CHEMISTRY FOR ENGINEERS

Hand-out No. 5: Gases

Hand-out No. 5 GASES Time Frame: 18 hours

Learning Objectives
 Discuss how a barometer works and interconvert units of pressure
 Discuss the gas laws (Boyle’s, Charles’s, Avogadro’s, Gay-Lussac’s, and Ideal Gas Law)
 Demonstrate how to use the ideal gas law to determine the molar mass of a gas, the density of a gas at different
temperatures, and the partial pressure of each gas in a mixture
 Solve problems involving chemical reaction using the properties of gases

Content Outline
1. Substances That Exist as Gases
2. Pressure of a Gas
3. The Gas Laws
4. The Ideal Gas Equation
5. Gas Stoichiometry
6. Dalton’s Law of Partial Pressure

AN OVERVIEW OF THE PHYSICAL STATES OF MATTER

Under appropriate conditions of pressure and temperature, most substances can exist as a solid, a liquid, or
a gas. Several other aspects of their behavior distinguish gases from liquids and solids:
1. Gas volume changes greatly with pressure.
2. Gas volume changes greatly with temperature.
3. Gases have relatively low viscosity.
4. Most gases have relatively low densities under normal conditions.
5. Gases are miscible.

GAS PRESSURE AND ITS MEASUREMENT

Pressure (P) is defined as the force exerted per unit of surface area:

Earth's gravitational attraction pulls the atmospheric gases toward its surface, where they exert a force
on all objects. The force, or weight, of these gases creates a pressure of about 14.7 pounds per square inch
(lb/in2; psi) of surface.

Measuring Atmospheric Pressure

The barometer is a common device used to measure atmospheric pressure. Invented in 1643 by
Evangelista Torricelli, the barometer is still basically just a tube about 1 m long, closed at one end, filled with
mercury, and inverted into a dish containing more mercury. Figure 5.1 shows an example of a mercury
barometer.

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Hand-out No. 5: Gases

Figure 5.1 A mercury barometer (Silberberg, 2007, p. 141)

Since the pressure of the mercury column is directly proportional to its height, a unit commonly used for
pressure is mmHg, the height of the column in millimeters (mm). At sea level and 0°C, normal atmospheric
pressure is 760 mmHg; at the top of Mt. Everest (29,028 ft, or 8848 m), the atmospheric pressure is only about
270 mmHg. Thus, pressure decreases with altitude: the column of air above the sea is taller and weighs more
than the column of air above Mt. Everest. Laboratory barometers contain mercury because its high density allows
the barometer to be a convenient size.
Note that, for a given pressure, the ratio of heights (h) of the liquid columns is inversely related to the
ratio of the densities (ρ) of the liquids:

Units of Pressure
Pressure results from a force exerted on an area. The SI unit of force is the newton (N): 1 N = 1
kg·m/s2. The SI unit of pressure is the pascal (Pa), which equals a force of one newton exerted on an area of
one square meter:

1 Pa = 1 N/m2

A much larger unit is the standard atmosphere (atm), the average atmospheric pressure measured at
sea level and 0°C. It is defined in terms of the pascal:

1 atm = 101.325 kilopascals (kPa) = 1.01325x105 Pa

Another common unit is the millimeter of mercury (mmHg), which is based on measurement with a
barometer. In honor of Torricelli, this unit has been named the torr:

The bar is coming into more common use in chemistry:

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Table 5.1 lists some important pressure units used in various scientific fields.

Table 5.1 Common Units of Pressure

Unit Atmospheric Pressure
pascal (PA); kilopascal (kPa)
atmosphere (atm)
millimeters of mercury (mmHg)
torr
pounds per square in (lb/in2 or psi) ⁄
bar

EXAMPLE 5.1
A geochemist heats a limestone (CaCO3) sample and collects the CO2 released in an evacuated flask. The CO2
pressure is 291.4 mmHg. Calculate the CO2 pressure in torrs, atmospheres, and kilopascals.

