrogen a group 1 element because hydrogen can lose an electron to form the cation, H+. It is also possible to consider hydrogen
to be a group 17 element because it needs only one electron to fill its valence orbital to form a hydride ion, H−, or it can share an
electron to form a single, covalent bond. In reality, hydrogen is a unique element that almost deserves its own location in the
periodic table.
18.6.0.0.1: Reactions with Elements
When heated, hydrogen reacts with the metals of group 1 and with Ca, Sr, and Ba (the more active metals in group 2). The
compounds formed are crystalline, ionic hydrides that contain the hydride anion, H−, a strong reducing agent and a strong base,
which reacts vigorously with water and other acids to form hydrogen gas.
The reactions of hydrogen with nonmetals generally produce acidic hydrogen compounds with hydrogen in the 1+ oxidation state.
The reactions become more exothermic and vigorous as the electronegativity of the nonmetal increases. Hydrogen reacts with
nitrogen and sulfur only when heated, but it reacts explosively with fluorine (forming HF) and, under some conditions, with
chlorine (forming HCl). A mixture of hydrogen and oxygen explodes if ignited. Because of the explosive nature of the reaction, it
is necessary to exercise caution when handling hydrogen (or any other combustible gas) to avoid the formation of an explosive
mixture in a confined space. Although most hydrides of the nonmetals are acidic, ammonia and phosphine (PH3) are very, very
weak acids and generally function as bases. There is a summary of these reactions of hydrogen with the elements in Table 18.1.
Chemical Reactions of Hydrogen with Other Elements
General Equation Comments
MH or MH2 ⟶ MOH or M(OH)

2
+ H2 ionic hydrides with group 1 and Ca, Sr, and Ba

General Equation Comments
H2 + C ⟶ (no reaction)
3H2 + N2 ⟶ 2NH3 requires high pressure and temperature; low yield
2H2 + O2 ⟶ 2H2 O exothermic and potentially explosive
H2 + S ⟶ H2 S requires heating; low yield
H2 + X2 ⟶ 2HX X = F, Cl, Br, and I; explosive with F2; low yield with I2
Table 18.1
18.6.0.0.2: Reaction with Compounds
Hydrogen reduces the heated oxides of many metals, with the formation of the metal and water vapor. For example, passing
hydrogen over heated CuO forms copper and water.
Hydrogen may also reduce the metal ions in some metal oxides to lower oxidation states:
Δ
H2 (g) + MnO 2 (s) −→ MnO(s) + H2 O(g)
18.6.0.1: Hydrogen Compounds

Other than the noble gases, each of the nonmetals forms compounds with hydrogen. For brevity, we will discuss only a few
hydrogen compounds of the nonmetals here.
18.6.0.0.1: Nitrogen Hydrogen Compounds
Ammonia, NH3, forms naturally when any nitrogen-containing organic material decomposes in the absence of air. The laboratory
preparation of ammonia is by the reaction of an ammonium salt with a strong base such as sodium hydroxide. The acid-base
reaction with the weakly acidic ammonium ion gives ammonia, illustrated in Figure 18.29. Ammonia also forms when ionic
nitrides react with water. The nitride ion is a much stronger base than the hydroxide ion:
Mg 3 N2 (s) + 6H2 O(l) ⟶ 3Mg (OH) (s) + 2NH3 (g)
2
The commercial production of ammonia is by the direct combination of the elements in the Haber process:
catalyst
N2 (g) + 3H2 (g) ⇌ 2NH3 (g) ΔH ° = −92 kJ
Figure 18.29 The structure of ammonia is shown with a central nitrogen atom and three hydrogen atoms.
Ammonia is a colorless gas with a sharp, pungent odor. Smelling salts utilize this powerful odor. Gaseous ammonia readily
liquefies to give a colorless liquid that boils at −33 °C. Due to intermolecular hydrogen bonding, the enthalpy of vaporization of
liquid ammonia is higher than that of any other liquid except water, so ammonia is useful as a refrigerant. Ammonia is quite soluble
in water (658 L at STP dissolves in 1 L H2O).
The chemical properties of ammonia are as follows:
1. Ammonia acts as a Brønsted base, as discussed in the chapter on acid-base chemistry. The ammonium ion is similar in size to
the potassium ion; compounds of the two ions exhibit many similarities in their structures and solubilities.
2. Ammonia can display acidic behavior, although it is a much weaker acid than water. Like other acids, ammonia reacts with
metals, although it is so weak that high temperatures are necessary. Hydrogen and (depending on the stoichiometry) amides

(salts of NH ), imides (salts of NH2−), or nitrides (salts of N3−) form.
2
−
3. The nitrogen atom in ammonia has its lowest possible oxidation state (3−) and thus is not susceptible to reduction. However, it
can be oxidized. Ammonia burns in air, giving NO and water. Hot ammonia and the ammonium ion are active reducing agents.
Of particular interest are the oxidations of ammonium ion by nitrite ion, NO , to yield pure nitrogen and by nitrate ion to
2
−
yield nitrous oxide, N2O.

4. There are a number of compounds that we can consider derivatives of ammonia through the replacement of one or more
hydrogen atoms with some other atom or group of atoms. Inorganic derivations include chloramine, NH2Cl, and hydrazine,
N2H4:
Chloramine, NH2Cl, results from the reaction of sodium hypochlorite, NaOCl, with ammonia in basic solution. In the presence of a
large excess of ammonia at low temperature, the chloramine reacts further to produce hydrazine, N2H4:
− −
NH3 (aq) + OCl (aq) ⟶ NH2 Cl(aq) + OH (aq)
− −
NH2 Cl(aq) + NH3 (aq) + OH (aq) ⟶ N2 H4 (aq) + Cl (aq) + H2 O(l)
Anhydrous hydrazine is relatively stable in spite of its positive free energy of formation:
∘ −1
N2 (g) + 2H2 (g) ⟶ N2 H4 (l) ΔG = 149.2 kJ mol
f
Hydrazine is a fuming, colorless liquid that has some physical properties remarkably similar to those of H2O (it melts at 2 °C, boils
at 113.5 °C, and has a density at 25 °C of 1.00 g/mL). It burns rapidly and completely in air with substantial evolution of heat:
−1
N2 H4 (l) + O2 (g) ⟶ N2 (g) + 2H2 O(l) ΔH ° = −621.5 kJ mol
Like ammonia, hydrazine is both a Brønsted base and a Lewis base, although it is weaker than ammonia. It reacts with strong acids
and forms two series of salts that contain the N H and N H
2 5
+
ions, respectively. Some rockets use hydrazine as a fuel.
2 6
2+
18.6.0.0.2: Phosphorus Hydrogen Compounds

The most important hydride of phosphorus is phosphine, PH3, a gaseous analog of ammonia in terms of both formula and structure.
Unlike ammonia, it is not possible to form phosphine by direct union of the elements. There are two methods for the preparation of
phosphine. One method is by the action of an acid on an ionic phosphide. The other method is the disproportionation of white
phosphorus with hot concentrated base to produce phosphine and the hydrogen phosphite ion:
+ 3+
AlP(s) + 3H3 O (aq) ⟶ PH3 (g) + Al (aq) + 3H2 O(l)
− 2−
P4 (s) + 4OH (aq) + 2H2 O(l) ⟶ 2HPO3 (aq) + 2PH3 (g)
Phosphine is a colorless, very poisonous gas, which has an odor like that of decaying fish. Heat easily decomposes phosphine
(4PH 3 ⟶ P + 6H ), and the compound burns in air. The major uses of phosphine are as a fumigant for grains and in
4 2
semiconductor processing. Like ammonia, gaseous phosphine unites with gaseous hydrogen halides, forming phosphonium
compounds like PH4Cl and PH4I. Phosphine is a much weaker base than ammonia; therefore, these compounds decompose in
water, and the insoluble PH3 escapes from solution.
18.6.0.0.3: Sulfur Hydrogen Compounds
Hydrogen sulfide, H2S, is a colorless gas that is responsible for the offensive odor of rotten eggs and of many hot springs.
Hydrogen sulfide is as toxic as hydrogen cyanide; therefore, it is necessary to exercise great care in handling it. Hydrogen sulfide is
particularly deceptive because it paralyzes the olfactory nerves; after a short exposure, one does not smell it.
The production of hydrogen sulfide by the direct reaction of the elements (H2 + S) is unsatisfactory because the yield is low. A
more effective preparation method is the reaction of a metal sulfide with a dilute acid. For example:

+ 2+
FeS(s) + 2H3 O (aq) ⟶ Fe (aq) + H2 S(g) + 2H2 O(l)
It is easy to oxidize the sulfur in metal sulfides and in hydrogen sulfide, making metal sulfides and H2S good reducing agents. In
acidic solutions, hydrogen sulfide reduces Fe3+ to Fe2+, MnO to Mn2+, Cr O
4
−
to Cr3+, and HNO3 to NO2. The sulfur in H2S
2 7
2−
usually oxidizes to elemental sulfur, unless a large excess of the oxidizing agent is present. In which case, the sulfide may oxidize
to SO 3
2−
or SO
4
2−
(or to SO2 or SO3 in the absence of water):
2H2 S(g) + O2 (g) ⟶ 2S(s) + 2H2 O(l)
This oxidation process leads to the removal of the hydrogen sulfide found in many sources of natural gas. The deposits of sulfur in
volcanic regions may be the result of the oxidation of H2S present in volcanic gases.
Hydrogen sulfide is a weak diprotic acid that dissolves in water to form hydrosulfuric acid. The acid ionizes in two stages, yielding
hydrogen sulfide ions, HS−, in the first stage and sulfide ions, S2−, in the second. Since hydrogen sulfide is a weak acid, aqueous
solutions of soluble sulfides and hydrogen sulfides are basic:
2− − −
S (aq) + H2 O(l) ⇌ HS (aq) + OH (aq)
− −
HS (aq) + H2 O(l) ⇌ H2 S(g) + OH (aq)
18.6.0.0.4: Halogen Hydrogen Compounds

Binary compounds containing only hydrogen and a halogen are hydrogen halides. At room temperature, the pure hydrogen halides
HF, HCl, HBr, and HI are gases.
In general, it is possible to prepare the halides by the general techniques used to prepare other acids. Fluorine, chlorine, and
bromine react directly with hydrogen to form the respective hydrogen halide. This is a commercially important reaction for
preparing hydrogen chloride and hydrogen bromide.
The acid-base reaction between a nonvolatile strong acid and a metal halide will yield a hydrogen halide. The escape of the gaseous
hydrogen halide drives the reaction to completion. For example, the usual method of preparing hydrogen fluoride is by heating a
mixture of calcium fluoride, CaF2, and concentrated sulfuric acid:
CaF2 (s) + H2 SO 4 (aq) ⟶ CaSO4 (s) + 2HF(g)
Gaseous hydrogen fluoride is also a by-product in the preparation of phosphate fertilizers by the reaction of fluoroapatite,
Ca5(PO4)3F, with sulfuric acid. The reaction of concentrated sulfuric acid with a chloride salt produces hydrogen chloride both
commercially and in the laboratory.
In most cases, sodium chloride is the chloride of choice because it is the least expensive chloride. Hydrogen bromide and hydrogen
iodide cannot be prepared using sulfuric acid because this acid is an oxidizing agent capable of oxidizing both bromide and iodide.
However, it is possible to prepare both hydrogen bromide and hydrogen iodide using an acid such as phosphoric acid because it is a
weaker oxidizing agent. For example:
− −
H3 PO4 (l) + Br (aq) ⟶ HBr(g) + H2 PO4 (aq)
All of the hydrogen halides are very soluble in water, forming hydrohalic acids. With the exception of hydrogen fluoride, which has
a strong hydrogen-fluoride bond, they are strong acids. Reactions of hydrohalic acids with metals, metal hydroxides, oxides, or
carbonates produce salts of the halides. Most chloride salts are soluble in water. AgCl, PbCl2, and Hg2Cl2 are the commonly
encountered exceptions.
The halide ions give the substances the properties associated with X−(aq). The heavier halide ions (Cl−, Br−, and I−) can act as
reducing agents, and the lighter halogens or other oxidizing agents will oxidize them:
− −
Cl2 (aq) + 2e ⟶ 2Cl (aq) E° = 1.36 V
− −
Br 2 (aq) + 2e ⟶ 2Br (aq) E° = 1.09 V
− −
I2 (aq) + 2e ⟶ 2I (aq) E° = 0.54 V
For example, bromine oxidizes iodine:

Br 2 (aq) + 2HI(aq) ⟶ 2HBr(aq) + I2 (aq) E° = 0.55 V

Hydrofluoric acid is unique in its reactions with sand (silicon dioxide) and with glass, which is a mixture of silicates:
SiO2 (s) + 4HF(aq) ⟶ SiF4 (g) + 2H2 O(l)
CaSiO3 (s) + 6HF(aq) ⟶ CaF2 (s) + SiF4 (g) + 3H2 O(l)
The volatile silicon tetrafluoride escapes from these reactions. Because hydrogen fluoride attacks glass, it can frost or etch glass
and is used to etch markings on thermometers, burets, and other glassware.
The largest use for hydrogen fluoride is in production of hydrochlorofluorocarbons for refrigerants, in plastics, and in propellants.
The second largest use is in the manufacture of cryolite, Na3AlF6, which is important in the production of aluminum. The acid is
also important in the production of other inorganic fluorides (such as BF3), which serve as catalysts in the industrial synthesis of
certain organic compounds.
Hydrochloric acid is relatively inexpensive. It is an important and versatile acid in industry and is important for the manufacture of
metal chlorides, dyes, glue, glucose, and various other chemicals. A considerable amount is also important for the activation of oil
wells and as pickle liquor—an acid used to remove oxide coating from iron or steel that is to be galvanized, tinned, or enameled.
The amounts of hydrobromic acid and hydroiodic acid used commercially are insignificant by comparison.
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Describe the preparation, properties, and uses of some representative metal carbonates
The chemistry of carbon is extensive; however, most of this chemistry is not relevant to this chapter. The other aspects of the
chemistry of carbon will appear in the chapter covering organic chemistry. In this chapter, we will focus on the carbonate ion and
related substances. The metals of groups 1 and 2, as well as zinc, cadmium, mercury, and lead(II), form ionic carbonates—
compounds that contain the carbonate anions, CO . The metals of group 1, magnesium, calcium, strontium, and barium also
3
2−
form hydrogen carbonates—compounds that contain the hydrogen carbonate anion, HCO , also known as the bicarbonate anion.
3
−
With the exception of magnesium carbonate, it is possible to prepare carbonates of the metals of groups 1 and 2 by the reaction of
carbon dioxide with the respective oxide or hydroxide. Examples of such reactions include:
Na2 O(s) + CO2 (g) ⟶ Na2 CO3 (s)
Ca (OH) (s) + CO2 (g) ⟶ CaCO3 (s) + H2 O(l)

2
The carbonates of the alkaline earth metals of group 12 and lead(II) are not soluble. These carbonates precipitate upon mixing a
solution of soluble alkali metal carbonate with a solution of soluble salts of these metals. Examples of net ionic equations for the
reactions are:
2+ 2−
Ca (aq) + CO3 (aq) ⟶ CaCO3 (s)
2+ 2−
Pb (aq) + CO3 (aq) ⟶ PbCO3 (s)
Pearls and the shells of most mollusks are calcium carbonate. Tin(II) or one of the trivalent or tetravalent ions such as Al3+ or Sn4+
behave differently in this reaction as carbon dioxide and the corresponding oxide form instead of the carbonate.
Alkali metal hydrogen carbonates such as NaHCO3 and CsHCO3 form by saturating a solution of the hydroxides with carbon
dioxide. The net ionic reaction involves hydroxide ion and carbon dioxide:
− −
OH (aq) + CO2 (aq) ⟶ HCO3 (aq)
It is possible to isolate the solids by evaporation of the water from the solution.
Although they are insoluble in pure water, alkaline earth carbonates dissolve readily in water containing carbon dioxide because
hydrogen carbonate salts form. For example, caves and sinkholes form in limestone when CaCO3 dissolves in water containing
dissolved carbon dioxide:
2+ −
CaCO3 (s) + CO2 (aq) + H2 O(l) ⟶ Ca (aq) + 2HCO3 (aq)
Hydrogen carbonates of the alkaline earth metals remain stable only in solution; evaporation of the solution produces the carbonate.
Stalactites and stalagmites, like those shown in Figure 18.30, form in caves when drops of water containing dissolved calcium
hydrogen carbonate evaporate to leave a deposit of calcium carbonate.

Figure 18.30 (a) Stalactites and (b) stalagmites are cave formations of calcium carbonate. (credit a: modification of work by Arvind
Govindaraj; credit b: modification of work by the National Park Service.)
The two carbonates used commercially in the largest quantities are sodium carbonate and calcium carbonate. In the United States,
sodium carbonate is extracted from the mineral trona, Na3(CO3)(HCO3)(H2O)2. Following recrystallization to remove clay and
other impurities, heating the recrystallized trona produces Na2CO3:
2Na3 (CO3 ) (HCO3 ) (H2 O) (s) ⟶ 3Na2 CO3 (s) + 5H2 O(l) + CO2 (g)
2
Carbonates are moderately strong bases. Aqueous solutions are basic because the carbonate ion accepts hydrogen ion from water in
this reversible reaction:
2− − −
CO3 (aq) + H2 O(l) ⇌ HCO3 (aq) + OH (aq)
Carbonates react with acids to form salts of the metal, gaseous carbon dioxide, and water. The reaction of calcium carbonate, the
active ingredient of the antacid Tums, with hydrochloric acid (stomach acid), as shown in Figure 18.31, illustrates the reaction:
CaCO3 (s) + 2HCl(aq) ⟶ CaCl2 (aq) + CO2 (g) + H2 O(l)

Figure 18.31 The reaction of calcium carbonate with hydrochloric acid is shown. (credit: Mark Ott)
Other applications of carbonates include glass making—where carbonate ions serve as a source of oxide ions—and synthesis of
oxides.
Hydrogen carbonates are amphoteric because they act as both weak acids and weak bases. Hydrogen carbonate ions act as acids
and react with solutions of soluble hydroxides to form a carbonate and water:
KHCO3 (aq) + KOH(aq) ⟶ K2 CO3 (aq) + H2 O(l)
With acids, hydrogen carbonates form a salt, carbon dioxide, and water. Baking soda (bicarbonate of soda or sodium bicarbonate) is
sodium hydrogen carbonate. Baking powder contains baking soda and a solid acid such as potassium hydrogen tartrate (cream of
tartar), KHC4H4O6. As long as the powder is dry, no reaction occurs; immediately after the addition of water, the acid reacts with
the hydrogen carbonate ions to form carbon dioxide:
− − 2−
HC4 H4 O6 (aq) + HCO3 (aq) ⟶ C4 H4 O6 (aq) + CO2 (g) + H2 O(l)
Dough will trap the carbon dioxide, causing it to expand during baking, producing the characteristic texture of baked goods.
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Describe the properties, preparation, and uses of nitrogen
Most pure nitrogen comes from the fractional distillation of liquid air. The atmosphere consists of 78% nitrogen by volume. This
means there are more than 20 million tons of nitrogen over every square mile of the earth’s surface. Nitrogen is a component of
proteins and of the genetic material (DNA/RNA) of all plants and animals.
Under ordinary conditions, nitrogen is a colorless, odorless, and tasteless gas. It boils at 77 K and freezes at 63 K. Liquid nitrogen
is a useful coolant because it is inexpensive and has a low boiling point. Nitrogen is very unreactive because of the very strong
triple bond between the nitrogen atoms. The only common reactions at room temperature occur with lithium to form Li3N, with
certain transition metal complexes, and with hydrogen or oxygen in nitrogen-fixing bacteria. The general lack of reactivity of
nitrogen makes the remarkable ability of some bacteria to synthesize nitrogen compounds using atmospheric nitrogen gas as the
source one of the most exciting chemical events on our planet. This process is one type of nitrogen fixation. In this case, nitrogen
fixation is the process where organisms convert atmospheric nitrogen into biologically useful chemicals. Nitrogen fixation also
occurs when lightning passes through air, causing molecular nitrogen to react with oxygen to form nitrogen oxides, which are then
carried down to the soil.

18.8.0.0.1: Nitrogen Fixation
All living organisms require nitrogen compounds for survival. Unfortunately, most of these organisms cannot absorb nitrogen
from its most abundant source—the atmosphere. Atmospheric nitrogen consists of N2 molecules, which are very unreactive
due to the strong nitrogen-nitrogen triple bond. However, a few organisms can overcome this problem through a process
known as nitrogen fixation, illustrated in Figure 18.32.

Figure 18.32 All living organisms require nitrogen. A few microorganisms are able to process atmospheric nitrogen using
nitrogen fixation. (credit “roots”: modification of work by the United States Department of Agriculture; credit “root nodules”:
modification of work by Louisa Howard)
Nitrogen fixation is the process where organisms convert atmospheric nitrogen into biologically useful chemicals. To date, the
only known kind of biological organisms capable of nitrogen fixation are microorganisms. These organisms employ enzymes
called nitrogenases, which contain iron and molybdenum. Many of these microorganisms live in a symbiotic relationship with
plants, with the best-known example being the presence of rhizobia in the root nodules of legumes.
Large volumes of atmospheric nitrogen are necessary for making ammonia—the principal starting material used for preparation of
large quantities of other nitrogen-containing compounds. Most other uses for elemental nitrogen depend on its inactivity. It is
helpful when a chemical process requires an inert atmosphere. Canned foods and luncheon meats cannot oxidize in a pure nitrogen
atmosphere, so they retain a better flavor and color, and spoil less rapidly, when sealed in nitrogen instead of air. This technology
allows fresh produce to be available year-round, regardless of growing season.
There are compounds with nitrogen in all of its oxidation states from 3− to 5+. Much of the chemistry of nitrogen involves
oxidation-reduction reactions. Some active metals (such as alkali metals and alkaline earth metals) can reduce nitrogen to form
metal nitrides. In the remainder of this section, we will examine nitrogen-oxygen chemistry.
There are well-characterized nitrogen oxides in which nitrogen exhibits each of its positive oxidation numbers from 1+ to 5+.
When ammonium nitrate is carefully heated, nitrous oxide (dinitrogen oxide) and water vapor form. Stronger heating generates
nitrogen gas, oxygen gas, and water vapor. No one should ever attempt this reaction—it can be very explosive. In 1947, there was a
major ammonium nitrate explosion in Texas City, Texas, and, in 2013, there was another major explosion in West, Texas. In the last
100 years, there were nearly 30 similar disasters worldwide, resulting in the loss of numerous lives. In this oxidation-reduction
reaction, the nitrogen in the nitrate ion oxidizes the nitrogen in the ammonium ion. Nitrous oxide, shown in Figure 18.33, is a
colorless gas possessing a mild, pleasing odor and a sweet taste. It finds application as an anesthetic for minor operations,
especially in dentistry, under the name “laughing gas.”
Figure 18.33 Nitrous oxide, N2O, is an anesthetic that has these molecular (left) and resonance (right) structures.
Low yields of nitric oxide, NO, form when heating nitrogen and oxygen together. NO also forms when lightning passes through air
during thunderstorms. Burning ammonia is the commercial method of preparing nitric oxide. In the laboratory, the reduction of
nitric acid is the best method for preparing nitric oxide. When copper reacts with dilute nitric acid, nitric oxide is the principal
reduction product:
3Cu(s) + 8HNO3 (aq) ⟶ 2NO(g) + 3Cu(NO3 ) (aq) + 4H2 O(l)
2
Gaseous nitric oxide is the most thermally stable of the nitrogen oxides and is the simplest known thermally stable molecule with
an unpaired electron. It is one of the air pollutants generated by internal combustion engines, resulting from the reaction of
atmospheric nitrogen and oxygen during the combustion process.
At room temperature, nitric oxide is a colorless gas consisting of diatomic molecules. As is often the case with molecules that
contain an unpaired electron, two molecules combine to form a dimer by pairing their unpaired electrons to form a bond. Liquid

and solid NO both contain N2O2 dimers, like that shown in Figure 18.34. Most substances with unpaired electrons exhibit color by
absorbing visible light; however, NO is colorless because the absorption of light is not in the visible region of the spectrum.
Figure 18.34 This shows the equilibrium between NO and N2O2. The molecule, N2O2, absorbs light.
Cooling a mixture of equal parts nitric oxide and nitrogen dioxide to −21 °C produces dinitrogen trioxide, a blue liquid consisting
of N2O3 molecules (shown in Figure 18.35). Dinitrogen trioxide exists only in the liquid and solid states. When heated, it reverts to
a mixture of NO and NO2.
Figure 18.35 Dinitrogen trioxide, N2O3, only exists in liquid or solid states and has these molecular (left) and resonance (right)
structures.
It is possible to prepare nitrogen dioxide in the laboratory by heating the nitrate of a heavy metal, or by the reduction of
concentrated nitric acid with copper metal, as shown in Figure 18.36. Commercially, it is possible to prepare nitrogen dioxide by
oxidizing nitric oxide with air.
Figure 18.36 The reaction of copper metal with concentrated HNO3 produces a solution of Cu(NO3)2 and brown fumes of NO2.
(credit: modification of work by Mark Ott)
The nitrogen dioxide molecule (illustrated in Figure 18.37) contains an unpaired electron, which is responsible for its color and
paramagnetism. It is also responsible for the dimerization of NO2. At low pressures or at high temperatures, nitrogen dioxide has a
deep brown color that is due to the presence of the NO2 molecule. At low temperatures, the color almost entirely disappears as
dinitrogen tetraoxide, N2O4, forms. At room temperature, an equilibrium exists:
2NO2 (g) ⇌ N2 O4 (g) KP = 6.86

Figure 18.37 The molecular and resonance structures for nitrogen dioxide (NO2, left) and dinitrogen tetraoxide (N2O4, right) are
shown.
Dinitrogen pentaoxide, N2O5 (illustrated in Figure 18.38), is a white solid that is formed by the dehydration of nitric acid by
phosphorus(V) oxide (tetraphosphorus decoxide):
P4 O10 (s) + 4HNO3 (l) ⟶ 4HPO3 (s) + 2N2 O5 (s)
It is unstable above room temperature, decomposing to N2O4 and O2.
Figure 18.38 This image shows the molecular structure and one resonance structure of a molecule of dinitrogen pentaoxide, N2O5.
The oxides of nitrogen(III), nitrogen(IV), and nitrogen(V) react with water and form nitrogen-containing oxyacids. Nitrogen(III)
oxide, N2O3, is the anhydride of nitrous acid; HNO2 forms when N2O3 reacts with water. There are no stable oxyacids containing
nitrogen with an oxidation state of 4+; therefore, nitrogen(IV) oxide, NO2, disproportionates in one of two ways when it reacts with
water. In cold water, a mixture of HNO2 and HNO3 forms. At higher temperatures, HNO3 and NO will form. Nitrogen(V) oxide,
N2O5, is the anhydride of nitric acid; HNO3 is produced when N2O5 reacts with water:
N2 O5 (s) + H2 O(l) ⟶ 2HNO3 (aq)
The nitrogen oxides exhibit extensive oxidation-reduction behavior. Nitrous oxide resembles oxygen in its behavior when heated
with combustible substances. N2O is a strong oxidizing agent that decomposes when heated to form nitrogen and oxygen. Because

one-third of the gas liberated is oxygen, nitrous oxide supports combustion better than air (one-fifth oxygen). A glowing splinter
bursts into flame when thrust into a bottle of this gas. Nitric oxide acts both as an oxidizing agent and as a reducing agent. For
example:
oxidizing agent: P4 (s) + 6NO(g) ⟶ P4 O6 (s) + 3N2 (g)
reducing agent: Cl2 (g) + 2NO(g) ⟶ 2ClNO(g)
Nitrogen dioxide (or dinitrogen tetraoxide) is a good oxidizing agent. For example:
NO2 (g) + CO(g) ⟶ NO(g) + CO2 (g)
NO2 (g) + 2HCl(aq) ⟶ NO(g) + Cl2 (g) + H2 O(l)
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upon request.


Describe the properties, preparation, and uses of phosphorus
The industrial preparation of phosphorus is by heating calcium phosphate, obtained from phosphate rock, with sand and coke:
Δ
2Ca3 (PO4 ) (s) + 6SiO2 (s) + 10C(s) −→ 6CaSiO3 (l) + 10CO(g) + P4 (g)
2
The phosphorus distills out of the furnace and is condensed into a solid or burned to form P4O10. The preparation of many other
phosphorus compounds begins with P4O10. The acids and phosphates are useful as fertilizers and in the chemical industry. Other
uses are in the manufacture of special alloys such as ferrophosphorus and phosphor bronze. Phosphorus is important in making
pesticides, matches, and some plastics. Phosphorus is an active nonmetal. In compounds, phosphorus usually occurs in oxidation
states of 3−, 3+, and 5+. Phosphorus exhibits oxidation numbers that are unusual for a group 15 element in compounds that contain
phosphorus-phosphorus bonds; examples include diphosphorus tetrahydride, H2P-PH2, and tetraphosphorus trisulfide, P4S3,
illustrated in Figure 18.39.
Figure 18.39 P4S3 is a component of the heads of strike-anywhere matches.
18.9.0.1: Phosphorus Oxygen Compounds

Phosphorus forms two common oxides, phosphorus(III) oxide (or tetraphosphorus hexaoxide), P4O6, and phosphorus(V) oxide (or
tetraphosphorus decaoxide), P4O10, both shown in Figure 18.40. Phosphorus(III) oxide is a white crystalline solid with a garlic-like
odor. Its vapor is very poisonous. It oxidizes slowly in air and inflames when heated to 70 °C, forming P4O10. Phosphorus(III)
oxide dissolves slowly in cold water to form phosphorous acid, H3PO3.

Figure 18.40 This image shows the molecular structures of P4O6 (left) and P4O10 (right).
Phosphorus(V) oxide, P4O10, is a white powder that is prepared by burning phosphorus in excess oxygen. Its enthalpy of formation
is very high (−2984 kJ), and it is quite stable and a very poor oxidizing agent. Dropping P4O10 into water produces a hissing sound,
heat, and orthophosphoric acid:
P4 O10 (s) + 6H2 O(l) ⟶ 4H3 PO4 (aq)
Because of its great affinity for water, phosphorus(V) oxide is an excellent drying agent for gases and solvents, and for removing
water from many compounds.
18.9.0.1: Phosphorus Halogen Compounds

Phosphorus will react directly with the halogens, forming trihalides, PX3, and pentahalides, PX5. The trihalides are much more
stable than the corresponding nitrogen trihalides; nitrogen pentahalides do not form because of nitrogen’s inability to form more
than four bonds.
The chlorides PCl3 and PCl5, both shown in Figure 18.41, are the most important halides of phosphorus. Phosphorus trichloride is a
colorless liquid that is prepared by passing chlorine over molten phosphorus. Phosphorus pentachloride is an off-white solid that is
prepared by oxidizing the trichloride with excess chlorine. The pentachloride sublimes when warmed and forms an equilibrium
with the trichloride and chlorine when heated.

Figure 18.41 This image shows the molecular structure of PCl3 (left) and PCl5 (right) in the gas phase.
Like most other nonmetal halides, both phosphorus chlorides react with an excess of water and yield hydrogen chloride and an
oxyacid: PCl3 yields phosphorous acid H3PO3 and PCl5 yields phosphoric acid, H3PO4.
The pentahalides of phosphorus are Lewis acids because of the empty valence d orbitals of phosphorus. These compounds readily
react with halide ions (Lewis bases) to give the anion PX . Whereas phosphorus pentafluoride is a molecular compound in all
6
−
states, X-ray studies show that solid phosphorus pentachloride is an ionic compound, [PCl ][PCl ], as are phosphorus
4
+
6
−
pentabromide, [PBr ][Br−], and phosphorus pentaiodide, [PI ][I−].

4
+
4
+
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Describe the properties, preparation, and compounds of oxygen
Describe the preparation, properties, and uses of some representative metal oxides, peroxides, and hydroxides
Oxygen is the most abundant element on the earth’s crust. The earth’s surface is composed of the crust, atmosphere, and
hydrosphere. About 50% of the mass of the earth’s crust consists of oxygen (combined with other elements, principally silicon).
Oxygen occurs as O2 molecules and, to a limited extent, as O3 (ozone) molecules in air. It forms about 20% of the mass of the air.
About 89% of water by mass consists of combined oxygen. In combination with carbon, hydrogen, and nitrogen, oxygen is a large
part of plants and animals.
Oxygen is a colorless, odorless, and tasteless gas at ordinary temperatures. It is slightly denser than air. Although it is only slightly
soluble in water (49 mL of gas dissolves in 1 L at STP), oxygen’s solubility is very important to aquatic life.
Most of the oxygen isolated commercially comes from air and the remainder from the electrolysis of water. The separation of
oxygen from air begins with cooling and compressing the air until it liquefies. As liquid air warms, oxygen with its higher boiling
point (90 K) separates from nitrogen, which has a lower boiling point (77 K). It is possible to separate the other components of air
at the same time based on differences in their boiling points.
Oxygen is essential in combustion processes such as the burning of fuels. Plants and animals use the oxygen from the air in
respiration. The administration of oxygen-enriched air is an important medical practice when a patient is receiving an inadequate
supply of oxygen because of shock, pneumonia, or some other illness.
The chemical industry employs oxygen for oxidizing many substances. A significant amount of oxygen produced commercially is
important in the removal of carbon from iron during steel production. Large quantities of pure oxygen are also necessary in metal
fabrication and in the cutting and welding of metals with oxyhydrogen and oxyacetylene torches.
Liquid oxygen is important to the space industry. It is an oxidizing agent in rocket engines. It is also the source of gaseous oxygen
for life support in space.
As we know, oxygen is very important to life. The energy required for the maintenance of normal body functions in human beings
and in other organisms comes from the slow oxidation of chemical compounds. Oxygen is the final oxidizing agent in these
reactions. In humans, oxygen passes from the lungs into the blood, where it combines with hemoglobin, producing oxyhemoglobin.
In this form, blood transports the oxygen to tissues, where it is transferred to the tissues. The ultimate products are carbon dioxide
and water. The blood carries the carbon dioxide through the veins to the lungs, where the blood releases the carbon dioxide and
collects another supply of oxygen. Digestion and assimilation of food regenerate the materials consumed by oxidation in the body;
the energy liberated is the same as if the food burned outside the body.
Green plants continually replenish the oxygen in the atmosphere by a process called photosynthesis. The products of
photosynthesis may vary, but, in general, the process converts carbon dioxide and water into glucose (a sugar) and oxygen using
the energy of light:
chlorophyll
6 CO2 (g)+ 6 H2 O(l) −−−−−−−→ C6 H12 O6 (aq)+ 6 O2 (g)

light
carbon water glucose oxygen
dioxide
Thus, the oxygen that became carbon dioxide and water by the metabolic processes in plants and animals returns to the atmosphere
by photosynthesis.
When dry oxygen is passed between two electrically charged plates, ozone (O3, illustrated in Figure 18.42), an allotrope of oxygen
possessing a distinctive odor, forms. The formation of ozone from oxygen is an endothermic reaction, in which the energy comes
from an electrical discharge, heat, or ultraviolet light:
electric discharge
3 O2 (g) −−−−−−−−−−→ 2 O3 (g) ΔH ° = 287 kJ

The sharp odor associated with sparking electrical equipment is due, in part, to ozone.
Figure 18.42 The image shows the bent ozone (O3) molecule and the resonance structures necessary to describe its bonding.
Ozone forms naturally in the upper atmosphere by the action of ultraviolet light from the sun on the oxygen there. Most
atmospheric ozone occurs in the stratosphere, a layer of the atmosphere extending from about 10 to 50 kilometers above the earth’s
surface. This ozone acts as a barrier to harmful ultraviolet light from the sun by absorbing it via a chemical decomposition reaction:
ultraviolet light
O3 (g) −−−−−−−−−−→ O(g) + O2 (g)
The reactive oxygen atoms recombine with molecular oxygen to complete the ozone cycle. The presence of stratospheric ozone
decreases the frequency of skin cancer and other damaging effects of ultraviolet radiation. It has been clearly demonstrated that
chlorofluorocarbons, CFCs (known commercially as Freons), which were present as aerosol propellants in spray cans and as
refrigerants, caused depletion of ozone in the stratosphere. This occurred because ultraviolet light also causes CFCs to decompose,
producing atomic chlorine. The chlorine atoms react with ozone molecules, resulting in a net removal of O3 molecules from
stratosphere. This process is explored in detail in our coverage of chemical kinetics. There is a worldwide effort to reduce the
amount of CFCs used commercially, and the ozone hole is already beginning to decrease in size as atmospheric concentrations of
atomic chlorine decrease. While ozone in the stratosphere helps protect us, ozone in the troposphere is a problem. This ozone is a
toxic component of photochemical smog.
The uses of ozone depend on its reactivity with other substances. It can be used as a bleaching agent for oils, waxes, fabrics, and
starch: It oxidizes the colored compounds in these substances to colorless compounds. It is an alternative to chlorine as a
disinfectant for water.
18.10.0.1: Reactions
Elemental oxygen is a strong oxidizing agent. It reacts with most other elements and many compounds.
18.10.0.0.1: Reaction with Elements
Oxygen reacts directly at room temperature or at elevated temperatures with all other elements except the noble gases, the
halogens, and few second- and third-row transition metals of low reactivity (those with higher reduction potentials than copper).
Rust is an example of the reaction of oxygen with iron. The more active metals form peroxides or superoxides. Less active metals
and the nonmetals give oxides. Two examples of these reactions are:
2Mg(s) + O2 (g) ⟶ 2MgO(s)
P4 (s) + 5 O2 (g) ⟶ P4 O10 (s)
The oxides of halogens, at least one of the noble gases, and metals with higher reduction potentials than copper do not form by the
direct action of the elements with oxygen.
18.10.0.0.2: Reaction with Compounds
Elemental oxygen also reacts with some compounds. If it is possible to oxidize any of the elements in a given compound, further
oxidation by oxygen can occur. For example, hydrogen sulfide, H2S, contains sulfur with an oxidation state of 2−. Because the
sulfur does not exhibit its maximum oxidation state, we would expect H2S to react with oxygen. It does, yielding water and sulfur
dioxide. The reaction is:
2 H2 S(g) + 3 O2 (g) ⟶ 2 H2 O(l) + 2 SO 2 (g)

It is also possible to oxidize oxides such as CO and P4O6 that contain an element with a lower oxidation state. The ease with which
elemental oxygen picks up electrons is mirrored by the difficulty of removing electrons from oxygen in most oxides. Of the
elements, only the very reactive fluorine can oxidize oxides to form oxygen gas.
18.10.0.1: Oxides, Peroxides, and Hydroxides

Compounds of the representative metals with oxygen fall into three categories: (1) oxides, containing oxide ions, O2−; (2)
peroxides, containing peroxides ions, O , with oxygen-oxygen covalent single bonds and a very limited number of superoxides,
2
2−
containing superoxide ions, O , with oxygen-oxygen covalent bonds that have a bond order of 1 , In addition, there are (3)
2
− 1
hydroxides, containing hydroxide ions, OH−. All representative metals form oxides. Some of the metals of group 2 also form
peroxides, MO2, and the metals of group 1 also form peroxides, M2O2, and superoxides, MO2.
18.10.0.0.1: Oxides
It is possible to produce the oxides of most representative metals by heating the corresponding hydroxides (forming the oxide and
gaseous water) or carbonates (forming the oxide and gaseous CO2). Equations for example reactions are:
Δ
2Al (OH) (s) −→ Al2 O3 (s) + 3 H2 O(g)
3
CaCO3 (s) −→ CaO(s) + CO2 (g)
However, alkali metal salts generally are very stable and do not decompose easily when heated. Alkali metal oxides result from the
oxidation-reduction reactions created by heating nitrates or hydroxides with the metals. Equations for sample reactions are:
Δ
2 KNO 3 (s) + 10K(s) −→ 6 K2 O(s) + N2 (g)
2LiOH(s) + 2Li(s) −→ 2 Li 2 O(s) + H2 (g)
With the exception of mercury(II) oxide, it is possible to produce the oxides of the metals of groups 2–15 by burning the
corresponding metal in air. The heaviest member of each group, the member for which the inert pair effect is most pronounced,
forms an oxide in which the oxidation state of the metal ion is two less than the group oxidation state (inert pair effect). Thus, Tl2O,
PbO, and Bi2O3 form when burning thallium, lead, and bismuth, respectively. The oxides of the lighter members of each group
exhibit the group oxidation state. For example, SnO2 forms from burning tin. Mercury(II) oxide, HgO, forms slowly when mercury
is warmed below 500 °C; it decomposes at higher temperatures.
Burning the members of groups 1 and 2 in air is not a suitable way to form the oxides of these elements. These metals are reactive
enough to combine with nitrogen in the air, so they form mixtures of oxides and ionic nitrides. Several also form peroxides or
superoxides when heated in air.
Ionic oxides all contain the oxide ion, a very powerful hydrogen ion acceptor. With the exception of the very insoluble aluminum
oxide, Al2O3, tin(IV), SnO2, and lead(IV), PbO2, the oxides of the representative metals react with acids to form salts. Some
equations for these reactions are:
Na2 O + 2 HNO3 (aq) ⟶ 2 NaNO3 (aq) + H2 O(l)
CaO(s) + 2HCL(aq) ⟶ CaCl2 (aq) + H2 O(l)
SnO(s) + 2 HClO4 (aq) ⟶ Sn(ClO4 ) (aq) + H2 O(l)

2
The oxides of the metals of groups 1 and 2 and of thallium(I) oxide react with water and form hydroxides. Examples of such
reactions are:
Na2 O(s) + H2 O(l) ⟶ NaOH(aq)
CaO(s) + H2 O(l) ⟶ Ca (OH) (aq)

2
Tl2 O(s) + H2 O(aq) ⟶ 2TlOH(aq)
The oxides of the alkali metals have little industrial utility, unlike magnesium oxide, calcium oxide, and aluminum oxide.
Magnesium oxide is important in making firebrick, crucibles, furnace linings, and thermal insulation—applications that require
chemical and thermal stability. Calcium oxide, sometimes called quicklime or lime in the industrial market, is very reactive, and its
principal uses reflect its reactivity. Pure calcium oxide emits an intense white light when heated to a high temperature (as illustrated

in Figure 18.43). Blocks of calcium oxide heated by gas flames were the stage lights in theaters before electricity was available.
This is the source of the phrase “in the limelight.”
Figure 18.43 Calcium oxide has many industrial uses. When it is heated at high temperatures, it emits an intense white light.
Calcium oxide and calcium hydroxide are inexpensive bases used extensively in chemical processing, although most of the useful
products prepared from them do not contain calcium. Calcium oxide, CaO, is made by heating calcium carbonate, CaCO3, which is
widely and inexpensively available as limestone or oyster shells:
CaCO3 (s) ⟶ CaO(s) + CO2 (g)
Although this decomposition reaction is reversible, it is possible to obtain a 100% yield of CaO by allowing the CO2 to escape. It is
possible to prepare calcium hydroxide by the familiar acid-base reaction of a soluble metal oxide with water:
CaO(s) + H2 O(l) ⟶ Ca (OH) (s)
2
Both CaO and Ca(OH)2 are useful as bases; they accept protons and neutralize acids.
Alumina (Al2O3) occurs in nature as the mineral corundum, a very hard substance used as an abrasive for grinding and polishing.
Corundum is important to the jewelry trade as ruby and sapphire. The color of ruby is due to the presence of a small amount of
chromium; other impurities produce the wide variety of colors possible for sapphires. Artificial rubies and sapphires are now
manufactured by melting aluminum oxide (melting point = 2050 °C) with small amounts of oxides to produce the desired colors
and cooling the melt in such a way as to produce large crystals. Ruby lasers use synthetic ruby crystals.
Zinc oxide, ZnO, was a useful white paint pigment; however, pollutants tend to discolor the compound. The compound is also
important in the manufacture of automobile tires and other rubber goods, and in the preparation of medicinal ointments. For
example, zinc-oxide-based sunscreens, as shown in Figure 18.44, help prevent sunburn. The zinc oxide in these sunscreens is
present in the form of very small grains known as nanoparticles. Lead dioxide is a constituent of charged lead storage batteries.
Lead(IV) tends to revert to the more stable lead(II) ion by gaining two electrons, so lead dioxide is a powerful oxidizing agent.
Figure 18.44 Zinc oxide protects exposed skin from sunburn. (credit: modification of work by "osseous"/Flickr)

18.10.0.0.2: Peroxides and Superoxides
Peroxides and superoxides are strong oxidizers and are important in chemical processes. Hydrogen peroxide, H2O2, prepared from
metal peroxides, is an important bleach and disinfectant. Peroxides and superoxides form when the metal or metal oxides of groups
1 and 2 react with pure oxygen at elevated temperatures. Sodium peroxide and the peroxides of calcium, strontium, and barium
form by heating the corresponding metal or metal oxide in pure oxygen:
Δ
2Na(s) + O2 (g) −→ Na2 O2 (s)
2 Na2 O(s) + O2 (g) −→ 2 Na2 O2 (s)
Δ
2SrO(s) + O2 (g) −→ 2 SrO 2 (s)
The peroxides of potassium, rubidium, and cesium can be prepared by heating the metal or its oxide in a carefully controlled
amount of oxygen:
2K(s) + O2 (g) ⟶ K2 O2 (s) (2 mol K per mol O2 )
With an excess of oxygen, the superoxides KO2, RbO2, and CsO2 form. For example:
K(s) + O2 (g) ⟶ KO 2 (s) (1 mol K per mol O2 )
The stability of the peroxides and superoxides of the alkali metals increases as the size of the cation increases.
18.10.0.0.3: Hydroxides
Hydroxides are compounds that contain the OH− ion. It is possible to prepare these compounds by two general types of reactions.
Soluble metal hydroxides can be produced by the reaction of the metal or metal oxide with water. Insoluble metal hydroxides form
when a solution of a soluble salt of the metal combines with a solution containing hydroxide ions.
With the exception of beryllium and magnesium, the metals of groups 1 and 2 react with water to form hydroxides and hydrogen
gas. Examples of such reactions include:
2Li(s) + 2 H2 O(l) ⟶ 2LiOH(aq) + H2 (g)
Ca(s) + 2 H2 O(l) ⟶ Ca (OH) (aq) + H2 (g)

2
However, these reactions can be violent and dangerous; therefore, it is preferable to produce soluble metal hydroxides by the
reaction of the respective oxide with water:
Li 2 O(s) + H2 O(l) ⟶ 2LiOH(aq)
CaO(s) + H2 O(l) ⟶ Ca (OH) 2 (aq)
Most metal oxides are base anhydrides. This is obvious for the soluble oxides because they form metal hydroxides. Most other
metal oxides are insoluble and do not form hydroxides in water; however, they are still base anhydrides because they will react
with acids.
It is possible to prepare the insoluble hydroxides of beryllium, magnesium, and other representative metals by the addition of
sodium hydroxide to a solution of a salt of the respective metal. The net ionic equations for the reactions involving a magnesium
salt, an aluminum salt, and a zinc salt are:
2+ −
Mg (aq) + 2 OH (aq) ⟶ Mg (OH) (s)
2
3+ −
Al (aq) + 3 OH (aq) ⟶ Al (OH) (s)
3
2+ −
Zn (aq) + 2 OH (aq) ⟶ Zn(OH) (s)
2
An excess of hydroxide must be avoided when preparing aluminum, gallium, zinc, and tin(II) hydroxides, or the hydroxides will
dissolve with the formation of the corresponding complex ions: Al(OH) , Ga(OH) , Zn(OH)
4
−
4
−
, and Sn(OH)
4
2−
(see 3
−
Figure 18.45). The important aspect of complex ions for this chapter is that they form by a Lewis acid-base reaction with the metal
being the Lewis acid.

Figure 18.45 (a) Mixing solutions of NaOH and Zn(NO3)2 produces a white precipitate of Zn(OH)2. (b) Addition of an excess of
NaOH results in dissolution of the precipitate. (credit: modification of work by Mark Ott)
Industry uses large quantities of sodium hydroxide as a cheap, strong base. Sodium chloride is the starting material for the
production of NaOH because NaCl is a less expensive starting material than the oxide. Sodium hydroxide is among the top 10
chemicals in production in the United States, and this production was almost entirely by electrolysis of solutions of sodium
chloride. This process is the chlor-alkali process, and it is the primary method for producing chlorine.
Sodium hydroxide is an ionic compound and melts without decomposition. It is very soluble in water, giving off a great deal of heat
and forming very basic solutions: 40 grams of sodium hydroxide dissolves in only 60 grams of water at 25 °C. Sodium hydroxide is
employed in the production of other sodium compounds and is used to neutralize acidic solutions during the production of other
chemicals such as petrochemicals and polymers.
Many of the applications of hydroxides are for the neutralization of acids (such as the antacid shown in Figure 18.46) and for the
preparation of oxides by thermal decomposition. An aqueous suspension of magnesium hydroxide constitutes the antacid milk of
magnesia. Because of its ready availability (from the reaction of water with calcium oxide prepared by the decomposition of
limestone, CaCO3), low cost, and activity, calcium hydroxide is used extensively in commercial applications needing a cheap,
strong base. The reaction of hydroxides with appropriate acids is also used to prepare salts.

Figure 18.46 Calcium carbonate, CaCO3, can be consumed in the form of an antacid to neutralize the effects of acid in your
stomach. (credit: “Midnightcomm”/Wikimedia Commons)

18.10.0.0.4: The Chlor-Alkali Process
Although they are very different chemically, there is a link between chlorine and sodium hydroxide because there is an
important electrochemical process that produces the two chemicals simultaneously. The process known as the chlor-alkali

process, utilizes sodium chloride, which occurs in large deposits in many parts of the world. This is an electrochemical process
to oxidize chloride ion to chlorine and generate sodium hydroxide.
Passing a direct current of electricity through a solution of NaCl causes the chloride ions to migrate to the positive electrode
where oxidation to gaseous chlorine occurs when the ion gives up an electron to the electrode:
− −
2 Cl (aq) ⟶ Cl2 (g) + 2 e (at the positive electrode)
The electrons produced travel through the outside electrical circuit to the negative electrode. Although the positive sodium ions
migrate toward this negative electrode, metallic sodium does not form because sodium ions are too difficult to reduce under the
conditions used. (Recall that metallic sodium is active enough to react with water and hence, even if produced, would
immediately react with water to produce sodium ions again.) Instead, water molecules pick up electrons from the electrode and
undergo reduction to form hydrogen gas and hydroxide ions:
− −
2 H2 O(l) + 2 e (from the negative electrode) ⟶ H2 (g) + 2 OH (aq)
The overall result is the conversion of the aqueous solution of NaCl to an aqueous solution of NaOH, gaseous Cl2, and gaseous
H2:
electrolysis
+ − + −
2 Na (aq) + 2 Cl (aq) + 2 H2 O(l) −−−−−−−→ 2 Na (aq) + 2 OH (aq) + Cl2 (g) + H2 (g)
18.10.0.1: Nonmetal Oxygen Compounds

Most nonmetals react with oxygen to form nonmetal oxides. Depending on the available oxidation states for the element, a variety
of oxides might form. Fluorine will combine with oxygen to form fluorides such as OF2, where the oxygen has a 2+-oxidation
state.
18.10.0.0.1: Sulfur Oxygen Compounds
The two common oxides of sulfur are sulfur dioxide, SO2, and sulfur trioxide, SO3. The odor of burning sulfur comes from sulfur
dioxide. Sulfur dioxide, shown in Figure 18.47, occurs in volcanic gases and in the atmosphere near industrial plants that burn fuel
containing sulfur compounds.
Figure 18.47 This image shows the molecular structure (left) and resonance forms (right) of sulfur dioxide.
Commercial production of sulfur dioxide is from either burning sulfur or roasting sulfide ores such as ZnS, FeS2, and Cu2S in air.
(Roasting, which forms the metal oxide, is the first step in the separation of many metals from their ores.) A convenient method for
preparing sulfur dioxide in the laboratory is by the action of a strong acid on either sulfite salts containing the SO ion or 3
2−
hydrogen sulfite salts containing HSO . Sulfurous acid, H2SO3, forms first, but quickly decomposes into sulfur dioxide and
3
−
water. Sulfur dioxide also forms when many reducing agents react with hot, concentrated sulfuric acid. Sulfur trioxide forms slowly
when heating sulfur dioxide and oxygen together, and the reaction is exothermic:
2 SO 2 (g) + O2 (g) ⟶ 2 SO 3 (g) ΔH ° = −197.8 kJ
Sulfur dioxide is a gas at room temperature, and the SO2 molecule is bent. Sulfur trioxide melts at 17 °C and boils at 43 °C. In the
vapor state, its molecules are single SO3 units (shown in Figure 18.48), but in the solid state, SO3 exists in several polymeric forms.

Figure 18.48 This image shows the structure (top) of sulfur trioxide in the gas phase and its resonance forms (bottom).
The sulfur oxides react as Lewis acids with many oxides and hydroxides in Lewis acid-base reactions, with the formation of
sulfites or hydrogen sulfites, and sulfates or hydrogen sulfates, respectively.
18.10.0.0.2: Halogen Oxygen Compounds
The halogens do not react directly with oxygen, but it is possible to prepare binary oxygen-halogen compounds by the reactions of
the halogens with oxygen-containing compounds. Oxygen compounds with chlorine, bromine, and iodine are oxides because
oxygen is the more electronegative element in these compounds. On the other hand, fluorine compounds with oxygen are fluorides
because fluorine is the more electronegative element.
As a class, the oxides are extremely reactive and unstable, and their chemistry has little practical importance. Dichlorine oxide,
formally called dichlorine monoxide, and chlorine dioxide, both shown in Figure 18.49, are the only commercially important
compounds. They are important as bleaching agents (for use with pulp and flour) and for water treatment.
Figure 18.49 This image shows the structures of the (a) Cl2O and (b) ClO2 molecules.
18.10.0.1: Nonmetal Oxyacids and Their Salts

Nonmetal oxides form acids when allowed to react with water; these are acid anhydrides. The resulting oxyanions can form salts
with various metal ions.

18.10.0.1: Nitrogen Oxyacids and Salts
Nitrogen pentaoxide, N2O5, and NO2 react with water to form nitric acid, HNO3. Alchemists, as early as the eighth century, knew
nitric acid (shown in Figure 18.50) as aqua fortis (meaning "strong water"). The acid was useful in the separation of gold from
silver because it dissolves silver but not gold. Traces of nitric acid occur in the atmosphere after thunderstorms, and its salts are
widely distributed in nature. There are tremendous deposits of Chile saltpeter, NaNO3, in the desert region near the boundary of
Chile and Peru. Bengal saltpeter, KNO3, occurs in India and in other countries of the Far East.
Figure 18.50 This image shows the molecular structure (left) of nitric acid, HNO3 and its resonance forms (right).
In the laboratory, it is possible to produce nitric acid by heating a nitrate salt (such as sodium or potassium nitrate) with
concentrated sulfuric acid:
Δ
NaNO3 (s) + H2 SO 4 (l) −→ NaHSO4 (s) + HNO3 (g)
The Ostwald process is the commercial method for producing nitric acid. This process involves the oxidation of ammonia to nitric
oxide, NO; oxidation of nitric oxide to nitrogen dioxide, NO2; and further oxidation and hydration of nitrogen dioxide to form
nitric acid:
4 NH3 (g) + 5 O2 (g) ⟶ 4NO(g) + 6 H2 O(g)
2NO(g) + O2 (g) ⟶ 2 NO2 (g)
3 NO2 (g) + H2 O(l) ⟶ 2 HNO3 (aq) + NO(g)
Or
4 NO2 (g) + O2 (g) + 2 H2 O(g) ⟶ 4 HNO3 (l)
Pure nitric acid is a colorless liquid. However, it is often yellow or brown in color because NO2 forms as the acid decomposes.
Nitric acid is stable in aqueous solution; solutions containing 68% of the acid are commercially available concentrated nitric acid. It
is both a strong oxidizing agent and a strong acid.
The action of nitric acid on a metal rarely produces H2 (by reduction of H+) in more than small amounts. Instead, the reduction of
nitrogen occurs. The products formed depend on the concentration of the acid, the activity of the metal, and the temperature.
Normally, a mixture of nitrates, nitrogen oxides, and various reduction products form. Less active metals such as copper, silver, and
lead reduce concentrated nitric acid primarily to nitrogen dioxide. The reaction of dilute nitric acid with copper produces NO. In
each case, the nitrate salts of the metals crystallize upon evaporation of the resultant solutions.
Nonmetallic elements, such as sulfur, carbon, iodine, and phosphorus, undergo oxidation by concentrated nitric acid to their oxides
or oxyacids, with the formation of NO2:
S(s) + 6 HNO3 (aq) ⟶ H2 SO 4 (aq) + 6 NO2 (g) + 2 H2 O(l)
C(s) + 4 HNO3 (aq) ⟶ CO2 (g) + 4 NO2 (g) + 2 H2 O(l)
Nitric acid oxidizes many compounds; for example, concentrated nitric acid readily oxidizes hydrochloric acid to chlorine and
chlorine dioxide. A mixture of one part concentrated nitric acid and three parts concentrated hydrochloric acid (called aqua regia,
which means royal water) reacts vigorously with metals. This mixture is particularly useful in dissolving gold, platinum, and other
metals that are more difficult to oxidize than hydrogen. A simplified equation to represent the action of aqua regia on gold is:
Au(s) + 4HCl(aq) + 3 HNO3 (aq) ⟶ HAuCl4 (aq) + 3 NO2 (g) + 3 H2 O(l)

Although gold is generally unreactive, you can watch a video of the complex mixture of compounds present in aqua regia
dissolving it into solution.
Nitrates, salts of nitric acid, form when metals, oxides, hydroxides, or carbonates react with nitric acid. Most nitrates are soluble in
water; indeed, one of the significant uses of nitric acid is to prepare soluble metal nitrates.
Nitric acid finds extensive use in the laboratory and in chemical industries as a strong acid and strong oxidizing agent. It is
important in the manufacture of explosives, dyes, plastics, and drugs. Salts of nitric acid (nitrates) are valuable as fertilizers.
Gunpowder is a mixture of potassium nitrate, sulfur, and charcoal.
The reaction of N2O3 with water gives a pale blue solution of nitrous acid, HNO2. However, HNO2 (shown in Figure 18.51) is
easier to prepare by the addition of an acid to a solution of nitrite; nitrous acid is a weak acid, so the nitrite ion is basic in aqueous
solution:
− +
NO2 (aq) + H3 O (aq) ⟶ HNO2 (aq) + H2 O(l)
Nitrous acid is very unstable and exists only in solution. It disproportionates slowly at room temperature (rapidly when heated) into
nitric acid and nitric oxide. Nitrous acid is an active oxidizing agent with strong reducing agents, and strong oxidizing agents
oxidize it to nitric acid.
Figure 18.51 This image shows the molecular structure of a molecule of nitrous acid, HNO2.
Sodium nitrite, NaNO2, is an additive to meats such as hot dogs and cold cuts. The nitrite ion has two functions. It limits the growth
of bacteria that can cause food poisoning, and it prolongs the meat’s retention of its red color. The addition of sodium nitrite to
meat products is controversial because nitrous acid reacts with certain organic compounds to form a class of compounds known as
nitrosamines. Nitrosamines produce cancer in laboratory animals. This has prompted the FDA to limit the amount of NaNO2 in
foods.
The nitrites are much more stable than the acid, but nitrites, like nitrates, can explode. Nitrites, like nitrates, are also soluble in
water (AgNO2 is only slightly soluble).
18.10.0.1: Phosphorus Oxyacids and Salts

Pure orthophosphoric acid, H3PO4 (shown in Figure 18.52), forms colorless, deliquescent crystals that melt at 42 °C. The common
name of this compound is phosphoric acid, and is commercially available as a viscous 82% solution known as syrupy phosphoric
acid. One use of phosphoric acid is as an additive to many soft drinks.
One commercial method of preparing orthophosphoric acid is to treat calcium phosphate rock with concentrated sulfuric acid:
Ca3 (PO4 )2 (s) + 3 H2 SO 4 (aq) ⟶ 2 H3 PO4 (aq) + 3 CaSO4 (s)
Figure 18.52 Orthophosphoric acid, H3PO4, is colorless when pure and has this molecular (left) and Lewis structure (right).

Dilution of the products with water, followed by filtration to remove calcium sulfate, gives a dilute acid solution contaminated with
calcium dihydrogen phosphate, Ca(H2PO4)2, and other compounds associated with calcium phosphate rock. It is possible to prepare
pure orthophosphoric acid by dissolving P4O10 in water.
The action of water on P4O6, PCl3, PBr3, or PI3 forms phosphorous acid, H3PO3 (shown in Figure 18.53). The best method for
preparing pure phosphorous acid is by hydrolyzing phosphorus trichloride:
PCl3 (l) + 3 H2 O(l) ⟶ H3 PO3 (aq) + 3HCl(g)
Heating the resulting solution expels the hydrogen chloride and leads to the evaporation of water. When sufficient water
evaporates, white crystals of phosphorous acid will appear upon cooling. The crystals are deliquescent, very soluble in water, and
have an odor like that of garlic. The solid melts at 70.1 °C and decomposes at about 200 °C by disproportionation into phosphine
and orthophosphoric acid:
4 H3 PO3 (l) ⟶ PH3 (g) + 3 H3 PO4 (l)
Figure 18.53 In a molecule of phosphorous acid, H3PO3, only the two hydrogen atoms bonded to an oxygen atom are acidic.
Phosphorous acid forms only two series of salts, which contain the dihydrogen phosphite ion, H PO , or the hydrogen phosphate
2 3
−
ion, HPO , respectively. It is not possible to replace the third atom of hydrogen because it is not very acidic, as it is not easy to
3
2−
ionize the P-H bond.
18.10.0.1: Sulfur Oxyacids and Salts

The preparation of sulfuric acid, H2SO4 (shown in Figure 18.54), begins with the oxidation of sulfur to sulfur trioxide and then
converting the trioxide to sulfuric acid. Pure sulfuric acid is a colorless, oily liquid that freezes at 10.5 °C. It fumes when heated
because the acid decomposes to water and sulfur trioxide. The heating process causes the loss of more sulfur trioxide than water,
until reaching a concentration of 98.33% acid. Acid of this concentration boils at 338 °C without further change in concentration (a
constant boiling solution) and is commercially concentrated H2SO4. The amount of sulfuric acid used in industry exceeds that of
any other manufactured compound.
Figure 18.54 Sulfuric acid has a tetrahedral molecular structure.

The strong affinity of concentrated sulfuric acid for water makes it a good dehydrating agent. It is possible to dry gases and
immiscible liquids that do not react with the acid by passing them through the acid.

Sulfuric acid is a strong diprotic acid that ionizes in two stages. In aqueous solution, the first stage is essentially complete. The
secondary ionization is not nearly so complete, and HSO is a moderately strong acid (about 25% ionized in solution of a
4
−
−2
HSO 4 salt: Ka = 1.2 × 10 ).
−
Being a diprotic acid, sulfuric acid forms both sulfates, such as Na2SO4, and hydrogen sulfates, such as NaHSO4. Most sulfates are
soluble in water; however, the sulfates of barium, strontium, calcium, and lead are only slightly soluble in water.
Among the important sulfates are Na2SO4⋅10H2O and Epsom salts, MgSO4⋅7H2O. Because the HSO ion is an acid, hydrogen
4
−
sulfates, such as NaHSO4, exhibit acidic behavior, and this compound is the primary ingredient in some household cleansers.
Hot, concentrated sulfuric acid is an oxidizing agent. Depending on its concentration, the temperature, and the strength of the
reducing agent, sulfuric acid oxidizes many compounds and, in the process, undergoes reduction to SO2, HSO , SO , S, H2S,3
−
3
2−
or S2−.
Sulfur dioxide dissolves in water to form a solution of sulfurous acid, as expected for the oxide of a nonmetal. Sulfurous acid is
unstable, and it is not possible to isolate anhydrous H2SO3. Heating a solution of sulfurous acid expels the sulfur dioxide. Like
other diprotic acids, sulfurous acid ionizes in two steps: The hydrogen sulfite ion, HSO , and the sulfite ion, SO , form.
3
−
3
2−
Sulfurous acid is a moderately strong acid. Ionization is about 25% in the first stage, but it is much less in the second (Ka1 = 1.2 ×
10−2 and Ka2 = 6.2 × 10−8).
In order to prepare solid sulfite and hydrogen sulfite salts, it is necessary to add a stoichiometric amount of a base to a sulfurous
acid solution and then evaporate the water. These salts also form from the reaction of SO2 with oxides and hydroxides. Heating
solid sodium hydrogen sulfite forms sodium sulfite, sulfur dioxide, and water:
Δ
2 NaHSO3 (s) −→ Na2 SO 3 (s) + SO 2 (g) + H2 O(l)
Strong oxidizing agents can oxidize sulfurous acid. Oxygen in the air oxidizes it slowly to the more stable sulfuric acid:
Δ
+ −
2 H2 SO 3 (aq) + O2 (g) + 2 H2 O(l) −→ 2 H3 O (aq) + 2 HSO 4 (aq)
Solutions of sulfites are also very susceptible to air oxidation to produce sulfates. Thus, solutions of sulfites always contain sulfates
after exposure to air.
18.10.0.1: Halogen Oxyacids and Their Salts

The compounds HXO, HXO2, HXO3, and HXO4, where X represents Cl, Br, or I, are the hypohalous, halous, halic, and perhalic
acids, respectively. The strengths of these acids increase from the hypohalous acids, which are very weak acids, to the perhalic
acids, which are very strong. Table 18.2 lists the known acids, and, where known, their pKa values are given in parentheses.
Oxyacids of the Halogens
Name Fluorine Chlorine Bromine Iodine
hypohalous HOF HOCl (7.5) HOBr (8.7) HOI (11)
halous HClO2 (2.0)
halic HClO3 HBrO3 HIO3 (0.8)
perhalic HClO4 HBrO4 HIO4 (1.6)
paraperhalic H5IO6 (1.6)
Table 18.2
The only known oxyacid of fluorine is the very unstable hypofluorous acid, HOF, which is prepared by the reaction of gaseous
fluorine with ice:
F2 (g) + H2 O(s) ⟶ HOF(g) + HF(g)

The compound is very unstable and decomposes above −40 °C. This compound does not ionize in water, and there are no known
salts. It is uncertain whether the name hypofluorous acid is even appropriate for HOF; a more appropriate name might be hydrogen
hypofluorite.
The reactions of chlorine and bromine with water are analogous to that of fluorine with ice, but these reactions do not go to
completion, and mixtures of the halogen and the respective hypohalous and hydrohalic acids result. Other than HOF, the
hypohalous acids only exist in solution. The hypohalous acids are all very weak acids; however, HOCl is a stronger acid than
HOBr, which, in turn, is stronger than HOI.
The addition of base to solutions of the hypohalous acids produces solutions of salts containing the basic hypohalite ions, OX−. It is
possible to isolate these salts as solids. All of the hypohalites are unstable with respect to disproportionation in solution, but the
reaction is slow for hypochlorite. Hypobromite and hypoiodite disproportionate rapidly, even in the cold:
− − −
3 XO (aq) ⟶ 2 X (aq) + XO3 (aq)
Sodium hypochlorite is an inexpensive bleach (Clorox) and germicide. The commercial preparation involves the electrolysis of
cold, dilute, aqueous sodium chloride solutions under conditions where the resulting chlorine and hydroxide ion can react. The net
reaction is:
electrical energy
− −
Cl (aq) + H2 O(l) −−−−−−−−−−→ ClO (aq) + H2 (g)
The only definitely known halous acid is chlorous acid, HClO2, obtained by the reaction of barium chlorite with dilute sulfuric
acid:
Ba (ClO2 ) (aq) + H2 SO 4 (aq) ⟶ BaSO 4 (s) + 2 HClO2 (aq)
2
Filtering the insoluble barium sulfate leaves a solution of HClO2. Chlorous acid is not stable; it slowly decomposes in solution to
yield chlorine dioxide, hydrochloric acid, and water. Chlorous acid reacts with bases to give salts containing the chlorite ion (shown
in Figure 18.55). Sodium chlorite finds an extensive application in the bleaching of paper because it is a strong oxidizing agent and
does not damage the paper.
Figure 18.55 Chlorite ions, ClO 2

−
, are produced when chlorous acid reacts with bases.
Chloric acid, HClO3, and bromic acid, HBrO3, are stable only in solution. The reaction of iodine with concentrated nitric acid
produces stable white iodic acid, HIO3:
I2 (s) + 10 HNO3 (aq) ⟶ 2 HIO3 (s) + 10 NO2 (g) + 4 H2 O(l)
It is possible to obtain the lighter halic acids from their barium salts by reaction with dilute sulfuric acid. The reaction is analogous
to that used to prepare chlorous acid. All of the halic acids are strong acids and very active oxidizing agents. The acids react with
bases to form salts containing chlorate ions (shown in Figure 18.56). Another preparative method is the electrochemical oxidation
of a hot solution of a metal halide to form the appropriate metal chlorates. Sodium chlorate is a weed killer; potassium chlorate is
used as an oxidizing agent.

Figure 18.56 Chlorate ions, ClO 3
−
, are produced when halic acids react with bases.
Perchloric acid, HClO4, forms when treating a perchlorate, such as potassium perchlorate, with sulfuric acid under reduced
pressure. The HClO4 can be distilled from the mixture:
KClO4 (s) + H2 SO 4 (aq) ⟶ HClO4 (g) + KHSO 4 (s)
Dilute aqueous solutions of perchloric acid are quite stable thermally, but concentrations above 60% are unstable and dangerous.
Perchloric acid and its salts are powerful oxidizing agents, as the very electronegative chlorine is more stable in a lower oxidation
state than 7+. Serious explosions have occurred when heating concentrated solutions with easily oxidized substances. However, its
reactions as an oxidizing agent are slow when perchloric acid is cold and dilute. The acid is among the strongest of all acids. Most
salts containing the perchlorate ion (shown in Figure 18.57) are soluble. It is possible to prepare them from reactions of bases with
perchloric acid and, commercially, by the electrolysis of hot solutions of their chlorides.
Figure 18.57 Perchlorate ions, ClO 4

−
, can be produced when perchloric acid reacts with a base or by electrolysis of hot solutions
of their chlorides.
Perbromate salts are difficult to prepare, and the best syntheses currently involve the oxidation of bromates in basic solution with
fluorine gas followed by acidification. There are few, if any, commercial uses of this acid or its salts.
There are several different acids containing iodine in the 7+-oxidation state; they include metaperiodic acid, HIO4, and paraperiodic
acid, H5IO6. These acids are strong oxidizing agents and react with bases to form the appropriate salts.
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Describe the properties, preparation, and uses of sulfur
Sulfur exists in nature as elemental deposits as well as sulfides of iron, zinc, lead, and copper, and sulfates of sodium, calcium,
barium, and magnesium. Hydrogen sulfide is often a component of natural gas and occurs in many volcanic gases, like those shown
in Figure 18.58. Sulfur is a constituent of many proteins and is essential for life.
Figure 18.58 Volcanic gases contain hydrogen sulfide. (credit: Daniel Julie/Wikimedia Commons)
The Frasch process, illustrated in Figure 18.59, is important in the mining of free sulfur from enormous underground deposits in
Texas and Louisiana. Superheated water (170 °C and 10 atm pressure) is forced down the outermost of three concentric pipes to the
underground deposit. The hot water melts the sulfur. The innermost pipe conducts compressed air into the liquid sulfur. The air
forces the liquid sulfur, mixed with air, to flow up through the outlet pipe. Transferring the mixture to large settling vats allows the
solid sulfur to separate upon cooling. This sulfur is 99.5% to 99.9% pure and requires no purification for most uses.

Figure 18.59 The Frasch process is used to mine sulfur from underground deposits.
Larger amounts of sulfur also come from hydrogen sulfide recovered during the purification of natural gas.
Sulfur exists in several allotropic forms. The stable form at room temperature contains eight-membered rings, and so the true
formula is S8. However, chemists commonly use S to simplify the coefficients in chemical equations; we will follow this practice in
this book.
Like oxygen, which is also a member of group 16, sulfur exhibits a distinctly nonmetallic behavior. It oxidizes metals, giving a
variety of binary sulfides in which sulfur exhibits a negative oxidation state (2−). Elemental sulfur oxidizes less electronegative
nonmetals, and more electronegative nonmetals, such as oxygen and the halogens, will oxidize it. Other strong oxidizing agents
also oxidize sulfur. For example, concentrated nitric acid oxidizes sulfur to the sulfate ion, with the concurrent formation of
nitrogen(IV) oxide:
+ 2−
S(s) + 6 HNO3 (aq) ⟶ 2 H3 O (aq) + SO 4 (aq) + 6 NO2 (g)
The chemistry of sulfur with an oxidation state of 2− is similar to that of oxygen. Unlike oxygen, however, sulfur forms many
compounds in which it exhibits positive oxidation states.
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upon request.


Describe the preparation, properties, and uses of halogens
Describe the properties, preparation, and uses of halogen compounds
The elements in group 17 are the halogens. These are the elements fluorine, chlorine, bromine, iodine, and astatine. These elements
are too reactive to occur freely in nature, but their compounds are widely distributed. Chlorides are the most abundant; although
fluorides, bromides, and iodides are less common, they are reasonably available. In this section, we will examine the occurrence,
preparation, and properties of halogens. Next, we will examine halogen compounds with the representative metals followed by an
examination of the interhalogens. This section will conclude with some applications of halogens.
18.12.0.1: Occurrence and Preparation

All of the halogens occur in seawater as halide ions. The concentration of the chloride ion is 0.54 M; that of the other halides is less
than 10–4 M. Fluoride also occurs in minerals such as CaF2, Ca(PO4)3F, and Na3AlF6. Chloride also occurs in the Great Salt Lake
and the Dead Sea, and in extensive salt beds that contain NaCl, KCl, or MgCl2. Part of the chlorine in your body is present as
hydrochloric acid, which is a component of stomach acid. Bromine compounds occur in the Dead Sea and underground brines.
Iodine compounds are found in small quantities in Chile saltpeter, underground brines, and sea kelp. Iodine is essential to the
function of the thyroid gland.
The best sources of halogens (except iodine) are halide salts. It is possible to oxidize the halide ions to free diatomic halogen
molecules by various methods, depending on the ease of oxidation of the halide ion. Fluoride is the most difficult to oxidize,
whereas iodide is the easiest.
The major method for preparing fluorine is electrolytic oxidation. The most common electrolysis procedure is to use a molten
mixture of potassium hydrogen fluoride, KHF2, and anhydrous hydrogen fluoride. Electrolysis causes HF to decompose, forming
fluorine gas at the anode and hydrogen at the cathode. It is necessary to keep the two gases separated to prevent their explosive
recombination to reform hydrogen fluoride.
Most commercial chlorine comes from the electrolysis of the chloride ion in aqueous solutions of sodium chloride; this is the chlor-
alkali process discussed previously. Chlorine is also a product of the electrolytic production of metals such as sodium, calcium, and
magnesium from their fused chlorides. It is also possible to prepare chlorine by the chemical oxidation of the chloride ion in acid
solution with strong oxidizing agents such as manganese dioxide (MnO2) or sodium dichromate (Na2Cr2O7). The reaction with
manganese dioxide is:
− + 2+
MnO 2 (s) + 2 Cl (aq) + 4 H3 O (aq) ⟶ Mn (aq) + Cl2 (g) + 6 H2 O(l)
The commercial preparation of bromine involves the oxidation of bromide ion by chlorine:
− −
2 Br (aq) + Cl2 (g) ⟶ Br 2 (l) + 2 Cl (aq)
Chlorine is a stronger oxidizing agent than bromine. This method is important for the production of essentially all domestic
bromine.
Some iodine comes from the oxidation of iodine chloride, ICl, or iodic acid, HlO3. The commercial preparation of iodine utilizes
the reduction of sodium iodate, NaIO3, an impurity in deposits of Chile saltpeter, with sodium hydrogen sulfite:
− − − 2−
2 IO3 (aq) + 5 HSO 3 (aq) ⟶ 3 HSO 4 (aq) + 2 SO 4 (aq) + H2 O(l) + I2 (s)
18.12.0.1: Properties of the Halogens

Fluorine is a pale yellow gas, chlorine is a greenish-yellow gas, bromine is a deep reddish-brown liquid, and iodine is a grayish-
black crystalline solid. Liquid bromine has a high vapor pressure, and the reddish vapor is readily visible in Figure 18.60. Iodine
crystals have a noticeable vapor pressure. When gently heated, these crystals sublime and form a beautiful deep violet vapor.

Figure 18.60 Chlorine is a pale yellow-green gas (left), gaseous bromine is deep orange (center), and gaseous iodine is purple
(right). (Fluorine is so reactive that it is too dangerous to handle.) (credit: Sahar Atwa)
Bromine is only slightly soluble in water, but it is miscible in all proportions in less polar (or nonpolar) solvents such as
chloroform, carbon tetrachloride, and carbon disulfide, forming solutions that vary from yellow to reddish-brown, depending on the
concentration.
Iodine is soluble in chloroform, carbon tetrachloride, carbon disulfide, and many hydrocarbons, giving violet solutions of I2
molecules. Iodine dissolves only slightly in water, giving brown solutions. It is quite soluble in aqueous solutions of iodides, with
which it forms brown solutions. These brown solutions result because iodine molecules have empty valence d orbitals and can act
as weak Lewis acids towards the iodide ion. The equation for the reversible reaction of iodine (Lewis acid) with the iodide ion
(Lewis base) to form triiodide ion, I , is:
3
−
− −
I2 (s) + I (aq) ⟶ I3 (aq)
The easier it is to oxidize the halide ion, the more difficult it is for the halogen to act as an oxidizing agent. Fluorine generally
oxidizes an element to its highest oxidation state, whereas the heavier halogens may not. For example, when excess fluorine reacts
with sulfur, SF6 forms. Chlorine gives SCl2 and bromine, S2Br2. Iodine does not react with sulfur.
Fluorine is the most powerful oxidizing agent of the known elements. It spontaneously oxidizes most other elements; therefore, the
reverse reaction, the oxidation of fluorides, is very difficult to accomplish. Fluorine reacts directly and forms binary fluorides with
all of the elements except the lighter noble gases (He, Ne, and Ar). Fluorine is such a strong oxidizing agent that many substances
ignite on contact with it. Drops of water inflame in fluorine and form O2, OF2, H2O2, O3, and HF. Wood and asbestos ignite and
burn in fluorine gas. Most hot metals burn vigorously in fluorine. However, it is possible to handle fluorine in copper, iron, or
nickel containers because an adherent film of the fluoride salt passivates their surfaces. Fluorine is the only element that reacts
directly with the noble gas xenon.
Although it is a strong oxidizing agent, chlorine is less active than fluorine. Mixing chlorine and hydrogen in the dark makes the
reaction between them to be imperceptibly slow. Exposure of the mixture to light causes the two to react explosively. Chlorine is
also less active towards metals than fluorine, and oxidation reactions usually require higher temperatures. Molten sodium ignites in
chlorine. Chlorine attacks most nonmetals (C, N2, and O2 are notable exceptions), forming covalent molecular compounds.
Chlorine generally reacts with compounds that contain only carbon and hydrogen (hydrocarbons) by adding to multiple bonds or by
substitution.
In cold water, chlorine undergoes a disproportionation reaction:
+ −
Cl2 (aq) + 2 H2 O(l) ⟶ HOCl(aq) + H3 O (aq) + Cl (aq)
Half the chlorine atoms oxidize to the 1+ oxidation state (hypochlorous acid), and the other half reduce to the 1− oxidation state
(chloride ion). This disproportionation is incomplete, so chlorine water is an equilibrium mixture of chlorine molecules,

hypochlorous acid molecules, hydronium ions, and chloride ions. When exposed to light, this solution undergoes a photochemical
decomposition:
sunlight
+ −
2HOCl(aq) + 2 H2 O(l) −−−−−→ 2 H3 O (aq) + 2 Cl (aq) + O2 (g)
The nonmetal chlorine is more electronegative than any other element except fluorine, oxygen, and nitrogen. In general, very
electronegative elements are good oxidizing agents; therefore, we would expect elemental chlorine to oxidize all of the other
elements except for these three (and the nonreactive noble gases). Its oxidizing property, in fact, is responsible for its principal use.
For example, phosphorus(V) chloride, an important intermediate in the preparation of insecticides and chemical weapons, is
manufactured by oxidizing the phosphorus with chlorine:
P4 (s) + 10 Cl2 (g) ⟶ 4 PCl5 (l)
A great deal of chlorine is also used to oxidize, and thus to destroy, organic or biological materials in water purification and in
bleaching.
The chemical properties of bromine are similar to those of chlorine, although bromine is the weaker oxidizing agent and its
reactivity is less than that of chlorine.
Iodine is the least reactive of the halogens. It is the weakest oxidizing agent, and the iodide ion is the most easily oxidized halide
ion. Iodine reacts with metals, but heating is often required. It does not oxidize other halide ions.
Compared with the other halogens, iodine reacts only slightly with water. Traces of iodine in water react with a mixture of starch
and iodide ion, forming a deep blue color. This reaction is a very sensitive test for the presence of iodine in water.
18.12.0.1: Halides of the Representative Metals

Thousands of salts of the representative metals have been prepared. The binary halides are an important subclass of salts. A salt is
an ionic compound composed of cations and anions, other than hydroxide or oxide ions. In general, it is possible to prepare these
salts from the metals or from oxides, hydroxides, or carbonates. We will illustrate the general types of reactions for preparing salts
through reactions used to prepare binary halides.
The binary compounds of a metal with the halogens are the halides. Most binary halides are ionic. However, mercury, the elements
of group 13 with oxidation states of 3+, tin(IV), and lead(IV) form covalent binary halides.
The direct reaction of a metal and a halogen produce the halide of the metal. Examples of these oxidation-reduction reactions
include:
Cd(s) + Cl2 (g) ⟶ CdCl2 (s)
2Ga(l) + 3 Br 2 (l) ⟶ 2 GaBr 3 (s)

Reactions of the alkali metals with elemental halogens are very exothermic and often quite violent. Under controlled
conditions, they provide exciting demonstrations for budding students of chemistry. You can view the initial heating of the
sodium that removes the coating of sodium hydroxide, sodium peroxide, and residual mineral oil to expose the reactive
surface. The reaction with chlorine gas then proceeds very nicely.
If a metal can exhibit two oxidation states, it may be necessary to control the stoichiometry in order to obtain the halide with the
lower oxidation state. For example, preparation of tin(II) chloride requires a 1:1 ratio of Sn to Cl2, whereas preparation of tin(IV)
chloride requires a 1:2 ratio:
Sn(s) + Cl2 (g) ⟶ SnCl 2 (s)
Sn(s) + 2 Cl2 (g) ⟶ SnCl 4 (l)
The active representative metals—those that are easier to oxidize than hydrogen—react with gaseous hydrogen halides to produce
metal halides and hydrogen. The reaction of zinc with hydrogen fluoride is:
Zn(s) + 2HF(g) ⟶ ZnF 2 (s) + H2 (g)

The active representative metals also react with solutions of hydrogen halides to form hydrogen and solutions of the corresponding
halides. Examples of such reactions include:
Cd(s) + 2HBr(aq) ⟶ CdBr 2 (aq) + H2 (g)
Sn(s) + 2HI(aq) ⟶ SnI 2 (aq) + H2 (g)
Hydroxides, carbonates, and some oxides react with solutions of the hydrogen halides to form solutions of halide salts. It is
possible to prepare additional salts by the reaction of these hydroxides, carbonates, and oxides with aqueous solution of other acids:
CaCo3 (s) + 2HCl(aq) ⟶ CaCl2 (aq) + CO2 (g) + H2 O(l)
TlOH(aq) + HF(aq) ⟶ TlF(aq) + H2 O(l)
A few halides and many of the other salts of the representative metals are insoluble. It is possible to prepare these soluble salts by
metathesis reactions that occur when solutions of soluble salts are mixed (see Figure 18.61). Metathesis reactions are examined in
the chapter on the stoichiometry of chemical reactions.
Figure 18.61 Solid HgI2 forms when solutions of KI and Hg(NO3)2 are mixed. (credit: Sahar Atwa)
Several halides occur in large quantities in nature. The ocean and underground brines contain many halides. For example,
magnesium chloride in the ocean is the source of magnesium ions used in the production of magnesium. Large underground
deposits of sodium chloride, like the salt mine shown in Figure 18.62, occur in many parts of the world. These deposits serve as the
source of sodium and chlorine in almost all other compounds containing these elements. The chlor-alkali process is one example.

