JEE MAIN AND ADVANCED Chapterwise PYQ Chemistry Prabhat Publication PDF

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Dr k g ojha
PhD, Rajasthan University, Jaipur
Retd Prof/HOD of Pure & Applied Chemistry
MDS University, Ajmer
Dr sUNITA
M Sc, M Tech, PhD, IIT Delhi
Asst Prof, Delhi University
Prabhat
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2019
JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

by Dr K G Ojha & Dr Sunita
Published by Prabhat Paperbacks

4/19 Asaf Ali Road, New Delhi–110 002
PREFACE
People seek careers in science or engineering for many reasons. Some have specific goals, some wish to cure diseases
or combat hunger or reduce pollution; or they dream of developing the next laser, transistor, or vehicle for space travel;
or they imagine building companies that capitalise on new engineering capabilities. Some choose careers in science or
engineering because they are curious about the natural world. Others are motivated by the excitement and beauty of
the intellectual world and hope to formulate theories that will lead to new ways of thinking about the world. Careers in
science and engineering are essentially hope-filled endeavours that can improve people’s lives and result in knowledge
that all people can share. As the techniques and products of science and technology have become more central to modern
society, a background in science and engineering has become essential to more and more careers.
Knowing what you value and desire, along with an assessment of your strengths and weaknesses, makes it possible
to establish personal goals. Most people already have a mix of short-term and long-term goals of some type in mind for
themselves. It is not unusual for short-term goals to support long-term goals. For example, a student’s long-term goal
to get in IIT-JEE might be supported by a series of short-term goals related to class attendance, studies habits, project
preparation, academic test performance and commitment to outside activities. JEE is a national level engineering entrance
exam for admission in some of the leading technical institutes of the country. This exam is at undergraduate level and is
divided into two parts – JEE Main and JEE Advanced. Candidates will first have to appear in JEE Main and qualify it.
In JEE Main, approximately 55% of the paper comes from class 12 while 45% of the paper comes from class 11
syllabus. JEE Main is the national level entrance test for the engineering students through IIT/NITs. Competition is
getting tough, with lakhs of students appearing every year. As per the information shared by the national testing agency
(NTA) a total of about 1 million candidates appeared for JEE Main last year. NCERT books are very important for board
examination as well as JEE Main. In JEE Main January exam, a lot of questions in Physics, Chemistry and Mathematics
were directly taken from NCERT books. Students who secured rank among Top 2.5 Lakh in JEE Main were allowed to
appear for JEE Advanced. Therefore, due to increase in a number of candidates to be shortlisted for JEE Advanced, the
cutoff marks of JEE Main can be low in comparison with last year.
Apart from subject knowledge, mock test helps to make a sound strategy for a good rank. Strategy helps you to
identify the topics you need to pick first, which questions need to be skipped, topics where you need to devote more time
etc. Mock tests help you to identify these sections which can be attempted effortlessly along with the required areas of
improvement. Speed and accuracy plays a vital role to increase your performance in the JEE Main exam. To get a good
rank and desired college through JEE Main, it becomes important to prepare well and practice enough. One of the best
methods to practice is attempting online mock tests.
Facing examinations, tests, competitions, interviews can help you to conquer with confidence and ease. If you have
‘will’, victory is yours. If you show courage, you can make the conquest. This “chapter-wise solved papers” book will
help you to discover hidden strength, latent power, forgotten talents, and untapped potentialities and also help you to
rediscover yourself. Each chapter begins with a ‘Quick Look’ setting the purpose to know the approach of concepts and
analytical view through solved problems. The JEE Main and Advanced demand that students have a sound knowledge of
the subject so that they can solve new types of problems. New ideas, practical tools and study strategies are essential not
only to attain success in JEE, but also a good rank. The most important element to prepare for any exam is good study
materials. Following the right JEE study material is very important for preparing for the examination. NCERT are the
best JEE books to prepare for the exam and good practice of previous years' questions which aspirants can pursue while
preparing for this Examination.
When you get into IIT or Engineering College and people ask you how you succeeded, make sure you drop me a line,
as well suggestions for the improvement of the book on [email protected]
I would like to read from you or to hear on 9462961150. May this book serve you as your lighthouse, compass and
map on your journey to the IIT! It is hoped that students will find the book useful in their preparation for JEE Main and
Advanced as well for other engineering entrance examinations.
You could be a successful student!
Forever striving for your success
JEE MAIN AND Advanced EXAM PATTERN

JEE Main Exam Pattern
The National Testing Agency (NTA) has released the official paper pattern of JEE Main. This year, Paper I and Paper
II will be conducted in two shifts per day. With that, Paper I will be held in fully computer-based mode for B Tech/ B E
aspirants, while Paper II will be partly computer-based (mathematics and aptitude test) and partly pen and paper based
(drawing test) for B Arch/ B Planning.
Paper I will comprise of objective type questions based on Mathematics, Chemistry, and Physics having equal
weightage in the total of 360 marks. Whereas, Paper II of JEE Main will be for 390 marks based on Mathematics,
Aptitude and Drawing skills. According to NTA now Papers I and II will be conducted in two shifts per day. Also, Paper
1 is being held in complete computer-based mode, while Paper II is conducted partly computer-based (mathematics and
aptitude test) and partly pen and paper based (drawing test).
From 2019, National Testing Agency (NTA) is conducting JEE Main twice a year in January and April, Paper I to be
held in computer-based mode only in 8 different slots and Paper II in two slots.
JEE Main 2019 Exam Pattern–Paper I
Parameters Particulars
Exam Mode Computer-based test mode
Exam Duration 3 hours
Subjects Physics, Chemistry, and Mathematics
Total Number of Questions 90 (Each subject will have 30 questions)
Type of Questions Objective having 4 options each with only 1 correct option
4 marks will be awarded for every correct response; for the incorrect response, 1 mark
Marking Scheme
will be deducted. No marks will be given for unattempted questions.
Maximum Marks Total of 360 Marks
English or Hindi (Candidates from Gujarat, Daman & Diu and Dadra and Nagar
Medium of Paper
Haveli can opt for Gujarati as well)
JEE Main Exam Pattern 2019–Paper II
Parameters Particulars
Mathematics and Aptitude test will be computer-based, whereas Drawing test will be
Exam Mode
conducted in the pen-and-paper mode
Exam Duration 3 hours
Subjects Mathematics, General Aptitude, and Drawing skills
Total Number of Questions 83 (Mathematics 30 questions, Aptitude 50 and Drawing 3)
Mathematics and Aptitude will be objective type while Drawing section will have
Type of Questions
questions to test the drawing and sketching skills
4 marks will be awarded for every correct response; for incorrect response 1 mark will
Marking Scheme
be deducted. No marks will be given for unattempted questions.
Total of 390 Marks (Drawing section will be of total 70 marks, marking of every
Maximum Marks
question will be given along with it.
English or Hindi (Candidates from Gujarat, Daman & Diu and Dadra and Nagar Haveli
Medium of Paper
can opt for Gujarati as well)
Candidates can also make use of the opportunity to practice before the exam as NTA has established a network of test
practice centres for students. NTA has identified various Schools/Engineering colleges where these Test Practice Centres
(TPC) has been opened for the JEE aspirants to get familiar with the computer-based exam pattern. To practice mock tests
in these centres, candidates will have to register first.
viii
JEE Advanced Exam Pattern

The computer-based exam consists of 2 papers–Paper I and Paper II of 3 hours duration each. Both the papers are
compulsory. There is no fixed pattern of the exam. The conducting body always surprises students taking the exam.
In JEE Advanced, the questions asked in the question paper are quite tough and quite tricky. The exam is further
designed to judge not just theoretical knowledge but also reasoning ability, comprehension skills and analytical
power of the students. Therefore, it is important to get familiar with the exam early on.
The exam is held in an online mode (computer-based test) where students need to have a basic knowledge
about the working of a computer and the mouse. Candidates have to use the mouse to click on the right option as
the answer.
JEE Advanced General Information
Exam Name JEE Advanced
Organising Insitute IIT
Mode of Examination Computer Based
Medium of Examination English/Hindi
Number of Papers 2 – Paper I and II
Number of Sections 3 – Physics, Chemistry and Mathematics
Time Duration of Exam 3 hours each paper
Types of Question Numerical and Objective Type
NOTE: The number of questions in JEE Advanced is not fixed. They vary every year. So, maximum marks cannot
be defined. JEE Advanced Exam Pattern can be like earlier years.
JEE Advanced Exam Pattern - Paper I
Pattern Section 1 Section 2 Section 3
Question Type One or more correct options Single digit integer Single option is correct
JEE Advanced Exam Pattern - Paper II

Pattern Section 1 Section 2 Section 3
Question Type One or more correct options Single digit integer Single option is correct
An Analysis of the IIT-JEE

The complexity of the IIT-JEE arises from the fact that the questions are always unique in their context, and solving
them often requires a combination of concepts from across different chapters. Nonetheless, some basic data analysis
can be quite revealing and could give some important insights into how one should go about preparing for each
subject. Such analyses form the basis of our understanding of the JEE. The section-wise percentage of breakup of
marks in the past years JEE mains and advance has been given below for your reference.
Class Physics Chemistry Math Total

Class 12 58% 67% 55% 60%
Class 11 42% 33% 45% 40%
Questions Toughness Level Percentage wise:

Toughness level Physics Chemistry Math Total
Difficult 35 24 30 30
Moderate 40 50 45 45
Easy 25 26 25 25
The problems and examinations in the chemistry

discipline not only test your knowledge of
chemistry but also enhance your skills in solving
problems. This book contains Quick Look of last
years solved papers of chemistry and mock tests
for honing your skills and become confident and
versatile problem-solver.
IIT-JEE Syllabus: Chemistry

Section-A: Physical Chemistry angular momentum and magnetic quantum number)
and their significance; shapes of s, p and d–orbitals,
Unit 1: Some Basic Concepts in Chemistry: Matter
electron spin and spin quantum number; Rules for filling
and its nature, Dalton’s atomic theory; Concept of atom,
molecule, element and compound; physical quantities electrons in orbitals - Uufbau principle, Pauli’s exclusion
and their measurements in Chemistry, precision and principle and Hund’s rule, electronic configuration of
accuracy, significant figures, S.I. Units, dimensional elements, extra stability of half-filled and completely
analysis; Laws of chemical combination; Atomic and filled orbitals.
molecular masses, mole concept, molar mass, percentage Unit 4: Chemical Bonding and Molecular Strucure:
composition, empirical and stoichiometry. Kossel-Lewis approach to chemical bond formation,
Unit 2: States of Matter: Classification of matter into concept of ionic and covalent bonds.
solid, liquid and gaseous states. Ionic Bonding: Formation of ionic bonds, factors
Gaseous State: Measurable properties of gases; Gas affecting the formation of ionic bonds; calculation of
laws—Boyle’s law, Charle’s, law, Graham’s law of lattice enthalpy
diffusion, Avogadro’s law, Dalton’s law of partial Covalent Bonding: Concept of electronegativity, Fajan’s
pressure; Concept of Absolute scale of temperature; ideal rule, dipole moment; Valence Shell Electron Pair Repulsion
gas equation; Kinetic theory of gases (only postulates); (VSEPR) theory and shapes of simple molecules.
Concept of average, root mean square and most probable
velocities; Real gases, deviation from Ideal behaviour, Quantum Mechanical Approach to Covalent Bonding:
compressibility factor and van der Waals equation. Valence bond theory - Its important features, concept of
hybridisation involving s, p and d orbitals; Resonance.
Liquid State: Properties of liquids-vapour pressure,
viscosity and surface tension and effect of temperature Molecular Orbital Theory: Its important features,
on them (qualitative treatment only). LCAOs, types of molecular orbitals (bonding,
antibonding), sigma and pi-bonds, molecular orbital
Solid State: Classification of solid: molecular, electronic configurations of homonuclear diatomic
ionic, covalent and metallic solids, amorphous and molecules, concept of bond order, bond length and bond
crystalline solids (elementary idea); Bragg’s Law and energy. Elementary idea of metallic bonding. Hydrogen
its applications; Unit cell and lattices, packing in solids bonding and its applications.
(fcc, bcc and hcp lattices), voids, calculations involving
unit cell parameters, imperfection in solids; Electrical Unit 5: Chemical Thermodynamics: Fundamentals of
and magnetic properties. thermodynamics: System and surroundings, extensive
and intensive properties, state functions, types of
Unit 3: Atomic Structure: Thomson and Rutherford processes.
atomic models and their limitations: Nature of
electromagnetic radiation, photoelectric effect; First Law of Thermodynamics: Concept of work,
Spectrum of hydrogen atom, Bohr model of hydrogen heat internal energy and enthalpy, heat capacity, molar
atom—its postulates, derivation of the relations for heat capacity; Hess’s law of constant heat summation;
energy of the electron and radii of the different orbits, Enthalpies of bond dissociation, combustion, formation,
atomisation, sublimation, phase transition, hydration,
limitations of Bohr’s model; Dual nature of matter, de-
ionisation and solution.
Broglie’s relationship, Heisenberg uncertainty principle.
Elementary ideas of quantum mechanics, model of atom, Second Law of Thermodynamics: Spontaneity of
its important features. Concept of atomic orbitals as one processes; S of the universe and G of the system as
electron wave functions; Variation of and with r for criteria for spontaneity, G° (Standard Gibbs energy
1s and 2s orbitals; various quantum numbers (principal, change) and equilibrium constant.
xii
Unit 6: Solutions: Different methods for expressing Unit 9: Chemical Kinetics: Rate of a chemical reaction,
concentration of solution-molality, molarity, mole factors affecting the rate of reactions: concentration,
fraction, percentage (by volume and mass both), vapour temperature, pressure and catalyst; elementary and
pressure of solutions and Raoult’s Law—Ideal and non- complex reactions, order and molecularity of reactions,
ideal solutions, vapour pressure- composition, plots for rate law, rate constant and its units, differential nad
ideal and non-ideal solutions; Colligative properties of integral forms of zero and first order reactions, their
dilute solutions-relative lowering of vapour pressure, characteristics and half-lives, effect of temperature on
depression of freezing point, elevation of boiling point rate of reactions—Arrhenius theory, activation energy
and osmotic pressure; Determination of molecular mass and its calculation, collision theory of bimolecular
using colligative properties; Abormal value of molar gaseous reaction (no derivation).
mass, van’t Hoff factor and its significance.
Unit 10: Surface Chemistry:Adsorption: Physisorption
Unit 7: Equilibrium: Meaning of equilibrium, concept and chemisorptions and their characteristics, factors
of dynamic equilibrium. affecting adsorption of gases on solids-Freundlich
Equilibrium Involving Physical Processes: Solid- and Langmuir adsoption isotherms, adsorption from
liquid, liquid – gas and solid – gas equilibria, Henry’s solution.
law, general characterics of equilibrium involving Catalysis: Homogeneous and heterogeneous, activity
physical processes. and selectivity of solid catalysts, enzyme catalysis and
Equlibria Involving Chemical Processes: Law of its mechanism.
chemical equilibrium, equilibrium constants (Kp and Colloidal State: Distinction among true solutions,
Kc) and their significance, significance of and in colloids and suspensions, classification of colloids-
chemical equilibria, temperature, effect of catalyst; Le lyophilic, lyophobic; multimolecular, macromolecular
Chateliers’ principle. and associated colloids (micelles), preparation and
Ionic Equilibrium: weak and strong electrolytes, properties of colloids—Tyndall effect, Brownian
ionisation of electrolytes, various concepts of acids movement, electrophoresis, dialysis, coagulation and
and bases (Arrhenius, Lowry and Lewis) and their flocculation; Emulsions and their characteristics.
ionisation, acid-base equilibria (including multistage Section-B: Inorganic Chemistry
ionisation) and ionisation constants, ionisation of water,
Unit 11: Classification of Elements and Periodicity in
pH scale, common ion effect, hydrolysis of salts and pH
Properties: Modem periodic law and present form of
of their solutions, solubility of sparingly soluble salts
the periodic table, s, p, d and f-block elements, periodic
and solubility products, buffer solutions.
trends in properties of elements atomic and ionic radii,
Unit 8: Redox Reactions and Electrochemistry: ionisation enthalpy, electron gain enthalpy, valence,
Electronic concepts of oxidation and reduction, redox oxidation sates and chemical reactivity.
reactions, oxidation number, rules for assigning
Unit 12: General Principles and Processes of Isolation
oxidation number, balancing of redox reactions.
of Metals: Modes of occurrence of elements in nature,
Eectrolytic and metallic conduction, conductance in
minerals, ores; Steps involved in the extraction of metals-
electrolytic solutions, molar conductivities and their
concentration, reduction (chemical and electrolytic
variation with concentration: Kohlrausch’s law and its
methods) and refining with special reference to the
applications. Electrochemical cells—Electrolytic and
extraction of Al, Cu, Zn and Fe; Thermodynamic and
Galvanic cells, different types of electrodes, electrode
electrochemical principles involved in the extraction of
potentials including standard electrode potential, half- metals.
cell and cell reactions, emf of a Galvanic cell and its
measurement; Nernst equation and its applications; Unit 13: Hydrogen: Position of hydrogen in periodic
Relationship between cell potential and Gibbs’ energy table, isotopes, preparation, properties and uses of
change; Dry cell and lead accumulator; Fuel cells. hydrogen; Physical and chemical properties of water
xiii
and heavy water; Structure, preparation, reactions and Group-18: Occurrence and uses of noble gases;
uses of hydrogen peroxide; Classification of hydrides- Structures of fluorides and oxides of xenon.
ionic, covalent and interstitial; Hydrogen as a fuel.
Unit 16: d-and f-Block Elements:
Unit 14: S-Block Elements (Alkali and Alkaline
Transition Elements: General introduction, electronic
Earthmetals:
configuration, occurrence and characteristics, general
Group-1 and 2 Elements: General introduction, trends in properties of the first row transition elements
electronic configuration and general trends in physical – physical properties, ionisation enthalpy, oxidation
and chemical properties of elements, anomalous states, atomic radii, colour, catalytic behaviour, magnetic
properties of the first element of each group, diagonal properties, complex formation, interstitial compounds,
relationships. alloy formation; Preparation, properties and uses of its
Preparation and properties of some important compounds elements.
– sodium carbonate and sodium hydroxide and sodium Inner Transition Elements:
hydrogen carbonate; Industrial uses of lime, limestone,
Lanthanoids – Electronic configuration, oxidation states
Plaster of Paris and cement; Biological significance of
and lanthanoid contraction.
Na, K, Mg and Ca.
Actinoids – Electronic configuration and oxidation
Unit 15: P-Block Elements:
states.
Group-13 to Group 18 Elements: General introduction-
Unit 17: Coordination Compounds: Introduction to
Electronic configuration and general trends in physical
coordination compounds, Werner’s theory; ligands,
and chemical properties of elements across the periods
coordination number, denticity, chelation; IUPAC
and down the groups; unique behaviour of the first
nomenclature of mononuclear coordination compounds,
element in each group.
isomerism; Bonding-Valence bond approach and basic
Groupwise Study of the p-Block Elements ideas of Crystal field theory, colour and magnetic
Group-13: Preparation, properties and uses of boron properties; Importance of coordination compound (in
and aluminium; Structure, properties and uses of borax, qualitative analysis, extraction of metals and in biological
boric acid, diborane, boron trifluoride, aluminium systems).
chloride and alums.
Unit 18: Environmental Chemistry:
Group-14: Tendency for catenation; Structure,
Environmental Pollution: Atmospheric, water and soil.
properties and uses of Allotropes and oxides of carbon,
silicon tetrachloride, silicates, zeolites and silicones. Atmospheric Pollution: Tropospheric and Stratospheric
Group-15: Properties and uses of nitrogen and Tropospheric Pollutants – Gaseous Pollutants: Oxides
phosphorus; Allotropic forms of phosphorus; Preparation, of carbon, nitrogen and sulphur, hydrocarbons; their
properties, structure and uses of ammonia, nitric acid, sources, harmful effects and prevention; Greenhouse
phosphine and phosphorus halides; Structures of oxides effect and Global warming; Acid rain;
and oxoacids of nitrogen and phosphorus. Particulate Pollutionts: Smoke, dust, smog, fumes,
Group-16: Preparation, properties, structures and mist; their sources, harmful effects and prevention.
uses of ozone; Allotropic forms of sulphur; properties,
Stratospheric Pollution: Formation and breakdown of
structures and uses of sulphuric acid (including its
ozone, depletion of ozone layer – its mechanism and
industrial preparation); Structures of oxoacids of
effects.
sulphur.
Group-17: Preparation, properties and uses of Water Pollution: Major pollutants such as: Pesticides
hydrochloric acid; Trends in the acidic nature of (insecticides, herbicides and fungicides), their harmful
hydrogen halides; Structures of interhalogen compounds effects and prevention.
and oxides and oxoacids of halogens. Strategies to control environmental pollution.
xiv
Section-C: Organic Chemistry Alkynes: Acidic character; Addition of hydrogen,

halogens, water and hydrogen halides; Polymerisation.
Unit 19: Purification and Characterisation of
Organic Compounds: Aromatic hydrocarbons: Nomenclature, benzene-
Purification: Crystallisation, sublimation, distillation, structure and aromaticity; Mechanism of electrophilic
differential extraction and chromatography-principles substitution: halogenations, nitration, Friedel-Craft’s
and their applications. alkylation and acylation, directive influence of functional
group in mono-substituted benzene.
Qualitative Analysis: Detection of nitrogen, sulphur,
phosphorous and halogens. Unit 22: Organic Compounds Containing Halogens:
General methods of preparation, properties and reactions;
Quantitative Analysis: (basic principles only) – Nature of C-X bond; Mechanisms of substitution
Estimation of carbon, hydrogen, nitrogen, halogens, reactions.
sulphur, phosphorous.
Uses; Environmental effects of chloroform, iodoform
Calculations of empirical formulae and molecular
freons and DDT.
formulae; Numerical problems in organic quantitative
analysis. Unit 23: Organic Compounds Containing Oxygen:
General methods of preparation, properties, reactions
Unit 20: Some Basic Principles of Organic Chemistry: and uses.
Tetravalency of carbon; Shapes of simple molecules
Alcohols, Phenols and Ethers
– hybridisation (s and p); Classification of organic
compounds based on functional groups: and those Alcohols: Identification of primary, secondary and
containing halogens, oxygen, nitrogen and sulphur; tertiary alcohols; mechanism of dehydration.
Homologous series; Isomerism – structural and
Phenols: Acidic nature, electrophilic substitution
stereoisomerism.
reactions: halogenations, nitration and sulphonation,
Nomenclature (Trivial and IUPAC) Reimer-Tiemann reaction.
Covalent bond fission: Homolytic and heterolytic: Ethers: Structure.
free radicals, carbocations and carbanions; stability
Aldehyde and Ketones: Nature of carbonyl group;
of carbocations and free radicals, electrophiles and
Nucleophilic addition to group, relative reactivities of
nucleophiles.
aldehydes and ketones; Important reactions such as –
Electronic Displacement in a Covalent Bond Nucleophilic addition reactions (addition of HCN, and
its derivaties), Grignard reagent; oxidation; reduction
Inductive effect, electromeric effect, resonance and (Wolff Kishner and Clemmensen); acidity of hydrogen,
hyperconjugation. aldol condensation, Cannizzaro reaction, Haloform
Common types of organic reactions: Substitution, reaction; Chemical tests to distinguish between
addition, elimination and rearrangement. aldehydes and Ketones.
Unit 21: Hydrocarbons: Classification, isomerism, Carboxylic Acids: Acidic strength and factors affecting
IUPAC Nomenclature, general methods of preparation, it.
properties and reactions. Unit 24: Organic Compounds Containing Nitrogen:
Alkanes: Conformations: Sawhorse and Newman General methods of preparation, properties, reactions
projections (of ethane); Mechanism of halogenations of and uses.
alkanes. Amines: Nomenclature, classification, structure, basic
Alkenes: Geometrical isomerism; Mechanism of character and identification of primary, secondary and
electrophilic addition: addition of hydrogen, halogens, tertiary amines and their basic character.
water, hydrogen halides (Markownikoff’s and peroxide Diazonium Salts: Importance in synthetic organic
effect); Ozonolysis and polymerisation. chemistry.
xv
Unit 25: Polymers: General introduction and Unit 28: Principles Related to Practical Chemistry:
classification of polymers, general methods
l Detection of extra elements (N, S, halogens) in
of polymerisation-addition and condensation,
organic compounds; Detection of the following
copolymerisation;
functional group: hydroxyl (alcoholic and phenolic),
Natural and synthetic rubber and vulcanisation; some carbonyl (aldehyde and ketone), carboxyl and amino
important polymers with emphasis on their monomers groups in organic compounds.
and uses—polythene, nylon, polyester and bakelite.
l Chemistry involved in the preparation of the
Unit 26: Biomolecules: General introduction and following:
importance of biomolecules. Inorganic Compounds: Mohr’s salt, potash alum.
Carbohydrates: Classification: aldoses and ketoses; Organic Compounds:Acetanilide, p-nitroacetanilide,
monosaccharides (glucose and fructose) and constituent aniline yellow, iodoform.
monosaccharides of oligosaccharides (sucrose, lactose
and maltose). l Chemistry involved in the titrimetric excercises –
Acids, Bases and the use of indicators, oxalic acid
Proteins: Elementary idea of amino acids, peptide bond, vs. KMnO 4 , Mohr’s salt vs. KMnO 4 .
polypeptides; Proteins: primary, secondary, tertiary and
quaternary structure (qualitative idea only), denaturation l Chemical principles involved in the qualitative salt
of proteins, enzymes. analysis:
Vitamins: Classification and functions. Cations: Pb 2+ , Cu 2+ , A3 , Fe3 , Zn 2+ , Ni 2+ , Ca 2+ , Ba 2+
Nucleic Acids: Chemical constitution of DNA and RNA. Anions: CO 2  , S2  , SO 42  , NO  , NO  , C  , Br  , I  .
3 3 2
Biological functions of nucleic acids. (Insoluble salts excluded).

Unit 27: Chemistry in Everyday Life: Chemicals l Chemical principles involved in the following
in Medicines: Analgesics, tranquilizers, antiseptics, experiments:
disinfectants, antimicrobials, antifertility drugs, 1. Enthalpy of solution of
antibiotics, antacids, antihistamins–their meaning and
common examples. 2. Enthalpy of neutralisation of strong acid and
strong base.
Chemicals in Food: Preservatives, artificial sweetening
agents—common examples. 3. Preparation of lyophilic and lyophobic sols.
Cleansing Agents: Soaps and detergents, cleansing 4. Kinetic study of reaction of iodide ion with
action. hydrogen peroxide at room temperature.
CONTENTS
Preface...................................................................................................................................................................... v
JEE Main and Advanced Exam Pattern...........................................................................................................vii-viii
An Analysis of the IIT-JEE....................................................................................................................................... ix
IIT-JEE Syllabus: Chemistry.............................................................................................................................. xi-xv
1. Stoichiometry................................................................................................................................................ 1–8
2. Solid State.................................................................................................................................................... 9–16
3. Solutions.................................................................................................................................................... 17–26
4. Gaseous State............................................................................................................................................ 27–36
5. Atomic Structure....................................................................................................................................... 37–48
6. Redox......................................................................................................................................................... 49–54
7. Electrochemistry........................................................................................................................................ 55–64
8. Chemical Bonding..................................................................................................................................... 65–74
9. Chemical Equilibrium............................................................................................................................... 75–80
10. Ionic Equilibrium...................................................................................................................................... 81–88
11. Chemical Kinetics................................................................................................................................... 89–100
12. Surface Chemistry................................................................................................................................. 101–106
13. Chemical Thermodynamics................................................................................................................... 107–122
14. Nuclear Chemistry................................................................................................................................. 123–130
15. Some Basic Principles of Organic Chemistry....................................................................................... 131–140
16. Nomenclature and Isomerism................................................................................................................ 141–154
17. Hydrocarbons........................................................................................................................................ 155–166
xviii
18. Alkyl and Aryl Halides.......................................................................................................................... 167–178

19. Alcohols, Phenols and Ethers................................................................................................................ 179–192
20. Aldehydes and Ketones......................................................................................................................... 193–212
21. Carboxylic Acids and their Derivatives................................................................................................. 213–226
22. Nitrogen-containing Compounds.......................................................................................................... 227–242
23. Polymers................................................................................................................................................ 243–246
24. Biomolecules......................................................................................................................................... 247–258
25. Environmental Chemistry & Chemistry in Everyday Life.................................................................... 259–272
26. Chemical Periodicity............................................................................................................................. 273–280
27. Representative Elements: s- and p-Blocks............................................................................................ 281–300
28. Transition Elements: d- and f-Blocks.................................................................................................... 301–308
29. Coordination Compounds...................................................................................................................... 309–322
30. Analytical Chemistry and Experimental Skills..................................................................................... 323–332
MOCK TEST
l
Mock Test – 1........................................................................................................................................ 335–351
l Mock Test – 2........................................................................................................................................ 352–362
l Mock Test – 3........................................................................................................................................ 363–373
l Mock Test – 4........................................................................................................................................ 374–384
l Mock Test – 5........................................................................................................................................ 385–394
Stoichiometry 1
1 Stoichiometry
QUICK LOOK Mass of solute
∴ Moles = M × V(in litre ) . . . (vii)
Moles mass of solute
The concentration of a solution can be expressed in number of
∴ Milli moles = M × V in mL
ways.
Mass of solute
× 1000 . . . (viii)
Normality Molar mass of solute
It is defined as the number of equivalent of a solute present in 1
litre of solution. Note
Equivalent of a solute Eq Moles and milli moles of reactants react according to
N= = . . .(i)
Volume of solution in litre V ( in L ) stoichiometry of equation and give products accordingly.
∵ Equivalent of substance (Eq) Moles
Molarity =
Mass of substance Volume ( in litre )
Eq =
Equivalent mass of substance Equivalent
Normality =
Mass of solute ×100 Volume ( in litre )
N=
Equivalent mass of solute × V in mL M Moles W × Eq. mass 1
∴ = ; =
N ⋅ E ⋅ V ( in mL ) N Equivalent Molar mass × W Valence factor
or W = . . .(ii)
1000 Molarity × Valence factor = Normality . . .(ix)
Equivalent Analytical molarity (usually molarity) and equilibrium
Mass of solute
= N × V ( in litre ) = . . .(iii) molarity are two different terms. Equilibrium molarity
Equivalent mass of solute represents the moles of particular species in 1 litre of
Also, Milli equivalent of solute = N × V ( in mL ) . . .(iv) solutions.
The equilibrium molarity of a strong electrolyte is zero. For
Mass of solute
Meq. of solute N = × 1000 . . .(v) example consider analytical molarity of 1 M HCl. The
Eq. mass of solute
equilibrium molarity of HCl is zero because of 100%
ionisation as.
Note
→ H + + Cl –
HCl 
Equivalent and milli equivalent reacts in equal number to give 1 0 0
the same number of equivalent of milli equivalent of products. 0 1 1
An equivalent represents the mass of material providing
Whereas equilibrium molarities of H + and Cl – and 1 M each.
Avogadro’s number of electrons from reacting unit.
Similarly a solution of a strong electrolyte say Ax By having
Normality of any solute depends up on the nature of
reaction (like equivalent mass) but molarity not. analytical molarity 1 M shows equilibrium molarities of
A x By , A y + and B x- as 0 M, xM and yM respectively.
Molarity: It is defined as the number of moles of solute In case of weak electrolytes (either a weak acid or weak
present in 1 litre of solution. base) analytical molarity of CHA has the equilibrium
M=
Moles of a solute molarities of HA, H + and A− are C (1 − α ) , Cα and Cα
Volume of solution in litre
respectively. Since it shows partial dissociation
Mass of solute × 1000
M= HA ↽ ⇀ H + + A−
Molar mass of solute × V (in mL) 1 α 0 ( α is a degree of dissociation)
Molarity × Molar mass × V ( in mL ) 1−α α α
W= . . .(vi) In case of non electrolytes analytical molarity and
1000 in mL
equilibrium molarity are same.
2 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

Molality: It is defined as number of moles of solute present in 20°C, then (since density of water at 20°C is 0.99823 g /
1 kg of solvent. mL) Density = specific gravity × 0.99823.
Moles of solute
m= . . .(x)
Mass of solute in kg Mole Fraction
Mass of solute × 1000 Mole fraction of solute ( X A )
m= . . .(xi)
Molar mass of solute × Mass of solvent in gram
Moles of solute
Mass of solvent = mass of solution – mass of solute ( XA ) =
Total moles present in solution
Moles of solute n
Note = =
Moles of solute + Moles of solvent n + N
Molarity, normality and molality are extensive properties.
Mole fraction of solvent ( X B )
Strength of Solution: It is expressed as amount of solute (in g) Moles of solvent
in 1 litre of solution. (XB ) =
Total moles present in solution
Mass of solute w
S= = . . .(xii) Moles of solvent N
Volume of solution in litre V ( in L ) = =
Moles of solute + Moles of solvent n + N
w S
∵ N= = . . .(xiii) n w/m
E×V ( in L ) E Also, X A = = . . .(xviii)
n + N (w / m) + (W / M)
Also, S = N × E or S = M × Molar mass . . .(xiv)
N W/M
XB = = . . .( xix)
n + N (w / m) + (W / M)
In Terms of Percentage
Mass of solute × 100 Also, for a binary system X A + X B = 1 . . .( xx)
% by mass (or w/w) = . . .( xv)
Mass of solution i.e., sum of all the mole fractions in a solution is unity.
Volume of solute × 100 XA n
% by strength (or V/V) = . . .( xvi) Also, = . . .( xxi)
Volume of solution XB N
Mass of solute × 100
% by volume (or mass/volume) = . .( xvii)
Volume of solution Note
A solution is 65% by… Molality, % by mass, mole fractions are independent of
65% by mass, i.e., 100 g solution has 65 g solute temperature since all these involve mass which does not
65% by strength, i.e., 100 mL solution has 65 mL solute depend upon temperature.
65% by volume, i.e., 100 mL solution has 65 g solute Standard solution: The solution whose molarity or
normality is known. A standard solution is prepared by
Note dissolving an accurately weighed quantity of a highly pure
Use of specific gravity: Specific gravity term is used for material called a primary standard (e.g., oxalic acid, Borax
density in case of solution. The term ‘density’ refers for the (Na 2 B4 O7 ⋅10 H 2 O) Na 2 CO3 ⋅10 H 2 O and potassium acid
ratio (mass/volume) for pure solvent. phthalate, etc.) and diluting to an accurately known volume
Mass of solvent of solution. If the material is not sufficiently pure (e.g.,
Density=
Volume of solvent NaOH) a solution is prepared to give approximately the
i.e., density is the mass of 1 mL of solvent. desired concentration and this is standardized by titrating a
Density is the mass per unit volume at the specified weighed quantity of primary standard. Such solutions are
temperature, usually g/mL or g/cm3 at 20°C. Specific called secondary standard.
gravity is defined as the ratio of the mass of a solution at Normal or Molar solution: Solution having normality = 1
20°C, to the mass of an equal volume of water at 4°C (or N or molarity = 1 M respectively.
sometimes 20°C). Thus, specific gravity is a dimensionless On diluting a solution: Normality, molarity and molality
quantity. The density of water at 4°C is 1.0000 g / mL . change with dilution whereas, equivalent, milliequivalent,
Density and specific gravity are equal when referred to moles or milli moles of solute do not change or during
water at 4°C. When specific gravity is referred to water at dilution conservation of moles of solute take place.
Stoichiometry 3
The volume of a liquid increases with temperature. It is 3. The number of sodium atoms in 2 moles of sodium
therefore, 5 litre of C6 H6 masses more in winter than in ferrocyanide is
summer. a. 12 ×1023 b. 26 ×1023
c. 34 ×1023 d. 48 ×1023
Formality: Some confusion can arise concerning the molar
mass of substances in which no discrete molecule exists. For 4. How many moles of electron weighs one kilogram?
example in ionic solids say NaCl, there are no identifiable 1
a. 6.023 × 10 23 b. × 10 31
+ − 9.108
NaCl molecules, only ions of Na and Cl are present. In such
cases the term formula mass is used which refers for sum of 6.023 1
c. × 10 54 d. × 10 8
masses of each ion present in one molecule and therefore, the 9.108 9.108 × 6.023
molar mass of NaCl mean only the mass of material that 5. Which has maximum number of atoms?
contains 6.023 ×1023 ions of each type and carry no implication a. 24 g of C (12) b. 56 g of Fe (56)
about the existence of molecule in crystal. Strictly, we should c. 27 g of Al (27) d. 108 g of Ag (108)
refer to the formula masses in case of ionic molecules.
6. Mixture X = 0.02 mole of [Co (NH3)5SO4] Br and 0.02
Therefore, the concentrations of ionic solids are normally
expressed in terms of formality since neither the substance is mole of [Co (NH3)5 Br] SO4 was prepared in 2 L solution.
composed of molecules nor their molar masses determined 1 L of mixture X + excess of AgNO3 solution →Y
accurately by experiments. We normally use their formula 1 L of mixture X + excess of BaCl2 solution → Z
mass as molar mass. Number of moles of Y and Z are:
Weight of solute a. 0.01, 0.01 b. 0.02, 0.01
Formality = …(xxii)
Formula mass × V(litre) c. 0.01, 0.02 d. 0.02, 0.02
7. Given that the abundances of isotopes 54Fe, 56Fe, and 57Fe,

Note are 5%, 90% and 5%, respectively, the atomic mass of Fe
However the word molar mass are frequently used for
is;
formula mass of such substances.
a. 55.85 b. 55.95
For all practical purposes formality of an ionic compound is
c. 55.75 d. 56.05
its molarity.
8. Dissolving 120 g of urea (mol. wt. 60 g) in 1000 g of
Ionic Strength: The ionic strength ( µ ) of solution obtained by water gave a solution of density 1.15 g/mL. The molarity
mixing two or more ionic compounds is given by: of the solution is:
1 a. 1.78 M b. 2.00 M
µ = ∑ cZ 2 …(xxiii)
2 c. 2.05 M d. 2.22 M
Where, c is the concentration (molarity) of that ion and Z is its
9. The molarity of a solution obtained by mixing 750 mL of
valence.
0.5 (M) HCl with 250 mL of 2 (M) HCl will be:
Multiple Choice Questions a. 0.875 M b. 1.00 M
One and More than One Correct c. 1.75 M d. 0.0975 M
10. The ratio of masses of oxygen and nitrogen of a particular
1. Total number of atoms represented by the compound
gaseous mixture is 1:4. The ratio of number of their
CuSO4.5H2O is : [BHU 2005]
molecule is:
a. 27 b. 21
c. 5 d. 8 a. 1 : 4 b. 7 : 32
c. 1 : 8 d. 3: 16
2. The equivalent weight of phosphoric acid (H 3 PO 4 ) in the
11. 1 gram of a carbonate (M 2 CO 3 ) on treatment with excess
reaction, NaOH + H 3PO4 
→ NaH 2 PO 4 + H 2 O is:
HCl produces 0.01186 mole of CO2. The molar mass of
[BHU 2005] M2CO3 in g mol–1is: [JEE Main 2017]
a. 25 b. 49
a. 11.86 b. 1186
c. 59 d. 98
c. 84.3 d. 118.6

12. The most abundant elements by mass in the body of a 19. The volume strength of 1M H2O2 is:
healthy human adult are: Oxygen (61.4%); Carbon (Molar mass of H2O2 = 34 g mol–1) [JEE Main 2019]
(22.9%); Hydrogen (10.0%); and Nitrogen (2.6%). The a. 16.8 b. 11.35
weight which a 75 kg person would gain if all atoms are c. 22.4 d. 5.6
replaced by 2 H atoms is: [JEE Main 2017]
a. 10 kg b. 15 kg Integer and Subjective
c. 37.5 kg d. 7.5 kg 20. Find the molarity of water. Given: ρ = 1000 kg / m 3
13. The ratio of mass percent of C and H of an organic 21. In a solution 100 mL, 0.5 M acetic acid, one gram of
compound (CXHYOZ) is 6 : 1. If one molecule of the active charcoal is added, which adsorbs acetic acid. It is
above compound (CXHYOZ) contains half as much oxygen found that the concentration of acetic acid becomes 0.49
as required to burn one molecule of compound CXHY M. If surface are of charcoal is 3.01×102 m 2 , calculate the
completely to CO2 and H2O. The empirical formula of
area in 10 −19 m 2 occupied by single acetic acid molecule
compound CXHYOZ is: [JEE Main 2018]
a. C2H4O3 b. C3H6O3 on surface of charcoal.
c. C2H4O d. C3H4O2 22. 20% surface sites have adsorbed N 2 . On heating N 2 . gas
14. 8 g of NaOH is dissolved in 18 g of H2O. Mole fraction of evolved from sites and were collected at 0.001 atm and 298 K
NaOH in solution and molality (in mol kg–1) of the in a container of volume is 2.46 cm3. Density of surface sites is
solutions respectively are: [JEE Main 2019] 6.023 × 1014 / cm 2 and surface area is 1000 cm2, find out the
a. 0.167, 11.11 b. 0.2, 22.20 number of surface sites occupied per molecule of N 2 .
c. 0.2, 11.11 d. 0.167, 22.20
23. Galena (an ore) is partially oxidised by passing air
15. The strength of 11.2 volume solution of H2O2 is: [Given
through it at high temperature. After some time, the
that molar mass of H = 1 g mol–1 and O = 16 g mol–1]
passage of air is stopped, but the heating is continued in a
[JEE Main 2019]
closed furnace such that the contents undergo self-
a. 13.6% b. 3.4% c. 34% d. 1.7%
reduction. The weight (in kg) of Pb produced per kg of O2
16. A mixture of 100 m mol of Ca(OH)2 and 2g of sodium consumed is ______. (Atomic weights in g mol–1:
sulphate was dissolved in water and the volume was made O = 16, S = 32, Pb = 207) [JEE Adv. 2018 P-II]
up to 100 mL. The mass of calcium sulphate formed and
24. To measure the quantity of MnCl2 dissolved in an aqueous
the concentration of OH– in resulting solution,
solution, it was completely converted to KMnO4 using the
respectively, are: (Molar mass of Ca(OH)2, Na2SO4 and
CaSO4 are 74, 143 and 136 g mol–1, respectively; Ksp of reaction, MnCl2 + K2S2 O8 + H2 O → KMnO4 + H2SO4 + HCl
Ca(OH)2 is 5.5 × 10–6) MnCl
MnCl2 +
2 +
KK2 S22SO
[JEE 2O 8++
HH2 O
8 Main 2O→→KMnO
KMnO44 ++ H
2019] H22SO 4 + HCl
HCl (equation not balanced). Few drops of
a. 1.9 g, 0.14 mol L–1 b. 13.6 g, 0.14 mol L–1 concentrated HCl were added to this solution and gently
c. 1.9 g, 0.28 mol L–1 d. 13.6 g, 0.28 mol L–1 warmed. Further, oxalic acid (225 mg) was added in
17. 25 ml of the given HCl solution requires 30 mL of 0.1 M portions till the colour of the permanganate ion
sodium carbonate solution. What is the volume of this disappeared. The quantity of MnCl2 (in mg) present in
HCl solution required to titrate 30 mL of 0.2 M aqueous the initial solution is _____. [JEE Adv. 2018 P-II]
NaOH solution? [JEE Main 2019] (Atomic weights in g mol–1: Mn = 55, Cl = 35.5)
a. 25 mL b. 50 Ml 25. On dissolving 0.5 g of non – volatile, non-ionic to 39 g of
c. 12.5 mL d. 75 mL benzene, its vapour pressure decreases from 650 mm of
18. Freezing point of a 4% aqueous solution of X is equal to Hg. The depression of freezing point of benzene (in K)
freezing point of 12% aqueous solution of Y. If molecular upon addition of the solute is ______.
weight of X is A, then molecular weight of Y is: [JEE Adv. 2019 P-II]
[JEE Main 2019] 26. 1 mole of Rhombic sulphur is treated with conc. HNO3
a. A b. 3A c. 4A d. 2A
Find the mass of H2O formed. [JEE Adv. 2019 P-II]
Stoichiometry 5
Fill in the Blanks 56
Number of atoms in 56 g of Fe = NA = NA
56
27. The value of n in the molecular formula Be n Al2Si 6 O18 is
27
…………… [JEE 2010] Number of atoms in 27 g of Al = NA = NA
27
28. A student performs a titration with different burettes and 108
Number of atoms in 108 g of Ag = NA = NA
finds titre values of 25.2 mL, 25.25 mL, and 25.0 mL. 108
The number of significant figures in the average titre Hence, 24 g of carbon has the maximum number of atoms.
value is …………… [JEE 2010] 6. (a) 1.0L of mixture X contain 0.01 mole of each
29. Silver (atomic weight 108 g mol−1 ) has a density of [(Co(NH 3 )5 SO 4 )] [Co(NH 3 )5 Br]SO 4 . Also, with
10.5gcm−3 . The number of silver atoms on a surface of AgNO3, only [(Co(NH3)5 SO4)] Br reacts to give AgBr
precipitate as
area 10−12 m2 can be expressed in scientific notation as
[Co(NH3 )5 SO4 ]Br + AgNO3 
→
Y × 10− x , The value of x is …………… [JEE 2010] 1.0 mole excess
[Co(NH 3 )5 SO 4 ]NO 3 + AgBr

30. Among the following, the number of elements showing 1.0 mol
only one non-zero oxidation state is…………… With BaCl 2 , only [Co(NH 3 )5 Br]SO 4 reacts giving
O, Cl, F, N, P, Sn, Tl, Na, Ti [JEE 2010]
BaSO 4 precipitates as
31. The total number of electrons present in 18 mL of water is
[Co(NH3 )5 Br]SO4 + BaCl2 
→
…………… [JEE 2010] 1.0 mole excess
[Co(NH3 )5 Br]Cl2 + BaSO4

1mol
ANSWERS and SOLUTIONS
Hence, moles of Y and Z are 0.01 each.
1. (b)
7. (b) From the given relative abundance, the average
2. (d) NaOH + H 3 PO 4 
→ NaH 2 PO 4
(PO 4−3 ) (NaPO 4−2 ) weight of Fe can be calculated as:
54 × 5 + 56 × 90 + 57 × 5
MW 98 A= = 55.95
EW = = . 100
no. of ionisable H + 1
Moles of solute
3. (d) As we know that four sodium atom are present in 8. (c) Molarity = moles of urea
Volume of solution (L)
sodium ferrocyanide [Na 4 Fe(CN)6 ]
120
Hence, number of Na atoms = No. of moles × number of = =2
60
atom × Avogadro’s number Weight of solution = weight of solvent + weight of solute
2 × 4 × 6.023 ×1023 = 48 ×1023 = 1000 + 120 = 1120 g
1120g 1
4. (d) Mass of an electron = 9.108 × 1031 kg ⇒ Volume = ×
1.15g / mL 1000mL / L
∵ 9.108 × 10 −31 kg = 1.0 electron
= 0.974L
1
∴ 1kg = electron ⇒ Molarity =
2.000
= 2.05M
9.108 × 10 −31 0.974
1031 1
= × 9. (a) From the formula,
9.108 6.023 ×1023 M V + M 2 V2
1 Mf = 1 1
= × 10 8 mole of electrons. V1 + V2
9.108 × 6.023
Given, V1 = 750mL, M1 = 0.5M
5. (a) Number of atoms = number of moles × Avogadro’s V2 = 250mL, M 2 = 2M
number (NA)
750 × 0.5 + 250 × 2 875
24 = = = 0.875 M
⇒ Number of atoms in 24 g C = × N A = 2N A 750 + 250 1000
12

(m O2 ) 13. (d) Mass in the body of a healthy human adult has:
n O2 (M O 2 ) Oxygen = 64.4%, Carbon
10. (b) n =
N2
(m N 2 ) = 22.9%, Hydrogen = 10.0% and Nitrogen
(M N 2 ) = 2.6%
Where, m O 2 = given mass of O2 Total weight of person
= 75 kg Mass due to 1H is
m N 2 = given mass of N2
10
= 75 × = 7.5 kg
MO2 = molecular mass of O2 100
1
H atoms are replaced by 2H atoms.
M N2 = molecular mass of N2
So, mass gain by person = 7.5 kg
n O2 = number of moles of O2
14. (a) 8 g NaOH, mol of NaOH
n N2 = number of moles of N2
8
= = 0.2 mol
 mO  28 1 28 7 40
= 2  = × = 18g H2O, mol of H2O
 m N2  32 4 32 32
18
= = 1 mol
11. (c) Given chemical equation 18
M 2CO3 + 2HCl 
→ 2MCl + H 2O + CO2 0.2
1 gm 0.01186 mol ∴ X NaOH = = 0.167
1.2
1
From the balanced chemical equation = 0.01186 0.2 × 1000
M Molality =
18
⇒ M = 84.3 gm / mol
= 11.11 m
12. (a)
15. (b) Volume strength = 11.2 × molarity = 11.2
Element Relative Relative Simplest whole
mass mole number ratio ⇒ molarity = 1 M
⇒ strength = 34 g/L
C 6 6 1 34
= 0.5 ⇒ %w / w = × 100 = 3.4%
12 1000
H 1 1 2
=1
1 16. (c) Ca(OH) 2 + Na 2 SO 4 
→ CaSO 4 + 2NaOH
So, X = 1, Y= 2
100 m mol 14 m mol — —
Equation for combustion of CXHY
— — 14 m mol 28 m mol
 Y Y wCaSO =14×10–3× 136 =1.9 gm
C X H Y +  X +  O 2 
→ XCO 2 + H 2 O
 4 2
28
Oxygen atoms required [OH – ]= = 0.28M
100
 Y
= 2 X +  17. (a) HCl with Na2CO3
 4
Eq. of HCl = Eq. of Na2CO3
 Y
As per information, 2  X +  = 2Z 25
× M ×1 =
30
× 0.1 × 2
 4 1000 1000
 2 6
⇒ 1 +  = Z M= M
 4 25
⇒ Z = 1.5 Eq. of HCl = Eq. of NaOH
Molecule can be written 6 V 30
×1× = × 0.2 × 1
C XH YO Z ⇒ C1H2O3/2 25 1000 1000
V = 25 mL
⇒ C 2H 4O 3.
Stoichiometry 7
18. (b) For same freezing point, molality of both solution Number of sites
=
should be same. Number of molecules
mx = my 2 × 6.023 ×1016
4 ×100 12 ×100
= =2
= 6.023 ×1016
96 × M x 88 × M y
23. 2PbS + 3O2 
→ 2PbO + 2SO2
96 ×12
My = M x = 3.27A
4 × 88 2PbO + PbS 
→ 3Pb + SO2
19. (b) 1L – 1M H2O2 solution will produce 11.35 L O2 gas at 3 moles of O 2 produce 3 moles of lead
STP. 96 kg of oxygen produce 621 kg of lead.
1 kg of oxygen produce
20. Mass if 1.0 L water = 1000 g
621
⇒ Molarity = 6.468 = 6.47 kg
96
1000
= = 55.56 ~ 56 mol L−1
18 24. From POAC,
m moles of MnCl 2 = m moles of KMnO 4 = x(let) and,
21. Initial millimole of
CH3COOH = 100 × 0.5 = 50 meq of KMnO 4 = meq of oxalic acid
Millimole of CH 3COOH remaining after adsorption  225 

x×5 =  × 2
= 100 × 0.49 = 49  90 
⇒ millimole of CH 3COOH adsorbed = 50 – 49 = 1 x =1
⇒ Number of molecules of CH 3COOH adsorbed ∴ m moles of MnCl 2 = 1 mg of
1 MnCl2 = (55 + 71) = 126 mg

= × 6.023 × 10 23 = 6.023 × 10 20
1000
P o Ps n 
⇒ Area covered up by one molecule 25. = i  solute 
Ps n
 solvent 
3.01×102
= = 5 ×10−19 m 2 650 − 640 0.5 × 78
6.02 ×1020 = 1×
640 M × 39
22. Partial pressure of
⇒ M solute = 64 gm
N 2 = 0.001 atm,
0.5 × 78
T = 298K, V = 2.46dm 3 . From ideal gas law: pV = nRT ∆Tf = K f × m = 5.12 ×
64 × 39
pV
n(N 2 ) = ⇒ ∆Tf = 1.02
RT
0.001 × 2.46 → 8H 2 SO 4 + 48H ⊕ + 48e ⊙
32H 2 O + S8 
= = 10 −7 26.
0.082 × 298
[e ⊙ + H ⊕ + HNO3  → NO 2 + H 2 O] × 48
⇒ No. of molecules of N 2 = 6.023 × 1023 × 10 −7
S8 + 48HNO 3  → 8H 2SO 4 + 48NO 2 + 16H 2 O
= 6.023 × 1016 1mol 16mol
Now, total surface sites available ⇒ Mass of H 2 O formed = (16) (18) g = 288 g
= 6.023 × 1014 × 1000 = 6.023 × 1017 27. Be n Al 2Si 6 O18

Surface sites used in adsorption
(2n) + (3 × 2) + (4 × 6) + (−2 ×18) = 0
20
= × 6.023 × 1017 = 2 × 6.023 × 1016 Or 2n + 30 − 36 = 0
100
⇒ Sites occupied per molecules Or 2n = 6 or n=3

28. A student performs a titration with different burettes and  10.5 
1/ 2
 3 N ×10−8 Silver atoms present in 10−12 m 2 .

finds titre values of 25.2 mL, 25.25 mL and 25.0 mL. 
 108 
The number of significant figures in the average titre
On solving,
value is 3. This is according to the rules of significant
we get 1.5 ×10−7 = Y ×10− x
figures. If two or more numbers having different
∴ x=7
precision are to be added or subtracted, the answer
should be taken as the number of decimal places in the 30. O, Cl, F, N, P, Sn, Ti, Na, Ti
number having less decimal place.
Na shows only + 1. F shows only – 1.
−1
29. Density = 10.5gcc So, the number of elements showing only one non-zero
3
This means 10.5 g silver is present in 1cm . oxidation state is 2.
10.5 31. Number of electron in one molecule of H 2 O is

3
mol silver is present in 1cm .
108 2 + 8 = 10
Density = 1
10.5 3
N silver atoms present in 1cm . 18 mL means 18 g
108
18
10.5 Moles = = 1 molecules
3 N Silver atoms present in 1 cm 18
108
= 6.023 ×1023
1/ 2
 10.5  Electrons = 6.023 ×1023 ×10
Silver atoms present is 1cm . 10−12 m2 is
2
 3 N

 108  = 6.023 ×1024
equal to 10−8 cm 2 . The total number of electrons present in 18 mL of water
is: (6.023 × 1024).
Solid State 9
2 Solid State
QUICK LOOK It has high relative density (about 3.5). Its relative density is 2.3
It is transparent and has high It has black in colour and opaque.
refractive index (2.45).
Solids can be broadly classified into following two types:
It is non-conductor of heat and Graphite is a good conductor of
(i) Crystalline solids/True solids electricity. heat and electricity.
(ii) Amorphous solids/Pseudo solids It burns in air at 90 0 ° C to give CO 2 It burns in air at 700°C to give
CO 2
Table 2.1: Crystalline vs. Amorphous
It occurs as octahedral crystals. It occurs as hexagonal crystals.
Crystalline solids Amorphous solids
They have long range order. They have short range order.
They have definite melting point. Not have definite melting point.
Unit Cell: It is defined as that volume of the solid from which
They have a definite heat of fusion. Not have definite heat of fusion. the entire crystal structure can be constructed by the
They are rigid and incompressible. Not be compressed to any translational repetition in three-dimensions. The length of three
appreciable extent. sides of a unit cell (3D) are called primitives or lattice constant,
They are given cleavage i.e. they They are given irregular cleavage
they are denoted by a, b, c as shown in following figures:
break into two pieces with plane i.e. they break into two pieces with
surfaces. irregular surface.
They are anisotropic because of They are isotropic because of these
→
b
these substances show different substances show same property in
property in different direction. all directions.
β α →
a
There is a sudden change in volume There is no sudden change in →
b φ →
c γ
when it melts. volume on melting.
→
a
These possess symmetry. Not possess any symmetry.
These possess interfacial angles. Not possess interfacial angles. Figure: 2.1
Crystalline and Amorphous Silica (SiO2): Silica occurs in Cubic Lattices: Different Symmetry
crystalline as well as amorphous states. Quartz is a typical Centre of Symmetry: An imaginary point within the
example of crystalline silica. Quartz and the amorphous silica crystal that any line drawn through it intersects the surface
differ considerably in their properties. of the crystal at equal distances in both directions.
Table 2.2: Quartz vs. Amorphous Silica Plane of Symmetry: It is an imaginary plane which passes
Quartz Amorphous silica through the centre of a crystal and divides it into two equal
It is crystalline in nature. It is light (fluffy) white powder. portions such that one part is exactly the mirror image of
All four corners of SiO44− The SiO44− tetrahedral are the other.
tetrahedron are shared by others randomly joined, giving rise to
to give a network solid. polymeric chains, sheets or
three-dimensional units.
It has high and sharp melting It does not have sharp melting
point (1710°C). point.
(a) (b) (c)
Diamond and Graphite: Diamond and graphite are two
allotropes of carbon. Diamond and graphite both are covalent Figure: 2.2
crystals. But, they differ considerably in their properties. Axis of Symmetry: An axis of symmetry or axis of rotation
Table 2.3: Diamond vs. Graphite is an imaginary line, passing through the crystal such that
Diamond Graphite when the crystal is rotated about this line, it presents the
It occurs naturally in free state It occurs naturally, as well as
same appearance more than once in one complete
manufactured artificially
It is the hardest natural substance It is soft and greasy to touch
revolution, i.e., in a rotation through 360°. Suppose, the
known. same appearance of crystal is repeated, on rotating it

through an angle of 360°/n, around an imaginary axis, the the crystal looks the same when viewed from any equivalent
axis is called an n-fold axis. lattice point, namely those separated by the translation of one
unit cell (the motive), there are 14 possible Bravais lattices in
three-dimensional space.
Table: 2. 4 Bravais Lattices

The five fundamental
two-dimensional
Axis of four-fold symmetry (three) Axis of three-fold symmetry (four) Bravais lattices; In
a2 φ a2 φ
Because of six faces Because of eight faces addition to the stated
conditions, the centred a1 a1
rectangular lattice
| a |≠|| a |, ϕ = 90° | a |≠|| a |, ϕ = 90°
1 2 2 2
fulfills 2a 2 − a1 ⊥ a1.
1. Oblique 2. Rectangle
This orthogonality
condition leads to the
rectangular pattern
Axis of two-fold symmetry (six) indicated and implies
Because of twelve faces ϕ = 90 °.
Figure: 2.3
A cubical crystal possesses 13 axes of symmetry in all. a2 φ
a1 a2 φ
Elements of symmetry: The total number of planes, axes a2
φ | a | = | a |, ϕ = 120° a1
and centre of symmetry possessed by a crystal are termed a1 1 2
4. Hexagonal | a | = | a |, ϕ = 90°
as elements of symmetry. A cubic crystal possesses a total | a | ≠ || a |, ϕ = 90° 1 2
1 2
of 23 elements of symmetry. 5. Square
3. Rhombic
Planes of symmetry = (3 + 6) = 9 , Axes of symmetry
= (3 + 4 + 6) = 13, Centre of symmetry = 1. Total number of The lattice centering are: Primitive (P): lattice points on the cell
corners only; Body (I): one additional lattice point at the centre
symmetry elements = 23
of the cell; Face (F): one additional lattice point at the centre of
each of the faces of the cell; Base (A, B or C): one additional
Different lattice in cubic crystals: There are three lattices
lattice point at the centre of each of one pair of the cell faces.
in the cubic system.
a
1. The simple cubic (sc) lattice. Atomic Radius: Atomic Radius for simple cubic is r =
2. The body-centred cubic (bcc). 2
3. The face-centred cubic (fcc). 3 1
For bcc, r = a ; for fcc, r = a
4 2 2
The half of the distance between two atoms in contact is
defined as atomic radius.
D C
r r
r r a
sc bcc fcc
a
Figure: 2.4 r r a
a C
In geometry and crystallography, a Bravais lattice, studied by r r
a
Auguste Bravais (1850), is an infinite array of discrete points A a B
A a B
r fcc unit cell
generated by a set of discrete translation operations described bcc unit cell
sc unit cell
by: R = n1 a 1 + n 2 a 2 + n 3 a 3 or translation vector T = n1a r = a/2 r = 3a/4
r = a/2 2
+ n 2 b + n 3 c where a, b, c are primitives and n i are any Figure: 2.5
integers and a i are known as the primitive vectors which lie in nA

Density of a crystalline solid ρ = where, A = mass
different directions and span the lattice. VN
A crystal is made up of a periodic arrangement of one or more number, n = number of lattice points per unit , V = volume
atoms (the basis) repeated at each lattice point. Consequently, of one cell abc, N = Avogadro Number
Solid State 11
1/ 3 Rhombohedral or
 nA 
Lattice constant, a = V1/ 3 =   Trigonal
 Nρ 
a =b=c α = β = γ ≠ 90 ° Calcite, As,
nv
Atomic pacing factor f = where, n= number of Sb, Bi etc.
V a
atoms/cell υ = volume occupied per cell, V = volume of β γ

c α b
π
one cell for simple cubic, f = = 52% Number of lattices = 1
6
Hexagonal
3π π
For bcc = = 68% and for fcc = = 74%
8 3 2
c
a=b≠c α = β = 90° Zn, Cd, Ni
Table 2.5: Different Crystal Systems and γ = 120 ° etc.
β α b
System Lattice Angle Examples a γ
constants between Number of lattices = 1
lattice
constants
Cubic Table 2.6: Classification of Crystalline Solids
Diamond, Types of Constitue Bonding Examples Physical Electrical
NaCl, Li, Ag, Solid nts Nature Conducti
c a =b=c α = β = γ = 90 ° vity
Cu, NH4Cl,
β α Ionic Positive Coulombic NaCl, KCl, Hard but Conducto
Pb, etc.
γ a
and CaO, brittle r
b negative MgO, LiF, (in
ions ZnS, molten
Number of lattices = 3
network BaSO4 and state and
Tetragonal
systematica K2SO4 etc. in
lly arranged aqueous
solution)
c a=b≠c α = β = γ = 90 ° White tin, Covalent Atoms Electron SiO2 Hard Insulator
NiSO4, etc. connected sharing (Quartz), Hard except
β α
in covalent SiC, C Hard graphite
a γ bonds (diamond),
b
C(graphite
Number of lattices = 2 ) etc.
Orthorhombic Molecular Polar or (i) I2,S8, P4, Soft Insulator
non-polar Molecular CO2, CH4,
c molecules interaction CCl4 etc.
β α a≠b≠c α = β = γ = 90 °
HgCl2 ,KNO3 , s Soft Insulator
γ a (intermole Starch,
b gallium, etc.
cu-lar sucrose,
Number of lattices = 4 forces) water, dry
Monoclinic (ii) ice or dry
Hydrogen cold (solid
bonding CO2) etc.
a≠b≠c α = γ = 90° KclO3 ,FeSO4
β c and β ≠ 90 °
α etc.
Metallic Cations in a Metallic Sodium , Ductile Conduc-
γ sea of Au, Cu, malleable tor
b a electrons magnesiu
Number of lattices = 2 m, metals
Triclinic and alloys
Atomic Atoms London Noble Soft Poor

β α c a≠b≠c α ≠ β ≠ γ ≠ 90 ° K2Cr2O7 ,CuSO4 dispersion gases thermal
γ etc. force and elec-
b a trical
conduc-
tors
Number of lattices = 1

Properties of Solids: Some of the properties of solids which Table: 2.7 Magnetic Properties of Solids
Properties Description Alignment of Examp Applicatio
are useful in electronic and magnetic devices such as,
Magnetic les ns
transistor, computers, and telephones etc., are summarised Dipoles
below: Diamagnetic Feebly All paired TiO2, Insulator
repelled by electrons V2O5,
the magnetic NaCl,
Electrical Properties: Solids are classified into following fields. Non- C6H6
classes depending on the extent of conducting nature. metallic (benze
Conductors: The solids which allow the electric current to elements ne)
(excepts O2,
pass through them are called conductors. These are further
S) inert gases
of two types; Metallic conductors and electrolytic and species
conductors. The electrical conductivity of these solids is with paired
electrons are
high in the range 10 4 − 106 ohm −1cm −1 . Their conductance
diamagnetic
decrease with increase in temperature. Paramagnetic Attracted by At least one O2 , Electronic
Insulators: The solids which do not allow the current to the magnetic unpaired 2+ appliances
Cu ,
field due to the electron
pass through them are called insulators, e.g., rubber, wood Fe 3+ ,
presence of
plastic, etc. the electrical conductivity of these solids is very permanent TiO,
− 12 − 22 −1 −1
low i.e., 10 − 10 ohm cm . magnetic Ti 2 O 3 ,
dipoles VO,
Semiconductors: The solids whose electrical
(unpaired VO 2 ,
conductivity lies between those of conductors and electrons). In CuO
insulators are called semiconductors. The conductivity of magnetic field,
these tend to
these solid is due to the presence of impurities, e.g.
orient
Silicon and Germanium. Their conductance increase themselves
with increase in temperature. The electrical conductivity parallel to the
of these solids is increased by adding impurity. This is direction of
the field and
called Doping . When silicon is doped with P (or As, thus, produce
group 5th elements), we get n-type semiconductor. This magnetism in
is because P has five valence electrons. It forms four the substances.
Ferromagnetic Permanent Dipoles are Fe, Ni, CrO2 is
covalent bonds with silicon and the fifth electron
magnetism aligned in the Co, used in
remains free and is loosely bound. This give rise to n- even in the same direction CrO2 audio and
type semiconductor because current is carried by absence of video tapes
magnetic
electrons when silicon is doped with Ga (or in In/Al,
field, Above a
group 3rd elements), we get p-type semiconductors temperature
called Curie
Superconductivity: When any material loses its resistance for temperature,
there is no
electric current, then it is called superconductor, Kamerlingh ferromagnetis
Onnes (1913) observed this phenomenon at 4K in mercury. The m.
materials offering no resistance to the flow of current at very low Antiferroma This arises MnO, –
gnetic when the MnO2,
temperature (2–5K) are called superconducting materials and
dipole Mn2O,
phenomenon is called superconductivity. alignment is FeO,
Examples: Nb 3 Ge alloy (Before 1986) zero due to Fe2O3;
equal and NiO,
La1.25 Ba 0.15 CuO 4 (1986); YBa 2 Cu 3O7 (1987) opposite Cr2O3,
alignment. CoO,
Co3O4,
Magnetic Properties: Based on the behavior of substances Ferrimagnetic This arises Fe3O4, –
when placed in the magnetic field, there are classified into five when there is ferrites
classes. net dipole
moment
Solid State 13
Dielectric Properties: A dielectric substance is that which 1 1 1 1 1 1 1
a. , b. 1, c. , d. ,
does not allow the electricity to pass through them but on 2 8 4 2 2 4 8
applying the electric field, induced charges are produced on its 6. The correct statement(s) for cubic close packed (ccp)
faces. In an insulator, the electrons are strongly held by the three dimensional structure is (are)
individual atoms. When an electric field is applied polarization [JEE Adv. 2016 P-II]
takes place because nuclei are attracted to one side and the a. The number of the nearest neighbours of an atom
electron cloud to the other side. As a result, dipoles are created. present in the topmost layer is 12
Such type of crystals shows the following properties. b. The efficiency of atom packing is 74%
c. The number of octahedral and tetrahedral voids per
Multiple Choice Questions atom are 1 and 2, respectively
One and More than One Correct d. The unit cell edge length is 2 2 times the radius of the
1. The correct statement(s) regarding defects in solids is (are) atom
[ JEE 2009 P-I] 7. A metal crystallises in a face centered cubic structure. If the
a. Frenkel defect is usually favoured by a very small edge length of its unit cell is 'a', the closest approach between
difference in the sizes of cation and anion two atoms in metallic crystal will be
b. Frenkel defect is a dislocation defect [JEE Main 2017]
c. Trapping of an electron in the lattice leads to the a
formation of F-centre a. b. 2 a c. 2 2 a d. 2 a
2
d. Schottky defects have no effect on the physical
8. Which type ‘defect’ has the presence of cations in the
properties of solids
interstitial sites? [JEE Main 2018]
2. The packing efficiency of the two-dimensional square
a. Metal deficiency defect b. Schottky defect
unit cell shown below is: [ JEE 2010 P-II]
c. Vacancy defect d. Frenkel defect
9. Element 'B' forms ccp structure and 'A' occupies half of
the octahedral voids, while oxygen atoms occupy all the
tetrahedral voids. The structure of bimetallic oxide is:
L [JEE Main 2019]
a. 39.27 % b. 68.02% a. A2BO4 b. A2B2O
c. 74.05% d. 78.54% c. A4B2O d. AB2O4
10. The statement that is incorrect about the interstitial
3. The arrangement of X − ions around A + ion in solid AX
compounds is: [JEE Main 2019]
is given in the figure (not drawn to scale). If the radius of
a. They have high melting points
X − is 250 pm, the radius of A + is: [JEE Adv. 2013 P-I] b. They are chemically reactive
A+ X− c. They have metallic conductivity
d. They are very hard
11. Consider the bcc unit cells of the solids 1 and 2 with the
position of atoms as shown below. The radius of atom B
a. 104 pm b. 125 pm c. 183 pm d. 57 pm is twice that of atom A. The unit cell edge length is 50%
4. Sodium metal crystallises in a body centred cubic lattice more in solid 2 than in 1. What is the approximate
with a unit cell edge of 4.29 Å. The radius of sodium packing efficiency in solid 2? [JEE Main 2019]
atom is approximately: [JEE Main 2015] A A A
A
a. 1.86 Å b. 3.22 Å A A A
A
c. 5.72 Å d. 0.93 Å B
A
5. If the unit cell of a mineral has cubic close packed (ccp) A A A
A
array of oxygen atoms with m fraction of octahedral holes A
A A A
occupied by aluminium ions and n fraction of tetrahedral Solid 1 Solid 2
holes occupied by magnesium ions, m and n, respectively, a. 45% b. 65%
are: [JEE Adv. 2015 P-I] c. 90% d. 75%

12. At 100°C, copper (Cu) has FCC unit cell structure with (C) Cubic and tetragonal 3. have only two
cell edge length of x Å. What is the approximate density crystallography angles of 90°
of Cu (in g cm–3) at this temperature? (D) Hexagonal and 4. belong to same crystal
[Atomic Mass of Cu = 63.55u] [JEE Main 2019] monoclinic system
105 211 a. A→1,4; B→ 1,2; C→2; D→2,3
a. b.
x3 x3 b. A→1,2; B→ 1,3; C→4; D→2,4
205 422 c. A→1,4; B→ 1,2; C→3; D→1,2
c. 3 d. 3
x x d. A→1,3; B→ 1,2; C→4; D→2,3
13. Which primitive unit cell has unequal edge lengths (a ≠ b
≠ c) and all axial angles different from 90°? Paragraph
[JEE Main 2019] Paragraph for Question Nos. 18 to 20
a. Tetragonal b. Hexagonal
In hexagonal systems of crystals, a frequently encountered
c. Monoclinic d. Triclinic
arrangement of atoms is described as a hexagonal prism. Here,
14. A compound of formula A2B3 has the hcp lattice. Which the top and bottom of the cell are regular hexagons and three
atom forms the hcp lattice and what fraction of tetrahedral atoms are sandwiched in between them. A space-filling model
voids is occupied by the other atoms: of this structure, called hexagonal close-packed (HCP), is
[JEE Main 2019] constituted of a sphere on a flat surface surrounded in the same
2 plane by six identical spheres as closely as possible. Three
a. hcp lattice-A, tetrahedral voids-B
3 spheres are then placed over the first layer so that they touch
1 each other and represent the second layer. Each one of these
b. hcp lattice-B, tetrahedral voids-A
3 three spheres touches three spheres of the bottom layer.
2 Finally, the second layer is covered with a third layer that is
c. hcp lattice-B, tetrahedral voids-A
3 identical to the bottom layer in relative position. Assume radius
1 of every sphere to be ‘r’. [IIT JEE 2008 P-II]
d. hcp lattice-A tetrahedral voids-B
3
15. A solid having density of 9 × 103 kg m–3 forms face
centred cubic crystals of edge length 200 2 pm. What is
the molar mass of the solid? [JEE Main 2019]
23 –1
(Avogadro constant ≅ 6 × 10 mol , π ≅ 3)
a. 0.0216 kg mol–1 b. 0.0305 kg mol–1
c. 0.4320 kg mol–1 d. 0.0432 kg mol–1
16. The radius of the largest sphere which fits properly at the 18. The number of atoms on this HCP unit cell is:
centre of the edge of body centred cubic unit cell is: a. 4 b. 6 c. 12 d. 17
(Edge length is represented by 'a'): [JEE Main 2019]
19. The volume of this HCP unit cell is:
a. 0.134 a b. 0.027 a
64r 3
c. 0.067 a d. 0.047 a a. 24 2r 3 b. 16 2r 3 c. 12 2r 3 d.
Matrix Match/Column Match 3 3
17. Match the crystal system/unit cells mentioned in Column I 20. The empty space in this HCP unit cell is:
with their characteristic features mentioned in Column II. a. 74% b. 47.6% c. 32% d. 26%
. [IIT JEE 2007 P- II]
Column I Column II Integer and Subjective
(A) Simple cubic and 1. have these cell 21. An element crystallises in FCC lattice have edge length 400
face-centred cubic parameters a = b = c and pm. Calculate the maximum diameter of atom which can be
α=β=γ placed in interstitial site without distorting the structure in
(B) Cubic and rhombohedral 2. are two crystal systems pm. [JEE 2005]
Solid State 15
22. The edge length of unit cell of a metal having molecular 5. (a) In ccp lattice:
weight 75 g/mol is 5 Å which crystallises in cubic lattice. Number of O atoms 
→4
If the density is 2 g/cc then find the radius of metal atom.
Number of Octahedral voids 
→4
(N A = 6 ×1023 ). Give the answer in pm
Number of tetrahedral voids 
→8
[JEE 2006]
23. The number of hexagonal faces that are present in a Number of Al3 + = 4 × m
trenched octahedron is: [JEE 2011 P-II] Number of Mg 2 + = 8 × n
24. A crystalline solid of a pure substance has a face-centred Due to charge neutrality 4(–2) + 4m(3) + 8n(+2) = 0
cubic structure with a cell edge of 400 pm. If the density 1 1
∴ m= and n =
of the substance in the crystal is 8 g cm–3, then the 2 8
number of atoms present in 256 g of the crystal is N × 6. (b, c, d) (a) For any atom in top most layer, coordination
1024. The value of N is: [JEE Adv. 2017 P-I] number is not 12 since there is no layer above top most
25. Consider an ionic solid MX with NaCl structure. Construct a layer, (b) Fact, (c) Fact, (d) 2 a = 4R
new structure (Z) whose unit cell is constructed from the unit So, a=2 2R
cell of MX following the sequential instructions given
below. Neglect the charge balance. [JEE Adv. 2018 P-I] 7. (a) In FCC unit cell atoms are constant along face
(i) Remove all the anions (X) except the central one diagonal
(ii) Replace all the face centered cations (M) by anions (X) So, 2 a = 4R
(iii) Remove all the corner cations (M) 2a a
(iv) Replace the central anion (X) with cation (M)
∴ Closest distance (2R) = =
2 2
 Number of anions 
The value of   in Z is ______. 8. (d) In Frenkel defect, cation is dislocated from its normal
 Number of cations  lattice asite to an interstitial site.
1
ANSWERS and SOLUTIONS 9. (d) Z B = 4, Z A = 4 ×
= 2, ZO = 8
2
1. (a, c)
Formula; A2B2O8 ≡ AB2O4
2. (d) a = (2 2r)
10. (b) Generally interstitial compounds are chemically inert.
 4 3  4 3
 z eff × πrA  +  z eff × πrB 
 3 A  3 B
11. (c) P.f = 3
a
2 × π r2 2π r 2 π 2(rA + rB ) = 3a ⇒ 2(rA + 2rA ) = 3a ⇒ 2 3rA = a
P.F. = = =
(2 2r) 2
8r 2 4 4 4 4
1 × πrA3 + π(8rA3 ) 9 × π
⇒ P.f = 3 3 = 3 = π
3. (a) According to the given figure, A + is present in the
−
8 × 3 3rA
3
8×3 3 2 3
octahedral void of X . The limiting radius in octahedral
π
void is related to the radius of sphere as P. efficiency = ×100 ≃ 90%
rvoid = 0.414 rsphere
2 3
12. (d) FCC unit cell Z = 4
rA+ = 0.414 4rX−
63.5 × 4
= 0.414 × 250 pm = 103.5 ≈ 104 pm d= g / cm
6 ×1023 × x3 ×10−24
4. (a) For BCC 6 unit cell, 3a = 4r 63.5 × 4 ×10
d= g / cm3
6
3 3
r= a= × 4.29 423.33 422
4 4 d= ≃ 3
Å = 1.85 Å x3 x

13. (d) In triclinic unit cell a ≠ b ≠ c &α ≠ β ≠ γ ≠ 90° 20. (d) Packing fraction = 74% ; Empty space = 26%
14. (b) A2B3 has HCP lattice 21. In FCC, interstitial sites will be octahedral voids &
3
th tetrahedral voids.
If A form HCP, then of THV must occupied by B to
4 r
For octahedral voids 1 = 0.414
form A2B3 r2
th
1 r1
If B form HCP, then of THV must occupied by A to For tetrahedral voids = 0.225
3 r2
form A2B3
Where, r1 = radius of atom in interstitial sites r2 = radius
15. (b)
of atom arranged in FCC i.e., 4r2 = 2 a . For maximum
R r
16. (c) diameter of atom in interstitial site, octahedral voids will
be considered.
400
Diameter = 2r1 = 2(0.414 r2 ) = 2 × 0.414 × = 117.1 pm
2 2
ZA
22. ρ=
NV
a = 2(R + r)
ρ NV 2 × 6 × 10 23 × (5 × 10 −8 )3
Z= = ⇒=2
a A 75
= (R + r) . . .(i)
2
3 3
a 3 = 4R . . .(ii) r= a= × 5 = 2.165Å = 216.5 pm
4 4
a a 3 2− 3 Note: Answer may be 216 pm or 217 pm.
= = r ⇒a =r
Using (i) and (ii)
2 4  4 
  23. Answer is 8.
r = 0.067a
256 g
17. (a) A→1,4; B→ 1,2; C→2; D→2,3 24. Volume of the crystal = = 32 cm3
8 g cm −3
Crystals class Axial distances Angles
32 cm3 1
Cubic a =b = c α = β = γ = 90º Number of unit cell = = ×1024
Tetragonal a=b≠c α = β = γ = 90º (4 × 10−8 cm)3 2
Orthorhombic a ≠ b ≠ c α = β = γ = 90º In a FCC unit cell, 4 atoms are present
Hexagonal a=b≠c α = β = 90º, 1
γ = 120º ⇒ Number of atom = 4 × × 1024 = 2 ×1024
2
Trigonal and a=b=c α = β = γ ≠ 90º So, N = 2.
rhombohedral
Monoclinic a≠b≠c α = β =90º, 25. MX has NaCl type structure. From instructions it is clear
γ ≠ 90º that in MX ionic solid. Cation M undergoes CCP anion X
Triclinic a≠b≠c α ≠ β ≠ γ ≠ 90º occupies all octahedral voids.
(i) No. of anions left = 1
18. (b) Total effective number of atoms (ii) No. of anions added = 3
1 1 No. of cations left = 1
= 12 × + 2 × + 3 = 6
6 2 (iii) No. of cations left = 0
2 (iv) No. of cations added = 1
19. (a) Height of unit cell = 4r No. of anions left = 3
3
Final no. of cations in an unit cell = 1
3
Base area = 6 × (2r) 2 Final no. of anions in an unit cell = 3
4
3
Volume = height × base area = 24 2r 3 ∴ ratio = = 3.00
1
Solutions 17
3 Solutions
QUICK LOOK An alloy is a mixture or metallic solid solution composed of
two or more elements and the properties of alloys are usually
A solution is a mixture in which substances are intermixed so different from those of its component elements. Alloy
intimately that they cannot be observed as separate constituents are usually measured by mass. Some well-known
components. The dispersed phase or the substance which is to alloys include bronze (three-quarters copper, one-quarter tin);
be dissolved is called solute, while the dispersion medium in brass (two-thirds copper, one-third zinc); pewter (a mixture of
which the solute is dispersed to get a homogenous mixture is tin and copper with traces of antimony); and numerous alloys
called the solvent. And the Solubility of a substance may be of iron-particularly steel-as well as alloys involving other
defined as the amount of solute dissolved in 100 g of a solvent metals.
to form a saturated solution at a given temperature as with Kinds of Solutions: Gas, liquid and solid, these three states of
change in temperature solubility changes. matter either behave as solvent or solute Depending on the
A saturated solution is a solution which contains at a given state of solute or solvent, mainly there may be following nine
temperature as much solute as it can hold in presence of types of binary solutions. Among these solutions the most
dissolve ding solvent. Any solution may contain less solute significant type of solutions are those which are in liquid phase
than would be necessary to saturate it. Such a solution is and may be categorised as:
known as unsaturated solution. When the solution contains Solid in liquid solutions,
more solute than would be necessary to saturate it then it is Liquid in liquid solutions
termed as supersaturated solution. Gas in liquid solutions.
An aqueous solution is a solution in which the solvent is water. Table 3.1: Solvent, Solute and Example
Example of an aqueous solution: acetic acid as solute and Solvent Solute Example
water as solvent and nonaqueous solvents are ethyl acetate, Gas Gas Mixture of gases, air.
Gas Liquid Water vapours in air, mist.
used in nail polish removers, and turpentine, used to clean paint
Gas Solid Sublimation of a solid into a gas, smoke.
brushes. Aqueous-solution reactions can lead to the formation Liquid Gas CO gas dissolved in water .
2
of a solid, as when a solution of potassium chromate (K2CrO4)
Liquid Liquid Mixture of miscible liquids, e.g., alcohol in water.
is added to an aqueous solution of barium nitrate Ba[NO3]2 to
Liquid Solid Salt in water, sugar in water.
form solid barium chromate (BaCrO4) and a solution of Solid Gas Adsorption of gases over metals; hydrogen over
potassium nitrate (KNO3). palladium.
We have primarily discussed liquid solutions, and in particular Solid Liquid Mercury in zinc, mercury in gold, CuSO 4 .5H 2O
aqueous solutions. It should be stressed, however, that Solid Solid Homogeneous mixture of two or more metals
solutions can also exist in the gaseous or solid phases. The air (alloys), e.g., copper in gold.
we breathe is a solution, not a compound; there is no such thing
Water and oil and immiscible due to their respective molecule
as an “air molecule” in its place, it is made up of diatomic
structures, and hence their inherent characteristics of
elements; monatomic elements; one element in a triatomic
intermolecular bonding. Water molecules are polar, meaning
molecule; and two compounds
that the positive electric charge is at one end of the molecule,
The “solvent” in air is nitrogen, a diatomic element that while the negative charge is at the other end. Oil, on the other
accounts for 78% of Earth's atmosphere. Oxygen, also hand, is non-polar-charges are more evenly distributed
diatomic, constitutes an additional 21%. Argon, which like all throughout the molecule. The immiscible quality of oil and
noble gases is monatomic, ranks a distant third, with 0.93%. water in relation to one another explains a number of
The remaining 0.07% is made up of traces of other noble gases; phenomena from the everyday world.
the two compounds mentioned, carbon dioxide and water (in The dispersion of two substances in an emulsion is achieved
vapour form); and, high in the atmosphere, the triatomic form through the use of an emulsifier or surfactant. Made up of
of oxygen known as ozone (O3 ). molecules that are both water-and oil-soluble, an emulsifier or

surfactant acts as an agent for joining other substances in an Purity of Liquid: Pure liquid always has a vapour pressure
emulsion. The two words are virtually synonymous, but greater than its solution.
“emulsifier” is used typically in reference to foods, whereas
“surfactant” most often refers to an ingredient in detergents and Raoult’s Law: When a non-volatile substance is dissolved
related products. in a liquid, the vapour pressure of the liquid (solvent) is
lowered. According to Raoult’s law (1887), at any given
In an emulsion, millions of surfactants surround the dispersed
temperature the partial vapour pressure (pA) of any
droplets of solute, known as the internal phase, shielding them
component of a solution is equal to its mole fraction (X A)
from the solvent or external phase. Surfactants themselves are
multiplied by the vapour pressure of this component in the
often used in laundry or dish detergent, because most stains on
plates or clothes are oil-based, whereas the detergent itself is pure state (p°A ). That is, p A = p°A × X A
applied to the clothes in a water-based external phase. The The vapour pressure of the solution (Ptotal) is the sum of the
emulsifiers in milk help to bond oily particles of milk fat partial pressures of the components, i.e., for the solution of two
(cream) and protein to the external phase of water that volatile liquids with vapour pressures p A and p B .
comprises the majority of milk's volume. Ptotal = p A + p B = (p°A × X A ) + (p°B × X B )
Colligative Properties: Certain properties of dilute solutions Relative lowering of vapour pressure is defined as the ratio of
containing non-volatile solute do not depend upon the nature of lowering of vapour pressure to the vapour pressure of the pure
the solute dissolved but depend only upon the concentration solvent. It is determined by Ostwald-Walker method.
i.e., the number of particles of the solute present in the
w
solution. Such properties are called colligative properties. p° − p n
Thus according to Raoult’s law, = = m
Lowering of vapour pressure of the solvent. p° n+N w + W
Osmotic pressure of the solution. m M
Elevation in boiling point of the solvent. Where, p = Vapour pressure of the solution
Depression in freezing point of the solvent.
p° = Vapour pressure of the pure solvent
n = Number of moles of the solute
Since colligative properties depend upon the number of solute
N = Number of moles of the solvent
particles present in the solution, the simple case will be that
when the solute is a non-electrolyte. In case the solute is an w and m = weight and mol. wt. of solute
electrolyte, it may split to a number of ions each of which acts W and M = weight and mol. wt. of the solvent.
as a particle and thus will affect the value of the colligative
property. Each colligative property is exactly related to other, Limitations of Raoult’s Law
Relative lowering of vapour pressure, elevation in boiling point Raoult’s law is applicable only to very dilute solutions.
and depression in freezing point are directly proportional to Raoult’s law is applicable to solutions containing non-
osmotic pressure. volatile solute only.
Raoult’s law is not applicable to solutes which dissociate or
Vapour Pressure: The pressure exerted by the vapours above associate in the particular solution.
the liquid surface in equilibrium with the liquid at a given
Table 3.2: Ideal and Non-ideal Solutions
temperature is called vapour pressure of the liquid. The vapour
Ideal solutions Non-ideal solutions
pressure of a liquid depends on: Positive deviation Negative deviation
Nature of Liquid: Liquids, which have weak p o
pB from Raoult's law
° from Raoult's law
A P = pA + pB
intermolecular forces, are volatile and have greater vapour PA = p oA χ A p oA
Total vapour o
p oB p A Total vapour p oB
Vapour pressure
Vapour pressure
pressure. For example, dimethyl ether has greater vapour

Vapour pressure
PB = poBXB
pressure than ethyl alcohol.
Ideal
Temperature: Vapour pressure increases with increase in Mole fraction
temperature. This is due to the reason that with increase in χA = 1 χA = 0 Ideal
Mole fraction
Mole fraction
χB = 0 χB = 1 χA = 1 χB = 1 χA = 1 χA = 0
temperature more molecules of the liquid can go into
χB = 0 χA = 0 χB = 0 χB = 1
vapour phase.
Solutions 19
Obey Raoult's law at Do not obey Raoult's Do not obey Raoult's w RT  w
every range of law. law. π= ∴ n = 
concentration.
m V  m 
∆H mix = 0; neither ∆H mix > 0. ∆H mix < 0. Here, C = concentration of solution in moles per litre
heat is evolved nor Endothermic Exothermic R = gas constant
absorbed during dissolution; heat is dissolution; heat is T = temperature
absorbed.
dissolution. evolved. n = number of moles of solute
∆Vmix = 0; total ∆Vmix > 0. Volume is ∆Vmix < 0. Volume is V = volume of solution
volume of solution is increased after decreased during m = molecular weight of solute
equal to sum of dissolution. dissolution.
w = weight of solute
volumes of the
components.
P = pA + pB Relation of Osmotic Pressure with Different Colligative
p A > p oA X A p A < p oA X A ;
P = p A + pB = poA X A + poB X B Properties: Osmotic pressure is related to relative lowering of
p B > p oB X B p B < p oB X B
°
vapour pressure, elevation of boiling point and depression of
i.e., p A = p X A : p B ∴ pA + pB <
A
∴ p A + p B > p °A freezing point according to the following relations,
°
= p XB X A + p°B XB p °A X A + p °A X B
B
 Po − P  dRT
A–A, A–B, B–B A–B attractive force A–B attractive force
(a) π =  A o A ×
 PA  M
interactions should be should be weaker than should be greater than
same, i.e., 'A' and 'B' are A–A and B–B A–A and B–B dRT
(b) π = ∆Tb ×
identical in shape, size attractive forces. 'A' attractive forces. 'A' 1000 × K b
and character. and 'B' have different and 'B' have different
dRT
shape, size and shape, size and (c) π = ∆Tf ×
character. character. 1000 × K f
Escaping tendency of 'A' and 'B' escape Escaping tendency of
'A' and 'B' should be easily showing higher both components 'A' In the above relations,
same in pure liquids vapour pressure than and 'B' is lowered π = Osmotic pressure
and in the solution. the expected value. showing lower vapour
pressure than expected
d = Density of solution at temperature T
ideally. R = Universal gas constant
Examples: Dilute Examples: Acetone + Examples: Acetone + M = Mol. Mass of solute
solutions; benzene + ethanol acetone + CS2: aniline; acetone +
K b = Molal elevation constant of solvent
toluene: n-hexane + n- water + methanol; chloroform; CH3OH +
heptane; water + ethanol; CCl4+ CH3COOH; H2O + K f = Molal depression constant of solvent
chlorobenzene + toluene; CCl4+CHCl3 ; HNO3 chloroform +
bromobenzene; ethyl acetone + benzene; diethyl ether; water + Isotonic, Hypertonic and Hypotonic Solutions
bromide+ ethyl iodide; CCl4+CH3OH; HCl; acetic acid + Isotonic or iso-osmotic solutions: Two solutions of
n-butyl chloride + n- cyclohexane + ethanol pyridine; chloroform +
different substances having same osmotic pressure at same
butyl bromide benzene
temperature are known as isotonic solutions.
For isotonic solutions, π 1 = π 2 Primary Condition . . .(i)
Osmotic Pressure (π): The osmotic pressure is a colligative
Also, C1 = C 2
property. For a given solvent the osmotic pressure depends
only upon the molar concentration of solute but does not n1 n 2
or =
depend upon its nature. The following relation relates osmotic V1 V2
pressure to the number of moles of the solute, w1 w2 Secondary Conditions
or = . . .(ii)
According to Boyle Van't m1V1 m 2 V2
Hoff law (at conc. temp.) π ∝ C . . .(i)
Equation (ii) holds good only for those solutes which neither
According to Gay lussac Van't Hoff law (at conc. temp.)
possess the tendency to get associate nor dissociate in
π ∝T . . .(ii)
solution, e.g.,
From equation (i) and (ii) we get π ∝ CT,
Urea and glucose are isotonic then, π 1 = π 2 and C1 = C 2
π = CRT (Van't Hoff equation)
Urea and NaCl are isotonic then, π 1 = π 2 but C1 ≠ C 2
n  n (dissociate)
π = RT ∴ C =  ;
V  V  Urea and Benzoic acid are isotonic then, π1 = π2 but C1 ≠ C2
(associate)

Hypertonic and Hypotonic Solution: The solution which Cryoscopy: Depression in freezing point is determined by
has more osmotic pressure than the other solution is called Beckmann’s method and Rast’s camphor method. Study of
as hypertonic solution and the solution which has lesser depression in freezing point of a liquid in which a non-volatile
osmotic pressure than the other is called as hypotonic solute is dissolved in it is called as cryoscopy.
solution. The flow of solvent is always from lower osmotic
pressure to higher osmotic pressure i.e. from hypotonic to Freezing point is the temperature at which the liquid and the
hypertonic solution. solid states of a substance are in equilibrium with each other or
it may be defined as the temperature at which the liquid and the
Ebullioscopy: Elevation in boiling point is determined by solid states of a substance have the same vapour pressure. It is
Landsberger’s method and Cottrell’s method. Study of observed that the freezing point of a solution is always less
elevation in boiling point of a liquid in which a non-volatile than the freezing point of the pure solvent. Thus, the freezing
solute is dissolved is called as ebullioscopy. point of sea water is low than that of pure water. The
depression in freezing point (∆T or ∆Tf ) of a solvent is the
Boiling point of a liquid may be defined as the temperature at
which its vapour pressure becomes equal to atmospheric difference in the freezing point of the pure solvent (Ts ) and the
pressure, i.e., 760 mm. Since the addition of a non-volatile solution (Tsol. ).
solute lowers the vapour pressure of the solvent, solution Ts − Tsol = ∆Tf or ∆T
always has lower vapour pressure than the solvent and hence it
NaCl or CaCl 2 (anhydrous) are used to clear snow on roads.
must be heated to a higher temperature to make its vapour
They depress the freezing point of water and thus reduce the
pressure equal to atmospheric pressure with the result the
temperature of the formation of ice.
solution boils at a higher temperature than the pure solvent.
Thus sea water boils at a higher temperature than distilled
Important Relations Concerning Depression in Freezing Point
water. If Tb is the boiling point of the solvent and T is the
Depression in freezing point is directly proportional to the
boiling point of the solution, the difference in the boiling point
lowering of vapour pressure. ∆Tf ∝ p 0 − p
(∆T or (∆Tb ) is called the elevation of boiling point.
∆Tf = K f × m
T − Tb = ∆Tb or ∆T
Where K f = molal depression constant or cryoscopic
Important Relations Concerning Elevation in Boiling Point constant; m = Molality of the solution (i.e., no. of moles of
The elevation of boiling point is directly proportional to the solute per 1000g of the solvent); ∆Tf = Depression in
lowering of vapour pressure, i.e., ∆Tb ∝ p0 − p freezing point.
∆Tb = K b × m 1000 × K f × w 1000 × K f × w
∆ Tf = or m =
Where, Kb= molal elevation constant or ebullioscopic m×W ∆Tf × W
constant of the solvent; m = Molality of the solution, i.e., Where K f is molal depression constant and defined as the
number of moles of solute per 1000 g of the solvent; depression in freezing point produced when 1 mole of the
∆Tb = Elevation in boiling point. solute is dissolved in 1 kg of the solvent. W and w are the
1000 × K b × w
∆Tb = or m = 1000 × K b × w weights of solute and solvent and m is the molecular weight
m× W ∆Tb × W of the solute.
Where, Kb is molal elevation constant and defined as the R(T0 )2 0.002(T0 ) 2
Kf = =
elevation in b.pt. produced when 1 mole of the solute is lf 1000 lf
dissolved in 1 kg of the solvent. W and w are the weights of Where, T0 = Normal freezing point of the solvent; lf =
solute and solvent and m is the molecular weight of the solute.
Latent heat of fusion/g of solvent; K f for water is
0.002(T0 )2
Kb = 1.86 deg − kg mol−1
lV
Where T0= Normal boiling point of the pure solvent; 1v= Colligative Properties of Electrolytes: The colligative
Latent heat of evaporation in cal / g of pure solvent; Kb for properties of solutions, viz. lowering of vapour pressure,
water is 0.52 deg − kg mol−1. osmotic pressure, elevation in b.p. and depression in freezing
Solutions 21
point, depend on the total number of solute particles present in Degree of Association (α): It is defined as the fraction of the
solution. Since the electrolytes ionise and give more than one total number of molecules which associate or combine together
particle per formula unit in solution, the colligative effect of an resulting in the formation of bigger molecules.
electrolyte solution is always greater than that of a non- i −1
α= ; m = number of particles in solution.
electrolyte of the same molar concentration. All colligative 1/ m − 1
properties are used for calculating molecular masses of non-
volatile solutes. However osmotic pressure is the best Multiple Choice Questions
colligative property for determining molecular mass of a non- One and More than One Correct
volatile substance.
1. For a dilute solution containing 2.5 g of a non-volatile
Van’t Hoff’s Factor (i): In 1886, Van’t Hoff introduced a non-electrolyte solute in 100 g of water, the elevation in
factor ‘i’ called Van’t Hoff’s factor, to express the extent of boiling point at 1 atm pressure is 2°C. Assuming
association or dissociation of solutes in solution. It is ratio of concentration of solute is much lower than the
the normal and observed molecular masses of the solute, i.e., concentration of solvent, the vapour pressure (mm of Hg)
Normal molecular mass of the solution is: (take K b = 0.76 K kg mol −1 )
i=
Observed molecular mass [JEE 2012 P-II]
In case of association, observed molecular mass being more a. 724 b. 740 c. 736 d. 718
than the normal, the factor i has a value less than 1. But in case 2. The vapour pressure of acetone at 20ºC is 185 torr. When 1.2
of dissociation, the Van’t Hoff’s factor is more than 1 because g of a non-volatile substance was dissolved in 100 g of
the observed molecular mass has a lesser value than the normal acetone at 20ºC, its vapour pressure was 183 torr. The molar
molecular mass. In case there is no dissociation the value of ‘i’ mass (g mol–1) of the substance is: [JEE Main 2015]
becomes equal to one. a. 32 b. 64 c. 128 d. 488
Since, colligative properties are inversely proportional to 3. 18 g glucose (C6 H I2 P6 ) is added to 178.2 g water. The
molecular masses, the Van’t Hoff’s factor may also be written
vapor pressure of water (in torr) for this aqueous solution
as,
is : [JEE Main 2016]
Observed value of colligative property
i= a. 7.6 b. 76.0 c. 752.4 d. 759.0
Calculated value of colligative property assuming no
association or dissociation 4. Mixture(s) showing positive deviation from Raoult’s law
No. of particles after association or dissociation at 35ºC is(are): [JEE Adv. 2016 P-II]
i=
No. of particles before association or dissociation a. carbon, tetrahedral + methanol
b. carbon disulphide + acetone
Introduction of the Van’t Hoff factor modifies the equations for
c. benzene + toluene
the colligative properties as follows,
d. phenol + aniline
PAo − PA
Relative lowering of vapour pressure = = iX B 5. The freezing point of benzene decreases by 0.45°C when
PAo
0.2 g of acetic acid is added to 20 g of benzene. If acetic
Elevation of boiling point, ∆Tb = ik b m
acid associates to form a dimer in benzene, percentage
Depression in freezing point, ∆Tb = ik f m association of acetic acid in benzene will be: (for benzene =
inRT 5.12 K kg) [JEE Main 2017]
Osmotic pressure, π = ;π = iCRT
V a. 94.6% b. 64.6%
From the value of ‘i’, it is possible to calculate degree of c. 80.4% d. 74.6%
dissociation or degree of association of substance.
6. For a solution formed by mixing liquids L and M. the
vapour pressure of L plotted against the mole fraction of
Degree of Dissociation (α)
M in solution is shown in the following figure. Here x L
It is defined as the fraction of total molecules which dissociate
into simpler molecules or ions. and xM represent mole fractions of L and M,
i −1 respectively, in the solution. The correct statement(s)
α= l m = number of particles in solution applicable to this system is(are): [JEE Adv. 2017 P-I]
m −1

is 0.5 in the mixture. The vapour pressure of the final
Z
solution, the mole fraction of components A and B in
PL vapour phase, respectively are: [JEE Main 2019]
a. 500 mmHg, 0.5, 0.5 b. 450 mmHg, 0.4, 0.6
c. 450 mmHg, 0.5, 0.5 d. 500 mmHg, 0.4, 0.6
1 XM 12. If solubility product of Zr3(PO4)4 is denoted by Ksp and its
a. Attractive intermolecular interactions between L – L. in molar solubility is denoted by S, then which of the
pure liquid L and M – M in pure liquid M are stronger following relation between S and Ksp is correct.
than those between L – M when mixed in solution [JEE Main 2019]
b. The point Z represents vapour pressure of pure liquid 1/ 9 1/ 7
K  K 
M and Raoult's law is obeyed when x L → 0 a. S=  sp  b. S=  sp 
 929   216 
c. The point Z represents vapour pressure of pure liquid M
1/ 6 1/ 7
and Raoult’s law is obeyed from x L → 0 to x L → 1 K   K 
c. S=  sp  d. S=  sp 
d. The point Z represents vapour pressure of pure liquid L  144   6912 
and Raoult’s law is obeyed when x L → 1 13. For the solution of the gases w, x, y and z in water at 298K,
7. For 1 molal aqueous solution of the following the Henry’s law constants (KH) are 0.5, 2, 35 and 40 kbar,
compounds, which one will show the highest freezing respectively. The correct plot for the given data is:
point? [JEE Main 2018] [JEE Main 2019]
a. [Co(H 2O)3 Cl3 ].3H 2O b. [Co(H 2O)6 ]Cl3 z
y
c. [Co(H 2O)5 Cl]Cl2 .H 2O d. [Co(H 2O) 4 Cl2 ]Cl.2H 2O
Partical x
8. An aqueous solution contains an unknown concentration a. pressure w
of Ba2+. When 50 mL of a 1 M solution of Na2SO4 is
added, BaSO4 just begins to precipitate. The final volume
(0,0) Mole
is 500 mL. The solubility product of BaSO4 is 1 × 10–10.
fraction of
What is original concentration of Ba2+? [JEE Main 2018]
z
a. 1 × 10–10 M b. 5 × 10–9 M
c. 2 × 10–9 M d.1.1 × 10–9 M Partical y
b.
pressure x
9. When metal ‘M’ is treated with NaOH, a white gelatinous
precipitate ‘X’ is obtained, which is soluble in excess of w
NaOH. Compound ‘X’ when heated strongly gives an (0,0) Mole
oxide which is used in chromatography as an adsorbent. fraction of
The metal ‘M’ is: [JEE Main 2018]
a. Fe b. Zn c. Ca d. Al
Partical
10. An aqueous solution contains 0.10 M H2Sand 0.20 M c. pressure z
HCl. If the equilibrium constant for the formation of HS − y
x w
is 1.0 ×10−7 and that of S2− from HS− ions is 1.2 × 10 −13 Mole fraction
then the concentration of S2− ions in aqueous solution is: of water
[JEE Main 2018]
a. 5 × 10−19 b. 5 × 10 −8 z
−20 −21
c. 3 × 10 d. 6 × 10 Partical y
d. pressure
11. The vapour pressures of pure liquids A and B are 400 and x
600 mmHg, respectively at 298 K. On mixing the two w
liquids, the sum of their initial volumes is equal to the (0,0) Mole fraction
of water
volume of the final mixture. The mole fraction of liquid B
Solutions 23
14. Which one of the following statements regarding Henry’s Paragraph
law not correct? [JEE Main 2019] Paragraph for Question Nos. 22 to 23
a. The value of KH increases with function of the nature The electrochemical cell shown below is a concentration cell.
of the gas. M|M2+ (saturated solution of sparingly soluble salt,
b. Higher the value of KH at a given pressure, higher is
MX2)|M2+(0.001 mol dm–3)|M The emf of the cell depends on
the solubility of the gas in the liquids.
the difference in concentration of M2+ ions at the two
c. The partial of the gas in vapour phase is proportional to
electrodes. The emf of the cell at 298 K is 0.059 V.
the mole fraction of the gas in the solution.
[JEE 2012 P-II]
d. Different gases have different KH (Henry’s law
22. The value of ∆ G (kJ mol −1 ) for the given cell is (take 1 F
constant) values at the same temperature.
= 96500 C mol −1 )
15. A solution of sodium sulfate contains 92 g of Na+ ions per
kilogram of water, the molality of Na+ ions in that a. –5.7 b. 5.7
solution in mol kg–1 is: [JEE Main 2019] c. 11.4 d. –11.4
a. 16 b. 8 c. 4 d. 12 23. The solubility product (K sp ; mol3 dm−9 ) of at 298 K
16. Liquids A and B form an ideal solution in the entire based on the information available for the given
composition range. At 350 K, the vapor pressures of pure concentration cell is (take 2.303 × R × 298/F = 0.059 V)
A and pure B are 7 × 103 Pa and 12 × 103 Pa,
a. 1× 10−15 b. 4 × 10−15
respectively. The composition of the vapor in equilibrium
with a solution containing 40 mole percent of A at this c. 1× 10−12 d. 4 × 10−12
temperature is: [JEE Main 2019]
a. xA = 0.37; xB = 0.63 b. xA = 0.28; xB = 0.72 Integer and Subjective
c. xA = 0.76; xB = 0.24 d. xA = 0.4; xB = 0.6 24. A compound H 2 X with molar weight of 80 g dissolved
17. The amount of sugar (C12H22O11) required to prepare 2 L in a solvent having density of 0.4 g ml−1. Assuming no
of its 0.1 M aqueous solution is: [JEE Main 2019]
change in volume upon dissolution, the molality of a 3.2
a. 68.4 g b. 17.1 g
molar solution is: [JEE Adv. 2014 P-I]
c. 34.2 g d. 136.8 g
25. The mole fraction of a solute in a solution is 0.1. At 298
18. Elevation in the boiling point for 1 molal solution of
K, molarity of this solution is the same as its molality.
glucose is 2 K. The depression in the freezing point of 2
Density of this solution at 298 K is 2.0 g
molal solutions of glucose in the same solvent is 2 K. The
cm–3. The ratio of the molecular weights of the solute and
relation between Kb and Kf is: [JEE Main 2019]
a. Kb = 0.5 Kf b. Kb = 2 Kf  MWsolute 
solvent,   , is: [JEE Adv. 2016 P-I]
c. Kb = 1.5 Kf d. Kb = Kf  MWsolvent 
19. The concentration of dissolved oxygen (DO) in cold water 26. Liquids A and B form ideal solution over the entire range
can go upto: [JEE Main 2019] of composition. At temperature T, equimolar binary
a. 10 ppm b. 14 ppm solution of liquids A and B has vapour pressure 45 Torr. At
c. 16 ppm d. 8 ppm the same temperature, a new solution of A and B having
20. 8g of NaOH is dissolved in 18g of H2O. Mole fraction of mole fractions xA and xB, respectively, has vapour pressure
NaOH in solution and molality (in mol kg–1) of the of 22.5 Torr. The value of xA/xB in the new solution is ___.
solutions respectively are: [JEE Main 2019] (given that the vapour pressure of pure liquid A is 20 Torr
a. 0.167, 11.11 b. 0.2, 22.20 at temperature T) [JEE Adv. 2018 P-I]
c. 0.2, 11.11 d. 0.167,22.20 27. The plot given below shows P – T curves (where P is the
–12
21. If Ksp of Ag2CO3 is 8×10 , the molar solubility of pressure and T is the temperature) for two solvents X and
Ag2CO3 in 0.1M AgNO3 is : [JEE Main 2019] Y and isomolal solutions of NaCl in these solvents. NaCl
a. 8×10–12 M b. 8×10–10 M completely dissociates in both the solvents.
c. 8×10–11 M d. 8×10–13 M [JEE Adv. 2018 P-I]