SOLUTION
Using the conversion factors given in Table 5.1, we have

9 𝟐𝟗𝟏 𝟒 𝐭𝐨𝐫𝐫

9 𝟎 𝟑𝟖𝟑 𝐚𝐭𝐦

9 𝟑𝟖 𝟖𝟓 𝐤𝐏𝐚

THE GAS LAWS AND THEIR EXPERIMENTAL FOUNDATIONS

The physical behavior of a sample of gas can be described completely by four variables: pressure (P),
volume (V), temperature (T), and amount (number of moles, n). The variables are interdependent: any one of
them can be determined by measuring the other three.
Three key relationships exist among the four gas variables - Boyle's, Charles's, and Avogadro's laws.
Each of these gas laws expresses the effect of one variable on another, with the remaining two variables held
constant. These three laws are special cases of an all-encompassing relationship among gas variables called the
ideal gas law. This unifying observation quantitatively describes the state of a so-called ideal gas, one that
exhibits simple linear relationships among volume, pressure, temperature, and amount. Although no ideal gas
actually exists, most simple gases, such as N 2, O2, H2, and the noble gases, show nearly ideal behavior at
ordinary temperatures and pressures.

The Relationship between Volume and Pressure: Boyle's Law

The great 17th century English chemist Robert Boyle performed a series of experiments that led him to
conclude that at a given temperature, the volume occupied by a gas is inversely related to its pressure.
The generalization of Boyle's observations is known as Boyle's law: at constant temperature, the
volume occupied by a fixed amount of gas is inversely proportional to the applied (external) pressure, or

( )

This relationship can also be expressed as

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Hand-out No. 5: Gases

( )

The Relationship between Volume and Temperature: Charles's Law

The modern statement of the volume-temperature relationship is known as Charles's law: at constant
pressure, the volume occupied by a fixed amount of gas is directly proportional to its absolute (Kelvin)
temperature, or

( )

This relationship can also be expressed as

( )

If T increases, V increases, and vice versa.

Other Relationships Based on Boyle's and Charles's Laws

Two other important relationships in gas behavior emerge from an understanding of Boyle's and Charles's
laws:
1. The pressure-temperature relationship. Charles's law is expressed as the effect of a temperature
change on gas volume. However, volume and pressure are interdependent, so the effect of temperature
on volume is closely related to its effect on pressure (sometimes referred to as Amontons’s law). Thus,
at constant volume, the pressure exerted by a fixed amount of gas is directly proportional to the
absolute temperature:

( )

2. The combined gas law. A simple combination of Boyle's and Charles's laws gives the combined gas
law, which applies to situations when two of the three variables ( V, P, T) change and you must find the
effect on the third:

The Relationship between Volume and Amount: Avogadro's Law

Figure 5.2 An experiment to study the relationship between the volume and amount of a gas (Silberberg, 2007, p. 146)

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At a given external P and T, a given amount (n1) of CO2(s) is put into the tube. When the CO2 changes
from solid to gas, it pushes up the piston until Pgas = Patm, at which point it occupies a given volume of the
cylinder. B, When twice the amount (n2) of CO2(s) is used, twice the volume of the cylinder becomes occupied.
Thus, at fixed P and T, the volume (V) of a gas is directly proportional to the amount of gas (n).

At fixed temperature and pressure, the volume occupied by a gas is directly proportional to the amount
(mol) of gas:

( )

As n increases, V increases, and vice versa. This relationship is also expressed as

The constant is the same for all gases at a given temperature and pressure. This relationship is another
way of expressing Avogadro's law, which states that at fixed temperature and pressure, equal volumes of any
ideal gas contain equal numbers of particles (or moles).

Gas Behavior at Standard Conditions

To better understand the factors that influence gas behavior, chemists use a set of standard conditions
called standard temperature and pressure (STP):

STP: 0°C (273.15 K) and 1 atm (760 torr)

Under these conditions, the volume of 1 mol of an ideal gas is called the standard molar volume:

Standard molar volume = 22.414 L

Figure 5.3 compares the properties of three simple gases at STP.

Figure 5.3 Standard Molar Volume (Silberberg, 2007, p. 147)

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The Ideal Gas Law

Each of the gas laws focuses on the effect that changes in one variable have on gas volume:
 Boyle’s law focuses on pressure .
 Charles's law focuses on temperature .
 Avogadro's law focuses on amount (mol) of gas .

We can combine these individual effects into one relationship, called the ideal gas law (or ideal gas
equation):

where R is a proportionality constant known as the universal gas constant.