Figure 18.62 Underground deposits of sodium chloride are found throughout the world and are often mined. This is a tunnel in the
Kłodawa salt mine in Poland. (credit: Jarek Zok)
18.12.0.1: Interhalogens
Compounds formed from two or more different halogens are interhalogens. Interhalogen molecules consist of one atom of the
heavier halogen bonded by single bonds to an odd number of atoms of the lighter halogen. The structures of IF3, IF5, and IF7 are
illustrated in Figure 18.63. Formulas for other interhalogens, each of which comes from the reaction of the respective halogens, are
in Table 18.3.

Figure 18.63 The structure of IF3 is T-shaped (left), IF5 is square pyramidal (center), and IF7 is pentagonal bipyramidal (right).
Note from Table 18.3 that fluorine is able to oxidize iodine to its maximum oxidation state, 7+, whereas bromine and chlorine,
which are more difficult to oxidize, achieve only the 5+-oxidation state. A 7+-oxidation state is the limit for the halogens. Because
smaller halogens are grouped about a larger one, the maximum number of smaller atoms possible increases as the radius of the
larger atom increases. Many of these compounds are unstable, and most are extremely reactive. The interhalogens react like their
component halides; halogen fluorides, for example, are stronger oxidizing agents than are halogen chlorides.
The ionic polyhalides of the alkali metals, such as KI3, KICl2, KICl4, CsIBr2, and CsBrCl2, which contain an anion composed of at
least three halogen atoms, are closely related to the interhalogens. As seen previously, the formation of the polyhalide anion I is 3
−
responsible for the solubility of iodine in aqueous solutions containing an iodide ion.
Interhalogens
YX YX3 YX5 YX7
ClF(g) ClF3(g) ClF5(g)
BrF(g) BrF3(l) BrF5(l)
BrCl(g)
IF(s) IF3(s) IF5(l) IF7(g)
ICl(l) ICl3(s)
IBr(s)
Table 18.3
18.12.0.1: Applications
The fluoride ion and fluorine compounds have many important uses. Compounds of carbon, hydrogen, and fluorine are replacing
Freons (compounds of carbon, chlorine, and fluorine) as refrigerants. Teflon is a polymer composed of –CF2CF2– units. Fluoride
ion is added to water supplies and to some toothpastes as SnF2 or NaF to fight tooth decay. Fluoride partially converts teeth from
Ca5(PO4)3(OH) into Ca5(PO4)3F.

Chlorine is important to bleach wood pulp and cotton cloth. The chlorine reacts with water to form hypochlorous acid, which
oxidizes colored substances to colorless ones. Large quantities of chlorine are important in chlorinating hydrocarbons (replacing
hydrogen with chlorine) to produce compounds such as tetrachloride (CCl4), chloroform (CHCl3), and ethyl chloride (C2H5Cl), and
in the production of polyvinyl chloride (PVC) and other polymers. Chlorine is also important to kill the bacteria in community
water supplies.
Bromine is important in the production of certain dyes, and sodium and potassium bromides are used as sedatives. At one time,
light-sensitive silver bromide was a component of photographic film.
Iodine in alcohol solution with potassium iodide is an antiseptic (tincture of iodine). Iodide salts are essential for the proper
functioning of the thyroid gland; an iodine deficiency may lead to the development of a goiter. Iodized table salt contains 0.023%
potassium iodide. Silver iodide is useful in the seeding of clouds to induce rain; it was important in the production of photographic
film and iodoform, CHI3, is an antiseptic.
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Describe the properties, preparation, and uses of the noble gases
The elements in group 18 are the noble gases (helium, neon, argon, krypton, xenon, and radon). They earned the name “noble”
because they were assumed to be nonreactive since they have filled valence shells. In 1962, Dr. Neil Bartlett at the University of
British Columbia proved this assumption to be false.
These elements are present in the atmosphere in small amounts. Some natural gas contains 1–2% helium by mass. Helium is
isolated from natural gas by liquefying the condensable components, leaving only helium as a gas. The United States possesses
most of the world’s commercial supply of this element in its helium-bearing gas fields. Argon, neon, krypton, and xenon come
from the fractional distillation of liquid air. Radon comes from other radioactive elements. More recently, it was observed that this
radioactive gas is present in very small amounts in soils and minerals. Its accumulation in well-insulated, tightly sealed buildings,
however, constitutes a health hazard, primarily lung cancer.
The boiling points and melting points of the noble gases are extremely low relative to those of other substances of comparable
atomic or molecular masses. This is because only weak London dispersion forces are present, and these forces can hold the atoms
together only when molecular motion is very slight, as it is at very low temperatures. Helium is the only substance known that does
not solidify on cooling at normal pressure. It remains liquid close to absolute zero (0.001 K) at ordinary pressures, but it solidifies
under elevated pressure.
Helium is used for filling balloons and lighter-than-air craft because it does not burn, making it safer to use than hydrogen. Helium
at high pressures is not a narcotic like nitrogen. Thus, mixtures of oxygen and helium are important for divers working under high
pressures. Using a helium-oxygen mixture avoids the disoriented mental state known as nitrogen narcosis, the so-called rapture of
the deep. Helium is important as an inert atmosphere for the melting and welding of easily oxidizable metals and for many
chemical processes that are sensitive to air.
Liquid helium (boiling point, 4.2 K) is an important coolant to reach the low temperatures necessary for cryogenic research, and it
is essential for achieving the low temperatures necessary to produce superconduction in traditional superconducting materials used
in powerful magnets and other devices. This cooling ability is necessary for the magnets used for magnetic resonance imaging, a
common medical diagnostic procedure. The other common coolant is liquid nitrogen (boiling point, 77 K), which is significantly
cheaper.
Neon is a component of neon lamps and signs. Passing an electric spark through a tube containing neon at low pressure generates
the familiar red glow of neon. It is possible to change the color of the light by mixing argon or mercury vapor with the neon or by
utilizing glass tubes of a special color.
Argon was useful in the manufacture of gas-filled electric light bulbs, where its lower heat conductivity and chemical inertness
made it preferable to nitrogen for inhibiting the vaporization of the tungsten filament and prolonging the life of the bulb.
Fluorescent tubes commonly contain a mixture of argon and mercury vapor. Argon is the third most abundant gas in dry air.
Krypton-xenon flash tubes are used to take high-speed photographs. An electric discharge through such a tube gives a very intense
light that lasts only 1
of a second. Krypton forms a difluoride, KrF2, which is thermally unstable at room temperature.
50,000
Stable compounds of xenon form when xenon reacts with fluorine. Xenon difluoride, XeF2, forms after heating an excess of xenon
gas with fluorine gas and then cooling. The material forms colorless crystals, which are stable at room temperature in a dry
atmosphere. Xenon tetrafluoride, XeF4, and xenon hexafluoride, XeF6, are prepared in an analogous manner, with a stoichiometric
amount of fluorine and an excess of fluorine, respectively. Compounds with oxygen are prepared by replacing fluorine atoms in the
xenon fluorides with oxygen.
When XeF6 reacts with water, a solution of XeO3 results and the xenon remains in the 6+-oxidation state:
XeF6 (s) + 3H2 O(l) ⟶ XeO3 (aq) + 6HF(aq)

Dry, solid xenon trioxide, XeO3, is extremely explosive—it will spontaneously detonate. Both XeF6 and XeO3 disproportionate in
basic solution, producing xenon, oxygen, and salts of the perxenate ion, XeO , in which xenon reaches its maximum oxidation
6
4−
sate of 8+.
Radon apparently forms RnF2—evidence of this compound comes from radiochemical tracer techniques.
Unstable compounds of argon form at low temperatures, but stable compounds of helium and neon are not known.
This page titled 18.13: Occurrence, Preparation, and Properties of the Noble Gases is shared under a CC BY 4.0 license and was authored,

18.14: Key Terms
acid anhydride
compound that reacts with water to form an acid or acidic solution
alkaline earth metal

any of the metals (beryllium, magnesium, calcium, strontium, barium, and radium) occupying group 2 of the periodic table;
they are reactive, divalent metals that form basic oxides
allotropes
two or more forms of the same element, in the same physical state, with different chemical structures
amorphous
solid material such as a glass that does not have a regular repeating component to its three-dimensional structure; a solid but not
a crystal
base anhydride
metal oxide that behaves as a base towards acids
bicarbonate anion
salt of the hydrogen carbonate ion, HCO 3
−
bismuth
heaviest member of group 15; a less reactive metal than other representative metals
borate
compound containing boron-oxygen bonds, typically with clusters or chains as a part of the chemical structure
carbonate
salt of the anion CO 3
2−
; often formed by the reaction of carbon dioxide with bases
chemical reduction
method of preparing a representative metal using a reducing agent
chlor-alkali process
electrolysis process for the synthesis of chlorine and sodium hydroxide
disproportionation reaction
chemical reaction where a single reactant is simultaneously reduced and oxidized; it is both the reducing agent and the
oxidizing agent
Downs cell
electrochemical cell used for the commercial preparation of metallic sodium (and chlorine) from molten sodium chloride
Frasch process
important in the mining of free sulfur from enormous underground deposits
Haber process
main industrial process used to produce ammonia from nitrogen and hydrogen; involves the use of an iron catalyst and elevated
temperatures and pressures
halide
compound containing an anion of a group 17 element in the 1− oxidation state (fluoride, F−; chloride, Cl−; bromide, Br−; and
iodide, I−)
Hall–Héroult cell
electrolysis apparatus used to isolate pure aluminum metal from a solution of alumina in molten cryolite
hydrogen carbonate
salt of carbonic acid, H2CO3 (containing the anion HCO 3
−
) in which one hydrogen atom has been replaced; an acid carbonate;
also known as bicarbonate ion
hydrogen halide
binary compound formed between hydrogen and the halogens: HF, HCl, HBr, and HI
hydrogen sulfate
HSO ion
4
−
hydrogen sulfite
HSO ion
3
−
hydrogenation
addition of hydrogen (H2) to reduce a compound
hydroxide
compound of a metal with the hydroxide ion OH− or the group −OH
interhalogen
compound formed from two or more different halogens
metal (representative)
atoms of the metallic elements of groups 1, 2, 12, 13, 14, 15, and 16, which form ionic compounds by losing electrons from
their outer s or p orbitals
metalloid
element that has properties that are between those of metals and nonmetals; these elements are typically semiconductors
nitrate
NO3
−
ion; salt of nitric acid
nitrogen fixation
formation of nitrogen compounds from molecular nitrogen
Ostwald process
industrial process used to convert ammonia into nitric acid
oxide
binary compound of oxygen with another element or group, typically containing O2− ions or the group –O– or =O
ozone
allotrope of oxygen; O3
passivation
metals with a protective nonreactive film of oxide or other compound that creates a barrier for chemical reactions; physical or
chemical removal of the passivating film allows the metals to demonstrate their expected chemical reactivity
peroxide
molecule containing two oxygen atoms bonded together or as the anion, O 2
2−
photosynthesis
process whereby light energy promotes the reaction of water and carbon dioxide to form carbohydrates and oxygen; this allows
photosynthetic organisms to store energy
Pidgeon process
chemical reduction process used to produce magnesium through the thermal reaction of magnesium oxide with silicon
polymorph
variation in crystalline structure that results in different physical properties for the resulting compound
representative element
element where the s and p orbitals are filling
representative metal
metal among the representative elements
silicate
compound containing silicon-oxygen bonds, with silicate tetrahedra connected in rings, sheets, or three-dimensional networks,
depending on the other elements involved in the formation of the compounds
sulfate
SO 4
2−
ion
sulfite
SO 3
2−
ion
superoxide
oxide containing the anion O 2
−
18.15: Summary
18.1 Periodicity
This section focuses on the periodicity of the representative elements. These are the elements where the electrons are entering the s
and p orbitals. The representative elements occur in groups 1, 2, and 12–18. These elements are representative metals, metalloids,
and nonmetals. The alkali metals (group 1) are very reactive, readily form ions with a charge of 1+ to form ionic compounds that
are usually soluble in water, and react vigorously with water to form hydrogen gas and a basic solution of the metal hydroxide. The
outermost electrons of the alkaline earth metals (group 2) are more difficult to remove than the outer electron of the alkali metals,
leading to the group 2 metals being less reactive than those in group 1. These elements easily form compounds in which the metals
exhibit an oxidation state of 2+. Zinc, cadmium, and mercury (group 12) commonly exhibit the group oxidation state of 2+
(although mercury also exhibits an oxidation state of 1+ in compounds that contain Hg ). Aluminum, gallium, indium, and
2
2+
thallium (group 13) are easier to oxidize than is hydrogen. Aluminum, gallium, and indium occur with an oxidation state 3+
(however, thallium also commonly occurs as the Tl+ ion). Tin and lead form stable divalent cations and covalent compounds in
which the metals exhibit the 4+-oxidation state.
18.2 Occurrence and Preparation of the Representative Metals

Because of their chemical reactivity, it is necessary to produce the representative metals in their pure forms by reduction from
naturally occurring compounds. Electrolysis is important in the production of sodium, potassium, and aluminum. Chemical
reduction is the primary method for the isolation of magnesium, zinc, and tin. Similar procedures are important for the other
representative metals.
18.3 Structure and General Properties of the Metalloids

The elements boron, silicon, germanium, arsenic, antimony, and tellurium separate the metals from the nonmetals in the periodic
table. These elements, called metalloids or sometimes semimetals, exhibit properties characteristic of both metals and nonmetals.
The structures of these elements are similar in many ways to those of nonmetals, but the elements are electrical semiconductors.
18.4 Structure and General Properties of the Nonmetals

Nonmetals have structures that are very different from those of the metals, primarily because they have greater electronegativity
and electrons that are more tightly bound to individual atoms. Most nonmetal oxides are acid anhydrides, meaning that they react
with water to form acidic solutions. Molecular structures are common for most of the nonmetals, and several have multiple
allotropes with varying physical properties.
18.5 Occurrence, Preparation, and Compounds of Hydrogen

Hydrogen is the most abundant element in the universe and its chemistry is truly unique. Although it has some chemical reactivity
that is similar to that of the alkali metals, hydrogen has many of the same chemical properties of a nonmetal with a relatively low
electronegativity. It forms ionic hydrides with active metals, covalent compounds in which it has an oxidation state of 1− with less
electronegative elements, and covalent compounds in which it has an oxidation state of 1+ with more electronegative nonmetals. It
reacts explosively with oxygen, fluorine, and chlorine, less readily with bromine, and much less readily with iodine, sulfur, and
nitrogen. Hydrogen reduces the oxides of metals with lower reduction potentials than chromium to form the metal and water. The
hydrogen halides are all acidic when dissolved in water.
18.6 Occurrence, Preparation, and Properties of Carbonates

The usual method for the preparation of the carbonates of the alkali and alkaline earth metals is by reaction of an oxide or
hydroxide with carbon dioxide. Other carbonates form by precipitation. Metal carbonates or hydrogen carbonates such as limestone
(CaCO3), the antacid Tums (CaCO3), and baking soda (NaHCO3) are common examples. Carbonates and hydrogen carbonates
decompose in the presence of acids and most decompose on heating.
18.7 Occurrence, Preparation, and Properties of Nitrogen

Nitrogen exhibits oxidation states ranging from 3− to 5+. Because of the stability of the N≡N triple bond, it requires a great deal of
energy to make compounds from molecular nitrogen. Active metals such as the alkali metals and alkaline earth metals can reduce
nitrogen to form metal nitrides. Nitrogen oxides and nitrogen hydrides are also important substances.
18.8 Occurrence, Preparation, and Properties of Phosphorus
Phosphorus (group 15) commonly exhibits oxidation states of 3− with active metals and of 3+ and 5+ with more electronegative
nonmetals. The halogens and oxygen will oxidize phosphorus. The oxides are phosphorus(V) oxide, P4O10, and phosphorus(III)
oxide, P4O6. The two common methods for preparing orthophosphoric acid, H3PO4, are either the reaction of a phosphate with
sulfuric acid or the reaction of water with phosphorus(V) oxide. Orthophosphoric acid is a triprotic acid that forms three types of
salts.
18.9 Occurrence, Preparation, and Compounds of Oxygen

Oxygen is one of the most reactive elements. This reactivity, coupled with its abundance, makes the chemistry of oxygen very rich
and well understood.
Compounds of the representative metals with oxygen exist in three categories (1) oxides, (2) peroxides and superoxides, and (3)
hydroxides. Heating the corresponding hydroxides, nitrates, or carbonates is the most common method for producing oxides.
Heating the metal or metal oxide in oxygen may lead to the formation of peroxides and superoxides. The soluble oxides dissolve in
water to form solutions of hydroxides. Most metals oxides are base anhydrides and react with acids. The hydroxides of the
representative metals react with acids in acid-base reactions to form salts and water. The hydroxides have many commercial uses.
All nonmetals except fluorine form multiple oxides. Nearly all of the nonmetal oxides are acid anhydrides. The acidity of oxyacids
requires that the hydrogen atoms bond to the oxygen atoms in the molecule rather than to the other nonmetal atom. Generally, the
strength of the oxyacid increases with the number of oxygen atoms bonded to the nonmetal atom and not to a hydrogen.
18.10 Occurrence, Preparation, and Properties of Sulfur

Sulfur (group 16) reacts with almost all metals and readily forms the sulfide ion, S2−, in which it has as oxidation state of 2−. Sulfur
reacts with most nonmetals.
18.11 Occurrence, Preparation, and Properties of Halogens

The halogens form halides with less electronegative elements. Halides of the metals vary from ionic to covalent; halides of
nonmetals are covalent. Interhalogens form by the combination of two or more different halogens.
All of the representative metals react directly with elemental halogens or with solutions of the hydrohalic acids (HF, HCl, HBr, and
HI) to produce representative metal halides. Other laboratory preparations involve the addition of aqueous hydrohalic acids to
compounds that contain such basic anions, such as hydroxides, oxides, or carbonates.
18.12 Occurrence, Preparation, and Properties of the Noble Gases

The most significant property of the noble gases (group 18) is their inactivity. They occur in low concentrations in the atmosphere.
They find uses as inert atmospheres, neon signs, and as coolants. The three heaviest noble gases react with fluorine to form
fluorides. The xenon fluorides are the best characterized as the starting materials for a few other noble gas compounds.
18.16: Exercises
18.16.0.1: 18.1 Periodicity
1.
How do alkali metals differ from alkaline earth metals in atomic structure and general properties?
2.
Why does the reactivity of the alkali metals decrease from cesium to lithium?
3.
Predict the formulas for the nine compounds that may form when each species in column 1 of the table reacts with each species in
column 2.
1 2
Na I
Sr Se
Al O
4.
Predict the best choice in each of the following. You may wish to review the chapter on electronic structure for relevant examples.
(a) the most metallic of the elements Al, Be, and Ba
(b) the most covalent of the compounds NaCl, CaCl2, and BeCl2
(c) the lowest first ionization energy among the elements Rb, K, and Li
(d) the smallest among Al, Al+, and Al3+
(e) the largest among Cs+, Ba2+, and Xe
5.
Sodium chloride and strontium chloride are both white solids. How could you distinguish one from the other?
6.
The reaction of quicklime, CaO, with water produces slaked lime, Ca(OH)2, which is widely used in the construction industry to
make mortar and plaster. The reaction of quicklime and water is highly exothermic:
−1
CaO(s) + H2 O(l) ⟶ Ca (OH) (s) ΔH = −350 kJ mol
2
(a) What is the enthalpy of reaction per gram of quicklime that reacts?
(b) How much heat, in kilojoules, is associated with the production of 1 ton of slaked lime?
7.
Write a balanced equation for the reaction of elemental strontium with each of the following:
(a) oxygen
(b) hydrogen bromide
(c) hydrogen
(d) phosphorus
(e) water
8.
How many moles of ionic species are present in 1.0 L of a solution marked 1.0 M mercury(I) nitrate?

9.
What is the mass of fish, in kilograms, that one would have to consume to obtain a fatal dose of mercury, if the fish contains 30
parts per million of mercury by weight? (Assume that all the mercury from the fish ends up as mercury(II) chloride in the body and
that a fatal dose is 0.20 g of HgCl2.) How many pounds of fish is this?
10.
The elements sodium, aluminum, and chlorine are in the same period.
(a) Which has the greatest electronegativity?
(b) Which of the atoms is smallest?
(c) Write the Lewis structure for the simplest covalent compound that can form between aluminum and chlorine.
(d) Will the oxide of each element be acidic, basic, or amphoteric?
11.
Does metallic tin react with HCl?
12.
What is tin pest, also known as tin disease?
13.
Compare the nature of the bonds in PbCl2 to that of the bonds in PbCl4.
14.
Is the reaction of rubidium with water more or less vigorous than that of sodium? How does the rate of reaction of magnesium
compare?
18.16.0.1: 18.2 Occurrence and Preparation of the Representative Metals

15.
Write an equation for the reduction of cesium chloride by elemental calcium at high temperature.
16.
Why is it necessary to keep the chlorine and sodium, resulting from the electrolysis of sodium chloride, separate during the
production of sodium metal?
17.
Give balanced equations for the overall reaction in the electrolysis of molten lithium chloride and for the reactions occurring at the
electrodes. You may wish to review the chapter on electrochemistry for relevant examples.
18.
The electrolysis of molten sodium chloride or of aqueous sodium chloride produces chlorine.
Calculate the mass of chlorine produced from 3.00 kg sodium chloride in each case. You may wish to review the chapter on
electrochemistry for relevant examples.
19.
What mass, in grams, of hydrogen gas forms during the complete reaction of 10.01 g of calcium with water?
20.
How many grams of oxygen gas are necessary to react completely with 3.01 × 1021 atoms of magnesium to yield magnesium
oxide?
21.
Magnesium is an active metal; it burns in the form of powder, ribbons, and filaments to provide flashes of brilliant light. Why is it
possible to use magnesium in construction?
22.
Why is it possible for an active metal like aluminum to be useful as a structural metal?

23.
Describe the production of metallic aluminum by electrolytic reduction.
24.
What is the common ore of tin and how is tin separated from it?
25.
A chemist dissolves a 1.497-g sample of a type of metal (an alloy of Sn, Pb, Sb, and Cu) in nitric acid, and metastannic acid,
H2SnO3, is precipitated. She heats the precipitate to drive off the water, which leaves 0.4909 g of tin(IV) oxide. What was the
percentage of tin in the original sample?
26.
Consider the production of 100 kg of sodium metal using a current of 50,000 A, assuming a 100% yield.
(a) How long will it take to produce the 100 kg of sodium metal?
(b) What volume of chlorine at 25 °C and 1.00 atm forms?
27.
What mass of magnesium forms when 100,000 A is passed through a MgCl2 melt for 1.00 h if the yield of magnesium is 85% of
the theoretical yield?
18.16.0.1: 18.3 Structure and General Properties of the Metalloids

28.
Give the hybridization of the metalloid and the molecular geometry for each of the following compounds or ions. You may wish to
review the chapters on chemical bonding and advanced covalent bonding for relevant examples.
(a) GeH4
(b) SbF3
(c) Te(OH)6
(d) H2Te
(e) GeF2
(f) TeCl4
(g) SiF 6
2−
(h) SbCl5
(i) TeF6
29.
Write a Lewis structure for each of the following molecules or ions. You may wish to review the chapter on chemical bonding.
(a) H3BPH3
(b) BF 4
−
(c) BBr3
(d) B(CH3)3
(e) B(OH)3
30.
Describe the hybridization of boron and the molecular structure about the boron in each of the following:
(a) H3BPH3
(b) BF 4
−
(c) BBr3

(d) B(CH3)3
(e) B(OH)3
31.
Using only the periodic table, write the complete electron configuration for silicon, including any empty orbitals in the valence
shell. You may wish to review the chapter on electronic structure.
32.
Write a Lewis structure for each of the following molecules and ions:
(a) (CH3)3SiH
(b) SiO 4
4−
(c) Si2H6
(d) Si(OH)4
(e) SiF 6
2−
33.
Describe the hybridization of silicon and the molecular structure of the following molecules and ions:
(a) (CH3)3SiH
(b) SiO 4
4−
(c) Si2H6
(d) Si(OH)4
(e) SiF 6
2−
34.
Describe the hybridization and the bonding of a silicon atom in elemental silicon.
35.
Classify each of the following molecules as polar or nonpolar. You may wish to review the chapter on chemical bonding.
(a) SiH4
(b) Si2H6
(c) SiCl3H
(d) SiF4
(e) SiCl2F2
36.
Silicon reacts with sulfur at elevated temperatures. If 0.0923 g of silicon reacts with sulfur to give 0.3030 g of silicon sulfide,
determine the empirical formula of silicon sulfide.
37.
Name each of the following compounds:
(a) TeO2
(b) Sb2S3
(c) GeF4
(d) SiH4
(e) GeH4
38.

Write a balanced equation for the reaction of elemental boron with each of the following (most of these reactions require high
temperature):
(a) F2
(b) O2
(c) S
(d) Se
(e) Br2
39.
Why is boron limited to a maximum coordination number of four in its compounds?
40.
Write a formula for each of the following compounds:
(a) silicon dioxide
(b) silicon tetraiodide
(c) silane
(d) silicon carbide
(e) magnesium silicide
41.
From the data given in Appendix G, determine the standard enthalpy change and the standard free energy change for each of the
following reactions:
(a) BF 3 (g) + 3H2 O(l) ⟶ B(OH) 3 (s) + 3HF(g)
(b) BCl 3 (g) + 3H2 O(l) ⟶ B(OH) (s) + 3HCl(g)

3
(c) B 2 H6 (g) + 6H2 O(l) ⟶ 2B(OH) (s) + 6H2 (g)

3
42.
A hydride of silicon prepared by the reaction of Mg2Si with acid exerted a pressure of 306 torr at 26 °C in a bulb with a volume of
57.0 mL. If the mass of the hydride was 0.0861 g, what is its molecular mass? What is the molecular formula for the hydride?
43.
Suppose you discovered a diamond completely encased in a silicate rock. How would you chemically free the diamond without
harming it?
18.16.0.1: 18.4 Structure and General Properties of the Nonmetals

44.
Carbon forms a number of allotropes, two of which are graphite and diamond. Silicon has a diamond structure. Why is there no
allotrope of silicon with a graphite structure?
45.
Nitrogen in the atmosphere exists as very stable diatomic molecules. Why does phosphorus form less stable P4 molecules instead of
P2 molecules?
46.
Write balanced chemical equations for the reaction of the following acid anhydrides with water:
(a) SO3
(b) N2O3
(c) Cl2O7
(d) P4O10

(e) NO2
47.
Determine the oxidation number of each element in each of the following compounds:
(a) HCN
(b) OF2
(c) AsCl3
48.
Determine the oxidation state of sulfur in each of the following:
(a) SO3
(b) SO2
(c) SO 3
2−
49.
Arrange the following in order of increasing electronegativity: F; Cl; O; and S.
50.
Why does white phosphorus consist of tetrahedral P4 molecules while nitrogen consists of diatomic N2 molecules?
18.16.0.1: 18.5 Occurrence, Preparation, and Compounds of Hydrogen

51.
Why does hydrogen not exhibit an oxidation state of 1− when bonded to nonmetals?
52.
The reaction of calcium hydride, CaH2, with water can be characterized as a Lewis acid-base reaction:
CaH2 (s) + 2H2 O(l) ⟶ Ca (OH) (aq) + 2H2 (g)
2
Identify the Lewis acid and the Lewis base among the reactants. The reaction is also an oxidation-reduction reaction. Identify the
oxidizing agent, the reducing agent, and the changes in oxidation number that occur in the reaction.
53.
In drawing Lewis structures, we learn that a hydrogen atom forms only one bond in a covalent compound. Why?
54.
What mass of CaH2 is necessary to react with water to provide enough hydrogen gas to fill a balloon at 20 °C and 0.8 atm pressure
with a volume of 4.5 L? The balanced equation is:
CaH2 (s) + 2H2 O(l) ⟶ Ca (OH) (aq) + 2H2 (g)
2
55.
What mass of hydrogen gas results from the reaction of 8.5 g of KH with water?
KH + H2 O ⟶ KOH + H2
18.16.0.1: 18.6 Occurrence, Preparation, and Properties of Carbonates

56.
Carbon forms the CO 3
2−
ion, yet silicon does not form an analogous SiO 3
2−
ion. Why?
57.
Complete and balance the following chemical equations:
(a) hardening of plaster containing slaked lime
Ca (OH) + CO2 ⟶
2
(b) removal of sulfur dioxide from the flue gas of power plants
CaO + SO 2 ⟶

(c) the reaction of baking powder that produces carbon dioxide gas and causes bread to rise
NaHCO3 + NaH2 PO4 ⟶
58.
Heating a sample of Na2CO3⋅xH2O weighing 4.640 g until the removal of the water of hydration leaves 1.720 g of anhydrous
Na2CO3. What is the formula of the hydrated compound?
18.16.0.1: 18.7 Occurrence, Preparation, and Properties of Nitrogen

59.
Write the Lewis structures for each of the following:
(a) NH2−
(b) N2F4
(c) NH 2
−
(d) NF3
(e) N 3
−
60.
For each of the following, indicate the hybridization of the nitrogen atom (for N
3
−
, the central nitrogen).
(a) N2F4
(b) NH 2
−
(c) NF3
(d) N 3
−
61.
Explain how ammonia can function both as a Brønsted base and as a Lewis base.
62.
Determine the oxidation state of nitrogen in each of the following. You may wish to review the chapter on chemical bonding for
relevant examples.
(a) NCl3
(b) ClNO
(c) N2O5
(d) N2O3
(e) NO 2
−
(f) N2O4
(g) N2O
(h) NO 3
−
(i) HNO2
(j) HNO3
63.
For each of the following, draw the Lewis structure, predict the ONO bond angle, and give the hybridization of the nitrogen. You
may wish to review the chapters on chemical bonding and advanced theories of covalent bonding for relevant examples.
(a) NO2
(b) NO 2
−
(c) NO 2
+

64.
How many grams of gaseous ammonia will the reaction of 3.0 g hydrogen gas and 3.0 g of nitrogen gas produce?
65.
Although PF5 and AsF5 are stable, nitrogen does not form NF5 molecules. Explain this difference among members of the same
group.
66.
The equivalence point for the titration of a 25.00-mL sample of CsOH solution with 0.1062 M HNO3 is at 35.27 mL. What is the
concentration of the CsOH solution?
18.16.0.1: 18.8 Occurrence, Preparation, and Properties of Phosphorus

67.
Write the Lewis structure for each of the following. You may wish to review the chapter on chemical bonding and molecular
geometry.
(a) PH3
(b) PH 4
+
(c) P2H4
(d) PO 4
3−
(e) PF5
68.
Describe the molecular structure of each of the following molecules or ions listed. You may wish to review the chapter on chemical
bonding and molecular geometry.
(a) PH3
(b) PH 4
+
(c) P2H4
(d) PO 4
3−
69.
Complete and balance each of the following chemical equations. (In some cases, there may be more than one correct answer.)
(a) P 4 + Al ⟶
(b) P 4 + Na ⟶
(c) P 4 + F2 ⟶
(d) P 4 + Cl2 ⟶
(e) P 4 + O2 ⟶
(f) P 4 O6 + O2 ⟶
70.
Describe the hybridization of phosphorus in each of the following compounds: P4O10, P4O6, PH4I (an ionic compound), PBr3,
H3PO4, H3PO3, PH3, and P2H4. You may wish to review the chapter on advanced theories of covalent bonding.
71.
What volume of 0.200 M NaOH is necessary to neutralize the solution produced by dissolving 2.00 g of PCl3 is an excess of water?
Note that when H3PO3 is titrated under these conditions, only one proton of the acid molecule reacts.
72.
How much POCl3 can form from 25.0 g of PCl5 and the appropriate amount of H2O?
73.

How many tons of Ca3(PO4)2 are necessary to prepare 5.0 tons of phosphorus if the yield is 90%?
74.
Write equations showing the stepwise ionization of phosphorous acid.
75.
Draw the Lewis structures and describe the geometry for the following:
(a) PF 4
+
(b) PF5
(c) PF 6
−
(d) POF3
76.
Why does phosphorous acid form only two series of salts, even though the molecule contains three hydrogen atoms?
77.
Assign an oxidation state to phosphorus in each of the following:
(a) NaH2PO3
(b) PF5
(c) P4O6
(d) K3PO4
(e) Na3P
(f) Na4P2O7
78.
Phosphoric acid, one of the acids used in some cola drinks, is produced by the reaction of phosphorus(V) oxide, an acidic oxide,
with water. Phosphorus(V) oxide is prepared by the combustion of phosphorus.
(a) Write the empirical formula of phosphorus(V) oxide.
(b) What is the molecular formula of phosphorus(V) oxide if the molar mass is about 280.
(c) Write balanced equations for the production of phosphorus(V) oxide and phosphoric acid.
(d) Determine the mass of phosphorus required to make 1.00 × 104 kg of phosphoric acid, assuming a yield of 98.85%.
18.16.0.1: 18.9 Occurrence, Preparation, and Compounds of Oxygen

79.
Predict the product of burning francium in air.
80.
Using equations, describe the reaction of water with potassium and with potassium oxide.
81.
Write balanced chemical equations for the following reactions:
(a) zinc metal heated in a stream of oxygen gas
(b) zinc carbonate heated until loss of mass stops
(c) zinc carbonate added to a solution of acetic acid, CH3CO2H
(d) zinc added to a solution of hydrobromic acid
82.

(a) cadmium burned in air
(b) elemental cadmium added to a solution of hydrochloric acid
(c) cadmium hydroxide added to a solution of acetic acid, CH3CO2H
83.
Illustrate the amphoteric nature of aluminum hydroxide by citing suitable equations.
84.
(a) metallic aluminum burned in air
(b) elemental aluminum heated in an atmosphere of chlorine
(c) aluminum heated in hydrogen bromide gas
(d) aluminum hydroxide added to a solution of nitric acid
85.
(a) sodium oxide added to water
(b) cesium carbonate added to an excess of an aqueous solution of HF
(c) aluminum oxide added to an aqueous solution of HClO4
(d) a solution of sodium carbonate added to solution of barium nitrate
(e) titanium metal produced from the reaction of titanium tetrachloride with elemental sodium
86.
What volume of 0.250 M H2SO4 solution is required to neutralize a solution that contains 5.00 g of CaCO3?
87.
Which is the stronger acid, HClO4 or HBrO4? Why?
88.
Write a balanced chemical equation for the reaction of an excess of oxygen with each of the following. Remember that oxygen is a
strong oxidizing agent and tends to oxidize an element to its maximum oxidation state.
(a) Mg
(b) Rb
(c) Ga
(d) C2H2
(e) CO
89.
Which is the stronger acid, H2SO4 or H2SeO4? Why? You may wish to review the chapter on acid-base equilibria.
18.16.0.1: 18.10 Occurrence, Preparation, and Properties of Sulfur

90.
Explain why hydrogen sulfide is a gas at room temperature, whereas water, which has a lower molecular mass, is a liquid.
91.
Give the hybridization and oxidation state for sulfur in SO2, in SO3, and in H2SO4.
92.
Which is the stronger acid, NaHSO3 or NaHSO4?
93.

Determine the oxidation state of sulfur in SF6, SO2F2, and KHS.
94.
Which is a stronger acid, sulfurous acid or sulfuric acid? Why?
95.
Oxygen forms double bonds in O2, but sulfur forms single bonds in S8. Why?
96.
Give the Lewis structure of each of the following:
(a) SF4
(b) K2SO4
(c) SO2Cl2
(d) H2SO3
(e) SO3
97.
Write two balanced chemical equations in which sulfuric acid acts as an oxidizing agent.
98.
Explain why sulfuric acid, H2SO4, which is a covalent molecule, dissolves in water and produces a solution that contains ions.
99.
How many grams of Epsom salts (MgSO4⋅7H2O) will form from 5.0 kg of magnesium?
18.16.0.1: 18.11 Occurrence, Preparation, and Properties of Halogens

100.
What does it mean to say that mercury(II) halides are weak electrolytes?
101.
Why is SnCl4 not classified as a salt?
102.
The following reactions are all similar to those of the industrial chemicals. Complete and balance the equations for these reactions:
(a) reaction of a weak base and a strong acid
NH3 + HClO4 ⟶
(b) preparation of a soluble silver salt for silver plating

Ag2 CO3 + HNO3 ⟶
(c) preparation of strontium hydroxide by electrolysis of a solution of strontium chloride

electrolysis
SrCl 2 (aq) + H2 O(l) −−−−−−−→
103.
Which is the stronger acid, HClO3 or HBrO3? Why?
104.
What is the hybridization of iodine in IF3 and IF5?
105.
Predict the molecular geometries and draw Lewis structures for each of the following. You may wish to review the chapter on
chemical bonding and molecular geometry.
(a) IF5
(b) I 3
−

(c) PCl5
(d) SeF4
(e) ClF3
106.
Which halogen has the highest ionization energy? Is this what you would predict based on what you have learned about periodic
properties?
107.
Name each of the following compounds:
(a) BrF3
(b) NaBrO3
(c) PBr5
(d) NaClO4
(e) KClO
108.
Explain why, at room temperature, fluorine and chlorine are gases, bromine is a liquid, and iodine is a solid.
109.
What is the oxidation state of the halogen in each of the following?
(a) H5IO6
(b) IO 4
−
(c) ClO2
(d) ICl3
(e) F2
110.
Physiological saline concentration—that is, the sodium chloride concentration in our bodies—is approximately 0.16 M. A saline
solution for contact lenses is prepared to match the physiological concentration. If you purchase 25 mL of contact lens saline
solution, how many grams of sodium chloride have you bought?
18.16.0.1: 18.12 Occurrence, Preparation, and Properties of the Noble Gases

111.
Give the hybridization of xenon in each of the following. You may wish to review the chapter on the advanced theories of covalent
bonding.
(a) XeF2
(b) XeF4
(c) XeO3
(d) XeO4
(e) XeOF4
112.
What is the molecular structure of each of the following molecules? You may wish to review the chapter on chemical bonding and
molecular geometry.
(a) XeF2
(b) XeF4

(c) XeO3
(d) XeO4
(e) XeOF4
113.
Indicate whether each of the following molecules is polar or nonpolar. You may wish to review the chapter on chemical bonding
and molecular geometry.
(a) XeF2
(b) XeF4
(c) XeO3
(d) XeO4
(e) XeOF4
114.
What is the oxidation state of the noble gas in each of the following? You may wish to review the chapter on chemical bonding and
molecular geometry.
(a) XeO2F2
(b) KrF2
(c) XeF 3
+
(d) XeO 6
4−
(e) XeO3
115.
A mixture of xenon and fluorine was heated. A sample of the white solid that formed reacted with hydrogen to yield 81 mL of
xenon (at STP) and hydrogen fluoride, which was collected in water, giving a solution of hydrofluoric acid. The hydrofluoric acid
solution was titrated, and 68.43 mL of 0.3172 M sodium hydroxide was required to reach the equivalence point. Determine the
empirical formula for the white solid and write balanced chemical equations for the reactions involving xenon.
116.
Basic solutions of Na4XeO6 are powerful oxidants. What mass of Mn(NO3)2•6H2O reacts with 125.0 mL of a 0.1717 M basic
solution of Na4XeO6 that contains an excess of sodium hydroxide if the products include Xe and solution of sodium permanganate?

CHAPTER OVERVIEW
19: Transition Metals and Coordination Chemistry

General Chemistry
Transition metals are defined as those elements that have (or readily form) partially filled d orbitals. These include the d-block
(groups 3–11) and f-block element elements. The variety of properties exhibited by transition metals is due to their complex
valence shells. Unlike most main group metals where one oxidation state is normally observed, the valence shell structure of
transition metals means that they usually occur in several different stable oxidation states. In addition, electron transitions in these
elements can correspond with absorption of photons in the visible electromagnetic spectrum, leading to colored compounds.
Because of these behaviors, transition metals exhibit a rich and fascinating chemistry.
19.1: Introduction
19.2: Occurrence, Preparation, and Properties of Transition Metals and Their Compounds
19.5: Key Terms
19.6: Summary
19.7: Exercises
This page titled 19: Transition Metals and Coordination Chemistry is shared under a CC BY 4.0 license and was authored, remixed, and/or
upon request.
1
19.1: Introduction
Figure 19.1 Transition metals often form vibrantly colored complexes. The minerals malachite (green), azurite (blue), and proustite
(red) are some examples. (credit left: modification of work by James St. John; credit middle: modification of work by Stephanie
Clifford; credit right: modification of work by Terry Wallace)
Chapter Outline
19.1 Occurrence, Preparation, and Properties of Transition Metals and Their Compounds
19.2 Coordination Chemistry of Transition Metals
19.3 Spectroscopic and Magnetic Properties of Coordination Compounds
We have daily contact with many transition metals. Iron occurs everywhere—from the rings in your spiral notebook and the cutlery
in your kitchen to automobiles, ships, buildings, and in the hemoglobin in your blood. Titanium is useful in the manufacture of
lightweight, durable products such as bicycle frames, artificial hips, and jewelry. Chromium is useful as a protective plating on
plumbing fixtures and automotive detailing.
In addition to being used in their pure elemental forms, many compounds containing transition metals have numerous other
applications. Silver nitrate is used to create mirrors, zirconium silicate provides friction in automotive brakes, and many important
cancer-fighting agents, like the drug cisplatin and related species, are platinum compounds.
The variety of properties exhibited by transition metals is due to their complex valence shells. Unlike most main group metals
where one oxidation state is normally observed, the valence shell structure of transition metals means that they usually occur in
several different stable oxidation states. In addition, electron transitions in these elements can correspond with absorption of
photons in the visible electromagnetic spectrum, leading to colored compounds. Because of these behaviors, transition metals
exhibit a rich and fascinating chemistry.
19.2: Occurrence, Preparation, and Properties of Transition Metals and Their
Compounds
Transition metals are defined as those elements that have (or readily form) partially filled d orbitals. As shown in Figure 19.2, the
d-block elements in groups 3–11 are transition elements. The f-block elements, also called inner transition metals (the lanthanides
and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals. The d orbitals fill with the
copper family (group 11); for this reason, the next family (group 12) are technically not transition elements. However, the group 12
elements do display some of the same chemical properties and are commonly included in discussions of transition metals. Some
chemists do treat the group 12 elements as transition metals.
Figure 19.2 The transition metals are located in groups 3–11 of the periodic table. The inner transition metals are in the two rows
below the body of the table.
The d-block elements are divided into the first transition series (the elements Sc through Cu), the second transition series (the
elements Y through Ag), and the third transition series (the element La and the elements Hf through Au). Actinium, Ac, is the first
member of the fourth transition series, which also includes Rf through Rg.
The f-block elements are the elements Ce through Lu, which constitute the lanthanide series (or lanthanoid series), and the elements
Th through Lr, which constitute the actinide series (or actinoid series). Because lanthanum behaves very much like the lanthanide
elements, it is considered a lanthanide element, even though its electron configuration makes it the first member of the third
transition series. Similarly, the behavior of actinium means it is part of the actinide series, although its electron configuration makes
it the first member of the fourth transition series.

19.2.0.1: Example 19.1
19.2.0.0.1: Valence Electrons in Transition Metals
Review how to write electron configurations, covered in the chapter on electronic structure and periodic properties of elements.
Recall that for the transition and inner transition metals, it is necessary to remove the s electrons before the d or f electrons.
Then, for each ion, give the electron configuration:
(a) cerium(III)
(b) lead(II)
(c) Ti2+
(d) Am3+
(e) Pd2+
For the examples that are transition metals, determine to which series they belong.
For ions, the s-valence electrons are lost prior to the d or f electrons.
(a) Ce3+[Xe]4f1; Ce3+ is an inner transition element in the lanthanide series.
(b) Pb2+[Xe]6s25d104f14; the electrons are lost from the p orbital. This is a main group element.
(c) titanium(II) [Ar]3d2; first transition series
(d) americium(III) [Rn]5f6; actinide
(e) palladium(II) [Kr]4d8; second transition series
Give an example of an ion from the first transition series with no d electrons.
19.2.0.1: Answer:
V5+ is one possibility. Other examples include Sc3+, Ti4+, Cr6+, and Mn7+.

19.2.0.0.1: Uses of Lanthanides in Devices
Lanthanides (elements 57–71) are fairly abundant in the earth’s crust, despite their historic characterization as rare earth
elements. Thulium, the rarest naturally occurring lanthanoid, is more common in the earth’s crust than silver (4.5 × 10−5%
versus 0.79 × 10−5% by mass). There are 17 rare earth elements, consisting of the 15 lanthanoids plus scandium and yttrium.
They are called rare because they were once difficult to extract economically, so it was rare to have a pure sample; due to
similar chemical properties, it is difficult to separate any one lanthanide from the others. However, newer separation methods,
such as ion exchange resins similar to those found in home water softeners, make the separation of these elements easier and
more economical. Most ores that contain these elements have low concentrations of all the rare earth elements mixed together.
The commercial applications of lanthanides are growing rapidly. For example, europium is important in flat screen displays
found in computer monitors, cell phones, and televisions. Neodymium is useful in laptop hard drives and in the processes that
convert crude oil into gasoline (Figure 19.3). Holmium is found in dental and medical equipment. In addition, many alternative
energy technologies rely heavily on lanthanoids. Neodymium and dysprosium are key components of hybrid vehicle engines
and the magnets used in wind turbines.

Figure 19.3 (a) Europium is used in display screens for televisions, computer monitors, and cell phones. (b) Neodymium
magnets are commonly found in computer hard drives. (credit b: modification of work by “KUERT Datenrettung”/Flickr)
As the demand for lanthanide materials has increased faster than supply, prices have also increased. In 2008, dysprosium cost
$110/kg; by 2014, the price had increased to $470/kg. Increasing the supply of lanthanoid elements is one of the most
significant challenges facing the industries that rely on the optical and magnetic properties of these materials.
The transition elements have many properties in common with other metals. They are almost all hard, high-melting solids that
conduct heat and electricity well. They readily form alloys and lose electrons to form stable cations. In addition, transition metals
form a wide variety of stable coordination compounds, in which the central metal atom or ion acts as a Lewis acid and accepts one
or more pairs of electrons. Many different molecules and ions can donate lone pairs to the metal center, serving as Lewis bases. In
this chapter, we shall focus primarily on the chemical behavior of the elements of the first transition series.
19.2.0.1: Properties of the Transition Elements

Transition metals demonstrate a wide range of chemical behaviors. As can be seen from their reduction potentials (see Appendix
H), some transition metals are strong reducing agents, whereas others have very low reactivity. For example, the lanthanides all
form stable 3+ aqueous cations. The driving force for such oxidations is similar to that of alkaline earth metals such as Be or Mg,
forming Be2+ and Mg2+. On the other hand, materials like platinum and gold have much higher reduction potentials. Their ability to
resist oxidation makes them useful materials for constructing circuits and jewelry.
Ions of the lighter d-block elements, such as Cr3+, Fe3+, and Co2+, form colorful hydrated ions that are stable in water. However,
ions in the period just below these (Mo3+, Ru3+, and Ir2+) are unstable and react readily with oxygen from the air. The majority of
simple, water-stable ions formed by the heavier d-block elements are oxyanions such as MoO 4and ReO .
2−
4
−
Ruthenium, osmium, rhodium, iridium, palladium, and platinum are the platinum metals. With difficulty, they form simple cations
that are stable in water, and, unlike the earlier elements in the second and third transition series, they do not form stable oxyanions.
Both the d- and f-block elements react with nonmetals to form binary compounds; heating is often required. These elements react
with halogens to form a variety of halides ranging in oxidation state from 1+ to 6+. On heating, oxygen reacts with all of the

transition elements except palladium, platinum, silver, and gold. The oxides of these latter metals can be formed using other
reactants, but they decompose upon heating. The f-block elements, the elements of group 3, and the elements of the first transition
series except copper react with aqueous solutions of acids, forming hydrogen gas and solutions of the corresponding salts.
Transition metals can form compounds with a wide range of oxidation states. Some of the observed oxidation states of the elements
of the first transition series are shown in Figure 19.4. As we move from left to right across the first transition series, we see that the
number of common oxidation states increases at first to a maximum towards the middle of the table, then decreases. The values in
the table are typical values; there are other known values, and it is possible to synthesize new additions. For example, in 2014,
researchers were successful in synthesizing a new oxidation state of iridium (9+).
Figure 19.4 Transition metals of the first transition series can form compounds with varying oxidation states.
For the elements scandium through manganese (the first half of the first transition series), the highest oxidation state corresponds to
the loss of all of the electrons in both the s and d orbitals of their valence shells. The titanium(IV) ion, for example, is formed when
the titanium atom loses its two 3d and two 4s electrons. These highest oxidation states are the most stable forms of scandium,
titanium, and vanadium. However, it is not possible to continue to remove all of the valence electrons from metals as we continue
through the series. Iron is known to form oxidation states from 2+ to 6+, with iron(II) and iron(III) being the most common. Most
of the elements of the first transition series form ions with a charge of 2+ or 3+ that are stable in water, although those of the early
members of the series can be readily oxidized by air.
The elements of the second and third transition series generally are more stable in higher oxidation states than are the elements of
the first series. In general, the atomic radius increases down a group, which leads to the ions of the second and third series being
larger than are those in the first series. Removing electrons from orbitals that are located farther from the nucleus is easier than
removing electrons close to the nucleus. For example, molybdenum and tungsten, members of group 6, are limited mostly to an
oxidation state of 6+ in aqueous solution. Chromium, the lightest member of the group, forms stable Cr3+ ions in water and, in the
absence of air, less stable Cr2+ ions. The sulfide with the highest oxidation state for chromium is Cr2S3, which contains the Cr3+
ion. Molybdenum and tungsten form sulfides in which the metals exhibit oxidation states of 4+ and 6+.
19.2.0.1: Example 19.2

19.2.0.0.1: Activity of the Transition Metals
Which is the strongest oxidizing agent in acidic solution: dichromate ion, which contains chromium(VI), permanganate ion,
which contains manganese(VII), or titanium dioxide, which contains titanium(IV)?
First, we need to look up the reduction half reactions (in Appendix L) for each oxide in the specified oxidation state:
2− + − 3+
Cr2 O7 + 14 H + 6e ⟶ 2 Cr + 7 H2 O +1.33 V
− + − 2+
MnO 4 + 8H + 5e ⟶ Mn + H2 O +1.51 V
+ − 2+
TiO2 + 4 H + 2e ⟶ Ti + 2 H2 O −0.50 V
A larger reduction potential means that it is easier to reduce the reactant. Permanganate, with the largest reduction potential, is
the strongest oxidizer under these conditions. Dichromate is next, followed by titanium dioxide as the weakest oxidizing agent
(the hardest to reduce) of this set.
Predict what reaction (if any) will occur between HCl and Co(s), and between HBr and Pt(s). You will need to use the standard
reduction potentials from Appendix L.
19.2.0.1: Answer:

Co(s) + 2HCl ⟶ H2 + CoCl2 (aq); no reaction because Pt(s) will not be oxidized by H+
19.2.0.1: Preparation of the Transition Elements

Ancient civilizations knew about iron, copper, silver, and gold. The time periods in human history known as the Bronze Age and
Iron Age mark the advancements in which societies learned to isolate certain metals and use them to make tools and goods.
Naturally occurring ores of copper, silver, and gold can contain high concentrations of these metals in elemental form (Figure 19.5).
Iron, on the other hand, occurs on earth almost exclusively in oxidized forms, such as rust (Fe2O3). The earliest known iron
implements were made from iron meteorites. Surviving iron artifacts dating from approximately 4000 to 2500 BC are rare, but all
known examples contain specific alloys of iron and nickel that occur only in extraterrestrial objects, not on earth. It took thousands
of years of technological advances before civilizations developed iron smelting, the ability to extract a pure element from its
naturally occurring ores and for iron tools to become common.
Figure 19.5 Transition metals occur in nature in various forms. Examples include (a) a nugget of copper, (b) a deposit of gold, and
(c) an ore containing oxidized iron. (credit a: modification of work by http://images-of-elements.com/copper-2.jpg; credit c:
modification of work by http://images-of-elements.com/iron-ore.jpg)
Generally, the transition elements are extracted from minerals found in a variety of ores. However, the ease of their recovery varies
widely, depending on the concentration of the element in the ore, the identity of the other elements present, and the difficulty of
reducing the element to the free metal.
In general, it is not difficult to reduce ions of the d-block elements to the free element. Carbon is a sufficiently strong reducing
agent in most cases. However, like the ions of the more active main group metals, ions of the f-block elements must be isolated by
electrolysis or by reduction with an active metal such as calcium.
We shall discuss the processes used for the isolation of iron, copper, and silver because these three processes illustrate the principal
means of isolating most of the d-block metals. In general, each of these processes involves three principal steps: preliminary
treatment, smelting, and refining.
1. Preliminary treatment. In general, there is an initial treatment of the ores to make them suitable for the extraction of the metals.
This usually involves crushing or grinding the ore, concentrating the metal-bearing components, and sometimes treating these
substances chemically to convert them into compounds that are easier to reduce to the metal.
2. Smelting. The next step is the extraction of the metal in the molten state, a process called smelting, which includes reduction of
the metallic compound to the metal. Impurities may be removed by the addition of a compound that forms a slag—a substance
with a low melting point that can be readily separated from the molten metal.
3. Refining. The final step in the recovery of a metal is refining the metal. Low boiling metals such as zinc and mercury can be
refined by distillation. When fused on an inclined table, low melting metals like tin flow away from higher-melting impurities.
Electrolysis is another common method for refining metals.
19.2.0.1: Isolation of Iron

The early application of iron to the manufacture of tools and weapons was possible because of the wide distribution of iron ores
and the ease with which iron compounds in the ores could be reduced by carbon. For a long time, charcoal was the form of carbon

used in the reduction process. The production and use of iron became much more widespread about 1620, when coke was
introduced as the reducing agent. Coke is a form of carbon formed by heating coal in the absence of air to remove impurities.
The first step in the metallurgy of iron is usually roasting the ore (heating the ore in air) to remove water, decomposing carbonates
into oxides, and converting sulfides into oxides. The oxides are then reduced in a blast furnace that is 80–100 feet high and about
25 feet in diameter (Figure 19.6) in which the roasted ore, coke, and limestone (impure CaCO3) are introduced continuously into
the top. Molten iron and slag are withdrawn at the bottom. The entire stock in a furnace may weigh several hundred tons.
Figure 19.6 Within a blast furnace, different reactions occur in different temperature zones. Carbon monoxide is generated in the
hotter bottom regions and rises upward to reduce the iron oxides to pure iron through a series of reactions that take place in the
upper regions.
Near the bottom of a furnace are nozzles through which preheated air is blown into the furnace. As soon as the air enters, the coke
in the region of the nozzles is oxidized to carbon dioxide with the liberation of a great deal of heat. The hot carbon dioxide passes
upward through the overlying layer of white-hot coke, where it is reduced to carbon monoxide:
CO2 (g) + C(s) ⟶ 2CO(g)
The carbon monoxide serves as the reducing agent in the upper regions of the furnace. The individual reactions are indicated in
Figure 19.6.
The iron oxides are reduced in the upper region of the furnace. In the middle region, limestone (calcium carbonate) decomposes,
and the resulting calcium oxide combines with silica and silicates in the ore to form slag. The slag is mostly calcium silicate and
contains most of the commercially unimportant components of the ore:
CaO(s) + SiO2 (s) ⟶ CaSiO3 (l)

Just below the middle of the furnace, the temperature is high enough to melt both the iron and the slag. They collect in layers at the
bottom of the furnace; the less dense slag floats on the iron and protects it from oxidation. Several times a day, the slag and molten
iron are withdrawn from the furnace. The iron is transferred to casting machines or to a steelmaking plant (Figure 19.7).
Figure 19.7 Molten iron is shown being cast as steel. (credit: Clint Budd)
Much of the iron produced is refined and converted into steel. Steel is made from iron by removing impurities and adding
substances such as manganese, chromium, nickel, tungsten, molybdenum, and vanadium to produce alloys with properties that
make the material suitable for specific uses. Most steels also contain small but definite percentages of carbon (0.04%–2.5%).
However, a large part of the carbon contained in iron must be removed in the manufacture of steel; otherwise, the excess carbon
would make the iron brittle.

You can watch an animation of steelmaking that walks you through the process.
19.2.0.1: Isolation of Copper

The most important ores of copper contain copper sulfides (such as covellite, CuS), although copper oxides (such as tenorite, CuO)
and copper hydroxycarbonates [such as malachite, Cu2(OH)2CO3] are sometimes found. In the production of copper metal, the
concentrated sulfide ore is roasted to remove part of the sulfur as sulfur dioxide. The remaining mixture, which consists of Cu2S,
FeS, FeO, and SiO2, is mixed with limestone, which serves as a flux (a material that aids in the removal of impurities), and heated.
Molten slag forms as the iron and silica are removed by Lewis acid-base reactions:
CaCO3 (s) + SiO2 (s) ⟶ CaSiO3 (l) + CO2 (g)
FeO(s) + SiO2 (s) ⟶ FeSiO3 (l)
In these reactions, the silicon dioxide behaves as a Lewis acid, which accepts a pair of electrons from the Lewis base (the oxide
ion).
Reduction of the Cu2S that remains after smelting is accomplished by blowing air through the molten material. The air converts
part of the Cu2S into Cu2O. As soon as copper(I) oxide is formed, it is reduced by the remaining copper(I) sulfide to metallic
copper:

2Cu2 S(l) + 3O2 (g) ⟶ 2Cu2 O(l) + 2SO2 (g)
2Cu2 O(l) + Cu2 S(l) ⟶ 6Cu(l) + SO 2 (g)
The copper obtained in this way is called blister copper because of its characteristic appearance, which is due to the air blisters it
contains (Figure 19.8). This impure copper is cast into large plates, which are used as anodes in the electrolytic refining of the
metal (which is described in the chapter on electrochemistry).
Figure 19.8 Blister copper is obtained during the conversion of copper-containing ore into pure copper. (credit: “Tortie
tude”/Wikimedia Commons)
19.2.0.1: Isolation of Silver

Silver sometimes occurs in large nuggets (Figure 19.9) but more frequently in veins and related deposits. At one time, panning was
an effective method of isolating both silver and gold nuggets. Due to their low reactivity, these metals, and a few others, occur in
deposits as nuggets. The discovery of platinum was due to Spanish explorers in Central America mistaking platinum nuggets for
silver. When the metal is not in the form of nuggets, it often useful to employ a process called hydrometallurgy to separate silver
from its ores. Hydrology involves the separation of a metal from a mixture by first converting it into soluble ions and then
extracting and reducing them to precipitate the pure metal. In the presence of air, alkali metal cyanides readily form the soluble
dicyanoargentate(I) ion, [Ag(CN) ] , from silver metal or silver-containing compounds such as Ag2S and AgCl. Representative
2
−
equations are:
− − −
4Ag(s) + 8CN (aq) + O2 (g) + 2H2 O(l) ⟶ 4 [Ag (CN) ] (aq) + 4OH (aq)
2
− − −
2Ag S(s) + 8CN (aq) + O2 (g) + 2H2 O(l) ⟶ 4 [ Ag(CN) ] (aq) + 2S(s) + 4OH (aq)
2 2
− − −
AgCl(s) + 2CN (aq) ⟶ [Ag (CN)2 ] (aq) + Cl (aq)

Figure 19.9 Naturally occurring free silver may be found as nuggets (a) or in veins (b). (credit a: modification of work by
“Teravolt”/Wikimedia Commons; credit b: modification of work by James St. John)
The silver is precipitated from the cyanide solution by the addition of either zinc or iron(II) ions, which serves as the reducing
agent:
− 2−
2 [Ag (CN) ] (aq) + Zn(s) ⟶ 2Ag(s) + [Zn(CN) ] (aq)
2 4
19.2.0.1: Example 19.3

19.2.0.0.1: Refining Redox
One of the steps for refining silver involves converting silver into dicyanoargenate(I) ions:
− − −
4Ag(s) + 8CN (aq) + O2 (g) + 2 H2 O(l) ⟶ 4 [Ag (CN)2 ] (aq) + 4OH (aq)
Explain why oxygen must be present to carry out the reaction. Why does the reaction not occur as:
− −
4Ag(s) + 8CN (aq) ⟶ 4 [Ag (CN) ] (aq)?
2
The charges, as well as the atoms, must balance in reactions. The silver atom is being oxidized from the 0 oxidation state to the
1+ state. Whenever something loses electrons, something must also gain electrons (be reduced) to balance the equation.
Oxygen is a good oxidizing agent for these reactions because it can gain electrons to go from the 0 oxidation state to the 2−
state.
During the refining of iron, carbon must be present in the blast furnace. Why is carbon necessary to convert iron oxide into
iron?
19.2.0.1: Answer:
The carbon is converted into CO, which is the reducing agent that accepts electrons so that iron(III) can be reduced to
iron(0).
19.2.0.1: Transition Metal Compounds

The bonding in the simple compounds of the transition elements ranges from ionic to covalent. In their lower oxidation states, the
transition elements form ionic compounds; in their higher oxidation states, they form covalent compounds or polyatomic ions. The
variation in oxidation states exhibited by the transition elements gives these compounds a metal-based, oxidation-reduction
chemistry. The chemistry of several classes of compounds containing elements of the transition series follows.

19.2.0.0.1: Halides
Anhydrous halides of each of the transition elements can be prepared by the direct reaction of the metal with halogens. For
example:
2Fe(s) + 3Cl2 (g) ⟶ 2FeCl3 (s)
Heating a metal halide with additional metal can be used to form a halide of the metal with a lower oxidation state:
Fe(s) + 2FeCl3 (s) ⟶ 3FeCl2 (s)
The stoichiometry of the metal halide that results from the reaction of the metal with a halogen is determined by the relative
amounts of metal and halogen and by the strength of the halogen as an oxidizing agent. Generally, fluorine forms fluoride-
containing metals in their highest oxidation states. The other halogens may not form analogous compounds.
In general, the preparation of stable water solutions of the halides of the metals of the first transition series is by the addition of a
hydrohalic acid to carbonates, hydroxides, oxides, or other compounds that contain basic anions. Sample reactions are:
NiCO3 (s) + 2HF(aq) ⟶ NiF2 (aq) + H2 O(l) + CO2 (g)
Co (OH) (s) + 2HBr(aq) ⟶ CoBr2 (aq) + 2H2 O(l)

2
Most of the first transition series metals also dissolve in acids, forming a solution of the salt and hydrogen gas. For example:
Cr(s) + 2HCl(aq) ⟶ CrCl2 (aq) + H2 (g)
The polarity of bonds with transition metals varies based not only upon the electronegativities of the atoms involved but also upon
the oxidation state of the transition metal. Remember that bond polarity is a continuous spectrum with electrons being shared
evenly (covalent bonds) at one extreme and electrons being transferred completely (ionic bonds) at the other. No bond is ever 100%
ionic, and the degree to which the electrons are evenly distributed determines many properties of the compound. Transition metal
halides with low oxidation numbers form more ionic bonds. For example, titanium(II) chloride and titanium(III) chloride (TiCl2
and TiCl3) have high melting points that are characteristic of ionic compounds, but titanium(IV) chloride (TiCl4) is a volatile liquid,
consistent with having covalent titanium-chlorine bonds. All halides of the heavier d-block elements have significant covalent
characteristics.
The covalent behavior of the transition metals with higher oxidation states is exemplified by the reaction of the metal tetrahalides
with water. Like covalent silicon tetrachloride, both the titanium and vanadium tetrahalides react with water to give solutions
containing the corresponding hydrohalic acids and the metal oxides:
SiCl4 (l) + 2 H2 O(l) ⟶ SiO2 (s) + 4HCl(aq)
TiCl4 (l) + 2 H2 O(l) ⟶ TiO2 (s) + 4HCl(aq)
19.2.0.0.2: Oxides
As with the halides, the nature of bonding in oxides of the transition elements is determined by the oxidation state of the metal.
Oxides with low oxidation states tend to be more ionic, whereas those with higher oxidation states are more covalent. These
variations in bonding are because the electronegativities of the elements are not fixed values. The electronegativity of an element
increases with increasing oxidation state. Transition metals in low oxidation states have lower electronegativity values than oxygen;
therefore, these metal oxides are ionic. Transition metals in very high oxidation states have electronegativity values close to that of
oxygen, which leads to these oxides being covalent.
The oxides of the first transition series can be prepared by heating the metals in air. These oxides are Sc2O3, TiO2, V2O5, Cr2O3,
Mn3O4, Fe3O4, Co3O4, NiO, and CuO.
Alternatively, these oxides and other oxides (with the metals in different oxidation states) can be produced by heating the
corresponding hydroxides, carbonates, or oxalates in an inert atmosphere. Iron(II) oxide can be prepared by heating iron(II)
oxalate, and cobalt(II) oxide is produced by heating cobalt(II) hydroxide:
FeC2 O4 (s) ⟶ FeO(s) + CO(g) + CO2 (g)
Co(OH) (s) ⟶ CoO(s) + H2 O(g)

2
With the exception of CrO3 and Mn2O7, transition metal oxides are not soluble in water. They can react with acids and, in a few
cases, with bases. Overall, oxides of transition metals with the lowest oxidation states are basic (and react with acids), the

intermediate ones are amphoteric, and the highest oxidation states are primarily acidic. Basic metal oxides at a low oxidation state
react with aqueous acids to form solutions of salts and water. Examples include the reaction of cobalt(II) oxide accepting protons
from nitric acid, and scandium(III) oxide accepting protons from hydrochloric acid:
CoO(s) + 2HNO3 (aq) ⟶ Co (NO3 ) (aq) + H2 O(l)
2
Sc 2 O3 (s) + 6HCl(aq) ⟶ 2ScCl3 (aq) + 3H2 O(l)
The oxides of metals with oxidation states of 4+ are amphoteric, and most are not soluble in either acids or bases. Vanadium(V)
oxide, chromium(VI) oxide, and manganese(VII) oxide are acidic. They react with solutions of hydroxides to form salts of the
oxyanions VO , CrO , and MnO . For example, the complete ionic equation for the reaction of chromium(VI) oxide with
4
3−
4
2−
4
−
a strong base is given by:

+ − + 2−
CrO3 (s) + 2Na (aq) + 2OH (aq) ⟶ 2Na (aq) + CrO4 (aq) + H2 O(l)
Chromium(VI) oxide and manganese(VII) oxide react with water to form the acids H2CrO4 and HMnO4, respectively.
19.2.0.0.3: Hydroxides
When a soluble hydroxide is added to an aqueous solution of a salt of a transition metal of the first transition series, a gelatinous
precipitate forms. For example, adding a solution of sodium hydroxide to a solution of cobalt sulfate produces a gelatinous pink or
blue precipitate of cobalt(II) hydroxide. The net ionic equation is:
2+ −
Co (aq) + 2OH (aq) ⟶ Co (OH) 2 (s)
In this and many other cases, these precipitates are hydroxides containing the transition metal ion, hydroxide ions, and water
coordinated to the transition metal. In other cases, the precipitates are hydrated oxides composed of the metal ion, oxide ions, and
water of hydration:
3+ −
4Fe (aq) + 6OH (aq) + n H2 O(l) ⟶ 2 Fe2 O3 ⋅(n + 3)H2 O(s)
These substances do not contain hydroxide ions. However, both the hydroxides and the hydrated oxides react with acids to form
salts and water. When precipitating a metal from solution, it is necessary to avoid an excess of hydroxide ion, as this may lead to
complex ion formation as discussed later in this chapter. The precipitated metal hydroxides can be separated for further processing
or for waste disposal.
19.2.0.0.4: Carbonates
Many of the elements of the first transition series form insoluble carbonates. It is possible to prepare these carbonates by the
addition of a soluble carbonate salt to a solution of a transition metal salt. For example, nickel carbonate can be prepared from
solutions of nickel nitrate and sodium carbonate according to the following net ionic equation:
2+ 2−
Ni (aq) + CO3 ⟶ NiCO3 (s)
The reactions of the transition metal carbonates are similar to those of the active metal carbonates. They react with acids to form
metals salts, carbon dioxide, and water. Upon heating, they decompose, forming the transition metal oxides.
19.2.0.0.5: Other Salts
In many respects, the chemical behavior of the elements of the first transition series is very similar to that of the main group metals.
In particular, the same types of reactions that are used to prepare salts of the main group metals can be used to prepare simple ionic
salts of these elements.
A variety of salts can be prepared from metals that are more active than hydrogen by reaction with the corresponding acids:
Scandium metal reacts with hydrobromic acid to form a solution of scandium bromide:
2Sc(s) + 6HBr(aq) ⟶ 2 ScBr 3 (aq) + 3H2 (g)
The common compounds that we have just discussed can also be used to prepare salts. The reactions involved include the reactions
of oxides, hydroxides, or carbonates with acids. For example:
+ − 2+ −
Ni (OH) (s) + 2 H3 O (aq) + 2ClO4 (aq) ⟶ Ni (aq) + 2ClO4 (aq) + 4H2 O(l)
2
Substitution reactions involving soluble salts may be used to prepare insoluble salts. For example:

2+ − + 2− + −
Ba (aq) + 2Cl (aq) + 2K (aq) + CrO4 (aq) ⟶ BaCrO4 (s) + 2K (aq) + 2Cl (aq)
In our discussion of oxides in this section, we have seen that reactions of the covalent oxides of the transition elements with
hydroxides form salts that contain oxyanions of the transition elements.

19.2.0.0.6: High Temperature Superconductors
A superconductor is a substance that conducts electricity with no resistance. This lack of resistance means that there is no
energy loss during the transmission of electricity. This would lead to a significant reduction in the cost of electricity.
Most currently used, commercial superconducting materials, such as NbTi and Nb3Sn, do not become superconducting until
they are cooled below 23 K (−250 °C). This requires the use of liquid helium, which has a boiling temperature of 4 K and is
expensive and difficult to handle. The cost of liquid helium has deterred the widespread application of superconductors.
One of the most exciting scientific discoveries of the 1980s was the characterization of compounds that exhibit
superconductivity at temperatures above 90 K. (Compared to liquid helium, 90 K is a high temperature.) Typical among the
high-temperature superconducting materials are oxides containing yttrium (or one of several rare earth elements), barium, and
copper in a 1:2:3 ratio. The formula of the ionic yttrium compound is YBa2Cu3O7.
The new materials become superconducting at temperatures close to 90 K (Figure 19.10), temperatures that can be reached by
cooling with liquid nitrogen (boiling temperature of 77 K). Not only are liquid nitrogen-cooled materials easier to handle, but
the cooling costs are also about 1000 times lower than for liquid helium.
Further advances during the same period included materials that became superconducting at even higher temperatures and with
a wider array of materials. The DuPont team led by Uma Chowdry and Arthur Sleight identified Bismouth-Strontium-Copper-
Oxides that became superconducting at temperatures as high as 110 K and, importantly, did not contain rare earth elements.
Advances continued through the subsequent decades until, in 2020, a team led by Ranga Dias at University of Rochester
announced the development of a room-temperature superconductor, opening doors to widespread applications. More research
and development is needed to realize the potential of these materials, but the possibilities are very promising.
Figure 19.10 The resistance of the high-temperature superconductor YBa2Cu3O7 varies with temperature. Note how the
resistance falls to zero below 92 K, when the substance becomes superconducting.
Although the brittle, fragile nature of these materials presently hampers their commercial applications, they have tremendous
potential that researchers are hard at work improving their processes to help realize. Superconducting transmission lines would
carry current for hundreds of miles with no loss of power due to resistance in the wires. This could allow generating stations to

be located in areas remote from population centers and near the natural resources necessary for power production. The first
project demonstrating the viability of high-temperature superconductor power transmission was established in New York in
2008.
Researchers are also working on using this technology to develop other applications, such as smaller and more powerful
microchips. In addition, high-temperature superconductors can be used to generate magnetic fields for applications such as
medical devices, magnetic levitation trains, and containment fields for nuclear fusion reactors (Figure 19.11).
Figure 19.11 (a) This magnetic levitation train (or maglev) uses superconductor technology to move along its tracks. (b) A
magnet can be levitated using a dish like this as a superconductor. (credit a: modification of work by Alex Needham; credit b:
modification of work by Kevin Jarrett)

Watch how a high-temperature superconductor levitates around a magnetic racetrack in the video.
This page titled 19.2: Occurrence, Preparation, and Properties of Transition Metals and Their Compounds is shared under a CC BY 4.0 license
and was authored, remixed, and/or curated by OpenStax via source content that was edited to the style and standards of the LibreTexts platform; a
detailed edit history is available upon request.


List the defining traits of coordination compounds
Describe the structures of complexes containing monodentate and polydentate ligands
Use standard nomenclature rules to name coordination compounds
Explain and provide examples of geometric and optical isomerism
Identify several natural and technological occurrences of coordination compounds
The hemoglobin in your blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of
polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
Many of these compounds are highly colored (Figure 19.12). In the remainder of this chapter, we will consider the structure and
bonding of these remarkable compounds.
Figure 19.12 Metal ions that contain partially filled d subshell usually form colored complex ions; ions with empty d subshell (d0)
or with filled d subshells (d10) usually form colorless complexes. This figure shows, from left to right, solutions containing
[M(H2O)6]n+ ions with M = Sc3+(d0), Cr3+(d3), Co2+(d7), Ni2+(d8), Cu2+(d9), and Zn2+(d10). (credit: Sahar Atwa)
Remember that in most main group element compounds, the valence electrons of the isolated atoms combine to form chemical
bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms
to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula
unit NaCl (Figure 19.13). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a
form of the Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an
electron acceptor (Lewis acid). The Lewis acid in coordination complexes, often called a central metal ion (or atom), is often a
transition metal or inner transition metal, although main group elements can also form coordination compounds. The Lewis base
donors, called ligands, can be a wide variety of chemicals—atoms, molecules, or ions. The only requirement is that they have one
or more electron pairs, which can be donated to the central metal. Most often, this involves a donor atom with a lone pair of
electrons that can form a coordinate bond to the metal.

Figure 19.13 (a) Covalent bonds involve the sharing of electrons, and ionic bonds involve the transferring of electrons associated
with each bonding atom, as indicated by the colored electrons. (b) However, coordinate covalent bonds involve electrons from a
Lewis base being donated to a metal center. The lone pairs from six water molecules form bonds to the scandium ion to form an
octahedral complex. (Only the donated pairs are shown.)
The coordination sphere consists of the central metal ion or atom plus its attached ligands. Brackets in a formula enclose the
coordination sphere; species outside the brackets are not part of the coordination sphere. The coordination number of the central
metal ion or atom is the number of donor atoms bonded to it. The coordination number for the silver ion in [Ag(NH3)2]+ is two
(Figure 19.14). For the copper(II) ion in [CuCl4]2−, the coordination number is four, whereas for the cobalt(II) ion in [Co(H2O)6]2+
the coordination number is six. Each of these ligands is monodentate, from the Greek for “one toothed,” meaning that they connect
with the central metal through only one atom. In this case, the number of ligands and the coordination number are equal.
Figure 19.14 The complexes (a) [Ag(NH3)2]+, (b) [Cu(Cl)4]2−, and (c) [Co(H2O)6]2+ have coordination numbers of two, four, and
six, respectively. The geometries of these complexes are the same as we have seen with VSEPR theory for main group elements:
linear, tetrahedral, and octahedral.
Many other ligands coordinate to the metal in more complex fashions. Bidentate ligands are those in which two atoms coordinate to
the metal center. For example, ethylenediamine (en, H2NCH2CH2NH2) contains two nitrogen atoms, each of which has a lone pair
and can serve as a Lewis base (Figure 19.15). Both of the atoms can coordinate to a single metal center. In the complex
[Co(en)3]3+, there are three bidentate en ligands, and the coordination number of the cobalt(III) ion is six. The most common
coordination numbers are two, four, and six, but examples of all coordination numbers from 1 to 15 are known.
Figure 19.15 (a) The ethylenediamine (en) ligand contains two atoms with lone pairs that can coordinate to the metal center. (b)
The cobalt(III) complex [Co(en) ] contains three of these ligands, each forming two bonds to the cobalt ion.
3
3+
Any ligand that bonds to a central metal ion by more than one donor atom is a polydentate ligand (or “many teeth”) because it can
bite into the metal center with more than one bond. The term chelate (pronounced “KEY-late”) from the Greek for “claw” is also
used to describe this type of interaction. Many polydentate ligands are chelating ligands, and a complex consisting of one or more
of these ligands and a central metal is a chelate. A chelating ligand is also known as a chelating agent. A chelating ligand holds the
metal ion rather like a crab’s claw would hold a marble. Figure 19.15 showed one example of a chelate. The heme complex in
hemoglobin is another important example (Figure 19.16). It contains a polydentate ligand with four donor atoms that coordinate to
iron.