1 2 ⇒ ∆P = 0.01P°
Pressure (mmHg) 3 4
760
= 0.01× 760 = 7.6 torr
1. solvent X PS = 760 − 7.6 = 752.4 torr
2. solution of NaCl in solvent X
3. solvent Y 4. (a, b)(a) CCl4 + CH 3 OH ⇒ Positive deviation from Raoult’s
4. solution of NaCl in solvent Y
law O
360
362
367
368
Temperature (K) C
On addition of equal number of moles of a non-volatile (b) CS2 + CH
3 CH 3 ⇒ Positive deviation from
solute S in equal amount (in kg) of these solvents, the Raoult’s law
elevation of boiling point of solvent X is three times that of (c) C6 H 6 + C7 H8 ⇒ Ideal solution
solvent Y. Solute S is known to undergo dimerization in NH 2
O
these solvents. If the degree of dimerization is 0.7 in
solvent Y, the degree of dimerization in solvent X is _____. (d) +
28. Mole fraction of urea in 900 gram water is 0.05. Density
of solution is 1.2 g/cm3. Find molarity of solution. ⇒ Negative deviation from Raoult’s law.
[JEE Adv. 2019 P-II] 5. (a) In benzene 2CH 3 COOH → (CH 3COOH ) 2
1  α
ANSWERS and SOLUTIONS i = 1 +  − 1 α i = 1 − here, α is a degree of
2  1
Ws
1. (a) ∆TL = k b × m = k b × association ∆Tf = iK f m
M s × Wsolution
 α (0.2 / 60)
2.5 × 1000 0.45 = 1 −  (5.12)
2 = 0.76 ×  2 20 /100
Ms ×100 α
1 − = 0.527
0.76 × 2.5 × 1000 2
Ms = = 9.5
100 × 2 ⇒ α=0.945% degree of association = 94.5%
760 − x ns 6. (a, d) Attractive intermolecular interactions between L –
= Xs =
760 n solution L. in pure liquid L and M – M in pure liquid M are
Ws stronger than those between L – M when mixed in
Ws 2.5 × 18 solution. The point Z represents vapour pressure of pure
= = = 36.0 liquid L and Raoult’s law is obeyed when x L → 1.
Wsolv 9.5 × 100
M solv 7. (a) The solution which shows maximum freezing point
x = 760 − 36 = 724 must have minimum number of solute particles.
→ [Co(H 2O)3 Cl3 ]i = 1
(a) [Co(H 2 O)3 Cl3 ].3H 2 O 
P0 − P n1
2. (b) = X solute = → [Co(H 2 O) 6 ]3+ + 3Cl − ,i = 4
(b) [Co(H 2O)6 ]Cl3 
P0 n1 + n 2
185 − 183 2 1.2 / M → [Co(H2O)5 Cl]2+ + 2Cl− , i = 3
(c) [Co(H 2O)5 Cl]Cl 2 .H 2O 
= =
185 185 1.2 + 100 → [Co(H 2 O) 5 Cl]+ + Cl − , i = 2
(d) [Co(H2O)4 Cl2 ]Cl.2H2O 
M 58
So, Solution of 1 molal [Co(H2O)3 Cl3 ].3H 2O
⇒ M = 64
will have minimum number of particles in aqueous state.
18 Hence, option (a) is correct.
3. (c or Bonus) Moles of glucose = = 0.1
180 8. (d) Final concentration of [SO 4−− ]
178.2 [50 × 1]
Moles of water = = 9.9 = = 0.1M
18 [500]
⇒ n Total = 10 Ksp of BaSO4, [Ba 2+ ][so 42 − ] = 1× 10 −10
∆P 0.1 10 −10
⇒ = [Ba 2 + ][0.1] = = 10 −9 M
P° 10 0.1
Solutions 25
2+
Concentration of Ba in final solution 92
15. (d) n Na = =4
= 10–9M Concentration of Ba2+ in the original solution. 23
M 1V 1= M 2 V 2 So, molality = 4
M1 (500 – 50) = 10–9(500)
M1 = 1.11 × 10–9 M PA PO X
16. (b) x A = = O A AO
So, option (d) correct PTolal PA X A × PB X B
7 × 10 3 × 0.4
3+
Excess
=
9. (d) Al 
→ Al(OH)3 ↓ → NaAlO2
NaOH NaOH
7 × 10 × 0.4 + 12 × 10 3 × 0.6
3
Whitegelatinous ppt. Sodium meta

aluminate 2.8
(soluble)
= = 0.28 ⇒ xB = 0.72
10
2Al(OH)3 
Strong heating
→ Al 2 O3 + 3H 2 O
Al2O3 is used in column chromatography. (n)solute
17. (a) Molarity =
10. (c) In presence of external H+ Vsolution (in lit)
H 2S → 2H + + S 2 − , K a1 , K a 2 = K eq wt / 342
0.1 =
2
[H + ]2 [S2− ]
∴ = 1 × 10 −7 × 1.2 × 10 −13 wt (C12H22O11) = 68.4 gram
H 2S
[0.2]2 [S2− ] ∆Tb i.m × k b
= 1.2 × 10−20 18. (b) =
[0.1] ∆Tf i × m × k f
[S2–] = 3 ×10–20 2 1× 1× k b
= Kb = 2 Kf
2 1× 2 × k f
11. (d) Ptotal = X A .PA0 = X B .PB0 = 0.5 × 400 + 0.5 × 600
= 500 mmHg 19. (a) In cold water, dissolved oxygen (DO) can reach a
Now, mole fraction of A in vapour, concentration up to 10 ppm.
PA 0.5 × 400 20. (a) 8g NaOH, mol of NaOH
YA = = = 0.4
Ptotal 500 8
= = 0.2mol
and mole fraction of B in vapour, 40
YB = 1 – 0.4 = 0.6 18
18g H2O, mol of H2O = = 1mol
12. (d) 18
Zr3 (PO 4 ) 4 (s) → 3Zr 4+ (aq.) + 4 PO 3-4 (aq.)
3S M 4S M 0.2
∴ X NaOH = = 0.167
1.2
Ksp = [Zr4+ ]3 [PO3-4 ]4 = (3S)3 .(4S)4 = 6912 S7
0.2 ×1000
1/ 7 Molality = = 11.11 m
 K sp  18
∴ S=  
 6912 
21. (b) Ag 2 CO 3 (s) → 2Ag + (aq.) + CO 3–2 (aq)
(0.1+ 2S)M MS
 n gas 
13. (c) P = k H ×   + 2
K sp = [Ag ] [CO ] –2
 n H O + n gas  3
 2  8 × 10–12 = (0.1 + 2S)2 (S)
 n H2 O  S = 8 × 10–10 M
= k H × 1 − 
 n H O + n gas 
 2 
⇒ p = k H − k H × χ H2 O
22. (d) ∆G = −nFE cell
p = (−k H ) × χ H2 O + k H = −2 × 96500 × 0.059
14. (b) Liquid solution = −11.387 kJ mol −1

Pgas = KH × X gas = −11.4 kJ
More is KH less is solubility, lesser solubility is at higher −0.0591 C
23. (b) E = log10 −3
temperature. So more is temperature more is KH. 2 10

−0.0591  C  27. When, NaCl as solute is used
0.059 = log10  −3 
2  10  For solvent X For solvent Y
C 2 = 2K b m 1 = 2 × K 'b m
10 −2 = ⇒ C = [M 2 + ] = 10 −5 M.
10 −3 Kb
∴ =2
+2 − 2 −5 3 −15
K sp = [M ] [X ] = 4s = 4(40 ) = 4 ×10
3 K 'b
When solute S is used then molality in both solvent is equal.
24. Here, Vsolution ≈ Vsolvent For solvent X For solvent Y
Since, in 1ℓ solution, 3.2 moles of solute are present, α 0.7
So, 1ℓ solution ≈ 1ℓ solvent i = 1− i = 1− = 0.65
2 2
(d = 0.4g / ml) ≈ 0.4 kg  α
∆Tb =  1 −  K b m ∆T 'b = (0.65)K 'b m
moles of solute 3.2  2
So, molality(m) = = =8
mass of solvent (kg) 0.4
 α
1− × 2
25. Molality (m) =
x solute ×1000
=
0.1× 1000 ∆Tb  2 
X solvent × M solvent 0.9 × M solvent 3= =
∆T 'b 0.65
0.1× 2 ×1000 α 3
Molarity (M) = 1− = × 0.65
0.1 M solute + 0.9 M solvent 2 2
As Molality = Molarity, α 3
= 1 − × 0.65
0.1×1000 0.1× 2 × 1000 2 2
So =
0.9 × M solvent 0.1 M solute + 0.9 M solvent α = 0.05
So 0.1 M solute + 0.9 M solvent 28. (3) wt H2 O = 900g
= 1.8 M solvent . 900
⇒ n H2 O = = 50
M solute 18
So =9
M solvent Let moles of urea = y
So, Answer is = 9 y 50
⇒ x urea = = 0.05 ⇒ y =
y + 50 19
26. PAº = 20 Torr
 50  3000
For equimolar binary solution: ∴ Wt urea =   × 60 =
1  19  19
xA = xB = 3000 (201)
2 ∴ Wt solution = = 900 = ×100
PAº + PBº 19 19
∴ = 45 ρsolution = 1.2g / cm3
2
⇒ PBº = 70 Torr wt  201  100
⇒ Vsolution = = ×
If mole fractions are x A & x B ρ  19  1.2
PBº + (PAº − PBº )x A = 22.5  50 

  × 1000
× 1000 =  
n urea 19
⇒ 70 + (20 − 70)x A = 22.5 ⇒ M urea =
Vml  201  100
 ×
47.5 2.5  19  1.2
⇒ xA = and x B =
50 50 (500)(1.2) 600
= = = 2.985
xA 47.5 201 201
= = 19.00
xB 2.5 Answer after truncation = 2.98
Gaseous State 27
4 Gaseous State
QUICK LOOK 8 RT  2 
= =  v = 0.92 v rms
π M  3π  rms
Ideal gas molecules possess no size and do not exert
It is thus evident that v rms > v av > v mp
intermolecular forces. Ideal gas equation PV = RT holds for
high temperature and low pressure. Gas constant R is universal A planet or satellite will have atmosphere only and only if
constant. It is independent of volume, temperature and
pressure. Its value is 8.3 J/mol K for all gases.
(
vrms < vvescape = 2gR . )
Pressure exerted by an ideal gas
Table 4.1: Different forms of Gas Equation 1 mnc2 1 2 2 E k
P= . = ρc = .
Quantity of gas Equation Constant 3 V 2 3 V
R = universal gas
1 mole gas PV = RT n = total number of molecules,
constant
c = root mean square speed
µ mole gas PV = µ RT
 R  k = Boltzmann's
ρ = density,
1 molecule of gas PV =   T = kT
 NA  constant E k = total kinetic energy
N molecules of gas P V = N kT
V = volume
R r = Specific gas
1 g of gas PV =   T = rT
M constant Table 4.2: Various Translational Kinetic Energies
m g of gas P V = m rT Quantity of gas Kinetic energy
3
1 mole gas RT; R = Universal gas constant
2
Different Types of Speeds of Gas Molecules: Root mean
3
square speed: It is defined as the square root of mean of µ mole gas µRT
2
squares of the speed of different molecules, i.e.,
3
1 molecule kT; k = Boltzmann’s constant
v 2 + v 22 + ... 2
v rms = 1 = v2
N 3
N molecule NkT
and according to the kinetic theory of gases, 2
3
3 PV 1 g gas rT; r = Specific gas constant
v rms = 2
mass of gas
3
m g gas mrT
3 RT 3 kT 2
= =
M m Degrees of freedom associated with each molecule of gas
Ï3 for monatomic gas
Most Probable Speed: It is the speed which maximum Ô
f = Ì5 for distomic gas
number of molecules in a gas has at constant temperature and Ô6 for triatomic or polyatomic gas
Ó
is given by:
Law of equipartition of energy: Mean kinetic energy
2PV 2 1
v mp = = v rms = 0.816 v rms associated per degree of freedom ε = kT
M 3 2
Relation between degree of freedom and γ
Average Speed: It is the arithmetic mean of the speed of
Cp 2
molecules in a gas at a given temperature, γ= = 1+
Cv f
v1 + v 2 + v 3 + ...
i.e., vav = 1 kT
N Mean free path = =
and according to kinetic theory of gases 2πσ n 2πσ p

3 Gas Laws
Average translational kinetic energy per molecule = kT
2
(for all gases)
Total average kinetic energy per molecule
È = 23 kT for monatomic gases
Í
E Í = 53 kT for diatomic gases 6 6
pressure pressure
ÍÎ = 23 kT for triatomic or polyatomic gases volume 5 volume 5
4 4
1.0 1.5 1.0 1.5
Total average kinetic energy per mole: 3 0.5 2.0
temperature 3 0.5 2.0
temperature
0 2.5 2 0 2.5
3 2
• RT for monatomic gases 200 300 200 300
2 1 400
1
100 400 100
0
5 0 500 500
• RT for diatomic gases
2
Figure: 4.2
• 3 RT for triatomic or polyatomic gases
Gay-Lussac’s Law: According to it, for a given mass of an
Maxwell’s distribution of law of speeds:
ideal gas at constant volume, pressure of a gas is directly
3
 M 2 2  − Mv 2  proportional to its absolute temperature, i.e.,

f (v) = 4π   v exp  
 2π RT   2RT  P α T if m and V = constant
P
2
Pressure law = constant at constant V and given mass
 m  3 2 − mv 2 / 2kT T
n v dv = 4N   ve dv
 2π kT 
V1 < V2 < V3 < V4
vp v
vrms V1
Most probable speed
Maxwell Speed
Mean speed
V2
Distribution
Pressure (bar)
Root mean squared
V3
speed
V4
0
Molecular speed 100 200 300 400
Figure: 4.1 Temperature (K)
Figure: 4.3
Mean free path: The distance travelled by a gas molecule Boyle’s Law: According to it for a given mass of an ideal gas
between two successive collision. at constant temperature, the volume of a gas is inversely
1 m proportional to its pressure, i.e.,
λ= =
2π nd 2
2πρ d 2 1
Vα if mass of gas and T = constant
P
Where, d diameter of molecule and n number of molecules per
P V = constant at constant T and constant mass
unit volume and ρ density as m mass of each molecule and mn P
For a fixed mass of gas
mass per unit volume or density. Degree of freedom, f: possible at constant temperature T3
T1 < T2 < T2
independent motions – translator, rotatory and vibratory.
T1
Pressure
T3
Monatomic f = 3 translatory (e.g.: He, Ne, Ar, etc.)
Pressur
Diatomic f = 5 (3 translatory and 2 rotatory e.g.: H 2 , O 2 etc. ) T2

T3 < T2 < T1
Triatomic f = 6 (3 translatory, 2 rotatory and 1 vibratory e.g.: T1
H 2 O etc.) O
0 vfixed Volume 1/V
V
f = 7 (3 translatory, 2 rotatory and 2 vibratory e.g.: CO 2 etc.)
Figure: 4.4
Gaseous State 29
Charles’ Law: According to it for a given mass of an ideal gas Avogadro’s Law: According to it, at same temperature and
at constant pressure, volume of a gas is directly proportional to pressure, equal volumes of all the gases contain equal number
its absolute temperature i.e. V ∝ T, if m and P = constant then of molecules, i.e., N1 = N 2 if P, V and T are same.
V
= constant  α 
T Van der Waal’s equation  P + 2  (V − b) = RT for 1 mole
 V 
T Critical temperature, pressure and volume
8α 8α
55
Tc = , Pc = , Vc = 3b
50 27 Rb 27 b 2
45 Temperature (K)
a 27
40
Boyle’s temperature, TB = = TC
Pressure (Pa) Rb 8
35
30 Multiple Choice Questions

25 One and More than One Correct
20 V
Volume (M )3 1. A monatomic ideal gas undergoes a process in which the
ratio of P to V at any instant is constant and equals to 1.
What is the molar heat capacity of the gas? [JEE 2006]
4R 3R
Amount (moles) a. b.
Number of molecules – T 2 2
Figure: 4.5 5R
c. d. 0
Dalton’s Law: According to it, the pressure exerted by a 2
gaseous mixture is equal to the sum of partial pressure of each 2. The given graph represents the variation of Z
component present in the mixture, i.e., PV
(compressibility factor = ) versus P, for three real
P = P1 + P2 + ... nRT
gases A, B and C. Identify the only incorrect statement.
[JEE 2006]
C
A
A
Ideal gas
B
Oxygen Nitrogen Oxygen 1
C
Pressure P2 Pressure P1 +P2 Pressure Z
P1 B
159 mm Hg 593 mm Hg 752 mm Hg
0 P (atm)
Figure: 4.6
Graham’s Law: According to it, at constant pressure and
a. For the gas A, a = 0 and its dependence on P is linear
temperature, the rate of diffusion of a gas is inversely
at all pressure
proportional to the square root of its density i.e., b. For the gas B, b = 0 and its dependence on P is linear
1 at all pressure
Rate of diffusion ’r’ ∝ if P and T = constant
ρ c. For the gas C, which is typical real gas for which
neither a nor b = 0. By knowing the minima and the
point of intersection, with Z = 1, a and b can be
calculated
Diffusion d. At high pressure, the slope is positive for all real gases
Partition 3. A gas described by van der Waal’s equation
[JEE 2008 P- I]
a. behaves similar to an ideal gas in the limit of large
molar volumes
Effusion b. behaves similar to an ideal gas in the limit of large
pressures
Figure: 4.7

c. is characterized by van der Waal’s coefficients that are a. MX b. MX 2
dependent on the identity of the gas but are c. M 2 X d. M 5 X14
independent of the temperature
d. has the pressure that is lower than the pressure exerted 9. For an ideal gas, consider only P–V work in going from an
by the same gas behaving ideally initial state X to the final state Z. The final state Z can be
reached by either of the two paths shown in the figure.
4. The Henry’s law constant for the solubility of N 2 gas in
Which of the following choice(s) is (are) correct? [take ∆ S
water at 298 K is 1.0×10–5 atm. Mole fraction of N 2 in air as change in entropy and W as work done].
is 0.8. The number of moles of N 2 from air dissolved in 10 [JEE 2012 P-I]
moles at 298 K and 5 atm pressure is: [JEE 2009 P-I]
P (atmosphere)
–4 –5
a. 4.0 × 10 b. 4.0 × 10 X Y
c. 5.0 × 10–4 d. 4.0 × 10–6
5. The term that corrects for the attractive forces present in a
Z
real gas in the van der Waals equation is: [JEE 2009 P-I]
V(litre)
an 2 an 2
a. nb b. c. − d. –nb a. ∆Sx →z = ∆Sx →y + ∆Sy→z b. Wx→z = Wx→y + Wy→z
V2 V2
6. According to kinetic theory of gases [JEE 2011 P -I] c. Wx →y→z = Wx→y d. ∆Sx→y→z = ∆Sx→y
a. collision are always elastic
10. The reversible expansion of an ideal gas under adiabatic
b. heavier molecules transfer more momentum to the wall
and isothermal conditions is shown in the figure. Which
of the container
of the following statement(s) is (are) correct?
c. only a small number of molecules have very high
[JEE 2012 P-II]
velocity
(P1 , V1 , T1 )
d. between collision, the molecules move in straight lines
with constant velocities isothermal
P
7. For one mole of a van der Waals gas when b = 0 and T = adiabatic (P2 , V2 , T2 )
(P3 , V2 , T3 )
300 K, the PV vs. 1/V plot is shown below. The value of
the van der Waals constant a (atm. liter2 mol2) is:
V
[JEE 2012 P-I]
a. T1 = T2 b. T3 > T1
PV (litre-atm mol–1)
24.6 (Graph not to scale)

23.1 c. Wisothermal > Wadiabatic d. ∆U isothermal > ∆U adibatic
21.6
20.1 11. A piston filled with 0.04 mol of an ideal gas expands
reversibly from 50.0 mL to 375 mL at a constant
temperature of 37.0°C. As it does so, it absorbs 208 J of
1
0 2.0 3.0 heat. The values of q and w for the process will be:
1
(mol liter −1 ) (R = 8.314 J / mol K) (ln 7.5 = 2.01) [JEE Main 2013]
V
a. 1.0 b. 4.5 c. 1.5 d. 3.0 a. q = +208 J, w = −208 J b. q = −208 J, w = − 208 J
8. A compound MpXq has cubic close packing (ccp) c. q = − 208 J, w = +208 J d. q = +208 J, w = +208 J
arrangement of X. Its unit cell structure is shown below. 12. For a gaseous state, if most probable speed is denoted by
The empirical formula of the compound is: C*, average speed by C and mean square speed by C,
[IIT JEE 2012 P-I]
then for a large number of molecules the ratio of these
speeds are: [JEE Main 2013]
M= a. C*: C : C = 1.225 :1.128 :1
X=
b. C*: C : C = 1.128 :1.1225 :1
c. C* : C : C = 1:1.228 :1.225
d. C* : C : C = 1:1.225 :1.128
Gaseous State 31
13. An ideal gas in thermally insulated vessel at internal T1 T1 T1 T2
pressure = P1 , volume = V1 and absolute temperature = T1 Pi , V Pi , V ⇒ Pf ,V Pf ,V
expands irreversibly against zero external pressure, as

shown in the diagram. The final internal pressure, volume
 TT   T1 
and absolute temperature of the gas are P2 , V2 and T2 , a. p i  1 2  b. 2pi  
 T1 + T2   T1 + T2 
respectively. For this expansion. [JEE Adv. 2014 P-I]
 T2   TT 
c. 2pi   d. 2pi  1 2 
 T1 + T2   T1 + T2 
Pext = 0 Irreversible Pext = 0 16. 0.5 moles of gas A and x moles of gas B exert a pressure of
P1 , V2 , T2 200 Pa in a container of volume 10 m3 at 1000K given R is
P1 , V2 , T2 the gas constant in JK–1 mol–1 m, x is: [JEE Main 2019]
2R 2R
a. b.
Thermal insulation 4 + 12 4−R
a. q = 0 b. T2 = T1 4−R 4+R
c. d.
2R 2R
γ γ
c. P2 V2 = P1 V1 d. P2 V2 = P1V1
17. The volume of gas A is twice than that of gas B. The
14. One mole f a monatomic real gas satisfies the equation compressibility factor of gas A is thrice than that of gas B
p(V-b) = RT where b is a constant. The relationship of at same temperature. The pressures of the gases for equal
interatomic potential V(r) and interatomic distance r for number of moles are: [JEE Main 2019]
the gas is given by: [JEE Adv. 2015 P-II] a. 2PA = 3PB b. PA = 3PB
c. PA = 2PB d. 3PA = 2PB
V(r)
18. Which of the following is/are correct regarding root
a. 0
r mean square speed (Urms) and average translation
K.E.(Eav) of molecule in a gas at equilibrium.
[JEE Adv. 2019 P-I]
V(r)
a. Eav is doubled when its temperature is increased 4
b. 0 times
r
b. Urms is inversely proportional to the square root of its
molecular mass
V(r) c.Eav at a given temperature doesn’t depend on its
molecular mass
c. 0
r d. Urms is doubled when its temperature is increased 4 times
Matrix Match/Column Match
V(r) 19. Match gases under specified conditions listed in Column-I
d. with their properties/laws in Column-II. [JEE 2007 P- I]
0
r Column I Column II
(A) Hydrogen gas (P=200 1. Compressibility factor
atm, T =273K) ≠1
15. Two closed bulbs of equal volume (V) containing an ideal
gas initially at pressure p i and temperature T1 are (B) Hydrogen gas 2. Attractive forces are
(P ∼ 0, T = 273K) dominant
connected through a narrow tube of negligible volume as
shown in the figure below. The temperature of one of the (C) CO2 (P =1 atm, T = 273K) 3. P = nRT
bulbs is then I raised to T2 . The final pressure p f is: (D) Real gas with very 4. P(V − nb) = nRT
[JEE Main 2016] large molar volume

a. A→ 1,2; B→ 3; C→ 1, 2; D→ 1,4 22. The equilibrium constant K p for this reaction at 298 K, in
b. A→ 1,3; B→ 4, 2; C→ 3; D→ 4,1
terms of β equilibrium , is:
c. A→ 3,4; B→ 2, 1; C→ 1,2; D→ 1,4
d. A→ 3,4; B→ 2, 4; C→ 2; D→ 1 8 β equilibrium
2
8 β equilibrium
2
a. b.
2 − β equilibrium 4 − β equilibrium
2
Paragraph 4 β equilibrium
2
4 β equilibrium
2
c. d.
Paragraph for Question Nos. 20 to 21 2 − β equilibrium 4 − β equilibrium
2
X and Y are two volatile liquids with molar weights of 10 g

23. The incorrect statement among the following, for this
mol–1 and 40 g mol–1 respectively. Two cotton plugs, one
reaction is
soaked in X and the other soaked in Y, are simultaneously
a. Decrease in the total pressure will result in formation of
placed at the ends of a tube of length L = 24 cm, as shown in
more moles of gaseous X
the figure. The tube is filled with an inert gas at 1 atmosphere
b. At the start of the reaction, dissociation of gaseous X2
pressure and a temperature of 300 K. Vapours of X and Y react
takes place spontaneously
to form a product which is first observed at a distance d cm
from the plug soaked in X. Take X and Y to have equal c. β equlibrium = 0.7
molecular diameters and assume ideal behaviour for the inert d. K C < 1
gas and the two vapours. [JEE Adv. 2014 P-II]
L = 24 cm Integer and Subjective
24. At 400 K, the root mean square (rms) speed of a gas X
d
(molecular weight = 40) is equal to the most probable
Cotton wool Initial formation of Cotton wool
Soaked in X The product Soaked in Y speed of gas Y at 60 K. The molecular weight of the gas
Y is: [JEE 2009 P- II]
20. The value of d in cm (shown in the figure), as estimated
from Graham’s law, is 25. One mole of an ideal gas is taken from a to b along two paths
a. 8 b. 12 c. 16 d. 20 denoted by the solid and the dashed lines as shown in the
21. The experimental value of d is found to be smaller than graph below. If the work done along the solid line path is ws
the estimate obtained using Graham’s law. This is due to and that along the dotted line path is wd, then the integer
a. larger mean free path for X as compared to that of Y closest to the ratio wd/ws is: [JEE 2010 P-II]
b. larger mean free path for Y as compared to that of X 4.5
4.0 a
c. increased collision frequency of Y with the inert gas as 3.5
compared to that of X with the inert gas P
atm. 3.0
d. increased collision frequency of X with the inert gas 2.5
2.0
ascompared to that of Y with the inert gas
1.5
1.0
Paragraph for Question Nos. 22 to 23 0.5 b
Thermal decomposition of gaseous X 2 to gaseous X at 298 K 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
V (lit.)
takes place according to the following equation:
X 2 (g) → 2X(g) . The standard reaction Gibbs energy, ∆ r G° of 26. If the value of Avogadro number is 6.023 × 10 23 mol −1 and
this reaction is positive. At the start of the reaction, there is one the value of Boltzmann constant is 1.380 × 10 −23 JK −1 , then
mole of X 2 and no X. As the reaction proceeds, the number of the number of significant digits in the calculated value of the
universal gas constant is: [JEE Adv. 2014 P-I]
moles of X formed is given by β. Thus β equilibrium is the number
27. The diffusion coefficient of an ideal gas is proportional to its
of moles of X formed at equilibrium. The reaction is carried mean free path and mean speed. The absolute temperature of
out at a constant total pressure of 2 bar. Consider the gases to an ideal gas is increased 4 times and its pressure is increased
behave ideally. (Given: R = 0.083 L bar K −1 mol −1 ) 2 times. As a result, the diffusion coefficient of this gas
[JEE Adv. 2016 P-II] increases x times. The value of x is: [JEE Adv. 2016 P-I]
Gaseous State 33
28. A closed tank has two compartments A and B, both filled 7. (c) b = 0, T = 300 K, n = 1
with oxygen (assumed to be ideal gas). The partition
 an 2 
separating the two compartments is fixed and is a perfect P + 2  (V − nb) = RT
 V 
heat insulator (Figure 1). If the old partition is replaced by
a new partition which can slide and conduct heat but does  a 
 P + 2  (V) = RT
NOT allow the gas to leak across (Figure 2), the volume  V 
(in m3) of the compartment A after the system attains a
equilibrium is ____. [JEE Adv. 2018 P-I] ⇒ PV + = RT
V
1m3 ,5bar 3m3 ,1bar 1
400 K
A
300 K
B
PV = −a ×   + RT
V
Figure 1
y = mx + C Slope = – a
A B y2 − y1 20.1 − 21.6
Slope = = 1.5
Figure 2 x 2 − x1 3−2
1 1
ANSWERS and SOLUTIONS 8. (b) X : 8 × + 6 × = 4
8 2
1. (a) 1
M= × 4 + 1 = 2;
2. (b) 4
3. (a, c, d) M 2 X 4 = MX 2
 n 2a  9. (a, c) Wx→z = Wx→y + Wy→z
 P +  (V − nb) = nRT
 V2 
As work done is not a state function so it depends on the
At low pressure, when the sample occupies a large volume, path.
the molecules are so far apart for most of the time that the Wx→y→z = Wx→y (as volume is constant)
intermolecular forces play no significant role, and the gas
behaves virtually perfectly, a and b are characteristic of a ⇒ Wy→z = 0 ∆Sx →z = ∆Sx →y + ∆Sy→z
gas and are independent of temperature. (since ∆ S is a state function, it does not depend on the
 n a 2 path).
The term  P + 2  represents the pressure exerted by an
 V  10. (a, c, d) Process is isothermal implies T1 = T2 A is correct
ideal gas while P represents the pressure exerted by a real gas. T1 V1γ −1 = T3 V2γ −1
4. (a) P = K H χ N2 T3  V1 
=   V2 > V1
T1  V2 
0.8 × 5 = 1× 105 × χ N2
From the diagram
χ N × 4 ×10−5 (in 10 moles of water)
2
V1
⇒ <1
n N2 V2
⇒ 4 × 10 −5 =
n N 2 + 10 γ −1
 V1 
−5
n N2 × 5 ×10 + 4 ×10 = n N2 −4 ⇒   <1
 V2 
⇒ n N2 = 4 ×10−4 ⇒ T3 < T1
5. (b) The measure of force of attraction for ‘n’ moles of Option b is correct.
Work done is area under the curve, clearly the area under the
 n 2a   n 2a 
real gas  2   P + 2  curve for isothermal process is greater. Option (c) is correct.
V   V 
For an ideal gas, internal energy is a function of
(V − nb) = nRT Temperature. Final temperature for adiabatic process is
6. (a, c, d) less than its initial temperature, while initial and final

temperature for isothermal process is same. Hence, 4
− 1 = 2x
internal energy change for isothermal process is greater R
than internal energy change for adiabatic process 4−R
=x
( ∆U iso = 0 and ∆U adia < 0) 2R
11. (a) q = + 208 J, (as it absorb heat)
17. (a) VA = 2VB
v  ZA = 3ZB
w Re w = −2.303 nRT log10  2 
 v1  PA VA 3 ⋅ PB ⋅ VB
=
 375  n A RTA n B ⋅ RTB
= −2.303 × (0.04 × 8.314 × (310) log10   = −208 J
 50  2PA = 3PB
2RT 8RT 3RT 3 3RT

12. (c) C*: C : C = = = 18. (b, c, d) E av = RT U rms =
M πM M 2 M
1
8 & U rms ∝
2: = 3 M
3.14
1 : 1.128 : 1.225 EAV doesn’t depend on its molecular mass.
13. (a, b, c) Since container is thermally insulated. So, q = 0, 19. (a) A→ 1,2; B→ 3; C→ 1, 2; D→ 1,4
and it is a case of free expansion therefore W = 0 and PVm
(A) Z = at high pressure and low temperature.
∆E = 0 RT
So, T1 = T2  an 2 
Equation  P + 2  (V − nb) = nRT
 V 
Also, P1 V1 = P2 V2
reduces to P(V − nb) = nRT.
14. (c) At large inter-ionic distances (because a → 0) the P.E.
(B) For hydrogen gas value of Z = 1 at P = 0 and it increase
would remain constant. However, when r → 0; repulsion continuously on increasing pressure.
suddenly increase. (C) CO2 molecules have larger attractive forces, under normal
15. (c) Initial moles = final moles conditions.
Pi × V Pi × V Pf × V Pf × V PVm
+ = + (D) Z = , at very large molar volume Z ≠ 1.
RT1 RT1 RT2 RT1 RT
Pi Pi Pf Pf For Question Nos. 20 to 21

+ = +
T1 T1 T2 T1 rX d 40
20. (c) = = =2
rY 24 − d 10
2Pi 1 1
= Pf  +  d = 48 − 2d
T1  T2 T1 
3d = 48 ⇒ d = 16 cm
2Pi  T + T2 
= Pf  1 
T1  T1T2 
21. (d) As the collision frequency increases then molecular
speed decreases then the expected.
 T2 
Pf = 2Pi ×  
 T1 + T2  For Question Nos. 22 to 23
22. (b) Paragraph-1
16. (c) n T = (0.5 + x) X 2 (g) → 2X(g)
PV = n × R × T Initial mole 1 0
200 × 10 = (0.5 + x) × R × 1000 t = t eq. (1 − α ) 2 α
2 = (0.5 + x)R Given 2α = β equilibrium
2 1
= +x βequilibrium
R 2 So, α =
2
Gaseous State 35
Total mole at equilibrium So, K< 1 K p − K c (RT) ∆ng. (RT > 1)
 β eq  Kp
= (1 + α ) = (1 +   Kc = ⇒ Kc < Kp
 2  RT
 β eq.  So, Kc < 1
1 − 
Px 2 =  2 P 
24. Vrms ( Xgas )( 400 K ) = Vmp ( Ygas )( 60 K )
 β eq.
total

1 + 2  M.W.(X gas) = 40; M.W.(Ygas) = x
 2 − β eq  3RT1 2RT1
= Ptotal  =
 2 + β eq  M1 M2
 2 − β eq  400 × 3 2 × 60
= Ptotal  =
 2 + β eq  40 x
120
  ⇒ 30 = , x=4
 β eq  x
Px (g ) = Ptotal 
 β eq  25. w d = 4 × 1.5+1× 1 + 2.5 × 2/3 = 8.65
1 + 2  Process is isothermal
5.5
 2 β eq  w s 2 × 2.303log =2 × 2.303 × log11= 2 × 2.303 × 1.041
= Ptotal  0.5
 2 + β eq 
w 2 × 2.303log =2 × 2.303 × log11= 2 × 2.303 × 1.0414 = 4.79
(Px)2
So, Kp =
(Px 2 ) Wd 8.65
= = 1.80 ≃ 2
2 Ws 4.79
 2β eq. 
 × Ptotal  R
 2 + β eq.  26. k=
= NA
 2 − β eq. 
 × Ptotal  R = kN A
 (2 + β eq ) 
= 1.380 ×10−23 × 6.023 ×1023
4β 2
eq. = 8.31174 ≈ 8.312
⇒ Kp = × Ptotal
4 − βeq.
2
27. Diffusion coefficient
D ∝ (λ ×ν mean )
 8β eq2 
=  T
 4−β2  T 
 eq  D ∝  × 
P M 
23. (c) (a) Correct statement: As one decrease in pressure
reaction move indirection where no. of gaseous T T Di
D∝ ;
molecules increase. P M D f
(b) Correct statement: As the start of reaction Q p < K p so T T

dissociation of X 2 take place spontaneously = P
4T 4T
.
(c) Incorrect statement as 2P
1 1
8βeq2 8 × (0.7)2 = =
Kp = = > 1, but 4× 2 4
4 − βeq2 4 − (0.7)2
2
(d) Correct statement: As Df 4
∆G° > 0 & ∆G° = −RTℓ n K p = .
Di 1
∆G° > 1, so K p should be less than 1.
So, answer is 4.

28. From figure – 1 5 1
⇒ =
5 ×1 5 400 R.VA 100R.VB
nA = =
R × 400 400 R VA 5 4
⇒ = ⇒ VB = VA
1× 3 3 1 VB 4 5
nB = = =
R × 300 300R 100R ∵ VA + VB = 4 m3
Figure 2 - after the system attains equilibrium
4
PA = PB and TA = TB = T ⇒ VA + VA = 4
5
n A RT n B RT
∴ = 20
VA VB ⇒ VA = = 2.22 ≈ 2 m3
9
Atomic Structure 37
5 Atomic Structure
QUICK LOOK Bohr Model: (For hydrogen like atoms): The quantum theory
to atomic model was first of all applied by Bohr. Bohr
Structure of Atom quantised angular momentum of electron. The consequence of
The specific charge ( e / m ) of proton is 9.58 × 10 7 C / kg . it was that all the quantities radius, velocity, linear momentum,
angular momentum and energy were quantised. Bohr’s theory
Mass of 1 mole proton = N × m p = 6.023 × 10 23 ×1.673 ×
is applicable only to atoms containing one electron only e.g.,
10−27 kg 1.0076 × 10 −3 kg = 1.0076 g. He, He + , Li + + etc.
−13
The radius of proton = 1.53 ×10 cm.
Here e = elementary charge, r = radius of orbit, m = mass of
πr = × × (1.53 × 10 −13 )
4 3 4 22 3
The volume of proton =
3 3 7 electron, v = speed of electron, h = Planck’s constant, n =
= 1.50 ×10−38 cm3 . integer = principal quantum number.
The charge on positive rays is usually + 1 but it may have + mv2 1 Ze2
Conditions of circular orbit = ⋅
2, +3 values. r 4πε 0 r 2
circumference of orbit h
Number of waves in an orbit = Condition of quantisation: mvr = n
wavelength 2π
2πr 2πr ⋅ mu 2π ( mur ) n Condition of transition : hv = E1 ∼ E 2
= = = = 2π × =n
λ h h 2π ε 0h 2n 2 n2
Radius of nth orbit: rn = = 0.53 Å
 nh  π mZe 2 Z
∵ mur = 
 2π  According to Bohr’s theory, radius of nth orbit rn ∝ n 2 .
Number of revolution f an electron per second in the nth
The radius of first Bohr orbit is 0.53Å
orbit
e Z c Z
speed of electron u Speed of electron in nth orbit: vn = ⋅ = ⋅
= = n 2ε 0 h n 137 n
circumference 2π rn
where c = speed of light.
The wavelength of an electron accelerated by a potential
The velocity of electron in first Bohr orbit is
1
difference V can be given by = mu 2 = eV c
2 = 2.2 × 106 m / s.
137
2eV
∴ u= 1 Ze2
m Kinetic energy: E k = ⋅
4πε 0 r
h h
∴ λ= = .
mu 2meV 1 Ze2
Potential energy: U = − ⋅
h 4πε 0 r
For a gas molecule, λ =
m ⋅ u rms 1 Ze2
Total energy: E = − ⋅
1 3 RT 4πε 0 2r
∵ Average kinetic energy = mu 2 =
2 2 N 1
Total energy of electron, E ∝ .
R 1 3 3kT n2
k= = 1.38 × 10 −23 J / K Or mu 2 = kT u =
N 2 2 m For hydrogen atom in lowest orbit (n = 1).E = −13.6 eV
h h The total energy increases as the electron reaches in higher
∴ λ= =
3kT 3mkT orbits, but kinetic energy decreases.
m×
m In free state (out of atom), electron can have any energy
Where, k is Boltzmann’s constant. (continuous state).

The energy ∆E is released when electron jumps from higher The Wave Functions for Hydrogen
orbit to lower orbit. The corresponding wavelength of According to quantum mechanics, the atom has no sharply
12375 defined boundary as suggested by the Bohr theory. The
emitted radiation is λ = Å probability distribution in figure a suggests that the charge of
∆E
When electron jumps from higher to lower orbit, photon is the electron can be modeled as being extended throughout a
region of space, commonly referred to as an electron cloud.
emitted and the atom recoils. The momentum of recoiled
The darkest portion of the distribution appears at r = a0 ,
h
atom is equal to the momentum of photon i.e., p N = corresponding to the most probable value of r for the electron.
λ
Sommerfeld introduced the idea of elliptical orbits. For P1s(r) y
principal quantum number n, there are n orbits, out of
which (n – 1) are elliptical while on is circular.
r = a0
Energy Spectrum:
x
Z 2 Rhc Z2
th
For n orbit E n = = −13.6. eV
n2 n2
n = 4, k = 2 a0 = 0.0529 nm
a b
Figure: 5.2
The next-simplest wave function for the hydrogen atom is the

n = 4, k = 1
n = 4, k = 3 one corresponding to the 2s state (n = 2, l = 0). The normalised
n = 4, k = 4
wave function for this state is:
Figure: 5.1
3/ 2
1  1   r  −2 / 2 a0
me2 ψ 2s (r) =   2− e
Where, R = 2 3 = Rydberg constant 4 2  a0  a
8ε 0 ch  0 
P(r)
E − E2 0.6
Frequency of emitted radiation V = 1
h 0.5
1s
 1 1  0.4
= Rc  2 − 2 
 n1 n 2  0.3
Wave number v or wavelength (λ ) of emitted radiation: 2s
0.2
1  1 1  0.1
v= = R 2 − 2 
λ n
 1 n 2  0.0 r/a0
0 4 8 12 16 20
Figure: 5.3
Series
Again notice that ψ 2s depends only on r and is spherically
1 1 1 
Lyman Series = R  2 − 2  , n = 2,3, 4,5,... symmetric. The energy corresponding to this state is
λ 1 n 
E 2 = −(13.606 / 4)eV = −3.401eV. The plot for the 2s states
1  1 1 
Balmer Series = R  2 − 2  , n = 3, 4,5,... has two peaks. These models were against the Heisenberg
λ  2 n  uncertainty principle. The principle states that it is impossible
1 1 1  to determine momentum and position of a sub-atomic particle
Paschen Series = R 2 − 2  , n = 4,5, 6,... precisely and simultaneously.
λ 3 n 
 h 
1 1 1  ∆p ⋅ ∆x ≥   ;
Brackett Series = R  2 − 2  , n = 5, 6, 7,...  4π 
λ 4 n 
 h 
1  1 1  Or m ⋅ ∆u ⋅ ∆x ≥  
Pfund Series = R  2 − 2  , n = 6, 7,8,...  4π 
λ 5 n 
Atomic Structure 39
 h  ℏ ℏ A collection of orbitals with the same value of n is called an

Or ∆u ⋅ ∆x ≥   ≥ ≥ electron shell, e.g., all the orbitals with n = 3 are said to be
 4π m  2π m 2m
in 3rd shell. One or more orbitals with same values of n and
h h
ℏ = and ℏ = l is called a sub-shell. Each sub-shell is designated by a
2 2π
number (the value of n) and a letter (s, p, d or f
∆p is uncertainty in momentum;
corresponding to the values of l), e.g., all the orbitals with n
∆x is uncertainty in position along one axis; = 3 and l = 1 are collectively referred as 3p-orbitals and are
∆u is uncertainty in velocity along same axis. said to be in 3p-sub-shell.
As the mass of particle increases the uncertainty values An orbital may also be represented as ψ 4, 2, 0 which means
decrease and thus, uncertainty principle and de-Broglie concept for n = 4, l = 2, ml = 0, i.e., 4d-orbital.
loses its significance in case of large objects. The three quantum numbers ( n, l , ml ) derived from
Uncertainty principle is also valid for a conjugate pair of quantum mechanical concept also have classical analogue
variable which are to be measured simultaneously. Some other but the two quantum mechanical spin states have no
simultaneous measurements for angular momentum (ω ) and classical analogue.
The plane and point at which zero electron density exists
angle (θ ) , for energy (E) and time (t), we can have
(i.e., ψ 2 = 0 ) is known as nodal plane or nodal point, e.g.,
_ h
∆ω ⋅ ∆θ > the probability of find electron between 1s and 2s-orbitals
4π
or between two lobes of p-orbitals is zero.
h
∆E ⋅ ∆ t ≥ An orbital with quantum number n and l possesses :
4π
Angular or non-spherical nodes = l
Note
Bohr’s model assumes the existence of well defined orbits Radial or spherical nodes = n – l – 1
in which both the position and momentum of the electrons Thus, total nodes in an orbital = n – l – 1 + l = n – 1
are known exactly. On the other hand, Heisenberg For one electron systems (an atom or an ion) the energy of
concluded that position and momentum of any sub atomic orbital depends only on the number of nodes, i.e., on n and
particle cannot be evaluated precisely and simultaneously. +
not on l or m. It is therefore, in H-atom or He energy
The uncertainly principle has negligible effect for macroscopic
levels of orbitals in a shell are same, i.e., energy level of 3s
particles. For example, if the uncertainties in velocity of an
= 3p = 3d.
electron and a cricket ball (mass = 0.15 kg) are in order of 1 Å,
As r approaches zero, the wave function vanishes for all
then uncertainty in velocity obtained from Heisenberg principle
orbitals except the s-orbitals, thus, only an electron in 1s-
are 5.8 ×105 ms −1 and 3.51×10−24 ms −1 respectively. Thus,
orbital can penetrate the nucleus, i.e., have a finite
uncertainty in velocity of cricket ball is definitely negligible. probability of being found right at the nucleus.
Heisenberg uncertainty principle can be best understood Actually these rules were framed to explain the
with the help of an example. To observe an electron we can
experimental facts. For example 46 Pd was found
illuminate it with light or electromagnetic radiation having
10
wavelength smaller than the dimensions or an electron. But diamagnetic and thus its configuration was written as 4d
 1 and not 4s 2 4p 6 4d 8 , 5s s .
photon of such light having high energy  E ∝  would
 λ  Write configuration of atoms up to atomic number 57 and
change the energy of electron when it strikes on electron. No note the exceptions. No new rule is needed for them. Some
doubt we can evaluate the position of electron but we would notable exceptions in writing electronic configurations are:
know very little about the velocity of electron after collision. 41 Nb : [ Kr ] 4d 4 ,5s1 , 44 Ru : [ Kr ] 4d 7 ,5s1
If ∆u along X-axis and ∆x along Y-axis is predicted.
45 Rh : [ Kr ] 4d8 ,5s1 46 Pd : [ Kr ] 4d10
Heisenberg uncertainty principle is not valid.
The wavelength of any particle showing dual nature of wave and 78 Pt : [ Xe] 4f 14 ,5d 9 ,6s1 79 Au : [ Xe] 4f 14 ,5d10 ,6s1
h The outer shell electrons are often referred to as valence
particle proposed by de-Broglie as λ = is independent of the
mu electrons. The electrons in the inner shells are called core
nature of charge (i.e., +ve or –ve or neutral). electrons.

The energy of atomic orbitals for H-atom or He is (as the
+ About X-ray photon
energy depends on the value of n): hc
Energy of X-ray photon = hv =
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f λ
The energy of orbitals other than H-atom depends upon n + hv h
Momentum of X-ray photon = =
l value and varies as: c λ
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s Rest mass X-ray photon = 0
< 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d hv h
Dynamic mass of X-ray photon = =
c 2 cλ
Cu + is diamagnetic whereas Cu 2+ is paramagnetic.
Alkali metals are paramagnetic but their salts are diamagnetic. Duane–Hunt Rule: Minimum wavelength of continuous X-
+ hc
Cu 2+ +
aq. is more stable than Cu aq. inspite of the fact that Cu ray spectrum λmin =
eV
+
has completely filled d-orbitals as Cu aq. undergoes
Maximum frequency limit of continuous X-rays spectrum
disproportionate in aqueous solutions as: c eV
v min = =
+
2Cu aq 
→ Cu aq.
2+
+ Cu λmin h
However, 2Cu 2 I 2 is more stable than CuI 2 because I− is Moseley's Law: Frequency of ν of characteristic X-ray
strongest reducing agent among halides and thus, CuI 2 spectrum v = a(Z − σ )
shows redox change as Where, a and σ are constants for given radiation.
2CuI 2 
→ Cu 2 I 2 + I 2 Bragg’s Law: The directions of maximum of X-ray
Whereas, CuCl2 is more stable than Cu 2Cl2 . diffracted form crystal 2d sin θ = nλ (n = 1, 2,3,...)
Intensity of X-rays transmitted through a thickness d of the
Compton Effect: Compton allowed the monochromatic X-rays
material I = I 0 e − kd
to fall on lighter elements such as carbon and noticed that
scattered X-rays have wavelength larger than incident X-rays. (k = a constant for a substance)
In other words: Where, k = Cz 4 dx 4 , wave length, d thickness, C constant,
λScattered X -rays > λincident X -rays atomic number.
or E Scattered X -rays > E incident X -rays
X-ray continuum radiation
or v Scattered X -rays > v incident X -rays (Bremsstrahlung)
10 Kα
This phenomenon of increase in wavelength of X-rays after 50kV
Relative intensity
8 3 Characteristic
Relative intensity
scattering from the surface of light element is known as X-rays

Compton effect. The scattering of X-rays is due to interaction of 6
2 X-ray from a
After K
photons (X-rays) and electrons and thus, supports quantum 40kV baltt Molybdenum
4
theory of light and illustrates uncertainty principle. Furthermore 30 kV 1 Bremsstrahlung
continuum
target at 35 kV
X-rays deflected by larger angles show a loss of larger energy. 2
20kV
.02 .04 .06 .08 .10 .12
X-rays .02 .04 .06 .08 .10
Wavelength (nm)
Wavelength (nm)
Incident
electron Figure: 5.5
X-ray
X-rays are electromagnetic waves of wavelength
Bremsstrahlung
1Å − 100Å. Wavelength of X-rays is of the same order as
Crystal
X-ray Elasticity spacing between crystal atoms, hence X-rays may be used
tube Scattered
Electrons for study of crystal structure.
Collimator Photographic film Inelasticity Scattered
Electron Bremsstrahlung or Continuous X-rays are caused due to
Figure: 5.4 deceleration of bombarding electrons in the electric field of
Atomic Structure 41
heavy nucleus. Continuous spectrum has a short Because, energy level of 1s < 2s.
hc
wavelength limit. It extends form λmin = up to infinity.
eV Hund’s Rules: In filling a group or orbitals of equal energy (or
Characteristic X-ray is produced due to jumping of subshells) it is preferred to assign electrons to empty orbitals
electrons form higher to lower vacant shells in atoms of rather than pair them in a particular subshell, because the
heavy substances. former arrangement leads to lower energy level. Same spin of
Screening constant, σ = 1 for Kα = radiation of all unpaired electrons in sub-sub shell also gives rise to lower
elements. energy level.
K-electrons: They are very close to nucleus; play an
e.g., 7 N : For 2p 3
important role in the production of characteristic X-ray
spectrum. is correct
is wrong (statement a)
Atomic Number: Atomic number and mass number are whole is wrong (statement b)
numbers and are never fractional.
(n + l) rule: The subshell with lower values of (n + l) possesses
Number of Neutrons = Mass no. – Atomic no.
lower energy level and should be filled first. e.g., K:
Atomic mass = [No. of p × its mass + no. of neutrons × its 19
mass + No. of ‘e’ × its mass] 1s 2 , 2s 2 , 2p 6 ,3s 2 3p 6 3d1 is wrong.

Mass loss due to binding energy. 1s 2 , 2s 2 2p 6 ,3s 2 3p 6 , 4s1 is correct.
Neglecting small masses of ‘e’ and assuming proton and n = l of 4s = 4 + 0 = 4, n = l of 3d = 3 + 2 = 5
neutron of nearly 1 amu each, one can have atomic mass =
Thus, 4s should be filled first.
mass number.
If (n + l) is same for two subshells, the one with lower values
Relative atomic mass: The relative atomic mass of an
of n possess lower energy should be filled first.
element is the mass of an atom of the element relative to
e.g., Sc : 1s 2 , 2s 2 2p 6 ,3s 2 3p 6 , 4s 2 4p1 is wrong.
one-twelfths the mass of one (C )
12
carbon atom where
21
1s 2 , 2s 2 2p 6 ,3s 2 3p 6 ,3d1 4s 2 is correct.

mass is taken as 12 amu.
Atomic mass: The average isotopic mass. n = l of 4p = 4 + 1 = 5, n = l of 3d = 3 + 2 = 5
Average atomic mass Thus, 3d should be filled first. ∵ n of 3d < n of 4s
A=
∑A X 1 1
A subshell having nearly full filled or nearly half filled
∑X Total
configuration tends to acquire exactly full filled or exactly half
filled nature in order to attain stability i.e., lower energy level.
% of I isotope × Relative atomic mass of I isotope
e.g., Cr : 1s 2 , 2s 2 2p 6 ,3s 2 3p 6 3d 4 , 4s 2 is wrong.
+ % of II × Relative atomic mass of II isotope + ... 24
A=
100 1s 2 , 2s 2 2p 6 ,3s 2 3p 6 3d 5 , 4s1 is correct.
Note 29 Cu : 1s 2 , 2s 2 2p 6 ,3s 2 3p 6 3d 9 , 4s 2 is wrong.
Both atomic mass and molecular mass are just ratios and
1s 2 , 2s 2 2p 6 ,3s 2 3p 6 3d10 , 4s1 is correct.
have no units.
Accurate determination of atomic masses and their relative 46 Pd : 1s 2 , 2s 2 2p 6 ,3s 2 3p 6 3d10 , 4s 2 4p 6 4d 8 ,5s 2 is wrong.
abundance of the isotopes was determined using Aston’s 1s 2 , 2s 2 2p 6 ,3s 2 3p 6 3d10 , 4s 2 4p 6 4d10 is correct.
mass spectrometer.
Actual masses of atoms are not equal to the sum of the
Multiple Choice Questions
masses of p, n and e present in it.
One and More than One Correct
Aufbau Principles: The electronic configuration is written on
the basis of the electrons in a poly electronic atom are filled 1. Assuming that Hund’s rule is violated, the bond order and
one by one in order of increasing energy level. magnetic nature of the diatomic molecule B2 is:
1
e.g., 1 H : 1s is correct [JEE 2010 P-II]
a. 1 and diamagnetic b. 0 and diamagnetic
2s1 is wrong
c. 1 and paramagnetic d. 0 and paramagnetic

2. The kinetic energy of an electron in the second Bohr orbit of a 10. P is the probability of finding the 1s electron of hydrogen
hydrogen atom is [a0 is Bohr radius]. [JEE 2012 P-I] atom in a spherical shell of infinitesimal thickness, dr, at a
h2 h2 distance r from the nucleus. The volume of this shell is
a. b. 4π r 2 dr. The qualitative sketch of the dependence of P on
4π 2ma 02 16π 2 ma 02
r is: [JEE Adv. 2016 P-I]
h2 h2
c. d. a.P b. P
32π 2 ma 02 64π 2 ma 02
3. Which of the following represents the correct order of

increasing first ionisation enthalpy for Ca, Ba, S, Se and
Ar? [JEE Main 2013] 0 r 0 r
a. Ca < S < Ba < Se < Ar b. S < Se < Ca < Ba < Ar c.P d. P
c. Ba < Ca < Se < S < Ar d. Ca < Ba < S < se < Ar
 Z2 
4. Energy of an electron is given be E = −2.178 × 1018 J  2 .
n 
0 r 0 r
Wavelength of light required to excite an electron in an
11. The radius of the second Bohr orbit for hydrogen atom is:
hydrogen atom from level n=1 to n=2 will be (h=6.62×10–
−8 −1
(Planck's const. h = 6.6262 ´ 10–34 Js; Mass of electron =
34
Js and c = 3.0 ×10 ms ) [JEE Main 2013]
9.1091 ´ 10–31 kg charge of electron e = 1.60210 ´ 10–19 C;
a. 1.214 ×10−7 m b. 2.816 ×10−7 m permittivity of vacuum ∈0 = 8.854185 × 10 −12 kg −1m −3 A 2 )
c. 6.500 ×10−7 m d. 8.500 ×10−7 m [JEE Main 2017]
5. The first ionisation potential of Na is 5.1 eV. The value of a. 2.12 Å b. 1.65Å
c. 4.76 Å d. 0.529 Å
electron gain enthalpy of Na + will be: [JEE Main 2013]
a. –2.55 eV b. −5.1 eV 12. According to molecular orbital, which of the following
will not be a viable molecule? [JEE Main 2018]
c. −10.2 eV d. +2.55 eV
a. H 22 − b. He 22 +
6. Which of the following is the energy of a possible excited
c. He +2 d. H −2
state of hydrogen? [JEE Main 2015]
a. +13.6 eV b. − 6.8 eV 13. The correct statement(s) regarding the binary transition
c. − 3.4 eV d. + 6.8 eV metal carbonyl compounds is(are) (Atomic numbers:
Fe = 26, Ni = 28) [JEE adv. 2018 P-I]
7. The ionic radii (in Å) of N 3− , O 2− and F− are respectively: a. Total number of valence shell electrons at metal centre
[JEE Main 2015] in Fe(CO)5 or Ni(CO) 4 is 16
a. 1.36, 1.40 and 1.71 b. 1.36, 1.71 and 1.40 b. These are predominantly low spin in nature
c. 1.71, 1.40 and 1.36 d. 1.71, 1.36 and 1.40 c. Metal-carbon bond strengthens when the oxidation
8. A stream of electrons from a heated filament was passed state of the metal is lowered
between two charged plates kept at a potential difference V d. The carbonyl C–O bond weakens when the oxidation
esu. If e and m are charge and mass of an electron, state of the metal is increased
respectively, then the value of h / λ (where λ is wavelength 14. The quantum number of four electrons are given below:
associated with electron wave) is given by: I. n = 4, l = 2, ml = –2, ms = – ½
[JEE Main 2016] II. n = 3, l = 2, ml = 1, ms = + ½
a. meV b. 2 meV III. n = 4, l = 1, ml = 0, ms = + ½
c. meV d. 2 meV IV. n = 3, l = 1, ml = 1, ms = – ½
The correct order of their increasing energies will be –
9. Which of the following atoms has the highest first [JEE Main 2019]
ionisation energy? [JEE Main 2016] a. IV < III < II < I b. IV < II < III < I
a. Rb b. Na c. I < II < III < IV d. I < III < II < IV
c. K d. Sc
Atomic Structure 43
15. If p is the momentum of the fastest electron ejected from a 20. Which of the graphs shown below does not represent the
metal surface after the irradiation of light having relationship between incident light and the electron
wavelengthλ, then for 1.5 p momentum of the photoelectron, ejected from metal surface? [JEE Main 2019]
the wavelength of the light should be: Number K.E. of
of e–s e–s
(Assume kinetic energy of ejected photoelectron to be very
high in comparison to work function) [JEE Main 2019] a. b.
1 3 0 Frequency of 0 Intensity of
a. λ b. λ light light
2 4
2 4 K.E. of K.E. of
c. λ d. λ e–s e–s
3 9
c. d.
16. For emission line of atomic hydrogen from n1= 8 to nf = 0 Frequency of 0 Energy of
 1 light light
the plot of wave number (v) against  2  will be (The
n  21. The ground state energy of hydrogen atom is –13.6 eV.
Rydberg constant, RH is in wave number unit) The energy of second excited state He+ ion in eV is:
[JEE Main 2019] [JEE Main 2019]
a. Linear with slope - RH a. –6.04 b. –27.2
b. Linear with intercept - RH c. –54.4 d. –3.4
c. Non-linear 22. Heat treatment of muscular pain involves radiation of
d. Linear with slope RH wavelength of about 900 nm. Which spectral line of H-
17. The highest value of the calculated spin only magnetic atom is suitable for this purpose? [JEE Main 2019]
moment (in BM) among all the transition metal [RH = 1 × 105 cm–1, h = 6.6 × 10–34 Js, c = 3 × 108 ms–1]
complexes is: [JEE Main 2019] a. Paschen, 5 → 3 b. Paschen, ∞ → 3
a. 5.92 b. 3.87 c. Lyman, ∞ → 1 d. Balmer, ∞ → 2
c. 6.93 d. 4.90 23. The de Broglie wavelength (λ) associated with a
18. Which of the following combination of statements is true photoelectron varies with the frequency (v) of the incident
regarding the interpretation of the atomic orbitals? radiation as, [v0 is threshold frequency]:
[JEE Main 2019]
1. An electron in an orbital of high angular momentum
1 1
stays away from the nucleus than an electron in the orbital a. λ ∝ b. λ ∝
of lower angular momentum. (v − v0 )3 / 2 (v − v0 )1/ 2
2. For a given value of the principal quantum number, the 1 1
c. λ ∝ d. λ ∝
size of the orbit is inversely proportional to the azimuthal (v − v0 )1/ 4 (v − v 0 )
quantum number. 24. What is the work function of the metal if the light of
3. According to wave mechanics, the ground state angular wavelength 4000 Å generates photoelectrons of velocity 6
h × 105 ms–1 form it ? [JEE Main 2019]
momentum of h equal to –31
(Mass of electron = 9 × 10 kg
2π
Velocity of light = 3 × 108 ms–1
4. The plot of Ψ Vs r for various azimuthal quantum
Planck's constant = 6.626 × 10–34 Js
numbers, shown peak shifting towards higher r value.
Charge of electron = 1.6 × 10–19 JeV–1)
[JEE Main 2019]
a. 0.9 eV b. 4.0 eV
a. 2, 3 b. 1, 4
c. 2.1 eV d. 3.1 eV
c. 1.2 d. 1, 3
25. The upper stratosphere consisting of the ozone layer
19. The metal used for making X-ray tube window is: protects us from the sun's radiation that falls in the
[JEE Main 2019] wavelength region of: [JEE Main 2019]
a. Mg b. Na a. 600-750 nm b. 0.8-1.5 nm
c. Ca d. Be c. 400-550 nm d. 200-315 nm

26. If the de Broglie wavelength of the electron in nth Bohr (D) Probability density of 4. Electron spin
orbit in a hydrogenic atom is equal to 1.5 πa0(a0 is Bohr electron at the nucleus in quantum number
radius), then the value of n/z is: [JEE Main 2019] hydrogen-like atom
a. 1.0 b. 0.75 a. A→ 1; B→ 1, 2, 3; C→ 1, 4; D→ 1,2
c. 0.40 d. 1.50 b. A→ 2; B→ 4; C→ 1, 2, 3; D→ 1, 2, 3
27. For He+ the electron is in orbit with energy equal to c. A→ 3; B→ 1, 3; C→ 2; D→ 1,2,3,4
3.4eV. The azimuthal quantum number for that orbit is 2 d. A→ 1, 3; B→ 1,2,3,4; C→ 2; D→ 1,2,3
and magnetic quantum number is 0. Then which of the
Match the Columns for Question Nos. 30 to 32
following is/are correct. [JEE Adv. 2019 P-II]
The information are given in the three columns of the
a. The subshell is 4d.
following table. [JEE Adv. 2017 P-I]
b. The number of angular nodes in it is 2.
The wave function, ψ n, ℓmℓ is a mathematical function whose
c. The numbers of radial nodes in it is 3.
d. The nuclear charge experienced in n = 4 is 2e less than value depends upon spherical polar coordinates of the electron
that in n = 1, where e is electronic charge. and characterised by the quantum numbers n, ℓ and mℓ . Here,
r is distance from nucleus, θ is co-latitude and φ is azimuth. In
the mathematical functions given in the Table is atomic
28. According to Bohr’s theory, E n = Total energy , K n = number and a0 is Bohr radius.
Kinetic energy Vn = Potential energy rn = Radius of nth
Column I Column II Column III
orbit. Match the following: [ JEE 2006]
(I) 1s orbital (i) ψ n,ℓ,mℓ (A)
Column I Column II
3
Ψ n, l, m, (r)
(A) Vn / K n = ? 1. 0  Zr 
 Z  2 − a 
(B) If radius on nth orbit 2. –1 ∝  e  0
 a0 
∝E ,x=?
x
n
0 r/a0
(C) Angular momentum 3. –2
in lowest orbital (II) 2s orbital (ii) One radial (B) Probability
4. 1 node density at
1
(D) ∝ Zy , y = ? 1
rn nucleus ∝ 3
a0
a. A→ 3; B→ 2; C→ 1; D→ 4
b. A→ 1; B→ 2; C→ 3; D→ 4 (III) 2pz orbital (iii) ψ n,ℓ,mℓ (C) Probability
c. A→ 3; B→ 1; C→ 2; D→ 4 5
density is
d. A→ 3; B→ 4; C→ 2; D→ 1  Z 2 maximum at
∝ 
nucleus
 a0 
29. Match the entries in Column I with the correctly related
 Zr 
quantum number(s) in Column II. [JEE 2008 P-II] − 
2a 
Column I Column II re  0  cos θ
(A) Orbital angular momentum 1. Principal quantum (IV) 3dz2 orbital (iv) xy-plane is (D) Energy needed
of the electron in a number a nodal plane to excite electron
hydrogen-like atomic from n = 2 state
orbital to n = 4 state is
(B) A hydrogen-like one- 2. Azimuthal 27
times the
electron wave function quantum number 32
obeying Pauli principle energy needed to
excite electron
(C) Shape, size and 3. Magnetic quantum
from n = 2 state
orientation of hydrogen- number
to n = 6 state
like atomic orbitals
Atomic Structure 45
30. For He + ion, the only incorrect combination is: Integer and Subjective
a. (I) (i) (C) b. (II) (ii) (B) 38. The maximum number of electrons that can have
c. (I) (i) (D) d. (I) (iii) (C) principal quantum number, n = 3, and spin quantum
31. For the given orbital in Column I, the only correct 1
number, ms = − , is: [JEE 2011 P-I]
combination for any hydrogen-like species is: 2
a. (I) (ii) (D) b. (IV) (iv) (C)
39. The work function (φ ) of some metals is listed below.
c. (III) (iii) (A) d. (II) (ii) (A)
The number of metals which will show photoelectric
32. For hydrogen atom, the only correct combination is: effect when light of 300 nm wavelength falls on the metal
a. (II) (i) (A) b. (I) (iv) (B) is: [JEE 2011 P-I]
c. (I) (i) (C) d. (I) (i) (D) Metal Li N K M C A Fe Pt W
For Question Nos. 33 to 34 φ (eV) 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75
Match the Columns: [JEE Adv. 2019 P-II] 40. The atomic masses of He and Ne are 4 and 20 a.m.u.,
Column I Column II respectively. The value of the de Broglie wavelength of
(A) Radius 1. ∝ n −1 He gas at − 73 ° C is “M” times that of the de Broglie
(B) Angular momentum 2. ∝ n −2 wavelength of Ne at 727 °C. M is: [JEE Adv. 2013 P-I]
(C) Kinetic energy 3. ∝ n −0 41. In an atom, the total number of electrons having quantum
(D) Potential energy 4. ∝ n 1
1
number n = 4,| mℓ | = 1 and ms = − is:
5. ∝ n 2
2
33. Which of the following is correct? [JEE Adv. 2014 P-I]
a. A → 1 b. A → 2 42. Not considering the electronic spin, the degeneracy of the
c. A → 5 d. A → 3 second excited state (n = 3) of H atom is 9, while the
34. Which of the following is correct? degeneracy of the second excited state of H− is:
a. D → 4 b. C → 1 [JEE Adv. 2015 P-I]
43. (a) Calculate velocity of electron in first Bohr orbit of
c. C → 2 d. D → 3
hydrogen atom (Given r = a 0 )
Paragraph (b) Find de-Broglie wavelength of the electron in first
Paragraph for Question Nos. 35 to 37 Bohr orbit.
The hydrogen-like species Li 2+ is in a spherically symmetric state (c) Find the orbital angular momentum of 2p orbital in
terms of h / 2π units. [JEE 2005]
S1 with one radial node. Upon absorbing light the ion undergoes
transition to a state S2. The state S2 has one radial node and its ANSWERS and SOLUTIONS
energy is equal to the ground state energy of the hydrogen atom.
1. (a) B2 (10) = σ 1s2 σ *1s2σ 2s2 σ *2s2 π 2p2
[ JEE 2010 P-II] x
35. The state S1 is: Bond order

6−4
a. 1s b. 2s = = 1 (nature diamagnetic as no unpaired electron)
c. 2p d. 3s 2
nh
36. Energy of the state S1 in units of the hydrogen atom 2. (c) mvr =
2π
ground state energy is:
mv 2 e 2
a. 0.75 b. 1.50 and = 2 ⇒ mv 2 r = e2
r r
c. 2.25 d. 4.50
e2 × 2π
37. The orbital angular momentum quantum number of the ⇒ v=
nh
state S2 is:
nh
a. 0 b. 1 ∴ (mvr = )
2π
c. 2 d. 3

1 4 2 −1
me × 4π 2 He 2+ σ 1s σ 1s*
2 1 = 0.5
1 2 2
⇒ K.E. = mv =
2
. . .(i)
2 n 2h 2 2 −1
H 2− σ 1s 2 σ 1s* 1 = 0.5
h2 2
Expression for a 0 =
4π 2 me2 2−2
H 22 − σ 1s 2 σ 1s* 2 =0
h2 2
⇒ me2 = . . .(ii) 2−0
4π 2a 0 He 22 + σ 1s 2 =1
2
h2 1 Molecule having zero bond order will not be a viable
⇒ K.E. = × . . .(iii)
8ma 02π 2 n 2 molecule.
For n = 2 K.E. 13. (b, c, a) Valence shell electrons in iron in compound
2
h Fe(CO)5 . Fe(26) – 1s 2 , 2s 2 , 2p 6 , 3s 2 , 3p 6 , 3d 8
=
32π ma 2 2
0 (After pairing of electrons)
3. (a)
3d 4s 4p
1  1 1  dsp³ Hybridisation
4. (a) = R H Z2  2 − 2 
λ  n1 n 2  Valence = 2 + 6 + 8 = 16 Electrons (3rd shell)
Valence shell electrons in nickel in compound Ni(CO) 4
Z =1 n1 = 1
Ni(28) – 1s 2 , 2s 2 ,3s 2 ,3p 6 , 3d10
n2 = 2
λ = 1.214 × 10 −7 m 3d
sp³ Hybridisation
5. (b) E.A. = Ionisation potential
Valence electrons (3rd shell) = 2 + 6 + 10 = 18
∴ EA of Na = −5.1 eV +
(b) Both complexes are formed in low spin condition due
6. (c) Energy in 1st excited state to strong field ligand 'CO'.
= −3.4 eV (c) Metal carbon bond strengthens when complex is
7. (c) Ionic Radii order: formed in lower oxidation number of metal. Since in
lower oxidation number; number of electrons in d-
N3− > O2− > F−
subshell are higher, so it 4 can donate more electrons in
8. (d) K.E. = eV ABMO of ligands and increases the double bond
h character between metal and carbon.
λ=
2meV (d) In higher oxidation number, metal may have less
h number of electrons in d-orbitals, which decreases the
= 2meV
λ extent of synergic bonding.
9. (d) I. P1 = Sc > Na > K > Rb 14. (b) According to (n+ ℓ ) rule: 3p < 3d < 4p < 4d
10. (d) For 1s electron in H-atom, plot of radial probability 15. (d) hv = φ = KE
function (4π r R ) V/s r is as shown.
2 2
 hc 
⇒   = KE + φ
 λ incident
4π r 2 R 2
 hc 
  ≃ KE
 λ incident
P2 hc hc
r KE = = = . . . (i)
2m λ incident λ
11. (a) Radius of nth Bohr orbit in H-atom = 0.53 n2 Å P 2 × (1.5) 2 hc
Radius of II Bohr orbit = 0.53 × (2)2 = 2.12 Å ⇒ = . . . (ii)
2m λ′
12. (a) Electronic configuration bond order Divide (i) and (ii)
Atomic Structure 47
λ 4λ 1 1 1 
(1.5) 2 = ⇒ λ′ = mv 2 = hc  − 
λ′ 9 2  λ λº 
 1 1
1 1  hv = φ + mv 2
16. (d) = v = R H z2  2 − 2  2
λ  η1 η2 
6.626 × 10−34 × 3 × 108 1
 1 1 φ= − × 9 × 10−31 × (6 × 105 ) 2
v = RH × 2 − 2  4000 × 10−10 2
 η1 8  φ = 3.35 × 10 −19 J
1 RH ⇒ φ = 2.1 eV
v = RH × −
η2 82
25. (d) Ozone protects most of the medium frequencies
1 R ultraviolet light from 200 to 315 nm of wavelength.
v = RH × 2 − H
η 64
26. (b) According to de-Broglie’s hypothesis
m = RH
2πrn = nλ
Linear with slope RH
n2
⇒ 2π ⋅ a 0 = = n × 1.5πa 0
17. (a) µ = n (n + 2) B.M z
N = Number of unpaired electrons n
= 0.75
N = Maximum number of unpaired electron = 5 z
Ex: Mn2+ complex.
(2) 2 −13.6
18. (d) Refer Theory 27. (a, b) E He+ = −13.6 × = −3.4 =
n2 4
19. (d) "Be" Metal is used in x-ray window is due to n2 = 2
transparent to x-rays. so n=4
1 Quantum numbers are
20. (c) E = W + mv 2 n = 4, ℓ = 2, m = 0
2
So, subshell is = d.
K.E = hv − 4v 0
Radial node = [n − ℓ − 1] = 4 − 2 − 1 = 1
K.E = hv + (− hv0 )
y = mx + C 28. (a) A→ 3; B→ 2; C→ 1; D→ 4
29. (b) A→ 2; B→ 4; C→ 1,2,3; D→ 1,2,3
Z2
21. (a) (E) n th = (E GND )H ⋅
n2 For Question Nos. 30 to 32
22 30. (d) 1s orbital is non-directional so ψ will not depend
E 3rd = (He + ) = ( −13.6eV) 2 = –6.04eV
3 upon cosθ. Hence’d’ is incorrect.
22. (b) 31. (d) For H-like species only d is correct because
23. (b) For electron In (A) 1s orbital has no radial node
1 In (B) for 3dz2, xy plane is not nodal plane.
λDB (de Broglie wavelength) In (C) 2pz orbital has no radial node
2mK.E.
By photoelectric effect 32. (d) For H-atom
3
hv = hv0 + KE  Zr 
 Z  2 − a 
KE = hv–hv0 1s-orbital ψ ∝   e  0 
 a0 
h 3
λ DB = Also, E 4 − E 2 =
2m × (hv − hv 0 ) 16
h 2
λ DB ∝= E6 − E2 =
(v − v 0 )1/ 2 9
27
24. (c) hv = φ + hvº Hence (E 6 − E 2 ) × = E4 − E2
32

For Question Nos. 33 to 34 h h
40. Since, λ = = (since K.E. ∝ T)
n  2 mV 2M K.E.
rn = 0.529   A ⇒ rn ∝ n 2
 z  1
⇒ λ∝
Angular momentum ( ℓ ) = MT
2
1 2 1  z   nh  For two gases,
K.E. = mv = m 2.18 ×106    ⇒ rn ∝ n1
2 2  n  Z  λHe M Ne TNe 20 1000
= = × =5
Z 2 λNe M He THe 4 200
K.E. =∝ ⇒ K.E. ∝ n −2
n2
41. n = 4 ℓ = 0,1, 2, 3
Z2
P.E. = − 2K.E. ⇒ P.E. ∝ 2 ⇒ P.E. ∝ − n −2 | mℓ | = 1 ⇒ ± 1
n
1
33. (c) A →5 ms = − For ℓ − 0, m ℓ = 0
2
34. (c) C→2 ℓ = 1, mℓ = −1, 0, +1
For Question Nos. 35 to 37 ℓ = 2, m ℓ = −2, −1, 0, +1, +2
35. (b) For, S1 (spherically symmetrical) node =1 ℓ = 3, m ℓ = −3, −2, −1, 0, +1, +2, +3
⇒ n −1 = 1 n=2 1
For S2 , radial node = 1 So, 6 electrons can have | m ℓ | = 1 & ms = −
2
−13.6 × z 2 42. Single electron species don’t follow the (n + ℓ ) rule but
E s2 = = EH
n2
multi electron species do.
in ground state = −13.6
Ground state of H − = 1s 2
−13.6 × 9
E= ⇒n=3 First excited state of H − = 1s1 , 2s1
n2
So, state S1 is 2s and S2 is 3p. Second excited state of
H − = 1s1 , 2s0 , 2p1
E s1 −13.6 × 9
36. (c) = = 2.25
E H (ground ) 4 × ( −13.6)
Px Py Pz
37. (b) Azimuthal quantum number for (3 degenerate orbitals)
S2 = ℓ = 1 So, answer is 3.
nh
38. Number of orbital for 43. (a) mvr =
2π
n = 3 is = n 2 = 9 r = a 0 = 0.529 Å
1 nh
Number of electron n = 3 and ms = − =9 v= = 2.18 × 106 m / sec (n = 1)
2 2π mr
h 6.63 × 10 −34
39. For photoelectric effect to occur (b) λ = = = 0.33 × 10 −9 m = 3.3 Å
mv 9.1× 10 −31 × 2.18 × 106
E ≥ φ ⇒ ≤ 4.14 eV (c) For 2p value of ℓ = 1
∴ Li, Na, Ka, Mg will show photoelectric effect when light Orbital angular momentum
300 nm wavelength falls on the metal is (4). h h
= ℓ (ℓ + 1) = 2
2π 2π
Redox 49
6 Redox
QUICK LOOK Ionic equations: When the reactants and products involved
in a chemical change are ionic compounds, these will be
Redox Reaction: Redox reactions may be regarded as electron present in the form of ions in the solution. The chemical
transfer reactions in which the electrons are transferred from change is written in ionic forms in chemical equation, it is
one reactant to the other. As the result substance which losses termed as ionic equation.
electrons is called a reducing agent or reductant while another Example
which accepts the electrons is called an oxidissing agent or M nO 2 + 4 H + + 4 C l −  
→ M n 2+ + 2 C l− + 2 H 2O + C l2
oxidant. In above example the reactants and products have been written
Oxidation in ionic forms, thus the equation is termed as ionic equation.
Zn (s) + 2H + (aq )  
→ Zn 2 + (aq ) + H 2 (g) Spectator ions: In ionic equations, the ions which do not
(Reducing agent) undergo any change and equal in number in both reactants
Oxidation and products are termed as spectator ions and are not
included in the final balanced equations.
Al + Fe 2 O 3  
→ Al 2 O 3 + 2Fe
(Reducing agent) (Reducing agent) Example
Reduction Zn + 2H + + 2C l−   → Z n 2 + + H 2 + 2 C l − (Ionic equation)
Z n + 2H +  
→ Zn 2 + + H 2 (Final ionic equation)
Types of Redox Reaction In above example, the Cl − ions are the spectator ions and
Direct redox reaction: The reactions in which oxidation hence are not included in the final ionic balanced equation.
and reduction takes place in the same vessel are called
direct redox reactions. Redox Titrations: These involve the titration of an oxidizing
Indirect redox reaction: The reactions in which oxidation agent against a reducing agent or vice-versa.
and reduction takes place in different vessels are called The most important fact for solving the problems of redox
indirect redox reactions. Indirect redox reactions are the changes is to evaluate equivalent weight of redox correctly
basis of electro-chemical cells. using the formula: Eq. wt. of reductant or oxidant
Intermolecular redox reactions: In which one substance is Mol. weight of reductant or oxidant
oxidised while the other is reduced. =
No. of electrons lost or gained by one molecule
For example, 2 A l + Fe 2 O 3  
→ A l 2 O 3 + 2 Fe
Calculate the Meq. of desired substance and then calculate
Here, Al is oxidised to Al 2 O 3 while Fe 2 O 3 is reduced to Fe. Wt.
its weight by: Meq. = × 1000 This equation gives
Intramolecular redox reactions: In which one element of Eq. wt.
a compound is oxidised while the other is reduced. weight of substance whose Eq. wt. is substituted.
For example, 2 K C lO 3  ∆→ 2 K C l + 3 O 2 Be careful in deciding equivalent weights. First write redox
Here, Cl + 5 in KClO 3 is reduced to C l − 1 in KCl while O 2 − in change for each and then derive no. of electrons lost or
KClO 3 is oxidised to O02 .
gained by one molecule of reductant or oxidant.
In case balanced equation is given, it is always advised to
Molecular equations: When the reactants and products
proceed with mole concept to avoid complications in
involved in a chemical change are written in molecular
equivalent weight determination.
forms in the chemical equation, it is termed as molecular
equation. Note
For example, M nO 2 + 4 H C l  
→ M nC l 2 + 2 H 2 O + C l 2 Sometimes a reaction is slow to go to completion and a sharp
In above example the reactants and products have been end point cannot be obtained. For example, in titration of
written in molecular forms, thus the equation is termed as antacid tablets with a strong base such as HCl, a back titration
molecular equation. is often used to get better results. In this technique, a measured

amount (in excess) of the reagent, which would normally be n 1 > n 2 A − n1  
→
A − n 2 + ( n 1 − n 2 )e  
→ A − n1
titrant is added to the sample. After the reaction with the A − n 2 + (n 1 − n 2 )e
analyte is allowed to go to completion, the amount of excess
Oxidants are substance which
unreacted titrant is determined by titrating it with another
(a) oxidise other.
standard solution. Thus, Meq. of acid in antacid = Meq. of HCl
(b) are reduced themselves
taken –Meq. of HCl back titrated. (c) show electronation
(d) show a decrease in oxidation no. during a redox change.
Indicators: The process of determining the strength of a
(e) has higher oxidation no. in a conjugate pair of redox.
solution of an acid by titration against standard solution of
Reductants are substances which:
alkali is called acidimetry. Similarly, the process of
(a) reduce other
determining the strength of an alkali by titrating it against a
(b) are oxidised themselves
standard acid solution is called alkalimetry. Titration of a
(c) show de-electronation
weak acid H 3 PO 4 with NaOH can be made in different stages
(d) show an increase in oxidation no. during a redox change
using different indicators as: (e) has lower oxidation no. in a conjugate pair of redox.
Step (i): Bromocresol green an indicator is used for neutralisation A redox change is one in which a reductant is oxidised to
of H 3 PO 4 upto H 2 PO −4 liberate electrons, which are then used up by an oxidant to
.
get itself reduced.
Step (ii): Thymolphthalein is used for neutralisation of H 3 PO 4
M1  → M +2 n + n e Oxidation
upto HPO 24 − .
M +2 n + n e  
→M2 Reduction
Note 2 
M 1 + M +n → M 1+n +M 2 Redox reaction
Saponification value: It is the amount of KOH in mg A redox change occurs simultaneously.
required to neutralise a fatty acid obtained by the hydrolysis Oxidation Number
of 1 g of oil. Oxidation no. of an element in a particular compound
Trace concentrations are usually expressed in small units represents the no. of electrons lost or gained by an element
such as parts per thousand (ppt), parts per million (ppm) or during its change from free-state into that compound.
parts per billion (ppb). Or
mass of solute(g) Oxidation no. of an element in a particular compound
ppt(w / w) = × 103
mass of sample(g) represents the extent of oxidation or reduction of an element
mass of solute (g) during its change from free-state into that compound.
ppm(w / w) = × 106
mass of sample (g) Oxidation no. is given positive sign if electrons are lost.
mass of solute (g) Oxidation no. is given negative sign if electrons are gained.
ppb(w/w) = × 109
mass of sample (g) Oxidation no. represents real change in case of ionic
compounds. However, in covalent compounds it represents
Part per trillion = m ass of solute ( g ) × 10 12 imaginary charge.
m ass of sample ( g )
Loss of electrons (also known as de-electronation)
−4 −3 −2 −1 0 +1 +2 +3 +4
Oxidation-Reduction M M M M M M M M M
Oxidation is a process which liberates electrons, i.e, de-
−e− −e− −e− −e− −e− −e− −e− −e− −e−
electronation.
Reduction is a process which gains electrons, i.e., Loss of electrons
electronation. (a) H 0  → H + + e− (Formation of proton)
Oxidation Reduction (b) M n O 24 −  
→ M n O −4 + e − (De-electronation of MnO 42 −
→ M + n + ne
M  M + n + ne 
→M
→ 2 F e 3+ + 6 e −
(c) 2 F e 0   (De-electronation of iron)
A − n 
→ A + ne → A −n
A + ne 
Increase in oxidation number
n 2 > n 1 M + n1  
→ M + n 2 + (n 2 − n 1 )e → M g 2+
(a) M g 0   (From 0 to +2)
M + n 2 + (n 2 − n 1 )e → M + n1

Redox 51
+2 4− +3 3− Decrease in +ve valency
(b) [Fe (CN) ] 
→ [Fe (CN)6 ] (From +2 to +3)
(a) F e 3 +   → F e 2 + (+ve valency decreases)
(c) 2 C l −  
→ C l 02 (From –1 to 0)
(b) [ F e ( C N ) 6 ] 3 −  
→ [ F e (C N ) 6 ] 4 − (–ve valency increases)
Rules of Deriving Oxidation Number: Following rules have
been arbitrarily adopted to decide oxidation no. of elements on Gain of electrons (also known as electronation)
−4 −3 −2 −1 0 +1 +2 +3 +4
the basis of their periodic properties. M M M M M M M M M
In uncombined state or free-state, oxidation no. of an
+e− +e− +e− +e− +e− +e− +e− +e− +e−
element is zero.
In combined state oxidation no. of …… Gain of electrons
(a) …… F is always –1. (a) Z n 2 + (a q ) + 2 e −   2+
→ Z n (S ) (Electronation of Zn )
(b) ……O is –2. In peroxides it is –1. However in F2 O it is +2.
(b) Pb 2+ + 2e −  → Pb 0 (Electronation of Pb 2+ )
(c) …… H is +1. In ionic hydrides it is –1. (i.e., IA, IIA and
(c) [ F e (C N ) 6 ] 3 − + e −  → [ F e (C N ) 6 ] 4 −
IIIA metals)
(d) …… halogens as halide is always –1. (Electronation of [ F e(C N ) 6 ]3 − )
(e) …… sulphur as sulphide is always –2. Decrease in oxidation number
(f) …… metals is always + ve. (a) M g 2 +  
→ Mg0 (From +2 to 0)
(g) …… alkali metals (i.e., I A group – Li, Na, K, Rb, Cs,
(b) [ Fe(CN) 6 ] 
→ [ Fe(CN) 6 ]
3− 4−
(From +3 to +2)
Fr) is always +1.
(h) ……alkaline earth metals (i.e., II A group -Be, Mg, Ca, → 2C l−
(c) C l 02   (From 0 to –1)
Sr, Ba, Ra) is always +2.
The algebraic sum of all the oxidation no. of elements in a Balancing of Redox Equations: Two methods are commonly
compound is equal to zero, e.g., KMnO 4 . used for this purpose.
The algebraic sum of all the oxidation no. of elements in a Ion Electrons Method: It involves three sets of rules
radical is equal to the net charge on the radical, e.g., CO 3−2 depending upon the nature of medium (i.e., neutral, acid or
Oxidation no. of C + 3 × (Oxidation no. of O) = −2 alkaline) in which reactions occurs.
Oxidation number can be zero, + ve, − ve (integer or
fraction) Neutral Medium, e.g., H 2 C 2 O 4 + KMnO4 
→
Maximum oxidation no. of an element is = Group no. CO 2 + K 2 O + MnO + H 2 O
(Except O and F)
Step (i): Select the oxidant, reductant atoms and write their half
Minimum oxidation no. of an element is = Group no. –8
reactions, one representing oxidation and other reduction.
(Except metals) +7
→ 2C + 4 + 2e , 5e + Mn 
i.e., C +2 3   → Mn +2
Oxidation State: It is defined as oxidation no. per atom, e.g., Step (ii): Balance the no. of electrons and add the two equations.
in K M nO 4 5C +2 3  
→ 1 0 C +4 + 1 0 e
.
Oxidation no. of Mn is + 7 10e + 2Mn +7 
→ 2Mn +2
Oxidation state of Mn is = Mn +7 5C 2+3 + 2Mn +7 

→ 10C +4 + 2Mn +2
Step (iii): Write complete molecule of the reductant and
Reduction: Reduction is just reverse of oxidation. Reduction is a oxidant from which respective redox atoms were
process which involves; removal of oxygen, addition of obtained.
hydrogen, removal of non-metal, addition of metal, decrease in 5H 2 + C 2O 4 + 2 K M nO 4  
→ 10C O 2 + 2M nO
+ve valency, gain of electrons and decrease in oxidation number. Step (iv): Balance other atoms if any (except H and O). In
Removal of oxygen: CuO + C  → Cu + CO above example K is unbalanced, therefore,
Addition of hydrogen: C l 2 + H 2  → 2HCl 5H 2 C 2 O 4 + 2 K M nO 4  
→ 10C O 2 + 2 M n O + K 2 O
Removal of non-metal: 2HgCl 2 + SnCl 2 

→ Hg 2 Cl2 (mentioned as product)
Step (v): Balance O atom using H 2 O on desired side.
+SnCl4
5H 2 C2 O4 + 2KMnO4 
→
Addition of metal : HgCl2 + Hg 
→ Hg2Cl2
10CO 2 + 2MnO + K 2 O + 5H 2 O

− H+ − + Balancing of Half Reactions
Acidic Medium: e.g., NO + H 2S → HSO + NH .
3 4 4
Example
Proceed like neutral medium for Step 1 to 4.
→ IO 3− (Acid medium)
I2  
Step (i): 8e + N +5 
→ N −3 , S −2 
→ S +6 + 8e
Step (i): Balance atoms other than O and H if needed i.e.,
Step (ii): N +5 + S −2 
→ N − 3S + 6
Step (iii): N O 3− + H 2 S   → 2IO3−
I2 
→ N H +4 + H S O −4
Step (iv): No other atom (except H and O) is unbalanced and Step (ii): Balance O atoms using H+ and H 2 O as reported
thus, no need for this step. earlier.
Step (v): Balance O atom: Balancing of O atoms is made by → 2 IO 3− + 1 2 H +
I2 + 6H 2O  
using H 2 O and H+ ions. Add desired molecules of H 2 O Step (iii): Balance charge by electrons.
on the side deficient with O atom and double H on + → 2IO3− + 12H + + 10e .
I 2 + 6H 2 O 
opposite side. Therefore, This is balanced half reaction.
− + − +
H 2 O + N O + H 2S  
3 → NH + HSO + 2H4 4 Example
Step (vi): Balance charge by H + : S 2 O 3− 2  
→ SO 2 (Basic medium)
+ − + − +
3H + H 2 O + NO + H 2S 
3 → NH + HSO + 2H 4 4 Step (i): As above S 2 O 3− 2  
→ 2S O 2
∴ Finally balanced equation is, H + + H2 O + NO3− + H 2S Step (ii): Balance O atom by H 2 O and OH − as reported earlier
→ NH +4 + HSO−4
 2 O H − + S 2 O 3− 2  
→ 2S O 2 + H 2 O
Step (iii): Balance charge by electron
OH −
Alkaline Medium: e.g., Fe + N 2 H 4 
→ Fe(OH) 2 + NH 3 . 2OH − + S2 O3−2 
→ 2SO2 +
Proceed like neutral medium for step 1 to step 4. H 2 O + 4e This is balanced half reaction.
→ Fe +2 + 2e , 2e + N 2− 2  
Step (i): Fe  → 2 N −3
Step (ii): F e + N 2− 2   Multiple Choice Questions
→ F e +2 + 2 N −3
Step (iii): F e + N 2 H 4  
→ F e(O H ) 2 + 2 N H 3
1. Reduction of the metal centre in aqueous permanganate
Step (iv): No other atom (except H and O) is unbalanced and
ion involves [JEE 2011 P-II]
thus, no need for this step.
a. 3 electrons in neutral medium
Step (v): Balancing of O atom is made by using H 2 O and OH −
b. 5 electrons in neutral medium
ions. c. 3 electrons in alkaline medium
Step (vi): Balancing charge by H + : 4OH − + 4H + + Fe + N 2 H 4 d. 5 electrons in acidic medium

→ Fe(OH) 2 + 2NH3 + 2H 2 O 2. The equilibrium 2Cu I → Cu° + Cu II in aqueous medium at
∴ Finally balanced equation is, 2H 2 O + Fe + N 2 H 4 25ºC shifts towards the left in the presence of

→ Fe(OH) 2 + + NH3 [JEE 2011 P-II]
a. NO3− b. Cl– c. SCN– d. CN–
Oxidation State Method: e.g., KMnO 4 + H 2 C2 O4 
→
3. → Cl− + HSO−4
For the reaction: I − + ClO3− + H 2SO4 
CO 2 + K 2 O + MnO + H 2 O
+ I 2 The correct statement(s) in the balanced equation
The initial step I should be written as
is/are [JEE Adv. 2014 P-I]
Step (i): Mn +7 
→ Mn +2 i.e., change in oxidation no. of Mn
a. Stoichiometric coefficient of HSO −4 is 6
(+7 
→+2) = 5 units
b. Iodide is oxidised
C2+3 
→ 2C+4 i.e., change in oxidation no. of C c. Sulphur is reduced
(+6  
→ +8) = 2 units d. H2O is one of the products.
Step (ii): Proceed from step II last step for neutral, acidic or 4. From the following statements regarding H 2O 2 , choose
alkaline medium as in ion electrons method. the incorrect statement [JEE Main 2015]
Redox 53
a. It can act only as an oxidising agent 13. Iodine reacts with concentrated HNO3 to yield Y along with
b. It decomposes on exposure to light other products. The oxidation state of iodine in Y is:-
c. It has to be stored in plastic or wax lined glass bottles in dark [JEE Main 2019]
d. It has to be kept away from dust a. 5 b. 3 c. 1 d. 7
5. Which of the following reactions is an example of redox
reaction? [JEE Main 2017] Matrix Match/Column Match
a. XeF6 + 2H 2 O  → XeO 2 F2 + 4HF 14. The standard reduction potential data at 25°C is given
b. XeF4 + O 2 F2 
→ XeF6 + O 2 below: E °(Fe 3 + , Fe 2 + ) = + 0.77 V; [JEE Adv. 2013 P-II]
→ [ XeF ] PF6 − E °(Fe 2 + , Fe) = − 0.44V
+
c. XeF2 + PF5 
d. XeF6 + H 2 O 
→ XeOF4 + 2HF E °(Cu 2 + , Cu) = + 0.34V; E °(Cu + , Cu) = + 0.52V
E °[O 2 (g) + 4H + + 4e − 
→ 2H 2 O] = + 1.23V;
6. The oxidation states of Cr in [Cr(H2O)6]Cl3.[Cr(C6H6)2],
and K2 [Cr (CN)2(O)2(O)2 (NH3)] respectively are: E°[O 2 (g) + 2H 2 O + 4e − 
→ 4OH − ] = + 0.40V
[JEE Main 2018] E °(Cr 3 + , Cr) = − 0.74V; E °(Cr 2 + , Cr) = − 0.91 V
a. +3, 0 and +4 b. +3, +4 and +6
Match E° of the redox pair in Column I with the values
c. +3, +2 and +4 d. +3, 0 and +6
given in Column II and select the correct answer using the
7. In order to oxidise a mixture one mole of each of FeC2O4,
code given below the lists:
Fe2(C2O4)3, FeSO4 and Fe2(SO4)3 in acidic medium , the
Column I Column II
number of moles of KMnO4 required is: [JEE Main 2019] 3+
(A) E °(Fe , Fe) 1. – 0.18 V
a. 3 b. 2 c. 1 d. 1.5
(B) E°(4H 2 O ↽ ⇀ 4+ + 4OH − ) 2. – 0.4 V
8. The one that is extensively used as a piezoelectric material is:
[JEE Main 2019] (C) E°(Cu 2 + + Cu 
→ 2Cu + ) 3. – 0.04 V
a. Quartz b. Amorphous silica (D) E °(Cr 3 + , Cr 2 + ) 4. – 0.83 V
c. Mica d. Tridymite
a. A→ 3; B→ 4; C→ 1; D→ 2
9. Lood reducing nature of H3PO2 attributed to the presence b. A→ 1; B→ 2; C→ 3; D→ 4
of: c. A→ 3; B→ 1; C→ 2; D→ 4
[JEE Main 2019] d. A→ 3; B→ 4; C→ 2; D→ 1
a. one P-OH bond b. one P-H bond
c. two P-H bonds d. two P-OH bonds Integer and Subjective
10. The chemical nature of hydrogen peroxide is:- 15. Among the following the number of elements showing
[JEE Main 2019] only one non-zero oxidation state is O, Cl, F, N, P, Sn, Tl,
a. Oxidising and reducing agent in acidic medium, but not Na, Ti. [JEE 2010 P-II]
in basic medium.
b. Oxidising and reducing agent in both acidic and basic ANSWERS and SOLUTIONS
medium 1. (a, d) In acidic medium,
c. Reducing agent in basic medium, but not in acidic MnO −4 + 8H + + 5e− 
→ Mn 2 + + 4H 2 O
medium In neutral medium,
d. Oxidising agent in acidic medium, but not in basic MnO 4− + 2H 2 O + 3e − 
→ MnO 2 + 4OH −
medium.
Hence, number of electron loose in acidic and neutral
11. The element that usually does not show variable oxidation
medium 5 and 3 electrons respectively.
states is: [JEE Main 2019]
a. V b. Ti c. Sc d. Cu 2. (b, c, d) Cu2+ ions will react with CN– and SCN– forming
[Cu(CN)4]3–and [Cu(sCN)4]3– leading the reaction in the
12. The relative stability of +1 oxidation state of group 13
backward direction.
elements follows the order:- [JEE Main 2019]
Cu 2 + + 2CN − 
→ Cu(CN) 2
a. Al < Ga < Tl < In b. Tl < In < Ga < Al
c. Al < Ga < In < Tl d. Ga < Al < In < Tl 2Cu(CN)2 
→ 2CuCN + (CN) 2

− 3−
CuCN + 3CN 
→ [Cu(CN) 4 ] → 2H + + O 2 + 2e Θ (In acidic medium)
H 2 O2 
Cu 2 + + 4SCN − 
→ [Cu(SCN) 4 ]3− H2 O2 + 2OHΘ 
→ 2H2 O + O2 + 2eΘ (In basic medium)
Cu 2 + also combines with CuCl2 which reacts with Cu to 11. (c) Usually Sc(Scandium) does not show variable
produce CuCl pushing the reaction in the backward oxidation states.
direction. CuCl2 + Cu 
→ 2CuCl ↓ Most common oxidation states of:
(i) Sc : +3
3. (a, b, d) (ii) V : +2, +3, +4, +5
ClO3− + 6I− + 6H2SO4 
→ 3I2 + Cl− + 6HSO4− + 3H 2O (iii) Ti : +2, +3, +4
(iv) Cu : +1, +2
4. (a) It can acts as an oxidising as well as reducing agent.
+4 +1 +6 12. (c) Due to inert pair effect as we move down the group in
5. (b) In the reaction X eF4 + O 2 F2 
→ X eF6 + O02 13th group lower oxidation state becomes more stable.
Xenon undergoes oxidation while oxygen undergoes Al < Ga < In < T ℓ
reduction.
13. (a) I 2 + 10HNO3 
→ 2HIO3 + 10NO2 + 4H 2 O
6. (d) [Cr (H2O)6]Cl3 In HIO3 oxidation state of iodine is +5.
⇒ x +0 × 6 –1 × 3 = 0 Closest option is (a).
∴ x = +3 [Cr (C6H6)2]
14. (a) A→ 3; B→ 4; C→ 1; D→ 2
⇒ x+ 2 × 0 = 0
x=0 (A) ∆G oFe3+ / Fe = ∆G oFe3+ / Fe2+ + ∆G oFe2+ / Fe
K2 [Cr(CN)2(O2)(O2) NH3] ⇒ −3 × FEo(Fe+3 / Fe) = − 1× FE o(Fe+3 / Fe+2 ) + (−2 × FE oFe+2 / Fe )
⇒ 1 × 2 + x – 1× 2 – 2 × 2 – 2 × 1 = 0
⇒ E oFe+3 / Fe = − 0.04 V
⇒ x– 6 = 0 ⇒ x = +6
7. (b) n eq. KMnO4 = n eq. [FeC2 O4 + Fe2 (C2 O4 )3 + FeSO4 ] (B) O 2 (g) + 2H 2 O + 4e − 
→ 4OH
or n × 5 = 1 × 3 + 1 × 6 + 1 × 1 E° = 0.40 V . . .(i)
∴ n=2 → O 2 (g) + 4H + + 4e−
2H 2 O 
8. (a) Quartz (Information) E° = − 1.23 V . . .(ii)
9. (c) H3PO2 is good reducing agent due to presence of two So 4H 2 O ↽ ⇀ 4H + + 4OH . . .(iii)
P—H bonds. rd
E° For III reduction
O
= 0.40 − 1.23 = − 0.83 V.
(C) ∆G o(Cu +2 / Cu ) = −1× FE oCu +2 / Cu + + (−1× F × E oCu + / Cu )
P
O H −2 × FE oCu +2 / Cu = − 1× FE oCu +2 / Cu + + (−1× F × E oCu + / Cu )
H H
⇒ E oCu +2 / Cu = − 0.18 V.
10. (b) H2O2 act as oxidising agent and reducing agent in (D) ∆G oCr +3 / Cr +2 = ∆G oCr +3 / Cr + ∆G oCr / Cr +2
acidic medium as well as basic medium.
H2O2 act as oxidant:- −1× F × EoCr +3 / Cr +2 = −3 × F × E oCr +3 / Cr + (−2 × F × E oCr / Cr +2 )
H 2 O2 + 2H ⊕ + 2eΘ 
→ 2H 2 O (In acidic medium) ⇒ E oCr +3 / Cr +2 = − 0.4 V.
H 2 O + 2e Θ 
→ 2OH Θ (In basic medium)
15. Na, F show only one non-zero oxidation state. Answer is
H2O2 Act as reductant: no. of elements is 2.
Electrochemistry 55
7 Electrochemistry
QUICK LOOK Reaction occurring at anode →
−
Oxidation reaction (Loss of e )
Electrolytes: Chemical substances which dissolve in water and
furnish ions are called electrolytes. The phenomenon of the Cl − 
→ Cl + e − (Go to anode) (Primary reaction)
production of ions in solution is called dissociation or Cl + Cl 
→ Cl2 (g) (Primary reaction)
Molecule
ionisation.
Strong: Concentration of dissociated ions largely dominate
on the concentration of undissociated molecule. Preferential Discharging Theory: If more than one type of
+ −
ions are available during electrolysis, then that ion is
NaCl ↽ ⇀ Na + Cl
Neglibilbel Very large discharged first at respective electrodes which requires least
concentration concentration
energy i.e. discharging potential.
Weak: Lesser concentration of dissociated ions Electrolysis of sodium chloride solution: Ions produced
CH 3COOH ↽ ⇀ CH 3COO − + H + during electrolysis:
Large concentration Small concentration
NaCl ↽ ⇀ Na + + Cl − H 2 O ↽ ⇀ H + + OH −
Degree of Dissociation (α) At cathode, H+ ions are discharged in preference to Na+ ions
Moles of dissociated molecules / ions as the discharge potential of H + ions is lower than Na+ ions.
Total moles of molecules / ions Similarly at anode, Cl– ions are discharged in preference to
OH– ions.
Range of α ⇒ 0 < α < 1
At cathode: 2H + + 2e − 
→ H2
Factors Affecting of Degree of Dissociation At anode: 2Cl− 
→ Cl2 + 2e −
Nature of electrolytes Thus Na + and OH − remain in solution.
Nature of solvent Electrolysis of copper sulphate solution using platinum
Presence of other solute (common ion effect) electrodes:
Dilution
CuSO 4 ↽ ⇀ Cu ++ + SO −−
4 H 2 O ↽ ⇀ H + + OH −
Temperature
At cathode: Cu ++ + 2e − 
→ Cu
Electrolysis: Process in which electrolyte is decomposed into At anode: 2OH − 
→ H 2 O + 12 O 2 + 2e −
its constituents by passing electricity through its aqueous Electrolysis of sodium sulphate solution using inert
solution or fused (molten) state.
electrodes:
Na 2SO4 ↽ ⇀ 2Na + + SO4−− H 2O4 ↽ ⇀ H+ + OH−
Cathode Anode
At cathode: 2H + + 2e − 
→ H2
Deposition of At anode: 2OH − 

→ H 2 O + 12 O 2 + 2e −
Deposition of
cations Electrolysis of copper sulphate solution using copper
anions
Electrolytic solution
electrodes : CuSO 4 ↽ ⇀ Cu ++ + SO −−
4
Figure: 7.1 At cathode, copper is deposited. Cu ++ + 2e − 

→ Cu
Electrolyte = C + + A − At anode, Cu – electrode oxidised to Cu ++ ions which
NaCl ↽ ⇀ Na + + Cl − dissolve equivalent amount of copper at the anode.
Reaction occurring at cathode → Reduction reaction (Gain of e–) → Cu ++ + 2e− Cu + SO 4−− ↽ ⇀ CuSO 4 + 2e −
Cu 
Na + + e − (from cathode) 
→ Na During electrolysis, copper is transferred from anode to cathode.