Rearranging gives the most common form of the ideal gas law:

PV=nRT

We can obtain a value of R by measuring the volume, temperature, and pressure of a given amount of
gas and substituting the values into the ideal gas law.
For example, using standard conditions for the gas variables, we have

This numerical value o f R corresponds to the gas variables P, V, and T expressed in these units. R has
a different numerical value when different units are used. For example, R has the value 8.314 J/mol·K.

EXAMPLE 5.2
Boyle's apprentice finds that the air trapped in a J tube occupies 24.8 cm 3 at 1.12 atm. By adding mercury to the tube, he
increases the pressure on the trapped air to 2.64 atm. Assuming constant temperature, what is the new volume of air (in L)?

SOLUTION
These are the given conditions in the problem:
3
𝑉1 𝑃 𝑉 ?
𝑃1 𝑇

To solve for the new volume of air in L, we use Boyle’s Law

𝑉
𝑃
𝑉1 𝑃
𝑉 𝑃1
3( )
𝑉1 𝑃1
𝑉
𝑃

3
𝑉 3
,

𝑽𝟐 𝟎 𝟎𝟏𝟎𝟓𝟐 𝐋

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EXAMPLE 5.3
A steel tank used for fuel delivery is fitted with a safety valve that opens if the internal pressure exceeds 3
. It is
filled with methane at 23°C and 0.991 atm and placed in boiling water at exactly 100°C. Will the safety valve open?

SOLUTION
These are the given conditions in the problem:
𝑇1 °C 𝑇 °C 𝑃1 99
𝑉 ( )

To determine if the safety valve of a steel tank will open, we need to solve for the pressure of the tank at 100⁰C. If its internal
pressure exceeds 3
, the safety valve will open. Using Pressure-Temperature relationship, we have

𝑃1 𝑇1
𝑃 𝑇

𝑃1 𝑇
𝑉
𝑇1

Note that when dealing with gas problems, one should use the absolute temperature to get the correct answer.

99 ( + )
𝑃
( + )

𝑷𝟐 𝟗𝟒𝟖 𝟗𝟖 𝐭𝐨𝐫𝐫

The valve will not pen because the internal pressure is less than 3
.

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EXAMPLE 5.4
A scale model of a blimp rises when it is filled with helium to a volume of 55.0 dm3. When 1.10 mol of He is added to the blimp,
the volume is 26.2 dm3. How many more grams of He must be added to make it rise? Assume constant T and P.

SOLUTION
These are the given conditions in the problem:
3
𝑛1 𝑉 𝑇
3
𝑉1 𝑛 ? 𝑃

To solve this, we should use Avogadro’s Law

𝑉 𝑛

𝑉1 𝑛1
𝑉 𝑛

( 3)
𝑛1 𝑉
𝑛 3
𝑉1

The scale model of a blimp should contain 2.31 moles of helium for it to rise. The problem requires for the mass of helium in
grams to be added from its initial amount of 1.10 mol,

h 𝑛 − 𝑛1 −

h 𝟒 𝟖𝟒 𝐠𝐫𝐚𝐦𝐬 𝐨𝐟 𝐇𝐞

EXAMPLE 5.5
A steel tank has a volume of 438 L and is filled with 0.885 kg of O 2. Calculate the pressure of O2 at 21°C.

SOLUTION
These are the given conditions in the problem:
y 𝑚 O 𝑃 ?
𝑉 𝐿 𝑇 °𝐶

Using the Ideal Gas Law,

𝑃𝑉 𝑛𝑅𝑇

n R T

, O O
O ( + )
O ( ) O
𝑃

V
𝐏 𝟏 𝟓𝟐 𝐚𝐭𝐦

FURTHER APPLICATIONS OF THE IDEAL GAS LAW

The Density of a Gas

One mole of any gas occupies nearly the same volume at a given temperature and pressure, so differences in
gas density (ρ=m/V) depend on differences in molar mass.