Figure 19.16 The single ligand heme contains four nitrogen atoms that coordinate to iron in hemoglobin to form a chelate.
Polydentate ligands are sometimes identified with prefixes that indicate the number of donor atoms in the ligand. As we have seen,
ligands with one donor atom, such as NH3, Cl−, and H2O, are monodentate ligands. Ligands with two donor groups are bidentate
ligands. Ethylenediamine, H2NCH2CH2NH2, and the anion of the acid glycine, NH CH CO (Figure 19.17) are examples of
2 2 2
−
bidentate ligands. Tridentate ligands, tetradentate ligands, pentadentate ligands, and hexadentate ligands contain three, four, five,
and six donor atoms, respectively. The ligand in heme (Figure 19.16) is a tetradentate ligand.
Figure 19.17 Each of the anionic ligands shown attaches in a bidentate fashion to platinum(II), with both a nitrogen and oxygen
atom coordinating to the metal.
19.3.0.1: The Naming of Complexes

The nomenclature of the complexes is patterned after a system suggested by Alfred Werner, a Swiss chemist and Nobel laureate,
whose outstanding work more than 100 years ago laid the foundation for a clearer understanding of these compounds. The
following five rules are used for naming complexes:
1. If a coordination compound is ionic, name the cation first and the anion second, in accordance with the usual nomenclature.
2. Name the ligands first, followed by the central metal. Name the ligands alphabetically. Negative ligands (anions) have names
formed by adding -o to the stem name of the group. For examples, see Table 19.1. For most neutral ligands, the name of the
molecule is used. The four common exceptions are aqua (H2O), ammine (NH3), carbonyl (CO), and nitrosyl (NO). For
example, name [Pt(NH3)2Cl4] as diamminetetrachloroplatinum(IV).
Examples of Anionic Ligands
Anionic Ligand Name

Anionic Ligand Name
F− fluoro
Cl− chloro
Br− bromo
I− iodo
CN− cyano
NO3
−
nitrato
OH− hydroxo
O2– oxo
C2 O4
2−
oxalato
CO3
2−
carbonato
Table 19.1
3. If more than one ligand of a given type is present, the number is indicated by the prefixes di- (for two), tri- (for three), tetra-
(for four), penta- (for five), and hexa- (for six). Sometimes, the prefixes bis- (for two), tris- (for three), and tetrakis- (for four)
are used when the name of the ligand already includes di-, tri-, or tetra-, or when the ligand name begins with a vowel. For
example, the ion bis(bipyridyl)osmium(II) uses bis- to signify that there are two ligands attached to Os, and each bipyridyl
ligand contains two pyridine groups (C5H4N).
When the complex is either a cation or a neutral molecule, the name of the central metal atom is spelled exactly like the name of
the element and is followed by a Roman numeral in parentheses to indicate its oxidation state (Table 19.2 and Table 19.3). When
the complex is an anion, the suffix -ate is added to the stem of the name of the metal, followed by the Roman numeral designation
of its oxidation state (Table 19.4). Sometimes, the Latin name of the metal is used when the English name is clumsy. For example,
ferrate is used instead of ironate, plumbate instead leadate, and stannate instead of tinate. The oxidation state of the metal is
determined based on the charges of each ligand and the overall charge of the coordination compound. For example, in
[Cr(H2O)4Cl2]Br, the coordination sphere (in brackets) has a charge of 1+ to balance the bromide ion. The water ligands are
neutral, and the chloride ligands are anionic with a charge of 1− each. To determine the oxidation state of the metal, we set the
overall charge equal to the sum of the ligands and the metal: +1 = −2 + x, so the oxidation state (x) is equal to 3+.
Examples in Which the Complex Is a Cation
[Co(NH3)6]Cl3 hexaamminecobalt(III) chloride
[Pt(NH3)4Cl2]2+ tetraamminedichloroplatinum(IV) ion
[Ag(NH3)2]+ diamminesilver(I) ion
[Cr(H2O)4Cl2]Cl tetraaquadichlorochromium(III) chloride
[Co(H2NCH2CH2NH2)3]2(SO4)3 tris(ethylenediamine)cobalt(III) sulfate

Table 19.2
Examples in Which the Complex Is Neutral
[Pt(NH3)2Cl4] diamminetetrachloroplatinum(IV)
[Ni(H2NCH2CH2NH2)2Cl2] dichlorobis(ethylenediamine)nickel(II)
Table 19.3
Examples in Which the Complex Is an Anion
[PtCl6]2− hexachloroplatinate(IV) ion
Na2[SnCl6] sodium hexachlorostannate(IV)
Table 19.4

Do you think you understand naming coordination complexes? You can look over more examples and test yourself with online
quizzes at the University of Sydney’s site.
19.3.0.1: Example 19.4

19.3.0.0.1: Coordination Numbers and Oxidation States
Determine the name of the following complexes and give the coordination number of the central metal atom.
(a) Na2[PtCl6]
(b) K3[Fe(C2O4)3]
(c) [Co(NH3)5Cl]Cl2
(a) There are two Na+ ions, so the coordination sphere has a negative two charge: [PtCl6]2−. There are six anionic chloride
ligands, so −2 = −6 + x, and the oxidation state of the platinum is 4+. The name of the complex is sodium
hexachloroplatinate(IV), and the coordination number is six. (b) The coordination sphere has a charge of 3− (based on the
potassium) and the oxalate ligands each have a charge of 2−, so the metal oxidation state is given by −3 = −6 + x, and this is an
iron(III) complex. The name is potassium trisoxalatoferrate(III) (note that tris is used instead of tri because the ligand name
starts with a vowel). Because oxalate is a bidentate ligand, this complex has a coordination number of six. (c) In this example,
the coordination sphere has a cationic charge of 2+. The NH3 ligand is neutral, but the chloro ligand has a charge of 1−. The
oxidation state is found by +2 = −1 + x and is 3+, so the complex is pentaamminechlorocobalt(III) chloride and the
coordination number is six.
The complex potassium dicyanoargenate(I) is used to make antiseptic compounds. Give the formula and coordination number.
19.3.0.1: Answer:
K[Ag(CN)2]; coordination number two
19.3.0.1: The Structures of Complexes

For transition metal complexes, the coordination number determines the geometry around the central metal ion. The most common
structures of the complexes in coordination compounds are square planar, tetrahedral, and octahedral, corresponding to
coordination numbers of four, four, and six, respectively. Coordination numbers greater than six are less common and yield a
variety of structures (see Figure 19.18 and Table 19.5):

Figure 19.18 These are geometries of some complexes with coordination numbers of seven and eight.
Coordination Numbers and Molecular Geometry
Coordination Number Molecular Geometry Example
2 linear [Ag(NH3)2]+
3 trigonal planar [Cu(CN)3]2−
4 tetrahedral(d0 or d10), low oxidation states for M [Ni(CO)4]
4 square planar (d8) [Ni(CN)4]2−
5 trigonal bipyramidal [CoCl5]2−
5 square pyramidal [VO(CN)4]2−
6 octahedral [CoCl6]3−
7 pentagonal bipyramid [ZrF7]3−
8 square antiprism [ReF8]2−
8 dodecahedron [Mo(CN)8]4−
9 and above more complicated structures [ReH9]2−
Table 19.5
Unlike main group atoms in which both the bonding and nonbonding electrons determine the molecular shape, the nonbonding d-
electrons do not change the arrangement of the ligands. Octahedral complexes have a coordination number of six, and the six donor
atoms are arranged at the corners of an octahedron around the central metal ion. Examples are shown in Figure 19.19. The chloride
and nitrate anions in [Co(H2O)6]Cl2 and [Cr(en)3](NO3)3, and the potassium cations in K2[PtCl6], are outside the brackets and are
not bonded to the metal ion.

Figure 19.19 Many transition metal complexes adopt octahedral geometries, with six donor atoms forming bond angles of 90°
about the central atom with adjacent ligands. Note that only ligands within the coordination sphere affect the geometry around the
metal center.
For transition metals with a coordination number of four, two different geometries are possible: tetrahedral or square planar. Unlike
main group elements, where these geometries can be predicted from VSEPR theory, a more detailed discussion of transition metal
orbitals (discussed in the section on Crystal Field Theory) is required to predict which complexes will be tetrahedral and which will
be square planar. In tetrahedral complexes such as [Zn(CN)4]2− (Figure 19.20), each of the ligand pairs forms an angle of 109.5°. In
square planar complexes, such as [Pt(NH3)2Cl2], each ligand has two other ligands at 90° angles (called the cis positions) and one
additional ligand at an 180° angle, in the trans position.
Figure 19.20 Transition metals with a coordination number of four can adopt a tetrahedral geometry (a) as in K2[Zn(CN)4] or a
square planar geometry (b) as shown in [Pt(NH3)2Cl2].
19.3.0.1: Isomerism in Complexes

Isomers are different chemical species that have the same chemical formula. Transition metal complexes often exist as geometric
isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space.
Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For
example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers. In the cis configuration, the two chloride ligands are adjacent to each
other (Figure 19.21). The other isomer, the trans configuration, has the two chloride ligands directly across from one another.

Figure 19.21 The cis and trans isomers of [Co(H2O)4Cl2]+ contain the same ligands attached to the same metal ion, but the spatial
arrangement causes these two compounds to have very different properties.
Different geometric isomers of a substance are different chemical compounds. They exhibit different properties, even though they
have the same formula. For example, the two isomers of [Co(NH3)4Cl2]NO3 differ in color; the cis form is violet, and the trans
form is green. Furthermore, these isomers have different dipole moments, solubilities, and reactivities. As an example of how the
arrangement in space can influence the molecular properties, consider the polarity of the two [Co(NH3)4Cl2]NO3 isomers.
Remember that the polarity of a molecule or ion is determined by the bond dipoles (which are due to the difference in
electronegativity of the bonding atoms) and their arrangement in space. In one isomer, cis chloride ligands cause more electron
density on one side of the molecule than on the other, making it polar. For the trans isomer, each ligand is directly across from an
identical ligand, so the bond dipoles cancel out, and the molecule is nonpolar.
19.3.0.1: Example 19.5

19.3.0.0.1: Geometric Isomers
Identify which geometric isomer of [Pt(NH3)2Cl2] is shown in Figure 19.20. Draw the other geometric isomer and give its full
name.
In the Figure 19.20, the two chlorine ligands occupy cis positions. The other form is shown in Figure 19.22. When naming
specific isomers, the descriptor is listed in front of the name. Therefore, this complex is trans-diamminedichloroplatinum(II).
Figure 19.22 The trans isomer of [Pt(NH3)2Cl2] has each ligand directly across from an adjacent ligand.
Draw the ion trans-diaqua-trans-dibromo-trans-dichlorocobalt(II).
19.3.0.1: Answer:
Another important type of isomers are optical isomers, or enantiomers, in which two objects are exact mirror images of each other
but cannot be lined up so that all parts match. This means that optical isomers are nonsuperimposable mirror images. A classic
example of this is a pair of hands, in which the right and left hand are mirror images of one another but cannot be superimposed.
Optical isomers are very important in organic and biochemistry because living systems often incorporate one specific optical
isomer and not the other. Unlike geometric isomers, pairs of optical isomers have identical properties (boiling point, polarity,
solubility, etc.). Optical isomers differ only in the way they affect polarized light and how they react with other optical isomers. For
coordination complexes, many coordination compounds such as [M(en)3]n+ [in which Mn+ is a central metal ion such as iron(III) or
cobalt(II)] form enantiomers, as shown in Figure 19.23. These two isomers will react differently with other optical isomers. For
example, DNA helices are optical isomers, and the form that occurs in nature (right-handed DNA) will bind to only one isomer of
[M(en)3]n+ and not the other.

Figure 19.23 The complex [M(en)3]n+ (Mn+ = a metal ion, en = ethylenediamine) has a nonsuperimposable mirror image.
The [Co(en)2Cl2]+ ion exhibits geometric isomerism (cis/trans), and its cis isomer exists as a pair of optical isomers (Figure 19.24).
Figure 19.24 Three isomeric forms of [Co(en)2Cl2]+ exist. The trans isomer, formed when the chlorines are positioned at a 180°
angle, has very different properties from the cis isomers. The mirror images of the cis isomer form a pair of optical isomers, which
have identical behavior except when reacting with other enantiomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two
different atoms. For example, the CN ligand can bind through the carbon atom (cyano) or through the nitrogen atom (isocyano).
Similarly, SCN− can be bound through the sulfur or nitrogen atom, affording two distinct compounds ([Co(NH3)5SCN]2+ or
[Co(NH3)5NCS]2+).
Ionization isomers (or coordination isomers) occur when one anionic ligand in the inner coordination sphere is replaced with the
counter ion from the outer coordination sphere. A simple example of two ionization isomers are [CoCl6][Br] and [CoCl5Br][Cl].
19.3.0.1: Coordination Complexes in Nature and Technology

Chlorophyll, the green pigment in plants, is a complex that contains magnesium (Figure 19.25). This is an example of a main group
element in a coordination complex. Plants appear green because chlorophyll absorbs red and purple light; the reflected light
consequently appears green. The energy resulting from the absorption of light is used in photosynthesis.

Figure 19.25 (a) Chlorophyll comes in several different forms, which all have the same basic structure around the magnesium
center. (b) Copper phthalocyanine blue, a square planar copper complex, is present in some blue dyes.

19.3.0.0.1: Transition Metal Catalysts
One of the most important applications of transition metals is as industrial catalysts. As you recall from the chapter on kinetics,
a catalyst increases the rate of reaction by lowering the activation energy and is regenerated in the catalytic cycle. Over 90% of
all manufactured products are made with the aid of one or more catalysts. The ability to bind ligands and change oxidation
states makes transition metal catalysts well suited for catalytic applications. Vanadium oxide is used to produce 230,000,000
tons of sulfuric acid worldwide each year, which in turn is used to make everything from fertilizers to cans for food. Plastics
are made with the aid of transition metal catalysts, along with detergents, fertilizers, paints, and more (see Figure 19.26). Very
complicated pharmaceuticals are manufactured with catalysts that are selective, reacting with one specific bond out of a large
number of possibilities. Catalysts allow processes to be more economical and more environmentally friendly. Developing new
catalysts and better understanding of existing systems are important areas of current research.

Figure 19.26 (a) Detergents, (b) paints, and (c) fertilizers are all made using transition metal catalysts. (credit a: modification of
work by “Mr. Brian”/Flickr; credit b: modification of work by Ewen Roberts; credit c: modification of work by
“osseous”/Flickr)

19.3.0.0.2: Deanna D’Alessandro
Dr. Deanna D’Alessandro develops new metal-containing materials that demonstrate unique electronic, optical, and magnetic
properties. Her research combines the fields of fundamental inorganic and physical chemistry with materials engineering. She
is working on many different projects that rely on transition metals. For example, one type of compound she is developing
captures carbon dioxide waste from power plants and catalytically converts it into useful products (see Figure 19.27).
Figure 19.27 Catalytic converters change carbon dioxide emissions from power plants into useful products, and, like the one
shown here, are also found in cars.
Another project involves the development of porous, sponge-like materials that are “photoactive.” The absorption of light
causes the pores of the sponge to change size, allowing gas diffusion to be controlled. This has many potential useful
applications, from powering cars with hydrogen fuel cells to making better electronics components. Although not a complex,
self-darkening sunglasses are an example of a photoactive substance.
Watch this video to learn more about this research and listen to Dr. D’Alessandro (shown in Figure 19.28) describe what it is
like being a research chemist.

Figure 19.28 Dr. Deanna D’Alessandro is a functional materials researcher. Her work combines the inorganic and physical
chemistry fields with engineering, working with transition metals to create new systems to power cars and convert energy
(credit: image courtesy of Deanna D'Alessandro).
Many other coordination complexes are also brightly colored. The square planar copper(II) complex phthalocyanine blue (from
Figure 19.25) is one of many complexes used as pigments or dyes. This complex is used in blue ink, blue jeans, and certain blue
paints.
The structure of heme (Figure 19.29), the iron-containing complex in hemoglobin, is very similar to that in chlorophyll. In
hemoglobin, the red heme complex is bonded to a large protein molecule (globin) by the attachment of the protein to the heme
ligand. Oxygen molecules are transported by hemoglobin in the blood by being bound to the iron center. When the hemoglobin
loses its oxygen, the color changes to a bluish red. Hemoglobin will only transport oxygen if the iron is Fe2+; oxidation of the iron
to Fe3+ prevents oxygen transport.

Figure 19.29 Hemoglobin contains four protein subunits, each of which has an iron center attached to a heme ligand (shown in red),
which is coordinated to a globin protein. Each subunit is shown in a different color.
Complexing agents often are used for water softening because they tie up such ions as Ca2+, Mg2+, and Fe2+, which make water
hard. Many metal ions are also undesirable in food products because these ions can catalyze reactions that change the color of food.
Coordination complexes are useful as preservatives. For example, the ligand EDTA, (HO2CCH2)2NCH2CH2N(CH2CO2H)2,
coordinates to metal ions through six donor atoms and prevents the metals from reacting (Figure 19.30). This ligand also is used to
sequester metal ions in paper production, textiles, and detergents, and has pharmaceutical uses.

Figure 19.30 The ligand EDTA binds tightly to a variety of metal ions by forming hexadentate complexes.
Complexing agents that tie up metal ions are also used as drugs. British Anti-Lewisite (BAL), HSCH2CH(SH)CH2OH, is a drug
developed during World War I as an antidote for the arsenic-based war gas Lewisite. BAL is now used to treat poisoning by heavy
metals, such as arsenic, mercury, thallium, and chromium. The drug is a ligand and functions by making a water-soluble chelate of
the metal; the kidneys eliminate this metal chelate (Figure 19.31). Another polydentate ligand, enterobactin, which is isolated from
certain bacteria, is used to form complexes of iron and thereby to control the severe iron buildup found in patients suffering from
blood diseases such as Cooley’s anemia, who require frequent transfusions. As the transfused blood breaks down, the usual
metabolic processes that remove iron are overloaded, and excess iron can build up to fatal levels. Enterobactin forms a water-
soluble complex with excess iron, and the body can safely eliminate this complex.

Figure 19.31 Coordination complexes are used as drugs. (a) British Anti-Lewisite is used to treat heavy metal poisoning by
coordinating metals (M), and enterobactin (b) allows excess iron in the blood to be removed.
19.3.0.1: Example 19.6

19.3.0.0.3: Chelation Therapy
Ligands like BAL and enterobactin are important in medical treatments for heavy metal poisoning. However, chelation
therapies can disrupt the normal concentration of ions in the body, leading to serious side effects, so researchers are searching
for new chelation drugs. One drug that has been developed is dimercaptosuccinic acid (DMSA), shown in Figure 19.32.
Identify which atoms in this molecule could act as donor atoms.

Figure 19.32 Dimercaptosuccinic acid is used to treat heavy metal poisoning.
All of the oxygen and sulfur atoms have lone pairs of electrons that can be used to coordinate to a metal center, so there are six
possible donor atoms. Geometrically, only two of these atoms can be coordinated to a metal at once. The most common
binding mode involves the coordination of one sulfur atom and one oxygen atom, forming a five-member ring with the metal.
Some alternative medicine practitioners recommend chelation treatments for ailments that are not clearly related to heavy
metals, such as cancer and autism, although the practice is discouraged by many scientific organizations.1 Identify at least two
biologically important metals that could be disrupted by chelation therapy.
19.3.0.1: Answer:
Ca, Fe, Zn, and Cu
Ligands are also used in the electroplating industry. When metal ions are reduced to produce thin metal coatings, metals can clump
together to form clusters and nanoparticles. When metal coordination complexes are used, the ligands keep the metal atoms isolated
from each other. It has been found that many metals plate out as a smoother, more uniform, better-looking, and more adherent
surface when plated from a bath containing the metal as a complex ion. Thus, complexes such as [Ag(CN)2]− and [Au(CN)2]− are
used extensively in the electroplating industry.
In 1965, scientists at Michigan State University discovered that there was a platinum complex that inhibited cell division in certain
microorganisms. Later work showed that the complex was cis-diamminedichloroplatinum(II), [Pt(NH3)2(Cl)2], and that the trans
isomer was not effective. The inhibition of cell division indicated that this square planar compound could be an anticancer agent. In
1978, the US Food and Drug Administration approved this compound, known as cisplatin, for use in the treatment of certain forms
of cancer. Since that time, many similar platinum compounds have been developed for the treatment of cancer. In all cases, these
are the cis isomers and never the trans isomers. The diammine (NH3)2 portion is retained with other groups, replacing the dichloro
[(Cl)2] portion. The newer drugs include carboplatin, oxaliplatin, and satraplatin.
19.3.0.1: Footnotes
1National Council against Health Fraud, NCAHF Policy Statement on Chelation Therapy, (Peabody, MA, 2002).
This page titled 19.3: Coordination Chemistry of Transition Metals is shared under a CC BY 4.0 license and was authored, remixed, and/or
upon request.


Outline the basic premise of crystal field theory (CFT)
Identify molecular geometries associated with various d-orbital splitting patterns
Predict electron configurations of split d orbitals for selected transition metal atoms or ions
Explain spectral and magnetic properties in terms of CFT concepts
The behavior of coordination compounds cannot be adequately explained by the same theories used for main group element
chemistry. The observed geometries of coordination complexes are not consistent with hybridized orbitals on the central metal
overlapping with ligand orbitals, as would be predicted by valence bond theory. The observed colors indicate that the d orbitals
often occur at different energy levels rather than all being degenerate, that is, of equal energy, as are the three p orbitals. To explain
the stabilities, structures, colors, and magnetic properties of transition metal complexes, a different bonding model has been
developed. Just as valence bond theory explains many aspects of bonding in main group chemistry, crystal field theory is useful in
understanding and predicting the behavior of transition metal complexes.
19.4.0.1: Crystal Field Theory

To explain the observed behavior of transition metal complexes (such as how colors arise), a model involving electrostatic
interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has
been developed. This electrostatic model is crystal field theory (CFT). It allows us to understand, interpret, and predict the colors,
magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on the nonbonding electrons on the central metal ion in coordination complexes not on the metal-ligand bonds. Like
valence bond theory, CFT tells only part of the story of the behavior of complexes. However, it tells the part that valence bond
theory does not. In its pure form, CFT ignores any covalent bonding between ligands and metal ions. Both the ligand and the metal
are treated as infinitesimally small point charges.
All electrons are negative, so the electrons donated from the ligands will repel the electrons of the central metal. Let us consider the
behavior of the electrons in the unhybridized d orbitals in an octahedral complex. The five d orbitals consist of lobe-shaped regions
and are arranged in space, as shown in Figure 19.33. In an octahedral complex, the six ligands coordinate along the axes.
Figure 19.33 The directional characteristics of the five d orbitals are shown here. The shaded portions indicate the phase of the
orbitals. The ligands (L) coordinate along the axes. For clarity, the ligands have been omitted from the d 2orbital so that the
x −y
2
axis labels could be shown.

In an uncomplexed metal ion in the gas phase, the electrons are distributed among the five d orbitals in accord with Hund's rule
because the orbitals all have the same energy. However, when ligands coordinate to a metal ion, the energies of the d orbitals are no
longer the same.
In octahedral complexes, the lobes in two of the five d orbitals, the d and d
z2 orbitals, point toward the ligands (Figure 19.33).
x2 −y 2
These two orbitals are called the eg orbitals (the symbol actually refers to the symmetry of the orbitals, but we will use it as a

convenient name for these two orbitals in an octahedral complex). The other three orbitals, the dxy, dxz, and dyz orbitals, have lobes
that point between the ligands and are called the t2g orbitals (again, the symbol really refers to the symmetry of the orbitals). As six
ligands approach the metal ion along the axes of the octahedron, their point charges repel the electrons in the d orbitals of the metal
ion. However, the repulsions between the electrons in the eg orbitals (the d and d z
orbitals) and the ligands are greater than
2 2
x −y
2
the repulsions between the electrons in the t2g orbitals (the dzy, dxz, and dyz orbitals) and the ligands. This is because the lobes of the
eg orbitals point directly at the ligands, whereas the lobes of the t2g orbitals point between them. Thus, electrons in the eg orbitals of
the metal ion in an octahedral complex have higher potential energies than those of electrons in the t2g orbitals. The difference in
energy may be represented as shown in Figure 19.34.
Figure 19.34 In octahedral complexes, the eg orbitals are destabilized (higher in energy) compared to the t2g orbitals because the
ligands interact more strongly with the d orbitals at which they are pointed directly.
The difference in energy between the eg and the t2g orbitals is called the crystal field splitting and is symbolized by Δoct, where oct
stands for octahedral.
The magnitude of Δoct depends on many factors, including the nature of the six ligands located around the central metal ion, the
charge on the metal, and whether the metal is using 3d, 4d, or 5d orbitals. Different ligands produce different crystal field splittings.
The increasing crystal field splitting produced by ligands is expressed in the spectrochemical series, a short version of which is
given here:
− − − − 2− − −
I <Br <Cl <F <H2 O<C2 O4 <NH3 <en<NO2 <CN
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−→
a few ligands of the spectrochemical series, in order of increasing field strength of the ligand
In this series, ligands on the left cause small crystal field splittings and are weak-field ligands, whereas those on the right cause
larger splittings and are strong-field ligands. Thus, the Δoct value for an octahedral complex with iodide ligands (I−) is much
smaller than the Δoct value for the same metal with cyanide ligands (CN−).
Electrons in the d orbitals follow the aufbau (“filling up”) principle, which says that the orbitals will be filled to give the lowest
total energy, just as in main group chemistry. When two electrons occupy the same orbital, the like charges repel each other. The
energy needed to pair up two electrons in a single orbital is called the pairing energy (P). Electrons will always singly occupy each
orbital in a degenerate set before pairing. P is similar in magnitude to Δoct. When electrons fill the d orbitals, the relative
magnitudes of Δoct and P determine which orbitals will be occupied.
In [Fe(CN)6]4−, the strong field of six cyanide ligands produces a large Δoct. Under these conditions, the electrons require less
energy to pair than they require to be excited to the eg orbitals (Δoct > P). The six 3d electrons of the Fe2+ ion pair in the three t2g
orbitals (Figure 19.35). Complexes in which the electrons are paired because of the large crystal field splitting are called low-spin
complexes because the number of unpaired electrons (spins) is minimized.

Figure 19.35 Iron(II) complexes have six electrons in the 5d orbitals. In the absence of a crystal field, the orbitals are degenerate.
For coordination complexes with strong-field ligands such as [Fe(CN)6]4−, Δoct is greater than P, and the electrons pair in the lower
energy t2g orbitals before occupying the eg orbitals. With weak-field ligands such as H2O, the ligand field splitting is less than the
pairing energy, Δoct less than P, so the electrons occupy all d orbitals singly before any pairing occurs.
In [Fe(H2O)6]2+, on the other hand, the weak field of the water molecules produces only a small crystal field splitting (Δoct < P).
Because it requires less energy for the electrons to occupy the eg orbitals than to pair together, there will be an electron in each of
the five 3d orbitals before pairing occurs. For the six d electrons on the iron(II) center in [Fe(H2O)6]2+, there will be one pair of
electrons and four unpaired electrons (Figure 19.35). Complexes such as the [Fe(H2O)6]2+ ion, in which the electrons are unpaired
because the crystal field splitting is not large enough to cause them to pair, are called high-spin complexes because the number of
unpaired electrons (spins) is maximized.
A similar line of reasoning shows why the [Fe(CN)6]3− ion is a low-spin complex with only one unpaired electron, whereas both
the [Fe(H2O)6]3+ and [FeF6]3− ions are high-spin complexes with five unpaired electrons.
19.4.0.1: Example 19.7

19.4.0.0.1: High- and Low-Spin Complexes
Predict the number of unpaired electrons.
(a) K3[CrI6]
(b) [Cu(en)2(H2O)2]Cl2
(c) Na3[Co(NO2)6]
The complexes are octahedral.
(a) Cr3+ has a d3 configuration. These electrons will all be unpaired.
(b) Cu2+ is d9, so there will be one unpaired electron.
(c) Co3+ has d6 valence electrons, so the crystal field splitting will determine how many are paired. Nitrite is a strong-field
ligand, so the complex will be low spin. Six electrons will go in the t2g orbitals, leaving 0 unpaired.

The size of the crystal field splitting only influences the arrangement of electrons when there is a choice between pairing
electrons and filling the higher-energy orbitals. For which d-electron configurations will there be a difference between high-
and low-spin configurations in octahedral complexes?
19.4.0.1: Answer:
d4, d5, d6, and d7
19.4.0.1: Example 19.8

19.4.0.0.4: CFT for Other Geometries
CFT is applicable to molecules in geometries other than octahedral. In octahedral complexes, remember that the lobes of the eg
set point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but now we have only four ligands
located between the axes (Figure 19.36). None of the orbitals points directly at the tetrahedral ligands. However, the eg set
(along the Cartesian axes) overlaps with the ligands less than does the t2g set. By analogy with the octahedral case, predict the
energy diagram for the d orbitals in a tetrahedral crystal field. To avoid confusion, the octahedral eg set becomes a tetrahedral e
set, and the octahedral t2g set becomes a t2 set.
Figure 19.36 This diagram shows the orientation of the tetrahedral ligands with respect to the axis system for the orbitals.
Since CFT is based on electrostatic repulsion, the orbitals closer to the ligands will be destabilized and raised in energy relative
to the other set of orbitals. The splitting is less than for octahedral complexes because the overlap is less, so Δtet is usually
small (Δ tet =
4
9
Δoct ) :

Explain how many unpaired electrons a tetrahedral d4 ion will have.
19.4.0.1: Answer:
4; because Δtet is small, all tetrahedral complexes are high spin and the electrons go into the t2 orbitals before pairing

The other common geometry is square planar. It is possible to consider a square planar geometry as an octahedral structure with a
pair of trans ligands removed. The removed ligands are assumed to be on the z-axis. This changes the distribution of the d orbitals,
as orbitals on or near the z-axis become more stable, and those on or near the x- or y-axes become less stable. This results in the
octahedral t2g and the eg sets splitting and gives a more complicated pattern, as depicted below:

19.4.0.1: Magnetic Moments of Molecules and Ions
Experimental evidence of magnetic measurements supports the theory of high- and low-spin complexes. Remember that molecules
such as O2 that contain unpaired electrons are paramagnetic. Paramagnetic substances are attracted to magnetic fields. Many
transition metal complexes have unpaired electrons and hence are paramagnetic. Molecules such as N2 and ions such as Na+ and
[Fe(CN)6]4− that contain no unpaired electrons are diamagnetic. Diamagnetic substances have a slight tendency to be repelled by
magnetic fields.
When an electron in an atom or ion is unpaired, the magnetic moment due to its spin makes the entire atom or ion paramagnetic.
The size of the magnetic moment of a system containing unpaired electrons is related directly to the number of such electrons: the
greater the number of unpaired electrons, the larger the magnetic moment. Therefore, the observed magnetic moment is used to
determine the number of unpaired electrons present. The measured magnetic moment of low-spin d6 [Fe(CN)6]4− confirms that iron
is diamagnetic, whereas high-spin d6 [Fe(H2O)6]2+ has four unpaired electrons with a magnetic moment that confirms this
arrangement.
19.4.0.1: Colors of Transition Metal Complexes

When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main
group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be
detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the
visible range to be absorbed.
The human eye perceives a mixture of all the colors, in the proportions present in sunlight, as white light. Complementary colors,
those located across from each other on a color wheel, are also used in color vision. The eye perceives a mixture of two
complementary colors, in the proper proportions, as white light. Likewise, when a color is missing from white light, the eye sees its
complement. For example, when red photons are absorbed from white light, the eyes see the color green. When violet photons are
removed from white light, the eyes see lemon yellow. The blue color of the [Cu(NH3)4]2+ ion results because this ion absorbs
orange and red light, leaving the complementary colors of blue and green (Figure 19.37).

Figure 19.37 (a) An object is black if it absorbs all colors of light. If it reflects all colors of light, it is white. An object has a color if
it absorbs all colors except one, such as this yellow strip. The strip also appears yellow if it absorbs the complementary color from
white light (in this case, indigo). (b) Complementary colors are located directly across from one another on the color wheel. (c) A
solution of [Cu(NH3)4]2+ ions absorbs red and orange light, so the transmitted light appears as the complementary color, blue.
19.4.0.1: Example 19.9

19.4.0.0.1: Colors of Complexes
The octahedral complex [Ti(H2O)6]3+ has a single d electron. To excite this electron from the ground state t2g orbital to the eg
orbital, this complex absorbs light from 450 to 600 nm. The maximum absorbance corresponds to Δoct and occurs at 499 nm.
Calculate the value of Δoct in Joules and predict what color the solution will appear.
Using Planck's equation (refer to the section on electromagnetic energy), we calculate:
8
c 3.00 × 10 m/s
14
v = so = 6.01 × 10 Hz
λ 499 nm × 1 m
9
10 nm
−34 14 −19
E = hν so 6.63 × 10 J⋅s × 6.01 × 10 Hz = 3.99 × 10 Joules/ion
Because the complex absorbs 600 nm (orange) through 450 (blue), the indigo, violet, and red wavelengths will be transmitted,
and the complex will appear purple.
A complex that appears green, absorbs photons of what wavelengths?
19.4.0.1: Answer:
red, 620–800 nm
Small changes in the relative energies of the orbitals that electrons are transitioning between can lead to drastic shifts in the color of
light absorbed. Therefore, the colors of coordination compounds depend on many factors. As shown in Figure 19.38, different
aqueous metal ions can have different colors. In addition, different oxidation states of one metal can produce different colors, as
shown for the vanadium complexes in the link below.
3 3 2

Figure 19.38 The partially filled d orbitals of the stable ions Cr3+(aq), Fe3+(aq), and Co2+(aq) (left, center and right, respectively)
give rise to various colors. (credit: Sahar Atwa)
The specific ligands coordinated to the metal center also influence the color of coordination complexes. For example, the iron(II)
complex [Fe(H2O)6]SO4 appears blue-green because the high-spin complex absorbs photons in the red wavelengths (Figure 19.39).
In contrast, the low-spin iron(II) complex K4[Fe(CN)6] appears pale yellow because it absorbs higher-energy violet photons.
Figure 19.39 Both (a) hexaaquairon(II) sulfate and (b) potassium hexacyanoferrate(II) contain d6 iron(II) octahedral metal centers,
but they absorb photons in different ranges of the visible spectrum.

Watch this video of the reduction of vanadium complexes to observe the colorful effect of changing oxidation states.
In general, strong-field ligands cause a large split in the energies of d orbitals of the central metal atom (large Δoct). Transition
metal coordination compounds with these ligands are yellow, orange, or red because they absorb higher-energy violet or blue light.
On the other hand, coordination compounds of transition metals with weak-field ligands are often blue-green, blue, or indigo
because they absorb lower-energy yellow, orange, or red light.
A coordination compound of the Cu+ ion has a d10 configuration, and all the eg orbitals are filled. To excite an electron to a higher
level, such as the 4p orbital, photons of very high energy are necessary. This energy corresponds to very short wavelengths in the
ultraviolet region of the spectrum. No visible light is absorbed, so the eye sees no change, and the compound appears white or
colorless. A solution containing [Cu(CN)2]−, for example, is colorless. On the other hand, octahedral Cu2+ complexes have a
vacancy in the eg orbitals, and electrons can be excited to this level. The wavelength (energy) of the light absorbed corresponds to
the visible part of the spectrum, and Cu2+ complexes are almost always colored—blue, blue-green violet, or yellow (Figure 19.40).
Although CFT successfully describes many properties of coordination complexes, molecular orbital explanations (beyond the
introductory scope provided here) are required to understand fully the behavior of coordination complexes.

Figure 19.40 (a) Copper(I) complexes with d10 configurations such as CuI tend to be colorless, whereas (b) d9 copper(II)
complexes such as Cu(NO3)2·5H2O are brightly colored.
This page titled 19.4: Spectroscopic and Magnetic Properties of Coordination Compounds is shared under a CC BY 4.0 license and was authored,

19.5: Key Terms
actinide series
(also, actinoid series) actinium and the elements in the second row or the f-block, atomic numbers 89–103
bidentate ligand
ligand that coordinates to one central metal through coordinate bonds from two different atoms
central metal
ion or atom to which one or more ligands is attached through coordinate covalent bonds
chelate
complex formed from a polydentate ligand attached to a central metal
chelating ligand
ligand that attaches to a central metal ion by bonds from two or more donor atoms
cis configuration
configuration of a geometrical isomer in which two similar groups are on the same side of an imaginary reference line on the
molecule
coordination compound
stable compound in which the central metal atom or ion acts as a Lewis acid and accepts one or more pairs of electrons
coordination compound
substance consisting of atoms, molecules, or ions attached to a central atom through Lewis acid-base interactions
coordination number
number of coordinate covalent bonds to the central metal atom in a complex or the number of closest contacts to an atom in a
crystalline form
coordination sphere
central metal atom or ion plus the attached ligands of a complex
crystal field splitting (Δoct)

difference in energy between the t2g and eg sets or t and e sets of orbitals
crystal field theory

model that explains the energies of the orbitals in transition metals in terms of electrostatic interactions with the ligands but
does not include metal ligand bonding
d-block element
one of the elements in groups 3–11 with valence electrons in d orbitals
donor atom
atom in a ligand with a lone pair of electrons that forms a coordinate covalent bond to a central metal
eg orbitals
set of two d orbitals that are oriented on the Cartesian axes for coordination complexes; in octahedral complexes, they are
higher in energy than the t2g orbitals
f-block element
(also, inner transition element) one of the elements with atomic numbers 58–71 or 90–103 that have valence electrons in f
orbitals; they are frequently shown offset below the periodic table
first transition series
transition elements in the fourth period of the periodic table (first row of the d-block), atomic numbers 21–29
fourth transition series

transition elements in the seventh period of the periodic table (fourth row of the d-block), atomic numbers 89 and 104–111
geometric isomers
isomers that differ in the way in which atoms are oriented in space relative to each other, leading to different physical and
chemical properties
high-spin complex
complex in which the electrons maximize the total electron spin by singly populating all of the orbitals before pairing two
electrons into the lower-energy orbitals
hydrometallurgy
process in which a metal is separated from a mixture by first converting it into soluble ions, extracting the ions, and then
reducing the ions to precipitate the pure metal
ionization isomer
(or coordination isomer) isomer in which an anionic ligand is replaced by the counter ion in the inner coordination sphere
lanthanide series
(also, lanthanoid series) lanthanum and the elements in the first row or the f-block, atomic numbers 57–71
ligand
ion or neutral molecule attached to the central metal ion in a coordination compound
linkage isomer
coordination compound that possesses a ligand that can bind to the transition metal in two different ways (CN− vs. NC−)
low-spin complex
complex in which the electrons minimize the total electron spin by pairing in the lower-energy orbitals before populating the
higher-energy orbitals
monodentate
ligand that attaches to a central metal through just one coordinate covalent bond
optical isomer
(also, enantiomer) molecule that is a nonsuperimposable mirror image with identical chemical and physical properties, except
when it reacts with other optical isomers
pairing energy (P)

energy required to place two electrons with opposite spins into a single orbital
platinum metals
group of six transition metals consisting of ruthenium, osmium, rhodium, iridium, palladium, and platinum that tend to occur in
the same minerals and demonstrate similar chemical properties
polydentate ligand
ligand that is attached to a central metal ion by bonds from two or more donor atoms, named with prefixes specifying how
many donors are present (e.g., hexadentate = six coordinate bonds formed)
rare earth element

collection of 17 elements including the lanthanides, scandium, and yttrium that often occur together and have similar chemical
properties, making separation difficult
second transition series
transition elements in the fifth period of the periodic table (second row of the d-block), atomic numbers 39–47
smelting
process of extracting a pure metal from a molten ore
spectrochemical series
ranking of ligands according to the magnitude of the crystal field splitting they induce
steel
material made from iron by removing impurities in the iron and adding substances that produce alloys with properties suitable
for specific uses
strong-field ligand
ligand that causes larger crystal field splittings
superconductor
material that conducts electricity with no resistance
t2g orbitals
set of three d orbitals aligned between the Cartesian axes for coordination complexes; in octahedral complexes, they are
lowered in energy compared to the eg orbitals according to CFT
third transition series

transition elements in the sixth period of the periodic table (third row of the d-block), atomic numbers 57 and 72–79
trans configuration
configuration of a geometrical isomer in which two similar groups are on opposite sides of an imaginary reference line on the
molecule
weak-field ligand
ligand that causes small crystal field splittings
19.6: Summary
19.1 Occurrence, Preparation, and Properties of Transition Metals and Their Compounds
The transition metals are elements with partially filled d orbitals, located in the d-block of the periodic table. The reactivity of the
transition elements varies widely from very active metals such as scandium and iron to almost inert elements, such as the platinum
metals. The type of chemistry used in the isolation of the elements from their ores depends upon the concentration of the element in
its ore and the difficulty of reducing ions of the elements to the metals. Metals that are more active are more difficult to reduce.
Transition metals exhibit chemical behavior typical of metals. For example, they oxidize in air upon heating and react with
elemental halogens to form halides. Those elements that lie above hydrogen in the activity series react with acids, producing salts
and hydrogen gas. Oxides, hydroxides, and carbonates of transition metal compounds in low oxidation states are basic. Halides and
other salts are generally stable in water, although oxygen must be excluded in some cases. Most transition metals form a variety of
stable oxidation states, allowing them to demonstrate a wide range of chemical reactivity.
19.2 Coordination Chemistry of Transition Metals

The transition elements and main group elements can form coordination compounds, or complexes, in which a central metal atom
or ion is bonded to one or more ligands by coordinate covalent bonds. Ligands with more than one donor atom are called
polydentate ligands and form chelates. The common geometries found in complexes are tetrahedral and square planar (both with a
coordination number of four) and octahedral (with a coordination number of six). Cis and trans configurations are possible in some
octahedral and square planar complexes. In addition to these geometrical isomers, optical isomers (molecules or ions that are mirror
images but not superimposable) are possible in certain octahedral complexes. Coordination complexes have a wide variety of uses
including oxygen transport in blood, water purification, and pharmaceutical use.
19.3 Spectroscopic and Magnetic Properties of Coordination Compounds

Crystal field theory treats interactions between the electrons on the metal and the ligands as a simple electrostatic effect. The
presence of the ligands near the metal ion changes the energies of the metal d orbitals relative to their energies in the free ion. Both
the color and the magnetic properties of a complex can be attributed to this crystal field splitting. The magnitude of the splitting
(Δoct) depends on the nature of the ligands bonded to the metal. Strong-field ligands produce large splitting and favor low-spin
complexes, in which the t2g orbitals are completely filled before any electrons occupy the eg orbitals. Weak-field ligands favor
formation of high-spin complexes. The t2g and the eg orbitals are singly occupied before any are doubly occupied.
19.7: Exercises
19.7.0.1: 19.1 Occurrence, Preparation, and Properties of Transition Metals and Their Compounds
1.
Write the electron configurations for each of the following elements:
(a) Sc
(b) Ti
(c) Cr
(d) Fe
(e) Ru
2.
Write the electron configurations for each of the following elements and its ions:
(a) Ti
(b) Ti2+
(c) Ti3+
(d) Ti4+
3.
Write the electron configurations for each of the following elements and its 3+ ions:
(a) La
(b) Sm
(c) Lu
4.
Why are the lanthanoid elements not found in nature in their elemental forms?
5.
Which of the following elements is most likely to be used to prepare La by the reduction of La2O3: Al, C, or Fe? Why?
6.
Which of the following is the strongest oxidizing agent: VO 4
3
, CrO4
2−
, or MnO 4
−
?
7.
Which of the following elements is most likely to form an oxide with the formula MO3: Zr, Nb, or Mo?
8.
The following reactions all occur in a blast furnace. Which of these are redox reactions?
(a) 3Fe 2 O3 (s) + CO(g) ⟶ 2Fe3 O4 (s) + CO2 (g)
(b) Fe 3 O4 (s) + CO(g) ⟶ 3FeO(s) + CO2 (g)
(c) FeO(s) + CO(g) ⟶ Fe(l) + CO2 (g)
(d) C(s) + O 2 (g) ⟶ CO2 (g)
(e) C(s) + CO 2 (g) ⟶ 2CO(g)
(f) CaCO 3 (s) ⟶ CaO(s) + CO2 (g)
(g) CaO(s) + SiO 2 (s) ⟶ CaSiO3 (l)
9.
Why is the formation of slag useful during the smelting of iron?

10.
Would you expect an aqueous manganese(VII) oxide solution to have a pH greater or less than 7.0? Justify your answer.
11.
Iron(II) can be oxidized to iron(III) by dichromate ion, which is reduced to chromium(III) in acid solution. A 2.5000-g sample of
iron ore is dissolved and the iron converted into iron(II). Exactly 19.17 mL of 0.0100 M Na2Cr2O7 is required in the titration. What
percentage of the ore sample was iron?
12.
How many cubic feet of air at a pressure of 760 torr and 0 °C is required per ton of Fe2O3 to convert that Fe2O3 into iron in a blast
furnace? For this exercise, assume air is 19% oxygen by volume.
13.
Find the potentials of the following electrochemical cell:
Cd | Cd2+, M = 0.10 ‖ Ni2+, M = 0.50 | Ni
14.
A 2.5624-g sample of a pure solid alkali metal chloride is dissolved in water and treated with excess silver nitrate. The resulting
precipitate, filtered and dried, weighs 3.03707 g. What was the percent by mass of chloride ion in the original compound? What is
the identity of the salt?
15.
The standard reduction potential for the reaction [Co(H O) ] (aq) + e ⟶ [Co(H O) ] (aq) is about 1.8 V. The reduction
2 6
3+ −
2 6
2+
potential for the reaction [Co(NH ) ] (aq) + e ⟶ [Co(NH ) ] (aq) is +0.1 V. Calculate the cell potentials to show
3 6
3+ −
3 6
2+
whether the complex ions, [Co(H2O)6]2+ and/or [Co(NH3)6]2+, can be oxidized to the corresponding cobalt(III) complex by
oxygen.
16.
Predict the products of each of the following reactions. (Note: In addition to using the information in this chapter, also use the
knowledge you have accumulated at this stage of your study, including information on the prediction of reaction products.)
(a) MnCO 3 (s) + HI(aq) ⟶
(b) CoO(s) + O 2 (g) ⟶
(c) La(s) + O 2 (g) ⟶
(d) V(s) + VCl 4 (s) ⟶
(e) Co(s) + xsF 2 (g) ⟶
(f) CrO 3 (s) + CsOH(aq) ⟶
17.
Predict the products of each of the following reactions. (Note: In addition to using the information in this chapter, also use the
knowledge you have accumulated at this stage of your study, including information on the prediction of reaction products.)
(a) Fe(s) + H 2 SO 4 (aq) ⟶
(b) FeCl 3 (aq) + NaOH(aq) ⟶
(c) Mn(OH) 2
(s) + HBr(aq) ⟶
(d) Cr(s) + O 2 (g) ⟶
(e) Mn 2 O3 (s) + HCl(aq) ⟶
(f) Ti(s) + xsF 2 (g) ⟶
18.
Describe the electrolytic process for refining copper.
19.

Predict the products of the following reactions and balance the equations.
(a) Zn is added to a solution of Cr2(SO4)3 in acid.
(b) FeCl2 is added to a solution containing an excess of Cr 2 O7
2−
in hydrochloric acid.
2+
(c) Cr is added to Cr 2 O7
2−
in acid solution.
(d) Mn is heated with CrO3.
(e) CrO is added to 2HNO3 in water.
(f) FeCl3 is added to an aqueous solution of NaOH.
20.
What is the gas produced when iron(II) sulfide is treated with a nonoxidizing acid?
21.
Predict the products of each of the following reactions and then balance the chemical equations.
(a) Fe is heated in an atmosphere of steam.
(b) NaOH is added to a solution of Fe(NO3)3.
(c) FeSO4 is added to an acidic solution of KMnO4.
(d) Fe is added to a dilute solution of H2SO4.
(e) A solution of Fe(NO3)2 and HNO3 is allowed to stand in air.
(f) FeCO3 is added to a solution of HClO4.
(g) Fe is heated in air.
22.
Balance the following equations by oxidation-reduction methods; note that three elements change oxidation state.
Co (NO3 ) (s) ⟶ Co2 O3 (s) + NO2 (g) + O2 (g)
2
23.
Dilute sodium cyanide solution is slowly dripped into a slowly stirred silver nitrate solution. A white precipitate forms temporarily
but dissolves as the addition of sodium cyanide continues. Use chemical equations to explain this observation. Silver cyanide is
similar to silver chloride in its solubility.
24.
Predict which will be more stable, [CrO4]2− or [WO4]2−, and explain.
25.
Give the oxidation state of the metal for each of the following oxides of the first transition series. (Hint: Oxides of formula M3O4
are examples of mixed valence compounds in which the metal ion is present in more than one oxidation state. It is possible to write
these compound formulas in the equivalent format MO·M2O3, to permit estimation of the metal’s two oxidation states.)
(a) Sc2O3
(b) TiO2
(c) V2O5
(d) CrO3
(e) MnO2
(f) Fe3O4
(g) Co3O4
(h) NiO
(i) Cu2O

19.7.0.1: 19.2 Coordination Chemistry of Transition Metals
26.
Indicate the coordination number for the central metal atom in each of the following coordination compounds:
(a) [Pt(H2O)2Br2]
(b) [Pt(NH3)(py)(Cl)(Br)] (py = pyridine, C5H5N)
(c) [Zn(NH3)2Cl2]
(d) [Zn(NH3)(py)(Cl)(Br)]
(e) [Ni(H2O)4Cl2]
(f) [Fe(en)2(CN)2]+ (en = ethylenediamine, C2H8N2)
27.
Give the coordination numbers and write the formulas for each of the following, including all isomers where appropriate:
(a) tetrahydroxozincate(II) ion (tetrahedral)
(b) hexacyanopalladate(IV) ion
(c) dichloroaurate(I) ion (note that aurum is Latin for "gold")
(d) diamminedichloroplatinum(II)
(e) potassium diamminetetrachlorochromate(III)
(f) hexaamminecobalt(III) hexacyanochromate(III)
(g) dibromobis(ethylenediamine) cobalt(III) nitrate
28.
Give the coordination number for each metal ion in the following compounds:
(a) [Co(CO3)3]3− (note that CO32− is bidentate in this complex)
(b) [Cu(NH3)4]2+
(c) [Co(NH3)4Br2]2(SO4)3
(d) [Pt(NH3)4][PtCl4]
(e) [Cr(en)3](NO3)3
(f) [Pd(NH3)2Br2] (square planar)
(g) K3[Cu(Cl)5]
(h) [Zn(NH3)2Cl2]
29.
Sketch the structures of the following complexes. Indicate any cis, trans, and optical isomers.
(a) [Pt(H2O)2Br2] (square planar)
(b) [Pt(NH3)(py)(Cl)(Br)] (square planar, py = pyridine, C5H5N)
(c) [Zn(NH3)3Cl]+ (tetrahedral)
(d) [Pt(NH3)3Cl]+ (square planar)
(e) [Ni(H2O)4Cl2]
(f) [Co(C2O4)2Cl2]3− (note that C 2 O4
2−
is the bidentate oxalate ion, −O
2 CCO2
−
)
30.
Draw diagrams for any cis, trans, and optical isomers that could exist for the following (en is ethylenediamine):
(a) [Co(en)2(NO2)Cl]+

(b) [Co(en)2Cl2]+
(c) [Pt(NH3)2Cl4]
(d) [Cr(en)3]3+
(e) [Pt(NH3)2Cl2]
31.
Name each of the compounds or ions given in Exercise 19.28, including the oxidation state of the metal.
32.
Name each of the compounds or ions given in Exercise 19.30.
33.
Specify whether the following complexes have isomers.
(a) tetrahedral [Ni(CO)2(Cl)2]
(b) trigonal bipyramidal [Mn(CO)4NO]
(c) [Pt(en)2Cl2]Cl2
34.
Predict whether the carbonate ligand CO 3
2−
will coordinate to a metal center as a monodentate, bidentate, or tridentate ligand.
35.
Draw the geometric, linkage, and ionization isomers for [CoCl5CN][CN].
19.7.0.1: 19.3 Spectroscopic and Magnetic Properties of Coordination Compounds

36.
Determine the number of unpaired electrons expected for [Fe(NO2)6]3−and for [FeF6]3− in terms of crystal field theory.
37.
Draw the crystal field diagrams for [Fe(NO2)6]4− and [FeF6]3−. State whether each complex is high spin or low spin, paramagnetic
or diamagnetic, and compare Δoct to P for each complex.
38.
Give the oxidation state of the metal, number of d electrons, and the number of unpaired electrons predicted for [Co(NH3)6]Cl3.
39.
The solid anhydrous solid CoCl2 is blue in color. Because it readily absorbs water from the air, it is used as a humidity indicator to
monitor if equipment (such as a cell phone) has been exposed to excessive levels of moisture. Predict what product is formed by
this reaction, and how many unpaired electrons this complex will have.
40.
Is it possible for a complex of a metal in the transition series to have six unpaired electrons? Explain.
41.
How many unpaired electrons are present in each of the following?
(a) [CoF6]3− (high spin)
(b) [Mn(CN)6]3− (low spin)
(c) [Mn(CN)6]4− (low spin)
(d) [MnCl6]4− (high spin)
(e) [RhCl6]3− (low spin)
42.

Explain how the diphosphate ion, [O3P−O−PO3]4−, can function as a water softener that prevents the precipitation of Fe2+ as an
insoluble iron salt.
43.
For complexes of the same metal ion with no change in oxidation number, the stability increases as the number of electrons in the
t2g orbitals increases. Which complex in each of the following pairs of complexes is more stable?
(a) [Fe(H2O)6]2+ or [Fe(CN)6]4−
(b) [Co(NH3)6]3+ or [CoF6]3−
(c) [Mn(CN)6]4− or [MnCl6]4−
44.
Trimethylphosphine, P(CH3)3, can act as a ligand by donating the lone pair of electrons on the phosphorus atom. If
trimethylphosphine is added to a solution of nickel(II) chloride in acetone, a blue compound that has a molecular mass of
approximately 270 g and contains 21.5% Ni, 26.0% Cl, and 52.5% P(CH3)3 can be isolated. This blue compound does not have any
isomeric forms. What are the geometry and molecular formula of the blue compound?
45.
Would you expect the complex [Co(en)3]Cl3 to have any unpaired electrons? Any isomers?
46.
Would you expect the Mg3[Cr(CN)6]2 to be diamagnetic or paramagnetic? Explain your reasoning.
47.
Would you expect salts of the gold(I) ion, Au+, to be colored? Explain.
48.
[CuCl4]2− is green. [Cu(H2O)6]2+is blue. Which absorbs higher-energy photons? Which is predicted to have a larger crystal field
splitting?

CHAPTER OVERVIEW
20: Organic Chemistry

General Chemistry
Organic chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic
materials, i.e., matter in its various forms that contain carbon atoms. Study of structure includes many physical and chemical
methods to determine the chemical composition and the chemical constitution of organic compounds and materials. Study of
properties includes both physical properties and chemical properties, and uses similar methods as well as methods to evaluate
chemical reactivity, with the aim to understand the behavior of the organic matter.
20.1: Introduction
20.2: Hydrocarbons
20.6: Key Terms
20.7: Summary
20.8: Exercises
This page titled 20: Organic Chemistry is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source
1
20.1: Introduction
Figure 20.1 All organic compounds contain carbon and most are formed by living things, although they are also formed by
geological and artificial processes. (credit left: modification of work by Jon Sullivan; credit left middle: modification of work by
Deb Tremper; credit right middle: modification of work by “annszyp”/Wikimedia Commons; credit right: modification of work by
George Shuklin)

20.1 Hydrocarbons
20.2 Alcohols and Ethers
20.3 Aldehydes, Ketones, Carboxylic Acids, and Esters
20.4 Amines and Amides
All living things on earth are formed mostly of carbon compounds. The prevalence of carbon compounds in living things has led to
the epithet “carbon-based” life. The truth is we know of no other kind of life. Early chemists regarded substances isolated from
organisms (plants and animals) as a different type of matter that could not be synthesized artificially, and these substances were
thus known as organic compounds. The widespread belief called vitalism held that organic compounds were formed by a vital force
present only in living organisms. The German chemist Friedrich Wohler was one of the early chemists to refute this aspect of
vitalism, when, in 1828, he reported the synthesis of urea, a component of many body fluids, from nonliving materials. Since then,
it has been recognized that organic molecules obey the same natural laws as inorganic substances, and the category of organic
compounds has evolved to include both natural and synthetic compounds that contain carbon. Some carbon-containing compounds
are not classified as organic, for example, carbonates and cyanides, and simple oxides, such as CO and CO2. Although a single,
precise definition has yet to be identified by the chemistry community, most agree that a defining trait of organic molecules is the
presence of carbon as the principal element, bonded to hydrogen and other carbon atoms.
Today, organic compounds are key components of plastics, soaps, perfumes, sweeteners, fabrics, pharmaceuticals, and many other
substances that we use every day. The value to us of organic compounds ensures that organic chemistry is an important discipline
within the general field of chemistry. In this chapter, we discuss why the element carbon gives rise to a vast number and variety of
compounds, how those compounds are classified, and the role of organic compounds in representative biological and industrial
settings.

20.2: Hydrocarbons

Explain the importance of hydrocarbons and the reason for their diversity
Name saturated and unsaturated hydrocarbons, and molecules derived from them
Describe the reactions characteristic of saturated and unsaturated hydrocarbons
Identify structural and geometric isomers of hydrocarbons
The largest database1 of organic compounds lists about 10 million substances, which include compounds originating from living
organisms and those synthesized by chemists. The number of potential organic compounds has been estimated2 at 1060—an
astronomically high number. The existence of so many organic molecules is a consequence of the ability of carbon atoms to form
up to four strong bonds to other carbon atoms, resulting in chains and rings of many different sizes, shapes, and complexities.
The simplest organic compounds contain only the elements carbon and hydrogen, and are called hydrocarbons. Even though they
are composed of only two types of atoms, there is a wide variety of hydrocarbons because they may consist of varying lengths of
chains, branched chains, and rings of carbon atoms, or combinations of these structures. In addition, hydrocarbons may differ in the
types of carbon-carbon bonds present in their molecules. Many hydrocarbons are found in plants, animals, and their fossils; other
hydrocarbons have been prepared in the laboratory. We use hydrocarbons every day, mainly as fuels, such as natural gas, acetylene,
propane, butane, and the principal components of gasoline, diesel fuel, and heating oil. The familiar plastics polyethylene,
polypropylene, and polystyrene are also hydrocarbons. We can distinguish several types of hydrocarbons by differences in the
bonding between carbon atoms. This leads to differences in geometries and in the hybridization of the carbon orbitals.
20.2.0.1: Alkanes
Alkanes, or saturated hydrocarbons, contain only single covalent bonds between carbon atoms. Each of the carbon atoms in an
alkane has sp3 hybrid orbitals and is bonded to four other atoms, each of which is either carbon or hydrogen. The Lewis structures
and models of methane, ethane, and pentane are illustrated in Figure 20.2. Carbon chains are usually drawn as straight lines in
Lewis structures, but one has to remember that Lewis structures are not intended to indicate the geometry of molecules. Notice that
the carbon atoms in the structural models (the ball-and-stick and space-filling models) of the pentane molecule do not lie in a
straight line. Because of the sp3 hybridization, the bond angles in carbon chains are close to 109.5°, giving such chains in an alkane
a zigzag shape.
The structures of alkanes and other organic molecules may also be represented in a less detailed manner by condensed structural
formulas (or simply, condensed formulas). Instead of the usual format for chemical formulas in which each element symbol appears
just once, a condensed formula is written to suggest the bonding in the molecule. These formulas have the appearance of a Lewis
structure from which most or all of the bond symbols have been removed. Condensed structural formulas for ethane and pentane
are shown at the bottom of Figure 20.2, and several additional examples are provided in the exercises at the end of this chapter.

Figure 20.2 Pictured are the Lewis structures, ball-and-stick models, and space-filling models for molecules of methane, ethane,
and pentane.
A common method used by organic chemists to simplify the drawings of larger molecules is to use a skeletal structure (also called
a line-angle structure). In this type of structure, carbon atoms are not symbolized with a C, but represented by each end of a line or
bend in a line. Hydrogen atoms are not drawn if they are attached to a carbon. Other atoms besides carbon and hydrogen are
represented by their elemental symbols. Figure 20.3 shows three different ways to draw the same structure.

Figure 20.3 The same structure can be represented three different ways: an expanded formula, a condensed formula, and a skeletal
structure.
20.2.0.1: Example 20.1

20.2.0.0.1: Drawing Skeletal Structures
Draw the skeletal structures for these two molecules:
Each carbon atom is converted into the end of a line or the place where lines intersect. All hydrogen atoms attached to the
carbon atoms are left out of the structure (although we still need to recognize they are there):

Draw the skeletal structures for these two molecules:
20.2.0.1: Answer:
20.2.0.1: Example 20.2

20.2.0.0.4: Interpreting Skeletal Structures
Identify the chemical formula of the molecule represented here:

There are eight places where lines intersect or end, meaning that there are eight carbon atoms in the molecule. Since we know
that carbon atoms tend to make four bonds, each carbon atom will have the number of hydrogen atoms that are required for
four bonds. This compound contains 16 hydrogen atoms for a molecular formula of C8H16.
Location of the hydrogen atoms:
Identify the chemical formula of the molecule represented here:
20.2.0.1: Answer:
C9H20

All alkanes are composed of carbon and hydrogen atoms, and have similar bonds, structures, and formulas; noncyclic alkanes all
have a formula of CnH2n+2. The number of carbon atoms present in an alkane has no limit. Greater numbers of atoms in the
molecules will lead to stronger intermolecular attractions (dispersion forces) and correspondingly different physical properties of
the molecules. Properties such as melting point and boiling point (Table 20.1) usually change smoothly and predictably as the
number of carbon and hydrogen atoms in the molecules change.
Properties of Some Alkanes3
Alkane Molecular Formula Melting Point (°C) Boiling Point (°C) Phase at STP4 Number of Structural Isomers
methane CH4 –182.5 –161.5 gas 1
ethane C2H6 –183.3 –88.6 gas 1
propane C3H8 –187.7 –42.1 gas 1
butane C4H10 –138.3 –0.5 gas 2
pentane C5H12 –129.7 36.1 liquid 3
hexane C6H14 –95.3 68.7 liquid 5
heptane C7H16 –90.6 98.4 liquid 9
octane C8H18 –56.8 125.7 liquid 18
nonane C9H20 –53.6 150.8 liquid 35
decane C10H22 –29.7 174.0 liquid 75
tetradecane C14H30 5.9 253.5 solid 1858
octadecane C18H38 28.2 316.1 solid 60,523
Table 20.1
Hydrocarbons with the same formula, including alkanes, can have different structures. For example, two alkanes have the formula
C4H10: They are called n-butane and 2-methylpropane (or isobutane), and have the following Lewis structures:

The compounds n-butane and 2-methylpropane are structural isomers (the term constitutional isomers is also commonly used).
Constitutional isomers have the same molecular formula but different spatial arrangements of the atoms in their molecules. The n-
butane molecule contains an unbranched chain, meaning that no carbon atom is bonded to more than two other carbon atoms. We
use the term normal, or the prefix n, to refer to a chain of carbon atoms without branching. The compound 2–methylpropane has a
branched chain (the carbon atom in the center of the Lewis structure is bonded to three other carbon atoms)
Identifying isomers from Lewis structures is not as easy as it looks. Lewis structures that look different may actually represent the
same isomers. For example, the three structures in Figure 20.4 all represent the same molecule, n-butane, and hence are not
different isomers. They are identical because each contains an unbranched chain of four carbon atoms.

Figure 20.4 These three representations of the structure of n-butane are not isomers because they all contain the same arrangement
of atoms and bonds.
20.2.0.1: The Basics of Organic Nomenclature: Naming Alkanes

The International Union of Pure and Applied Chemistry (IUPAC) has devised a system of nomenclature that begins with the names
of the alkanes and can be adjusted from there to account for more complicated structures. The nomenclature for alkanes is based on
two rules:
1. To name an alkane, first identify the longest chain of carbon atoms in its structure. A two-carbon chain is called ethane; a three-
carbon chain, propane; and a four-carbon chain, butane. Longer chains are named as follows: pentane (five-carbon chain),

hexane (6), heptane (7), octane (8), nonane (9), and decane (10). These prefixes can be seen in the names of the alkanes
described in Table 20.1.
2. Add prefixes to the name of the longest chain to indicate the positions and names of substituents. Substituents are branches or
functional groups that replace hydrogen atoms on a chain. The position of a substituent or branch is identified by the number of
the carbon atom it is bonded to in the chain. We number the carbon atoms in the chain by counting from the end of the chain
nearest the substituents. Multiple substituents are named individually and placed in alphabetical order at the front of the name.
When more than one substituent is present, either on the same carbon atom or on different carbon atoms, the substituents are listed
alphabetically. Because the carbon atom numbering begins at the end closest to a substituent, the longest chain of carbon atoms is
numbered in such a way as to produce the lowest number for the substituents. The ending -o replaces -ide at the end of the name of
an electronegative substituent (in ionic compounds, the negatively charged ion ends with -ide like chloride; in organic compounds,
such atoms are treated as substituents and the -o ending is used). The number of substituents of the same type is indicated by the
prefixes di- (two), tri- (three), tetra- (four), and so on (for example, difluoro- indicates two fluoride substituents).
20.2.0.1: Example 20.3

20.2.0.0.1: Naming Halogen-substituted Alkanes
Name the molecule whose structure is shown here:

The four-carbon chain is numbered from the end with the chlorine atom. This puts the substituents on positions 1 and 2
(numbering from the other end would put the substituents on positions 3 and 4). Four carbon atoms means that the base name
of this compound will be butane. The bromine at position 2 will be described by adding 2-bromo-; this will come at the
beginning of the name, since bromo- comes before chloro- alphabetically. The chlorine at position 1 will be described by
adding 1-chloro-, resulting in the name of the molecule being 2-bromo-1-chlorobutane.
Name the following molecule:
20.2.0.1: Answer:
3,3-dibromo-2-iodopentane
We call a substituent that contains one less hydrogen than the corresponding alkane an alkyl group. The name of an alkyl group is
obtained by dropping the suffix -ane of the alkane name and adding -yl:

The open bonds in the methyl and ethyl groups indicate that these alkyl groups are bonded to another atom.
20.2.0.1: Example 20.4

20.2.0.0.4: Naming Substituted Alkanes
Name the molecule whose structure is shown here:
The longest carbon chain runs horizontally across the page and contains six carbon atoms (this makes the base of the name
hexane, but we will also need to incorporate the name of the branch). In this case, we want to number from right to left (as
shown by the blue numbers) so the branch is connected to carbon 3 (imagine the numbers from left to right—this would put the
branch on carbon 4, violating our rules). The branch attached to position 3 of our chain contains two carbon atoms (numbered
in red)—so we take our name for two carbons eth- and attach -yl at the end to signify we are describing a branch. Putting all
the pieces together, this molecule is 3-ethylhexane.
20.2.0.1: Answer:
4-propyloctane
Some hydrocarbons can form more than one type of alkyl group when the hydrogen atoms that would be removed have different
“environments” in the molecule. This diversity of possible alkyl groups can be identified in the following way: The four hydrogen
atoms in a methane molecule are equivalent; they all have the same environment. They are equivalent because each is bonded to a

carbon atom (the same carbon atom) that is bonded to three hydrogen atoms. (It may be easier to see the equivalency in the ball and
stick models in Figure 20.2. Removal of any one of the four hydrogen atoms from methane forms a methyl group. Likewise, the six
hydrogen atoms in ethane are equivalent (Figure 20.2) and removing any one of these hydrogen atoms produces an ethyl group.
Each of the six hydrogen atoms is bonded to a carbon atom that is bonded to two other hydrogen atoms and a carbon atom.
However, in both propane and 2–methylpropane, there are hydrogen atoms in two different environments, distinguished by the
adjacent atoms or groups of atoms:
Each of the six equivalent hydrogen atoms of the first type in propane and each of the nine equivalent hydrogen atoms of that type
in 2-methylpropane (all shown in black) are bonded to a carbon atom that is bonded to only one other carbon atom. The two purple
hydrogen atoms in propane are of a second type. They differ from the six hydrogen atoms of the first type in that they are bonded to
a carbon atom bonded to two other carbon atoms. The green hydrogen atom in 2-methylpropane differs from the other nine
hydrogen atoms in that molecule and from the purple hydrogen atoms in propane. The green hydrogen atom in 2-methylpropane is
bonded to a carbon atom bonded to three other carbon atoms. Two different alkyl groups can be formed from each of these
molecules, depending on which hydrogen atom is removed. The names and structures of these and several other alkyl groups are
listed in Figure 20.5.

Figure 20.5 This listing gives the names and formulas for various alkyl groups formed by the removal of hydrogen atoms from
different locations.
Note that alkyl groups do not exist as stable independent entities. They are always a part of some larger molecule. The location of
an alkyl group on a hydrocarbon chain is indicated in the same way as any other substituent:
Alkanes are relatively stable molecules, but heat or light will activate reactions that involve the breaking of C–H or C–C single
bonds. Combustion is one such reaction:
CH4 (g) + 2 O2 (g) ⟶ CO2 (g) + 2 H2 O (g)
Alkanes burn in the presence of oxygen, a highly exothermic oxidation-reduction reaction that produces carbon dioxide and water.
As a consequence, alkanes are excellent fuels. For example, methane, CH4, is the principal component of natural gas. Butane,
C4H10, used in camping stoves and lighters is an alkane. Gasoline is a liquid mixture of continuous- and branched-chain alkanes,
each containing from five to nine carbon atoms, plus various additives to improve its performance as a fuel. Kerosene, diesel oil,
and fuel oil are primarily mixtures of alkanes with higher molecular masses. The main source of these liquid alkane fuels is crude
oil, a complex mixture that is separated by fractional distillation. Fractional distillation takes advantage of differences in the boiling
points of the components of the mixture (see Figure 20.6). You may recall that boiling point is a function of intermolecular
interactions, which was discussed in the chapter on solutions and colloids.

Figure 20.6 In a column for the fractional distillation of crude oil, oil heated to about 425 °C in the furnace vaporizes when it enters
the base of the tower. The vapors rise through bubble caps in a series of trays in the tower. As the vapors gradually cool, fractions
of higher, then of lower, boiling points condense to liquids and are drawn off. (credit left: modification of work by Luigi Chiesa)
In a substitution reaction, another typical reaction of alkanes, one or more of the alkane’s hydrogen atoms is replaced with a
different atom or group of atoms. No carbon-carbon bonds are broken in these reactions, and the hybridization of the carbon atoms
does not change. For example, the reaction between ethane and molecular chlorine depicted here is a substitution reaction:
The C–Cl portion of the chloroethane molecule is an example of a functional group, the part or moiety of a molecule that imparts a
specific chemical reactivity. The types of functional groups present in an organic molecule are major determinants of its chemical
properties and are used as a means of classifying organic compounds as detailed in the remaining sections of this chapter.

Want more practice naming alkanes? Watch this brief video tutorial to review the nomenclature process.
20.2.0.1: Alkenes
Organic compounds that contain one or more double or triple bonds between carbon atoms are described as unsaturated. You have
likely heard of unsaturated fats. These are complex organic molecules with long chains of carbon atoms, which contain at least one
double bond between carbon atoms. Unsaturated hydrocarbon molecules that contain one or more double bonds are called alkenes.
Carbon atoms linked by a double bond are bound together by two bonds, one σ bond and one π bond. Double and triple bonds give
rise to a different geometry around the carbon atom that participates in them, leading to important differences in molecular shape
and properties. The differing geometries are responsible for the different properties of unsaturated versus saturated fats.
Ethene, C2H4, is the simplest alkene. Each carbon atom in ethene, commonly called ethylene, has a trigonal planar structure. The
second member of the series is propene (propylene) (Figure 20.7); the butene isomers follow in the series. Four carbon atoms in the
chain of butene allows for the formation of isomers based on the position of the double bond, as well as a new form of isomerism.

Figure 20.7 Expanded structures, ball-and-stick structures, and space-filling models for the alkenes ethene, propene, and 1-butene
are shown.
Ethylene (the common industrial name for ethene) is a basic raw material in the production of polyethylene and other important
compounds. Over 135 million tons of ethylene were produced worldwide in 2010 for use in the polymer, petrochemical, and plastic
industries. Ethylene is produced industrially in a process called cracking, in which the long hydrocarbon chains in a petroleum
mixture are broken into smaller molecules.

20.2.0.0.1: Recycling Plastics
Polymers (from Greek words poly meaning “many” and mer meaning “parts”) are large molecules made up of repeating units,
referred to as monomers. Polymers can be natural (starch is a polymer of sugar residues and proteins are polymers of amino
acids) or synthetic [like polyethylene, polyvinyl chloride (PVC), and polystyrene]. The variety of structures of polymers
translates into a broad range of properties and uses that make them integral parts of our everyday lives. Adding functional
groups to the structure of a polymer can result in significantly different properties (see the discussion about Kevlar later in this
chapter).
An example of a polymerization reaction is shown in Figure 20.8. The monomer ethylene (C2H4) is a gas at room temperature,
but when polymerized, using a transition metal catalyst, it is transformed into a solid material made up of long chains of –
CH2– units called polyethylene. Polyethylene is a commodity plastic used primarily for packaging (bags and films).
Figure 20.8 The reaction for the polymerization of ethylene to polyethylene is shown.
Polyethylene is a member of one subset of synthetic polymers classified as plastics. Plastics are synthetic organic solids that
can be molded; they are typically organic polymers with high molecular masses. Most of the monomers that go into common
plastics (ethylene, propylene, vinyl chloride, styrene, and ethylene terephthalate) are derived from petrochemicals and are not
very biodegradable, making them candidate materials for recycling. Recycling plastics helps minimize the need for using more
of the petrochemical supplies and also minimizes the environmental damage caused by throwing away these nonbiodegradable
materials.
Plastic recycling is the process of recovering waste, scrap, or used plastics, and reprocessing the material into useful products.
For example, polyethylene terephthalate (soft drink bottles) can be melted down and used for plastic furniture, in carpets, or for
other applications. Other plastics, like polyethylene (bags) and polypropylene (cups, plastic food containers), can be recycled
or reprocessed to be used again. Many areas of the country have recycling programs that focus on one or more of the
commodity plastics that have been assigned a recycling code (see Figure 20.9). These operations have been in effect since the
1970s and have made the production of some plastics among the most efficient industrial operations today.

Figure 20.9 Each type of recyclable plastic is imprinted with a code for easy identification.
The name of an alkene is derived from the name of the alkane with the same number of carbon atoms. The presence of the double
bond is signified by replacing the suffix -ane with the suffix -ene. The location of the double bond is identified by naming the
smaller of the numbers of the carbon atoms participating in the double bond:
20.2.0.0.2: Isomers of Alkenes
Molecules of 1-butene and 2-butene are structural isomers; the arrangement of the atoms in these two molecules differs. As an
example of arrangement differences, the first carbon atom in 1-butene is bonded to two hydrogen atoms; the first carbon atom in 2-

butene is bonded to three hydrogen atoms.
The compound 2-butene and some other alkenes also form a second type of isomer called a geometric isomer. In a set of geometric
isomers, the same types of atoms are attached to each other in the same order, but the geometries of the two molecules differ.
Geometric isomers of alkenes differ in the orientation of the groups on either side of a C = C bond.
Carbon atoms are free to rotate around a single bond but not around a double bond; a double bond is rigid. This makes it possible to
have two isomers of 2-butene, one with both methyl groups on the same side of the double bond and one with the methyl groups on
opposite sides. When structures of butene are drawn with 120° bond angles around the sp2-hybridized carbon atoms participating in
the double bond, the isomers are apparent. The 2-butene isomer in which the two methyl groups are on the same side is called a cis-
isomer; the one in which the two methyl groups are on opposite sides is called a trans-isomer (Figure 20.10). The different
geometries produce different physical properties, such as boiling point, that may make separation of the isomers possible:
Figure 20.10 These molecular models show the structural and geometric isomers of butene.
Alkenes are much more reactive than alkanes because the C = C moiety is a reactive functional group. A π bond, being a weaker
bond, is disrupted much more easily than a σ bond. Thus, alkenes undergo a characteristic reaction in which the π bond is broken
and replaced by two σ bonds. This reaction is called an addition reaction. The hybridization of the carbon atoms in the double bond
in an alkene changes from sp2 to sp3 during an addition reaction. For example, halogens add to the double bond in an alkene instead
of replacing hydrogen, as occurs in an alkane:
20.2.0.1: Example 20.5

20.2.0.0.3: Alkene Reactivity and Naming

Provide the IUPAC names for the reactant and product of the halogenation reaction shown here:
The reactant is a five-carbon chain that contains a carbon-carbon double bond, so the base name will be pentene. We begin
counting at the end of the chain closest to the double bond—in this case, from the left—the double bond spans carbons 2 and 3,
so the name becomes 2-pentene. Since there are two carbon-containing groups attached to the two carbon atoms in the double
bond—and they are on the same side of the double bond—this molecule is the cis-isomer, making the name of the starting
alkene cis-2-pentene. The product of the halogenation reaction will have two chlorine atoms attached to the carbon atoms that
were a part of the carbon-carbon double bond:

This molecule is now a substituted alkane and will be named as such. The base of the name will be pentane. We will count
from the end that numbers the carbon atoms where the chlorine atoms are attached as 2 and 3, making the name of the product
2,3-dichloropentane.
Provide names for the reactant and product of the reaction shown:
20.2.0.1: Answer:
reactant: cis-3-hexene product: 3,4-dichlorohexane
20.2.0.1: Alkynes
Hydrocarbon molecules with one or more triple bonds are called alkynes; they make up another series of unsaturated hydrocarbons.
Two carbon atoms joined by a triple bond are bound together by one σ bond and two π bonds. The sp-hybridized carbons involved
in the triple bond have bond angles of 180°, giving these types of bonds a linear, rod-like shape.
The simplest member of the alkyne series is ethyne, C2H2, commonly called acetylene. The Lewis structure for ethyne, a linear
molecule, is:
The IUPAC nomenclature for alkynes is similar to that for alkenes except that the suffix -yne is used to indicate a triple bond in the
chain. For example, CH CH C ≡ CH is called 1-butyne.
3 2
20.2.0.1: Example 20.6

20.2.0.0.1: Structure of Alkynes
Describe the geometry and hybridization of the carbon atoms in the following molecule:

Carbon atoms 1 and 4 have four single bonds and are thus tetrahedral with sp3 hybridization. Carbon atoms 2 and 3 are
involved in the triple bond, so they have linear geometries and would be classified as sp hybrids.
Identify the hybridization and bond angles at the carbon atoms in the molecule shown:
20.2.0.1: Answer:
carbon 1: sp, 180°; carbon 2: sp, 180°; carbon 3: sp2, 120°; carbon 4: sp2, 120°; carbon 5: sp3, 109.5°
Chemically, the alkynes are similar to the alkenes. Since the C ≡ C functional group has two π bonds, alkynes typically react even
more readily, and react with twice as much reagent in addition reactions. The reaction of acetylene with bromine is a typical
example:
Acetylene and the other alkynes also burn readily. An acetylene torch takes advantage of the high heat of combustion for acetylene.
20.2.0.1: Aromatic Hydrocarbons

Benzene, C6H6, is the simplest member of a large family of hydrocarbons, called aromatic hydrocarbons. These compounds contain
ring structures and exhibit bonding that must be described using the resonance hybrid concept of valence bond theory or the
delocalization concept of molecular orbital theory. (To review these concepts, refer to the earlier chapters on chemical bonding).
The resonance structures for benzene, C6H6, are:
Valence bond theory describes the benzene molecule and other planar aromatic hydrocarbon molecules as hexagonal rings of sp2-
hybridized carbon atoms with the unhybridized p orbital of each carbon atom perpendicular to the plane of the ring. Three valence
electrons in the sp2 hybrid orbitals of each carbon atom and the valence electron of each hydrogen atom form the framework of σ
bonds in the benzene molecule. The fourth valence electron of each carbon atom is shared with an adjacent carbon atom in their
unhybridized p orbitals to yield the π bonds. Benzene does not, however, exhibit the characteristics typical of an alkene. Each of the
six bonds between its carbon atoms is equivalent and exhibits properties that are intermediate between those of a C–C single bond
and a C = C double bond. To represent this unique bonding, structural formulas for benzene and its derivatives are typically drawn
with single bonds between the carbon atoms and a circle within the ring as shown in Figure 20.11.