Faraday’s Law of Electrolysis Electrolytic Conductance: Property of electrolytic conductor
Faraday’s first law: The amount of substance deposited on which facilitates the flow of electricity through it. It is equal to
respective electrodes is directly proportional to the quantity 1
the reciprocal of resistance i.e. conductance (c) =
of electricity passed. R
i.e. w ∝ Q
Or, w = Z× i × t Specific Conductance (k): It is the reciprocal of specific
resistance or it is the conductance produced by one centimetre
Where, w = weight of deposited substance,
cube of an electrolytic conductor.
i = amp
t = time in seconds
If i = 1 amp and t = 1 sec 1 cm
w = z,
Where, z is electrochemical equivalent. It is the mass of
substance deposited by one coulomb of charge. 1 cm
1 cm
Faraday’s second law: When same amount of electricity
Figure: 7.3
passed through different electrolytes, then deposited mass of
respective electrodes will be in the ratio of their equivalent ℓ
If R ∝
masses. a
Where, ℓ = length of conductor,
a = cross sectional area of conductor
ℓ
∴ R = ρ⋅
a
1 1 ℓ
or, = ×
H2SO4 CuSO4 AgNO3 ZnCl2 ρ R a
Figure: 7.2 or, k = C × cell constant
Mass of hydrogen E H Mass of Copper E Cu
= =
Mass of copper E Cu Mass of Silver E Ag 1
Representation of specific conductance: k = = conductance cm–1
ρ
Mass of silver E Ag Mass of zinc E
= = Zn
Mass of zinc E Zn Mass of hydrogen E H Unit at specific conductance: ohm−1cm −1or Ω−1cm −1or Scm −1
Faraday's Law for Gaseous Electrolytic Product for the (C.G.S)
gases, we use
It Ve Equivalent Conductance (Λeq): Conductance of all ions which
V= where, V = Volume of gas evolved at S.T.P. at
96500 are produced by the ionisation of one equivalent of an
an electrode electrolyte in a given solution.
Ve = Equivalent volume = Volume of gas evolved at an i.e. Equivalent conductance
electrode at S.T.P. by 1 Faraday charge (Λ ) = specific conductance × V(ml)
Quantitative Aspects of Electrolysis: We know that, one or, Λ = k × V(ml)
Faraday (1F) of electricity is equal to the charge carried by one K × 1000
or, Λ =
mole (6.023 × 10 23 ) of electrons. So, in any reaction, if one N
mole of electrons are involved, then that reaction would Unit of equivalent conductance is ohm −1 cm 2 equiv −1.
consume or produce 1F of electricity. Since 1F is equal to
96,500 Coulombs, hence 96,500 Coulombs of electricity would Molar Conductance: The units of molar conductance can be
cause a reaction involving one mole of electrons. If in any κ × 1000
reaction, n moles of electrons are involved, then the total derived from the formula, Λ = .
M
electricity (Q) involved in the reaction is given by, Q = nF = n
The units of κ are S cm −1 and
× 96,500C.
Electrochemistry 57
cm 3 • A strong electrolyte containing same anion of (a) and
Units of Λ = S cm −1 × = Scm 2 mol −1 = S cm 2 mol −1 .
mol cation of (b) i.e. NaCl.
According to SI system, molar conductance is expressed as Λ om of CH3COOH is then given as:
Sm2mol−1 , if concentration is expressed as mol m −3 . Λ om (CH3COOH) = Λ om (HCl) + Λ om (CH3COONa) − Λ om (NaCl)
∧°m (NaCl)
Effect of Dilution on Conductance
When we increase the dilution of electrolyte, magnitude of Proof: Λ om (HCl) = λ Ho + λCl− . . .(i)
specific conductance decreases, because number of ions in 1 Λ om (CHCOONa) = λCH
o
COO −
+ λNa + . . .(ii)
cm3 volume of electrolyte decreases.
3
When dilution of electrolyte increases, magnitude of molar Λom (NaCl) = λNa

o
+ +λ −
o
Cl
. . .(iii)
conductance and equivalent conductance increases, because Adding equation (i) and equation (ii) and subtracting (iii)
number of ions increases after dilution. from them:
The molar conductivity of strong electrolytes is found to Λ o(HCl) + Λ o(CH3COONa ) − Λ (oNaCl) = λ(H + + λ = Λ 0(CH 3COOH)
o o
) (CH COOo )
3
vary with concentration according to the equation.
Determination of degree of dissociation (α)
Λ cm = Λ om − b c
Number of molecules ionised Λ
α= = om
Λ°
Strong electrolyte total number of molecules dissolved Λ m
Determination of ionic product of water: From
Kohlrausch’s law, we determine Λ of H 2 O where Λ om is
o
m
conductance
Equivalent
the molar conductance of water at infinite dilution when one

Weak electrolyte
mole of water is completely ionised to give one mole of
H+ and one mole of OH − ions i.e., Λ om (H 2 O) = λH0 + λOH
0
+ −
concentration
Again using the following equation,
Figure: 7.4 κ × 1000
Λm = , where C = molar concentration i.e. mol L–
Where, Å = equivalent conductivity at fixed concentration C
1
Å = equivalent conductivity of infinite dilution or mol dm–3
Λcm κ
Degree of dissociation (α ) = ⇒ Λm = , where, C = concentration in mol m–3
Λom C
Assuming that Λ m differs very little from Λ om
Kohlrausch’s Law of Independent Migration of Ions: At κ
Λ om =
infinite dilution, conductance of any electrolyte is the sum of C
contribution of its constituents ions i.e. anions and cations. κ
⇒ C=
For an electrolyte of the type of Ax By , Λ om
Specific conductance (κ) of pure water is determined
We have Λm = xλ+ + yλ−
o o o
experimentally. Thereafter, molar concentration of

dissociated water is determined using the above equation.
Application of Kohlrausch’s Law
K w is then calculated as: Kw = C
2
Determination of Λ om of a weak electrolyte: In order to
calculate Λ om of a weak electrolyte say CH3COOH, we Heat of Reaction in an Electrochemical Cell: Let n Faraday
determine experimentally Λ om values of the following three charge flows out of a cell of emf E, then
strong electrolytes: −∆G = nFE . . .(i)
• A strong electrolyte containing same cation as in the Gibbs–Helmholtz equation from thermodynamics may be given
test electrolyte, say HCl as
• A strong electrolyte containing same anion as in the  ∂∆G 
∆G = ∆H + T   . . .(ii)
test electrolyte, say CH3COONa  ∂T  P

From equation (i) and (ii) we get, 0.0591 1
E Mn+ / M = E M
o
n+ − log n +
 ∂ (− nFE)   ∂E 
/M
n [M (aq)]
− nFE = ∆H + T   = ∆H − nFT  
 ∂T  P  ∂T  P For an electrode (half - cell) corresponding to the electrode
reaction,
 ∂E 
∆H = −nFE + nFT   −
 ∂T  P Oxidised form + ne 
→ Reduced form
The Nernst equation for the electrode is written as,
 ∂E 
Where,   = Temperature coefficient of cell 2.303RT [Reduced form ]
 ∂T P E half −cell = E ohalf −cell − log
nF [Oxidised form]
At 298 K, the Nernst equation can be written as,
 ∂E 
Case (i): When   = 0, then ∆H = −nFE E half −cell = E ohalf −cell −
0.0591 [Reduced form ]
 ∂T  P n
log
[Oxidised form]
 ∂E 
Case (ii): When   > 0, then nFE > ∆H, i.e. process inside
 ∂T  Nernst’s equation for cell EMF: For a cell in which the
the cell is endothermic. net cell reaction involving n electrons is,
 ∂E  aA + bB 
→ cC + dD
Case (iii): When   < 0, then nFE < ∆H, i.e., process inside
 ∂T  The Nernst equation is written as,
the cell is exothermic. RT [C]c [D]d
E cell = E cell
o
− ln
nF [A]a [B]b
Nernst's Equation
Where, Ecell = Ecathode − Eanode .
o o o
Nernst’s equation for electrode potential: The potential
o
of the electrode at which the reaction, The Ecell is called the standard cell potential.
M n + (aq) + ne− 
→ M(s) takes place is described by the 2.303RT [C]c [D]d
or E cell = E ocell − log
RT [M(s)] nF [A]a [B]b
equation, E M n + / M = E oMn + / M − ln
nF [M n + (aq.)] At 298 K, above eq. can be written as,
2.303 RT [M(s)] 0.0592 [C]c [D]d
Or E Mn + / M = E oMn + / M − log n + or E cell = E ocell − log
nF [M (aq)] n [A]a [B]b
Above eq. is called the Nernst equation. It may be noted here, that the concentrations of A, B, C and
Where, E Mn+ / M = the potential of the electrode at a given D referred in the eqs. are the concentrations at the time the
concentration, cell emf is measured.
Nernst’s Equation for Daniell Cell: Daniell cell consists
EoMn+ / M = the standard electrode potential
of zinc and copper electrodes. The electrode reactions in
R = the universal gas constant, 8.31 J K −1 mol −1 Daniell cell are,
T = the temperature on the absolute scale, → Zn2+ (aq) + 2e−
At anode: Zn(s) 
n = the number of electrons involved in the electrode 2+ −
At cathode: Cu (aq) + 2e 
→ Cu(s)
reaction,
F = the Faraday constant: (96500 C), Net cell reaction: Zn(s) + Cu 2 + (aq) 
→ Cu(s) + Zn 2 + (aq)
[M(s)] = the concentration of the deposited metal,
[M n + (aq)] = the molar concentration of the metal ion in the Therefore, the Nernst equation for the Daniell cell is,
solution, 2.303RT [Cu(s)][Zn 2+ (aq)]
E cdll = E ocell − log
The concentration of pure metal M(s) is taken as unity. So, 2F [Zn(s)][Cu 2+ (aq)]
the Nernst equation for the Mn+/M electrode is written as, Since, the activities of pure copper and zinc metals are
2.303 RT 1 taken as unity, hence the Nernst equation for the Daniell
E M n + / M = E oM n + / M − log n +
nF [M (aq)] 2.303RT [Zn 2+ (aq]
cell is, Ecdll = Eocell − log
At 298 K, the Nernst equation for the M n + / M electrode 2F [Cu 2+ (aq)]
can be written as, The above eq. at 298 K is,
Electrochemistry 59
2+ H2O drop −
O 2 + 2H 2 O + 4e 
→
0.0591 [Zn (aq]
E cdll = Eocell − log V
2 [Cu 2+ (aq)]
e−
0
For Daniell cell, Ecell = 1.1V
→ Fe2+ + 2e−
Fe 
Iron piece
Nernst's equation and equilibrium constant: For a cell, in
which the net cell reaction involving n electrons is, Figure: 7.5
aA + bB 
→ cC + dD Cathode reaction O 2 + 2H 2 O + 4e − 
→ 4OH −
RT [C]c [D]d → 2Fe ( OH ) 2
The overall reaction is 2Fe + O 2 + 2H 2 O 
The Nernst equation is Ecell = Eocell − ln . . .(i)
nF [A]a [B]b
Fe(OH)2 may dehydrate to form its oxide FeO, which than
At equilibrium, the cell cannot perform any useful work. So
at equilibrium, E Cell is zero. Also at equilibrium, the ratio further gets oxidised to Fe2 O3 . Which is further hydrated to
form rust?
[C]c [D]d  [C]c [D]d 
=  = Kc → Fe2O3 .nH 2O ( rust )
Fe2O3 + nH2O 
[A]a [B]b [A]a [B]b  equilibrium
Corrosion of a metal weakness the metal and hence is
undesirable. The following methods are used to protect a metal
Relation Among Potential, Gibbs Energy and Equilibrium
from corrosion.
Constant: The electrical work (electrical energy) is equal to the
Applying a protective film such as metal oxide.
product of the EMF of the cell and electrical charge that flows
Plating the metal with a more electropositive metal, which
through the external circuit i.e.,
loses electrons in preference to the less electropositive metal
Wmax = nFEcell . . .(i)
e.g. Zn is coated on steel. (Galvanisation)
According to thermodynamics the free energy change (∆G) is By connecting the metal with more electropositive metal
equal to the maximum work. In the cell work is done on the (Electrical protection)
surroundings by which electrical energy flows through the
external circuit, So − Wmax, = ∆G . . .(ii) Multiple Choice Questions
From eq. (i) and (ii) ∆G = − nFE cell One and More than One Correct
1. Electrolysis of dilute aqueous NaCl solution was carried
In standard conditions ∆G o = − nFE ocell
out by passing 10 milli ampere current. The time required
Where ∆G o = standard free energy change to liberate 0.01 mol of H2 gas at the cathode is (1 Faraday
2.303
But E ocell = RT log K c = 96500 C mol−1 ) [JEE 2008 P-II]
nF 4 4
a. 9.65×10 sec b. 19.3×10 sec
2.303
∴ ∆G o = −nF × RT log K c c. 28.95×104sec d. 38.6×104sec
nF
∆G o = − 2.303 RT log K c or ∆G = ∆G ° + 2.303RT log Q 2. Among the electrolytes Na2SO4, CaCl2, Al2, (SO4)3 and
NH4Cl, the most effective coagulating agent for Sb2S3 sol
∆G o = − RT ln K c (2.303log X = ln X)
is: [JEE 2009 P-I]
a. Na2SO4 b. CaCl2
Corrosion: The conversion of a metal into undesirable c. Al2(SO4)3 d. NH4Cl
compounds by the action of air, moisture is called corrosion; In
case of iron corrosion it is called rusting. Corrosion is a redox 3 AgNO3(aq.) was added to an aqueous KCI solution
reaction by which metal gets oxidised by air in presence of gradually and the conductivity of the solution was
moisture. Small cathode and anodic cells are set up on metal. measured. The plot of conductance (^) versus the volume
The area of metal in contact with water acts as anode. Metal of AgNO3 is: [JEE 2011 P-I]
loses electrons to form cations. + +
a. + + b. +
→ Fe2+ + 2e−
Fe  Λ + ++ Λ
+ ++
The electrons flow along the metal into the cathode area. +
Where, O2 is reduced to hydroxyl ions in presence of H2O. volume volume
+ a. 2.303 RT–2.2 F b. 1.1 F

c. d. + c. – 2.2 F d. 2.303 RT+1.1 F
Λ +
Λ ++ + + + + + + +
11. How long (approximate) should water be electrolysed by
passing through 100 amperes current so that the oxygen
volume volume
released can completely burn 27.66 g of
4. Consider the following cell reaction: 2Fe (S) + O 2(g ) + 4H 0(aq ) diborane?(Atomic weight of B = 10.8u) [JEE Main 2018]
2+ −3
→ 2Fe 2(aq+ ) + 2H 2 O (l) E° = 1.67V At[Fe ] = 10 M, P(O2 )
 a. 1.6 hours b. 6.4 hours
c. 0.8 hours d. 3.2 hours
= 0.1 atm and pH = 3, the cell potential at 25°C is :
12. Given that:
[JEE 2011 P-II] 0
E O 2 /H 2 O = +1.23V
a. 1.47 V b. 1.77 V
c. 1.87 V d. 1.57 V E S0 O2 / SO2 = 2.05V
2 8 4
5. Given: E 0Cr3+ / Cr = −0.74 V; E 0MnO− / Mn 2+ = 1.51 V E °Cr O 2−

/ Cr 3+
E 0
= +1.09V
4 2 7 Br2 / Br
= 1.33V; E 0
Cl / Cl−
= 1.36 V Based on the data given above, E 0
= +1.4V
Au 3+ / Au
strongest oxidizing agent will be: [JEE Main 2013] The strongest oxidising agent is [JEE Main 2019]
2+
a. Cl −
b. Cr 3+
c. Mn d. MnO −4 a. O2 b. Br2 c. S2 O 82− d. Au 3+
6. In a galvanic cell, the salt bridge [JEE Adv. 2014 P-I] 13. Calculate the standard cell potential in (V) of the cell in
a. does not participate chemically in the cell reaction. which following reaction takes place:
b. stops the diffusion of ions from one electrode to Fe 2+ (aq) + Ag+(aq) 
→ Fe 3+ (aq) + Ag(s)
another. Given that
c. is necessary for the occurrence of the cell reaction
E oAg+ /Ag = xV
d. ensures mixing of the two electrolytic solutions
7. Two Faraday of electricity is passed through a solution of E oFe2+ / Fe = yV
CuSO4. The mass of copper deposited at the cathode is: E oFe3+ / Fe = zV [JEE Main 2019]
[JEE Main 2015]
a. x + 2y – 3z b. x – z
a. 0 g b. 63.5 g c. 2 g d. 127 g
c. x – y d. x + y – z
8. For the following electrochemical cell at 298 K, Pt(s) | H 2 14. The anodic half cell of lead acid battery is recharged using
(g,1 bar) H + (aq,1 M) || M 4+ (aq), M 2+ (aq) | Pt(s) E cell = electricity of 0.05 Faraday. The amount of PbSO4
electrolysed in g during the process in: (Molar mass of
[M 2+ (aq)]
0.092Vwhen = 10 x. Given: E 0M 4+ / M 2+ = 0.151V; PbSO4 = 303 g mol–1) [JEE Main 2019]
[M 4+ (aq)]
a. 22.8 b. 15.2 c. 7.6 d. 11.4
RT
2.303 = 0.059V The value of x is: 15. If the standard electrode potential for a cell is 2 V at 300
F
K, the equilibrium constant (K) for the reaction
[JEE Adv. 2016-II]
a. –2 b. –1 c. 1 d. 2 Zn(s) + Cu 2+ (aq) → Zn 2+ (aq) + Cu(s)
at 300 K is approximately. [JEE Main 2019]
9. Given E o
C l2 / C l−
= 1 .3 6 V , E o
C r3+ / C r
= − 0 .7 4 V , –1 –1 –1
(R = 8 JK mol , F = 96000 C mol )
E oCr O 2− = 1.33 V, E oMnO − / Mn 2 + = 1.51V Among the following, a. e160 b. e 320 c. e 320 d. e -80
2 7 4
the strongest reducing agent is : [JEE 16. Consider the following reduction processes:
Main. 2017] Zn 2+ + 2e – 
→ Zn(s); E° = – 0.76 V
− 3+
a. Cl b. Cr c. Mn2+ d. Cr Ca 2+ + 2e – 
→ Ca(s); E° = – 2.87 V
10. For the following cell, Zn(s) | ZnSO4(aq) || CuSO4(aq) | Mg 2+ + 2e – 
→ Mg(s); E° = – 2.36 V
Cu(s) when the concentration of Zn2+ is 10 times the
Ni 2+ + 2e – 
→ Ni(s); E° = – 0.25 V
concentration of Cu2+, the expression for ∆ G (in J mol–1)
The reducing power of the metals increases in the order:
is [F is Faraday constant; R is gas constant; T is
[JEE Main 2019]
temperature; E°(cell) = 1 .1 V ] [JEE Adv. 2017 P-II]
Electrochemistry 61
a. Ca < Zn < Mg < Ni b. Ni < Zn < Mg < Ca
c. Zn < Mg < Ni < Ca d. Ca < Mg < Zn < Ni
17. In the cell Pt(s)|H2(g,1bar|HCl(aq)|Ag(s)|Pt(s) the cell λm λm
potential is 0.92 when a 10–6 molal HCl solution is used. c. CMC d. CM
The standard electrode potential of (AgCl/Ag,Cl–) electrode C
C C
2.303RT
is: {given, =0.06Vat 298K} [JEE Main 2019]
F
a. 0.20 V b. 0.76 V Matrix Match/Column Match
c. 0.40 V d. 0.94 V 22. An aqueous solution of X is added slowly to an aqueous
18. The electrolytes usually used in the electroplating of gold solution of Y as shown in Column I. The variation in
and silver, respectively, are: [JEE Main 2019] conductivity of these reactions shown in Column II.
a. [Au(OH)4]– and [Ag(OH)2]– [JEE Adv. 2013 P-II]
b. [Au(CN)2]– and [Ag CI2]– Column I Column II
c. [Au(NH3)2]+ and [Ag(CN)2]– (A) (C 2 H 5 )3 N + CH 3 COOH 1. Conductivity decre-
d. [Au(CN)2]– and [Ag(CN)2]– X Y
ases and then
19. For the cell Zn(s) | Zn2+(aq) || Mx+ (aq) | M(s), different increases
half cells and their standard electrode potentials are given (B) 2. Conductivity decre-
below: KI(0.1M)+ AgNO3 (0.01 M) ases and then does
X Y
Mx+(aq Au3+(aq)/ Au+(aq) Fe3+ Fe2+(aq) / not change much
/M(s) Au(s) /Au(s) (aq)/ Fe (aq) (C) CH3 COOH + KOH 3. Conductivity incre-
X Y
Fe (aq) ases and then does
not change much
Eº x+ ( v) 1.40 0.80 0.77 –0.44
(D) NaOH+ HI
M /M
4. Conductivity does
X Y
If E º
zn2 + / Zn
= −0.76V, which cathode will give a not change much
º and then increases
maximum value of E cell per electron transferred?
a. A → 2; B → 3; C → 1; D → 4
[JEE Main 2019]
b. A → 1; B → 2; C → 3; D → 4
a. Fe3+ / Fe2+ +
b. Ag / Ag
c. A → 2; B → 1; C → 3; D → 4
c. Au3+ / Au d. Fe2+ / Fe
d. A → 3; B → 4; C → 2; D → 1
20. Given the equilibrium constant:
KC of the reaction:
Paragraph
Cu(s) + 2Ag+ (aq) 
→ Cu 2+ (aq) + 2Ag(s)
0
Paragraph for Question Nos. 23 to 25
10 × 1015, calculate the Ecell of this reaction at 298 K
Chemical reactions involve interaction of atoms and molecules.
RT A large number of atoms/molecules (approximately 6.023 ×
[ 2.303 at 298 K = 0.059V] [JEE Main 2019]
F 1023) are present in a few grams of any chemical compound
a. 0.04736 V b. 0.4736 V varying with their atomic/molecular masses. To handle such
c. 0.4736 mV d. 0.04736 mV large numbers conveniently, the mole concept was introduced.
21. Which of the following plot is correct regarding its This concept has implications in diverse areas such as
conductance? analytical chemistry, biochemistry, electrochemistry and
[JEE Adv. 2019 P-I] radiochemistry. The following example illustrates a typical
case, involving chemical/electrochemical reaction, which
CM CM requires a clear understanding of the mole concept. A 4.0 molar
λm λm C aqueous solution of NaCl is prepared and 500 mL of this
a. b. solution is electrolysed. This leads to the evolution of chlorine
gas at one of the electrodes (atomic mass: Na=23, Hg =200,
C C 1 Faraday= 96500 coulombs) [JEE 2007 P- I]

23. The total number of moles of chlorine gas evolved is 30. For the electrochemical cell, Mg(s) | Mg +2 (aq,1M) || Cu 2 +
a. 0.5 b. 1.0 c. 2.0 d. 3.0
(aq,1M)Cu(s) the standard emf of the cell is 2.70 V at 300 K.
24. If the cathode is a Hg electrode, the maximum weight (g) When the concentration of Mg2+ is changed to x M, the cell
of amalgam formed from this solution is:
potential changes to 2.67 V at 300 K. The value of x is_____.
a. 200 b. 225 c. 400 d. 446
F
25. The total charge (coulombs) required for complete (Given, = 11500 KV −1 , where F is the Faraday constant
R
electrolysis is: and R is the gas constant, ln(10) = 2.30) [JEE Adv. 2018 P-
a. 24125 b. 48250
I]
c. 96500 d. 193000
31. Consider an electrochemical cell: A(s) | An+ (aq, 2 M) || B2n+
Paragraph for Question Nos. 26 to 27 (aq, 1 M) | B(s). The value of ∆HΘ for the cell reaction is
The concentration of potassium ions inside a biological cell is twice that of ∆G Θ at 300 K. If the emf of the cell is zero, the
at least twenty times higher than the outside. The resulting
∆ SΘ (in J K–1 mol–1) of the cell reaction per mole of B
potential difference across the cell is important in several
formed at 300 K is:
processes such as transmission of nerve impulses and
(Given: ln(2) = 0.7, R (universal gas constant) = 8.3 J K–1
maintaining the ion balance. A simple model for such a
mol–1. H, S and G are enthalpy, entropy and Gibbs energy,
concentration cell involving a metal M is:
respectively.) [JEE Adv. 2018 P-II]
M(S) | M + (aq;0.05molar) || M + (aq),1molarM(s) For the above
electrolytic cell the magnitude of the cell potential
1. (b) Q = i × t Q = 10 × 10−3 × t
|Ecell |=70mV. [JEE 2010 P-I]
2H 2O + 2e − 
→ H 2 + 2OH −
26. For the above cell
To liberate 0.01 mole of H 2 0.02 Faraday charge is
a. Ecell < 0; ∆G > 0 b. Ecell > 0; ∆G < 0
required Q = 0.02 × 96500 C
c. E cell < 0; ∆G° > 0 d. E cell > 0; ∆G° > 0
+
∴ 0.02 × 96500 = 10−2 × t
27. If the 0.05 molar solution of M is replaced by 0.0025
t = 19.30 ×104 sec
molar M + solution, then the magnitude of the cell potential
would be 2. (c) As Sb 2S3 is a negative solution. So, Al2 (SO 4 )3 will be
a. 35 mV b. 70 mV c. 140 mV d. 700 mV the most effective coagulant due to higher charge density
on Al3+ in accordance with Hardy-Schulze rule. Order of
Integer and Subjective
effectiveness of cations:
28. The molar conductivity of a solution of a weak acid HX
Al3+ > Ca ++ > Na + > NH +4
(0.01 M) is 10 times smaller than the molar conductivity
of a solution of a weak acid HY (0.10 M). If λX0 − ≈ λY0 − , 3. (d)
4. (d) 2Fe(s) + O 2 (g) + 4H + (aq) 
→ 2Fe +2 (aq) + 2H 2 O( ℓ )
the difference in their pK a values, pK a (HX) pK a (HY),
is (consider degree of ionisation of both acids to be << 1) N = 4 (no. of moles of electron involved)
[JEE Adv. 2015 P-II] From Nernst’s equation,
0.0591
29. The conductance of a 0.0015 M aqueous solution of a weak E cell = E °cell − log Q
monobasic acid was determined by using a conductivity cell
n
0.0597 (10−3 ) 2
consisting of platinised Pt electrodes. The distance between
the electrodes is 120 cm with an area of cross section of
= 1.67 −
4
log
0.1× (10−3 ) 4
{∵ [H +
] = 10 − pH }
1cm 2 . The conductance of this solution was found to be = 1.67 − 0.106 = 1.57 V
5 × 10 −7 S . The pH of the solution is 4. The value of limiting 5. (d) MnO−4 is strongest oxidising agent.
molar conductivity ( Λ 0m ) of this weak monobasic acid in 6. (a)
2 −1 −1
aqueous solution is Z × 10 Scm mol . The value of Z is: 7. (b) Cu +2 + 2e − 
→ Cu (s)
[JEE Adv. 2017 P-I] 2 mol 1 mol = 63.5
Electrochemistry 63
0.059 2+
[M ][H ] + 2
∆ G = ∆ G − ∆ G = ( − 2Fy + 3Fz) = − Fm
o o o
(d) E cell = E ocell −

3 1 2
8. log10
2 [M 4+ ]pH 2 ⇒ m = (2y – 3z)
0.059 ⇒ E ocell = (x + 2y –3z)V
0.092 = 0.151 = log10 10 x
2
14. (b) (i) PbSO 4 (s)+ 2OH − 
→ PbO2 + H 2SO4 + 2e−
∴ x=2 0.05 / 2mole 0.05F
9. (a) E oMnO− / Mn+2 = 1.51 V . . .(i) (ii) PbSO4 + 2e− + 2H + 

→ Pb(s) + H 2SO4
4 0.05 / 2mole 0.05F
EoCl − = 1.36 V . . .(ii) n T (PbSO 4 ) = 0.05mole

2 / Cl
E oCr O−2 / Cr +3 = 1.33 V . . .(iii) m PbSO 4 = 0.05 × 303 = 15.2gm

2 7
E oCr+3 / Cr = − 0.74 . . .(iv) 15. (a) ∆Gº = –RTlnk = –nFE cell

º
Since, Cr+3 is having least reducing potential, so Cr is the n × F × Eº 2 × 96000 × 2

ln k = =
best reducing agent. R×T 8 × 300
10. (a) Zn | ZnSO 4 || CuSO 4 | Cu lnk =160 k = e160
(aq ) (aq )
16. (b) Higher the oxidation potential better will be reducing
∆G = ∆G ° + RT ln Q
power.
 [Zn +2 ] 10 
∆G = ∆G ° + 2.303RT log Q  Q = =  17. (a) Pt(s) H 2 (g, 1bar) HCl(aq) AgCl(s) Ag(s) |Pt(s)
 [Cu +2 ] 1 
∆G° = −nFE°Cell = − 2F × 1.1 = − 2 .2 F For 10–6mol HCl
→ 2H + + 2e × 1
Anode: H 2 
11. (d) B2 H 6 + 3O2 
→ B2 O3 + 3H 2O
Cathode: e – + AgCl(s) 
→ Ag(s) + Cl – (aq) × 2
27.66 of B2H6 = 1 mole of B2H6 which requires three
moles of oxygen (O2) for complete burning H 2 (g)l + AgCl(s) 
→ 2H + +2Ag(s) + 2Cl – (aq)
6H 2 O 
→ 6H 2 + 3O2 (On electrolysis) 0.06
E cell = E cell
0
− log10 ((H + ) 2 ⋅ (Cl − ) 2 )
Number of faraday 2
=12 = Amount of charge
12 × 96500 = i × t
.925 = E 0H ( 2 / H+ )
+ E 0Agcl / Ag,Cl− −
0.06
2
(
log10 (10−6 )2 (10−6 ) 2 )
12 × 96500 = 100 × t .92 = 0 + E 0Agcl / Ag,Cl− −0.03log10 (10−6 )4
12 × 96500
t= seconds E 0AgCl / Ag,Cl− = .92 + .03 × − 24 = 0.2V
100
12 × 96500 18. (d)
t= hours ⇒t = 3.2 hours
100 × 3600
19. (b)
12. (c) For strongest oxidising agent, standard reduction
0.059
potential should be highest. 20. (b) E cell = E cell
º
− log Q
n
13. (a) Fe 2+ (aq) + Ag+(aq) 
→ Fe 3+ (aq) + Ag(s) At equilibrium
Cell reaction 0.059
= E cell
º
− log1016 = 0.059×8 = 0.472V
→ Fe +3 (aq) + e Θ ; E Fe+2 /Fe+3 = mV
o
Anode: Fe +2 (aq)  n
o
Cathode: Ag + (aq) + e Θ 
→ Ag(s) ; E Ag + /Ag = xV 21. (b)
⇒ cell standard potential = (m + x)V 22. (d) A →3; B → 4; C → 2; D→1

∴ to find 'm'; (A) → (C2 H5 )3 NH+CH3COO−
(C2 H5 )3 + N + CH3COOH 
Θ X Y
Fe +2
+ 2e 
→ Fe ; E1o = yV ⇒ ∆1o G = − (2Fy)
Initially conductivity increases due to ion formation after
Fe +3 + 3eΘ 
→ Fe ; E o2 = zV ⇒ ∆ o2 G = − (3Fz) that it becomes practically constant because X alone
→ Fe +3 (aq) + e Θ ; E o3 =mV ⇒ ∆ 3o G = − (1Fm)
Fe +2 (aq)  cannot form ions. Hence (3) is the correct match.

(B) KI(0.1 M)+ A gNO3 (0.01 M) 
→ AgI ↓ + KNO3 Λm for HX = Λ m 1
Λm for HY = Λ m 2
X Y
1
Number of ions in the solution remains constant until all Λ m1 = Λ m2 Ka = Cα 2
the AgNO3 precipitated as AgI. Thereafter conductance 10
increases due to increases in number of ions. Hence (4) is  Λm 
2
 Λm 
2
the correct match. Ka1 = C1 ×  0 1  Ka 2 = C2 ×  0 2 

(C) Initially conductance decreases due to the decrease in the  Λ m1   Λ m2 
2 2
number of OH ions thereafter it slowly increases due to Ka1 C1  Λm1  0.01  1 
= ×  = × = 0.001
the increases in number of H+ ions. Hence (2) is the Ka 2 C 2  Λm 2  0.1  10 
correct match.
pKa 1 − pKa 2 = 3
(D) Initially it decreases due to decrease in H+ ions and then
increases due to the increases in OH ions. Hence (1) is Gl 120 cm
29. κ= = 5 × 10 −7 S × = 6 × 10 −5 S cm −1
the correct match. A 1 cm 2
For Question Nos. 23 to 25 κ 6 × 10−5 S cm −1
+ − −
λm = = = 40 S cm 2 mol−1
23. (b) NaCl 
→ Na + Cl At anode: 2Cl 
→ Cl 2 C 0.0015 mol / L
−
Moles of Cl = 2 in 500 ml. 1.0 × 10−4 M 1
pH = 4.0 so, α = =
Therefore 1 mole of Cl2 evolves. 15 × 10−4 M 15
Hence (b) is correct. λ cm 40
α= 0
= S cm 2 mol−1
24. (d) Na — Hg (amalgam) formed = 2 moles at cathode. λ m 1/15
Hence (d) is correct. λ 0m = 6 × 10 2 S cm 2 mol −1 ⇒ Z = 6.
25. (d) 2 moles of electrons (2 Faraday) are required.
30. Cell reaction
1F = 96500, 2F = 193000
Mg ( s ) + Cu +2 (1M) → Cu ( s ) + Mg +2 (xM)
Hence (d) is correct.
2.303T
For Question Nos. 26 to 27 E cell = Eº cell − log x
F/R
26. (b) M(s) + M +(aq )1M 
→ M (+aq ).05M + M(s)
2.303 × 300
According to Nernst equation, 2.67 = 2.70 − log x
+
11500 × 2
2.303RT M
E cell = 0 − log .05M
+ 2.303 × 3 0.03 × 115 × 2
F M 1M 0.03 = log x ⇒ log x = =1
115 × 2 2.303 × 3
log ( 5 × 10−2 ) = + ve
2.303RT
= 0− x = 10.00
F
Hence, | Ecell |= Ecell = 0.70V and ∆G < 0 for the feasibility 31. → A n + + ne−
A 
of the reaction. B2 n + + 2ne − 
→B
2.303RT 2A + B2 n + → 2A n + + B
27. (c) Form above equation = 0.0538
F ∆Hº = 2 ∆Gº , E cell = 0
0.0538
So, E cell = E°cell − log 0.0025 ∆Gº = ∆Hº −T∆Sº
1
∆Gº
= 0−
0.0538
log 0.0025 ≈ 0.13988 V ≈ 140 mV ⇒ ∆Gº = T∆Sº ⇒ ∆Sº =
1 T
− RT ln K [A n + ]2
[H + ] [X − ] ∆Sº = = − R ln
28. HX → H + X + −
Ka = T [B 2 n + ]
[HX]
[H + ] [Y − ] 22
HY → H + Y + −
Ka = = −8.3 × ln ⇒ ∆Sº = −1.6JK −1mol −1
[HY] 1
Chemical Bonding 65
8 Chemical Bonding
QUICK LOOK Larger the anion, more will be its polarisability
A molecule is formed if it is more stable and has lower energy than Covalent Bond: Covalent bond is formed by mutual sharing of
the individual atoms. Normally only electrons in the outermost electrons so as to complete their octet or duplet in case of H, Li
shell of an atom are involved in bond formation and in this process and Be. Depending upon whether one, two and three electrons
each atom attains a stable electronic configuration of inert gas. are shared by each atom, single, double and triple bonds are
Atoms may attain stable electronic configuration in three different respectively formed. The number of electrons contributed by
ways by loosing or gaining electrons by sharing electrons. The each atom for sharing is called its Covalency.
attractive forces which hold various constituents (atoms, ions, etc) When two half-filled atomic orbitals overlap along their
together in different chemical species are called chemical bonds. internuclear axis, the bond formed is called the sigma bond (or
Elements may be divided into three classes. σ - bond). It may be formed by the overlap of two s-orbitals, two
Electropositive elements, whose atoms give up one or more p-orbitals, one s- and one p-orbital. Accordingly these bonds are
electrons easily, they have low ionisation potentials. designated as s-s, p-p and s-p sigma bonds. On the other hand,
Electronegative elements, which can gain electrons. They covalent bond formed by sideways or lateral overlap of p-orbitals
have higher value of electronegativity. is called pi-bond (or π - bond). It may be noted that
Elements which have little tendency to loose or gain All single bonds are σ - bonds.
electrons. Multiple bonds contain one σ - bonds and the rest are π -
Three different types of bond may be formed depending on bonds.
electropositive or electronegative character of atoms involved. A π - bond is never formed alone. First, σ - bonds is formed
Electropositive element + Electronegative element = Ionic bond and then the formation of the π - bond takes place.
(electrovalent bond) A sigma bond is always stronger than pi-bond because the
Electronegative element + Electronegative element = Covalent bond extent of overlapping of atomic orbitals along internuclear
or less Electropositive + Electronegative element = Covalent bond axis is greater than sideways overlapping.
Electropositive + Electropositive element = Metallic bond. Coordinate or Dative Bon: This type of bond formation
occurs by one sided sharing of electrons, i.e., one atom donates
Fajan Rules: In Ionic bond, some covalent character is a pair of electrons while the other simply shares it so as to
introduced because of the tendency of the cation to polarise the complete its octet. The atom that donates a pair of electrons is
anion. In fact cation attracts the electron cloud of the anion and called the donor while the other which accepts these electrons
pulls electron density between the two nuclei. is called the acceptor. The coordinate bond is usually
represented by an arrow pointing from the donor towards the
accept
+
Cation H  H 
Anion Polarised electron |  | 
Figure: 8.1 cloud of anion → H + or  H — N— H 
Example: H — N : 
|  | 
According to Fajan rules, the magnitude of covalent character H  H 
 
in the ionic bond depends upon the extent of polarisation
Coordinate bond is also present in SO 2 ,SO 3 , O 3 , H 3 O + , NO 3−
caused by cation. In general,
Smaller the size of cation, large is its polarising power. or HNO3 etc.
Among two cations of similar size, the polarising power of This coordinate bond has some polar character, it is also called
cation with noble gas configuration (ns 2 np 6 nd10 ) is larger dative or semi-polar bond.
than cation with noble gas configuration (ns 2 np 6 ) e.g., In terms of VB theory, a coordinate bond is formed by overlap
of a fully filled orbital containing a lone pair of electrons with
Polarising power of Ag + is more than K +
an empty orbital of another atom.

Examples of molecules in which all the three types of bonds, N 2 O3 / O = N −N=O NO 3− / SO3 / O ← S = O
↓ ↓
i.e., ionic, covalent and coordinate bonds are present: O − O
O−N =O
↓
CuSO 4 . 5H 2 O, NH 4 Cl, K 4 Fe (CN )6 , Cu ( NH 3 )4 SO 4 , etc. O
Besides these bonds, CuSO 4 . 5H 2O also contains a H-bond. HClO 3 / SOCl 2 / HIO3 / H − O − I → O
↓
H − O − Cl → O O ← S − Cl O
Characteristics of coordinate compounds are: ↓ |
O Cl
Since coordinate compounds are in fact covalent compound,
H 2 O2 / H − O − O − H Cl
therefore, their properties are almost similar to those of |
SO2Cl2 / O ← S → O
covalent compounds. For example, or H − O → O |
|
Cl
H
Like covalent compound, they are insoluble in H 2O but are
HNO 2 / H − O − N = O O
soluble in organic solvents. ↑
HClO4 / H − O − Cl → O
They usually do not conduct electricity. ↓
Their melting and boiling points are higher than those of O
covalent compounds but lower than those of ionic compounds. NO −2 / SO 2 / O
↑
Like covalent bonds, coordinate bonds are directional and −
O−N =O O←S=O H 2SO4 / H − O − S − O − H
↓
hence these compounds also exhibit stereoisomerism O
N2O4 / O = N − N = O SO 32 − / H3PO4 /
Table: 8.1 Bond Formula or Dash Formula of Molecules Showing Different ↓ ↓
− − −
Type of Bonding O O O − S− O O − S − O−
↓
O ↓
(1) Compounds having (2) Compounds having covalent bonds only O
electrovalent bonds
N2O5 / O = N− O − N = O
only ↓ ↓
Molecular H 2O / H − O − H O O
HCl / H − Cl
formula/Dash formula (5) Compounds having electrovalent bonds only
NaCl / Na + Cl− H 2S / H − S − H HCN / H − C ≡ N +
 H 
MgCl2 / Cl Mg Cl − ++ −
C2 H2 / H − C ≡ C − H  | 
NH4Cl /  H − N → H  Cl−
|
CaCl2 / Cl Ca Cl− ++ − H H H  
| | |  H 
NH3 / H—N C2H 6 / H — C — C — H
| | |  C≡N 
H H H  
N ≡ C C≡N
++ −−
MgO / Mg O H Cl K 4 [Fe(CN)6 ] / 4k  Fe 
| |  
CH 4 / H — C — H PCl3 / Cl — P N ≡ C C≡N
| |  C≡N 
H Cl  
Na 2S / N a + S − − N a + H H H Table: 8.2 Comparison of Ionic, Covalent and Coordinate Compounds

| | | Property Ionic Covalent Coordinate
C2 H 4 / C == C PH3 / H — P
| | |
H H H 1.Binding Between ions Between molecules In between
CaH2 / H − Ca + + H − force strong smaller (Van der
(coulombic) Waal’s)
AlF3 / F−Al3+ F−
2.mp/bp High Less than ionic In between
F−
3. Condition conductor of Bad conductor Greater than
(3) Compounds having electrovalent and covalent bonds
electricity in covalent
NaOH / Na + [O − H]− fused state and
KCN / K + [C ≡ N]− in aqueous
2− solution
 
  4. Solubility in High Less In between
CaCO3 / Ca ++ O − C− O polar solvent
||
 O  (H2O)
5. Solubility in Low High In between
(4) Compounds having covalent and coordinate bonds non polar
CO / solvent (ether)
N 2O / HNO 3 / H − O − N = O
↓ 6. Physical generally solid Liquid and Solid, liquid
C=O N≡N→O O state gaseous gas
Chemical Bonding 67
Hybridisation: The concept of hybridisation was introduced to Both half-filled and completely filled orbitals can
explain the shapes of molecules. It involves the intermixing of participate in hybridisation
two or more atomic orbitals of slightly different energies but of Hybridisation never takes place in isolated atoms but occurs
the same atom so that a redistribution of energy takes place only at the time of bond formation.
between them resulting in the formation of an equal number of Hybrid orbitals form stronger bonds than pure atomic
new orbitals (called hybrid orbitals) having same energy, size orbitals.
and shape. It may be noted that:
Table: 8.3 Types of Hybridisation
Type of Hybridisation Character Shape of the molecule or ion Example

o
sp s-character = 50%, 180 BeF2 , BeH2 , CO2 , C2 H2 ,
p-character = 50%. : A : HCN, HgCl2 , CS2 , N 2 O,
Linear Hg 2 Cl 2 , [Ag(NH 3 ) 2 ]+
sp 2 s-character = 33.33%, .. BF3 , SO2 , SO3 , C2 H 4 ,

p-character = 66.67%
O
||
120o CO32− , NO3− ,H — C — H, CH 3+ , AlCl 3 ,
A
Benzene, graphite,
: :
C 2 Cl 4 , C2 H 2 Cl2 , C2 H5 CHO, BeCl 2
Triangular planar
sp3 s-character = 25%, .. CH 4 , CCl4 , SiF4 , H 2 O, NH 3 , H 3 O + ,

p-character = 75%
ClO −4 , SO 42− , NH 4+ ,[BeF4 ]− , ClO 3− , NF3 ,
(as s-character decreases,
p-character increases, bond 109o28′ XeO3 , XeO4 , CH 3− , NH 2− , [AlCl 4 ]− , [PH 4 ]+ ,
angle decreases). A SnCl4 ,
: :
Diamond, Silica, H3O, AsCl3 , Si(CH 3 ) 4 ,
..
SiC, [BF4 ]− , ClO−2 , NH +4 , SF2 , ClO −4 , NH −2
Tetrahedral
3
sp d s-character = 20%, .. XeO 3 F2 , XeF2 , ClF3 , SF4 , PCl5 , PF5 ,
p-character = 60%, 90o : + −
AsF5 , SbCl5 , PCl , PCl
4 6
d-character = 20% : A
120o
..
..
Trigonal bipyramidal
sp3d 2 s-character = 16.66%, .. SF6 , M oF6 , XeF4 , BrF5 , XeOF4 , [BiCl6 ]− ,

p-character = 49.98%, o − 3+
90 [PF6 ] , [Co(NH 3 )6 ]
d-character = 33.33%
o A
90
..
Octahedral
3 3
sp d s-character = 14.28%, .. .. IF7 , XeF6 , [ZrF7 ]3− , [UF7 ]3− , [UO2 F5 ]3−
p-character = 42.86%, etc.
d-character = 42.86% 90o
72o
A :
..
..
Pentagonal bipyramidal

Method of Predicting the Hybrid State of the Central Atom In case of certain molecules, a single Lewis structure cannot
in Covalent Molecules or Polyatomic Ions: The hybrid state explain all the properties of the molecule. The molecule is then
of the central atom in simple covalent molecule or polyatomic supposed to have many structures, each of which can explain
ion can be predicted by using the generalised formula as most of the properties of the molecule but none can explain all
described below: the properties of the molecule. The actual structure is in
between of all these contributing structures and is called
Simple molecule Polyatomic Anion Polyatomic Cation
resonance hybrid and the different individual structures are
1 1 1
X=  V + G  X= V + G + a  X= V + G − c
2 2 2 called resonating structures or canonical forms. This
In the above formulae: phenomenon is called resonance.
V = Number of monovalent atoms or groups attached to the
Valence Shell Electron Pair Repulsion (VSEPR) Theory
central atom
and Shapes of Molecules: According to this theory, the
G = Number of outer shell electrons in ground state of the
electron pairs (bond pairs as well as lone pairs) present around
central atom
the central atom repel each other and hence move as far apart as
a = Magnitude of charge on anion, c = Magnitude of charge on
possible so that there are no further repulsions between them.
cation
As a result, the molecule has minimum energy and maximum
stability. The direction of the electron pairs gives a definite
Calculate the value of X and decide the hybrid state of central
geometry to the molecule. If the central atom in a molecule is
atom as follows:
surrounded by only one kind of atoms and bond pairs, the
X 2 3 4 5 6 7
molecule is said to possess regular geometry. If on the other
Hybrid sp sp 2 sp3 sp 3d sp3d2 sp3d3
hand, the central atom in a molecule is surrounded by both lone
state
pairs and bond pairs, the geometry of the molecule is distorted
to some extent. Such molecules are said to possess irregular
Examples: Central atom is surrounded by monovalent atoms
geometry. This distortion is due to the reason that: Lone pair-
only BeF2 , BCl3 CCl4 , NCl3 , PCl3 , PCl5 , NH 3 , TeCl 4 , OF2 ,
Lone pair repulsion > Lone pair-Bond pair repulsion > Bond
H 2 O, SCl 2 , IF7 , CIF3 , SF4 , SF6 , XeF2 , XeF4 , etc. pair-Bond pair repulsion (i.e., lp-lp > lp-bp > bp-bp).
Depending upon the number of bond pairs and lone pairs, the
Resonance: The phenomenon of resonance was put forward by geometries of various types of molecules are summarised
Heisenberg to explain the properties of certain molecules. below in table:
Table 8.4: Geometries of Various Types of Molecules
Type Total no. of No. of bond No. of lone Pairs Type of Geometry of Examples
of molecule electron pairs pairs hybridisation molecule
involved
+
AB2 2 2 0 Sp Linear BeF2 ,  Ag ( NH 3 )2 
AB3 3 3 0 sp2 Trigonal planar BF3 ,AlCl3 , NO32− ,CO32−
AB2L 3 2 1 sp2 V-shaped SnCl 2 , PbCl 2
AB4 4 4 0 sp3 Tetraheral CH 4 ,SiF4 , NH +4 ,CCl4
Trigonal
AB3L 4 3 1 sp3 NH 3 , PX 3 (X = F, Cl, Br, l)
pyramidal
AB2L2 4 2 2 sp3 V-shaped H 2 O,OF2 , SCl2 , NH −2
Trigonal
AB5 5 5 0 sp3d PF5 ,PCl5 ,SbCl5 ,Fe(CO)5
Bipyramidal
AB4L 5 4 1 sp3d See saw SF5 ,TeBr4

Chemical Bonding 69
AB2L2 5 3 2 sp3d T-shaped ClF3 ,XeOF2
AB2L3 5 2 3 sp3d Linear XeF2 ,lCl 2− ,l 3−
−
AB6 6 6 0 sp3d2 Octahedral SF6 , SbF6 
2−
AB5L 6 5 1 sp3d2 Square pyramidal lF5,ClF5, SbF5  ,XeOF4
AB4L2 6 4 2 sp3d2 Square planar SF4 ,XeF4 ,lCl 4−
Pentagonal
AB7 7 7 0 sp3d2 lF7 , XeF6
bipyramidal
Molecular Orbital (MO) Theory: When two atomic orbitals Be2 K K σ (2s) 2 σ * (2s) 2
0 (does
–
not exist)
(AO’s) combine, they lose their identity and form new orbitals
K K σ (2s) 2 σ * (2s) 2
called molecular orbitals (MO’s) ; one of which is bonding B2 1 Paramagnetic
π (2Px )1 π (2Py )1
molecular orbital (BMO) while the other is antibonding
K K σ (2s) 2 σ * (2s) 2
molecular orbital (ABMO). C2 2 Diamagnetic
π (2Px )2 π (2Py )1
Energy Level Diagrams: There are two types of energy-level K K σ (2s) 2 σ * (2s) 2
N2 3 Diamagnetic
diagrams π (2Px )2 π (2Py )1 σ (2Pz )2
For molecules up to N 2 i.e., B 2C2 and N2 (Where the K K σ (2s) 2 σ * (2s) 2
N+2 2.5 Paramagnetic
difference in energies between 2s and 2p-orbitals is small π (2Px )2 π (2Py )1 σ (2Pz )2
and hence can interact) the order of filling of orbitals is K K σ (2s) 2 σ * (2s) 2
σ(1s), σ * (1s)σ(2s), σ * (2s), π(2p x ) O2 σ (2Pz )2 π (2Px )1 π (2Py )1 2 Paramagnetic
= π(2Py ), σ(2Pz ), π * (2Px ) = π * (2Py )σ * (2Pz ). π (2Px )2 π (2Py )1
For molecules after N 2 i.e. O 2 ,F2 and NC 2 etc. (where the K K σ (2s) 2 σ * (2s) 2
O + σ (2Pz )2 π (2Px )1 π (2Py )1 2.5 Paramagnetic

energy difference between 2s and 2p-orbitals is large and 2
hence cannot interact) the order of filling of orbitals is π (2Px )

* 1
σ(1s), σ * (1s)σ(2s), σ * (2s), π(2p z )π(2Px ) K K σ (2s) 2 σ * (2s) 2
O−2 σ (2Pz )2 π (2Px )1 π (2Py )1 1.5 Paramagnetic

= π(2Py ), π * (2Px ) = π * (2Py )σ * (2Pz ).
π (2Px ) π (2Py )
1 1
K K σ (2s) 2 σ * (2s) 2
Magnetic Properties: The MO diagram can predict whether
the molecules or molecular ions are paramagnetic if O 22− σ (2Pz )2 π (2Px )1 π (2Py )1 1.0 Diamagnetic
unpaired electron/s are present or diamagnetic if all the π *(2Px ) π *(2Py )

2 2
electrons are paired. The MO diagrams, bond order and K K σ (2s) 2 σ * (2s) 2
magnetic properties of some common molecules and their F2 σ (2Pz ) 2 π (2Px )1 π (2Py )1 1.0 Diamagnetic
ions are summarised below: π *(2Px ) π *(2Py )
2 2
Table 8.5: Molecular Orbital (MO) Configuration K K σ (2s) 2 σ * (2s) 2
Molecule/ Molecular Orbital (MO) Bond Magnetic σ (2Pz )2 π (2Px )1 π *(2Py )2 0

ions Configuration order character Ne2 (does not Diamagnetic
π *(2Px ) π (2Py )1 2
exit)
H2 σ (1s) 2 1 Diamagnetic
σ * (2Pz )2
H+2 σ (1s)1 1
2 Paramagnetic
K K σ (2s) 2 σ * (2s) 2
H−2 σ (1s) 2 σ * (1s)1 1
Paramagnetic CN 2.5 Paramagnetic
2 π (2Px )1 π (2Py )1 σ (2Pz )1
He +2 σ (1s) 2 σ * (1s) 1
Paramagnetic
2 K K σ (2s) 2 σ * (2s) 2
CN − 3.0 Diamagnetic
Li 2 K K σ (2s) 2
1 Diamagnetic π (2Px )1 π (2Py )1 σ (2Pz )2

K K σ (2s) σ (2s) H − F H − Cl H−Br H − I
2 * 2
NO π (2Px )1 π (2Py )1 σ (2Pz )2 2.5 Paramagnetic

2.1 4.0 2.1 3.0 2.1 2.8 2.1 2.5
EN : 1.9 0.9 0.7 0.4
π * (2Px )1 →
Difference in EN Ionic character decreases as the differencein electronegativity decreases
K K σ (2s) 2 σ * (2s) 2 EN = Electronegativity
NO + 3.0 Diamagnetic
π (2Px )1 π (2Py )1 σ (2Pz )2 Pauling has estimated the approximate percentage of ionic
K K σ (2s) 2 σ * (2s) 2 character in various A-B covalent bonds from the (XA − XB )
CO 3.0 Diamagnetic
π (2Px )1 π (2Py )1 σ (2Pz )2 values i.e., electronegativity difference of the two atoms
forming the covalent bond.
Here, KK represents non-bonding molecular orbitals of 1s-
XA − X B % ionic character Nature of A – B bond
atomic orbitals, i.e., KK = σ (1s) 2 σ * (1s) 2
0 0 Purely covalent
Hydrogen Bonds: When in a molecule, H atom is linked to a 0.1 to 0.8 0.5 – 15 Covalent
highly electronegative atom (F, O or N), this end becomes 0.9 to 1.6 19 – 47 Polar covalent
negative while the H-end becomes positive. The negative end 1.7 50 50% ionic and 50% covalent
of one molecule is then attracted by the positive end of the 1.8 to 3.2 55 – 93 Ionic
other. The bond thus formed is called hydrogen bond and is Hanny and Smith gave the following equation for calculating
represented by a dotted line the percentage of ionic character in A–B bond on the basis of the
δ+ δ− δ+ δ− δ+ δ−
.....H — F .....H— F ........H — F values of electronegativity of the atoms A and B. % ionic
Since hydrogen bond involves only a weak electrostatic character = [16(X A − X B ) + 3.5(X A − X B ) 2 ]
−1 This equation gives approximate calculation of % ionic
attraction, therefore, its energy is only 8 to 42 kJmol . The actual
character, e.g., 50% ionic character corresponds to (x A ~ x B )
strength of any H-bond depends upon the electronegative
equal to 2.1.
difference between the electronegative atom and the hydrogen
atom. Thus, the strength of H-bond decreases in the order: Multiple Choice Questions
δ+ δ− δ+ δ− δ+ δ−
F — H ..... F > O — H.....O > N — H...... N One and More than One Correct
Hydrogen bond can be classified into the following two 1. The species having bond order different from that in CO
categories is [JEE 2007 P-I]
− + −
a. N O b. N O c. C N d. N 2
Metallic Bond: The metallic crystal consists of the assemblage
of positive kernels occupying fixed positions and arranged in 2. Among the following, the least stable resonance structure
some definite pattern immersed in the sea of mobile valence is [JEE 2007 P-II]
electrons. The attractive force between mobile electrons and the a. O b. O
metallic kernels is referred to as metallic bonds, e.g., Gold, N N
silver, copper, sodium, etc.
O O
Polarity in Covalent Bond and Dipole Moment: A covalent c. O d. O
bond, in which electrons are shared unequally and the bonded N N
atoms acquire a partial positive and negative charge, is called a
O O
polar covalent bond or a covalent bond between two dissimilar
atoms is a polar covalent bond. Two kinds of notation are used 3. The bond energy (in kcal mol−1 ) of C – C single bond is
+δ −δ approximately: [JEE 2010 P-I]
to indicate a polar covalent bond e.g. H— F or H — F Polar a. 1 b. 10
covalent bonds may be thought of as being intermediate c. 100 d. 1000
between the non-polar bonds and pure ionic bonds. Bond
4. The species having pyramidal shape is: [JEE 2010 P-II]
polarity is described in terms of ionic character, which usually
a. SO4 b. BrF3
increases with increasing difference in the electronegativity
2−
between bonded atoms. c. SiO 3
d. OSF2
Chemical Bonding 71
5. Which one of the following molecules is expected 14. According to Molecular Orbital Theory,
diamagnetic behaviour? [JEE Main 2013] [JEE Adv. 2016 P-II]
a. C2 b. N 2 c. O2 d. S2 a. C 2−
is expected to be diamagnetic
2
6. Which of the following is the wrong statement? b. O 22 + is expected to have a longer bond length than O2
[JEE Main 2013] c. N +2 and N −2 have the same bond order
−
a. ONCF and ONO are not isoelectronic
d. He+2 has the same energy as two isolated He atoms
b. O3 molecules is bent
c. Ozone is violet–black in solid state 15. Which of the following species is not paramagnetic?
d. Ozone is diamagnetic gas [JEE Main 2017]
7. In which of the following pairs of molecules/ions, both the a. B2 b. NO c. CO d. O2
species are not likely to exist? [JEE Main 2013] 16. Which of the following compounds contain(s) no covalent
+ 2− − 2−
a. H , He
2 2 b. H , He
2 2 bound(s)?
2+ − 2+ KCl, PH 3 ,O 2 B2 H 6 , H 2SO 4 [JEE Main 2018]
c. H , He2
2 d. H , He
2 2
− + a. KCl, B2 H 6 b. KCl, B2 H 6 , PH 3
8. Stability of the species of Li2 , Li2 and Li2 increase in
the order of [JEE Main 2013] c. KCl,H 2SO 4 d. KCl
a. Li 2 < Li +2 < Li −2 b. Li −2 < Li +2 < Li 2 17. Total number of lone pair electrons in l3− ion is:
c. Li 2 < Li 2− < Li 2+ d. Li −2 < Li 2 < Li 2+ [JEE Main 2018]
9. Hydrogen bonding plays a central role in the following a. 12 b. 3 c. 6 d. 9
phenomena: [JEE Adv. 2014 P-I] 18. According to molecular orbital theory, which of the
a. Ice floats in water
following is true with respect to Li+2 and Li −2 ?
b. Higher Lewis basicity of primary amines than tertiary
amines in aqueous solutions [JEE Main 2019]
c. Formic acid is more acidic than acetic acid. a. Both are unstable
d. Dimerisation of acetic acid in benzene b. Li+2 is unstable and Li −2 is stable
10. Assuming 2s-2p mixing is NOT operative, the c. Li+2 is stable and Li −2 is unstable
paramagnetic species among the following is:
d. Both are stable
[JEE Adv. 2014 P-II]
a. Be 2 b. B2 c. C 2 d. N2 19. In which of the following processes the, bond order has
increased and paramagnetic character has changed to
11. The intermolecular interaction that is dependent on the
diamagnetic? [JEE Main 2019]
inverse cube of distance between the molecules is:
[JEE Main 2015] a. N 2 
→N +
2 → NO +
b. NO 
a. ion-ion interaction b. ion-dipole interaction → O −2 2
c. O 2  → O +2
d. O2 
c. London force d. hydrogen bond
20. The pair that contains two P–H bonds in each of the
12. Which one of the following statements about water is oxoacids is: [JEE Main 2019]
false? [JEE Main 2016] a. H3PO2 and H4P2O5 b. H4P2O5 and H4P2O6
a. Water is oxidised to oxygen during photosynthesis
c. H3PO3 and H3PO2 d. H4P2O5 and H3PO3
b. Water can act both as an acid as a base
c. There is extensive intramolecular hydrogen bonding in 21. The element that shows greater ability to form p π-pπ
the condensed phase multiple bonds is: [JEE Main 2019]
d. Ice formed by heavy water sinks in normal water a. Si b. Ge c. Sn d. C
13. The compound(s) with two lone pairs of electrons on the Matrix Match/Column Match
central atom is (are) [JEE Adv. 2016 P-I] 22. Match each of the diatomic molecules in Column I with
a. BrF5 b. ClF3 c. XeF4 d. SF4 its property/properties in Column II. [IIT JEE 2009 P-I]

Column I Column II Integer and Subjective
(A) B2 1. Paramagnetic 25. Based on VSEPR theory, the number of 90 degree
(B) N2 2. Undergoes oxidation F−Br−F angles in BrF5 is: [JEE 2010 P-I]
(C) O −2 3. Undergoes reduction
26. Among the triatomic molecules/ions, BeCl2 , N 3− , N 2 O,
(D) O2 4. Bond order ≥ 2
NO +2 ,O 3 ,SCl 2 , ICl−2 , I3− and XeF2 , the total number of
5. Mixing of ‘s’ and ‘p’
linear molecule(s)/ion(s) where the hybridisation of the
orbitals
central atom does not have contribution from the d-
a. A → 1, 4, 5; B → 3, 5; C → 2, 3; D → 1, 3, 4 orbital(s) is [Atomic number: S = 16, Cl = 17, I = 53 and
b. A → 2, 3, 5; B → 1, 5; C → 1, 2; D → 1, 2, 4 Xe = 54]
c. A → 2, 3, 5; B → 3, 5; C → 1, 2; D → 1, 2, 4 [JEE Adv. 2015 P-I]
d. A → 1, 3, 5; B → 4, 5; C → 1, 2; D → 1, 2, 4
27. The sum of the number of lone pairs of electrons on each
23. Match the orbital overlap figures shown in Column I with
[ TeBr6 ]
2−
central atom in the following species is: ,
the description given in Column II and select the correct
[ BrF2 ] ,SNF3 ,and [ XeF3 ] (Atomic numbers: N = 7, F = 9,
+ −
answer using the code given below the Columns. {en =
H2NCH2CH2NH2; atomic number: Ti = 22, Cr = 24, Co = S = 16, Br = 35, Te = 52, Xe = 54) [JEE Adv. 2017 P-I]
27; Pt = 78) [JEE Adv. 2014 P-II]
28. Among H 2 , He 2 + , Li 2 , Be 2 , C 2 , N 2 , O 2− , and F2, the number
Column I Column II
of diamagnetic species is: (Atomic numbers: H = 1, He =
(A) 1. p-d π antibonding 2, Li = 3, Be = 4, B = 5, C = 6, N = 7, O = 8, F = 9)
[JEE Adv. 2017 P-I]
29. XeF4 + O2F2 
→ product. The total number of lone pair
on the xenon containing product is: [JEE Adv. 2019 P-I]
(B) 2. d-d σ bonding
30. Which of the following compounds contain bound
between same types of atoms. [JEE Adv. 2019 P-I]
N2O4, B3N3H6, H2S2O3, N2O, H2S2O8, B2H6
(C) 3. p-d π bonding
31. Number of N − Mn − Cl bonds [N–Mn bonds is cis to n–Cl
bond] in cis [Mn(en)2Cl2] are …… [JEE Adv. 2019 P-II]
(D) 4. d-d σ antibonding
1. (a) N O − (16 electron system) Bond order =2.NO+, CN–
and N2 are isoelectronic with CO therefore all have same
bond order (=3).
a. A→ 1; B→ 3; C→ 2; D→4 Hence (a) is correct.
b. A→ 1; B→ 2; C→ 3; D→ 4 O
c. A→ 1; B→ 3; C→ 4; D→ 2 2. (a) (a) N
d. A→ 3; B→ 4; C→ 2; D→ 1
O
Statement/Assertion and Reason Same charges are present at nearest position (Less stable)
O O
24. Statement-I Band gap in germanium is small. Because
(b) N (c) N
Statement-II The energy spread of each germanium atomic
energy level is infinitesimally small. [JEE 2007 P-II] O O
a. Statement-I is True, Statement-II is True; Statement-II O
is a correct explanation for Statement-I (d) N
b. Statement-I is True, Statement-II is True; Statement-I is
O
not a correct explanation for Statement-I
c. Statement-I is True, Statement-II is False Hence (a) is correct.
d. Statement-I is False, Statement-II is True 3. (c)
Chemical Bonding 73
4. (d) F
13. (b, c) F
F
S Cl
Br
F F F F
O F F
F
5. (c) O2 is expected to diamagnetic in nature but actually it (Square Shape) (T-Shape)
is paramagnetic. → One lone pair → Two lone pair

6. (a) ONCF and ONO– are isoelectronic in nature. on central atom (Br) on central atom (Cl)
F
7. (c) H 22+ and He 2 does not exist. F
S
8. (b) B.O. of Li+2 = 0.5 , B.O. of Li−2 = 0.5 F F
Xe
F
Hence, stability order = Li −2 < Li +2 < Li 2 F F F
(See-saw Shape)
9. (a, b, d) (a) Ice has cage-like structure in which each
→ Square planar → One lone pair
water molecule is surrounded by four other water
molecules tetrahedral through hydrogen bonding, due to → Two lone pair on central atom (S)
this density of ice is less than water and it floats in water. on central atom (Xe)
⊕ Only, ClF3 and XeF4 contains two lone pair of electrons
(b) R – NH 2 + H – OH ↽ ⇀ NH 3 + OH −
(I) on central atom.
⊕
(R)3 N + H – OH ↽ ⇀ (R)3 − NH + OH − 14. (a, c) (a) C 22 − Total no. of electrons
(II)
The cation (I) more stabilised through hydrogen boding = 14 so it is diamagnetic

than cation (II). So, R–NH2 is better base than (R)3N in (b) O 22 + Bond order = 3; O 2 Bond order = 2
aqueous solution.
∴ Bond length in O 22 + is less than bond length in O 2 .
(c) HCOOH is stronger acid than CH3COOH due to
inductive effect and not due to hydrogen bonding. (c) Bond order of N +2 = 2.5 Bond order of He +2 = 1 / 2
(d) Acetic acid dimerise in benzene through intermolecular ∴ Some energy is released during the formation of He+2 from
hydrogen bonding. two isolated He atoms.
O H O
H3C C C CH 3 15. (c) NO ⇒ One unpaired electron is present in π*

O H O molecular orbital.
10. (c) Assuming that no 2s-2p mixing takes place CO ⇒ No unpaired electron is present.
(a) Be 2 → σ 1s , σ *1s , σ 2s , σ * 2s (diamagnetic)
2 2 2 2 O2 ⇒ Two unpaired electrons are present in π* molecular
π 2p0x orbitals.
(b) B2 → σ 1s 2 , σ *1s 2 , σ 2s 2 , σ * 2s 2 , σ 2p 2z , π 2p0y
(diamagnetic)
B2 ⇒ Two unpaired electrons are present in π bonding
(diamagnetic) molecular orbitals.
, σ 2p z2 , π 2p1x , π *2p0x , σ
1 0
(c) C2 → σ 1s , σ *1s , σ 2s , σ * 2s
2 2 2 2
* 2p 0z16.
(paramagnetic)
(d) KCl – Ionic bond between K+ and Cl–.
π 2p y π *2p y
2p1x *2p0x PH3 – Covalent bond between P and H.

2p z2 , 2p1y
, *2p0y
,σ * 2p 0z (paramagnetic)
O2 – Covalent bond between O atoms.
, σ 2p 2z , π 2p2x , π *2p0x , σ
2 0
(d) N 2 → σ 1s , σ *1s , σ 2s , σ * 2s
2 2 2 2
* 2p 0z (diamagnetic)
B2 H 6 – Covalent bond between B and H atoms.
π 2p y π *2p y
2p 2x *2p0x H 2SO 4 – Covalent bond between S and O and also

2p 2z , 2p 2y
, *2p0y
,σ * 2p 0z (diamagnetic)
between O and H.
11. (b) ∴ Compound having no covalent bonds is KCl only.
12. (c) There is extensive intermolecular hydrogen bonding in
17. (d) Structure of l3−
the condensed phase.

: ɺɺI −: I 3−  → linear ICl 2− 
→ sp 3 d  → sp 3 d 
→ linear
: Number of lone pairs in l3Θ is 9. XeF2 
→ sp 3 d 
→ linear
:
So among the following only four (4) has linear shape and
: no d-orbital is involved in hybridisation.
2–
: ɺɺI: 27. Br Br +
ɺɺ ɺɺ
:Br F
Te Br
18. (d) Both Li+2 and Li −2 has 0.5 bond order and hence both
Br Br F Br
are stable.
Total number of lone pairs on central atoms = 1 + 2 + 0 +
19. (c)
3 = 6.
Process Change in mag Bond
-netic nature Order Change 28. H 2 σ1s2 Diamagnetic
N 2 
→N +
2
Dia →Para 3→2.1 He +2 σ1s2 σ1s*1 Paramagnetic
NO  → NO +
Para→ Dia 2.5→3
Li 2 σ1s2 σ1s*2σ 2s
2
Diamagnetic
→ O −2 2
O 2  Para→ Dia 2 →1
→ O+2
O2  Para→ Para 2→2.5 Be 2 σ1s2 σ *2s 2 σ 22s σ *2s 2 Diamagnetic
20. (a) B2 σ σ σ σ π
2
1s
*2
1s
2
2s
* 2 1
2s 2p x =π 1
2p y Paramagnetic
21. (d) carbon atom have 2p orbitals able to form strongest pπ C 2σ1s2 σ1s* 2σ22s σ*2s 2 π22px = π22px Diamagnetic
- pπ bonds.
N 2σ1s2 σ1s* 2σ 22s σ*2s 2 π 22px = π 22px σ22px Diamagnetic
22. (d) A → 1, 3, 5;B → 4, 5;C → 1, 2;D → 1, 2, 4
23. (c) A→ 1; B→ 3; C→ 4; D→ 2 O2σ1s2 σ1s* 2σ22sσ*2s2σ22pz π2p
2
x
= π2p
2
y
π*1
2px = π2py Paramagnetic
*1
F2σ1s2 σ1s* 2σ22s σ*2s 2σ22pz π22px = π22py , π*2

2p x = π 2p y Diamagnetic
*2

→ d-d σ bonding
So, answer is 6.
F

→ p-d π bonding 29. F F
Xe
F F

→ p-d π antibonding F
XeF4 + O2F2 
→ XeF6 + O2

→ d-d π antibonding So, answer is 19.
30. N 2 O 4 , B3 N 3 H 6 , H 2S 2 O3 , N 2 O, H 2S2 O8 , B2 H 6
S
24. (c) O O
S N ≡≡ N 
→O
N—N
O OH
O O OH
Br
25. F F S S
S S
F F
OH O O OH
F O O
All four planar bonds (F−Br−F) will reduce from 90° to So, answer is 4.
84.8° after ℓp − bp repulsion. So, answer is zero. 31. Cl Cl
26. BeCl2 , N 3− , N 2 O, NO +2 , O3 ,SCl 2 , ICl −2 , I3− , XeF2 Cl
N Cl
BeC 2 
→ sp 
→ linear N 3− 
→ sp 
→ linear en Mn ≡≡ Mn
N
⊕ N
N 2 O 
→ sp 
→ linear NO2 
→ sp 
→ linear en N
O3 
→ sp 2 
→ linear SCl 2 
→ sp 3 
→ linear So, answer is 6
Chemical Equilibrium 75
9 Chemical Equilibrium
QUICK LOOK equilibrium. At that point rate of melting of ice is equal to
rate of freezing of water. The equilibrium is represented as
It is an experimental fact that most of the process including H 2 O(s) ↽ ⇀ H 2 O(l )
chemical reactions, when carried out in a closed vessel, do not
Liquid-gas equilibrium: Evaporation of water in a closed
go to completion. They proceed to some extent leaving
vessel is an example of liquid–gas equilibrium. Where rate
considerable amounts of reactants and products. When such
of evaporation is equal to rate of condensation. The
stage is reached in a reaction, it is said that the reaction has
attained the state of equilibrium. Equilibrium represents the equilibrium is represented as H 2 O(l ) ↽ ⇀ H 2 O(g)
state of a process in which the properties like temperature, Solid-solution equilibrium: If you add more and more salt
pressure, concentration, etc of the system do not show any in water taken in a container of a glass and stirred with a
change with passage of time. In all processes which attain glass rod, after dissolving of some amount. You will find
equilibrium, two opposing processes are involved. Equilibrium out no further salt is going to the solution and it settles
is attained when the rates of the two opposing processes down at the bottom. The solution is now said to be saturated
become equal. and in a state of equilibrium. At this stage, many molecule
of salt from the undissolved salt go into the solution
If the opposing processes involve only physical changes, the (dissolution) and same amount of dissolved salt are
equilibrium is called Physical Equilibrium. If the opposing deposited back (Precipitation). Thus, at equilibrium rate of
processes are chemical reactions, the equilibrium is called dissolution is equal to rate of precipitation.
Chemical Equilibrium. Some common physical equilibria are: Salt(Solid) ↽ ⇀ Salt ( in solution )
Solid → Liquid
Gas-solution equilibrium: Dissolution of a gas in a liquid
Liquid → Gas
under pressure in a closed vessel established a gas – liquid
Gas → Solution
equilibrium. The best example of this type of equilibrium is
Generally, a chemical equilibrium is represented as
cold drink bottles. The equilibrium that exists within the
aA + bB ↽ ⇀ xX + yY bottle is:
Where A, B are reactants and X, Y are products. CO 2( g ) ↽ ⇀ CO 2 ( in solution )
Note
Irreversible and Reversible Reactions: The chemical reactions
The double arrow between the left hand part and right hand part
are primarily classified as:
shows that changes is taking place in both the directions.
Irreversible reactions: These are chemical reactions in
On the basis of extent of reaction, before equilibrium is attained which the products are not capable of giving back the
chemical reactions may be classified into three categories. reactants. For example 2KClO3  → 2KCl + 3O 2 ;
Those reactions which proceed to almost completion. AgNO3 + HCl  → AgCl + HNO3
Those reactions which precede to almost only up to little Reversible reactions: These are chemical reactions in
extent. which the products are capable of reacting to give back the
Those reactions which proceed to such an extent, that the reactants. Such reactions can be made to occur in either
concentrations of reactants and products at equilibrium are direction by suitable variations in the conditions.
comparable. Example: 2SO 2 (g) + O 2 (g) ↽ ⇀ 2SO3 (g);
Equilibrium in Physical Process: The different types of
3Fe(s) + 4H 2 O(g) ↽ ⇀ Fe 3 O 4 (s) + 4H 2 (g)
physical equilibrium are briefly described below:
Solid-liquid equilibrium: The equilibrium that exists Reversible Chemical Reactions are Classified into Two Types
between ice and water is an example of solid – liquid Heterogeneous reactions: The reversible reactions in
equilibrium. In a close system, at 0°C ice and water attain which more than one phase is present.

e.g. 2Na 2O 2 (s) + 2H 2 O(l) 
→ 4NaOH(l) + O 2 (g) It is dynamic in nature i.e. both forward and backward
Homogenous reactions: The reversible reactions in which reactions are in progress at equilibrium state.
only one phase is present. It readjusts with the changing conditions and goes back to
the original state spontaneously when the factors
e.g. H 2 (g) + I 2 (g) ↽ ⇀ 2HI(g)
responsible for the change are removed.
At constant temperature certain observable properties like
Homogenous Reversible Reactions are Further Classified pressure, concentration, density and colour remain
into Three Types unchanged at equilibrium.
First type: When there is no change in number of The state of equilibrium continues indefinitely until it is
molecules, i.e. ∆n = 0 . disturbed by external factors like variation of concentration,
H 2 + I 2 ↽ ⇀ 2HI; 2NO ↽ ⇀ N 2 + O 2 ; temperature, pressure, etc.
Catalyst does not affect the final state of the equilibrium.
CH 3COOH + C2 H 5OH ↽ ⇀ CH 3COOC2 H 5 + H 2 O
However, it enables the system to attain equilibrium state
Second type: When there is increase in number of
quickly by providing an alternative path which involves
molecules, i.e., ∆n = + ve
lower energy of activation.
PCl5 ↽ ⇀ PCl3 + Cl2 ; 2NH 3 ↽ ⇀ N 2 + 3H 2
Third type: When there is a decrease in number of Law of Chemical Equilibrium: The law of mass action is
molecules, i.e., ∆n = − ve applicable to the individual single step reactions. We can apply
N 2 + 3H 2 ↽ ⇀ 2NH 3 ; 2SO 2 + O 2 ↽ ⇀ 2SO3 the law of mass action to both the forward and the backward
reactions in a reversible reaction in a state of equilibrium.
Chemical Equilibrium: When a reversible reaction is carried

out in a closed vessel then it is observed that a constancy in Example: Let us consider the reaction. A + B ↽ ⇀ C + D
properties like intensity of colour, pressure concentration, etc. It Rate of forward reaction (R f ) ∝ [A][B] = K f [A][B], here K f is
is achieved under a given set of condition. Such a state is the rate constant for the forward reaction. Rate of backward
referred as an equilibrium state. reaction (R b ) ∝ [C][D] = K b [C][D], here K b is the rate
constant for the backward reaction.
When the equilibrium is reacted, the concentration of reactant
At the equilibrium R f = R b .
as well as product remains constant. At this stage reaction
K f [C][D]
seems to be stopped but in actual the reaction is going in Therefore K f [A][B] = K b [C][D] or = = Kc
forward as well as reverse direction with same rate and hence K b [A][B]
this equilibrium is called as dynamic equilibrium. Here K c represents the equilibrium constant for the reversible
reaction.
[C]c [D]d
Forward Reaction For the reaction: aA + bB ↽ ⇀ cC + dD, ⇒ K c =
[A]a ][B]b
Equilibrium point
Rate
The expression is according to the law of chemical equilibrium

Reverse Reaction which states that: “For a reversible reaction in a state of
equilibrium, the ratio of the product of the molar concentrations
of the products to that of the molar concentrations of the
Time
Figure: 9.1 Reactants each concentration term raised to a power equal to its
A chemical equilibrium is a state at which the composition of stoichiometric coefficient in the balanced chemical equation, is
the chemical system becomes constant under given set of a constant known as the equilibrium constant provided the
conditions. It must be noted that at equilibrium, the chemical temperature is constant”.
reaction does not stop but both the forward as well as backward
reactions takes place at the same rate. The following are the Here, [C],[D],[A] and [B] represents the molar concentrations
Characteristics of the equilibrium state. of C, D, A and B respectively at the equilibrium. For gaseous
It can be attained from either side. reactions, the equilibrium constant can be calculated from the
respective partial pressure of the gaseous species. The The value of Kc and Kp depends on concentration,
equilibrium constant determined from the partial pressures is temperature, pressure and volume.
represented by Kp. Equilibrium constant varies with temperature. It's variation
Example: N2 (g) + 3H2 (g) ↽ ⇀ 2NH3 (g) with temperature can be described by the following relation:
K2 ∆H  T2 − T1 
(PNH3 ) 2 [NH 3 ]2 log =  ;
Kp = ;, K c = K1 2.303R  T1T2 
(PH 2 )3 × (PN 2 ) [N 2 ][H 2 ]3
Where, ∆H= Enthalpy change,
R= Universal gas constant.
∆n
Relation between Kp and Kc: Kp = Kc (RT) K1 and K12 = Equilibrium constants at temperatures T1 and T2
Where, Kp = Equilibrium constant when partial pressures are respectively.
considered. When∆H = 0; K2 = K1 (i.e., heat of reaction at constant volume
Kc = equilibrium constant when molar concentrations are is zero)
considered. When ∆H = + ve; K2 > K1 (i.e., endothermic reaction)
R=Gas constant, T= Temperature in Kelvin, When ∆H = − ve; K2 < K1 (i.e., exothermic reaction)
∆n= Change in the number of gaseous moles.
If ∆n= 0 then , K p = K c Le Chatelier's Principle: The principle states that, “If a system
in equilibrium is subjected to a change of temperature, pressure or
2HI ↽ ⇀ H 2 (g) + I 2 (g); concentration, the equilibrium is disturbed and shifts in the
direction in which the effect of the change is imposed”.
N 2 (g) + O 2 (g) ↽ ⇀ 2NO(g)
Thus according to this principle:
If ∆ n = + ve then K p > K c
Increase in the concentration of a substance at equilibrium
PCl5 (g) ↽ ⇀ PCl3 (g) + Cl2 (g) shifts the equilibrium in that direction in which the added
If ∆ n = − ve then, K p < K c substance is consumed. Thus addition of a reactant at
equilibrium favours forward reaction. i.e. more of products will
N 2 + 3H 2 ↽ ⇀ 2NH 3 be formed.
The units of K c and K p are mol L−1 and KPa respectively. The Table 9.1: Change Mode and Shift of Equilibrium
Change mode at equilibrium Shift of equilibrium
unit of R is 0.082 L atm k −1 mol −1 . Any reactant added Forward direction, product formed
Any product removed Forward direction, product formed.
Factors Affecting the Kc and Kp Any reactant removed Backward direction, product
The value of K c is independent of initial concentration of consumed.
Any product added Backward direction, product
reactants. It depends only on the concentration at consumed, reactant formed
equilibrium.
1 Order of ease of removal of substance is:
Equation constant K Forward = .
K Backward Gases > Liquid > Solid
(Most easily removed) (Most difficult to remove)
The value of K c depends on the stoichiometry of reactants The increase of temperature will make the reaction go in
and products at the point of equilibrium. that direction in which heat is absorbed i.e., towards
Example: 2NO + O 2 ↽ ⇀ 2NO 2 … K1 endothermic reaction. Thus, higher yields of products are
obtained at higher temperatures in endothermic reactions.
1
and NO + O 2 ↽ ⇀ NO 2 … K 2 are related as, K1 = (K 2 ) 2 Exothermic reversible reactions are favoured at low
2
temperature, because the effect of lowering of temperature
The numerical value of K c depends on the equation for the
is annulled by evolution of heat, i.e., when the reaction goes
reaction. towards the products. In exothermic reactions, higher yields
If the reaction is multiplied by 2, the equilibrium constant is of products are obtained at low temperature.
squared. The increase of pressure at equilibrium shifts the system in
The value of Kc gives us a relative idea about the extent to that direction in which there is a decrease in volume, i.e.
which a reaction proceeds. number of moles.

One and More than One Correct a. T1 b. T2
% Yield
1. Ag + + NH 3 ↽ ⇀ [Ag (NH3 ) + ] ; k1 = 3.5 × 10 −3 % Yield
[Ag(NH 3 )]+ + NH 3 ↽ ⇀ [Ag (NH 3 ) 2 ]+ ; k 2 = 1.7 × 10−3 Time Time

+
T1 T2
Then the formation constant of [Ag (NH 3 ) 2 ] is
c. T2 d. T2
[JEE 2006] % Yield % Yield
a. 6.08 × 10−6 b. 6.08 × 106
c. 6.08 ×10−9 d. None Time Time
3. The equilibrium constant at 298 K for a reaction

2. N 2 + 3H 2 ↽ ⇀ 2NH 3 Which is correct statement if N 2
A + B ↽ ⇀ C + D is 100. If the initial concentration of
is added at equilibrium condition? [JEE 2006]
all the four species were 1 M each, then equilibrium
a. The equilibrium will shift to forward direction because
concentration of D (in mol L−1 ) will be:[JEE Main 2016]
according to IInd law of thermodynamics the entropy must
increases in the direction of spontaneous reaction a. 0.182 b. 0.818 c. 1.818 d. 1.182
b. The condition for equilibrium is G N2 + 3G H2 = 2G NH3 6. For the following reactions, equilibrium constants are
given [JEE Main 2019]
where G is Gibbs free energy per mole of the gaseous
52
species measured at that partial pressure. The condition of S(s) + O 2 (g) ↽ ⇀ SO 2 (g) ;K1 =10
equilibrium is unaffected by the use of catalyst, which 2S(s) + 3O 2 (g) ↽ ⇀ 2SO3 (g); K 2 = 10129
increases the rate of both the forward and backward The equilibrium constant for the reaction,
reactions to the same extent
2SO2 (g) + O2 (g) ↽ ⇀ 2SO3 (g) is:
c. The catalyst will increase the rate of forward reaction
a. 10181 b. 10154 c. 1025 d. 1077
by α and that of backward reaction by β .
d. Catalyst will not alter the rate of either of the reaction 7. 5.1g NH4SH is introduced in 3.0 L evacuated flask at
327°C. 30% of the solid NH4SH decomposed to NH3 and
4. The thermal dissociation equilibrium of CaCO3(s) is H2S as gases. The Kp of the reaction at 327°C is (R =
studied under different conditions. CaCO3(s) → CaO(s) + 0.082 L atm mol–1K–1, Molar mass of S = 32 g mol–1,
CO2(g) For this equilibrium, the correct statement(s) is molar mass of N = 14g mol–1) [JEE Main 2019]
(are): [JEE Adv. 2013 P-II] a. 1 × 10–4 atm2 b. 4.9 × 10–3 atm2
a. ∆H is dependent on T c. 0.242 atm2 d. 0.242 × 10–4 atm2
b. K is independent of the initial amount of CaCO3 8. Consider the reaction,
c. K is dependent on the pressure of CO2 at a given N 2 (g) + 3H 2 (g) → 2NH 3 (g)
d. ∆H is independent of the catalyst, if any
The equilibrium constant of the above reaction is KP. If
5. The % yield of ammonia as a function of time in the pure ammonia is left to dissociate, the partial pressure of
reaction N 2 (g) + 3H 2 (g) ↽ ⇀ 2NH 3 (g), ∆H < 0 at (P, T1) ammonia at equilibrium is given by (Assume that NH3
total PN H << Ptotal at equilibrium)
3
[JEE Main 2019]
is given below: If this reaction is conducted at (P, T2 ),
3 1
3 1
with T2 > T1 , the % yield of ammonia as a function of 2
3 K P 2 2 32 K P2 P2
P
a. b.
time is represented by: [JEE Adv. 2015 P-I] 4 16
1
1
KP2 P2 K 2 P2
T1 c. d. P
% Yield 16 4
9. For the equilibrium, 2H 2O → H 3O+ + OH – , the value of

Time ∆Gº at 298 K is approximately: [JEE Main 2019]
a. –80 kJ mol–1 b. –100 kJ mol–1 ANSWERS and SOLUTIONS
c. 100 kJ mol–1 d. 80 kJ mol–1 1. (a)
10. In a chemical reaction, A + 2B → 2C + D, the initial 2. (b)
concentration of B was 1.5 times of the concentration of 3. (a, b, d) For the equilibrium CaCO3 (s) ↽ ⇀ + CO 2 (g).
A, but the equilibrium concentrations of A and B were The equilibrium constant (K) is independent of initial
found to be equal. The equilibrium constant (K) for the amount of CaCO3 where as at a given temperature is
aforesaid chemical reaction is: [JEE Main 2019] independent of pressure of CO2. ∆H is independent of
a. 16 b. 4 c. 1 d. 1/4 catalyst and it depends on temperature. Hence (A), (B)
and (D) are correct.
11. Two solids dissociate as follows [JEE Main 2019]
2
4. (b) N 2 (g) + 2H 2 (g)
A(s) → B(g) + C(g) ; K p1 = x atm
N 2 (g) + 2H 2 (g) ↽ ⇀ 2NH 3 (g); ∆H < 0
D(s) → C(g) + E(g) ; K p2 = y atm 2
Increasing the temperature lowers equilibrium yield of
The total pressure when both the solids dissociate ammonia.
simultaneously is:- However, at higher temperature the initial rate of forward
a. x 2 + y 2 atm b. x 2 – y 2 atm reaction would be greater than at lower temperature that is
why the percentage yield of NH 3 too would be more
c. 2( x + y )atm d. x + y atm
initially.
Integer and Subjective 5. (c) A + B ↽⇀ C + D

12. MX2 dissociates into M2+ and X– ions in an aqueous solution, t=0 1 1 1 1
with a degree of dissociation (α) of 0.5. The ratio of the teq 1− x 1− x 1+ x 1+ x
observed depression of freezing point of the aqueous solution (1 + x) 2 1+ x
⇒ = 100 ⇒ = 10
to the value of the depression of freezing point in the absence (1 − x) 2 1− x
of ionic dissociation is: [JEE Adv. 2014 P-I] ⇒ 1 + x = 10 − 10x ⇒ 11x = 9
9
13. For the given compound X, the total number of optically ⇒ x=
11
active stereoisomer is _________. [JEE Adv. 2018 P-II]
9
HO HO ⇒ [D] = 1 +
11
⇒ [D] = 1.818
6. (c) S(s) + O 2 (g) ↽ ⇀ SO 2 (g); K1 = 1052 . . .(i)
2S(s) + 3O 2 (g) ↽ ⇀ 2SO3 (g); K 2 = 10129 . . .(ii)

HO
X HO
This type of bond indicates that the configuration 2SO2 (g) + O2 (g) ↽ ⇀ 2SO3 (g) K3 = x
at the specific carbon and the geometry of the Multiplying equation (i) by 2;
double bond is fixed
This type of bond indicates that the configuration at 2SO(s) + 2O2 (g) → 2SO2 (g) 104 K 1′ = 10104 . . .(iii)
the specific carbon and the geometry of the double ⇒ Subtracting (iii) from (ii); we get
bond is NOT fixed
2SO2 (g)+O2 (g) → 2SO3 (g);
14. For the following reaction, equilibrium constant Kc at 298
K eq = 10(129 – 104) = 1025
K is 1.6 × 1017
(c) NH 4SH(s) ↽ NH 3 (g) + H 2S(g)

Fe 2+
+ S 2 − → FeS(s) ⇀
(aq ) (aq ) 7.
When equal volume of 0.06 M Fe+2 and 0.2 M S-2 solution 5.1
n= = .1mole 0 0
are mixed, then equilibrium concentration of Fe+2 is found 51
be Y × 10-17 M . Y is: [JEE Adv. 2019 P-II] .1(−1 − α) .1α .1α

α = 30% = .3 Now total pressure
So number of moles at equilibrium PT = PC + PB + PE
0.1(1 − .3) 0.1 × 3 0.1 × .3
= (P1 + P2 ) + P1 + P2 = 2(P1 + P2 )
= 0.07 = 0.03 = 0.03
PT = 2( x + y )
Now use PV = nRT at equilibrium
Ptotal × 3lit = (0.3 + .03) × 0.82 × 600
12. MX 2 ↽ ⇀ M 2 + + 2X −
1−α α 2α
Ptotal = 0.984 atm
i = 1 + 2α {α = 0.5} i=2
At equilibrium
So, k p = PH2S ⋅ PH2S = (0.492)(0.492) 13.
HO OH
k p = 0.242 atm 2
8. (b)
+ – –14
9. (d) 2H2O = H3O + OH K = 10
HO
∆G° = –RT ℓn K OH
–8.314 Only three streocentre are present.
= × 298 × ℓn10 –14 = 80 KJ/Mole
14 ∴ Total isomer = 23 = 8
A + 2B → 2C + D But one is optically inactive. So, answer is 7.
10. (b) t = 0 a 0 1.5a 0 0 0
t = t eq a 0 − x 1.5a 0 − 2x 2x x
14.
At equilibrium [A] = [B] 2+
Fe + S2 − → FeS(s)
a0 – x = 1.5a0 – 2x ⇒ x = 0.5a0 (aq ) (aq)
0.06M 0.2M
t = teq 0.5a0 0.5a0 a0 0.5a0 After mixing 0.03M 0.1M
? 0.07M
[C]2 [D] (a 0 ) 2 (0.5a 0 )
KC = 2
= =4 K c =1.6 ×1017
[A][B] (0.5a 0 )(0.5a 0 ) 2
1
1.6 ×1017 =
11. (c) A(s) → B(g) + C(g) K P1 = x = PB ⋅ PC [Fe 2+ ] × 0.07
P1 P1 x = P1 (P1 + P2 ) . . .(i) 10−17 10−15 100

or [Fe 2 + ] = = ×10 −17
1.6 × 0.07 11 11.2
D(s) → C(g) + E(g) K P2 = y = PC ⋅ PE
= 8.928 ×10−17 = Y ×10−17
P2 P2 y = (P1 + P2 )(P2 ) . . .(ii)
Answer after rounding of is = 8.93
Adding (i) and (ii) x + y = (P1 + P2 ) 2
Answer after truncation of is = 8.92
Ionic Equilibrium 81
10 Ionic Equilibrium
QUICK LOOK Ostwald Dilution Law (Ionisation of Weak Electrolytes): It
is the law of mass action as applied to weak electrolytes like
Most of the chemical reactions occur in solutions. When a CH 3COOH, NH 4 OH, HCN, etc. Consider a binary electrolyte
given substance is dissolved in the solvents like water. In an AB which dissociates into its ions, there exist a dynamic
ionic solution the substance splits up into ions whereas in equilibrium between ions and unionised molecule of the
molecular solution, the substance remains as such. Both the electrolyte as:
solutions can be represented as:
AB + aq ↽ ⇀ A + (aq) + B− (aq)
XY(s) + aq ↽ ⇀ XY(aq) ↽ ⇀ X + (aq) + Y− (aq) Initial conc.
when t = 0 C 0 0 . . .(i)
(for ionic solution) Conc. at
XY(s) + aq ↽ ⇀ XY(aq) (For molecular solution) equilibrium C - Cα Cα Cα
Apply the law of mass action to equilibrium (i)
Electrolyte (Conducting): Those substances whose aqueous [A + (aq)] [B− (aq)]
K=
solution or molten form can conduct electricity. They are [AB]
further classified into:
Cα × Cα Cα 2
Strong electrolyte: Those substances whose aqueous = =
[C − Cα ] 1 − α
solution or molten form conduct electricity to a greater
extent. They almost completely ionised in water. For weak electrolyte, α <<< 1, ⇒ 1 − α ≈ 1 i.e. α < 5%
e.g. NaCl, H 2SO 4 , HCl, NaOH, NH 4 Cl K = Cα 2
Since strong electrolyte completely ionised in aqueous K
Or α = . .(ii)
solution so their ionisation is represented as, C
→ H + (aq) + Cl− (aq)
HCl + aq  .
Weak electrolyte: Those substances whose aqueous If one mole of electrolyte is dissolved in V litre of solution
solution or molten form conducts electricity to a lesser 1
i.e. C =
extent. They do not completely ionised in water i.e. partly V
ionised. They behave as poor conductor of electricity. α = KV . . .(iii)
e.g. when CH 3COOH is dissolved in water, it is ionised partly Thus “degree of dissociation of a weak electrolyte is
and an equilibrium is setup between the ions and the proportional to the square root of dilution”. This is called
unionised electrolyte. Ostwald law.
CH 3COOH + aq ↽ ⇀ CH 3 COO − (aq) + H + (aq)
Note
If α > 5% then we cannot neglect α from denominator
Non-electrolyte/Non-conducting: Those substances whose
aqueous solution or molten form does not conduct electricity to Cα 2
K=
any extent. They are bad conductor of electricity, e.g. aqueous (1 − α )
solution of sugar, urea, etc. do not conduct electricity. α can be calculate by quadratic equation (ax 2 + bx + c = 0)
Degree of ionisation is represented by 'α ' . It may be defined as
−b ± b 2 − 4ac
“fraction of total number of molecules which dissociates into Cα 2 − (1 − α )K = α =
2a
ion”.
Here, b = −(1 − α ), a = C and c = 0
Number of molecules dissociated as ions
α=
Total number of molecules dissolved Relative Strength of Weak Acids and Bases: The relative
Number of moles dissociated strength of weak acids and bases are generally determined by
=
Total number of moles dissolved their dissociation constant K a and K b respectively.