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All gases are miscible, but if two or more gases are not thoroughly mixed, a more dense gas will sink below the
less dense one(s).
We can rearrange the ideal gas law to calculate the density of a gas from its molar mass. Recall that the number
of moles (n) is the mass (m) divided by the molar mass ( ), ⁄ . Substituting for n in the ideal gas law
gives

Rearranging to isolate m/V gives

Two important ideas are expressed by the equation above:

• The density of a gas is directly proportional to its molar mass because a given amount of a heavier gas
occupies the same volume as that amount of a lighter gas (Avogadro's law).
• The density of a gas is inversely proportional to the temperature. As the volume of a gas increases with
temperature (Charles’s law), the same mass occupies more space; thus, the density is lower.

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EXAMPLE 5.6
A chemical engineer uses waste CO2 from a manufacturing process, instead of chlorofluorocarbons, as a "blowing agent" in the
production of polystyrene containers. Find the density (in g/L) of CO 2 and the number of molecules per liter
a. at STP (0°C and 1 atm) and
b. at room conditions (20°C and 1.00 atm).

SOLUTION
The problem requires finding the density and number of molecules of CO 2 at two different conditions.
a. at STP, these are the properties and conditions of CO2
𝑇 °C 𝑃 CO

Calculating for the density of CO2 at STP,

𝑃
𝜌CO
𝑅𝑇

( )( )
𝜌CO
( + )

𝝆𝐂𝐎𝟐 𝟏 𝟗𝟔 𝐠 𝐋

To get the number of molecules of CO2 per liter, we need to convert from mass/L to molecules/L,
3
CO 9 CO CO CO
CO CO

𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐞𝐬 𝐂𝐎𝟐 𝟐 𝟔𝟗 𝟏𝟎𝟐𝟐 𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐞𝐬 𝐂𝐎𝟐

𝐋 𝐋

b. at room conditions, these are the properties of CO 2

𝑇 °C 𝑃 CO

Calculating for the density of CO2 at room conditions,

𝑃
𝜌CO
𝑅𝑇
( )( )
𝜌CO
( + )

𝝆𝐂𝐎𝟐 𝟏 𝟖𝟑 𝐠 𝐋

To get the number of molecules of CO2 per liter, we need to convert from mass/L to molecules/L,
3
CO CO CO CO
CO CO

𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐞𝐬 𝐂𝐎𝟐 𝟐𝟓 𝟏𝟎𝟐𝟐 𝐦𝐨𝐥𝐞𝐜𝐮𝐥𝐞𝐬 𝐂𝐎𝟐

𝐋 𝐋

The Molar Mass of a Gas

We can determine the molar mass of an unknown gas or volatile liquid (one that is easily vaporized):

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EXAMPLE 5.7
An organic chemist isolates a colorless liquid from a petroleum sample. She places the liquid in a flask and puts the flask in a
boiling water bath, which vaporizes the liquid and fills the flask with gas. She closes the flask, reweighs it, and obtains the
following data:
Volume of flask = 213 mL T = 100.0°C P = 754 torr
Mass of flask + gas = 78.416 g Mass of empty flask = 77.834 g
Calculate the molar mass of the liquid.

SOLUTION
These are the given conditions in the problem:
V 𝑇 °C 𝑃
+ py

We need to determine first the mass of gas before we solve for the molar mass of the liquid,
𝑚g s ( + )−( py )
𝑚g s ( − )

To solve for the molar mass, we have

𝑚𝑅𝑇 ( ) ( + )
𝑃𝑉

𝐠
𝓜 𝟖𝟒 𝟑𝟒
𝐦𝐨𝐥

The Partial Pressure of a Gas in a Mixture of Gases

The ideal gas law holds for virtually any gas, whether pure or a mixture, at ordinary conditions for two reasons:
 Gases mix homogeneously (form a solution) in any proportions.
 Each gas in a mixture behaves as if it were the only gas present (assuming no chemical interactions).