Figure 20.11 This condensed formula shows the unique bonding structure of benzene.
There are many derivatives of benzene. The hydrogen atoms can be replaced by many different substituents. Aromatic compounds
more readily undergo substitution reactions than addition reactions; replacement of one of the hydrogen atoms with another
substituent will leave the delocalized double bonds intact. The following are typical examples of substituted benzene derivatives:
Toluene and xylene are important solvents and raw materials in the chemical industry. Styrene is used to produce the polymer
polystyrene.
20.2.0.1: Example 20.7

20.2.0.0.1: Structure of Aromatic Hydrocarbons
One possible isomer created by a substitution reaction that replaces a hydrogen atom attached to the aromatic ring of toluene
with a chlorine atom is shown here. Draw two other possible isomers in which the chlorine atom replaces a different hydrogen
atom attached to the aromatic ring:

Since the six-carbon ring with alternating double bonds is necessary for the molecule to be classified as aromatic, appropriate
isomers can be produced only by changing the positions of the chloro-substituent relative to the methyl-substituent:

Draw three isomers of a six-membered aromatic ring compound substituted with two bromines.
20.2.0.1: Answer:

20.2.0.1: Footnotes
1This is the Beilstein database, now available through the Reaxys site (www.elsevier.com/online-tools/reaxys).
2Peplow, Mark. “Organic Synthesis: The Robo-Chemist,” Nature 512 (2014): 20–2.
3Physical properties for C4H10 and heavier molecules are those of the normal isomer, n-butane, n-pentane, etc.
4STP indicates a temperature of 0 °C and a pressure of 1 atm.
This page titled 20.2: Hydrocarbons is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source


Describe the structure and properties of alcohols
Describe the structure and properties of ethers
Name and draw structures for alcohols and ethers
In this section, we will learn about alcohols and ethers.
20.3.0.1: Alcohols
Incorporation of an oxygen atom into carbon- and hydrogen-containing molecules leads to new functional groups and new families
of compounds. When the oxygen atom is attached by single bonds, the molecule is either an alcohol or ether.
Alcohols are derivatives of hydrocarbons in which an –OH group has replaced a hydrogen atom. Although all alcohols have one or
more hydroxyl (–OH) functional groups, they do not behave like bases such as NaOH and KOH. NaOH and KOH are ionic
compounds that contain OH– ions. Alcohols are covalent molecules; the –OH group in an alcohol molecule is attached to a carbon
atom by a covalent bond.
Ethanol, CH3CH2OH, also called ethyl alcohol, is a particularly important alcohol for human use. Ethanol is the alcohol produced
by some species of yeast that is found in wine, beer, and distilled drinks. It has long been prepared by humans harnessing the
metabolic efforts of yeasts in fermenting various sugars:
Large quantities of ethanol are synthesized from the addition reaction of water with ethylene using an acid as a catalyst:
Alcohols containing two or more hydroxyl groups can be made. Examples include 1,2-ethanediol (ethylene glycol, used in
antifreeze) and 1,2,3-propanetriol (glycerine, used as a solvent for cosmetics and medicines):
20.3.0.0.1: Naming Alcohols

The name of an alcohol comes from the hydrocarbon from which it was derived. The final -e in the name of the hydrocarbon is
replaced by -ol, and the carbon atom to which the –OH group is bonded is indicated by a number placed before the name.5
20.3.0.1: Example 20.8

20.3.0.0.2: Naming Alcohols
Consider the following example. How should it be named?
The carbon chain contains five carbon atoms. If the hydroxyl group was not present, we would have named this molecule
pentane. To address the fact that the hydroxyl group is present, we change the ending of the name to -ol. In this case, since the
–OH is attached to carbon 2 in the chain, we would name this molecule 2-pentanol.
20.3.0.1: Answer:
2-methyl-2-pentanol
20.3.0.1: Ethers
Ethers are compounds that contain the functional group –O–. Ethers do not have a designated suffix like the other types of
molecules we have named so far. In the IUPAC system, the oxygen atom and the smaller carbon branch are named as an alkoxy
substituent and the remainder of the molecule as the base chain, as in alkanes. As shown in the following compound, the red
symbols represent the smaller alkyl group and the oxygen atom, which would be named “methoxy.” The larger carbon branch
would be ethane, making the molecule methoxyethane. Many ethers are referred to with common names instead of the IUPAC
system names. For common names, the two branches connected to the oxygen atom are named separately and followed by “ether.”
The common name for the compound shown in Example 20.9 is ethylmethyl ether:
20.3.0.1: Example 20.9

20.3.0.0.1: Naming Ethers
Provide the IUPAC and common name for the ether shown here:
IUPAC: The molecule is made up of an ethoxy group attached to an ethane chain, so the IUPAC name would be ethoxyethane.
Common: The groups attached to the oxygen atom are both ethyl groups, so the common name would be diethyl ether.
Provide the IUPAC and common name for the ether shown:
20.3.0.1: Answer:
IUPAC: 2-methoxypropane; common: isopropylmethyl ether

Ethers can be obtained from alcohols by the elimination of a molecule of water from two molecules of the alcohol. For example,
when ethanol is treated with a limited amount of sulfuric acid and heated to 140 °C, diethyl ether and water are formed:
In the general formula for ethers, R—O—R, the hydrocarbon groups (R) may be the same or different. Diethyl ether, the most
widely used compound of this class, is a colorless, volatile liquid that is highly flammable. It was first used in 1846 as an
anesthetic, but better anesthetics have now largely taken its place. Diethyl ether and other ethers are presently used primarily as
solvents for gums, fats, waxes, and resins. Tertiary-butyl methyl ether, C4H9OCH3 (abbreviated MTBE—italicized portions of
names are not counted when ranking the groups alphabetically—so butyl comes before methyl in the common name), is used as an
additive for gasoline. MTBE belongs to a group of chemicals known as oxygenates due to their capacity to increase the oxygen
content of gasoline.

Want more practice naming ethers? This brief video review summarizes the nomenclature for ethers.

20.3.0.0.4: Carbohydrates and Diabetes
Carbohydrates are large biomolecules made up of carbon, hydrogen, and oxygen. The dietary forms of carbohydrates are foods
rich in these types of molecules, like pastas, bread, and candy. The name “carbohydrate” comes from the formula of the
molecules, which can be described by the general formula Cm(H2O)n, which shows that they are in a sense “carbon and water”
or “hydrates of carbon.” In many cases, m and n have the same value, but they can be different. The smaller carbohydrates are
generally referred to as “sugars,” the biochemical term for this group of molecules is “saccharide” from the Greek word for
sugar (Figure 20.12). Depending on the number of sugar units joined together, they may be classified as monosaccharides (one
sugar unit), disaccharides (two sugar units), oligosaccharides (a few sugars), or polysaccharides (the polymeric version of
sugars—polymers were described in the feature box earlier in this chapter on recycling plastics). The scientific names of sugars
can be recognized by the suffix -ose at the end of the name (for instance, fruit sugar is a monosaccharide called “fructose” and
milk sugar is a disaccharide called lactose composed of two monosaccharides, glucose and galactose, connected together).
Sugars contain some of the functional groups we have discussed: Note the alcohol groups present in the structures and how
monosaccharide units are linked to form a disaccharide by formation of an ether.

Figure 20.12 The illustrations show the molecular structures of fructose, a five-carbon monosaccharide, and of lactose, a
disaccharide composed of two isomeric, six-carbon sugars.
Organisms use carbohydrates for a variety of functions. Carbohydrates can store energy, such as the polysaccharides glycogen
in animals or starch in plants. They also provide structural support, such as the polysaccharide cellulose in plants and the
modified polysaccharide chitin in fungi and animals. The sugars ribose and deoxyribose are components of the backbones of
RNA and DNA, respectively. Other sugars play key roles in the function of the immune system, in cell-cell recognition, and in
many other biological roles.
Diabetes is a group of metabolic diseases in which a person has a high sugar concentration in their blood (Figure 20.13).
Diabetes may be caused by insufficient insulin production by the pancreas or by the body’s cells not responding properly to the
insulin that is produced. In a healthy person, insulin is produced when it is needed and functions to transport glucose from the

blood into the cells where it can be used for energy. The long-term complications of diabetes can include loss of eyesight, heart
disease, and kidney failure.
In 2013, it was estimated that approximately 3.3% of the world’s population (~380 million people) suffered from diabetes,
resulting in over a million deaths annually. Prevention involves eating a healthy diet, getting plenty of exercise, and
maintaining a normal body weight. Treatment involves all of these lifestyle practices and may require injections of insulin.
Even after treatment protocols were introduced, the need to continually monitor their glucose levels posed a challenge for
people with diabetes. The first tests required a doctor or lab, and therefore limited access and frequency. Eventually,
researchers developed small tablets that would react to the presence of glucose in urine, but these still required a relatively
complex process. Chemist Helen Free, who was working on improvements to the tablets, conceived a simpler device: a small
test strip. With her husband and research partner, Alfred Free, she produced the first such product for measuring glucose; soon
after, she expanded the technology to provide test strips for other compounds and conditions. While very recent advances (such
as breath tests, discussed earlier in the text) have shown promise in replacing test strips, they have been widely used for
decades and remain a primary method today.
Figure 20.13 Diabetes is a disease characterized by high concentrations of glucose in the blood. Treating diabetes involves
making lifestyle changes, monitoring blood-sugar levels, and sometimes insulin injections. (credit: “Blausen Medical
Communications”/Wikimedia Commons)
20.3.0.1: Footnotes
5The IUPAC adopted new nomenclature guidelines in 2013 that require this number to be placed as an “infix” rather than a
prefix. For example, the new name for 2-propanol would be propan-2-ol. Widespread adoption of this new nomenclature will
take some time, and students are encouraged to be familiar with both the old and new naming protocols.
This page titled 20.3: Alcohols and Ethers is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via


Describe the structure and properties of aldehydes, ketones, carboxylic acids and esters
Another class of organic molecules contains a carbon atom connected to an oxygen atom by a double bond, commonly called a
carbonyl group. The trigonal planar carbon in the carbonyl group can attach to two other substituents leading to several subfamilies
(aldehydes, ketones, carboxylic acids and esters) described in this section.
20.4.0.1: Aldehydes and Ketones

Both aldehydes and ketones contain a carbonyl group, a functional group with a carbon-oxygen double bond. The names for
aldehyde and ketone compounds are derived using similar nomenclature rules as for alkanes and alcohols, and include the class-
identifying suffixes -al and -one, respectively:
In an aldehyde, the carbonyl group is bonded to at least one hydrogen atom. In a ketone, the carbonyl group is bonded to two
carbon atoms:
As text, an aldehyde group is represented as –CHO; a ketone is represented as –C(O)– or –CO–.

In both aldehydes and ketones, the geometry around the carbon atom in the carbonyl group is trigonal planar; the carbon atom
exhibits sp2 hybridization. Two of the sp2 orbitals on the carbon atom in the carbonyl group are used to form σ bonds to the other
carbon or hydrogen atoms in a molecule. The remaining sp2 hybrid orbital forms a σ bond to the oxygen atom. The unhybridized p
orbital on the carbon atom in the carbonyl group overlaps a p orbital on the oxygen atom to form the π bond in the double bond.
Like the C = O bond in carbon dioxide, the C = O bond of a carbonyl group is polar (recall that oxygen is significantly more
electronegative than carbon, and the shared electrons are pulled toward the oxygen atom and away from the carbon atom). Many of
the reactions of aldehydes and ketones start with the reaction between a Lewis base and the carbon atom at the positive end of the
polar C = O bond to yield an unstable intermediate that subsequently undergoes one or more structural rearrangements to form the
final product (Figure 20.14).

Figure 20.14 The carbonyl group is polar, and the geometry of the bonds around the central carbon is trigonal planar.
The importance of molecular structure in the reactivity of organic compounds is illustrated by the reactions that produce aldehydes
and ketones. We can prepare a carbonyl group by oxidation of an alcohol—for organic molecules, oxidation of a carbon atom is
said to occur when a carbon-hydrogen bond is replaced by a carbon-oxygen bond. The reverse reaction—replacing a carbon-
oxygen bond by a carbon-hydrogen bond—is a reduction of that carbon atom. Recall that oxygen is generally assigned a –2
oxidation number unless it is elemental or attached to a fluorine. Hydrogen is generally assigned an oxidation number of +1 unless
it is attached to a metal. Since carbon does not have a specific rule, its oxidation number is determined algebraically by factoring
the atoms it is attached to and the overall charge of the molecule or ion. In general, a carbon atom attached to an oxygen atom will
have a more positive oxidation number and a carbon atom attached to a hydrogen atom will have a more negative oxidation
number. This should fit nicely with your understanding of the polarity of C–O and C–H bonds. The other reagents and possible
products of these reactions are beyond the scope of this chapter, so we will focus only on the changes to the carbon atoms:
20.4.0.1: Example 20.10

20.4.0.0.1: Oxidation and Reduction in Organic Chemistry
Methane represents the completely reduced form of an organic molecule that contains one carbon atom. Sequentially replacing
each of the carbon-hydrogen bonds with a carbon-oxygen bond would lead to an alcohol, then an aldehyde, then a carboxylic
acid (discussed later), and, finally, carbon dioxide:
CH4 ⟶ CH3 OH ⟶ CH2 O ⟶ HCO2 H ⟶ CO2
What are the oxidation numbers for the carbon atoms in the molecules shown here?
In this example, we can calculate the oxidation number (review the chapter on oxidation-reduction reactions if necessary) for
the carbon atom in each case (note how this would become difficult for larger molecules with additional carbon atoms and
hydrogen atoms, which is why organic chemists use the definition dealing with replacing C–H bonds with C–O bonds
described). For CH4, the carbon atom carries a –4 oxidation number (the hydrogen atoms are assigned oxidation numbers of +1
and the carbon atom balances that by having an oxidation number of –4). For the alcohol (in this case, methanol), the carbon
atom has an oxidation number of –2 (the oxygen atom is assigned –2, the four hydrogen atoms each are assigned +1, and the
carbon atom balances the sum by having an oxidation number of –2; note that compared to the carbon atom in CH4, this carbon
atom has lost two electrons so it was oxidized); for the aldehyde, the carbon atom’s oxidation number is 0 (–2 for the oxygen
atom and +1 for each hydrogen atom already balances to 0, so the oxidation number for the carbon atom is 0); for the
carboxylic acid, the carbon atom’s oxidation number is +2 (two oxygen atoms each at –2 and two hydrogen atoms at +1); and
for carbon dioxide, the carbon atom’s oxidation number is +4 (here, the carbon atom needs to balance the –4 sum from the two
oxygen atoms).
Indicate whether the marked carbon atoms in the three molecules here are oxidized or reduced relative to the marked carbon
atom in ethanol:

There is no need to calculate oxidation states in this case; instead, just compare the types of atoms bonded to the marked
carbon atoms:
20.4.0.1: Answer:
(a) reduced (bond to oxygen atom replaced by bond to hydrogen atom); (b) oxidized (one bond to hydrogen atom replaced
by one bond to oxygen atom); (c) oxidized (2 bonds to hydrogen atoms have been replaced by bonds to an oxygen atom)
Aldehydes are commonly prepared by the oxidation of alcohols whose –OH functional group is located on the carbon atom at the
end of the chain of carbon atoms in the alcohol:
Alcohols that have their –OH groups in the middle of the chain are necessary to synthesize a ketone, which requires the carbonyl
group to be bonded to two other carbon atoms:
An alcohol with its –OH group bonded to a carbon atom that is bonded to no or one other carbon atom will form an aldehyde. An
alcohol with its –OH group attached to two other carbon atoms will form a ketone. If three carbons are attached to the carbon
bonded to the –OH, the molecule will not have a C–H bond to be replaced, so it will not be susceptible to oxidation.
Formaldehyde, an aldehyde with the formula HCHO, is a colorless gas with a pungent and irritating odor. It is sold in an aqueous
solution called formalin, which contains about 37% formaldehyde by weight. Formaldehyde causes coagulation of proteins, so it
kills bacteria (and any other living organism) and stops many of the biological processes that cause tissue to decay. Thus,
formaldehyde is used for preserving tissue specimens and embalming bodies. It is also used to sterilize soil or other materials.
Formaldehyde is used in the manufacture of Bakelite, a hard plastic having high chemical and electrical resistance.
Dimethyl ketone, CH3COCH3, commonly called acetone, is the simplest ketone. It is made commercially by fermenting corn or
molasses, or by oxidation of 2-propanol. Acetone is a colorless liquid. Among its many uses are as a solvent for lacquer (including
fingernail polish), cellulose acetate, cellulose nitrate, acetylene, plastics, and varnishes; as a paint and varnish remover; and as a
solvent in the manufacture of pharmaceuticals and chemicals.
20.4.0.1: Carboxylic Acids and Esters

The odor of vinegar is caused by the presence of acetic acid, a carboxylic acid, in the vinegar. The odor of ripe bananas and many
other fruits is due to the presence of esters, compounds that can be prepared by the reaction of a carboxylic acid with an alcohol.
Because esters do not have hydrogen bonds between molecules, they have lower vapor pressures than the alcohols and carboxylic
acids from which they are derived (see Figure 20.15).

Figure 20.15 Esters are responsible for the odors associated with various plants and their fruits.
Both carboxylic acids and esters contain a carbonyl group with a second oxygen atom bonded to the carbon atom in the carbonyl
group by a single bond. In a carboxylic acid, the second oxygen atom also bonds to a hydrogen atom. In an ester, the second
oxygen atom bonds to another carbon atom. The names for carboxylic acids and esters include prefixes that denote the lengths of
the carbon chains in the molecules and are derived following nomenclature rules similar to those for inorganic acids and salts (see
these examples):
The functional groups for an acid and for an ester are shown in red in these formulas.
The hydrogen atom in the functional group of a carboxylic acid will react with a base to form an ionic salt:

Carboxylic acids are weak acids (see the chapter on acids and bases), meaning they are not 100% ionized in water. Generally only
about 1% of the molecules of a carboxylic acid dissolved in water are ionized at any given time. The remaining molecules are
undissociated in solution.
We prepare carboxylic acids by the oxidation of aldehydes or alcohols whose –OH functional group is located on the carbon atom
at the end of the chain of carbon atoms in the alcohol:
Esters are produced by the reaction of acids with alcohols. For example, the ester ethyl acetate, CH3CO2CH2CH3, is formed when
acetic acid reacts with ethanol:
The simplest carboxylic acid is formic acid, HCO2H, known since 1670. Its name comes from the Latin word formicus, which
means “ant”; it was first isolated by the distillation of red ants. It is partially responsible for the pain and irritation of ant and wasp
stings, and is responsible for a characteristic odor of ants that can be sometimes detected in their nests.
Acetic acid, CH3CO2H, constitutes 3–6% vinegar. Cider vinegar is produced by allowing apple juice to ferment without oxygen
present. Yeast cells present in the juice carry out the fermentation reactions. The fermentation reactions change the sugar present in
the juice to ethanol, then to acetic acid. Pure acetic acid has a penetrating odor and produces painful burns. It is an excellent solvent
for many organic and some inorganic compounds, and it is essential in the production of cellulose acetate, a component of many
synthetic fibers such as rayon.
The distinctive and attractive odors and flavors of many flowers, perfumes, and ripe fruits are due to the presence of one or more
esters (Figure 20.16). Among the most important of the natural esters are fats (such as lard, tallow, and butter) and oils (such as
linseed, cottonseed, and olive oils), which are esters of the trihydroxyl alcohol glycerine, C3H5(OH)3, with large carboxylic acids,
such as palmitic acid, CH3(CH2)14CO2H, stearic acid, CH3(CH2)16CO2H, and oleic acid, CH (C H ) CH = CH(CH ) C O H.
3 2 7 2 7 2
Oleic acid is an unsaturated acid; it contains a C = C double bond. Palmitic and stearic acids are saturated acids that contain no
double or triple bonds.

Figure 20.16 Over 350 different volatile molecules (many members of the ester family) have been identified in strawberries.
(credit: Rebecca Siegel)
This page titled 20.4: Aldehydes, Ketones, Carboxylic Acids, and Esters is shared under a CC BY 4.0 license and was authored, remixed, and/or
upon request.


Describe the structure and properties of an amine
Describe the structure and properties of an amide
Amines are molecules that contain carbon-nitrogen bonds. The nitrogen atom in an amine has a lone pair of electrons and three
bonds to other atoms, either carbon or hydrogen. Various nomenclatures are used to derive names for amines, but all involve the
class-identifying suffix –ine as illustrated here for a few simple examples:
In some amines, the nitrogen atom replaces a carbon atom in an aromatic hydrocarbon. Pyridine (Figure 20.17) is one such
heterocyclic amine. A heterocyclic compound contains atoms of two or more different elements in its ring structure.
Figure 20.17 The illustration shows one of the resonance structures of pyridine.

20.5.0.0.1: DNA in Forensics and Paternity
The genetic material for all living things is a polymer of four different molecules, which are themselves a combination of three
subunits. The genetic information, the code for developing an organism, is contained in the specific sequence of the four
molecules, similar to the way the letters of the alphabet can be sequenced to form words that convey information. The
information in a DNA sequence is used to form two other types of polymers, one of which are proteins. The proteins interact to
form a specific type of organism with individual characteristics.
A genetic molecule is called DNA, which stands for deoxyribonucleic acid. The four molecules that make up DNA are called
nucleotides. Each nucleotide consists of a single- or double-ringed molecule containing nitrogen, carbon, oxygen, and
hydrogen called a nitrogenous base. Each base is bonded to a five-carbon sugar called deoxyribose. The sugar is in turn bonded
to a phosphate group (−PO ) When new DNA is made, a polymerization reaction occurs that binds the phosphate group of
4
3−
one nucleotide to the sugar group of a second nucleotide. The nitrogenous bases of each nucleotide stick out from this sugar-
phosphate backbone. DNA is actually formed from two such polymers coiled around each other and held together by hydrogen
bonds between the nitrogenous bases. Thus, the two backbones are on the outside of the coiled pair of strands, and the bases
are on the inside. The shape of the two strands wound around each other is called a double helix (see Figure 20.18).
It probably makes sense that the sequence of nucleotides in the DNA of a cat differs from those of a dog. But it is also true that
the sequences of the DNA in the cells of two individual pugs differ. Likewise, the sequences of DNA in you and a sibling differ
(unless your sibling is an identical twin), as do those between you and an unrelated individual. However, the DNA sequences
of two related individuals are more similar than the sequences of two unrelated individuals, and these similarities in sequence
can be observed in various ways. This is the principle behind DNA fingerprinting, which is a method used to determine
whether two DNA samples came from related (or the same) individuals or unrelated individuals.

Figure 20.18 DNA is an organic molecule and the genetic material for all living organisms. (a) DNA is a double helix
consisting of two single DNA strands hydrogen bonded together at each nitrogenous base. (b) This detail shows the hydrogen
bonding (dotted lines) between nitrogenous bases on each DNA strand and the way in which each nucleotide is joined to the
next, forming a backbone of sugars and phosphate groups along each strand. (c) This detail shows the structure of one of the
four nucleotides that makes up the DNA polymer. Each nucleotide consists of a nitrogenous base (a double-ring molecule, in
this case), a five-carbon sugar (deoxyribose), and a phosphate group.
Using similarities in sequences, technicians can determine whether a man is the father of a child (the identity of the mother is
rarely in doubt, except in the case of an adopted child and a potential birth mother). Likewise, forensic geneticists can
determine whether a crime scene sample of human tissue, such as blood or skin cells, contains DNA that matches exactly the
DNA of a suspect.

Watch this video animation of how DNA is packaged for a visual lesson in its structure.

Like ammonia, amines are weak bases due to the lone pair of electrons on their nitrogen atoms:
The basicity of an amine’s nitrogen atom plays an important role in much of the compound’s chemistry. Amine functional groups
are found in a wide variety of compounds, including natural and synthetic dyes, polymers, vitamins, and medications such as
penicillin and codeine. They are also found in many molecules essential to life, such as amino acids, hormones, neurotransmitters,
and DNA.

20.5.0.0.1: Addictive Alkaloids
Since ancient times, plants have been used for medicinal purposes. One class of substances, called alkaloids, found in many of
these plants has been isolated and found to contain cyclic molecules with an amine functional group. These amines are bases.
They can react with H3O+ in a dilute acid to form an ammonium salt, and this property is used to extract them from the plant:
+ − + −
R3 N + H3 O + Cl ⟶ [ R3 NH ] Cl + H2 O
The name alkaloid means “like an alkali.” Thus, an alkaloid reacts with acid. The free compound can be recovered after
extraction by reaction with a base:
+ − − −
[ R3 NH ] Cl + OH ⟶ R3 N + H2 O + Cl
The structures of many naturally occurring alkaloids have profound physiological and psychotropic effects in humans.
Examples of these drugs include nicotine, morphine, codeine, and heroin. The plant produces these substances, collectively
called secondary plant compounds, as chemical defenses against the numerous pests that attempt to feed on the plant:

In these diagrams, as is common in representing structures of large organic compounds, carbon atoms in the rings and the
hydrogen atoms bonded to them have been omitted for clarity. The solid wedges indicate bonds that extend out of the page.
The dashed wedges indicate bonds that extend into the page. Notice that small changes to a part of the molecule change the
properties of morphine, codeine, and heroin. Morphine, a strong narcotic used to relieve pain, contains two hydroxyl functional
groups, located at the bottom of the molecule in this structural formula. Changing one of these hydroxyl groups to a methyl
ether group forms codeine, a less potent drug used as a local anesthetic. If both hydroxyl groups are converted to esters of
acetic acid, the powerfully addictive drug heroin results (Figure 20.19).

Figure 20.19 Poppies can be used in the production of opium, a plant latex that contains morphine from which other opiates,
such as heroin, can be synthesized. (credit: Karen Roe)
Amides are molecules that contain nitrogen atoms connected to the carbon atom of a carbonyl group. Like amines, various
nomenclature rules may be used to name amides, but all include use of the class-specific suffix -amide:

Amides can be produced when carboxylic acids react with amines or ammonia in a process called amidation. A water molecule is
eliminated from the reaction, and the amide is formed from the remaining pieces of the carboxylic acid and the amine (note the
similarity to formation of an ester from a carboxylic acid and an alcohol discussed in the previous section):
The reaction between amines and carboxylic acids to form amides is biologically important. It is through this reaction that amino
acids (molecules containing both amine and carboxylic acid substituents) link together in a polymer to form proteins.

20.5.0.0.1: Proteins and Enzymes
Proteins are large biological molecules made up of long chains of smaller molecules called amino acids. Organisms rely on
proteins for a variety of functions—proteins transport molecules across cell membranes, replicate DNA, and catalyze
metabolic reactions, to name only a few of their functions. The properties of proteins are functions of the combination of amino
acids that compose them and can vary greatly. Interactions between amino acid sequences in the chains of proteins result in the
folding of the chain into specific, three-dimensional structures that determine the protein’s activity.
Amino acids are organic molecules that contain an amine functional group (–NH2), a carboxylic acid functional group (–
COOH), and a side chain (that is specific to each individual amino acid). Most living things build proteins from the same 20
different amino acids. Amino acids connect by the formation of a peptide bond, which is a covalent bond formed between two
amino acids when the carboxylic acid group of one amino acid reacts with the amine group of the other amino acid. The
formation of the bond results in the production of a molecule of water (in general, reactions that result in the production of
water when two other molecules combine are referred to as condensation reactions). The resulting bond—between the carbonyl
group carbon atom and the amine nitrogen atom is called a peptide link or peptide bond. Since each of the original amino acids
has an unreacted group (one has an unreacted amine and the other an unreacted carboxylic acid), more peptide bonds can form
to other amino acids, extending the structure. (Figure 20.20) A chain of connected amino acids is called a polypeptide. Proteins
contain at least one long polypeptide chain.

Figure 20.20 This condensation reaction forms a dipeptide from two amino acids and leads to the formation of water.
Enzymes are large biological molecules, mostly composed of proteins, which are responsible for the thousands of metabolic
processes that occur in living organisms. Enzymes are highly specific catalysts; they speed up the rates of certain reactions.
Enzymes function by lowering the activation energy of the reaction they are catalyzing, which can dramatically increase the
rate of the reaction. Most reactions catalyzed by enzymes have rates that are millions of times faster than the noncatalyzed
version. Like all catalysts, enzymes are not consumed during the reactions that they catalyze. Enzymes do differ from other
catalysts in how specific they are for their substrates (the molecules that an enzyme will convert into a different product). Each
enzyme is only capable of speeding up one or a few very specific reactions or types of reactions. Since the function of enzymes

is so specific, the lack or malfunctioning of an enzyme can lead to serious health consequences. One disease that is the result of
an enzyme malfunction is phenylketonuria. In this disease, the enzyme that catalyzes the first step in the degradation of the
amino acid phenylalanine is not functional (Figure 20.21). Untreated, this can lead to an accumulation of phenylalanine, which
can lead to intellectual disabilities.
Figure 20.21 A computer rendering shows the three-dimensional structure of the enzyme phenylalanine hydroxylase. In the
disease phenylketonuria, a defect in the shape of phenylalanine hydroxylase causes it to lose its function in breaking down
phenylalanine.

20.5.0.0.1: Kevlar
Kevlar (Figure 20.22) is a synthetic polymer made from two monomers 1,4-phenylene-diamine and terephthaloyl chloride
(Kevlar is a registered trademark of DuPont). The material was developed by Susan Kwolek while she worked to find a
replacement for steel in tires. Kwolek's work involved synthesizing polyamides and dissolving them in solvents, then spinning
the resulting solution into fibers. One of her solutions proved to be quite different in initial appearance and structure. And once
spun, the resulting fibers were particularly strong. From this initial discovery, Kevlar was created. The material has a high
tensile strength-to-weight ratio (it is about 5 times stronger than an equal weight of steel), making it useful for many
applications from bicycle tires to sails to body armor.
Figure 20.22 This illustration shows the formula for polymeric Kevlar.
The material owes much of its strength to hydrogen bonds between polymer chains (refer back to the chapter on intermolecular
interactions). These bonds form between the carbonyl group oxygen atom (which has a partial negative charge due to oxygen’s
electronegativity) on one monomer and the partially positively charged hydrogen atom in the N–H bond of an adjacent
monomer in the polymer structure (see dashed line in Figure 20.23). There is additional strength derived from the interaction
between the unhybridized p orbitals in the six-membered rings, called aromatic stacking.

Figure 20.23 The diagram shows the polymer structure of Kevlar, with hydrogen bonds between polymer chains represented by
dotted lines.
Kevlar may be best known as a component of body armor, combat helmets, and face masks. Since the 1980s, the US military
has used Kevlar as a component of the PASGT (personal armor system for ground troops) helmet and vest. Kevlar is also used
to protect armored fighting vehicles and aircraft carriers. Civilian applications include protective gear for emergency service
personnel such as body armor for police officers and heat-resistant clothing for fire fighters. Kevlar based clothing is
considerably lighter and thinner than equivalent gear made from other materials (Figure 20.24). Beyond Kevlar, Susan Kwolek
was instrumental in the development of Nomex, a fireproof material, and was also involved in the creation of Lycra. She
became just the fourth woman inducted into the National Inventors Hall of Fame, and received a number of other awards for
her significant contributions to science and society.
Figure 20.24 (a) These soldiers are sorting through pieces of a Kevlar helmet that helped absorb a grenade blast. Kevlar is also
used to make (b) canoes and (c) marine mooring lines. (credit a: modification of work by “Cla68”/Wikimedia Commons; credit
b: modification of work by “OakleyOriginals”/Flickr; credit c: modification of work by Casey H. Kyhl)
In addition to its better-known uses, Kevlar is also often used in cryogenics for its very low thermal conductivity (along with
its high strength). Kevlar maintains its high strength when cooled to the temperature of liquid nitrogen (–196 °C).
The table here summarizes the structures discussed in this chapter:

This page titled 20.5: Amines and Amides is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via

20.6: Key Terms
addition reaction
reaction in which a double carbon-carbon bond forms a single carbon-carbon bond by the addition of a reactant. Typical
reaction for an alkene.
alcohol
organic compound with a hydroxyl group (–OH) bonded to a carbon atom
aldehyde
organic compound containing a carbonyl group bonded to two hydrogen atoms or a hydrogen atom and a carbon substituent
alkane
molecule consisting of only carbon and hydrogen atoms connected by single (σ) bonds
alkene
molecule consisting of carbon and hydrogen containing at least one carbon-carbon double bond
alkyl group
substituent, consisting of an alkane missing one hydrogen atom, attached to a larger structure
alkyne
molecule consisting of carbon and hydrogen containing at least one carbon-carbon triple bond
amide
organic molecule that features a nitrogen atom connected to the carbon atom in a carbonyl group
amine
organic molecule in which a nitrogen atom is bonded to one or more alkyl group
aromatic hydrocarbon
cyclic molecule consisting of carbon and hydrogen with delocalized alternating carbon-carbon single and double bonds,
resulting in enhanced stability
carbonyl group
carbon atom double bonded to an oxygen atom
carboxylic acid
organic compound containing a carbonyl group with an attached hydroxyl group
ester
organic compound containing a carbonyl group with an attached oxygen atom that is bonded to a carbon substituent
ether
organic compound with an oxygen atom that is bonded to two carbon atoms
functional group
part of an organic molecule that imparts a specific chemical reactivity to the molecule
ketone
organic compound containing a carbonyl group with two carbon substituents attached to it
organic compound
natural or synthetic compound that contains carbon
saturated hydrocarbon
molecule containing carbon and hydrogen that has only single bonds between carbon atoms
skeletal structure
shorthand method of drawing organic molecules in which carbon atoms are represented by the ends of lines and bends in
between lines, and hydrogen atoms attached to the carbon atoms are not shown (but are understood to be present by the context
of the structure)
substituent
branch or functional group that replaces hydrogen atoms in a larger hydrocarbon chain
substitution reaction
reaction in which one atom replaces another in a molecule
20.7: Summary
20.1 Hydrocarbons
Strong, stable bonds between carbon atoms produce complex molecules containing chains, branches, and rings. The chemistry of
these compounds is called organic chemistry. Hydrocarbons are organic compounds composed of only carbon and hydrogen. The
alkanes are saturated hydrocarbons—that is, hydrocarbons that contain only single bonds. Alkenes contain one or more carbon-
carbon double bonds. Alkynes contain one or more carbon-carbon triple bonds. Aromatic hydrocarbons contain ring structures with
delocalized π electron systems.
20.2 Alcohols and Ethers

Many organic compounds that are not hydrocarbons can be thought of as derivatives of hydrocarbons. A hydrocarbon derivative
can be formed by replacing one or more hydrogen atoms of a hydrocarbon by a functional group, which contains at least one atom
of an element other than carbon or hydrogen. The properties of hydrocarbon derivatives are determined largely by the functional
group. The –OH group is the functional group of an alcohol. The –R–O–R– group is the functional group of an ether.
20.3 Aldehydes, Ketones, Carboxylic Acids, and Esters

Functional groups related to the carbonyl group include the –CHO group of an aldehyde, the –CO– group of a ketone, the –CO2H
group of a carboxylic acid, and the –CO2R group of an ester. The carbonyl group, a carbon-oxygen double bond, is the key
structure in these classes of organic molecules: Aldehydes contain at least one hydrogen atom attached to the carbonyl carbon
atom, ketones contain two carbon groups attached to the carbonyl carbon atom, carboxylic acids contain a hydroxyl group attached
to the carbonyl carbon atom, and esters contain an oxygen atom attached to another carbon group connected to the carbonyl carbon
atom. All of these compounds contain oxidized carbon atoms relative to the carbon atom of an alcohol group.
20.4 Amines and Amides

The addition of nitrogen into an organic framework leads to two families of molecules. Compounds containing a nitrogen atom
bonded in a hydrocarbon framework are classified as amines. Compounds that have a nitrogen atom bonded to one side of a
carbonyl group are classified as amides. Amines are a basic functional group. Amines and carboxylic acids can combine in a
condensation reaction to form amides.
20.8: Exercises
20.8.0.1: 20.1 Hydrocarbons
1.
Write the chemical formula and Lewis structure of the following, each of which contains five carbon atoms:
(a) an alkane
(b) an alkene
(c) an alkyne
2.
What is the difference between the hybridization of carbon atoms’ valence orbitals in saturated and unsaturated hydrocarbons?
3.
On a microscopic level, how does the reaction of bromine with a saturated hydrocarbon differ from its reaction with an unsaturated
hydrocarbon? How are they similar?
4.
On a microscopic level, how does the reaction of bromine with an alkene differ from its reaction with an alkyne? How are they
similar?
5.
Explain why unbranched alkenes can form geometric isomers while unbranched alkanes cannot. Does this explanation involve the
macroscopic domain or the microscopic domain?
6.
Explain why these two molecules are not isomers:
7.
Explain why these two molecules are not isomers:
8.
How does the carbon-atom hybridization change when polyethylene is prepared from ethylene?
9.
Write the Lewis structure and molecular formula for each of the following hydrocarbons:

(a) hexane
(b) 3-methylpentane
(c) cis-3-hexene
(d) 4-methyl-1-pentene
(e) 3-hexyne
(f) 4-methyl-2-pentyne
10.
Write the chemical formula, condensed formula, and Lewis structure for each of the following hydrocarbons:
(a) heptane
(b) 3-methylhexane
(c) trans-3-heptene
(d) 4-methyl-1-hexene
(e) 2-heptyne
(f) 3,4-dimethyl-1-pentyne
11.
Give the complete IUPAC name for each of the following compounds:
(a) CH3CH2CBr2CH3
(b) (CH3)3CCl
(c)
(d) CH 3 CH2 C ≡ CH CH3 CH2 C ≡ CH
(e)
(f)
(g) (CH 3 ) 2 CHCH2 CH = CH2
12.
(a) (CH3)2CHF
(b) CH3CHClCHClCH3
(c)

(d) CH 3 CH2 CH = CHCH3
(e)
(f) (CH 3 ) 3 CCH2 C ≡ CH
13.
Butane is used as a fuel in disposable lighters. Write the Lewis structure for each isomer of butane.
14.
Write Lewis structures and name the five structural isomers of hexane.
15.
Write Lewis structures for the cis–trans isomers of CH 3 CH = CHCl.
16.
Write structures for the three isomers of the aromatic hydrocarbon xylene, C6H4(CH3)2.
17.
Isooctane is the common name of the isomer of C8H18 used as the standard of 100 for the gasoline octane rating:
(a) What is the IUPAC name for the compound?

(b) Name the other isomers that contain a five-carbon chain with three methyl substituents.
18.
Write Lewis structures and IUPAC names for the alkyne isomers of C4H6.
19.
Write Lewis structures and IUPAC names for all isomers of C4H9Cl.
20.
Name and write the structures of all isomers of the propyl and butyl alkyl groups.
21.
Write the structures for all the isomers of the –C5H11 alkyl group.
22.
Write Lewis structures and describe the molecular geometry at each carbon atom in the following compounds:
(a) cis-3-hexene
(b) cis-1-chloro-2-bromoethene
(c) 2-pentyne
(d) trans-6-ethyl-7-methyl-2-octene

23.
Benzene is one of the compounds used as an octane enhancer in unleaded gasoline. It is manufactured by the catalytic conversion
of acetylene to benzene:
3 C2 H2 ⟶ C6 H6
Draw Lewis structures for these compounds, with resonance structures as appropriate, and determine the hybridization of the
carbon atoms in each.
24.
Teflon is prepared by the polymerization of tetrafluoroethylene. Write the equation that describes the polymerization using Lewis
symbols.
25.
Write two complete, balanced equations for each of the following reactions, one using condensed formulas and one using Lewis
structures.
(a) 1 mol of 1-butyne reacts with 2 mol of iodine.
(b) Pentane is burned in air.
26.
structures.
(a) 2-butene reacts with chlorine.
(b) benzene burns in air.
27.
What mass of 2-bromopropane could be prepared from 25.5 g of propene? Assume a 100% yield of product.
28.
Acetylene is a very weak acid; however, it will react with moist silver(I) oxide and form water and a compound composed of silver
and carbon. Addition of a solution of HCl to a 0.2352-g sample of the compound of silver and carbon produced acetylene and
0.2822 g of AgCl.
(a) What is the empirical formula of the compound of silver and carbon?
(b) The production of acetylene on addition of HCl to the compound of silver and carbon suggests that the carbon is present as the
acetylide ion, C . Write the formula of the compound showing the acetylide ion.
2
2−
29.
Ethylene can be produced by the pyrolysis of ethane:
C2 H6 ⟶ C2 H4 + H2
How many kilograms of ethylene is produced by the pyrolysis of 1.000 × 103 kg of ethane, assuming a 100.0% yield?
20.8.0.1: 20.2 Alcohols and Ethers

30.
Why do the compounds hexane, hexanol, and hexene have such similar names?
31.
Write condensed formulas and provide IUPAC names for the following compounds:
(a) ethyl alcohol (in beverages)
(b) methyl alcohol (used as a solvent, for example, in shellac)
(c) ethylene glycol (antifreeze)
(d) isopropyl alcohol (used in rubbing alcohol)
(e) glycerine

32.
(a)
(b)
(c)
33.
Give the complete IUPAC name and the common name for each of the following compounds:
(a)
(b)
(c)
34.
Write the condensed structures of both isomers with the formula C2H6O. Label the functional group of each isomer.
35.
Write the condensed structures of all isomers with the formula C2H6O2. Label the functional group (or groups) of each isomer.
36.
Draw the condensed formulas for each of the following compounds:
(a) dipropyl ether
(b) 2,2-dimethyl-3-hexanol

(c) 2-ethoxybutane
37.
MTBE, Methyl tert-butyl ether, CH3OC(CH3)3, is used as an oxygen source in oxygenated gasolines. MTBE is manufactured by
reacting 2-methylpropene with methanol.
(a) Using Lewis structures, write the chemical equation representing the reaction.
(b) What volume of methanol, density 0.7915 g/mL, is required to produce exactly 1000 kg of MTBE, assuming a 100% yield?
38.
Write two complete balanced equations for each of the following reactions, one using condensed formulas and one using Lewis
structures.
(a) propanol is converted to dipropyl ether
(b) propene is treated with water in dilute acid.
39.
structures.
(a) 2-butene is treated with water in dilute acid
(b) ethanol is dehydrated to yield ethene
20.8.0.1: 20.3 Aldehydes, Ketones, Carboxylic Acids, and Esters

40.
Order the following molecules from least to most oxidized, based on the marked carbon atom:
41.
Predict the products of oxidizing the molecules shown in this problem. In each case, identify the product that will result from the
minimal increase in oxidation state for the highlighted carbon atom:
(a)
(b)
(c)
42.

Predict the products of reducing the following molecules. In each case, identify the product that will result from the minimal
decrease in oxidation state for the highlighted carbon atom:
(a)
(b)
(c)
43.
Explain why it is not possible to prepare a ketone that contains only two carbon atoms.
44.
How does hybridization of the substituted carbon atom change when an alcohol is converted into an aldehyde? An aldehyde to a
carboxylic acid?
45.
Fatty acids are carboxylic acids that have long hydrocarbon chains attached to a carboxylate group. How does a saturated fatty acid
differ from an unsaturated fatty acid? How are they similar?
46.
Write a condensed structural formula, such as CH3CH3, and describe the molecular geometry at each carbon atom.
(a) propene
(b) 1-butanol
(c) ethyl propyl ether
(d) cis-4-bromo-2-heptene
(e) 2,2,3-trimethylhexane
(f) formaldehyde
47.
Write a condensed structural formula, such as CH3CH3, and describe the molecular geometry at each carbon atom.
(a) 2-propanol
(b) acetone
(c) dimethyl ether
(d) acetic acid
(e) 3-methyl-1-hexene
48.

The foul odor of rancid butter is caused by butyric acid, CH3CH2CH2CO2H.
(a) Draw the Lewis structure and determine the oxidation number and hybridization for each carbon atom in the molecule.
(b) The esters formed from butyric acid are pleasant-smelling compounds found in fruits and used in perfumes. Draw the Lewis
structure for the ester formed from the reaction of butyric acid with 2-propanol.
49.
Write the two-resonance structures for the acetate ion.
50.
structures:
(a) ethanol reacts with propionic acid
(b) benzoic acid, C6H5CO2H, is added to a solution of sodium hydroxide
51.
structures.
(a) 1-butanol reacts with acetic acid
(b) propionic acid is poured onto solid calcium carbonate
52.
Yields in organic reactions are sometimes low. What is the percent yield of a process that produces 13.0 g of ethyl acetate from
10.0 g of CH3CO2H?
53.
Alcohols A, B, and C all have the composition C4H10O. Molecules of alcohol A contain a branched carbon chain and can be
oxidized to an aldehyde; molecules of alcohol B contain a linear carbon chain and can be oxidized to a ketone; and molecules of
alcohol C can be oxidized to neither an aldehyde nor a ketone. Write the Lewis structures of these molecules.
20.8.0.1: 20.4 Amines and Amides

54.
Write the Lewis structures of both isomers with the formula C2H7N.
55.
What is the molecular structure about the nitrogen atom in trimethyl amine and in the trimethyl ammonium ion, (CH3)3NH+? What
is the hybridization of the nitrogen atom in trimethyl amine and in the trimethyl ammonium ion?
56.
Write the two resonance structures for the pyridinium ion, C5H5NH+.
57.
Draw Lewis structures for pyridine and its conjugate acid, the pyridinium ion, C5H5NH+. What are the hybridizations, electron
domain geometries, and molecular geometries about the nitrogen atoms in pyridine and in the pyridinium ion?
58.
Write the Lewis structures of all isomers with the formula C3H7ON that contain an amide linkage.
59.
Write two complete balanced equations for the following reaction, one using condensed formulas and one using Lewis structures.
Methyl amine is added to a solution of HCl.
60.
structures.

Ethylammonium chloride is added to a solution of sodium hydroxide.
61.
Identify any carbon atoms that change hybridization and the change in hybridization during the reactions in Exercise 20.26.
62.
63.

CHAPTER OVERVIEW
21: Nuclear Chemistry

General Chemistry
The chemical reactions that we have considered in previous chapters involve changes in the electronic structure of the species
involved, that is, the arrangement of the electrons around atoms, ions, or molecules. Nuclear structure, the numbers of protons and
neutrons within the nuclei of the atoms involved, remains unchanged during chemical reactions. This chapter will introduce the
topic of nuclear chemistry, which began with the discovery of radioactivity in 1896 by French physicist Antoine Becquerel and has
become increasingly important during the twentieth and twenty-first centuries, providing the basis for various technologies related
to energy, medicine, geology, and many other areas.
21.1: Introduction
21.8: Key Terms
21.9: Key Equations
21.10: Summary
21.11: Exercises
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1
21.1: Introduction
Figure 21.1 Nuclear chemistry provides the basis for many useful diagnostic and therapeutic methods in medicine, such as these
positron emission tomography (PET) scans. The PET/computed tomography scan on the left shows muscle activity. The brain
scans in the center show chemical differences in dopamine signaling in the brains of addicts and nonaddicts. The images on the
right show an oncological application of PET scans to identify lymph node metastasis.
Chapter Outline
21.1 Nuclear Structure and Stability
21.2 Nuclear Equations
21.3 Radioactive Decay
21.4 Transmutation and Nuclear Energy
21.5 Uses of Radioisotopes
21.6 Biological Effects of Radiation
The chemical reactions that we have considered in previous chapters involve changes in the electronic structure of the species
involved, that is, the arrangement of the electrons around atoms, ions, or molecules. Nuclear structure, the numbers of protons and
neutrons within the nuclei of the atoms involved, remains unchanged during chemical reactions.
This chapter will introduce the topic of nuclear chemistry, which began with the discovery of radioactivity in 1896 by French
physicist Antoine Becquerel and has become increasingly important during the twentieth and twenty-first centuries, providing the
basis for various technologies related to energy, medicine, geology, and many other areas.

Describe nuclear structure in terms of protons, neutrons, and electrons
Calculate mass defect and binding energy for nuclei
Explain trends in the relative stability of nuclei
Nuclear chemistry is the study of reactions that involve changes in nuclear structure. The chapter on atoms, molecules, and ions
introduced the basic idea of nuclear structure, that the nucleus of an atom is composed of protons and, with the exception of H, 1
1
neutrons. Recall that the number of protons in the nucleus is called the atomic number (Z) of the element, and the sum of the
number of protons and the number of neutrons is the mass number (A). Atoms with the same atomic number but different mass
numbers are isotopes of the same element. When referring to a single type of nucleus, we often use the term nuclide and identify it
by the notation X, where X is the symbol for the element, A is the mass number, and Z is the atomic number (for example, C).
A
Z
14
6
Often a nuclide is referenced by the name of the element followed by a hyphen and the mass number. For example, C is called 14
6
“carbon-14.”
Protons and neutrons, collectively called nucleons, are packed together tightly in a nucleus. With a radius of about 10−15 meters, a
nucleus is quite small compared to the radius of the entire atom, which is about 10−10 meters. Nuclei are extremely dense compared
to bulk matter, averaging 1.8 × 1014 grams per cubic centimeter. For example, water has a density of 1 gram per cubic centimeter,
and iridium, one of the densest elements known, has a density of 22.6 g/cm3. If the earth’s density were equal to the average
nuclear density, the earth’s radius would be only about 200 meters (earth’s actual radius is approximately 6.4 × 106 meters, 30,000
times larger). Example 21.1 demonstrates just how great nuclear densities can be in the natural world.
21.2.0.1: Example 21.1

21.2.0.0.1: Density of a Neutron Star
Neutron stars form when the core of a very massive star undergoes gravitational collapse, causing the star’s outer layers to
explode in a supernova. Composed almost completely of neutrons, they are the densest-known stars in the universe, with
densities comparable to the average density of an atomic nucleus. A neutron star in a faraway galaxy has a mass equal to 2.4
solar masses (1 solar mass = M☉ = mass of the sun = 1.99 × 1030 kg) and a diameter of 26 km.
(a) What is the density of this neutron star?
(b) How does this neutron star’s density compare to the density of a uranium nucleus, which has a diameter of about 15 fm (1
fm = 10–15 m)?
We can treat both the neutron star and the U-235 nucleus as spheres. Then the density for both is given by:
m 4 3
d = with V = πr
V 3
(a) The radius of the neutron star is 1
2
× 26 km =
1
2
× 2.6 × 10
4
m = 1.3 × 10
4
m, so the density of the neutron star is:
30
m m 2.4 (1.99 × 10 kg)
17 3
d = = = = 5.2 × 10 kg/m
V 4 3 4 4 3
πr π (1.3 × 10 m)
3 3
(b) The radius of the U-235 nucleus is 1
2
× 15 × 10
−15
m = 7.5 × 10
−15
m, so the density of the U-235 nucleus is:
−27
1.66 × 10 kg
235 amu ( )
m m 1 amu
17 3
d = = = = 2.2 × 10 kg/m
4 3
V πr
3 4 −15
3
π (7.5 × 10 m)
3
These values are fairly similar (same order of magnitude), but the neutron star is more than twice as dense as the U-235
nucleus.

Find the density of a neutron star with a mass of 1.97 solar masses and a diameter of 13 km, and compare it to the density of a
hydrogen nucleus, which has a diameter of 1.75 fm (1 fm = 1 × 10–15 m).
21.2.0.1: Answer:
The density of the neutron star is 3.4 × 1018 kg/m3. The density of a hydrogen nucleus is 6.0 × 1017 kg/m3. The neutron
star is 5.7 times denser than the hydrogen nucleus.
To hold positively charged protons together in the very small volume of a nucleus requires very strong attractive forces because the
positively charged protons repel one another strongly at such short distances. The force of attraction that holds the nucleus together
is the strong nuclear force. (The strong force is one of the four fundamental forces that are known to exist. The others are the
electromagnetic force, the gravitational force, and the nuclear weak force.) This force acts between protons, between neutrons, and
between protons and neutrons. It is very different from the electrostatic force that holds negatively charged electrons around a
positively charged nucleus (the attraction between opposite charges). Over distances less than 10−15 meters and within the nucleus,
the strong nuclear force is much stronger than electrostatic repulsions between protons; over larger distances and outside the
nucleus, it is essentially nonexistent.

Visit this website for more information about the four fundamental forces.
21.2.0.1: Nuclear Binding Energy

As a simple example of the energy associated with the strong nuclear force, consider the helium atom composed of two protons,
two neutrons, and two electrons. The total mass of these six subatomic particles may be calculated as:
(2 × 1.0073 amu) + (2 × 1.0087 amu) + (2 × 0.00055 amu) = 4.0331 amu
protons neutrons electrons
However, mass spectrometric measurements reveal that the mass of an He atom is 4.0026 amu, less than the combined masses of
4
2
its six constituent subatomic particles. This difference between the calculated and experimentally measured masses is known as the
mass defect of the atom. In the case of helium, the mass defect indicates a “loss” in mass of 4.0331 amu – 4.0026 amu = 0.0305
amu. The loss in mass accompanying the formation of an atom from protons, neutrons, and electrons is due to the conversion of
that mass into energy that is evolved as the atom forms. The nuclear binding energy is the energy produced when the atoms’
nucleons are bound together; this is also the energy needed to break a nucleus into its constituent protons and neutrons. In
comparison to chemical bond energies, nuclear binding energies are vastly greater, as we will learn in this section. Consequently,
the energy changes associated with nuclear reactions are vastly greater than are those for chemical reactions.
The conversion between mass and energy is most identifiably represented by the mass-energy equivalence equation as stated by
Albert Einstein:
2
E = mc
where E is energy, m is mass of the matter being converted, and c is the speed of light in a vacuum. This equation can be used to
find the amount of energy that results when matter is converted into energy. Using this mass-energy equivalence equation, the
nuclear binding energy of a nucleus may be calculated from its mass defect, as demonstrated in Example 21.2. A variety of units
are commonly used for nuclear binding energies, including electron volts (eV), with 1 eV equaling the amount of energy necessary
to the move the charge of an electron across an electric potential difference of 1 volt, making 1 eV = 1.602 × 10–19 J.
21.2.0.1: Example 21.2

21.2.0.0.1: Calculation of Nuclear Binding Energy
Determine the binding energy for the nuclide 4
2
He in:
(a) joules per mole of nuclei
(b) joules per nucleus
(c) MeV per nucleus

The mass defect for a He nucleus is 0.0305 amu, as shown previously. Determine the binding energy in joules per nuclide
4
2
using the mass-energy equivalence equation. To accommodate the requested energy units, the mass defect must be expressed in
kilograms (recall that 1 J = 1 kg m2/s2).
(a) First, express the mass defect in g/mol. This is easily done considering the numerical equivalence of atomic mass (amu) and
molar mass (g/mol) that results from the definitions of the amu and mole units (refer to the previous discussion in the chapter
on atoms, molecules, and ions if needed). The mass defect is therefore 0.0305 g/mol. To accommodate the units of the other
terms in the mass-energy equation, the mass must be expressed in kg, since 1 J = 1 kg m2/s2. Converting grams into kilograms
yields a mass defect of 3.05 × 10–5 kg/mol. Substituting this quantity into the mass-energy equivalence equation yields:
−5 2
3.05 × 10 kg 2.998 × 10
8
m −1
2 12 2 −2
E = mc = × ( ) = 2.74 × 10 kg m s mol
mol s
12 −1 −1
= 2.74 × 10 J mol = 2.74 TJ mol
Note that this tremendous amount of energy is associated with the conversion of a very small amount of matter (about 30 mg,
roughly the mass of typical drop of water).
(b) The binding energy for a single nucleus is computed from the molar binding energy using Avogadro’s number:
1 mol
12 −1 −12
E = 2.74 × 10 J mol × = 4.55 × 10 J = 4.55 pJ
23
6.022 × 10 nuclei
(c) Recall that 1 eV = 1.602 × 10–19 J. Using the binding energy computed in part (b):
−12
1 eV 7
E = 4.55 × 10 J × = 2.84 × 10 eV = 28.4 MeV
−19
1.602 × 10 J

What is the binding energy for the nuclide 19
9
F (atomic mass: 18.9984 amu) in MeV per nucleus?
21.2.0.1: Answer:
148.4 MeV
Because the energy changes for breaking and forming bonds are so small compared to the energy changes for breaking or forming
nuclei, the changes in mass during all ordinary chemical reactions are virtually undetectable. As described in the chapter on
thermochemistry, the most energetic chemical reactions exhibit enthalpies on the order of thousands of kJ/mol, which is equivalent
to mass differences in the nanogram range (10–9 g). On the other hand, nuclear binding energies are typically on the order of
billions of kJ/mol, corresponding to mass differences in the milligram range (10–3 g).
21.2.0.1: Nuclear Stability

A nucleus is stable if it cannot be transformed into another configuration without adding energy from the outside. Of the thousands
of nuclides that exist, about 250 are stable. A plot of the number of neutrons versus the number of protons for stable nuclei reveals
that the stable isotopes fall into a narrow band. This region is known as the band of stability (also called the belt, zone, or valley of
stability). The straight line in Figure 21.2 represents nuclei that have a 1:1 ratio of protons to neutrons (n:p ratio). Note that the
lighter stable nuclei, in general, have equal numbers of protons and neutrons. For example, nitrogen-14 has seven protons and
seven neutrons. Heavier stable nuclei, however, have increasingly more neutrons than protons. For example: iron-56 has 30
neutrons and 26 protons, an n:p ratio of 1.15, whereas the stable nuclide lead-207 has 125 neutrons and 82 protons, an n:p ratio
equal to 1.52. This is because larger nuclei have more proton-proton repulsions, and require larger numbers of neutrons to provide
compensating strong forces to overcome these electrostatic repulsions and hold the nucleus together.

Figure 21.2 This plot shows the nuclides that are known to exist and those that are stable. The stable nuclides are indicated in blue,
and the unstable nuclides are indicated in green. Note that all isotopes of elements with atomic numbers greater than 83 are
unstable. The solid line is the line where n = Z.

The nuclei that are to the left or to the right of the band of stability are unstable and exhibit radioactivity. They change
spontaneously (decay) into other nuclei that are either in, or closer to, the band of stability. These nuclear decay reactions convert
one unstable isotope (or radioisotope) into another, more stable, isotope. We will discuss the nature and products of this radioactive
decay in subsequent sections of this chapter.
Several observations may be made regarding the relationship between the stability of a nucleus and its structure. Nuclei with even
numbers of protons, neutrons, or both are more likely to be stable (see Table 21.1). Nuclei with certain numbers of nucleons,
known as magic numbers, are stable against nuclear decay. These numbers of protons or neutrons (2, 8, 20, 28, 50, 82, and 126)
make complete shells in the nucleus. These are similar in concept to the stable electron shells observed for the noble gases. Nuclei
that have magic numbers of both protons and neutrons, such as He, O, Ca, and
4
2
16
8
40
20
208
82
Pb, are called “double magic” and are
particularly stable. These trends in nuclear stability may be rationalized by considering a quantum mechanical model of nuclear
energy states analogous to that used to describe electronic states earlier in this textbook. The details of this model are beyond the
scope of this chapter.
Stable Nuclear Isotopes
Number of Stable Isotopes Proton Number Neutron Number
157 even even
53 even odd
50 odd even
5 odd odd
Table 21.1
The relative stability of a nucleus is correlated with its binding energy per nucleon, the total binding energy for the nucleus divided
by the number or nucleons in the nucleus. For instance, we saw in Example 21.2 that the binding energy for a He nucleus is 28.4
4
2
MeV. The binding energy per nucleon for a He nucleus is therefore:

4
2
28.4 MeV
= 7.10 MeV/nucleon
4 nucleons
In Example 21.3, we learn how to calculate the binding energy per nucleon of a nuclide on the curve shown in Figure 21.3.

Figure 21.3 The binding energy per nucleon is largest for nuclides with mass number of approximately 56.
21.2.0.1: Example 21.3

21.2.0.0.1: Calculation of Binding Energy per Nucleon
The iron nuclide Fe lies near the top of the binding energy curve (Figure 21.3) and is one of the most stable nuclides. What
56
26
is the binding energy per nucleon (in MeV) for the nuclide Fe (atomic mass of 55.9349 amu)?
56
26
As in Example 21.2, we first determine the mass defect of the nuclide, which is the difference between the mass of 26 protons,
30 neutrons, and 26 electrons, and the observed mass of an Fe atom: 56
26
Mass defect = [(26 × 1.0073 amu) + (30 × 1.0087 amu) + (26 × 0.00055 amu)] − 55.9349 amu
= 56.4651 amu − 55.9349 amu
= 0.5302 amu
We next calculate the binding energy for one nucleus from the mass defect using the mass-energy equivalence equation:
−27
1.6605 × 10 kg 2
2 8
E = mc = 0.5302 amu × × (2.998 × 10 m/s)
1 amu
−11 2
= 7.913 × 10 kg⋅ m/s
−11
= 7.913 × 10 J
We then convert the binding energy in joules per nucleus into units of MeV per nuclide:
−11
1 MeV
7.913 × 10 J × = 493.9 MeV
−13
1.602 × 10 J
Finally, we determine the binding energy per nucleon by dividing the total nuclear binding energy by the number of nucleons
in the atom:
493.9 MeV
Binding energy per nucleon = = 8.820 MeV/nucleon
56
Note that this is almost 25% larger than the binding energy per nucleon for 4
2
He.
(Note also that this is the same process as in Example 21.1, but with the additional step of dividing the total nuclear binding
energy by the number of nucleons.)
What is the binding energy per nucleon in 19
9
F (atomic mass, 18.9984 amu)?
21.2.0.1: Answer:
7.810 MeV/nucleon
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Identify common particles and energies involved in nuclear reactions
Write and balance nuclear equations
Changes of nuclei that result in changes in their atomic numbers, mass numbers, or energy states are nuclear reactions. To describe
a nuclear reaction, we use an equation that identifies the nuclides involved in the reaction, their mass numbers and atomic numbers,
and the other particles involved in the reaction.
21.3.0.1: Types of Particles in Nuclear Reactions

Many entities can be involved in nuclear reactions. The most common are protons, neutrons, alpha particles, beta particles,
positrons, and gamma rays, as shown in Figure 21.4. Protons ( p, also represented by the symbol H) and neutrons ( n) are the
1
1
1
1
1
0
constituents of atomic nuclei, and have been described previously. Alpha particles ( He, also represented by the symbol α) are
4
2
4
2
high-energy helium nuclei. Beta particles ( β, also represented by the symbol e) are high-energy electrons, and gamma rays
0
−1
0
−1
are photons of very high-energy electromagnetic radiation. Positrons ( e, also represented by the symbol β) are positively
0
+1 +1
0
charged electrons (“anti-electrons”). The subscripts and superscripts are necessary for balancing nuclear equations, but are usually
optional in other circumstances. For example, an alpha particle is a helium nucleus (He) with a charge of +2 and a mass number of
4, so it is symbolized He. This works because, in general, the ion charge is not important in the balancing of nuclear equations.
4
2
Figure 21.4 Although many species are encountered in nuclear reactions, this table summarizes the names, symbols,
representations, and descriptions of the most common of these.
Note that positrons are exactly like electrons, except they have the opposite charge. They are the most common example of
antimatter, particles with the same mass but the opposite state of another property (for example, charge) than ordinary matter.
When antimatter encounters ordinary matter, both are annihilated and their mass is converted into energy in the form of gamma
rays (γ)—and other much smaller subnuclear particles, which are beyond the scope of this chapter—according to the mass-energy
equivalence equation E = mc2, seen in the preceding section. For example, when a positron and an electron collide, both are
annihilated and two gamma ray photons are created:
0 0
e+ e ⟶ γ+γ
−1 +1

As seen in the chapter discussing light and electromagnetic radiation, gamma rays compose short wavelength, high-energy
electromagnetic radiation and are (much) more energetic than better-known X-rays that can behave as particles in the wave-particle
duality sense. Gamma rays are a type of high energy electromagnetic radiation produced when a nucleus undergoes a transition
from a higher to a lower energy state, similar to how a photon is produced by an electronic transition from a higher to a lower
energy level. Due to the much larger energy differences between nuclear energy shells, gamma rays emanating from a nucleus have
energies that are typically millions of times larger than electromagnetic radiation emanating from electronic transitions.
21.3.0.1: Balancing Nuclear Reactions

A balanced chemical reaction equation reflects the fact that during a chemical reaction, bonds break and form, and atoms are
rearranged, but the total numbers of atoms of each element are conserved and do not change. A balanced nuclear reaction equation
indicates that there is a rearrangement during a nuclear reaction, but of nucleons (subatomic particles within the atoms’ nuclei)
rather than atoms. Nuclear reactions also follow conservation laws, and they are balanced in two ways:
1. The sum of the mass numbers of the reactants equals the sum of the mass numbers of the products.
2. The sum of the charges of the reactants equals the sum of the charges of the products.
If the atomic number and the mass number of all but one of the particles in a nuclear reaction are known, we can identify the
particle by balancing the reaction. For instance, we could determine that O is a product of the nuclear reaction of N and He if
17
8
14
7
4
2
we knew that a proton, H, was one of the two products. Example 21.4 shows how we can identify a nuclide by balancing the
1
1
nuclear reaction.
21.3.0.1: Example 21.4

21.3.0.0.1: Balancing Equations for Nuclear Reactions
The reaction of an α particle with magnesium-25 ( 25
12
Mg) produces a proton and a nuclide of another element. Identify the new
nuclide produced.
The nuclear reaction can be written as:
25 4 1 A
Mg + He ⟶ H+ X
12 2 1 Z
where A is the mass number and Z is the atomic number of the new nuclide, X. Because the sum of the mass numbers of the
reactants must equal the sum of the mass numbers of the products:
25 + 4 = A + 1, or A = 28
Similarly, the charges must balance, so:

12 + 2 = Z + 1, and Z = 13
Check the periodic table: The element with nuclear charge = +13 is aluminum. Thus, the product is 28
13
Al.

The nuclide I combines with an electron and produces a new nucleus and no other massive particles. What is the equation
125
53
for this reaction?
21.3.0.1: Answer:
125 0 125
I+ e ⟶ Te
53 −1 52
Following are the equations of several nuclear reactions that have important roles in the history of nuclear chemistry:
The first naturally occurring unstable element that was isolated, polonium, was discovered by the Polish scientist Marie Curie
and her husband Pierre in 1898. It decays, emitting α particles:
212 208 4
Po ⟶ Pb + He
84 82 2
The first nuclide to be prepared by artificial means was an isotope of oxygen, 17O. It was made by Ernest Rutherford in 1919 by
bombarding nitrogen atoms with α particles:
14 4 17 1
N+ He ⟶ O+ H
7 2 8 1

James Chadwick discovered the neutron in 1932, as a previously unknown neutral particle produced along with 12C by the
nuclear reaction between 9Be and 4He:
9 4 12 1
Be + He ⟶ C+ n
4 2 6 0
The first element to be prepared that does not occur naturally on the earth, technetium, was created by bombardment of
molybdenum by deuterons (heavy hydrogen, H), by Emilio Segre and Carlo Perrier in 1937:
2
1
2 97 1 97
H+ Mo ⟶ 2 n + Tc
1 42 0 43
The first controlled nuclear chain reaction was carried out in a reactor at the University of Chicago in 1942. One of the many
reactions involved was:
235 1 87 146 1
U+ n ⟶ Br + La + 3 n
92 0 35 57 0
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Recognize common modes of radioactive decay
Identify common particles and energies involved in nuclear decay reactions
Write and balance nuclear decay equations
Calculate kinetic parameters for decay processes, including half-life
Describe common radiometric dating techniques
Following the somewhat serendipitous discovery of radioactivity by Becquerel, many prominent scientists began to investigate this
new, intriguing phenomenon. Among them were Marie Curie (the first woman to win a Nobel Prize, and the only person to win two
Nobel Prizes in different sciences—chemistry and physics), who was the first to coin the term “radioactivity,” and Ernest
Rutherford (of gold foil experiment fame), who investigated and named three of the most common types of radiation. During the
beginning of the twentieth century, many radioactive substances were discovered, the properties of radiation were investigated and
quantified, and a solid understanding of radiation and nuclear decay was developed.
The spontaneous change of an unstable nuclide into another is radioactive decay. The unstable nuclide is called the parent nuclide;
the nuclide that results from the decay is known as the daughter nuclide. The daughter nuclide may be stable, or it may decay itself.
The radiation produced during radioactive decay is such that the daughter nuclide lies closer to the band of stability than the parent
nuclide, so the location of a nuclide relative to the band of stability can serve as a guide to the kind of decay it will undergo (Figure
21.5).
Figure 21.5 A nucleus of uranium-238 (the parent nuclide) undergoes α decay to form thorium-234 (the daughter nuclide). The
alpha particle removes two protons (green) and two neutrons (gray) from the uranium-238 nucleus.

Although the radioactive decay of a nucleus is too small to see with the naked eye, we can indirectly view radioactive decay in
an environment called a cloud chamber. Click here to learn about cloud chambers and to view an interesting Cloud Chamber
Demonstration from the Jefferson Lab.
21.4.0.1: Types of Radioactive Decay

Ernest Rutherford’s experiments involving the interaction of radiation with a magnetic or electric field (Figure 21.6) helped him
determine that one type of radiation consisted of positively charged and relatively massive α particles; a second type was made up
of negatively charged and much less massive β particles; and a third was uncharged electromagnetic waves, γ rays. We now know
that α particles are high-energy helium nuclei, β particles are high-energy electrons, and γ radiation compose high-energy
electromagnetic radiation. We classify different types of radioactive decay by the radiation produced.

Figure 21.6 Alpha particles, which are attracted to the negative plate and deflected by a relatively small amount, must be positively
charged and relatively massive. Beta particles, which are attracted to the positive plate and deflected a relatively large amount,
must be negatively charged and relatively light. Gamma rays, which are unaffected by the electric field, must be uncharged.
Alpha (α) decay is the emission of an α particle from the nucleus. For example, polonium-210 undergoes α decay:
210 4 206 210 4 206
Po ⟶ He + Pb or Po ⟶ α+ Pb
84 2 82 84 2 82
Alpha decay occurs primarily in heavy nuclei (A > 200, Z > 83). Because the loss of an α particle gives a daughter nuclide with a
mass number four units smaller and an atomic number two units smaller than those of the parent nuclide, the daughter nuclide has a
larger n:p ratio than the parent nuclide. If the parent nuclide undergoing α decay lies below the band of stability (refer to Figure
21.2), the daughter nuclide will lie closer to the band.
Beta (β) decay is the emission of an electron from a nucleus. Iodine-131 is an example of a nuclide that undergoes β decay:
131 0 131 131 0 131
I ⟶ e+ Xe or I ⟶ β+ Xe
53 −1 54 53 −1 54
Beta decay, which can be thought of as the conversion of a neutron into a proton and a β particle, is observed in nuclides with a
large n:p ratio. The beta particle (electron) emitted is from the atomic nucleus and is not one of the electrons surrounding the
nucleus. Such nuclei lie above the band of stability. Emission of an electron does not change the mass number of the nuclide but
does increase the number of its protons and decrease the number of its neutrons. Consequently, the n:p ratio is decreased, and the
daughter nuclide lies closer to the band of stability than did the parent nuclide.
Gamma emission (γ emission) is observed when a nuclide is formed in an excited state and then decays to its ground state with the
emission of a γ ray, a quantum of high-energy electromagnetic radiation. The presence of a nucleus in an excited state is often
indicated by an asterisk (*). Cobalt-60 emits γ radiation and is used in many applications including cancer treatment:
60 0 60
Co* ⟶ γ+ Co
27 0 27
There is no change in mass number or atomic number during the emission of a γ ray unless the γ emission accompanies one of the
other modes of decay.
Positron emission (β+ decay) is the emission of a positron from the nucleus. Oxygen-15 is an example of a nuclide that undergoes
positron emission:
15 0 15 15 0 15
O ⟶ e+ N or O ⟶ β+ N
8 +1 7 8 +1 7
Positron emission is observed for nuclides in which the n:p ratio is low. These nuclides lie below the band of stability. Positron
decay is the conversion of a proton into a neutron with the emission of a positron. The n:p ratio increases, and the daughter nuclide
lies closer to the band of stability than did the parent nuclide.

Electron capture occurs when one of the inner electrons in an atom is captured by the atom’s nucleus. For example, potassium-40
undergoes electron capture:
40 0 40
K+ e ⟶ Ar
19 −1 18
Electron capture occurs when an inner shell electron combines with a proton and is converted into a neutron. The loss of an inner
shell electron leaves a vacancy that will be filled by one of the outer electrons. As the outer electron drops into the vacancy, it will
emit energy. In most cases, the energy emitted will be in the form of an X-ray. Like positron emission, electron capture occurs for
“proton-rich” nuclei that lie below the band of stability. Electron capture has the same effect on the nucleus as does positron
emission: The atomic number is decreased by one and the mass number does not change. This increases the n:p ratio, and the
daughter nuclide lies closer to the band of stability than did the parent nuclide. Whether electron capture or positron emission
occurs is difficult to predict. The choice is primarily due to kinetic factors, with the one requiring the smaller activation energy
being the one more likely to occur.
Figure 21.7 summarizes these types of decay, along with their equations and changes in atomic and mass numbers.
Figure 21.7 This table summarizes the type, nuclear equation, representation, and any changes in the mass or atomic numbers for
various types of decay.

21.4.0.0.1: PET Scan
Positron emission tomography (PET) scans use radiation to diagnose and track health conditions and monitor medical
treatments by revealing how parts of a patient’s body function (Figure 21.8). To perform a PET scan, a positron-emitting
radioisotope is produced in a cyclotron and then attached to a substance that is used by the part of the body being investigated.
This “tagged” compound, or radiotracer, is then put into the patient (injected via IV or breathed in as a gas), and how it is used
by the tissue reveals how that organ or other area of the body functions.

Figure 21.8 A PET scanner (a) uses radiation to provide an image of how part of a patient’s body functions. The scans it
produces can be used to image a healthy brain (b) or can be used for diagnosing medical conditions such as Alzheimer’s
disease (c). (credit a: modification of work by Jens Maus)
For example, F-18 is produced by proton bombardment of 18O ( O + p ⟶ F + n) and incorporated into a glucose
18
8
1
1
18
9
1
0
analog called fludeoxyglucose (FDG). How FDG is used by the body provides critical diagnostic information; for example,
since cancers use glucose differently than normal tissues, FDG can reveal cancers. The 18F emits positrons that interact with
nearby electrons, producing a burst of gamma radiation. This energy is detected by the scanner and converted into a detailed,
three-dimensional, color image that shows how that part of the patient’s body functions. Different levels of gamma radiation
produce different amounts of brightness and colors in the image, which can then be interpreted by a radiologist to reveal what
is going on. PET scans can detect heart damage and heart disease, help diagnose Alzheimer’s disease, indicate the part of a
brain that is affected by epilepsy, reveal cancer, show what stage it is, and how much it has spread, and whether treatments are
effective. Unlike magnetic resonance imaging and X-rays, which only show how something looks, the big advantage of PET
scans is that they show how something functions. PET scans are now usually performed in conjunction with a computed
tomography scan.
21.4.0.1: Radioactive Decay Series

The naturally occurring radioactive isotopes of the heaviest elements fall into chains of successive disintegrations, or decays, and
all the species in one chain constitute a radioactive family, or radioactive decay series. Three of these series include most of the
naturally radioactive elements of the periodic table. They are the uranium series, the actinide series, and the thorium series. The
neptunium series is a fourth series, which is no longer significant on the earth because of the short half-lives of the species
involved. Each series is characterized by a parent (first member) that has a long half-life and a series of daughter nuclides that
ultimately lead to a stable end-product—that is, a nuclide on the band of stability (Figure 21.9). In all three series, the end-product
is a stable isotope of lead. The neptunium series, previously thought to terminate with bismuth-209, terminates with thallium-205.

Figure 21.9 Uranium-238 undergoes a radioactive decay series consisting of 14 separate steps before producing stable lead-206.
This series consists of eight α decays and six β decays.
21.4.0.1: Radioactive Half-Lives

Radioactive decay follows first-order kinetics. Since first-order reactions have already been covered in detail in the kinetics
chapter, we will now apply those concepts to nuclear decay reactions. Each radioactive nuclide has a characteristic, constant half-
life (t1/2), the time required for half of the atoms in a sample to decay. An isotope’s half-life allows us to determine how long a
sample of a useful isotope will be available, and how long a sample of an undesirable or dangerous isotope must be stored before it
decays to a low-enough radiation level that is no longer a problem.

For example, cobalt-60, an isotope that emits gamma rays used to treat cancer, has a half-life of 5.27 years (Figure 21.10). In a
given cobalt-60 source, since half of the Co nuclei decay every 5.27 years, both the amount of material and the intensity of the
60
27
radiation emitted is cut in half every 5.27 years. (Note that for a given substance, the intensity of radiation that it produces is
directly proportional to the rate of decay of the substance and the amount of the substance.) This is as expected for a process
following first-order kinetics. Thus, a cobalt-60 source that is used for cancer treatment must be replaced regularly to continue to be
effective.
Figure 21.10 For cobalt-60, which has a half-life of 5.27 years, 50% remains after 5.27 years (one half-life), 25% remains after
10.54 years (two half-lives), 12.5% remains after 15.81 years (three half-lives), and so on.
Since nuclear decay follows first-order kinetics, we can adapt the mathematical relationships used for first-order chemical
reactions. We generally substitute the number of nuclei, N, for the concentration. If the rate is stated in nuclear decays per second,
we refer to it as the activity of the radioactive sample. The rate for radioactive decay is:
decay rate = λN with λ = the decay constant for the particular radioisotope
The decay constant, λ, which is the same as a rate constant discussed in the kinetics chapter. It is possible to express the decay
constant in terms of the half-life, t1/2:
ln 2 0.693 ln 2 0.693
λ = = or t1/2 = =
t1/2 t1/2 λ λ
The first-order equations relating amount, N, and time are:
−λt
1 Nt
Nt = N0 e or t =− ln ( )
λ N0
where N0 is the initial number of nuclei or moles of the isotope, and Nt is the number of nuclei/moles remaining at time t. Example
21.5 applies these calculations to find the rates of radioactive decay for specific nuclides.
21.4.0.1: Example 21.5

21.4.0.0.1: Rates of Radioactive Decay
60
27
Co decays with a half-life of 5.27 years to produce 60
28
Ni.
(a) What is the decay constant for the radioactive disintegration of cobalt-60?
(b) Calculate the fraction of a sample of the 60
27
Co isotope that will remain after 15 years.

(c) How long does it take for a sample of 60
27
Co to disintegrate to the extent that only 2.0% of the original amount remains?
(a) The value of the rate constant is given by:
ln 2 0.693 −1
λ = = = 0.132 y
t1/2 5.27 y
Rearranging the first-order relationship Nt = N0e–λt to solve for

Nt
(b) The fraction of 60
27
Co that is left after time t is given by N0
.
this ratio yields:

Nt
−λt −(0.132/y)(15×y)
=e =e = 0.138
N0
The fraction of Co that will remain after 15.0 years is 0.138. Or put another way, 13.8% of the
60
27
60
27
Co originally present will
remain after 15 years.
(c) 2.00% of the original amount of 60
27
Co is equal to 0.0200 × N0. Substituting this into the equation for time for first-order
kinetics, we have:
1 Nt 1 0.0200 × N0
t =− ln ( ) = − ln ( ) = 29.6 y
N0 −1 N0
λ 0.132 y

Radon-222, Rn, has a half-life of 3.823 days. How long will it take a sample of radon-222 with a mass of 0.750 g to decay
222
86
into other elements, leaving only 0.100 g of radon-222?
21.4.0.1: Answer:
11.1 days
Because each nuclide has a specific number of nucleons, a particular balance of repulsion and attraction, and its own degree of
stability, the half-lives of radioactive nuclides vary widely. For example: the half-life of Bi is 1.9 × 10
19 years;
209
Ra is 24,000
239
83 94
–3
years; 222
86
Rn is 3.82 days; and element-111 (Rg for roentgenium) is 1.5 × 10 seconds. The half-lives of a number of radioactive
isotopes important to medicine are shown in Table 21.2, and others are listed in Appendix M.
Half-lives of Radioactive Isotopes Important to Medicine
Type1 Decay Mode Half-Life Uses
F-18 β+ decay 110. minutes PET scans
Co-60 β decay, γ decay 5.27 years cancer treatment
Tc-99m γ decay 8.01 hours scans of brain, lung, heart, bone
I-131 β decay 8.02 days thyroid scans and treatment
Tl-201 electron capture 73 hours heart and arteries scans; cardiac stress tests
Table 21.2
21.4.0.1: Radiometric Dating

Several radioisotopes have half-lives and other properties that make them useful for purposes of “dating” the origin of objects such
as archaeological artifacts, formerly living organisms, or geological formations. This process is radiometric dating and has been
responsible for many breakthrough scientific discoveries about the geological history of the earth, the evolution of life, and the
history of human civilization. We will explore some of the most common types of radioactive dating and how the particular
isotopes work for each type.

21.4.0.0.1: Radioactive Dating Using Carbon-14
The radioactivity of carbon-14 provides a method for dating objects that were a part of a living organism. This method of
radiometric dating, which is also called radiocarbon dating or carbon-14 dating, is accurate for dating carbon-containing substances
that are up to about 30,000 years old, and can provide reasonably accurate dates up to a maximum of about 50,000 years old.
Naturally occurring carbon consists of three isotopes: C, which constitutes about 99% of the carbon on earth; C, about 1% of
12
6
13
6
the total; and trace amounts of C. Carbon-14 forms in the upper atmosphere by the reaction of nitrogen atoms with neutrons
14
6
from cosmic rays in space:

14 1 14 1
N+ n ⟶ C+ H
7 0 6 1
All isotopes of carbon react with oxygen to produce CO2 molecules. The ratio of C O to C O depends on the ratio of CO
14
6 2
12
6 2
14
6
to CO in the atmosphere. The natural abundance of CO in the atmosphere is approximately 1 part per trillion; until recently,
12
6
14
6
this has generally been constant over time, as seen is gas samples found trapped in ice. The incorporation of C C O and 14
6
14
6 2
C O into plants is a regular part of the photosynthesis process, which means that the C ratio found in a living plant is the
12 14 12
2 C:
6 6 6
same as the C: C ratio in the atmosphere. But when the plant dies, it no longer traps carbon through photosynthesis. Because
14
6
12
6
C is a stable isotope and does not undergo radioactive decay, its concentration in the plant does not change. However, carbon-14
12
6
decays by β emission with a half-life of 5730 years:

14 14 0
C ⟶ N+ e
6 7 −1
Thus, the C: C ratio gradually decreases after the plant dies. The decrease in the ratio with time provides a measure of the time
14
6
12
6
that has elapsed since the death of the plant (or other organism that ate the plant). Figure 21.11 visually depicts this process.