For weak acid CH3COOH: pH may be defined as logarithm of reciprocal of [H3O+] or
CH 3COOH + aq ↽ a ⇀ CH 3COO − (aq) + H + (aq)
K negative logarithm of hydronium ion concentration.
Initially C 0 0 pH = − log[H3O+ ]
At equilibrium C - Cα Cα Cα pH = − log[H+ ]
The pH range is taken from 0 to 14. The acidity or alkalinity of
Cα × Cα Cα 2
Ka = = ( 1 − α ≈ 1 assuming α is very a solution can be represented on pH scale as:
C − Cα 1− α
small). pH value 0,1,2,3,4, 5,6, 7, 8,9,10, 11,12,13,14
∴ K a = Cα 2
strongly weakly neutral weakly strongly
Where, K a is equilibrium constant of weak acid which depends acidic acidic alkaline alkaline
on temperature. Greater the value of K a , more is the strength of In similar manner, we can define pOH scale as
−
an acid. Similarly for base NH 4 OH pOH = − log[OH ]
Both pH and pOH scale are related as
K b = Cα 2
[H + ][OH − ] = 10−14 at25°C − log[H + ] − log[OH − ] = 14
Where, Kb is the equilibrium constant for weak base.
For two acids having equimolar concentrations: pH + pOH = 14
Strength of acid I K a1 Limitations of pH Scale

= , pH value of solutions do not give immediate idea of their
Strength of acid II K a2
relative strength.
Strength of base I K b1 pH value can be negative too.
Similarly for two bases: =
Strength of base II K b2 A 10−8 M solution of acid cannot have pH = 8. Since the
value of pH of acid may close to 7 but < 7.
Self Ionisation of Water (Ionic Product of Water): Pure
water is a weak electrolyte and itself ionises as Buffer Solutions: A buffer solution is a solution which resists
a change in its pH when such a change is caused by the addition
H 2O + H 2O ↽ ⇀ H3O+ + OH − or simply
of a small amount of acid or base. This does not mean that the
H 2O ↽ ⇀ H+ + OH− pH of the buffer solution does not change (we make this
Applying law of mass action assumption while doing numerical problems). It only means
that the change in pH would be less than the pH that would
[H + ] [OH − ] [H 3O + ] [OH − ]
K= Or K= have changed for a solution that is not a buffer.
[H 2 O] [H 2O]2
Where, K is called dissociation constant. Ostwald Theory of Indicators: An indicator generally a weak
Since the ionisation of water is very small it means very few organic acid or weak organic bases is a substance which is used
H 2 O molecule are dissociated into H and OH − ions i.e. to determine the end point in a titration. They change their
colours within a certain pH range generally the colour change is
1000
[H 2 O] = constant = = 55.55 mole/litre due to shifting of indicator equilibrium, e.g., for
18
phenolphthalein (HPh).
10 −14
At 25 ° C, the value of K is HPh ↽ ⇀ H + + Ph −
55.55
Colourless pink
+ 10−14
−
K × [H 2O] = [H ] [OH ] = × 55.55 or Shifting of this equilibrium from left to right produces pink
55.55 colour.
K w = [H + ] [OH − ] = 10−14
 H +   Ph −   Ph − 
K w is called ionic product of water. KIn =    and pH = pK In + 
[ HPh ] [ HPh ]
At equilibrium point [Ph − ] = [HPh]
pH Scale: Sorensen gave the best way of expressing the acidic
or basic nature of solution. This is a logarithmic scale in which ∴ pH = pK In . also K In = [H+ ]
hydrogen ion concentration ranges from 10–14 to 1 mole/litre. Where K In is the ionisation constant of the indicator.
−12
Solubility Product: Consider a binary electrolyte A x By ith 4. The K sp of Ag 2CrO 4 is 1.1× 10 at 298K. The solubility
solubility S mole/litre. (in mol/L) of Ag 2CrO 4 in a 0.1M AgNO3 solution is:
A x By ↽ ⇀ xA + y + yB− x [x + y ]x [B − x ]y
K eq = [JEE Adv. 2013 P-II]
xS yS [A x B y ]
a. 1.1×10−11 b. 1.1×10−10
+y x −x y +y x −x y y (x + y)
K eq [A x By ] = [x ] [B ] K sp = [x ] [B ] = x y S x
c. 1.1×10−12 d. 1.1×10−9
K sp is called solubility product. Solubility product may be
5. pKa of a weak acid [HA] and pKb of a weak base [BOH]
defines as “the product of the concentration of ions in a
are 3.2 and 3.4, respectively. The pH of their salt (AB)
saturated solution of an electrolyte at a given temperature”.
solution is: [JEE Main 2017]
From solubility product, we may conclude that;
Case (i): If, [ionic product] < K sp . Then, the solution is a. 1.0 b. 7.2
c. 6.9 d. 7.0
unsaturated i.e. more solute go into the solution.
Case (ii): If, [ionic product] = K sp . The solution is just 6. An alkali is titrated against an acid with methyl orange as
saturated i.e. no more solute can be dissolved. indicator, which of the following is a correct
Case (iii): If, [ionic product] > K sp . The solution is combination? [JEE Main 2018]
supersaturated i.e. precipitation takes place. Knowing the Base Acid Endpoint
values of K sp and K a , solubility of the salt can be calculated. a. Strong Strong pink to colourless
b. Weak Strong Colourless to pink
Multiple Choice Questions c. Strong Strong Pinkish red to yellow
One and More than One Correct d. Weak Strong Yellow to pinkish red
2 7. Which of the following are Lewis acids?
1. 2.5 mL of M M weak monoacid base (K b = 1× 10 −12 at
5 [JEE Main 2018]
2
25°C) is titrated with M HCl in water at 25°C. The a. BCl3 and AlCl3 b. PH3 and BCl3
15
c. AlCl3 and SiCl4 d. PH3 and SiCl4
concentration of H+ at equivalence point is: (K W = 1× 10−14
at 25ºC) [JEE 2008 P-I] 8. Which of the following salts is the most basic in aqueous
a. 3.7 × 10 −13
M b. 3.2 × 10 M −7 solution? [JEE Main 2018]
c. 3.2 × 10 −2 M d. 2.7 × 10 −2 M a. Pb(CH3COO)2 b. Al(CN)3
c. CH3COOK d. FeCl3
2. Solubility product constant (Ksp) of salts of types MX, MX2
and M3X at temperature ‘T’ are 4.0 × 10–8, 3.2 × 10–14 and 9. The maximum prescribed concentration of copper in
−3
2.7 × 10–15, respectively. Solubilities (mole dm ) of the drinking water is: [JEE Main 2019]
salts at temperature ‘T’ are in the order. a. 5 ppm b. 0.5 ppm
[JEE 2008 P-II] c. 0.05 ppm d. 3 ppm
a. MX > MX2 > M3X b. M3X > MX2 > MX
10. The correct decreasing order for acid strength is:
c. MX2 > M3X > MX d. MX> M3X >MX2
[JEE Main 2019]
3. Aqueous solutions of HNO3 , KOH, CH 3COOH, and
a. NO2CH2COOH > NCCH2COOH > FCH2COOH >
CH 3COONa of identical concentrations are provided. The CICH2COOH
pair (s) of solutions which form a buffer upon mixing is b. FCH2COOH > NCCH2COOH > NO2CH2COOH >
(are): [JEE 2010 P-I]
CICH2COOH
a. HNO3 and CH 3COOH
c. NO2CH2COOH > FCH2COOH > CNCH2COOH >
b. KOH and CH 3COONa CICH2COOH
c. HNO3 and CH 3COONa d. CNCH2COOH > O2NCH2COOH > FCH2COOH >
d. CH3COOH and CH3COONa CICH2COOH

11. 20 mL of 0.1 MH2SO4 solution is added to 30 mL of 0.2M 18. The correct structure of histidine in a strongly acidic
NH4ON solution. The pH of the resultant mixture is: [pkb solution (pH = 2) is: [JEE Main 2019]
of NH4OH = 4.7] [JEE Main 2019] ⊕
H3 N— CH — COOH ⊕
a. 9.4 b. 5.0
H3 N— CH — COOH
c. 9.0 d. 5.2 NH ⊕
a. b. NH2
12. The increasing basicity order of the following compounds
is: [JEE Main 2019] N⊕
H N
CH 2 CH3 ⊕ Θ
(A) CH3 CH 2 NH 2 (B) | ⊕ Θ H 3 N— CH — CO O
CH3 CH 2 NH H 3 N— CH — CO O
NH
CH3 CH3 c. ⊕ d.
(C) | (D) | NH2
H3C—N—CH3 Ph—N—H N⊕
N H
a. (D)<(C)<(A)<(B) b. (A)<(B)<(D)<(C)
c. (A)<(B)<(C)< (D) d. (D)<(C)<(B)<(A)
13. The pH of rain water is approximately: 19. Dilution processes of different aqueous solutions, with water,
[JEE Main 2019] are given in Column I. The effects of dilution of the solutions
a. 6.5 b. 7.5 c. 5.6 d. 7.0 on [H+] are given in Column II.
(Note: Degree of dissociation (α ) of weak acid and weak
14. Consider the given plots for a reaction obeying Arrhenius
base is << 1; degree of hydrolysis of salt <<1; [H+]
equation (0°C < T < 300°C): (k and Ea are rate constant
represents the concentration of H+ ions)
and activation energy, respectively) [JEE Main 2019]
Column I Column II
k k
(A) (10 mL of 0.1 M 1. The value of [H+]
NaOH + 20 mL of 0.1 does not change on
Ea-I T(ºC)-II M acetic acid) diluted dilution
Choose the correct option: to 60 mL
a. Both I and II are wrong (B) (20 mL of 0.1 M 2. The value of [H+]
b. I is wrong but II is right NaOH + 20 mL of 0.1 changes to half of its
c. Both I and II are correct M acetic acid) diluted initial value on
d. I is right but II is wrong to 80 mL dilution
(C) (20 mL of 0.1 M HCl 3. The value of [H+]
15. If a reaction follows the Arrhenius equation, the plot lnk vs + 20 mL of 0.1 M changes to two times
1 ammonia solution) of its initial value on
gives straight line with a gradient (–y) unit. The energy
(RT) diluted to 80 mL dilution
required to activate the reactant is: [JEE Main 2019] (D) 10 mL saturated 4. The value of [H+]
a. y unit b. –y unit solution of Ni(OH)2 in 1
c. yR unit d. y/R unit equilibrium with excess changes to times
2
solid Ni(OH)2 is diluted of its initial value on
16. NaH is an example of: [JEE Main 2019] to 20 mL (solid dilution.
a. Electron-rich hydride b. Molecular hydride Ni(OH)2 is still present
c. Saline hydride d. Metallic hydride after dilution).
5. The value of [H+]
17. K2HgI4 is 40% ionised in aqueous solution. The value of
changes to 2 times
its van't Hoff factor (i) is: [JEE Main 2019]
of its initial value on
a. 1.8 b. 2.2
dilution.
c. 2.0 d. 1.6
a. A →1; B→5; C →4; D →1 25. The solubility of a salt of weak acid (AB) at pH 3 is
d. A →2; B→5; C →4; D →3 Y × 10 −3 mol L−1 . The value of Y is ___. (Given that the
c. A →3; B→5; C →4; D →2 value of solubility product of AB(K sp ) = 2 ×10−10 and the
d. A →1; B→5; C →3; D →2
value of ionization constant of HB (K a ) = (1× 10 −8 )
Paragraph [JEE Adv. 2018 P-I]
Paragraph for Questions Nos. 20 to 21
When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M
1. (d) BOH + HCl 
→ BCl+ H 2 O
NaOH in an insulated beaker at constant pressure, a C
temperature increase of 5.7°C was measured for the beaker and +

B + H 2 O ↽ ⇀ BOH + H
+
C(1− h ) Ch Ch
its contents (Expt. 1). Because the enthalpy of neutralization of
Volume of HCl used
a strong acid with a strong base is a constant (–57.0 kJ mol −1 ),
2
this experiment could be used to measure the calorimeter 2.5 ×
= 5 = 7.5ml
constant. In a second experiment (Expt. 2), 100 mL of 2.0 M 2 /15
acetic acid (K a = 2.0 × 10 −5 ) was mixed with 100 mL of 1.0 M Concentration of Salt,
NaOH (under identical conditions to Expt. 1) where a 2
2.5 ×
temperature rise of 5.6°C was measured. (Consider heat C= 5 = 0.1 M
capacity of all solutions as 4.2 Jg −1 K −1 and density of all 10
2
Ch K
solutions as 1.0 g mL−1 ) [JEE Adv. 2015 P-II] ∴ = w Solving h = 0.27
1 − h K5
20. Enthalpy of dissociation (in kJ mol −1 ) of acetic acid
[H + ] = Ch = 0.1× 0.27 = 2.7 × 10−2 M
obtained from the Expt. 2 is:
a. 1.0 b. 10.0 2. (d) Solubility of
c. 24.5 d. 51.4 (MX) = 4 ×10−8 = 2 ×10−4
21. The pH of the solution after Expt. 2 is :
Solubility of (MX 2 ) = 8 × 10 −5
a. 2.8 b. 4.7 Solubility of
c. 5.0 d. 7.0 (M3 X) = 1× 10−4
∴ MX > M 3 X > MX 2 .
3. (c, d) In option (c), if HNO3 is present in limiting amount
22. We have taken a saturated solution of AgBr. Ksp of AgBr
is 12×10–14. If 10–7 moles of AgNO3 are added to 1 litre of then this mixture will be a buffer and the mixture given in
this solution find conductivity (specific conductance) of option (d), contains a weak acid (CH 3COOH) and its salt
this solution in terms of 10–7Sm–1 units. Given, λ°(Ag+ ) with strong base NaOH,
i.e. CH 3COONa.
= 6 × 10−3 Sm 2 mol −1 , λ(Br
o
−
)
= 8 × 10−3 S m 2 mol−1 ,
2
−3 −1 4. (b) K sp = 1.1 × 10−12 =  Ag +   CrO 4−2 
λ o
( NO3− )
= 7 × 10 S m mol .
2
[JEE 2006]
1.1 × 10 −12 = [0.1]2 [s]
23. The dissociation constant of a substituted benzoic acid at
25°C is 1.0 ×10−4. The pH of a 0.01M solution of its s = 1.1×1010
sodium salt is: [JEE 2009 P-II] 5. (d) Given pKa (HA) = 3.2
24. Amongst the following, the total number of compounds pKb (BOH) = 3.4
whose aqueous solution turns red litmus paper blue is: As given salt is of weak acid and weak base
[JEE 2010 P-I] 1 1
∴ pH = 7 + pK a − pK b
KCN K 2SO4 (NH 4 )2 C 2 O 4 NaCl Zn(NO 3 ) 2 FeCl3 2 2
1 1
K 2 CO3 NH 4 NO3 LiCN = 7 + (3.2) − (3.4) = 6.9
2 2

6. (d) The pH range of methyl orange is NH +4
pOH = pK b + log
3.9 4.5 NH 4 OH
Pinkish red Yellow
= 4.7 + log 2 = 4.7 + 0.3 = 5
Weak base is having pH greater than 7. When methyl
orange is added to weak base solution, the solution pH = 14 – 5 = 9
becomes yellow. This solution is titrated by strong acid
CH 3 CH 3
and at the end point pH will be less than 3.1. Therefore | |
solution becomes pinkish red. 12. (a) Ph—N—H < CH 3 —N—CH 3
↑ ↑
Lone pare delocalised More steric hinderence then,
7. (a)* BCl3 – electron deficient, incomplete octet less solutions energy
AlCl3 – electron deficient, incomplete octet
CH 2 —CH 3
Ans - (1) BCl3 and AlCl3 |
SiCl4 can accept lone pair of electron in d-orbital of < CH 3 —CH 2 —NH < CH 3 —CH 2 —NH 2
↑
silicon hence it can act as Lewis acid.
*Although the most suitable answer is (a). However, both 13. (c) pH of rain water is approximate 5.6.
option (a) and (c) can be considered as correct answers.
14. (d) On increasing Ea, K decreases.
e.g. hydrolysis of SiCl4
15. (a)
Cl Cl
H
Si ɺɺ : 
+ H 2O → Si 16. (c) NaH is an example of ionic hydride which is also
O
Cl Cl Cl Cl H known as saline hydride.
Cl Cl
↓ 17. (a) For K2[HgI4]
Cl
| i = 1 + 0.4 (3 – 1) = 1.8
Cl − Si − OH + HCl
| 18. (a) Histidine is:
Cl ⊕ Θ
Hence, option (c), AlCl3 and SiCl4 is also correct. ⊕ Θ H3 N— CH — COOH

H 3 N— CH — CO O H
(c) CH3COOK + H2O  H N
8. →CH3COOH + KOH FeCl3 – atpH=2
Basic N 
Acidicmedium
→
Acidic solution Al(CN)3- Salt of weak acid and weak. N
Base Pb(CH3COO)2- Salt of weak acid and strong base. N |
CH3COOK is salt of weak acid and strong base. H
Hence, solution of CH3COOK is basic. Zwitterionic form
pIn = 7.59
9. (d) The maximum prescribed concentration of Cu in
drinking water is 3 ppm. 19. (a) A →1; B→5; C →4; D →1
20 × 0.1 − 10 × 0.1 1
10. (a) EWG in increasing order of acidic strength (A) [CH 3 COOH]old = =
30 30
NO2CH2COOH > NCCH2COOH > FCH2COOH >
1
CICH2COOH [CH 3 COO − ]old =
30
11. (c) 20 ml 0.1 M H2SO4 ⇒ ηH + = 4 Buffer with [Salt] = [Acid]
30 ml 0.2 M NH4OH ⇒ η NH 4 OH = 6 pH does not change on dilution (A) → (1)
NH 4 OH + H + → NH 4+ + H 2 O 20 × 0.1 2
(B) [CH 3 COO Θ ]old = =
6 4 0 0 40 40
2 0 4 4 2
[CH 3 COO Θ ]new =
80
Solution is basic buffer
CH 3 COO + H 2 O  Θ
→ CH 3 COOH + OH − m.s × 5.7 = 912
c x x
ms = 160 Joule / °C [Calorimeter constant]
x2 [OH − ]old
2
[OH − ]2new
Kh = = = Energy evolved by neutralisation of CH 3COOH and
c 2 / 40 2 / 80
NaOH
Θ 2
[OH − ]old
2
⇒ [OH ] new = = 200 × 4.2 × 5.6 + 160 × 5.6 = 5600 Joule

2
So, energy used in dissociation of 0.1 mole
[OH − ]old
⇒ [OH − ]new = CH 3COOH = 5700 − 5600 = 100 Joule
2
Enthalpy of dissociation
∴ [H + ]new = 2[H + ]old
= 1 kJ / mole
(B) → (5)
20 × 0.1 2 1× 100 1
(C) [NH +4 ]old = = 21. (b) CH 3COOH = =
40 40 200 2
1× 100 1
+
2 CH 3CONa = =
[NH ] 4 new = 200 2
80
[salt]
NH 4+ + H 2 O ↽ ⇀ NH 4 OH + H + pH = pK a + log
c y y
[acid]
1/ 2
y2 [H + ]old
2 +
[H new ]2 pH = 5 − log 2 + log
Kh = = = 1/ 2
c (2 / 40) (2 / 80)
⇒ pH= 4.7
+
+
[H old ]2
⇒ [H new
2
] = 22. The solubility of AgBr in presence of 10 −7 molar
2
[H + ]old AgNO 3 is 3 × 10 −7 M.
+
[H new ]=
2 Therefore [Br − ] = 3 × 10−4 m3 , [Ag + ] = 4 × 10−4 m3
(C) → (4) and [NO3− ] = 10−4 m3
(D) For a saturated solution, [OH − ] = 3 2K sp Therefore κ total = κ Br − + κ Ag+ + κ NO− = 55 Sm −1
3
Irrespective of volume of solution.

23. K a (C 6 H 5COOH = 1× 10 −4
[H + ] remains constant.
pH of 0.01M C6 H 5COONa
(D) → (1)
C6 H 5COO − + H 2 ↽ ⇀ C6 H 5COOH + OH −1
0.01(1− h ) 0.01h 0.01h
For Question Nos. 20 to 21
20. (a) HCl + NaOH 
→ NaCl + H 2O K w 0.01h 2
Kh = =
Ka 1− h
n = 100 ×1 = 100 m mole = 0.1 mole
10−14 10−2 h 2
Energy evolved due to neutralization of HCl and NaOH = (1 − h ≃ 1)
10−4 1− h
= 0.1× 57 = 5.7 kJ = 5700 Joule
[OH − ] = 0.01h = 0.01× 10 −4 = 10 −6
Energy used to increase temperature of solution
[H + ] = 10 −8
= 200 × 4.2 × 5.7 = 4788 Joule
pH = 8
Energy used to increase temperature of calorimeter
= 5700 − 4788 = 912 Joule
24. KCN , K 2CO3 ,- LiCN are basic in nature and their
ms. ∆t = 912 aqueous solution turns red litmus paper blue. So, answer is 3.

25. +
AB(s) → A (aq) + B (aq) −
s − x = x ×10−5
s s− x
Ksp = [A + ][B− ]
−1 +
B + H−3 → HB
s− x 10 = s(s − x) = 2 ×10−10
K a of HB = 1×10−8 Sx = 2 ×10−5
[H + ][B− ] s 2 − sx = 2 ×10−10
Ka =
[HB] s 2 = 2 ×10−10 + 2 ×10−6
(s − x) × 10 −3 s−x s2 = 2 ×10−5
−5
= ⇒ = 10
x x s = 20 ×10−3 = 4.47 ×10−3
Chemical Kinetics 89
11 Chemical Kinetics
QUICK LOOK ∆x OA
= = = slope of the tan
tangent
gent
The reactions involving strong bond-breaking occur at ∆t OB
relatively slower rate while those involving weak bond- 0.05
breaking occur at relatively faster rate. On the basis of rate,
Conc. (mole/lit)
0.04 A
reactions are classified as.
0.03
Instantaneous or extremely fast reactions i.e. reactions with P
0.02
half-life of the order of fraction of second.
Extremely slow reactions i.e. reactions with half-life of the 0.01
θ
(180-θ)
order of years. O
5 10 15 20 B 25
Reactions of moderate or measurable rate. Time (min.)
Figure: 11.2
In general, for a reaction, n1 A + n 2 B 
→ m1C + m 2 D
Thus the rate of reaction at time 10 minutes
1 ∆[A] −1 ∆[B] 1 ∆[C] 1 ∆t = 20 × 60 = 1200 sec.
The rate is expressed as: − = = =
n1 ∆t n 2 ∆t m1 ∆t m2
∆x = 0.04 moles
∆[D]
0.04
∆t rins = = 3.35 × 10−5 mol lit −1 sec −1
1200
Instantaneous Rate: With the progress of reaction the
concentration of reactants decreases while that of product Factors Affecting Rate of a Reaction: The rate of a chemical
increases. According to law of mass action the rate of reaction reaction depends on the following things given below.
decreases moment to moment as shown by graph of rate vs.
time. Rate varies from moment to moment so rate of reaction Nature of Reactants
has to be specified at a given instant of time called Physical state of reactants: This has considerable effect over
instantaneous rate. rate of reaction.

satae > Liquid state > Solid state
Gaseous state
 →
Decreasing rate of reaction
Rate
Physical size of the reactants: Among the solids, rate

increases with decrease in particle size of the solid.
Chemical nature of the reactants:
Time Reactions involving polar and ionic substances including
Figure: 11.1 the proton transfer reactions are usually very fast. On the
dC other hand, the reaction in which bonds is rearranged, or
rins or rt = ±
dt electrons transferred are slow.
Where, dC is the infinitesimal change in conc. during Oxidation-reduction reactions, which involve transfer of
infinitesimal time interval dt after time t i.e. between t and t + dt. electrons, are also slow as compared to the ionic substance.
Consider a reaction A 
→ B, To know the rate of reaction at Substitution reactions are relatively much slower.
any time t, a tangent is drawn to curve at the point
corresponding to that time and it is extended on either side so Effect of Temperature: The rate of chemical reaction
as to cut the axes, say at the point A and B. Then generally increases on increasing the temperature. The rate of a
Change in the conc. reaction becomes almost double or tripled for every 10o C rise
Rate of reaction =
Time in temperature. Temperature coefficient of a reaction is defined

as the ratio of rate constants at two temperatures differing by Where, x and y are the orders with respect to individual
(generally 25°C and 35°C ) 10°C. reactants.
If reaction is in the form of reaction mechanism then the order
k at (t + 10o C) k 35o C
µ=Temperature coefficient = = is determined by the slowest step of mechanism.
k at t o C k 25o C
2A + 3B 
→ A 2 B3
Concentration of Reactants: The rate of a chemical reaction is
A + B 
→ AB (fast)
directly proportional to the concentration of the reactants means
rate of reaction decreases with decrease in concentration. AB + B 2 
→ AB3 (slow) (Rate determining step)
Reaction path AB3 + A 
→ A 2 B3 (fast)
Without catalyst
(Here, the overall order of reaction is equal to two.)
Ea
Molecularity of a reaction is derived from the mechanism of the
Ea Reaction
path with given reaction. Molecularity cannot be greater than three because
Potential Energy
catalyst more than three molecules may not mutually collide with each other.
Reactants
Energy of Reaction Molecularity of a reaction can't be zero, negative or
Products fractional. Order of a reaction may be zero, negative,
A catalyst changes the reaction path
positive or in fraction and greater than three. Infinite and
imaginary values are not possible.
Figure: 11.3
When one of the reactants is present in the large excess, the
Presence of Catalyst: The function of a catalyst is to lower
second order reaction conforms to the first order and is
down the activation energy. The greater the decrease in the
known as pseudo unimolecular reaction.
activation energy caused by the catalyst, higher will be the
reaction rate. Pseudo First Order Reaction: Reaction whose actual order is
different from that expected using rate law expression are
Effect of Sunlight: There are many chemical reactions whose
called pseudo – order reactions, e.g.
rate is influenced by radiations particularly by ultraviolet and
RCl + H 2 O 
→ ROH + HCl
visible light. Such reactions are called photochemical reactions.
For example, Photosynthesis, Photography, Blue printing, Expected rate law:
Photochemical synthesis of compounds, etc. The radiant energy Rate = K [RCl] [H 2 O], Expected order = 1 + 1 = 2
initiates the chemical reaction by supplying the necessary Actual rate law: Rate = K′ [RCl], Actual order = 1
activation energy required for the reaction. Water is taken in excess; therefore, its concentration may be
taken constant. This reaction is therefore, pseudo first order.
Rate Law: Molecularity and Order of a Reaction:
Similarly, the acid catalysed hydrolysis of ester, viz, follows
Molecularity is the sum of the number of molecules of reactants
first order kinetics.
involved in the balanced chemical equation. Molecularity of a
complete reaction has no significance and overall kinetics of RCOOR ′ + H 2 O ↽ ⇀ RCOOH + R ′OH
the reaction depends upon the rate determining step. Slowest Rate = K [RCOOR ′]
step is the rate-determining step. This was proposed by Van't It is also a pseudo-first order reaction.
Hoff.
Difference between Order and Molecularity
Example: NH 4 NO 2 
→ N 2 + 2H 2 O (Unimolecular) Order is an experimental property while molecularity is the
NO + O3 
→ NO 2 + O 2 (Bimolecular) theoretical property.
2NO + O 2 
→ 2NO 2 (Trimolecular) Order concerns with kinetics (rate law) while molecularity
The total number of molecules or atoms whose concentration concerns with mechanism.
determines the rate of reaction is known as order of reaction. Order may be any number, fraction, integral or even zero
Order of reaction = Sum of exponents of the conc. terms in rate whereas molecularity is always an integer expecting zero.
law. For the reaction xA + yB 
→ Products Reactions of Various Orders
The rate law is Rate = [A]x [B[ y Zero Order Reactions: A reaction is said to be zero order if its
rate is independent of the conc. of the reactants, consider the
Then, the overall order of reaction: n = x + y
general reactions: A 
→ Pr oducts Consider the reaction
If it is reaction of zero order A 
→ Pr oducts
−d[A] Let ‘a’ be the conc. of A at the start and after time t, the conc.
Rate = = K[A]o = K or d[A] = − K dt
dt becomes (a – x), i.e., x has been changed into products. The
Integrating both sides, we get [A] = −Kt + I . . .(i) rate of reaction after time ‘t’ is given by the expression
Where, I is a constant of integration At t = 0,[A] = [A]o dx dx
= K(a − x) or = K dt
dt (a − x)
∴ [A]o = I
dx
Substituting this value of I in equation (i), we get Upon integration of above equation, ∫ (a − x) = K ∫ dt
[A] = − Kt + [A]o . . .(ii)
Or − log e (a − x) = Kt + c
or Kt = [A]o − [A] K =
1
t
{ [ A ]o − [ A t ]} Where, c is integration constant when t = 0, x = 0
Some important characteristics of reaction of zero order. ∴ c = − log e a
Any reaction of zero order must obey equation Putting the value of ‘c’, − log e (a − x) = Kt − log e a
As it is a equation of straight line (y = mx + c), the plot of Or loge a − log e (a − x) = Kt
[A] versus t will be a straight line with slope = −K and
a 2.303 a
intercept on the conc. axis = [A]o as shown in figure. log e = Kt K = log10
(a − x) t (a − x)
If the initial concentration is [A]o and the concentration after
Concentration
time t is [A], then putting a = [A]o and (a − x) = [A], equation

Rate
becomes
2.303 [A]o
K= log
t [A]
Time Concentration This equation can be written in the exponential form as
Figure: 11.4 Figure: 11.5
[A]o [A]
= e kt or = e− Kt or [A] = [A]o e − Kt
Half reaction period: Half life period (t1/ 2 ) is the time in [A]t [A]o
which half of the substance has reacted. When [A] =
Some Complex First Order Reactions: Parallel Reactions in
[A ]
[A] = o , t = t1/ 2 substituting those values in equation (iii), we get such reactions (mostly organic) a single reactant gives two
2
products B and C with different rate constants. If we assume
that both of them are first order, we get.
Concentration
B
k1
Time k2
Figure: 11.6 C
Figure: 11.7
1 [A]o  [A]o [A]o
t1/ 2 = [A]o − = t1/ 2 = −d [ A ]
K  2  2 K 2K = k1 [ A ] + k 2 [ A ] = ( k1 + k 2 ) [ A ] . . .(i)
dt
molar conc. mol L−1 d [ B]
Unit of K: K = = = mole L−1 time −1 = k1 [ A ] . . .(ii)
Time time dt
First order Reaction: A reaction is said to be of the first order d[C]
And = k 2 [A] . . .(iii)
if the rate of the reaction depends upon one conc. term only. dt

Let us assume that in a time interval, dt, x moles / lit of B was Threshold Activated complex
Et energy (Et)
produced and y moles / lit of C was produced.
Energy barrier
d[B] x d[C] y
∴ = and = Ea (activation energy)
dt dt dt dt
d[B]/ dt x Er Energy of the
∴ = Reactants
∆E reaction
d[C]/ dt y (Er)
Ep
We can also see that from (ii) and (iii),
Products (Ep)
d[B] / dt k 1
=
d[C] / dt k 2 Progress of reaction
Figure: 11.8
x k1
∴ =
y k2 The activation energy (E a ) depends upon the nature of
This means that irrespective of how much time is elapsed, the chemical bonds undergoing rupture and is independent of
ratio of concentration of B to that of C from the start (assuming enthalpies of reactants and products. According to the concept
no B and C in the beginning) is a constant equal to k1 / k 2 . of activation energy, the reactants do not change directly into the
products. The reactant first absorbs energy equal to activation
Sequential Reactions: A 
k1
→ B 
k2
→ C. In this A energy and form activated complex. At this state, the molecules
decomposes to B which in turn decomposes to C. must have energy at least equal to the threshold energy. This
−d [ A ] means that the reaction involves some energy barrier which must
∴ = k1[A] . . .(i)
dt be overcome before products are formed. The energy barrier is
d [ B] known as activation energy barrier.
=k1[A] − k 2 [B] . . .(ii)
dt
Transition State Theory
d [C]
k 2 [B] . . .(iii) According to transition state theory the activated complex is
dt
supposed to be in equilibrium with the reactant molecules.
1 K
∴ t max = In 1 . . .(iv) Once the transition state is formed it can either return to the
K1 − K 2 K 2
initial reactants or proceeds to form the products.
Substituting equation (iv) in equation (iii), we get Assuming that once formed the transition state precedes to
k 2 / k1 − k 2
k  products we can say that rate is proportional to
B max = B max = [A]o  2 
 k1  concentration of transition state.
Mathematically, Rate ∝ Transition state
Concept of Activation Energy Rate = Constant × Transition state
The excess energy (Over and above the average energy of the
The activation energy for the forward reaction, (E fa ) and the
reactants) which must be supplied to the reactants to undergo
chemical reactions is called activation energy (E a ), activation energy for the reverse reaction (E ar ) are related to
E a = E (Threshold energy) − E (Reactants) the enthalpy ( ∆ H) of the reaction by the equation

∆H = E fa − E ar .
Activation energy = Threshold energy – Average kinetic energy
(a) For endothermic reactions, ∆H > 0, so that E ar < E af
of the reacting molecules
Zero activation energy = Fraction of effective collision (f) (b) For exothermic reaction, ∆H < 0, so that E ar > E af .
will be very large = Very fast reaction (Instantaneous
reaction). Arrhenius Equation: The variation of equilibrium constant of
Low activation energies = Fraction of effective collision a reaction with temperature is described by van’t Hoff equation
(f) will be large = Fast reactions. of thermodynamics which is as follows:
High activation energies = Fraction of effective collision d ln K p ∆H
=
(f) will be small = Slow reaction. dT RT 2
If k1 and k2 be the rate constants of forward reaction and molecules of the reactant present in the reaction vessel
backward reaction, respectively then K p = k 1 / k 2 . n Ea
respectively, then = e− Ea / RT
Further, ∆H = Ea1 −Ea2. Putting these in the above equation we get, n
Equation (ii) may also be put as logk
d ln k1 d ln k 2 E a1 Ea
− = − 22  Ea  1
dT dT RT 2
RT = −  + log A . . .(iv)
 2.303R  T
Splitting into two parts
Ea 1 Ea
d ln k1 Since and logA both are constants for a given reaction.
= + Z (For FR) 2.303R
dT RT 2
1
d ln k 2 Ea So from equation (iv) it is evident that a plot of log k vs. will
= 22 + Z (For BR) T
dT RT
be a straight line of the slope equal to
Where, Z is constant
Ea
− and intercept equal to logA as shown below.
Arrhenius sets Z equal to zero and without specifying FR and 2.303R
BR, he gave the following equation called Arrhenius equation. −E a 0A
= tan θ = − tan(180 − θ ) = −
d ln k Ea 2.303R OB
= . . .(i)
dT RT 2 OA
∴ ∴ Ea = × 2.303R logA = OA
From this equation it is evident that rate of change of logarithm OB
of rate constant with temperature depends upon the magnitude
of energy of activation of the reaction. Higher the Ea smaller
the rate of change of logarithm of rate constant with
temperature. That is, rate of the reaction with low Ea increases logK
slowly with temperature while rate of the reaction with high 180 – θ θ
O 1/T
Ea increases rapidly with temperature. It is also evident that
Figure: 11.9
rate of increase of logarithm of rate constant will go on
decreasing with increase of temperature. Thus, from this plot Ea and A both can be determined
Integrating Equation (i) assuming Ea to be constant we get, accurately. If k1 be the rate constant of a reaction at two
Ea different temperature T1 and T2 respectively then from equation
ln k = − + ln A . . .(ii)
RT (iv), we may write
k Ea Ea 1
Or ln =− or k = Ae − Ea / RT . . .(iii) log k1 = − . + log A
A RT 2.303R T1
Equation (iii) is integrated form of Arrhenius equation. The Ea 1

and log k2 = − . + log A
constant A called pre-exponential factor is the frequency factor 2.303R T2
since it is somewhat related with collision frequency. It is a Subtracting former from the latter we get
constant for a given reaction. From Equation (iii) it is evident k2 Ea 1 1 
log =  −  . . .(v)
that as T→∝, K→A. Thus, the constant A is the rate constant k1 2.303R  T1 T2 
of reaction at infinity temperature. The rate constant goes on
With the help of this equation it is possible to calculate Ea of a
increasing with temperature. So, when T approaches infinity, k
reaction provided, rate constants of reaction at two different
will be maximum. That is to say, A is the maximum rate
temperatures are known. Alternatively one can calculate rate
constant of a reaction. It is also to be noted that the exponential
constant of a reaction at a given temperature provided that rate
term i.e., e–Ea/RT measures the fraction of total number of
constant of the reaction at some other temperature and also Ea
molecules in the activated state or fraction of the total number
of the reaction is known.
of effective collisions. If nEa and n be the number of molecules
230
of reactant in the activated state and the total number of
230
90 →90 Th + γ
Th *  (γ − emission)

Mechanism of the Reaction Reactant molecule
Absorption of photon (As
Reaction Involving First Order Consecutive Reactions per Einstein law)
In such reactions, the reactions form a stable intermediate Knock out the
Excitation of electron from the
compound before they are finally converted into the products. electronic level reactant species
For example, reactants (R) are first converted to intermediate Excited molecule Photoelectric effect
(I) which is then converted to product (P) as
R 
k1
→ I 
k2
→P Photophysical process Photochemical process
Fluorescence Oxidation
Phosphorescence Reduction
P
Dissociation
Double decomposition
Concentration
Isomeric transformation
I
Photosensitisation
R
Time Multiple Choice Questions
Concentration profile of reactants (R),
intermediate (I) and products (P) as a function of One and More than One Correct
Figure: 11.10
1. Consider a reaction aG + bH → Products. When
concentration of both the reactants G and H is doubled,
Therefore, the reaction takes place in two steps, both of which the rate increases by eight times. However, when
are first order i.e., concentration of G is doubled keeping the concentration
Step (i): R 
k1
→ I; of H fixed, the rate is doubled. The overall order of the
reaction is: [JEE 2007 P-II]
Step (ii): I 
k2
→P
a. 0 b. 1 c. 2 d. 3
This means that I is produced by step (i) and consumed by step 2. For a first order reaction A → P, the temperature (T)
(ii). In these reactions, each stage will have its own rate and dependent rate constant (k) was found to follow the
rate constant the reactant concentration will always decrease 1
equation log k = −(2000) + 6.0. The pre-exponential
and product concentration will always increase as shown in T
above figure. factor A and the activation energy Ea, respectively, are:
a. 1.0 × 106 s −1 and 9.2 kJmol −1 [JEE 2009 P-II]
Reaction Involving Slow Step: When a reaction occurs by a b. 6.0s −1 and 16.6 kJmol −1
sequence of steps and one of the step is slow, then the rate
c. 1.0 ×106 s−1 and 16.6 kJmol −1
determining step is the slow step. For example in the reaction
d. 1.0 ×106 s−1 and 38.3 kJmol −1
R → I;
k1
I → P,
k2
3. Plots showing the variation of the rate constant (k) with

If k1 << k 2 then I is converted into products as soon as it is
temperature (T) are given below. The plot that follows
formed, we can say that Arrhenius equation is: [JEE 2010 P-I]
−d[R] d[P]
= = k1[R] a. b.
dt dt
Photochemical Reaction: Absorption of radiant energy by
k
reactant molecules brings in photophysical as well as

T T
photochemical changes. According to Einstein's law of
photochemical equivalence, the basic principle of photo c. d.
processes, each reactant molecule is capable of absorbing only
k
one photon of radiant energy. The absorption of photon by a

reactant molecule may lead to any of the photo process. T T
4. For the first order reaction 9. Higher order (> 3) reactions are rare due to:
2N 2 O5 (g) 
→ 4NO 2 (g) + O 2 (g) [JEE 2011 P-II] a. low probability of simultaneous collision of all the
reacting species [JEE Main 2015]
a. The concentration of the reactant decreases
b. increase in entropy and activation energy as more
exponentially with time
molecules are involved
b. The half-life of the reaction decreases with increasing
c. shifting of equilibrium towards reactants due to elastic
temperature
collisions
c. The half-life of the reaction depends on the initial
d. loss of active species on collision
concentration of the reactant
d. The reaction proceeds to 99.6% completion in eight 10. Decomposition of H2O2 follows a first order reaction. In
half-life duration fifty minutes the concentration of H2O2 decreases from 0.5
to 0.125 M in one such decomposition. When the
5. In the reaction, P + Q 
→ R + S the time taken for 75% concentration of H2O2 reaches 0.05 M, the rate of
reaction of P is twice the time taken for 50% reaction of P. formation of O2 will be: [JEE Main 2016]
The concentration of Q varies with reaction time as shown a. 6.93 × 10−2 mol min −1
in the figure. The overall order of the reaction is: b. 6.93 × 10−4 mol min −1
[JEE Adv. 2013 P-I]
c. 2.66 L min −1 at STP
[Q]0 d. 1.34 × 10−2 mol min −1

[Q
11. According to the Arrhenius equation
[JEE Adv 2016 P-I]
Tim
a. A high activation energy usually implies a fast
reaction
a. 2 b. 3
b. Rate constant increases with increase in temperature.
c. 0 d. 1
This is due to a greater number of collisions whose
6. The rate of a reaction doubles when its temperature energy exceeds the activation energy
changes from 300 K to 310 K. Activation of such a c. Higher the magnitude of activation energy, stronger is
−1
reaction will be: (R = 8.314 JK and log 2 = 0.301) the temperature dependence of the rate constant
d. The pre-exponential factor is a measure of the rate at
[JEE Main 2013]
which collisions occur, irrespective of their energy
a. 53.6 kJ mol−1 b. 48.6 kJ mol −1
12. Two reactions R1 and R 2 have identical pre-exponential
c. 58.6 kJ mol−1 d. 60.5 kJ mol−1
factors. Activation energy of R1 exceeds that of R1 by 10 kJ
7. The initial rate of hydrolysis of methyl acetate (1 M) by a mol–1. If k1 and k2 are rate constants for reactions R1 and
weak acid (HA,1M) is 1/100th of that of a strong acid (HX, k 
R2 respectively at 300K, then ln  2  is equal to:
1M), at 25 °C. The K a of HA is [JEE Adv. 2013 P-I]  k1 
a. 1×10−4 b. 1×10−5 (R = 8.314 J mol−1 K −1 ) [JEE Main 2017]
c. 1×10−6 d. 1×10−3 a. 4 b. 8
c. 12 d. 6
8. For the elementary reaction M → N, the rate of 13. At 518° C, the rate of decomposition of a sample of
disappearance of M increases by a factor of 8 upon gaseous acetaldehyde, initially at a pressure of 363 torr,
doubling the concentration of M. The order of the reaction was 1.00 torr s–1 when 5% had reacted and 0.5 torr s–1
with respect to M is: [JEE Adv. 2014 P-II] when 33% had reacted. The order of the reaction is
a. 4 b. 3 a. 0 b. 2 [JEE Main 2018]
c. 2 d. 1 c. 3 d. 1

14. For a first order reaction A(g) → 2B(g) + C(g) at constant a. Order of the reaction with respect to B is 2
volume and 300 K, the total pressure at the beginning b. Order of the reaction with respect to A is 2
c. Total Order of the reaction is 4
(t = 0) and at time t are P0 and Pt, respectively. Initially,
d. Order of the reaction with respect to B is 1
only A is present with concentration [A]0 and t1/3 is the time 18. Consider the following reversible chemical reactions:
required for the partial pressure of A to reach 1/3rd of its K
A 2 (g) + Br2 (g) K1 ↽ 1 ⇀ 2AB(g) . . .(i)
initial value. The correct option(s) is (are) (Assume that all
these gases behave as ideal gases) [JEE Adv. 2018 P-II] 6AB(g) → 3A2 (g) + 3B2 (g) . . .(ii)
The relation between K1 and K2 is: [JEE Main 2019]
a. K 2 = K3
b. K 2 = K1−3
ln(3P0-Pt)
1
t1/3
a. b. c. K1K 2 = 3 d. K1K 2 =
3
Time [A]0 19. The value of Kp/KC for the following reactions at 300K
are respectively: (At 300K, RT = 24.62 dm3 atm mol–1)
N2 (g) + O2 (g) → 2NO(g)
Rate constant
ln(P0-Pt)
N2O4 (g) → 2NO2 (g)

c. d. N2 (g) + 3H2 (g) → 2NH3 (g) [JEE Main 2019]
Time [A]0 a. 1, 24.62 dm3atm mol–1, 606.0 dm6atm2mol–2

b. 1, 4.1 × 10–2 dm–3atm–1 mol–1, 606.0 dm6 atm2 mol–2
15. For the e reaction 2A + B → C, the values of initial rate at c. 606.0 dm6atm2mol–2, 1.65 × 10–3 dm3atm–2 mol–1
different reactant concentrations are given in the table d. 1, 24.62 dm3atm mol–1, 1.65 × 10–3 dm–6atm–2 mol2
below. The rate law for the reaction is:
20. Among the following reactions of hydrogen with
[JEE Main 2019]
halogens, the one that requires a catalyst is:
[A] (mol L–1) [B] (mol L–1) Initial Rate(mol L–1s–
1
[JEE Main 2019]
)
a. H2 + I2 → 2HI b. H2 + F2 → 2HF
0.05 0.05 0.045
c. H2 + Cl2 → 2HCI d. H2 + Br2 → 2HBr
0.10 0.05 0.090
0.20 0.10 0.72 21. For an elementary chemical reaction, A 2 → 2A,
2 2
a. Rate = k [A][B] b. Rate = k [A] [B] d[A]
The expression for is:
2 2 dt
c. Rate = k [A][B] d. Rate = k [A] [B]
[JEE Main 2019]
16. For a reaction scheme A → B 
k2
→ C, if the rate of
k1
2
a. 2k1[A2]–k–1[A] b. k1[A2]–k–1[A]2
formation of B is set to be zero then the concentration of
c. 2k1[A2]–2k–1[A]2 d. k1[A2]+k–1[A]2
B is given by: [JEE Main 2019] 22. For a reaction consider the plot of lnk versus 1/T given in
k  the figure. If the rate constant of this reaction at 400 K is
a.  1  [A] b. (k1 + k2) [A]
 k2  10–5 s–1, then the rate constant at 500 K is:
c. k1k2[A] d. (k1 – k2) [A] [JEE Main 2019]
17. For the reaction 2A + B → products, when the

concentration of A and B both were doubles, the rate of In k
Slope = –4606K
the reaction increased from 0.3 mol L–1s–1 to 2.4 mol.
L–1s–1 .When the concentration of A alone is doubled, the
rate increased from 0.3 mol L–1s–1 to 0.6 mol L–1s–1 1/T
Which one of the following statement is correct? a. 2×10–4 s–1 b. 10–4 s–1
[JEE Main 2019] c. 10–6 s–1 d. 4×10–4 s–1
Integer and Subjective 2000
2. (d) Given, log K = 6 −
23. 2X(g) 
→ 3Y(g) + 2Z(g) T
Ea
Time (in Min) 0 100 200 Since, log K = log A −
2.303RT
Partial pressure of X (in mm 800 400 200
So, A = 106 sec−1 and
of Hg)
Assuming ideal gas condition. Calculate [JEE 2005]
a. Order of reaction
k
b. Rate constant.
c. Time taken for 75% completion of reaction. T
d. Total pressure when Px = 700 mm. Ea = 38.3kJ / mole
24. An organic compound undergoes first-order decomposition.
3. (a) k = Ae− Ea / RT
1 1
The time taken for its decomposition to and of its initial As T ↑: k ↑ exponentially.
8 10
concentration are t1/ 8 and t1/10 respectively. What is the value 4. (a, b, d) For first order reaction [A] = [A]0 e− kt
[t1/ 8 ] Hence concentration of [NO2 ] decreases exponentially,
of × 10? (take log10 2 = 0.3) [JEE 2012 P-I]
[t1/10 ]
0.693
25. In dilute aqueous H 2SO 4 , the complex diaquodioxalato Also, t1/ 2 = . which is independent of concentration
K
ferrate (II) is oxidised by MnO −4 . For this reaction, the and t1/ 2 decrease with the increase of temperature.
+
ratio of the rate of change of [H ] to the rate of change of
[MnO −4 ] is: [JEE Adv. 2015 P-II] 2.303  100 
t 99.6 = log  
26. A + B + C → Product [JEE Adv. 2019 P-I] K  0.4 
Ex. [A] [B] [C] Rate of reaction 2.303 0.693
t 99.6 = (2.4) = 8 × = 8 t1/ 2
1. 0.2 0.1 0.1 6 × 10 -5 K K
2. 0.2 0.2 0.1 6 × 10-5 5. (d) Overall order of reaction can be decided by the data
3. 0.2 0.1 0.2 1.2 × 10-4 given t 75% = 2t 50% .
4. 0.3 0.1 0.1 9 × 10-5
∴ It is a first order reaction with respect to P.
When, [A] = 0.15
From graph [Q] is linearly decreasing with time, i.e., order
[B] = 0.25
of reaction with respect to Q is zero and the rate
[C] = 0.15
expression is r = k[P]1[Q]0 .
Rate of reaction is Y × 10-5 M/S Find Y.
27. In following reaction the value of K is 5 × 10 −4 S −1 . Hence (d) is correct.
∆
2N 2 O 5  → 2N 2 O 4 + O 2 Ea  T2 − T1 
6. (a) 0.3010 =  
Initial pressure was 1 atm, while the final pressure was 2.303R  T1T2 
1.45 atm at time y × 103 sec. calculate ‘y’. Ea  310 − 300 
⇒ 0.3010 =  
[JEE Adv. 2019 P-II] 2.303 × 8.314 × 10 −3  310 × 300 
E a = 53.6 kJ mol
1
1. (d) aG + bH 
→ Product
7. (a) Rate in weak acid = (rate in strong acid)
100
rate ∝ [G ]a [H]b a = 1, b = 2 1
∴ [H + ]weak acid = [H + ]strong acid
Hence (d) is correct 100

1 13. (b) Assume the order of reaction with respect to
∴ [H + ]weak acid = M = 10−2 M
100 acetaldehyde is x.
Condition-1:
∴ Cα = 10−2
Rate = k[CH3 CHO]x
∴ K a = 10−4
1= k[363 × 0.95]
1= k[344.85]x . . .(i)
r1 1 [M]n
8. (b) = = ⇒n=3 Condition-2
r2 8 [2M]n
0.5 = k[363 × 0.67]x
9. (a) 0.5 = k[243.21]x . . . (ii)
Divide equation (i) by (ii)
1 x
10. (b) In 50 minutes, concentration of H2O2 becomes of 1  344.85 
4 = 
0.5  243.21 
initial.
⇒ 2 = (1.444) ⇒ x = 2
⇒ 2 × t1/ 2 = 50 minutes
⇒ t1/ 2 = 25 minutes 14. (a, d)
ln(3P0-Pt)
0.693
⇒ K= per minute
25
0.693
⇒ rH2O2 = × 0.05 = 1.386 × 10−3
25 Time
2H 2 O 2 
→ 2H 2 O + O 2 A 
→ 2B + C
1 P0 – –
rO2 = × rH2 O2
2 P0 − P 2P P
−3
⇒ rO2 = 0.693 × 10 Pt = P0 + 2P
rO2 = 6.93 × 10−4 mol/minute × litre Pt − P0

P=
2
− Ea / RT
11. (b, d, d) K = A e  P0  2P0
Kt = ln   = ln
P −P 3P0 − Pt
dk
=K
Ea dk
∝ Ea  P0 −  t 0  
dT RT 2 dT   2 
A → Frequency factor Kt = ln 2P0 − ln(3P0 − Pt )
= No of collisions per unit time per unit volume. Rate constant of reaction is independent of initial
concentration.
12. (a) From Arrhenius equation
K = A ⋅ e− Ea / RT 15. (c) r = K [A]x [B]y
0.045 = K (0.05)x (0.05)y . . .(i)
So, K1 = A ⋅ e− Ea1 / RT . . . (i)
0.090 = K (0.10)x (0.05)y . . . (ii)
K 2 = A ⋅ e − Ea 2 / RT . . . (ii) 0.72 = K (0.20)x (0.10)y . . . (iii)
So, equation (i) / (ii) From (i) ÷ (ii)
x
K2 ( E − E ) / RT 0.045  0.05 
⇒ = e a1 a1 =  ⇒x =1
K1 0.090  0.10 
(As pre-exponential factors of both reactions is same) From (ii) ÷ (iii)
 K  Ea − Ea2
x y
0.090  0.10   0.05 
ln  2  = 1 =  ⋅ 
 K1  RT 0.720  0.20   0.10 
10, 000 ⇒ y=2

= =4
8.314 × 300 Hence r = K [A][B]2
16. (a) A → B → C,

k1 k2
K2
2.303log
d[B] 10−5
= 0 = K1[A] − K 2 [B]
dt  1 1 
= 4606  − 
K1  400 500 
⇒ [B] = [A]
K2 ⇒ K2 = 10–4 s–1
23. 2X(g) 
→ 3Y(g) + 2Z(g)
17. (a) r = K[A]x [B]y
(a) By the given data, we can observed that t1/ 2 of the X
⇒ 8 = 23 = 2 x + y
is constant i.e. 100 min. therefore order of reaction is one.
⇒ x+y=3 . . . (i)
0.693 0.693
(b) Rate constant K = = = 6.93 × 10 −3 min −1
⇒ 2 = 2x t1/ 2 100
⇒ x = 1, y = 2 (c) Time taken for 75% completion of reaction = 2 t1/ 2
Order w.r.t A =1 (d) 2X 
→ 3Y + 2Z
Order w.r.t B =2 Initial pressure 800 0 0
18. (b) A2 (g) + B2 (g) → 2AB . . .(i) At any time 800 – x 3/2 x x
Given 800 − x = 700 min
⇒ Equation (i) × 3
⇒ x = 100 mm
6 AB(g) → 3A2 (g) + 3B2 (g)
Total pressure = 700 + 150 + 100 = 950 mm
3
1
⇒   = k2 2.302  a 
 k1  24. K= log  0 
t  a0 − x 
⇒ k 2 = (k1 ) −3
 
2.303  a 
19. (d) N 2 (g) + O 2 (g) → 2NO(g) K= log  0 
t1/ 8  1 a0 
kp ∆n g 8 
= (RT) = (RT) 0 = 1
kc
 
N 2 O4 (g) → 2NO2 (g) 2.303  a0  t1/8 log8
K= log  ⇒ =
t1/10 1
 a0  t 1/10 log10
kp  10 
= (RT)1 = 24.62
kc
2.303 a0 t1/ 8 log 8
= ⇒ ⇒ t = log10
N 2 (g) + 3H 2 (g) → 2NH 3 (g) t1/10 1/10
kp
= (RT) −2 t1/ 8
kc ⇒ × 10 = log8 × 10 = 3log 2 × 10 = 3 × 0.3 × 10 = 9
t1/10
1
= = 1.65 × 10−3 25. [Fe(C2 O 4 )(H 2 O)]2 − + MnO24 − + 8H + 
→
(RT) 2
Mn 2 + + Fe3+ + 4CO2 + 6H 2 O
20. (a)
So, the ratio of rate of change of [H + ] to that of rate of
21. (c) A 2 → 2A, change of [MnO4 ] is 8.
d[A]
=2k1[A2]–2k–1[A]2
dt
26. r = k[A]a [B]b [C]c
K 2 Ea  1 1  By experiment no. 1 and 2 b = 0
22. (b) ℓn =  − 
K1 R  T1 T2  By experiment no. 1 and 3 c = 1
By experiment no. 1 and 4 a = 1

r = k[A] [B] [C]
1 0 1
P
t=t (1-P) P
From experiment no 1 6 × 10 = k (0.2) (0.1)
-5 2
Given [A] = 0.15 [B] = 0.25 [C] = 0.15 t =∞ 0 1 atm 0.5 atm
r = k[A] [B] [C]
1 0 1 P0 = 1 atm, Pt = 1.45atm P∞ = 1.5atm
= 3 × 10 × 0.15 × 1 × 0.15
-3
1  P − P0 
t= ln  ∞ 
= 3 × 0.025 × 10-3 2K  P∞ − Pt 
= 6.75 × 10-5 mol L–11sec–1
2.303  1.5 − 1 
= Y = 6.75 ~ 7 t= log  
2 × 5 × 10−4  1.5 − 1.45 
27. From unit of K reaction is first order t = 2.303 × 103 = y × 103
∆
2N 2 O 5 
→ 2N 2 O 4 + O 2
So, y = 2.303
t=0 1 atm 0 0 Answer after rounding off and truncation = 2.30.
Surface Chemistry 101
12 Surface Chemistry
QUICK LOOK gas adsorbed by the adsorbents per gm (unit mass), k and n
are constant at a particular temperature and for a particular
The phenomenon of attracting and retaining the molecules of adsorbent and adsorbate (gas), n is always greater than one,
the substance on the surface of a liquid or a solid resulting into indicating that the amount of the gas adsorbed does not
a higher concentration of molecules on the surface is called increase as rapidly as the pressure.
adsorption. The substance thus adsorbed on the surface is called At low pressure, the extent of adsorption varies linearly
the adsorbate and the substance on which it is adsorbed is x
with pressure. ∝ p′
called adsorbent. The reverse process, i.e. removal of the m
adsorbed substance from the surface is called desorption (which At high pressure, it becomes independent of pressure.
can be brought about by heating or reducing the pressure). The x
∝ p°
adsorption of gases on the surface of metals is called occlusion. m
x
Table: 12.1: Difference between Adsorption and Absorption At moderate pressure depends upon pressure raised to
m
Adsorption Absorption
x
It is a surface phenomenon, It is a bulk phenomenon, i.e. powers ∝ p1/ n
i.e. it occurs only at the occurs throughout the body m
x x
∝ p1 ∝ p°
surface of the adsorbent. of the material. m m
In this phenomenon the In this phenomenon, the
concentration on the surface concentration is same
log (x/m)
1
of adsorbent is different throughout the material. x/m slope =
x n
∝ p 1/ n
from that in the bulk. m
intercept = log k
Adsorption Isotherms: A mathematical equation, which p log p
describes the relationship between pressure (p) of the gaseous Freundlich adsorption isotherm: Plot of log x/m against log p for the
plot of x/m against p adsorption of a gas on a solid
adsorbate and the extent of adsorption at any fixed temperature,
is called adsorption isotherms. The extent of adsorption is Figure: 12.1
expressed as mass of the adsorbate adsorbed on one unit mass
of the adsorbent. The Langmuir-adsorption Isotherms: One of the drawbacks
Thus, if x g of an adsorbate is adsorbed on m g of the of Freundlich adsorption isotherm is that it fails at high
x pressure of the gas. Irving Langmuir derived a simple
adsorbent, then Extent of adsorption = adsorption isotherm, on theoretical considerations based on
m
Various adsorption isotherms are commonly employed in kinetic theory of gases.
describing the adsorption data. Adsorption takes place on the surface of the solid only till
the whole of the surface is completely covered with a
Freundlich Adsorption Isotherm unimolecular layer of the adsorbed gas.
Freundlich adsorption isotherm is obeyed by the adsorptions Adsorption consists of two opposing processes, namely
where the adsorbate forms a monomolecular layer on the Condensation of the gas molecules on the solid surface and
surface of the adsorbent. Evaporation (desorption) of the gas molecules from the
x x surface back into the gaseous phase.
= kp1/ n (Freundlich adsorption isotherm) or log
m m The rate of condensation depends upon the uncovered (bare)
1 surface of the adsorbent available for condensation.
= log k + log p
n Naturally, at start when whole of the surface is uncovered
Where, x is the weight of the gas adsorbed by m gm of the the rate of condensation is very high and as the surface is
adsorbent at a pressure p, thus x/m represents the amount of covered more and more, the rate of condensation

progressively decreases. On the contrary, the rate of Affinity for dispersion medium.
evaporation depends upon the covered surface and hence Size i.e. macromolecular or associated or multimolecular.
increases as more and more of the surface is covered
ultimately an equilibrium will be set up at a stage when the Table: 12.2 On the Basic of Size
rate of condensation becomes equal to the rate of Multimolecular Macromolecular Associated colloids
colloids colloids
evaporation (adsorption equilibrium).
They are formed by They are molecules of They are formed by
The rate of condensation also depends upon the pressure of the aggregation of a large size e.g. aggregation of a large
the gas since according the kinetic theory of gases, the large number of atoms Polymers like rubber, no. of ions
number of molecules striking per unit area is proportional to or molecules which nylon, starch, etc. inconcentrated
generally have solution e.g. Soap sol.
the pressure.
diameters less than 1
x ap nm, e.g. sols of gold,
Mathematically, = , where a and b are constants and sulphur, etc.
m 1 + bp
Their molecular masses They have high Their molecular masses
their value depends upon the nature of gas (adsorbate), nature are not very high. molecular masses. are generally high.
of the solid adsorbent and the temperature. Their values can be Their atoms or Due to long chain, the Higher is the
determined from the experimental data. molecules are held van der Waal’s forces concentration, greater
together by weak van holding them are are the van der Waal’s
Catalysis: Catalyst is a substance which can change the speed der Waal’s forces. comparatively stronger. forces.
of a chemical reaction without being used up in that reaction They usually have They usually have Their molecules
lyophilic character. lyophobic character. contain both lyophilic
and the phenomenon is known as catalysis. If a catalyst
and lyophobic groups.
increases speed of a reaction, it is called a positive catalyst and
the phenomenon is called positive catalysis. While if a catalyst Purification of Colloidal Solution: The process of reducing
decreases the speed of a reaction, it is called a negative catalyst the impurities (electrolytes or soluble substances) to a requisite
and the phenomenon is called negative catalysis. For example, minimum in a colloidal solution is known as purification of
oxidation of SO2 to SO3 in presence of NO (lead chamber colloidal solution.
process) or in presence of V2O5 (contact process) are examples
Dialysis: The separation of soluble impurities from a colloidal
of positive catalysis, decomposition of H2O2 in presence of
solution on the basis of their different rates of diffusion through
phosphoric acid and oxidation of chloroform in presence of
a parchment paper (semipermeable membrane) is known as
alcohol are examples of negative catalysis. A catalyst lowers
dialysis. The small molecular or ionic species pass (diffuse)
the activation energy for the forward reaction as well as for the
through the membrane pores while the colloidal particles which
backward reaction. As a result, the reaction follows an alternate
are larger in size do not pass through the membrane pores. In
path and the rate of forward reaction as well as that of the
case of ionic nature of impurities, dialysis can be accelerated by
backward reaction are accelerated to the same extent. Hence,
taking advantage of electricity and the process is known as
equilibrium constant of the reaction remains unaffected.
Similarly, it may be noted that the enthalpy change of the electrodialysis.
reaction also remains unaffected. In the presence of catalyst, the Coagulation Value: The minimum concentration of the
equilibrium is however attained quickly. electrolyte in millimoles per litre of the solution, required to
Colloidal State: A heterogeneous system of two immiscible cause coagulation of a particular sol is called coagulation value
phases is called colloidal state. These two phases are dispersion or flocculation value of the electrolyte for the sol. Therefore,
medium and dispersed phase. In these two first is continuous 1
Flocculation value ∝
phase while second one is discontinuous phase. Coagulating power
On the basis of particle size substances are of three types: An electrolyte having greater coagulation value has smaller
−9 coagulating power.
True solution (10 m)
Colloidal solution (10 −9 to 10 −7 m) Hardy Schulze Rule: Different electrolytes are known to have
−7
Suspensions (10 m) different coagulation values. The coagulating behaviour is
governed by Hardly Schulze rule according to which:
Colloids can be Classified as Follows:
The ion having opposite charge to sol particles cause
State of appearance i.e. rigid appearance (called gels) or
coagulation and
fluid like appearance (called sols).

Coagulating power of an electrolyte depends on the valency k 
of ion i.e., greater the valency more is the coagulating power. kinetics, respectively. Ratio  1  of the rate constants for
 k0 
The decreasing order of flocculation value of electrolytes
first order (k1 ) and zero order (k0 ) of the reactions is:
for a –ve sol is, NaCl > BaCl 2 > AlCl3 > SnCl4
[JEE 2008 P-I]
The decreasing order of flocculation value of electrolytes −1
a. 0.5 mol dm 3
b. 1.0 mol dm −3
for a +ve sol is, KCl > Na 2SO 4 > a 3 PO 4 > K 4 [Fe(CN) 6 ]
c. 1.5 mol dm −3 d. 2.0 mol −1 dm 3
Gold Number: Lyophilic colloids protect the lyophobic 2. Among the following, the surfactant that will form micelles
colloids against their coagulation by addition of electrolytes. in aqueous solution at the lowest molar concentration at
The protecting power of a lyophilic colloid is expressed in ambient conditions is: [JEE 2008 P-II]
terms of gold number. a. CH3 (CH 2 )15 N + (CH3 )3 Br −
The number of milligrams of the protective colloid which just b. CH3 (CH 2 )11 OSO3− Na +
prevent the coagulation of 10 ml of standard red gold sol when c. CH3 (CH 2 )6 COO − Na +
1 mol of 10% solution of sodium chloride is added to it.
d. CH3 (CH 2 )11 N + (CH3 )3 Br −
Smaller the gold number of the protective colloid greater is its
protecting power. 3. The correct statement (s) pertaining to the adsorption of a
gas on a solid surface is (are) [JEE 2011 P-I]
Emulsions: Emulsion is a colloidal solution of two immiscible
a. Adsorption is always exothermic
liquids in which one liquid acts as the dispersed phase while the b. Physisorption may transform into chemisorption at high
other liquid acts as the dispersion medium. There are two types temperature
of emulsions i.e., c. Physisorption increases with increasing temperature but
Oil in water - Examples: Milk, cream, face cream, etc. chemisorption decreases with increasing temperature
Water in oil - Examples: Butter, cold cream etc. d. Chemisorption is more exothermic than physisorption,
however it is very slow due to higher energy of activation.
Table: 12.3 Properties of Emulsions
Property Water in oil Oil in water 4. Choose the correct reason(s) for the stability of the
Dispersed phase Water Oil lyophobic colloidal particles. [JEE 2012 P-I]
Dispersion medium Oil Water a. Preferential adsorption of ions on their surface from the
Examples Butter, cold cream, cod Milk, face creams, solution
liver oil butter creams
b. Preferential adsorption of solvent on their surface from
Viscosity More than water Slightly more than
water
the solution
Appearance Oily, opaque and Watery, opaque and c. Attraction between different particles having opposite
translucent translucent. charges on their surface
Electrical conductivity Very low Nearly equal to water. d. Potential difference between the fixed layer and the
Dilution test More oil added is More water added is diffused layer of opposite charges around the colloidal
soluble but not water soluble but not oil particles
Spreading test Spreads easily on an Spreads readily on
5. The given graphs/data I, II, III and IV represent general
oily layer. watery layer
Dye test: Addition of Dye dissolves giving a Dye remains insoluble
trends observed for different physisorption and
oil soluble dye like bright colour in the form of coloured chemisorption processes under mild conditions of
methylene blue droplets. temperature and pressure. Which of the following choice(s)
about I, II, III and IV is (are) correct? [JEE 2012 P-II]
P=constant
P=constan
Amount of gas adsorbed
(I) (II) P=constant

P constant
One and More than One Correct t
1. Under the same reaction conditions, initial concentration

of 1.386 mol dm −3 of a substance becomes half in 40
seconds and 20 seconds through first order and zero order
T T
(III) (IV) a. I : KCl II : CH 3 OH III : CH 3 (CH 2 )11 OSO 3− Na +
Potential Energy
200
b. I: CH 3 (CH 2 )11 OSO 3− Na + II : CH 3 OH III : KCl

250 ε ads
c. I : KCl II : CH 3 (CH 2 )11 OSO 3− Na + III : CH 3 OH
∆H ads = 150 kJ mol−1
d. I : CH 3 OH II : KCl III : CH 3 (CH 2 )11 OSO 3− Na +
T T 11. The Tyndall effect is observed only when following

a. I is physisorption and II is chemisorptions conditions are satisfied [JEE Main. 2017]
b. I is physisorption and III is chemisorptions A. The diameter of the dispersed particles is much smaller
c. IV is chemisorption and II is chemisorptions than the wavelength of the light used.
d. IV is chemisorption and III is chemisorption B. The diameter of the dispersed particle is not much
6. The coagulating power of electrolytes having ions smaller than the wavelength of the light used.
Na + , Al3+ and Ba 2 + for arsenic sulphide sol increases in C. The refractive indices of the dispersed phase and
the order [JEE Main 2013] dispersion medium are almost similar in magnitude.
D. The refractive indices of the dispersed phase and
a. Al3+ < Ba 2+ < Na + b. Na < Ba 2+ < Al3+ +
dispersion medium differ greatly in magnitude.

c. Ba 2 + < Na + < Al3+ d. Al3+ < Na + < Ba 2 +
a. B and C b. A and D
7. 3 g of activated charcoal was added to 50 mL of acetic acid c. B and D d. A and C
solution (0.06 N) in a flask. After an hour it was filtered and
12. The correct statements about surface properties is (are):
the strength of the filtrate was found to be 0.042 N. The
amount of acetic acid adsorbed (per gram of charcoal) is: [JEE Adv. 2017 P-II]
[JEE Main 2015] a. Adsorption is accompanied by decrease in enthalpy and
a. 18 mg b. 36 mg c. 42 mg d. 54 mg decrease in entropy of the system
b. Cloud is an emulsion type of colloid in which liquid is
8. When O2 is adsorbed on a metallic surface, electron transfer
dispersed phase and gas is dispersion medium
occurs from the metal to O2. The TRUE statement(s)
regarding this adsorption is (are): [JEE Adv. 2015 P-II] c. The critical temperatures of ethane and nitrogen are 563
a. O2 is physisorbed K and 126 K, respectively. The adsorption of ethane will
be more than that of nitrogen on same amount of activated
b. heat is released
charcoal at a given temperature
c. occupancy of π 2p*
of O2 is increased
d. Brownian motion of colloidal particles does not depend on
d. bond length of O2 is increased the size of the particles but depends on viscosity of the solution
9. For a linear plot of log (x/m) versus log p in a Freundlich 13. For coagulation of arscnious sulphide sol, which one of
adsorption isotherm, which of the following statements is the following salt solution will be most effective?
correct? [JEE Main 2016] [JEE Main 2019]
a. Both k and 1/n appear in the slope term b. 1/n appears a. AlCl3 b. NaCl
as the intercept c. BaCl2 d. Na3PO4
c. Only 1/n appears as the slope 14. If dichloromethane (DCM) and water (H2O) are used for
d. log (1/n) appears as the intercept.
differential extraction, which one of the following
10. The qualitative sketches I, II and III given below show the statements is correct? [JEE Main 2019]
variation of surface tension with molar concentration of a. DCM and H2O would stay as lower and upper layer
three different aqueous solutions of KCl, CH 3 OH and respectively in the S.F.
CH 3 (CH 2 )11 OSO 3− Na + at room temperature. The correct b. DCM and H2O will be miscible clearly
assignment of the sketches is [JEE Adv. 2016 P-II] c. DCM and H2O would stay as upper and lower layer
respectively in the separating funnel (S.F.)
Surface tension
II
Surface tension
Surface tension
III
I d. DCM and H2O will make turbid/colloidal mixture
15. The freezing point of a diluted milk sample is found to be
–0.2°C, while it should have been –0.5°C for pure milk.
How much water has been added to pure milk to make the
Concentration Concentration Concentration
diluted sample? [JEE Main 2019]

a. 2 cups of water to 3 cups of pure milk Integer and Subjective
b. 1 cup of water to 3 cups of pure milk 21. 20% surface sites have adsorbed N2 . On heating N 2 gas
c. 3 cups of water to 2 cups of pure milk evolved from sites and were collected at 0.001 atm and
d. 1 cup of water to 2 cups of pure milk 298 K in a container of volume is 2.46 cm3. Density of
16. Among the colloids cheese (C), milk (M) and smoke (S), surface sites is 6.023 ×1014 / cm2 and surface area is 1000
the correct combination of the dispersed phase and cm2, find out the no. of surface sites occupied per
dispersion medium, respectively is: [JEE Main 2019] molecule of N2 . [JEE 2005]
a. C : solid in liquid; M : solid in liquid; S : solid in gas
b. C : solid in liquid; M : liquid in liquid; S : gas in solid 22. Silver (atomic weight = 108 g mol−1) has a density of 10.5
g cm−3. The number of silver atoms on a surface of area
c. C : liquid in solid; M : liquid in solid; S : solid in gas
d. C : liquid in solid; M : liquid in liquid; S : solid in gas 10−12 m2 can be expressed in scientific notation as y ×10x.
17. The molecule that has minimum/no role in the formation The value of x is: [JEE 2010 P-II]
of photochemical smog is: [JEE Main 2019]
a. CH2 = O b. N2 ANSWERS and SOLUTIONS
c. O3 d. NO 0.693 0.693
1. (a) k1 = =
18. The compound that is not a common component of t1/ 2 40
photochemical smog is: [JEE Main 2019] A0 1.386
a. O3 b. CH2 = CHCHO k0 = =
2t1/ 2 2 × 20
c. CF2Cl2 d. H3C—C—OONO2 k1 0.693 40 0.693
|| = × = = 0.5 mol −1 litre
O k0 40 1.386 1.386
19. Among the following, the false statement is: 2. (a) Critical concentration for micelle formation decreases
[JEE Main 2019] as the molecular weight of hydrocarbon chain of
surfactant grows because in this case true solubility
a. Latex is a colloidal solution of rubber particles which
diminishes and the tendency of surfactant molecule to
are positively charged
associate increases.
b. Tyndall effect can be used to distinguish between a
colloidal solution and a true solution. 3. (a, b, c)
c. It is possible to cause artificial rain by throwing 4. (a, d) (a) Preferential adsorption of ions on surface from
electrified sand carrying charge opposite to the one on the solution.
clouds from an aeroplane. (c) Attraction between particles having same charges on
d. Lyophilic sol can be coagulated by adding an electrolyte. their surface accounts for the Brownian motion.
(d) Definition of Zeta Potential.
Statement/Assertion and Reason 5. (a, c) I: In physisorption, as the temperature increases the
amount of gas adsorbed decreases.
20. Statement-I: Micelles are formed by surfactant molecules
II: In chemisorption, as the temperature increases the
above the critical micellar concentration (CMC). And
amount of gas adsorbed increases (to a certain range of
Statement-II: The conductivity of a
temperature)
solution having surfactant molecules decreases sharply at III: Fruendlich adsorption isotherms for physisorption
the CMC.
x
[JEE 2007 P-I] = kp1/ n (at constant T)
m
a. Statement-I is True, Statement-II is True; Statement -II IV: ∆H ads = 150 KJ is in the range for chemisorptions.
is a correct explanation for Statement-I.
b. Statement-I is True, Statement-II is True; Statement -II 6. (b) Factual
is not a correct explanation for Statement-I. 7. (a) Amount of acetic acid adsorbed
c. Statement -I is True, Statement-II is False. (0.06 − 0.042) × 50 ×10−3 × 60
= = 16 × 10 −3 = 18 mg
d. Statement -I is False, Statement-II is True. 3

8. (b, c, d) *Adsorption of O2 on metal surface is exothermic. 18. (c) Freons (CFC's) are not common components of photo
* During electron transfer from metal to O2 electrons chemical smog.
occupies π 2p
*
orbital of O2 . 19. (a) Colloidal solution of rubber are negatively charged.
* Due to electron transfer to O2 the bond order of O2 20. (b) The formation of micelles takes places only above a
decreases hence bond length increases. particular temperature called Kraft temperature (Tk ) and
9. (c) According to the Freundlich adsorption isotherm above a particular concentration called critical micelle
x x 1 concentration (CMC). Each micelle contains at least 100
= kP1/ n log = log K + log P
m m n molecules. Therefore conductivity of the solution
decreases sharply at the CMC.
10. (d) Impurities affect surface tension appreciably. It is
Hence (b) is correct.
observed that impurities which tend to concentrate on surface
of liquids, compared to its bulk lower the surface tension. 21. PN2 = 0.001 atm, T = 298 K, V = 2.46 cm 2
Substance like detergents, soaps (CH 3 (CH 2 )11 S O3− Na + ) By ideal gas, PV = nRT
decreases the surface tension sharply. Those like alcohol (e.g. PV 0.001× 2.46 ×10−3
n N2 = = = 1.0 × 10−7
–CH 3 OH, C 2 H 5 OH) lower the surface tension slightly. RT 0.0821× 298
This can also be related to the fact that CH 3 OH has smaller Now molecules of
dielectric constant. Dielectric constant is directly proportional N 2 = 6.023 × 1023 × 1× 10−7 = 6.023 × 1016
to surface tension. So, on adding CH 3 OH in water, overall Now total surface sites available
dielectric constant decreases and surface tension decreases. = 6.023 ×1014 ×1000 = 6.023 ×1017
Inorganic impurities present in bulk of a liquid such as KCl ∴ Surface site used to adsorb
tend to increase the surface tension of water. 20
N2 = × 6.023 × 1017 = 12.04 × 1016
100
11. (c) As per NCERT book (fact).
∴ Sites occupied per molecule of
12. (a, c) Adsorption in an exothermic process and is
12.04 × 1016
accompanied by decrease is entropy, ∆H < 0, ∆S < 0 N2 = =2
sys sys 6.02 ×1016
More is critical temperature (Tc), more are intermolecular
mass
forces of attraction. 22. d = ⇒ 10.5g / cc means in 1cc ⇒ 10.5g
10.5 g of Ag is
V
∴ More is extent of adsorption.
present.
13. (a) Sulphide is –ve charged colloid so cation with 10.5
Number of atoms of Ag in 1 cc ⇒ × NA
maximum charge will be most effective for coagulation. 108
Al3+ > Ba2+ > Na+ coagulating power.
10.5
In 1 cm, number of atoms of Ag = 3 NA
14. (a) DCM and H2O would stay as lower and upper layer 108
2/3
respectively in the S.F.  10.5 
In 1 cm 2 , number of atoms of Ag =  NA 
15. (c)  108 
16. (d) In 10−12 m2 or 10−8 cm 2 , number of atoms of Ag
2/3
Dispersed Phase Dispersion Medium  10.5 
= NA  × 10−8
Cheese Liquid Solid  108 
Milk Liquid Liquid 2/ 3
 1.05 × 6.022 × 1024 
Smoke Solid Gas =  × 10−8 = 1.5 × 107
 108 
17. (b) Chiefly NO2, O3 and hydrocarbon are responsible for
Hence x = 7
build up smog.
Chemical Thermodynamics 107
13 Chemical Thermodynamics
QUICK LOOK additional energy has to be supplied for raising its temperature
by 1°C relative to that required under constant volume
Thermochemistry: “Thermochemistry is a branch of physical conditions, i.e.,
chemistry which is concerned with energy changes Cp > Cv
accompanying chemical transformation. It is also termed as
or Cp = C v + Work done in expansion, P∆V(= R)
chemical energetics. It is based on the first law of
thermodynamics.” where, Cp = molar heat capacity at constant pressure
Cv = molar heat capacity at constant volume.
Enthalpy and Enthalpy Change: Heat content of a system at
constant pressure is called enthalpy denoted by ‘H’. Some Useful Relations between Cp and Cv
From first law of thermodynamics, q = E + PV . . .(i) C p − C v = R = 2 calories = 8.314J
Heat change at constant pressure can be given as
3 3
∆q = ∆E + P∆V . . .(ii) Cv = R (for monoatomic gas) and Cv = + x (for di and
2 2
At constant pressure heat can be replaced with enthalpy. polyatomic gas), where x varies from gas to gas.
∆H = ∆E + P∆V . . .(iii) Cp
∴ ∆H = Heat change or heat of reaction (in chemical process) = γ (Ratio of molar capacities)
Cv
at constant pressure
For monoatomic gas, Cv = 3calories whereas,
∆E = Heat change or heat of reaction at constant volume. (E
Cp=Cv+R=5 calories.
or U Internal Energy)
5
In case of solids and liquids participating in a reaction, R
Cp
∆H = ∆E(P∆V ≈ 0) For monoatomic gas, (γ ) = = 2 = 1.66
Cv 3 R
Difference between ∆H and ∆E is significant when gases are 2
involved in chemical reaction. 7
R
∆H = ∆E + P∆V ⇒ ∆H = ∆E + ∆nRT Cp
For diatomic gas, (γ ) = = 2 = 1.40
P∆V = ∆nRT Cv 5 R
Here, ∆n = n p − n R 2
Cp 8R
For triatomic gas, (γ ) = = = 1.33
Specific and Molar Heat Capacity Cv 6R
Specific Heat (or specific heat capacity) of a substance is the
quantity of heat (in calories, joules, kcal, or kilo joules) Spontaneous Process and Enthalpy Change: A spontaneous
required to raise the temperature of 1g of that substance process is accompanied by decrease in internal energy or
through 1°C. It can be measured at constant pressure (cp) and enthalpy, i.e., work can be obtained by the spontaneous
at constant volume (cv). process. It indicates that only exothermic reactions are
Molar Heat Capacity of a substance is the quantity of heat spontaneous. But the melting of ice and evaporation of water
required to raise the temperature of 1 mole of the substance by are endothermic processes which also proceeds spontaneously.
1°C. It means, there is some other factor in addition to enthalpy
∴ Molar heat capacity = Specific heat capacity × Molecular change (∆H) which explains the spontaneous nature of the
weight, system. This factor is entropy.
i.e., Cv = cv × M and C p = c p × M.
M
Entropy and Entropy Change: Entropy is a thermodynamic
Since gases on heating show considerable tendency towards
state quantity which is a measure of randomness or disorder of
expansion if heated under constant pressure conditions, an
the molecules of the system.

Entropy is represented by the symbol “S”. It is difficult to When T and V are two variables,
define the actual entropy of a system. It is more convenient to T2 V
∆S = nC V ln + nR ln 2 . Assuming C v is constant.
define the change of entropy during a change of state. T1 V1
The entropy change of a system may be defined as the integral
T2 p
of all the terms involving heat exchanged (q) divided by the When T and p are two variables, ∆S = nC P ln − nR ln 2
T1 p1
absolute temperature (T) during each infinitesimally small
change of the process carried out reversibly at constant Assuming Cp , is constant
temperature. (a) Thus, for an isothermal process (T constant),
q V2 p
∆S = Sfinal − Sinitial = rev ∆S = nR ln or = −nR ln 2
T V1 p1
If heat is absorbed, then ∆S = + ve and if heat is evolved, then T2
(b) For isobaric process (p constant), ∆S = n Cp ln
∆S = − ve. T1
Entropy, S is related to thermodynamic probability (W) by
T2
the relation, (c) For isochoric process (V constant), ∆S = n Cv ln
T1
S = k loge W
(d) Entropy change during adiabatic expansion: In such
and S = 2.303k log10 W
process q = 0 at all stages.
where, k is Boltzmann's constant
Hence ∆S = 0. Thus, reversible adiabatic processes are
called isoentropic processes.
Units of Entropy: Since entropy change is expressed by a heat
term divided by temperature, it is expressed in terms of calorie Table 13.1: Criteria for Spontaneity of Reaction
per degree, i.e., cal deg–1 . In SI units, the entropy is expressed ∆H ∆S ∆G Reaction Example
−1 characteristics
in terms of joule per degree Kelvin, i.e., JK .
– + Always Reaction is 2O3 (g) 
→3O2 (g)
Entropy Change during Phase Transition negative spontaneous at
The change of matter from one state (solid, liquid or gas) to all temperatures
another is called phase transition. Such changes occur at + – Always Reaction is non 3O2 (g) 
→ 2O3 (g)
definite temperature such as melting point (solid to liquid). positive spontaneous at
boiling point (liquid to vapours) etc, and are accompanied by all temperatures
absorption or evolution of heat.
When a solid changes into a liquid at its fusion temperature, – – Negative at Reaction is CaO(s) + CO 2 (g)
there is absorption of heat (latent heat). Let ∆Hf be the molar low spontaneous at

→ CaCO3 (s)
temperature but low temperature
heat of fusion. The entropy change will be positive at high but becomes
∆H f temperature non
∆Sf = spontaneous at
Tf
high
Similarly, if the latent heat of vaporisation and sublimation are temperature
denoted by ∆H vap and ∆Hsub , respectively, the entropy of + + Positive at Reaction is non CaCO3 (s) 
→
vaporisation and sublimation are given by low spontaneous at
temperature low temperature CaO(s) + CO 2 (g)
∆H vap ∆H sub
∆Svap = and ∆Ssub = but negative at but becomes
Tb Ts high spontaneous at
temperature high
Since ∆ H f , ∆H vap and ∆HSub are all positive, these processes temperature
are accompanied by increase of entropy and the reverse

Exothermic and Endothermic Reactions
processes are accompanied by decrease in entropy.
Exothermic Reactions: The chemical reactions which proceed
Entropy Change for an Ideal Gas: In going from initial to
with the evolution of heat energy are called exothermic
final state, the entropy change, ∆ S for an ideal gas is given by
reactions. The heat energy produced during the reactions is
the following relations,

indicated by writing +q or more precisely by giving the actual condenses. Hence, physical state always affects the heat of
numerical value on the products side. In general exothermic reaction.
reactions may be represented as, Allotropic forms of the element: Heat energy is also
A + B 
→ C + D + q (heat energy) involved when one allotropic form of an element is
In the exothermic reactions the enthalpy of the products will be converted into another. Thus, the value of ∆H depends on
less than the enthalpy of the reactants, so that the enthalpy the allotropic form used in the reaction. For example, the
change is negative as shown below value of ∆H is different when carbon in the form of
∆H = H p − H r ; H p < H r ; ∆H = − ve diamond or in amorphous form is used.
→ CO 2 (g); ∆H = − 94.3kcal
C (diamond) + O 2 (g) 
Endothermic Reactions: The chemical reactions which → CO 2 (g); ∆H = − 97.6kcal
C (amorphous) + O 2 (g) 
proceed with the absorption of heat energy are called The difference between the two values is equal to the heat
endothermic reactions. Since the heat is added to the reactants absorbed when 12g of diamond is converted into 12g of
in these reactions, the heat absorbed is indicated by either amorphous carbon. This is termed as heat of transition.
putting (–) or by writing the actual numerical value of heat on Temperature: Heat of reaction has been found to depend
the reactant side A + B 
→ C + D − q (heat energy) upon the temperature at which reaction is occurring. The
The heat absorbed at constant temperature and constant variation of the heat of reaction with temperature can be
pressure measures enthalpy change. Because of the absorption ascertained by using Kirchhoff's equation.
of heat, the enthalpy of products will be more than the enthalpy ∆H T2 − ∆H T1
= ∆C P
of the reactants. Consequently, ∆H will be positive (+ ve) for T2 − T1
the endothermic reactions. Kirchhoff's equation at constant volume may be given as,
∆H = H p − H r ; H p > H r ; ∆H = + ve ∆E T2 − ∆E T1
= ∆Cν
T2 − T1
Heat of Reaction or Enthalpy of Reaction: Heat of reaction is
Reaction carried out at constant pressure or constant
defined as the amount of heat evolved or absorbed when volume: When a chemical reaction occurs at constant
quantities of the substances indicated by the chemical equation volume, the heat change is called the internal energy of
have completely reacted. The heat of reaction (or enthalpy of reaction at constant volume. However, most of the reactions
reaction) is actually the difference between the enthalpies of the are carried out at constant pressure; the enthalpy change is
products and the reactants when the quantities of the reactants then termed as the enthalpy of reaction at constant pressure.
indicated by the chemical equation have completely reacted. The difference in the values is negligible when solids and
Mathematically, Enthalpy of reaction (heat of reaction) liquids are involved in a chemical change. But, in reactions
= ∆H = ΣH P − ΣH R which involve gases, the difference in two values is
considerable.
Factors Which Influence the Heat of Reaction: There are a ∆E + ∆nRT = ∆H or q v + ∆nRT = q p
number of factors which affect the magnitude of heat of ∆E = q v = heat change at constant volume;
reaction. ∆H = q p = heat change at constant pressure,
Physical state of reactants and products: Heat energy is
∆n = total number of moles of gaseous product – total
involved for changing the physical state of a chemical
number of moles of gaseous reactants.
substance. For example, in the conversion of water into
steam, heat is absorbed and heat is evolved when steam is
Heat of Reaction: The heat evolved or absorbed in a chemical
condensed. Considering the following two reactions
reaction is measured by carrying out the reaction in an
H 2 (g) + 12 O 2 (g) = H 2 O(g); ∆H = − 57.8kcal apparatus called calorimeter. The principle of measurement is
H 2 (g) + 12 O 2 (g) = H 2 O(l ); ∆H = − 68.32kcal that heat given out is equal to heat taken, i.e.,
It is observed that there is difference in the value of ∆H if Q = (W + m) × s × (T2 − T1 ),
water is obtained in gaseous or liquid state. ∆H value in
Where Q is the heat of the reaction (given out), W is the water
second case is higher because heat is evolved when steam
equivalent of the calorimeter and m is the mass of liquid in the

calorimeter and s its specific heat, T2 is the final temperature Multiple Choice Questions
and T1 the initial temperature of the system. Different types of One and More than One Correct
calorimeters are used but two of the common types are, 1. The direct conversion of A to B is difficult, hence it is carried
(i) Water calorimeter and (ii) Bomb calorimeter. out by the following shown path. Given ∆S(A→ C) = 50 e.u. ,
∆S(C→ D) = 30 e.u. , ∆S(B → D) = 20 e.u. Where e.u. is entropy
Bomb Calorimeter: This is commonly used to find the heat of
combustion of organic substances. unit then ∆S(A → B) is [JEE 2006]
Since the reaction in a bomb calorimeter proceeds at constant C D
volume, the heat of combustion measured is ∆E
(W + m)(t 2 − t1 ) × s
∆E = × M kcal B
w1 A
Where, M is the molecular mass of the substance, w 1 is the a. +100 e.u. b. +60 e.u.
c. –100 e.u. d. –60 e.u.
weight of substance taken, W is the water equivalent of
calorimeter, m is the mass of liquid in the calorimeter and s is 2. When 20 g of naphthoic acid(C11H8O2) is dissolved in 50
the specific heat of liquid. g of benzene (Kf = 1.72K kg mol–1), a freezing point
∆H can be calculated from the relation, ∆H = ∆E + ∆nRT depression of 2 K is observed. The van’t Hoff factor (i) is
Laws of Thermochemistry a. 0.5 b. 1 [JEE 2007 P-I]
Levoisier and Laplace Law: According to this law enthalpy of c. 2 d. 3
decomposition of a compound is numerically equal to the 3. The value of log10 K for a reaction A ⇌ B is
enthalpy of formation of that compound with opposite sign. For (Given ∆ r Go298K = −54.07 kJmol−1 , ∆rSo298K = 10JK−1mol−1 and
example,
R = 8.314JK −1mol−1 ; 2.303 × 8.314 × 298 = 5705)
C(s) + O 2 
→ CO 2 (g); ∆H = − 94.3kcal
a. 5 b. 10 [JEE 2007 P-I]
CO 2 (g) 
→ C(s) + O 2 (g); ∆H = + 94.3kcal c. 95 d. 100
4. For the process H 2 O(l)(1bar,373K) 
→ H 2 O(g)(1bar,
Hess's Law: “If a chemical reaction can be made to take place in a
373K), the correct set of thermodynamic parameters is
number of ways in one or in several steps, the total enthalpy
change (total heat change) is always the same, i.e. the total [JEE 2007 P-II]
a. ∆G = 0, ∆S = +ve b. ∆G = 0, ∆S = –ve
enthalpy change is independent of intermediate steps involved in
c. ∆G = +ve, ∆S = 0 d. ∆G = –ve, ∆S = +ve
the change.” The enthalpy change of a chemical reaction depends
5. Among the following, the state function(s) is(are)
on the initial and final stages only. Let a substance A be changed in a. Internal energy [JEE 2009 P-II]
three steps to D with enthalpy change from A to B, ∆H1 calorie, b. Irreversible expansion work
from B to C , DH 2 calorie and from C to D, DH 3 calorie. Total c. Reversible expansion work
d. Molar enthalpy
enthalpy change from A to D will be equal to the sum of enthalpies
involved in various steps, 6. For the reduction NO 3− ion in an aqueous solution, Eº is+
Total enthalpy change ∆Hsteps = ∆H1 + ∆H 2 + ∆H3 0.96V. Values of Eº for some metal ions are given below
[JEE 2009 P-II]
Now if D is directly converted into A, let the enthalpy change 2+ −
V (aq) + 2e → V E° = −1.19 V
be ∆H direct . According to Hess's law ∆Hsteps + ∆H direct = 0, i.e.
Fe3+ (aq) + 3e − → Fe E° = −0.04 V
∆H steps must be equal to ∆H direct numerically but with opposite
Au 3+ (aq) + 3e − → Au E° = +1.40 V
sign. In case it is not so, say ∆H steps (which is negative) is 2+ −
Hg (aq) + 2e → Hg E° = +0.86 V
more that ∆H direct (which is positive), then in one cycle, some
The pair(s) of metals that is(are) oxidised by 3 NO 3− in
energy will be created which is not possible on the basis of first aqueous solution is(are)
law of thermodynamics. Thus, ∆H steps must be equal to ∆H direct a. V and Hg b. Hg and Fe
numerically. c. Fe and Au d. Fe and V

7. Among the following, the intensive property is (properties a. R(298)ℓn (1.6 × 10 ) − 86600
12
are) [JEE 2010 P-I]

b. 86600 + R(298) ℓn (1.6 × 1012 )
a. molar conductivity b. electromotive force
c. resistance d. heat capacity ℓn (1.6 × 1012 )
c. 86600 −
8. The species which by definition has zero standard molar R(298)
enthalpy of formation at 298 K is [JEE 2010 P-I] d. 0.5[2 × 86600 − R(298) ℓn (1.6 × 1012 )]
a. Br2 (g) b. Cl2 (g)
15. The standard Gibbs energy change at 300 K for the
c. H 2 O(g) d. CH 4 (g)
reaction 2A ↽ ⇀ B + C is 2494.2 J. At a given time, the
9. The freezing point (in ºC)of a solution containing 0.1 g of
K3[Fe(CN)6](Mol. Wt. 329) in 100 g of water (Kf =1.86K composition of the reaction mixture is [A] = 12 , [B] = 2 and
kg mol–1) is [JEE 2011 P-II] [C] = 12 . The reaction proceeds in the: [R = 8.314 J/K/mol,
a. −2.3 × 10−2 b. −5.7 × 10−2 e = 2.718] [JEE Main 2015]
−3 −2
c. −5.7 × 10 d. −1.2 × 10 a. forward direction because Q>Kc
10. Using the data provided, calculate the multiple bond b. reverse direction because Q>Kc
energy (kJmol −1 ) of C ≡ C bond in C2 H 2 . That energy is c. forward direction because Q<Kc
d. reverse direction because Q<Kc
(take the bond energy of a C − H bond as 350 kJ mol −1 )
16. At 300 K and 1 atm, 15 mL of a gaseous hydrocarbon
2C(s)
2C(s)H → C 2 H 2 (g) ∆ H = 225 kJ mol −1
+ 2 (g) 
requires 375 mL air containing 20% O 2 by volume for
→ 2C(g) ∆H = 1410 kJ mol −1
2C(s)  [JEE 2012 P-II]
complete combustion. After combustion the gases occupy
−1
→ 2H(g) ∆ H = 330 kJ mol
H 2 (g)  330 mL. Assuming that the water formed is in liquid form
a. 1165 b. 837 c. 865 d. 815 and the volumes were measured at the same temperature
11. Methylene blue, from its aqueous solution, is adsorbed on and pressure, the formula of the hydrocarbon is:
activated charcoal at 25ºC. For this process, the correct [JEE Main 2016]
statement is [JEE Adv. 2013 P-I] a. C3 H 6 b. C3 H8
a. The adsorption requires activation at 25ºC
c. C 4 H8 d. C4 H10
b. The adsorption is accompanied by a decrease in enthalpy
c. The adsorption increases with increase of temperature 17. The heats of combustion of carbon and carbon monoxide
d. The adsorption is irreversible are –393.5 and –283.5 kJ mol –1 , respectively. The heat of
12. The standard enthalpies of formation of CO2 (g), H 2 O(l) and formation (in kJ) of carbon monoxide per mole is :
glucose(s) at 25º C are – 400 kJ/mol, –300 kJ/mol and –1300 [JEE Main 2016]
kJ/mol, respectively. The standard enthalpy of combustion a. 110.5 b. 676.5 c. –676.5 d. –110.5
per gram of glucose at 25°C is [JEE Adv. 2013 P-I] 18. One mole of an ideal gas at 300 K in thermal contact with
a. + 2900 kJ b. – 2900 kJ surroundings expands isothermally from 1.0 L to 2.0 L
c. – 16.11 kJ d. +16.11 kJ against a constant pressure of 3.0 atm. In this process, the
13. Benzene and naphthalene form an ideal solution at room change in entropy of surroundings [JEE Adv. 2016 P-I]
temperature. For this process, the true statement(s) is(are) ( ∆ S surr ) in JK −1 is : (1 L atm = 101.3 J)
[JEE Adv. 2013 P-I] a. 5.763 b. 1.013 c. –1.013 d. –5.763
a. ∆G is positive b. ∆Ssystem is positive
19. ∆U is equal to [JEE Main 2017]
c. ∆Ssurroundings = 0 d. ∆H = 0
a. Isothermal work b. Isochoric work
14. The following reaction is performed at 298 K. c. Isobaric work d. Adiabatic work
2NO(g) + O2 (g) ↽ ⇀ 2NO2 (g) 20. Given C(graphite) + O2 (g) 
→ CO2 (g); ∆r H° = −393.5kJ mol−1
The standard free energy of formation of NO(g) is 86.6 → H 2 O (ℓ ); ∆ r H ° = − 285.8 kJ mol −1
H 2 (g) + 12 O 2 (g) 
kJ/mol at 298 K. What is the standard free energy of
CO2 (g) + 2H 2 O(ℓ) 
→ CH 4 (g) + 2O 2 (g); ∆ r H° = +
formation of NO2(g) at 298 K? (Kp = 1.6 × 1012)
[JEE Main 2015] 890.3 kJ mol −1

Based on the above thermochemical equations, the value
a. 1 b. Water
of D f H ∞ at 298 K for the reaction C (graphite) + Water
Ice
V.P./bar
V.P./bar
1
→ CH 4 (g) will be
2H 2 (g)  Ice Water + Ethanol
a. –144.0 kJ mol–1 b. +74.8 kJ mol–1 Water + Ethanol

270 273 271 273
c. +144.0 kJ mol–1 d. –74.8 kJ mol–1 T/K T/K
21. An ideal gas is expanded from ( p1 , V1 , T1 ) to ( p 2 , V2 , T2 ) c. Water d. 1

Water
Ice
under different conditions. The correct statements among
V.P./bar
V.P./bar
1
the following is(are) [JEE Adv. 2017 P-I] Ice Water +
Ethanol Water + Ethanol
a. If the expansion is carried out freely, it is simultane-
270 273 271 273
ously both isothermal as well as adiabatic T/K T/K
b. The work done by the gas is less when it is expanded
reversibly from V1 to V2 under adiabatic conditions as 24. For a reaction taking place in a container in equilibrium
compared to that when expanded reversibly from V1 to with its surroundings, the effect of temperature on its
V2 under isothermal conditions equilibrium constant K in terms of change in entropy is
c. The work done on the gas is maximum when it is described by [JEE Adv. 2017 P-II]
compressed irreversibly from ( p2 , V2 ) to ( p1 , V1 ) a. With increase in temperature, the value of K for
exothermic reaction decreases because favourable change
against constant pressure p1
in entropy of the surroundings decreases
d. The change in internal energy of the gas is (i) zero, if it
b. With increase in temperature, the value of K for
is expanded reversibly with T1 = T2 , and (ii) positive, if
exothermic, reaction decreases because the entropy
it is expanded reversibly under adiabatic conditions change of the system is positive
with T1 ≠ T2 c. With increase in temperature, the value of K for
22. The standard state Gibbs free energies of formation of C endothermic reaction increases because the entropy
change of the system is negative
(graphite) and C (diamond) at T = 298K are ∆ f G 0 [C
d. With increase in temperature, the value of K for
(graphite)] = 0 kJ mol–1 ∆ f G 0 [C(diamond)] =2.9 kJ mol–1. endothermic reaction increases because unfavourable
The standard state means that the pressure should be 1 bar, change in entropy of the surroundings decreases
and substance should be pure at a given temperature. The 25. Which of the following lines correctly show the
conversion of graphite [C(graphite)] to diamond temperature dependence of equilibrium constant K, for an
[C(diamond)] reduces its volume by 2×10 m mol–1. If C
–6 3 exothermic reaction? [JEE Main 2018]
In K A
(graphite) is converted to C(diamond) isothermally at T= B
1
298 K, the pressure at which C (graphite) is in equilibrium (0,0) T(K)
with C(diamond), is [Useful information: 1 J = 1 kg m2 s–2;
C
1 Pa=1 kgm–1s–2; 1 bar=105Pa] [JEE Adv. 2017 P-II]
D
a. 14501 bar b. 29001 bar
c. 1450 bar d. 58001 bar a. A and D b. A and B
23. Pure water freezes at 273 K and 1 bar. The addition of c. B and C d. C and D
34.5 g of ethanol to 500 g of water changes the freezing 26. The combustion of benzene (l) gives CO2 (g) and H2O (l).
point of the solution. Use the freezing point depression Given that heat of combustion of benzene at constant
constant of water as 2 K kg mol–1. The figures shown volume is –3263.9 kJ mol–1 at 25°C; heat of combustion
below represent plots of vapour pressure (V.P.) versus (in kJ mol–1) of benzene at constant pressure will be
temperature (T). [molecular weight of ethanol is 46 g mol–1] (R = 8314JK–1 mol–1) [JEE Main 2019]
Among the following, the option representing change in a. – 3267.6 b. 4152.6
the freezing point is [JEE Adv. 2017 P-II] c. – 452.46 d. 3260