Dalton's Law of Partial Pressures

John Dalton observed that when water vapor is added to dry air, the total air pressure increases by an increment
equal to the pressure of the water vapor:

In other words, each gas in the mixture exerts a partial pressure, a portion of the total pressure of the mixture
that is the same as the pressure it would exert by itself. This observation is formulated as Dalton's law of partial
pressures: in a mixture of unreacting gases, the total pressure is the sum of the partial pressures of the individual
gases:

1 + + 3 +

As an example, suppose you have a tank of fixed volume that contains nitrogen gas at a certain pressure, and
you introduce a sample of hydrogen gas into the tank. Each gas behaves independently, so we can write an
ideal gas law expression for each:

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Because each gas occupies the same total volume and is at the same temperature, the pressure of each gas
depends only on its amount, n. Thus, the total pressure is

( + )
+ +

Each component in a mixture contributes a fraction of the total number of moles in the mixture, which is the mole
fraction (X) of that component. Multiplying X by 100 gives the mole percent. Keep in mind that the sum of the
mole fractions of all components in any mixture must be 1, and the sum of the mole percent must be 100%. For
N2, the mole fraction is

The total pressure is due to the total number of moles, so the partial pressure of gas A is the total pressure
multiplied by the mole fraction of A, XA:

EXAMPLE 5.8
In a study of O2 uptake by muscle at high altitude, a physiologist prepares an atmosphere consisting of 79 mole % N 2, 17 mole %
16O2, and 4.0 mole % 18O2. (The isotope 18O2 will be measured to determine O 2 uptake.) The total pressure is 0.75 atm to

simulate high altitude. Calculate the mole fraction and partial pressure of 18O2 in the mixture.

SOLUTION
To solve for the mole fraction of 18
⬚O , we use the formula below

𝑛18O
⬚
𝑋18O
⬚ 𝑛

𝑿𝟏𝟖𝐎𝟐 𝟎 𝟎𝟒
⬚

Solving for the partial pressure of 18

⬚O ,

𝑃 18O 𝑋18O 𝑃
⬚ ⬚
𝑷𝟏𝟖𝐎𝟐 𝟎 𝟎𝟑 𝐚𝐭𝐦
⬚

THE IDEAL GAS LAW AND REACTION STOICHIOMETRY

From the balanced equation, we used stoichiometrically equivalent molar ratios to calculate the amounts (moles)
of reactants and products and converted these quantities into masses, numbers of molecules, or solution
volumes.

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EXAMPLE 5.9
Hot H2 can reduce copper (II) oxide, forming the pure metal and H 2O. What volume of H2 at 765 torr and 225°C is needed to
reduce 35.5 g of copper (II) oxide?

SOLUTION
First, we need to write and balance the chemical equation
C O+ →C + O

To solve for the volume of H2 produced, we need to determine first the number of moles.

C O
C O
( + ) C O C O

Using the ideal gas law to solve for its volume, we have
𝑃𝑉 𝑛𝑅𝑇

𝑛𝐻 𝑅𝑇𝐻 ( + )
𝑉𝐻
𝑃𝐻

𝑽𝑯𝟐 𝟏𝟖 𝟏𝟑 𝐋

EXAMPLE 5.10
What mass of potassium chloride forms when 5.25 L of chlorine gas at 0.950 atm and 293 K reacts with 17.0 g of potassium?

SOLUTION
The problem requires for the mass of potassium chloride that will form. To do this, we need to write and balance the chemical
equation first.
+C → C

Next, we need to determine the number of moles of chlorine gas at 0.950 atm and 293 K. Using the ideal gas law, we have

𝑃𝐶𝑙 𝑉𝐶𝑙 9 ( )
𝑛𝐶𝑙 C
𝑅𝑇𝐶𝑙 ( 9 )

We also need to determine which of the following reactants is limiting.

C
C C 𝐥𝐢𝐦𝐢𝐭𝐢𝐧𝐠
C

C
C
9

Lastly, we need to convert the number of moles of potassium chloride produced into number of grams.

( 9 + ) C
C 𝟑𝟎 𝟗𝟏 𝐠 𝐊𝐂𝐥
C

GRAHAM’S LAW OF EFFUSION

Effusion is a process in which gas molecules pass through a small opening in a container from a region
of high pressure to one of low pressure. Graham examined the rate of this process in 1829 and observed that
under the same conditions the relative rates of effusion of two gases at the same temperature are inversely
proportional to the square root of their densities. Since the densities of gases are directly proportional to their

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atomic or molecular weights, Graham’s Law may be stated: The rate of effusion of a gas is inversely
proportional to the square root of the atomic or molecular weight. For two gases the mathematical relationship is

1 √
√
√ 1 1

where r1 and r2 represent the rates of effusion of the two gases and m1 and m2 are the corresponding atomic or
molecular weights.