Figure 21.11 Along with stable carbon-12, radioactive carbon-14 is taken in by plants and animals, and remains at a constant level
within them while they are alive. After death, the C-14 decays and the C-14:C-12 ratio in the remains decreases. Comparing this
ratio to the C-14:C-12 ratio in living organisms allows us to determine how long ago the organism lived (and died).
For example, with the half-life of C being 5730 years, if the C: C ratio in a wooden object found in an archaeological dig is
14
6
14
6
12
6
half what it is in a living tree, this indicates that the wooden object is 5730 years old. Highly accurate determinations of C: C 14
6
12
6
ratios can be obtained from very small samples (as little as a milligram) by the use of a mass spectrometer.

Visit this website to perform simulations of radiometric dating.
21.4.0.1: Example 21.6

21.4.0.0.2: Radiocarbon Dating
A tiny piece of paper (produced from formerly living plant matter) taken from the Dead Sea Scrolls has an activity of 10.8
disintegrations per minute per gram of carbon. If the initial C-14 activity was 13.6 disintegrations/min/g of C, estimate the age
of the Dead Sea Scrolls.
The rate of decay (number of disintegrations/minute/gram of carbon) is proportional to the amount of radioactive C-14 left in
the paper, so we can substitute the rates for the amounts, N, in the relationship:
1 Nt 1 Ratet
t =− ln ( ) ⟶ t =− ln ( )
λ N0 λ Rate0
where the subscript 0 represents the time when the plants were cut to make the paper, and the subscript t represents the current
time.
The decay constant can be determined from the half-life of C-14, 5730 years:
ln 2 0.693
−4 −1
λ = = = 1.21 × 10 y
t1/2 5730 y
Substituting and solving, we have:
1 Ratet 1 10.8 dis/min/g C

t =− ln ( ) = − ln ( ) = 1910 y
−4
λ Rate0 1.21 × 10 −1
y 13.6 dis/min/g C
Therefore, the Dead Sea Scrolls are approximately 1900 years old (Figure 21.12).

Figure 21.12 Carbon-14 dating has shown that these pages from the Dead Sea Scrolls were written or copied on paper made
from plants that died between 100 BC and AD 50.
More accurate dates of the reigns of ancient Egyptian pharaohs have been determined recently using plants that were preserved
in their tombs. Samples of seeds and plant matter from King Tutankhamun’s tomb have a C-14 decay rate of 9.07
disintegrations/min/g of C. How long ago did King Tut’s reign come to an end?
21.4.0.1: Answer:
about 3350 years ago, or approximately 1340 BC
There have been some significant, well-documented changes to the C: C ratio. The accuracy of a straightforward application
14
6
12
6
of this technique depends on the C: C ratio in a living plant being the same now as it was in an earlier era, but this is not
14
6
12
6
always valid. Due to the increasing accumulation of CO2 molecules (largely C O ) in the atmosphere caused by combustion of
12
6 2
fossil fuels (in which essentially all of the C has decayed), the ratio of C: C in the atmosphere may be changing. This
14
6
14
6
12
6
manmade increase in C O in the atmosphere causes the C: C ratio to decrease, and this in turn affects the ratio in currently
12
6 2
14
6
12
6
living organisms on the earth. Fortunately, however, we can use other data, such as tree dating via examination of annual growth
rings, to calculate correction factors. With these correction factors, accurate dates can be determined. In general, radioactive dating
only works for about 10 half-lives; therefore, the limit for carbon-14 dating is about 57,000 years.
21.4.0.0.5: Radioactive Dating Using Nuclides Other than Carbon-14
Radioactive dating can also use other radioactive nuclides with longer half-lives to date older events. For example, uranium-238
(which decays in a series of steps into lead-206) can be used for establishing the age of rocks (and the approximate age of the oldest
rocks on earth). Since U-238 has a half-life of 4.5 billion years, it takes that amount of time for half of the original U-238 to decay
into Pb-206. In a sample of rock that does not contain appreciable amounts of Pb-208, the most abundant isotope of lead, we can
assume that lead was not present when the rock was formed. Therefore, by measuring and analyzing the ratio of U-238:Pb-206, we
can determine the age of the rock. This assumes that all of the lead-206 present came from the decay of uranium-238. If there is
additional lead-206 present, which is indicated by the presence of other lead isotopes in the sample, it is necessary to make an
adjustment. Potassium-argon dating uses a similar method. K-40 decays by positron emission and electron capture to form Ar-40
with a half-life of 1.25 billion years. If a rock sample is crushed and the amount of Ar-40 gas that escapes is measured,
determination of the Ar-40:K-40 ratio yields the age of the rock. Other methods, such as rubidium-strontium dating (Rb-87 decays
into Sr-87 with a half-life of 48.8 billion years), operate on the same principle. To estimate the lower limit for the earth’s age,
scientists determine the age of various rocks and minerals, making the assumption that the earth is older than the oldest rocks and
minerals in its crust. As of 2014, the oldest known rocks on earth are the Jack Hills zircons from Australia, found by uranium-lead
dating to be almost 4.4 billion years old.
21.4.0.1: Example 21.7

21.4.0.0.6: Radioactive Dating of Rocks
An igneous rock contains 9.58 × 10–5 g of U-238 and 2.51 × 10–5 g of Pb-206, and much, much smaller amounts of Pb-208.
Determine the approximate time at which the rock formed.
The sample of rock contains very little Pb-208, the most common isotope of lead, so we can safely assume that all the Pb-206
in the rock was produced by the radioactive decay of U-238. When the rock formed, it contained all of the U-238 currently in
it, plus some U-238 that has since undergone radioactive decay.

The amount of U-238 currently in the rock is:
⎛ 1 mol U ⎞
−5 −7
9.58 × 10 g U × = 4.03 × 10 mol U
⎝ 238 g U ⎠
Because when one mole of U-238 decays, it produces one mole of Pb-206, the amount of U-238 that has undergone radioactive
decay since the rock was formed is:
⎛ 1 mol Pb ⎞ 1 mol U
−5 −7
2.51 × 10 g Pb × × ( ) = 1.22 × 10 mol U
⎝ 206 g Pb ⎠ 1 mol Pb
The total amount of U-238 originally present in the rock is therefore:

−7 −7 −7
4.03 × 10 mol + 1.22 × 10 mol = 5.25 × 10 mol U
The amount of time that has passed since the formation of the rock is given by:
1 Nt
t = − ln ( )
λ N0
with N0 representing the original amount of U-238 and Nt representing the present amount of U-238.
U-238 decays into Pb-206 with a half-life of 4.5 × 109 y, so the decay constant λ is:
ln 2 0.693 −10 −1
λ = = = 1.54 × 10 y
9
t1/2 4.5 × 10 y
Substituting and solving, we have:

−7
1 4.03 × 10 mol U
9
t = − ln ( ) = 1.7 × 10 y
−10 −1 −7
1.54 × 10 y 5.25 × 10 mol U
Therefore, the rock is approximately 1.7 billion years old.

A sample of rock contains 6.14 × 10–4 g of Rb-87 and 3.51 × 10–5 g of Sr-87. Calculate the age of the rock. (The half-life of
the β decay of Rb-87 is 4.7 × 1010 y.)
21.4.0.1: Answer:
3.7 × 109 y
21.4.0.1: Footnotes
1The “m” in Tc-99m stands for “metastable,” indicating that this is an unstable, high-energy state of Tc-99. Metastable isotopes
emit γ radiation to rid themselves of excess energy and become (more) stable.
This page titled 21.4: Radioactive Decay is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via source


Describe the synthesis of transuranium nuclides
Explain nuclear fission and fusion processes
Relate the concepts of critical mass and nuclear chain reactions
Summarize basic requirements for nuclear fission and fusion reactors
After the discovery of radioactivity, the field of nuclear chemistry was created and developed rapidly during the early twentieth
century. A slew of new discoveries in the 1930s and 1940s, along with World War II, combined to usher in the Nuclear Age in the
mid-twentieth century. Scientists learned how to create new substances, and certain isotopes of certain elements were found to
possess the capacity to produce unprecedented amounts of energy, with the potential to cause tremendous damage during war, as
well as produce enormous amounts of power for society’s needs during peace.
21.5.0.1: Synthesis of Nuclides

Nuclear transmutation is the conversion of one nuclide into another. It can occur by the radioactive decay of a nucleus, or the
reaction of a nucleus with another particle. The first manmade nucleus was produced in Ernest Rutherford’s laboratory in 1919 by a
transmutation reaction, the bombardment of one type of nuclei with other nuclei or with neutrons. Rutherford bombarded nitrogen
atoms with high-speed α particles from a natural radioactive isotope of radium and observed protons resulting from the reaction:
14 4 17 1
N+ He ⟶ O+ H
7 2 8 1
The 17
8
O and 1
1
H nuclei that are produced are stable, so no further (nuclear) changes occur.
To reach the kinetic energies necessary to produce transmutation reactions, devices called particle accelerators are used. These
devices use magnetic and electric fields to increase the speeds of nuclear particles. In all accelerators, the particles move in a
vacuum to avoid collisions with gas molecules. When neutrons are required for transmutation reactions, they are usually obtained
from radioactive decay reactions or from various nuclear reactions occurring in nuclear reactors. The Chemistry in Everyday Life
feature that follows discusses a famous particle accelerator that made worldwide news.

21.5.0.0.1: CERN Particle Accelerator
Located near Geneva, the CERN (“Conseil Européen pour la Recherche Nucléaire,” or European Council for Nuclear
Research) Laboratory is the world’s premier center for the investigations of the fundamental particles that make up matter. It
contains the 27-kilometer (17 mile) long, circular Large Hadron Collider (LHC), the largest particle accelerator in the world
(Figure 21.13). In the LHC, particles are boosted to high energies and are then made to collide with each other or with
stationary targets at nearly the speed of light. Superconducting electromagnets are used to produce a strong magnetic field that
guides the particles around the ring. Specialized, purpose-built detectors observe and record the results of these collisions,
which are then analyzed by CERN scientists using powerful computers.

Figure 21.13 A small section of the LHC is shown with workers traveling along it. (credit: Christophe Delaere)
In 2012, CERN announced that experiments at the LHC showed the first observations of the Higgs boson, an elementary
particle that helps explain the origin of mass in fundamental particles. This long-anticipated discovery made worldwide news
and resulted in the awarding of the 2013 Nobel Prize in Physics to François Englert and Peter Higgs, who had predicted the
existence of this particle almost 50 years previously.

Famous physicist Brian Cox talks about his work on the Large Hadron Collider at CERN, providing an entertaining and
engaging tour of this massive project and the physics behind it.
View a short video from CERN, describing the basics of how its particle accelerators work.
Prior to 1940, the heaviest-known element was uranium, whose atomic number is 92. Now, many artificial elements have been
synthesized and isolated, including several on such a large scale that they have had a profound effect on society. One of these—
element 93, neptunium (Np)—was first made in 1940 by McMillan and Abelson by bombarding uranium-238 with neutrons. The
reaction creates unstable uranium-239, with a half-life of 23.5 minutes, which then decays into neptunium-239. Neptunium-239 is
also radioactive, with a half-life of 2.36 days, and it decays into plutonium-239. The nuclear reactions are:

238 1 239
U+ n ⟶ U
92 0 92
239 239 0
U ⟶ Np + e half-life = 23.5 min
92 93 −1
239 239 0
Np ⟶ Pu + e half-life = 2.36 days
93 94 −1
Plutonium is now mostly formed in nuclear reactors as a byproduct during the fission of U-235. Additional neutrons are released
during this fission process (see the next section), some of which combine with U-238 nuclei to form uranium-239; this undergoes β
decay to form neptunium-239, which in turn undergoes β decay to form plutonium-239 as illustrated in the preceding three
equations. These processes are summarized in the equation:
− −
β β
238 1 239 239 239
U+ n ⟶ U −→
− Np −→
− Pu
92 0 92 93 94
Heavier isotopes of plutonium—Pu-240, Pu-241, and Pu-242—are also produced when lighter plutonium nuclei capture neutrons.
Some of this highly radioactive plutonium is used to produce military weapons, and the rest presents a serious storage problem
because they have half-lives from thousands to hundreds of thousands of years.
Although they have not been prepared in the same quantity as plutonium, many other synthetic nuclei have been produced. Nuclear
medicine has developed from the ability to convert atoms of one type into other types of atoms. Radioactive isotopes of several
dozen elements are currently used for medical applications. The radiation produced by their decay is used to image or treat various
organs or portions of the body, among other uses.
The elements beyond element 92 (uranium) are called transuranium elements. As of this writing, 22 transuranium elements have
been produced and officially recognized by IUPAC; several other elements have formation claims that are waiting for approval.
Some of these elements are shown in Table 21.3.
Preparation of Some of the Transuranium Elements
Name Symbol Atomic Number Reaction
americium Am 95 239
94
Pu +
1
0
n ⟶
240
95
Am +
−1
0
e
curium Cm 96 239
94
Pu +
4
2
He ⟶
242
96
Cm +
1
0
n
californium Cf 98 242
96
Cm +
4
2
He ⟶
245
98
Cf +
1
0
n
einsteinium Es 99 238
92
U + 15 n ⟶
1
0
253
99
Es + 7
−1
0
e
mendelevium Md 101 253

99
Es +
4
2
He ⟶
256
101
Md +
1
0
n
nobelium No 102 246

96
Cm +
12
6
C ⟶
254
102
No + 4 n
1
0
rutherfordium Rf 104 249

98
Cf +
12
6
C ⟶
257
104
Rf + 4 n
1
0
seaborgium Sg 106 206

82
Pb +
54
24
Cr ⟶
257
106
Sg + 3 n
1
0
249 18 263 1
Cf + O ⟶ Sg + 4 n
98 8 106 0
meitnerium Mt 107 209

83
Bi +
58
26
Fe ⟶
266
109
Mt +
1
0
n
Table 21.3

21.5.0.1: Nuclear Fission
Many heavier elements with smaller binding energies per nucleon can decompose into more stable elements that have intermediate
mass numbers and larger binding energies per nucleon—that is, mass numbers and binding energies per nucleon that are closer to
the “peak” of the binding energy graph near 56 (see Figure 21.3). Sometimes neutrons are also produced. This decomposition is
called fission, the breaking of a large nucleus into smaller pieces. The breaking is rather random with the formation of a large
number of different products. Fission usually does not occur naturally, but is induced by bombardment with neutrons. The first
reported nuclear fission occurred in 1939 when three German scientists, Lise Meitner, Otto Hahn, and Fritz Strassman, bombarded
uranium-235 atoms with slow-moving neutrons that split the U-238 nuclei into smaller fragments that consisted of several neutrons
and elements near the middle of the periodic table. Since then, fission has been observed in many other isotopes, including most
actinide isotopes that have an odd number of neutrons. A typical nuclear fission reaction is shown in Figure 21.14.
Figure 21.14 When a slow neutron hits a fissionable U-235 nucleus, it is absorbed and forms an unstable U-236 nucleus. The U-
236 nucleus then rapidly breaks apart into two smaller nuclei (in this case, Ba-141 and Kr-92) along with several neutrons (usually
two or three), and releases a very large amount of energy.
Among the products of Meitner, Hahn, and Strassman’s fission reaction were barium, krypton, lanthanum, and cerium, all of which
have nuclei that are more stable than uranium-235. Since then, hundreds of different isotopes have been observed among the
products of fissionable substances. A few of the many reactions that occur for U-235, and a graph showing the distribution of its
fission products and their yields, are shown in Figure 21.15. Similar fission reactions have been observed with other uranium
isotopes, as well as with a variety of other isotopes such as those of plutonium.

Figure 21.15 (a) Nuclear fission of U-235 produces a range of fission products. (b) The larger fission products of U-235 are
typically one isotope with a mass number around 85–105, and another isotope with a mass number that is about 50% larger, that is,
about 130–150.

View this link to see a simulation of nuclear fission.
A tremendous amount of energy is produced by the fission of heavy elements. For instance, when one mole of U-235 undergoes
fission, the products weigh about 0.2 grams less than the reactants; this “lost” mass is converted into a very large amount of energy,
about 1.8 × 1010 kJ per mole of U-235. Nuclear fission reactions produce incredibly large amounts of energy compared to
chemical reactions. The fission of 1 kilogram of uranium-235, for example, produces about 2.5 million times as much energy as is
produced by burning 1 kilogram of coal.
As described earlier, when undergoing fission U-235 produces two “medium-sized” nuclei, and two or three neutrons. These
neutrons may then cause the fission of other uranium-235 atoms, which in turn provide more neutrons that can cause fission of
even more nuclei, and so on. If this occurs, we have a nuclear chain reaction (see Figure 21.16). On the other hand, if too many
neutrons escape the bulk material without interacting with a nucleus, then no chain reaction will occur.

Figure 21.16 The fission of a large nucleus, such as U-235, produces two or three neutrons, each of which is capable of causing
fission of another nucleus by the reactions shown. If this process continues, a nuclear chain reaction occurs.
Material that can sustain a nuclear fission chain reaction is said to be fissile or fissionable. (Technically, fissile material can
undergo fission with neutrons of any energy, whereas fissionable material requires high-energy neutrons.) Nuclear fission becomes
self-sustaining when the number of neutrons produced by fission equals or exceeds the number of neutrons absorbed by splitting
nuclei plus the number that escape into the surroundings. The amount of a fissionable material that will support a self-sustaining
chain reaction is a critical mass. An amount of fissionable material that cannot sustain a chain reaction is a subcritical mass. An
amount of material in which there is an increasing rate of fission is known as a supercritical mass. The critical mass depends on the
type of material: its purity, the temperature, the shape of the sample, and how the neutron reactions are controlled (Figure 21.17).

Figure 21.17 (a) In a subcritical mass, the fissile material is too small and allows too many neutrons to escape the material, so a
chain reaction does not occur. (b) In a critical mass, a large enough number of neutrons in the fissile material induce fission to
create a chain reaction.
An atomic bomb (Figure 21.18) contains several pounds of fissionable material, U or
235
92
Pu, a source of neutrons, and an
239
94
explosive device for compressing it quickly into a small volume. When fissionable material is in small pieces, the proportion of
neutrons that escape through the relatively large surface area is great, and a chain reaction does not take place. When the small
pieces of fissionable material are brought together quickly to form a body with a mass larger than the critical mass, the relative
number of escaping neutrons decreases, and a chain reaction and explosion result.

Figure 21.18 (a) The nuclear fission bomb that destroyed Hiroshima on August 6, 1945, consisted of two subcritical masses of U-
235, where conventional explosives were used to fire one of the subcritical masses into the other, creating the critical mass for the
nuclear explosion. (b) The plutonium bomb that destroyed Nagasaki on August 9, 1945, consisted of a hollow sphere of plutonium
that was rapidly compressed by conventional explosives. This led to a concentration of plutonium in the center that was greater
than the critical mass necessary for the nuclear explosion.
21.5.0.0.1: Fission Reactors
Chain reactions of fissionable materials can be controlled and sustained without an explosion in a nuclear reactor (Figure 21.19).
Any nuclear reactor that produces power via the fission of uranium or plutonium by bombardment with neutrons must have at least
five components: nuclear fuel consisting of fissionable material, a nuclear moderator, reactor coolant, control rods, and a shield and
containment system. We will discuss these components in greater detail later in the section. The reactor works by separating the
fissionable nuclear material such that a critical mass cannot be formed, controlling both the flux and absorption of neutrons to
allow shutting down the fission reactions. In a nuclear reactor used for the production of electricity, the energy released by fission
reactions is trapped as thermal energy and used to boil water and produce steam. The steam is used to turn a turbine, which powers
a generator for the production of electricity.

Figure 21.19 (a) The Diablo Canyon Nuclear Power Plant near San Luis Obispo is the only nuclear power plant currently in
operation in California. The domes are the containment structures for the nuclear reactors, and the brown building houses the
turbine where electricity is generated. Ocean water is used for cooling. (b) The Diablo Canyon uses a pressurized water reactor, one
of a few different fission reactor designs in use around the world, to produce electricity. Energy from the nuclear fission reactions
in the core heats water in a closed, pressurized system. Heat from this system produces steam that drives a turbine, which in turn
produces electricity. (credit a: modification of work by “Mike” Michael L. Baird; credit b: modification of work by the Nuclear
Regulatory Commission)
21.5.0.1: Nuclear Fuels

Nuclear fuel consists of a fissionable isotope, such as uranium-235, which must be present in sufficient quantity to provide a self-
sustaining chain reaction. In the United States, uranium ores contain from 0.05–0.3% of the uranium oxide U3O8; the uranium in
the ore is about 99.3% nonfissionable U-238 with only 0.7% fissionable U-235. Nuclear reactors require a fuel with a higher
concentration of U-235 than is found in nature; it is normally enriched to have about 5% of uranium mass as U-235. At this
concentration, it is not possible to achieve the supercritical mass necessary for a nuclear explosion. Uranium can be enriched by
gaseous diffusion (the only method currently used in the US), using a gas centrifuge, or by laser separation.
In the gaseous diffusion enrichment plant where U-235 fuel is prepared, UF6 (uranium hexafluoride) gas at low pressure moves
through barriers that have holes just barely large enough for UF6 to pass through. The slightly lighter 235UF6 molecules diffuse
through the barrier slightly faster than the heavier 238UF6 molecules. This process is repeated through hundreds of barriers,
gradually increasing the concentration of 235UF6 to the level needed by the nuclear reactor. The basis for this process, Graham’s
law, is described in the chapter on gases. The enriched UF6 gas is collected, cooled until it solidifies, and then taken to a fabrication
facility where it is made into fuel assemblies. Each fuel assembly consists of fuel rods that contain many thimble-sized, ceramic-
encased, enriched uranium (usually UO2) fuel pellets. Modern nuclear reactors may contain as many as 10 million fuel pellets. The
amount of energy in each of these pellets is equal to that in almost a ton of coal or 150 gallons of oil.
21.5.0.1: Nuclear Moderators

Neutrons produced by nuclear reactions move too fast to cause fission (refer back to Figure 21.17). They must first be slowed to be
absorbed by the fuel and produce additional nuclear reactions. A nuclear moderator is a substance that slows the neutrons to a
speed that is low enough to cause fission. Early reactors used high-purity graphite as a moderator. Modern reactors in the US
exclusively use heavy water ( H O) or light water (ordinary H2O), whereas some reactors in other countries use other materials,
2
1 2
such as carbon dioxide, beryllium, or graphite.

21.5.0.1: Reactor Coolants
A nuclear reactor coolant is used to carry the heat produced by the fission reaction to an external boiler and turbine, where it is
transformed into electricity. Two overlapping coolant loops are often used; this counteracts the transfer of radioactivity from the
reactor to the primary coolant loop. All nuclear power plants in the US use water as a coolant. Other coolants include molten
sodium, lead, a lead-bismuth mixture, or molten salts.
21.5.0.1: Control Rods

Nuclear reactors use control rods (Figure 21.20) to control the fission rate of the nuclear fuel by adjusting the number of slow
neutrons present to keep the rate of the chain reaction at a safe level. Control rods are made of boron, cadmium, hafnium, or other
elements that are able to absorb neutrons. Boron-10, for example, absorbs neutrons by a reaction that produces lithium-7 and alpha
particles:
10 1 7 4
B+ n ⟶ Li + He
5 0 3 2
When control rod assemblies are inserted into the fuel element in the reactor core, they absorb a larger fraction of the slow
neutrons, thereby slowing the rate of the fission reaction and decreasing the power produced. Conversely, if the control rods are
removed, fewer neutrons are absorbed, and the fission rate and energy production increase. In an emergency, the chain reaction can
be shut down by fully inserting all of the control rods into the nuclear core between the fuel rods.

Figure 21.20 The nuclear reactor core shown in (a) contains the fuel and control rod assembly shown in (b). (credit: modification of
work by E. Generalic, http://glossary.periodni.com/glossar...en=control+rod)
21.5.0.1: Shield and Containment System

During its operation, a nuclear reactor produces neutrons and other radiation. Even when shut down, the decay products are
radioactive. In addition, an operating reactor is thermally very hot, and high pressures result from the circulation of water or
another coolant through it. Thus, a reactor must withstand high temperatures and pressures, and must protect operating personnel
from the radiation. Reactors are equipped with a containment system (or shield) that consists of three parts:
1. The reactor vessel, a steel shell that is 3–20-centimeters thick and, with the moderator, absorbs much of the radiation produced
by the reactor
2. A main shield of 1–3 meters of high-density concrete
3. A personnel shield of lighter materials that protects operators from γ rays and X-rays
In addition, reactors are often covered with a steel or concrete dome that is designed to contain any radioactive materials might be
released by a reactor accident.

Click here to watch a 3-minute video from the Nuclear Energy Institute on how nuclear reactors work.
Nuclear power plants are designed in such a way that they cannot form a supercritical mass of fissionable material and therefore
cannot create a nuclear explosion. But as history has shown, failures of systems and safeguards can cause catastrophic accidents,
including chemical explosions and nuclear meltdowns (damage to the reactor core from overheating). The following Chemistry in
Everyday Life feature explores three infamous meltdown incidents.

21.5.0.0.1: Nuclear Accidents
The importance of cooling and containment are amply illustrated by three major accidents that occurred with the nuclear
reactors at nuclear power generating stations in the United States (Three Mile Island), the former Soviet Union (Chernobyl),
and Japan (Fukushima).
In March 1979, the cooling system of the Unit 2 reactor at Three Mile Island Nuclear Generating Station in Pennsylvania
failed, and the cooling water spilled from the reactor onto the floor of the containment building. After the pumps stopped, the
reactors overheated due to the high radioactive decay heat produced in the first few days after the nuclear reactor shut down.
The temperature of the core climbed to at least 2200 °C, and the upper portion of the core began to melt. In addition, the
zirconium alloy cladding of the fuel rods began to react with steam and produced hydrogen:
Zr(s) + 2H2 O(g) ⟶ ZrO 2 (s) + 2H2 (g)
The hydrogen accumulated in the confinement building, and it was feared that there was danger of an explosion of the mixture
of hydrogen and air in the building. Consequently, hydrogen gas and radioactive gases (primarily krypton and xenon) were
vented from the building. Within a week, cooling water circulation was restored and the core began to cool. The plant was
closed for nearly 10 years during the cleanup process.
Although zero discharge of radioactive material is desirable, the discharge of radioactive krypton and xenon, such as occurred
at the Three Mile Island plant, is among the most tolerable. These gases readily disperse in the atmosphere and thus do not
produce highly radioactive areas. Moreover, they are noble gases and are not incorporated into plant and animal matter in the
food chain. Effectively none of the heavy elements of the core of the reactor were released into the environment, and no
cleanup of the area outside of the containment building was necessary (Figure 21.21).

Figure 21.21 (a) In this 2010 photo of Three Mile Island, the remaining structures from the damaged Unit 2 reactor are seen on
the left, whereas the separate Unit 1 reactor, unaffected by the accident, continues generating power to this day (right). (b)
President Jimmy Carter visited the Unit 2 control room a few days after the accident in 1979.
Another major nuclear accident involving a reactor occurred in April 1986, at the Chernobyl Nuclear Power Plant in Ukraine,
which was still a part of the former Soviet Union. While operating at low power during an unauthorized experiment with some
of its safety devices shut off, one of the reactors at the plant became unstable. Its chain reaction became uncontrollable and
increased to a level far beyond what the reactor was designed for. The steam pressure in the reactor rose to between 100 and
500 times the full power pressure and ruptured the reactor. Because the reactor was not enclosed in a containment building, a
large amount of radioactive material spewed out, and additional fission products were released, as the graphite (carbon)
moderator of the core ignited and burned. The fire was controlled, but over 200 plant workers and firefighters developed acute
radiation sickness and at least 32 soon died from the effects of the radiation. It is predicted that about 4000 more deaths will
occur among emergency workers and former Chernobyl residents from radiation-induced cancer and leukemia. The reactor has
since been encapsulated in steel and concrete, a now-decaying structure known as the sarcophagus. Almost 30 years later,
significant radiation problems still persist in the area, and Chernobyl largely remains a wasteland.
In 2011, the Fukushima Daiichi Nuclear Power Plant in Japan was badly damaged by a 9.0-magnitude earthquake and resulting
tsunami. Three reactors up and running at the time were shut down automatically, and emergency generators came online to
power electronics and coolant systems. However, the tsunami quickly flooded the emergency generators and cut power to the
pumps that circulated coolant water through the reactors. High-temperature steam in the reactors reacted with zirconium alloy
to produce hydrogen gas. The gas escaped into the containment building, and the mixture of hydrogen and air exploded.
Radioactive material was released from the containment vessels as the result of deliberate venting to reduce the hydrogen
pressure, deliberate discharge of coolant water into the sea, and accidental or uncontrolled events.
An evacuation zone around the damaged plant extended over 12.4 miles away, and an estimated 200,000 people were
evacuated from the area. All 48 of Japan’s nuclear power plants were subsequently shut down, remaining shuttered as of
December 2014. Since the disaster, public opinion has shifted from largely favoring to largely opposing increasing the use of
nuclear power plants, and a restart of Japan’s atomic energy program is still stalled (Figure 21.22).

Figure 21.22 (a) After the accident, contaminated waste had to be removed, and (b) an evacuation zone was set up around the
plant in areas that received heavy doses of radioactive fallout. (credit a: modification of work by “Live Action Hero”/Flickr)
The energy produced by a reactor fueled with enriched uranium results from the fission of uranium as well as from the fission of
plutonium produced as the reactor operates. As discussed previously, the plutonium forms from the combination of neutrons and
the uranium in the fuel. In any nuclear reactor, only about 0.1% of the mass of the fuel is converted into energy. The other 99.9%
remains in the fuel rods as fission products and unused fuel. All of the fission products absorb neutrons, and after a period of
several months to a few years, depending on the reactor, the fission products must be removed by changing the fuel rods.
Otherwise, the concentration of these fission products would increase and absorb more neutrons until the reactor could no longer
operate.
Spent fuel rods contain a variety of products, consisting of unstable nuclei ranging in atomic number from 25 to 60, some
transuranium elements, including plutonium and americium, and unreacted uranium isotopes. The unstable nuclei and the
transuranium isotopes give the spent fuel a dangerously high level of radioactivity. The long-lived isotopes require thousands of
years to decay to a safe level. The ultimate fate of the nuclear reactor as a significant source of energy in the United States probably
rests on whether or not a politically and scientifically satisfactory technique for processing and storing the components of spent fuel
rods can be developed.

Explore the information in this link to learn about the approaches to nuclear waste management.
21.5.0.1: Nuclear Fusion and Fusion Reactors

The process of converting very light nuclei into heavier nuclei is also accompanied by the conversion of mass into large amounts of
energy, a process called fusion. The principal source of energy in the sun is a net fusion reaction in which four hydrogen nuclei fuse
and produce one helium nucleus and two positrons. This is a net reaction of a more complicated series of events:
1 4 0 +
4 H ⟶ He + 2 e
1 2 +1
A helium nucleus has a mass that is 0.7% less than that of four hydrogen nuclei; this lost mass is converted into energy during the
fusion. This reaction produces about 3.6 × 1011 kJ of energy per mole of He produced. This is somewhat larger than the energy
4
2
produced by the nuclear fission of one mole of U-235 (1.8 × 1010 kJ), and over 3 million times larger than the energy produced by
the (chemical) combustion of one mole of octane (5471 kJ).
It has been determined that the nuclei of the heavy isotopes of hydrogen, a deuteron, H and a triton,
2
1
3
1
H, undergo fusion at
extremely high temperatures (thermonuclear fusion). They form a helium nucleus and a neutron:
2 3 4 1
H+ H ⟶ He + n
1 1 2 0

This change proceeds with a mass loss of 0.0188 amu, corresponding to the release of 1.69 × 109 kilojoules per mole of He 4
2
formed. The very high temperature is necessary to give the nuclei enough kinetic energy to overcome the very strong repulsive
forces resulting from the positive charges on their nuclei so they can collide.
Useful fusion reactions require very high temperatures for their initiation—about 15,000,000 K or more. At these temperatures, all
molecules dissociate into atoms, and the atoms ionize, forming plasma. These conditions occur in an extremely large number of
locations throughout the universe—stars are powered by fusion. Humans have already figured out how to create temperatures high
enough to achieve fusion on a large scale in thermonuclear weapons. A thermonuclear weapon such as a hydrogen bomb contains a
nuclear fission bomb that, when exploded, gives off enough energy to produce the extremely high temperatures necessary for
fusion to occur.
Another much more beneficial way to create fusion reactions is in a fusion reactor, a nuclear reactor in which fusion reactions of
light nuclei are controlled. Because no solid materials are stable at such high temperatures, mechanical devices cannot contain the
plasma in which fusion reactions occur. Two techniques to contain plasma at the density and temperature necessary for a fusion
reaction are currently the focus of intensive research efforts: containment by a magnetic field and by the use of focused laser beams
(Figure 21.23). A number of large projects are working to attain one of the biggest goals in science: getting hydrogen fuel to ignite
and produce more energy than the amount supplied to achieve the extremely high temperatures and pressures that are required for
fusion. At the time of this writing, there are no self-sustaining fusion reactors operating in the world, although small-scale
controlled fusion reactions have been run for very brief periods.
Figure 21.23 (a) This model is of the International Thermonuclear Experimental Reactor (ITER) reactor. Currently under
construction in the south of France with an expected completion date of 2027, the ITER will be the world’s largest experimental
Tokamak nuclear fusion reactor with a goal of achieving large-scale sustained energy production. (b) In 2012, the National Ignition
Facility at Lawrence Livermore National Laboratory briefly produced over 500,000,000,000 watts (500 terawatts, or 500 TW) of
peak power and delivered 1,850,000 joules (1.85 MJ) of energy, the largest laser energy ever produced and 1000 times the power
usage of the entire United States in any given moment. Although lasting only a few billionths of a second, the 192 lasers attained
the conditions needed for nuclear fusion ignition. This image shows the target prior to the laser shot. (credit a: modification of work
by Stephan Mosel)
This page titled 21.5: Transmutation and Nuclear Energy is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by


List common applications of radioactive isotopes
Radioactive isotopes have the same chemical properties as stable isotopes of the same element, but they emit radiation, which can
be detected. If we replace one (or more) atom(s) with radioisotope(s) in a compound, we can track them by monitoring their
radioactive emissions. This type of compound is called a radioactive tracer (or radioactive label). Radioisotopes are used to follow
the paths of biochemical reactions or to determine how a substance is distributed within an organism. Radioactive tracers are also
used in many medical applications, including both diagnosis and treatment. They are used to measure engine wear, analyze the
geological formation around oil wells, and much more.
Radioimmunossays (RIA), for example, rely on radioisotopes to detect the presence and/or concentration of certain antigens.
Developed by Rosalyn Sussman Yalow and Solomon Berson in the 1950s, the technique is known for extreme sensitivity, meaning
that it can detect and measure very small quantities of a substance. Prior to its discovery, most similar detection relied on large
enough quantities to produce visible outcomes. RIA revolutionized and expanded entire fields of study, most notably
endocrinology, and is commonly used in narcotics detection, blood bank screening, early cancer screening, hormone measurement,
and allergy diagnosis. Based on her significant contribution to medicine, Yalow received a Nobel Prize, making her the second
woman to be awarded the prize for medicine.
Radioisotopes have revolutionized medical practice (see Appendix M), where they are used extensively. Over 10 million nuclear
medicine procedures and more than 100 million nuclear medicine tests are performed annually in the United States. Four typical
examples of radioactive tracers used in medicine are technetium-99 ( Tc), thallium-201 ( Tl), iodine-131 ( I), and sodium-
99
43
201
81
131
53
24 ( Na) . Damaged tissues in the heart, liver, and lungs absorb certain compounds of technetium-99 preferentially. After it is
24
11
injected, the location of the technetium compound, and hence the damaged tissue, can be determined by detecting the γ rays
emitted by the Tc-99 isotope. Thallium-201 (Figure 21.24) becomes concentrated in healthy heart tissue, so the two isotopes, Tc-99
and Tl-201, are used together to study heart tissue. Iodine-131 concentrates in the thyroid gland, the liver, and some parts of the
brain. It can therefore be used to monitor goiter and treat thyroid conditions, such as Grave’s disease, as well as liver and brain
tumors. Salt solutions containing compounds of sodium-24 are injected into the bloodstream to help locate obstructions to the flow
of blood.

Figure 21.24 Administering thallium-201 to a patient and subsequently performing a stress test offer medical professionals an
opportunity to visually analyze heart function and blood flow. (credit: modification of work by “Blue0ctane”/Wikimedia
Commons)
Radioisotopes used in medicine typically have short half-lives—for example, the ubiquitous Tc-99m has a half-life of 6.01 hours.
This makes Tc-99m essentially impossible to store and prohibitively expensive to transport, so it is made on-site instead. Hospitals
and other medical facilities use Mo-99 (which is primarily extracted from U-235 fission products) to generate Tc-99. Mo-99
undergoes β decay with a half-life of 66 hours, and the Tc-99 is then chemically extracted (Figure 21.25). The parent nuclide Mo-

99 is part of a molybdate ion, MoO ; when it decays, it forms the pertechnetate ion, TcO . These two water-soluble ions are
4
2−
4
−
separated by column chromatography, with the higher charge molybdate ion adsorbing onto the alumina in the column, and the
lower charge pertechnetate ion passing through the column in the solution. A few micrograms of Mo-99 can produce enough Tc-99
to perform as many as 10,000 tests.
Figure 21.25 (a) The first Tc-99m generator (circa 1958) is used to separate Tc-99 from Mo-99. The MoO is retained by the
4
2−
matrix in the column, whereas the TcO passes through and is collected. (b) Tc-99 was used in this scan of the neck of a patient
4
−
with Grave’s disease. The scan shows the location of high concentrations of Tc-99. (credit a: modification of work by the
Department of Energy; credit b: modification of work by “MBq”/Wikimedia Commons)
Radioisotopes can also be used, typically in higher doses than as a tracer, as treatment. Radiation therapy is the use of high-energy
radiation to damage the DNA of cancer cells, which kills them or keeps them from dividing (Figure 21.26). A cancer patient may
receive external beam radiation therapy delivered by a machine outside the body, or internal radiation therapy (brachytherapy) from
a radioactive substance that has been introduced into the body. Note that chemotherapy is similar to internal radiation therapy in
that the cancer treatment is injected into the body, but differs in that chemotherapy uses chemical rather than radioactive substances
to kill the cancer cells.

Figure 21.26 The cartoon in (a) shows a cobalt-60 machine used in the treatment of cancer. The diagram in (b) shows how the
gantry of the Co-60 machine swings through an arc, focusing radiation on the targeted region (tumor) and minimizing the amount

of radiation that passes through nearby regions.
Cobalt-60 is a synthetic radioisotope produced by the neutron activation of Co-59, which then undergoes β decay to form Ni-60,
along with the emission of γ radiation. The overall process is:
59 1 60 60 0 0
Co + n ⟶ Co ⟶ Ni + β +2 γ
27 0 27 28 −1 0
The overall decay scheme for this is shown graphically in Figure 21.27.
Figure 21.27 Co-60 undergoes a series of radioactive decays. The γ emissions are used for radiation therapy.
Radioisotopes are used in diverse ways to study the mechanisms of chemical reactions in plants and animals. These include
labeling fertilizers in studies of nutrient uptake by plants and crop growth, investigations of digestive and milk-producing processes
in cows, and studies on the growth and metabolism of animals and plants.
For example, the radioisotope C-14 was used to elucidate the details of how photosynthesis occurs. The overall reaction is:
6CO2 (g) + 6H2 O(l) ⟶ C6 H12 O6 (s) + 6O2 (g),
but the process is much more complex, proceeding through a series of steps in which various organic compounds are produced. In
studies of the pathway of this reaction, plants were exposed to CO2 containing a high concentration of C. At regular intervals,
14
6
the plants were analyzed to determine which organic compounds contained carbon-14 and how much of each compound was
present. From the time sequence in which the compounds appeared and the amount of each present at given time intervals,
scientists learned more about the pathway of the reaction.
Commercial applications of radioactive materials are equally diverse (Figure 21.28). They include determining the thickness of
films and thin metal sheets by exploiting the penetration power of various types of radiation. Flaws in metals used for structural
purposes can be detected using high-energy gamma rays from cobalt-60 in a fashion similar to the way X-rays are used to examine
the human body. In one form of pest control, flies are controlled by sterilizing male flies with γ radiation so that females breeding
with them do not produce offspring. Many foods are preserved by radiation that kills microorganisms that cause the foods to spoil.

Figure 21.28 Common commercial uses of radiation include (a) X-ray examination of luggage at an airport and (b) preservation of
food. (credit a: modification of work by the Department of the Navy; credit b: modification of work by the US Department of
Agriculture)
Americium-241, an α emitter with a half-life of 458 years, is used in tiny amounts in ionization-type smoke detectors (Figure
21.29). The α emissions from Am-241 ionize the air between two electrode plates in the ionizing chamber. A battery supplies a
potential that causes movement of the ions, thus creating a small electric current. When smoke enters the chamber, the movement
of the ions is impeded, reducing the conductivity of the air. This causes a marked drop in the current, triggering an alarm.

Figure 21.29 Inside a smoke detector, Am-241 emits α particles that ionize the air, creating a small electric current. During a fire,
smoke particles impede the flow of ions, reducing the current and triggering an alarm. (credit a: modification of work by
“Muffet”/Wikimedia Commons)
This page titled 21.6: Uses of Radioisotopes is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by OpenStax via


Describe the biological impact of ionizing radiation
Define units for measuring radiation exposure
Explain the operation of common tools for detecting radioactivity
List common sources of radiation exposure in the US
The increased use of radioisotopes has led to increased concerns over the effects of these materials on biological systems (such as
humans). All radioactive nuclides emit high-energy particles or electromagnetic waves. When this radiation encounters living cells,
it can cause heating, break chemical bonds, or ionize molecules. The most serious biological damage results when these radioactive
emissions fragment or ionize molecules. For example, alpha and beta particles emitted from nuclear decay reactions possess much
higher energies than ordinary chemical bond energies. When these particles strike and penetrate matter, they produce ions and
molecular fragments that are extremely reactive. The damage this does to biomolecules in living organisms can cause serious
malfunctions in normal cell processes, taxing the organism’s repair mechanisms and possibly causing illness or even death (Figure
21.30).
Figure 21.30 Radiation can harm biological systems by damaging the DNA of cells. If this damage is not properly repaired, the
cells may divide in an uncontrolled manner and cause cancer.
21.7.0.1: Ionizing and Nonionizing Radiation

There is a large difference in the magnitude of the biological effects of nonionizing radiation (for example, light and microwaves)
and ionizing radiation, emissions energetic enough to knock electrons out of molecules (for example, α and β particles, γ rays, X-
rays, and high-energy ultraviolet radiation) (Figure 21.31).

Figure 21.31 Lower frequency, lower-energy electromagnetic radiation is nonionizing, and higher frequency, higher-energy
electromagnetic radiation is ionizing.
Energy absorbed from nonionizing radiation speeds up the movement of atoms and molecules, which is equivalent to heating the
sample. Although biological systems are sensitive to heat (as we might know from touching a hot stove or spending a day at the
beach in the sun), a large amount of nonionizing radiation is necessary before dangerous levels are reached. Ionizing radiation,
however, may cause much more severe damage by breaking bonds or removing electrons in biological molecules, disrupting their
structure and function. The damage can also be done indirectly, by first ionizing H2O (the most abundant molecule in living
organisms), which forms a H2O+ ion that reacts with water, forming a hydronium ion and a hydroxyl radical:
Because the hydroxyl radical has an unpaired electron, it is highly reactive. (This is true of any substance with unpaired electrons,
known as a free radical.) This hydroxyl radical can react with all kinds of biological molecules (DNA, proteins, enzymes, and so
on), causing damage to the molecules and disrupting physiological processes. Examples of direct and indirect damage are shown in
Figure 21.32.

Figure 21.32 Ionizing radiation can (a) directly damage a biomolecule by ionizing it or breaking its bonds, or (b) create an H2O+
ion, which reacts with H2O to form a hydroxyl radical, which in turn reacts with the biomolecule, causing damage indirectly.
21.7.0.0.1: Biological Effects of Exposure to Radiation
Radiation can harm either the whole body (somatic damage) or eggs and sperm (genetic damage). Its effects are more pronounced
in cells that reproduce rapidly, such as the stomach lining, hair follicles, bone marrow, and embryos. This is why patients
undergoing radiation therapy often feel nauseous or sick to their stomach, lose hair, have bone aches, and so on, and why particular
care must be taken when undergoing radiation therapy during pregnancy.
Different types of radiation have differing abilities to pass through material (Figure 21.33). A very thin barrier, such as a sheet or
two of paper, or the top layer of skin cells, usually stops alpha particles. Because of this, alpha particle sources are usually not
dangerous if outside the body, but are quite hazardous if ingested or inhaled (see the Chemistry in Everyday Life feature on Radon
Exposure). Beta particles will pass through a hand, or a thin layer of material like paper or wood, but are stopped by a thin layer of
metal. Gamma radiation is very penetrating and can pass through a thick layer of most materials. Some high-energy gamma
radiation is able to pass through a few feet of concrete. Certain dense, high atomic number elements (such as lead) can effectively
attenuate gamma radiation with thinner material and are used for shielding. The ability of various kinds of emissions to cause
ionization varies greatly, and some particles have almost no tendency to produce ionization. Alpha particles have about twice the
ionizing power of fast-moving neutrons, about 10 times that of β particles, and about 20 times that of γ rays and X-rays.

Figure 21.33 The ability of different types of radiation to pass through material is shown. From least to most penetrating, they are
alpha < beta < neutron < gamma.

21.7.0.0.2: Radon Exposure
For many people, one of the largest sources of exposure to radiation is from radon gas (Rn-222). Radon-222 is an α emitter
with a half–life of 3.82 days. It is one of the products of the radioactive decay series of U-238 (Figure 21.9), which is found in
trace amounts in soil and rocks. The radon gas that is produced slowly escapes from the ground and gradually seeps into homes
and other structures above. Since it is about eight times more dense than air, radon gas accumulates in basements and lower
floors, and slowly diffuses throughout buildings (Figure 21.34).

Figure 21.34 Radon-222 seeps into houses and other buildings from rocks that contain uranium-238, a radon emitter. The radon
enters through cracks in concrete foundations and basement floors, stone or porous cinderblock foundations, and openings for
water and gas pipes.
Radon is found in buildings across the country, with amounts depending on where you live. The average concentration of
radon inside houses in the US (1.25 pCi/L) is about three times the levels found in outside air, and about one in six houses have
radon levels high enough that remediation efforts to reduce the radon concentration are recommended. Exposure to radon
increases one’s risk of getting cancer (especially lung cancer), and high radon levels can be as bad for health as smoking a
carton of cigarettes a day. Radon is the number one cause of lung cancer in nonsmokers and the second leading cause of lung
cancer overall. Radon exposure is believed to cause over 20,000 deaths in the US per year.

21.7.0.1: Measuring Radiation Exposure
Several different devices are used to detect and measure radiation, including Geiger counters, scintillation counters (scintillators),
and radiation dosimeters (Figure 21.35). Probably the best-known radiation instrument, the Geiger counter (also called the Geiger-
Müller counter) detects and measures radiation. Radiation causes the ionization of the gas in a Geiger-Müller tube. The rate of
ionization is proportional to the amount of radiation. A scintillation counter contains a scintillator—a material that emits light
(luminesces) when excited by ionizing radiation—and a sensor that converts the light into an electric signal. Radiation dosimeters
also measure ionizing radiation and are often used to determine personal radiation exposure. Commonly used types are electronic,
film badge, thermoluminescent, and quartz fiber dosimeters.
Figure 21.35 Devices such as (a) Geiger counters, (b) scintillators, and (c) dosimeters can be used to measure radiation. (credit c:
modification of work by “osaMu”/Wikimedia commons)
A variety of units are used to measure various aspects of radiation (Figure 21.36). The SI unit for rate of radioactive decay is the
becquerel (Bq), with 1 Bq = 1 disintegration per second. The curie (Ci) and millicurie (mCi) are much larger units and are
frequently used in medicine (1 curie = 1 Ci = 3.7 × 1010 disintegrations per second). The SI unit for measuring radiation dose is the
gray (Gy), with 1 Gy = 1 J of energy absorbed per kilogram of tissue. In medical applications, the radiation absorbed dose (rad) is
more often used (1 rad = 0.01 Gy; 1 rad results in the absorption of 0.01 J/kg of tissue). The SI unit measuring tissue damage
caused by radiation is the sievert (Sv). This takes into account both the energy and the biological effects of the type of radiation
involved in the radiation dose. The roentgen equivalent for man (rem) is the unit for radiation damage that is used most frequently
in medicine (100 rem = 1 Sv). Note that the tissue damage units (rem or Sv) includes the energy of the radiation dose (rad or Gy)
along with a biological factor referred to as the RBE (for relative biological effectiveness) that is an approximate measure of the
relative damage done by the radiation. These are related by:
number of rems = RBE × number of rads
with RBE approximately 10 for α radiation, 2(+) for protons and neutrons, and 1 for β and γ radiation.

Figure 21.36 Different units are used to measure the rate of emission from a radioactive source, the energy that is absorbed from
the source, and the amount of damage the absorbed radiation does.
21.7.0.0.1: Units of Radiation Measurement
Table 21.4 summarizes the units used for measuring radiation.
Units Used for Measuring Radiation
Measurement Unit Quantity Measured Description
Purpose
activity of source becquerel (Bq) radioactive decays or amount of sample that undergoes 1 decay/second
emissions
curie (Ci) amount of sample that undergoes 3.7 × 1010
decays/second
absorbed dose gray (Gy) energy absorbed per kg of 1 Gy = 1 J/kg tissue

tissue

Measurement Unit Quantity Measured Description
Purpose
radiation absorbed dose 1 rad = 0.01 J/kg tissue

(rad)
biologically effective sievert (Sv) tissue damage Sv = RBE × Gy

dose
roentgen equivalent for man Rem = RBE × rad
(rem)
Table 21.4
21.7.0.1: Example 21.8

21.7.0.0.2: Amount of Radiation
Cobalt-60 (t1/2 = 5.26 y) is used in cancer therapy since the γ rays it emits can be focused in small areas where the cancer is
located. A 5.00-g sample of Co-60 is available for cancer treatment.
(a) What is its activity in Bq?
(b) What is its activity in Ci?
The activity is given by:
ln 2 ln 2 g
Activity = λN = ( )N = ( ) × 5.00 g = 0.659 of Co−60 that decay
t1/2 5.26 y y
And to convert this to decays per second:
23
g 1 y 1 d 1 h 1 mol 6.02 × 10 atoms 1 decay
0.659 × × × × × ×
y 365 d 24 h 3600 s 59.9 g 1 mol 1 atom
14 decay
= 2.10 × 10
s
1 decay
(a) Since 1 Bq = s
, the activity in Becquerel (Bq) is:
decay ⎛ 1 Bq ⎞
14 14
2.10 × 10 × = 2.10 × 10 Bq
decay
s ⎝ ⎠
1
s
11
3.7 × 10 decay
(b) Since 1 Ci = s
, the activity in curie (Ci) is:
decay ⎛ 1 Ci ⎞
14 2
2.10 × 10 × ⎜ ⎟ = 5.7 × 10 Ci
11
s ⎝
3.7 × 10 decay
⎠
s

Tritium is a radioactive isotope of hydrogen (t1/2 = 12.32 y) that has several uses, including self-powered lighting, in which
electrons emitted in tritium radioactive decay cause phosphorus to glow. Its nucleus contains one proton and two neutrons, and
the atomic mass of tritium is 3.016 amu. What is the activity of a sample containing 1.00mg of tritium (a) in Bq and (b) in Ci?
21.7.0.1: Answer:
(a) 3.56 × 1011 Bq; (b) 0.962 Ci

21.7.0.1: Effects of Long-term Radiation Exposure on the Human Body
The effects of radiation depend on the type, energy, and location of the radiation source, and the length of exposure. As shown in
Figure 21.37, the average person is exposed to background radiation, including cosmic rays from the sun and radon from uranium
in the ground (see the Chemistry in Everyday Life feature on Radon Exposure); radiation from medical exposure, including CAT
scans, radioisotope tests, X-rays, and so on; and small amounts of radiation from other human activities, such as airplane flights
(which are bombarded by increased numbers of cosmic rays in the upper atmosphere), radioactivity from consumer products, and a
variety of radionuclides that enter our bodies when we breathe (for example, carbon-14) or through the food chain (for example,
potassium-40, strontium-90, and iodine-131).
Figure 21.37 The total annual radiation exposure for a person in the US is about 620 mrem. The various sources and their relative
amounts are shown in this bar graph. (source: U.S. Nuclear Regulatory Commission)
A short-term, sudden dose of a large amount of radiation can cause a wide range of health effects, from changes in blood chemistry
to death. Short-term exposure to tens of rems of radiation will likely cause very noticeable symptoms or illness; a dose of about 500
rems is estimated to have a 50% probability of causing the death of the victim within 30 days of exposure. Exposure to radioactive
emissions has a cumulative effect on the body during a person’s lifetime, which is another reason why it is important to avoid any
unnecessary exposure to radiation. Health effects of short-term exposure to radiation are shown in Table 21.5.
Health Effects of Radiation2
Exposure (rem) Health Effect Time to Onset (without treatment)
5–10 changes in blood chemistry —

Exposure (rem) Health Effect Time to Onset (without treatment)
50 nausea hours
55 fatigue —
70 vomiting —
75 hair loss 2–3 weeks
90 diarrhea —
100 hemorrhage —
400 possible death within 2 months
1000 destruction of intestinal lining —
internal bleeding —
death 1–2 weeks
2000 damage to central nervous system —
loss of consciousness; minutes
death hours to days
Table 21.5
It is impossible to avoid some exposure to ionizing radiation. We are constantly exposed to background radiation from a variety of
natural sources, including cosmic radiation, rocks, medical procedures, consumer products, and even our own atoms. We can
minimize our exposure by blocking or shielding the radiation, moving farther from the source, and limiting the time of exposure.
21.7.0.1: Footnotes
2Source: US Environmental Protection Agency
This page titled 21.7: Biological Effects of Radiation is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

21.8: Key Terms
alpha (α) decay
loss of an alpha particle during radioactive decay
alpha particle
(α or He or
4
2
4
2
α) high-energy helium nucleus; a helium atom that has lost two electrons and contains two protons and two
neutrons
antimatter
particles with the same mass but opposite properties (such as charge) of ordinary particles
band of stability
(also, belt of stability, zone of stability, or valley of stability) region of graph of number of protons versus number of neutrons
containing stable (nonradioactive) nuclides
becquerel (Bq)
SI unit for rate of radioactive decay; 1 Bq = 1 disintegration/s
beta (β) decay

breakdown of a neutron into a proton, which remains in the nucleus, and an electron, which is emitted as a beta particle
beta particle
(β or e or high-energy electron
0 0
β)
−1 −1
binding energy per nucleon

total binding energy for the nucleus divided by the number of nucleons in the nucleus
chain reaction
repeated fission caused when the neutrons released in fission bombard other atoms
chemotherapy
similar to internal radiation therapy, but chemical rather than radioactive substances are introduced into the body to kill cancer
cells
containment system
(also, shield) a three-part structure of materials that protects the exterior of a nuclear fission reactor and operating personnel
from the high temperatures, pressures, and radiation levels inside the reactor
control rod
material inserted into the fuel assembly that absorbs neutrons and can be raised or lowered to adjust the rate of a fission reaction
critical mass
amount of fissionable material that will support a self-sustaining (nuclear fission) chain reaction
curie (Ci)
larger unit for rate of radioactive decay frequently used in medicine; 1 Ci = 3.7 × 1010 disintegrations/s
daughter nuclide
nuclide produced by the radioactive decay of another nuclide; may be stable or may decay further
electron capture
combination of a core electron with a proton to yield a neutron within the nucleus
electron volt (eV)
measurement unit of nuclear binding energies, with 1 eV equaling the amount energy due to the moving an electron across an
electric potential difference of 1 volt
external beam radiation therapy

radiation delivered by a machine outside the body
fissile (or fissionable)

when a material is capable of sustaining a nuclear fission reaction
fission
splitting of a heavier nucleus into two or more lighter nuclei, usually accompanied by the conversion of mass into large amounts
of energy
fusion
combination of very light nuclei into heavier nuclei, accompanied by the conversion of mass into large amounts of energy
fusion reactor
nuclear reactor in which fusion reactions of light nuclei are controlled
gamma (γ) emission

decay of an excited-state nuclide accompanied by emission of a gamma ray
gamma ray
(γ or γ) short wavelength, high-energy electromagnetic radiation that exhibits wave-particle duality
0
0
Geiger counter
instrument that detects and measures radiation via the ionization produced in a Geiger-Müller tube
gray (Gy)
SI unit for measuring radiation dose; 1 Gy = 1 J absorbed/kg tissue
half-life (t1/2)
time required for half of the atoms in a radioactive sample to decay
internal radiation therapy

(also, brachytherapy) radiation from a radioactive substance introduced into the body to kill cancer cells
ionizing radiation
radiation that can cause a molecule to lose an electron and form an ion
magic number
nuclei with specific numbers of nucleons that are within the band of stability
mass defect
difference between the mass of an atom and the summed mass of its constituent subatomic particles (or the mass “lost” when
nucleons are brought together to form a nucleus)
mass-energy equivalence equation

Albert Einstein’s relationship showing that mass and energy are equivalent
millicurie (mCi)
larger unit for rate of radioactive decay frequently used in medicine; 1 Ci = 3.7 × 1010 disintegrations/s
nonionizing radiation
radiation that speeds up the movement of atoms and molecules; it is equivalent to heating a sample, but is not energetic enough
to cause the ionization of molecules
nuclear binding energy

energy lost when an atom’s nucleons are bound together (or the energy needed to break a nucleus into its constituent protons
and neutrons)
nuclear chemistry
study of the structure of atomic nuclei and processes that change nuclear structure
nuclear fuel
fissionable isotope present in sufficient quantities to provide a self-sustaining chain reaction in a nuclear reactor
nuclear moderator
substance that slows neutrons to a speed low enough to cause fission
nuclear reaction
change to a nucleus resulting in changes in the atomic number, mass number, or energy state
nuclear reactor
environment that produces energy via nuclear fission in which the chain reaction is controlled and sustained without explosion
nuclear transmutation
conversion of one nuclide into another nuclide
nucleon
collective term for protons and neutrons in a nucleus
nuclide
nucleus of a particular isotope
parent nuclide
unstable nuclide that changes spontaneously into another (daughter) nuclide
particle accelerator
device that uses electric and magnetic fields to increase the kinetic energy of nuclei used in transmutation reactions
positron (+1
0
β or 0
+1
e)
antiparticle to the electron; it has identical properties to an electron, except for having the opposite (positive) charge
positron emission
(also, β+ decay) conversion of a proton into a neutron, which remains in the nucleus, and a positron, which is emitted
radiation absorbed dose (rad)

SI unit for measuring radiation dose, frequently used in medical applications; 1 rad = 0.01 Gy
radiation dosimeter
device that measures ionizing radiation and is used to determine personal radiation exposure
radiation therapy
use of high-energy radiation to damage the DNA of cancer cells, which kills them or keeps them from dividing
radioactive decay
spontaneous decay of an unstable nuclide into another nuclide
radioactive decay series
chains of successive disintegrations (radioactive decays) that ultimately lead to a stable end-product
radioactive tracer
(also, radioactive label) radioisotope used to track or follow a substance by monitoring its radioactive emissions
radioactivity
phenomenon exhibited by an unstable nucleon that spontaneously undergoes change into a nucleon that is more stable; an
unstable nucleon is said to be radioactive
radiocarbon dating
highly accurate means of dating objects 30,000–50,000 years old that were derived from once-living matter; achieved by
calculating the ratio of C: C in the object vs. the ratio of C: C in the present-day atmosphere
14
6
12
6
14
6
12
6
radioisotope
isotope that is unstable and undergoes conversion into a different, more stable isotope
radiometric dating
use of radioisotopes and their properties to date the formation of objects such as archeological artifacts, formerly living
organisms, or geological formations
reactor coolant
assembly used to carry the heat produced by fission in a reactor to an external boiler and turbine where it is transformed into
electricity
relative biological effectiveness (RBE)

measure of the relative damage done by radiation
roentgen equivalent man (rem)

unit for radiation damage, frequently used in medicine; 100 rem = 1 Sv
scintillation counter
instrument that uses a scintillator—a material that emits light when excited by ionizing radiation—to detect and measure
radiation
sievert (Sv)
SI unit measuring tissue damage caused by radiation; takes into account energy and biological effects of radiation
strong nuclear force

force of attraction between nucleons that holds a nucleus together
subcritical mass
amount of fissionable material that cannot sustain a chain reaction; less than a critical mass
supercritical mass
amount of material in which there is an increasing rate of fission
transmutation reaction
bombardment of one type of nuclei with other nuclei or neutrons
transuranium element
element with an atomic number greater than 92; these elements do not occur in nature
21.9: Key Equations
E = mc2
decay rate = λN
ln 2 0.693
t1/2 = =
λ λ
rem = RBE × rad
Sv = RBE × Gy
21.10: Summary
21.1 Nuclear Structure and Stability
An atomic nucleus consists of protons and neutrons, collectively called nucleons. Although protons repel each other, the nucleus is
held tightly together by a short-range, but very strong, force called the strong nuclear force. A nucleus has less mass than the total
mass of its constituent nucleons. This “missing” mass is the mass defect, which has been converted into the binding energy that
holds the nucleus together according to Einstein’s mass-energy equivalence equation, E = mc2. Of the many nuclides that exist,
only a small number are stable. Nuclides with even numbers of protons or neutrons, or those with magic numbers of nucleons, are
especially likely to be stable. These stable nuclides occupy a narrow band of stability on a graph of number of protons versus
number of neutrons. The binding energy per nucleon is largest for the elements with mass numbers near 56; these are the most
stable nuclei.
21.2 Nuclear Equations

Nuclei can undergo reactions that change their number of protons, number of neutrons, or energy state. Many different particles can
be involved in nuclear reactions. The most common are protons, neutrons, positrons (which are positively charged electrons), alpha
(α) particles (which are high-energy helium nuclei), beta (β) particles (which are high-energy electrons), and gamma (γ) rays
(which compose high-energy electromagnetic radiation). As with chemical reactions, nuclear reactions are always balanced. When
a nuclear reaction occurs, the total mass (number) and the total charge remain unchanged.
21.3 Radioactive Decay

Nuclei that have unstable n:p ratios undergo spontaneous radioactive decay. The most common types of radioactivity are α decay, β
decay, γ emission, positron emission, and electron capture. Nuclear reactions also often involve γ rays, and some nuclei decay by
electron capture. Each of these modes of decay leads to the formation of a new nucleus with a more stable n:p ratio. Some
substances undergo radioactive decay series, proceeding through multiple decays before ending in a stable isotope. All nuclear
decay processes follow first-order kinetics, and each radioisotope has its own characteristic half-life, the time that is required for
half of its atoms to decay. Because of the large differences in stability among nuclides, there is a very wide range of half-lives of
radioactive substances. Many of these substances have found useful applications in medical diagnosis and treatment, determining
the age of archaeological and geological objects, and more.
21.4 Transmutation and Nuclear Energy

It is possible to produce new atoms by bombarding other atoms with nuclei or high-speed particles. The products of these
transmutation reactions can be stable or radioactive. A number of artificial elements, including technetium, astatine, and the
transuranium elements, have been produced in this way.
Nuclear power as well as nuclear weapon detonations can be generated through fission (reactions in which a heavy nucleus is split
into two or more lighter nuclei and several neutrons). Because the neutrons may induce additional fission reactions when they
combine with other heavy nuclei, a chain reaction can result. Useful power is obtained if the fission process is carried out in a
nuclear reactor. The conversion of light nuclei into heavier nuclei (fusion) also produces energy. At present, this energy has not
been contained adequately and is too expensive to be feasible for commercial energy production.
21.5 Uses of Radioisotopes

Compounds known as radioactive tracers can be used to follow reactions, track the distribution of a substance, diagnose and treat
medical conditions, and much more. Other radioactive substances are helpful for controlling pests, visualizing structures, providing
fire warnings, and for many other applications. Hundreds of millions of nuclear medicine tests and procedures, using a wide variety
of radioisotopes with relatively short half-lives, are performed every year in the US. Most of these radioisotopes have relatively
short half-lives; some are short enough that the radioisotope must be made on-site at medical facilities. Radiation therapy uses
high-energy radiation to kill cancer cells by damaging their DNA. The radiation used for this treatment may be delivered externally
or internally.
21.6 Biological Effects of Radiation

We are constantly exposed to radiation from a variety of naturally occurring and human-produced sources. This radiation can affect
living organisms. Ionizing radiation is the most harmful because it can ionize molecules or break chemical bonds, which damages
the molecule and causes malfunctions in cell processes. It can also create reactive hydroxyl radicals that damage biological
molecules and disrupt physiological processes. Radiation can cause somatic or genetic damage, and is most harmful to rapidly
reproducing cells. Types of radiation differ in their ability to penetrate material and damage tissue, with alpha particles the least
penetrating but potentially most damaging and gamma rays the most penetrating.
Various devices, including Geiger counters, scintillators, and dosimeters, are used to detect and measure radiation, and monitor
radiation exposure. We use several units to measure radiation: becquerels or curies for rates of radioactive decay; gray or rads for
energy absorbed; and rems or sieverts for biological effects of radiation. Exposure to radiation can cause a wide range of health
effects, from minor to severe, and including death. We can minimize the effects of radiation by shielding with dense materials such
as lead, moving away from the source, and limiting time of exposure.
21.11: Exercises
21.11.0.1: 21.1 Nuclear Structure and Stability
1.
Write the following isotopes in hyphenated form (e.g., “carbon-14”)
(a) 24
11
Na
(b) 29
13
Al
(c) 73
36
Kr
(d) 194
77
Ir
2.
Write the following isotopes in nuclide notation (e.g., " 14
6
C")
(a) oxygen-14
(b) copper-70
(c) tantalum-175
(d) francium-217
3.
For the following isotopes that have missing information, fill in the missing information to complete the notation
(a) 34
14
X
(b) 36
X
P
(c) 57
X
Mn
(d) 121
56
X
4.
For each of the isotopes in Exercise 21.1, determine the numbers of protons, neutrons, and electrons in a neutral atom of the
isotope.
5.
Write the nuclide notation, including charge if applicable, for atoms with the following characteristics:
(a) 25 protons, 20 neutrons, 24 electrons
(b) 45 protons, 24 neutrons, 43 electrons
(c) 53 protons, 89 neutrons, 54 electrons
(d) 97 protons, 146 neutrons, 97 electrons
6.
Calculate the density of the 24
12
Mg nucleus in g/mL, assuming that it has the typical nuclear diameter of 1 × 10–13 cm and is
spherical in shape.
7.
What are the two principal differences between nuclear reactions and ordinary chemical changes?
8.
The mass of the atom 23
11
Na is 22.9898 amu.
(a) Calculate its binding energy per atom in millions of electron volts.
(b) Calculate its binding energy per nucleon.
9.

Which of the following nuclei lie within the band of stability shown in Figure 21.2?
(a) chlorine-37
(b) calcium-40
(c) 204Bi
(d) 56Fe
(e) 206Pb
(f) 211Pb
(g) 222Rn
(h) carbon-14
10.
Which of the following nuclei lie within the band of stability shown in Figure 21.2?
(a) argon-40
(b) oxygen-16
(c) 122Ba
(d) 58Ni
(e) 205Tl
(f) 210Tl
(g) 226Ra
(h) magnesium-24
21.11.0.1: 21.2 Nuclear Equations

11.
Write a brief description or definition of each of the following:
(a) nucleon
(b) α particle
(c) β particle
(d) positron
(e) γ ray
(f) nuclide
(g) mass number
(h) atomic number
12.
Which of the various particles (α particles, β particles, and so on) that may be produced in a nuclear reaction are actually nuclei?
13.
Complete each of the following equations by adding the missing species:
(a) 27
13
Al +
4
2
He ⟶ ? +
1
0
n
(b) 239
94
Pu+? ⟶
242
96
Cm +
1
0
n
(c) 14
7
N+
4
2
He ⟶ ? +
1
1
H
(d) 235
92
U ⟶ ?+
135
55
Cs + 4 n
1
0
14.

Complete each of the following equations:
(a) 7
3
Li + ? ⟶ 2 He
4
2
(b) 14
6
C ⟶
14
7
N+?
(c) 27
13
Al +
4
2
He ⟶ ? +
1
0
n
(d) 250
96
Cm ⟶ ? +
98
38
Sr + 4 n
1
0
15.
Write a balanced equation for each of the following nuclear reactions:
(a) the production of 17O from 14N by α particle bombardment
(b) the production of 14C from 14N by neutron bombardment
(c) the production of 233Th from 232Th by neutron bombardment
(d) the production of 239U from 238U by 2
1
H bombardment
16.
Technetium-99 is prepared from 98Mo. Molybdenum-98 combines with a neutron to give molybdenum-99, an unstable isotope that
emits a β particle to yield an excited form of technetium-99, represented as 99Tc*. This excited nucleus relaxes to the ground state,
represented as 99Tc, by emitting a γ ray. The ground state of 99Tc then emits a β particle. Write the equations for each of these
nuclear reactions.
17.
The mass of the atom 19
9
F is 18.99840 amu.
(a) Calculate its binding energy per atom in millions of electron volts.
(b) Calculate its binding energy per nucleon.
18.
For the reaction 14
6
C ⟶
14
7
N + ?, if 100.0 g of carbon reacts, what volume of nitrogen gas (N2) is produced at 273K and 1 atm?
21.11.0.1: 21.3 Radioactive Decay

19.
What are the types of radiation emitted by the nuclei of radioactive elements?
20.
What changes occur to the atomic number and mass of a nucleus during each of the following decay scenarios?
(a) an α particle is emitted
(b) a β particle is emitted
(c) γ radiation is emitted
(d) a positron is emitted
(e) an electron is captured
21.
What is the change in the nucleus that results from the following decay scenarios?
(a) emission of a β particle
(b) emission of a β+ particle
(c) capture of an electron
22.
Many nuclides with atomic numbers greater than 83 decay by processes such as electron emission. Explain the observation that the
emissions from these unstable nuclides also normally include α particles.

23.
Why is electron capture accompanied by the emission of an X-ray?
24.
Explain, in terms of Figure 21.2, how unstable heavy nuclides (atomic number > 83) may decompose to form nuclides of greater
stability (a) if they are below the band of stability and (b) if they are above the band of stability.
25.
Which of the following nuclei is most likely to decay by positron emission? Explain your choice.
(a) chromium-53
(b) manganese-51
(c) iron-59
26.
The following nuclei do not lie in the band of stability. How would they be expected to decay? Explain your answer.
(a) 34
15
P
(b) 239
92
U
(c) 38
20
Ca
(d) 3
1
H
(e) 245
94
Pu
27.
The following nuclei do not lie in the band of stability. How would they be expected to decay?
(a) 28
15
P
(b) 235
92
U
(c) 37
20
Ca
(d) 9
3
Li
(e) 245
96
Cm
28.
Predict by what mode(s) of spontaneous radioactive decay each of the following unstable isotopes might proceed:
(a) 6
2
He
(b) 60
30
Zn
(c) 235
91
Pa
(d) 241
94
Np
(e) 18F
(f) 129Ba
(g) 237Pu
29.
Write a nuclear reaction for each step in the formation of 218
Po from
84
238
98
U, which proceeds by a series of decay reactions
involving the step-wise emission of α, β, β, α, α, α particles, in that order.
30.
Write a nuclear reaction for each step in the formation of Pb from
208
82
228
90
Th, which proceeds by a series of decay reactions
involving the step-wise emission of α, α, α, α, β, β, α particles, in that order.
31.

Define the term half-life and illustrate it with an example.
32.
A 1.00 × 10–6-g sample of nobelium, 254
102
No, has a half-life of 55 seconds after it is formed. What is the percentage of 254
102
No
remaining at the following times?

(a) 5.0 min after it forms
(b) 1.0 h after it forms
33.
239Pu is a nuclear waste byproduct with a half-life of 24,000 y. What fraction of the 239Pu present today will be present in 1000 y?
34.
The isotope 208Tl undergoes β decay with a half-life of 3.1 min.
(a) What isotope is produced by the decay?
(b) How long will it take for 99.0% of a sample of pure 208Tl to decay?
(c) What percentage of a sample of pure 208Tl remains un-decayed after 1.0 h?
35.
If 1.000 g of Ra produces 0.0001 mL of the gas
226
88
222
86
Rn at STP (standard temperature and pressure) in 24 h, what is the half-life
of 226Ra in years?
36.
The isotope Sr is one of the extremely hazardous species in the residues from nuclear power generation. The strontium in a
90
38
0.500-g sample diminishes to 0.393 g in 10.0 y. Calculate the half-life.

37.
Technetium-99 is often used for assessing heart, liver, and lung damage because certain technetium compounds are absorbed by
damaged tissues. It has a half-life of 6.0 h. Calculate the rate constant for the decay of Tc. 99
43
38.
What is the age of mummified primate skin that contains 8.25% of the original quantity of 14C?
39.
A sample of rock was found to contain 8.23 mg of rubidium-87 and 0.47 mg of strontium-87.
(a) Calculate the age of the rock if the half-life of the decay of rubidium by β emission is 4.7 × 1010 y.
(b) If some Sr was initially present in the rock, would the rock be younger, older, or the same age as the age calculated in (a)?
87
38
Explain your answer.

40.
A laboratory investigation shows that a sample of uranium ore contains 5.37 mg of 238
92
U and 2.52 mg of 206
82
Pb. Calculate the age
9
of the ore. The half-life of U is 4.5 × 10 yr.
238
92
41.
Plutonium was detected in trace amounts in natural uranium deposits by Glenn Seaborg and his associates in 1941. They proposed
that the source of this 239Pu was the capture of neutrons by 238U nuclei. Why is this plutonium not likely to have been trapped at
the time the solar system formed 4.7 × 109 years ago?
42.
A Be atom (mass = 7.0169 amu) decays into a Li atom (mass = 7.0160 amu) by electron capture. How much energy (in millions
7
4
7
3
of electron volts, MeV) is produced by this reaction?

43.
A B atom (mass = 8.0246 amu) decays into a B atom (mass = 8.0053 amu) by loss of a β+ particle (mass = 0.00055 amu) or by
8
5
8
4
electron capture. How much energy (in millions of electron volts) is produced by this reaction?

44.
Isotopes such as 26Al (half-life: 7.2 × 105 years) are believed to have been present in our solar system as it formed, but have since
decayed and are now called extinct nuclides.
(a) 26Al decays by β+ emission or electron capture. Write the equations for these two nuclear transformations.
(b) The earth was formed about 4.7 × 109 (4.7 billion) years ago. How old was the earth when 99.999999% of the 26Al originally
present had decayed?
45.
(a) bismuth-212 decays into polonium-212
(b) beryllium-8 and a positron are produced by the decay of an unstable nucleus
(c) neptunium-239 forms from the reaction of uranium-238 with a neutron and then spontaneously converts into plutonium-239
(d) strontium-90 decays into yttrium-90
46.
(a) mercury-180 decays into platinum-176
(b) zirconium-90 and an electron are produced by the decay of an unstable nucleus
(c) thorium-232 decays and produces an alpha particle and a radium-228 nucleus, which decays into actinium-228 by beta decay
(d) neon-19 decays into fluorine-19
21.11.0.1: 21.4 Transmutation and Nuclear Energy

47.
Write the balanced nuclear equation for the production of the following transuranium elements:
(a) berkelium-244, made by the reaction of Am-241 and He-4
(b) fermium-254, made by the reaction of Pu-239 with a large number of neutrons
(c) lawrencium-257, made by the reaction of Cf-250 and B-11
(d) dubnium-260, made by the reaction of Cf-249 and N-15
48.
How does nuclear fission differ from nuclear fusion? Why are both of these processes exothermic?
49.
Both fusion and fission are nuclear reactions. Why is a very high temperature required for fusion, but not for fission?
50.
Cite the conditions necessary for a nuclear chain reaction to take place. Explain how it can be controlled to produce energy, but not
produce an explosion.
51.
Describe the components of a nuclear reactor.
52.
In usual practice, both a moderator and control rods are necessary to operate a nuclear chain reaction safely for the purpose of
energy production. Cite the function of each and explain why both are necessary.
53.
Describe how the potential energy of uranium is converted into electrical energy in a nuclear power plant.
54.

The mass of a hydrogen atom ( H) is 1.007825 amu; that of a tritium atom ( H) is 3.01605 amu; and that of an α particle is
1
1
3
1
4.00150 amu. How much energy in kilojoules per mole of He produced is released by the following fusion reaction:
4
2
1 3 4
H+ H ⟶ He.
1 1 2
21.11.0.1: 21.5 Uses of Radioisotopes

55.
How can a radioactive nuclide be used to show that the equilibrium:
+ −
is a dynamic equilibrium?
56.
Technetium-99m has a half-life of 6.01 hours. If a patient injected with technetium-99m is safe to leave the hospital once 75% of
the dose has decayed, when is the patient allowed to leave?
57.
Iodine that enters the body is stored in the thyroid gland from which it is released to control growth and metabolism. The thyroid
can be imaged if iodine-131 is injected into the body. In larger doses, I-133 is also used as a means of treating cancer of the thyroid.
I-131 has a half-life of 8.70 days and decays by β− emission.
(a) Write an equation for the decay.
(b) How long will it take for 95.0% of a dose of I-131 to decay?
21.11.0.1: 21.6 Biological Effects of Radiation

58.
If a hospital were storing radioisotopes, what is the minimum containment needed to protect against:
(a) cobalt-60 (a strong γ emitter used for irradiation)
(b) molybdenum-99 (a beta emitter used to produce technetium-99 for imaging)
59.
Based on what is known about Radon-222’s primary decay method, why is inhalation so dangerous?
60.
Given specimens uranium-232 (t1/2 = 68.9 y) and uranium-233 (t1/2 = 159,200 y) of equal mass, which one would have greater
activity and why?
61.
A scientist is studying a 2.234 g sample of thorium-229 (t1/2 = 7340 y) in a laboratory.
(a) What is its activity in Bq?
(b) What is its activity in Ci?
62.
Given specimens neon-24 (t1/2 = 3.38 min) and bismuth-211 (t1/2 = 2.14 min) of equal mass, which one would have greater activity
and why?