27. Which one of the following equations does not correctly 33. The entropy change associated with the conversion of
represent the first law of thermodynamics for the given 1 kg of ice at 273 K to water vapours at 383 K is:
processes involving an ideal gas? (Assume non-expansion (Specific heat of water liquid and water vapour are 4.2 kJ
work is zero) [JEE Main 2019] K–1 kg–1 and 2.0 kJ K–1 kg–1 ; heat of liquid fusion and
a. Cyclic process : q = – w vapourisation of water are 344 kJ kg–1 and 2491 kJ kg–1,
b. Isothermal process : q = – w respectively) [JEE Main 2019]
c. Adiabatic process : ∆U = – w (log 273 = 2.436, log 373 = 2.572, log 383 = 2.583)
d. Isochoric process : ∆U = q a. 7.90 kJ kg–1 K–1 b. 2.64 kJ kg–1 K–1
c. 8.49 kJ kg–1 K–1 d. 4.26 kJ kg–1 K–1
28. The correct order of hydration enthalpies of alkali metal ions
is - [JEE Main 2019] 34. A solution containing 62 g ethylene glycol in 250 g water
a. Li+ > Na+ > K+ > Rb+ > Cs+ is cooled to –10°C. If Kf for water is 1.86 K kg mol 1, the
b. Li+ > Na+ > K+ > Cs+ > Rb+ amount of water (in g) separated as ice is:
c. Na+ > Li+ > K+ > Rb+ > Cs+ [JEE Main 2019]
d. Na+ > Li+ > K+ > Cs+ > Rb+ a. 32 b. 48
c. 16 d. 64
29. For silver, Cp(JK–1 mol–1) = 23 + 0.01T. If the
temperature (T) of 3 moles of silver is raised from 300K 35. When the first electron gain enthalpy (∆egH) of oxygen is
to 1000 K at 1 atm pressure, the value of DH will be close –141 kJ/mol, its second electron gain enthalpy is:
to [JEE Main 2019] [JEE Main 2019]
a. 21 kJ b. 16 kJ c. 13 kJ d. 62 kJ a. almost the same as that of the first
b. negative, but less negative than the first
30. 5 moles of an ideal gas at 100 K are allowed to undergo
c. a positive value
reversible compression till its temperature becomes 200
d. a more negative value than the first
K. If CV = 28 JK–1mol–1, calculate ∆U and ∆pV for this
process. (R = 8.0 JK–1 mol–1] [JEE Main 2019] 36. A process has ∆H = 200 Jmol–1 and ∆S = 40 JK–1mol–1.
Out of the values given below, choose the minimum
a. ∆U = 14 kJ; ∆ (pV) = 4 kJ
temperature above which the process will be spontaneous:
b. ∆U = 14 kJ; ∆(pV) = 18 kJ
[JEE Main 2019]
c. ∆U = 2.8 kJ; ∆(pV) = 0.8 kJ
a. 5 K b. 4 K
d. ∆U = 14 kJ; ∆(pV) = 0.8 kJ c. 20 K d. 12 K
31. Consider the reversible isothermal expansion of an ideal 37. An ideal gas undergoes isothermal compression from 5 m3
gas in a closed system at two different temperatures T1 against a constant external pressure of 4 Nm–2. Heat
and T2 (T1 < T2). The correct graphical depiction of the released in this process is used to increase the temperature
dependence of work done (w) on the final volume (V) is: of 1 mole of Al. If molar heat capacity of Al is 24 J mol–1
[JEE Main 2019] K–1, the temperature of Al increases by: [JEE Main 2019]
T2 T2 3 2
|W| T1 |W| T1 a. K b. K
2 3
a. b. c. 1 K d. 2 K
O O 38. The process with negative entropy change is:
In V In V
a. Dissolution of iodine in water [JEE Main 2019]
T2
|W| |W| T2 b. Synthesis of ammonia from N2 and H2
T1 T1 c. Dissolution of CaSO4(s) to CaO(s) and SO3(g)
c. d. d. Sublimation of dry ice
O O 39. Twp blocks of the same metal having same mass and at
In V In V
temperature T1 and T2, respectively are brought in contact
32. The transition element that has lowest enthalpy of with each other and allowed to attain thermal equilibrium
atomisation, is: [JEE Main 2019] at constant pressure. The change in entropy, ∆S, for this
a. Zn b. Cu c. V d. Fc process is: [JEE Main 2019]

T +T   (T + T ) 1/ 2
 Based on the above thermochemical equations, find out
a. 2CP ln  1 2  b. 2CP ln  1 2  which one of the following algebraic relationships is
 4T1T2   T1T2 
correct ? [JEE Main 2019]
 (T + T )2   T + T2  a. z = x + y b. x = y – z
c. 2CP ln  1 2  d. 2CP ln  1 
 4T1T2   2T1T2  c. x = y + z d. y = 2z – x
40. For the chemical reaction X ↽ ⇀ Y , the standard 45. An open vessel at 27°C is heated until two fifth of the air
(assumed as an ideal gas) in it has escaped from the
reaction Gibbs energy depends on temperature T (in K) as:
vessel. Assuming that the volume of the vessel remains
3
∆ r Gº (in kJ mol –1 ) = 120 – T constant, the temperature at which the vessel has been
8
heated is: [JEE Main 2019]
The major component of the reaction mixture at T is:
a. 750°C b. 500°C
[JEE Main 2019]
c. 750 K d. 500 K
a. X if T = 315 K b. X if T = 350 K
c. Y if T = 300 K d. Y if T = 280 K 46. Choose the reaction, for which the standard enthalpy of
reaction is equal to standard enthalpy of formation:
41. The reaction, MgO(s) + C(s) 
→ Mg(s) + CO(g), for
a. 2C(g) + 3H2(g) 
→ C2H6 (g) [JEE Adv. 2019 P-I]
which ∆ r Hº = + 491.1 kJ mol–1 and ∆r Sº = 198.0 JK–1
3
mol–1, is not feasible at 298 K. Temperature above which b. O2(g)  → O3(g)
2
reaction will be feasible is :- [JEE Main 2019] 1
a. 1890.0 K b. 2480.3 K c. S8(s) + O2(g)  → SO2(g)
8
c. 2040.5 K d. 2380.5 K
d. 2H2(g) + O2(g) 
→ 2H2O( ℓ )
42. The standard reaction Gibbs energy for a chemical
reaction at an absolute temperature T is given by
Matrix Match / Column Match
∆ r Gº = A – Bt
47. Match the transformations in column I with appropriate
Where A and B are non-zero constants. Which of the
options in column II [JEE 2011 P-II]
following is TRUE about this reaction? [JEE Main 2019]
Column I Column II
a. Exothermic if B < 0
b. Exothermic if A > 0 and B < 0 (A) CO 2 (s) → CO 2 (g) 1. phase transition
c. Endothermic if A < 0 and B > 0 (B) CaCO3 (s) → CaO(s) + CO2 (g) 2. allotropic change
d. Endothermic if A > 0 (C) 2H⋅ → H 2 (g) 3. ∆H is positive
43. For diatomic ideal gas in a closed system, which of the following (D) M P(white, solid) → P(red, solid) 4. ∆Sis positive
plots does not correctly describe the relation between various
5. ∆S is negative
thermodynamic quantities? [JEE Main 2019]
a. A → 1,3,4; B → 3,4; C → 5; D → 1,2,5
CP b. A → 1,3,2; B → 3,2; C → 5; D → 1,2,5
a. Cv b.
c. A → 1,3,4; B → 3,4; C → 4; D → 1,2,5
T P d. A → 1,3,5; B → 3,4; C → 1; D → 1,2,5
48. Match the thermodynamic processes given under Column
Cv
c. d. U I with the expression given under Column II:
[JEE Adv. 2015 P-I]
V T Column I Column II
44. Given: (A) Freezing of water at 273 1. q = 0
(i) C(graphite) + O2 (g) 
→ CO2 (g); ∆ r H° = x kJ mol.–1 K and 1 atm
1 (B) Expansion of 1 mol of an 2. w = 0
(ii) C(graphite)+ O2 (g) 
→ CO2 (g); ∆ r H° = y kJ mol.–1
2 ideal gas into a vacuum
1 under isolated conditions
(iii) CO(g)+ O 2 (g) 
→ CO 2 (g); ∆ r H° = z kJ mol.–1
2

(C) Mixing of equal volumes 3. ∆Ssys < 0 +
Ag + e  −
→ Ag; E o
red = 0.8V
of two ideal gases at
C6 H12O6 + H 2O 
→ Gluconic acid
constant temperature and
pressure in an isolated (C6 H12 O7 ) + 2H + + 2e − ; E ooxd = −0.05V
container Ag(NH3 )+2 + e 
→ Ag(s) + 2NH3 ;E ooxd = 0.337V
(D) Reversible heating of 4. ∆U = 0 RT F
H 2 (g) at 1 atm from [Use 2.303 × = 0.0592 and = 38.92 at 298K
F RT
300 K to 600 K, followed
by reversible cooling to 51. 2Ag − + C6 H12O6 + H 2O 
→ 2Ag(s) + C6 H12O7 + 2H +
300 K at 1 atm Find ln K of this reaction.
5. ∆G = 0 a. 66.13 b. 58.38
a. A →1,5; B → 1,3,4; C→1,2,4; D→ 1,2,4,5 c. 28.30 d. 46.29
b. A →3,5; B →1,2,4; C →1,2,4; D →1,2,4,5 52. When ammonia is added to the solution, pH is raised to
c. A→ 1,5; B →1,5,4; C →1,3,4; D →1,2,4,5 11. Which half-cell reaction is affected by pH and by how
d. A→ 1,5; B →1,2,4; C →1,2,5; D →1,2,4,3 much?
a. E oxd will increase by a factor of 0.65 from E ooxd
Statement/Assertion and Reason
b. E oxd will decrease by a factor of 0.65 from E ooxd
49. Statement-I: For every chemical reaction at equilibrium,
standard Gibbs energy of reaction is zero. And c. Ered will increase by a factor of 0.65 from Eored
Statement-II: At constant temperature and pressure, d. Ered will decrease by a factor of 0.65 from Eored
chemical reactions are spontaneous in the direction of
decreasing Gibbs energy. [JEE 2008 P-I] 53. Ammonia is always added in this reaction. Which of the
a. Statement-I is True, Statement-II is True; Statement-II following must be incorrect?
is correct explanation for Statement-I a. NH 3 combines with Ag + to form a complex
b. Statement-I is True, statement-II is True; statement-II is
b. Ag(NH3 )2+ is a stronger oxidising reagent than Ag +
not a correct explanation for statement-I
c. In absence of NH3 silver salt of gluconic acid is formed
c. Statement-I is True, statement-II is False
d. Statement-I is False, statement-II is True d. NH 3 has affected the standard reduction potential of
glucose/gluconic acid electrode
50. Statement-I: There is a natural asymmetry between
converting work to heat and converting heat to work. And Paragraph for Question Nos. 54 to 56
Statement-II: No process is possible in which the sole
Redox reactions play a pivotal role in chemistry and biology.
result is the absorption of heat from a reservoir and its
The values of standard redox potential (Eº) of two half-cell
complete conversion into work. [JEE 2008 P-II]
reactions decide which way the reaction is expected to proceed.
a. Statement-I is True, Statement-II is True; Statement-II
A simple example is a Daniel cell in which zinc goes into
is correct explanation for Statement-I
solution and copper gets deposited. Given below are a set of
b. Statement-I is True, statement-II is True; statement-II is
half-cell reactions (acidic medium) along with their Eº (V with
respect to normal hydrogen electrode) values.
c. Statement-I is True, statement-II is False
d. Statement-I is False, statement-II is True [JEE 2007 P-II]
− −
I 2 + 2e 
→ 2I E° = 0.54
Paragraph Cl 2 + 2e − 
→ 2Cl − E° = 1.36
3+ − 2+
Paragraph for Question Nos. 51 to 53 Mn + e 
→ Mn E ° = 1.50
Tollen’s reagent is used for the detection of aldehyde when a Fe3+ + e − 
→ Fe 2+ E ° = 0.77
solution of AgNO3 is added to glucose with NH4OH then
O 2 + 4H + + 4e − 
→ 2H 2 O E ° = 1.23
gluconic acid is formed [JEE 2006]

54. Among the following, identify the correct statement. 59. The succeeding operations that enable this transformation
a. Chloride ion is oxidised by O2 of states are
b. Fe 2+ is oxidised by iodine a. Heating, cooling, heating, cooling
c. Iodide ion is oxidised by chlorine b. Cooling, heating, cooling, heating
c. Heating, cooling, cooling, heating
d. Mn 2+ is oxidised by chlorine
d. Cooling, heating, heating, cooling
55. While Fe3+ is stable, Mn 3+ is not stable in acid solution 60. The pair of isochoric processes among the transformation
because of states is
a. O2 oxidises Mn 2+ to Mn 3+ a. K to L and L to M b. L to M and N to K
b. O2 oxidises both Mn 2+ and Fe2+ to Fe3+ c. L to M and M to N d. M to N and N to K
c. Fe3+ oxidises H 2O to O2
d. Mn 3+ oxidises H 2 O to O2
Thermal decomposition of gaseous X 2 to gaseous X at 298 K
56. Sodium fusion extract, obtained from aniline, on treatment takes place according to the following equation:
with iron (II) sulphate and H2SO4 in presence of air gives
X 2 (g) ↽ ⇀ 2X(g) . The standard reaction Gibbs energy,
a Prussian blue precipitate. The blue colour is due to the
formation of ∆r G° of this reaction is positive. At the start of the reaction,
a. Fe 4 [ Fe(CN)6 ]3 b. Fe3 [ Fe(CN)6 ]2 there is one mole of X 2 and no X. As the reaction proceeds, the
c. Fe 4 [ Fe(CN)6 ]2 d. Fe3 [ Fe(CN)6 ]3 number of moles of X formed is given by β . Thus βequilibrium is
the number of moles of X formed at equilibrium. The reaction
Paragraph for Question Nos. 57 to 58 is carried out at a constant total pressure of 2 bar. Consider the
The electrochemical cell shown below is a concentration cell. gases to behave ideally. (Given: R = 0.083 L bar K −1 mol−1 )
M|M2+(saturated solution of sparingly soluble salt, (MX2) ||M2+
(0.001 mol dm–3)|M. The emf of the cell depends on the
61. The equilibrium constant K p for this reaction at 298 K, in
difference in concentration of M 2 + ions at the two electrodes.
terms of βequilibrium , is
The emf of the cell at 298 K is 0.059 V. [JEE 2012 P-II]
8β equilibrium
2
8β equilibrium
2
57. The value of ∆G (kJ mol −1 ) for the given cell is (take 1 F a. b.
2
= 96500 C mol−1 )
4 β equilibrium
2
4 β equilibrium
2
a. –5.7 b. 5.7 c. 11.4 d. –11.4 c. d.

2
3 −9
58. The solubility product (K sp ; mol dm ) of MX2 at 298 K
based on the information available for the given
reaction, is [JEE Adv. 2019 P-I]
concentration cell is (take 2.303 × R × 298 / F = 0.059 V)
a. Decrease in the total pressure will result in formation of
a. 1×10−15 b. 4 × 10−15 more moles of gaseous X
c. 1×10−12 d. 4 × 10−12 b. At the start of the reaction, dissociation of gaseous X 2
takes place spontaneously
A fixed mass ‘m’ of a gas is subjected to transformation of c. βequlibrium = 0.7
states from K to L to M to N and back to K as shown in the d. K C < 1
figure [JEE Adv. 2013 P-II]
K L
63. (i) Calculate ∆G 0r of the following reaction
Pressure
Ag + (aq) + Cl − (aq) 
→ AgCl(s)
N M Given ∆G of (AgCl) −109 KJ / mol
Volume
∆G of (Cl− ) −129 KJ / mol

+
∆G (Ag )
o
f 77 KJ / mol (Given: total pressure = 1 bar, R (universal gas constant) =
Represent the above reaction in form of a cell. Calculate 8 J K–1 mol–1, ln(10) = 2.3. Cu(s) and Cu2O(s) are
Eº of the cell. Find log10 K sp of AgCl. mutually immiscible.
1
(ii) 6.539 × 10 −2 g of metallic Zn (amu = 65.39) was added At 1250 K: 2Cu(s) + O2 (g) → Cu 2 O(s);
2
to 100 ml of saturated solution of AgCl. Calculate
1
[Zn 2+ ] ∆G Θ = −78,000 J mol−1 H 2 (g) + O2 (g);
log10 . Given that [JEE 2005] 2
[Ag + ]2
∆G Θ = −1, 78, 000 J mol −1 ;
+ −
Ag + e 
→ Ag E° = 0.80 V
G is the Gibbs energy) [JEE Adv. 2018 P-II]
2+ −
Zn + 2e 
→ Zn E° = −0.76 V
Also find how many moles of Ag will be formed? ANSWERS and SOLUTIONS
1. (b) ∆S(A→ B) = ∆S(A → C) + ∆S(C→ D) − ∆S(B→ D) = 50 + 30 − 20
64. 75.2 g of C6 H 5OH (phenol) is dissolved in a solvent of
K f = 14. If the depression in freezing point is 7 K then 2. (a) ∆Tf = K f × molality × i
find the % of phenol that dimerises. [JEE 2006] 20 1000
2 = 1.72 × × ×i
→ 2CO 2 ; ∆H = −560 kJ.
65. For the reaction, 2CO + O 2  172 50
⇒ i = 0.5
Two moles of CO and one mole of O2 are taken in a
Hence (a) is correct.
container of volume 1 L. They completely form two moles
of CO2, the gases deviate appreciably from ideal 3. (b) ∆G ° = ∆H° − T∆S° = −54.07 × 1000 − 298 × 10
behaviour. If the pressure in the vessel changes from 70 to = −57050 J mol−1 − 57050 = −5705log10 K
40 atm, find the magnitude (absolute value) of ∆U at 500
log10 K = 10
K (1 L atm = 0.1 kJ) [JEE 2006]
66. In a constant volume calorimeter, 3.5 g of a gas with
molecular weight 28 was burnt in excess oxygen at 298.0 4. (a) H 2 O (ℓ) ↽ ⇀ H 2 O (g)
(1 bar, 373 K) (1 bar, 373 K)
K. The temperature of the calorimeter was found to
increase from 298.0 K to 298.45 K due to the combustion At 100°C . H 2O(ℓ) has equilibrium with H 2O(g) therefore,
process. Given that the heat capacity of the calorimeter is ∆G = 0
2.5kJ K–1, the numerical value for the enthalpy of Because liquid molecules are converting into gaseous
combustion of the gas in kJmol−1 is___. [JEE 2009 P-II] molecules therefore, ∆S = + ve
67. All the energy released from the reaction X→Y. ∆rG00 =
5. (a, b)
–193 kJ mol–1 is used for oxidizing M+ as M+→M3++2e–,
E0 = – 0.25V. Under standard conditions, the number of 6. (a, b, d) E° NO− (aq) = 0.96 V
3
moles of M+ oxidized when one mole of X is converted to

(SRP )
Y is________ [F=96500 C mol–1] [JEE Adv. 2015 P-I] All V, Fe Hg have less SRP w.r.t. NO 3− .
68. The surface of copper gets tarnished by the formation of So, V, Fe, Hg can be oxidized by NO 3− in aqueous solution.
copper oxide. N2 gas was passed to prevent the oxide
7. (a, b) Resistance and heat capacity are mass dependent
formation during heating of copper at 1250 K. However,
properties, hence extensive.
the N2 gas contains 1 mole % of water vapour as impurity.
8. (b) Cl2 is gas at 298 K while Br2 is a liquid.
The water vapour oxidises copper as per the reaction
given below: 9. → 3K + + [Fe(CN)6 ]3−
(a) K 3 [Fe(CN) 6 ] 
2Cu(s) + H 2 O(g) → Cu 2 O(s) + H 2 (g)
i=4
p H2 is the minimum partial pressure of H2 (in bar) needed
m 1000 0.1 1000
∆Tf = Kf × i × × = 1.86 × 4 × × = 2.3×10−2
to prevent the oxidation at 1250 K. The value of ln (p H2 ) M W 329 100
is ________. Tf′ = −2.3 × 10−2

10. (d) 2C(s) + H 2 (g) 
→ C 2 H 2 (g) (H − C ≡ C − H)  y y
C x H y (g) +  x +  O 2 (g) 
→ xCO 2 (g) + H 2 O(ℓ)
⇒ B ⋅ E(H 2 ) + ∆HSub (C) − B ⋅ E(C − H) × 2 + B ⋅ E(C ≡ C) = ∆H rxn  4  2
⇒ 330 + 1410 − [350 × 2 + x] = 225 15 ml 75 ml 30 ml
⇒ x = 815 x 30
=
1 15
11. (b) Adsorption of methylene blue on activated charcoal is
⇒ x=2
physical adsorption hence it is characterised by decrease
y
in enthalpy. Hence (b) is correct. x+
⇒ 4 = 75
12. (c) Combustion of glucose 1 15
C6 H12 O 6 + 6O 2 
→ 6CO 2 + 6H 2 O y
⇒ x+ =5
∆H combustion = (6 × ∆H f CO 2 + 6 × ∆H f H 2 O) − ∆H f C 6 H12 O 6 4
⇒ y = 12
= (6 × −400 + 6 × −300) − (−1300)
⇒ C 2 H12
= −2900 kJ / mol
Confirmed: Such compound is impossible and also not in
= −2900 /180 kJ / g option. So it should be bonus. However, if we seriously
= −16.11 kJ / g wish to give an answer then by looking at options, we can
Hence (c) is correct. see that only C3H8 is able to consume 75 ml O2. So (1) can
also be given as answer.
13. (b, c, d) For ideal solution, ∆Ssystem > 0
17. (d) C(s) + O 2 (g) 
→ CO 2 (g) ; ∆ H = −393.5kJ / mol.
∆Ssurrounding = 0
1
∆H mixing = 0 CO(g) + O 2 (g) 
→ CO 2 (g) ; ∆ H = −283.5kJ / mol.
2
14. (d) ∆G Rx n = 2∆G NO2 − 2∆G NO 1
C(s) + O 2 (g) 
→ CO(g) ;
∆G NO2 = ∆G NO + ∆G Rx
1
2
2
∆H = −393.5 + 283.5 kJ / mol = −110 kJ / mol
= ∆G NO + 12 (− RT ln e K p )
= 0.5[2 × 86600 − R(298) ℓn (1.6 × 1012 )] qSurr q sys Wsys
18. (c) ∆SSurr = =− =
T T T
15. (b) ∆G = −RT ln e K c (∵ Isothermal process ⇒ ∆U = 0)
2494.2 = 8.314 × 300 ln e K c ⇒ K c = e−1 − Pext (Vf − Vi ) −3(2 − 1)
∆SSurr = = ×101.3
1 T 300
K c = e −1 = = 0.36
2.718 = −1.013 J / K
(B)(C) 2× 1
Q= = =4
2
19. (d) From 1st law : ∆U = q + w
[A]2 [1/ 2]2
For adiabatic process: q = 0
Q > K c , i.e. backward reaction.
∴ ∆U = w
16. (b) ∴ Work involved in adiabatic process is at the expense of
 y y change in internal energy of the system.
C x H y (g) +  x +  O 2 (g) 
→ xCO 2 (g) + H 2 O(ℓ)
 4 2
20. (d) CO2 (g) + 2H 2O(ℓ) 
→ CH 4 (g) + 2O2 (g);
15 ml, Volume of O2 used
∆ r H° = 890.3
20
= × 375 = 75ml
75ml. ∆ r H° − 393.5 − 285.8 ? 0
100
Volume of air remaining = 300 ml ∆ r H ° = ∑ ( ∆ r H °) products − ∑ ( ∆ r H °) Reactants 0
Total volume of gas left after combustion = 330 ml 890.3 = [1 × ( ∆ f H °) CH 4 + 2 × 0] − [1 × ( − 395.5) + 2( −285.8)]
Volume of CO2 gases after combustion
( ∆ f H °) CH 4 = 890.3 − 965.1 = − 74.8 kJ / mol
= 330 – 300 = 30 ml.

21. (a, b, c) q = 0 therefore, slope = +ve
∴ process is adiabatic w = 0 In K A
Isothermal P1 B 1
P (0,0) T(K)
P2
Hence, option (b) is correct.

V1 V2
V
15
26. (a) C 6 H 6 (ℓ ) + O 2 (g) 
→ 6CO 2 (g) + 3H 2 O( ℓ )
⇒ ∆E = 0 2
∴ Process is isothermal 15 3
∆n g = 6 − =−
Area under the curve in P-V diagram for adiabatic process 2 2
is smaller than that of isothermal process. Shaded area for ∆H = ∆U + ng RT
any process ≤ P1 (V2 − V1 ).  3
= −3263.9 +  −  × 8.314 × 298 × 100 −3
 2
22. (a) ∆G ° = ∆V ⋅ ∆P
= −3263.9 + (−3.71)
⇒ 2900 = 2 × 10 −6 ∆P
= − 3267.6 kJ mol −1
2900 × 106
⇒ ∆P = Pa
2 27. (c) For cyclic process : ∆ = 0 ⇒ q = – w
PF − 1 = 14500 bar For isothermal process : ∆U = 0 ⇒ q = – w
⇒ PF = 14501bar For adiabatic process : q = 0 ⇒∆U = W
 W × 1000  For isochoric process : w = 0 ⇒ ∆U = q
23. (c) ∆Tf = iK f  2 
 M 2 × W1  28. (a) Hydration enthalpy depends upon ionic potential
 34.5 × 1000  (charge/size). As ionic potential increases, hydration
= 1× 2  = 3K
 46 × 500  enthalpy increases.
273(K) − Tf = 3(K) T2 1000
29. (d) ∆H = n Cp.m dT = 3 × (23 + 0.01T) dT

⇒ Tf = 270K
T1 300
Also, with decrease in temperature, V.P. decreases.
0.01
∴ Graph (C) is correct. = 3[23(1000 − 300) + (10002 − 3002 )]
2
24. (a, b, d) Whether reaction is endothermic or exothermic in = 61950J≈ 62 kJ
forward direction increase in temperature cause intake of
30. (a) n = 5; Ti = 100 K; Tf = 200 K;
heat from surrounding to system in endothermic direction CV = 28 J/mol K; Ideal gas
due to which entropy change in system is positive and ∆ S ∆U = nCV∆T
of surrounding is negative. = 5 mol × 28 J/mol
∆H °
K × (200 – 100) K
A  −
25. (b) Equilibrium constant K =  f  e RT = 14,000 J = 14 kJ
 Ab  ⇒ Cp = Cv + R
 A  ∆H°  1  = (28 + 8) J/mol K
In K = In  f  −  
 Ab  R  T  = 36 J/mol K
Y=C+m x ⇒ ∆H = nCp∆T = 5 mol × 36 J/mol K × 100 K
Comparing with equation of straight line, = 18000 J = 18 kJ
−∆ H ° ∆H = ∆U + ∆ (PV)
Slope =
R
⇒ ∆ (PV) = ∆H –∆U
since, reaction is exothermic ∆H° = –ve, = (18 – 14) kJ = 4 kJ

V2 ∆U = 0
31. (b) w = − nRT ln
V1 q = –w
Vb = –16 Nm = – 16 J
w = − nRT ln Heat used to increase temperature of A ℓ
Vi
q = n Cm DT
Vb
| w |= nRT ln J
Vi 16 J = 1 × 24 × ∆T
mol.K
| w |= nRT(ln Vb − ln Vi ) 2
∆T = K
| w |= nRT ln Vb − n RT ln Vi 3
Y = mx−C 38. (b) N 2 (g) + 3H 2 (g) ↽ ⇀ 2NH 3 (g) ; ∆n g < 0
So, slope of curve 2 is more than curve 1 and intercept of 39. (c)
curve 2 is more negative than the curve 1.
40. (a)
32. (b) Since Zn is not a transition element so transition element
∆H 491.1×1000
having lowest atomisation energy out of Cu,V, Fe is Cu. 41. (b) Teq = = = 2480.3 K
∆S 198
H 2 O(s) →
∆S1
H 2 O(ℓ) 
∆S2
→ H 2 O(ℓ)
33. (d) 42. (d)
273K 273K 373K
→ H 2 O(g)  → H 2 O(g) 43. (b) At higher temperature, rotational degree of freedom
∆S3 ∆S4
373K 383K becomes active.
∆Hfusion 334 7
CP = R = (Independent of P)
∆S1 = = = 1.22 3
273 273
7
 363  CV = R = (Independent of V)
∆S2 = 4.2ℓN   = 1.31 3
 273  Variation of U vs. T is similar as CV vs. T.
∆H vap 2491
∆S3 = = = 6.67 → CO2 (g) ∆r H° = x kJ /mol.–1 . . .(i)
44. (c) C(graphite) + O2 (g) 
373 373
 383  1
∆S4 = 2.0ℓn  → CO2 (g); ∆ r H° = y kJ /mol.–1 . . .(ii)
C(graphite) + O2 (g) 
 = 0.05 2
 373 
1
∆ S total = 4.26 kJ kg–1 K–1 CO(g)+ O2 (g)  → CO2 (g) ∆ r H° = z kJ/ mol.–1 . . .(iii)
2
34. (d) ∆Tf = K f ⋅ m (i) = (ii) + (iii)
62 / 62 x = y+ z
10 = 1.86 ×
Wkg 2
45. (d) air escaped from vessel,
W = 0.186 Kg 5
∆ W = (250 – 186) = 64 gm 3
∴ air remain in vessel. P, V constant
35. (c) Second electron gain enthalpy is always positive for 5
every element. n1T1 = n 2 T2
O− (g) + e − 
→ O−2 (g) ; ∆H = positive
3 
n1 (300) =  n1  T2 ⇒ T2 = 500K
36 (a) ∆G = ∆H − T∆S 5 
∆H 200 46. (b, c) Standard enthalpy of formation: “The standard
T= = = 5K
∆S 40 enthalpy of formation of a compound is the change in the
37. (b) Work done on isothermal irreversible for ideal gas standard enthalpy when one mole of the compound is
= –Pext (V2 – V1) formed is starting from the requisite amounts of elements
= –4 N/m2 (1m3 – 5m3)= 16 Nm in their stable of aggregation”.
Isothermal process for ideal gas 47. (a) A→1,3,4; B → 3,4; C → 5; D→ 1,2,5
48. (b) A→3,5; B→ 1,2,4; C→1,2,4; D→ 1,2,4,5 59. (c)

60. (b)
49. (d) At equilibrium ∆G = 0, ∆Gº of a reaction may or may
not be zero. For Question Nos. 61 to 62
For a spontaneous process ∆G <0 61. (b) Paragraph-1
X 2 (g) ↽ ⇀ 2X(g)
50. (b)
Initial mole 1 0
t = t eq. (1 − α ) 2α
RT
51. (b) E ocell = ln K Given 2α = β equilibrium
nF
1 0.0592 βequilibrium
(0.8 − 0.05) = × ln K So, α =
2 2.303 2
(0.8 − 0.05) × 22.303  β eq 
ln k = = 58.38 Total mole at equilibrium = (1 + α ) = (1 +  
0.0592  2 
52. (a) On increasing concentration of NH3, the concentration  βeq. 
1 − 
of H+ ion decreases. Therefore, Ered increases.
Px 2 =  2 P  =  2 − βeq P  =  2 − βeq P 
1 + βeq.   2 + βeq   2 + βeq
total total total
53. (d) 
 2 
54. (c) Reduction potential of I 2 is less than Cl2.  
 β eq   2β eq 
Px (g) = Ptotal  =  Ptotal 
55. (d) Reaction of Mn3+ with H2O is spontaneous.  1 + β eq   2 + β eq 
56. (a)  2 
2
For Question Nos. 57 to 58  2 β eq. 
 × Ptotal 
57. (d) ∆G = −nFE cell 2
 2 + β eq. 
= 
(Px)
So K p =
= –2 × 96500 × 0.059 (Px 2 )  2 − β eq. 
 × Ptotal 
=–11.387 kJ mol–1 = –11.4 kJ  (2 + β eq ) 
−0.0591 C 4βeq.
2
 8β eq2 
58. (b) E = log10 −3 Kp = × P =   So Ans. is = (b)
4 − βeq.  4 − βeq
2 total 2
2 10 
−0.0591  C 
0.059 = log10  −3  62. (c) (a) Correct statement.
2  10  As one decrease in pressure reaction move indirection
C where no. of gaseous molecules increase
10 −2 =
10 −3 (b) Correct statement
C = [M 2 + ] = 10 −5 M. As the start of reaction Q p < K p so dissociation of X2 take
K sp = [M +2 ] [X − ]2 = 4s3 = 4(40−5 )3 = 4 ×10−15 place spontaneously

(c) Incorrect statement as
8 β eq2 8 × (0.7) 2
Kp = = > 1, but
K L 4 − β eq 4 − (0.7) 2
2
Pressure
(d) Correct statement.

As ∆ G ° > 0 & ∆ G ° = − RT ℓ n K p
N M ∆ G ° > 1, so K p should be less than 1. So K < 1
Volume
K p − K c (RT) ∆ng. (RT > 1)
K – L heating, isobaric
Kp
L – M cooling, isochoric Kc =
M – N cooling, isobaric RT
N – K heating, isochoric K c < K p So K c < 1

–6
63. (i- 1, 53) (ii- 53, 10 ) Cell reactions are  2 −α 
7 = 14 × 0.8  
Ag + 12 Cl2 
→ AgCl . . .(i)  2 
→ Ag + + e−
Ag  . . .(ii) ⇒ α = 0.75 = 75%
−
1
2 Cl2 + e 
→ Cl . . .(iii) 65. ∆H = ∆U + ∆(PV)
∆ H = ∆ U + V∆ P
Ag + + Cl− 
→ AgCl . . .(i – ii – iii)
∆U = ∆H − V∆P = −560 × 1 × 30 × 0.1 = −557
Hence cell representation is Ag | Ag | AgCl | Cl− | Cl2 , Pt
+
Absolute value =557kJ
Ag + (aq) + Cl − (aq) 
→ AgCl(s); 66. Energy release at constant volume due to combustion of
Σ∆G − Σ∆G
o
P
o
R
3.5 gm of a gas
=2.5 × 0.45
(i) ∆G ° = −109 − (−129 + 77) = −109 + 129 − 77
Hence energy released due to the combustion of 28 gm
= 20 − 77 = −57 = −1× F × E° − 57 = 1× 96500 × E°
(i.e., 1 mole) of a gas
57000
⇒ E° = = 0.59 Volts
= 2.5 × 0.45 ×
28
= 9 kJmol −1
965000
3.5
(ii) −57 = −2.303R log K 0
67. X 
→ Y ∆ r G 0 = − 193KJ / mol
57 × 1000
log K 0 = = 9.98 ≈ 10 M + 
→ M 3 + + 2e − E 0 = − 0.25V
2.303 × 8.314 × 298
⇒ K0=1010 ∆G0 for the this reaction is
∴ Ksp = 1/K0 ∆G 0 = −nFE 0 = −2 × (−0.25) × 96500 = 48250 J / mol
∴ Ksp =10–10
48.25 KJ/mol
∴ log Ksp = −10
So the number of moles of M+ oxidized using X→Y will be
10AgCl (s) ↽ ⇀ Ag + (aq) + Cl − (aq) 193
S S = = 4 moles
48.25
10−10 = S2
∴ S = 10−5 m / L 68.
1
65.39 ×10−2 (i) 2Cu(s) + O2 (g)  → Cu 2 O(s), ∆Gº = −78kJ / mole
When = 10−3 moles of Zn has been added. 2
65.39
2Ag + + 2e 
→ 2Ag E° = 0.80 V 1
(ii) H 2 (g) + O2 (g) 
→ H 2 O(g), ∆Gº = −178 kJ / mole
2
→ Zn 2+ + 2e
Zn  E° = 0.77 V
(i) – (ii)
2Ag + (aq) + Zn (s) 
→ Zn 2+ (aq) + 2Ag (s) 2Cu(s) + H 2 O(g) 
→ Cu 2 O(s) + H 2 (g), ∆Gº = 100 kJ
Eº=1.57V ∆G = ∆Gº + RT ln K ≥ 0
10–6 mol 10–3 moles
 pH 
log10 K(aq) = 52.8 ⇒ 105 + 8 ×1250ln  2  ≥ 0
 pH O 
Therefore, this reaction will move in forward direction  2 
completely.  pH 
Hence moles of Ag formed will be 10–6 104 ln  2  + 105 ≥ 0
 pH O 
At equilibrium, (Ecell = 0)  2 
ln p H 2 − ln p H 2 ≥ −10
+ 0.0591 [Zn 2+ ]
E ocell = log10
2 [Ag + ]2 Now, pH2O = XH2O × PTotal = 0.01×1 = 10
−2
1.56 × 2 [Zn 2+ ] ∴ ln p H 2 + 2 ln10 ≥ −10

∴ = log = 52.8
0.0591 [Ag + ]2
ln p H2 + 4.6 ≥ −10
64. 2C6 H 5OH ↽ ⇀ (C6 H 5OH) 2 ln p H 2 ≥ −14.60
C − Cα Cα / 2
Nuclear Chemistry 123
14 Nuclear Chemistry
QUICK LOOK a gamma ray. these are photons, just like light, except of
much higher energy, typically from several keV to several
Radioactivity refers to the particles which are emitted from MeV. X-Rays and gamma rays are really the same thing,
nuclei as a result of nuclear instability. Because the nucleus the difference is how they were produced. Depending on
experiences the intense conflict between the two strongest their energy, they can be stopped by a thin piece of
forces in nature, it should not be surprising that there are many aluminum foil, or they can penetrate several inches of lead.
Nucleus consists of protons and neutrons. The number of
nuclear isotopes which are unstable and emit some kind of
electrons in every nucleus is zero.
radiation. The most common types of radiation are called alpha,
Proton was discovered by Rutherford and neutron by
beta, and gamma radiation, but there are several other varieties
Chadwick.
of radioactive decay.
B Magnetic
N α field
β N Beta emission is
N
N N preferentially in I
N N
N N the direction
N Electric Nuclear
opposite the 60
Co spin
nuclear spin, in
Nuclear
violation of
conservation
γ of parity.
Figure: 14.1
Wu, 1957
There are three primary types of radiation:
Alpha - the nucleus releases an alpha particle (a helium-4
nucleus) consisting of two neutrons and two protons; these
60
Co → 60
Ni + e + v e
are fast moving helium atoms. They have high energy,
typically in the MeV range, but due to their large mass, they e–
are stopped by just a few inches of air, or a piece of paper.
Beta - the nucleus ejects an electron (or a positron).
Note: this is not the same as an electron being removed Figure: 14.3
from orbital’s around the nucleus; these are fast moving
electrons. They typically have energies in the range of a few
Nuclear density is nearly 1017 kg / m3 and is independent of
hundred keV to several MeV. Since electrons are might
lighter than helium atoms, they are able to penetrate further, mass number of nucleus.
through several feet of air, or several millimeters of plastic Mass number of nucleus A = N + Z ,
or less of very light metals. where N = neutron number,
α (alpha) Z =proton number.
γ (gamma)
Radius of nucleus R = R 0 A1/ 3 where R 0 = 1.2 × 10 −5 m = 1.2
β (beta) = 1.2 Fermi
Size of nucleus is of the order of 10−14 m,
Nuclear density : E = 1017 kg / m3 (independent of mass
Figure: 14.2 Radioactive source number)1 amu = 1.66 × 10−27 kg = 931 MeV
Gamma - the protons and neutrons within the nucleus
Mass defect, ∆m = Zm p + (A − Z)m m − M(Z, A)
rearrange into a more stable form, and energy is emitted as

mass defect It may be pointed out that it is not necessary that in
Packing fraction f =
mass number eachfission of uranium, the two fragments Ba141and Kr92are
M−A formed but they may be any stable isotopes of middle
f= weight atoms. The most probable division is into two
A
fragments containing about 40% and 60% of the original
where M = mass of nucleus, A=mass number
nucleus with the emission of 2 or 3 neutrons per fission.
Binding energy of nucleus
Most of energy released appears in the form of kinetic
energy of fission fragments.
Fe
yield from nuclear fission The fission of U238 takes place by fast neutrons.
Binding energy per nuclear particle (nucleon) in MeV
The “iron group” of isotopes

8 are the most tightly bound
62 Nuclear Fusion: Synthesis of lighter nuclei into heavier ones.
28 Ni (most tightly bound)
It takes at high temperature (2 × 107 K) and high pressure.
6 62 Source of energy of the sun and stars is nuclear fusion.
28 Fe Elements heavier than
iron can yield energy by
Have 8.8 MeV per
56
Fe nuclear fission Deuterium
26 nucleon binding Helium
4 energy
yield from Average mass

nuclear fission offission fragments
2 is about 118.
235 Energy
U
Mass number, A
Figure: 14.4 Tritium Neutron
Figure: 14.6
With increase of mass number the binding energy increase,
becomes maximum and then it decreases. For the fusion to take place, the component nuclei must be
B = [(∆m)in amu] × 931MeV brought to within a distance of 10 −4 m. For this they must
[(∆m)in amu] × 931 be imparted high energies to overcome the repulsive force
Binding energy per nucleon B MeV
A between nuclei. This is possible when temperature is
Order of binding energy per nucleon = 8MeV enormously high.
The principle of hydrogen bomb is also based on nuclear
Nuclear Fission: Breaking of heavy nucleus in two nuclei fusion. To start a fusion bomb very high temperature is
92 U 235 + 0 n1 
→ X + Y + p( 0 n1 ) + 200 (Slow neutron)where X required. This is achieved by bombarding an atom bomb.
and Y are any two isotopes having mass number about 40% to The source of energy of sun and other stars is nuclear
60% of original nucleus and p is number of neutron which may fusion of thermo-nuclear reactions. There are two possible
be 2 or 3. U 235 is fissioned by slow neutron. cycles.
Magic Number: It is found that nuclei with even numbers of

protons and neutrons are more stable than those with odd
235
U numbers. In particular, there are "magic numbers" of neutrons
and protons which seem to be particularly favoured in terms of
nuclear stability: 2,8,20,28,50,82,126. Nuclei which have both
236
U neutron number and proton number equal to one of the magic
numbers can be called "doubly magic", and are found to be
particularly stable. For example, 42 He 16 40 48
8 O 20 Ca 20 Ca
208
82 Pb .
141
92 Ba
Kr Isotopes: These are the elements having same atomic
number but different mass number. They have the same
atomic number because the number of protons inside their
Figure: 14.5 nuclei remains the same. The difference in their mass

number is due to the difference in their number of neutrons. KA=fraction penetrating a radiation shield
Let us see some examples 1 H1 , 1H 2 , 1H3 are all isotopes of Laws of radioactive disintegration: The no. of atoms
hydrogen. The isotope can occur either naturally or can be present in the radioactive substance depends upon the rate
produced artificially in the laboratory. of disintegration.
Isobars: Isotopes are chemically same and physically dN
− ∝ N (– sign is for disintegration)
different. But the converse is true in isobars. That is isobars dt
are elements, which are chemically different but physically dN
same. So, isobars are atoms of different elements having the = −λ N where λ is decay constant
dt
same atomic mass but different atomic number. Since their
log e N = −λ t + log e N0
number of electrons is different, their chemical properties are
N
different. The light nuclei have unstable isobars. Heavy loge = −λ t
nuclei have stable isobars and these occur in pairs. Suppose N0
the number of protons of one isobar matches with that of N
= e−λ t
another they are called as mirror-nuclides of each other. N0
76
Examples of isobars are 32 Ce, 76
34 Se &
58
26 Fe, 58
27 Ni. ⇒ N = N0 e − λ t
Isotones:Isotones are elements having the same number of Half life: Half life of a radioactive substance is defined as
neutrons. Examples of isotones are Chlorine – 37 and the time period during which half of the no. of atoms of the
Potassium – 39. Both have 20 neutrons in their nuclei. substance remains undecayed.
Pair Production
N0
Pair production If N =
2
and t = t1/ 2
Gamma ray photon Gamma ray photon
N0
= N 0 e− λ t1/ 2
2
2 = eλ t1/ 2 ;log a 2 = λ t 1/ 2 ;0.693 = λ t1/ 2
0.693
Electron Positron t1/ 2 = T1/ 2 = = 0.693τ
λ
Figure: 14.7
−t 0.693t −t
When two high energy gamma-ray photons collide, an N = N0 2 T1/ 2

= N 0θ T1/ 2
= N 0e−λt = N 0e τ
electron/positron pair are produced (the energy is converted
into mass E = mc 2 ) Mean lifetime: The decay of particles is commonly
→ e + e+ (Must occur near a nucleus)
γ  expressed in terms of half-life, decay constant or mean
lifetime. The probability for decay can be expressed as a
1
E k,e+ ≈ E k,e+ ≈ hv − m e c02 E nucleus ≈ 0 distribution function
2
fdecay (t) = Ne− λ t where λ is called the decay constant. The
σ p ∝ hvZ2 when hv > 2m2 C02
average survival time is then the mean value of time using
σ p = cross section of pair production this probability function. The integral becomes: (can be
integrated through by parts)
k R CK A t
Dose: D = 1
∞
1 ∞ 1
λ∫
d2 t = τ = − xe − x ∞
= −e −x
dx = 0 +  −e − x  =
0
0
λ 0 λ
kR = dose rate from diagram
C = strength of source 1 T1/ 2 T
τ= = ≈ 1/ 2
d = distance λ ln 2 0.693

The mean life and "probability per second" Maximum yield of daughter element: A radioactive
element A decays to given a daughter element B which
100 % 100 %
Probability, oramount
of daughter present
further decays to another daughter element C and so on till a
Amount remaining
1/τ
stable element is formed (A→B→C).
Also if number of daughter atoms at t = 0 is zero and parent
atom is much more lived than daughter (i.e., λ A < λ B ),
where λ A and λ B are decay constant of A and B
T1/2 τ Time 1 τ Time
Figure: 14.8 respectively, then number of atoms of daughter element B
after time t is
Radioactive equilibrium: A state ultimately reached when
N0 λ A − λA t − λBt
a radioactive substance of slow decay yields a radioactive NB = [e − e ] . . .(i)
λB − λ A
product on disintegration. This product also decay to give a
Maximum activity of daughter element can be expressed at
further radioactive substance and so on to produce a t max :
radioactive series. The amount of any daughter radioactive
2.303 λ 
product present, after equilibrium has been reached, remains t max = log10  B  . . .(ii)
λB − λA  λA 
constant, the loss due to decay being counter balanced by
gain from the decay of immediate product A→B→C. Table: 14.1 Some Radioactive Tracers used in Medicine
At equilibrium, rate of formation of B= rate of decay of B Organ/tissue Tracers Uses
General body 3 24
H, Na, K, Br 42 82 Used to measure volumes of
K A .NA = K B .NB
composition body fluids and estimate
K A NB quantities of salts (eg of
or =
KB NA sodium, potassium, chlorine)
Blood 32 51 125 131 132 Used to measure volumes of
K A N B t1/ 2 B τ B P, Cr, I, ,I I
∴ = = = blood and the different
K B NA t1/ 2 A τ A
components of blood
K is decay constant (plasma, red blood cells) and
 1 1  the volumes of blood in
∴ K ∝ and K ∝ 
 τ t1/ 2  different organs. Also used to
locate internal bleeding sites
Parallel path decay: A radioactive element A decays to B
Bone 45
Ca, 47 Ca, 85Sr Used to investigate absorption
and C in two parallel paths as:
of calcium, location of bone
Say emission of α disease and how bone
B
metabolises minerals
A Cancerous 32 Used to detect, locate and
P, 40Co, 99mTc,131 I
Say emission of β
C tumours 60
Co is
diagnose tumours,
Figure: 14.9
used to treat tumours
Heart and lungs 99m
Tc, I, 131 198
Au Used to measure cardiac
The average decay constant for the element A can be expressed as
action: blood flow, volume
λ average = λ α path + λβ path . . .(i) and circulation. Labelled
Eq. (i) can be expressed in Eq. (ii) and (iii) as: gases used in investigations
λ α path = [Fractional yield of B] × λav. . . .(ii) of respiratory activity
Liver 32
P, 99m Tc, 131I, 198 Au Used in diagnosing liver
λ β path = [Fractional yield of C] × λav. . . .(iii)
disease and disorder in
hepatic circulation

Multiple Choice Questions 7. The total number of isotopes of hydrogen and number of
One and More than One Correct radioactive isotopes among them, respectively, are:
23 [JEEMain 2019]
1. A positron is emitted from Na11. The ratio of the atomic
a. 2 and 0 b. 3 and 2
mass and atomic number of the resulting nuclide is
c. 3 and 1 d. 2 and 1
[JEE 2007 P-II]
8. The reaction 2X → B is a zeroth order reaction. If the
a. 22 /10 b. 22 /11
initial concentration of X is 0.2 M, the half-life is 6 h.
c. 23 /10 d. 23 /12
When the initial concentration of X is 0.5 M, the time
54
2. Given that the abundances of isotopes Fe, 56 Fe and 57 Fe required to reach its final concentration of 0.2 M will be:-
are 5%, 90% and 5% respectively, the atomic mass of Fe [JEEMain 2019]
is [JEE 2009 P-I] a. 18.0 h b. 7.2 h
a.55.85 b.55.95 c. 9.0 h d. 12.0 h
c. 55.75 d. 56.05 9. Decomposition of X exhibits a rate constant of 0.05 µg/year.
3. Bombardment of aluminium by α-particle leads to its How many years are required for the decomposition of 5 µg
artificial disintegration in two ways, (i) and (ii) as shown. of X into 2.5 µg? [JEEMain 2019]
Products X,Y and Z respectively are [JEE 2011 P-I] a. 50 b. 25
27
Al
(ii) 30
P+Y
c. 20 d. 40
13 15
10. The size of the iso-electronic species Cl–, Ar and Ca2+ is

(i)
affected by - [JEE Main 2019]
30
14 Si + X 30
14 Si + Z a. Principal quantum number of valence shell
a. proton, neutron, positron b. Nuclear charge
b. neutron, positron, proton c. Azimuthal quantum number of valence shell
c.proton, positron, neutron d. Electron-electron interaction in the outer orbitals
d. positron, proton, neutron 11. The following results were obtained during kinetic studies
S of the reaction: [JEE Main 2019]
4. In the nuclear transmutation 9
Be + Z 
→4 Be + Y
4
2A + B 
→ Products
(X, Y) is (are) [JEE Adv. 2013 P-II]
Experiment [A] [B] Initial Rate
a. (γ , n) b. (p,D) (in mol L–1 ) (in mol of reaction
c. (n, D) d. (γ , P) L–1) (in mol L–1
min–1)
5. A plot of the number of neutrons (N) against the number
(I) 0.10 0.20 6.93×10–3
of protons (P) of stable nuclei exhibits upwards deviation
(II) 0.10 0.25 6.93×10–3
from linearity for atomic number, Z > 20. For an unstable
(III) 0.20 0.30 1.386×10–2
nucleus having N/P ratio less than 1, the possible mode(s)
The time (in minutes) required to consume half of A is:
of decay is (are) [JEE Adv. 2016 P-I]
−
a. 10 b. 5 c. 100 d. 1
a. β - decay (β emission)
238 234 234
b.orbital or K-electrons capture 12. U  1x
→ Th →
x 2
Pa  x3
→ 234 Z
92 90 91
c.neutron emission
230
+
d. β - decay (positron emission) →
x 4
Th X1, X2, X3, X4, are either particles or
90
6. The isotopes of hydrogen are: [JEEMain 2019] radiation. Then [JEE Adv. 2019 P-I]
a. Tritium and protium only a. X1 is deflected toward negatively charged plate.
b. Deuterium and tritium only b. X2 is ß- particle.
c. Protium and deuterium only c. X3 is γ - radiation.
d. Protium, deuterium and tritium d. Z is isotope of 238 U

Statement/Assertion and Reason 15. What should be the age of fossil for meaningful
13. Statement-I: The plot of atomic number (y-axis) versus determination of its age?
number of neutrons (x-axis) for stable nuclei shows a a. 6 years
curvature towards x-axis from the line of 45° slope as the b. 6000 years
atomic number is increased. And c. 60,000 years
Statement-II: Proton-proton electrostatic repulsions d. It can be used to calculate any age
begin to overcome attractive forces involving protons and
16. A nuclear explosion has taken place leading to increase in
neutrons and neutrons in heavier nuclides.
[JEE 2008 P-I] concentration of C 14 in nearby areas. C 14 concentration is
a. statement-I is True, statement-II is True; statement-II is C1 in nearby areas and C2 in areas far away. If the age of
correct explanation for statement-1 the fossil is determined to be T1 and T2 at the places
b. statement-I is True, statement-II is True; statement-II is
respectively then
a. The age of the fossil will increase at the place where
c. statement-I is True, statement-II is False
1 C1
d. statement-I is False, statement-II is True explosion has taken place and T1 − T2 = ln
λ C2
Paragraph b. The age of the fossil will decrease at the place where
Paragraph for Question Nos. 14 to 16 1 C1
explosion has taken place and T1 − T2 = ln
Carbon–14 is used to determine the age of organic material. λ C2
The procedure is based on the formation of 14 C by neutron c. The age of fossil will be determined to be same
capture in the upper atmosphere 14
N + 0 n 
1
→ C + 1n
14 1
T1 C1
7 6 d. =
14
C is absorbed by living organisms during photosynthesis. The
T2 C2
14
C content is constant in living organism once the plant or
animal dies, the uptake of carbon dioxide by it ceases and the Integer and Subjective
level of 14 C in the dead being, falls due to the decay which 17. Fill in the blanks
−
14
C undergoes
14
6 → N + β . The half life period of
C  14
7 a. 235
U 92 + 0 n1 
→ 137 A 52 + 97 B40 + ..........
14
C is 5770 years. The decay constant (λ ) can be calculated b. 82 Se34 
→ 2 −1 e° + .......... [JEE 2005]
0.693
by using the following formula λ = . The comparison of 18. The total number of α and β particles emitted in the
t1/ 2
the β - activity of the dead matter with that of the carbon still in nuclear reaction 238
92 U → 82
214
Pb is [JEE 2009 P-II]
circulation enables measurement of the period of the isolation 235

19. The number of neutrons emitted when 92 U undergoes
of the material from the living cycle. The method however,
142 90
ceases to be accurate over periods longer than 30,000 years. controlled nuclear fission to 54 Xe and 38 Sr is
14 12 12
The proportion of C to C in living matter is 1 : 10 . [JEE 2010 P-I]
[JEE 2006] 20. The periodic table consist of 18 groups. An isotope of
14. Which of the following option is correct? copper, on bombardment with protons, undergoes a
a. In living organisms, circulation of 14 C from atmosphere nuclear reaction yielding element X as shown below. To
is high so the carbon content is constant in organism which group, element X belongs in the periodic table?
b. Carbon dating can be used to find out the age of earth 63
→ 610 n + α + 211 H + X
Cu +11 H 
crust and rocks
29 [JEE 2012 P-I]
c. Radioactive absorption due to cosmic radiation is equal 21. A closed vessel with rigid walls contains 1 mol of 238
U
92
to the rate of radioactive decay, hence the carbon
and 1 mol of air at 298 K. Considering complete decay of
content remains constant in living organism
238 206
d. Carbon dating cannot be used to determine concentration 92 U to 82 Pb, the ratio of the final pressure to the initial
of 14 C in dead beings pressure of the system at 298 K is [JEE Adv. 2015 P-II]

ANSWERS and SOLUTIONS 9. (a) Rate constant (K) = 0.05 µg/year
1. (c) On positron emission from nucleus, proton converts means zero order reaction
into neutron therefore, atomic number decreases by one a0 5µg
t1/ 2 = =
but atomic mass remains constant. 3K 2 × 0.05µg / year
Atomic mass 23 = 50 years
=
Atomic number 10 10. (b) For isoelectronic species the size is compared by
Hence, (c) is correct. nuclear charge.
ΣA i x i 11. (b) 6.93 × 10 −3 = K × (0.1) x (0.2) y
2. (b) A =
Σx i
6.93 × 10 −3 = K × (0.1) x (0.25) y
A = 54 × 0.05 + 56 × 0.90 + 57 × 0.05
So y=0
(where A is atomic mass of Fe)
and 1.386 × 10 −2 = K × (0.2) x (0.30) y
A = 55.95
x
1 1
3. (a) 4
He + 27
Al 
→ P+ 30
n 1 =  x =1
2 13 15 0 2 2
(Y) → neutron
4
He + 13
27
Al 
→ 15
30
Si + n 1 So r = K × (0.1) × (0.2)0
2 1
(X) → proton
6.93 × 10 −3 = K × 0.1 × (0.2)0
4 27
2 He + 13 Al → 30
14 Si + e+
positron 0.693
t1/ 2 =
2K
S
4. (a, b) 9
4 Be + γ 
→4 Be +10 n 0.693 10
= −1
= =5
9
Be +11 P 
→ Be +12 H
S 0.693 × 10 × 2 2
4 4
Hence (a) and (b) are correct. 12. (a, b, c)

n X1 =α
5. (b, d) should increase
P X2 = β
0
−1
e + 1P 
→ 1n 1 0
(K-electron capture) X3 = β
or X4 =α
1 P1 
→ 1n 0 + +1B0 (B+ -decay) 13. (a)
No. of protons
6. (d) Isotopes of hydrogen are Protium, deuterium, tritium
7. (c) Total number of isotopes of hydrogen is 3 Stable

nuclei
⇒ 1
1 H, 12 H or 12 D, 13 H or 13 T
No. of neutrons
and only 13 H or 13 T is a radioactive element.
8. (a) For zero order If the curve does not bend down towards the x-axis then
[A0]–[At] = kt the proton-proton repulsion would overcome the attractive
0.2 – 0.1 = k × 6 force of proton and neutron.
Therefore, the curve bends down.
1
k= M/hr For Question Nos. 14 to 16
60
14. (c)
1
and 0.5 − 0.2 = ×t 15. (b)
60
t = 18 hrs 16. (a)

17. (a) 235 1
U 92 + 0 n 
→ 137 97 1
A52 + B40 + 2 0 n 20. Compound X is 26Fe and it belongs to group No – 8.
82 82 238 206
(b) Se34 
→ 2−1 e° + Kr36 21. In conversion of 92 U to 82 Pb, 8α - particles and 6β
particles are ejected.
−6 α −2 β
18. 92 U 238  → 80 X 214  → 82 Pb 214
The number of gaseous moles initially = 1 mol
(6α ,2β ), total 8 particles. The number of gaseous moles finally = 1 + 8 mol; (1 mol
235 142 90 1
19. 92 U → 54 Xe + 38Sr + 30 n from air and 8 mol of 2 He 4 )
So, Answer is 3. So, the ratio = 9 /1 = 9
Some Basic Principles of Organic Chemistry

Some Basic Principles of 131
15 Organic Chemistry
QUICK LOOK +
Stability of carbocations: 3º > 2º > 1º > C H 3 . Electron release:
Most of organic reactions occur through the involvement of certain Disperses charge, stabilisation. The stability order of carbocation is
chemical species. These are generally short lived (106 seconds to a +
explained by hyperconjugation. In vinyl cations (CH 2 = C H),
few seconds) and highly reactive and hence cannot be isolated.
resonance stability lacks completely and therefore are very much
These short lived highly reactive chemical species, through which
the majority of the organic reactions occur, are called reactive less stable. Stability ∝hyperconjugated structures ∝ number of α
intermediates. These intermediates are detected by spectroscopic hydrogen.
methods or trapped chemically or their presence is confirmed by
indirect evidence. On the other hand, synthetic intermediates are Carbanions: Chemical species bearing a negative charge on
stable products which are prepared, isolated and purified and carbon and possessing eight electrons in its valence shell are
subsequently used as starting materials in a synthetic sequence. called carbanions. These are produced by heterolytic cleavage
of covalent bonds in which the shared pair of electrons remain
Carbocations (Earlier Called as CarboniumIons) with the carbon atom.
Carbocations are the key intermediates in several reactions, Structure: A carbanion possess an unshared pair of
particularly in nucleophilic substitution reactions and electrophilic electron and thus represents a base. The best likely
addition reactions. description is that the central carbon atom is sp3 hybridised
Structure: Generally in the carbocations, the positively with the unshared pair occupying one apex of the
charged carbon atom is bonded to three others atoms and tetrahedron. Carbanions would thus have pyramidal
has no nonbonding electrons. It is sp2 hybridised with a structures similar to those of amines. It is believed that
planer structure and bond angles are of about 120º. There is carbanions undergo a rapid interconversion between two
a vacant unhybridised p-orbital which (e.g. in the case of pyramidal forms.
+
C H 3 ) lies perpendicular to the plane of C—Hbonds. Stability and generation: The Grignard reagent is the best
known member of a broad class of substances, called
unhybrid p-orbital vacant organometallic compounds where carbon is bonded to a metal
R lithium, potassium, sodium, zinc, mercury, lead, thallium
σ
120° C +−− R almost any metal known. Whatever the metal it is less
σ
R sp2-hybridised carbon orbital electronegative than carbon and the carbon metal bond like the
& structure of carbocations one in the Grignard reagent is highly polar. Although the
organic group is not a full fledgedcarbanion an anion in which
Stability: There is an increase in carbocation stability with carbon carries negative charge, it however, has carbanion
additional alkyl substitution. Thus one finds that addition of character. Organometallic compounds can serve as a source
HX to three typical olefins decreases in the order from which carbon is readily transferred with its electrons. On
(CH3)2C = CH2> CH3 — CH = CH2> CH2 = CH2 treatment with a metal, in RX the direction of the original
This is due to the relative stabilities of the carbocations dipole moment is reversed (reverse polarisation).
formed in the rate determining step which in turn follows δ+ δ− δ− δ+
from the fact that the stability is increased by the electron CH 3 CH 2 — Br + Mg 
→ CH 3 CH 2 — Mg— Br
releasing methyl group (+I), three such groups being more
effective than two, and two more effective than one. R — C ≡≡ C − Considerable carbanion
CH 3 Also acetylide ion character
Stabilised by three electron releasing
Free radicals: Free radicals are usually detected by electron
+ + +
CH 3 C > H 3C — CH — CH 3 > —H 2 C — CH 3 spin resonance, which is also termed electron paramagnetic
resonance. Simple alkyl radicals have a planar (trigonal)
CH 3 structure i.e., these have sp 2 bonding with the odd electron

in a p orbital. The pyramidal structure is another possibility It is important to know not only what happens in a chemical
when the bonding may be sp3 and the odd electron is in reaction but also how it happens. Most of the reactions are
ansp3orbital. The planar structure is in keeping with loss of complex and take place via reactive intermediates which may
activity when a free radical is generated at a chiral centre. be or may not be isolated. The reaction intermediates are
Thus, a planar radical will be attacked at either face after its generally very reactive which readily react with other species
formation with equal probability to give enantiomers unlike present in the environment to form the products. The detailed
carbocations, the free radicals can be generated at bridge. step by step description of chemical reaction is called its
This shows that pyramidal geometry for radicals is also mechanism. Mechanism is only a hypothesis to explain various
possible and that free radicals need to be planar. facts regarding a chemical reaction.
H Substrate  → Reactive intermediates 

→ Products
H H p − orbital H sp3–−hybridised
hybridizedorbital
orbital Br
|
C C —CH — CH 3 — Br− —C+ H — CH3
| H →
H
Pyramidalstructure
Intermediate
Substrate OH
Stability: As in the case of carbocation, the stability of free |
radicals is tertiary > secondary > primary and is explained −
—CH — CH 3

OH
→
on the basis of hyperconjugation. The stabilising effects in
allylic radicals and benzyl radicals is due to vinyl and Product
phenyl groups in terms of resonance structures. Bond By knowing the mechanism we can predict the product of a
dissociation energies shows that 19 kcal/mol less energy is chemical reaction, adjust the experimental conditions to
improve the yield of the products or even alter the course of
needed to form the benzyl radicals from toluene than the
reaction to get the different products.
formation of methyl radical from methane. The triphenyl
Most of the attacking reagents carry either positive charge (an
methyl type radicals are no doubt stabilised by resonance,
electron deficient species) or a negative charge (electron rich
however the major cause of their stability is the steric
species). The positively charged reagents attack the substrate at
hindrance to dimerisation.
points of high electron density while (negatively) charged reagents
C H CH → C H CH ɺ ɺ ; ∆H = +85 kcal
+H
6 5 3 6 5 2 attack the point of low electron density. The organic reactions
Toluene Benzyl radical
essentially involve changes in the existing covalent bonds present
Ease of formation of alkyl free radicals,
in the molecules. These changes may involve electronic
Benzyl > 3° > 2° > 1° > C + H 3 > Vinyl displacements in covalent bonds, breaking of some of the existing
Electronic Displacement in Covalent Bonds: The bonds (bond fission), formation of new bonds as well as energy
following four types of electronic effects operates in change accompanying the bond fission and bond cleavage.
covalent bonds
We can understand the mechanism of various organic reactions
(i) Inductive effect
in terms of following well established basic concepts.
(ii) Electromeric effect
Electronic displacement in covalent bond
(iii) Resonance and mesomeric effect
Fission (cleavage) of covalent bonds
(iv) Hyperconjugation
Nature of attacking reagents
Mechanism of Organic Reaction: A chemical equation is only
a symbolic representation of chemical reaction which indicates Note
the initial reactants and final products involved in a chemical The higher the polarity of solvent, greater the tendency for
change. Reactants generally consist of two species. SN1 reaction.
(i) Substrate: One which is being attacked in a chemical High concentration of the nucleophile favours SN2 reaction
reaction while low concentration favours SN1 reaction.
(ii) Reagents: The species which attack the substrate molecule Rearrangement of the carbocation (formed in SN1 reaction)
Substrate + Reagent  → Product / Products leading to more stable carbocation is observed in SN1
Br reaction (discussed latter).
| In general SN2 mechanism is strongly inhibited by
CH3 — CH— CH3 + OH−  → CH3 — CH == CH2 + H2O + Br −
substrate Reagent Pr oducts increasing steric bulk of the reagents. In such case SN1
mechanism is favoured.
Some Basic Principles of Organic Chemistry 133

Elimination Reactions: An elimination reaction is one which Cl
Cl H Cl | H Cl
involves the loss of two atoms or groups of atoms from the same −
C + OH 
− H2 O
→ C 
→ C : + Cl−
or adjacent atoms of a substrate molecule leading to formation of Cl Cl Cl Cl Cl
multiple (double or triple) bond. These are of two types.
β-elimination reactions. In these reactions, loss of two Dichlorocarbene is the reactive intermediate involved in
atoms or groups occurs from the adjacent atoms of the carbylamine reaction and Reimer-Tiemann reaction.
substrate molecule e.g., acid catalysed dehydration of alcohol
and base catalysed dehydrogenation of alkyl halides. Multiple Choice Questions
H One and More than One Correct
H 3C → H 3 C
conc.H 2 SO4
CH 2 + H 2 O 1. Hyperconjugation involves overlap of the following
H OH orbitals [JEE 2008 P-I]
a. σ − σ b. σ − p
Mechanism
H c. p − p d. π − π
| H+
:CH 3 — CH — CH 2 — OH → 2. The correct stability order for the following species is
H
| [JEE 2008 P-II]
→ CH 3 — CH == CH 2 + H +
CH 3 — CH — CH 2 — OH 2+ 
⊕ ⊕
−
OH H O
| α (I) (II)
CH 3 — CH — C H 2 — Br 
KOH
(alc.)
→ CH 3 — CH == CH 2 + KBr + H 2 O
⊕
CH 3 — CH — C H 2 — Br 
→ CH 3 — CH == CH 2 + KBr + H 2 O ⊕
O
(III) (IV)
E1 Mechanism
a. (II) > (IV) > (I) > (III) b. (I) > (II) > (III) > (IV)
H H B: H
| | | | | | c. (II) > (I) > (IV) > (III) d. (I) > (III) > (II) > (IV)
+ −
—C — C 
slow
→ —C — C — + X —C — C+ —
| | | | 3. In the following carbocation. H/CH3 that is most likely to
X migrate to the positively charged carbon is
→
fast
C == C + H : B [JEE 2009 P-II]
H H
1 |2 + |4 5
E2 Mechanism H 3 C— C— 3C— C— C H3
+ |H : B| |
OH H CH 3
B: H B⋯H
| | ⋮ a. CH3 at C − 4 b. H at C − 4
−
—C — C — 
slow
→ — C⋯C —  → C == C + : X + HB
| | | ⋮ c. CH 3 at C − 2 d. H at C − 2
X X
Transition state 4. The correct stability order of the following resonance
E1 –– CB Mechanism structures is [JEE 2009 P-II]
+ − + − − + − +
H H 2 C = N = N H 2 C − N = N H 2 C − N ≡ N H 2 C− N = N
CH 3 | CH 3 − H+
CH 3 CH 3 (I) (II) (III) (IV)
C—C ↽ fast ⇀ C− — C
CH 3 | CH 3 CH 3 | CH 3 a. (I) > (I) > (IV) > (III) b. (I) > (III) > (II) > (IV)
L L
c. (II) > (I) > (III) > (IV) d. (III) > (I) > (IV) > (II)
CH 3
− L−
CH 3
↽ slow ⇀ C == C 5. The compounds P, Q and S
CH 3 CH 3
O
COOH OCH3 ||
α-elimination reactions: In these reactions, loss of two atoms
C
or groups occurs from the same atom of the substrate molecule. O
H 3C H 3C
E.g., base catalyseddehydrohalogenation of chloroform to form
dichlorocarbene. P Q S

were separately subjected to nitration using HNO3/H2SO4 10. The hyperconjugative stabilities of tert-butyl cation and
mixture. The major product formed in each case 2-butene, respectively, are due to [JEE Adv. 2013 P-I]
respectively, is [JEE 2010 P-II] a. σ → p (empty) and σ → π * electron delocalisations
O
|| b. σ → σ * and σ → π electron delocalisations
COOH OCH 3 C
O c. σ → p (filled) and σ → π electron delocalisations
a. HO H 3C NO 2 d. p(filled) → σ * and σ − π * electron delocalisations
NO 2 NO 2
11. Among P, Q, R and S, the aromatic compound(s) is/are
O
COOH OCH 3 || [JEE Adv. 2013 P-I]
C
b. HO O
NO 2 H 3C 
NaH
→Q
NO 2 NO 2 
AlCl3
→P
COOH OCH3 O NO2
|| O
c. HO C
H 3C O 
( NH 4 )2 CO3
→R
NO2 100 −115° C  
HCl
→S
NO 2 O O
O
COOH OCH3 || a. P b. Q
C c. R d. S
d. HO O NO2
H3C NO2
NO2
12. Which of the following molecules is least resonance
stabilized? [JEE Main. 2017]
6. In allene(C3H4), the type(s) of hybridization of the carbon
atoms is (are) [JEE 2012 P-I] a. b.
a. sp and sp 3 b. sp and sp 2 O
c. only sp 2 d. sp 2 and sp3 c. d.

O N
7. Which of the following molecules, in pure form, is (are)
unstable at room temperature? [JEE 2012 P-I] 13. The order of basicity among the following compounds is:
[JEE Main. 2017]
a. b. NH NH2
|| ||
N N HN N
O O H 3C NH2 H 2N NH
I II III IV
c. d.
a. IV > I > II > III b. IV > II > III > I
8. The order of stability of the following carbocations c. I > IV > III > II d. II> I > IV> III
[JEE Main 2013] 14. The major product of the following reaction is
+ [JEE Main 2018]
CH 2 OMe OMe
+ +
CH 2 = CH − C H 2 ; CH 3 = CH 2 − C H 2 ; is a. b.
I II
III
a. III > II > I b. II > III > I
c. d.
c. I > II > III d. III > I > II
9. A gaseous hydrocarbon gives upon combustion 0.72 g of 15. The reaction(s) leading to the formation of 1,3,5-
trimethylbenzene is (are) [JEE Adv. 2018 P-I]
water and 3.08 g of CO2 . The empirical formula of the
O
hydrocarbon is [JEE Main 2013] Conc. H2SO4
a. ∆ →
a. C2 H 4 b. C3H 4
heated iron tube
c. C6 H5 d. C7 H8
b. Me 
H      →
873 K

O 20. The increasing order of the reactivity of the following
with LiAlH4 is: [JEE Main 2019]
(1)Br2 , NaOH O O
c. (2)H O+

3 → (A) (B)
(3)sodalime, ∆
C2H5 NH2 C2H5 OCH3
O O
CHO O O O
(C) (D)
C2H5 Cl C2H5 O C2H5
d. Zn / Hg,HCl a. (A) < (B) < (D) < (C)
→
CHO b. (A) < (B) < (C) < (D)
OHC
c. (B) < (A) < (D) < (C)
16. A reversible cyclic process for an ideal gas is shown d. (B) < (A) < (C) < (D)
below. Here, P, V, and T are pressure, volumeand
21. The major product of the following reaction is:
temperature, respectively. The thermodynamic parameters
[JEE Main 2019]
q, w, H and U are heat, work, enthalpy and internal
H 3C O
energy, respectively (i)NaNO2 H+
NH2 
(ii)CrCO3 / H+
→
(iii)H2SO4 (conc.) ∆
A(P1 , V1 , T1 ) C(P2 , V1 , T2 ) O
O
Volume (V)
HO
a.
B(P2 , V2 , T1 )
Temperature (T)
CH3 O
b.
The correct option(s) is (are)
O
a. q AC = ∆U BC and w AB = P2 (V2 − V1 ) O
O
b. w BC = P2 (V2 − V1 ) and q BC = ∆H AC
CH3 O
c. ∆H CA < ∆U CA and q AC = ∆U ac c.
d. q BC = ∆H AC and ∆H CA > ∆U CA O
17. Which of the following compounds is not aromatic? HO
[JEE Main 2019] d.
O
a. b.
22. ATin-chloride ‘P’ gives following reaction (unbalanced
N reaction) [JEE Adv. 2019 P- I]
P + Cl- 
→ X [ Monoanion pyramidal ]
c. d.
N P + Me3N 
→Y
⊕ H P + CuCl2  → Z + CuCl
18. Two pi and half sigma bonds are present in: Then which of the following is/are correct?
[JEE Main 2019] a. Y contains coordinate bond.
a. N +2 b. N2 b. X is sp3hybridised.
c. Oxidation state of Sn in X is + 1.
c. O+2 d. O2
d. X contain lone pair on central atom.
19. 50 mL of 0.5 M oxalic acid is needed to neutralize 25 mL of
sodium hydroxide solution. The amount of NaOH in 50 mL Matrix Match/Column Match
of the given sodium hydroxide solution is: [JEE Main 2019] 23. Match each of the compounds given in ColumnI with the
a. 4 g b. 20 g reactions, that they can undergo given in Column II.
c. 80 g d. 10 g [JEE 2009 P-II]

Column I Column II a. A→ 1, 2, 3; B→ 2, 3; C→ 1, 4; D→ 1, 2
Br 1. Nucleophilic b. A→ 3, 4; B→ 2; C→ 3; D→2, 4
substitution c. A→ 1, 3; B→ 1; C→ 2; D→ 1, 4
(A) d. A→ 3, 4, 5; B→ 1,4; C→ 3,4; D→ 2,3
O
25. Match each set of hybrid orbitals from Column-I with
OH 2. Elimination complexes given in Column-II. [JEE Adv. 2018 P- II]
(B) Column-I Column-II
(A) dsp2 1. [FeF6]4–
CHO 3. Nucleophilic addition (B) sp3 2. [Ti(H2O)3Cl3]
(C) (C) sp3d2 3. [Cr(NH3)6]3+
OH (D) d2sp3 4. [FeCl4]2–
Br 4. Esterification with 5. Ni(CO)4
(D) acetic anhydride 6. [Ni(CO)4]2–
NO2 a. A → 4, 6; B → 5, 6; C → 1, 2, 3; D → 3
5. Dehydrogenation b. A →1, 3, 5; B → 1,2, 4; C → 2, 3; D → 2
a. A→ 1, 3, 5; B → 2, 1, 5; C → 3, 4; D → 1 c. A →1, 2, 5; B → 1, 3, 2; C → 2, 4; D → 1
b. A → 1, 3, 5; B → 1, 3; 5; C → 3, 5; D → 1 d. A →1, 3, 4; B →1, 3, 5; C → 1, 2; D → 5
c. A → 1, 2, 5; B → 1; 4; 5; C → 3, 4; D → 1 26. The desired product X can be prepared by reacting the
d. A→ 1, 2, 5; B → 1, 3, 5; C → 1, 4; D → 5 major product of the reactions in ColumnI with one or
more appropriate reagents in ColumnII (given, order of
24. Match the reactions in Column I with appropriate types of
migratory aptitude: aryl > alkyl > hydrogen)
steps/reactive intermediate involved in these reactions as
[JEE Adv. 2018 P- II]
given in Column II. [JEE.2011 P-II]
O
Column I Column II Ph
H 3C 1. Nucleophilic substitu- OH
O
O tion

aq. NaOH
→ Me Ph
X
O Column I Column II
(A)
Ph 1. l 2 , NaOH
(A)HO
Ph Me
OH
O 2. Electrophilic substitu- Me
tion +H2SO4
CH 2 CH 2 CH 2 Cl
Ph 2. [Ag(NH 3 ) 2 ]OH
O (B) H2O
(B) H
Ph
OH

→
CH 3MgI
Me
CH 3
+HNO2
O 3. Dehydration
18 Ph 3. Fehling solution
CH 2CH 2 CH 2 OH (C) HO
Me Ph
18
(C) O OH
Me

H 2SO 4
→ +H2SO4
Ph 4. HCHO, NaOH
CH2CH2 CH2C(CH3 )2 4. Nucleophilic addition (D) Br
Ph H
OH OH
(D) 5. Carbanion Me

H 2SO 4
→
+ AgNO3
H 3C CH 3
5. NaOBr

a. A → 1, 2; B → 2, 3; C → 1, 2; D → 3 CH3 CH3
b. A → 1, 3, 5; B → 1, 1, 4; C → 2, 3; D → 2 (I)
⊕C
CH2 C ⊕ CH2
ɺɺ O
c. A → 1,5; B → 2, 3; C → 1, 5;D → 2,3 H 3C O
ɺɺ
CH3 H 3C CH3
d. A → 1, 2, 4; B → 1, 4, 5; C → 1, 2; D → 1 Stabilises by resonance and have six α-hydrogen atoms
27. ColumnIcontains reactions and ColumnII contains major (hyperconjugation)
products. [JEE Adv. 2018 P- II] (III)
ColumnI Column II ⊕ CH3 ⊕ CH3
H3C — CH — O — HC H3C — CH == O — HC
CH3 CH3
(A) + 1.
ONa Br OH
Stabilises by resonance and have only three α-hydrogen
(B) + HBr 2. atoms.
OMe Br
⊕ CH3
(II) H3C — CH — CH2 — HC
(C) + NaOMe 3. CH3
Br OMe
have five α-hydrogen atoms.
(D) + MeBr 4.
ONa ⊕
(IV) H2C CH3
— CH2 — CH2 — HC
CH3
O
5. have only two α-hydrogen atoms.
a. A → 4, 6; B → 5; C → 1; D → 2 ∴ I > III > II > IV.
b. A → 1, 4; B → 2; C → 4; D → 3 H H
c. A → 5; B → 1; C → 2, 4; D → 1 |2 +
1 |4 5 1 + 3 4
H - shift C2 to C3 H C— C— C H — CH
3. (d) H 3 C— C— C— C— CH 3 æææææ Æ3 2
d.A → 1, 4; B → 1; C →1; D → 5 | | 3
| | |
OH H CH 3 OH
Integer and Subjective 1 2 + 4 5 1 + 3 4
H 3 C— C— C— C— C H 3  → H3 C— C— C H 2 — C H − CH 3
28. The total number of contributing| structure
| showing |2 |
H
hyperconjugation (involving C—H bonds) for the OH CH 3
following carbocation is [JEE 2011 P-II] (driving force is conjugation from oxygen)
H 3C ⊕ CH 2 CH 3 4. (b) On the basis of stability of resonating structures.
COOH O2 N COOH–OH gp is

HNO3
H2SO4
→ more
5. (c) HO HO
(P) activating
29 Among the following, the number of aromatic compound
(s) is [JEE Adv. 2017 P- II] OCH3 OCH3
NO2
⊕ → HNO3
(-OCH 3 gpis more activating)
⊕ H2SO4
CH3 CH3
⊕ (Q)
O O NO 2
|| ||
C C
O 
HNO3
H2SO4
→ O
H H
1. (b) Hyperconjugation involves overlap of σ − p orbitals. 6. (b) C == C == C (allene)
H sp 2 sp sp 2 H
2. (d)

7. (b, c) ɺɺ
NH 2
|
(b –antiaromatic
13. (a) H2N NH
–
O IV
+ ɺɺ groups increases electron
Resonance with two — NH 2
(c) is antiaromatic density on ‘N’ = NH
NH
8. (d) On the basis of number of resonating structure ||
(III) > (I) > (II)
CH3 ɺɺ
NH 2
 y y
9. (d) C x H y +  x +  O 2  → xCO 2 + H 2 O Lesser increase of electron density on = NH due to only
 4 2 one resonance with one
y 3 .08 0.72 2x 3.08 18 7 x 7
x: = : ⇒ = × = i.e. = N:
2 44 18 y 44 0.72 4 y 8
CH 3 Nɺɺ
| H
10. (a) H 2 C — C⊕ H 3 C — CH == CH — CH 3 III
| σ − π * (antibonding)
CH 3 The LPe− is not available as it is involved in aromatic Sextet.
σ − p(empty)
‘N’ is bonded to sp 2 C on both sides.
11. (a, b, c, d) N:
H Θ
Cl ɺɺ
⊕ Na+
 
→ A lC l 3
 
→
N aH
+H2 ↑
ɺɺ
N
AlCl−4 (P) H
(aromatic) (aromatic) (Q) II
This LPe− is not involved in aromaticity. So more
   
→
( N H 2 ) 2 CO 3
100 − 115 ° C (R) (aromatic) available. Also, ‘N’ is bonded to sp 3C on one side.
O O N
∴ IV > I > II > III
∆
Mechanism: (NH 4 ) 2 CO3  → 2NH 3 + CO 2 + H 2 O 14. (c) CH 3 O − is a strong base and strong nucleophile, so
favourable condition is SN 2 / E2. Given alkyl halide is 2° and
O OH
+ NH 3 → → →
ɺɺ
NH
β C’s are 4° and 2°, so sufficiently hindered, therefore, E2
O O N O 2
CH 3 N
| dominates over SN 2. Also polarity of CH 3OH (solvent) is
H

→ HCl not as high as H 2 O, so E1 also dominated by E2.
+ Cl
−
−H2O 4° OMe
N β
O OH (aromatic) α −
(s)

CH3OH
E2
→
O β H
2°
12. (a) H
H
15. (a, b, d) (a) C
HO
is nonaromatic and hence least reasonance stabilised Me C C Me Conc.
∆
O C H
HH HH
(b) Benzene is aromatic
C C O
H
(c) furan is aromatic Me
Me Me
O +3H2O
(d) pyridine is aromatic
N Me

Me
(a) N ⊕2 ⇒ BO = 2.5 ⇒  π — Bond = 2 & σ — Bond = 
1
Me Me 18.
C H  2
H C C
(b) Heated iron tube →
 N2 ⇒ BO = 3.0 ⇒ [ π-Bond = 2 & σ-Bond = 1]
Me C C 873 K
C Me
Me O⊕2 ⇒ BO = 2.5 ⇒ [ π-Bond = 1.5 & σ-Bond = 1]
O2 ⇒ BO = 2 ⇒ [ π-Bond ⇒ 1& σ-Bond = 1]
H
O
C Me 19. (a) H 2 C 2 O 4 + 2NaOH 
→ Na 2 C 2 O 4 + 2H 2 O
meq of H2C2O4 = meqNaOH
Br2/NaOH 50 × 0.5 × 2 = 25 × MNaOH× 1
(c) Me Me (Haloform
C C reaction) ∴ MNaOH = 2 M
O O Now 1000 ml solution = 2 × 40 gram NaOH
O ∴ 50 ml solution = 4 gram NaOH
O Na
C
20. (a) Rate of nucleophilic Electrophilicity of
∝
attack on carbonyl Carbonyl
O O
C C O Na || ii ||
Na O C 2 H 5 — C — N H 2 < C2 H 5 — C — OCH 3 <
O O +m +m
+
3H3O O O O
COOH || || ||
C 2 H 5 — C — O — C — C 2 H 5 < C 2 H 5 — C — Cl
+m −I
Soda lime
 ∆
→ H 3C O
COOH COOH (decarboxylation) 21. (b) NH2
CHO CH3 O
H+ NaNO2
Zn/Hg,HCl
 →
(d) (Clemmensen reduction)
H 3C O
OHC CHO CH3 CH3 OH
16. (b, c) A – C (Isochoric process) ⇒WAC =0 and O
∆U AC = q AC CrO3 H+
B – C (Isobaric process) ⇒ ∆U BC = q BC + w BC
O
w BC = − P2 (V1 − V2 ) = P2 (V2 − V1 ) q BC = ∆H BC
H 3C O C
∵ ( ∆T) A − C = ( ∆T) B − C OH
∴ ∆U BC = ∆U AC = q AC ∆H BC = ∆H AC = q BC O
Conc.H2SO4 ∆
∵ T2> T1∆HCA and ∆UCA are negative
∆H CA = ∆U CA + V ∆ P
( − ve ) CH3 O
∴ ∆H CA < ∆U CA A – B (Isothermal process)
O
V2 O
∆U AB = ∆H AB = 0 w AB = − nRT1 ln
V1 22. (a, b, c) SnCl2 + Cl- 
→ SnCl-3
(P) (X)
17. (c) Do not have (4n + 2)π electron. It has 4n π SnCl2 + Me3N 
→ SnCl2 [N(CH3)3]
⊕ (P) (Y)
electrons.So it is anti-aromatic. SnCl2 + 2CuCl2 

→ SnCl4 + CuCl
(P) (Z)

23. (c) A → 1, 2, 5; B → 1, 4, 5; C → 3, 4; D → 1 Ph H
24. (d) A→ 3, 4, 5; B→ 1, 4; C→ 3, 4; D→ 2, 3 (B) Me OH + HNO2
Ph Me
25. (a) A →4, 6; B → 5, 6; C → 1, 2; D → 3
Ph O Ph
1. [FeF6 ]4 − [Ag(NH3 )2 ]OH
→
Me Me COOH
3d 4s 4p
Ph H Ph
Fe+2
High spin complex because F– is weak field ligand. Ph

3 2 NaOBr COOH
sp d Solution
Me
Ph
2. [Ti(H 2 O)3 Cl3 ]
Ph Ph Ph O
Ti3+ d2sp3
(C) HO OH + H2SO4 Ph
d2sp3 Me Me Me Me
3. [Cr( NH 3 ) 6 ]3 +
NaOBr 12/NaOH
Cr3+ d2sp3
Ph Ph
d2sp3 Me COOH Me COOH
4. [FeCl 4 ]2 − Ph Ph
Fe +2 : 3d 6 , Cl − is weak field ligand. Ph
Ph Ph
3d 4s 4p (D) Ph OH + AgNO3 Ph CHO
Br Me Me Me
sp3 Fehling solution [Ag(NH3)2]OH
5. Ni(CO) 4 Ph Ph
Ni 0 − 3d8 4s 2 , CO is strong field ligand Ph COOH Ph COOH
Ni Me Me
27. (b)A → 1, 4; B → 2; C → 4; D → 3
sp3 (A) + +
2−
ONa Br OH
6. [ Ni(CN) 4 ]
With 3º halide, elimination predominates.
Ni+2
dsp2
– (B) + HBr + MeOH
CN is strong field ligand. OMe Br
26. (c) A → 1,5; B → 2, 3; C → 1, 5;D → 2,3
Ph (C) + NaOMe
Me Br
(A) HO + H2SO4
Ph HO Me (D) + MeBr
ONa OMe
Ph O O
Ph
l2 / NaOH
Me → Me C OH 28. 6×H–atoms are there.
Ph Me Ph
⊕
O ⊕
Ph 29.
NaOBr C OH
Me
Ph
Answer is 5.
Nomenclature and Isomerism 141
16 Nomenclature and Isomerism

QUICK LOOK The alkynes are represented by the general formula CnH2n–2.
Alcohols: Alcohols are derived from alkanes by the
Nomenclature of Organic Compounds
replacement of one, two or three hydrogen atoms by the
In order to systematise the nomenclature of organic
same number of –OH groups. As a result, mono, di, and
compounds, IUPAC (International Union of Pure and Applied
trihydric alcohols are obtained respectively.
Chemistry) system of nomenclature was first introduced in
Monohydric alcohols are derived from the corresponding
1947. These rules underwent modifications from time to time
alkanes by replacing the –e in the alkane by –ol. Alcohols
and the most exhaustic rules for nomenclature of organic
are thus known as alkanols.
compounds were first published in 1979 and later revised and
Example:
updated in 1993. The rules discussed are the latest and are
based upon 1979 and 1993 editions of the IUPAC nomenclature CH3
3 2 1
|
of organic compounds. CH3 — CH2OH CH2 == CH 2 — CH 2 — OH CH3 — C — OH
IUPAC Names of Homologous Series Ethanol 2-Propen -1-ol |
H
Alkanes or Paraffins: These are represented by the general 2-Propanol
(Alkyl alcohol)
formula Cn H 2n + 2 . According to IUPAC system, they are
called alkanes and the names of all alkanes will be ending Dihydric alcohols are known as diols. They are obtained by
with the suffix –ane. adding the suffix diol to the name of the parent alkane. The
Examples: numbers indicating the positions of the two − OH groups
CH3 — CH3 CH2 — CH3 CH3 — CH2 — CH2 — CH3 may appear first or come between the two.
Ethane Propane Butane
Examples
CH3 CH2 OH
| |
4 3 2 1 2 3 4 5 CH 2 OH CH3 — CHOH CH2
CH 3 — CH 2 — CH 3 — CH 3 — CH 2 — C — CH 2 — CH 3 | | |
| | CH2 OH
CH 2 OH CH 2 OH
CH 3 CH3 1,2 Ethanediol or Ethane 1,2,diol 1,2 Propanediol or prppane 1,2,diol 1,3 Propanediol or propylene 1,3,diol
2-m ethyl butane 3, 3 dimethylpentane (Ethylene glycol) (Propylene glycol) (Trimethylene glycol)
The IUPAC name of the trihydric alcohols is derived by

Alkenes or Olefins: These are characterised by the
adding suffix –triol to the name of the corresponding alkane
presence of a double bond between two carbon atoms and
and indicating the positions of the -OH groups by numerals.
thus they contain two hydrogen atoms less than the
Examples:
corresponding alkane. They are represented by the general
formula Cn H 2n . According to IUPAC system olefins are CH 2 — CH — CH 2
| | |
derived from the corresponding alkanes by replacing the OH OH OH
Propane-1,2,3-triol (Glycerol)
suffix – ane by – ene. Thus olefins are called alkenes.
Examples: Ethers: The ethers are known as alkoxy hydrocarbons, i.e,
CH 2 == CH 2 CH3 — CH == CH 2 hydrocarbons in which a hydrogen atom is replaced by alkoxy
Ethene Propene group, –RO. The larger alkyl group is chosen as the parent
1 2 3 4 4 3 2 1
C H 2 == C H — C H 2 — C H3 C H3 — C H == C H — C H3
hydrocarbon, saturated or unsaturated. The name of the
Butane 2-butane hydrocarbon (alkane) is prefixed by the name of the alkoxy
Acetylenes: According to IUPAC system acetylenes are group and position number.
called alkynes. The name is derived from the corresponding Examples:
alkanes by replacing the ending suffix –ane by yne. The CH3
position of triple bond is indicated by number. |
Examples: CH3 — O — CH3 CH3 — O — C2 H5 CH3 — O — CH — CH3
Methoxy methane Methoxy ethane 2-methoxypropane
1 2 3 4 1 2 3 4 Thio alcohols: Commonly these are known as mercaptans.

CH == CH CH3C ≡≡ CH C H3 C ≡≡ C C H 3 C H ≡≡ C ⋅ C H 2 — C H 3 According to IUPAC system, the names are obtained by
Ethyne Propyne 2 − Butyne I − butyne

adding the suffix thiol to the name of the corresponding Examples:
alkane. H — COOH CH 3 — COOH
Methanoic acid Ethanoic acid
Examples:
CH SH C 2 H 5SH CH 3 CH 2 CH 2SH (CH 3 ) 2 CHCH 2SH CH 3 .CH 2 — COOH CH 3 CH 2 CH 2 COOH
3 Propanoic acid Butanoic acid
Methane thiol Ethane thiol 1-Propane thiol 2-Methyl propane thiol
The SH group is the functional group in thiols. The –SH CH 3 CH 2 CH 2 CH 2 COOH

Pentanoic acid
group is called thiol group or mercapto group or sulphydryl
The general formula of monocarboxylic acids is
group.
C n H 2n +1 − COOH or R − COOH. The functional group is
Thioethers or Alkyl sulphides: According to IUPAC
system, thioethers are named as alkylthio alkanes. Smaller –COOH. In IUPAC system, dicarboxylic acids are named as
alkyl group to the sulphur atom is regarded as the alkanedioic acids, i.e. the suffix dioic acid is added to the
substituent. name of parent alkane. The position of substituents is
CH 3 — S — CH 3 CH 3 — S — CH 2 CH 2 CH 3 indicated by numbers.
Methyl thiomethane 1-Methyl lthiopropane
COOH CH 2 — COOH
(Dimethyl sulphide) (Methyl propyl sulphide) COOH |
| H2C CH 2 — COOH
C 2 H 5 — S — C3 H 7 COOH COOH
Ethyl thiopropane Butanedioic acid
Ethanedioic acid Propanedioic acid (1,2 Ethane dicarboxylic acid
(Ethyl propyl sulphide)
(Oxalic acid) (Malonic acid) or succinic acid)
The characteristic functional group for thioethers is –S–.

CH — COOH
Aldehydes : In IUPAC system the name of an aldehyde is ||
(CH 2 ) 4 (COOH) 2 CH — COOH
derived by replacing the ending –e of the corresponding Hexanedioic acid Butenedioic acid
(Adipic acid) (Maleic or Fumaric acid)
alkane with –al.
Examples: Acid derivatives: Acid halides or Acyl halides–The IUPAC
names of these compounds are derived by replacing the –e
CH 3 CHO CH 3 CH 2 CHO CH 3 CH 2 CH 2 CHO HCHO
Methanal
Ethanal Propanal Butanal of the alkane by oyl halide. They can also be obtained by
The general formula for aldehydes is C n H 2n +1 CHO or replacing the suffix oic acid of the carboxylic acids by –oyl
R − CHO and functional group is −CHO. halide.
Ketones: In IUPAC system ketones are named by replacing HCOCl CH3COCl C2 H5 COCl C3 H 7 COCl
Methanoyl chloride Ethanoyl chloride Propanoyl chloride Butanoyl chloride
the ending - e of the corresponding alkane with –one. The
The general formula of acid halides is C n H 2n +1 COX or
chain is then numbered to give the carbonyl carbon the
lowest possible number. The latter is then employed to R − COX and the functional group is –COX.
designate the position of carbonyl group. Acid amides: According to IUPAC system, amides are
O named by replacing the final –e of the alkane by amide.
O
|| || Examples:
CH 3 — C — CH 3 CH 3 CH 2 — C — CH 3
Propanone-2 Butanone-2
HCONH 2 CH 3 CONH 2
Methanamide Ethanamide
(Formamide) (Acetamide)
O
|| CH 3 CH 2 CONH 2 C3 H 7 CONH 2
CH 3 CH 2 CH 2 — C — CH 3 Propanamide Butanamide
(Propionamide) (Butyramide)
2-Pentanone
Cl Cl The general formula of amides is C n H 2n +1 CONH 2 or

| |
CH 3 — CH — CO — CH 2 — CH 2 C 2 H 5 — CO — C 2 H 5 R − CONH 2 . The functional group is −CONH 2 .
5 4 3 2 1 Pentanone-2
1,4, dichloro-3-pentanone Acid anhydrides:In IUPAC system, anhydrides are named
The general formula for ketones is C n H 2n +1 − CO − C n H 2n +1 by replacing the word acid in the name of the parent acid by
anhydride.
or R-CO-R and functional group is > C = O.
Examples:
Carboxylic acids: These are derived by replacing one or
two hydrogen atoms of the alkanes by carboxylic group, (– CH 3 — CO — O — CO — CH 3
Acetic anhydride
(Ethanoic Anhydride)
COOH). The names of monocarboxylic acids are derived
from alkanes, by replacing the terminal -e by the suffix oic CH 3 CH 2 — CO — O — CO — CH 2 CH 3
Propionic anhydride
acid. (Propanoic Anhydride)

Esters: In IUPAC system, the names are obtained by first CH 3 CN C3 H 7 CN (CH3 )2 CH — CN
Ethane nitrile Butane nitrile 2-methyl propane nitrile
writing the name of the alkyl part of the –OR group
followed by the IUPAC name of the acid in which suffix –ic The general formula of alkyl nitriles is R – CNand
is replaced by –ate. functional group is –CN.
Alkyl isocyanides: These are derived by replacing a
HCOOCH3 CH 3 COOCH 2 CH 3 CH 3 CH 2 COOCH 2 CH 2
Methyl formate Ethyl acetate Ethyl propionate hydrogen atom of alkanes by the isonitrile (–NC) group.
Methyl methanoate Ethyl ethanoate Ethyl propanoate
(IUPAC name) (IUPAC name) (IUPAC name) Commonly they are known as alkyl isocyanides. According
The general formula of esters is R − COOR ' and functional to IUPAC system the word carbylamine is added to the
group is − COOR '. name of the alkyl radical.
Aliphatic amines: Commonly amines are named by adding CH NC 3 C H NC
2 5 C H NC
4 9
Methyl carbylamine Ethyl Carbylamine Butyl carbylamine
the word amine to the name of the alkyl groups attached to
Nitroalkanes or Nitroparaffins: These are derived from
the nitrogen atom.
alkanes by the replacement of a hydrogen atom by –NO2
Examples:
group. Their general formula is R–NO2 and functional group
CH3 — NH2 CH 3 — CH 2 — NH 2 CH 3 CH 2 CH 2 — NH 2
Methyl amine Ethyl amine Propyl amine is –NO2. Their common and IUPAC names are generally
According to IUPAC system, these primary amines the same and derived by adding the suffix nitro before the
(containing –NH2group) are named as amino derivatives of name of the corresponding alkane.
alkanes. They are, therefore named after the parent alkane, Examples: CH 3 NO 2 C 2 H 5 NO 2
Nitromethane Nitroethane
and the position of –NH2 group is indicated by the lowest
possible number. IUPAC Nomenclature of Complex Compounds
Examples: According to IUPAC system of nomenclature any given
CH 3 organic compound can be represented by one and only one
| molecular structure. In general, the IUPAC system of naming
CH 3 — CH 2 — NH 2 CH3 — C — CH 3 CH 3 − C − CH 3
Amino ethane | | an organic compound consists of three parts:
(Ethyl amine)
NH 2 NH 2
2-amino propane 2-amino-2-methyl
(a) Prefix(es) (b) Root word (c) Suffix(es).
Propane (teriary butyl amine)
The root word depends on the number of carbon atoms present
The general formula of primary amines is R–NH2and in a suitable chain, called the parent chain, containing the
functional group is –NH2(amino group). The secondary and functional group and as many of carbon-carbon multiple
tertiary amines containing –NH and N groups respectively bonds(s) as possible. Appropriate suffix(es) is then added to the
are named as alkyl amino alkanes and dialkyl amino alkanes root word to denote the saturated or unsaturated character of the
respectively. The general formulae of secondary and tertiary parent chain and also the functional group present theirin.
amines are R − NH − R and R 3 N respectively. Finally, prefix(es) is put to indicate the nature and position of
CH3 — NH — C2 H5 CH 3 — N — CH 3 the side chain or substituents. The basic rules for IUPAC
N-methyl amino ethane | system are: Longest Chain Rule–The longest possible
(N methyl-ethylamine) CH 3
(Ethyl methyl amine)
N, N, Dimethyl amino methane continuous chain of carbon atoms containing the functional
(N,N, Dimethyl methyl amine)
(Trimethyl amine) group and carbon-carbon multiple bonds is first selected and
Alkyl cyanides: Their common names are derived by the root word corresponding to it is noted.
replacing a hydrogen atom of the alkane. They can also be CH 3 — CH 2 — CH 2 — CH 2 — CH — CH 3
|
regarded as derivatives of carboxylic acid in which bivalent CH 3
oxygen, together with monovalent –OH group have been |
CH 3 — CH 2 — CH 2 — CH 2 — CH 2 — CH 3
replaced by a trivalent nitrogen.
O
|| Table 16.1: Number of Carbons and Root Words
− ,O − OH
R — C — H  +N
→ R — C ≡≡ N Alkyl nitrile No. of carbons Root word No. of carbons Root word
1 Meth – 6 Hex –
According to IUPAC system alkyl cyanides are called 2 Eth – 7 Hept –
nitriles. The parent name is derived from the longest carbon 3 Prop – 8 Oct –
chain containing the –CNgroup. The position is indicated by 4 But – 9 Non –
5 Pent – 10 Dec –
a number.