NOTE: The gas with the lower molar mass effuses faster because the most probable speed of its
molecules is higher; therefore, more molecules escape per unit time.

EXAMPLE 6.11
A compound of oxygen and sulfur effuses at a rate that is one quarter that of helium. What is the molecular weight of the
compound?

SOLUTION
To solve this, we let
𝑚1 w h h p y
𝑟1 h p y
𝑚 w h h
𝑟 h
𝑟1 𝑟
Using Graham’s Law, we have
𝑟1 𝑚
√
𝑟 𝑚1

𝑟 𝑚
√
𝑟 𝑚1

𝑟 𝑚
√
𝑟 𝑚1

𝑚
𝑚1

𝑚
𝑚1 𝟔𝟒 𝟎𝟓 𝐠 𝐦𝐨𝐥

EXERCISES:

1. On a cool, rainy day, the barometric pressure is 725 mmHg. Calculate the barometric pressure in
centimeters of water (cmH20) (ρ of Hg = 13.5 g/mL; ρ of H20 = 1.00 g/mL).

2. Convert the following:

a. 0.745 atm to mmHg
b. 365 kPa to atm
c. 74.8 cmHg to atm

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d. 8.50 atm to bar

e. 992 torr to bar
f. 804 mmHg to kPa
g. 27.0 atm to kPa
h. 0.907 kPa to torr

3. A sample of sulfur hexafluoride gas occupies a volume of 5.10 L at 198°C. Assuming that the pressure
remains constant, what temperature (in °C) is needed to reduce the volume to 2.50 L?

4. You have 207 mL of chlorine trifluoride gas at 699 mmHg and 45°C. What is the mass (in g) of the
sample?

5. How many moles of gaseous arsine (AsH3) will occupy 0.0400 L at STP? What is the density of
gaseous arsine?

6. When 0.600 L of Ar at 1.20 atm and 227°C is mixed with 0.200 L of O 2 at 501 torr and 127°C in a 400-
mL flask at 27°C, what is the pressure in the flask?

7. How many grams of phosphorus react with 35.5 L of O2 at STP to form tetraphosphorus decaoxide?
+ → 1

8. Aluminum reacts with excess hydrochloric acid to form aqueous aluminum chloride and 35.8 mL of
hydrogen gas over water at 27°C and 751 mmHg. How many grams of aluminum reacted?

9. At a given pressure and temperature, it takes 4.55 min for a 1.5-L sample of He to effuse through a
membrane. How long does it take for 1.5 L of F2 to effuse under the same conditions?

10. How many moles of aluminum metal are required to produce 4.04 L of hydrogen gas at 1.11 atm and
27°C and by reaction with HCl?

11. Calculate the final volume of a sample of gas initially occupying 355 mL after its pressure is increased
25% and its absolute temperature is decreased 10.0%.

NOTE: All Examples and Exercise Problems used in this module is taken from
the textbook Fundamentals of Chemistry by David E. Goldberg.

References:
Silberberg, Martin S. (2007). Principles of General Chemistry. 1st Edition
Goldberg, David E. (2007). Fundamentals of Chemistry. 5th Edition
The Periodic Table of Elements

Rubric No. 1 Assessing and Grading of Ability to Perform Mathematical Computations

Level 100% 70% 40% 0%
Criteria* Does not meet
Exceeds expectations Meets expectations Needs improvement
expectations
Mathematical The task is worked out The task is worked out The task is worked An insignificant
Content to completion, the steps to completion and out partially and the amount of the task is
(70%) shown are steps shown are steps shown are done, and/or the

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Mechanical Engineering Department, College of Engineering and Architecture [email protected]
CHEMISTRY FOR ENGINEERS
Hand-out No. 5: Gases

mathematically error- mathematically error- correct and could steps shown are
free, and the result is free; the result is potentially lead to a mathematically
correct and expressed correct but still correct result if wrong, unrelated or
in its required form. requires one or two worked through. inappropriate.
steps to bring it to its
required form.
The output is submitted The output is The output is The output is
Timeliness on time. submitted a day after submitted two days submitted eight days
(30%) the set deadline. to a week after the after the set deadline.
set deadline.

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Mechanical Engineering Department, College of Engineering and Architecture [email protected]