CHAPTER OVERVIEW
22: Appendices

General Chemistry
22.14: Answer Key
22.14.1: Chapter 1
22.14.2: Chapter 2
22.14.3: Chapter 3
22.14.4: Chapter 4
22.14.5: Chapter 5
22.14.6: Chapter 6
22.14.7: Chapter 7
22.14.8: Chapter 8
22.14.9: Chapter 9
22.14.10: Chapter 10
22.14.11: Chapter 11
22.14.12: Chapter 12
22.14.13: Chapter 13
22.14.14: Chapter 14
22.14.15: Chapter 15
22.14.16: Chapter 16
22.14.17: Chapter 17
22.14.18: Chapter 18
22.14.19: Chapter 19
22.14.20: Chapter 20
22.14.21: Chapter 21
1
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2
Figure A1
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22.2.1: Exponential Arithmetic
Exponential notation is used to express very large and very small numbers as a product of two numbers. The first number of the
product, the digit term, is usually a number not less than 1 and not equal to or greater than 10. The second number of the product,
the exponential term, is written as 10 with an exponent. Some examples of exponential notation are:
3
1000 = 1 × 10
2
100 = 1 × 10
1
10 = 1 × 10
0
1 = 1 × 10
−1
0.1 = 1 × 10
−3
0.001 = 1 × 10
3
2386 = 2.386 × 1000 = 2.386 × 10
−1
0.123 = 1.23 × 0.1 = 1.23 × 10
The power (exponent) of 10 is equal to the number of places the decimal is shifted to give the digit number. The exponential
method is particularly useful notation for very large and very small numbers. For example, 1,230,000,000 = 1.23 × 109, and
0.00000000036 = 3.6 × 10−10.
22.2.1.1: Addition of Exponentials

Convert all numbers to the same power of 10, add the digit terms of the numbers, and if appropriate, convert the digit term back to
a number between 1 and 10 by adjusting the exponential term.
Example B1
22.2.1.1.1: Adding Exponentials
Add 5.00 × 10−5 and 3.00 × 10−3.
−3 −5
3.00 × 10 = 300 × 10
−5 −5 −5 −3
(5.00 × 10 ) + (300 × 10 ) = 305 × 10 = 3.05 × 10
22.2.1.2: Subtraction of Exponentials

Convert all numbers to the same power of 10, take the difference of the digit terms, and if appropriate, convert the digit term back
to a number between 1 and 10 by adjusting the exponential term.
Example B2
22.2.1.2.1: Subtracting Exponentials
Subtract 4.0 × 10−7 from 5.0 × 10−6.
−7 −6
4.0 × 10 = 0.40 × 10
−6 −6 −6
(5.0 × 10 ) − (0.40 × 10 ) = 4.6 × 10
22.2.1.3: Multiplication of Exponentials

Multiply the digit terms in the usual way and add the exponents of the exponential terms.
Example B3

22.2.1.3.1: Multiplying Exponentials
Multiply 4.2 × 10−8 by 2.0 × 103.
−8 3 (−8)+(+3) −5
(4.2 × 10 ) × (2.0 × 10 ) = (4.2 × 2.0) × 10 = 8.4 × 10
22.2.1.4: Division of Exponentials

Divide the digit term of the numerator by the digit term of the denominator and subtract the exponents of the exponential terms.
Example B4
22.2.1.4.1: Dividing Exponentials
Divide 3.6 × 10–5 by 6.0 × 10−4.
−5
3.6 × 10 3.6
(−5)−(−4) −1 −2
=( ) × 10 = 0.60 × 10 = 6.0 × 10
−4 6.0
6.0 × 10
22.2.1.5: Squaring of Exponentials

Square the digit term in the usual way and multiply the exponent of the exponential term by 2.
Example B5
22.2.1.5.1: Squaring Exponentials
Square the number 4.0 × 10−6.
−6 2 2 × (−6) −12 −11
(4.0 × 10 ) = 4 × 4 × 10 = 16 × 10 = 1.6 × 10
22.2.1.6: Cubing of Exponentials

Cube the digit term in the usual way and multiply the exponent of the exponential term by 3.
Example B6
22.2.1.6.1: Cubing Exponentials
Cube the number 2 × 104.
4 3 3 × 4 12
(2 × 10 ) = 2 × 2 × 2 × 10 = 8 × 10
22.2.1.7: Taking Square Roots of Exponentials

If necessary, decrease or increase the exponential term so that the power of 10 is evenly divisible by 2. Extract the square root of
the digit term and divide the exponential term by 2.
Example B7
22.2.1.7.1: Finding the Square Root of Exponentials
Find the square root of 1.6 × 10−7.
−7 −8
1.6 × 10 = 16 × 10
− −−−−−−−− −− −−−− −−
8
−
√ 16 × 10−8 = √16 × √10−8 = √16 × 10 2 = 4.0 × 10
−4

22.2.2: Significant Figures
A beekeeper reports that he has 525,341 bees. The last three figures of the number are obviously inaccurate, for during the time the
keeper was counting the bees, some of them died and others hatched; this makes it quite difficult to determine the exact number of
bees. It would have been more reasonable if the beekeeper had reported the number 525,000. In other words, the last three figures
are not significant, except to set the position of the decimal point. Their exact values have no useful meaning in this situation.
When reporting quantities, use only as many significant figures as the accuracy of the measurement warrants.
The importance of significant figures lies in their application to fundamental computation. In addition and subtraction, the sum or
difference should contain as many digits to the right of the decimal as that in the least certain of the numbers used in the
computation (indicated by underscoring in the following example).
Example B8
22.2.2.0.1: Addition and Subtraction with Significant Figures
Add 4.383 g and 0.0023 g.
4.383 g
–
0.0023 g
–
4.385 g
–
In multiplication and division, the product or quotient should contain no more digits than that in the factor containing the least
number of significant figures.
Example B9
22.2.2.0.1: Multiplication and Division with Significant Figures
Multiply 0.6238 by 6.6.
0.6238 × 6.6 = 4.1

– – –
When rounding numbers, increase the retained digit by 1 if it is followed by a number larger than 5 (“round up”). Do not change
the retained digit if the digits that follow are less than 5 (“round down”). If the retained digit is followed by 5, round up if the
retained digit is odd, or round down if it is even (after rounding, the retained digit will thus always be even).
22.2.3: The Use of Logarithms and Exponential Numbers

The common logarithm of a number (log) is the power to which 10 must be raised to equal that number. For example, the common
logarithm of 100 is 2, because 10 must be raised to the second power to equal 100. Additional examples follow.
Logarithms and Exponential Numbers
Number Number Expressed Exponentially Common Logarithm
1000 103 3
10 101 1
1 100 0
0.1 10−1 −1
0.001 10−3 −3

Table B1
What is the common logarithm of 60? Because 60 lies between 10 and 100, which have logarithms of 1 and 2, respectively, the
logarithm of 60 is 1.7782; that is,
1.7782
60 = 10
The common logarithm of a number less than 1 has a negative value. The logarithm of 0.03918 is −1.4069, or
−1.4069
1
0.03918 = 10 =
1.4069
10
To obtain the common logarithm of a number, use the log button on your calculator. To calculate a number from its logarithm, take
the inverse log of the logarithm, or calculate 10x (where x is the logarithm of the number).
The natural logarithm of a number (ln) is the power to which e must be raised to equal the number; e is the constant 2.7182818. For
example, the natural logarithm of 10 is 2.303; that is,
2.303 2.303
10 = e = 2 .7182818
To obtain the natural logarithm of a number, use the ln button on your calculator. To calculate a number from its natural logarithm,
enter the natural logarithm and take the inverse ln of the natural logarithm, or calculate ex (where x is the natural logarithm of the
number).
Logarithms are exponents; thus, operations involving logarithms follow the same rules as operations involving exponents.
1. The logarithm of a product of two numbers is the sum of the logarithms of the two numbers.
log xy = log x + log y, and ln xy = ln x + ln y
2. The logarithm of the number resulting from the division of two numbers is the difference between the logarithms of the two
numbers.
x x
log = log x − log y, and ln = ln x − ln y
y y
3. The logarithm of a number raised to an exponent is the product of the exponent and the logarithm of the number.
n n
log x = nlog x and ln x = nln x
22.2.4: The Solution of Quadratic Equations

Mathematical functions of this form are known as second-order polynomials or, more commonly, quadratic functions.
2
ax + bx + c = 0
The solution or roots for any quadratic equation can be calculated using the following formula:
− − −−−−−
2
−b ± √ b − 4ac
x =
2a
Example B10
22.2.4.0.1: Solving Quadratic Equations
Solve the quadratic equation 3x2 + 13x − 10 = 0.
Substituting the values a = 3, b = 13, c = −10 in the formula, we obtain
−−−−−−−−−−−−−−−−−−−
2
−13 ± √ (13) − 4 × 3 × (−10)
x =
2 × 3
− −−−−− −− −−−
−13 ± √ 169 + 120 −13 ± √289 −13 ± 17
x = = =
6 6 6
The two roots are therefore

−13 + 17 2 −13 − 17
x = = and x = = −5
6 3 6
Quadratic equations constructed on physical data always have real roots, and of these real roots, often only those having positive
values are of any significance.
22.2.5: Two-Dimensional (x-y) Graphing

The relationship between any two properties of a system can be represented graphically by a two-dimensional data plot. Such a
graph has two axes: a horizontal one corresponding to the independent variable, or the variable whose value is being controlled (x),
and a vertical axis corresponding to the dependent variable, or the variable whose value is being observed or measured (y).
When the value of y is changing as a function of x (that is, different values of x correspond to different values of y), a graph of this
change can be plotted or sketched. The graph can be produced by using specific values for (x,y) data pairs.
Example B11
22.2.5.0.1: Graphing the Dependence of y on x
x y
1 5
2 10
3 7
4 14
This table contains the following points: (1,5), (2,10), (3,7), and (4,14). Each of these points can be plotted on a graph and
connected to produce a graphical representation of the dependence of y on x.

If the function that describes the dependence of y on x is known, it may be used to compute x,y data pairs that may subsequently be
plotted.
Example B12
22.2.5.0.1: Plotting Data Pairs
If we know that y = x2 + 2, we can produce a table of a few (x,y) values and then plot the line based on the data shown here.
x y = x2 + 2
1 3
2 6
3 11
4 18
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Units of Length
meter (m) = 39.37 inches (in.)

= 1.094 yards (yd)
centimeter (cm) = 0.01 m (exact, definition)
millimeter (mm) = 0.001 m (exact, definition)
kilometer (km) = 1000 m (exact, definition)
angstrom (Å) = 10–8 cm (exact, definition)

= 10–10 m (exact, definition)
yard (yd) = 0.9144 m
inch (in.) = 2.54 cm (exact, definition)
mile (US) = 1.60934 km
Table C1
Units of Volume
liter (L) = 0.001 m3 (exact, definition)

= 1000 cm3 (exact, definition)
= 1.057 (US) quarts
milliliter (mL) = 0.001 L (exact, definition)

= 1 cm3 (exact, definition)
microliter (μL) = 10–6 L (exact, definition)

= 10–3 cm3 (exact, definition)
liquid quart (US) = 32 (US) liquid ounces (exact, definition)

= 0.25 (US) gallon (exact, definition)
= 0.9463 L
dry quart = 1.1012 L
cubic foot (US) = 28.316 L
Table C2
Units of Mass
gram (g) = 0.001 kg (exact, definition)
milligram (mg) = 0.001 g (exact, definition)
kilogram (kg) = 1000 g (exact, definition)

= 2.205 lb

ton (metric) =1000 kg (exact, definition)
= 2204.62 lb
ounce (oz) = 28.35 g
pound (lb) = 0.4535924 kg
ton (short) =2000 lb (exact, definition)

= 907.185 kg
ton (long) = 2240 lb (exact, definition)

= 1.016 metric ton
Table C3
Units of Energy
4.184 joule (J) = 1 thermochemical calorie (cal)
1 thermochemical calorie (cal) = 4.184 × 107 erg
erg = 10–7 J (exact, definition)
electron-volt (eV) = 1.60218 × 10−19 J = 23.061 kcal mol−1
liter·atmosphere = 24.217 cal = 101.325 J (exact, definition)
nutritional calorie (Cal) = 1000 cal (exact, definition) = 4184 J
British thermal unit (BTU) = 1054.804 J1
Table C4
Units of Pressure
torr = 1 mm Hg (exact, definition)
pascal (Pa) = N m–2 (exact, definition)

= kg m–1 s–2 (exact, definition)
atmosphere (atm) = 760 mm Hg (exact, definition)

= 760 torr (exact, definition)
= 101,325 N m–2 (exact, definition)
= 101,325 Pa (exact, definition)
bar = 105 Pa (exact, definition)

= 105 kg m–1 s–2 (exact, definition)
Table C5
22.3.0.1: Footnotes
1BTU is the amount of energy needed to heat one pound of water by one degree Fahrenheit. Therefore, the exact relationship of
BTU to joules and other energy units depends on the temperature at which BTU is measured. 59 °F (15 °C) is the most widely
used reference temperature for BTU definition in the United States. At this temperature, the conversion factor is the one
provided in this table.

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Fundamental Physical Constants
Name and Symbol Value
atomic mass unit (amu) 1.6605402 × 10−27 kg
Avogadro’s number 6.02214076 × 1023 mol−1
Boltzmann’s constant (k) 1.380649 × 10−23 J K−1
charge-to-mass ratio for electron (e/me) 1.75881962 × 1011 C kg−1
fundamental unit of charge (e) 1.602176634 × 10−19 C
electron rest mass (me) 9.1093897 × 10−31 kg
Faraday’s constant (F) 9.6485309 × 104 C mol−1
gas constant (R) 8.205784 × 10−2 L atm mol−1 K−1 = 8.314510 J mol−1 K−1
molar volume of an ideal gas, 1 atm, 0 °C 22.41409 L mol–1
molar volume of an ideal gas, 1 bar, 0 °C 22.71108 L mol–1
neutron rest mass (mn) 1.6749274 × 10−27 kg
Planck’s constant (h) 6.62607015 × 10−34 J s
proton rest mass (mp) 1.6726231 × 10−27 kg
Rydberg constant (R) 1.0973731534 × 107 m−1 = 2.1798736 × 10−18 J
speed of light (in vacuum) (c) 2.99792458 × 108 m s−1
Table D1
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Water Density (g/mL) at Different Temperatures (°C)
Temperature Density (g/mL)
0 0.9998395
4 0.9999720 (density maximum)
10 0.9997026
15 0.9991026
20 0.9982071
22 0.9977735
25 0.9970479
30 0.9956502
40 0.9922
60 0.9832
80 0.9718
100 0.9584
Table E1

Water Vapor Pressure at Different Temperatures (°C)
Temperature Vapor Pressure (torr) Vapor Pressure (Pa)
0 4.6 613.2812
4 6.1 813.2642
10 9.2 1226.562
15 12.8 1706.522
20 17.5 2333.135
22 19.8 2639.776
25 23.8 3173.064
30 31.8 4239.64
35 42.2 5626.188
40 55.3 7372.707
45 71.9 9585.852
50 92.5 12332.29

Temperature Vapor Pressure (torr) Vapor Pressure (Pa)
55 118.0 15732
60 149.4 19918.31
65 187.5 24997.88
70 233.7 31157.35
75 289.1 38543.39
80 355.1 47342.64
85 433.6 57808.42
90 525.8 70100.71
95 633.9 84512.82
100 760.0 101324.7
Table E2
Water Kw and pKw at Different Temperatures (°C)

Temperature Kw 10–14 pKw1

Temperature Kw 10–14 pKw1
0 0.112 14.95
5 0.182 14.74
10 0.288 14.54
15 0.465 14.33
20 0.671 14.17
25 0.991 14.00
30 1.432 13.84
35 2.042 13.69
40 2.851 13.55
45 3.917 13.41
50 5.297 13.28
55 7.080 13.15
60 9.311 13.03
75 19.95 12.70
100 56.23 12.25
Table E3

Specific Heat Capacity for Water
C°(H2O(l)) = 4.184 J·g-1·°C-1
C°(H2O(s)) = 1.864 J·K−1·g−1
C°(H2O(g)) = 2.093 J·K−1·g−1
Table E4
Standard Water Melting and Boiling Temperatures and Enthalpies of the Transitions
Temperature (K) ΔH (kJ/mol)
melting 273.15 6.088
boiling 373.15 40.656 (44.016 at 298 K)
Table E5
Water Cryoscopic (Freezing Point Depression) and Ebullioscopic (Boiling Point Elevation) Constants
Kf = 1.86°C·kg·mol−1 (cryoscopic constant)
Kb = 0.51°C·kg·mol−1 (ebullioscopic constant)
Table E6

Figure E1 The plot shows the extent of light absorption versus wavelength for water. Absorption is reported in reciprocal meters
and corresponds to the inverse of the distance light may travel through water before its intensity is diminished by 1/e (~37%).
22.5.0.1: Footnotes
1pKw = –log10(Kw)
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Composition of Commercial Acids and Bases
Acid or Base1 Density (g/mL)2 Percentage by Mass Molarity
acetic acid, glacial 1.05 99.5% 17.4
aqueous ammonia3 0.90 28% 14.8
hydrochloric acid 1.18 36% 11.6
nitric acid 1.42 71% 16.0
perchloric acid 1.67 70% 11.65
phosphoric acid 1.70 85% 14.7
sodium hydroxide 1.53 50% 19.1
sulfuric acid 1.84 96% 18.0
Table F1
22.6.0.1: Footnotes
1Acids and bases are commercially available as aqueous solutions. This table lists properties (densities and concentrations) of
common acid and base solutions. Nominal values are provided in cases where the manufacturer cites a range of concentrations
and densities.
2This column contains specific gravity data. In the case of this table, specific gravity is the ratio of density of a substance to the
density of pure water at the same conditions. Specific gravity is often cited on commercial labels.
3This solution is sometimes called “ammonium hydroxide,” although this term is not chemically accurate.
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upon request.

Standard Thermodynamic Properties for Selected Substances
Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
(kJ mol–1) S° (J K–1 mol–1)
aluminum
Al(s) 0 0 28.3
Al(g) 324.4 285.7 164.54
Al3+(aq) –531 –485 –321.7
Al2O3(s) –1676 –1582 50.92
AlF3(s) –1510.4 –1425 66.5
AlCl3(s) –704.2 –628.8 110.67
AlCl3·6H2O(s) –2691.57 –2269.40 376.56
Al2S3(s) –724.0 –492.4 116.9
Al2(SO4)3(s) –3445.06 –3506.61 239.32
antimony
Sb(s) 0 0 45.69
Sb(g) 262.34 222.17 180.16
Sb4O6(s) –1440.55 –1268.17 220.92
SbCl3(g) –313.8 –301.2 337.80
SbCl5(g) –394.34 –334.29 401.94
Sb2S3(s) –174.89 –173.64 182.00
SbCl3(s) –382.17 –323.72 184.10
SbOCl(s) –374.0 — —
arsenic
As(s) 0 0 35.1
As(g) 302.5 261.0 174.21
As4(g) 143.9 92.4 314

Substance ΔH
∘
f
(kJ mol–1) ΔG
∘
f
As4O6(s) –1313.94 –1152.52 214.22
As2O5(s) –924.87 –782.41 105.44
AsCl3(g) –261.50 –248.95 327.06
As2S3(s) –169.03 –168.62 163.59
AsH3(g) 66.44 68.93 222.78
H3AsO4(s) –906.3 — —
barium
Ba(s) 0 0 62.5
Ba(g) 180 146 170.24
Ba2+(aq) –537.6 –560.8 9.6
BaO(s) –548.0 –520.3 72.1
BaCl2(s) –855.0 –806.7 123.7
BaSO4(s) –1473.2 –1362.3 132.2
beryllium
Be(s) 0 0 9.50
Be(g) 324.3 286.6 136.27
BeO(s) –609.4 –580.1 13.8
bismuth
Bi(s) 0 0 56.74
Bi(g) 207.1 168.2 187.00
Bi2O3(s) –573.88 –493.7 151.5
BiCl3(s) –379.07 –315.06 176.98
Bi2S3(s) –143.1 –140.6 200.4
boron

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
B(s) 0 0 5.86
B(g) 565.0 521.0 153.4
B2O3(s) –1273.5 –1194.3 53.97
B2H6(g) 36.4 87.6 232.1
H3BO3(s) –1094.33 –968.92 88.83
BF3(g) –1136.0 –1119.4 254.4
BCl3(g) –403.8 –388.7 290.1
B3N3H6(l) –540.99 –392.79 199.58
HBO2(s) –794.25 –723.41 37.66
bromine
Br2(l) 0 0 152.23
Br2(g) 30.91 3.142 245.5
Br(g) 111.88 82.429 175.0
Br–(aq) –120.9 –102.82 80.71
BrF3(g) –255.60 –229.45 292.42
HBr(g) –36.3 –53.43 198.7
cadmium
Cd(s) 0 0 51.76
Cd(g) 112.01 77.41 167.75
Cd2+(aq) –75.90 –77.61 –73.2
CdO(s) –258.2 –228.4 54.8
CdCl2(s) –391.5 –343.9 115.3
CdSO4(s) –933.3 –822.7 123.0
CdS(s) –161.9 –156.5 64.9

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
calcium
Ca(s) 0 0 41.6
Ca(g) 178.2 144.3 154.88
Ca2+(aq) –542.96 –553.04 –55.2
CaO(s) –634.9 –603.3 38.1
Ca(OH)2(s) –985.2 –897.5 83.4
CaSO4(s) –1434.5 –1322.0 106.5
CaSO4·2H2O(s) –2022.63 –1797.45 194.14
CaCO3(s) (calcite) –1220.0 –1081.4 110.0
CaSO3·H2O(s) –1752.68 –1555.19 184.10
carbon
C(s) (graphite) 0 0 5.740
C(s) (diamond) 1.89 2.90 2.38
C(g) 716.681 671.2 158.1
CO(g) –110.52 –137.15 197.7
CO2(g) –393.51 –394.36 213.8
CO3 2–(aq) –677.1 –527.8 –56.9
CH4(g) –74.6 –50.5 186.3
CH3OH(l) –239.2 –166.6 126.8
CH3OH(g) –201.0 –162.3 239.9
CCl4(l) –128.2 –62.5 214.4
CCl4(g) –95.7 –58.2 309.7
CHCl3(l) –134.1 –73.7 201.7
CHCl3(g) –103.14 –70.34 295.71

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
CS2(l) 89.70 65.27 151.34
CS2(g) 116.9 66.8 238.0
C2H2(g) 227.4 209.2 200.9
C2H4(g) 52.4 68.4 219.3
C2H6(g) –84.0 –32.0 229.2
CH3CO2H(l) –484.3 –389.9 159.8
CH3CO2H(g) –434.84 –376.69 282.50
C2H5OH(l) –277.6 –174.8 160.7
C2H5OH(g) –234.8 –167.9 281.6
HCO3 –(aq) –691.11 –587.06 95
C3H8(g) –103.8 –23.4 270.3
C6H6(g) 82.927 129.66 269.2
C6H6(l) 49.1 124.50 173.4
CH2Cl2(l) –124.2 –63.2 177.8
CH2Cl2(g) –95.4 –65.90 270.2
CH3Cl(g) –81.9 –60.2 234.6
C2H5Cl(l) –136.52 –59.31 190.79
C2H5Cl(g) –112.17 –60.39 276.00
C2N2(g) 308.98 297.36 241.90
HCN(l) 108.9 125.0 112.8
HCN(g) 135.5 124.7 201.8
cesium
Cs+(aq) –248 –282.0 133
chlorine

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
Cl2(g) 0 0 223.1
Cl(g) 121.3 105.70 165.2
Cl–(aq) –167.2 –131.2 56.5
ClF(g) –54.48 –55.94 217.78
ClF3(g) –158.99 –118.83 281.50
Cl2O(g) 80.3 97.9 266.2
Cl2O7(l) 238.1 — —
Cl2O7(g) 272.0 — —
HCl(g) –92.307 –95.299 186.9
HClO4(l) –40.58 — —
chromium
Cr(s) 0 0 23.77
Cr(g) 396.6 351.8 174.50
CrO4 2–(aq) –881.2 –727.8 50.21
Cr2O7 2–(aq) –1490.3 –1301.1 261.9
Cr2O3(s) –1139.7 –1058.1 81.2
CrO3(s) –589.5 — —
(NH4)2Cr2O7(s) –1806.7 — —
cobalt
Co(s) 0 0 30.0
Co2+(aq) –67.4 –51.5 –155
Co3+(aq) 92 134 –305.0
CoO(s) –237.9 –214.2 52.97
Co3O4(s) –910.02 –794.98 114.22

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
Co(NO3)2(s) –420.5 — —
copper
Cu(s) 0 0 33.15
Cu(g) 338.32 298.58 166.38
Cu+(aq) 51.9 50.2 –26
Cu2+(aq) 64.77 65.49 –99.6
CuO(s) –157.3 –129.7 42.63
Cu2O(s) –168.6 –146.0 93.14
CuS(s) –53.1 –53.6 66.5
Cu2S(s) –79.5 –86.2 120.9
CuSO4(s) –771.36 –662.2 109.2
Cu(NO3)2(s) –302.9 — —
fluorine
F2(g) 0 0 202.8
F(g) 79.4 62.3 158.8
F–(aq) –332.6 –278.8 –13.8
F2O(g) 24.7 41.9 247.43
HF(g) –273.3 –275.4 173.8
hydrogen
H2(g) 0 0 130.7
H(g) 217.97 203.26 114.7
H+(aq) 0 0 0
OH–(aq) –230.0 –157.2 –10.75
H3O+(aq) –285.8 69.91

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
H2O(l) –285.83 –237.1 70.0
H2O(g) –241.82 –228.59 188.8
H2O2(l) –187.78 –120.35 109.6
H2O2(g) –136.3 –105.6 232.7
HF(g) –273.3 –275.4 173.8
HCl(g) –92.307 –95.299 186.9
HBr(g) –36.3 –53.43 198.7
HI(g) 26.48 1.70 206.59
H2S(g) –20.6 –33.4 205.8
H2Se(g) 29.7 15.9 219.0
HNO3 –206.64 — —
iodine
I2(s) 0 0 116.14
I2(g) 62.438 19.3 260.7
I(g) 106.84 70.2 180.8
I–(aq) –55.19 –51.57 11.13
IF(g) 95.65 –118.49 236.06
ICl(g) 17.78 –5.44 247.44
IBr(g) 40.84 3.72 258.66
IF7(g) –943.91 –818.39 346.44
HI(g) 26.48 1.70 206.59
iron
Fe(s) 0 0 27.3
Fe(g) 416.3 370.7 180.5

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
Fe2+(aq) –89.1 –78.90 –137.7
Fe3+(aq) –48.5 –4.7 –315.9
Fe2O3(s) –824.2 –742.2 87.40
Fe3O4(s) –1118.4 –1015.4 146.4
Fe(CO)5(l) –774.04 –705.42 338.07
Fe(CO)5(g) –733.87 –697.26 445.18
FeCl2(s) –341.79 –302.30 117.95
FeCl3(s) –399.49 –334.00 142.3
FeO(s) –272.0 –255.2 60.75
Fe(OH)2(s) –569.0 –486.5 88.
Fe(OH)3(s) –823.0 –696.5 106.7
FeS(s) –100.0 –100.4 60.29
Fe3C(s) 25.10 20.08 104.60
lead
Pb(s) 0 0 64.81
Pb(g) 195.2 162. 175.4
Pb2+(aq) –1.7 –24.43 10.5
PbO(s) (yellow) –217.32 –187.89 68.70
PbO(s) (red) –218.99 –188.93 66.5
Pb(OH)2(s) –515.9 — —
PbS(s) –100.4 –98.7 91.2
Pb(NO3)2(s) –451.9 — —
PbO2(s) –277.4 –217.3 68.6
PbCl2(s) –359.4 –314.1 136.0

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
lithium
Li(s) 0 0 29.1
Li(g) 159.3 126.6 138.8
Li+(aq) –278.5 –293.3 13.4
LiH(s) –90.5 –68.3 20.0
Li(OH)(s) –487.5 –441.5 42.8
LiF(s) –616.0 –587.5 35.7
Li2CO3(s) –1216.04 –1132.19 90.17
magnesium
Mg2+(aq) –466.9 –454.8 –138.1
manganese
Mn(s) 0 0 32.0
Mn(g) 280.7 238.5 173.7
Mn2+(aq) –220.8 –228.1 –73.6
MnO(s) –385.2 –362.9 59.71
MnO2(s) –520.03 –465.1 53.05
Mn2O3(s) –958.97 –881.15 110.46
Mn3O4(s) –1378.83 –1283.23 155.64
MnO4 –(aq) –541.4 –447.2 191.2
MnO4 2–(aq) –653.0 –500.7 59
mercury
Hg(l) 0 0 75.9
Hg(g) 61.4 31.8 175.0
Hg2+(aq) 164.8

Substance ΔH
∘
f
(kJ mol–1) ΔG
∘
f
Hg2+(aq) 172.4 153.9 84.5
HgO(s) (red) –90.83 –58.5 70.29
HgO(s) (yellow) –90.46 –58.43 71.13
HgCl2(s) –224.3 –178.6 146.0
Hg2Cl2(s) –265.4 –210.7 191.6
HgS(s) (red) –58.16 –50.6 82.4
HgS(s) (black) –53.56 –47.70 88.28
HgSO4(s) –707.51 –594.13 0.00
nickel
Ni2+(aq) –64.0 –46.4 –159
nitrogen
N2(g) 0 0 191.6
N(g) 472.704 455.5 153.3
NO(g) 90.25 87.6 210.8
NO2(g) 33.2 51.30 240.1
N2O(g) 81.6 103.7 220.0
N2O3(g) 83.72 139.41 312.17
NO3 –(aq) –205.0 –108.7 146.4
N2O4(g) 11.1 99.8 304.4
N2O5(g) 11.3 115.1 355.7
NH3(g) –45.9 –16.5 192.8
NH4 +(aq) –132.5 –79.31 113.4
N2H4(l) 50.63 149.43 121.21
N2H4(g) 95.4 159.4 238.5

Substance ΔH
∘
f
(kJ mol–1) ΔG
∘
f
NH4NO3(s) –365.56 –183.87 151.08
NH4Cl(s) –314.43 –202.87 94.6
NH4Br(s) –270.8 –175.2 113.0
NH4I(s) –201.4 –112.5 117.0
NH4NO2(s) –256.5 — —
HNO3(l) –174.1 –80.7 155.6
HNO3(g) –133.9 –73.5 266.9
HNO3(aq) –207.4 –110.5 146
oxygen
O2(g) 0 0 205.2
O(g) 249.17 231.7 161.1
O3(g) 142.7 163.2 238.9
phosphorus
P4(s) 0 0 164.4
P4(g) 58.91 24.4 280.0
P(g) 314.64 278.25 163.19
PH3(g) 5.4 13.5 210.2
PCl3(g) –287.0 –267.8 311.78
PCl5(g) –374.9 –305.0 364.4
P4O6(s) –1640.1 — —
P4O10(s) –2984.0 –2697.0 228.86
PO4 3–(aq) –1277 –1019 –222
HPO3(s) –948.5 — —
HPO4 2–(aq) –1292.1 –1089.3 –33

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
H2PO4 2–(aq) –1296.3 –1130.4 90.4
H3PO2(s) –604.6 — —
H3PO3(s) –964.4 — —
H3PO4(s) –1279.0 –1119.1 110.50
H3PO4(l) –1266.9 –1124.3 110.5
H4P2O7(s) –2241.0 — —
POCl3(l) –597.1 –520.8 222.5
POCl3(g) –558.5 –512.9 325.5
potassium
K(s) 0 0 64.7
K(g) 89.0 60.5 160.3
K+(aq) –252.4 –283.3 102.5
KF(s) –576.27 –537.75 66.57
KCl(s) –436.5 –408.5 82.6
rubidium
Rb+(aq) –246 –282.2 124
silicon
Si(s) 0 0 18.8
Si(g) 450.0 405.5 168.0
SiO2(s) –910.7 –856.3 41.5
SiH4(g) 34.3 56.9 204.6
H2SiO3(s) –1188.67 –1092.44 133.89
H4SiO4(s) –1481.14 –1333.02 192.46
SiF4(g) –1615.0 –1572.8 282.8

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
SiCl4(l) –687.0 –619.8 239.7
SiCl4(g) –662.75 –622.58 330.62
SiC(s, beta cubic) –73.22 –70.71 16.61
SiC(s, alpha hexagonal) –71.55 –69.04 16.48
silver
Ag(s) 0 0 42.55
Ag(g) 284.9 246.0 172.89
Ag+(aq) 105.6 77.11 72.68
Ag2O(s) –31.05 –11.20 121.3
AgCl(s) –127.0 –109.8 96.3
Ag2S(s) –32.6 –40.7 144.0
sodium
Na(s) 0 0 51.3
Na(g) 107.5 77.0 153.7
Na+(aq) –240.1 –261.9 59
Na2O(s) –414.2 –375.5 75.1
NaCl(s) –411.2 –384.1 72.1
strontium
Sr2+(aq) –545.8 –557.3 –32.6
sulfur
S8(s) (rhombic) 0 0 256.8
S(g) 278.81 238.25 167.82
S2–(aq) 41.8 83.7 22
SO2(g) –296.83 –300.1 248.2

Substance ΔH
∘
f
(kJ mol–1) ΔG
∘
f
SO3(g) –395.72 –371.06 256.76
SO4 2–(aq) –909.3 –744.5 20.1
S2O3 2–(aq) –648.5 –522.5 67
H2S(g) –20.6 –33.4 205.8
HS–(aq) –17.7 12.6 61.1
H2SO4(l) –813.989 –690.00 156.90
HSO4 2–(aq) –885.75 –752.87 126.9
H2S2O7(s) –1273.6 — —
SF4(g) –728.43 –684.84 291.12
SF6(g) –1220.5 –1116.5 291.5
SCl2(l) –50 — —
SCl2(g) –19.7 — —
S2Cl2(l) –59.4 — —
S2Cl2(g) –19.50 –29.25 319.45
SOCl2(g) –212.55 –198.32 309.66
SOCl2(l) –245.6 — —
SO2Cl2(l) –394.1 — —
SO2Cl2(g) –354.80 –310.45 311.83
tin
Sn(s) 0 0 51.2
Sn(g) 301.2 266.2 168.5
SnO(s) –285.8 –256.9 56.5
SnO2(s) –577.6 –515.8 49.0
SnCl4(l) –511.3 –440.1 258.6

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
SnCl4(g) –471.5 –432.2 365.8
titanium
Ti(s) 0 0 30.7
Ti(g) 473.0 428.4 180.3
TiO2(s) –944.0 –888.8 50.6
TiCl4(l) –804.2 –737.2 252.4
TiCl4(g) –763.2 –726.3 353.2
tungsten
W(s) 0 0 32.6
W(g) 849.4 807.1 174.0
WO3(s) –842.9 –764.0 75.9
zinc
Zn(s) 0 0 41.6
Zn(g) 130.73 95.14 160.98
Zn2+(aq) –153.9 –147.1 –112.1
ZnO(s) –350.5 –320.5 43.7
ZnCl2(s) –415.1 –369.43 111.5
ZnS(s) –206.0 –201.3 57.7
ZnSO4(s) –982.8 –871.5 110.5
ZnCO3(s) –812.78 –731.57 82.42
complexes
[Co(NH3)4(NO2)2]NO3, cis –898.7 — —
[Co(NH3)4(NO2)2]NO3, trans –896.2 — —
NH4[Co(NH3)2(NO2)4] –837.6 — —

Substance ΔH
f
∘
(kJ mol–1) ΔG
∘
f
[Co(NH3)6][Co(NH3)2(NO2)4]3 –2733.0 — —
[Co(NH3)4Cl2]Cl, cis –874.9 — —
[Co(NH3)4Cl2]Cl, trans –877.4 — —
[Co(en)2(NO2)2]NO3, cis –689.5 — —
[Co(en)2Cl2]Cl, cis –681.2 — —
[Co(en)2Cl2]Cl, trans –677.4 — —
[Co(en)3](ClO4)3 –762.7 — —
[Co(en)3]Br2 –595.8 — —
[Co(en)3]I2 –475.3 — —
[Co(en)3]I3 –519.2 — —
[Co(NH3)6](ClO4)3 –1034.7 –221.1 615
[Co(NH3)5NO2](NO3)2 –1088.7 –412.9 331
[Co(NH3)6](NO3)3 –1282.0 –524.5 448
[Co(NH3)5Cl]Cl2 –1017.1 –582.5 366.1
[Pt(NH3)4]Cl2 –725.5 — —
[Ni(NH3)6]Cl2 –994.1 — —
[Ni(NH3)6]Br2 –923.8 — —
[Ni(NH3)6]I2 –808.3 — —
Table G1
This page titled 22.7: Standard Thermodynamic Properties for Selected Substances is shared under a CC BY 4.0 license and was authored,

Ionization Constants of Weak Acids
Acid Formula Ka at 25 °C Lewis Structure
acetic CH3CO2H 1.8 × 10−5
arsenic H3AsO4 5.5 × 10−3
1.7 × 10−7
3.0 × 10−12
arsenous H3AsO3 5.1 × 10−10
boric H3BO3 5.4 × 10−10
carbonic H2CO3 4.3 × 10−7
4.7 × 10−11
cyanic HCNO 2 × 10−4
formic HCO2H 1.8 × 10−4

hydrazoic HN3 2.5 × 10−5
hydrocyanic HCN 4.9 × 10−10
hydrofluoric HF 6.4 × 10−4
hydrogen peroxide H2O2 2.4 × 10−12
hydrogen selenide H2Se 1.29 × 10−4
HSe– 1 × 10−12
hydrogen sulfate ion 1.2 × 10−2
hydrogen sulfide H2S 8.9 × 10−8
HS– 1.0 × 10−19
hydrogen telluride H2Te 2.3 × 10−3
HTe– 1.6 × 10−11
hypobromous HBrO 2.8 × 10−9
hypochlorous HClO 2.9 × 10−8
nitrous HNO2 4.6 × 10−4
oxalic H2C2O4 6.0 × 10−2
6.1 × 10−5
phosphoric H3PO4 7.5 × 10−3

6.2 × 10−8
4.2 × 10−13
phosphorous H3PO3 5 × 10−2
2.0 × 10−7
sulfurous H2SO3 1.6 × 10−2
6.4 × 10−8
Table H1
This page titled 22.8: Ionization Constants of Weak Acids is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

Ionization Constants of Weak Bases
Base Lewis Structure Kb at 25 °C
ammonia 1.8 × 10−5
dimethylamine 5.9 × 10−4
methylamine 4.4 × 10−4
phenylamine (aniline) 4.3 × 10−10
trimethylamine 6.3 × 10−5
Table I1
This page titled 22.9: Ionization Constants of Weak Bases is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

Solubility Products
Substance Ksp at 25 °C
aluminum
Al(OH)3 2 × 10−32
barium
BaCO3 1.6 × 10−9
BaC2O4·2H2O 1.1 × 10−7
BaSO4 2.3 × 10−8
BaCrO4 8.5 × 10−11
BaF2 2.4 × 10−5
Ba(OH)2·8H2O 5.0 × 10−3
Ba3(PO4)2 6 × 10−39
Ba3(AsO4)2 1.1 × 10−13
bismuth
BiO(OH) 4 × 10−10
BiOCl 1.8 × 10−31
Bi2S3 1 × 10−97
cadmium
Cd(OH)2 5.9 × 10−15
CdS 1.0 × 10−28
CdCO3 5.2 × 10−12
calcium
Ca(OH)2 1.3 × 10−6
CaCO3 8.7 × 10−9
CaSO4·2H2O 6.1 × 10−5

CaC2O4·H2O 1.96 × 10−8
Ca3(PO4)2 1.3 × 10−32
CaHPO4 7 × 10−7
CaF2 4.0 × 10−11
chromium
Cr(OH)3 6.7 × 10−31
cobalt
Co(OH)2 2.5 × 10−16
CoS(α) 5 × 10−22
CoS(β) 3 × 10−26
CoCO3 1.4 × 10−13
Co(OH)3 2.5 × 10−43
copper
CuCl 1.2 × 10−6
CuBr 6.27 × 10−9
CuI 1.27 × 10−12
CuSCN 1.6 × 10−11
Cu2S 2.5 × 10−48
Cu(OH)2 2.2 × 10−20
CuS 8.5 × 10−45
CuCO3 2.5 × 10−10
iron
Fe(OH)2 1.8 × 10−15
FeCO3 2.1 × 10−11

FeS 3.7 × 10−19
Fe(OH)3 4 × 10−38
lead
Pb(OH)2 1.2 × 10−15
PbF2 4 × 10−8
PbCl2 1.6 × 10−5
PbBr2 4.6 × 10−6
PbI2 1.4 × 10−8
PbCO3 1.5 × 10−15
PbS 7 × 10−29
PbCrO4 2 × 10−16
PbSO4 1.3 × 10−8
Pb3(PO4)2 1 × 10−54
magnesium
Mg(OH)2 8.9 × 10−12
MgCO3·3H2O ca 1 × 10−5
MgNH4PO4 3 × 10−13
MgF2 6.4 × 10−9
MgC2O4 7 × 10−7
manganese
Mn(OH)2 2 × 10−13
MnCO3 8.8 × 10−11
MnS 2.3 × 10−13
mercury

Hg2O·H2O 3.6 × 10−26
Hg2Cl2 1.1 × 10−18
Hg2Br2 1.3 × 10−22
Hg2I2 4.5 × 10−29
Hg2CO3 9 × 10−15
Hg2SO4 7.4 × 10−7
Hg2S 1.0 × 10−47
Hg2CrO4 2 × 10−9
HgS 1.6 × 10−54
nickel
Ni(OH)2 1.6 × 10−16
NiCO3 1.4 × 10−7
NiS(α) 4 × 10−20
NiS(β) 1.3 × 10−25
potassium
KClO4 1.05 × 10−2
K2PtCl6 7.48 × 10−6
KHC4H4O6 3 × 10−4
silver
1
2
Ag O( Ag
2
+
+ OH
−
) 2 × 10−8
AgCl 1.6 × 10−10
AgBr 5.0 × 10−13
AgI 1.5 × 10−16
AgCN 1.2 × 10−16

AgSCN 1.0 × 10−12
Ag2S 1.6 × 10−49
Ag2CO3 8.1 × 10−12
Ag2CrO4 9.0 × 10−12
Ag4Fe(CN)6 1.55 × 10−41
Ag2SO4 1.2 × 10−5
Ag3PO4 1.8 × 10−18
strontium
Sr(OH)2·8H2O 3.2 × 10−4
SrCO3 7 × 10−10
SrCrO4 3.6 × 10−5
SrSO4 3.2 × 10−7
SrC2O4·H2O 4 × 10−7
thallium
TlCl 1.7 × 10−4
TlSCN 1.6 × 10−4
Tl2S 6 × 10−22
Tl(OH)3 6.3 × 10−46
tin
Sn(OH)2 3 × 10−27
SnS 1 × 10−26
Sn(OH)4 1.0 × 10−57
zinc
ZnCO3 2 × 10−10
Table J1

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Formation Constants for Complex Ions
Equilibrium Kf
Al
3+
+ 6F
−
⇌ [AlF 6 ]
3−
7 × 1019
Cd
2+
+ 4NH3 ⇌ [Cd ( NH3 ) ]
2+
1.3 × 107
4
Cd
2+
+ 4CN
−
⇌ [Cd (CN) ]
2−
3 × 1018
4
Co
2+
+ 6NH3 ⇌ [Co( NH3 ) ]
2+
1.3 × 105
6
Co
3+
+ 6NH3 ⇌ [Co( NH3 ) ]
3+
2.3 × 1033
6
Cu
+
+ 2CN ⇌ [Cu (CN) ]
2
−
1.0 × 1016
Cu
2+
+ 4NH3 ⇌ [Cu ( NH3 ) ]
2+
1.7 × 1013
4
Fe
2+
+ 6CN
−
⇌ [Fe(CN) ]
4−
1.5 × 1035
6
Fe
3+
+ 6CN
−
⇌ [Fe(CN) ]
3−
2 × 1043
6
Fe
3+
+ 6SCN
−
⇌ [Fe(SCN) ]
3−
3.2 × 103
6
Hg
2+
+ 4Cl
−
⇌ [HgCl ]
4
2−
1.1 × 1016
Ni
2+
+ 6NH3 ⇌ [Ni( NH3 ) ]
2+
2.0 × 108
6
Ag
+
+ 2Cl
−
⇌ [AgCl ]
2
−
1.8 × 105
Ag
+
+ 2CN
−
⇌ [Ag(CN) ]
2
−
1 × 1021
Ag
+
+ 2NH3 ⇌ [Ag( NH3 ) ]
2
+
1.7 × 107
Zn
2+
+ 4CN
−
⇌ [Zn (CN) ]
2−
2.1 × 1019
4
Zn
2+
+ 4OH
−
⇌ [Zn (OH) ]
2−
2 × 1015
4
Fe
3+
+ SCN
−
⇌ [Fe (SCN)]
2+
8.9 × 102
Ag
+
+ 4SCN
−
⇌ [Ag(SCN) ]
3−
1.2 × 1010
4
Pb
2+
+ 4I
−
⇌ [PbI4 ]
2−
3.0 × 104
Pt
2+
+ 4Cl
−
⇌ [PtCl4 ]
2−
1 × 1016

Equilibrium Kf
Cu
2+
+ 4CN ⇌ [Cu (CN) ]
2−
1.0 × 1025
4
Co
2+
+ 4SCN
−
⇌ [Co(SCN) ]
2−
1 × 103
4
Table K1
This page titled 22.11: Formation Constants for Complex Ions is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by

Standard Electrode (Half-Cell) Potentials
Ag
+
+e
−
⟶ Ag +0.7996
AgCl + e
−
⟶ Ag + Cl
−
+0.22233
[Ag(CN) ]
2
−
+e
−
⟶ Ag + 2CN
−
−0.31
Ag CrO4 + 2e
2
−
⟶ 2Ag + CrO4
2−
+0.45
[Ag( NH3 ) ]
2
+
+e
−
⟶ Ag + 2NH3 +0.373
[Ag( S2 O3 ) ]
3+
+e
−
⟶ Ag + 2S2 O3
2− +0.017
2
[AlF 6 ]
3−
+ 3e
−
⟶ Al + 6F
− −2.07
Al
3+
+ 3e
−
⟶ Al −1.662
Am
3+
+ 3e
−
⟶ Am −2.048
Au
3+
+ 3e
−
⟶ Au +1.498
Au
+
+e
−
⟶ Au +1.692
Ba
2+
+ 2e
−
⟶ Ba −2.912
Be
2+
+ 2e
−
⟶ Be −1.847
Br 2 (aq) + 2e
−
⟶ 2Br
−
+1.0873
Ca
2+
+ 2e
−
⟶ Ca −2.868
Ce
3
+ 3e
−
⟶ Ce −2.483
Ce
4+
+e
−
⟶ Ce
3+
+1.61
Cd
2+
+ 2e
−
⟶ Cd −0.4030
[Cd (CN) ]
2−
+ 2e
−
⟶ Cd + 4CN
−
−1.09
4
[Cd ( NH3 ) ]
2+
+ 2e
−
⟶ Cd + 4NH3 −0.61
4
CdS + 2e
−
⟶ Cd + S
2−
−1.17
Cl2 + 2e
−
⟶ 2Cl
−
+1.35827

ClO4
−
+ H2 O + 2e
−
⟶ ClO3
−
+ 2OH
−
+0.36
ClO3
−
+ H2 O + 2e
−
⟶ ClO2
−
+ 2OH
−
+0.33
ClO2
−
+ H2 O + 2e
−
⟶ ClO
−
+ 2OH
−
+0.66
ClO
−
+ H2 O + 2e
−
⟶ Cl
−
+ 2OH
−
+0.89
ClO4
−
+ 2H3 O
+
+ 2e
−
⟶ ClO3
−
+ 3H2 O +1.189
ClO3
−
+ 3H3 O
+
+ 2e
−
⟶ HClO2 + 4H2 O +1.21
HClO + H3 O
+
+ 2e
−
⟶ Cl
−
+ 2H2 O +1.482
HClO + H3 O
+
+e
−
⟶
1
Cl2 + 2H2 O +1.611
2
HClO2 + 2H3 O
+
+ 2e
−
⟶ HClO + 3H2 O +1.628
Co
3+
+e
−
⟶ Co
2+
(2 mol // H2 SO4 ) +1.83
Co
2+
+ 2e
−
⟶ Co −0.28
[Co( NH3 ) ]
3+
+e
−
⟶ [Co( NH3 ) ]
2+
+0.1
6 6
Co(OH)
3
+e
−
⟶ Co(OH)
2
+ OH
−
+0.17
Cr
3
+ 3e
−
⟶ Cr −0.744
Cr
3+
+e
−
⟶ Cr
2+
−0.407
Cr
2+
+ 2e
−
⟶ Cr −0.913
[Cu (CN) ]
2
−
+e
−
⟶ Cu + 2CN
−
−0.43
CrO4
2−
+ 4H2 O + 3e
−
⟶ Cr (OH)
3
+ 5OH
−
−0.13
Cr2 O7
2−
+ 14H3 O
+
+ 6e
−
⟶ 2Cr
3+
+ 21H2 O +1.232
[Cr (OH) ]
4
−
+ 3e
−
⟶ Cr + 4OH
−
−1.2
Cr (OH)
3
+ 3e
−
⟶ Cr + 3OH
−
−1.48
Cu
2+
+e
−
⟶ Cu
+
+0.153
Cu
2+
+ 2e
−
⟶ Cu +0.34

Cu
+
+e
−
⟶ Cu +0.521
F2 + 2e
−
⟶ 2F
−
+2.866
Fe
2+
+ 2e
−
⟶ Fe −0.447
Fe
3+
+e
−
⟶ Fe
2+
+0.771
[Fe(CN) ]
3−
+e
−
⟶ [Fe(CN) ]
4−
+0.36
6 6
Fe(OH)
2
+ 2e
−
⟶ Fe + 2OH
−
−0.88
FeS + 2e
−
⟶ Fe + S
2−
−1.01
Ga
3+
+ 3e
−
⟶ Ga −0.549
Gd
3+
+ 3e
−
⟶ Gd −2.279
1
H2 + e
−
⟶ H
−
−2.23
2
2H2 O + 2e
−
⟶ H2 + 2OH
−
−0.8277
H2 O2 + 2H3 O
+
+ 2e
−
⟶ 4H2 O +1.776
2H3 O
+
+ 2e
−
⟶ H2 + 2H2 O 0.00
HO2
−
+ H2 O + 2e
−
⟶ 3OH
−
+0.878
Hf
4+
+ 4e
−
⟶ Hf −1.55
Hg
2+
+ 2e
−
⟶ Hg +0.851
2Hg
2+
+ 2e
−
⟶ Hg2
2+
+0.92
Hg
2
2+
+ 2e
−
⟶ 2Hg +0.7973
[HgBr ]
4
2−
+ 2e
−
⟶ Hg + 4Br
−
+0.21
Hg Cl2 + 2e
2
−
⟶ 2Hg + 2Cl
−
+0.26808
[Hg(CN) ]
2−
+ 2e
−
⟶ Hg + 4CN
−
−0.37
4
[HgI ]
4
2−
+ 2e
−
⟶ Hg + 4I
−
−0.04
HgS + 2e
−
⟶ Hg + S
2−
−0.70

I2 + 2e
−
⟶ 2I
−
+0.5355
In
3+
+ 3e
−
⟶ In −0.3382
K
+
+e
−
⟶ K −2.931
La
3+
+ 3e
−
⟶ La −2.52
Li
+
+e
−
⟶ Li −3.04
Lu
3+
+ 3e
−
⟶ Lu −2.28
Mg
2+
+ 2e
−
⟶ Mg −2.372
Mn
2+
+ 2e
−
⟶ Mn −1.185
MnO2 + 2H2 O + 2e
−
⟶ Mn (OH)
2
+ 2OH
−
−0.05
MnO4
−
+ 2H2 O + 3e
−
⟶ MnO2 + 4OH
−
+0.558
MnO2 + 4H
+
+ 2e
−
⟶ Mn
2+
+ 2H2 O +1.23
MnO4
−
+ 8H
+
+ 5e
−
⟶ Mn
2+
+ 4H2 O +1.507
Na
+
+e
−
⟶ Na −2.71
Nd
3+
+ 3e
−
⟶ Nd −2.323
Ni
2+
+ 2e
−
⟶ Ni −0.257
[Ni( NH3 ) ]
2+
+ 2e
−
⟶ Ni + 6NH3 −0.49
6
NiO 2 + 4H
+
+ 2e
−
⟶ Ni
2+
+ 2H2 O +1.593
NiO 2 + 2H2 O + 2e
−
⟶ Ni(OH)
2
+ 2OH
−
+0.49
NiS + 2e
−
⟶ Ni + S
2−
+0.76
NO3
−
+ 4H
+
+ 3e
−
⟶ NO + 2H2 O +0.957
NO3
−
+ 3H
+
+ 2e
−
⟶ HNO2 + H2 O +0.92
NO3
−
+ H2 O + 2e
−
⟶ NO2
−
+ 2OH
−
+0.10
Np
3+
+ 3e
−
⟶ Np −1.856
O2 + 2H2 O + 4e
−
⟶ 4OH
−
+0.401

O2 + 2H
+
+ 2e
−
⟶ H2 O2 +0.695
O2 + 4H
+
+ 4e
−
⟶ 2H2 O +1.229
Pb
2+
+ 2e
−
⟶ Pb −0.1262
PbO2 + SO4
2−
+ 4H
+
+ 2e
−
⟶ PbSO4 + 2H2 O +1.69
PbS + 2e
−
⟶ Pb + S
2−
−0.95
PbSO4 + 2e
−
⟶ Pb + SO4
2−
−0.3505
Pd
2+
+ 2e
−
⟶ Pd +0.987
[PdCl4 ]
2−
+ 2e
−
⟶ Pd + 4Cl
−
+0.591
Pt
2+
+ 2e
−
⟶ Pt +1.20
[PtBr 4 ]
2−
+ 2e
−
⟶ Pt + 4Br
−
+0.58
[PtCl4 ]
2−
+ 2e
−
⟶ Pt + 4Cl
−
+0.755
[PtCl6 ]
2−
+ 2e
−
⟶ [PtCl4 ]
2−
+ 2Cl
−
+0.68
Pu
3
+ 3e
−
⟶ Pu −2.03
Ra
2+
+ 2e
−
⟶ Ra −2.92
Rb
+
+e
−
⟶ Rb −2.98
[RhCl6 ]
3−
+ 3e
−
⟶ Rh + 6Cl
−
+0.44
S + 2e
−
⟶ S
2−
−0.47627
S + 2H
+
+ 2e
−
⟶ H2 S +0.142
Sc
3+
+ 3e
−
⟶ Sc −2.09
Se + 2H
+
+ 2e
−
⟶ H2 Se −0.399
[SiF6 ]
2−
+ 4e
−
⟶ Si + 6F
− −1.2
SiO3
2−
+ 3H2 O + 4e
−
⟶ Si + 6OH
−
−1.697
SiO2 + 4H
+
+ 4e
−
⟶ Si + 2H2 O −0.86

Sm
3+
+ 3e
−
⟶ Sm −2.304
Sn
4+
+ 2e
−
⟶ Sn
2+
+0.151
Sn
2+
+ 2e
−
⟶ Sn −0.1375
[SnF6 ]
2−
+ 4e
−
⟶ Sn + 6F
− −0.25
SnS + 2e
−
⟶ Sn + S
2−
−0.94
Sr
2+
+ 2e
−
⟶ Sr −2.89
TeO2 + 4H
+
+ 4e
−
⟶ Te + 2H2 O +0.593
Th
4+
+ 4e
−
⟶ Th −1.90
Ti
2+
+ 2e
−
⟶ Ti −1.630
U
3+
+ 3e
−
⟶ U −1.79
V
2+
+ 2e
−
⟶ V −1.19
Y
3+
+ 3e
−
⟶ Y −2.37
Zn
2+
+ 2e
−
⟶ Zn −0.7618
[Zn (CN) ]
2−
+ 2e
−
⟶ Zn + 4CN
−
−1.26
4
[Zn ( NH3 ) ]
2+
+ 2e
−
⟶ Zn + 4NH3 −1.04
4
Zn (OH)
2
+ 2e
−
⟶ Zn + 2OH
−
−1.245
[Zn (OH) ]
2
+ 2e
−
⟶ Zn + 4OH
−
−1.199
4
ZnS + 2e
−
⟶ Zn + S
2−
−1.40
Zr
4
+ 4e
−
⟶ Zr −1.539
Table L1
This page titled 22.12: Standard Electrode (Half-Cell) Potentials is shared under a CC BY 4.0 license and was authored, remixed, and/or curated
by OpenStax via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon
request.

Half-Lives for Several Radioactive Isotopes
Isotope Half-Life1 Type of Emission2 Isotope Half-Life3 Type of Emission4
14
6
C 5730 y (β
−
)
210
83
Bi 5.01 d (β
−
)
13
7
N 9.97 m (β
+
)
212
83
Bi 60.55 m (α or β
−
)
15
9
F 4.1 × 10−22 s (p)
210
84
Po 138.4 d (α)
24
11
Na 15.00 h (β
−
)
212
84
Po 3 × 10−7 s (α)
32
15
P 14.29 d (β
−
)
216
84
Po 0.15 s (α)
40
19
K 1.27 × 109 y (β or E. C . )
218
84
Po 3.05 m (α)
49
26
Fe 0.08 s (β
+
)
215
85
At 1.0 × 10−4 s (α)
60
26
Fe 2.6 × 106 y (β
−
)
218
85
At 1.6 s (α)
60
27
Co 5.27 y (β
−
)
220
86
Rn 55.6 s (α)
87
37
Rb 4.7 × 1010 y (β
−
)
222
86
Rn 3.82 d (α)
90
38
Sr 29 y (β
−
)
224
88
Ra 3.66 d (α)
115
49
In 5.1 × 1015 y (β
−
)
226
88
Ra 1600 y (α)
131
53
I 8.040 d (β
−
)
228
88
Ra 5.75 y (β
−
)
142
58
Ce 5 × 1015 y (α)
228
89
Ac 6.13 h (β
−
)
208
81
Tl 3.07 m (β
−
)
228
90
Th 1.913 y (α)
210
82
Pb 22.3 y (β
−
)
232
90
Th 1.4 × 1010 y (α)
212
82
Pb 10.6 h (β
−
)
233
90
Th 22 m (β
−
)
214
82
Pb 26.8 m (β
−
)
234
90
Th 24.10 d (β
−
)
206
83
Bi 6.243 d (E. C . )
233
91
Pa 27 d (β
−
)
233
92
U 1.59 × 105 y (α)
242
96
Cm 162.8 d (α)
234
92
U 2.45 × 105 y (α)
243
97
Bk 4.5 h (α or E. C . )
235
92
U 7.03 × 108 y (α)
253
99
Es 20.47 d (α)
Isotope Half-Life1 Type of Emission2 Isotope Half-Life3 Type of Emission4
238
92
U 4.47 × 109 y (α)
254
100
Fm 3.24 h (α or S. F . )
239
92
U 23.54 m (β
−
)
255
100
Fm 20.1 h (α)
239
93
Np 2.3 d (β
−
)
256
101
Md 76 m (α or E. C . )
239
94
Pu 2.407 × 104 y (α)
254
102
No 55 s (α)
239
94
Pu 6.54 × 103 y (α)
257
103
Lr 0.65 s (α)
241
94
Pu 14.4 y (α or β
−
)
260
105
Ha 1.5 s (α or S. F . )
241
95
Am 432.2 y (α)
263
106
Sg 0.8 s (α or S. F . )
Table M1
Footnotes
1y = years, d = days, h = hours, m = minutes, s = seconds
2E.C. = electron capture, S.F. = Spontaneous fission
3y = years, d = days, h = hours, m = minutes, s = seconds
4E.C. = electron capture, S.F. = Spontaneous fission
22.13: Half-Lives for Several Radioactive Isotopes is shared under a not declared license and was authored, remixed, and/or curated by
LibreTexts.
22.14: Answer Key
22.14: Answer Key is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.
22.14.1: Chapter 1
1.
Place a glass of water outside. It will freeze if the temperature is below 0 °C.
3.
(a) law (states a consistently observed phenomenon, can be used for prediction); (b) theory (a widely accepted explanation of the
behavior of matter); (c) hypothesis (a tentative explanation, can be investigated by experimentation)
5.
(a) symbolic, microscopic; (b) macroscopic; (c) symbolic, macroscopic; (d) microscopic
7.
Macroscopic. The heat required is determined from macroscopic properties.
9.
Liquids can change their shape (flow); solids can’t. Gases can undergo large volume changes as pressure changes; liquids do not.
Gases flow and change volume; solids do not.
11.
The mixture can have a variety of compositions; a pure substance has a definite composition. Both have the same composition from
point to point.
13.
Molecules of elements contain only one type of atom; molecules of compounds contain two or more types of atoms. They are
similar in that both are comprised of two or more atoms chemically bonded together.
15.
Answers will vary. Sample answer: Gatorade contains water, sugar, dextrose, citric acid, salt, sodium chloride, monopotassium
phosphate, and sucrose acetate isobutyrate.
17.
(a) element; (b) element; (c) compound; (d) mixture; (e) compound; (f) compound; (g) compound; (h) mixture
19.
In each case, a molecule consists of two or more combined atoms. They differ in that the types of atoms change from one substance
to the next.
21.
Gasoline (a mixture of compounds), oxygen, and to a lesser extent, nitrogen are consumed. Carbon dioxide and water are the
principal products. Carbon monoxide and nitrogen oxides are produced in lesser amounts.
23.
(a) Increased as it would have combined with oxygen in the air thus increasing the amount of matter and therefore the mass. (b) 0.9
g
25.
(a) 200.0 g; (b) The mass of the container and contents would decrease as carbon dioxide is a gaseous product and would leave the
container. (c) 102.3 g
27.
(a) physical; (b) chemical; (c) chemical; (d) physical; (e) physical
29.
physical
31.
22.14.1.1 https://chem.libretexts.org/@go/page/415324
The value of an extensive property depends upon the amount of matter being considered, whereas the value of an intensive
property is the same regardless of the amount of matter being considered.
33.
Being extensive properties, both mass and volume are directly proportional to the amount of substance under study. Dividing one
extensive property by another will in effect “cancel” this dependence on amount, yielding a ratio that is independent of amount (an
intensive property).
35.
about a yard
37.
(a) kilograms; (b) meters; (c) meters/second; (d) kilograms/cubic meter; (e) kelvin; (f) square meters; (g) cubic meters
39.
(a) centi-, × 10−2; (b) deci-, × 10−1; (c) Giga-, × 109; (d) kilo-, × 103; (e) milli-, × 10−3; (f) nano-, × 10−9; (g) pico-, × 10−12; (h)
tera-, × 1012
41.
(a) m = 18.58 g, V = 5.7 mL. (b) d = 3.3 g/mL (c) dioptase (copper cyclosilicate, d = 3.28—3.31 g/mL); malachite (basic copper
carbonate, d = 3.25—4.10 g/mL); Paraiba tourmaline (sodium lithium boron silicate with copper, d = 2.82—3.32 g/mL)
43.
(a) displaced water volume = 2.8 mL; (b) displaced water mass = 2.8 g; (c) The block mass is 2.76 g, essentially equal to the mass
of displaced water (2.8 g) and consistent with Archimedes’ principle of buoyancy.
45.
(a) 7.04 × 102; (b) 3.344 × 10−2; (c) 5.479 × 102; (d) 2.2086 × 104; (e) 1.00000 × 103; (f) 6.51 × 10−8; (g) 7.157 × 10−3
47.
(a) exact; (b) exact; (c) uncertain; (d) exact; (e) uncertain; (f) uncertain
49.
(a) two; (b) three; (c) five; (d) four; (e) six; (f) two; (g) five
51.
(a) 0.44; (b) 9.0; (c) 27; (d) 140; (e) 1.5 × 10−3; (f) 0.44
53.
(a) 2.15 × 105; (b) 4.2 × 106; (c) 2.08; (d) 0.19; (e) 27,440; (f) 43.0
55.
(a) Archer X; (b) Archer W; (c) Archer Y
57.
1.0936 yd
(a) 1 m
; (b) 0.94635 L
1 qt
; (c) 2.2046 lb
1 kg
59.
2.0 L 0.030 L
=
67.6 fl oz 1 fl oz
Only two significant figures are justified.

61.
68–71 cm; 400–450 g
63.
355 mL
65.
8 × 10−4 cm
67.
yes; weight = 89.4 kg
69.
5.0 × 10−3 mL
71.
(a) 1.3 × 10−4 kg; (b) 2.32 × 108 kg; (c) 5.23 × 10−12 m; (d) 8.63 × 10−5 kg; (e) 3.76 × 10−1 m; (f) 5.4 × 10−5 m; (g) 1 × 1012 s;
(h) 2.7 × 10−11 s; (i) 1.5 × 10−4 K
73.
45.4 L
75.
1.0160 × 103 kg
77.
(a) 394 ft; (b) 5.9634 km; (c) 6.0 × 102; (d) 2.64 L; (e) 5.1 × 1018 kg; (f) 14.5 kg; (g) 324 mg
79.
0.46 m; 1.5 ft/cubit
81.
Yes, the acid’s volume is 123 mL.
83.
62.6 in (about 5 ft 3 in.) and 101 lb
85.
(a) 3.81 cm × 8.89 cm × 2.44 m; (b) 40.6 cm
87.
2.70 g/cm3
89.
(a) 81.6 g; (b) 17.6 g
91.
(a) 5.1 mL; (b) 37 L
93.
5371 °F, 3239 K
95.
−23 °C, 250 K
97.
−33.4 °C, 239.8 K
99.
113 °F
22.14.1: Chapter 1 is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.
22.14.2: Chapter 2
1.
The starting materials consist of one green sphere and two purple spheres. The products consist of two green spheres and two
purple spheres. This violates Dalton’s postulate that that atoms are not created during a chemical change, but are merely
redistributed.
3.
This statement violates Dalton’s fourth postulate: In a given compound, the numbers of atoms of each type (and thus also the
percentage) always have the same ratio.
5.
Dalton originally thought that all atoms of a particular element had identical properties, including mass. Thus, the concept of
isotopes, in which an element has different masses, was a violation of the original idea. To account for the existence of isotopes, the
second postulate of his atomic theory was modified to state that atoms of the same element must have identical chemical properties.
7.
Both are subatomic particles that reside in an atom’s nucleus. Both have approximately the same mass. Protons are positively
charged, whereas neutrons are uncharged.
9.
(a) The Rutherford atom has a small, positively charged nucleus, so most α particles will pass through empty space far from the
nucleus and be undeflected. Those α particles that pass near the nucleus will be deflected from their paths due to positive-positive
repulsion. The more directly toward the nucleus the α particles are headed, the larger the deflection angle will be. (b) Higher-energy
α particles that pass near the nucleus will still undergo deflection, but the faster they travel, the less the expected angle of
deflection. (c) If the nucleus is smaller, the positive charge is smaller and the expected deflections are smaller—both in terms of
how closely the α particles pass by the nucleus undeflected and the angle of deflection. If the nucleus is larger, the positive charge
is larger and the expected deflections are larger—more α particles will be deflected, and the deflection angles will be larger. (d) The
paths followed by the α particles match the predictions from (a), (b), and (c).
11.
(a) 133Cs+; (b) 127I−; (c) 31P3−; (d) 57Co3+
13.
(a) Carbon-12, 12C; (b) This atom contains six protons and six neutrons. There are six electrons in a neutral 12C atom. The net
charge of such a neutral atom is zero, and the mass number is 12. (c) The preceding answers are correct. (d) The atom will be stable
since C-12 is a stable isotope of carbon. (e) The preceding answer is correct. Other answers for this exercise are possible if a
different element of isotope is chosen.
15.
(a) Lithium-6 contains three protons, three neutrons, and three electrons. The isotope symbol is 6Li or 6
3
Li. (b) 6Li+ or 6
3
Li
+
17.
(a) Iron, 26 protons, 24 electrons, and 32 neutrons; (b) iodine, 53 protons, 54 electrons, and 74 neutrons
19.
(a) 3 protons, 3 electrons, 4 neutrons; (b) 52 protons, 52 electrons, 73 neutrons; (c) 47 protons, 47 electrons, 62 neutrons; (d) 7
protons, 7 electrons, 8 neutrons; (e) 15 protons, 15 electrons, 16 neutrons
21.
Let us use neon as an example. Since there are three isotopes, there is no way to be sure to accurately predict the abundances to
make the total of 20.18 amu average atomic mass. Let us guess that the abundances are 9% Ne-22, 91% Ne-20, and only a trace of
Ne-21. The average mass would be 20.18 amu. Checking the nature’s mix of isotopes shows that the abundances are 90.48% Ne-
20, 9.25% Ne-22, and 0.27% Ne-21, so our guessed amounts have to be slightly adjusted.
23.
79.90 amu
25.
Turkey source: 20.3% (of 10.0129 amu isotope); US source: 19.1% (of 10.0129 amu isotope)
27.
The symbol for the element oxygen, O, represents both the element and one atom of oxygen. A molecule of oxygen, O2, contains
two oxygen atoms; the subscript 2 in the formula must be used to distinguish the diatomic molecule from two single oxygen atoms.
29.
(a) molecular CO2, empirical CO2; (b) molecular C2H2, empirical CH; (c) molecular C2H4, empirical CH2; (d) molecular H2SO4,
empirical H2SO4
31.
(a) C4H5N2O; (b) C12H22O11; (c) HO; (d) CH2O; (e) C3H4O3
33.
(a) CH2O; (b) C2H4O
35.
(a) ethanol
(b) methoxymethane, more commonly known as dimethyl ether
(c) These molecules have the same chemical composition (types and number of atoms) but different chemical structures. They are
structural isomers.
37.
(a) metal, inner transition metal; (b) nonmetal, representative element; (c) metal, representative element; (d) nonmetal,
representative element; (e) metal, transition metal; (f) metal, inner transition metal; (g) metal, transition metal; (h) nonmetal,
representative element; (i) nonmetal, representative element; (j) metal, representative element
39.
(a) He; (b) Be; (c) Li; (d) O
41.
(a) krypton, Kr; (b) calcium, Ca; (c) fluorine, F; (d) tellurium, Te
43.
(a) 23
11
Na ; (b) 129
54
; (c)
Xe
73
33
As ; (d) 226
88
Ra
45.
Ionic: KCl, MgCl2; Covalent: NCl3, ICl, PCl5, CCl4
47.
(a) covalent; (b) ionic, Ba2+, O2−; (c) ionic, NH 4
+
, CO3
2−
; (d) ionic, Sr2+, H
2 PO4
−
; (e) covalent; (f) ionic, Na+, O2−
49.
(a) CaS; (b) (NH4)2SO4; (c) AlBr3; (d) Na2HPO4; (e) Mg3 (PO4)2
51.
(a) cesium chloride; (b) barium oxide; (c) potassium sulfide; (d) beryllium chloride; (e) hydrogen bromide; (f) aluminum fluoride
53.
(a) RbBr; (b) MgSe; (c) Na2O; (d) CaCl2; (e) HF; (f) GaP; (g) AlBr3; (h) (NH4)2SO4
55.
(a) ClO2; (b) N2O4; (c) K3P; (d) Ag2S; (e) AIF3·3H2O; (f) SiO2
57.
(a) chromium(III) oxide; (b) iron(II) chloride; (c) chromium(VI) oxide; (d) titanium(IV) chloride; (e) cobalt(II) chloride
hexahydrate; (f) molybdenum(IV) sulfide
59.
(a) K3PO4; (b) CuSO4; (c) CaCl2; (d) TiO2; (e) NH4NO3; (f) NaHSO4
61.
(a) manganese(IV) oxide; (b) mercury(I) chloride; (c) iron(III) nitrate; (d) titanium(IV) chloride; (e) copper(II) bromide
22.14.3: Chapter 3
1.
(a) 12.01 amu; (b) 12.01 amu; (c) 144.12 amu; (d) 60.05 amu
3.
(a) 123.896 amu; (b) 18.015 amu; (c) 164.086 amu; (d) 60.052 amu; (e) 342.297 amu
5.
(a) 56.107 amu; (b) 54.091 amu; (c) 199.9976 amu; (d) 97.9950 amu
7.
Use the molecular formula to find the molar mass; to obtain the number of moles, divide the mass of compound by the molar mass
of the compound expressed in grams.
9.
Formic acid. Its formula has twice as many oxygen atoms as the other two compounds (one each). Therefore, 0.60 mol of formic
acid would be equivalent to 1.20 mol of a compound containing a single oxygen atom.
11.
The two masses have the same numerical value, but the units are different: The molecular mass is the mass of 1 molecule while the
molar mass is the mass of 6.022 × 1023 molecules.
13.
(a) 256.48 g/mol; (b) 72.150 g mol−1; (c) 378.103 g mol−1; (d) 58.080 g mol−1; (e) 180.158 g mol−1
15.
(a) 197.382 g mol−1; (b) 257.163 g mol−1; (c) 194.193 g mol−1; (d) 60.056 g mol−1; (e) 306.464 g mol−1
17.
(a) 0.819 g; (b) 307 g; (c) 0.23 g; (d) 1.235 × 106 g (1235 kg); (e) 765 g
19.
(a) 99.41 g; (b) 2.27 g; (c) 3.5 g; (d) 222 kg; (e) 160.1 g
21.
(a) 9.60 g; (b) 19.2 g; (c) 28.8 g
23.
zirconium: 2.038 × 1023 atoms; 30.87 g; silicon: 2.038 × 1023 atoms; 9.504 g; oxygen: 8.151 × 1023 atoms; 21.66 g
25.
AlPO4: 1.000 mol, or 26.98 g Al; Al2Cl6: 1.994 mol, or 53.74 g Al; Al2S3: 3.00 mol, or 80.94 g Al; The Al2S3 sample thus contains
the greatest mass of Al.
27.
3.113 × 1025 C atoms
29.
0.865 servings, or about 1 serving.
31.
20.0 g H2O represents the least number of molecules since it has the least number of moles.
33.
(a) % N = 82.24%, % H = 17.76%; (b) % Na = 29.08%, % S = 40.56%, % O = 30.36%; (c) % Ca2+ = 38.76%
35.
% NH3 = 38.2%
37.
(a) CS2; (b) CH2O
39.
C6H6
41.
Mg3Si2H3O8 (empirical formula), Mg6Si4H6O16 (molecular formula)
43.
C15H15N3
45.
We need to know the number of moles of sulfuric acid dissolved in the solution and the volume of the solution.
47.
(a) 0.679 M; (b) 1.00 M; (c) 0.06998 M; (d) 1.75 M; (e) 0.070 M; (f) 6.6 M
49.
(a) determine the number of moles of glucose in 0.500 L of solution; determine the molar mass of glucose; determine the mass of
glucose from the number of moles and its molar mass; (b) 27 g
51.
(a) 37.0 mol H2SO4, 3.63 × 103 g H2SO4; (b) 3.8 × 10−7 mol NaCN, 1.9 × 10−5 g NaCN; (c) 73.2 mol H2CO, 2.20 kg H2CO; (d)
5.9 × 10−7 mol FeSO4, 8.9 × 10−5 g FeSO4
53.
(a) Determine the molar mass of KMnO4; determine the number of moles of KMnO4 in the solution; from the number of moles and
the volume of solution, determine the molarity; (b) 1.15 × 10−3 M
55.
(a) 5.04 × 10−3 M; (b) 0.499 M; (c) 9.92 M; (d) 1.1 × 10−3 M
57.
0.025 M
59.
0.5000 L
61.
1.9 mL
63.
(a) 0.125 M; (b) 0.04888 M; (c) 0.206 M; (d) 0.0056 M
65.
11.9 M
67.
1.6 L
69.
(a) The dilution equation can be used, appropriately modified to accommodate mass-based concentration units:
% mass 1 × mass = % mass
1 2 × mass . This equation can be rearranged to isolate mass1 and the given quantities substituted
2
into this equation. (b) 58.8 g

71.
114 g
73.
1.75 × 10−3 M
75.
95 mg/dL
77.
2.38 × 10−4 mol
79.
0.29 mol
22.14.4: Chapter 4
1.
An equation is balanced when the same number of each element is represented on the reactant and product sides. Equations must be
balanced to accurately reflect the law of conservation of matter.
3.
(a) PCl (s) + H O(l) ⟶ POCl (l) + 2HCl(aq); (b) 3Cu (s) + 8HNO (aq) ⟶ 3Cu(NO ) (aq) + 4H O(l) + 2NO(g);
5 2 3 3 3 2 2
(c) H (g) + I (s) ⟶ 2HI(s); (d) 4Fe(s) + 3O (g) ⟶ 2Fe O (s); (e) 2Na(s) + 2H O(l) ⟶ 2NaOH(aq) + H (g);
2 2 2 2 3 2 2
(f) (NH ) Cr O (s) ⟶ Cr O (s) + N (g) + 4 H O(g);

4 2 2 7 (g)2 P (s) + 6 Cl (g) ⟶ 4 PCl (l);
3 2 2 (h) 4 2 3
PtCl4 (s) ⟶ Pt(s) + 2 Cl2 (g)
5.
(a) CaCO3 (s) ⟶ CaO(s) + CO2 (g); (b) 2 C4 H10 (g) + 13 O2 (g) ⟶ 8 CO2 (g) + 10 H2 O(g); (c)
MgC12 (aq) + 2NaOH(aq) ⟶ Mg (OH) 2 (s) + 2NaCl(aq); (d) 2H 2 O(g) + 2Na(s) ⟶ 2NaOH(s) + H2 (g)
7.
(a) Ba(NO3)2, KClO3; (b) 2 KClO3 (s) ⟶ 2KCl(s) + 3 O2 (g); (c) 2Ba (NO3 ) (s) ⟶ 2BaO(s) + 2 N2 (g) + 5 O2 (g);
2
(d)
2Mg(s) + O2 (g) ⟶ 2MgO(s); 4Al(s) + 3 O2 (g) ⟶ 2 Al2 O3 (s); 4Fe(s) + 3 O2 (g) ⟶ 2 Fe2 O3 (s)
9.
(a) 4HF(aq) + SiO2 (s) ⟶ SiF4 (g) + 2 H2 O(l); (b) complete ionic equation:
2 Na
+
(aq) + 2 F
−
(aq) + Ca
2+
(aq) + 2 Cl
−
(aq) ⟶ Ca F2 (s) + 2 Na
+
(aq) + 2 Cl
−
(aq), net ionic equation:
− 2+
2F (aq) + Ca (aq) ⟶ CaF2 (s)
11.
(a) 2K
+
(aq) + C2 O4
2−
(aq) + Ba
2+
(aq) + 2 OH
−
(aq) ⟶ 2 K
+
(aq) + 2 OH
−
(aq) + BaC2 O4 (s) (complete)
2+ 2−
Ba (aq) + C2 O4 (aq) ⟶ BaC2 O4 (s) (net)
2+ − + 2− + −
Pb (aq) + 2 NO3 (aq) + 2 H (aq) + SO 4 (aq) ⟶ PbSO 4 (s) + 2 H (aq) + 2 NO3 (aq) (complete)
(b) 2+ 2−
Pb (aq) + SO 4 (aq) ⟶ PbSO 4 (s) (net)
(c) CaCO3 (s) + 2 H