Primary Suffix: A primary suffix is to be added to the root word CH 3 C2 H 5
| |
to indicate saturation and unsaturation in the selected chain. The CH3 — CH 2 — CH — CH 2 — CH 2 — CH3
generic root word for any carbon chain is alk - (from alkane). 1 2 3 4
3-ethyl-2-methyl hexane
5 6
CH 3 CH 3
Table 16.2:Suffix and Generic Name | |
CH 3 — CH — CH — CH3
Chain Type Suffix Generic Name 1 2 3 4
2,3-dimethyl butane
Saturated – ane Alk + ane
Unsaturated with one double – ene Alk + ene
bond Lowest Sum Rule: The sum of the numbers used to indicate
Unsaturated with one triple bond – yne Alk + yne the position of substituents should be minimum. The parent
Alkane - 1H – yl Alk + yl
carbon chain is to be numbered from one end. The position of
substituents and functional groups is indicated by the number of
Secondary Suffix: A secondary suffix is added to indicate the
carbon atoms to which they are attached.
nature of functional group, if present in the compound. Some
X X
functional groups are given below: | |
(i) C— C— C— C— C— C C— C— C— C— C— C
1 2 3 4 5 6 6 5 4 3 2 1
(Correct ) (Incorrect )
Table 16.3:Functional Group and Secondary Suffix CH 3 CH 3

Functional Secondary Functional Secondary 1 |3 24 5 6 6 5 |4 3 2 1
(ii) CH 3 — CH 2 — C — CH 2 — CH— CH 3 CH 3 — CH 2 — C —CH 2 — CH— CH 3
Group Suffix Group Suffix | | | |
CH 3 CH 3 CH 3 CH 3
Alcohol (–OH) – ol Ester (– COOR) – oate 3, 3, 5 trimethyl hexane (I) (Incorrect) 2,4,4 trimethyl hexane (II) (correct)
In case II, the sum of numbers of substituents is 2 + 4 + 4 = 10,

Aldehyde – al Amide – amide
(–CHO) (– CONH2) which is less than in I, where the number of substituents is 3 +
Ketone – one Acid chloride – oyl chloride 3 + 5 = 11. When two or more groups are located in equivalent
(> C = O) (–COCl) position in the carbon chain, the lower number is assigned to
Carboxylic acid – oic acid that group which is written first in the name of the compound in
(–COOH)
the alphabetical order.
The terminal "e" of the primary suffix is replaced by secondary CH3 CH 2 CH3
| |
suffix. CH3 — CH 2 — C H — CH 2 — CH 2 — CH 2 — C H — CH3
8 7 6 5 4 3 2 1
Table 16.4:Formula andIUPAC Name
In case the substituent on the parent chain is complex
Formula No. of Root Primary Seconda- IUPAC
carbons word suffix ry suffix Name (containing more than 4 carbon atoms) it is named as
HCHO 1 meth – – an – al Methanal substituted alkyl group whose carbon chain is numbered from
CH3CH2OH 2 eth – – an – ol Ethanol the carbon carbon – atom attached to the main chain.
3
CH3COOH 2 eth – – an – oic Ethanoic
C H3
acid acid |2
CH3CH2 CH3 3 prop – – ane – Propane CH3 — C H
|1
CH3CH = CH 2 3 prop – – ene – Propene CH3 — C H
|
CH 3 − C ≡ CH 3 prop – – yne – Propyne
CH3 — CH 2 — CH 2 — CH 2 —
− CH—CH 2 —CH 2 — CH 2 — CH3
1 2 3 4 5 6 7 8 9
CH 3COCH 2 CH3 4 but – – an – one Butanone 5-(1,2 dimethyl propyl) nonane
The position of a double bond (or triple bond) in alkenes (or

Prefixes Rule: Prefixes are to be added to the root word to alkynes) is indicated by prefixing the number of the carbon
represent the side chains and substituents. proceeding such a bond, the carbon chain being numbered from
the end which assigns lower positional number to the double
Alphabetical Arrangement of Prefixes Rule: If there are
(or triple) bond.
more than one side chains/substituents, they should be prefixed
CH3
in the alphabetical order. When two or more identical side |
chains/substituents are present, their location and number are CH3
1 2 4 5 |
represented by prefixing di (2), tri (3), tetra (4) etc. before the CH3 —CH == CH —CH2 —CH3 CH3 —CH2 —CH2 —C == CH2
2-pentene 5 4 3 2 1
substituents/side chains. 2-ethyl-2 pentene

CH3 CH 3 1
| | CHO CH 3
CH 3 — C H — C H — C ≡ C− CH 3 |2 |3 4
6 5 4 3 2 1 CH 2 — CH 2 — C H — C H — C H 3
4, 5-dimethyl-2-hexyne 2-ethyl-3-methyl butanol
O CH 3
Lowest Number of Functional Group Rule: When a functional || |
group is present in a compound, the lowest number must be CH 3 — CH 2 — C3 — CH 2 — CH— CH 2
1 2 3 4 5 6
5-ethyl hexanone-3
given to the functional group, even if it violates the lowest sum
rule. Carbon Multiple Bonds Numbering: While numbering the
CH 3 CH 3 parent chain containing carbon-carbon multiple bonds, the
1 |2 3 4 4 3| 2 1 lower number of two carbons involved in the multiple bonds, is
C H 3 — C— C H — C H 3 C H 3 — C — C H — C H 3
| | | | used to indicate the position of the multiple bond. Number 2,
CH 3 OH CH 3 OH for example, is used to indicate the position of the double bond
3-hydroxy, 2, 2 dimethyl butane (Incorrect) 2-hydroxy, 3, 3 dimethyl butane (Correct)
in the alkene, (III).
The parent chain in a halogen substituted alcohol (I) would be CH3
1 2 3 4| 5 6
numbered so as to give the lower number to the functional CH3 — CH == CH— C H — CH 2 − CH 3
group –OH. (III)
4 3 2 1 1 2 3 4
4-methyl hexene-2
C H 3 — C H — C H — C H 3 ≡≡ C H 3 — C H — C H — C H 3 Prefix for Alicyclic Compounds: The word cyclo is prefixed
| | | |
Cl OH Cl OH to the root word if the compound being named is an alicyclic
(Correct ) (Incorrect ) compound. When alicyclic compounds contain side chains
The numbering of the parent chain in the alcohol II can be done and/or substituents, they appear as secondary prefixes before
in two days: the word cyclo.
CH 3 CH 3
1 3|
2 4 5 6 4| Naming
3 6 2 Polyfunctional
5
1 Compounds: When a compound
C H 3 — C H 2 — C— C H — C H 2 — C H 3 C H 3 — C H 2 — C—contains
C H — Ctwo H2 — C H
or more 3 different functional groups, one of the
| | | |
CH 3 OH functional
CH 3 OH groups is chosen as the principal functional group
(A) and the remaining functional groups (secondary functional
(B)
CH 3 CH 3 groups) are treated as substituents in the IUPAC names. The

3| 4 5 6 6 5 4| 3 2 1 following guidelines determine the choice of the principal and
— C— C H — C H 2 — C H 3 ≡≡ C H 3 — C H 2 — C— C H — C H 2 — C H 3
| | | | secondary functional group while giving IUPAC names to
CH 3 OH CH 3 OH polyfunctional organic compounds.
(A) (B)
When two or more than two functional groups are present in
In case B the functional group –OH gets the lower number 3, but
a compound, the principal functional group generally gets
in the case A it gets the higher number 4. However, the sum
the following order of preference: Acids > Acid derivatives
numbers used to indicate the position of the functional group and
excluding nitriles > Aldehydes > Nitriles > Ketones >
side chains in B is 4 + 4 + 3 = 11, and in case A it is 3 + 3 + 4 = 10.
Alcohols > Amines > Ethers > Alkenes > Alkynes
In accordance with this rule, the former system of numbering is
While selecting the parent chain in a polyfunctional
preferred. compound, it should be ensured that it includes the
Numbering the Carbon in Terminal and Non-terminal maximum number of functional groups present, including
Functional Groups: The carbon in chain terminating functional the principal functional group.
groups such as—COOH, —CHO, —CONH2, CNetc. must While numbering the parent chain in such cases, the
always be given number 1. The carbon of non-terminal group following is the decreasing order of preferences for giving
(e.g. >C=O) may or may not be assigned number 1. the lowest numbers. Principal functional group > Double
bond > Triple bond > Substituents.
Examples:
If branching alkyl groups (side chains) contain multiple
CH 2 CH 3
| bonds and functional groups, the side chain is numbered
CH 3 .CH 2 .CH 2 .CH.CH 2 .COOH separately so that the carbon atom in the side chain which is
6 5 4 3 2 1
3-ethyl hexanoic acid itself bonded to the parent chain is designated as. The

application of these rules may be demonstrated by the both the bridge heads is called a bridge. The bridge may, contain 0,
following examples: 1, 2 ……etc., carbon atoms. This is illustrated by the following
3 2 1 examples:
CH 3 — CH 2 — C H — CH 2 Br
| Bridge head atom
CH 3 Zero carbon bridge
1, bromo-2-methyl butane
CH 2 — CH
Two carbonbridge | | CH 2
CH 3 CH 2 — CH
|
CH 3 — C H — CH 2 — CH 2 — CH 2 — CH 3 One carbonbridge
1 2 3 4 5 6 Bridge head atom
2-methyl hexane
Bridge headatom
CH 3 CH 3
| | CH
H 3 C — C — CH 2 — CH — CH 3
|
CH 3 CH 2 CH 2
2, 2, 4-trimethyl pentane Two carbonbridge | CH 2 | Two carbonbridge
5 4 2 2 1
CH 2 CH 2
CH 3 — CH == CH— CH == CH 3
One carbonbridge CH
1, 3-pentadiene
To derive the structure of a compound from IUPAC name, the

Bridge head atom
following steps are to be followed :
Identify the root word and write the parent carbon chain and A bicyclic compound is named by attaching the prefix ‘bicyclo’ to
then number it from one end. the hydrocarbon having the same total number of carbon atoms as
Identify the primary suffix and then the multiple bonds, if in the two rings. The number of carbon atoms in each of these
present. Locate them at the proper place in the parent chain. three bridges connecting the two bridge head carbon atoms is
Now attach the functional group(s) and substituents at the indicated by Arabic numerals i.e., 0, 1, 2, 3…etc. These Arabic
specified carbons as indicated by the suffixes and prefixes numerals are arranged in descending order, separated from one
of IUPAC name. another by full stops and then enclosed in square brackets. The
Finally required number of hydrogen atoms are placed on each complete name of the hydrocarbon is then obtained by placing
carbon in the parent chain to satisfy the tetravalency of carbon. these brackets between the prefix bicyclo and the name of the
alkane.
Bond Line Notations of Organic Molecules: It is a more Examples:
accurate, simple and convenient method of representing
structures of organic molecules. In this notation bonds are
represented by lines and carbon atoms by line ends and
intersections. It is further assumed that required number of Bicyclo [2.1.0] pentane Bicyclo [1.1.0] butane
hydrogen atoms are present wherever they are necessary to
satisfy the tetracovalency of carbon. Sometime symbols like
Me (for methyl), Et (for ethyl) are used to indicate the presence Bicyclo [3.1.1] haptane Bicyclo [4.4.0] decane
of these groups.
CH3 or 2
1 | 23 4
4
CH 2 == C — CH == CH 2 1 3 Bicyclo [2.2.1] haptane Bicyclo [2.2.2] octane
2 − methylbuta −1,3 − diene
7 4 7 4
1 2 3 4 5 2 4 3
CH 2 == CH— CH 2 — CH == CH 2 or 5
5 3
Penta −1,4 − diene
1 3 5
1
1 2
6 2 6
2.6
IUPAC Rules for Nomenclature of Polycyclic Compounds: Bicyclo [2.2.1] heptane Tricyclo [2.2.1.0 ] heptane decane
Many a time, hydrocarbons of their derivatives contain two or
If a substituent is present, the bicyclic ring is numbered with
more rings. The carbon atoms common to both the rings are called
one of the bridge head atom. It is numbered as 1. Numbering
bridge head atoms. Each bond or chain of carbon atoms connecting

proceeds first along the bridge passing through the second hydrocarbon unit. The numerical prefixes used in this
bridge head atom, continues along the next longest bridge nomenclature are given below:
passing through the second bridge head atom, continues along No. of cyclic Two Three Four Five
the next longest bridge to the first bridge head and finally hydrocabon units
completed along the shortest path. This is illustrated by the Prefix bi ter quater quinque
following examples.
1 2 Starting from either end, the carbon atoms of each repetitive

8 Br
27 1 3 hydrocarbon unit are numbered with unprimed and primed
6
36 5 7 4 Arabic numerals such as 1, 2, 3,…1′, 2′, 3′,…:1′′, 2′′, 3′′,…etc.
4
The point of attachment of the repetitive hydrocabon units are
5
8-Bromobicyclo [3.2.1] octane 2,6,6-Trimetylbicyclo indicated by placing the appropriate locants before the name.
[3.1.1] hept-2-ene Examples:
2 3 4 4′′ 3′′
1 2′
2 O 1′
Cl 6 1 1′ 2′
1 8
3 2 1 1′′ 2′′
7
5 3 3′
3 3 4′ 3′
4 6 7 4 1, 1′–Bicyclopropane 1, 1′, 2′ 1′′–Tercyclobutane
5 1,7,7-Trimethylbicyclo
3′
8-Chlorobicyclo[4.2.0] oct-2-ene [2.2.1] heptan-2-one 2
2′′
1 1′′
1′ 2′
IUPAC Rules for Nomenclature of Spiro Compounds:
3′′
Compounds in which one carbon atom is common to two
1, 1′, 2′, 1′′–Tercyclopropane
different rings are called spiro compounds. The carbon atom
common to the two rings is called the spiro atom. The IUPAC
As an exception, unbranched assemblies consisting of benzene
name for a spiro compound begins with the word ‘spiro’
rings are named by using appropriate prefix with the name
followed by brackets containing the number of carbon atoms, in
phenyl instead of benzene.
ascending order, in each ring connected to the common carbon
Examples:
atoms and then by the name of the parent hydrocarbon
3 2 2′ 3′ 2′′ 3′′ 3 2 6′ 5′
containing the total number of carbon atoms in the two rings.
1 4′ 1 1′ 4′
The numbering begins with the ring atom next to the spiro atom 4 4′′ 4
1′ 1′′
and then proceed first around the smaller ring and then to the 5 6 6′ 5′ 6′′ 5′′ 5 6 2′ 3′
spiro atom and finally around the large ring. This is illustrated 1, 1′, 4′, 1′′–Terphenyl
1′′
by the following examples. 2′′
6′′
7 6 1 9 10 1 5′′ 3′′
Cl CH3
2 2 4′′
8 8
5 5 1, 1′, 3′, 1′′–Terphenyl
3 3
9 10 4 7 6 4 Replacement Nomenclature: IUPAC recommend its use in
2-Chlorospiro [ 4.5] decane 2-methylspiro [ 4.5] deca 1, 6 diene case of unsymmetrical structures with several chalcogen atoms.
5 1 4
1
5 Examples:
6 2 15 14 13 11−12 10 8−9 7 5−6 4 2−3
4 6 3 CH 3 — CH 2 — O— [CH 2 ]2 — O— [CH 2 ]2 — O— [CH 2 ]2 — O— [CH 2 ]2 —
2 4,7,10,13-Tetraoxapentandecanoic acic
7 3 7
15
Spiro [3.3]14heptane13 11−12 10 [2.4]8 −heptane
Spiro 9 7 5−6 4 2−3 1
CH 3 — CH 2 — O— [CH 2 ]2 — O— [CH 2 ]2 — O— [CH 2 ]2 — O— [CH 2 ]2 — COOH
IUPAC rules for nomenclature of unbranched assemblies
consisting of two or more identical cyclic hydrocarbon units Functional Class Names of Ratio-functional Names: IUPAC
joined by a single bond: These systems are named by placing recommend its use for naming isocyanides, ethers with
a suitable numerical prefix before the name of the repetitive substituents not having priority for citation as suffix.

Examples: Multiple Choice Questions
→ One and More than One Correct
CH 3 N == C
Methyl isocyanide
1. The IUPAC name of C6H5COCl is [JEE 2006]
2 1 1 2
ClCH 2 — CH 2 — O — CH 2 — CH 2 Cl a. Benzoyl chloride
Bis (2-chloroethyl) ether b. Benzene chloro ketone
These names are not written as one word. c. Benzene carbonyl chloride
d. Chloro phenyl ketone
Isomerism: In the study of organic chemistry we come across
many cases when two or more compounds are made of equal 2. The number of structural isomers for C6H14 is
number of like atoms. A molecular formula does not tell the [JEE 2007 P-I]
nature of organic compound; sometimes several organic a. 3 b. 4 c. 5 d. 6
compounds may have same molecular formula. These 3. The number of stereoisomers obtained by bromination of
compounds possess the same molecular formula but differ from trans-2-butene is [JEE 2007 P-II]
each other in physical or chemical properties, are called
a. 1 b. 2 c. 3 d. 4
isomers and the phenomenon is termed isomerism (Greek, isos
= equal; meros = parts). 4. The correct statement(s) about the compound given below
is (are) [JEE 2008 P-I]
Since isomers have the same molecular formula, the difference Cl
in their properties must be due to different modes of the H
combination or arrangement of atoms within the molecule. H 3C
Broadly speaking, isomerism is of two types.
CH3
Structural Isomerism Cl H
Stereoisomerism
a. The compound is optically active
ISOMERISM b. The compound possesses centre of symmetry
c. The compound possesses plane of symmetry
d. The compound possesses axis of symmetry
STRUCTURAL STEREOISOME
ISOMERISM RISM 5. The correct statement (s) concerning the structures E, F
and G is (are) [JEE 2008 P-I]
H 3C O H 3C OH
GEOMETRICAL OPTICAL
ISOMERISM ISOMERISM
H 3C CH 3 H 3C CH3
(E) (F)
H 3C CH 3
FUNCTIONAL POSITIONAL CHAIN METAMERISM TAUTOMERISM
ISOMERISM ISOMERISM ISOMERISM H 3C OH
(G)
Figure: 16.1
a. E, F and G are resonance structures
Specific Rotation: The specific rotation [α ]λ is an inherent T b. E, F and E, G are tautomers
physical property of an enantiomer, which varies with the c. F and G are geometrical isomers
solvent used, temp (in °C) and wavelength of the light used. It d. F and G are diasteromers
is calculated from the observed rotation α as follows. 6. The IUPAC name of [Ni(NH3)4][NiCl4] is
T a [JEE 2008 P-II]
[α ]λ =
l ¥C a. Tetrachloronickel (II) – tetraamminenickel (II)
Where ℓ = length of tube in decimetres (dm) b. Tetraamminenickel (II) – tetrachloronickel (II)
C = Concentration in gram cm–3, for a solution density in gcm–3, c. Tetraamminenickel (II) – tetrachloronickelate (II)
for a pure liquid. d. Tetrachloronickel (II) – tetraamminenickelate (II)

7. The correct statement(s) about the compound H3C(HO)HC– Cl
HO H HO H
CH=CH–CH(OH)CH3(X)is(are) [JEE 2009 P-I] H
OH
a. The total number of stereoisomers possible for X is 6 HO Cl H CH3 HO
H OH H
b. The total number of diastereomers possible for X is 3
c. If the stereochemistry about the double bond in X is CH 3 Cl CH 3
M N O
trans, the number of enantiomers possible for X is 4
d. If the stereochemistry about the double bond in X is cis, CH 3 CH 3
the number of enantiomers possible for X is 2 H OH HO H
8. The IUPAC name of the following compound is HO H HO H

[JEE 2009 P-I]
Cl Cl
OH
P Q
a. M and N are non mirror image stereoisomers

CN b. M and O are identical
Br c. M and P are enantiomers
a. 4-Bromo-3-cyanophenol d. M and Q are identical
b. 2-Bromo-5-hydroxybenzonitrile 14. A solution of (–)-1-chloro-1-phenylethane in toluene
c. 2-Cyano-4-hydroxybromobenzene racemises slowly in the presence of a small amount of
d. 6-Bromo-3-hdyroxybenzonitrile
SbCl5 , due to the formation of [JEE Main 2013]
9. In the Newman projection for 2, 2-dimethyl butane X and a. carbanion b. carbine
Y can respectively be [JEE 2010 P-I] c. carbocation d. free radical
X
15. The correct combination of names for isomeric alcohols with
H 3C CH3
molecular formula C4 H10 O is/are [JEE Adv. 2014 P-I]
H H a. tert-butanol and 2-methylpropan-2-ol
Y b. tert-butanol and 1,1-dimethylethan-1-ol
a. H and H b. H and C2H5 c. n-butanol and butan-1-ol
c. C2H5and H d. CH3and CH3 d. isobutyl alcohol and 2-methylpropan-1-ol
10. Amongst the given options, the compound(s) in which all 16. Which of the following compounds will exhibit
the atoms are in one plane in all the possible geometrical isomerism? [JEE Main 2015]
conformations (if any), is (are) [JEE 2011 P-I] a. 1-Phenyl-2-butene b. 3-Phenyl-1-butene
H H
a. C−C b. H c. 2-Phenyl-1-butene d. 1,1-Diphenyl-2-propane
H−C ≡ C—C
H2C CH 2 CH 2 17. Compound(s) that on hydrogenation produce(s) optically
c. H 2 C = C = O d. H 2 C = C = CH 2 inactive compound(s) is (are) [JEE Adv. 2015 P-I]
H Br
a. b. H Br
11. As per IUPAC nomenclature, the name of the complex CH H 2C CH3
H 3C 3
[Co(H 2 O) 4 (NH3 ) 2 ]Cl3 is [JEE 2012 P-I]
H Br
a. Tetraaquadiaminecobalt (III) chloride H 3C
c. CH3 d. Br H
b. Tetraaquadiaminecobalt (III) chloride
CH H 3C CH3
c. Diaminetetraaquacobalt (III) chloride 3
d. Diamminetetraaquacobalt (III) chloride 18. The IUPAC name(s) of the following compound is (are)
[JEE Adv. 2015 P-I]
12. The carboxyl functional group (—COOH) is present in
[JEE 2012 P -I] H 3C Cl
a. picric acid b. barbituric acid
a. 1 -chloro-4-methyIbenzene
c. ascorbic acid d. aspirin
b. 4-chlorotoluene
13. Which of the given statement(s) about N, O, P and Q with c. 1-methyl-4-chlorobeny,cnc
respect to M is (are) correct? [JEE 2012 P-II] d. 4-methylchlorobenzene

19. The absolute configuration of [JEE Main 2016] 25. What is the IUPAC name of the following compound?
CO 2 H [JEE Main 2019]
CH3 CH3
H OH
H
H
H Cl CH3 Br
CH 3 a. 3-Bromo-1, 2-dimethylbut-1-ene
is:
b. 4-Bromo-3-methylpent-2-ene
a. (2R, 3S) b. (2S, 3R)
c. 2-Bromo-3-methylpent-3-ene
c. (2S, 3S) d. (2R, 3R)
d. 3-Bromo-3-methyl-1, 2-dimethylprop-1-ene
20. Consider the following reaction and statements
+ −
[Co(NH 3 ) 4 Br2 ] + Br 
→[Co(NH 3 )3 Br3 ] + NH 3 Statement/Assertion and Reason
(i) Two isomers are produced if the reactant complex ion 26. Statement-I: Molecules that are not superimposable on
is a cis-isomer their mirror images are chiral. Because
(ii) Two isomers are produced if the reactant complex ion Statement-II: All chiral molecules have chiral centres
is a trans-isomer . [JEE 2007 P - II]
(iii) Only one isomer is produced if the reactant complex a. Statement-I is True, Statement-II is True; Statement-II
ion is a trans-isomer is a correct explanation for Statement-I
(iv) Only one isomer is produced if the reactant complex b. Statement-I is True, Statement-II is True; Statement-II
ion is a cis-isomer [JEE Main 2019] is not a correct explanation for Statement-I
a. (II) and (IV) b. (I) and (II) c. Statement-I is True, Statement-II is False
c. (I) and (III) d. (III) and (IV) d. Statement-I is False, Statement-II is True
21. The IUPAC name of the following compound is : 27. Statement-I: The geometrical isomers of the complex
[JEE Main 2019] [M(NH3 )4 Cl2 ] are optically inactive.and
CH 3 OH Statement-II: Both geometrical isomers of the complex
| |
H 3 C — CH —CH —CH 2 —COOH [M(NH3 )4 Cl2 ] possess axis of symmetry.
a. 2-Methyl-3Hydroxypentan-5-oic acid [JEE 2008 P-II]
b. 4,4-Dimethyl-3-hydroxy butanoic acid a. Statement-I is True, Statement-II is True; Statement-II
c. 3-Hydroxy-4 -methylpentanoic acid is a correct explanation for Statement-I
d. 4-Methyl-3-hydroxypentanoic acid b. Statement-I is True, Statement-II is True; Statement-II
is not a correct explanation for Statement-I
22. The IUPAC symbol for the element with atomic number
c. Statement-I is True, Statement-II is False
119 would be : [JEE Main 2019]
d. Statement-I is False, Statement-II is True
a. unh b. uun
c. une d. uue
Paragraph
23. The total number of isomers for a square planar complex
[M(F)(Cl)(SCN)(NO2)] is : [JEE Main 2019]
P and Q are isomers of dicarboxylic acid C4 H4 OH Both
a. 12 b. 8
c. 16 d. 4 decolorize Br2 / H2O. On heating, P forms the cyclic anhydrie.
24. A reaction of cobalt(III) chloride and ethylenediamine in a Upon treatment with diulute alkaline KMnO4 , P as well as Q
1 : 2 mole ratio generates two isomeric products A (violet could produce one or more than one from S, T & U.
coloured) B (green coloured). A can show optical actively, [JEE Adv. 2013 P-II]
B is optically inactive. What type of isomers does A and B COOH COOH COOH
represent ? [JEE Main 2019] H OH H OH HO H
a. Geometrical isomers b. Ionisation isomers H OH HO H H OH
c. Coordination isomers d. Linkage isomers COOH COOH COOH
S T U

28. Compounds formed from P and Q are, respectively a. Write stable conformer for Z—CH2—CH2—Z in
a. Optically active S and optically active pair (T, U) Newman’s projection. If µsolution = 1.0 D and mole fraction
b. Optically inactive S and optically inactive pair (T, U) of anti form =0.82, find µ Gouche .
c. Optically active pair (T, U) and optically active S
CHDY
d. Optically inactive pair (T, U) and optically inactive S b. Write most stable meso conformer of | .
CHDY
29. In the following reaction sequences V and W are,
H 2 / Ni
If (i) Y = CH3 about C2 — C3 rotation and (ii) Y=OH
respectively Q  ∆
→V about C1 — C2 rotation. [JEE 2015]
AlCl3 (anhydrrous) 1. Zn − Hg / HCl

35. For the given compound X, the total number of optically
+ V  →  →W
2. H3 PO4 active stereoisomers is _________.[JEE Adv. 2018 P-II]
O HO HO
CH2OH
a. O and b. O and
CH2OH
O V W
V W
HO
X HO
O HOH2C This type of bond indicates that the configuration at
thespecific carbon and the geometry of the double bond is
c. d. and fixedtype of bond indicates that the configuration at the specific
This
O and
carbon and the geometry of the double bond is not fixed
CH2OH CH2OH
O V W
V W ANSWERS and SOLUTIONS
1. (c)
2. (c) C6H14
30. The total number of cyclic structural as well as stereo
H3C—CH2—CH2—CH2—CH2—CH3
isomers possible for a compound with the molecular
H 3C — CH — CH 2 — CH 2 — CH 3
formula C5H10 is…………… [JEE 2009 P-II] |
CH 3
31. The total number of cyclic isomers possible for a
hydrocarbon with the molecular formula C4H6 is H 3C — CH — CH — CH 2 — CH 3
|
[JEE 2010 P-I] CH 3
32. The maximum number of isomers (including H 3C — CH — CH — CH 3
stereoisomers) that are possible on monochlorination of | |
CH 3 CH 3
the following compound is…….. [JEE 2011 P-II]
CH 3 CH3
|
C H 3C — C — CH 2 — CH 3
|
CH 3 CH 2 CH 2 CH 3 CH 3
H
Hence (c) is correct
33. The total number(s) of stable conformers with non-zero
dipole moment for the following compound is (are)……. H3 C H Br2
C == C 
(Anti addition)
→
[JEE Adv. 2014 P-I] 3. (a)
Cl H CH3
Br Meso product. Hence (a) is correct.
CH 3
Br Cl H H M
H C
CH 3 M C H C
4. (a, d) C ⇒ ≡
34. µ obs = Σµi x i Where µ1 is the dipole moment of stable C H
C H
M M
conformer and xi is the mole fraction of that conformer M M

The molecule is optically active. 17. (b, d)
Cl H H H CH3 CH3
Cl Cl (1) H3C —CH == CH — C H2/Pt
 → H3C —CH2 —CH2 —C
2 CH3
1 rotatingcarbon −1by180°
 → 2 1 H Br H Br
H3 C Optically active
H
Cl Me Me H /Pt
(2) H3C == CH —C — CH2 —CH3  → H3C — CH — C—CH2 —CH3
2
The molecule possesses an axis of symmetry (C2) H Br H Br

Optically inactive
perpendicular to the C – C bond. H
(3) H 2 C == C — C — C H 3  H/Pt→ H 3 C — C — C — CH3
2
5. (b, c, d) H 2C H Br H 2C H Br
Optically inactive
6. (c) IUPAC name is tetraamminenickel (II) – H /Pt
(4) H2C == CH —C —CH2 —CH3  → H3C —CH2 —C—CH2 —CH3
2
tetrachloronickelate (II). H Br H Br
Optically inactive
7. (a, d)
18. (a, b) IUPAC name
8. (b) Priority of CN is highest.
Cl
CH 3 1
| 2
(A) 1- chloro -4-methylbenzene
9. (b, d) H 3 C— C H 2 — C— C H3 3
4 3 |2 1 4
CH 3 CH3
On C2 — C3bond axis X = CH3, Y = CH3, CH3
On C1 — C2bond axis 1
2
X = H, Y = C2H5 (B) 4-chlorotoluene
3
4
10. (b, c) Cl
11. (d) [CO(H2O)4(NH3)2Cl3] 1 3
Diamminetetraaquacobalt (III) chloride CO 2 H CO 2 H
1
2
O H OH H OH 2S
|| 2
O — C — CH 3
19. (b) H 3 Cl H Cl 3R
1
COOH 4
CH 3 3
CH 3
12. (d) IUPAC numbering Numbering according to
(Aspirin) CIP rules for R/S naming
13. (a, b, c) Factual Br

20. (d) NH3 Br
14. (c) Racemises slowly due to formation of intermediate
carbocation.
15. (a, c, d) Isomeric alcohols of C 4 H10 O are NH3 NH3
NH3
H3 C — CH 2 — CH 2 — CH 2 — OH, H3 C — CH 2 — CH — CH3 ,
n-butanol | cis-isomer
or
butan-1-ol OH +Br–
sec − butyl alcohol
or
bu tan − 2 − ol
CH3 CH3
| | Br Br
H3 C — CH — CH 2 — OH, H3 C — C — CH3
2 − methylpropan −1− ol | NH3 Br NH3 Br
or
isobutyl alcohol OH
tert-butanol
or
2-methylpropan-2-ol
Ph − CH 2 CH3 Ph − CH 2 H NH3 Br NH3 NH3

16. (a) C == C C == C NH3 Br
H H H CH3 (2 isomer)
trans fac- mer-
cis

Br Br For Question Nos. 28 to 29
NH3 NH3 NH3 NH3 28. (b)
H COOH COOH
C
KMnO 4 H OH
→OH
NH3 NH3 NH3 Br C H OH
H COOH
Br Br COOH
trans mer(1 isomer) P
So option (d) is correct. S → optically inactive
CH 3 H COOH COOH COOH

| C
3 2 1
KMnO4 H OH OH H
21. (c) C H 3 — C H— C H— C H 2 — C OOH →
OH
5 4 | C HO H H OH
OH HOOC H
COOH COOH
3-Hydroxy-4-methylpentanoic acid Q T U
–COOH principal functional group Optically inactive pair
22. (d) Symbol Atomic number
unh 106 29. (a)
uun 110 O
une 109
H2 / Ni
uue 119 Q ∆
→ O
23. (a) The total number of isomers for a square planar
complex [M(F)(Cl )(SCN)(NO2)] is 12. O
O
F SCN O
C
M + O
→ AlCl3 Zn − Hg, HCl
  →
Cl NO 2 / SCN / Cl C
(3) O H
O C
F NCS H
O
M H 3PO4
Cl NO 2 / NCS / Cl
(3)
F SCN O
30. Cyclic C5 H10
M
Cl NO 2 / SCN / Cl
(3)
For 3rd structure 2 cis-trans and 1 optical isomer are possible.
F NCS
Total 7 isomers.
M
31. In C4 H 6 , possible cyclic isomers are 5, i.e.,
Cl ONO / NCS/ Cl
(3)
24. (a) , , , ,
25. (b) CH 3
26 (c)
32. CH 3 CH 2 C*− CH 2 CH 2 Cl Enantiomeric pair = 2
27. (b) The molecule should not possess alternate axis of
symmetry to be optically active. H

CH 3 Z
CH 3 CH 2 C*− CHCH 3 (Two

Two Enantiomeric pairs = 44) H Z
*
H H H
CH 3 H
Gauche
CH 3 CH 2 C − CH 2 CH 3 1
Mole fraction of anti form = 0.82
H Mole fraction of Gauche form = 0.18
CH 2 Cl 1 = µ (anti) × 0.82 + µm(Gauch
⇒ ) ×¥0.18
(Gauche) 0.18
CH 3 CH 2 C*− CH 2 CH 3 1 ⇒ µ (anti) = 0
H ∴ 1 = µ(Gauche) × 0.18
Total = 2 + 4 + 1 + 1 = 8 1
⇒ µ Gauche = = 5.55 D
Cl Cl 0.18
33. Br Br Me
Br CH 3 CH3 O H
60°
≡
Br Br D H D OH
CH 3 (b) (i) (ii)
Cl Me
(unstable) H D D H
Cl Br Me CH3 H
Br Me Cl Me
60° 35.
60°
HO OH
Br Me
Cl Cl Br
(stable µ ≠ 0) (unstable)
Me Br Br
Br Me Me Br Me Br Me HO
60° 60° OH
Only three stereocentre are present.
Cl Br Cl
Cl Cl
Me ∴ Total isomer = 23 = 8
Cl Cl
(stable µ ≠ 0) (unstable) (stable µ ≠ 0) But one is optically inactive.
So, Answer is 3. HO OH
Z
34. (a)
H H
H H HO
OH
Z
Anti So, optically active stereoisomers is 7.
Hydrocarbons 155
17 Hydrocarbons
QUICK LOOK gives : conversion to
(i) Gas oil, gasoline by
(ii) Fuel oil, cracking.
Compounds containing only C and H are known as Diesel oil.
hydrocarbons. The main sources of hydrocarbons are Residual oil. On 350 − 400°C C18 − C40 Lubrication
Natural gas → Methane (90%), Ethane, Butanes and refractionation
C18 − C20
Candles, boot
gives: polishes, wax
Hexanes in decreasing quantities.
(i) Lubricating C 20 − C30 paper, taprolin
Petroleum → Aliphatic hydrocarbons oil cloth and
Coal → Aromatic hydrocarbons (ii) Paraffin wax C30 – C40 electrical
(iii) Petroleum insulation.
jelly In medicines,
Petroleum, Crude oil or Mineral oil: It is a dark coloured (Vaseline) cosmetics,
viscous oil (with unpleasant smell due to sulphur compounds) toilets and
found deep in earth’s crust. It may be of three types: lubricants.
Paraffinic base type → It contains mainly of saturated Residue, which > 400°C Pitch is used in
may be either water proofing of
hydrocarbons. pitch (asphalt) roofs, road
Asphaltic base type → It contains mainly cycloparaffins or petroleum making,
Mixed base type → It contains both paraffinic and coke. stabiliser for
wood and metal.
Asphaltic hydrocarbons.
Petroleum coke
Crude oil as such is of little importance. However, it can be is used as fuel.
separated into a number of useful fractions by fractional
distillation. Thus petroleum is a source of infinite number of useful
compounds, it is said to be more precious than gold and hence
Table 17.1: Temperature Range of Condensation also named as liquid gold or black gold.
Name of the Temperature Approximate Uses
fraction range of composition Octane Number
condensation
Octane number of a gasoline is defined as the percentage of iso-
Uncondensed Upto 30°C C1 − C5 Domestic fuel,
gases synthesis of octane present in a mixture of iso-octane and n-heptane which
organic matches the fuel (gasoline) in knocking; higher the octane
chemicals, number of a gasoline better is its quality.
production of
carbon black. CH 3 CH 3
Gasoline 30 − 200°C C5 − C10 | |
(Petrol). On As a solvent for CH 3 ⋅ (CH 2 )5 ⋅ CH 3 CH 3 − C − CH 2 − CH − CH 3
30 − 80°C C5 − C 6 n -Heptane |
refractionation fat, oil, varnish (Octane number = 0)
80 − 200°C CH 3
gives : C6 − C10 and rubber Iso-octane (2, 2, 4-Trimethylpentane)
(i) Petroleum Fuel for the (Octane number = 100)
ether internal
(ii) Gasoline combustion Ordinarily gasolines having an octane number of 74 are used in
or petrol engines of
motor cars, scooters and motorcycles. These gasolines are
automobiles and
aeroplanes, known as regular gasolines. Gasolines having octane number
solvent and dry- lower than this value are called third grade gasolines, while
cleaning. gasolines having an octane number of 84 and above are known
Kerosene 200 − 300°C C10 − C16 Illuminant, fuel
as premium gasolines.
for stoves, for
making oil gas. Compounds having more than 100 and less than 0 octane
Heavy oil. On 300 − 350°C C16 − C18 Fuel for diesel numbers are also known. For example, triptane (2, 2, 3-
refractionation engines, for trimethylbutane) has an octane number of 125, while n-nonane

has an octane number of 45. Aviation gasoline (gasoline used Cetane Number: It is used for measuring the knocking
as fuel in aeroplanes) has an octane number of 100 or more. character of fuel used in diesel engines. Cetane (n-hexadecane,
Presence of following types of organic compounds increases the n − C16 H 34 ) ignites very readily and is given a cetane number of
octane number of gasoline. 100 while α - methylnaphthalene ignites very sluggishly in a
In case of straight chain hydrocarbons, octane number diesel engine and hence is given zero cetane number.
decreases with increase in the length of the chain. α CH 4
Branching of chain increases the value of octane number.
CH 3 ⋅ (CH 2 )14 ⋅ CH 3
β β
Introduction of double or triple bond in an alkane increases
the value of octane number. β β
Hexadecane or Cetane
Cyclic alkanes have relatively higher value of octane α α
(cetane number = 100) α-Methylnaphthalene
number than the corresponding n-alkanes. Spontaneous ignition (cetane number = 0) Slow ignition
The octane number of aromatic hydrocarbons are exceptionally
high. Centane number of a fuel is defined as the percentage of cetane in
The Octane number of gasolines can be improved by following a mixture of cetane and α-methylnaphthalene that will have the
methods: same ignition characteristics as the fuel under examination.
By cracking,
By alkylation, Synthetic Petrol
By isomerisation, Bergius process: Finely powdered coal (coal is a mixture
By adding gasoline additives (e.g. TEL), of high molecular complex organic compounds deficient in
By adding BTX (benzene, toluene and xylene) hydrogen) is heated with a catalyst (organic compound of
tin) in presence of hydrogen.
Knocking: The objectionable metallic sound produced during the 400∞ C - 500∞ C
Coal + H 2 æææææ Æ Hydrocarbons(1)
250 atm
working of an internal combustion engine is known as knocking. It
Fischer–Tropsch process: Hard coke is the raw material.
leads to wastage of fuel. Knocking depends upon the composition
Steam is passed over red hot coke to give water gas (a
of the fuel, it falls off in the following order: Straight chain
mixture of CO and hydrogen). Carbon monoxide is
paraffins > Branched chain paraffins > Olefins > Aromatic
removed from a part of the water gas. Hydrogen so obtained
hydrocarbons. Knocking may also be prevented or minimised by
is mixed with rest of the water gas in a ratio of synthesis gas
adding small amounts of certain compounds known as anti-knock
(i.e. H 2 and CO in a ratio of 2 : 1) which is heated in
compounds, e.g. tetraethyl lead (TEL) [(C2H5)4Pb]. Such petrol is
known as leaded petrol or ethyl petrol. Tetraethyl lead is used as a presence of a catalyst (cobalt-thorium oxide).
mixture of TEL (63%), ethylene bromide (26%), ethylene chloride n CO + n H 2 
Co,Cu
→ C n H 2n + nH 2O ;
Zn Oxide
(9%) and methylene blue (2%). About 0.5-0.6 ml of this mixture is
n CO + (2n + 1) H 2 
→ Cn H 2n + 2 + nH 2O
added to 1 litre of petrol.
In the cylinder of combustion engine, TEL decomposes to produce The overall yield of Fischer–Tropsch process (66%) is higher
radicals which combine with the radicals produced due to irregular than that obtained from Bergius process (60%) and thus, unlike
combustion. As a result, the reaction chains are broken and smooth Bergius process, it can be operated commercially on a small
scale. Petroleum products (e.g. ethylene, propylene, isobutene,
burning of fuel occurs. This prevents knocking,
acetylene, etc.) are used in preparing thousands of organic
Pb(C 2 H 5 ) 4 
heat
→ Pb + 4C 2 H 5
chemicals and products like dyes, drugs, explosive, plastics,
This lead is deposited in the cylinder which is removed by fibers, rubber, etc. Hence petroleum is literally called as liquid
ethylene bromide to form lead bromide volatile at the ignition gold or black gold.
temperature,
Petrochemicals
→ CH 2 = CH 2 + Br2 ,
BrCH 2 − CH 2 Br  Organic compounds obtained directly or indirectly from natural gas
Pb + Br2 
→ PbBr2 (volatile)
(volatite) or petroleum are called petrochemicals. Some petrochemicals are:
However, use of TEL in petrol is facing a serious problem of Saturated hydrocarbons–Methane, ethane, propane, butanes,
lead pollution. To avoid this, a new compound cyclopentadiene pentanes, hexanes, cyclohexanes etc.
-lmanganese carbonyl (called as AK-33-X) is used in Unsaturated hydrocarbons–Ethylene, propylene, butylenes,
developed countries, as anti-knocking compound. acetylene etc.
Hydrocarbons 157
Aromatic hydrocarbons – Benzene, toluene, etc. Coal tar: It is a thick black viscous liquid with a disagreeable
Halogen derivatives– CH3Cl,CH2Cl2 ,CHCl3 ,CCl4 ,CH = CHCl smell. It is a rich source of aromatic hydrocarbons (arenes)
(Vinyl chloride). such as benzene, toluene, 1, 2-, 1, 3- and 1, 4-
Alcohols – Methyl alcohol, ethyl alcohol, allyl alcohol, dimethylbenzenes (xylenes), naphthalene, anthracene and
butyl alcohol, glycol etc.
phenanthrene. These are obtained by fractional distillation of
Aldehydes and Ketones–Formaldehyde, acetadehyde, acetone
coal tar into a number of fractions.
etc.
Alkenes and alkadienes – Styrene, 1, 3-butadiene etc.
Table: 17.2 Fractions of Coal Tar Distillation
Acids – acetic acid.
Name of the Fraction Temperature Major components
Nitriles – acrylonitrile. range (in K)
These petrochemicals are widely used in the manufacture of
Light oil Upto 443 Benzene, Toluene, Xylenes
iso-octane (aviation fuel), plastics (polythene, polyvinyl
Middle oil or Carbolic 443 – 503 Phenol, Naphthalene,
chloride (PVC) etc), synthetic fibers (nylone terylene, dacron oil Pyridine
etc.), synthetic rubber, insecticides, pesticides, detergents, dyes, Heavy oil or Creosote 503 – 543 Methyl and higher alkyl
perfumes, explosives etc. oil phenols, naphthalene,
Coal: It is believed to be formed beneath earth’s surface by the naphthols, etc.
Green oil or 543 – 633 Anthracene, phenanthrene.
slow decomposition of vegetable matter over the years. Coal is
Anthracene oil
mainly made up of carbon. Its carbon content, however, varies
Pitch (left as residue) Non - volatile 92 – 94% carbon (used for
with the type of coal. For example, common varieties of coal such
making black paints, varnish
as anthracite contains 90% carbon, bituminous contains 70% C, for wood and for water
lignite contains 40% C and peat contains 10–15% C. Coal also proofing).
contains a number of arenes (aromatic hydrocarbons) such as
benzene, toluene, xylenes, naphthalene and anthracene in addition Classification of Hydrocarbons: Hydrocarbons can be
to some organic compounds of sulphur and nitrogen. classified as follows:
Aromatic Hydrocarbons from Coal: Aromatic hydrocarbons are Hydrocarbons
obtained by destructive distillation of coal. When coal is subjected
to destructive distillation, i.e., heated to 1270K to 1675K in the
absence of air, it decomposes to give the following main products. Aliphatic or Alicyclic or Aromatic
Coal Open chain Cyclic chain or
Arenes
Heated to 1270-1675 K
(Destructive distillation)
Saturated Unsaturated
Coke Hot vapours and gases
(Solid residue), nearly 70% (Cooled and passed through water)
Alkanes or Alkenes or Alkynes or

Condensed liquid is allowed to Coal gas (Mainly contains Paraffins Olefins acetylenes
stand and the two layer low molecular mass
formed are separated alkanes and alkenes)
Ammonical liquor Coal tar
(Upper layer), nearly (Lower layer),
8-10% nearly 4–5% 1. CH 3 — CH == CH 2 + NOCl 
→ P Identify the adduct
Coke: It is the solid residue left after the distillation. It is [JEE 2006]
mainly used as a fuel and as a reducing agent in metallurgy. a. CH 3 — CH — CH 2 b. CH 3 — CH — CH 2
Coal gas: It mainly consists of low molecular mass alkanes | | | |
Cl NO NO Cl
and alkenes. It is used as a fuel.
Ammonical liquor: It is a solution of ammonium in water NO
|
and is removed by absorbing in a suitable mineral acid like c. CH 3 — CH 2 — CH d. CH 2 — CH 2 — CH 2
dil. H2SO4 . The ammonium sulphate thus produced is used | | |
Cl NO Cl
as a fertiliser.

2. In the following reaction, [JEE 2007 P-I] 8. Isomers of hexane, based on their branching, can be
O divided into three distinct classes as shown in the figure
N  
conc. HNO3
→X
H conc. H 2SO 4 and
I and II III
the structure of the major product ‘X’ is
O2N The correct order of their boiling point is
O O
NO2
a. I > II > III b. III > II > I
a. N b. N
H H c. II > III > I d. III > I > II
9. Which compound would give 5-keto-2-methyl hexanal
O O upon ozonolysis? [JEE Main 2015]
CH3
c. N d. O2N N
H H CH3 H
NO2
3. The reagent(s) for the following conversion, a. CH3 b.
Br CH3
Br  ?
→H H CH3
is/are [JEE 2007 P-I]
CH3
a. alcoholic KOH
b. alcoholic KOH followed by NaNH2 c. d. H 3C
c. aqueous KOH followed by NaNH2 CH 3
d. Zn/CH3OH
10. In the following sequence of reactions: Toluene → KMnO 2
4. The trans-alkenes are formed by the reduction of alkynes
[JEE Main 2008] → A  → B  → C, the product C is: [JEE Main 2015]
KMnO2 SOCl2 H2 / Pd
with BaSO4
a. Sn- HCl b. H2 - Pd/C, BaSO4 a. C 6 H 5 COOH b. C6 H5CH3

c. NaBH4 d. Na/liq. NH3
c. C6 H 5CH 2 OH d. C 6 H 5CHO
5. The synthesis of 3–octyne is achieved by adding a
bromoalkane into a mixture of sodium amide and an alkyne. 11. In the following reaction, the major product is
The bromoalkane and alkyne respectively are [JEE Adv. 2015 P-I]
[JEE 2010 P-I] CH 3
a. BrCH 2 CH 2 CH 2 CH 2 CH 3 and CH 3CH 2 C ≡ CH CH 2 1 equivalent HBr
→
b. BrCH 2 CH 2 CH 3 and CH 3CH 2 CH 2 C ≡ CH H 3C
c. BrCH 2 CH 2 CH 2 CH 2 CH 3 and CH 3C ≡ CH CH 3 CH 3
d. BrCH 2 CH 2 CH 2CH 3 and CH 3CH 2 C ≡ CH CH 3
a. H 3C b. H C
3
6. The major product of the following reaction is Br Br
[JEE 2011 P-II] CH 3 CH 3
c. d.

RCH 2 OH
H + (anhydrous)
→ H 3C Br H 3C Br
O 12. In the following reactions, the product S is

a. a hemiacetal b. an acetal [JEE Adv. 2015 P-II]
c. an ether d. an ester
7. The number of optically active products obtained from the
H 3C
 i. O3
→ R 
NH3
→S
complete ozonolysis of the given compound is ii. Zn ,H2 O
[JEE 2012 P-I]

H 3C H 3C N
CH3 H N
a. b.
CH3 —CH == CH —C—CH == CH —C—CH == CH —CH3

N N
H CH3 c. d.
a. 0 b. 1 c. 2 d. 4 H 3C H 3C
Hydrocarbons 159
13. The product of the reaction given below is:[JEE Main 2016] 18. The percentage composition of carbon by mole in methane
is: [JEE Main 2019]
1. NBS / hν

2. H 2 O / K 2 CO3
→X a. 80% b. 25% c. 75% d. 20%
19. Which one of the following alkenes when treated with
OH HCl yields majorly an anti Markovnikov product?
[JEE Main 2019]
a. b.
a. F3C — CH = CH2 b. Cl — CH = CH2
c. CH3O — CH = CH2 d. H2N — CH = CH2
O CO 2 H
20. The major product in the following reaction is:
c. d. [JEE Main 2019]

(i)Br2
(ii)EtOH
→
14. The reaction of propene with HOCl (Cl2 + H2O) proceeds
through the intermediate: [JEE Main 2016] OEt OEt
OEt
a. CH 3 + CH + − CH 2 − OH
a. b.
b. CH 3 − CH + − CH 2 − Cl
c. CH 3 − CH(OH) − CH 2+ Br OEt
OEt Br
d. CH 3 − CHCl − CH 2+ c. d.
15. 3-Methyl-pent-2-ene on reaction with HBr in presence of
peroxide forms an addition product. The number of possible 21. Which of the following is not an example of
stereoisomers for the product is [JEE Main. 2017] heterogeneous catalytic reaction? [JEE Main 2019]
a. Four b. Six c. Zero d. Two a. Ostwald's process
b. Haber's process
16. The correct statement(s) for the following addition c. Combustion of coal
reactions is (are) [JEE Adv. 2017 P-I] d. Hydrogenation of vegetable oils
H3C CH3 22. The number of 2-centre-2-electron and 3-centre-2-electron
(i) 
Br2 / CHCl3
→ O and P bonds in B2H6, respectively, are: [JEE Main 2019]
a. 2 and 4 b. 2 and 1
H H c. 2 and 2 d. 4 and 2
H3C H
23. Which is the most suitable reagent for the following
(ii) 
Br2 / CHCl3
→ M and N
transformation ? [JEE Main 2019]
H CH3 OH
|
a. O and P are identical molecules CH3 —CH=CH—CH 2 —CH—CH 3  →
b. Bromination proceeds through trans-addition in both
CH3 —CH=CH—CH 2 CO 2 H
the reactions
c. (M and O) and (N and P) are two pairs of enantiomers a. alkaline KMnO4 b. I2/NaOH
d. (M and O) and (N and P) are two pairs of diastereomers c. Tollen's reagent d. CrO2/CS2
17. The order of the oxidation state of the phosphorus atom in 24. Th correct statements among (a) to (d) regarding H2 as a
H3PO2 , H3PO4 , H3PO3 and H4P2O6 is [JEE Adv. 2017 P-II] fuel are:
(a) It produces less pollutant than petrol
a. H3PO4 > H 4 P2O6 > H3PO3 > H3PO2
(b) A cylinder of compressed dihydrogen weighs ~ 30
b. H3PO2 > H3PO3 > H4P2O6 > H3PO4 times more than a petrol tank producing the same amount
c. H3PO4 > H3PO2 > H3PO3 > H4 P2O6 of energy
(c) Dihydrogen is stored in tanks of metal alloys like NaNi5
d. H3PO3 > H3PO2 > H3PO4 > H4P2O6
(d) On combustion, values of energy released per gram of

liquid dihydrogen and LPG are 50 and 142 kJ, 29. Choose the correct option that gives aromatic compound
respectively [JEE Main 2019] as major product: [JEE Adv. 2019 P-II]
a. b and d only b. a, b and c only
c. b, c and d only d. a and c only 
NaOEt
→
a.
25. Which compound(s) out of the following is/are not CH3
Br  →
(i)Alc.KOH1 NaNH 2
aromatic ? [JEE Main 2019] b. (ii) Red hot iron tube 873 K
Br
Br
⊕ ⊕ c. 
NaOEt
→
(A) (B) (C) (D)
d. + Cl2 
UV
500 K
→
a. C and D b. B, C and D
c. A and C d. B
26. Among the following four aromatic compounds, which Paragraph
one will have the lowest melting point? Paragraph for Question Nos. 30 to 32
[JEE Main 2019]
O A tertiary alcohol H upon acid catalysed dehydration gives a
product I. Ozonolysis of I leads to compounds J and K.
OH Compound J upon reaction with KOH gives benzyl alcohol and
a. b. OH a compound L, whereas K on reaction with KOH gives only M,
[JEE 2008 P-II]
O
CH3 O
H3C Ph
HO M=
O
c. O d. H3C H
30. Compound H is formed by the reaction of

CH3
O
27. The correct order for acid strength of compounds CH ≡ CH,
CH3 — C ≡ CH and CH2 = CH2 is as follows: a. + PhMgBr
[JEE Main 2019] Ph CH 3
a. CH ≡ CH > CH2 = CH2 > CH3 — C ≡ CH O
b. HC ≡ CH > CH3 — C ≡ CH > CH2 = CH2
b. + PhCH2MgBr
c. CH3 — C ≡ CH > CH2 = CH2 > HC ≡ CH
Ph CH 3
d. CH3 — C ≡ CH > CH ≡ CH > CH2 = CH2
O
[JEE Main 2019] c. + PhCH2MgBr
H 3C Ph H
CH2 HCl O Me
 →
H d. +
CH2—Cl Ph H Ph MgBr
CH3
a. CH2 b.
CH3 31. The structure of compound I is
Cl
Ph CH 3 H3C Ph
H H a. b.
CH3 H Ph H Ph
CH3
c. CH2—Cl d. Ph CH3
CH3 H 3C CH3
c. d.
H CH2 Ph Ph H
H Cl H
Hydrocarbons 161
32. The structures of compounds J, K and L, respectively, are 36. In the following reaction sequences V and W are, respectively
a. PhCOCH 3 , PhCH 2 COCH 3 and PhCH 2 COO − K + Q 
H 2 / Ni
→V
∆
b. PhCHO, PhCH 2 CHO and PhCOO − K + PhCOO – K +

1. Zn − Hg / HCl
+ V 
AlCl3 (anhydrrous)
→  →W
c. PhCOCH 3 , PhCH 2 CHO and CH 3COO − K + 2. H 3 PO 4
d. PhCHO, PhCOCH 3 and PhCOO − K + O
Paragraph for Question Nos. 33 to 34 a. O and

An acyclic hydrocarbon P, having molecular formula C6H10
gave acetone as the only organic product through the following O
sequence of reactions, in which Q is an intermediate organic O
V W
compound. [JEE 2011 P-I] CH2OH
O b. O and
P     
(i) dil.H 2SO 4 / HgSO 4
(ii ) NaBH 4 / ethanol
→ Q 
(i) conc.(catalytic amount )( − H 2 O )
    → 2
( C 6 H10 ) (iii) dil.acid
(ii) O 3
(iii) Zn / H 2 O C CH2OH
H3C CH 3
V W
33. The structure of compound P is
O
a. CH3 CH 2 CH 2 − C ≡ C − H
b. H3 CH 2 C − C ≡ C − C − CH 2 CH 3 O and
c.
H3C
c. H − C − C ≡ C − CH3
H3C O
V W
H3C HOH2C
d. H3C − C − C ≡ C − H d.
H3C and
34. The structure of the compound Q is CH2OH

V CH2OH W
OH OH
H3C H3C
a. H − C − C − CH2 CH3 b. H3C − C − C − CH3 Paragraph for Question Nos. 37 to 38
H3C H3C
H H Schemes 1 and 2 describe sequential transformation of alkynes
OH
H3C OH M and N. Consider only the major products formed in each step
c. H − C − CH 2 CHCH3 d. for both schemes. [JEE Adv. 2014 P-II]
H3C CH3 CH 2 CH 2 CHCH 2 CH 3 1. NaNH 2 (excess)
2. CH CH I(1 equivalent)
H 
3 2
3. CH I(1 equivalent )

→ X Scheme − 1
Paragraph for Question Nos. 35 to 36 3
4. H 2 , Lindlar 's catalyst
HO M
P and Q are isomers of dicarboxylic acid C4H4O4. Both decolorize 1. NaNH 2 (2 equivalent)
Br2/H2O. On heating, P forms the cyclic anhydride. Upon treatment 2. Br
OH
with dilute alkaline KMnO4, P as well as Q could produce one or N


+ → Y Scheme − 2
more than one from S, T and U. [JEE Adv. 2013 P-II] 3. H3O (mild)
4. H 2 , Pd / C
COOH COOH COOH 5. CrO3
H OH H OH HO H 37. The product X is

H OH HO H H OH H3CO H
COOH COOH COOH

S T U a. b. H
H H H3CO
35. Compounds formed from P and Q are, respectively
CH3CH 2 O H
a. Optically active S and optically active pair (T, U)
b. Optically inactive S and optically inactive pair (T, U)
c. Optically active pair (T, U) and optically active S c. d. H
d. Optically inactive pair (T, U) and optically inactive S H H CH3CH 2 O

38. The correct statement with respect to product Y is (H3C)3C CO2Et
a. It gives a positive Tollens test and is a functional 
→ Q 
→ R 
→ S
isomer of X
P
b. It gives a positive Tollens test and is a geometrical
isomer of X 41. The reaction, Q to R and R to S, are
c. It gives a positive iodoform test and is a functional a. Dehydration and Friedel-Crafts acylation
isomer of X b. Friedel-Crafts alkylation, dehydration and Friedel-
d. It gives a positive iodoform test and is a geometrical Crafts acylation
isomer of X c. Friedel-Crafts alkylation and Friedel-Crafts acylation
d. Aromatic sulfonation and Friedel-Crafts acylation
Paragraph for Question Nos. 39 to 40 42. The product S is
In the following reactions [JEE Adv. 2015 P-II] HO3S H3COC
(H3C)3C O CH3 (H3C)3 C H3C CH3
Pd − BaSO 4
C8 H 6 → C8 H 8 → X
H2
i. B2 H 2
ii. H 2 O 2 . NaOH, H 2 O
a. b.
H 2O
HgSO 4 , H 2SO 4 COCH3
C 8 H 8 O 
i. EtMgBr , H 2 O
ii. H + , heat
→Y H3C
CH3 COCH3
(H3C)3 C CH3
(H3C)3 C
c. d.
39. Compound X is
O OH COCH3
CH3 CH3
a. b. Integer and Subjective
NaBr + MnO
OH 43. (Brown fumes and pungent smell) A 
2
→
CH3
CHO
c. d. B 
conc.HNO3
→ C (intermediate) 
→ D (Explosive
product), Find A, B, C and D. Also write equations A to B
40. The major compound Y is and A to C. [JEE 2005]
44. The number of hydroxyl group(s) in Q is………..
a. CH3 b. CH3
+
CH3 H 
H

heat
→ P 
aqueous dilute KMnO4 (excess)
0° C
→Q
CH2
HO
CH3 H 3C CH 3
CH3
c. d.
45. Monomer A of a polymer on ozonolysis yields two moles
of HCHO and one mole of CH3COCHO. [JEE 2005]
Paragraph for Question Nos. 41 to 42 a. Deduce the structure of A.
The reaction of compound P with CH3MgBr (excess) in
b. Write the structure of “all cis” – form of polymer of
( C 2 H 5 )2 O followed by addition of H 2O gives Q. The compound compound A.
Q on treatment with H 2SO4 at 0°C gives R. The reaction of R OH
with CH 3COCl in the presence of anhydrous AlCl3 in CH 2 Cl2 46. +

H /∆
 → X 
1. O2
→ Y 
NaOH
→
2. Zn / CH3COOH
followed by treatment with H 2O produces compound S. [Et in

Identify X and Y. [JEE 2005]
compound P is ethyl group] [JEE Adv. 2017 P-II]
Hydrocarbons 163
ANSWERS and SOLUTIONS CH3 H
| |
+ 2CH3 — COOH + HOOC — C — COOH + HOOC — C — COOH
1. (a) N O Cl − 
→ Markonikov’s Addition | |
H CH3
2. (b)
None of optical isomers is active due to absence of chiral
O
|| carbon.
ɺɺ — C —
—N 
conc. HNO3
→ O2 N
conc. H 2SO4
| 8. (b) III > II > I More the branching in an alkane, lesser
H O
|| will be the surface area, lesser will be the boiling point.
ɺɺ — C —
—NH
CH3 CH3
Due to presence of lone pair of electron on nitrogen atom, O
it will activate the ring and it will stabilise intermediate 9. (b) O3
→ CHO
Zn / H 2 O
cation at o- and p-positions. CH3 CH3

5-keto-2-methyl hexanal
10. (d)
H 2 C — CH 2 
Alc. KOH
→ H 2 C == CH →
NaNH
HC ≡≡ CH CH3 COOH
3. (b) | | |
Br Br Br
→
KMnO2

SOCl2
→
CH 2 
Alc. KOH
→ H 2 C == CH →
NaNH 2
HC ≡≡ CH
| |
Br Br Toluene Benzoic acid
COCl
Because CH 2 = CH − Br has partial C − Br double bond
character, it requires more stronger base to remove HBr. 
H2 / Pd
→
BaSO4
Benzoyl chloride Benzaldehyde
4. CH3 − C ≡ C − CH3 →
(a) CH3 Na / liq.NH3
CH3 CH3
| H+ + BrΘ
|
CH 3 H H2 C == C —CH == CH2  → H3C —C —CH == CH2 
→
C=C 11. (d)
H CH 3
Transalkene H3C H3C
Θ Θ
:
So, option (a) is correct. C == CH — CH2 
Br

→ C == CH —CH2 —Br
H3C H3C
5. (d) CH 2 – CH 2 – C ≡ CH → CH 2 – CH 2C ≡ C Na
NaNH 2 – +
O
||
CH 3 – CH 2 – CH 2 − CH 2 Br + Na + − C ≡ C − CH 2 − CH 3 
→ CH 3 – CH 212.
– CH (a)
2 H 3C H 3C C—H
ɺɺ
 (  →
(i) O3
ii ) Zn .H 2 O
 N
H3
→
CH 2 — C — H
C ≡ C − CH 2 − CH 3 
→ CH 3 – CH 2 – CH 2 −CH 2 − C ≡ C–CH 2 –CH 3 R ||
3-octyne O
13. (b)
+
6 (b) + H 
→
O O
⊕ 
1. NBS
hv
→ ←
→ 
→
R
→
:O—H
O O — CH 2 − R Br Br
Acetal + 
K 2 CO3
2H 2 O
→
7. (a)
CH3
| HO OH
CH3 —CH == CH —C—CH == CH —CH —CH == CH —CH3 +
| |
H CH3
O3 / H2O
14. (2 or Bonus) CH 3 − CH + − CH 2 − Cl

O O 18. (d) CH4 % by mole of carbon
.
|| ||
H 3C C—H H 3C C—H
1 mol atom
CH 2 — CH — NH 3
+
CH 2 — CH — NH 2
..
= ×100 = 20%
||
O−
|| 5 mol atom
OH
O− OH H
+
H 3C N
H 3C
NH 2 H 3C NH − 2H 2 O
| ⊕
CH 19. (a) CF3 — CH = CH 2 

HCl
→ CF3 — CH— C H2
(S)
CH 2 OH OH
↓
H Cl
Br | |
2 4 CF3 — CH — CH 2
15. (a) 3
1 5 Due to higher e– withdrawing nature of CF3 group.
It follow antimarkovnikov product.
3-methyl pent-2-ene Antimarkovnikov product
(4 stereoisomers possible due to 2 Br
chiral centre as molecule is nonsymmetric) ⊕
CH3 CH3 20. (d) →
Br2
H Br Br H
H CH3 H 3C H OEt
Br
Et Et
(I) (II) 
→ EtOH
− H⊕
CH3 CH3
21. (c) No catalyst is required for combustion of coal.
Br H H Br
H CH3 H3C H 22. (d)
Et Et 23. (b)
(III) (IV) 24. (b) Option (a), (b) & (c) are correct answers (NCERT
16. (b, d) theory based)
Br Br ⊕
25. (b) Out of the given options only is aromatic.

Br2 / CHCl3
trans
→ Hence (b), (c) and (d) are not aromatic.
26. (a) M.P. of Napthalene ≃ 80°C
M Br N Br
27. (b) CH ≡ CH > CH3 — C ≡ CH > CH2 = CH2
M and N are identical (meso)
(Acidic strength order)
Br Br
⊕ Θ
28. (a) 

H Cl
→
⊕

Br2 / CHCl3
trans
→
Cl
O Br P Br
O and P are enantiomers.
Cl
17. (a) Oxidation state
O O
H3PO4 P = +5
29. (b) Ph — C — CH 3 + PhCH 2 MgBr 
→ Ph — C — CH 3
H4 P2O6 P = +4
H2C—Ph
H3PO3 P = +3
H3PO2 P = +1
H 3 PO 4 > H 4 P2 O6 > H 3 PO3 > H 3PO 2 30. (a, b) (A) 
NaOEt
→
Hydrocarbons 165
CH H COOH COOH COOH
Br 
(i) Alc. KOH1 NaNH 2
→ C
(B) H OH OH H
 →
KMnO 4
Br C OH
HO H H OH
HOOC H
COOH COOH
red hot iron tube
   → Q T U
Optically inactive pair
Aromatic
36. (a)
O
OH CH3
H /∆ + Q  H →
2 / Ni
O
31. (a) Ph — C — CH33 
CH − H2O
→ Ph — C == CH — Ph ∆
(1)
O O
H2C–Ph O
C
CH3 CH3 Zn − Hg , HCl
   →
O   →
AlCl
+ 3
C C
32. (d) Ph — CH == CH  O3
H 2 O / Zn
→ Ph — C == O + Ph — CHO O
HO HO
(K) (J) O O
H 3 PO 4
Ph
Hence, (d) is the correct answer. O
For Question Nos. 33 to 34 For Question Nos. 37 to 38

Θ
CH 3 H 
2
→
NaNH
C 
3 2
→
CH CH I
CH 3 | Θ
HO M O
CH 3 C − C ≡ CH

(1) H 2 SO 4 | HgSO4
→ CH 3 — C — C — CH 3
(D)
CH 3 | |
Θ
CH 3 O O
CH3I
 →O
H , Lindlar's catalyst

2
→
CH3 H3CO
|
H+ Θ

NaBH4 / C2 H5OH
dil. acid
→ CH3 —C —CH —CH3  → H 
NaNH
2
→ C
1equivalent
| | N
CH3 OH H H
X
CH3 CH3 OH
| | Br
CH3 —C —CH —CH3  → CH3 —C —CH —CH3  → H O+ H ,Pd/C
| | | +
NaNH (1eq)
2 
3
→ 
2
→
Θ mild
CH3 OH O
+ CH3 OH
OH
O
CH3 CH3 CH3
| | | CrO3

→
→ CH3 —C —CH —CH3 
 →CH3 —C == C —CH3
+ | Y
CH3 X and Y are function isomers of each other.
 (i) O3
(ii) Zn / H2 O
→ CH3COCH3 37. (a)
33. (d) 38. (c)

34. (b)
For Question Nos. 35 to 36 6
C8 H 6 
→ = double bond equivalent = 8 + 1 − =6
H COOH COOH 2
35. (b) C
H OH C ≡ CH CH = CH 2
→
KMnO4
OH
C H OH
H COOH
COOH
(1) B 2 H 8
P HgSO4 , H 2SO4 , H 2O
S → optically inactive (2) H 2 O 2 , NaOH, H 2 O

O Reactions involved are:
||
C — CH 3 CH 2 − CH 2 − OH 2 H 2SO4 + 2 NaBr + MnO2 
→ Br2 + Na 2SO4 + MnSO4 + 2H
(A) (B)(Brownfumes)
2H 2SO4 + 2 NaBr + MnO2 

→ Br
Br 22
+ Na 2SO4 + MnSO4 + 2H2 O
(A) (B)(Brownfumes)
(B) (Brown fumes)
(i) EtM gBr
(X)
(ii) H 2 O CH3 CH3
OH CH 3 O 2N NO2
| +
| + 3 NO ⊕2 
→ + 3H +
H / heat
Ph — C — CH 3  → Ph — C == CH — CH 3
| (Y)
Et NO2
39. (c) (D) Explosive
40. (d)
+
For Question Nos. 41 to 42 H H

∆
→
O − + 44. +
|| OMgBr
C (CH3)3
C − OEt C (CH3)3 | HO
CH3 − C − CH3
CH3MgBr(excess) /(C2H5 )2 O
→

→
H2O
H H O−H
⊕
| (P) aqueous dilute KMnO4
O C (CH3)3 CH 3 − C − CH3 (excess) 0°C
C (CH3)3 |
C(CH 3 ) 2 OH
H 2SO 4 /
←
0° C
(Q)
–H2O (dehydration) HO OH
CH 3 HO (Q)
C (CH3)3 CH 3
C (CH3)3 ⊕ No. of hydroxyl groups is 4.
C(CH3 )2
 → CH3 O O O
(alkylation )
45. (a) CH2 +
(R) Ozonolysis
 →2
H2C H H H3C H
O
CH 3 || H3C H H3C H
C (CH3)3 CH 3 CH3 − C − Cl / AlCl3 CH2
(Acylation)
CH2
(b) CH2 CH2
H3C H
“all cis” form of polymer of A
COCH 2
(S)
46. H
41. (b) OH O CH2
42. (c) H
+
H /∆ ring expansion
 → →  →
CH3
⊕
O 2N NO2 O
−H
43. (A) H 2SO 4 ; (B) Br2 ; (C) NO ⊕2 ; (D) O

O
O3
NaOH
←  H ←
Zn / CH3COOH

NO2
CH3
(Y) (X)
Alkyl and Aryl Halides 167
18 Alkyl and Aryl Halides

QUICK LOOK Markownikoff’s rule: In the addition reactions of
unsymmetrical alkenes the −ve part attaches to the carbon
Alkyl halides or haloalkanes are compounds in which a halogen atom having lesser number of H-atoms. E.g.,
is bonded to an alkyl group. They have the general formula RX Cl
(where R is alkyl group CnH2n+1 ). X is halogen atom. |
− H, + X
H 3C — CH == CH 2 + HCl  → H 3C — CH — CH 3
RH → RX
alkane alkyl halide In case of HBr if peroxide is added antimarkownikoff’s
Alkyl halides are classified as primary, secondary and tertiary addition takes place which is also called Kharash effect or
alky halides depending on whether the halogen atom is attached peroxide effect e.g.,
to a primary, secondary or tertiary carbon atom respectively. Peroxide
CH3 —CH == CH2 + HBr   →CH3 —CH2 —CH2 —Br
Aromatic Halogen Compounds or Haloarenes: These are the From silver salt of carboxylic acids
CCl4
halogen compounds which contain atleast one aromatic ring. RCOOAg + Br2  → R — Br + CO 2 + AgBr
Halogen derivatives of aromatic compounds are of two types. This reaction is called Hunsdiecker–Borodin reaction.
Aryl halides: In this type of compounds, the halogen atom Finkelstein reaction: Alkyl chlorides and bromides react
is directly linked to the carbon of benzene nucleus e.g. with NaI in acetone to give alkyl iodides.
Cl Acetone
R − Cl + NaI → R − I + NaCl
Chlorobenzene This reaction is possible because NaI is soluble in acetone

but NaCl and NaBr are insoluble in acetone.
Alkyl halides: In this type of compounds, halogen is linked
to the carbon atom of the side chain. Physical Properties
CH 2 Cl Haloalkanes
Boiling point: The boiling points of haloalkanes are in the
1- Chloro- 1 - phenyl methane order RCl < RBr < RI. It is because with increase in size
and mass of halogen atom the magnitude of van der Waal’s
forces of attraction increases. Among isomeric alkyl
Nomenclature of Alkyl and Aryl Halides: In the common halides, the boiling point decreases with increase in
system, aliphatic halogen derivatives are named as alkyl branching in alkyl group. e.g. the decreasing order of
halides. The words n-, sec-, tert-, neo- and amyl are usually boiling point among the isomers of butane is
used in writing the common names. In IUPAC nomenclature CH3 (CH 2 )CH 2 Cl > H3 C — CH — CH 2 CH3 >
they are named as haloalkanes. |
Cl
Preparation H 3 C — CHCH 2 Cl > (CH 3 )3 CCl
From alkanes |
CH 3
Alkanes react with halogens in the presence of light to give
alkyl halides. For same halogen, the boiling point increases with increase
hv in molecular mass. e.g. CH3Cl has lower boiling point than
RH + Cl 2 → RCl + HCl
CH3CH2Cl. The boiling points of various halogen
hv
CH 4 + Cl 2  → CH 3 Cl + HCl compounds increase with increase in number of halogen
Alkyl halides formed further react with halogen to give di, atoms. For e.g. boiling point of CCl4 is more than boiling
tri and tetra halogen compounds. point of CHCl3 which is further more than CH2Cl2.
From alkenes: Alkenes add halogen acids to give halides.
For Example, Haloarenes
CH 2 == CH 2 + HCl 
→ CH 3 — CH 2 Cl Boiling point: The boiling points of mono halogen derivatives
of benzene follows the order: Iodo > Bromo > Chloro. The

boiling points of isomeric dihalo benzenes are nearly the same. Trichloromethane (Chloroform)
However their melting points are quite different. The melting Preparation
point of para isomer is generally 70 – 100 degrees more than From methane: Chloroform is manufactured by
the melting points of ortho & meta isomers. chlorination of methane in presence of light or catalyst.
Cl Cl Cl CH 4 + Cl 2 
→ CH3Cl + HCl
Cl
CH3Cl + Cl 2 
→ CH 2Cl 2 + HCl
Cl CH 2 Cl2 + Cl2 
→ CHCl3 + HCl
Cl
CHCl3 + Cl2 
→ CCl4 + HCl
B.P 453 K 46 K 448 K
M.P. 256 K 249 K 325 K CHCl3 can be separated by fractional distillation.
The higher melting point of p-isomer is due to its symmetry From chloral hydrate
which leads to more close packing of its molecules in the NaOH + CCl3CHO 
Distillation
→ HCOONa + CHCl3
Sodium formate
crystal lattice. Chloral Chloroform
Solubility: Haloarenes are insoluble in water, acids or base Laboratory method: In this method chloroform is obtained
but are soluble in organic solvents. Haloarenes are insoluble from ethanol or acetone by reaction with a paste of
in water because they cannot form hydrogen bonds with bleaching powder and water.
water molecules. → Ca ( OH )2 + Cl 2
CaOCl2 + H 2 O 
Density: They are all heavier than water. Their densities bleaching
Powder
follow the order: Iodo > Bromo > Chloro.
CH 3CH 2 OH + Cl2 
Oxidation
→ CH 3CHO + 2HCl
Chemical Properties: Haloalkanes are highly reactive class of
CH 3CHO+ Cl2 →
Chlorination
CCl3CHO+ 3HCl
aliphatic compounds. Their reactivity is due to the presence of chloral
polar carbon-halogen bond in their molecule. In general for a
Ca ( OH )2 + 2CCl3CHO 
→ 2CHCl3 + ( HCOO )2 Ca
hydrolysis
given alkyl group, the order of reactivity decreases as: Iodides chloroform calcium formate
> Bromides > Chlorides. The explanation of above order is that From carbon tetrachloride: By partial reduction of carbon
reaction of alkyl halides involve cleavage of C – X bond. So tetrachloride with iron filings and water.
higher the bond dissociation energy, smaller reactivity and the
CCl 4 + 2 [ H ] →
Fe / H 2 O
∆
CHCl3 + HCl
bond dissociation energy decreases with increase in size of
halogen atom. Uses of Chloroform
The Chemical Reactions of Haloalkanes are of four types: As solvent in oils and varnishes
Nucleophilic substitution reactions In medicine
Dehydro halogenation reactions As preservative
Reactions with metals As laboratory reagent
Reduction reactions
Triiodomethane (Iodoform)
Polyhalogen Compounds: Carbon compounds containing Preparation
more than one halogen atom are usually referred to as It is prepared by heating ethanol or acetone with sodium
polyhalogen compounds. Some important polyhalogen hydroxide and iodine or sodium carbonate and iodine in water.
compounds are: CH3CH 2 OH + 6NaOH + 4I 2 
Heat
→
Ethanol
Dichloromethane (Methylene Chloride) CHI3 + HCOONa + 5H 2 O + 5NaI

Preparation: It is prepared industrially by direct chlorination
of methane. The mixture so obtained is separated by fractional CH 3COCH3 + 4NaOH + 3I 2 
Heat
→
Acetone
distillation.
CHI3 + CH3 COONa + 3H 2 O + 3NaI
Properties: It is a colourless, sweet smelling, volatile liquid
boiling point = 313K. Because of its low boiling point & low Uses
inflammability, it is an effective extraction solvent used in It is used as antiseptic for dressing wounds.
pharmaceutical and food industries. It is used to manufacture pharmaceuticals.

Tetrachloromethane (Carbon Tetrachloride) Properties: It is a white powder insoluble in water but soluble
Preparation: CCl4 is manufactured by following methods: in oils.
(a) From methane: By chlorination of methane in the Uses: It is a powerful insecticide. However it is highly stable
presence of sunlight.
hv
and is not easily decomposed in the environment. Therefore its
CH 4 + 4Cl2  → CCl4 + 4HCl
long term effect could be potentially dangerous and its use is
(b) From carbon disulphide: By reaction of chlorine banned in many countries.
with CS2 in presence of AlCl3 as catalyst.
AlCl3
CS2 + 3Cl 2  → CCl 4 + S Cl
2 2 Multiple Choice Questions
Sulphur mono chloride
Uses
As industrial solvent. CH3
for the manufacture of chloroform. Cl 2 , h v
1.  → N (isomeric products)
As laboratory reagents. H 3C
In dry cleaning. CH3
As a fire extinguisher. C 5 H 11Cl  fractional
 distillation
 → M (isomeric products).
p-Dichlorobenzene: It is prepared by chlorination of benzene.
What are N and M ? [JEE 2006]
Properties: It is white volatile solid, M.P. = 325K, which readily
a. 6, 6 b. 6, 4 c. 4, 4 d. 3, 3
sublimes.
Uses 2. The major product of the following reaction is
As insecticide. [JEE 2008 P-I]
As germicide. Me Br
As soil fumigant.
As deodrant and moth repellent. F
Θ ⊕
Ph S N a
Perfluorocarbons (PFC’s) 
dim ethylforamide
Dimethyl foramide
→
Preparation: They are prepared by controlled fluorination of

alkanes in vapour phase. The reaction mixture is diluted with NO2
nitrogen in order to control the reaction
Vapour phase, N 2
C7 H16 + 16F2  → CF + 16HF Me SPh
3000 C, CoF 2
7 16
Perflourohep tan e
Me SPh
Teflon is a common perfluorocarbon.
F F
Properties: They are non-toxic, non-inflammable, non- a. b.
corrosive and extremely stable compounds.
Uses
As lubricants. NO 2 NO2
For surface coating.
As electrical insulator. Me Br Me SPh
Benzene Hexachloride: These are popularly known as lindane
and gammaxene. It is commercially prepared by the addition of SPh SPh
chlorine to benzene in presence of ultraviolet light.
Use: As a pesticide in agriculture. c. d.
P - P′ – Dichloro diphenyl trichloro ethane (DDT): It is
NO 2 NO 2
manufactured by condensation of chlorobenzene with trichloro
acetaldehyde (chloral) in the presence of sulphuric acid. 3. In the following reaction sequence, the correct structures
CCl3 H 2SO 4 of E, F and G are [JEE 2008 P-II]
Cl– + | + —Cl  → Cl —
CHO O O
Chloral
Chlorobenzene
CCl3
| Ph * OH
—CH— —Cl (* implies 13C labeled carbon) 
heat
 I2
→ [E] 
NaOH
→ [F] + [G]

O O 5. Compound (a), C8 H 9 Br, gives a white precipitate when
a. E = F= G = CHI3 warmed with alcoholic AgNO3. Oxidation of (a) gives an
* * Θ ⊕ acid (b), C8H6O4. (b) easily forms anhydride on heating.
Ph CH 3 Ph ONa
Identify the compound (a). [JEE Main 2013]
O O CH 2 Br
b. E = F= G = CHI3 C2H5
* Θ ⊕ a. b.
Ph CH 3 Ph ONa CH 3 Br
O O
CH 2 Br
c. E = F=
Θ ⊕ G = * CHI3
*
CH 3 Ph ONa CH 2 Br
Ph c. d.
O O CH 3 CH 3
d. E = F= G =*CHI3 6. KI in acetone, undergoes SN2 reaction with each of P, Q,
*
CH Θ ⊕ R and S. The rates of the reaction vary as
Ph 3 Ph ONa
[JEE Adv. 2013 P-I]
4. The major product of the following reaction is O
[JEE 2011 P-I] Cl
H 3 C–Cl Cl
O Cl
C
(i) P Q R
NH S
C (ii) B CH2Cl
a. P > Q > R > S b. S > P > R > Q
O c. P > R > Q > S d. R > P > S > Q
O
C 7. For the process H 2 O(ℓ) 
→ H 2 O(g) at T=100ºC and 1
a. N – CH 2
atmosphere pressure, the correct choice is
C [JEE Adv. 2014 P-II]
O a. ∆Ssystem > 0 and ∆Ssurrounding > 0
O
b. ∆Ssystem > 0 and ∆Ssurrounding < 0
C
b. N c. ∆Ssystem < 0 and ∆Ssurrounding > 0
C CH Cl d. ∆Ssystem < 0 and ∆Ssurrounding < 0
O 8. The correct order of acidity for the following compounds
O is [JEE Adv. 2016 P-II]
C CO 2 H CO 2 H CO 2 H CO 2 H
c. N HO OH OH
O − CH 2 Br OH
O OH
C (I) (II) (III) (IV)
a. I > II > III > IV b. III > I > II > IV
d. N
c. III > IV > II > I d. I > III > IV > II
Br CH 2 Cl 9. Among the following reaction(s) which gives(give) tert-

butyl benzene as the major product is(are)

Br 14. Compounds P and R upon ozonolysis produce Q and S,
Cl
a.  → b.  → respectively. The molecular formula of Q and S is C8 H8O.
NaOC2 H5 AlCl3
Q undergoes Cannizzaro reaction but not haloform
OH reaction, whereas S undergoes haloform reaction but not
c.  → d.  → Cannizzaro reaction. [JEE Adv. 2017 P-II]
H2SO4 BF3 .OEt 2
( i ) O 3 / CH 2 Cl 2 () 3
i O / CH Cl
(i) P 
( ii ) Zn / H 2 O → Q
(ii) R 
( ii ) Zn / H2O → S
2 2
( C8 H 8 O ) ( C8H8O )
10. Which of the following, upon treatment with tert-BuONa
The option(s) with suitable combination of P and R,
followed by addition of bromine water, fails to
respectively, is(are)
decolourize the colour of bromine? [JEE Main 2017]
H 3C CH3
O
O CH3 CH3
a. b. a. and
Br Br CH3
C6H5 O CH3
c. d. b. H3C and
Br Br
CH3
11. The increasing order of the reactivity of the following H 3C
halides for the reaction is [JEE Main 2017]
CH3 CH3
(I) CH 3CHCH 2 CH 3 (II) CH 3CH 2 CH 2 Cl c. and
|
Cl CH3
(III) p − H 3CO − C6 H 4 − CH 2 Cl H 3C
a. (II) < (III) < (I) b. (III) < (II) < (I) d. H3C and H3C
c. (II) < (I) < (III) d. (I) < (III) < (II) CH3
12. The major product obtained in the following reaction is 15. The major product of the following reaction is:
Br O Cl
H
C6H5 O+ 
(i)AlCl3 ,heat
(ii)H2 O
→
C6H5
(+ )
a. ( − ) C 6 H 5CH (O t Bu) CH 2 C 6 H 5 O
O
b. ( ± ) C 6 H 5 CH (O Bu) CH 2 C 6 H 5
t
CO2H
Cl
c. C6 H 5CH = CHC6 H 5 a. b.
d. ( + ) C 6 H 5 CH (O t Bu) CH 2 C 6 H 5
Cl
13. For the following compounds, the correct statement (s) O O
O O Cl
with respect to nucleophilic substitution reactions is (are)
c. d.
CH3
CH 3 CO2H Cl
| O
Br Br B3C − C − Br Br
| 16. The major product of the following reaction is:
CH 3 [JEE Main 2019]
I II
III IV CN3
a. I and III follow S N 1 mechanism
b. Compound IV undergoes inversion of configuration 
(i)Cl2 / hv
(ii)H2 O,∆
→
c. The order of reactivity for I, III and IV is: IV > I >III
d. I and II follow SN 2 mechanism Cl

CH2OH CHCl2 CO2H CHO 21. The chloride that CANNOT get hydrolysed is:
[JEE Main 2019]
a. b. c. d. a. SiCl4 b. SnCl4
c. PbCl4 d. CCl4
Cl Cl Cl Cl
22. Which of the following compounds will produce a
17. Polysubstitution is a major drawback in: [JEE Main 2019]
precipitate with AgNO3? [JEE Main 2019]
a. Reimer Tiemann reaction b. Friedel Craft's acylation
Br
c. Friedel Craft's alkylation d. Acetylation of aniline Br
18. The major product of the following reaction is: a. b.
[JEE Main 2019] N
Br Br
Br 
→ (1)KOH (aqueous)
(2)CrO3 / H +
(3)H 2 SO 4 / ∆ c. d.
Br
O 23. The increasing order of reactivity of the following
O
compounds towards reaction with alkyl halides directly is:
a. b. [JEE Main 2019]
O
O
HO Br
O O NH
NH2
c. d. O
(A) (B)
OH Br
CN
19. Which hydrogen in compound (E) is easily replaceable NH2 NH2
during bromination reaction in presence of light:
CH3 — CH 2 — CH 2 = CH 2 [JEE Main 2019]
δ γ β α
(C) (D)
a. β – hydrogen b. γ – hydrogen
a. (B) < (A) < (D) < (C)
c. δ – hydrogen d. α – hydrogen
b. (B) < (A) < (C) < (D)
20. The major product of the following reaction is: c. (A) < (C) < (D) < (B)
[JEE Main 2019] d. (A) < (B) < (C) < (D)
OH
→ Br2 (excess) [JEE Main 2019]
CH2CH3
SO3H
OH
H 3C C Cl 
NaOEt
∆
→
OH
Br Br Br
COOCH2CH3
a. b. CH2CH3 OCH2C
a. b
Br SO3H H 3C C OCH2CH3 H3CH2 C CO2CH2C
OH OH
Br Br COOCH2C CH
CO 2 CH 2 CH 3
c. d. c. | d. CH 3 CH 2 C == CH 2
Br Br CH 3 C == CHCH 3 |
Br SO3H CO 2 CH 2 CH 3

25. The major product of the following reaction is: Matrix Match/Column Match
CH 3 CH 2 CH—CH 2 → (i) KOH alc. 28. Match the statement of Column I with those in Column II:
(ii) NaOH
| | in liq NH3
[JEE 2006]
Br Br
Column I Column II
a. CH3CH2C≡CH (A) CH3–CHBr–CD3 on 1. E1 reaction
treatment with alc. KOH
b. CH3 CH 2 CH—CH 2
| | gives CH2 = CH–CD3 as a
NH 2 NH 2 major product.
c. CH3CH=C=CH2 (B) Ph–CHBr–CH3 reacts 2. E2 reaction
d. CH3CH=CHCH2NH2 faster than Ph–CHBr–
CH3
26. C6H10O 
(1)CH 3MgBr
→ Q 
Conc.HCl
→ S
(2)H 2 O
(Major) (Major) (C) Ph–CH2–CH2Br on 3. E1 cb reaction
treatment with
Q 
20%H3 PO4
360K
→ R 
(1)H 2 / Ni
(2)Br2 / hv
→ T
(Major) (Major) (Major)
C2H5OD/C2H2O– gives
HBr / ∆
(R) 
Ph − C − O − O − C − Ph
→ (U) [JEE Adv. 2019P-I] Ph– CD=CH2 as the
(Major) || || (Major)
O O major product.
CH3 CH3 (D) PhCH2CH2Br and 4. First order reaction
Br PhCD2Br react with
Br Cl
a. S = T= same rate.
a. A→ 2; B→ 2; C→ 3, 4; D→ 1,4
CH3 CH3 b. A→ 1, 2; B→ 2; C→ 2, 3; D→ 1, 3
Br
Cl Cl
c. A→ 1, 3; B→ 1, 2; C→ 1,2; D→ ,3,4
b. U = S=
d. A→ 3, 2; B→ 3,4; C→ 3,2; D→ 1,2
29. Match the chemical conversions in Column I with
CH3 CH3
Br appropriate reagents in Column II and select the correct
Cl Cl
c. U = S= answer using the code given below the Columns:
CH3 CH3 Column I Column II
Cl 1. (i) Hg (OAc)2;
Cl Br
(A) Cl 
→
d. S = U= (ii) NaBH4
2. NaOEt
27. Which of the following reaction produce propane as major ONa 
→
(B)
product? [JEE Adv. 2019P-II]
OEt
CH3
a. 
Electrolysis
→
COONa OH 3. Et-Br
Br 
→
(C)
b. Br 
Zn
→ 4. (i) BH3;
H 3C 
→
(D) (ii) H2O2/NaOH
Cl OH

Zn ,dilHCl
→
c. H3C a. A→ 1; B→ 3; C→ 4; D→ 2
b. A→ 1; B→ 2; C→ 3; D→ 4
CH3
d. c. A→ 2; B→ 3; C→ 2 D→ 4

NaOH,CaO,∆
→
COONa d. A→ 3; B→ 4; C→ 2; D→ 1

Statement/Assertion and Reason Integer and Subjective
30. Statement-I: Bromobenzene upon reaction with Br2 / Fe 33. Given reasons: [IIT-JEE 2005]
gives 1, 4 – dibromobenzene as the major product. And H3C
Statement-II: In bromobenzene, the inductive effect of the Br
bromo group is more dominant than the mesomeric effect in (a) (i) CH2 
C2 H5OH (aq)
→ acid solution
directing the incoming electrophile. [IIT JEE 2008 P-I]
a. Statement-I is True, Statement-II is True; Statement-II
CH3
is correct explanation for Statement-I (ii) Br 
C2 H5OH (aq)
→ neutral
b. Statement-I is True, Statement-II is True; Statement-II CH3
F
(b) (i) 
NaOH(aq)
→F− (liberated)
d. Statement-I is False, Statement-II is True. O2N
CH3
Paragraph
F
(ii) 
NaOH(aq)
→F− is not liberated
+ H3C
Treatment of compound O with KMnO4 / H gave P, which on
heating with ammonia gave Q. The compound Q on treatment CH2NO2
O O O
with Br2 / NaOH produced R. On strong heating, Q gave S,
N N N
which on further treatment with ethyl 2-bromopropanoate in the
(c) (i) NO2
presence of KOH followed by acidification, gave a compound 
Conc. HNO3
 → +
Conc. H2SO4
T. [JEE Adv. 2016 P-II]
NO2 NO2 NO2
(ii) 
Conc. HNO3

Conc. H2SO4
→
NO2
(O) 
Pd/C
→
(d) 3mol of H2 is formed
31. The compound R is
O
34. The total number of alkenes possible by dehydromination
NH 2 Br of 3-bromo-3-cyclopentylhexane using alcoholic KOH is:
a. b.
[JEE 2011 P-I]
NH 2 Br
35. In the following monobromination reaction, the number of
O
possible chiral products is: [JEE Adv. 2016 P-I]
O
O
NHBr CH 2 CH 2 CH 3
c. d. NBr
NHBr
H Br 
Br2 (1.0 mole)
→
300° C
O O
CH 3
32. The compound T is
(1.0 mole)
a. glycine b. alanine (enantiomerically pure)
c. valine d. serine

ANSWERS and SOLUTIONS 6. (b) Relative reactivity for SN2 reaction in the given
CH3 CH3 structure is
1. (b)
Cl Substrate O CH3Cl H2C=CH–
* Cl Cl
H 3C H 3C * CH2Cl
CH3 CH3
1,d (S) (P) (R) (Q)
1,d
CH3 CH3 Relative 100000 200 79 0.02
Rates
CH3
Toward
H3C Cl H 3C SN2
CH2Cl
M → d, 1 cannot be separated by fractional distillation. 7. (b) At 100 ºC and 1 atmosphere pressure H2O(ℓ) ↽ ⇀H2O(g)
2. (a) is at equilibrium. For equilibrium
Me Br Me SPh ∆Stotal = 0 and ∆Ssystem + ∆Ssurrounding = 0
F F ∴ ∆Ssystem > 0 and ∆Ssurrounding < 0

− +
PhS Na

dimethyl foramide
→ 8. (a) Due to ortho effect, ortho substituted benzoic acid is
more acidic than meta and para isomers.
NO 2 NO 2 or
It is easier to do nucleophilic substitution on alkyl halides Due to strong hydrogen bond in conjugate base of ortho
than on aryl halides. hydroxybenzoic acid, it is more acidic than its meta and
O O O para isomers.
* *
∆
3. (c) Ph — C — CH2 — C — OH 
→ Ph — C — CH3 + CO2 9. (b, c, d)
(E)
O O Cl
*
Ph — C — CH3 
I2
→ Ph — C — COONa + CHI3
*
→
NaOH
(F) (G)
4. (a)  →
H2SO4
O
(i) KOH
NH OH
(ii) Br CH2Cl 

BF3 .OEt 2
→
O
O
10. (b)
C
C6 H 5 C6 H 5
N − CH 2 Br tert −BuONa

→
C
Br
(it decolourises bromine solution)
O
O O
CH 2 − Br COOH 
→ tert −BuONa
5. (d) →
[O]
Br
CH 3 COOH (it decolourises bromine solution due
(A) (B) to unsaturation)
O O O
||
C
∆ tert −BuONa
 → O  →
C Br
(C) || (it decolourises bromine solution
O due to unsaturation)

11. (c) For any SN1 reaction reactivity is decided by ease of CH 2 O O
⊕ Θ || O3 / CH2Cl2 || ||
dissociation of alkyl halide R − X ↽ ⇀ R + X . Higher C 
Zn / H 2 O
→ C+ H − C − H
the stability of R ⊕ (carbocation) higher would be reactivity CH3 Undergoes CH3
of SN1 reaction. Since stability of cation follows order. haloform reaction
⊕ ⊕
CH 3 − CH 2 − C H 2 < CH 3 − C H − CH 2 − CH 3 CH3 
O3 / CH 2 Cl2
→
Zn / H 2 O
⊕
< p − H 3 CO − C6 H 4 − C H 2 CH3 O O
Hence correct order is (II) < (I) < (III) || ||
C − H + CH 3 − C − H
12. (c) Elimination reaction is highly favoured if
(a) bulkier base is used CH3 Undergoes
(b) Higher temperature is used Cannizzaro’s reaction
Hence in given reaction biomolecular elimination reaction CH3 CH3

provides major product. O CH3 CH3
||
Br
H 
O3 /CH2Cl2
Zn / H2O
→ C + ||
C6 H t C
C6H  →C6H + BuOH + Br⊕ CH3 CH3
CH3
C6 H Undergoes
Θ
H H Ot Bu Cannizzaro’s reaction
O Cl O
13. (a, b, d) When medium is highly polar and protic I and III
will follow SN1. C
Hence, (a) is correct. Option (b) is correct as 15. (c) O+ 
AlCl3
∆
→
COOH Cl
O
Br Nu
Friedel-Craft’s acylation reaction. —Cl group is an ortho
− and para directing.

Nu
→
SN 2 CN3 CHCl2 CHO
Inversion in case of SN2. 16. (d) Cl2 / ∆

 → 
H 2O
→
∆
(D) I & II will follow SN2 when medium is polar aprotic
and nucleophile is strong in high concentration. Cl Cl Cl
(C) is incorrect for both SN1 and SN2 conditions.
17. (c) In Friedal-Craft’s alkylation product obtained is more
14. (b, c) activated and hence polysubtitution will take place.
CH3 
(i)O3 / CH2Cl2
(ii) Zn / H2O
→
O O 18. (b) Br OH
|| ||
CH3 C−H+H−C−H
Undergoes
Br 
KOH
→ Br
Cannizzaro’s OH
reaction  →
CrO3
H⊕
Br O
CH3  →
O3 / CH 2 Cl2
Zn / H 2 O
⊕
CH3 →
H
O
O O
|| || Br
C − H + CH 3 − C − H During AES Br is o/p directing and major product will be
formed on less hindrance p position:
CH3 Undergoes
Cannizzaro’s reaction 19. (b)

20. (a) O CH3 CH3
OH Cl
OH OH
Br Br 26. (c, d) 
(1)CH3 MgBr
→ 
Conc.HCl
→
(2)H 2 O
→
Br2 /(excess) + SO 3 ↑
Due to Ipso attack (Q) (S)
SO3H SO3H CH3 CH3
OH CH3
Br
21. (d) CCl4 cannot get hydrolyzed due to the absence of

20%H3 PO4
360K
→ 
(1)H 2 / Ni
→
vacant orbital at carbon atom. (2)Br2 / HV
(Q) (R)
22. (d) (T)
Br CH3 CH3
⊕
Br

AgNO3
→ AgBr +  HBr / ∆
→
Ph − C − O − O − C − Ph
|| ||
O O
Aromatic cation (R) (U)
as it can produce aromatic cation so will produce Cl
precipitate with AgNO3. 27. (c, d) 
Zn ,dilHCl
→
H 3C
23. (b) Nucleophilicity order CH3
NaOH,CaO, ∆
 →
O O
O COONa
28. (a) A→ 2; B→ 2; C→ 3,4; D→ 1,4
NH < NH2 29. (c) A→ 2; B→ 3; C→ 2 D→ 4
(A) Cl 
NaOEt
→
O
(B) (A)
CN
ii (B) ONa 
EtBr
→ OEt
NH2
NH
< < OH
(C) 
(i) Hg(OAc)2
→
(C) (D) (ii) NaBH 4
CH2—CH3
(D)
24. (c) H3C NaOEt.∆
→ 
(i) BH3 (ii) H 2 O2 / NaOH
→
C Cl E 2 mechanism
↓
dehydrohalogenation OH
C
O—CH2—CH3 30. (c) In bromobenzene, it is the mesomeric effect which directs
O the incoming electrophile.
CO 2 CH 2 — CH 3
| 31. (a)
CH 3 — C == CHCH 3
32. (b) COOH
Saytzeff alkene KMnO 4 / H +

→
25. (b) CH 3 —CH 2 —CH—CH 2 COOH
| | (O) (P)
Br Br O
||
C − NH 2
Alc.KOH
NH3 / ∆
→
CH3 —CH 2 —C=CH 2 C − NH 2
| (Q) ||
Br O
NH 2
NaNH2 In liq. NH3
→
Br2 / NaOH
CH3 —CH 2 C ≡ CH NH 2
(R)

O F
CH 3 (ii) NaOH(aq)
 → + F– is not liberated
|
N − CH − C − OC 2 H 5
|| CH2NO2
O O
O Br O Bimolecular mechanism is not possible is this case.
| || (c) (i) Due to presence of lone pair on nitrogen atom NO
CH 3 − CH − C − OC 2 H 5
←
KOH
NH group is electron donating and ortho, para directing.
(ii) NO2 group is electron withdrawing and meta directing.
H 3O + (d) Due to reduction of central ring, three four membered
(S) O
(T) antiaromatic rings become stable while on reduction of
terminal ring only one antiaromatic ring can be stabilised.
CH 3 − CH − COOH Alanine 34.
|
NH 2
CH 3
| (Cis + trans) (Cis + trans)
C2 H5OH (aq )
33. (a) (i) H 5C 6 — C — Br  → The total no. of alkenes are 5.
| 35. CH 2CH2 CH3 CH 2CH2 CH3 CH 2CH2 CH3
CH 3
CH 3 H Br2
Br 
300°C
→H Br + Br Br +
|
H 5C6 — C — OC2 H 5 + HBr (acid) CH3 CH 2 Br CH3
|
chiral achiral
CH 3
CH 3
C2 H 5 C2 H 5
H Br
H Br Br H
CH 3 + + CH 2 +
| H Br H Br
(ii) CH
CH3 
NaOH(aq)
→ No reaction H Br
CH 3 CH 3
Br chiral product chiral product CH 3
achiral product
F OH CH 3
(b) (i)
NaOH(aq) CH 2 CH 2 CH 2 Br
 → Br H
O 2N O 2N
CH 2 + H Br
CH3 CH3
H Br
− CH 3
+ F is liberated . chiral product
CH 3
This is a bimolecular reaction. Rate of this reaction is chiral product
being enhanced by presence of electron withdrawing
groups at ortho and para positions. The no. of possible chiral products is 5.
Alcohols, Phenols and Ethers 179
19 Alcohols, Phenols and Ethers

QUICK LOOK Note
It is fast and convenient. The addition of water to an alkene is
Alcohols: Alcohols are compounds of the general formula anti-Markownikoff and free from rearrangement.
ROH, where R is alkyl or substituted alkyl group. The group
may be open chain or cyclic, it may contain double bond, a Hydroboration of Alkene
halogen atom, an aromatic ring or additional hydroxyl groups, 1
3CH3 − CH = CH2 + B2H6 
→(CH3 − CH2 − CH2 )3 B  3H2O2
OH− / H2O
→
Propene 2 Tripropyl boron
e.g., CH 3CH 2 CH 2 CH 2 OH . Diborane
Butanol-1 3CH − CH − CH − OH + H BO 3CH − CH − CH − OH + H
3 2 2 3 3
CH 2 − OH OH 1− propanol
Note
In this reaction addition of water to an alkene is syn, anti-
Markownikoff and free from rearrangement.
Benzyl alcohol Cyclohexanol
CH 2 − OH CH = CHCH 2 OH Hydrolysis of ethers: C 2 H 5 − O − C 2 H 5 + H 2 O 
dil.H 2 SO4
∆
→
2C 2 H 5 OH
By reaction of Grignard reagent with formaldehyde/
other aldehydes/ ketones
(1-cyclohexene) methanol Cinnamyl alcohol
(a) When Grignard reagent reacts with HCHO, it forms
Alcohols can be classified as, primary alcohol.
ALCOHOLS R R
| | X
H — C == O + RMgX 
→ H — C — OMgX 
→ H — C — OH + Mg
| | | OH
Trihydric alcohols H H H
Monohydric Dihydric alcohols
contain (3-OH groups) R R
contain (2-OH groups) | | X
alcohols e.g. Glycerol H — C == O + RMgX 
→ H — C — OMgX 
→ H — C — OH + Mg
contain (1-OH  CH2OH  | | | OH
group)   H H H
e.g. Glycol  | 
 CH OH  (b) Oxirane on reaction with Grignard reagent also forms
 2 
primary alcohol.
X
O + RMgX 
→RCH2CH2OMgX 
→RCH2CH2OH + Mg
Primary Secondary Tertiary OH
R 
(RCH 2OH)
 CHOH   R 
(c) Any aldehyde except formaldehyde when treated with
R  R C

OH 
 Grignard reagent forms secondary alcohol.
R 
  R R
| | X
R ′ — C == O + RMgX 
→ R ′ — C — OMgX 
→ R ′ — C — OH + Mg
Monohydric Alcohols: Preparation | | | OH
H H H
By oxymercuration - demercuration reaction of alkene :
CH 3 − CH = CH 2 + (CH 3COO) 2 Hg + H 2 O 
THF
CH3COOH
→ (d) When 2-alkyl oxirane reacts with Grignard reagent,
secondary alcohol is formed. The ring is opened from least
CH 3 − CH − CH 2 hindered site.
| | NaBH 4 /OH −
 →
−1/ 2B2 H 6 CH3 CH3
OH HgOCOCH 3 1 | | X
O +RMgX 
→ RCH2 —CH — OMgX 
→ RCH2 —C — OH + Mg
| OH
CH 3 − CH − CH3 + Hg + CH3 COO− 3 2 H
|
OH (e) When ketone reacts with Grignard reagent, it forms
2 − propanol
tertiary alcohol.