+
(aq) + SO 4
2−
(aq) ⟶ CaSO4 (s) + CO2 (g) + H2 O(l) (complete)
+ 2−
CaCO3 (s) + 2 H (aq) + SO 4 (aq) ⟶ CaSO4 (s) + CO2 (g) + H2 O(l) (net)
13.
(a) oxidation-reduction (addition); (b) acid-base (neutralization); (c) oxidation-reduction (combustion)
15.
It is an oxidation-reduction reaction because the oxidation state of the silver changes during the reaction.
17.
(a) H +1, P +5, O −2; (b) Al +3, H +1, O −2; (c) Se +4, O −2; (d) K +1, N +3, O −2; (e) In +3, S −2; (f) P +3, O −2
19.
(a) acid-base; (b) oxidation-reduction: Na is oxidized, H+ is reduced; (c) oxidation-reduction: Mg is oxidized, Cl2 is reduced; (d)
acid-base; (e) oxidation-reduction: P3− is oxidized, O2 is reduced; (f) acid-base
21.
(a) 2HCl(g) + Ca(OH) 2
(s) ⟶ CaCl2 (s) + 2 H2 O(l); (b) Sr(OH) 2
(aq) + 2 HNO3 (aq) ⟶ Sr(NO3 ) (aq) + 2 H2 O(l)
2
23.
(a) 2Al(s) + 3 F2 (g) ⟶ 2 AlF3 (s); (b) 2Al(s) + 3 CuBr 2 (aq) ⟶ 3Cu(s) + 2 AlBr3 (aq); (c)
P4 (s) + 5 O2 (g) ⟶ P4 O10 (s); (d) Ca(s) + 2H 2 O(l) ⟶ Ca (OH) (aq) + H2 (g)
2
25.
(a) Mg (OH) (s) + 2 HClO4 (aq) ⟶ Mg
2
2+
(aq) + 2 ClO4
−
(aq) + 2 H2 O(l); (b)
SO 3 (g) + 2 H2 O(l) ⟶ H3 O
+
(aq) + HSO 4
−
(aq), (a solution of H2SO4); (c) SrO(s) + H 2 SO 4 (l) ⟶ SrSO 4 (s) + H2 O
27.
H2 (g) + F2 (g) ⟶ 2HF (g)
29.
2NaBr(aq) + Cl2 (g) ⟶ 2NaCl(aq) + Br 2 (l)
31.
2LiOH(aq) + CO2 (g) ⟶ Li 2 CO3 (aq) + H2 O(l)
33.
(a) Ca(OH) 2
(s) + H2 S(g) ⟶ CaS(s) + 2 H2 O(l); (b) Na 2 CO3 (aq) + H2 S(g) ⟶ Na2 S(aq) + CO2 (g) + H2 O(l)
35.
(a) step 1: N2 (g) + 3 H2 (g) ⟶ 2 NH3 (g), step 2:
NH3 (g) + HNO3 (aq) ⟶ NH4 NO3 (aq) ⟶ NH4 NO3 (s) (after drying); (b) H2 (g) + Br 2 (l) ⟶ 2HBr(g); (c)
Zn(s) + S(s) ⟶ ZnS(s) and ZnS(s) + 2HCl(aq) ⟶ ZnCl2 (aq) + H2 S(g)
37.
(a) Sn
4+
(aq) + 2e
−
⟶ Sn
2+
(aq), (b) [Ag (NH3 ) ]
2
+
(aq) + e
−
⟶ Ag(s) + 2 NH3 (aq); (c)
Hg2 Cl2 (s) + 2 e
−
⟶ 2Hg(l) + 2 Cl
−
(aq); (d) 2 H2 O(l) ⟶ O2 (g) + 4 H
+
(aq) + 4 e
−
; (e)
6 H2 O(l) + 2 IO3
−
(aq) + 10 e
−
⟶ I2 (s) + 12 OH
−
(aq); (f) H O(l) + SO (aq) ⟶ SO (aq) + 2H (aq) + 2e ;
2 3
2−
4
2− + −
(g)
8H
+
(aq) + MnO 4
−
(aq) + 5 e
−
⟶ Mn
2+
(aq) + 4 H2 O(l); (h) Cl (aq) + 6OH (aq) ⟶ ClO (aq) + 3H O(l) + 6e
− −
3
−
2
−
39.
(a) Sn
2+
(aq) + 2 Cu
2+
(aq) ⟶ Sn
4+
(aq) + 2 Cu
+
(aq); (b)
H2 S(g) + Hg2
2+
(aq) + 2 H2 O(l) ⟶ 2Hg(l) + S(s) + 2 H3 O
+
(aq); (c)
5 CN
−
(aq) + 2 ClO2 (aq) + 3 H2 O(l) ⟶ 5 CNO
−
(aq) + 2 Cl
−
(aq) + 2 H3 O
+
(aq); (d)
Fe
2+
(aq) + Ce
4+
(aq) ⟶ Fe
3+
(aq) + Ce
3+
(aq); (e) 2HBrO(aq) + 2H 2 O(l) ⟶ 2 H3 O
+
(aq) + 2 Br
−
(aq) + O2 (g)
41.
(a) 2 MnO 4
−
(aq) + 3NO2
−
(aq) + H2 O(l) ⟶ 2 MnO 2 (s) + 3 NO3
−
(aq) + 2 OH
−
(aq); (b)
3 MnO 4
2−
(aq) + 2 H2 O(l) ⟶ 2 MnO 4
−
(aq) + 4 OH
−
(aq) + MnO 2 (s) (in base); (c)
+ − 2−
Br 2 (l) + SO 2 (g) + 2 H2 O(l) ⟶ 4 H (aq) + 2 Br (aq) + SO 4 (aq)
43.
(a) 0.435 mol Na, 0.217 mol Cl2, 15.4 g Cl2; (b) 0.005780 mol HgO, 2.890 × 10−3 mol O2, 9.248 × 10−2 g O2; (c) 8.00 mol
NaNO3, 6.8 × 102 g NaNO3; (d) 1665 mol CO2, 73.3 kg CO2; (e) 18.86 mol CuO, 2.330 kg CuCO3; (f) 0.4580 mol C2H4Br2,
86.05 g C2H4Br2
45.
(a) 0.0686 mol Mg, 1.67 g Mg; (b) 2.701 × 10−3 mol O2, 0.08644 g O2; (c) 6.43 mol MgCO3, 542 g MgCO3 (d) 768 mol H2O,
13.8 kg H2O; (e) 16.31 mol BaO2, 2762 g BaO2; (f) 0.207 mol C2H4, 5.81 g C2H4
47.
(a) volume HCl solution ⟶ mol HCl ⟶ mol GaCl3 ; (b) 1.25 mol GaCl3, 2.2 × 102 g GaCl3
49.
(a) 5.337 × 1022 molecules; (b) 10.41 g Zn(CN)2
51.
SiO2 + 3C ⟶ SiC + 2CO, 4.50 kg SiO2
53.
5.00 × 103 kg
55.
1.28 × 105 g CO2
57.
161.4 mL KI solution
59.
176 g TiO2
61.
The limiting reactant is Cl2.
63.
Percent yield = 31%
65.
g CCl4 ⟶ mol CCl4 ⟶ mol CCl2 F2 ⟶ g CCl2 F2 , percent yield = 48.3%
67.
percent yield = 91.3%
69.
Convert mass of ethanol to moles of ethanol; relate the moles of ethanol to the moles of ether produced using the stoichiometry of
the balanced equation. Convert moles of ether to grams; divide the actual grams of ether (determined through the density) by the
theoretical mass to determine the percent yield; 87.6%
71.
The conversion needed is mol Cr ⟶ mol H3 PO4 . Then compare the amount of Cr to the amount of acid present. Cr is the
limiting reactant.
73.
Na2C2O4 is the limiting reactant. percent yield = 86.56%
75.
Only four molecules can be made.
77.
This amount cannot be weighted by ordinary balances and is worthless.
79.
3.4 × 10−3 M H2SO4
81.
9.6 × 10−3 M Cl−
83.
22.4%
85.
The empirical formula is BH3. The molecular formula is B2H6.
87.
49.6 mL
89.
13.64 mL
91.
0.0122 M
93.
34.99 mL KOH
95.
The empirical formula is WCl4.
22.14.5: Chapter 5
1.
The temperature of 1 gram of burning wood is approximately the same for both a match and a bonfire. This is an intensive property
and depends on the material (wood). However, the overall amount of produced heat depends on the amount of material; this is an
extensive property. The amount of wood in a bonfire is much greater than that in a match; the total amount of produced heat is also
much greater, which is why we can sit around a bonfire to stay warm, but a match would not provide enough heat to keep us from
getting cold.
3.
Heat capacity refers to the heat required to raise the temperature of the mass of the substance 1 degree; specific heat refers to the
heat required to raise the temperature of 1 gram of the substance 1 degree. Thus, heat capacity is an extensive property, and specific
heat is an intensive one.
5.
(a) 47.6 J/°C; 11.38 cal °C−1; (b) 407 J/°C; 97.3 cal °C−1
7.
1310 J; 313 cal
9.
7.15 °C
11.
(a) 0.390 J/g °C; (b) Copper is a likely candidate.
13.
We assume that the density of water is 1.0 g/cm3(1 g/mL) and that it takes as much energy to keep the water at 85 °F as to heat it
from 72 °F to 85 °F. We also assume that only the water is going to be heated. Energy required = 7.47 kWh
15.
lesser; more heat would be lost to the coffee cup and the environment and so ΔT for the water would be lesser and the calculated q
would be lesser
17.
greater, since taking the calorimeter’s heat capacity into account will compensate for the thermal energy transferred to the solution
from the calorimeter; this approach includes the calorimeter itself, along with the solution, as “surroundings”: qrxn = −(qsolution +
qcalorimeter); since both qsolution and qcalorimeter are negative, including the latter term (qrxn) will yield a greater value for the heat of
the dissolution
19.
The temperature of the coffee will drop 1 degree.
21.
5.7 × 102 kJ
23.
38.5 °C
25.
−2.2 kJ; The heat produced shows that the reaction is exothermic.
27.
1.4 kJ
29.
22.6. Since the mass and the heat capacity of the solution is approximately equal to that of the water, the two-fold increase in the
amount of water leads to a two-fold decrease of the temperature change.
31.
11.7 kJ
33.
30%
35.
0.24 g
37.
1.4 × 102 Calories
39.
The enthalpy change of the indicated reaction is for exactly 1 mol HCL and 1 mol NaOH; the heat in the example is produced by
0.0500 mol HCl and 0.0500 mol NaOH.
41.
25 kJ mol−1
43.
81 kJ mol−1
45.
5204.4 kJ
47.
1.83 × 10−2 mol
49.
–802 kJ mol−1
51.
15.5 kJ/ºC
53.
7.43 g
55.
Yes.
57.
459.6 kJ
59.
−494 kJ/mol
61.
44.01 kJ/mol
63.
−394 kJ
65.
265 kJ
67.
90.3 kJ/mol
69.
(a) −1615.0 kJ mol−1; (b) −484.3 kJ mol−1; (c) 164.2 kJ; (d) −232.1 kJ
71.
−54.04 kJ mol−1
73.
−2660 kJ mol−1
75.
–66.4 kJ
77.
−122.8 kJ
79.
3.7 kg
81.
On the assumption that the best rocket fuel is the one that gives off the most heat, B2H6 is the prime candidate.
83.
−88.2 kJ
85.
(a) C 3 H8 (g) + 5 O2 (g) ⟶ 3 CO2 (g) + 4 H2 O (l) ; (b) 1570 L air; (c) −104.5 kJ mol−1; (d) 75.4 °C
22.14.6: Chapter 6
1.
The spectrum consists of colored lines, at least one of which (probably the brightest) is red.
3.
3.15 m
5.
3.233 × 10−19 J; 2.018 eV
7.
ν = 4.568 × 1014 s; λ = 656.3 nm; Energy mol−1 = 1.823 × 105 J mol−1; red
9.
(a) λ = 8.69 × 10−7 m; E = 2.29 × 10−19 J; (b) λ = 4.59 × 10−7 m; E = 4.33 × 10−19 J; The color of (a) is red; (b) is blue.
11.
E = 9.502 × 10−15 J; ν = 1.434 × 1019 s−1
13.
Red: 660 nm; 4.54 × 1014 Hz; 3.01 × 10−19 J. Green: 520 nm; 5.77 × 1014 Hz; 3.82 × 10−19 J. Blue: 440 nm; 6.81 × 1014 Hz;
4.51 × 10−19 J. Somewhat different numbers are also possible.
15.
5.49 × 1014 s−1; no
17.
Quantized energy means that the electrons can possess only certain discrete energy values; values between those quantized values
are not permitted.
19.
2.856 eV
21.
−8.716 × 10−18 J
23.
−3.405 × 10−20 J
25.
33.9 Å
27.
1.471 × 10−17 J
29.
Both involve a relatively heavy nucleus with electrons moving around it, although strictly speaking, the Bohr model works only for
one-electron atoms or ions. According to classical mechanics, the Rutherford model predicts a miniature “solar system” with
electrons moving about the nucleus in circular or elliptical orbits that are confined to planes. If the requirements of classical
electromagnetic theory that electrons in such orbits would emit electromagnetic radiation are ignored, such atoms would be stable,
having constant energy and angular momentum, but would not emit any visible light (contrary to observation). If classical
electromagnetic theory is applied, then the Rutherford atom would emit electromagnetic radiation of continually increasing
frequency (contrary to the observed discrete spectra), thereby losing energy until the atom collapsed in an absurdly short time
(contrary to the observed long-term stability of atoms). The Bohr model retains the classical mechanics view of circular orbits
confined to planes having constant energy and angular momentum, but restricts these to quantized values dependent on a single
quantum number, n. The orbiting electron in Bohr’s model is assumed not to emit any electromagnetic radiation while moving
about the nucleus in its stationary orbits, but the atom can emit or absorb electromagnetic radiation when the electron changes from
one orbit to another. Because of the quantized orbits, such “quantum jumps” will produce discrete spectra, in agreement with
observations.
31.
Both models have a central positively charged nucleus with electrons moving about the nucleus in accordance with the Coulomb
electrostatic potential. The Bohr model assumes that the electrons move in circular orbits that have quantized energies, angular
momentum, and radii that are specified by a single quantum number, n = 1, 2, 3, …, but this quantization is an ad hoc assumption
made by Bohr to incorporate quantization into an essentially classical mechanics description of the atom. Bohr also assumed that
electrons orbiting the nucleus normally do not emit or absorb electromagnetic radiation, but do so when the electron switches to a
different orbit. In the quantum mechanical model, the electrons do not move in precise orbits (such orbits violate the Heisenberg
uncertainty principle) and, instead, a probabilistic interpretation of the electron’s position at any given instant is used, with a
mathematical function ψ called a wavefunction that can be used to determine the electron’s spatial probability distribution. These
wavefunctions, or orbitals, are three-dimensional stationary waves that can be specified by three quantum numbers that arise
naturally from their underlying mathematics (no ad hoc assumptions required): the principal quantum number, n (the same one used
by Bohr), which specifies shells such that orbitals having the same n all have the same energy and approximately the same spatial
extent; the angular momentum quantum number l, which is a measure of the orbital’s angular momentum and corresponds to the
orbitals’ general shapes, as well as specifying subshells such that orbitals having the same l (and n) all have the same energy; and
the orientation quantum number m, which is a measure of the z component of the angular momentum and corresponds to the
orientations of the orbitals. The Bohr model gives the same expression for the energy as the quantum mechanical expression and,
hence, both properly account for hydrogen’s discrete spectrum (an example of getting the right answers for the wrong reasons,
something that many chemistry students can sympathize with), but gives the wrong expression for the angular momentum (Bohr
orbits necessarily all have non-zero angular momentum, but some quantum orbitals [s orbitals] can have zero angular momentum).
33.
n determines the general range for the value of energy and the probable distances that the electron can be from the nucleus. l
determines the shape of the orbital. m1 determines the orientation of the orbitals of the same l value with respect to one another. ms
determines the spin of an electron.
35.
(a) 2p; (b) 4d; (c) 6s
37.
(a) 3d; (b) 1s; (c) 4f
39.
41.
(a) x. 2, y. 2, z. 2; (b) x. 1, y. 3, z. 0; (c) x. 4 0 0 1
2
, y. 2 1 0 1
2
, z. 3 2 0 1
2
; (d) x. 1, y. 2, z. 3; (e) x. l = 0, ml = 0, y. l = 1, ml = –1, 0,
or +1, z. l = 2, ml = –2, –1, 0, +1, +2
43.
12
45.
n l ml s
4 0 0 +
1
4 0 0 −
1
4 1 −1 +
1
4 1 0 +
1
4 1 +1 +
1
4 1 −1 −
1
47.
For example, Na+: 1s22s22p6; Ca2+: 1s22s22p63s23p6; Sn2+: 1s22s22p63s23p63d104s24p64d105s2; F–: 1s22s22p6; O2–: 1s22s22p6; Cl–:
1s22s22p63s23p6.
49.
(a) 1s22s22p3; (b) 1s22s22p63s23p2; (c) 1s22s22p63s23p64s23d6; (d) 1s22s22p63s23p64s23d104p65s24d105p4; (e)
1s22s22p63s23p64s23d104p65s24d105p66s24f9
51.
The charge on the ion.
53.
(a)
(b)
(c)
(d)
(e)
55.
Zr
57.
Rb+, Se2−
59.
Although both (b) and (c) are correct, (e) encompasses both and is the best answer.
61.
K
63.
1s22s22p63s23p64s23d104p65s24d105p66s24f145d10
65.
Co has 27 protons, 27 electrons, and 33 neutrons: 1s22s22p63s23p64s23d7. I has 53 protons, 53 electrons, and 78 neutrons:
1s22s22p63s23p63d104s24p64d105s25p5.
67.
Cl
69.
O
71.
Rb < Li < N < F
73.
15 (5A)
75.
Mg < Ca < Rb < Cs
77.
Si4+ < Al3+ < Ca2+ < K+
79.
Se, As−
81.
Mg2+ < K+ < Br– < As3–
83.
O, IE1
85.
Ra
22.14.7: Chapter 7
1.
The protons in the nucleus do not change during normal chemical reactions. Only the outer electrons move. Positive charges form
when electrons are lost.
3.
P, I, Cl, and O would form anions because they are nonmetals. Mg, In, Cs, Pb, and Co would form cations because they are metals.
5.
(a) P3–; (b) Mg2+; (c) Al3+; (d) O2–; (e) Cl–; (f) Cs+
7.
(a) [Ar]4s23d104p6; (b) [Kr]4d105s25p6 (c) 1s2 (d) [Kr]4d10; (e) [He]2s22p6; (f) [Ar]3d10; (g) 1s2 (h) [He]2s22p6 (i) [Kr]4d105s2 (j)
[Ar]3d7 (k) [Ar]3d6, (l) [Ar]3d104s2
9.
(a) 1s22s22p63s23p1; Al3+: 1s22s22p6; (b) 1s22s22p63s23p63d104s24p5; 1s22s22p63s23p63d104s24p6; (c)
1s 2s 2p 3s 3p 3d 4s 4p 5s ; Sr : 1s 2s 2p 3s 3p 3d 4s 4p ; (d) 1s 2s ; Li : 1s ; (e) 1s22s22p63s23p63d104s24p3;
2 2 6 2 6 10 2 6 2 2+ 2 2 6 2 6 10 2 6 2 1 + 2
1s22s22p63s23p63d104s24p6; (f) 1s22s22p63s23p4; 1s22s22p63s23p6

11.
NaCl consists of discrete ions arranged in a crystal lattice, not covalently bonded molecules.
13.
ionic: (b), (d), (e), (g), and (i); covalent: (a), (c), (f), (h), (j), and (k)
15.
(a) Cl; (b) O; (c) O; (d) S; (e) N; (f) P; (g) N
17.
(a) H, C, N, O, F; (b) H, I, Br, Cl, F; (c) H, P, S, O, F; (d) Na, Al, H, P, O; (e) Ba, H, As, N, O
19.
N, O, F, and Cl
21.
(a) HF; (b) CO; (c) OH; (d) PCl; (e) NH; (f) PO; (g) CN
23.
(a) eight electrons:
(b) eight electrons:
(c) no electrons Be2+

(d) eight electrons:
(e) no electrons Ga3+
(f) no electrons Li+
(g) eight electrons:
25.
(a)
(b)
(c)
(d)
(e)
(f)
27.
29.
(a)
In this case, the Lewis structure is inadequate to depict the fact that experimental studies have shown two unpaired electrons in
each oxygen molecule.
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
31.
(a) SeF6:
(b) XeF4:
(c) SeCl3
+
:
(d) Cl2BBCl2:
33.
Two valence electrons per Pb atom are transferred to Cl atoms; the resulting Pb2+ ion has a 6s2 valence shell configuration. Two of
the valence electrons in the HCl molecule are shared, and the other six are located on the Cl atom as lone pairs of electrons.
35.
37.
39.
(a)
(b)
(c)
(d)
(e)
41.
43.
Each bond includes a sharing of electrons between atoms. Two electrons are shared in a single bond; four electrons are shared in a
double bond; and six electrons are shared in a triple bond.
45.
(a)
(b)
(c)
(d)
(e)
47.
49.
(a)
(b)
CO has the strongest carbon-oxygen bond because there is a triple bond joining C and O. CO2 has double bonds.
51.
(a) H: 0, Cl: 0; (b) C: 0, F: 0; (c) P: 0, Cl 0; (d) P: 0, F: 0
53.
Cl in Cl2: 0; Cl in BeCl2: 0; Cl in ClF5: 0
55.
(a)
(b)
(c)
(d)
57.
HOCl
59.
The structure that gives zero formal charges is consistent with the actual structure:
61.
NF3;
63.
65.
(a) −114 kJ; (b) 30 kJ; (c) −1055 kJ
67.
The greater bond energy is in the figure on the left. It is the more stable form.
69.
1 1 ∘ ∘
HCl (g) ⟶ H2 (g) + Cl2 (g) ΔH = −ΔH
2 2 1 f[HCl(g)]
1 ∘ ∘
H2 (g) ⟶ H (g) ΔH = ΔH
2 2 f[H(g)]
1 ∘ ∘
Cl2 (g) ⟶ Cl (g) ΔH = ΔH
2 3 f[Cl(g)]
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
∘ ∘ ∘ ∘
HCl (g) ⟶ H (g) + Cl (g) ΔH = ΔH + ΔH + ΔH
1 2 3
∘ ∘ ∘ ∘
DHCl = ΔH = ΔH + ΔH + ΔH
f[HCl(g)] f[H(g)] f[Cl(g)]
= −(−92.307 kJ) + 217.97 kJ + 121.3 kJ
= 431.6 kJ
71.
The S–F bond in SF4 is stronger.
73.
The C–C single bonds are longest.

75.
(a) When two electrons are removed from the valence shell, the Ca radius loses the outermost energy level and reverts to the lower
n = 3 level, which is much smaller in radius. (b) The +2 charge on calcium pulls the oxygen much closer compared with K, thereby
increasing the lattice energy relative to a less charged ion. (c) Removal of the 4s electron in Ca requires more energy than removal
of the 4s electron in K because of the stronger attraction of the nucleus and the extra energy required to break the pairing of the
electrons. The second ionization energy for K requires that an electron be removed from a lower energy level, where the attraction
is much stronger from the nucleus for the electron. In addition, energy is required to unpair two electrons in a full orbital. For Ca,
the second ionization potential requires removing only a lone electron in the exposed outer energy level. (d) In Al, the removed
electron is relatively unprotected and unpaired in a p orbital. The higher energy for Mg mainly reflects the unpairing of the 2s
electron.
77.
(d)
79.
4008 kJ/mol; both ions in MgO have twice the charge of the ions in LiF; the bond length is very similar and both have the same
structure; a quadrupling of the energy is expected based on the equation for lattice energy
81.
(a) Na2O; Na+ has a smaller radius than K+; (b) BaS; Ba has a larger charge than K; (c) BaS; Ba and S have larger charges; (d)
BaS; S has a larger charge
83.
(e)
85.
The placement of the two sets of unpaired electrons in water forces the bonds to assume a tetrahedral arrangement, and the
resulting HOH molecule is bent. The HBeH molecule (in which Be has only two electrons to bond with the two electrons from the
hydrogens) must have the electron pairs as far from one another as possible and is therefore linear.
87.
Space must be provided for each pair of electrons whether they are in a bond or are present as lone pairs. Electron-pair geometry
considers the placement of all electrons. Molecular structure considers only the bonding-pair geometry.
89.
As long as the polar bonds are compensated (for example. two identical atoms are found directly across the central atom from one
another), the molecule can be nonpolar.
91.
(a) Both the electron geometry and the molecular structure are octahedral. (b) Both the electron geometry and the molecular
structure are trigonal bipyramid. (c) Both the electron geometry and the molecular structure are linear. (d) Both the electron
geometry and the molecular structure are trigonal planar.
93.
(a) electron-pair geometry: octahedral, molecular structure: square pyramidal; (b) electron-pair geometry: tetrahedral, molecular
structure: bent; (c) electron-pair geometry: octahedral, molecular structure: square planar; (d) electron-pair geometry: tetrahedral,
molecular structure: trigonal pyramidal; (e) electron-pair geometry: trigonal bypyramidal, molecular structure: seesaw; (f) electron-
pair geometry: tetrahedral, molecular structure: bent (109°)
95.
(a) electron-pair geometry: trigonal planar, molecular structure: bent (120°); (b) electron-pair geometry: linear, molecular structure:
linear; (c) electron-pair geometry: trigonal planar, molecular structure: trigonal planar; (d) electron-pair geometry: tetrahedral,
molecular structure: trigonal pyramidal; (e) electron-pair geometry: tetrahedral, molecular structure: tetrahedral; (f) electron-pair
geometry: trigonal bipyramidal, molecular structure: seesaw; (g) electron-pair geometry: tetrahedral, molecular structure: trigonal
pyramidal
97.
All of these molecules and ions contain polar bonds. Only ClF5, ClO 2
−
, PCl3, SeF4, and PH 2
−
have dipole moments.
99.
SeS2, CCl2F2, PCl3, and ClNO all have dipole moments.
101.
P
103.
nonpolar
105.
(a) tetrahedral; (b) trigonal pyramidal; (c) bent (109°); (d) trigonal planar; (e) bent (109°); (f) bent (109°); (g) CH3CCH tetrahedral,
CH3CCH linear; (h) tetrahedral; (i) H2CCCH2 linear; H2CCCH2 trigonal planar
107.
109.
(a)
(b)
(c)
(d) CS 3 includes three regions of electron density (all are bonds with no lone pairs); the shape is trigonal planar; CS2 has only
2−
two regions of electron density (all bonds with no lone pairs); the shape is linear
111.
The Lewis structure is made from three units, but the atoms must be rearranged:
113.
The molecular dipole points away from the hydrogen atoms.
115.
The structures are very similar. In the model mode, each electron group occupies the same amount of space, so the bond angle is
shown as 109.5°. In the “real” mode, the lone pairs are larger, causing the hydrogens to be compressed. This leads to the smaller
angle of 104.5°.
22.14.8: Chapter 8
1.
Similarities: Both types of bonds result from overlap of atomic orbitals on adjacent atoms and contain a maximum of two electrons.
Differences: σ bonds are stronger and result from end-to-end overlap and all single bonds are σ bonds; π bonds between the same
two atoms are weaker because they result from side-by-side overlap, and multiple bonds contain one or more π bonds (in addition
to a σ bond).
3.
The specific average bond distance is the distance with the lowest energy. At distances less than the bond distance, the positive
charges on the two nuclei repel each other, and the overall energy increases.
5.
Bonding: One σ bond and one π bond. The s orbitals are filled and do not overlap. The p orbitals overlap along the axis to form a σ
bond and side-by-side to form the π bond.
7.
No, two of the p orbitals (one on each N) will be oriented end-to-end and will form a σ bond.
9.
Hybridization is introduced to explain the geometry of bonding orbitals in valance bond theory.
11.
There are no d orbitals in the valence shell of carbon.
13.
trigonal planar, sp2; trigonal pyramidal (one lone pair on A) sp3; T-shaped (two lone pairs on A sp3d, or (three lone pairs on A)
sp3d2
15.
(a) Each S has a bent (109°) geometry, sp3
(b) Bent (120°), sp2
(c) Trigonal planar, sp2
(d) Tetrahedral, sp3
17.
(a) XeF2
(b)
(c) linear (d) sp3d

19.
(a)
(b) P atoms, trigonal pyramidal; S atoms, bent, with two lone pairs; Cl atoms, trigonal pyramidal; (c) Hybridization about P, S, and
Cl is, in all cases, sp3; (d) Oxidation states P +1, S−1 1
3
, Cl +5, O –2. Formal charges: P 0; S 0; Cl +2: O –1
21.
Phosphorus and nitrogen can form sp3 hybrids to form three bonds and hold one lone pair in PF3 and NF3, respectively. However,
nitrogen has no valence d orbitals, so it cannot form a set of sp3d hybrid orbitals to bind five fluorine atoms in NF5. Phosphorus has
d orbitals and can bind five fluorine atoms with sp3d hybrid orbitals in PF5.
23.
A triple bond consists of one σ bond and two π bonds. A σ bond is stronger than a π bond due to greater overlap.
25.
(a)
(b) The terminal carbon atom uses sp3 hybrid orbitals, while the central carbon atom is sp hybridized. (c) Each of the two π bonds
is formed by overlap of a 2p orbital on carbon and a nitrogen 2p orbital.
27.
(a) sp2; (b) sp; (c) sp2; (d) sp3; (e) sp3; (f) sp3d; (g) sp3
29.
(a) sp2, delocalized; (b) sp, localized; (c) sp2, delocalized; (d) sp3, delocalized
31.
Each of the four electrons is in a separate orbital and overlaps with an electron on an oxygen atom.
33.
(a) Similarities: Both are bonding orbitals that can contain a maximum of two electrons. Differences: σ orbitals are end-to-end
combinations of atomic orbitals, whereas π orbitals are formed by side-by-side overlap of orbitals. (b) Similarities: Both are
quantum-mechanical constructs that represent the probability of finding the electron about the atom or the molecule. Differences: ψ
for an atomic orbital describes the behavior of only one electron at a time based on the atom. For a molecule, ψ represents a
mathematical combination of atomic orbitals. (c) Similarities: Both are orbitals that can contain two electrons. Differences:
Bonding orbitals result in holding two or more atoms together. Antibonding orbitals have the effect of destabilizing any bonding
that has occurred.
35.
An odd number of electrons can never be paired, regardless of the arrangement of the molecular orbitals. It will always be
paramagnetic.
37.
Bonding orbitals have electron density in close proximity to more than one nucleus. The interaction between the bonding positively
charged nuclei and negatively charged electrons stabilizes the system.
39.
The pairing of the two bonding electrons lowers the energy of the system relative to the energy of the nonbonded electrons.
41.
(a) H2 bond order = 1, H bond order = 0.5, H bond order = 0.5, strongest bond is H2; (b) O2 bond order = 2, O
2
+
2
−
bond order 2
2+
= 3; O 2 bond order = 1, strongest bond is O ; (c) Li2 bond order = 1, Be bond order = 0.5, Be2 bond order = 0, strongest
2−
2
2+
2
+
bond is Li ;(d) F2 bond order = 1, F bond order = 1.5, F bond order = 0.5, strongest bond is F ; (e) N2 bond order = 3, N
2 2
+
2
−
2
+
2
+
bond order = 2.5, N bond order = 2.5, strongest bond is N2

2
−
43.
(a) H2; (b) N2; (c) O; (d) C2; (e) B2
45.
Yes, fluorine is a smaller atom than Li, so atoms in the 2s orbital are closer to the nucleus and more stable.
47.
2+
49.
N2 has s-p mixing, so the π orbitals are the last filled in N2
2+
. O2 does not have s-p mixing, so the σp orbital fills before the π
orbitals.
22.14.9: Chapter 9
1.
The cutting edge of a knife that has been sharpened has a smaller surface area than a dull knife. Since pressure is force per unit
area, a sharp knife will exert a higher pressure with the same amount of force and cut through material more effectively.
3.
Lying down distributes your weight over a larger surface area, exerting less pressure on the ice compared to standing up. If you
exert less pressure, you are less likely to break through thin ice.
5.
0.809 atm; 82.0 kPa
7.
2.2 × 102 kPa
9.
Earth: 14.7 lb in–2; Venus: 1.30 × 103 lb in−2
11.
(a) 101.5 kPa; (b) 51 torr drop
13.
(a) 264 torr; (b) 35,200 Pa; (c) 0.352 bar
15.
(a) 623 mm Hg; (b) 0.820 atm; (c) 83.1 kPa
17.
With a closed-end manometer, no change would be observed, since the vaporized liquid would contribute equal, opposing pressures
in both arms of the manometer tube. However, with an open-ended manometer, a higher pressure reading of the gas would be
obtained than expected, since Pgas = Patm + Pvol liquid.
19.
As the bubbles rise, the pressure decreases, so their volume increases as suggested by Boyle’s law.
21.
(a) The number of particles in the gas increases as the volume increases. (b) temperature, pressure
23.
The curve would be farther to the right and higher up, but the same basic shape.
25.
About 12.5 L
27.
3.40 × 103 torr
29.
12.1 L
31.
217 L
33.
8.190 × 10–2 mol; 5.553 g
35.
(a) 7.24 × 10–2 g; (b) 23.1 g; (c) 1.5 × 10–4 g
37.
5561 L
39.
46.4 g
41.
For a gas exhibiting ideal behavior:
43.
(a) 1.85 L CCl2F2; (b) 4.66 L CH3CH2F
45.
0.644 atm
47.
The pressure decreases by a factor of 3.
49.
4.64 g L−1
51.
38.8 g
53.
72.0 g mol−1
55.
88.1 g mol−1; PF3
57.
141 atm, 107,000 torr, 14,300 kPa
59.
CH4: 276 kPa; C2H6: 27 kPa; C3H8: 3.4 kPa
61.
Yes
63.
740 torr
65.
(a) Determine the moles of HgO that decompose; using the chemical equation, determine the moles of O2 produced by
decomposition of this amount of HgO; and determine the volume of O2 from the moles of O2, temperature, and pressure. (b) 0.308
L
67.
(a) Determine the molar mass of CCl2F2. From the balanced equation, calculate the moles of H2 needed for the complete reaction.
From the ideal gas law, convert moles of H2 into volume. (b) 3.72 × 103 L
69.
(a) Balance the equation. Determine the grams of CO2 produced and the number of moles. From the ideal gas law, determine the
volume of gas. (b) 7.43 × 105 L
71.
42.00 L
73.
(a) 18.0 L; (b) 0.533 atm
75.
10.57 L O2
77.
5.40 × 105 L
79.
XeF4
81.
4.2 hours
83.
Effusion can be defined as the process by which a gas escapes through a pinhole into a vacuum. Graham’s law states that with a
1/2
mixture of two gases A and B: ( rate A
rate B
) =(
molar mass of B
molar mass of A
) . Both A and B are in the same container at the same temperature,
and therefore will have the same kinetic energy:
1 2
KE A = KE B KE = mv
2
Therefore, 1
2
mA v
2
A
=
1
2
mB v
2
B
2
v mB
A
=
v
2 mA
B
2 1/2 1/2
v mB
A
( ) =( )
v
2 mA
B
1/2
vA mB
=( )
vB mA
85.
F2, N2O, Cl2, H2S
87.
1.4; 1.2
89.
51.7 cm
91.
Yes. At any given instant, there are a range of values of molecular speeds in a sample of gas. Any single molecule can speed up or
slow down as it collides with other molecules. The average speed of all the molecules is constant at constant temperature.
93.
H2O. Cooling slows the speeds of the He atoms, causing them to behave as though they were heavier.
95.
(a) The number of collisions per unit area of the container wall is constant. (b) The average kinetic energy doubles. (c) The root
– −−−−−
mean square speed increases to √2 times its initial value; urms is proportional to √KE . avg
97.
(a) equal; (b) less than; (c) 29.48 g mol−1; (d) 1.0966 g L−1; (e) 0.129 g/L; (f) 4.01 × 105 g; net lifting capacity = 384 lb; (g) 270 L;
(h) 39.1 kJ min−1
99.
Gases C, E, and F
101.
The gas behavior most like an ideal gas will occur under the conditions that minimize the chances of significant interactions
between the gaseous atoms/molecules, namely, low pressures (fewer atoms/molecules per unit volume) and high temperatures
(greater kinetic energies of atoms/molecules make them less susceptible to attractive forces). The conditions described in (b), high
temperature and low pressure, are therefore most likely to yield ideal gas behavior.
103.
SF6
105.
(a) A straight horizontal line at 1.0; (b) When real gases are at low pressures and high temperatures, they behave close enough to
ideal gases that they are approximated as such; however, in some cases, we see that at a high pressure and temperature, the ideal
gas approximation breaks down and is significantly different from the pressure calculated by the ideal gas equation. (c) The greater
the compressibility, the more the volume matters. At low pressures, the correction factor for intermolecular attractions is more
significant, and the effect of the volume of the gas molecules on Z would be a small lowering compressibility. At higher pressures,
the effect of the volume of the gas molecules themselves on Z would increase compressibility (see Figure 9.35). (d) Once again, at
low pressures, the effect of intermolecular attractions on Z would be more important than the correction factor for the volume of
the gas molecules themselves, though perhaps still small. At higher pressures and low temperatures, the effect of intermolecular
attractions would be larger. See Figure 9.35. (e) Low temperatures
22.14.10: Chapter 10
1.
Liquids and solids are similar in that they are matter composed of atoms, ions, or molecules. They are incompressible and have
similar densities that are both much larger than those of gases. They are different in that liquids have no fixed shape, and solids are
rigid.
3.
They are similar in that the atoms or molecules are free to move from one position to another. They differ in that the particles of a
liquid are confined to the shape of the vessel in which they are placed. In contrast, a gas will expand without limit to fill the space
into which it is placed.
5.
All atoms and molecules will condense into a liquid or solid in which the attractive forces exceed the kinetic energy of the
molecules, at sufficiently low temperature.
7.
(a) Dispersion forces occur as an atom develops a temporary dipole moment when its electrons are distributed asymmetrically
about the nucleus. This structure is more prevalent in large atoms such as argon or radon. A second atom can then be distorted by
the appearance of the dipole in the first atom. The electrons of the second atom are attracted toward the positive end of the first
atom, which sets up a dipole in the second atom. The net result is rapidly fluctuating, temporary dipoles that attract one another
(e.g., Ar). (b) A dipole-dipole attraction is a force that results from an electrostatic attraction of the positive end of one polar
molecule for the negative end of another polar molecule (e.g., ICI molecules attract one another by dipole-dipole interaction). (c)
Hydrogen bonds form whenever a hydrogen atom is bonded to one of the more electronegative atoms, such as a fluorine, oxygen,
or nitrogen atom. The electrostatic attraction between the partially positive hydrogen atom in one molecule and the partially
negative atom in another molecule gives rise to a strong dipole-dipole interaction called a hydrogen bond (e.g., HF⋯HF ).
9.
The London forces typically increase as the number of electrons increase.
11.
(a) SiH4 < HCl < H2O; (b) F2 < Cl2 < Br2; (c) CH4 < C2H6 < C3H8; (d) N2 < O2 < NO
13.
Only rather small dipole-dipole interactions from C-H bonds are available to hold n-butane in the liquid state. Chloroethane,
however, has rather large dipole interactions because of the Cl-C bond; the interaction, therefore, is stronger, leading to a higher
boiling point.
15.
−85 °C. Water has stronger hydrogen bonds, so it melts at a higher temperature.
17.
The hydrogen bond between two hydrogen fluoride molecules is stronger than that between two water molecules because the
electronegativity of F is greater than that of O. Consequently, the partial negative charge on F is greater than that on O. The
hydrogen bond between the partially positive H and the larger partially negative F will be stronger than that formed between H and
O.
19.
H-bonding is the principle IMF holding the protein strands together. The H-bonding is between the N − H and C = O.
21.
(a) hydrogen bonding, dipole-dipole attraction, and dispersion forces; (b) dispersion forces; (c) dipole-dipole attraction and
dispersion forces
23.
The water molecules have strong intermolecular forces of hydrogen bonding. The water molecules are thus attracted strongly to
one another and exhibit a relatively large surface tension, forming a type of “skin” at its surface. This skin can support a bug or
paper clip if gently placed on the water.
25.
Temperature has an effect on intermolecular forces: The higher the temperature, the greater the kinetic energies of the molecules
and the greater the extent to which their intermolecular forces are overcome, and so the more fluid (less viscous) the liquid. The
lower the temperature, the less the intermolecular forces are overcome, and so the less viscous the liquid.
27.
(a) As the water reaches higher temperatures, the increased kinetic energies of its molecules are more effective in overcoming
hydrogen bonding, and so its surface tension decreases. Surface tension and intermolecular forces are directly related. (b) The same
trend in viscosity is seen as in surface tension, and for the same reason.
29.
1.7 × 10−4 m
31.
The heat is absorbed by the ice, providing the energy required to partially overcome intermolecular attractive forces in the solid and
causing a phase transition to liquid water. The solution remains at 0 °C until all the ice is melted. Only the amount of water existing
as ice changes until the ice disappears. Then the temperature of the water can rise.
33.
We can see the amount of liquid in an open container decrease and we can smell the vapor of some liquids.
35.
The vapor pressure of a liquid decreases as the strength of its intermolecular forces increases.
37.
As the temperature increases, the average kinetic energy of the molecules of gasoline increases and so a greater fraction of
molecules have sufficient energy to escape from the liquid than at lower temperatures.
39.
They are equal when the pressure of gas above the liquid is exactly 1 atm.
41.
approximately 95 °C
43.
(a) At 5000 feet, the atmospheric pressure is lower than at sea level, and water will therefore boil at a lower temperature. This
lower temperature will cause the physical and chemical changes involved in cooking the egg to proceed more slowly, and a longer
time is required to fully cook the egg. (b) As long as the air surrounding the body contains less water vapor than the maximum that
air can hold at that temperature, perspiration will evaporate, thereby cooling the body by removing the heat of vaporization
required to vaporize the water.
45.
Dispersion forces increase with molecular mass or size. As the number of atoms composing the molecules in this homologous
series increases, so does the extent of intermolecular attraction via dispersion forces and, consequently, the energy required to
overcome these forces and vaporize the liquids.
47.
The boiling point of CS2 is higher than that of CO2 partially because of the higher molecular weight of CS2; consequently, the
attractive forces are stronger in CS2. It would be expected, therefore, that the heat of vaporization would be greater than that of 9.8
kJ/mol for CO2. A value of 28 kJ/mol would seem reasonable. A value of −8.4 kJ/mol would indicate a release of energy upon
vaporization, which is clearly implausible.
49.
The thermal energy (heat) needed to evaporate the liquid is removed from the skin.
51.
1125 kJ
53.
(a) 13.0 kJ; (b) It is likely that the heat of vaporization will have a larger magnitude since in the case of vaporization the
intermolecular interactions have to be completely overcome, while melting weakens or destroys only some of them.
55.
At low pressures and 0.005 °C, the water is a gas. As the pressure increases to 4.6 torr, the water becomes a solid; as the pressure
increases still more, it becomes a liquid. At 40 °C, water at low pressure is a vapor; at pressures higher than about 75 torr, it
converts into a liquid. At −40 °C, water goes from a gas to a solid as the pressure increases above very low values.
57.
(a) gas; (b) gas; (c) gas; (d) gas; (e) solid; (f) gas
59.
61.
Yes, ice will sublime, although it may take it several days. Ice has a small vapor pressure, and some ice molecules form gas and
escape from the ice crystals. As time passes, more and more solid converts to gas until eventually the clothes are dry.
63.
(a)
(b)
(c)
(d)
(e) liquid phase (f) sublimation

65.
67.
Ice has a crystalline structure stabilized by hydrogen bonding. These intermolecular forces are of comparable strength and thus
require the same amount of energy to overcome. As a result, ice melts at a single temperature and not over a range of temperatures.
The various, very large molecules that compose butter experience varied van der Waals attractions of various strengths that are
overcome at various temperatures, and so the melting process occurs over a wide temperature range.
69.
(a) ionic; (b) covalent network; (c) molecular; (d) metallic; (e) covalent network; (f) molecular; (g) molecular; (h) ionic; (i) ionic
71.
X = ionic; Y = metallic; Z = covalent network
73.
(b) metallic solid
75.
The structure of this low-temperature form of iron (below 910 °C) is body-centered cubic. There is one-eighth atom at each of the
eight corners of the cube and one atom in the center of the cube.
77.
eight
79.
12
81.
(a) 1.370 Å; (b) 19.26 g/cm
83.
(a) 2.176 Å; (b) 3.595 g/cm3
85.
The crystal structure of Si shows that it is less tightly packed (coordination number 4) in the solid than Al (coordination number
12).
87.
In a closest-packed array, two tetrahedral holes exist for each anion. If only half the tetrahedral holes are occupied, the numbers of
anions and cations are equal. The formula for cadmium sulfide is CdS.
89.
Co3O4
91.
In a simple cubic array, only one cubic hole can be occupied be a cation for each anion in the array. The ratio of thallium to iodide
must be 1:1; therefore, the formula for thallium is TlI.
93.
59.95%; The oxidation number of titanium is +4.
95.
Both ions are close in size: Mg, 0.65; Li, 0.60. This similarity allows the two to interchange rather easily. The difference in charge
is generally compensated by the switch of Si4+ for Al3+.
97.
Mn2O3
99.
1.48 Å
101.
2.874 Å
103.
20.2°
105.
1.74 × 104 eV
22.14.11: Chapter 11
1.
A solution can vary in composition, while a compound cannot vary in composition. Solutions are homogeneous at the molecular
level, while other mixtures are heterogeneous.
3.
(a) The process is endothermic as the solution is consuming heat. (b) Attraction between the K+ and NO ions is stronger than
3
−
between the ions and water molecules (the ion-ion interactions have a lower, more negative energy). Therefore, the dissolution
process increases the energy of the molecular interactions, and it consumes the thermal energy of the solution to make up for the
difference. (c) No, an ideal solution is formed with no appreciable heat release or consumption.
5.
(a) ion-dipole forces; (b) dipole-dipole forces; (c) dispersion forces; (d) dispersion forces; (e) hydrogen bonding
7.
Heat is released when the total intermolecular forces (IMFs) between the solute and solvent molecules are stronger than the total
IMFs in the pure solute and in the pure solvent: Breaking weaker IMFs and forming stronger IMFs releases heat. Heat is absorbed
when the total IMFs in the solution are weaker than the total of those in the pure solute and in the pure solvent: Breaking stronger
IMFs and forming weaker IMFs absorbs heat.
9.
Crystals of NaCl dissolve in water, a polar liquid with a very large dipole moment, and the individual ions become strongly
solvated. Hexane is a nonpolar liquid with a dipole moment of zero and, therefore, does not significantly interact with the ions of
the NaCl crystals.
11.
(a) Fe(NO3)3 is a strong electrolyte, thus it should completely dissociate into Fe3+ and NO3
−
ions. Therefore, (z) best represents
the solution. (b) Fe(NO ) (s) ⟶ Fe (aq) + 3NO (aq)
3 3
3+
3
−
13.
(a) high conductivity (solute is an ionic compound that will dissociate when dissolved); (b) high conductivity (solute is a strong
acid and will ionize completely when dissolved); (c) nonconductive (solute is a covalent compound, neither acid nor base,
unreactive towards water); (d) low conductivity (solute is a weak base and will partially ionize when dissolved)
15.
(a) ion-dipole; (b) hydrogen bonds; (c) dispersion forces; (d) dipole-dipole attractions; (e) dispersion forces
17.
The solubility of solids usually decreases upon cooling a solution, while the solubility of gases usually decreases upon heating.
19.
40%
21.
2.8 g
23.
2.9 atm
25.
102 L HCl
27.
The strength of the bonds between like molecules is stronger than the strength between unlike molecules. Therefore, some regions
will exist in which the water molecules will exclude oil molecules and other regions will exist in which oil molecules will exclude
water molecules, forming a heterogeneous region.
29.
Both form homogeneous solutions; their boiling point elevations are the same, as are their lowering of vapor pressures. Osmotic
pressure and the lowering of the freezing point are also the same for both solutions.
31.
(a) Find number of moles of HNO3 and H2O in 100 g of the solution. Find the mole fractions for the components. (b) The mole
fraction of HNO3 is 0.378. The mole fraction of H2O is 0.622.
33.
(a) XNa2 CO3 = 0.0119; XH2 O = 0.988; (b) XNH4 NO3 = 0.0928; XH2 O = 0.907; (c) XCl2 = 0.192; XCH2 CI2 = 0.808; (d)
XC5 H9 N = 0.00426; XCHCl3 = 0.997
35.
In a 1 M solution, the mole is contained in exactly 1 L of solution. In a 1 m solution, the mole is contained in exactly 1 kg of
solvent.
37.
(a) Determine the molar mass of HNO3. Determine the number of moles of acid in the solution. From the number of moles and the
mass of solvent, determine the molality. (b) 33.7 m
39.
(a) 6.70 × 10−1 m; (b) 5.67 m; (c) 2.8 m; (d) 0.0358 m
41.
1.08 m
43.
(a) Determine the molar mass of sucrose; determine the number of moles of sucrose in the solution; convert the mass of solvent to
units of kilograms; from the number of moles and the mass of solvent, determine the molality; determine the difference between
the boiling point of water and the boiling point of the solution; determine the new boiling point. (b) 100.5 °C
45.
(a) Determine the molar mass of sucrose; determine the number of moles of sucrose in the solution; convert the mass of solvent to
units of kilograms; from the number of moles and the mass of solvent, determine the molality; determine the difference between
the freezing temperature of water and the freezing temperature of the solution; determine the new freezing temperature. (b) −1.8 °C
47.
(a) Determine the molar mass of Ca(NO3)2; determine the number of moles of Ca(NO3)2 in the solution; determine the number of
moles of ions in the solution; determine the molarity of ions, then the osmotic pressure. (b) 2.67 atm
49.
(a) Determine the molal concentration from the change in boiling point and Kb; determine the moles of solute in the solution from
the molal concentration and mass of solvent; determine the molar mass from the number of moles and the mass of solute. (b) 2.1 ×
102 g mol−1
51.
No. Pure benzene freezes at 5.5 °C, and so the observed freezing point of this solution is depressed by ΔTf = 5.5 − 0.4 = 5.1 °C.
The value computed, assuming no ionization of HCl, is ΔTf = (1.0 m)(5.14 °C/m) = 5.1 °C. Agreement of these values supports the
assumption that HCl is not ionized.
53.
144 g mol−1
55.
0.870 °C
57.
S8
59.
1.39 × 104 g mol−1
61.
54 g
63.
100.26 °C
65.
(a) X CH3 OH = 0.590; XC
2
H5 OH = 0.410; (b) Vapor pressures are: CH3OH: 55 torr; C2H5OH: 18 torr; (c) CH3OH: 0.75; C2H5OH:
0.25
67.
The ions and compounds present in the water in the beef lower the freezing point of the beef below −1 °C.
69.
1m ol Hg Cl
2
9.41g ×
271.496 g
Δbp = Kb m = (1.20 °C/m) ( ) = 1.27 °C

0.03275 kg
The observed change equals the theoretical change; therefore, no dissociation occurs.
71.
Colloidal System Dispersed Phase Dispersion Medium
starch dispersion starch water
smoke solid particles air
fog water air
pearl water calcium carbonate (CaCO3)
whipped cream air cream
floating soap air soap
jelly fruit juice pectin gel
milk butterfat water
ruby chromium(III) oxide (Cr2O3) aluminum oxide (Al2O3)
73.
Colloidal dispersions consist of particles that are much bigger than the solutes of typical solutions. Colloidal particles are either
very large molecules or aggregates of smaller species that usually are big enough to scatter light. Colloids are homogeneous on a
macroscopic (visual) scale, while solutions are homogeneous on a microscopic (molecular) scale.
75.
If they are placed in an electrolytic cell, dispersed particles will move toward the electrode that carries a charge opposite to their
own charge. At this electrode, the charged particles will be neutralized and will coagulate as a precipitate.
22.14.12: Chapter 12
1.
The instantaneous rate is the rate of a reaction at any particular point in time, a period of time that is so short that the concentrations
of reactants and products change by a negligible amount. The initial rate is the instantaneous rate of reaction as it starts (as product
just begins to form). Average rate is the average of the instantaneous rates over a time period.
3.
1 Δ[ CIF 3 ] Δ[ Cl2 ] 1 Δ[ F2 ]
rate = + =− =−
2 Δt Δt 3 Δt
5.
(a) average rate, 0 − 10 s = 0.0375 mol L−1 s−1; average rate, 10 − 20 s = 0.0265 mol L−1 s−1; (b) instantaneous rate, 15 s = 0.023
mol L−1 s−1; (c) average rate for B formation = 0.0188 mol L−1 s−1; instantaneous rate for B formation = 0.012 mol L−1 s−1
7.
Higher molarity increases the rate of the reaction. Higher temperature increases the rate of the reaction. Smaller pieces of
magnesium metal will react more rapidly than larger pieces because more reactive surface exists.
9.
(a) Depending on the angle selected, the atom may take a long time to collide with the molecule and, when a collision does occur, it
may not result in the breaking of the bond and the forming of the other. (b) Particles of reactant must come into contact with each
other before they can react.
11.
(a) very slow; (b) As the temperature is increased, the reaction proceeds at a faster rate. The amount of reactants decreases, and the
amount of products increases. After a while, there is a roughly equal amount of BC, AB, and C in the mixture and a slight excess of
A.
13.
(a) 2; (b) 1
15.
(a) The process reduces the rate by a factor of 4. (b) Since CO does not appear in the rate law, the rate is not affected.
17.
4.3 × 10−5 mol/L/s
19.
7.9 × 10−13 mol/L/year
21.
rate = k; k = 2.0 × 10−2 mol L−1 h−1 (about 0.9 g L−1 h−1 for the average male); The reaction is zero order.
23.
rate = k[NOCl]2; k = 8.0 × 10−8 L/mol/h; second order
25.
rate = k[NO]2[Cl2]; k = 9.1 L2 mol−2 h−1; second order in NO; first order in Cl2
27.
(a) The rate law is second order in A and is written as rate = k[A]2. (b) k = 7.88 × 10−3 L mol−1 s−1
29.
(a) 2.5 × 10−4 mol/L/min
31.
rate = k[I−][OCl−]; k = 6.1 × 10−2 L mol −1 s−1
33.
Plotting a graph of ln[SO2Cl2] versus t reveals a linear trend; therefore we know this is a first-order reaction:
k = 2.20 × 10–5 s−1

34.
The plot is nicely linear, so the reaction is second order. k = 50.1 L mol−1 h−1
36.
14.3 d
38.
8.3 × 107 s
40.
0.826 s
42.
The reaction is first order. k = 1.0 × 107 L mol−1 min−1
44.
1.16 × 103 s ; 20% remains
46.
252 days
48.
[A]0 (M) k × 103 (s−1)
4.88 2.45
3.52 2.51
2.29 2.53
1.81 2.58
5.33 2.36
4.05 2.47
2.95 2.48
1.72 2.43
50.
The reactants either may be moving too slowly to have enough kinetic energy to exceed the activation energy for the reaction, or
the orientation of the molecules when they collide may prevent the reaction from occurring.
52.
The activation energy is the minimum amount of energy necessary to form the activated complex in a reaction. It is usually
expressed as the energy necessary to form one mole of activated complex.
54.
−Ea
After finding k at several different temperatures, a plot of ln k versus 1
T
, gives a straight line with the slope R
from which Ea
may be determined.
56.
(a) 4-times faster (b) 128-times faster
58.
15 −1
3.9 × 10 s
60.
43.0 kJ/mol
62.
177 kJ/mol
64.
Ea = 108 kJ; A = 2.0 × 108 s−1; k = 3.2 × 10−10 s−1; (b) 1.81 × 108 h or 7.6 × 106 day; (c) Assuming that the reaction is
irreversible simplifies the calculation because we do not have to account for any reactant that, having been converted to product,
returns to the original state.
66.
The A atom has enough energy to react with BC; however, the different angles at which it bounces off of BC without reacting
indicate that the orientation of the molecule is an important part of the reaction kinetics and determines whether a reaction will
occur.
68.
No. In general, for the overall reaction, we cannot predict the effect of changing the concentration without knowing the rate law.
Yes. If the reaction is an elementary reaction, then doubling the concentration of A doubles the rate.
70.
Rate = k[A][B]2; Rate = k[A]3
72.
(a) Rate1 = k[O3]; (b) Rate2 = k[O3][Cl]; (c) Rate3 = k[ClO][O]; (d) Rate2 = k[O3][NO]; (e) Rate3 = k[NO2][O]
74.
(a) Doubling [H2] doubles the rate. [H2] must enter the rate law to the first power. Doubling [NO] increases the rate by a factor of
4. [NO] must enter the rate law to the second power. (b) Rate = k [NO]2[H2]; (c) k = 5.0 × 103 mol−2 L−2 min−1; (d) 0.0050 mol/L;
(e) Step II is the rate-determining step. If step I gives N2O2 in adequate amount, steps 1 and 2 combine to give
2NO + H 2 ⟶ H O + N O.
2 2 This reaction corresponds to the observed rate law. Combine steps 1 and 2 with step 3, which
occurs by supposition in a rapid fashion, to give the appropriate stoichiometry.
76.
The general mode of action for a catalyst is to provide a mechanism by which the reactants can unite more readily by taking a path
with a lower reaction energy. The rates of both the forward and the reverse reactions are increased, leading to a faster achievement
of equilibrium.
78.
(a) Chlorine atoms are a catalyst because they react in the second step but are regenerated in the third step. Thus, they are not used
up, which is a characteristic of catalysts. (b) NO is a catalyst for the same reason as in part (a).
80.
The lowering of the transition state energy indicates the effect of a catalyst. (a) B; (b) B
82.
The energy needed to go from the initial state to the transition state is (a) 10 kJ; (b) 10 kJ.
84.
Both diagrams describe two-step, exothermic reactions, but with different changes in enthalpy, suggesting the diagrams depict two
different overall reactions.
22.14.13: Chapter 13
1.
The reaction can proceed in both the forward and reverse directions.
3.
When a system has reached equilibrium, no further changes in the reactant and product concentrations occur; the forward and
reverse reactions continue to proceed, but at equal rates.
5.
Not necessarily. A system at equilibrium is characterized by constant reactant and product concentrations, but the values of the
reactant and product concentrations themselves need not be equal.
7.
Equilibrium cannot be established between the liquid and the gas phase if the top is removed from the bottle because the system is
not closed; one of the components of the equilibrium, the Br2 vapor, would escape from the bottle until all liquid disappeared.
Thus, more liquid would evaporate than can condense back from the gas phase to the liquid phase.
9.
(a) Kc = [Ag+][Cl−] < 1. AgCl is insoluble; thus, the concentrations of ions are much less than 1 M; (b) Kc =
2+
1
− 2
>1
[ Pb ] [Cl ]
because PbCl2 is insoluble and formation of the solid will reduce the concentration of ions to a low level (<1 M).
11.
[ C6 H6 ]
Since Kc = 3
, a value of Kc ≈ 10 means that C6H6 predominates over C2H2. In such a case, the reaction would be
[ C2 H2 ]
commercially feasible if the rate to equilibrium is suitable.

13.
Kc > 1
15.
2 2 2
[ CH3 Cl][HCl] [NO] [ SO 3 ] [Br]
(a) Qc =
[ CH4 ][ Cl2 ]
; (b) Qc =
[ N2 ] [ O2 ]
; (c) Qc = 2
; (d) Qc = [SO2]; (e) Qc =
1
5
; (f) Qc =
[ Br2 ]
; (g)
[ SO 2 ] [ O2 ] [ P4 ] [ O2 ]
(h) Qc = [H2O]5
[ CO2 ]
Qc = 2
;
[ CH4 ] [ O2 ]
17.
(a) Qc 25 proceeds left; (b) QP 0.22 proceeds right; (c) Qc undefined proceeds left; (d) QP 1.00 proceeds right; (e) QP 0 proceeds
right; (f) Qc 4 proceeds left
19.
The system will shift toward the reactants to reach equilibrium.
21.
(a) homogenous; (b) homogenous; (c) homogenous; (d) heterogeneous; (e) heterogeneous; (f) homogenous; (g) heterogeneous; (h)
heterogeneous
23.
This situation occurs in (a) and (b).
25.
(a) KP = 1.6 × 10−4; (b) KP = 50.2; (c) Kc = 5.34 × 10−39; (d) Kc = 4.60 × 10−3
27.
KP = PH2 O = 0.042.
29.
+ −
[ NH4 ][ OH ]
Qc =
[ NH3 ]
31.
The amount of CaCO3 must be so small that P is less than KP when the CaCO3 has completely decomposed. In other words, the
CO2
starting amount of CaCO3 cannot completely generate the full P required for equilibrium.
CO2
33.
The change in enthalpy may be used. If the reaction is exothermic, the heat produced can be thought of as a product. If the reaction
is endothermic the heat added can be thought of as a reactant. Additional heat would shift an exothermic reaction back to the
reactants but would shift an endothermic reaction to the products. Cooling an exothermic reaction causes the reaction to shift
toward the product side; cooling an endothermic reaction would cause it to shift to the reactants’ side.
34.
No, it is not at equilibrium. Because the system is not confined, products continuously escape from the region of the flame;
reactants are also added continuously from the burner and surrounding atmosphere.
36.
Add N2; add H2; decrease the container volume; heat the mixture.
38.
(a) T increase = shift right, V decrease = shift left; (b) T increase = shift right, V = no effect; (c) T increase = shift left, V decrease =
shift left; (d) T increase = shift left, V decrease = shift right.
40.
[ CH3 OH]
(a) Kc = 2
; (b) [H2] increases, [CO] decreases, [CH3OH] increases; (c), [H2] increases, [CO] decreases, [CH3OH]
[ H2 ] [CO]
decreases; (d), [H2] increases, [CO] increases, [CH3OH] increases; (e), [H2] increases, [CO] increases, [CH3OH] decreases; (f), no
changes.
42.
[CO][ H2 ]
(a) K c =
[ H2 O]
; (b) [H2O] no change, [CO] no change, [H2] no change; (c) [H2O] decreases, [CO] decreases, [H2] decreases;
(d) [H2O] increases, [CO] increases, [H2] decreases; (e) [H2O] decreases, [CO] increases, [H2] increases. In (b), (c), (d), and (e),
the mass of carbon will change, but its concentration (activity) will not change.
44.
Only (b)
46.
Add NaCl or some other salt that produces Cl− to the solution. Cooling the solution forces the equilibrium to the right, precipitating
more AgCl(s).
48.
Though the solution is saturated, the dynamic nature of the solubility equilibrium means the opposing processes of solid dissolution
and precipitation continue to occur (just at equal rates, meaning the dissolved ion concentrations and the amount of undissolved
solid remain constant). The radioactive Ag+ ions detected in the solution phase come from dissolution of the added solid, and their
presence is countered by precipitation of nonradioactive Ag+.
50.
2
[C]
Kc = 2
. [A] = 0.1 M, [B] = 0.1 M, [C] = 1 M; and [A] = 0.01, [B] = 0.250, [C] = 0.791.
[A][B]
52.
Kc = 6.00 × 10−2
54.
Kc = 0.50
56.
KP = 1.9 × 103
58.
KP = 3.06
60.
(a) −2x, +2x; (b) 4
3
,
x –
2
3
, −2x; (c) −2x, 3x; (d) x, –x, −3x; (e) +x; (f) –
x
1
4
x
62.
Activities of pure crystalline solids equal 1 and are constant; however, the mass of Ni does change.
64.
[NH3] = 9.1 × 10−2 M
66.
PBrCl = 4.9 × 10−2 atm
68.
[CO] = 2.04 × 10−4 M
70.
−3
PH O = 3.64 × 10 atm
2
72.
Calculate Q based on the calculated concentrations and see if it is equal to Kc. Because Q does equal 4.32, the system must be at
equilibrium.
74.
(a) [NO2] = 1.17 × 10−3 M; [N2O4] = 0.128 M; (b) The assumption that x is negligibly small compared to 0.129 is confirmed by
comparing the initial concentration of the N2O4 to its concentration at equilibrium (they differ by just 1 in the least significant
digit’s place).
76.
(a) [H2S] = 0.810 atm, [H2] = 0.014 atm, [S2] = 0.0072 atm; (b) The assumption that 2x is negligibly small compared to 0.824 is
confirmed by comparing the initial concentration of the H2S to its concentration at equilibrium (0.824 atm versus 0.810 atm, a
difference of less than 2%).
78.
[PCl5] = 1.80 M; [Cl2] = 0.195 M; [PCl3] = 0.195 M.
79.
507 g
81.
330 g
84.
(a) 0.33 mol. (b) [CO2] = 0.50 M. Added H2 forms some water as a result of a shift to the left after H2 is added.
86.
4 7
[ NH3 ] [ O2 ]
(a) Kc = 4 6
. (b) [NH3] must increase for Qc to reach Kc. (c) The increase in system volume would lower the partial
[ NO2 ] [ H2 O]
pressures of all reactants (including NO2). (d) P O2 = 49 torr
88.
PN2 O3 = 1.90 atm and PNO = PNO2 = 1.90 atm
22.14.14: Chapter 14
1.
One example for NH3 as a conjugate acid: NH2
−
+H
+
⟶ NH3 ; as a conjugate base:
+ −
NH4 (aq) + OH (aq) ⟶ NH3 (aq) + H2 O(l)
3.
(a) H3 O
+
(aq) ⟶ H
+
(aq) + H2 O(l); (b) HCl(aq) ⟶ H
+
(aq) + Cl
−
(aq); (c) NH3 (aq) ⟶ H
+
(aq) + NH2
−
(aq); (d)
CH3 CO2 H(aq) ⟶ H
+
(aq) + CH3 CO2
−
(aq); (e) NH4
+
(aq) ⟶ H
+
(aq) + NH3 (aq); (f)
− + 2−
HSO 4 (aq) ⟶ H (aq) + SO 4 (aq)
5.
(a) H2 O(l) + H
+
(aq) ⟶ H3 O
+
(aq); (b) OH
−
(aq) + H
+
(aq) ⟶ H2 O(l); (c) NH3 (aq) + H
+
(aq) ⟶ NH4
+
(aq); (d)
CN
−
(aq) + H
+
(aq) ⟶ HCN(aq); (e) S 2−
(aq) + H
+
(aq) ⟶ HS
−
(aq); (f) H 2 PO4
−
(aq) + H
+
(aq) ⟶ H3 PO4 (aq)
7.
(a) H2O, O2−; (b) H3O+, OH−; (c) H2CO3, CO3
2−
; (d) NH4
+
, NH2
−
; (e) H2SO4, SO 4
2−
; (f) H3 O2
+
, HO2
−
; (g) H2S; S2−; (h)
, H4N2
2+
H N 6 2
9.
The labels are Brønsted-Lowry acid = BA; its conjugate base = CB; Brønsted-Lowry base = BB; its conjugate acid = CA. (a)
HNO3(BA), H2O(BB), H3O+(CA), NO (CB); (b) CN−(BB), H2O(BA), HCN(CA), OH−(CB); (c) H2SO4(BA), Cl−(BB),
3
−
HCl(CA), HSO (CB); (d) HSO (BA), OH−(BB), SO (CB), H2O(CA); (e) O2−(BB), H2O(BA) OH−(CB and CA); (f)
4
−
4
−
4
2−
[Cu(H2O)3(OH)]+(BB), [Al(H2O)6]3+(BA), [Cu(H2O)4]2+(CA), [Al(H2O)5(OH)]2+(CB); (g) H2S(BA), NH (BB), HS−(CB), 2

−
NH3(CA)
11.
Amphiprotic species may either gain or lose a proton in a chemical reaction, thus acting as a base or an acid. An example is H2O.
As an acid: H O(aq) + NH (aq) ⇌ NH (aq) + OH (aq). As a base: H O(aq) + HCl(aq) ⇌ H O (aq) + Cl (aq)
2 3 4
+ −
2 3
+ −
13.
amphiprotic: (a) NH3 + H3 O
+
⟶ NH4 OH + H2 O, NH3 + OCH3
−
⟶ NH2
−
+ CH3 OH; (b)
HPO4
2−
+ OH
−
⟶ PO4
3−
+ H2 O, HPO4
2−
+ HClO4 ⟶ H2 PO4
−
+ ClO4
−
; not amphiprotic: (c) Br−; (d) NH4
+
; (e)
3−
AsO 4
15.
In a neutral solution [H3O+] = [OH−]. At 40 °C, [H3O+] = [OH−] = (2.910 × 10−14)1/2 = 1.7 × 10−7.
17.
x = 3.051 × 10−7 M = [H3O+] = [OH−]; pH = −log3.051 × 10−7 = −(−6.5156) = 6.5156; pOH = pH = 6.5156
19.
(a) pH = 3.587; pOH = 10.413; (b) pOH = 0.68; pH = 13.32; (c) pOH = 3.85; pH = 10.15; (d) pOH = −0.40; pH = 14.4
21.
[H3O+] = 3.0 × 10−7 M; [OH−] = 3.3 × 10−8 M
23.
[H3O+] = 1 × 10−2 M; [OH−] = 1 × 10−12 M
25.
[OH−] = 3.1 × 10−12 M
27.
The salt ionizes in solution, but the anion slightly reacts with water to form the weak acid. This reaction also forms OH−, which
causes the solution to be basic.
29.
[H2O] > [CH3CO2H] > [H 3O
+
] ≈ [CH 3 CO2
−
] > [OH−]
31.
The oxidation state of the sulfur in H2SO4 is greater than the oxidation state of the sulfur in H2SO3.
33.
2+ −
Mg (OH) (s)+ 2HCl(aq) ⟶ Mg (aq)+ 2 Cl (aq) + 2H2 O(l)
2
BB BA CB CA
35.
−11
Ka = 2.3 × 10
37.
The stronger base or stronger acid is the one with the larger Kb or Ka, respectively. In these two examples, they are (CH3)2NH and
+
CH3 NH3 .
39.
triethylamine
41.
(a) HSO ; higher electronegativity of the central ion. (b) H2O; NH3 is a base and water is neutral, or decide on the basis of Ka
4
−
values. (c) HI; PH3 is weaker than HCl; HCl is weaker than HI. Thus, PH3 is weaker than HI. (d) PH3; in binary compounds of
hydrogen with nonmetals, the acidity increases for the element lower in a group. (e) HBr; in a period, the acidity increases from left
to right; in a group, it increases from top to bottom. Br is to the left and below S, so HBr is the stronger acid.
43.
(a) NaHSeO3 < NaHSO3 < NaHSO4; in polyoxy acids, the more electronegative central element—S, in this case—forms the
stronger acid. The larger number of oxygen atoms on the central atom (giving it a higher oxidation state) also creates a greater
release of hydrogen atoms, resulting in a stronger acid. As a salt, the acidity increases in the same manner. (b)
; the basicity of the anions in a series of acids will be the opposite of the acidity in their oxyacids. The
− − −
ClO 2 < BrO < IO 2 2
acidity increases as the electronegativity of the central atom increases. Cl is more electronegative than Br, and I is the least
electronegative of the three. (c) HOI < HOBr < HOCl; in a series of the same form of oxyacids, the acidity increases as the
electronegativity of the central atom increases. Cl is more electronegative than Br, and I is the least electronegative of the three. (d)
HOCl < HOClO < HOClO2 < HOClO3; in a series of oxyacids of the same central element, the acidity increases as the number of
oxygen atoms increases (or as the oxidation state of the central atom increases). (e) HTe < HS << PH < NH ; PH − −
2
−
2
−
2
−
and NH are anions of weak bases, so they act as strong bases toward H+. HTe and HS− are anions of weak acids, so they have
2
− −
less basic character. In a periodic group, the more electronegative element has the more basic anion. (f)
< BrO ; with a larger number of oxygen atoms (that is, as the oxidation state of the central ion
− − − −
BrO 4 < BrO < BrO 3 2
increases), the corresponding acid becomes more acidic and the anion consequently less basic.
45.
+ − − −
[ H2 O] > [ C6 H4 OH(CO2 H)] > [H ] 0 > [C H4 OH(CO2 ) ] ≫ [ C6 H4 O(CO2 H) ] > [ OH ]
6
47.
1. Assume that the change in initial concentration of the acid as the equilibrium is established can be neglected, so this
concentration can be assumed constant and equal to the initial value of the total acid concentration. 2. Assume we can neglect the
contribution of water to the equilibrium concentration of H3O+.
48.
(b) The addition of HCl
50.
(a) Adding HCl will add H3O+ ions, which will then react with the OH− ions, lowering their concentration. The equilibrium will
shift to the right, increasing the concentration of HNO2, and decreasing the concentration of NO ions. (b) Adding HNO2 2
−
increases the concentration of HNO2 and shifts the equilibrium to the left, increasing the concentration of NO ions and 2
−
decreasing the concentration of OH− ions. (c) Adding NaOH adds OH− ions, which shifts the equilibrium to the left, increasing the
concentration of NO ions and decreasing the concentrations of HNO2. (d) Adding NaCl has no effect on the concentrations of
2
−
the ions. (e) Adding KNO2 adds NO ions and shifts the equilibrium to the right, increasing the HNO2 and OH− ion
2
−
concentrations.
52.
This is a case in which the solution contains a mixture of acids of different ionization strengths. In solution, the HCO2H exists
primarily as HCO2H molecules because the ionization of the weak acid is suppressed by the strong acid. Therefore, the HCO2H
contributes a negligible amount of hydronium ions to the solution. The stronger acid, HCl, is the dominant producer of hydronium
ions because it is completely ionized. In such a solution, the stronger acid determines the concentration of hydronium ions, and the
ionization of the weaker acid is fixed by the [H3O+] produced by the stronger acid.
54.
(a) K b = 1.8 × 10
−5
; (b) K a = 4.5 × 10
−4
; (c) K b = 6.4 × 10
−5
; (d) Ka
−10
= 5.6 × 10
56.
−2
Ka = 1.2 × 10
58.
(a) Kb = 4.3 × 10
−12
(b) Ka = 1.6 × 10
10
(c) Kb = 5.9 × 10
8
(d) Kb = 4.2 × 10
−3
(e) Kb = 2.3 × 10
5
(f)
−13
Kb = 6.3 × 10
60.
+ −
[ H3 O ][ ClO ] (x)(x) (x)(x)
(a) [HClO]
=
(0.0092−x)
≈
0.0092
= 2.9 × 10
−8
Solving for x gives 1.63 × 10−5 M. This value is less than 5% of 0.0092, so the assumption that it can be neglected is valid. Thus,
the concentrations of solute species at equilibrium are:
[H3O+] = [ClO–] = 1.6 × 10−5 M
[HClO–] = 0.0092 M
[OH−] = 6.1 × 10−10 M;
+ −
[ C6 H5 NH3 ][ OH ] (x)(x) (x)(x)
(b) [ C6 H5 NH2 ]
=
(0.0784−x)
≈
0.0784
= 4.3 × 10
−10
−6
Solving for x gives 5.81 × 10 M. This value is less than 5% of 0.0784, so the assumption that it can be neglected is valid. Thus,
− −6
] = [OH ] = 5.8 × 10 M
+
[ C H5 NH
6 3
[C6H5NH2] = 0.0784 M
[H3O+] = 1.7× 10−9 M;
+ −
[ H3 O ][ CN ] (x)(x) (x)(x)
(c) [HCN]
=
(0.0810−x)
≈
0.0810
= 4.9 × 10
−10
[H3O+] = [CN−] = 6.3 × 10−6 M
[HCN] = 0.0810 M
[OH−] = 1.6 × 10−9 M;
+ −
[ ( CH3 ) NH ][ OH ] (x)(x) (x)(x)
(d) 3
[ ( CH3 ) N]
=
(0.11−x)
≈
0.11
= 6.3 × 10
−5
Solving for x gives 2.63 × 10−3 M. This value is less than 5% of 0.11, so the assumption that it can be neglected is valid. Thus, the
concentrations of solute species at equilibrium are:
[(CH3)3NH+] = [OH−] = 2.6 × 10−3 M
[(CH3)3N] = 0.11 M
[H3O+] = 3.8 × 10−12 M;
+ +
[Fe( H2 O) ( OH) ][ H3 O ] (x)(x) (x)(x)
(e) 5
[Fe( H2 O)
2+
]
=
(0.120−x)
≈
0.120
= 1.6 × 10
−7
[Fe(H2O)5(OH)+] = [H3O+] = 1.4 × 10−4 M
] = 0.120 M
2+
[Fe(H2 O)
6
[OH ] = 7.2 × 10−11 M

−
62.
pH = 2.41
64.
[C10H14N2] = 0.049 M; [C10H14N2H+] = 1.9 × 10−4 M; [C 10 H14 N2 H2
2+
] = 1.4 × 10−11 M; [OH−] = 1.9 × 10−4 M; [H3O+] = 5.3
−11
× 10 M
66.
−2
Ka = 1.2 × 10
68.
−5
Kb = 1.77 × 10
70.
(a) acidic; (b) basic; (c) acidic; (d) neutral
72.
[H3O+] and [HCO 3
−
] are practically equal
74.
[C6H4(CO2H)2] 7.2 × 10−3 M, [C6H4(CO2H)(CO2)−] = [H3O+] 2.8 × 10−3 M, [ C6 H4 (CO2 )
2
2−
3.9
] × 10−6 M, [OH−] 3.6 ×
10−12 M
76.
(a) K a2 = 1.5 × 10
−11
;
(b) K b = 4.3 × 10
−12
;
2− +
[ Te ][ H3 O ] (x)(0.0141+x) (x)(0.0141)
(c) −
=
(0.0141−x)
≈
0.0141
= 1.5 × 10
−11
[ HTe ]
Solving for x gives 1.5 × 10−11 M. Therefore, compared with 0.014 M, this value is negligible (1.1 × 10−7%).
78.
Excess H3O+ is removed primarily by the reaction: H O (aq) + H PO 3
+
2 4
−
(aq) ⟶ H3 PO4 (aq) + H2 O(l)
Excess base is removed by the reaction: OH (aq) + H PO (aq) ⟶ H −

3 4 2 PO4
−
(aq) + H2 O(l)
80.
[H3O+] = 1.5 × 10−4 M
82.
[OH−] = 4.2 × 10−4 M
84.
(a) The added HCl will increase the concentration of H3O+ slightly, which will react with CH CO and produce CH3CO2H in 3 2
−
the process. Thus, [CH CO ] decreases and [CH3CO2H] increases. (b) The added KCH3CO2 will increase the concentration of
3 2
−
+ +
] which will react with H3O and produce CH3CO2 H in the process. Thus, [H3O ] decreases slightly and [CH3CO2H]
−
[ CH CO3 2
increases. (c) The added NaCl will have no effect on the concentration of the ions. (d) The added KOH will produce OH− ions,
which will react with the H3O+, thus reducing [H3O+]. Some additional CH3CO2H will dissociate, producing [CH CO ] ions in 3 2
−
the process. Thus, [CH3CO2H] decreases slightly and [CH CO ] increases. (e) The added CH3CO2H will increase its
3 2
−
concentration, causing more of it to dissociate and producing more [CH CO ] and H3O+ in the process. Thus, [H3O+] increases 3 2
−
slightly and [CH CO ] increases. 3 2

−
86.
pH = 8.95
88.
37 g (0.27 mol)
90.
(a) pH = 5.222; (b) The solution is acidic. (c) pH = 5.220
92.
At the equivalence point in the titration of a weak base with a strong acid, the resulting solution is slightly acidic due to the
presence of the conjugate acid. Thus, pick an indicator that changes color in the acidic range and brackets the pH at the equivalence
point. Methyl orange is a good example.
94.
(a) pH = 2.50; (b) pH = 4.01; (c) pH = 5.60; (d) pH = 8.35; (e) pH = 11.08
22.14.15: Chapter 15
1.
(a)
+ −
AgI(s) ⇌ Ag (aq)+ I (aq)
x x
–
–
(b)
2+ 2−
CaCO3 (s) ⇌ Ca (aq)+ CO3 (aq)
x x
–
–
(c)
2+ −
Mg (OH) (s) ⇌ Mg (aq) + 2 OH (aq)
2
x 2x
–––
(d)
2+ 3−
Mg 3 (PO4 )2 (s) ⇌ 3Mg (aq)+ 2PO4 (aq)
2
x x
–
– 3
(e)
2+ 3− −
Ca5 (PO4 ) OH(s) ⇌ 5Ca (aq)+ 3PO4 (aq)+ OH (aq)
3
5x 3x x
––– –––
3.
There is no change. A solid has an activity of 1 whether there is a little or a lot.
5.
The solubility of silver bromide at the new temperature must be known. Normally the solubility increases and some of the solid
silver bromide will dissolve.
7.
CaF2, MnCO3, and ZnS
9.
− 3
(a) LaF (s) ⇌ La (aq) + 3F (aq)
3
3+ −
Ksp = [ La
3+
] [F ] ;
(b) CaCO (s) ⇌ Ca (aq) + CO

3
2+
3
2−
(aq) Ksp = [ Ca
2+
][ CO3
2−
];
+ 2
(c) Ag SO (s) ⇌ 2Ag (aq) + SO
2 4
+
4
2−
(aq) Ksp = [ Ag ] [ SO 4
2−
];
− 2
(d) Pb(OH) 2
(s) ⇌ Pb
2+
(aq) + 2OH
−
(aq) Ksp = [ Pb
2+
] [ OH ]
11.
(a)1.77 × 10–7; (b) 1.6 × 10–6; (c) 2.2 × 10–9; (d) 7.91 × 10–22
13.
(a) 2 × 10–2 M; (b) 1.5 × 10–3 M; (c) 2.27 × 10–9 M; (d) 2.2 × 10–10 M
15.
(a) 6.4 × 10−9 M = [Ag+], [Cl−] = 0.025 M. Check:
−9
6.4 × 10
0.025 M
M
× 100% = 2.6 × 10
−5
%, an insignificant change;
−5 2+ −
−5
(b) 2.2 × 10 M = [Ca ], [F ] = 0.0013 M. Check: 2.26 × 10
0.00133 M
M
× 100% = 1.70%. This value is less than 5% and can be
ignored.
(c) 0.2238 M = [SO ]; [Ag+] = 7.4 × 10–3 M. Check:
−3
4
2− 3.7 × 10
0.2238
× 100% = 1.64 × 10
−2
; the condition is satisfied.
– –3 −12 2+
x is less than 5% of [OH–] and
−12
(d) [OH ] = 2.8 × 10 M; 5.7 × 10 M = [Zn ]. Check: 5.7 × 10

−3
× 100% = 2.0 × 10
−7
%;
2.8 × 10
is, therefore, negligible.
17.
(a) [Cl–] = 7.6 × 10−3 M
−3
Check: 7.6 × 10
× 100% = 30%
0.025
This value is too large to drop x. Therefore solve by using the quadratic equation:
[Ti+] = 3.1 × 10–2 M
[Cl–] = 6.1 × 10–3
(b) [Ba2+] = 7.7 × 10–4 M
−4
Check: 7.7 × 10
× 100% = 2.4%
0.0313
Therefore, the condition is satisfied.

[Ba2+] = 7.7 × 10–4 M
[F–] = 0.0321 M;
(c) Mg(NO3)2 = 0.02444 M
2− −5
[ C2 O4 ] = 2.9 × 10
−5
Check: 2.9 × 10
× 100% = 0.12%
0.02444
The condition is satisfied; the above value is less than 5%.

2− −5
[ C2 O4 ] = 2.9 × 10 M
2+
[Mg ] = 0.0244 M
(d) [OH–] = 0.0501 M
[Ca2+] = 3.15 × 10–3
−3
Check: 3.15 × 10
× 100% = 6.28%
0.050
This value is greater than 5%, so a more exact method, such as successive approximations, must be used.
[Ca2+] = 2.8 × 10–3 M
[OH–] = 0.053 × 10–2 M
19.
The changes in concentration are greater than 5% and thus exceed the maximum value for disregarding the change.
21.
CaSO4·2H2O is the most soluble Ca salt in mol/L, and it is also the most soluble Ca salt in g/L.
23.
4.8 × 10–3 M = [SO 4
2−
] = [Ca2+]; Since this concentration is higher than 2.60 × 10–3 M, “gyp” water does not meet the standards.
25.
Mass (CaSO4·2H2O) = 0.72 g/L
27.
(a) [Ag+] = [I–] = 1.3 × 10–5 M; (b) [Ag+] = 2.88 × 10–2 M, [SO ]= 1.44 × 10–2 M; (c) [Mn2+] = 3.7 × 10–5 M, [OH–] = 7.4
4
2−
×
10–5 M; (d) [Sr2+] = 4.3 × 10–2 M, [OH–] = 8.6 × 10–2 M; (e) [Mg2+] = 1.3 × 10–4 M, [OH–] = 2.6 × 10–4 M.
29.
(a) 1.45 × 10–4; (b) 8.2 × 10–55; (c) 1.35 × 10–4; (d) 1.18 × 10–5; (e) 1.08 × 10–10
31.
(a) CaCO3 does precipitate. (b) The compound does not precipitate. (c) The compound does not precipitate. (d) The compound
precipitates.
33.
3.03 × 10−7 M
35.
9.2 × 10−13 M
37.
[Ag+] = 1.8 × 10–3 M
39.
6.3 × 10–4
41.
(a) 2.25 L; (b) 7.2 × 10–7 g
43.
100% of it is dissolved
45.
(a) Hg 2
and Cu2+: Add SO . (b) SO
2+
4 and Cl–: Add Ba2+. (c) Hg2+ and Co2+: Add S2–. (d) Zn2+ and Sr2+: Add OH– until
2−
4
2−
– 2+ 2+
[OH ] = 0.050 M. (e) Ba and Mg : Add SO . (f) CO and OH–: Add Ba2+.
4
2−
3
2−
47.
AgI will precipitate first.
49.
1.5 × 10−12 M
51.
3.99 kg
53.
(a) 3.1 × 10–11; (b) [Cu2+] = 2.6 × 10–3; [IO 3
−
] = 5.3 × 10–3
55.
1.8 × 10–5 g Pb(OH)2
57.
2+ − 2+ − 2
Mg(OH) (s) ⇌ Mg + 2OH Ksp = [ Mg ] [ OH ]
2
−3
1.23 × 10 g Mg(OH)2
59.
MnCO3 will form first since it has the smallest Ksp value among these homologous compounds and is therefore the least soluble.
MgCO3•3H2O will be the last to precipitate since it has the largest K_sp value and is the most soluble. Ksp value.
62.
when the amount of solid is so small that a saturated solution is not produced
64.
1.8 × 10–5 M
66.
5 × 1023
68.
[Cd2+] = 9.5 × 10–5 M; [CN–] = 3.8 × 10–4 M

70.
[Co3+] = 3.0 × 10–6 M; [NH3] = 1.8 × 10–5 M
72.
1.3 g
74.
0.79 g
76.
(a)
(b)
(c)
(d)
(e)
78.
(a)
(b) H 3O
+
+ CH3
−
⟶ CH4 + H2 O
(c) CaO + SO 3 ⟶ CaSO4
(d) NH 4
+
+ C2 H5 O
−
⟶ C2 H5 OH + NH3
80.
0.0281 g
82.
+ − +
HNO3 (l) + HF(l) ⟶ H2 NO3 +F ; HF(l) + BF 3 (g) ⟶ H + BF 4
84.
(a) H BO + H O ⟶ H BO + H ; (b) The electronic and molecular shapes are the same—both tetrahedral. (c) The
3 3 2 4 4
− +
tetrahedral structure is consistent with sp3 hybridization.

86.
0.014 M
88.
7.2 × 10–15 M
90.
4.4 × 10−22 M
93.
[OH−] = 4.5 × 10−6; [Al3+] = 2 × 10–16 (molar solubility)
95.
[ SO 4
2−
; [Ba2+] = 4.7 × 10–7 (molar solubility)
] = 0.049 M
97.
[OH–] = 7.6 × 10−3 M; [Pb2+] = 2.1 × 10–11 (molar solubility)
99.
7.66
101.
(a) Ksp = [Mg2+][F–]2 = (1.21 × 10–3)(2 × 1.21 × 10–3)2 = 7.09 × 10–9
(b) 7.09 × 10–7 M
(c) Determine the concentration of Mg2+ and F– that will be present in the final volume. Compare the value of the ion product
[Mg2+][F–]2 with Ksp. If this value is larger than Ksp, precipitation will occur.
0.1000 L × 3.00 × 10–3 M Mg(NO3)2 = 0.3000 L × M Mg(NO3)2
M Mg(NO3)2 = 1.00 × 10–3 M
0.2000 L × 2.00 × 10–3 M NaF = 0.3000 L × M NaF
M NaF = 1.33 × 10–3 M
ion product = (1.00 × 10–3)(1.33 × 10–3)2 = 1.77 × 10–9 This value is smaller than Ksp, so no precipitation will occur.
(d) MgF2 is less soluble at 27 °C than at 18 °C. Because added heat acts like an added reagent, when it appears on the product side,
the Le Châtelier’s principle states that the equilibrium will shift to the reactants’ side to counter the stress. Consequently, less
reagent will dissolve. This situation is found in our case. Therefore, the reaction is exothermic.
103.
BaF2, Ca3(PO4)2, ZnS; each is a salt of a weak acid, and the [H 3O
+
] from perchloric acid reduces the equilibrium concentration of
the anion, thereby increasing the concentration of the cations
105.
Effect on amount of solid CaHPO4, [Ca2+], [OH–]: (a) increase, increase, decrease; (b) decrease, increase, decrease; (c) no effect,
no effect, no effect; (d) decrease, increase, decrease; (e) increase, no effect, no effect
22.14.16: Chapter 16
1.
A reaction has a natural tendency to occur and takes place without the continual input of energy from an external source.
3.
(a) spontaneous; (b) nonspontaneous; (c) spontaneous; (d) nonspontaneous; (e) spontaneous; (f) spontaneous
5.
Although the oxidation of plastics is spontaneous, the rate of oxidation is very slow. Plastics are therefore kinetically stable and do
not decompose appreciably even over relatively long periods of time.
7.
There are four initial microstates and four final microstates.
Wf −23 4
ΔS = k ln = 1.38 × 10 J/K × ln =0
Wi 4
9.
The probability for all the particles to be on one side is . This probability is noticeably lower than the result for the four-
1
32
1
particle system. The conclusion we can make is that the probability for all the particles to stay in only one part of the system will
decrease rapidly as the number of particles increases, and, for instance, the probability for all molecules of gas to gather in only one
side of a room at room temperature and pressure is negligible since the number of gas molecules in the room is very large.
11.
There is only one initial state. For the final state, the energy can be contained in pairs A-C, A-D, B-C, or B-D. Thus, there are four
final possible states.
Wf −23 4 −23
ΔS = k ln ( ) = 1.38 × 10 J/K × ln ( ) = 1.91 × 10 J/K
Wi 1
13.
The masses of these molecules would suggest the opposite trend in their entropies. The observed trend is a result of the more
significant variation of entropy with a physical state. At room temperature, I2 is a solid, Br2 is a liquid, and Cl2 is a gas.
15.
(a) C3H7OH(l) as it is a larger molecule (more complex and more massive), and so more microstates describing its motions are
available at any given temperature. (b) C2H5OH(g) as it is in the gaseous state. (c) 2H(g), since entropy is an extensive property,
and so two H atoms (or two moles of H atoms) possess twice as much entropy as one atom (or one mole of atoms).
17.
(a) Negative. The relatively ordered solid precipitating decreases the number of mobile ions in solution. (b) Negative. There is a net
loss of three moles of gas from reactants to products. (c) Positive. There is a net increase of seven moles of gas from reactants to
products.
19.
C6 H6 (l) + 7.5 O2 (g) ⟶ 3H2 O(g) + 6CO2 (g)
There are 7.5 moles of gas initially, and 3 + 6 = 9 moles of gas in the end. Therefore, it is likely that the entropy increases as a
result of this reaction, and ΔS is positive.
21.
(a) 107 J/K; (b) −86.4 J/K; (c) 133.2 J/K; (d) 118.8 J/K; (e) −326.6 J/K; (f) −171.9 J/K; (g) −7.2 J/K
23.
100.6 J/K
25.
(a) −198.1 J/K; (b) −348.9 J/K
27.
As ΔSuniv < 0 at each of these temperatures, melting is not spontaneous at either of them. The given values for entropy and enthalpy
are for NaCl at 298 K. It is assumed that these do not change significantly at the higher temperatures used in the problem.
29.
(a) 2.86 J/K; (b) 24.8 J/K; (c) −113.2 J/K; (d) −24.7 J/K; (e) 15.5 J/K; (f) 290.0 J/K
31.
The reaction is nonspontaneous at room temperature.
Above 400 K, ΔG will become negative, and the reaction will become spontaneous.
33.
(a) 465.1 kJ nonspontaneous; (b) −106.86 kJ spontaneous; (c) −291.9 kJ spontaneous; (d) −83.4 kJ spontaneous; (e) −406.7 kJ
spontaneous; (f) −154.3 kJ spontaneous
35.
(a) The standard free energy of formation is –1124.3 kJ/mol. (b) The calculation agrees with the value in Appendix G because free
energy is a state function (just like the enthalpy and entropy), so its change depends only on the initial and final states, not the path
between them.
37.
(a) The reaction is nonspontaneous; (b) Above 566 °C the process is spontaneous.
39.
(a) 1.5 × 102 kJ; (b) −21.9 kJ; (c) −5.34 kJ; (d) −0.383 kJ; (e) 18 kJ; (f) 71 kJ
41.
(a) K = 41; (b) K = 0.053; (c) K = 6.9 × 1013; (d) K = 1.9; (e) K = 0.04
43.
In each of the following, the value of ΔG is not given at the temperature of the reaction. Therefore, we must calculate ΔG from the
values ΔH° and ΔS and then calculate ΔG from the relation ΔG = ΔH° − TΔS°. (a) K = 1.07 × 10−13; (b) K = 2.51 × 10−3; (c) K =
4.83 × 103; (d) K = 0.219; (e) K = 16.1
45.
The standard free energy change is ΔG = −RT ln K = 4.84 kJ/mol. When reactants and products are in their standard states
∘
(1 bar or 1 atm), Q = 1. As the reaction proceeds toward equilibrium, the reaction shifts left (the amount of products drops while
the amount of reactants increases): Q < 1, and ΔG becomes less positive as it approaches zero. At equilibrium, Q = K, and ΔG = 0.
47.
The reaction will be spontaneous at temperatures greater than 287 K.
49.
K = 5.35 × 1015; The process is exothermic.
51.
1.0 × 10−8 atm. This is the maximum pressure of the gases under the stated conditions.
53.
−5
x = 1.29 × 10 atm = PO
2
55.
−0.16 kJ
56.
(a) 22.1 kJ; (b) 98.9 kJ/mol
58.
90 kJ/mol
60.
(a) Under standard thermodynamic conditions, the evaporation is nonspontaneous; (b) Kp = 0.031; (c) The evaporation of water is
spontaneous; (d) P must always be less than Kp or less than 0.031 atm. 0.031 atm represents air saturated with water vapor at
H2 O
25 °C, or 100% humidity.

62.
(a) Nonspontaneous as ΔG > 0; (b) ΔG = ΔG + RT ln Q, ΔG = 1.7
∘ °
× 10
3
+ (8.314 × 310 × ln
28
120
) = −2.1 kJ.
The forward reaction to produce F6P is spontaneous under these conditions.

64.
ΔG is negative as the process is spontaneous. ΔH is positive as with the solution becoming cold, the dissolving must be
endothermic. ΔS must be positive as this drives the process, and it is expected for the dissolution of any soluble ionic compound.
66.
(a) Increasing the oxygen partial pressure will yield a decrease in Q and ΔG thus becomes more negative. (b) Increasing the
oxygen partial pressure will yield a decrease in Q and ΔG thus becomes more negative. (c) Increasing the oxygen partial pressure
will yield an increase in Q and ΔG thus becomes more positive.
22.14.17: Chapter 17
1.
(a) reduction; (b) oxidation; (c) oxidation; (d) reduction
3.
(a) F2 + Ca ⟶ 2F
−
+ Ca
2+
; (b) Cl2 + 2Li ⟶ 2Li
+
+ 2Cl
−
; (c) 3Br2 + 2Fe ⟶ 2Fe
3+
+ 6Br
−
; (d)
— + +
MnO 4 + 4H + 3Ag ⟶ 3Ag + MnO 2 + 2H2 O
5.
Oxidized: (a) Sn2+; (b) Hg; (c) Al; reduced: (a) H2O2; (b) PbO2; (c) Cr 2 O7
2−
; oxidizing agent: (a) H2O2; (b) PbO2; (c) Cr 2 O7
2−
;
reducing agent: (a) Sn2+; (b) Hg; (c) Al

7.
Oxidized = reducing agent: (a) SO 3
2−
; (b) Mn(OH)2; (c) H2; (d) Al; reduced = oxidizing agent: (a) Cu(OH)2; (b) O2; (c) NO3
−
;
(d) CrO 4
2−
9.
In basic solution, [OH−] > 1 × 10−7 M > [H+]. Hydrogen ion cannot appear as a reactant because its concentration is essentially
zero. If it were produced, it would instantly react with the excess hydroxide ion to produce water. Thus, hydrogen ion should not
appear as a reactant or product in basic solution.
11.
(a) Mg(s) │ Mg2+ (aq)║Ni2+ (aq) │ Ni(s); (b) Cu(s) │ Cu2+ (aq)║Ag+ (aq) │ Ag(s); (c)
2+
│ Sn(s); (d) Pt(s) │ Cu
2+ 2+ + 3+
Mn(s) │ Mn (aq) ║Sn (aq) (aq ), Cu ║Au
(aq) (aq) │ Au(s)
13.
(a) Mg(s) + Cu 2+
(aq) ⟶ Mg
2+
(aq) + Cu(s); (b) 2Ag +
(aq) + Ni(s) ⟶ Ni
2+
(aq) + 2Ag(s)
15.
Species oxidized = reducing agent: (a) Al(s); (b) NO(g); (c) Mg(s); and (d) MnO2(s); Species reduced = oxidizing agent: (a) Zr4+
(aq); (b) Ag+(aq); (c) SiO (aq) ; and (d) ClO (aq)
3
2−
3
−
17.
Without the salt bridge, the circuit would be open (or broken) and no current could flow. With a salt bridge, each half-cell remains
electrically neutral and current can flow through the circuit.
19.
Active electrodes participate in the oxidation-reduction reaction. Since metals form cations, the electrode would lose mass if metal
atoms in the electrode were to oxidize and go into solution. Oxidation occurs at the anode.
21.
(a) +2.115 V (spontaneous); (b) +0.4626 V (spontaneous); (c) +1.0589 V (spontaneous); (d) +0.727 V (spontaneous)
23.
3Cu(s) + 2Au
3+
(aq) ⟶ 3Cu
2+
(aq) + 2Au(s); +1.16 V; spontaneous
25.
3Cd(s) + 2Al
3+
(aq) ⟶ 3Cd
2+
(aq) + 2Al(s); −1.259 V; nonspontaneous
27.
(a) 0 kJ/mol; (b) −83.7 kJ/mol; (c) +235.3 kJ/mol
29.
(a) standard cell potential: 1.50 V, spontaneous; cell potential under stated conditions: 1.43 V, spontaneous; (b) standard cell
potential: 1.405 V, spontaneous; cell potential under stated conditions: 1.423 V, spontaneous; (c) standard cell potential: −2.749 V,
nonspontaneous; cell potential under stated conditions: −2.757 V, nonspontaneous
31.
(a) 1.7 × 10−10; (b) 2.6 × 10−21; (c) 4.693 × 1021; (d) 1.0 × 10−14
33.
(b) 3.5 × 1015; (c) 5.6 × 10−9 M

2+
(a) anode: Cu(s) ⟶ Cu (aq) + 2e
−
E
∘
anode
= 0.34 V ;
+ − ∘
cathode: 2 × (Ag (aq) + e ⟶ Ag(s)) E = 0.7996 V
cathode
34.
Batteries are self-contained and have a limited supply of reagents to expend before going dead. Alternatively, battery reaction
byproducts accumulate and interfere with the reaction. Because a fuel cell is constantly resupplied with reactants and products are
expelled, it can continue to function as long as reagents are supplied.
36.
Ecell, as described in the Nernst equation, has a term that is directly proportional to temperature. At low temperatures, this term is
decreased, resulting in a lower cell voltage provided by the battery to the device—the same effect as a battery running dead.
38.
Mg and Zn
40.
Both examples involve cathodic protection. The (sacrificial) anode is the metal that corrodes (oxidizes or reacts). In the case of iron
(−0.447 V) and zinc (−0.7618 V), zinc has a more negative standard reduction potential and so serves as the anode. In the case of
iron and copper (0.34 V), iron has the smaller standard reduction potential and so corrodes (serves as the anode).
42.
While the reduction potential of lithium would make it capable of protecting the other metals, this high potential is also indicative
of how reactive lithium is; it would have a spontaneous reaction with most substances. This means that the lithium would react
quickly with other substances, even those that would not oxidize the metal it is attempting to protect. Reactivity like this means the
sacrificial anode would be depleted rapidly and need to be replaced frequently. (Optional additional reason: fire hazard in the
presence of water.)
46.
mass Li= 23.9 g mass Al= 31.0 g mass Cr= 59.8 g

(a) mass Ca= 69.1 g ; (b) ; (c) ; (d)
mass H 2 = 3.48 g mass Cl2 = 122 g mass Br 2 = 276 g
mass Cl2 = 122 g
48.
0.79 L
22.14.18: Chapter 18
1.
The alkali metals all have a single s electron in their outermost shell. In contrast, the alkaline earth metals have a completed s
subshell in their outermost shell. In general, the alkali metals react faster and are more reactive than the corresponding alkaline
earth metals in the same period.
3.
Na + I2 ⟶ 2NaI
2Na + Se ⟶ Na2 Se
2Na + O2 ⟶ Na2 O2
Sr + I2 ⟶ SrI 2
Sr + Se ⟶ SrSe
2Sr + O2 ⟶ 2SrO
2Al + 3I2 ⟶ 2AlI3
2Al + 3Se ⟶ Al2 Se 3
4Al + 3O2 ⟶ 2Al2 O3
5.
The possible ways of distinguishing between the two include infrared spectroscopy by comparison of known compounds, a flame
test that gives the characteristic yellow color for sodium (strontium has a red flame), or comparison of their solubilities in water. At
35.7 g 53.8 g
20 °C, NaCl dissolves to the extent of 100 mL
compared with 100 mL
for SrCl2. Heating to 100 °C provides an easy test, since the
39.12 g 100.8 g
solubility of NaCl is , but that of SrCl2 is
100 mL
. Density determination on a solid is sometimes difficult, but there is enough
100 mL
difference (2.165 g/mL NaCl and 3.052 g/mL SrCl2) that this method would be viable and perhaps the easiest and least expensive
test to perform.
7.
(a) 2Sr(s) + O2 (g) ⟶ 2SrO(s); (b) Sr(s) + 2HBr(g) ⟶ SrBr 2 (s) + H2 (g); (c) Sr(s) + H2 (g) ⟶ SrH 2 (s); (d)
6Sr(s) + P4 (s) ⟶ 2Sr3 P2 (s); (e) Sr(s) + 2H O(l) ⟶
2 Sr(OH) (aq) + H2 (g)
2
9.
11 lb
11.
Yes, tin reacts with hydrochloric acid to produce hydrogen gas.
13.
In PbCl2, the bonding is ionic, as indicated by its melting point of 501 °C. In PbCl4, the bonding is covalent, as evidenced by it
being an unstable liquid at room temperature.
15.
countercurrent
fractionating
tower
2CsCl(l) + Ca(g) −−−−−−−−−→ 2Cs(g) + CaCl2 (l)
17.
Cathode (reduction): 2Li
+
+ 2e
−
⟶ 2Li(l); Anode (oxidation): 2Cl
−
⟶ Cl2 (g) + 2e
−
; Overall reaction:
+ −
2Li + 2Cl ⟶ 2Li(l) + Cl2 (g)
19.
0.5035 g H2
21.
Despite its reactivity, magnesium can be used in construction even when the magnesium is going to come in contact with a flame
because a protective oxide coating is formed, preventing gross oxidation. Only if the metal is finely subdivided or present in a thin
sheet will a high-intensity flame cause its rapid burning.
23.
Extract from ore: AlO(OH)(s) + NaOH(aq) + H O(l) ⟶ Na [Al(OH)
2 4
] (aq)
Recover: 2Na [Al(OH) ] (s) + H SO (aq) ⟶ 2Al(OH) (s) + Na SO

4 2 4 3 2 4 (aq) + 2H2 O(l)
Sinter: 2Al(OH) (s) ⟶ Al O (s) + 3H O(g)

3 2 3 2
Dissolve in Na3AlF6(l) and electrolyze: Al + 3e ⟶ Al(s)

3+ −
25.
25.83%
27.
39 kg
29.
(a) H3BPH3:
(b) BF 4
−
:
(c) BBr3:
(d) B(CH3)3:
(e) B(OH)3:
31.
1s22s22p63s23p23d0.
33.
(a) (CH3)3SiH: sp3 bonding about Si; the structure is tetrahedral; (b) SiO 3
: sp bonding about Si; the structure is tetrahedral; (c)
4
4−
Si2H6: sp bonding about each Si; the structure is linear along the Si-Si bond; (d) Si(OH)4: sp3 bonding about Si; the structure is
3
3 2
tetrahedral; (e) SiF6 : sp d bonding about Si; the structure is octahedral
2−
35.
(a) nonpolar; (b) nonpolar; (c) polar; (d) nonpolar; (e) polar
37.
(a) tellurium dioxide or tellurium(IV) oxide; (b) antimony(III) sulfide; (c) germanium(IV) fluoride; (d) silane or silicon(IV)
hydride; (e) germanium(IV) hydride
39.
Boron has only s and p orbitals available, which can accommodate a maximum of four electron pairs. Unlike silicon, no d orbitals
are available in boron.
41.
(a) ΔH° = 87 kJ; ΔG° = 44 kJ; (b) ΔH° = −109.9 kJ; ΔG° = −154.7 kJ; (c) ΔH° = −510 kJ; ΔG° = −601.5 kJ
43.
A mild solution of hydrofluoric acid would dissolve the silicate and would not harm the diamond.
45.
In the N2 molecule, the nitrogen atoms have an σ bond and two π bonds holding the two atoms together. The presence of three
strong bonds makes N2 a very stable molecule. Phosphorus is a third-period element, and as such, does not form π bonds
efficiently; therefore, it must fulfill its bonding requirement by forming three σ bonds.
47.
(a) H = 1+, C = 2+, and N = 3−; (b) O = 2+ and F = 1−; (c) As = 3+ and Cl = 1−
49.
S < Cl < O < F
51.
The electronegativity of the nonmetals is greater than that of hydrogen. Thus, the negative charge is better represented on the
nonmetal, which has the greater tendency to attract electrons in the bond to itself.
53.
Hydrogen has only one orbital with which to bond to other atoms. Consequently, only one two-electron bond can form.
55.
0.43 g H2
57.
(a) Ca(OH) (aq) + CO (g) ⟶ CaCO (s) + H O(l); (b) CaO(s) + SO (g)
2 2 3 2 2 ⟶ CaSO3 (s);
(c) 2NaHCO (s) + NaH PO (aq) ⟶ Na PO (aq) + 2CO (g) + 2H O(l)

3 2 4 3 4 2 2
59.
(a) NH2−:
(b) N2F4:
(c) NH 2
−
:
(d) NF3:
(e) N 3
−
:
61.
Ammonia acts as a Brønsted base because it readily accepts protons and as a Lewis base in that it has an electron pair to donate.
Brønsted base: NH + H O ⟶ NH + H O3 3
+
4
+
2
Lewis base: 2NH + Ag ⟶ [H N − Ag − NH ]

3
+
3 3
+
63.
(a) NO2:
Nitrogen is sp2 hybridized. The molecule has a bent geometry with an ONO bond angle of approximately 120°.
(b) NO : 2
−
Nitrogen is sp2 hybridized. The molecule has a bent geometry with an ONO bond angle slightly less than 120°.
(c) NO :
2
+
Nitrogen is sp hybridized. The molecule has a linear geometry with an ONO bond angle of 180°.
65.
Nitrogen cannot form a NF5 molecule because it does not have d orbitals to bond with the additional two fluorine atoms.
67.
(a)
(b)
(c)
(d)
(e)
69.
(a) P4 (s) + 4Al(s) ⟶ 4AlP(s); (b) P4 (s) + 12Na(s) ⟶ 4Na3 P(s); (c) P4 (s) + 10F2 (g) ⟶ 4PF5 (l); (d)
P4 (s) + 6Cl2 (g) ⟶ 4PCl3 (l) or P4 (s) + 10Cl2 (g) ⟶ 4PCl5 (l); (e) P4 (s) + 3O2 (g) ⟶ P4 O6 (s) or
P4 (s) + 5O2 (g) ⟶ P4 O10 (s); (f) P
4 O6 (s) + 2O2 (g) ⟶ P4 O10 (s)
71.
291 mL
73.
28 tons
75.
(a)
(b)
(c)
(d)
77.
(a) P = 3+; (b) P = 5+; (c) P = 3+; (d) P = 5+; (e) P = 3−; (f) P = 5+
79.
FrO2
81.
(a) 2Zn(s) + O2 (g) ⟶ 2ZnO(s); (b) ZnCO3 (s) ⟶ ZnO(s) + CO2 (g); (c)
ZnCO3 (s) + 2 CH3 COOH(aq) ⟶ Zn(CH3 COO) (aq) + CO2 (g) + H2 O(l);
2
(d)
Zn(s) + 2HBr(aq) ⟶ ZnBr 2 (aq) + H2 (g)
83.
+ 3+ − −
Al (OH) (s) + 3 H (aq) ⟶ Al + 3 H2 O(l); Al (OH) (s) + OH ⟶ [Al (OH) ] (aq)
3 3 4
85.
(a) Na2 O(s) + H2 O(l) ⟶ 2NaOH(aq); (b) Cs2 CO3 (s) + 2HF(aq) ⟶ 2CsF(aq) + CO2 (g) + H2 O(l); (c)
Al2 O3 (s) + 6 HClO4 (aq) ⟶ 2Al (ClO4 )3 (aq) + 3 H2 O(l); (d)
Na2 CO3 (aq) + Ba (NO3 )2 (aq) ⟶ 2 NaNO3 (aq) + BaCO3 (s); (e) TiCl4 (l) + 4Na(s) ⟶ Ti(s) + 4NaCl(s)
87.
HClO4 is the stronger acid because, in a series of oxyacids with similar formulas, the higher the electronegativity of the central
atom, the stronger is the attraction of the central atom for the electrons of the oxygen(s). The stronger attraction of the oxygen
electron results in a stronger attraction of oxygen for the electrons in the O-H bond, making the hydrogen more easily released. The
weaker this bond, the stronger the acid.
89.
As H2SO4 and H2SeO4 are both oxyacids and their central atoms both have the same oxidation number, the acid strength depends
on the relative electronegativity of the central atom. As sulfur is more electronegative than selenium, H2SO4 is the stronger acid.
91.
SO2, sp2 4+; SO3, sp2, 6+; H2SO4, sp3, 6+
93.
SF6: S = 6+; SO2F2: S = 6+; KHS: S = 2−
95.
Sulfur is able to form double bonds only at high temperatures (substantially endothermic conditions), which is not the case for
oxygen.
97.
There are many possible answers including: Cu(s) + 2 H2 SO 4 (l) ⟶ CuSO 4 (aq) + SO 2 (g) + 2 H2 O(l) and
C(s) + 2 H2 SO 4 (l) ⟶ CO2 (g) + 2 SO 2 (g) + 2 H2 O(l)
99.
5.1 × 104 g
101.
SnCl4 is not a salt because it is covalently bonded. A salt must have ionic bonds.
103.
In oxyacids with similar formulas, the acid strength increases as the electronegativity of the central atom increases. HClO3 is
stronger than HBrO3; Cl is more electronegative than Br.
105.
(a)
(b)
(c)
(d)
(e)
107.
(a) bromine trifluoride; (b) sodium bromate; (c) phosphorus pentabromide; (d) sodium perchlorate; (e) potassium hypochlorite
109.
(a) I: 7+; (b) I: 7+; (c) Cl: 4+; (d) I: 3+; Cl: 1−; (e) F: 0
111.
(a) sp3d hybridized; (b) sp3d2 hybridized; (c) sp3 hybridized; (d) sp3 hybridized; (e) sp3d2 hybridized;
113.
(a) nonpolar; (b) nonpolar; (c) polar; (d) nonpolar; (e) polar
115.
The empirical formula is XeF6, and the balanced reactions are: Δ

Xe(g) + 3F2 (g) −→ XeF6 (s)
XeF6 (s) + 3H2 (g) ⟶ 6HF(g) + Xe(g)
22.14.19: Chapter 19
1.
(a) Sc: [Ar]4s23d1; (b) Ti: [Ar]4s23d2; (c) Cr: [Ar]4s13d5; (d) Fe: [Ar]4s23d6; (e) Ru: [Kr]5s24d6
3.
(a) La: [Xe]6s25d1, La3+: [Xe]; (b) Sm: [Xe]6s24f6, Sm3+: [Xe]4f5; (c) Lu: [Xe]6s24f145d1, Lu3+: [Xe]4f14
5.
Al is used because it is the strongest reducing agent and the only option listed that can provide sufficient driving force to convert
La(III) into La.
7.
Mo
9.
The CaSiO3 slag is less dense than the molten iron, so it can easily be separated. Also, the floating slag layer creates a barrier that
prevents the molten iron from exposure to O2, which would oxidize the Fe back to Fe2O3.
11.
2.57%
13.
0.167 V
15.
E° = −0.6 V, E° is negative so this reduction is not spontaneous. E° = +1.1 V
17.
(a) Fe(s) + 2 H3 O
+
(aq) + SO 4
2−
(aq) ⟶ Fe
2+
(aq) + SO 4
2−
(aq) + H2 (g) + 2 H2 O(l); (b)
FeCl3 (aq) + 3Na
+
(aq) + 3OH
−
(aq) ⟶ Fe(OH) 3 (s) + 3Na
+
(aq) + 3Cl
+
(aq); (c)
Mn(OH) (s) + 2 H3 O
2
+
(aq) + 2Br
−
(aq) ⟶ Mn
2+
(aq) + 2Br
−
(aq) + 4 H2 O(l); (d) 4Cr(s) + 3 O2 (g) ⟶ 2 Cr2 O3 (s);
(e) Mn 2 O3 (s) + 6 H3 O
+
(aq) + 6Cl
−
(aq) ⟶ 2 MnCl 3 (s) + 9 H2 O(l); (f) Ti(s) + xsF 2 (g) ⟶ TiF4 (g)
19.
(a) Cr2 (SO 4 )3 (aq) + 2Zn(s) + 2H3 O
+
(aq) ⟶ 2Zn
2+
(aq) + H2 (g) + 2H2 O(l) + 2Cr
2+
(aq) + 3SO4
2−
(aq); (b)
4TiCl3 (s) + CrO4
2−
(aq) + 8H
+
(aq) ⟶ 4Ti
4+
(aq) + Cr(s) + 4H2 O(l) + 12Cl
−
(aq); (c) In acid solution between pH 2
and pH 6, CrO4
2−
forms HCrO4
−
, which is in equilibrium with dichromate ion. The reaction is
2HCrO4
−
(aq) ⟶ Cr2 O7
2−
(aq) + H2 O(l). At other acidic pHs, the reaction is
3Cr
2+
(aq) + CrO4
2−
(aq) + 8H3 O
+
(aq) ⟶ 4Cr
3+
(aq) + 12H2 O(l); (d)
Δ
8CrO3 (s) + 9Mn(s) ⟶ 4Cr2 O3 (s) + 3Mn3 O4 (s); (e)
CrO(s) + 2H3 O
+
(aq) + 2NO3
−
(aq) ⟶ Cr
2+
(aq) + 2NO3
−
(aq) + 3H2 O(l); (f)
+ −
CrCl3 (s) + 3NaOH(aq) ⟶ Cr(OH) (s) + 3Na (aq) + 3Cl (aq)
3
21.
(a) 3Fe(s) + 4H2 O(g) ⟶ Fe3 O4 (s) + 4H2 (g); (b)
H2 O
3NaOH(aq) + Fe(NO3 ) (aq) −−−→ Fe(OH) (s) + 3Na

3 3
+
(aq) + 3 NO3
−
(aq); (c)
MnO
4−
+ 5 Fe
2+
+ 8H
+
⟶ Mn
2+
+ 5 Fe3 + 4 H2 O; (d)
Fe(s) + 2H3 O
+
(aq) + SO 4
2−
(aq) ⟶ Fe
2+
(aq) + SO 4
2−
(aq) + H2 (g) + 2H2 O(l); (e)
4Fe
2+
(aq) + O2 (g) + 4HNO3 (aq) ⟶ 4Fe
3+
(aq) + 2H2 O(l) + 4NO3
−
(aq); (f)
Δ
FeCO3 (s) + 2HClO4 (aq) ⟶ Fe(ClO4 )2 (aq) + H2 O(l) + CO2 (g); (g) 3Fe(s) + 2O 2 (g) ⟶ Fe3 O4 (s)
23.
As CN− is added,
+ −
Ag (aq) + CN (aq) ⟶ AgCN(s)
−
As more CN is added,
+ − −
Ag (aq) + 2 CN (aq) ⟶ [Ag (CN)2 ] (aq)
− −
AgCN(s) + CN (aq) ⟶ [Ag (CN) ] (aq)
2
25.
(a) Sc3+; (b) Ti4+; (c) V5+; (d) Cr6+; (e) Mn4+; (f) Fe2+ and Fe3+; (g) Co2+ and Co3+; (h) Ni2+; (i) Cu+
27.
(a) 4, [Zn(OH)4]2−; (b) 6, [Pd(CN)6]2−; (c) 2, [AuCl2]−; (d) 4, [Pt(NH3)2Cl2]; (e) 6, K[Cr(NH3)2Cl4]; (f) 6, [Co(NH3)6][Cr(CN)6];
(g) 6, [Co(en)2Br2]NO3
29.
(a) [Pt(H2O)2Br2]:
(b) [Pt(NH3)(py)(Cl)(Br)]:
(c) [Zn(NH3)3Cl]+ :
(d) [Pt(NH3)3Cl]+ :
(e) [Ni(H2O)4Cl2]:
(f) [Co(C2O4)2Cl2]3−:
31.
(a) tricarbonatocobaltate(III) ion; (b) tetraaminecopper(II) ion; (c) tetraaminedibromocobalt(III) sulfate; (d) tetraamineplatinum(II)
tetrachloroplatinate(II); (e) tris-(ethylenediamine)chromium(III) nitrate; (f) diaminedibromopalladium(II); (g) potassium
pentachlorocuprate(II); (h) diaminedichlorozinc(II)
33.
(a) none; (b) none; (c) The two Cl ligands can be cis or trans. When they are cis, there will also be an optical isomer.
35.
37.
39.
[Co(H2O)6]Cl2 with three unpaired electrons.
41.
(a) 4; (b) 2; (c) 1; (d) 5; (e) 0
43.
(a) [Fe(CN)6]4−; (b) [Co(NH3)6]3+; (c) [Mn(CN)6]4−
45.
The complex does not have any unpaired electrons. The complex does not have any geometric isomers, but the mirror image is
nonsuperimposable, so it has an optical isomer.
47.
No. Au+ has a complete 5d sublevel.
22.14.20: Chapter 20
1.
There are several sets of answers; one is:
(a) C5H12
(b) C5H10
(c) C5H8
3.
Both reactions result in bromine being incorporated into the structure of the product. The difference is the way in which that
incorporation takes place. In the saturated hydrocarbon, an existing C–H bond is broken, and a bond between the C and the Br can
then be formed. In the unsaturated hydrocarbon, the only bond broken in the hydrocarbon is the π bond whose electrons can be
used to form a bond to one of the bromine atoms in Br2 (the electrons from the Br–Br bond form the other C–Br bond on the other
carbon that was part of the π bond in the starting unsaturated hydrocarbon).
5.
Unbranched alkanes have free rotation about the C–C bonds, yielding all orientations of the substituents about these bonds
equivalent, interchangeable by rotation. In the unbranched alkenes, the inability to rotate about the C = C bond results in fixed
(unchanging) substituent orientations, thus permitting different isomers. Since these concepts pertain to phenomena at the
molecular level, this explanation involves the microscopic domain.
7.
They are the same compound because each is a saturated hydrocarbon containing an unbranched chain of six carbon atoms.
9.
(a) C6H14
(b) C6H14
(c) C6H12
(d) C6H12
(e) C6H10
(f) C6H10
11.
(a) 2,2-dibromobutane; (b) 2-chloro-2-methylpropane; (c) 2-methylbutane; (d) 1-butyne; (e) 4-fluoro-4-methyl-1-octyne; (f) trans-
1-chloropropene; (g) 4-methyl-1-pentene
13.
15.
17.
(a) 2,2,4-trimethylpentane; (b) 2,2,3-trimethylpentane, 2,3,4-trimethylpentane, and 2,3,3-trimethylpentane:
19.
21.
In the following, the carbon backbone and the appropriate number of hydrogen atoms are shown in condensed form:
23.
In acetylene, the bonding uses sp hybrids on carbon atoms and s orbitals on hydrogen atoms. In benzene, the carbon atoms are sp2
hybridized.
25.
(a) CH ≡ CCH 2 CH3 + 2 I2 ⟶ CHI2 CI2 CH2 CH3
(b) CH 3 CH2 CH2 CH2 CH3 + 8 O2 ⟶ 5 CO2 + 6H2 O
27.
65.2 g
29.
9.328 × 102 kg
31.
(a) ethyl alcohol, ethanol: CH3CH2OH; (b) methyl alcohol, methanol: CH3OH; (c) ethylene glycol, ethanediol: HOCH2CH2OH; (d)
isopropyl alcohol, 2-propanol: CH3CH(OH)CH3; (e) glycerine, l,2,3-trihydroxypropane: HOCH2CH(OH)CH2OH
33.
(a) 1-ethoxybutane, butyl ethyl ether; (b) 1-ethoxypropane, ethyl propyl ether; (c) 1-methoxypropane, methyl propyl ether
35.
HOCH2CH2OH, two alcohol groups; CH3OCH2OH, ether and alcohol groups
37.
(a)
(b) 4.593 × 102 L

39.
(a) CH 3 CH = CHCH3 + H2 O ⟶ CH3 CH2 CH(OH)CH
3
(b) CH 3 CH2 OH ⟶ CH2 = CH2 + H2 O
41.
(a)
(b)
(c)
43.
A ketone contains a group bonded to two additional carbon atoms; thus, a minimum of three carbon atoms are needed.
45.
Since they are both carboxylic acids, they each contain the –COOH functional group and its characteristics. The difference is the
hydrocarbon chain in a saturated fatty acid contains no double or triple bonds, whereas the hydrocarbon chain in an unsaturated
fatty acid contains one or more multiple bonds.
47.
(a) CH3CH(OH)CH3: all carbons are tetrahedral; (b) CH COCH : the end carbons are tetrahedral and the central carbon is
3 3
trigonal planar; (c) CH3OCH3: all are tetrahedral; (d) CH3COOH: the methyl carbon is tetrahedral and the acid carbon is trigonal
planar; (e) CH3CH2CH2CH(CH3)CHCH2: all are tetrahedral except the right-most two carbons, which are trigonal planar
49.
51.
(a) CH 3 CH2 CH2 CH2 OH + CH 3C (O) OH ⟶ CH3 C (O) OCH2 CH2 CH2 CH3 + H2 O:
(b) 2CH 3 CH2 COOH + CaCO3 ⟶ (CH3 CH2 COO) 2 Ca + CO2 + H2 O:
53.
55.
Trimethyl amine: trigonal pyramidal, sp3; trimethyl ammonium ion: tetrahedral, sp3
57.
59.
+ +
CH3 NH2 + H3 O ⟶ CH3 NH3 + H2 O
61.
CH3CH = CHCH3(sp2) + Cl ⟶ CH3CH(Cl)H(Cl)CH3(sp3); 2C6H6(sp2) + 15O2 ⟶ 12CO2(sp) + 6H2O
63.
The carbon in CO32−, initially at sp2, changes hybridization to sp in CO2.
22.14.21: Chapter 21
1.
(a) sodium-24; (b) aluminum-29; (c) krypton-73; (d) iridium-194
3.
(a) 34
14
Si; (b) 36
15
P; (c) 57
25
Mn; (d) 121
56
Ba
5.
(a) 45
25
Mn
+1
; (b) 69
45
Rh
+2
; (c) 142
53
I
−1
; (d) 243
97
Bk
7.
Nuclear reactions usually change one type of nucleus into another; chemical changes rearrange atoms. Nuclear reactions involve
much larger energies than chemical reactions and have measureable mass changes.
9.
(a), (b), (c), (d), and (e)
11.
(a) A nucleon is any particle contained in the nucleus of the atom, so it can refer to protons and neutrons. (b) An α particle is one
product of natural radioactivity and is the nucleus of a helium atom. (c) A β particle is a product of natural radioactivity and is a
high-speed electron. (d) A positron is a particle with the same mass as an electron but with a positive charge. (e) Gamma rays
compose electromagnetic radiation of high energy and short wavelength. (f) Nuclide is a term used when referring to a single type
of nucleus. (g) The mass number is the sum of the number of protons and the number of neutrons in an element. (h) The atomic
number is the number of protons in the nucleus of an element.
13.
(a) 27
13
Al +
4
2
He ⟶
30
15
P+
1
0
n; (b) 239
94
Pu +
4
2
He ⟶
242
96
Cm +
1
0
n; (c) 14
7
N+
4
2
He ⟶
17
8
O+
1
1
H; (d)
235 96 135 1
U ⟶ Rb + Cs + 4 n
92 37 55 0
15.
(a) 14
7
N+
4
2
He ⟶
17
8
O+
1
1
H; (b) 14
7
C+
1
0
n ⟶
14
6
C+
1
1
H; (c) 232
90
Th +
1
0
n ⟶
233
90
Th; (d) 238
92
U+
2
1
H ⟶
239
92
U+
1
1
H
17.
(a) 148.8 MeV per atom; (b) 7.808 MeV/nucleon
19.
α (helium nuclei), β (electrons), β+ (positrons), and η (neutrons) may be emitted from a radioactive element, all of which are
particles; γ rays also may be emitted.
21.
(a) conversion of a neutron to a proton: n ⟶ p + e; (b) conversion of a proton to a neutron; the positron has the same mass
1
0
1
1 +1
0
as an electron and the same magnitude of positive charge as the electron has negative charge; when the n:p ratio of a nucleus is too
low, a proton is converted into a neutron with the emission of a positron: p ⟶ n + e; (c) In a proton-rich nucleus, an inner 1
1
1
0 +1
0
atomic electron can be absorbed. In simplest form, this changes a proton into a neutron: p + e ⟶ p 1
1
0
−1
1
0
23.
The electron pulled into the nucleus was most likely found in the 1s orbital. As an electron falls from a higher energy level to
replace it, the difference in the energy of the replacement electron in its two energy levels is given off as an X-ray.
25.
Manganese-51 is most likely to decay by positron emission. The n:p ratio for Cr-53 is = 1.21; for Mn-51, it is = 1.04; for 29
24
26
25
Fe-59, it is = 1.27. Positron decay occurs when the n:p ratio is low. Mn-51 has the lowest n:p ratio and therefore is most likely
33
26
to decay by positron emission. Besides, Cr is a stable isotope, and Fe decays by beta emission.
53
24
59
26
27.
(a) β decay; (b) α decay; (c) positron emission; (d) β decay; (e) α decay
29.
238 234 4 234 234 0 234 234 0 234 230 4
U ⟶ Th + He; Th ⟶ Pa + e; Pa ⟶ U+ e; U ⟶ Th + He
92 90 2 90 91 −1 91 92 −1 92 90 2
230 226 4 226 222 4 222 218 4
Th ⟶ Ra + He Ra ⟶ Rn + He; Rn ⟶ Po + He
90 88 2 88 86 2 86 84 2
31.
Half-life is the time required for half the atoms in a sample to decay. Example (answers may vary): For C-14, the half-life is 5770
years. A 10-g sample of C-14 would contain 5 g of C-14 after 5770 years; a 0.20-g sample of C-14 would contain 0.10 g after 5770
years.
33.
0.04
(
1
2
) = 0.973 or 97.3%
35.
2 × 103 y
37.
0.12 h–1
39.
(a) 3.8 billion years; (b) The rock would be younger than the age calculated in part (a). If Sr was originally in the rock, the amount
produced by radioactive decay would equal the present amount minus the initial amount. As this amount would be smaller than the
amount used to calculate the age of the rock and the age is proportional to the amount of Sr, the rock would be younger.
41.
c = 0; This shows that no Pu-239 could remain since the formation of the earth. Consequently, the plutonium now present could not
have been formed with the uranium.
43.
17.5 MeV
45.
(a) 212
83
Bi ⟶
212
84
Po +
−1
0
e; (b) 8
5
B ⟶
8
4
Be +
0
−1
e; (c) 238
92
U+
1
0
n ⟶
239
93
Np +
−1
0
Np,
239
93
Np ⟶
239
94
Pu +
−1
0
e; (d)
90 90 0
Sr ⟶ Y+ e
38 39 −1
47.
(a) 241
95
Am +
4
2
He ⟶
244
97
Bk +
1
0
n; (b) 239
94
Pu + 15 n ⟶
1
0
254
100
Fm + 6
0
−1
e; (c) 250
98
Cf +
11
5
B ⟶
257
103
1
Lr + 4 n;
0
(d)
249 15 260 1
Cf + N ⟶ Db + 4 n
98 7 105 0
49.
Two nuclei must collide for fusion to occur. High temperatures are required to give the nuclei enough kinetic energy to overcome
the very strong repulsion resulting from their positive charges.
51.
A nuclear reactor consists of the following:
1. A nuclear fuel. A fissionable isotope must be present in large enough quantities to sustain a controlled chain reaction. The
radioactive isotope is contained in tubes called fuel rods.
2. A moderator. A moderator slows neutrons produced by nuclear reactions so that they can be absorbed by the fuel and cause
additional nuclear reactions.
3. A coolant. The coolant carries heat from the fission reaction to an external boiler and turbine where it is transformed into
electricity.
4. A control system. The control system consists of control rods placed between fuel rods to absorb neutrons and is used to adjust
the number of neutrons and keep the rate of the chain reaction at a safe level.
5. A shield and containment system. The function of this component is to protect workers from radiation produced by the nuclear
reactions and to withstand the high pressures resulting from high-temperature reactions.
53.
The fission of uranium generates heat, which is carried to an external steam generator (boiler). The resulting steam turns a turbine
that powers an electrical generator.
55.
Introduction of either radioactive Ag+ or radioactive Cl– into the solution containing the stated reaction, with subsequent time given
for equilibration, will produce a radioactive precipitate that was originally devoid of radiation.
57.
(a) 133
53
I ⟶
133
54
Xe +
0
−1
e; (b) 37.6 days
59.
Alpha particles can be stopped by very thin shielding but have much stronger ionizing potential than beta particles, X-rays, and γ-
rays. When inhaled, there is no protective skin covering the cells of the lungs, making it possible to damage the DNA in those cells
and cause cancer.
61.
(a) 7.64 × 109 Bq; (b) 2.06 × 10−2 Ci
Index
A amine B
absolute zero 20.5: Amines and Amides balanced equation
9.3: Relating Pressure, Volume, Amount, and Amonton's law 4.2: Writing and Balancing Chemical Equations
Temperature - The Ideal Gas Law 9.3: Relating Pressure, Volume, Amount, and band of stability
accuracy Temperature - The Ideal Gas Law
1.6: Measurement Uncertainty, Accuracy, and Amorphous
bar
Precision 18.4: Structure and General Properties of the
Metalloids 9.2: Gas Pressure
Acid anhydride barometer
18.5: Structure and General Properties of the amorphous solid
10.6: The Solid State of Matter 9.2: Gas Pressure
Nonmetals
acid ionization amphiphilic base anhydride
11.6: Colloids 18.10: Occurrence, Preparation, and Compounds of
Oxygen
acid ionization constant amphiprotic
base ionization
14.4: Relative Strengths of Acids and Bases 14.2: Brønsted-Lowry Acids and Bases
acidic amphoteric
base ionization constant
14.3: pH and pOH 14.2: Brønsted-Lowry Acids and Bases
Actinide amplitude
Basic
2.6: The Periodic Table 6.2: Electromagnetic Energy
14.3: pH and pOH
Actinide series analyte
battery
19.2: Occurrence, Preparation, and Properties of 4.6: Quantitative Chemical Analysis
Transition Metals and Their Compounds angular momentum quantum number
activated complex becquerel (unit)
12.6: Collision Theory anion
activation energy beta decay
12.6: Collision Theory anode
active electrode beta particle
17.3: Galvanic Cells antimatter
actual yield bicarbonate anion
18.7: Occurrence, Preparation, and Properties of
4.5: Reaction Yields aqueous solution Carbonates
addition reaction 3.4: Molarity bidentate ligand
20.2: Hydrocarbons aromatic hydrocarbon 19.3: Coordination Chemistry of Transition Metals
adhesive force 20.2: Hydrocarbons bimolecular reaction
10.3: Properties of Liquids Arrhenius equation 12.7: Reaction Mechanisms
alcohol 12.6: Collision Theory binary acid
20.3: Alcohols and Ethers atmosphere 2.8: Chemical Nomenclature
aldehyde 9.2: Gas Pressure binary compound
20.4: Aldehydes, Ketones, Carboxylic Acids, and atom 2.8: Chemical Nomenclature
Esters
1.3: Phases and Classification of Matter binding energy per nucleon
alkali metal atomic mass 21.2: Nuclear Structure and Stability
2.4: Atomic Structure and Symbolism Bismuth
alkaline battery atomic mass unit 18.2: Periodicity
2.4: Atomic Structure and Symbolism blackbody
alkaline earth metal atomic number 6.2: Electromagnetic Energy
2.4: Atomic Structure and Symbolism Bohr's model of the hydrogen atom
18.2: Periodicity
alkane atomic orbital 6.3: The Bohr Model
6.4: Development of Quantum Theory boiling point
20.2: Hydrocarbons
alkene aufbau principle 10.4: Phase Transitions
6.5: Electronic Structure of Atoms (Electron boiling point elevation
20.2: Hydrocarbons
Configurations)
alkyl group autoionization
20.2: Hydrocarbons boiling point elevation constant
alkyne average rate
20.2: Hydrocarbons bomb calorimeter
Allotropes Avogadro's law
5.3: Calorimetry
18.2: Periodicity bond angle
9.3: Relating Pressure, Volume, Amount, and
alloy Temperature - The Ideal Gas Law 7.7: Molecular Structure and Polarity
11.2: The Dissolution Process Avogadro's number bond dipole moment
alpha decay 3.2: Formula Mass and the Mole Concept 7.7: Molecular Structure and Polarity
21.4: Radioactive Decay axial position bond distance
alpha particle 7.7: Molecular Structure and Polarity 7.7: Molecular Structure and Polarity
2.3: Evolution of Atomic Theory bond energy
21.3: Nuclear Equations 7.6: Strengths of Ionic and Covalent Bonds
amide bond length
20.5: Amines and Amides 7.3: Covalent Bonding
borate Chemical Reduction coordination number
18.4: Structure and General Properties of the 18.3: Occurrence and Preparation of the 10.7: Lattice Structures in Crystalline Solids
Metalloids Representative Metals 19.3: Coordination Chemistry of Transition Metals
Boyle's Law chemical symbol coordination sphere
9.3: Relating Pressure, Volume, Amount, and 2.4: Atomic Structure and Symbolism 19.3: Coordination Chemistry of Transition Metals
Temperature - The Ideal Gas Law chemical thermodynamics core electron
Bragg equation 5.4: Enthalpy 6.5: Electronic Structure of Atoms (Electron
10.7: Lattice Structures in Crystalline Solids chemistry Configurations)
buffer 1.2: Chemistry in Context corrosion
14.7: Buffers Chemotherapy 17.7: Corrosion
Buffer Capacity 21.6: Uses of Radioisotopes covalent bond
14.7: Buffers circuit 2.7: Molecular and Ionic Compounds
Buret 7.3: Covalent Bonding
4.6: Quantitative Chemical Analysis cis configuration covalent compound
C coefficient covalent network solid
calorie 4.2: Writing and Balancing Chemical Equations
5.2: Energy Basics cohesive force covalent radius
calorimeter 10.3: Properties of Liquids
5.3: Calorimetry colligative property crenation
Calorimetry 11.5: Colligative Properties
5.3: Calorimetry collision theory critical mass
capillary action 12.6: Collision Theory
10.3: Properties of Liquids colloid critical point
Carbonate 11.6: Colloids
18.7: Occurrence, Preparation, and Properties of combustion analysis crystal field splitting
Carbonates 19.4: Spectroscopic and Magnetic Properties of
Coordination Compounds
carbonyl group Combustion Reaction
20.4: Aldehydes, Ketones, Carboxylic Acids, and
crystal field theory
Esters 19.4: Spectroscopic and Magnetic Properties of
common ion effect Coordination Compounds
carboxylic acid
15.2: Precipitation and Dissolution crystalline solid
Esters complete ionic equation 10.6: The Solid State of Matter
catalyst 4.2: Writing and Balancing Chemical Equations cubic centimeter
12.3: Factors Affecting Reaction Rates complex ion 1.5: Measurements
cathode 15.3: Lewis Acids and Bases cubic closest packing
17.3: Galvanic Cells compound 10.7: Lattice Structures in Crystalline Solids
cathodic protection 1.3: Phases and Classification of Matter cubic meter
17.7: Corrosion compressibility factor 1.5: Measurements
cation 9.7: Non-Ideal Gas Behavior curie (unit)
2.4: Atomic Structure and Symbolism concentrated 21.7: Biological Effects of Radiation
Cell Notation 3.4: Molarity Current
17.3: Galvanic Cells concentration 17.2: Review of Redox Chemistry
cell potential 3.4: Molarity
17.3: Galvanic Cells concentration cell D
Celsius 17.5: Potential, Free Energy, and Equilibrium d orbital
1.5: Measurements condensation 6.4: Development of Quantum Theory
central metal 10.4: Phase Transitions Dalton unit
19.3: Coordination Chemistry of Transition Metals conjugate acid 2.4: Atomic Structure and Symbolism
chain reaction 14.2: Brønsted-Lowry Acids and Bases Dalton's atomic theory
21.5: Transmutation and Nuclear Energy conjugate base 2.2: Early Ideas in Atomic Theory
chalcogen 14.2: Brønsted-Lowry Acids and Bases Dalton's Law of Partial Pressure
2.6: The Periodic Table containment system 9.4: Stoichiometry of Gaseous Substances, Mixtures,
Charles's Law 21.5: Transmutation and Nuclear Energy and Reactions
9.3: Relating Pressure, Volume, Amount, and continuous spectrum daughter nuclide
Temperature - The Ideal Gas Law 6.2: Electromagnetic Energy 21.4: Radioactive Decay
chelate control rod density
19.3: Coordination Chemistry of Transition Metals 21.5: Transmutation and Nuclear Energy 1.5: Measurements
chelating ligand conversion factors deposition
19.3: Coordination Chemistry of Transition Metals 1.7: Mathematical Treatment of Measurement 10.4: Phase Transitions
chemical change Results diffraction
1.4: Physical and Chemical Properties coordinate covalent bond 10.7: Lattice Structures in Crystalline Solids
chemical equation 15.3: Lewis Acids and Bases diffusion
4.2: Writing and Balancing Chemical Equations coordination compound 9.5: Effusion and Diffusion of Gases
chemical property 19.2: Occurrence, Preparation, and Properties of dilution
Transition Metals and Their Compounds
1.4: Physical and Chemical Properties 19.3: Coordination Chemistry of Transition Metals 3.4: Molarity
dimensional analysis electron density Faraday's constant
1.7: Mathematical Treatment of Measurement 6.4: Development of Quantum Theory 17.5: Potential, Free Energy, and Equilibrium
Results electron volt first law of thermodynamics
dipole moment 21.2: Nuclear Structure and Stability 5.4: Enthalpy
7.7: Molecular Structure and Polarity electronegativity first transition series
diprotic acid 7.3: Covalent Bonding 19.2: Occurrence, Preparation, and Properties of
14.6: Polyprotic Acids electroplating Transition Metals and Their Compounds
diprotic base 17.8: Electrolysis fissile
14.6: Polyprotic Acids element 21.5: Transmutation and Nuclear Energy
dispersed phase 1.3: Phases and Classification of Matter fission
11.6: Colloids elementary reaction 21.5: Transmutation and Nuclear Energy
dispersion 12.7: Reaction Mechanisms fissionable
10.2: Intermolecular Forces empirical formula 21.5: Transmutation and Nuclear Energy
dispersion medium 2.5: Chemical Formulas formal charge
11.6: Colloids empirical formula mass 7.5: Formal Charges and Resonance
disproportionation reaction 3.3: Determining Empirical and Molecular Formulas formation constant
18.5: Structure and General Properties of the emulsifying agent 15.3: Lewis Acids and Bases
Nonmetals formula mass
11.6: Colloids
dissociation emulsion 3.2: Formula Mass and the Mole Concept
11.3: Electrolytes fourth transition series
11.6: Colloids
dissociation constant End point 19.2: Occurrence, Preparation, and Properties of
15.3: Lewis Acids and Bases Transition Metals and Their Compounds
dissolved endothermic process Frasch process
3.4: Molarity 18.11: Occurrence, Preparation, and Properties of
5.2: Energy Basics
donor atom Sulfur
Energy Free radical
5.2: Energy Basics
double bond 7.4: Lewis Symbols and Structures
Enthalpy freezing
5.4: Enthalpy
Downs cell 10.4: Phase Transitions
Enthalpy change freezing point
18.3: Occurrence and Preparation of the
5.4: Enthalpy
Representative Metals 10.4: Phase Transitions
dry cell entropy freezing point depression
16.3: Entropy
17.6: Batteries and Fuel Cells 11.5: Colligative Properties
dynamic equilibrium equatorial position freezing point depression constant
10.4: Phase Transitions 11.5: Colligative Properties
equilibrium frequency
E 13.2: Chemical Equilibria
equilibrium constant frequency factor
Effective Nuclear Charge
6.6: Periodic Variations in Element Properties 12.6: Collision Theory
equivalence point fuel cell
effusion
9.5: Effusion and Diffusion of Gases 17.6: Batteries and Fuel Cells
ester functional group
eg orbitals
19.4: Spectroscopic and Magnetic Properties of 20.2: Hydrocarbons
Esters
Coordination Compounds
ether fundamental unit of charge
electrical potential 2.4: Atomic Structure and Symbolism
exact number fusion
electrical work 21.5: Transmutation and Nuclear Energy
1.6: Measurement Uncertainty, Accuracy, and
17.5: Potential, Free Energy, and Equilibrium Precision fusion reactor
Electrolysis excess reactant 21.5: Transmutation and Nuclear Energy
17.8: Electrolysis 4.5: Reaction Yields
electrolyte excited state G
11.3: Electrolytes 6.3: The Bohr Model galvanic cell
electrolytic cell exothermic process 17.3: Galvanic Cells
17.8: Electrolysis 5.2: Energy Basics galvanized iron
Electromagnetic Radiation expansion work 17.7: Corrosion
6.2: Electromagnetic Energy 5.4: Enthalpy gamma emission
electromagnetic spectrum extensive property 21.4: Radioactive Decay
6.2: Electromagnetic Energy 1.4: Physical and Chemical Properties gamma ray
electron external beam radiation therapy 21.3: Nuclear Equations
2.3: Evolution of Atomic Theory 21.6: Uses of Radioisotopes gas
Electron Affinity 1.3: Phases and Classification of Matter
6.6: Periodic Variations in Element Properties F Geiger counter
electron capture f orbital 21.7: Biological Effects of Radiation
21.4: Radioactive Decay gel
electron configuration Fahrenheit 11.6: Colloids
6.5: Electronic Structure of Atoms (Electron
1.7: Mathematical Treatment of Measurement
Configurations)
Results
geometric isomers hydrogen bonding intensity
19.4: Spectroscopic and Magnetic Properties of 10.2: Intermolecular Forces 6.2: Electromagnetic Energy
Coordination Compounds hydrogen carbonate intensive property
Gibbs Free Energy 18.7: Occurrence, Preparation, and Properties of 1.4: Physical and Chemical Properties
16.5: Free Energy Carbonates interference pattern
goiter hydrogen halide 6.2: Electromagnetic Energy
2.4: Atomic Structure and Symbolism 18.6: Occurrence, Preparation, and Compounds of interhalogen
Graham's law Hydrogen
18.13: Occurrence, Preparation, and Properties of the
9.5: Effusion and Diffusion of Gases hydrogen sulfate Noble Gases
gravimetric analysis 18.10: Occurrence, Preparation, and Compounds of intermediate
Oxygen
4.6: Quantitative Chemical Analysis 12.7: Reaction Mechanisms
gray (unit) hydrogen sulfite intermolecular force
18.10: Occurrence, Preparation, and Compounds of
21.7: Biological Effects of Radiation 10.2: Intermolecular Forces
Oxygen
ground state hydrogenation internal energy
6.3: The Bohr Model 5.4: Enthalpy
group Hydrogen internal radiation therapy
2.6: The Periodic Table hydrometallurgy 21.6: Uses of Radioisotopes
19.2: Occurrence, Preparation, and Properties of International System of Units
H Transition Metals and Their Compounds 1.5: Measurements
Haber Process hydrostatic pressure interstitial sites
18.6: Occurrence, Preparation, and Compounds of 9.2: Gas Pressure 10.6: The Solid State of Matter
Hydrogen hydroxide ion
halide 18.10: Occurrence, Preparation, and Compounds of 2.4: Atomic Structure and Symbolism
18.13: Occurrence, Preparation, and Properties of the Oxygen ion pair
Noble Gases hypertonic 11.5: Colligative Properties
halogen 11.5: Colligative Properties ionic bond
2.6: The Periodic Table hypervalent molecule 2.7: Molecular and Ionic Compounds
heat 7.4: Lewis Symbols and Structures 7.2: Ionic Bonding
5.2: Energy Basics hypothesis ionic compound
Heat capacity 1.2: Chemistry in Context 2.7: Molecular and Ionic Compounds
5.2: Energy Basics hypotonic ionic solid
Heisenberg Uncertainty Principle 11.5: Colligative Properties 10.6: The Solid State of Matter
6.4: Development of Quantum Theory ionic solvent
hemolysis I 17.8: Electrolysis
11.5: Colligative Properties ideal gas Ionization Energy
Henry's law 9.3: Relating Pressure, Volume, Amount, and 6.6: Periodic Variations in Element Properties
11.4: Solubility Temperature - The Ideal Gas Law ionization isomer
hertz ideal gas constant 19.3: Coordination Chemistry of Transition Metals
6.2: Electromagnetic Energy 9.3: Relating Pressure, Volume, Amount, and ionizing radiation
Hess's law Temperature - The Ideal Gas Law
5.4: Enthalpy ideal gas law isoelectronic
heterogeneous catalyst 9.3: Relating Pressure, Volume, Amount, and
Temperature - The Ideal Gas Law
12.8: Catalysis
ideal solution isomers
heterogeneous equilibria 2.5: Chemical Formulas
immiscible isomorphous
heterogeneous mixture 10.7: Lattice Structures in Crystalline Solids
11.4: Solubility
indicator isotonic
hexagonal closest packing 11.5: Colligative Properties
induced dipole isotope
hole 2.3: Evolution of Atomic Theory
inert electrode
homogeneous catalyst
J
12.8: Catalysis joule
inert gas
homogeneous equilibria 5.2: Energy Basics
inert pair effect
homogeneous mixture K
7.2: Ionic Bonding
initial rate Kc
Hund's rule 13.3: Equilibrium Constants
6.5: Electronic Structure of Atoms (Electron
Configurations) inner transition metal kelvin
2.6: The Periodic Table 1.5: Measurements
hybrid orbital
8.3: Hybrid Atomic Orbitals instantaneous dipole ketone
10.2: Intermolecular Forces 20.4: Aldehydes, Ketones, Carboxylic Acids, and
hybridization Esters
8.3: Hybrid Atomic Orbitals instantaneous rate
kilogram
hydrocarbon 1.5: Measurements
5.4: Enthalpy integrated rate law
Kinetic Energy
5.2: Energy Basics
kinetic molecular theory magnetic quantum number Molecular Structure
9.6: The Kinetic-Molecular Theory 6.4: Development of Quantum Theory 7.5: Formal Charges and Resonance
Kp manometer 7.7: Molecular Structure and Polarity
13.3: Equilibrium Constants 9.2: Gas Pressure molecularity
mass 12.7: Reaction Mechanisms
L 1.3: Phases and Classification of Matter molecule
mass defect 1.3: Phases and Classification of Matter
lanthanide
2.6: The Periodic Table 21.2: Nuclear Structure and Stability monatomic ion
mass number 2.7: Molecular and Ionic Compounds
lanthanide series
19.2: Occurrence, Preparation, and Properties of 2.4: Atomic Structure and Symbolism monodentate
Transition Metals and Their Compounds mass percentage 19.3: Coordination Chemistry of Transition Metals
Lattice Energy 3.5: Other Units for Solution Concentrations monoprotic acid
7.6: Strengths of Ionic and Covalent Bonds mean free path 14.6: Polyprotic Acids
law 9.5: Effusion and Diffusion of Gases multiple equilibrium
1.2: Chemistry in Context melting 15.4: Coupled Equilibria
law of conservation of matter 10.4: Phase Transitions
1.3: Phases and Classification of Matter melting point N
law of constant composition 10.4: Phase Transitions Nernst Equation
2.2: Early Ideas in Atomic Theory metal 17.5: Potential, Free Energy, and Equilibrium
law of definite proportions 2.6: The Periodic Table net ionic equation
2.2: Early Ideas in Atomic Theory 18.2: Periodicity 4.2: Writing and Balancing Chemical Equations
Law of Mass Action metallic solid neutral
13.3: Equilibrium Constants 10.6: The Solid State of Matter 14.3: pH and pOH
law of multiple proportions metalloid neutron
2.2: Early Ideas in Atomic Theory 2.6: The Periodic Table 2.3: Evolution of Atomic Theory
18.2: Periodicity
Le Chatelier's Principle Nitrate
meter 18.10: Occurrence, Preparation, and Compounds of
1.5: Measurements Oxygen
lead acid battery
Method of Initial Rates nitrogen fixation
12.4: Rate Laws 18.8: Occurrence, Preparation, and Properties of
length
1.5: Measurements
microscopic domain Nitrogen
leveling effect of water 1.2: Chemistry in Context noble gas

microstates 2.6: The Periodic Table
Lewis Acid 16.3: Entropy node

millicurie (unit) 6.2: Electromagnetic Energy
21.7: Biological Effects of Radiation 8.2: Valence Bond Theory
Lewis base nomenclature
milliliter
1.5: Measurements 2.8: Chemical Nomenclature
Lewis structure nonelectrolyte
miscible
11.4: Solubility 11.3: Electrolytes
Lewis symbol nonionizing radiation
mixture
1.3: Phases and Classification of Matter 21.7: Biological Effects of Radiation
ligand nonmetal
molality
11.5: Colligative Properties 2.6: The Periodic Table
limiting reactant molar mass nonpolar covalent bond
3.2: Formula Mass and the Mole Concept 7.3: Covalent Bonding
line spectrum molar solubility nonspontaneous process
15.2: Precipitation and Dissolution 16.2: Spontaneity
Linear molarity normal boiling point
3.4: Molarity 10.4: Phase Transitions
linkage isomer mole nuclear binding energy
3.2: Formula Mass and the Mole Concept 21.2: Nuclear Structure and Stability
liquid mole fraction Nuclear chemistry
9.4: Stoichiometry of Gaseous Substances, Mixtures, 21.2: Nuclear Structure and Stability
liter and Reactions nuclear fuel
1.5: Measurements
molecular compound 21.5: Transmutation and Nuclear Energy
lithium ion battery 2.7: Molecular and Ionic Compounds nuclear moderator
molecular equation 21.5: Transmutation and Nuclear Energy
lone pair 4.2: Writing and Balancing Chemical Equations nuclear reaction
molecular formula 21.3: Nuclear Equations
2.5: Chemical Formulas Nuclear Reactor
M molecular orbital theory 21.5: Transmutation and Nuclear Energy
8.5: Molecular Orbital Theory nuclear transmutation
macroscopic domain
molecular solid 21.5: Transmutation and Nuclear Energy
10.6: The Solid State of Matter nucleon
magic number 21.2: Nuclear Structure and Stability
nucleus pascal Potential Energy
2.3: Evolution of Atomic Theory 9.2: Gas Pressure 5.2: Energy Basics
nutritional calorie passivation pounds per square inch
5.3: Calorimetry 18.2: Periodicity 9.2: Gas Pressure
Pauli exclusion principle precipitate
O 6.4: Development of Quantum Theory 4.3: Classifying Chemical Reactions
Octahedral percent composition Precipitation reaction
7.7: Molecular Structure and Polarity 3.3: Determining Empirical and Molecular Formulas 4.3: Classifying Chemical Reactions
octahedral hole percent of ionization precision
10.7: Lattice Structures in Crystalline Solids 14.4: Relative Strengths of Acids and Bases 1.6: Measurement Uncertainty, Accuracy, and
percent yield Precision
octet rule
7.4: Lewis Symbols and Structures 4.5: Reaction Yields pressure
period 9.2: Gas Pressure
optical isomer
19.3: Coordination Chemistry of Transition Metals 2.6: The Periodic Table primary battery
periodic law 17.6: Batteries and Fuel Cells
orbital diagram
6.5: Electronic Structure of Atoms (Electron 2.6: The Periodic Table principal quantum number
Configurations) periodic table 6.4: Development of Quantum Theory
organic compound 2.6: The Periodic Table product
20.2: Hydrocarbons Peroxide 4.2: Writing and Balancing Chemical Equations
osmosis 18.10: Occurrence, Preparation, and Compounds of proton
11.5: Colligative Properties Oxygen 2.3: Evolution of Atomic Theory
osmotic pressure pH PSI (Unit)
11.5: Colligative Properties 14.3: pH and pOH 9.2: Gas Pressure
Ostwald process phase diagram pure covalent bond
18.10: Occurrence, Preparation, and Compounds of 10.5: Phase Diagrams 7.3: Covalent Bonding
Oxygen photon pure substance
overall reaction order 6.2: Electromagnetic Energy 1.3: Phases and Classification of Matter
12.4: Rate Laws photosynthesis
overlap 18.10: Occurrence, Preparation, and Compounds of Q
8.2: Valence Bond Theory Oxygen
Quantitative Analysis
overpotential Physical change 4.6: Quantitative Chemical Analysis
17.8: Electrolysis 1.4: Physical and Chemical Properties
Quantization
oxidation physical property 6.2: Electromagnetic Energy
4.3: Classifying Chemical Reactions 1.4: Physical and Chemical Properties
quantum mechanics
oxide pi bond 6.4: Development of Quantum Theory
18.10: Occurrence, Preparation, and Compounds of 8.2: Valence Bond Theory
quantum number
Oxygen Pidgeon process 6.3: The Bohr Model
oxidizing agent 18.3: Occurrence and Preparation of the
4.3: Classifying Chemical Reactions Representative Metals
plasma R
oxyacid
2.8: Chemical Nomenclature 1.3: Phases and Classification of Matter radiation absorbed dose
14.4: Relative Strengths of Acids and Bases platinum metals 21.7: Biological Effects of Radiation
oxyanion 19.2: Occurrence, Preparation, and Properties of radiation dosimeter
2.7: Molecular and Ionic Compounds Transition Metals and Their Compounds 21.7: Biological Effects of Radiation
Ozone pnictogen radiation therapy
18.10: Occurrence, Preparation, and Compounds of 2.6: The Periodic Table 21.6: Uses of Radioisotopes
Oxygen pOH radioactive decay
14.3: pH and pOH 21.4: Radioactive Decay
P polar covalent bond radioactive decay series
p orbital 7.3: Covalent Bonding 21.4: Radioactive Decay
6.4: Development of Quantum Theory polar molecule radioactive tracer
pairing energy 7.7: Molecular Structure and Polarity 21.6: Uses of Radioisotopes
19.4: Spectroscopic and Magnetic Properties of polarizability radioactivity
Coordination Compounds 10.2: Intermolecular Forces 21.2: Nuclear Structure and Stability
parent nuclide polyatomic ion radiocarbon dating
21.4: Radioactive Decay 2.7: Molecular and Ionic Compounds 21.4: Radioactive Decay
partial pressure polydentate ligand radioisotope
9.4: Stoichiometry of Gaseous Substances, Mixtures, 19.3: Coordination Chemistry of Transition Metals 21.2: Nuclear Structure and Stability
and Reactions Radiometric Dating
polymorph
partially miscible 18.4: Structure and General Properties of the 21.4: Radioactive Decay
11.4: Solubility Metalloids Raoult's Law
particle accelerator position of equilibrium 11.5: Colligative Properties
21.5: Transmutation and Nuclear Energy 13.4: Shifting Equilibria- Le Châtelier’s Principle rare earth element
parts per billion Positron 19.2: Occurrence, Preparation, and Properties of
3.5: Other Units for Solution Concentrations 21.3: Nuclear Equations Transition Metals and Their Compounds
Parts per million positron emission rate constant
3.5: Other Units for Solution Concentrations 21.4: Radioactive Decay 12.4: Rate Laws
rate expression secondary battery spin quantum number
12.2: Chemical Reaction Rates 17.6: Batteries and Fuel Cells 6.4: Development of Quantum Theory
rate law selective precipitation spontaneous change
12.4: Rate Laws 15.2: Precipitation and Dissolution 16.2: Spontaneity
rate of diffusion semipermeable membrane spontaneous process
9.5: Effusion and Diffusion of Gases 11.5: Colligative Properties 11.2: The Dissolution Process
rate of reaction series standard cell potential
12.2: Chemical Reaction Rates 2.6: The Periodic Table 17.4: Electrode and Cell Potentials
reactant shell standard conditions of temperature and
4.2: Writing and Balancing Chemical Equations 6.4: Development of Quantum Theory pressure
reaction mechanism SI units 9.3: Relating Pressure, Volume, Amount, and
12.7: Reaction Mechanisms 1.5: Measurements Temperature - The Ideal Gas Law
Reaction order sievert (unit) standard enthalpy of combustion
12.4: Rate Laws 21.7: Biological Effects of Radiation 5.4: Enthalpy
Reaction Quotient sigma bond Standard Enthalpy of Formation
13.3: Equilibrium Constants 8.2: Valence Bond Theory 5.4: Enthalpy
reactor coolant Significant figures standard entropy
21.5: Transmutation and Nuclear Energy 1.6: Measurement Uncertainty, Accuracy, and 16.4: The Second and Third Laws of
reduction Precision Thermodynamics
4.3: Classifying Chemical Reactions silicate standard entropy change
relative biological effectiveness 18.4: Structure and General Properties of the 16.4: The Second and Third Laws of
Metalloids Thermodynamics
representative element simple cubic structure standard free energy change
10.7: Lattice Structures in Crystalline Solids 16.5: Free Energy
18.2: Periodicity simple cubic unit cell standard free energy of formation
representative metal 10.7: Lattice Structures in Crystalline Solids 16.5: Free Energy
18.2: Periodicity single bond standard hydrogen electrode
resonance 7.4: Lewis Symbols and Structures 17.4: Electrode and Cell Potentials
7.5: Formal Charges and Resonance skeletal structure standard molar volume
8.4: Multiple Bonds 20.2: Hydrocarbons 9.3: Relating Pressure, Volume, Amount, and
resonance forms smelting Temperature - The Ideal Gas Law
7.5: Formal Charges and Resonance 19.2: Occurrence, Preparation, and Properties of standard reduction potential
resonance hybrid Transition Metals and Their Compounds 17.4: Electrode and Cell Potentials
7.5: Formal Charges and Resonance solid standard state
reversible process 1.3: Phases and Classification of Matter 5.4: Enthalpy
16.3: Entropy solubility standing wave
reversible reaction 11.4: Solubility 6.2: Electromagnetic Energy
13.2: Chemical Equilibria solubility product state function
roentgen equivalent man 15.2: Precipitation and Dissolution 5.4: Enthalpy
21.7: Biological Effects of Radiation solute Steel
root mean square velocity 3.4: Molarity 19.2: Occurrence, Preparation, and Properties of
solvation Transition Metals and Their Compounds
rounding 11.2: The Dissolution Process stepwise ionization
solvent 14.6: Polyprotic Acids
1.6: Measurement Uncertainty, Accuracy, and
Precision 3.4: Molarity stoichiometric factor
sp hybrid orbital 4.4: Reaction Stoichiometry
S 8.3: Hybrid Atomic Orbitals stoichiometry
sp2 hybrid orbital 4.4: Reaction Stoichiometry
s orbital
6.4: Development of Quantum Theory 8.3: Hybrid Atomic Orbitals STP
sp3 hybrid orbital 9.3: Relating Pressure, Volume, Amount, and
sacrificial anode Temperature - The Ideal Gas Law
17.7: Corrosion 8.3: Hybrid Atomic Orbitals
sp3d hybrid orbital stress
saturated 13.4: Shifting Equilibria- Le Châtelier’s Principle
11.4: Solubility 8.3: Hybrid Atomic Orbitals
sp3d2 hybrid orbital strong electrolyte
saturated hydrocarbon 11.3: Electrolytes
20.2: Hydrocarbons 8.3: Hybrid Atomic Orbitals
space lattice strong nuclear force
scientific method 21.2: Nuclear Structure and Stability
1.2: Chemistry in Context 10.7: Lattice Structures in Crystalline Solids
spatial isomers structural formula
scintillation counter 2.5: Chemical Formulas
21.7: Biological Effects of Radiation 2.5: Chemical Formulas
specific heat capacity structural isomers
second 2.5: Chemical Formulas
1.5: Measurements 5.2: Energy Basics
spectator ion subcritical mass
Second Law of Thermodynamics 21.5: Transmutation and Nuclear Energy
16.4: The Second and Third Laws of 4.2: Writing and Balancing Chemical Equations
Thermodynamics spectrochemical series sublimation
second transition series 19.4: Spectroscopic and Magnetic Properties of
19.2: Occurrence, Preparation, and Properties of Coordination Compounds subshell
Transition Metals and Their Compounds 6.4: Development of Quantum Theory
substituent third transition series Valence Electrons
20.2: Hydrocarbons 19.2: Occurrence, Preparation, and Properties of 6.5: Electronic Structure of Atoms (Electron
substitution reaction Transition Metals and Their Compounds Configurations)
20.2: Hydrocarbons titrant valence shell
sulfate 4.6: Quantitative Chemical Analysis 6.5: Electronic Structure of Atoms (Electron
titration analysis Configurations)
Oxygen 4.6: Quantitative Chemical Analysis valence shell electron pair repulsion
Sulfite titration curve theory
18.10: Occurrence, Preparation, and Compounds of 14.8: Acid-Base Titrations 7.7: Molecular Structure and Polarity
Oxygen torr van der Waals equation
superconductor 9.2: Gas Pressure 9.7: Non-Ideal Gas Behavior
19.2: Occurrence, Preparation, and Properties of trans configuration van der Waals force
Transition Metals and Their Compounds
19.3: Coordination Chemistry of Transition Metals 10.2: Intermolecular Forces
supercritical fluid transition metal van't Hoff factor
2.6: The Periodic Table 11.5: Colligative Properties
supercritical mass transmutation reaction vapor pressure
21.5: Transmutation and Nuclear Energy 10.4: Phase Transitions
superoxide transuranium element vapor pressure of water
21.5: Transmutation and Nuclear Energy 9.4: Stoichiometry of Gaseous Substances, Mixtures,
Oxygen
trigonal bipyramidal and Reactions
supersaturated vaporization
11.4: Solubility
Trigonal Planar 10.4: Phase Transitions
surface tension viscosity
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CHEMISTRY

Flowers, Theopold and Langley

Flowers, Theopold and Langley

This text was compiled on 12/05/2022

2: Atoms, Molecules, and Ions

3: Composition of Substances and Solutions

4: Stoichiometry of Chemical Reactions

6: Electronic Structure and Periodic Properties

7: Chemical Bonding and Molecular Geometry

8: Advanced Theories of Covalent Bonding

10: Liquids and Solids

11: Solutions and Colloids

13: Fundamental Equilibrium Concepts

14: Acid-Base Equilibria

15: Equilibria of Other Reaction Classes

18: Representative Metals, Metalloids, and Nonmetals

19: Transition Metals and Coordination Chemistry

20: Organic Chemistry

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1.2.0.1: Chemistry: The Central Science

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1.3.0.1: Classifying Matter

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1.3.0.1: Link to Learning

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oxygen O 49.20 chlorine Cl 0.19

silicon Si 25.67 phosphorus P 0.11

aluminum Al 7.50 manganese Mn 0.09

iron Fe 4.71 carbon C 0.08

calcium Ca 3.39 sulfur S 0.06

sodium Na 2.63 barium Ba 0.04

potassium K 2.40 nitrogen N 0.03

magnesium Mg 1.93 fluorine F 0.03

hydrogen H 0.87 strontium Sr 0.02

titanium Ti 0.58 all others - 0.47

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1.3.0.1: Chemistry in Everyday Life

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1.3.0.1: Chemistry in Everyday Life

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By the end of this section, you will be able to:

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1.4.0.1: Chemistry in Everyday Life

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