R R for ethanol we take ethylene obtained from petroleum :
R′ R′ | R′ | X
C == O + RMgX 
→ C — OMgX  → C — OH = CH 2 + H 2O(steam) 
CH+2 Mg H3PO4
300−350°C
→ CH3CH2OH
R ′′ R ′′ R ′′ OH
It is an Oxo process.
R R
R′ | R′ | X
O + RMgX 
→ C — OMgX 
→ C — OH + Mg Primary, Secondary and Tertiary alcohols can be
R ′′ R ′′ OH distinguished by Victor Meyer’s Method :
(f) When 2, 2-dialkyl oxirane reacts with Grignard reagent, (a) RCH 2 OH 
HI
→ RCH 2 I →
AgNO 2
RCH 2 NO 2 
OHNO
→
it forms tertiary alcohol. Primary alcohol
R 1 R — C — NO 2  → R — C — NO 2
NaOH
R1
O R1 | | || X ||
+ RMgX  → RCH 2 — C — OMgX  NOH
→ RCH 2 — C — OHNitrolic
+ Mg NONa
acid Red sodium salt or nitrolic acid
R2 | | OH
R2 R2 R R R
R1 R1 (b) CHOH  HI
→ CHI  AgNO2
→ CH — NO2
| | X R R R
MgX 
→ RCH 2 — C — OMgX  → RCH 2 — C — OH + Mg
Secondary alcohol
| | OH R
R2 R2 OHNO
→ C — NO2  NaOH
→ Blue colour
R |
By reduction of carbonyl compounds NO
Pseudo nitrolic acid
OH R R
C == + 2H 
→ C (c) R —C —OH 
HI
→ R — C — I 
HNO2
→ No reaction
H R R
The reduction can be carried out by using H 2 /catalyst like
Ni, Pt, Pd, LiAlH 4 , NaBH 4 , NaH, LiH. When the reduction Dihydric Alcohol/Glycol (Ethane – 1, 2- Di-ol)
is carried out by using metal/solvent combination it is known Preparation
as Bouveault blanc recduction. The intermediates are: 3CH 2 = CH 2 + 2KMnO 4 + 4H 2 O 
→
−
⋅⋅ −
⋅⋅ CH 2 — OH
R — C — OEt; R — CH — OEt; R — CH. In case of 3|+ 2MnO 2 + 2KOH
| | | CH 2 — OH
O O. O (Glycol)
.
metal hydride the reaction intermediate is R 2 — C — O Θ
| Trihydric Alcohol Glycerol (Propane - 1, 2, 3 - Triol)
H Preparation
By hydrolysis of ester : R1COOR2+KOH  → R1COOK By saponification of oils and fats
+ R2OH CH 2 — OCOR CH 2 — OH
| |
By reaction of alkyl boride with CO CH — OCOR + NaOH → CH — OH + 3RCOONa
Soap
O | |
|| OH CH 2 — OCOR CH 2 — OH
R 3 B + CO → R 2 — B — C — R  LiBH 4
→ R 2 BCH  → RCH 2 OH (Glycerol)
|| OH Θ
Phenols: Phenols are the organic compounds in which – OH

→ R 2 — B — C — R → R 2 BCH 
OH
H 2O
→ RCH 2 OH group is directly linked to aromatic ring system. The simplest
R
formula of such compound is phenol (C 6 H 5 OH). Structure of
By reaction of primary amines with nitrous acid
some common phenols is as follows:
RNH 2 + HNO 2 
→ ROH + N 2 + H 2 O OH OH OH OH
From glucose : C 6 H12 O 6 → 2CH 3CH 2 OH + 2CO 2
Zymase
CH 3
Industrial method for methanol and ethanol are as CH 3
Heat
follows : CH 4 + H 2 O  → CO + 3H 2 ;
P h en o l o -C reso l m -C re s o l CH3
ZnO + CrO
CO + 2H 2   3
400° C ,200atm
→ CH 3 OH p-Cresol

OH OH Phthalein Reaction
OH OH OH OH OH
OH OH
+
C a te c h o l R e s o rc in o l OH
Quinol O
||
Preparation: (1) Phenols can be prepared by reaction of C
C conc. H2SO4
 → O
O or ZnCl2 or AlCl3
C
benzene sulphonic acid with NaOH. C
|| ||
SO 3 H SO 3 Na O O
Phenolphthalei
Phthalic anhydrolic
n
+ NaOH 
→ note that H para to OH is removed.
OH
(i) NaOH Lederer-Manasse Reaction: When phenol reacts with

+ H2O 
(ii) HCl
→ + Na 2SO 3
formaldehyde in the presence of acid or alkali, it forms
bakelite, a thermostat polymer.
(2) Phenols can also be obtained by warming diazonium salt
OH OH
solution with hot dilute acid solution. OH OH
N2X OH HCHO
 →
H+ or OHΘ  →
− H 2O
H+
→ + HX + N2
CH 2 OH CH 2 CH 2
(3) Phenols can be prepared from aryl halides,
OH
CH 2
Cl Bakelite ←  +
300°C
+ NaOH →
200 atm
+ NaCl OH
Liebermann’s Nitroso Reaction
(4) By reaction of phenolic acid with soda lime. NaNO2 / conc. H 2SO4 H2O
Phenol  → deep green or blue colour  →
OH OH NaOH
+ NaOH(CaO) 
→ + Na 2 CO3 Red  → green or blue colour. The reactions are as
COOH follows:
OH OH OH
Kolbe Reaction or Kolbe–Schmitt Reaction: When sodium
phenoxide reacts with CO 2 at 120°C under 5-7 atmosphere NaNO2 / H2SO4
 → ↽⇀
⊕
followed by acidification with H, it forms salicylic acid.
NO NOH
quinone monoxime
ON OH p-nitrosophenol
120°C
+ CO2 →
5−7 atm ; H 2 SO 4
COON
O
OH
OH
H
⊕
COOH O
 → ⊕
OH
NaOH H2O
←  ← 
Saliylic acid N
The reaction intermediate (s) are: HSO Θ4

N OH
⊝ ⊝
O O OH N OH
⊝ ⊝ Phenol indophenol
COO COO ON Phenol indophenol hydrogen
; ; Sodium salt (Blue)
sulphate (Blue)

Nitrosation: If one group has no simple name, the compound may be named
OH OH as an alkoxy derivative:
⊕
CH 3 CH 2 CH 2 CHCH 2 CH 3 C 2 H5 O COOH
+ HNO2 →
H |
o
10 C OCH 3
3 − Methoxyhexane p − Ethoxybenzoic acid
NO CH 2 CH 2
p-nitrosophenol
| |
Hydrogenation: HO OCH 2 CH 3
2 − Ethoxyethanol
OH OH
The simplest aryl alkyl ether has the special name of anisole.
+ 3H 2 → Ni
150− 200° C OCH3
Cyclohexanol A n iso le
Oxidation If the two groups are identical, the ether is said to be
Phenols turn pink or red or brown when exposed to air and light symmetrical (e.g., diethyl ether, diphenyl ether), if different,
due to slow oxidation. The exact nature of these oxidation unsymmetrical (e.g., methyl tert-butyl ether, anisole).
products is not known; but probable products are quinones and
Preparation of Ethers
phenoquinones.
In the laboratory, the Williamson synthesis of ethers can be
OH O OH ⋯⋯ HOC 6 H 5 used to make unsymmetrical ethers as well as symmetrical
ethers.
 2 
C 6 H 5 OH
→ In the Williamson synthesis an alkyl halide (or substituted alkyl
halide) is allowed to react with a sodium alkoxide.
O O ⋯⋯ HOC6 H 5 → R − O − R′ + Na + X −
R − X + Na + − O − R ′ 
quinone Phenoquinone
Example:
When phenol is oxidised with potassium persulphate in alkaline
CH3 CH3
solution, it forms quinol and the reaction is known as Elbs | |
+ −
persulphate oxidation. CH3Br + Na O — C — CH3 
→ CH3 — O — C — CH3
| |
OH OH CH3 CH 3
Sodium tert -butoxide tert -Butyl methyl ether
  →
K 2S 2 O 8
OH Θ
Reaction involves nucleophilic substitution of alkoxide ion for
halide ion; it is strictly analogous to the formation of alcohols
O by treatment of alkyl halides with aqueous hydroxide.
quinol
Structure and Nomenclature of Ethers R ′O − + → R ′O — R

R — X  + X−
Ethers are compounds of the general formula Nucleophile Substrate Leaving group
R–O–R, Ar–O–R, or Ar – O –Ar.
To commonly name ethers we usually name the two groups that Since alkoxides and alkyl halides are both prepared from
are attached to oxygen, and follow these names by the word alcohols, the Williamson method ultimately involves the
ether: synthesis of an ether from two alcohols.
If we wish to make an unsymmetrical dialkyl ether, we have a
choice of two combinations of reagents; one of these is nearly
C 2 H 5OC 2 H 5 −O − always better than the other. In the preparation of tert-butyl ethyl
Ethyl ether Phenyl ether ether, for example, the following combinations are conceivable:
CH3 CH3 CH3
| | |
CH3 — O — C — CH3 CH3 — C — O — CH3CH 2 — O — C — CH3
| | |
CH3 H CH3
Methyl tert -butyl ether Isopropyl phenyl ether tert -Butyl ethyl ether

CH3 a. I < II < III < IV b. I < II < IV < III
|
CH3CH 2 Br + Na + −
O — C — CH3 Feasible c. IV < I < II < III d. IV < II < I < III
|
(i) O2 / ∆
CH3 3. + Cl − CH 2CH 2 − CH 3 
AlCl3
→ P 
(ii) H O+
→Q+
3
Phenol [JEE 2006]

CH3
| The major products P and Q are
CH3 — C — Cl + Na + −OCH 2CH3 Not Feasible
|
CH3
a. and CH 3 CH 2 CHO b. and CH 3 COCH 3
Which do we choose ? Alkoxides are not only nucleophiles, but
also strong bases which tend to react with alkyl halides by
elimination, to yield alkenes. Whenever we are trying to carry
out nucleophilic substitution, one must be aware of the danger
of a competing elimination reaction. The tendency of alkyl c. and CH 3 COCH 3 d. and CH 3 CH 2 CHO
halides to undergo elimination is 3° > 2° > 1°.
In the above example, the use of the tertiary halide is rejected 4. The correct acidity order of the following is
as it would be expected to yield mostly or all elimination [JEE 2009 P-I]
product; hence the other combination is used. Ethers are the OH OH COOH COOH
alkoxy derivatives of alkanes with general formula R OR′. If R
and R′ are same they are simple ethers while If R and R′ are
different they are mixed ethers.
Cl CH 3
Preparation of Ethers
(I) (II) (III) (IV)
Willlamson’s synthesis
a. III > IV > II > I b. IV > III > I > II
C2 H5ONa + C 2 H5 Br 
→
Sod. ethoxide Ethyl bromide
c. III > II > I > IV d. II > III > IV > I
Dehydration of alcohol
5. In the reaction OCH 3 
HBr
→ the products are
C2 H 5OH + C2 H 5OH → conc. H 2SO 4
413 K
C2H5OC2H5
Diethyl ether
a. Br — — OCH 3 and H 2 [JEE 2010 P-I]

From diazomethane
C 2 H5OH + CH 2 N 2 
HBF4
→
Diazomethane
b. — Br and CH3 Br
Reaction of alkyl halide
with dry silver oxide
c. — Br and CH3OH
∆
(CH3CH 2Br)2 + Ag 2O →
d. — OH and CH3 Br
One and More than One Correct OH
|
1. When benzene sulfonic acid and p-nitrophenol are treated
with NaHCO 3 , the gases released respectively are 6. In the reaction 
NaOH(aq)Br2
→ the intermediate (s)
a. SO2, NO2 b. SO2, NO [JEE 2006]

is (are) [JEE 2010 P-I]
c. SO2, CO2 d. CO 2 , CO 2
O− O
| Br ||
2. The increasing order of boiling points of above mentioned
alcohols is [JEE 2006] a. b.
(I) 1,2-dihydroxy benzene (II) 1,3-dihydroxy benzene |
(III) 1,4-dihydroxy benzene (IV) Hydroxy benzene Br Br Br

−
O OH OH O
| O− | | ||
| OHC CHO
c. d. 
OH − →?
CHCl3
| | |
Br Br CH 3 CH 3 H 3C CHCl 2
P Q
7. Arrange the following compounds in order of decreasing OH OH
| |
acidity [JEE Main 2013] CHO
OH OH OH OH
|
H 3C CHCl 2 CH
3
R S
Cl CH 3 NO 2 OCH 3 a. P (major) b. Q (minor) c. R (minor) d. S (major)
(I) (II) (III) (IV) 12. The acidic hydrolysis of ether (X) shown below is fastest
a. II > IV > I > III b. I > II > III > IV when [JEE Adv. 2014 P-II]
c. III > I > II > IV d. IV > III > I > II
8. An unknown alcohol is treated with the “Lucas reagent”
to determine whether the alcohol is primary, secondary or acid
OR  → OH + ROH
tertiary. Which alcohol reacts fastest and by what
mechanism? [JEE Main 2013]
a. secondary alcohol by SN1
a. one phenyl group is replaced by a methyl group
b. tertiary alcohol by SN1
b. one phenyl group is replaced by a para-methoxyphenyl
c. secondary alcohol by SN2
group
d. tertiary alcohol by SN2
c. two phenyl groups are replaced by two para-methoxy-
9. The compound that does NOT liberate CO2, on treatment phenyl groups
with aqueous sodium bicarbonate solution, is d. no structural change is made to X.
[JEE Adv. 2013 P-I]
13. The reactivity of compound Z with different halogens
a. Benzoic acid b. Benzenesulphonic acid
under appropriate conditions is given below:
c. Salicylic acid d. Carbolic acid (Phenol)
[JEE Adv. 2014 P-I]
10. The major product (s) of the following reaction is (are)
OH OH
| mono halo substituted derivative when X 2 = I 2
[JEE Adv. 2013 P-II] X2 di halo substituted derivative when X 2 = Br2
      
→?
aqueous Br2 (3.0 equivalents)
C(CH3)3 tri halo substituted derivative when X 2 = Cl2

| Z
SO 3 H OH
OH | The observed pattern of electrophilic substitution can be
| Br Br
a. P Br Br b. Q explained by
Br a. the steric effect of the halogen
Br |
| Br b. the steric effect of the tert-butyl group
SO 3 H c. the electronic effect of the phenolic group
Q
P
OH OH d. the electronic effect of the tert-butyl group
| |
Br 14. The major product of the following reaction is
c. R d. S
Br
[JEE Adv. 2015 P-I]
Br Br Br |
| O
Br SO 3 H
R S
11. In the following reaction, the product (s) formed is (are) CH3
i. KOH, H O
+
ii. H , heat
2
→
O

CH 3 CH 3 18. Phenol reacts with methyl chloroformate in the presence
O O of NaOH to form product A. A reacts with Br2 to form
a. b. product B. A and B are respectively [JEE Main 2018]
OH OH
O a.
O
CH 3 OCH and 3 OCH 3
c. CH 3 d. O Br O
OH Br OH
15. The major product U in the following reactions is b. and
OCH3 OCH3
+
O Br O
CH 2 = CH − CH3 , H
 → T 
radical initator, O2
→U
high pressure, heat O O O O
c. and
H O O
|
O O O O O
O and
H 3C CH3 d. O
O O
CH3 Br
a. b. O H
19. The major product formed in the following reaction
H O 
Hl
→
| Heat
O O [JEE Main 2018]
O CH2
CH2 O H I OH
H a. b.
c. d.
OH OH
16. 2-chloro-2-methylpentane on reaction with sodium I OH

c. d.
methoxide in methanol yields: [JEE Main 2016] I I
CH 3 20. An organic compound 'X' showing the following
|
(a) C 2 H 5 CH 2 C − OCH 3 (b) C2 H 5 CH 2 C = CH 2 solubility profile is – [JEE Main 2019]
| |
CH 3 CH 3 Water
Insoluble
(c) C2 H 5 CH = C − CH 3 ‘X’ 5% HCl
| Insoluble
CH 3
10% NaOH
a. All of these b. (a) and (c) Soluble
c. (c) only d. (a) and (b) 10% NaHCO3
Insoluble
17. The correct statement(s) about the following reaction a. m-Cresol b. Oleic acid
sequence is(are) (C9 H12 ) 
(i) O2
→ P 
CHCl3 / NaOH
→Q c. o-Toluidine d. Benzamide
(ii) H O+ 3
21. An organic compound neither reacts with neutral ferric

(major) + R(minor) Q 
→ S Cumene
NaOH
PhCH 2 Br
chloride solution nor with Fehling solution. It however,
[JEE Adv. 2016 P-I] reacts with Grignard reagent and gives positive iodoform
a. R is steam volatile test. The compound is - [JEE Main 2019]
b. Q gives dark violet coloration with 1% aqueous FeCl3 OH
solution O
c. S gives yellow precipitate with 2, 4-dinitrophenylhydrazine a. CH3 b. CH3
C2H5 H
d. S gives dark violet coloration with 1% aqueous FeCl3
solution O O

O O OH OH OH OH
CH3 C2 H 5
c. d.
CH3
OH O NO2
NO2 OMe
22. The compounds A and B in the following reaction are,
A B C D
respectively : [JEE Main 2019]
a. D < A < C < B b. B < C < D < A
c. C < B < A < D d. B < C < A < D
HCHO + HCl AgCN
→ A  →A 26. The major product of the following reaction is :-
a. A = Benzyl alcohol, B = Benzyl isocyanide [JEE Main 2019]
b. A = Benzyl alcohol, B = Benzyl cyanide HO
c. A = Benzyl chloride, B = Benzyl cyanide  (1) HCl
→
( 2)AlCl3 (Anhyd.)
d. A = Benzyl chloride, B = Benzyl isocyanide
Cl HO
23. The product formed in the reaction of cumene with O2. a. b.
followed by treatment with dil. HCl are:
[JEE Main 2019] O
OH O c. Cl d. HO
a. and H 3C CH3
CH3 OH
O |
27. CH 3 CH 2 — C — CH 3 cannot be prepared by:
|
b. and CH3—OH Ph
[JEE Main 2019]
OH a. HCHO + PhCH(CH3)CH2MgX
O
b. PhCOCH2CH3 + CH3MgX
c. and H 3C CH3 c. PhCOCH3 + CH3CH2MgX
d. CH3CH2COCH3 + PhMgX
O
28. The major product in the following conversion is:
d. and H 3C CH3 [JEE Main 2019]
24. The major product of the following reaction is CH3O CH == CH — CH 3  → ?

HBr (excess )
Heat
[JEE Main 2019]

a. HO CH 2 — CH — CH3
Br
→
KOHalc( Excess ) |
∆
Br
Ph
Br b. HO CH — CH 2 — CH3
|
Br
a. b.
Ph Ph c. CH3O CH 2 — CH — CH3
|
c. d. Br
Ph Ph d.
CH3O CH — CH 2 — CH 3
25. The increasing order of the pKa values of the |
Br
following compounds is: [JEE Main 2019]

Matrix Match/Column Match 31. For the synthesis of benzoic acid, the only correct
29. Match the compounds in Column I with their combination is
characteristic test(s)/reaction(s) given in Column II. a. (III) (iv) (C) b. (IV) (ii) (A)
[JEE 2008 P-II] c. (II) (i) (D) d. (I) (iv) (B)
Column I Column II 32. The only correct combination that gives two different
⊕ Θ 1. sodium fusion carboxylic acids is
(A) H 2 N — NH3 Cl
extract of the a. (IV) (iii) (B) b. (I) (i) (D)
compound gives c. (III) (iii) (A) d. (II) (iv) (C)
Prussian blue colour
33. The correct match between Column I and Column II is:
with FeSO4
⊕ Θ
[JEE Main 2019]
NH3 I 2. gives white precipitate
(B) HO
Column - I (compound) Column – II (reagent)
with AgNO3
COOH (A) Lysine 1. 1-naphthol
3. gives white precipitate (B) Furfural 2. ninhydrin

(c) HO
⊕
NH 3 Cl
Θ
with AgNO3 (C) Benzyl alcohol 3. KMnO4

(D) Styrene 4. Ceric ammonium
⊕ Θ 4. reacts with aldehydes
O2 N NH − NH3 Br
(D) to form the a. A→2; B→1; C→4; D→3
NO2 corresponding b. A→2; B→3; C→4; D→1
hydrazone derivative c. A→2; B→1; C→3; D→4
a. A →3, 4; B→1, 2; C→1, 2, 3; D→ 1, 4 d. A→3; B→1; C→2; D→4
b. A→2, 4; B→1, 2; C → 1, 2, 4; D→ 1, 3
c. A →1, 4; B→ 1, 4; C→ 1, 2, 3; D→ 1, 2 Paragraph
d. A→1, 2; B→2, 3; C → 1, 2, 3; D → 1, 4 Paragraph for Question Nos. 34 to 36
Match the Column for Question Nos. 30 to 32 Reimer-Tiemann reaction introduces an aldehyde group, on to
The information are given in the three columns of the following the aromatic ring of phenol, ortho to the hydroxyl group. This
table. Columns I, II and III contain starting materials, reaction reaction involves electrophilic aromatic substitution. This is a
conditions, and type of reactions, respectively. general method for the synthesis of substituted salicyldehydes
[JEE 2008 P-II] as depicted below. [IIT JEE 2007 P-II]
Column I Column II Column III OH ONa OH
(A) Condensation CHO CHO
(I) Toluene (i) NaOH / Br2 → [ I] 
 → 
aq. HCl
→
(B) Carboxylation
(II) Acetophenone (ii) Br2 / hv CH3 CH3 CH3
(I) (II) (III)
(iii) ( CH 3CO )2 O (C) Substitution
(III) Benzaldehyde 34. Which one of the following reagents is used in the above
/ CH 3COOK
reaction?
(D) Haloform a. aq. NaOH + CH 3 Cl b. aq. NaOH + CH 2 Cl 2
(IV) Phenol (iv) NaOH / CO 2
c. aq. NaOH + CHCl3 d. aq. NaOH + CCl 4
30. The only correct combination in which the reaction
35. The electrophile in this reaction is
proceeds through radical mechanism is
a. (II) (iii) (C) b. (III) (ii) (A) a.: CHCl b. + CHCl2
c. (IV) (i) (B) d. (I) (ii) (C) c.: CCl 2 d. .CCl2

36. The structure of the intermediate I is 39. The structures of compounds J, K and L, respectively, are
O Na O Na a. PhCOCH 3 , PhCH 2 COCH 3 and PhCH 2 COO – K +
CH2Cl CHCl2 b. PhCHO, PhCH 2 CHO and PhCOO– K +
a. b.
c. PhCOCH 3 , PhCH 2 CHO and CH 3COO – K +
CH3 CH3 d. PhCHO, PhCOCH 3 and PhCOO– K +
O Na O Na
CCl2 CH2OH Schemes 1 and 2 describe sequential transformation of alkynes
c. d.
M and N. Consider only the major products formed in each step
for both schemes. [JEE Adv. 2014 P-II]
CH3 CH3 1. NaNH 2 (excess)
H  
→ X
2. CH3 CH 2 I(1 equivalent)
H 
3. CH I(1 equivalent)
→ X Scheme −1 −1
Scheme
M 3
Paragraph for Question Nos. 37 to 39 HO 4. H 2 , Lindlar 's catalyst
A tertiary alcohol H upon acid catalysed dehydration gives a

product I. Ozonolysis of I leads to compounds J and K. 1. NaNH 2 (2 equivalent)
OH
Compound J upon reaction with KOH gives benzyl alcohol and 2. Br
a compound L, whereas K on reaction with KOH gives only M, N 


3. H3O +→ Y → Y Scheme −Scheme
(mild) 2 −2
4. H 2 , Pd / C
[JEE 2008 Paper -II] 5. CrO3
O 40. The product X is

H 3C H3CO H
Ph
M=
H 3C H a. b. H
H H H3CO
37. Compound H is formed by the reaction of
H
O CH3CH2O
+ PhMgBr
a. c. d. H
Ph CH 3 CH3CH2O
H H
O 41. The correct statement with respect to product Y is
+ PhCH2MgBr a. It gives a positive Tollens test and is a functional
b.
Ph CH 3 isomer of X
b. It gives a positive Tollens test and is a geometrical
O
isomer of X
+ PhCH2MgBr c. It gives a positive iodoform test and is a functional
c.
Ph H isomer of X
d. It gives a positive iodoform test and is a geometrical
O Me
isomer of X
d. +
Ph H Ph M gBr Integer and Subjective
38. The structure of compound I is 42. The number of resonance structures for N is
H 3C [JEE Adv. 2015 P-I]
Ph CH 3 Ph
a. b. OH
NaOH
→ N
H Ph H Ph
Ph CH 3 H 3C CH 3
c. d. 43. Calculate the total number of cyclic ether (including
H CH 2 Ph Ph H stereo) having formula C4 H8 O. [JEE 2019 P -II]

8. (b) Fastest reaction with Lucas reagent given by 3º R−OH
44. 
H 2 / Pd BaSO4
→'X' and it follow SN1 mech.

dil.KMnO4
→ 'Y ' 9. (d) pK3 of PhOH (carbolic acid) is 9.98 and that of
273K
carbonic acid (H2CO3) is 6.63 thus phenol does not give
Number of hydroxyl group in compound ‘Y’ is:
effervescence with HCO3− ion.
[JEE 2019 P -II]
OH OH
| |
ANSWERS and SOLUTIONS Br Br
10. (d) 
Br2 (3equivalents)
→
1. (d)
SO3 H SO3 Na | |
SO3H Br
+ NaHCO3 
→ + CO 2 + H 2 O (Q)
11. (b, d)
OH ONa
12. (c) When two phenyl groups are replaced by two para
methoxy group, carbocation formed will be more stable.
+ NaHCO3 
→ + CO 2 + H 2 O
Cl
|
13. (a) CH 3 — C — CH 2 — CH 3 →
MeONa
NO 2 NO 2 MeOH
|
2. (c) CH 3
3. (c) It is cumene hydroperoxide rearrangement reaction. CH 3 — C == CH — CH 2 — CH 3
|
4. (a) CH 3
OH OH COOH COOH + CH 2 == C — CH 2 — CH 2 — CH 3
|
CH 3
OCH 3
|
Cl CH 3 + CH 3 — C — CH 2 — CH 2 — CH 3
(I) (II) (III) (IV) |
pKa = 9.98 pKa = 9.38 pKa = 4.17 pKa = 4.37 CH 3
Elimination dominate over substitution in the given
Decreasing order of acidic strength: III > IV > II > I
reaction but all the products are possible.
5. (d) OH
14. (a, b, c)
ɺɺ — CH 
O 3
HBr
→ —OH + CH 3Br I
ɺɺ I2
Rxn (i )
→
CMe 3
6. (a, b, c) Phenoxide ion is para* and ortho directing. OH
OH
(*preferably) Br
ɺɺ :−
:O ɺɺ :−
:O :O: O  →Br2
Rxn (ii)
| | || || CMe 3
−
CMe 3
: Br
→
Br2
←
→ ← → OH
| | ɺɺ
Br ⊙ Cl Cl
Br Br → Cl 2
Rxn (iii)
O :O : ɺɺ :−
:O ɺɺ :− ɺɺ :− CMe 3
|| || | :O :O
| | Cl
Br
→ Br2
+ ←
→
15. (a)
+
Br O O
Br Br Br | ɺɺ Θ
:OH HO
Br  → →
2
CH2 Θ
7. (c) Acidic nature order CH3 CH CH
3
III > I > II > IV. O O

CH3 CH3 20. (a)
OH
O O Water
H+ ,H2O/∆ Insoluble
← 
OH 5% HCl
Insoluble
ONa
16. (b)
10% NaOH
+ soluble
+ H3C — CH — CH3 
→ → O2
Me
m-cresol 10% NaHCO3 Me
m-cresol
CH Insoluble
H 3C CH 3
T * Oleic acid is also soluble in NaHCO3
CH 3
| * o-toluidine is not soluble in NaOH as well as NaHCO3
C — CH 3 * Benzamide is also not soluble in NaOH & NaHCO3.
|
O 21. (a) OH
U O
H
–
CH3
OH3 O
O C — Et
OH − || ||

→ Cl − C − O − CH3

→
17. (d) O
Neutral
O FeCl3 –ve (FeCl3 test for
O
|| || phenolic group)
O − C − O − CH 3 O − C − O − CH 3 RMgX
Grignard reagent +ve Reaction *AcidicH 

Br2
→ * — C — 
NaOH+I2  || 
+ve (CHI3)  O 
Iodoform test
Reaction
O I  due — CH — CH 3 group 
18. (a) 
→
Hl
 | 
Heat + I  
O OH  OH 
OH
Hence, option (a) is correct.
CH2—Cl CH 2 — N == C
19. (b, c)
22. (d) 
HCHO
HCl
→ 
AgCN
(covalent)
→
OH OH
CHO
23. (c) Cumene hydroperoxide reaction

(i) O2
(ii) H O+
→ 
CHCl3 / NaOH
→
3
O—OH
P Q (major) →O2
OH OH O − CH 2 Ph
HCl
CHO CHO
+  
NaOH
PhCH 2 Br
→
OH
S
CHO
R (minor) +CH3—C—CH3
Q is steam volatile not R. ||
O
Q and R show positive test with 1% aqueous FeCl3 24. (c) Example of E2 elimination and conjugated diene is formed
Solution. with phenyl ring in conjugation which makes it very stable.
Q, R, S show positive 2,4-dinitrophenyl hydrazine. 25. (d) Acidic strength is inversely proportional to pka.

OH OH OH OH For Question Nos. 34 to 35
−
34. (c) OH − (aq) + CHCl3 ↽ ⇀ C Cl3 + H 2O
> > >
NO2 CCl3− 
→ Cl − + : CCl 2 dichlorocarbene intermediate
OMe NO2 −
35. (c) OH − (aq) + CHCl3 ↽ ⇀ C Cl3 + H 2O
26. (b)
CCl3− 
→ Cl − + : CCl 2 dichlorocarbene intermediate
HO C=C

HCl
→
AlCl3
O− O
OH CHCl2
H⊕ 36. (b) + : CCl 2 
→
Cl
⊕
HO HO
− AlCl3 CH3 CH3

− AlCl 4
→
O 37. (b)
|| O O
27. (a) H — C — H + Ph — CH — CH 2 MgX
| Ph — C — CH 3 + PhCH 2 MgBr 
→ Ph — C — CH 3
CH 3
H2C—Ph
Ph — CH — CH 2 — CH 2 — OH
| 38. (a)
CH 3
OH CH3
H+ / ∆
HBr
Ph — C — CH 3 
→ Ph — C == CH — Ph
− H2O
28. (b) H 3 CO CH == CH — CH 3  → (1)
Hydrolysis Electrophilic H2C–Ph
of ether addition
acc.to markonikoff 's
Rule
39. (d)
HO CH3 CH3
CH — CH 2 — CH3
| Ph — CH == CH 
→ Ph — C == O + Ph — CHO
O3
H 2 O / Zn
Br (K) (J)
Ph
29. (a) A→3,4; B→1, 2; C→ 1, 2, 3; D→ 1, 4 Hence, (d) is the correct answer.
30. (d) Θ
NaNH CH CH I
CH3 CH3Br H 2
→ C 
3 2
→
Θ
→Br2 / hv
(Free Radical Substitution) HO M O
Θ H , Lindlar's catalyst
O
CH I

3
→O 
2
→
31. (c)
H3CO
O O Θ
NaNH2
H 
1equivalent
→ C
N
CH3 →
NaOH / Br2
O– H H
(Haloform reaction) X
OH
32. (c) Br
H O+ H ,Pd/C
 → 
3
→ 
2
→
O O NaNH (1eq)
2 mild
OΘ OH
OH O
H  →
(CH 3CO)2 O OH CrO
CH3COOK 
3
→
(condensation)
(cis and trans) Y
X and Y are function isomers of each other and y vies
33. (a) A→2; B→1; C→4; D→3 iodoform test.

40. (a)
41. (c) 43. (10)
HO (R+S)
42. (9) 
→ N N is
NaOH
O–
(R+S)
(R,R), (S,S)
O– O O
(R,S) = (S,R) = 10
` 1 2 3 44. (6) 

H 2 / Pd BaSO 4
→
O O– O

dil.KMnO4
273 K
→
4 5 6 H H
O O O–
7 8 9
OH OH
Aldehydes and Ketones 193
20 Aldehydes and Ketones

QUICK LOOK replacing –ic acid by –aldehyde. The longest chain containing
the –CHO group is considered the parent structure and named
Aldehydes are the compounds which have general formula by replacing –e of the corresponding alkane by –al. The
RCHO, Ketones are compounds having general formula position of the substituent is indicated by a number, the
RR ′CO. The groups R and R′ may be aliphatic or aromatic, carbonyl carbon always being considered C-1. Here, as with the
similar or different alkyl/aryl groups. carbonyl acids, the C-2 of the IUPAC name corresponds to
H R alpha of the common name.
C=O C=O H H
R R H
| | |
An aldehyde A ketone
C — C == O C — C == O CH 3 — CH 2 — C == O
Formaldehyde Acetaldehyde Propionaldehyde
Both aldehydes and ketones contain the carbonyl group, Methanal Ethanal Propanal
C = O, and are often referred to collectively as carbonyl H

compounds. It is the carbonyl group that governs mainly the |
CH 3 — CH 2 — CH 2 C == O
chemistry of aldehydes and ketones. n-Butyraldehyde
Butanal
H
Structure of Carbonyl Group | H
Carbonyl carbon is joined to three other atoms by σ bonds; C == O |
CH 2 — C == O
since these bonds utilise sp 2 orbitals, they lie in a plane, and OH
are 120° apart. The remaining p-orbitals of carbon overlaps a Salicyladehyde Phenylacetaldehyde
(o-Hydroxybenzaldehyde) (Phenylethanal)
p-orbital of oxygen to form a π bond; carbon and oxygen are
thus joined by a double bond. The part of the molecule H
|
immediately surrounding carbonyl carbon lie in a plane. CH 3 — CH 2 — CH 2 — CH — C == O
|
The electrons of a carbonyl double bond hold together atoms of CH 3
quite different electronegativity and hence the electrons are not 2-Methylpentanal
equally shared; in particular the polar π - cloud is pulled H

|
strongly towards the more electronegative atom, oxygen. CH 3 — CH 2 — CH — CH 2 — C == O
|
R ′ δ+ δ– CH 3
C == O 3-Methylpentanal
120°
R H
The carbonyl group, C = O, governs the chemistry of |
CH 3 — CH — CH 2 — CH 2 — C == O
aldehydes and ketones. It does this in two ways: |
CH 3
By providing a site for nucleophilic addition, and 4-Methylpentanal
:Z
R′
C == O The simple aliphatic ketone has the common name acetone. For
R most other aliphatic ketones we name the two groups that are
By increasing the acidity of hydrogen atoms attached to the attached to carbonyl carbon and follow these names by the
alpha carbon. word ketone. A ketone in which the carbonyl group is attached
H to a benzene ring is named as phenone, as illustrated below.
|
R — C — C — R′ The positions of various groups are indicated by numbers.
| ||
H O CH 3 — C — CH 3 CH 3CH 2 — C — CH 3
|| ||
Nomenclature: The common name of aldehydes are derived O O
Acetone Methyl ethyl
from the names of the corresponding carboxylic acids by Propanone ketone Butaone

CH3 — CH 2 CH 2 — C — CH3 (C5 H 5 NH + CrO3Cl − ). It is abbreviated as PCC and is called
||
O Collin's reagent. This reagent is used in non-aqueous
Methyl-n-propyl ketone
2-Pentanone
solvents like CH2Cl2 (dichloro methane). It is prepared by
CH 3
| mixing pyridine, CrO3 and HCl in dichloromethane. This
CH3 — CH 2 — C — CH 2CH3 CH 3 — CH — C — CH 3
|| || is a very good reagent because it checks the further
O O oxidation of aldehydes to carboxylic acids and is suitable
3-Pentanone 3-Methyl-2-butanone
method for preparing α, β−unsaturated aldehydes.

—CH 2 — C — CH3
||
O Dehydrogenation of 1° and 2° alcohols by Cu/300°or
1-Phenyl-2-propanone
Ag/300°C.
—C — CH2CH2CH3 O
—C — CH 3 ||
|| || Cu / 300° C
O R — CH 2 OH  → R — C — H + H2
O
Acetophenone n −butyrophenon
OH O
| ||
Cu / 300° C
—C — R — CH — R ′  → R — C — R′ + H2
||
O
Benzophenone
From Carboxylic Acids
5′ 6′ 2 3 NO2
4′ Distillation of Ca, Ba, Sr or Th salts of monobasic acids
H3C C 4
|| O
3′ 2′ O 6 5 ||
(RCOO)2 Ca + (R′COO)2 Ca  ∆
→ 2R — C — R′ + 2CaCO3
3-Nitro-4′-methylbenzophenon
Thus in the product, one alkyl group comes from one
carboxylic acid and other alkyl group from other carboxylic
Preparation of Carbonyl Compounds
acid. Calcium salts of dibasic acid (1, 4 and higher) on
From Alcohols
distillation give cyclic ketones.
By oxidation
O
O HO ||
| || CH 2 — C — O
R — CH — R ′ 
Mild oxidising
agents
→ R — C — R′ | Ca ++ 
Distillation
→ O + CaCO3
Secondary alcohol Ketone
CH 2 — C — O
O || Cyclopropanone
|| O
R — CH 2 — OH 
Mild oxidisin g
→ R — C —H O
agents
Primary alchol Aldehyde  O 
 ||  ++
Mild oxidising agents are  O — C — (CH 2 )5 — COO  Ca   →
Distillation
 
(i) X 2 (Halogen) (ii) Fenton reagent (FeSO 4 + H 2 O 2 ) Cyclohexanone
⊕
Decarboxylation or Dehydration of acids by
(iii) K 2 Cr2 O7 / H (iv) Jones reagent
MnO/300°C.
(v) Sarett reagent(vi) MnO 2
This reaction takes place between two molecules of
(vii) Aluminium tertiary butoxide [Al(−O − C(CH 3 )3 )3 ] carboxylic acids. Both may be the same or different.
If one of the carboxylic acids is HCOOH then this acid
When the secondary alcohols can be oxidised to ketones by
undergoes decarboxylation because this acid is the only
aluminium tert-butoxide, [(CH 3 )3 CO]3 Al the reaction is
monobasic acid which undergoes decarboxylation even in
known as oppenauer oxidation. Unsaturated secondary
the absence of catalyst.
alcohols can also be oxidised to unsaturated ketones
Case (i): When both molecules are HCOOH
(without affecting double bond) by this reagent.
O O
The yield of aldehydes is usually low by this methods. The || ||
allylic alcohols can be converted to aldehydes by treating H —C —OH + H COO H  MnO
300°C
→ CO2 + HOH + H —C —H
formic acid formaldehyde
with oxidising agent pyridinium chloro-chromate

Case (ii): When only one molecule is formic acid. From Grignard Reagent
O O O
|| || O
/ 300 C °
R — C — OH + H — COO H  MnO  → R — C — H + CO 2 + HOH
||
R ′ —C—Cl
||
formic acid Aldehyde
 → R′ — C — R (Only ketone)
C arboxy acid
O
Case (iii): When none of the molecule is formic acid. ||
→
HCOOC2 H5
H — C — R (Aldehyde)
O O
||
MnO / 300° C
|| O
R — C — OH + R COO H → R — C — R + CO 2 + HOH ||
R ′COOC2H5
Ketone → R — C — R′ (Ketone)
Carboxylic acid
R − MgX O
||
From Gem Dihalides: Gem dihalides on hydrolysis give (Excess)
→
(i) HCN
+
(ii) H2O/ H
R — C —H
carbonyl compound O
R − CHX 2 
HOH / OH
→ R − CHO (i) R ′−CN
||
Aldehyde
→ +
(ii) H O/ H
R — C — R′
Gemdihalide 2
X O O O
| || || ||
R — C — R ′ 
HOH / OH
→ R — C — R′ CH2 == CH—C—H

→ R — CH2 — CH2 — C — H
|
X
From Acid Chloride
This method is not used much since aldehydes are affected
Acid chlorides give nucleophilic substitution reaction with
by alkali and dihalides are usually prepared from the
carbonyl compounds. dialkyl cadmium and dialkyl lithium cuprate to give
ketones. This is one of the most important method for the
From Alkenes preparation of ketones from acid chlorides.
Ozonolysis: Alkenes on reductive ozonolysis give carbonyl O O
|| R ′2 Cd
||
compounds R — C — Cl  → R — C — R′
R − CH = CH − R →(i) O3
(ii) H 2O/ Zn
R − CHO + RCHO O O
Alkene
|| ||
R ′2 CuLi
O O R — C — Cl → R — C — R ′
R R′ || ||
C == C → R — C — R + R′ — C — R′
(i) O3
(ii) H2O/ Zn (Only used for the preparation of ketones)
R R′
In this method product is always ketone because R ≠ H and
This method is used only for aliphatic carbonyl compounds.
also R ′ ≠ H.
Oxo process
Rosenmunds reduction: This reduction takes place in the
R − CH = CH 2 + CO + H 2    → R − CH 2 − CH 2 − CHO
CO 2 ( CO )8
150 ° C , 300 atm
presence of Lindlar’s catalyst.
    → R − CH 2 − CH 2 − CHO O O
|| ||
H 2 / Pd − BaSO4 − CaCO3
Oxo process is used only for the preparation of aldehydes. R — C — Cl  Xylene
→ R — C —H
Wacker process
O O
CH 2 = CH 2 →
PdCl2 / HOH
CH3 − CHO ||
H 2 / Pd − BaSO 4 − CaCO 3
||
air / Cu 2 Cl2
Ethene Ar — C — Cl  Xylene
→ Ar — C — H
O (Only used for aldehydes)
||
R — CH == CH 2 → R — C — CH 3 PdCl2 / HOH
air / Cu 2 Cl 2
Alkyl ethene
From Cyanides
From Alkynes
Stephen aldehyde synthesis: Conversion of cyanides into
O
|| aldehydes by partial reduction with SnCl2 / HCl, followed

→
H2O/ HgSO4 / H2SO4
R — C — CH3 by hydrolysis, is known as Stephens aldehyde synthesis.
R −C ≡ C−H R − C ≡ N  (i) SnCl2 / HCl / ether
→ R − CHO
(ii) H 2 O / ∆ or steam distillation
Alkyl cyanide Aldehyde

(i) SiO2BH3
(ii) H2O2 / OH

→ R —CH2 —CHO
(Only used for aldehydes)

From Vic Diols CHO
OH OH O
| | ||
R — CH — C — R 
HIO4
→ RCHO + R — C — R + H 2 O 
CO / HCl / Anhy.ZnCl2 / Cu 2Cl2
→
|
R Benzene Benzaldehyde
Pb(OCOCH 3 ) 4 also gives similar oxidation products. CH3 CH3 CH3

CHO

→ +
From Alkyl Halides and Benzyl Halides
o-methyl benzaldehyde
R − CH2Cl 
DMSO
→ R − CHO; Toluene CHO
p-methyl benzaldehyde
Cl O Cl
| || Cl Cl
R — CH — R → R — C — R
DMSO
CHO

→ +
C6 H 5 − CH 2 Cl 
DMSO or (i) (CH 2 )6 N 4
(ii) H O / H⊕ or Cu ( NO ) or Pb( NO )
→ C6 H 5 − CHO
2 3 2 3 2
Chloro benzene o-Chloro benzaldehyde

CHO
p-Chloro benzaldehyde
From Nitro Alkanes: Nitro alkanes having at least one α-
hydrogen atom give carbonyl compounds on treatment with Gattermann Formylation: This reaction is mainly given by
alkyl benzenes, phenols and phenolic ethers.
conc NaOH followed by 70% H2SO4 . The reaction is known as
CH3
Nef carbonyl synthesis. CH3 CH3
O O H2 OH CHO
R — CH 2 — N NaOH
→ R — CH == N (ii) H2O / ∆

(i) Zn(CN)2 / HCl gas
→ +
Tautomerisation
O O
(Aciform)
Toluene o-methyl benzaldehyde
CHO
p-methyl benzaldehyde
OH R O O OH
|| OH OH
→R—CHO
70%H2SO4
Aldehyde
CH — N 
(i) NaOH
(ii) H2SO4
→R — C — R
O R O Ketone CHO
(Iso − nitro alkane)  
(ii) H2O / ∆
→ +
o-salicyladehyde
Phenol CHO
Reaction with Excess of Alkyl Lithium: Carboxylic acids p-salicyladehyde
react with excess of organo lithium compound to give lithium OCH3

OCH3 OCH3
salt of gem diols which on hydrolysis give ketones.
CHO
O O  
→ +
|| || (ii) H2O / ∆
R ′ — C — OH →
(i) R -Li (excess)
(ii) HOH/H +
R′ — C — R CHO
Anisol o-methoxy benzaldehyde
p-methoxy benzaldehyde
Preparation of Only Aromatic Carbonyl Compounds Houben-Hoesch Reaction: This reaction is given by di and
From Methyl Arenes polyhydric benzenes.
OH OH
→
(i) CrO 2 Cl2
(ii) HOH (Etard 's reaction) C6H5CHO
C 6 H 5 − CH 3 
(i) CrO3 /(CH3CO)2 O / CH3COOH
→ 
(i) RCN/ HCl gas / Anhy. ZnCl2
→
Toluene (ii) H 2O C6H5CHO OH
(ii) H2O
OH
→ Air / MnO
500° C C6H5CHO Resorcinol
COR
2,4-dihydroxy ketone
From Chloromethyl OH OH
Cu(NO3 )2 / ∆
→ C6H5CHO 
(i) RCN/ HCl gas / Anhy. ZnCl2
(ii) H2O
→
Pb(NO ) / ∆
C6H5 − CH2Cl → C6H5 − CHO 3 2
HO OH HO OH
Phloroglucinol
COR
→
(i) (CH 2 )6 N 4
(ii) H 2 O C6H5 − CHO 2,4,6-triydroxy ketone
Gattermann-Koch Formylation: This reaction is mainly Reimer-Tiemann Reaction: Phenol gives o- and p- hydroxy
given by aromatic hydrocarbons and halobenzenes. benzaldehyde in this reaction.

OH OH OH Preparation
CHO By oxidation of ethyl alcohol with acidified potassium
(i) CHCl3 / Alc.KOH / ∆

(ii) H O/ H +
→ + dichromate or with air in presence of a catalyst like silver at
2
(Major)
300°C.
Phenol
CHO By dehydrogenation of ethyl alcohol. The vapours of ethyl
(Minor)
alcohol are passed over copper at 300°C.

By heating the mixture of calcium acetate and calcium
Some Commercially Important Aliphatic
formate.
Carbonyl Compounds
By heating ethylidene chloride with caustic soda or caustic
Formaldehyde: Formaldehyde is the first member of the
potash solution.
aldehyde series. It is present in green leaves of plants where its
By the reduction of acetyl chloride with hydrogen in
presence is supposed to be due to the reaction of CO2 with presence of a catalyst palladium suspended in barium
water in presence of sunlight and chlorophyll. sulphate (Rosenmund's reaction).
By the reduction of CH3CN with stannous chloride and
Preparation
HCl in ether and hydrolysis (Stephen's method).
2CH3 OH + O2 
Plantinised asbestos
300 − 400° C
→ HCHO By hydration of acetylene with dil. H2SO4 and HgSO 4 at
Formaldehyde
CH3OH + [O] 

K 2Cr2O7
→ HCHO + H2O 60°C.
H 2SO4
By ozonolysis of butene-2 and subsequent breaking of
CH 3 OH 
Cu or Ag
300 − 400° C
→ HCHO ozonide.
Formaldehyde
Laboratory preparation: Acetaldehyde is prepared in the
Ca(HCOO) 2 
→ HCHO Heat
Calcium formate Formaldehyde laboratory by oxidation of ethyl alcohol with acidified

potassium dichromate or acidified sodium dichromate.
CH 2 = CH 2 + O3 
H2
Pd
→ HCHO
Formaldehyde
K 2 Cr2 O7 + 4H 2SO 4 
→ K 2SO 4 + Cr2 (SO 4 )3 + 4H 2 O + 3[O]
Mo − oxide
CH + O2 
4 → HCHO Catalyst [CH 3CH 2 OH + O 
→ CH 3CHO + H 2 O] × 3
Methane Formaldehyde
CO + H 2 
Elec.discharge
→ HCHO K 2 Cr2O 7 + 3CH 3CH 2 OH + 4H 2SO 4 
→ K 2SO 4 + Cr2 (SO 4 )3 + 3CH 3CH
Formaldehyde Potassium Ethylalcohol Sulphuric acid Potassium Chromic Acetaldehyd
dichromate sulphate
Uses K 2 Cr2 O7 + 3CH 3CH 2OH + 4H 2SO 4  → K 2SO 4 + Cr2 (SO 4 )3 + 3CH 3CHO+ 7H 2 O
Potassium Ethylalcohol Sulphuric acid Potassium Chromic Acetaldehyde Water
The 40% solution of formaldehyde
dichromate (formalin) is used as sulphate sulphate
disinfectant, germicide and antiseptic. It is used for the

preservation of biological specimens. To recover acetaldehyde, the distillate is treated with dry
It is used in the preparation of hexamethylene tetramine ammonia when crystallised product, acetaldehyde ammonia, is
(urotropine) which is used as an antiseptic and germicide. formed. It is filtered and washed with dry ether. The dried
It is used in silvering of mirror. crystals are then distilled with dilute sulphuric acid when pure
It is employed in manufacture of synthetic dyes such as acetaldehyde is collected.
para-rosaniline, indigo, etc. OH
|
It is used in the manufacture of formamint (by mixing CH 3CHO + NH 3  → CH 3 — CH — NH 2 → CH 3CHO + (NH 4 ) 2 S
Acetaldehyde ammonia Acetaldehyde
formaldehyde with lactose) – a throat lozenges.
urea-+ NH 3  → CH 3 — CH — NH 2  → CH 3CHO + (NH 4 ) 2 SO 4
H 2SO4
CH 3CHO
It is used for making synthetic plastics like bakelite, Acetaldehyde ammonia Acetaldehyde
formaldehyde resin, etc.
Rongalite – a product obtained by reducing formaldehyde Manufacture: Acetaldehyde can be manufactured by one of
sodium bisulphite derivative with zinc dust and ammonia and is the following methods:
used as a reducing agent in vat dyeing. By air oxidation of ethyl alcohol
Acetaldehyde: Acetaldehyde is the second member of the 2CH 3CH 2 OH + O 2 
Ag
300° C
→ 2CH 3CHO + 2H 2 O
aldehyde series. It occurs in certain fruits. It was first prepared By dehydrogenation of alcohol
by Scheele in 1774 by oxidation of ethyl alcohol. CH 3CH 2 OH 
Cu
300° C
→ CH 3CHO

By hydration of acetylene CH 3
|
CH ≡ CH + H 2 O  HgSO4 ,(1%),60° C
→ CH 3CHO CH 3 — C == O H CH 3
H 2SO4 (40%) |
CH CH 3 — C == CH
From ethylene (Wacker process) H
H 2 C = CH 2 + O 2 
→ H 3C − CHO
PdCl2 ,CuCl 2
CH 3 C = O 
ZnCl2
dry.HCl
→ C=O
H2O
|
CH 3 — C == O H CH 3 — C == CH
CH |
Uses H CH 3
In the preparation of acetic acid, acetic anhydride, ethyl Acetone (3 molecule) phoron
acetate, chloral, 1,3-butadiene (used in rubbers), dyes and

Molecular mass of phorone = 3 mole of acetone – 2 mole of H2O
drugs.
As an antiseptic inhalent in nose troubles.
In the preparation of paraldehyde (hypnotic and soporific) and Reformatsky Reaction: This reaction involves the treatment of
metaldehyde (solid fuel). aldehyde and ketone with a bromo acid ester in presence of
In the preparation of acetaldehyde ammonia (a rubber metallic zinc to form β- hydroxy ester, which can be easily
accelerator). dehydrated into α, β- unsaturated ester.
+
Acetone: It is a symmetrical (simple) ketone and is the first BrCH 2 COOC2 H 5 + Zn →
Benzene
Br — Zn — CH 2 COOC 2 H 5
Organo zinc compound
member of the homologous series of ketones. In traces, it is
present in blood and urine. Addition to carbonyl group
Zn + Br
CH 3 |
Preparation: C = O + –CH 2 COOC 2 H 5 
→
∆
(CH 3COO) 2 Ca  → CH 3COCH 3 CH 3
calcium acetate
500° C CH 3
2CH 3CHOHCH 3 + O 2  → CH 3COCH 3 | HOH / H +
Isopropyl alcohol CH 3 — C — CH 2 CH 2 COOC 2 H 5 
 Br 
→
|  Zn 
CH 3CHOHCH 3 
Cu
→ CH 3COCH 3  OH 
300° C OZn + Br
2 propanol
(i) CH 3CH = CH 2 + PdCl 2 + H 2 O 

→ CH 3COCH 3 CH 3 CH 3
propene | |
CH3 — C — CH 2 
→ CH 3 — C = CH — COOC 2 H 5
(ii) CH3 CH = CH 2 + H 2SO4 
→ CH3CH(HSO 4 )CH3 
→ | |
propene OH CO OC2 H 5
β − hydroxyesters
+ H 2SO 4 
→ CH 3 CH(HSO 4 )CH 3 
H2O
→
CH 3 CH(OH)CH 3 
Cu
→ CH 3 COCH 3 Uses
300° C
Isopropyl alcohol As a solvent for cellulose acetate, cellulose nitrate,
2C3 H 5 OH + H 3O 
Zn(CrO2 )
500° C
→ CH 3COCH 3 celluloid, lacquers, resins, etc.
2CH ≡ CH + 3H 2 O 
catalyst
→ CH 3COCH 3 For storing acetylene.
420° C
In the manufacture of cordite – a smoke less powder
From Pyroligneous Acid: Pyroligneous acid containing acetic explosive.

acid, acetone and methyl alcohol is distilled in copper vessel In the preparation of chloroform, iodoform, sulphonal and
and the vapours are passed through hot milk of lime. Acetic chloretone. In the preparation of an artificial scent (ionone),
acid combines to form nonvolatile calcium acetate. The plexiglass (unbreakable glass) and synthetic rubber.
unabsorbed vapours of methanol and acetone are condensed As a nailpolish remover.
and fractionally distilled. Acetone distills at 56°C. The acetone
thus obtained is purified with the help of sodium bisulphite. If Tests
acetone would be in excess in ketal condensation or catalyst Legal's test: When a few drops of freshly prepared sodium
(ZnCl 2 / dry HCl) is used then three moles of acetone nitroprusside and sodium hydroxide solution are added to
undergoes condensation polymerisation and form a compound an aqueous solution of acetone, a wine colour is obtained
called ‘Phorone’. which changes to yellow on standing.

Indigo test: A small amount of orthonitrobenzaldehyde is By dry distillation of a mixture of calcium benzoate and
added to about 2 ml. of acetone and it is diluted with KOH calcium formate
solution and stirred. A blue colour of indigotin is produced. O
||
Iodoform test: Acetone gives iodoform test with iodine and C 6 H 5 COO O CH
Ca + Ca
sodium hydroxide or iodine and ammonium hydroxide. C 6 H 5 COO O CH
||
Calcium benzoate
O
Calcium formate
Aromatic Carbonyl Compounds

→ 2C6 H 5CHO + 2CaCO3
heat
Aromatic aldehydes are of two types : Benzaldehyde
(Major product)
The compounds in which – CHO group is attached directly to an
aromatic ring, e.g., benzaldehyde, C6 H 5CHO. By oxidation of benzyl alcohol: This involves the
Those in which aldehyde (– CHO) group is attached to side treatment of benzyl alcohol with dil. HNO3 or acidic
chain, e.g., phenyl acetaldehyde, C6 H 5CH 2 CHO. They closely potassium dichromate or chromic anhydride in acetic
resemble with aliphatic aldehydes. anhydride or with copper catalyst at 350°C.
Aromatic ketones are compounds in which a carbonyl group CH2OH 
[O]
→ CHO
( > C = O) is attached to either two aryl groups or one aryl
Benzyl alcohol Benzaldehyde
group and one alkyl group. Examples are:
This method is used for commercial production of
COCH 3 COC 6 H 5 OH
CHO benzaldehyde.
CHO By hydrolysis of benzal chloride
OH
CHCl 2 CH CHO
Acetophenone Benzophenone
Benzaldehyde
(Methyl phenyl ketone) (Diphenyl ketone)
Salicylaldehyde OH
CHO  
NaOH
Ca (OH ) 2
→  →
( − H 2O )
 
→ Benzal Chloride
 →Intermdeiate (unstable)
Benzaldehyde, C6H5CHO or Benzaldehyde
This is also an industrial method.

Benzaldehyde is the simplest aromatic aldehyde. It occurs in By oxidation of toluene
bitter almonds in the form of its glucoside, amygdalin
(C20 H 27 O11 N). When amygdalin is boiled with dilute acids, it CH 3 CHO
hydrolyses into benzaldehyde, glucose and HCN
CN + O 2 
V2 O 5
350° C
→ + H 2O
|
C6H5 CHOC12 H21O10 + 2H2O  → C6 H5CHO + 2C6 H12O6 + HCN toluene benzaldehyde
Amygdalin Benzaldehyde
Commercially the oxidation of toluene is done with air and
Benzaldehyde is also known as oil of bitter almonds.
diluted with nitrogen (to prevent complete oxidation) at 500°C
Preparation in the presence of oxides of Mn, Mo or Zr as catalyst.
Laboratory method: It is conveniently prepared by boiling Partial oxidation of toluene with manganese dioxide and dilute
benzyl chloride with copper nitrate or lead nitrate solution sulphuric acid at 35°C, also forms benzaldehyde.
in a current of carbon dioxide. +
CH33→
CC66HH55CH →
CrO 3
(CH 3CO)2 O
CH(OCOCH33))22
CC66HH55CH(OCOCH 
H / H 2O
→→
2C6 H 5CH 2 Cl + Cu(NO3 ) 2 
→ 2C6 H 5CHO + CuCl2 + 2HNO 2
heat
CO 2
Toluene
Toluene Benzylidene
Benzylideneacetate
acetate
or Benzaldehyde
Pb(NO3 ) 2 C6 H5CHO + 2CH3COOH
2C6 H 5CH 2 Cl + Cu(NO3 ) 2 
→ 2C6 H 5CHO + CuCl2 + 2HNO 2 Etard's reaction: C6 H 5CH 3 + 2CrO 2 Cl2 
→
or Benzaldehyde
C6 H 5CH 3 2CrO 2 Cl 2 
H 2O
→ C6 H 5 CHO
[2HNO 2 
→ NO + NO 2 + H 2 O] Brown addition product Benzaldehyde
Rosenmund reaction Gattermann-Koch aldehyde synthesis : Benzene is

C6 H 5COCl + H 2 
Pd / BaSO4
→ C 6 H 5CHO+ HCl converted into benzaldehyde by passing a mixture of carbon
xylene
Benzyl chloride Benzaldehyde monoxide and HCl gas under high pressure into the ether.

CHO
N = N − Cl + HCH = NOH 
→ CH = NOH + HCl + N 2 H 2 O CHO
+ CO + HCl  
AlCl3
→ + HCl Benzaldoxime Benzaldehyde
Benzene benzaldehyde Acetophenone, C6H5COCH3, Acetyl Benzene

Preparation
solution of benzene in presence of anhydrous aluminium Friedel-Craft's reaction: Acetyl chloride reacts with
chloride and cuprous chloride. benzene in presence of anhydrous aluminium chloride to
Gattermann reaction form acetophenone.
+
−
C6 H 5 H + Cl COCH 3 
AlCl3
→ C6 H 5COCH 3 + HCl
HC ≡ N + HCl + AlCl 3 
→ H C = NH + AlCl 4 Benzene Acetyl chloride Acetophenone
+ + By distillation of a mixture of calcium benzoate and

C 6 H 5 H + HC = NH 
→ C 6 H 5 CH = NH 2
Benzene
calcium acetate.
+ O
C6 H 5CH = NH 2 + H 2 O + AlCl 4− 
→ ||
C 6 H 5 COO O CCH 3
C6 H 5CHO + NH 3 + AlCl3 + HCl Ca + Ca
C 6 H 5 COO O CCH 3
CHO C alcium benzoate ||
O
C alcium acetate
Thus, + HCN + HCl + H 2 O 
AlCl3
→ + NH 4 Cl O
||
∆

→ 2C6 H5CCH3 + 2CaCO3
Acetophenone
+ HCN + HCl + H 2O 
→ + NH 4 Cl
By methylation of benzaldehyde with diazomethane.
Stephen's reaction: Benzaldehyde is obtained by partial
reduction of phenyl cyanide with stannous chloride and C6H5CHO + CH2 N2 
→ C6H5COCH3 + N2
passing dry HCl gas in ether solution followed by hydrolysis By treating benzoyl chloride with dimethyl cadmium.
of the aldimine stannic chloride with water. 2C6 H 5 COCl + (CH 3 )2 Cd 
→ 2C6 H 5COCH 3 + CdCl 2
C 6 H 5 C ≡ N 
HCl / SnCl2
→ [C 6 H 5 CH = NH]2 H 2SnCl6 By Grignard reagent
Phenyl cyanide Ether Aldimine complex
CH 3C ≡≡ N + C6 H 5 MgBr 
→ CH 3C == NMgBr 
H2O
→

→ 2C6H5CHO
H2 O |
C6 H5
By ozonolysis of styrene
O C6 H 5COCH 3 + NH 3 + Mg(OH)Br
C6 H 5 CH = CH 2 
O3
→ C 6 H 5 – CH CH 2 
H2O
→ O O
Vinyl benzene || || Br
O–O C6 H5MgBr+H5C2OCCH3 
→ C6 H5CCH3 +Mg
OC 2H 5
C6 H5CHO + HCHO + H2O2
Grignard reaction
Commercial preparation : Ethylbenzene is oxidised with
O
|| air at 126° C under pressure in presence of a catalyst
HCOC2 H 5 + BrMgC6 H 5 
→ manganese acetate.
Ethyl formate
CH 2 CH 3 COCH 3
O
|| Br
C6 H 5C — H + Mg + O 2 
Catalyst
126°C pressure
→ + H2O
Benzaldehyde OC 2 H 5
Other reagents like carbon monoxide or HCN can also be Uses: It is used in perfumery and as a sleep producing drug.
used in place of ethyl formate. Benzophenone, C6H5COC6H5
From Diazonium salt Preparation
From alkyl benzenes
N = N − Cl + HCH = NOH 
→ CH = NOHC+HHCl +N
6 5 − CH 2 − C 6 H 5 + 2O  → C6 H 5COC6 H 5
HNO3
Formaldoxime

Multiple Choice Questions OH
|
One and More than One Correct c. CH 3 — CH 2 — C — COOH
1. Which of the following reactants on reaction with conc. |
CH3
NaOH followed by acidification gives the following
lactone as the only product? [JEE Main 206] d. CH3 — CH == C — CO — NH 2
|
O CH3
C 6. After completion of the reactions (I and II), the organic
O compound(s) in the reaction mixtures is (are)
CH2 [JEE Adv. 2013 P-II]
COOCH3 COOH O
|| 
Br2 (1.0mol)
aqueous / NaOH
→
a. b. Reaction I: H 3C CH 3
COOH CHO (1.0mol)
CHO COOH O
|| →
Br2 (1,0mol)
c. d. CH 2 COOH
Reaction II: H 3C CH 3
CHO COOH
(1.0mol)
2. The smallest ketone and its next homologue are reacted O O O
with NH2OH to form oxime. [JEE Main 2006] || || ||
a. Two different oximes are formed H 3C CH 2 Br H 3C CBr3 Br3C CBr3
P Q R
b. Three different oximes are formed
O O
c. Two oximes are optically active || || CHBr3
d. All oximes are optically active BrH 2C CH 2 Br Br3C ONa U
S T
3. Cyclohexene on ozonolysis followed by reaction with zinc a. Reaction I: P and Reaction II : P
dust and water gives compound E. Compound E on b. Reaction I: U, acetone and Reaction II:Q, acetone
further treatment with aqueous KOH yields compound F. c. Reaction I : T, U, acetone and Reaction II : P
Compound F is [JEE 2007 P-II] d. Reaction I : R, acetone and Reaction II : S, acetone
a. CHO b. CHO
7. The major product in the following reaction is
COOH CO2H O
c. d.
CO2H
Cl 1. CH MgBr, dry ether, 0°C

3
2. aqueous acid
→
CH 3
4. The number of aldol reaction(s) that occurs in the given
transformation is [JEE 2012 P-I] O
OH OH a. H 3 C
CH 3
CH3CHO + 4HCHO 
→ conc.aq.NaOH
OH
HO OH
a. 1 b. 2 c. 3 d. 4
b. H 3 C CH 3
CH 3
5. The major product H of the given reaction sequence is
[JEE 2012 P-II]
CH 3
− c. d.
CH3 — CH2 — CO — CH3 
CN
→ G 
95%H2SO4
Heat
→H O CH 2 O CH 3
a. CH3 — CH == C — COOH 8. Positive Tollen’s test is observed for[JEE Adv. 2016 P-I]
| H
CH2 O
b. CH3 — CH == C — CN H CHO
a. H b.
|
CH3 H

OH O OH OH
Ph OMe Br
c. Ph d. Ph Ph a. b.
O
9. The major product obtained in the following reaction is OMe O

O c. d.
O
DIBAL−H
 → 13. The major product of the following reactions:
[JEE Main 2019]
COOH [JEE Adv. 2016 P-I]
OCH3
OH

ConcHBr(excess)
heat
→
CHO CHO
CH=CH2
a. b.
CHO COOH OH Br
a. b.
OH
CHO CHO CH2CH2Br CH2CH2Br

c. d. Br OH
CHO COOH c. d.
10. The correct sequence of reagents for the following

Br-CHCH3 Br-CHCH3
conversion will be [JEE Adv. 2016 P-I]
O HO CH3 14. The major product of the following reaction is:
[JEE Main 2019]

→
O
t
HO CH3 (i) BuOK
(ii)Conc.H2SO4 / ∆
→
CHO Cl
CH3
a. [Ag(NH 3 ) 2 ]+ OH − , CH 3 MgBr, H + / CH 3 OH
O
b. [Ag(NH 3 ) 2 ]+ OH − , H + / CH 3 OH, CH 3 MgBr
a.
c. CH 3 MgBr, H + / CH 3OH, [Ag(NH 3 ) 2 ]+ OH −
d. CH 3 MgBr, [Ag(NH 3 ) 2 ]+ OH − , H + / CH 3 OH
11. The compound R is [JEE Adv. 2018 P-I] O
HO2C b.
CO2H
a. b. O
c.
CO2H CO2H
c. d.
O
d.
12. The major product of the following reaction is: 15. Which of the following compounds will show the
[JEE Main 2019] maximum enol content? [JEE Main 2019]
O a. CH3COCH2COCH3
Br
→
NaBH 4 b. CH3COCH3
McOH,25ºC
c. CH3COCH2CONH2
d. CH3COCH2COOC2H5

16. The major product obtained in the following reaction is 19. The major product of the following reaction is:
CH3 O CH2O
→
(i)AlCl3 (anhyd)
CH2Cl (ii)H 2 O
OHC 
NaOH
∆
→
CH3 CH3O CH3O
H 3C
a. b.
H
CH3
a. b. CH3O
O
CH3O CH3
O CH3 c. d.
CH3
H 3C
H 20. The major product of the following reaction is
c. d. [JEE Main 2019]
O CH3
CH2 O OH

(i)aq.NaOH
→
17. The major of the following reaction is: (ii)CH3 I
[JEE Main 2019] CH3

O OH CH3
OH
CH3 a. b. HO
O
+ CH3
AlCl3 , ∆
→ CH3
OH OH CH3
H 3C CH3
CH3 HO
c. d. OCH3
a. O b.
O
CH3
OH 21. The major product obtained in the following reaction is:
OH HC3 [JEE Main 2019]
CH3
CO2Et
c. d. NaOEt / ∆
 →
O O
O
O
O
18. The major product formed in the following: O
[JEE Main 2019] a. CO2Et b.
O CH2 CO2Et
O
O O

dil.NaOH
→ CO2Et
H 3C H+
c. d.
OH O O CO2E
OH
[JEE Main 2019]
a. H3C b. H 3C
Cl
O O O OH (i)HBr
(ii)alcKOH
→
c. H3C d. H H 3C O

Cl O O
OH H 3C
a. b. H 3C H H
a. A = ;B =
OH O H 3C H 3C
Cl HO CH3 CH3
O O
OH CH3
c. d. C
H3 H H
b. A = ;B =
O O
H 3C H 3C
23. The major product of the following reaction is: CH3 CH3
O O
[JEE Main 2019] CH3 CH3
COCH3
(i) KMnO4 / KOH, ∆
( ii)H 2 SO4 (dil)
→ c. A = CH3 ; B = CH3
CH3 HO
O O
COCOOH CH3 CH3
a. d. A = CH3 ; B = CH3
HOOC
COOH HO
b. 26. In the following reaction

HOOC Aldehyde + Alcohol 
HCl
→ Acetal [JEE Main 2019]
COOH Aldehyde Alcohol
t
c. HCHO BuOH
OHC CH3CHO MeOH
COOH3 The best combinations is:
d. a. HCHO and MeOH b. HCHO and tBuOH
HOOC c. CH3CHO and MeOH d. CH3CHO and tBuOH
O
[JEE Main 2019]
CH3O 
NaBH
EtOH
→

(1)Cl2 / CCl4
(2)AlCl3 (anhyd.)
→
[JEE Main 2019]
OH
Cl Cl OH O OH
a. b. c. d.
a. CH3O b. CH3O
OEt
28. The aldehydes which will not form Grignard product with
CH3O one equivalent Grignard reagents are: [JEE Main 2019]
c. CH3O d. CHO
CHO
(A) (B)
Cl Cl
HO2C
25. In the following reactions, products A and B are: CHO CHO
[JEE Main 2019]
(C) (D)
O O HO3C HOH2C
a. (B),(C),(D) b. (B),(D)
H3C H3C CH3 →[A] [A]  →[B]
H3O
H 
dil NaOH
c. (B),(C) d. (C),(D)
∆

C ≡ C − CH 2 − CH = O Column I Column II
1. Racemic
N 2 Cl +
29. mixture
OH →
NaOH / H 2 O
0° C
OMe (A)
→
(1)HgSO4 / dilH2SO4
(2)AgNO3 / NH4 OH
'Q' 
(1)SOCl2 / Py
(2)AlCl3
→ R 
ZnHg / HCl
→S N == N OH
(3)ZnHg / HCl
[JEE Adv. 2019 P-II] OH OH 2. Addition

OH | |
reaction
(B) H 3C — C| — C| — CH 3
a. Q = ,R=
CH 3 CH 3
MeO MeO

H 2SO 4
→ O
|| CH 3
C
b. R = ,S= H 3C C — CH 3
MeO MeO CH 3
O
O 3. Substitution
c. R = ,S= C → 1.LiAlH4
2.H3O+
reaction
CH3
MeO MeO (C)
OH
O HC
CH3
CH
OH 4. Coupling
SH Cl 
Base
→
d. Q = ,S= reaction
(D) S
MeO MeO
5. Carbocation
Matrix Match/Column Match intermediate
30. Match the compounds/ions in Column I with their a A→ 1, 4, 5; B→ 1;C→1, 3;D→3
properties/reactions in Column II [JEE 2007 P-II] b. A→ 2, 4, 5;B→2;C→1, 3; D→5
Column I Column II c. A→3, 4, 5; B→5;C→ 1, 2; D→3
(A) C6 H5CHO 1. gives precipitate with 2, d. A→3, 4, 1;B→2;C→ 1, 5; D→1,3
4-dinitrophenylhydrazine 32. The correct match between Column - I and Column - II is:
[JEE Main 2019]
(B) CH3C ≡ CH 2. gives precipitate with
Column - I Column – II
AgNO3
(A) Benzaldehyde 1. Mobile phase
− 3. is a nucleophile
(C) CN
(B) Alumina 2. Adsorbent
(D) I − 4. is involved in
(C) Acetonitrile 3. Adsorbate
cyanohydrin formation
a. A→2; B→3; C→1 b. A→2; B→1; C→3
a. A→1, 2, 3; B→ 1, 2; C → 1, 3; D→2, 3 c. A→3; B→1; C→2 d. A→3; B→2; C→1
b. A→ 1, 3; B → 1; C → 1, 2, 4; D →2, 3 Paragraph
c. A→1, 2, 3; B→ 3; C→1, 2, 4; D→2, 3 Paragraph for Question Nos. 33 to 35
In the following sequence, products I, J and L are formed. K
d. A→1, 2, 3; B→2; C →1, 3, 4; D→2, 3
represents a reagent. [JEE 2008 P-I]
31. Match the reactions in Column I with appropriate options 1. Mg / ether
Hex − 3 − ynal 
1. NaBH 4
2. PBr3
→ I 
2. CO2
3. H O+
→ J 
K
→ Me
in Column II. [JEE 2010 P-II] 3

  → L
H2
Pd / BaSO 4
37. The structure of the products Q and R, respectively, are
quinoline
O
Cl H
a. Me ,
COMe
O Me Me Me Me
33. The structure of the product I is O
a.
Me Br H
b. ,
Me CHO
b. Me Et Me Et
Br
c. O
Me Br
d. Me Br H
c. ,
COH
34. The structure of compounds J and K respectively are Me Me Me Me
a. Me COOH Me O
and SOCl2
OH d. CH3
,
b. Me Me Me
CHO
Et
O and SO Cl 2 2
38. The structure of the product S is
c. Me
COOH O
and SOCl2
d. Me COOH a. b.
and CH3SO2Cl
O
35. The structure of product L is Me Me Me
a. Me CHO O
b. c. d. O
Me CHO
Me
CHO
c.
Me Me Me
d.
Me CHO
A carbonyl compound P, which gives positive iodoform test, In the following reaction sequence, the compound J is an
undergoes reaction with MeMgBr followed by dehydration to intermediate. I 
(CH 3 CO)2 O
CH 3 COONa
→ J 
(i) H 2 Pd / C
(ii) SOCl2
→ K J(C9 H8O2 )
give an olefin Q. Ozonolysis of Q leads to a dicarbonyl (iii) anhyd. AlCl3
compound R, which undergoes intramolecular aldol reaction to gives effervescence on treatment with NaHCO3 and a positive
give predominantly S. [JEE 2009 P-I]
Bayer’s test. [JEE 2012 P-II]
1. OH −
P  → Q  → R  → S
1. MeMgBr
2. H + , H 2 O
1. O3
2. Zn , H 2 O 2. ∆
3. H 2SO 4 , ∆ 39. The compound K is
36. The structure of the carbonyl compound P is
Me
a. b.
a. b.
Me Me O O
O O
O
c. d. c. d. O
O Et O
Me

40. The compound I is 3. (a)
O H OH CHO
 
O3 , H 2O
Zn
→ CHO
a. b.
(E)
 KOH  →
(aldol condensation ) CHO
(F)
H Hence (a) is correct.
O CH3 H
H O OH O
|| | ||
c. d. 4. (c) CH 3 — C — H  (i )→ CH 2 — C — H
HCHO
(ii) HCHO
CH 2 OH
Integer and Subjective |
H — OCH 2 — CH — CHO  → HOCH 2 — C — CHOHCHO
(iii )
41. In the scheme given below, the total number of intra | |
CH 2 OH CH 2 OH
molecular aldol condensation products formed from ‘Y’ is
(iv) OH − Cannizzaro
[JEE 2010 P-I] Re action
42. Consider all possible isomeric ketones, including

(HOCH 2 ) 4 C
stereoisomers of MW = 100. All these isomers are
1, 2, 3 are aldol products while 4 is Cannizzaro product.
independently reacted with NaBH4 (Note: stereoisomers
5. (a)
are also reacted separately). The total number of ketones
O O−
that give a racemic product(s) is/are [JEE Adv. 2014 P-I] || −
|
CH 2 — CH 2 — C — CH3 
C N
→ CH3 — CH2 — C — CH3 (G)
43. Among the following, the number of reaction(s) that |
CN
produce(s) benzaldehyde is [JEE Adv. 2015 P-II]
95%H 2SO4
I      
→
CO, HCl
Anhydrous AlCl 3 / CuCl
CH3 COOH
| ∆
|
CH3 — CH == C — COOH  → CH3 — CH 2 — C — CH3
(A) |
CHCl2 
H2O
→ OH
II 100° C
6. (c) Solve as per law of limiting reagent.

COCl   → H2 O OH OH
III Pd − BaSO 4 || | − H+ |
C
+
+ H ↽ +C
⇀ ↽ ⇀ C
H 3C CH3 H 3C CH3 H 2C CH3
CO2 Me → DIBAL-H
O
Toluene, −78° C H 2 O
IV ||
Br + BrCH 2 — C — CH3←2
− Br
7. (d)
ANSWERS and SOLUTIONS O
1. CH MgBr, dry ether, 0°C
1. (c) Cl 
3
→ OMgX
CH3 Cl
NOH CH3
|| CH3
2. (b) H 3C — C — CH 3
CH 3
OH HO aqueous acid
 →
N N O
|| || CH 3
C C
8. (a, b, c) Aldehydes and α-Hydroxyketone show positive
H 3C C2 H 5 H 3C C2 H 5
Tollen’s test.

H O COOH COOH
→ Silver mirror ↓
Tollen 's
Re agent
H oxidation O
H → +
H
CHO COOH
→
Tollen 's
Re agent
Silver mirror ↓ (P)
COOH
OH ozonolysis
O
Ph 
→ + Oxidised product
Ph →
Tollen 's
Re agent
Silver mirror ↓ ketone
O
9. (c) DIBAL - H is electrophilic reducing agent reduces (P)

cynide, esters, lactone, amide, carboxylic acid into O
corresponding Aldehyde (partial reduction). COOH COOH C–Cl
O O
H / Pd − C SOCl
2  →  →
2
[Ag ( NH3 )2 ]OH H + / CH3OH

10. (b) 
Tollens reagent
→ 
→
(esterification)
CHO CO2H (P)

O CH3 O Me
C–Me H–C–OH

CH3MgBr
→
MeMgBr, CdCl NaBH

2
→ 
4
→
C H3C C CH3
O OCH3
OH
(Q)
11. (a) (C11H12 O2 ) →
oxidation dibasic acid
P, Organic acid (P must have Me Me
multiple bond)
CH2 —CH2 CH–OH CH–Cl Me − CHΘ Mg+2 Cl−
| |
OH OH
→ 
→
HCl Mg,Et

2
→
O CO

2
→
O
O
C C –(CH2)2–O–
O
O (Q)
dacron Me − CH − COOMgCl Me − CH − COOH
dibasic acid must be terephthalic acid i.e.
COOH
H⊕ O

3
→
R
COOH 12. (d) Θ
to give dacron, compound must have benzene based structure O O Na ⊕
C11H12O2  → ketone + oxidised products of benzene.
Ozonolysis Br
COOH →
NaBH 4
McOH,25ºC
Br
Possible structure of P is (C11 H12 O 2 ) O


13. (d) H H
|
O—CH3 ⊕
O — CH 3 O O

conc.HBr
→ Br– CH—C C—CH3
excess SN2
CH
CH=CH2 Enol
CH=CH2
Due to intramolecular H-bonding and resonance
OH stabilisation enol content is maximum.
OH
CH3 O
←
HBr
 +CH3Br 16. (d)
OHC 
NaOH
∆
→
⊕
CH – CH 3 CH=CH3
Intramolecular
aldolcondensation
Br–
CH3
OH
O
Br 17. (d) OH
O t − BuOK
CH3
14. (d)  E2
→ O O
Cl ⊕ Θ
O: AlCl3 O — Al Cl3
O
OH OH
CH3 CH3
H+/∆
OH
+
O— H O
18 (a) Aldehyde reacts at a faster rate than keton during
aldol and stericall less hindered anion will be a better
nucleophile so self aldol at CH3 — C — H will be the
||
OH O
+ major product.
H 19. (b) CH3O


(i)AlCl3 (H2O)
→
CH2Cl
OH CH3O
O +
Tautomer
↽ ⇀ CH2
CH3O
O O + CH2
|| ||
15. (a) CH — C — CH — C — CH ⇀ 1,2 Shift of H

→
−
3 2 3↽
Keto

in raF.C.A
→

20. (d) H OMe
21. (d) 
MeOH
H+
→ C
Cl Cl H OMe
acetal
22. (a)
Br  →
alc
 ( →
i ) H Br
KOH 1
rate ∝
steric crowding of aldehyde
O O t-butanol can show formation of carbocation in acidic
↽
Tauto
⇀ medium.
OH
27. (d) NaBH4 can not reduce C=C
O
but can reduce —C— into OH
O ||
23. (b) || O
C — CH 3 COOH
O OH
(i) KMnO4 / KOH, ∆

( ii)H 2 SO4 (dil)
→ 
NaBH
EtOH
→
CH3 COOH
28. (b) Acid-base reaction of G.R. are fast
CH3O CHO
24. (b) →
Cl2
O
→
RMgX
C
Cl HO
MeO 
EAS
→ CHO
O +R–H
MeO C
XMgO
+H+
Cl
O CHO
O ||
25. (d) OH −
C — H  → 
RMgX
→
H2C
XMgO
O
O CHO
O ||
C — H + H2O +R–H
O H2C
H XMgO
O O
29. (a, b)
− H2 O
O

H2 O
→ HO ∆
→ C ≡ C − CH 2 − CH = O C ≡ C − CH 2 − CH = O
H (B)
(A) 
HgSO 4 / dilH 2 SO 4
→
26. (a) Me
:O OMe OMe
O OH
H O OH
H — C — H + H+ C +
C − CH 2 − CH 2 − C = O
H H
OH
OH Me 
AgNO3 / NH 4 OH
→
O CH2 — OMe + H+
C +H
rds OMe
H H

OH For Question Nos. 33 to 35
33. (d) CH3 − CH2 − C ≡ C − CH2 − CHO 
1. NaBH4
2. PBr3
→ CH3 − CH2 − C ≡ C − C
Zn − Hg
 → O
HCl
CH3 − CH 2 − C ≡ C − CH 2 − CHO 
→ CH3 − CH 2 − C ≡ C − CH 2 − CH 2 Br
MeO
Cl 34. (a) CH 3 − CH 2 − C ≡ C − CH 2 − CH 2 Br
1.Mg / Ether

SOCl2 / Py
→ 
2. CO2
→ J 
K
→ CH3 − CH2 − C ≡ C −CH 2 − COCl
O 3. H O+
3
MeO J = CH 3 − CH 2 − C ≡ C − CH 2 − COOH K = SOCl2

Zn − Hg
Hence, (a) is the correct answer.
 →

AlCl3
→ HCl 35. (c)
MeO MeO For Question Nos. 36 to 38
(R) O (S) Me Me

(i) CH3MgBr
→ Me
30. (d) A→1, 2, 3;B→ 2;C→ 1, 3, 4;D→2, 3 (ii) H +
O Me HO Me
(Note: Assuming AgNO3 is ammonical)
NO2 +
Me
H /∆
(A)  → Me
PhCHO + O 2 N NH − NH 2 
→ ⊕ Me
O2N
O
PhHC = N − NH NO2
(ppt.) C
H −
OO
PhCHO + Ag 2 O 
NH 3
→ PhCOO − + Ag ↓Ø
O ←
Θ
OH

(white ppt) C − CH 2 C − Me
CN Me Me Me Me
| (R)
PhCHO 
KCN
→ Ph — C — O −
| Me
H ←
O3 / Zn / H 2 O
 Me
Me
(B) CH 3C ≡ CH 
ammonical AgNO3
→ CH 3 − C ≡ C− Ag + ↓ (Q)
(White ppt)
OH
CN CH CH
| CH 2 ∆ CH
(C) → Ph — C — O − ;
PhCHO  KCN 
→
| C C
H O O
− Me Me Me Me
AgNO3 + CN 
→ AgCN ↓ (S)
(D) AgNO3 + I −  → AgI ↓ 36. (b)
31. (c) A→3, 4, 5; B→ 5; C→1, 2; D→3 37. (a)
(A) It is an example of electrophilic substitution reaction 38. (b)
which results in coupled product hence it is coupling For Question Nos. 39 to 40
reaction also. O
||
(B) Pinacole-pinacolone rearrangement. In this reaction C−H
intermediate is carbocation.  (  
CH 3 CO ) 2 O
C H 3 C OO Na
→
H 2 | Pd | C
(C) It is an example of addition reaction by carbonyl C=O (J)
|
compounds and both enantiomers will be formed. Hence, I OH
racemic mixture will be obtained.
←
AlCl3

O OL1+
|| || C=O
C C K O |
| CH + AlH Cl
CH 3 
LiAlH 4
→ H 3 3
(addition )
←
SOCl2

(D) It is an example of nucleophilic substitution. C=O
|
32. (d) A→3; B→2; C→1 OH

39. (c) CH 3 O
| ||
40. (a) (4) H 3C — C — C — CH 3
|
41. (a) CH 3
Will give a racemic mixture on reduction with NaBH 4

1.O3
2.Zn,H 2 O
→ Y 
1.NaOH(aq)
2.heat
→
O
O ||
(5) CH3 — CH 2 — C — CH 2 — CH 2 — CH3

1.O3
→ Will give a racemic mixture on reduction with NaBH 4
2.Zn,H 2 O
⊙ O
O ||
O (6) CH 3 — CH 2 — C — CH — CH 3
|

1.NaOH(aq)
→ CH 3
2.heat
Will give a racemic mixture on reduction with NaBH 4
O
|| 43. (4)
*
42. (5) (1) CH 3 — CH 2 — C H — C — CH 3 CHO
| I CO, HCl
Anhydrous AlCl3 / CuCl
→
CH 3
Will not give a racemic mixture on reduction with NaBH4
CHCl2  →
H O 2 CHO
O II
100° C
||
(2) CH 3 — CH 2 — CH 2 — CH 2 — C — CH 3
Will give a racemic mixture on reduction with NaBH4 COCl  H2
→ CHO
Pd − BaSO 4
O III
||
(3) CH 3 — CH — CH 2 — C — CH 3
| CO2Me CHO
CH 3 IV →BIBAL − H
Toluene,−78° C H 2 O
Will give a racemic mixture on reduction with NaBH4
Carboxylic Acids and their Derivatives 213
21 Carboxylic Acids and their Derivatives

QUICK LOOK Nomenclature: The aliphatic carboxylic acids are commonly
known by their initial names, which have been derived from the
Carboxylic acids are the compounds containing the carboxyl source of the particular acid.
 C — C — OH  Examples
functional group  ||  HCOOH Formic acid [Latin: Formica = ant]
 O
 
CH 3COOH Acetic acid [Latin: acetum = Vinegar]
The carboxyl group is made up of carbonyl (> C == O) and
CH 3 — CH 2 — COOH Propionic acid [Greek:
hydroxyl (—OH) group.
Proton = First; Pion = Fat]
O O
|| || CH 3 (CH 2 )2 COOH Butyric acid
—C — + —C — H ≡≡ —C — O — H
Carbonyl Hydroxyl Carboxyl [Latin: Butyrum = Butter]
Carboxylic acids may be aliphatic or aromatic CH 3 (CH 2 )3 COOH Valeric acid
O O CH3 (CH 2 )14 COOH Palmitic acid
R—C Ar — C
O—H O—H CH3 (CH 2 )16 COOH Stearic acid
Aliphatic carboxylic acid Aromatic carboxylic acid
(Where R = H or any alkyl group) (Where Ar is any aryl group)
Alternative system of nomenclature is naming the acids as the
derivatives of acetic acids. The only exception being formic
Comparison of Resonating Structures of Carboxylic Group
acid.
and Carbonyl Group: Carbonyl group has two resonance
Example
structures (I and II):
CH 3 — CH 2 — COOH Methyl acetic acid
+
C == O: ←→ ɺɺ :−
C == O (CH 3 )3 C — COOH Trimethyl acetic acid
ɺɺ ɺɺ
(I) (II)
However, for a carboxyl group, three resonance structures (A, According to the IUPAC system of nomenclature, the suffix of
B and C) can be written. the monocarboxylic acid is ‘oic acid’, which is added to the
name of the alkane corresponding to the longest carbon chain
O: +
ɺɺ:−
O ɺɺ:−
O containing the carboxyl group, e.g. HCOOH methanoic acid
—C ɺɺ ←→—C ɺɺ ←→ —C ɺɺ+
CH 3 — CH 2 — CH 2 — COOH butanoic acid.
ɺɺ — H
O ɺɺ — H
O C—H
ɺɺ ɺɺ ɺɺ The positions of side-chains (or substituents) are indicated by
(A) (B) (C)
numbers, the numbering to be started from the side of the
In both structures (A) and (C), the C – atom and the two O – carboxyl group.
atoms have eight electrons in their respective valence shells 5 5 4 4 3 32 2 1
while in structure (B), C – atom has only six electrons. CHCH

3 —3 CH
— CH— — CH
— CHCH
CH 2 —2 COOH
— COOH
| | | |
Therefore, structure (B) is less stable than structure (C), in CH 3 CHCH
3 3
other words the two important resonance structures of carboxyl 3,4-dimethylpentanoic acid
group are structures (A) and (C). In both these structures, Naming of Acyl Groups, Acid Chlorides and Anhydrides:
carboxyl carbon is electrically neutral. However in case of The group obtained from a carboxylic acid by the removal of
aldehydes and ketones, only one structure i.e. I is electrically the hydroxyl portion is known as an acyl group. The name of an
neutral. As a result, the carboxyl carbon of the resonance acyl group is created by changing the - ic acid at the end of the
hybrid is less positive and hence less electrophilic than the name of the carboxylic acid to –yl, examples:
carbonyl carbon of aldehydes and ketones. However, it may be O O
noted that like carbonyl group, carboxyl group is also polar due || ||
H — C — O — H  → H—C—
to resonance structures (B) and (C). Formic acid Formyl group

O O If the substituent on the nitrogen atom of an amide is a phenyl
|| ||
C — OH C— group, the ending for the name of the carboxylic acid is
changed to anilide.
Benzoic acid Benzoyl acid
O
Acid chlorides are named systematically as acyl chlorides.
H 3C NH
O
NH
H 3C
O
Cl N-phenylacetamide N-phenylbenzamide
Acetyl chloride
An acid anhydride is named by substituting anhydride for acid Some dicarboxylic acids form cylic amides in which two acyl
in the name of the acid from which it is derived. groups are bonded to the nitrogen atom. The suffix imide is
O O given to such compounds.
OH
O
O H
O N NH
O
O
O OH Dihydrofuran-2, 2-dione O
succinic acid Pyrrolidine-2, 5-dione 1N-isoindole-1, 3(2H)-dione
O
COOH
O Classification
COOH Carboxylic acids are classified as monocarboxylic acids,
O dicarboxylic acids, tricarboxylic acids etc. depending on the
phthalic acid 2-benzofuran-1, 3-dione
number of —COOH groups present in the molecule.
Naming of Salts and Esters: The name of the cation (in the CH 2 COOH
case of a salt) or the name of the organic group attached to the CH 2 COOH |
CH 3COOH | CHCOOH
oxygen of the carboxyl group (in the case of an ester) precedes CH 2 COOH |
the name of the acid. CH 2 COOH
Monocarboxylic acid Dicarboxylic acid Tricarboxylic
Tricarboxy lic acid
acid
O O
H 3C Monocarboxylic acids of aliphatic series are commonly
−
O Na + O known as fatty acids such as palmitic acid (C15 H 31COOH)
1-phenylethanone sodium Ethyl 4-methylbenzoate CH 3 and stearic acid (C17 H 35COOH).
benzoate
The general formula for monocarboxylic acids is
Naming of Amides and Imides: The names of amides are C n H 2n +1COOH or C n H 2n O 2 . Where n = number of carbon
formed by replacing –oic acid (or –ic acid for common names)
atoms.
by amide or –carboxylic acid by carboxamide.
The carboxylic acids may be aliphatic or aromatic
O O
depending upon whether —COOH group is attached to
H 3C aliphatic alkyl chain or aryl group respectively.
NH 2 NH 2
acetamide cyclohexanecarboxamide
Some of the Important uses of Carboxylic Acids are
If the nitrogen atom of the amide has any alkyl groups as Higher fatty acids are used in the manufacture of soaps.
substitutents, the name of the amide is prefixed by the capital Soaps are sodium potassium salts of higher fatty acids such
letter N; to indicate substitution on nitrogen, followed by the as stearic acid.
name(s) of alkyl group(s). Organic acids are used in foods, cold drinks, etc. For
O example, acetic acid is used as vinegar. Sodium salts of
H 3C some organic acids are used as preservatives.
N — CH 3 Organic acids are used for the preparation of many drugs
such as aspirin, phenacetin etc.
CH 3 Acetic acid is used as coagulant in the manufacture of rubber.
N-ethyl-N-methyl-4-nitrobenzamide

Acetic acid is also used in the manufacture of various dye The Grignard reagent adds to the carbon – oxygen double
stuffs, perfumes and rayon. bond of CO2 just as in the reaction with aldehydes and
ketones. The product is the magnesium salt of the
General Methods of Preparation carboxylic acid, from which the free acid is liberated by
1. Oxidation of Alcohols, Aldehydes and Ketones treatment with mineral acid.
[O] [O]
RCH 2 OH 
K 2 Cr2 O7
→ RCHO 
K 2 Cr2 O7
→ RCOOH O
alcohol Carboxylic acid ||
[O]
R — MgX + C
RCHO → RCOOH ||
Aldehyde monocarboxylic acid
Grignard's reagent O
Aldehyde can be oxidised to carboxylic acid with mild H +
→ R — COO − Mg + X 
 → R — COOH + Mg 2+ + X −
oxidising agents such as ammoniacal silver nitrate solution
[Ag 2 O or Ag(NH 3 ) 2+ OH − ] The Grignard’s reagent can be prepared from primary,
secondary, tertiary or aromatic halides. The method is
Methanoic acid cannot be prepared by oxidation method.
limited only by the presence of other reactive group in the
Ketones can be oxidised under drastic conditions using
molecule. The following synthesis illustrate the application
strong oxidising agent like K 2 Cr2 O 7 .
of this method.
Methyl ketones can also be converted to carboxylic acid CH 3 CH 3
through the haloform reaction. | |
HCl
∆
H 3C — C — OH  → H 3C — C — Cl
R — C — CH 3 + 3I2 + 3 NaOH 
H 2O
→ | |
|| CH 3 CH 3
O
CH 3 CH3
R — C — OH + CHI3 + 3 NaI + 3H 2 O | |
|| → H 3C — C| — COOH
+
Mg H
→ H 3C — C — MgCl 
O |
CH 3 CH 3
Trimethylacetic acid
2. Oxidation of Alkyl Benzenes: Although benzene and
alkane are quite unreactive towards the usual oxidising
4. Hydrolysis of Nitriles: Aliphatic nitriles are prepared by
agents (KMnO4, K2Cr2O7 etc). The benzene ring renders an
treatment of alkyl halides with sodium cyanide in a solvent
aliphatic side chain quite susceptible to oxidation. The side
that will dissolve both reactants. In dimethyl sulphoxide
chain is oxidised down to the ring and only a carboxyl
(DMSO), reaction occurs rapidly and exothermically at
group (COOH) remains to indicate the position of the room temperature. The resulting nitrile is then hydrolysed to
original side chain. Potassium permanganate is generally the acid by boiling with aqueous alkali or acid.
used for this purpose, although potassium dichromate or
dilute nitric acid can also be used. (Oxidation of a side chain DMSO
R — Cl + NaCN  → R — C ≡≡ N + H 2 O —
is more difficult, however, than oxidation of an alkene and +
H
requires prolonged treatment with hot KMnO4). → R — COOH + NH +4
−
OH
CH 2 CH 2 CH 2 CH 3
hot KMnO 4
COOH  → R — COO − + NH 3
  → + CO 2
n-butyl Benzoic acid 5. Use of alkoxide

+
H
RO − Na + + CO 
∆
dark
→ RCOONa  → RCOOH
This reaction is used for two purposes (a) synthesis of
carboxylic acids and (b) identification of alkyl benzenes. CH3O− Na + CO 
→ CH3COOH
210° C, pressure
CH3OH + CO 
Co(CO)8
→ CH3COOH
3. Carbonation of Grignard Reagents: The Grignard
synthesis of a carboxylic acid is carried out by bubbling
6. Carbonylation of Alkenes
gaseous CO 2 into the ether solution of the Grignard reagent
H3 PO4
CH 2 = CH 2 + CO + H 2 O 
300 − 400° C
→ CH 3CH 2 COOH
or by pouring the Grignard reagent on crushed dry ice (solid
H3PO4
CO 2 ). In the latter method dry ice serves not only as CH3CH == CH2 + CO + H2O 
300−400°C
→ CH3 —CH —COOH
|
reagent but also as cooling agent. CH3

7. Oxidative Cleavage of Alkenes, Alkynes and Cyclo Alkenes O O
|| ||
RC ≡≡ CR ′ → RCOOH + R 'COOH
(i)O3 or KMnO4
(ii) H 2 O R — C — Cl + R ′R ′′NH 
→ R — C — NR ′R ′′
CH 3C ≡≡ CCH 3 
(i)O3
→ 2CH 3COOH O O
(ii) H 2 O || ||
H 3C — C — Cl + H 2 NC 6 H 5 
→ C6 H 5 NHC — CH 3 + HCl
RCH == CHR 
(i)Alkaline KMnO 4
(ii) H + / ∆
→ 2RCOOH
O
CH 2 COOH ||
KMnO4 / ∆ / H+
→ | OH O — C — CH 3
CH 2 COOH + CH3COCl 
→
COOH COOH
Acetyl salicylic acid (aspirin)
Carboxylic Acid Derivatives: There are four carboxylic acid
O
|| Reaction of Acetyl Chloride with Olefins: Acetyl chlorides
derivatives. These are generally represented as R — C — Z,
add on to the double bond of an olefin in the presence of a
where Z is halogen (usually Cl), OCOR' , OR' or NH 2 (or catalyst ( AlCl3 or ZnCl 2 ) to form a chloro ketone which on
NHR' or NR'2 ) . heating, eliminates a molecule of hydrogen chloride to form an
unsaturated ketone.
When Z is halogen (usually Cl), the derivatives are called as H 3C — CH == CH 2 + CH 3COCl 
ZnCl 2
→ H 3C — CH — CH 2 — C — CH 3
O
acid chlorides. || O
R — C — Cl ||
H C — CH == CH + CH COCl
When Z is OR′, the derivatives are called as esters.
3 2 3  → H 3 C — CH — CH 2 — C — CH 3
|
O Cl2
||
When Z is —O — C — R', , the derivatives are called O
||
∆
carboxylic anhydrides.  → H 3C — CH == CH — C — CH 3 + HCl
Where Z is  NH2, the derivatives are called amides. When Conversion into acids: Hydrolysis.
Z is NHR′ or NR2′ they are called N – substituted O O
|| ||
amides. R — C — Cl + H 2 O  → R — C — OH + HCl
An acid
Synthesis of Acid Derivatives: Carboxylic acid derivatives are

exclusively prepared from carboxylic acids. The preparation Carboxylic acid anhydrides: Carboxylic acid anhydrides
methods of carboxylic acid derivatives are already discussed can be used to prepare esters and amides.
under the chemical reactions of carboxylic acids. O O O
|| || ||
R — C — O — C — R  R'OH
→ R — C — OR'
Chemical Reactions of Acid Derivatives
O
Acyl chloride: We have already seen that acyl chlorides are the ||
most reactive of all acid derivatives. As a result, acyl chlorides + R — C — OH 
NH3
Excess
→
are often selected as the starting material for the preparation any O O
|| ||
other acid derivative. Let us see how this is done. R — C — NH 2 + R — C — O − NH +4
O O O O Anhydrides can be hydrolysed to get back acids.
|| || − +
|| ||
R — C — Cl + R — C — O Na  → R — C — O — C — R' O O O
|| || ||
O O R — C — O — C — R  H 2O
→ 2R — C — OH
|| ||
R — C — Cl + R — OH 
→ R — C — O — R'
O O Esters
|| || Ester Hydrolysis: Acid catalysed esterification is an
R — C — Cl + NH 3 
→ R — C — NH 2
essentially reversible reaction. If you follow the backward
O O
|| || course of reactions of esterification it gives you the mechanism
R — C — Cl + R' NH 2 
→ R — C — NHR' for ester hydrolysis.

O O Reduction of Esters
|| ||
R — C — OR' + → R — C — OH + R' OH
H2O Catalytic hydrogenation
H
O
||
H 2 , CuO, Hg / H +
Base Promoted Hydrolysis of Esters CH 3CH 2 CH 2 C — O — CH 3 
1500 C high pressure
→ CH 3CH 2CH 2 CH 2 OH + C
Saponification: Esters undergo
CH 3CHbase promoted hydrolysis also.
2 CH 2 C — O — CH 3  → CH 3CH 2CH 2 CH 2 OH + CH 3OH
This reaction is known as saponification, because it is the way
most of the soaps are manufactured. Refluxing an ester with Chemical reduction
aqueous NaOH produces an alcohol and the sodium salt of the O
||
LiAlH4 / H +
acid. CH 3CH 2CH 2C — O — CH 3 
( or ) Na / C2 H5OH → CH 3CH 2 CH 2 CH 2 OH + CH
O O
|| CH 3CH 2 CH 2 C||— O — CH 3 
H2O
→ CH 3CH 2 CH 2 CH 2 OH + CH 3OH
R — C — OR' + NaOH ↽ ⇀ R — C — O − Na + + R' OH
Reaction of Esters with Grignard Reagents: The reaction of

This reaction is essentially irreversible because carboxylate ion
carboxylic esters with Grignard’s reagent is a good method for
is inert towards nucleophilic substitution.
the preparation of 3° alcohols.
O O
Mechanism || ||
R — C — OR'  → R — C — R''  →
R'' MgX R'' MgX
O O−
|| || OMgX OH
R — C — OR' ↽ ⇀ R — C — OR' ↽ ⇀ | H+
|
| R — C — R''  → R — C — R''
OH − OH | |
O R'' R''
O
|| ||
→ R — C — O − + ROH
R — C — OH + R 'O − 
Initially ketones are formed. However, as we know, ketones
themselves readily react with Grignard reagent to yield tertiary
If an ester is hydrolysed in a known amount of base (taken in alcohols.
excess), the amount of base used up can be measured and used to
calculate the saponification equivalent; the equivalent weight of Claisen Condensation: When ethyl acetate reacts with sodium
the ester, which is similar to the neutralisation equivalent of an ethoxide, it undergoes a condensation reaction. After
acid.
acidification, the product is a β - keto ester, ethyl aceto acetate
(commonly known as – aceto acetic ester).
Transesterification: Esters can also be prepared by
transesterification (an alcohol displacing another from an ester) O  O O 
||  || || 
O O 2CH 3COC 2 H 5 
NaOC2 H5
→  H3C — C — CHC — OC2 H5 
|| ||
C
HA
+ R'' — OH ↽ heat ⇀ C + R' — OH  Na + 
O O
R OR' R OR'' || ||
+ C2 H 5OH  HCl
− NaOC2 H5
→ CH 3CCH 2 COC 2 H5
The mechanism of this reaction is quite similar to esterification.

O Condensation of this type is known as Claisen Condensation.
|| For esters, it is the exact counterpart of the Aldol Condensation.
H 2 C == CHCOCH 3 + CH 3CH 2 CH 2 CH 2 OH Like the Aldol Condensation, the Claisen Condensation
O involves nucleophilic attack by a carbanion on an electron-
|| deficient carbonyl compound.
↽ ⇀ H 2 C == CHCOCH 2CH 2 CH 2 CH3
In the Aldol Condensation, nucleophilic attack leads to addition

Transesterification is an equilibrium reaction. To shift the
(the typical reaction of aldehydes and ketones). In the Claisen
equilibrium to right, it is necessary to use a large excess of the
Condensation, nucleophilic attack leads to substitution (the
alcohol whose ester we wish to make or else to remove one of
typical reaction of acyl compounds).
the products from the reaction mixture.

Mechanism Amides
O Preparation: In the laboratory amides are prepared by the
||
Step (i): R — CH — C — OC2 H 5 + OC2 H 5 ↽ ⇀ reaction of ammonia with acid chlorides or, acid anhydrides.
|
H
Basic Character of Amides: Amides are very feebly basic and
O O− form unstable salts with strong inorganic acids. e.g.
|| ||
RCH — C — OC2 H 5 ←
→ RCH == C — OC 2 H 5 RCONH 2 HCl. The structure of these salts may be I or II.
+ +
O—H O
R —C Cl − or R —C Cl −
Step (ii): NH 2 NH 3
O (I) (II)
O ||
−
R — CH 2 C + HC — C — COC 2 H 5 ↽ ⇀
OC2 H 5 | Acidic Character of Amides: Amides are also feebly acidic
OC 2 H 5 e.g. they dissolve mercuric oxide to form covalent mercury
O− R O compound in which the mercury is probably linked to the
| | ||
RCH 2 — C — CH — C — OC2 H 5 nitrogen.
| 2RCONH 2 + HgO 
→ (RCONH) 2 Hg + H 2O
OC 2 H 5
O O Hydrolysis of amides: Amides undergo hydrolysis when
|| || they are heated with aqueous acid or aqueous base.
↽ ⇀ RCH 2 — C — CH — C — OC 2 H 5 + C 2 H 5O −
| Acidic hydrolysis:
R O O
|| ||
O H O +
R — C — NH 2 + H 3O  ∆
→ R — C — OH + NH +4
|| | || H 2O
Step (iii): RCH 2 C — C — COC2 H 5 + C2 H 5O − ↽ ⇀
| Basic hydrolysis:
R O O
|| ||
− ∆
O O R — C — NH 2 + OH 
H 2O
→ R — C — O − + NH 3
|| ||
RCH 2 C — C — C — OC2 H 5 + C2 H 5OH Reduction of amides: Amides are reduced by
|
R Na / C 2 H 5OH or by LiAlH 4 to a primary amine.
This step is highly favourable and draws the overall equilibrium O

||
toward the product formation R — C — NH2 + 4H 
Na / C2H5OH5
→R — CH2 — NH2 + H2O
O O Reaction with P2O5: When heated with P2O5 amides are
|| || H 3O +
Step (iv): RCH 2 C — C — C — OC 2 H 5  rapid
→ dehydrated to cyanides.
|
R O
||
R — C — NH 2  P2 O5
→ R — C ≡≡ N
O O O O − H2O
|| || || ||
RCH 2 CCHCOC2 H 5 ↽ ⇀ RCH 2 C == CCOC 2 H 5 Amides may also be converted to cyanides by PCl5.
| | O
R R ||
−2HCl
R — C — NH 2  PCl5
→ RCCl2 NH 2  → R — C ≡≡ N
When planning a Claisen condensation with an ester it is Hofmann rearrangement: Amides with no substituents on
important to use alkoxide ion that has the same alkyl group as the nitrogen react with solutions of Br2 or Cl 2 in NaOH to
the alkoxyl group of the ester. This is to avoid the possibility of yield amines through a reaction known as Hofmann
transesterification. An intramolecular Claisen condensation is rearrangement.
called Dieckmann condensation. In general, the Dieckmann O
||
condensation is useful only for the preparation of five and six R — C — NH 2 + Br2 + 4NaOH  → RNH 2 + 2NaBr + Na 2 CO3 + 2H 2
membered rings.
R — C — NH 2 + Br2 + 4NaOH  → RNH 2 + 2NaBr + Na 2 CO3 + 2H 2 O

Mechanism COOH CH 2 COOH
O O COOH O
|| H OH −
|| c. d.
R —C—N ɺɺ ↽ ⇀ R — C — N—ɺɺ H 
→
−
H
Br — Br
O H − 4. Identify the binary mixture(s) that can be separated into
|| | OH
R — C — N — Br + Br ↽ ⇀ individual compounds, by differential extraction, as
O
|| −
shown in the given scheme. [JEE 2012 P-I]
ɺɺ == C == O ←
R—N R — C — N— Br NaOH (aq)
− Br
Compound 1 + Compound 2
− Binary mixture
OH containing Compound 1
and Compound 2
NaHCO3 (aq)
Compound 1 + Compound 2
OH −
R — N == C ←
→ R — N — C == O a. C6 H 5OH and C6 H 5COOH
O − ɺɺ |
OH b. C6 H 5COOH and C6 H 5CH 2 OH
c. C6 H 5CH 2OH and C6 H 5OH
H
| O− d. C6 H 5CH 2 OH and C6 H 5CH 2 COOH
↽ ⇀ R —N—C 5. With reference to the scheme given, which of the given
ɺɺ O
statement(s) about T, U, V and W is(are) correct?
[JEE 2012 P-II]
→
H —OH
RNH 2 + CO 2 + OH −
O
HCO3−
O
H3C
One and More than One Correct T
1. Among the following compounds, the most acidic is LiAlH 4
[JEE 2011 P-I] ⊕
excess
V ←
CrO3 / H
 U 
(CH3 CO)2 O
→W
a. p-nitrophenol b. p-hydroxybenzoic acid
c. o-hydroxybenzoic aicd d. p-toluic acid a. T is soluble in hot aqueous NaOH
b. U is optically active
2. Among the compounds given, the one that would form a
c. Molecular formula of W is C10H18O4
brilliant colored dye on treatment with NaNO 2 in dil. d. V gives effervescence on treatment with aqueous
HCl followed by addition to an alkaline solution of β - NaHCO3
naphthol is [JEE 2011 P-II] 6. An organic compound A upon reacting with NH 3 gives
N(CH 3 ) 2 NHCH 3 B. On heating, B gives C. C in presence of KOH reacts
a. b. with Br2 to give CH3CH2NH2 . A is [JEE Main 2013]
a. CH3COOH b. CH 3CH 2 CH 2 COOH
NH 2 CH 2 NH 2 c. CH 3 — CH — COOH d. CH 3CH 2 COOH
c. d. |
H 3C CH 3
7. The major product of the following reaction sequence is

3. The compound that undergoes decarboxylation most
readily under mild condition is. [JEE 2012 P-II]
O
COOH COOH
CH 2 COOH O
a. b. →
(i) HCHO (excess) NaOH, heat
(ii) HCHO / H + (catalytic amount )

C
O O O O OH ||
C
a. b. COOH CH2 OH
a. b. |
COOH CH2 OH
O OH C
||
O O O
HO
CH2
c. d. COOH CH2 OH
OH |
c. d. CH2 OH
8. Reagent(s) which can be used to bring about the following COOH CH2
transformation is(are) [JEE Adv. 2016 P-II] 12. The decreasing order of ease of alkaline hydrolysis for the
following esters is: [JEE Main 2019]
O O
O O C (I) COOC2H5
C O
OH (II) Cl COOC2H5
O
O H
COOH
COOH (III) O2N COOC2H5
a. LiAlH 4 in (C2 H5 )2 O b. BH 3 in THF
(IV) CH3O COOC2H5
c. NaBH 4 in C2 H 5 OH d. Raney Ni / H 2 in THF
a. IV > II > III > I b. III > II > I > IV
9. Phenol on treatment with CO2 in the presence of NaOH
c. III > II > IV > I d. II > III > I > IV
followed by acidification produces compound X as the major
13. The major product 'X' formed in the following reaction is:
product. X on treatment with (CH3CO)2O in the presence of
[JEE Main 2019]
catalytic amount of H2SO4 produces [JEE Main 2018]
O
CO2H O ||
CH 2 — C — OCH 3
NaBH 4
MeOH
→X
CO2H O
a. CO2H b. O CH3
O CH3 O
OH O ||
O CO2H CH 2CH 2 OH CH 2 — C — H
O a. b.
O CH3
O O CH3 O
OH OH ||
O
c. d. O CH 2CH 2 OH CH 2 — C — OCH 3
OH
c. d.
CO2H
14. The major product obtained in the following conversion
10. Which of the following amines can be prepared by
is:- [JEE Main 2019]
Gabriel phthalimide reaction? [JEE Main 2019]
O
a. Neo-pentylamine b. n-butylamine
c. triethylamine d. t-butylamine O Br2(1 eqv.) 
MeOH
→
11. Which dicarboxylic acid in presence of a dehydrating
agent is least reactive to give an anhydride:
[JEE Main 2019] O

CH3 O Matrix Match/Column Match
Br CH3 O 18. Different possible thermal decomposition pathways for
a.
O b. peroxyesters are shown below. Match each pathway from
O OMe
Column-I with an appropriate structure from Column -II.
Br [JEE Adv. 2014 P-II]
O P
→ R i + R ′O i
O − CO ↑ 1
O CH3 O
CH3 Q
− CO ↑
→ R i + R ′O i 
→ R i + X i + carbonyl co
O 1
c. O Br d.
O 
→R +RO O i
 → R i + X i + carbonyl compound ↑
i
R O R′
OMe Br (Peroxyester)
R
− CO ↑
→ RCO 2i + R ′Oi 
− CO ↑
→ R i + X i + car
1 1
O O
 → RCO + R O  → R + X + carbonyl compound ↑
i i i i
15. Molecules of benzoic acid (C6H5COOH) dimerise in
benzene. 'w' g of the acid dissolved in 30 g of benzene S
→ RCO 2i + R ′O i 
 → R i + R ′O i
shows a depression in freezing point equal to 2K. If the  → RCO + R ′O 
i i
− CO1 ↑
→ R + R ′O
i i
percentage association of the acid to form dimer in the Column I Column II

solution is 80, then w is: (A) Pathway P O
–1
(Given that Kf = 5 K kg mol , Molar mass of benzoic acid O
O CH 3
= 122 g mol–1) [JEE Main 2019] 1. C6 H 5CH 2
a. 1.8 g b. 2.4 g (B) Pathway Q O
O
c. 1.0 g d. 1.5 g
CH O CH 3
2. 6 5
16. An aromatic compound 'A' having molecular formula (C) Pathway R O
C7H6O2 on treating with aqueous ammonia and heating O CH 3
forms compound 'B'. The compound 'B' on reaction with C6 H 5CH 2 O
CH 2 C6 H 5 CH 3
molecular bromine and potassium hydroxide provides 3.
compound 'C' having molecular formula C6H7N. The (D) Pathway S O
structure of 'A' is : [JEE Main 2019] O CH 3
CHO 4. C 6 H 5 O
C 6 H 5 CH 3
a. b.
O CH=CH—CHO OH a. A → 1; B → 3; C → 4; D → 2
b. A → 2; B → 3; C → 4; D → 2
COOH OHC
c. A → 1; B → 2; C → 4; D → 3
c. d.
d. A → 3; B → 2; C → 4; D → 1
OH
17. Find the correct acidic strength order: Match the Column for Question Nos. 19 to 20
[JEE Adv. 2019 P -I] Match the reactant in Column-I with the possible
(i) HC ≡≡ C–COOH intermediates and products of Column-II.
(ii) H2C=CH–COOH [JEE Adv. 2019 P -II]
Column I Column II
(iii) MeO COOH CN O
(A) O 1.
(iv) CH3–CH2–COOH O COOH
(i) DIBAL-H
a. (i) > (ii) > (iv) > (iii) b. (i) > (ii) > (iii) > (iv) → (ii) diLHCl
(iii) NaBH 4
c. (iii) > (ii)>(i) > (iv) d. (iii) > (ii) > (iv) > (ii) (iv) ConcH2 SO4

OH 22. Which one is not correct for tartaric acid?
(B) 2. (I) It is a unsaturated acid
COOH OH (II) It has two —OH group and two —COOH group
(i) O3
→(ii) Zn/h 2 O (III) It exist in four forms
(iii) NaBH 4
(iv) ConcH 2 SO 4 (IV) It gives pyruvic acid on heating
Cl (V) On heating it forms anhydride
(C) 3. O a. II, IV b. I, III, V
CO2CH3
c. I, II, V d. II, V
(i) KCN
(ii) Zn/H 2 O
→
(iii) LiAlH 2 Statement/Assertion and Reason
(iv) ConcH 2 SO 4
CO2Me OH 23. Statement-I: p-Hydroxybenzoic acid has a lower boiling

(D) point than o-hydroxybenzoic acid. Because
CO2Me3 4. Statement-II: o-Hydroxybenzoic acid has intramolecular
COOH
hydrogen bonding. [JEE 2007 P-I]
(i) LiAlH 4
→ a. Statement-I: is True, Statement-II is True; Statement-II:
(ii) Conc H2 SO4
COOH b. Statement-I is True, Statement-II: is True; Statement-II
5.
COOH
6. O Integer and Subjective
0
O 24. Amongst the following, the total number of compound
soluble in aqueous NaOH is [JEE 2010 P-I]
19. Which of the following is correct? CH 3
H 3C COOH OCH 2 CH 3 OH
a. A→2, 3; D→2,3 b. A→2, 4; D→ 2, 3 N CH 2 OH
c. A→3, 6; D→ 2, 3 d. A→2, 3; D→ 4,5
20. Which of the following is correct?
a. B→1, 4, 6; C→2, 3, 5 b. B→1, 3, 6; C→ 2, 4, 5
NO 2 OH
CH 2 CH 3 COOH
c. B→1, 2, 6; C→ 2, 3, 6 d. B→1, 4, 5; C→ 3, 4
CH 2 CH 3
Paragraph
N
Paragraph for Question Nos. 21 to 22 H 3C CH 3
Organic compounds having —COOH group are called
25. To an evacuated vessel with movable piston under
carboxylic acid. An organic compound having —OH group
external pressure of 1 atm, 0.1 mol of He and 1.0 mol. of
and —COOH group both, are called hydroxyl acid. Molecules
an unknown compound (vapour pressure 0.68 atm. At 0º
with two carboxylic groups are dibasic and those having 3
C) are introduced. Considering the ideal gas behaviour,
carboxy group are tribasic acid.
the total volume (in litre) of the gases at 0ºC is close to
A dibasic acid having two —COOH group on adjacent carbon
[JEE 2011 P-I]
atoms looses H 2O to form inner anhydride.
26. The total number of carboxylic acid groups in the product
Hydroxy acids behave both as acids and alcohols and the
P is [JEE Adv. 2013 P -I]
hydroxyl and carboxyl groups do not interfere with each other
O
when they are far apart. The heating of hydroxyl acids however O
gives different products depending upon the nature of α-, β-, γ-
+
1. H3 O , ∆
hydroxyl substituted acids. O 
2. O3
→P
3. H 2 O2
21. α - hydroxyl acid on heating forms:
a. lactides b. lactones O O
c. unsaturated acids d. None of these

ANSWERS and SOLUTIONS (d) C3 H 5 CH 2 OH + C6 H5 CH 2 COOH 
→1(insoluble)aq.NaOH
1 2
OH
COOH +2(soluble)
1. (c) aq.NaCO3
C3 H 5 CH 2 OH + C6 H 5 CH 2 COOH  → +1(insoluble)
1 2
because its carboxylate ion is stabilised due to +2(soluble)
intramolecular hydrogen bonding and due to ortho effect.
O–H 5. (a, c)
O O
C CH 2 − OH
O
H2C
O OH

LiAlH 4
→
C H CH 2
NaNO 2 + HCl
2. (c) H 3 C NH 2   
O ° C − 5° C
→ H3C H 3C CH 2
T U
CHO
H 3C N == N — C H2C
Cr2 O3 / H +
HO
H 3 C − CH
CHO
H CH 2
− V
H 3C N == N — Cl +  
OH
( coupling )
→
(CHCO)O3
excess
( β − Nepthol)
HO O
||
H3C N == N CH 2 — O — C — CH 3
CH 2
O
C H ||
O — C — CH 3
Brilliant Colour Dye H 3C (CH 2 ) 2
O W
O O
C — OH || ||
6. (d) CH3 — CH2 — C — OH 
NH3
∆
→ CH3 − CH2 — C — NH2
O is a β -keto acid which undergo
3. (b) 
Br2 / KOH
→ CH 3 — CH 2 — NH 2
decarboxylation on slight heating. O

O
−
7. (a)   
HCHO / OH
→
O — OH Cross aldol
O
O

→
Slight heating
− CO2 O
O −
4. (b, d)   →
HCHO / OH
Cross Cannizzaro
(b) C6 H 5 COOH + C6 H5 CH 2 OH  →1(soluble)

aq.NaOH
1 2
OH OH
+2(insoluble) O O
+ HCOOH
C6 H 5 COOH + C 6 H 5 CH 2 OH 
→1(soluble)
aq.NaCO3
−
1 2 →
HCHO / H
Nucleophilic addition
+2(insoluble)

8. (c, d) NaBH 4 / C 2 H 5 OH & Raney Ni / H 2 in T.H.F do not 15. (b) 2(C6 H 5 COOH) 
C6 H 6
→ (C6 H5 COOH) 2
(30g)
Wg diner
reduce acid (–COOH), ester
∆ f T =i k f m
(–COOR) & epoxide .
O w × 100
2 = 0.6 × 5 ×
122 × 30
OH OH
COOH (i = l – 0.8 + 0.4 = 0.6)
9. (2) 
→
CO2 , NaOH
Acidification
w = 2.44 g
O 16. (c)
OH O − C − CH 3 17. (b) pKa

COOH COOH
(i) HC ≡≡ C–COOH 1.89
→
(CH3CO)2 O
H 2SO 4
(ii) H2C=CH–COOH 4.3
10. (b) Gabriel phthalimide synthesis (iii) MeO COOH

O O 4.5
(iv) CH3–CH2–COOH 4.87
1.KOH
NH 
2R − X
→ N—R
(1ºhalide S
N2
) 18. (a) A → 1, B → 3, C → 4, D → 2
O O
O
H 2O O
(A) H 5 C6 CH 2 O CH3
COOH i i
C6 H 5 − C H 2 + CO 2 + CH 2 O
R – NH 2 +
COOH
O CH3
11. (d) Adipic acid CO2 H—(CH2 )4 —CO2 H → dehydrating O CH3
agent
H 5 C6 CH 2 O i
7 membered cyclic anhydride (Very unstable) (B) O
CH 2 C6 H 5
i |
12. (b) More is the electrophilic character of carbonyl group C6 H 5 — C H 2 + CO 2 + Ph — CH 2 — C — CH 3
|
of ester faster is the alkaline hydrolysis. CH3
i
13. (c) 
→ Ph — C H 2 + CH3 — CO — CH3
14. (b) O O
O CH3
O OMe O CH3
O (C) C H

Br2
MeOH
→ 6 5
O
C6 H 5 O
i
i |
O O –H+ C6 H 5 — CO 2 + CH3 + C — CH 3
|
Br2 CH3
i i
O O 
→ Ph + CH3 — CO — Ph + CH3
H
|
O O Me (D) O
O ⊕ O
Br+ 
MeOH
→ C6 H 5 O CH3
Br
i
O O
C6 H5 − CO 2 + CH3 Oi 
→ C6 H5i + CO2
For Question Nos. 19 to 20 CHOH ⋅ COOH ∆

22. (b) |  →
(A) CN CHO CHOH ⋅ COOH
O 
(i) DlBAL − H
→ O
CH 3 ⋅ CO ⋅ COOH + CO 2 + H 2 O
O O Pyruvic acid
D-, L-, DL- and meso forms are isolated.

NaBh 4
 dil.H
 Cl
→ COOH →
COOH O—H O
C — OH
OH 23. (d)
 Conc.H
 2 SO
4
→
OH O More stabilised by intramolecular hydrogen bonding
H O
(B) O3 H | ||
→
Zn / H2 SO4
CHO O O—C
COOH COOH
CH2OH
 NaBH
 → 4
 Conc.H
 2 SO
4
→ C—O O
COOH O || | H
O H
O
More stronger intermolecular forces increase the boiling
(C) point. Hence (d) is correct.
Cl KCN
CN
 →
CO2CH3 CO2CH3
COOH OH OH COOH
OH
⊕ LiAlH
H3 O
 → COOH   → 4
24.
OH
COOH
N
Conc.H 2 SO 4
   
→ H 3C CH 3
O
OH
(D) CO2Me These four are soluble in aqueous NaOH.
LiAlH 4
  → OH
CO2Me 25. Let unknown is X.
p He = p total − Px = (1 − 0.68) atm = 0.32 atm
Conc.H 2 SO 4
   
→
O RT
Now p He = n He
V
19. (a)
RT 0.10 × 0.082 × 273
∴ v= = =7
20. (a) p He 0.32
For Question Nos. 21 to 22 O O
RCHOH HOOC 26. +

H3 O
21. (a) | + | ∆
 → O  →
COOH HOCHR
RCH — O — CO
| | O O
CO — O — CHR
lactide

O
O
COOH −2CO2 O3 / H 2 O 2
O
∆
→  →
COOH HOOC
O
O HOOC
(P) O
So, the total no. of carboxylic acid in the product P is 2.
Nitrogen-containing Compounds 227
22 Nitrogen-containing Compounds
QUICK LOOK Amides
+
H 2O + H
 → RCOOH + NH+4
Nitro alkanes are derivatives of alkanes. They are isomeric to
nitrites (esters) classified as primary, secondary and tertiary 
NaOH

→ RCOONa + NH3
depending on the nature of carbon atom to which nitro group is P2 O5 / ∆
 → RC ≡≡ N

linked.
→ HNO2
RCOOH + N 2
O
R ||
RCH 2 NO 2 CHNO 2 R — C — NH2 
H2 / Pt or LiAlH4
→ RCH 2 NH2
R
Primary nitro alkane Secondary nitro alkane
→
Br2 / 4KOH
RNH 2 + K 2CO3 + 2KBr + H 2O
R
R C — NO 2 
Na
→ (RCONH)Na + 12 H2
R
Tertiary nitro alkane

Hgo
→ (RCONH)2 Hg + H2O
− NO2 group is an ambident group.

HCl
→ RCONH +4 CI–
 O
If it attacks through  —N  nitrogen it is called nitro and
 O 
 Cyanides (RCN) and Isocyanides (RNC): These are the
if it attacks through oxygen atom, it is called nitrite. Hence compounds containing —C ≡≡ N functional group.
nitrites and nitro compounds are isomers. They have general formula R — C ≡≡ N.
O
R—N is isomeric with R — O — N == O Preparation of Cyanides: The following methods can be
O
(Nitro) ( Nitrite) employed to prepare the cynides.
RX + KCN(alc) 
→ RCN + KX
(Main product)
Structures
Evidences show that nitrogen is attached to one of the oxygen Aryl cyanides cannot be prepared by this method because
atoms by a double bond and to the other by a dative bond. The aryl halides are less reactive towards nucleophilic
resonance hybrid is shown as under which confirms the substitution.
spectroscopic evidence that both nitrogen–oxygen bonds have RCONH2 + P2 O5 
Heat
→ RCN + H 2 O
same bond length. C6 H 5 N 2+ Cl− + CuCN 
KCN
→ C6 H 5CN + CuCl
δ− (CH3CO)2 O / ∆
+ O + O− + O RCH == NOH  → RC ≡≡ N + H 2O
R—N ←→ R — N ≡≡ R — N δ −
(Aldoxime)
O− O O Dry/ether
Resonating forms Hybride structure RMgX + ClCN  → R — C ≡≡ N + Mg(Cl) X
Out of three sp 2 hybrid orbitals of nitrogen one overlaps with Preparation of Isocyanides
alkyl group and two with oxygens while the unhybridised RX + AgCN  →
C2 H5 OH
RNC + AgX
(Major product )
p-orbital of N-atom containing a pair of electrons and lying ∆

RNH 2 + CHCl3 + 3KOH  → RNC + 3KCl + 3H 2 O
perpendicular to the plane of hybrid orbitals overlaps sideway (Carbylamine reaction)
with half filled 2p-orbitals of two oxygen atoms. This forms
π -bond above and below the plane of molecule. Reactions of Isocyanides: Some of the important reactions of
isocyanides are given below:
→
2HOH/ H +
RNH2 + HCOOH Reduction of alkanamides:
RCONH 2 + (H 2 / Pt or LiAlH 4 ) 
→ RCH 2 NH 2

→ RNH —CH3
Na / CC2H5OH(Reduction)
Reduction of aldoximes:
RCH = NOH + 4[H]  → RCH 2 NH 2 + H 2 O
Na / alc. or H / Pt
2
+ Cl2 or LiAlH
→ R— N == CCl2 4
(Alkyl iminocarbonyl chloride) Hydrolysis of isocyanate:

R − N = C = O + 2KOH 
→ RNH 2 + K 2 CO3
1S
R − N = C → R— N == C == S
8 8
(Alkyl isothiocyanate)
Hoffmann’s bromamide reaction:
+ 2HgO
→ R— N == C == O + Hg2O RCONH2 + Br2 + 4KOH 
→ RNH2 + 2KBr + K2CO3 + 2H2O
(Alkyl isocyanate)
Amide
+O3
→ R— N == C== O + O2 Hydrolysis of isocyanides:
(Alkyl isocyanate)
RNC + HOH  
HCl
→ RNH 2 + HCOOH
∆ ,Isomerisation

→ R ≡≡ N (More stable)
Ammonolysis of halides: RX + NH3 
→ RNH 2 + HX
(Excess)
Nitro Compounds (RNO2)
Ammonolysis of alcohols:
Preparation of Aliphatic nitro Compounds
ROH + NH 3 
575K, Al 2 O3
→ RNH 2 + H 2 O
2RX + 2AgNO 2 → RNO 2 + R − O − N = O
Alcohol
Heat
Nntroalkane
Nitroalkane Alkyl nitrite Reduction of nitro compounds:
(Major) (Minor)
(Major)
C6 H 5 NO 2 + 6[H] 
Sn/HCl
→ C 6 H 5 NH 2
2 RX + 2K + (O − N = O) 
→ R − O − N = O + RNO2
(X may be Alkyl nitrite Nitroalkane
Nntroalkane Gabriel’s Phthalimide synthesis
Br or I) (Minor) (Major)
(Major)
O O
CH3 − CH3 + HNO3 
700K
→ CH3CH 2 NO2 + H 2O || ||
Vapour Fuming Nitroethane
C C
R −X
Preparation of Aromatic Nitro Compounds: They are NH 
KOH(alc.)
− H2O
→ NK 
− KX
→
obtained by nitration of arenes with nitrating mixture C C
(H 2SO 4 + HNO3 ) . || ||
O O
NO2 O
|| O
C ||
+ conc. HNO3 → conc. H 2SO 4
+ H 2O C — OH
+
N − R 
H 2O / H
→ + RNH 2
(1° Amine)
This chemical reaction is typical example of electrophilic ring C C — OH
|| ||
substitution. Here, conc. H 2SO 4 reacts with HNO3 to produce O O
nitronium ion (NO +2 ) which acts as an electrophile while arene
Action of Heat: α -amino acids lose two molecules of water
behaves as the nucleophile.
and form cyclic amides.
Amines: These are derivatives of ammonia. They can be O
α-amino acid
classified into primary, secondary or tertiary amines if they ||
N H HO — C
| ∆
have functional groups — NH 2 , —NH
—NH ,——NN respectively. RCH CH — R  → R —OCH
| | | | ||
C — OH HN NH — C
Alkyl amines: RNH 2 , ||
OCH — R → R — CH CHR + 2H 2 O
Aryl amines: ArNH 2 (e.g. C 6 H 5 NH 2 ),
C — NH
Arylalkyl amines: ArCH 2 NH 2 (e.g., C6 H 5CH 2 NH 2 ) ||
O
Preparation of Amines β -amino acids lose a molecule of ammonia per molecule of
Reduction of alkyl cyanides: amino acid to yield α , β -unsaturated acids.
RCN + (H 2 /Ni or LiAlH 4 ) 
→ RCH 2 NH 2 (1°Amine) ∆
CH 2 — CH — COOH 
− NH3
→ CH 2 == CH — COOH
Reduction of isocyanides: | | Acrylic acid
(α , β -unsaturated acid)
NH 3 H
RNC + H 2 / Pt 
→ RNHCH 3 (2° Amine)

Multiple Choice Questions NH 2
1. CH 3 NH 2 + CHCl 3 + KOH  
→ Nitrogen containing

acetic anhydride
CH 2 Cl2
→ Product(s)
compound + KCl + H 2 O. Nitrogen containing compound NH 2
is [JEE 2006] O
a. CH 3 − C ≡ N b. CH 3 − NH − CH 3 H
− + + −
|
c. CH 3 − N ≡ C d. CH 3 N ≡ C N CH 3
O O
+ CH 3COOH
2. In the reaction H 2C C 
→T O
(1) NaOH / Br2
a.
NH 2 (2) C NH 2
Cl
O
the structure of the Product T is [JEE 2010 P-II]
NH 2
O
a. H 2C C O
O—C H + CH 3COOH
b. |
N CH 3
O O
b. NH H
C CH 3 |
N CH 3
O
O
H + H 2O
c. H 3C NH c. |
C N CH 3
O
O O
O ⊕
d. H 3C O N H 3CH 3COO −
NH — C
H
d. |
N CH 3
3. A compound with molecular mass 180 is acylated with O O

CH 3COCl to get a compound with molecular mass 390.
6. For the identification of β- naphthol using dye test, it is
The number of amino groups present per molecule of the
necessary to use [JEE Adv. 2014 P -II]
former compound is [JEE Main 2013]
a. dichloromethane solution of β- naphthol
a. 2 b. 5
c. 4 d. 6 b. acidic solution of β- naphthol
4. The gas leaked from a storage tank of the Union Carbide c. neutral solution of β- naphthol
plant in Bhopal gas tragedy was [JEE Main 2013] d. alkaline solution of β- naphthol
a. Methylisocyanate
NH3
b. Methylamine
c. Ammonia
 → D 
→ E + N2
NaNO / HCl
2 CuCN / KCN
7. In the reaction 0 −5ºC ∆
d. Phosgene
5. In the reaction shown below, the major product(s) formed CH3

is/are [JEE Adv. 2014 P -I] The product E is [JEE Main 2015]

COOH CH3 11. The product(s) of the following reaction sequence is (are)
NH 2
a. b.
(i) Acetic anhydride/pyridine
→
(ii) KBrO3 /HBr
(iii) H O+ , heat
[JEE Adv. 2016 P-I]
3
CH3 (iv) NaNO 2 / HCl, 273 − 278 K
(v) Cu/HBr
CN Br
c. d.H3C CH3
a.
Br
CH3
Br
8. The major product of the reaction is [JEE Adv. 2015 P-I]
H 3C CO 2 H
b.
→
NaNO2 , aqueous HCl
0° C
CH3 NH 2
Br
a. H3C NH 2 b. H3C CO2H Br
Br Br
CH3 OH CH3 OH
c.
c. H3C CO2 H d. H3C NH 2
Br
CH3 OH CH3 OH Br Br
9. In the following reactions, the major product W is d.
OH Br
NH 2

→ V 
NaNO 2 , HCl
→W
NaOH 12. The nitrogen containing compound produced in the reaction
0° C
of HNO3 with P4 O10 [JEE Adv. 2016 P-II]
a. can also be prepared by reaction of P4 and HNO 3
b. is diamagnetic
OH c. contains one N-N bond
a. b. d. reacts with Na metal producing a brown gas
N=N OH N=N 13. Which of the following compounds will form significant
amount of meta product during mono-nitration reaction?
[JEE Main 2017]
OH NHCOCH OH
3
OH
c. N=N a. b.
d. N=N
OCOCH3 NH2
10. In the Hofmann bromamide degradation reaction, the c. d.

number of moles of NaOH and Br2 used per mole of amine
14. The major product of the following reactions is
produced are: [JEE Main 2016]
a. One mole of NaOH and one mole of Br2 OH
b. Four moles of NaOH and two moles of Br2
(i) NaNO 2 , HCl,0° C
c. Two moles of NaOH and two moles of Br2 
(ii) aq.NaOH
→
d. Four moles of NaOH and one mole of Br2 NH2


O– Na+ 18. The compound that does not produce nitrogen gas by the
thermal decomposition is [JEE Main 2018]
a. a. (NH 4 ) 2 SO4 b. Ba(N 3 ) 2
N2Cl c. (NH 4 )2 Cr2 O7 d. NH 4 NO 2

OH 19. The compound(s) which generate(s) N 2 gas upon thermal
decomposition below 300ºC is (are) [JEE Adv. 2018 P-I]
b.
a. NH 4 NO3 b. (NH 4 ) 2 Cr2 O7
N=N c. Ba(N 3 ) 2 d. Mg 3 N 2
OH
20. Aniline reacts with mixed acid (conc. HNO3 and conc.
H2SO4) at 288 K to give P (51 %), Q (47%) and R (2%).
c.
The major product(s) of the following reaction sequence is
Cl (are) [JEE Adv. 2018 P-II]
N=N OH 1)Ac2O,pyridine
2)Br2 ,CH3CO2H
R  →
d. 3)H3O+
4)NaNO2 ,HCl/ 273−278K
15. Which of the following compounds will be suitable for 5)EtOH, ∆
Kjeldahl’s method for nitrogen estimation?
1)Sn / HCl
[JEE Main 2018]
2)Br2 / H 2O(excess)
N 2+ Cl− S  → major product(s)
a. b. 3) NaNO2 ,HCl/ 273− 278K
N 4)H3PO2
NH 2 NO 2 Br Br
c. d.
Br Br
a. b.
16. The predominate form of histamine present in human
Br Br
blood is (pKa, Histidine = 6.0) [JEE Main 2018]
Br Br
H H
N ⊕ N NH2 Br Br
N H3
a.
b.
N N c. d.
H H
⊕ N Br Br Br Br
N
N H3 Br
c. ⊕ d. ⊕
N N NH2 21. The major product in the following reaction is :
H H
[JEE Main 2019]
17. The increasing order of basicity of the following NH2
compound [JEE Main 2018]
N N
NH2 NH2
(a) (b) +CH3I 
Basc
→
N N
NH2 H
NH NHCH3 NH2
(c) (d)
NH2
a. (d) < (b) < (a) < (c) + N N
N N CH 3
b. (a) < (b) < (c) < (d) a. b.
c. (b) < (a) < (c) < (d) N N
N N |
d. (b) < (a) < (d) < (c) H CH3

NH2 Cl O
N N NHCH3 c.
n O
N N HN
c. N +
d.
| N NH2
| N N
H CH3 Cl
H
n
22. The major product obtained in the following reaction is: d.
[JEE Main 2019] O N
NH2
NH2 H
O

(i)CHCl3 / KOH
(ii)Pd / C/ H2
→ 24. The major product of following reaction is:
(1) AlH (i − Bu 2 )
CN O R — C ≡ N    →
( 2) H2O
[JEE Main 2019]
H a. RCHO b. RCOOH
N CH3
c. RCH2NH2 d. RCONH2
a.
25. The increasing order of pKa of the following amino acids
H 2N OH in aqueous solution is: [JEE Main 2019]
H Gly Asp Lys Arg
N CH3
a. Asp < Gly < Arg < Lys
b.
b. Arg < Lys < Gly < Asp
CN O c. Gly < Asp < Arg < Lys
H d. Asp < Gly < Lys < Arg
N CH3
26. Arrange the following amines in the decreasing order of
c.
basicity [JEE Main 2019]
CN OH
H
N CHCl2 N N N
d.
H H
CN OH (I) (II) (III)

23. Major product of the following reaction is: a. I > II > III b. III > II > I
[JEE Main 2019] c. I > III > II d. III > I > II
Cl 27. The correct sequence of amino acids present in the
Cl (1)Et 3 N
NH2  → tripeptide given below is : [JEE Main 2019]
(2)Free radical
+ H 2N polymerisation
O O Me Me
O OH
Cl H Me
a. n O N OH
NH2 H2N N
O N H C
H O OH
O Cl O
a. Leu - Ser - Thr b. Thr - Ser- Leu
b. n c. Thr - Ser - Val d. Val - Ser - Thr
HN
NH2 28. The major product obtained in the following reaction is:
O [JEE Main 2019]

OH O
(CH3CO)2 O/ pyridine(leqv.)

room temp.
→ a. O NH2 O
NH2 H
H 3C N N OH
COCH3 OH H
O
OCOCH3
a.
NH2 O
OCOCH3 O
NHCOCH3
H O
b. b. H3C N N
NH2 H
O
OH
OH
OCOCH3
c.
NHCOCH2 O OCOCH3
H
H 3C N N O
d.
NHCOCH2 c. H
O
OH
29. The major product of the following reaction is: NHCOCH3
[JEE Main 2019] O
O OCOCH3
O
H
C
NH2  H 3C N O
→ (i)Br2 / hv
(ii)KOH(dil)
N
d. H
CO2—CH3 O
OH
NH2
NH
a. b. NH
O
CH3
O [JEE Main 2019]
O
NH O
c. d. NH
OEt
CN
CH3
30. The major product formed in the reaction given below H

will be: [JEE Main 2019] O N
a. b.
NH2 
→ NaNO2 CNO
Aq.HCl,0 −5ºC
OH OH
c. NH d.
NO2
a. b. NH2
NH2 NO2 33. An organic compound is estimated through Dumus

c. d.
method and was found to evolve 6 moles of CO2, 4 moles
31. The correct structure of product 'P' in the following of H2O and 1 mole of nitrogen gas. The formula of the
reaction is: [JEE Main 2019] compound is: [JEE Main 2019]
a. C12H8N b. C12H8N2
Asn − Ser + (CH3CO)2 O 
NEt3
→P
(excess) c. C6H8N d. C6H8N2

34. In the following compound, [JEE Main 2019] 39. Coupling of benzene diazonium chloride with 1-napthol in
a alkaline medium will give [JEE Main 2019]
NH2
d
N N
b
N
e N N
H
c ||
the favourable site/s for protonation is/are :- N
OH OH
a. (b), (c) and (d) b. (a)
c. (a) and (e) d. (a) and (d) a. b.
35. Among the following compounds most basic amino acid N=N
is: [JEE Main 2019]
a. Lysine b. Asparagine
c. Serine d. Histidine OH
36. In the following compounds, the decreasing order of basic
strength will be - [JEE Main 2019]
a. (C2H5)2NH > C2H5NH2 > NH3 N
b. (C2H5)2NH > NH3 > C2H5NH2 || N
N ||
c. NH3 > C2H5NH2 > (C2H5)2NH
d. C2H5NH2 > NH3 > (C2H5)2NH N
c. d.
37. 0.27 g of a long chain fatty acid was dissolved in 100 cm3
of hexane. 10 mL of this solution was added dropwise to OH
the surface of water in a round watch glass. Hexane
evaporates and a monolayer is formed. The distance from Matrix Match/Column Match
edge to centre of the watch glass is 10 cm. What is the 40. Match each of the compounds in Column I with its
height of the monolayer? [Density of fatty acid = 0.9 g characteristic reaction(s) in Column II. [JEE 2009 P-I]
cm–3, π = 3] [JEE Main 2019] Column I Column II
–8 –6 –4
a. 10 m b. 10 m c. 10 m d. 10–2 m (A) CH 3CH 2 CH 2CN 1. Reduction with
38. The major product obtained in the following reaction Pd − C / H 2
[JEE Main 2019] (B) CH 3CH 2 OCOCH 3 2. Reduction with
O OH SnCl2 / HCl
(C) CH3 − CH = CH − CH2OH 3. Development of foul
Li AlH4 smell on treatment
CH3
→(excess)
with chloroform and
NO2 O alcoholic KOH
O OH (D) CH 3CH 2CH 2 CH 2 NH 2 4. Reduction with di-
OH
isobutyl aluminium
hydride (DIBAL-H)
a. CH3 b. CH3 5. Alkaline hydrolysis
a. A→1, 2, 4, 5; B→4, 5;C→1;D→3
NO2 OH NH2 OH b. A→ 1,2; B→ 2; C→ 1,2,3; D→ 4
OH OH c. A→ 3,4; B→ 1,2; C→ 2,3; D→ 2
d. A→ 1,2,3,4; B→ 4; C→ 2; D→ 1
c. CH3 d. CH3 41. Match the four starting materials (A, B, C, D) given in
Column-I with the corresponding reaction schemes (1, 2,
NO2 OH NO2 OH 3, 4) provided in Column-II. [JEE Adv. 2014 P-II]

Column I Column II O
(A) H H 1. Scheme I O C
−
(i ) KMnO4 ,HO heat
Cl N Cl
(ii) H+ , H2 O N − Br
(iii )SOCl2 ɺɺ
? → C7 H6 N2 O3 (iii) (iv)
(iv) NH3
+
OH 2. Scheme II OM
(i )Sn / HCl O
(ii ) CH3 COCl
(B) (iii ) conc.H2SO4 N Cl H 2N Cl
(iv) HNO3
( v ) dil.H2 O,heat
OH ( vi ) HO− H
? → C6 H 6 N 2 O3 (v) (vi)
In this reaction, RCONHBr is formed from which this reaction
NO 2 3. Scheme III
has derived its name. Electron donating group at phenyl
(i) red hot iron,873K
(ii)fuming HNO3 ,H2SO4 ,heat
(iii) H2S.NH3
activates the reaction. Hofmann degradation reaction is an
(C) (iv) NaNO2 ,H2SO4
intramolecular reaction [ JEE 2006]
? 
→ C6 H5 NO3
(v) hydrolysis
NO 2 4. Scheme IV 43. How can the conversion of (i) to (ii) be brought about?
(i ) conc.H 2SO4 ,60ºC a. KBr b. KBr + CH3ONa
(ii ) conc.HNO3 , conc.H 2SO4
(iii ) dil H 2SO4 , heat
(D) ? → C6 H5 NO3 c. KBr + KOH d. Br2 + KOH
CH 3 44. Which is the rate determining step in Hofmann

bromamide degradation?
a. A →3; B → 4; C → 2; D → 1
a. Formation of (i)
b. A→ 1; B→ 2; C→ 3; D→ 4
b. Formation of (ii)
c. A→ 3; B→ 1; C→ 2; D→ 4
c. Formation of (iii)
d. A→ 3; B→ 4; C→ 2; D→ 1
d. Formation of (iv)
Statement/Assertion and Reason 45. What are the constituent amines formed when the mixture of
42. Statement-I: Aniline on reaction with NaNO2/HCl at 0ºC (i) and (ii) undergoes Hofmann bromamide degradation?
followed by coupling with β - naphthol gives a dark blue CONH 2
15
CO N H 2
coloured precipitate. And
Statement-II: The colour of the compound formed in the D (i) (ii)
reaction of aniline with NaNO2/HCl at 0ºC followed by 15
a. NH 2 , N H2 ,
coupling with β-naphthol is due to the extended
conjugation. [JEE 2008 P-II] D D
a. Statement-I: is True, Statement-II is True; Statement-II: 15
is correct explanation for Statement-I NH 2 , N H2
b. statement-I is True, Statement-II: is True; statement-II
15
is not a correct explanation for statement-I b. NH 2 , NH 2
D
d. statement-I is False, statement-II is True
15 15
Paragraph c. N H2 , NH 2
RCONH 2 is converted into RNH2 by means of Hofmann 15
d. N HD ,
bromamide degradation
O O
Paragraph for Question No. 46
Cl Cl
NH2 NH–Br There are five students S1, S2, S3, S4 and S5 in a music class and
(i) (ii) for them there are five seats R1, R2, R3, R4 and R5 arranged in a

row, where initially the seat Ri is allotted to the student Si, NH 2
O O
i = 1, 2, 3, 4, 5. But, on the examination day, the five students
are randomly allotted the five seats. [JEE Adv. 2018 P-I] C C
H 3C O OH
46. For i = 1, 2, 3, 4, let Ti denote the event that the students Si
O
and Si + 1 do not sit adjacent to each other on the day of the C NH 2
examination. Then, the probability of the event NH C CH 3
O
T1 ∩ T2 ∩ T3 ∩ T4 is
1 1 + CH 3 COOH
a. b.
15 10
C NH 2
7 1
c. d. O
60 5
N = N-Ph
OH OH
Integer and Subjective ⊕
−
[Ph — N ≡ N]Cl
6. (d)  →
NH2 alkaline solution
47. 
(1)aq.Br2
→ (Q) +
(2) NaNO 2 / HCL
(3) CuCN / KCN NH3 N Cl − CN
(4) H 2 O / H ⊕
(5) SOCl2
7. (c)  
NaNO2 / HCl
0 −5° C
→ →
CuCN / KCN
∆
+ N2

(1) Oleum
(2) NaOH / H 2 O
→ (R)
(3) Br2 / CS2
CH3 CH3 CH3
(1)NaOH
R 
→T
(2)Q
OH
Number of atoms of Br in compound ‘T’are [JEE Adv. 2019 P-I] H 3C C O

→
NaNO / HCl
2
8. (c) CH — CH2 — CH
48. C5 H13 N 
→ Y (tertiary alcohol + other products).
NaNO2 , HCl
− N2 H 3C
(X)
(optically active) NH2
:OH
Find X and Y. Is Y optically active?
Write the intermediate steps. [JEE 2005] H 3C C O
CH — CH2 — HC
H 3C ⊕
ANSWERS and SOLUTIONS N≡N
1. (d) Isocyanide test/Carbylamine reaction ⊕ H
O H 3C O
|| CH — CH — CH — COOH ← H2 O
 CH — CH 2 — HC C
C — NH 2  →
NaOH / Br
2. (c) H 2C Hoffmann Brom −amidedeg radation
H 3C ||
O
NH 2 H3C
H 2C
CH — CH 2 — CH — COOH
O
|| H3C
C — Cl OH
O 9. (a)
|| + –
H 2C NH — C NH 2 N 2 Cl
NaNO , HCl
(T) →2
0 ºC
N = N − Ph
390 − 180 (V)
3. (b) No. of amino group = =5 OH
42
β − Napthol / NaOH
4. (a) Factual 
→
5. (a) Only amines undergo acetylation and not acid amides.
(W)

10. (d) Hofmann bromamide degradation reaction 14. (b)
O OH
|| OH
R − C − NH 2 + Br2 + 4NaOH 
→ R − NH 2 + Na 2 CO3 + 2NaBr + 2H 2 O NaNO2 +HCl
  → 
aq.NaOH
→
0°C
Br2 + 4NaOH 
→ R − NH 2 + Na 2 CO3 + 2NaBr + 2H 2 O
NH2 N+≡ NCl–
1 mole of bromine and 4 moles of NaOH are used for per
mole of amine produced. O O–
11. (b)
NH 2 NHAc NHAc
N =N H N+ ≡ N
    
→
(i ) Ac 2 O / Pyridine
   →
(ii ) KBrO 3 / HBr
OH
Br
∆ (iii) H 3 O +
Br N2 NH 2
N=N
NaNO 2 / HCl 15. (c) Kjeldahl’s method is not applicable for compounds
← 
Cu / HBr
∆
 273 − 278 K
containing nitrogen in nitro, and azo groups and nitrogen
in ring, as N of these compounds does not change to
Br Br Br
ammonium sulphate under these conditions. Hence only
12. (b, d) 4HNO3 + P4 O10 
→ 2N2 O5 + 4HPO3 aniline can be used for estimation of nitrogen by
So, nitrogen containing compound is N 2 O 5 . Kjeldahl’s method.
(A) P4 + 20HNO3 
→ 4H3 PO4 + 20NO2 + 4H2 O 16. (a) Histamine
H
N 2 O 5 can’t be prepared by reaction of P4 & HNO3 . N
(B) N 2 O 5 is diamagnetic.
ɺɺ
:O ɺɺ :
O
N ɺɺ N ɺɺ H
ɺɺ NH2
:O O O:
ɺɺ ɺɺ ɺɺ At pH (7.4) major form of histamine is protonated at
(C) Structure of N2O5 is (It does not contain N – N bond)
primary amine.
(D) N2 O5 + Na 
→ NaNO3 + NO2 ↑
H
13. (d) (i) Nitration is carried out in presence of concentrated N
HNO3 + concentrated H2SO4.

(ii) Aniline acts as base. In presence of H 2SO 4 its N
NH3+
protonation takes place and anilinium ion is formed.
⊕
17. (d)
NH2 N H3HSOΘ
4 NH2 Protonation
+
(a) N H3
1° & sp3
H⊕
 
→
H SO 2 4 (b) NH Protonation +
N H2
sp 2
(iii) Anilinium ion is strongly deactivating group and meta
directing in nature so it give meta nitration product in NH2 ii +
N H2 N H2
significant amount. Protonation
(c) NH +
N H2 NH 2
⊕
NH2 N H 3 HSO Θ
4 Protonation +
(d) NHCH3 NH2 − CH3
Conc. H 2SO 4
   →
+ conc. HNO 3 2° & sp3
NO2 ∴ Correct order of basicity

∆
18. (a) (NH 4 ) 2 Cr2 O 7 
→ N 2 + 4H 2 O + Cr2 O 3 O
∆ NH – C – CH3
NH 4 NO 2  → N 2 + 2H 2 O N2+ Cl−
∆
NO2
(NH 4 ) 2 SO 4  → 2NH 3 + H 2SO 4 NO2 NO2
EtOH
Ba(N 2 ) 2  ∆
→ Ba + 3N 2 ←
∆
NaNO ,HCl
←
2
273−278K
Among all the given compounds, only (NH 4 ) 2 SO 4 do Br

H2O+
Br Br
not form dinitrogen on heating, it produces ammonia gas. (S)
19. (b, c) NH 4 NO3 on heating at 250ºC decomposes to NH 2
NO2 NO2
Nitrous oxide and water. NO2
Sn/HCl Br2

→  →
NH4 NO3 
→ N2O + H2O H O (excess)
2
Nitrous oxide above 600°C decomposes to dinitrogen and Br Br

dioxygen gas. Br (S)
2N2 O 
→ 2N2 + O2 Br Br Br
Ammonium dichromate on heating decomposes to give NH2 N 2+ Cl −
H3 PO2
dinitrogen and chromium (III) oxide. ←
∆
(NH 4 ) 2 Cr2 O 7  → N 2 + Cr2 O 3 + 4H 2 O Br Br Br Br Br
Br
Barium azide on heating around 180°C decomposes to Br Br Br
give dinitrogen gas and barium. NaNO2, HCl
Ba(N3 )2 
→ 3N2 + Ba
Magnesium nitride decomposes above 700°C to give 21. (b) Because one double bond is missing in all the given
magnesium and dinitrogen gas. options. So aromaticity is lost in both the rings.
Mg3 N2 
→ 3Mg + N2 NH2 NC
CHCl / KOH
22. (a)  3
→
So below 300°C only (NH 4 ) 2 Cr2 O7 and Ba(N 3 ) 2 can Carbylamine
reaction
provide N 2 gas on heating

CN O CN O
NH2 NH2
Pd/C/H2
20. (d)  Conc.HNO

  SO
Conc.H
3
→ H
2 4
|
N
NO2
CH3
51%
(P)
NH2 NH2 NH2OH
NO2 Cl
+ + Cl
NH2
23. (d) (b) 
Et 3 N
→
NO2 + H2N
(a)
47% 2% O O
(Q) (R)
Cl NH2
O NH
NH2 NH – C – CH3 O
NO2 NO2 O
Br2
Ac2 O, Pyridine
→ →
CH COOH
3
NH2 (a) will act as nucleophile as (b) is having delocalised
(R) lone pair.
Cl NH2 Free radical

29. (c)
NH 
Polymerisation
→
O O
O
C
O NH3 
(i)Br2 / hv
(ii)KOH(dil)
→ NH
Cl
CH2—CH3
n CH3
O N
NH2
H O O
O
AIH(i −Bu2 ) C—NH2 C—NH
24. (a) R —C ≡ N   →R —C = N − 
H2 O
→R —C = N

KOH
→
25. (d) Order of acidic strength:
CH—CH3 CH—CH3
HOOC — CH 2 — CH — COOH > NH 2 — CH 2 — COO
| Br Br
NH 2
Aspartic acid Glycine OH
NH O 30. (b) Answer should be
> || ||
H 2 N — C — NH — CH 2 CH 2 CH 2 — CH — C — OH
| 31. (a) Asn–Ser is dipeptide having following structure
NH 2
Arginine
So pKa O CH 2 OH
|| |
Asp < Gly < Lys < Arg NH 2 — C — C — NH — CH — CO2 H
26. (d) Order of basic strength |
CH 2
|
> > CONH 2
N N
N
Asn − Ser + (CH3CO)2 O 
NEt3
→P
H H (excess)
P is
sp3N sp2N Delocalised
O
ℓ p of N
O NH2 O
27. (a) Leusine —CH — COOH
| H
H3C N
NH 2 N OH
H O
Serine NO — CH 2 — CH — COOH OCOCH3
|
NH 2 O
Thrconine H3 C — CH — CH — COOH 32. (b) ||
C — OEt
| | 
(1)H2 / Ni
→
OH NH 2 CN
O
28. (b) ||
CH 3 — C — O — C — CH 3 C — OEt
:NH2 || || CH2NH2
O O
DIBAL-H
OH
O
||
N ←
− H2O
C—H
NH — C — CH 3 
|| CH2NH2
O

Dumas
33. (d) [C x H y N z ]  → 6CO 2 + 4H 2 O + N 2
Method
NO 2 NH 2
Hence, C6H8N2
H S.NH NaNO
 2 3
→  2
→
34. (a) Localised lone pair e–. (selective reduction) H SO 2 4
.
NO 2 NO 2
35. (d) Histidine

N +2 HSO 4− OH
36. (a) Basic strength order
Hydrolysis
(CH3CH2)2 NH > CH3CH2NH2 > NH3 →
2º amine 1º amine NO 2 NO 2
.
37. (b) Radius of watchglass = 10 cm

⇒ Surface area = πr2 = 3 × (10 cm)2 = 300 cm2 OH OH
+
mass of fatty acid in 10 ml solution Conc. H SO NO
(B)  2
60° C
4
→ 
2
→
10 × 0.27 OH
= = 0.027gm OH
100 SO3 H
volume of fatty acid
0.027g
= OH OH
0.9g/ml O2 N O2 N
= 0.03 cm3 dil. H SO

2 4
→
∆
volume of fatty acid OH OH
⇒ Height =
surface area of watch glass SO3 H
0.03cm 3
= = 0.0001cm = 10 −6 m
300cm 2 NO 2 NH 2
(C)
38. (b) Sn / HCl CH COCl
  → 3 →
COOH CH 2 — OH
→
Li AlH 4
(excess) NHCOCH 3 NHCOCH 3
C — CH 3 C — CH 3
NO2 || NH2 | conc. H SO
O OH 
2 4
→ 
3 HNO
→
LiAlH4 will not affect C=C in this compound.
OH OH
SO3 H
39. (c)
+

Ph N 2
→
OH NHCOCH 3 NHCOCH 3 NH 2
NO 2 NO 2 NO 2
N=N dil. H SO

2 4
→ OH −
∆ 
→
α-naphthol Orange red dye
(l-naphthol) SO3 H
.
40. (a) A →1, 2, 4, 5; B→4, 5; C→1; D→3

NO 2 NO 2
41. (a) A→3; B→4; C→2; D→1
KMnO
(D)  4
− OH / ∆
→ 
3
→
H O+
(A) 3CH ≡ CH →
red hot fuming HNO3 / H 2SO4
 →
iron 873 K ∆
CH 3 COO −

.
NO 2 NO 2 NO 2 NH2
47. (4) NH2
Br Br
SOCl
→
2

3 NH
→  →AqBr2
COOH COCl CONH 2 Br

.
N2Cl CN
⊕ Θ
42. (d) C6 H 5 N 2 Cl Br Br Br Br
H 2 O / H⊕
gives scarlet red coloured dye with → NaNO 2
HCl 
→
β - naphthol.
Br Br
For Question Nos. 43 to 45 O
43. (d)
.
COO C-Cl
44. (d) Br Br Br Br
.
→ SOCl 2 
CuCN
KCN
→
45. (b)
.
46. (c) Method (1) Br Br

The possible arrangements are:
SO3H OH
(1) P1 P3 P5 P2 P4
(2) P1 P4 P2 P5 P3 
Oleum
→ 
Fused
(1) NaOH
→
( 2)H ⊕
(3) P2 P4 P1 P3 P5
(4) P2 P4 P1 P5 P3 OH
(5) P2 P5 P3 P1 P4

Br2
CS2
→ ‘R’
(6) P3 P1 P4 P2 P5
(7) P3 P1 P5 P2 P4 Br
Br
(8) P3 P5 P2 P4 P1 O
(9) P3 P5 P1 P4 P2 ii Cl — C Br
Br O
ii
(10) P4 P1 P3 P5 P2 Br
(11) P4 P2 P5 P1 P3
Br
O
(12) P4 P2 P5 P3 P1

→ Br O—C Br
(13) P5 P1 P3 P2 P4
‘T’ Br
(14) P5 P2 P4 P1 P3
∴ Required probability H C2 H5
| *
|
14 7 48. X is H 3C — C— NH 2 *
CH
= = |
120 60 CH OR
H3C CH 2
Method (2) |
H3C CH3 NH 2
5!− 4 C1 × 4!× 2!+ ( 3C1 × 3!× 2!+ 3C1 × 3!× 2!× 2!) (X)
at least one pair at least two pairs
(X)
H
− ( C1 × 2!× 2!+ C1 × 2 × 2!+ 2 C1 × 2 × 2!) + 2 = 14
2 2 |
NaNO2 + HCl
at least 3 pairs
H 3C — C — NH 2  →
|
Required probability CH
14 7 H3C CH3
= = (X)
5! 60
H H3 C H H OH
| ⊕ ⊕ | H3 C
+ |
H 3C — C — N 2 →  →
H 2O
C →
H shift
H 3C — C — H CH 2 — C — CH
| | | |
CH CH C CH 3
⊕
H3 C CH3 H3 C CH3 H3 C CH3 (X) Optically inactive

Polymers 243
23 Polymers
QUICK LOOK −CH 2 CHCH 2 CHCH 2CHCH 2 CH − or (—CH 2 CH—)n
| | | | |
G G G G G
Polymers are of two types: Polymer
Natural polymers: The polymers which are found in nature

Reaction occurs at the doubly bonded carbons—the vinyl
are called natural polymers e.g., proteins, polysaccharides,
groups— and is called vinyl polymerisation. A wide variety of
natural rubber are some examples.
unsaturated monomers may be used, to yield polymers with
Synthetic polymers: The polymers which are synthetic or
different pendant groups (G) attached to the polymer backbone.
manmade. e.g., polythene, nylon, dacron etc.
Copolymerisation: So far, we have discussed only polymerisation
Classification Based on Structure of Polymers: On the basis
of a single monomeric compound to form a homopolymer, a
of structure polymers are of three types:
polymer made up except, of course, at the two ends of the long
Linear polymers: Generally have higher magnitude of inter
molecule of identical units. Now, if a mixture of two (or more)
particle forces and thus possess high density and high m.pt.
monomers is allowed to undergo polymerisation, there is obtained
Such polymers have high tensile strength in the direction of
a copolymer—a polymer that contains two (or more) kinds of
polymer chain and very low tensile strength at right angle to it.
monomeric units in the same molecule.
Branched polymers: Generally have low density and low
Example
m.pt. Such polymers have almost equal tensile strength in
all directions which is less than that in linear chain polymers. CH 3
|
e.g. amylopectin, glycogen etc. CH 2 == CH + CH 2 == C →
initiator
— CH 2 — CH — CH 2 — C —
| | |
Three-dimensional network polymers: In these polymers Ph COOCH 3
the initially formed linear polymer chains are joined Styrene Methyl methacrylate Polystyrene co me
together through two or more cross-links to form three-

CH 3
dimensional network structure. These are also called cross- |
CH 2 e.g.,
linked polymers. These are hard, brittle and rigid CH CH 2 C — CH 2 — CH — CH 2 — C —
| | |
Bakelite, urea, formaldehyde, melmac etc. Ph COOCH 3
Styrene Methyl methacrylate Polystyrene ( co − methyl methacrylate )
Classification Based on Synthesis: The process by which the Condensation Polymerisation: In this process the simple
monomers are converted into polymers is called polymerization. monomers are combined together with the loss of simple
The number of times a monomer unit is repeated in a polymer molecules like H 2 O, NH3 etc. e.g,. Nylon, terylene etc. A diol,
is called degree of polymerisation.
for example, reacts with a dicarboxylic acid to form an ester;
Addition Polymerisation: In this process the simple but each moiety of the simple ester still contains a group that
monomers are joined together without loss of molecules like can react to generate another ester linkage and hence a larger
H2O, NH3 etc. for e.g., Polythene, Polystyrene, PVC etc. molecule, which itself can react further, and so on.
Free-radical Vinyl Polymerisation: The polymerisation of HOCH 2 CH 2 OH + HOOC COOH 

→
1, 2-Ethanediol
ethylene and substituted ethylenes under conditions where free
terephthalic acid
radicals are generated—typically in the presence of small
amounts of an initiator, such as peroxide.
H2CH2COH
O OH
nCH 2 = CH → initiator
| C C 
HOCH 2 CH 2 OH
→
G O O
Vinyl monomer

O 2. The molecular formula of a commercial resin used for
O exchanging ions in water softening is C8H7SO3Na (Mol.
O Wt. 206). What would be the maximum uptake of Ca2+
O 
p-C5 H4 (COOH)2
→ ions by the resin when expressed in mole per gram resin?
H [JEE Main 2015]
O 1 1
HOOC a. b.
O 103 206
O 2 1
O c. d.
306 412
O O
OH 3. Which polymer is used in the manufacture of paints and
O lacquers? [JEE Main 2015]
Terylene or Dacron a. Bakelite b. Glyptal
c. Polypropene d. Poly vinyl chloride
Coordination Polymerisation: In this process, the alkene is
4. Under hydrolytic conditions, the compounds used for
treated with a catalyst consisting of (C 2 H 5 )3 , Al + TiCl4 or preparation of linear polymer and for chain termination,
(TiCl3 ) (Ziegler-Natta catalyst) under suitable conditions. It is respectively, are [JEE Adv. 2015 P-II]
also called Ziegler-Natta polymerisation. a. CH3SiCl3 and Si(CH3)4
b.(CH3)2SiCl2 and (CH3)3SiCl
Table: 23.1 On the Basis of Synthesis, Polymers can be Classified into Two Types c. (CH3)2SiCl2 and (CH3)3SiCl2
Addition Polymers Condensation Polymers d. SiCl4 and (CH3)3SiCl
Formed by addition reaction. Formed by condensation polymerisation
Molecular mass is whole number Molecular mass is not whole 5. Which of the following statements about low density
multiple of monomer. number multiple of the monomer. polythene is false? [JEE Main 2016]
Generally involve one monomer unit. Generally involve more than one unit. a. Its synthesis requires high pressure
Monomers are unsaturated Monomer units must have two
b. It is poor conductor of electricity
molecules. active functional groups.
They are generally chain growth c. Its synthesis requires dioxygen or a peroxide initiator as
polymers. a catalyst
d. It is used in manufacture of buckets, dustbins etc.
Classification Based on Molecular Forces: On the basis of
intermolecular forces of attraction polymers can be classified in 6. On complete hydrogenation, natural rubber produces
following types: a. ethylene-propylene copolymer [JEE Adv. 2016 P-I]
Elastomers: In this type the polymer chains are held together b. vulcanised rubber
by weak intermolecular forces e.g., Natural rubber, vulcanised c. polypropylene
rubber, SBR (Styrene butadiene rubber) etc. d. polybutylene
Fibres: In this type, the intermolecular forces between the 7. The formation of which of the following polymer involves
chains are hydrogen bond or dipole-dipole interaction e.g. hydrolysis [JEE Main 2017]
Nylon, polyester and orlon etc. a. Terylene b. Nylon 6
Thermoplastics: In this type, the intermolecular forces are c. Bakelite d. Nylon 6, 6
intermediate between those of elastomers and fibres. e.g., 8. The structure of Nylon-6 is: [JEE Main 2019]
polystyrene, PMMA etc.  O H 
Thermosetting: They are highly cross-linked, hard, infusible and a.  || | 
— (CH 2 )6 — C — N  n
—
insoluble polymers e.g., Bakelite, phenol formaldehyde etc.
 O H 
Multiple Choice Questions b.  || | 
One and More than One Correct  (CH 2 )4 — C — N
—  n
—
1. B(OH)3 + NaOH ↽ ⇀ NaBO 2 + Na[B(OH) 4 ] + H 2 O  O H 

c.  || | 
How can this reaction is made to proceed in forward 
— C — (CH 2 )5 — N  n
—
direction? [JEE 2006]
 O H 
a. addition of cis 1, 2 diol b. addition of borax d.  || | 
c. addition of trans 1, 2 diol d. addition of Na2HPO4 
—  n
C — (CH 2 )6 — N —
Polymers 245
9. Correct statement among a to d regarding silicones are: a. 3-hydroxybutanoic acid and 4-hydroxypentanoic acid
1. They are polymers with hydrophobic character. b. 2-hydroxybutanoic acid and 3-hydroxypentanoic acid
2. They are biocompatible. c. 3-hydroxybutanoic acid and 2-hydroxypentanoic acid
3. In general, they have high thermal stability and low d. 3-hydroxybutanoic acid and 3-hydroxypentanoic acid
dielectric strength.
14. The two monomers for the synthesis of Nylone 6, 6 are:
4. Usually, they are resistant to oxidation and used as
greases. [JEE Main 2019] [JEE Main 2019]
a. 1, 2, and 3 only b. 1 and 2 only a. HOOC(CH2)6COOH, H2N(CH2)6NH2
c. 1, 2, 3 and 4 only d. 1, 2 and 4 only b. HOOC(CH2)4COOH, H2N(CH2)4NH2
c. HOOC(CH2)6COOH, H2N(CH2)4NH2
d. HOOC(CH2)4COOH, H2N(CH2)6NH2
[JEE Main 2019]
O CH3 (i)dil.HCl / ∆ 15. Which of the following is/are correct?

(ii)(COOH)2 / Polymerisation
→
[JEE Adv. 2019P-II]
CH3O O
OH a. Teflon is formed by polymerization of tetrafluoroethene.
O b. Natural rubber is the trans form of polyisoprene.
O O O c. Cellulose contains only α-D-glucose linkage
a. O O b. O n d. Nylon-6 contains amide linkage.
O n
OCOCH3 OCH3 Matrix Match/Column Match
O 16. Match the chemical substances in Column I with type of
O O O polymers/type of bonds in Column II. [JEE 2007 P-I]
c. O n d. O O Column I Column II
O n (A) cellulose 1. natural polymer
OH OH
(B) nylon-6, 6 2. synthetic polymer
11. The polymer obtained from the following reactions is: (C) protein 3. amide linkage
[JEE Main 2019]
(D) sucrose 4. glycoside linkage
NH2
(i ) NaNO 2 / H 3 O + a. A → 1,4; B → 2,3; C → 1,3; D → 4
HOOC     →
(ii )Polymerisation
b. A → 1,3; B → 2,4; C → 1,2; D → 4
   
c. A → 1,2; B → 2; C → 1,3; D → 4
a.  O  b.  O 
 || H   ||  d. A → 1,4; B → 2,3;C → 1,2, D →1
 C — (CH2 )4 — N —
—  n  O — (CH2 )4 — C —
—  n
   
 O  ANSWERS and SOLUTIONS
c.  O O  d.
 || || H  n  || 
 HNC(CH2 )4 —C — N —
—   OC(CH 2 ) 4 O
—  n
— 1. (a) Due to formation of chelated complex, the reaction
moves in forward direction.
12. The homopolymer formed from 4-hydroxybutanoic acid is:-
[JEE Main 2019] 2. (d) 2 moles of C8 H 7SO3 Na = 1 mole of Ca 2+
    2 × 206 g C8 H 7SO3 Na = 1 mole of Ca 2+
 O
a.  ||   O
b.  || 
  1
 C(CH 2 )3 — O —
—  n  OC(CH2 )3 — O —
—  n 1 g C8 H 7SO3 Na =
412
    3. (b) Glyptal is used in the manufacture of paints and lacquers.
 O
c.  ||   O
d.  || 
 
CH 3 CH 3
 C(CH 2 )2 — O —
—  n  C(CH 2 )2 — O —
—  n | |
4. (b) Cl — Si — Cl 
H 2O
→ HO — Si — OH 
→
13. Poly-β-hydroxybutyrate-co-β-hydroxyvalerate(PHBV)is a | |
CH 3 CH 3
copolymer of___. [JEE Main 2019]
CH 3 CH 3 Polymerisation
| |
H — O — Si — O — Si ——O — H
| |
CH 3 CH 3 n O
C
Me3SiCl, H 2 O
n
O
CH 3 CH 3 O  
Me
→  || 
| | Me O
Me 12. (a) 
Polymerisation

Si — O — Si — O — Si ——O — Si Me
Me | | Me OH —  C(CH2 )3 —O —
n
CH 3 CH 3 n OH
5. (d) Low density polythene is not used in the manufacturing 13. (d) PHBV is a polymer of 3-hydroxybutanoic acid and 3-
of buckets, dustbins etc. because and buckets, dustbins are hydroxypentanoic acid.
manufactured by high density polythene. 14. (d) Nylon-6,6 is polymer of
Hexamethylene diamine and Adipic acid
6. (a) Natural rubber 
H2 / Ni
→ ↓ ↓
H 2 N—(CH 2 ) 6 —NH 2 HOOC—(CH 2 ) 4 —COOH
15. (a, d)
Polymerisation
16. (a) A →1,4; B → 2,3; C → 1,3; D → 4
CH 2 = CH 2 + CH 2 = CH − CH 3 (A) Cellulose
ethylene Propylene
O O O
7. (a) Formation of Nylon-6 involves hydrolysis of its O O
monomer (caprolactum) in initial state.
NH O (Glycoside linkage)
Hydrolysis
→ − − − − − (B)− Nylon
− 6, 6
Caprolactum H O
| ||
O N C
+ || C N
→ H3 N − CH 2 − CH 2 − CH 2 − CH 2 − CH 2 − C − O − ||
O (Amide linkage)
∆ / Polymerisation
O (C) Protein
||
−[ HN −(CH 2 )−5 C −]n R H H O
Nylon −6 | ||
C N C
 O H  N C H
8. (c)  || |  | ||
R′ H |

— C — (CH 2 )5 — N  n
— H O N
(Amide linkage)
Nylon − 6
(D) Sucrose
9. (c) these are properties and uses of silicones. CH2OH
H O H
10. (c) H O CH2OH
NH2 OH H
OH O
11. (b) HOOC OH H

NaNO 2
H O−
→ O
3 H OH
OH H OH
HOOC (Glycoside linkage)
Biomolecules 247
24 Biomolecules
QUICK LOOK
Glycoside Linkage: The linkage which holds the
monosaccharide units in oligo or polysaccharides is called
Biomolecules are the complex organic compounds which built
glycoside linkage.
up living organisms and are required for their growth and
maintenance. For example, carbohydrates, proteins, lipids, Mutarotation: Glucose exist in two forms α–D glucose and β–
nucleic acids. D glucose. Optical rotation of α–D glucose is +112º whereas
Carbohydrates: Carbohydrates are defined as polyhydroxy that of β–D glucose is + 19 ° . The optical rotation of
aldehydes or polyhydroxy ketones or substances which give equilibrium mixture of α–D glucose and β–D glucose is 52° .
these on hydrolysis and contain at least one chiral carbon The process which involves the change in the optical rotation of
atom. It may be noted here that aldehydic and ketonic either form of glucose to that of equilibrium mixture is called
groups in carbohydrates are not present as such but usually mutarotation. The two forms of glucose α–D and β–D forms
exist in combination with one of the hydroxyl groups of the are also called anomers.
molecule in the form of hemiacetals and hemiketals
Cyclic Structure of Monosaccharides: We know that aldoses
respectively.
(and ketoses) react with alcohols to give first hemiacetals (and
hemiketals) and then acetals (and ketals), i.e.
Classification of Carbohydrates
Sugars: These are crystalline substances with sweet taste OH OR
| |
and are soluble in water. + ROH
—C == O + ROH ↽ ⇀ —C — OR  → —C — OR
– H2 O
| | |
Non-Sugars: These are naturally occurring polymers with
H H H
very high molecular mass and do not have sweet taste. Aldehyde Hemiketal Ketal
Monosaccharides: These are the simple carbohydrates OH OR

which do not hydrolyse to still simpler carbohydrates. | | + ROH
|
— C == O + ROH ↽ ⇀ — C — OR 
− H2O
→ — C — OR
Ketal
Chemically, they are polyhydroxy aldehydes or ketones. Ketone Hemiketal
Oligosaccharides: These are carbohydrates which on

hydrolysis give 2 to 9 units of monosaccharides. They can Since monosaccharides contain a number of hydroxyl groups
be further classified into di, tri and tetrasaccharides. and an aldehyde or a keto group, therefore, any one of the –OH
Common examples of : groups (usually C4 or C5 in aldohexoses and C5 or C6 in
Disaccharides are: Sucrose and maltose, Trisaccharides is: ketohexoses) may combine with the aldehyde or the keto
Raffinose, Tetrasaccharides is stachyose. group to form intramolecular hemiacetal or hemiketal.
Polysaccharides: These are carbohydrates, which on
hydrolysis give large number of monosaccharide units.
Cellulose and starch are common examples. O O
furan pyran
Reducing and Non-reducing Sugars: The carbohydrates The five membered rings containing one oxygen atom because
which are capable of reducing Fehling solution or Tollen’s of its similarity with furan is called the furanose form and the
reagent are called reducing sugars. They contain –CHO group six membered rings containing one oxygen atom because of its
in their molecules. On the other hand, sugars, which do not resemblance with pyran is called the pyranose form. In nut
reduce Fehling solution or Tollen’s reagent, are called non- shell, all the monosaccharides (pentoses and hexoses) in the
reducing sugars. free state always exist in the pyranose form.

Cyclic Structure of Glucose – Anomers 6 CH2OH 6 CH2OH
D-glucose exists in two stereoisomeric forms, i.e., α − D-
H 5 O H H 5 O OH
glucose and β − D-glucose as shown below: H H β
4 1 4 1
OH H α OH H
1
O — C — OH α H — 1C == O OH OH OH H
3 2 3 2
| |
H — 2 C — OH H OH H OH
O — 2 C — OH
| | I- α-D-Glucose II- β -D-Glucose
3
HO — 3C — OH O ↽ ⇀ HO — C — H or α-D(+)-Glucopyranose or β-D(+)-Glucopyranose
| |
H — 4C — OH H — 4 C — OH
| | Cyclic Structure of Fructose: Like glucose, fructose also has
H — 5C — O ɺɺ — H
O — 5C a cyclic structure. Since fructose contains a keto group, it forms
| | ɺɺ
6
6
CH 2 OH CH 2 OH an intramolecular hemiketal. In the hemiketal formation,
(I) α − D( + ) − Glucose or D(+) - Glucose
α − D( + ) − Glucopyranose (Open chain form) C5 − OH of the fructose combines with C 2 − keto group. As a
result, C2 becomes chiral and thus has two possible
β 1
HO — C — H arrangements of CH 2 OH and OH group around it.
|
H — 2 C — OH Thus, D-fructose exists in two stereoisomeric forms, i.e., α −
|
↽ ⇀ HO — 3C — H O D-fructopyranose and β–D- fructopyranose. However, in the
|
H — 4C — OH combined state (such as sucrose), fructose exists in furanose
| form as shown below:
H — 5C
| 6
(II) 6
CH 2 OH(II) 2 1 CH2OH O OH
β - D(+) - Glucose or HO — C— CH2OH
β - D(+) - Glucopyranose | 5 2
β
HO — 3C — H
In α − D-glucose, the OH group at C1 is towards right while | O ≡≡ H H OH CH2OH
H —4C — OH 1
in β- D-glucose, the OH group at C1 is towards left. Such a |
4 3
pair of stereoisomers which differ in configuration only around H —5C
| OH H
C1 are called anomers and the C1 carbon is called Anomeric 6
CH2OH
carbon or glycosidic carbon. β − D − Fructofuranose
The cyclic structures of monosaccharides can be better Epimerisation: It is a process of inversion of configuration at
represented by Haworth Projection formulae. To get such a one of the asymmetric (or chiral) centre of the molecule which
formula for any monosaccharide (say α − and β- D-glucose), contain several chiral centres.
draw a hexagon with its oxygen atom at the upper right hand
CHO CHO
corner. Place all the groups (on C1 , C 2 ,C3 and C 4 ) which are | |
H – *C – OH  →
Epimerisation
present on left hand side in structures I and II, above the plane HO — *C — OH
| |
of the ring and all those groups on the right hand side below the
(CHOH)3 (CHOH)3
plane of the ring. | |
CH 2 OH CH 2 OH
The terminal CH 2OH group is always placed above the plane D - Glucose D − Mannose
of the hexagon ring (in D-series). Following the above Peptides and Proteins: Proteins are formed by joining the
procedure, Haworth Projection Formulae for α − D-glucose (I) carboxyl group of one amino to the α − amino group of another
and β– D-glucose (II) are obtained as shown below: acid. The bond formed between two amino acids by the
elimination of water molecules is called peptide linkage.
Biomolecules 249
—C — OH + H — N — 
→ —C—N— animals and plants. These are essential constituents of all living
|| | || | cells. Structurally, proteins are long polymers of amino acids
O H O H
bonded by peptide linkages. The structure of proteins is
Carboxyl group of Amino group of Peptide bond
one amino acid another amino acid described as follows:
The product formed by linking amino acid molecules Primary structure: It refers to the sequence of various
through peptide linkage − CO − NH − is called a peptide. amino acids in proteins. The biological activity primarily
When two amino acids combine in this way the resulting depends upon primary structure.
product is called a dipeptide. Secondary structure: This refers to the arrangement of
polypeptide chains in space with respect to one another.
O H O Tertiary structure: This tertiary structure describes as to
|| | ||
H 2 N — CH 2 — C — OH + N — CH — C — OH how the proteins have coiled or folded up as a result of
| interparticle attraction.
CH 3
Glycine Alanine
Biological Functions of Proteins: (1) Structural material of
O H O animal tissues. (2) Transport agent (3) Enzyme (4) Antibodies
|| | || (5) Metabolic regulators.
− H 2O
 → H 2 N — C — N — CH — C — OH
|
CH 3 Denaturation of Proteins: When proteins are heated above the
A Dipeptide temperature characteristic of living organism or when they are
Peptide are further designated as tri, tetra or penta peptides subjected to unusual acidic or basic conditions they begin to
accordingly as they contain three, four or five amino acid undergo change in their secondary and tertiary structure. This is
molecules, same or different. referred to as denaturation of proteins.
In a peptide the amino acid that contains the free amino
group is called the N– terminal residue (written on L.H.S). Uses of Proteins
Proteins constitute as essential part of our food. Meat, eggs,
The amino acid that contains the free carboxyl group is
fish, cheese provide protein to human beings.
called the C − terminal residue (written on R.H.S).
Casein (a milk protein) is used in the manufacture of
O O O artificial wool and silk.
|| || || Amino acid needed for medicinal use and feeding
H2 N —CH2 —C — NH —CH —C — NH —CH —C —OH (C-terminal on r
| | experiment, are prepared by hydrolysis of proteins.
CH3 CH3 Gelatin is used in desserts, salads, candies, bakery goods
etc.
(C-terminal on right) Leather is obtained by tanning the protein of animal hides.
Haemoglobin present in blood is responsible for carrying
oxygen and CO 2 .
Glycylalanyphenylalanine (tripeptide) abbreviated as : Gly - Hormones control various processes.
Ala - phe Enzymes are the proteins produced by living system and
If a large number of α − amino acids (100 to 1000) are catalyse specific biological reactions.
joined by peptide bonds the resulting polyamide is called Amino Acids
polypeptide. Amino acids are organic compounds of both, an amino group
and carboxylic group.
H2 N — CH —CO — N — CH —CO — NH — CH —COOH
| | | | They are represented by general formula:
R H R n R Carboxyl group
By convention a peptide having molecular weight upto R—CH—COOH

|
10,000 is called polypeptide. NH
Side chain 2
While a peptide having a molecular mass more than 10,000 Amino group
is called a protein. These amino acids are very important because they are the
These are complex nitrogenous organic compounds found in building blocks of protein.

Protein is the natural polymer moving α-amino acids as electrodes and exists as a neutral dipolar ion, when placed
monomer. in electric field known as isoelectric point.
With the exceptions of glycine, all the other amino acids All amino acids do not have the same isoelectric point &
have chiral carbon and have two optically active isomers. it depends upon the nature of R − linked to α − carbon
All naturally occurring amino acids are in L-series in which atom.
− NH 2 group is on the left and − OH group in the right as Table 24.1 Different Amino Acids have Different Isoelectric Points.
in L − glyceraldehydes. Amino acid Isoelectric point
Neutral amino acids (pH 5.5 to 6.3)
CHO COOH COOH
| Glycine 5.7
| |
HO — C — H H2 N — C — H H2 N — C — H Alanine 6.1
| | |
H 2 C — OH R CH 3 Valine 6.0
L − Glyceraldehyde L-Alanine Serine 5.7
Threonine 5.6
These are the compounds containing carboxyl and amino Acidic amino acids (pH ≈ 3)
groups. Almost all amino acids obtained from proteins are α- Aspartic acid 2.8
amino acids i.e., amino group is linked to the carbon atom Glutamic acid 3.2
having carboxyl group attached to it. Some common examples Basic amino acids ( pH ≈ 10)
are glycine, α-alanine, valine etc. α-amino acids generally Lysine 9.7
exists in the form of zwitter ion structure. For example, zwitter Arginine 10.8
ion structure of glycine and α-alanine.
Peptides Linkage: The linkage which unites the α − amino
CH3 acid molecules together is called peptide linkage. It is,
+ +
|
H 3 N— CH — COO− , H3 N —CH — COO− − CO − NH − linkage.
Glycine α -Alanine
Nucleic Acids: Nucleic acids are biologically important
polymers which are present in all living cells, also called as
It may be noted that:
polynucleotides because repeating structural unit is nucleotide.
When ionised form of amino acid is placed in an electric
There are two types of nucleic acids:
field it will migrate towards the opposite electrode.
DNA (deoxyribonucleic acid)
In alkaline solutions amino acids exist as anion while in
RNA (Ribonucleic acid)
acidic medium they exist as cation.
+ OH − + OH − Composition of Nucleic Acids
NH 3 CH 2 COOH ↽ + ⇀ NH 3 CH 2 COO − ↽ + ⇀ NH 2 CH 2 COO −
Cation
H H 1. Phosphate Group: Phosphate group in nucleic acid is:
− − O
NH 3 CH 2 COOH ↽ H+ ⇀ NH 3 CH 2 COO − ↽ H + ⇀ NH 2 CH 2 COO −
OH OH
||
−
Anion
O — P — O−
|
O−
The pH of a solution of amino acids at which it exist in the
Phosphate group is bonded to a hydroxyl group of sugar.
form of a dipolar ion is called its isoelectric point.
Depending upon the pH of the medium following three 2. Sugar: Two types of sugars present in nucleic acids.
things may happen. RNA (D – ribose), DNA (D – deoxyribose)
(a) In acidic medium, the cation move towards cathode. 5
CH 2 OH O OH OHCH 2 O OH
(b) In basic medium, the anion move towards anode.
(c) The Zwitter ion does not move towards any of the 4 1
H H H H
electrodes. H H H H
At a certain pH (i.e. H + concentration), the amino acid 3 2
molecules show no tendency to migrate towards any of the OH OH HO H
D − ribose D − deoxyribose
Biomolecules 251
3. Nitrogenous Bases: There are two types of nitrogenous Transcription
bases, given below: (2) Protein synthesis
Purines – Adenine (A) and Guanine (G) Translation
Pyrimidines – Cytosine (C), Thymine (T) and Uracil (U)
Genetic Code: Segment of DNA is called gene and each triplet
NH2 O
N N of nucleotides is called a codon that specifies one amino acid.
N N N HN

→ This relationship between nucleotide triplets and amino acids is
N called genetic code, e.g.
N N N N
| N − A − U − G − C − C − U − G − C − U − a segment of mRNA
| H2 N |
H H H Codon for methionine Pr oline Pr oline
Purines Adenine (A) Guanine (G)
Lipids: These are oily, fatty or waxy substances present in
O O NH2 living organisms. Their main functions are to form a part of
CH3
N N HN N structure of biological membranes and to store energy for cells.

→
N O N O N O N Triglycerides : These are esters of glycerols and higher fatty
Pyrimidines | | | acids and are the main form in which fat is stored in plant and
H H H animal cells.
Thymine (T) Uracil (U) Cytosine (C)
These are biological significant polymers which are present in Phospholipids: These are mixed glycerides of higher fatty
all living cells. They direct the synthesis of proteins and are acids and phosphoric acid in which two of the OH groups of
responsible for the transfer of genetic information, i.e., glycerol are esterified by fatty acids and third OH group by
hereditary characteristics. The two types of nucleic acids are: some derivative of phosphoric acid.
RNA (Ribonucleic acid) and DNA (Deoxyribonucleic acid). Vitamins: These are group of organic substances other than
Both RNA and DNA are polymers of nucleotides. A nucleotide carbohydrates, proteins and fats, which are necessary to maintain
consists of a sugar unit linked to nitrogen base as well as normal health, growth and nutrition. Vitamins differ from
phosphoric acid unit as follows: hormones in the fact that these are supplied by the food stuff,
O whereas hormones are produced by the body’s own glands.
||
Base – Sugar — O — P — OH (A nucleotide) Although vitamins are complex molecules, yet for the sake of
| simplicity they are represented by letters A, B, C, D, E, K.
OH
Phosphoric acid unit
Table 24.3: Some Important Vitamins and Diseases Caused by their Deficiency
In RNA the sugar unit is : D-ribose and Bases are: Adenine, are being Given as Follows
guanine, uracil and cystosine. Deficient Diseases Symptoms
In DNA, the sugar unit is: Deoxyribose and Bases are: Vitamins
Adenine, guanine, thymine and cytosine. Vitamin A (i) Night blindness Inability to see in dim light.
(ii) Xerophthalmia Discharge of mucous from
Table 24.2: Some Important Points of Differences between RNA and DNA are eyes, corneal keratinisation,
Given Below clouding leading to ulceration
DNA RNA and photophobia.
It has a double helix structure. It has a single helix structure. Vitamin B1 Beriberi Retarded growth, loss in
appetite and weight, nervous
Sugar unit is deoxyribose. Sugar unit is ribose. degeneration, muscular
Base units are adenine, guanine, It contains uracil base instead of atrophy, oedema.
thymine and cytosine thyamine, other bases being same as Vitamin B2 Cheilosis Inflammation and sometimes
those in DNA cracking at corners of mouth.
Responsible for inheritance of It is responsible for protein
Niacin Pellagra Digestive disorder and
character. synthesis.
irritability.
Structure of RNA is similar to DNA except that it is a single Vitamin B6 Anaemia Retarded growth, loss of
appetite, apathy.
stranded structure.
Vitamin B12 Pernicious Anaemia Immature, enlarged and
Biological functions of nucleic acids: Important functions are nucleated RBCs deficient in
(1) Replication haemoglobin.

Vitamin C Scurvy Delayed healing, bleeding AcO
gums, fragile bones.
Vitamin D Rickets (in children), Bending and softening of AcO O O
H
Osteomalacia (in bones, swelling on joints. H
AcO O OH H
adults) H O
H H
Vitamin K Bleeding Disease Poor blood clotting.
H OH H
b. O O H H OH
H
OH H
Hormones: These are the chemical substances secreted by H H OH
O
ductless glands, which influence and control biological
reactions. Some important hormones alongwith their source H OH
AcO AcO AcO
and function are being given below :
H O H H O H H O O
Table 24.4: Hormones and Functions H H H
c.
Hormones Sources Functions OAc H O OAc H O OAc H
(1) Steroid hormones O H
(i) Testosterone Testis Regulates development of
(Androgens) reproductive male organs. H OAc H OAc H OAc
(ii) Estrogen and Ovary Female sex hormones : control AcO AcO AcO
progesterons (Uterus) normal functioning of female sex
organs. H O H H O H H O O
(iii) Cortisone and Adrenal Regulates the metabolism of fats, d. H H H
related hormones cortex proteins, carbohydrates and H H O H H O H H
mineral salts. O H
(2) Amine hormones OAc OAc OAc OAc OAc OAc

(i) Adrenaline Adrenal Increase the pulse rate and blood
(Epinephrine) medulla pressure : reduces glucose from 2. Among cellulose, poly(vinyl chloride), nylon and natural
glycogen and fatty acids from fats. rubber, the polymer in which the intermolecular force of
(ii) Thyroxine Thyroid Stimulates rate of oxidative attraction is weakest is [JEE 2009 P-I]
metabolism and regulates general
growth and development.
a. Nylon b. Poly(vinyl chloride)
(3) Peptide hormones c. Cellulose d. Natural Rubber
(i) Oxytocin Posterior Causes contraction of some
3. The correct statement(s) about the following sugars X and
pituitary smooth muscles. Also causes
contraction of uterus during child Y is (are) [JEE 2009 P-II]
(ii) Vasopressin Posterior birth. CH 2OH
pituitary Inhibits excretion of water from O H HOH C O H
(iii) Insulin Pancreas the body by way of urine. H 2
H H HO
(iv) Glucogen Pancreas Decreases blood glucose level. CH 2OH
Elevates blood glucose level.
HO OH H O
H OH OH H
Multiple Choice Questions X
One and More than One Correct CH 2 OH
O H
1. Cellulose upon acetylation with excess acetic anhydride H
CH 2 OH H
/ H 2SO 4 (catalytic) gives cellulose triacetate whose O
H OH
H O OH
structure is [JEE 2008 P-II] H
OH H OH H
AcO HO
H
AcO O O H OH
H
H Y
AcO O O
OAc H a. X is a reducing sugar and Y is a non-reducing sugar
H H
H b. X is a non-reducing sugar and Y is a reducing sugar
a. H O OAc H
H
O H H OAc c. The glucosidic linkages in X and Y are α and β ,
OAc H respectively
H H OAc
O
d. The glucosidic linkages in X and Y are β and α,
H OAc respectively
Biomolecules 253
4. The correct statement about the following disaccharide is CHO CHO
[JEE 2010 P-I] HO H HO H
CH 2 OH HO H HO H
H c. H OH d. HO H
O H O H
H HOH 2 C HO H H OH
OH H H OH
CH 2 OH CH 2 OH
HO OCH 2 CH 2O CH 2 OH
H OH H 9. Thiol group is present in: [JEE Main 2016]
OH
a. Cytosine b. Cystine
a. Ring (a) is pyranose with α -glycosidic link
c. Cysteine d. Methionine
b. Ring (a) is furanose with α -glycosidic link
c. Ring (b) is furanose with α -glycosidic link 10. Which of the following compounds will behave as a reducing
d. Ring (b) is pyranose with β -glycosidic link sugar in an aqueous KOH solution? [JEE Main 2017]
HOH2C
5. The following carbohydrate is [JEE 2011 P-II] O CH OCH
2 3
H
OH a.
HO OH
HO OH OH
HO OH
H OH
H HOH2C O CH2OH
H
b. HO
a. a ketohexose b. an aldohexose OCOCH3
c. an α -furanose d. an α -pyranose
OH
6. Synthesis of each molecule of glucose in photosynthesis HOH2C CH2OH
O
involves [JEE Main 2013]
c. HO
a. 18 molecules of ATP
b. 10 molecules of ATP
OH
c. 8 molecules of ATP
HOH2C O CH2OH
d. 6 molecules of ATP
d. HO
7. The synthesis of alkyl fluorides is best accomplished by OCH3
[JEE Main 2015] OH
a. Free radical fluorination b. Sandmeyer’s reaction
c. Finkelstein reaction d. Swarts reaction 11. In a bimolecular reaction, the steric factor P was
8. The structure of D-(+)-glucose is experimentally determined to be 4.5. The correct option(s)
CHO among the following is (are) [JEE Adv. 2017 P-II]
H OH a. The activation energy of the reaction is unaffected by the
HO H value of the steric factor
H OH b. Since P = 4.5, the reaction will not proceed unless an
H OH effective catalyst is used
CH 2 OH c. The value of frequency factor predicted by Arrhenius
The structure of L-(–)-glucose is [JEE Adv. 2015 P-I] equation is higher than that determined experimentally
CHO CHO d. Experimentally determined value of frequency factor is
HO H H OH higher than that predicted by Arrhenius equation
H OH HO H 12. Glucose on prolonged heating with HI gives
a. HO H b. H OH [JEE Main 2018]
HO H HO H a. 6-iodohexanal b. n-Hexane
CH 2 OH CH 2 OH c. 1-Hexene d. Hexanoic acid

13. The Fischer presentation of D-glucose is given below. 19. Among the following compound which one is found in
CHO RNA ? [JEE Main 2019]
H OH OH NH2
HO H CH3
H OH NH N
a. b.
H OH
N O N O
CH2OH | |
D-glucose H H
The correct structure(s) of β − L − glucopyranose is (are) O NH2
H H NH NMe
O O c. d.
HO CH2OH OH HO CH2OH OH N N
a. b. O O
| |
H H HO H H H H H H Me
OH H OH OH 20. The correct statement(s) among I to III with respect to
CH2OH H potassium ions that are abundant within the cell fluids is/are:
O O I. They activate many enzymes
H H OH HO CH2OH H II. They participate in the oxidation of glucose to produce ATP
c. d. III. Along with sodium ions, they are responsible for the
HO OH HO H H H HO OH transmission of nerve signals [JEE Main 2019]
a. I, II and III b. I and III only
H H OH H
c. III only d. I and II only
14. Maltose on treatment with dilute HCl gives: [JEE Main 2019]
a. D-Galactose Matrix Match/Column Match
b. D-Glucose 21. The correct match between Column I and Column II is:
c. D-Glucose and D-Fructose [JEE Main 2019]
d. D-Fructose Column I Column II
(Mixture) (Separation method)
15. The compound that inhibits the growth of tumors is:
(A) H2O : Sugar 1. Sublimation
[JEE Main 2019]
(B) H2O : Aniline 2. Recrystallization
a. cis-[Pd(Cl)2(NH3)2] b. cis-[Pt(Cl)2(NH3)2]
(C) H2O : Toluene 3. Steam distillation
c. trans-[Pt(Cl)2(NH3)2] d. trans-[Pd(Cl)2(NH3)2] 4. Differential extraction
16. Fructose and glucose can be distinguished by: a. A→3; B→2; C→4 b. A→3; B→1; C→4
[JEE Main 2019] c. A→4; B→2; C→1 d. A→3; B→2; C→1
a. Fehling's test b. Barfoed's test 22. Match the metals in Column I with the coordination
c. Benedict's test d. Seliwanoff's test compound (s) / enzyme(s) in Column II [JEE Main 2019]
17. For the following reaction, the mass of water produced Column I Column II
from 445 g of C57H110O6 is: [JEE Main 2019] [Metals] [Coordination
2C57 H110O6 (s) + 163O2 (g) 
→ 114CO2 (g) + 110 H2 OP(l) compound(s) / Enzyme(s)]
(A) Co 1. Wilkinson catalyst
a. 495 g b. 490 g
(B) Zn 2. Chlorophyll
c. 890 g d. 445 g
(C) Rh 3. Vitamin B12
18. Haemoglobin and gold sol are examples of:[JEE Main 2019] (D) Mg 4. Carbonic anhydrase
a. negatively charged sols a. A→2; B→1; C→4; D→3
b. positively charged sols b. A→3; B→4; C→1; D→2
c. negatively and positively charged sols, respectively c. A→3; B→4; C→2; D→1
d. positively and negatively charged sols, respectively d. A→2; B→4; C→1; D→3
Biomolecules 255
23. The correct match between Column I and Column II is: 26. The total number of basic groups in the following form of
[JEE Main 2019] lysine is_____. [JEE 2010 P-I]
Column I Column II ⊕
H 3 N − CH 2 − CH 2 − CH 2 − CH 2 O
(A) Allosteric effect 1. Molecule binding to CH − C
the active site of H2 N O−
enzyme
(B) Competitive inhibitor 2. Molecule crucial for 27. A decapeptide (Mol.Wt. 796) on complete hydrolysis
communication in the gives glycine (Mol.Wt.75), alanine and phenylalanine.
body Glycine contributes 47.0% to the total weight of the
(C) Receptor 3. Molecule binding to a hydrolysed products. The number of glycine units present
site other than the in the decapeptide is_____. [JEE 2011 P-I]
active site of enzyme 28. When the following aldohexose exists in its D–
(D) Poison covalently 4. Molecule binding to configuration, the total number of stereoisomers in its
the enzyme pyranose form is_____. [JEE 2012 P-I]
a. A→1; B→3; C→4; D→2 CHO
|
b. A→3; B→1; C→4; D→2 CH 2
c. A→3; B→3; C→2; D→4 |
CHOH
d. A→3; B→1; C→2; D→4 |
CHOH
|
Statement/Assertion and Reason CHOH
24. Statement-I Glucose gives a reddish-brown precipitate |
CH 2OH
with Fehling’s solution. Because
Statement-II Reaction of glucose with Fehling’s solution 29. The substituents R 1 and R 2 for nine peptides are listed in
gives CuO and gluconic acid. [JEE 2007 P-II] the table given below. How many of these peptides are
a. Statement-I: is True, Statement-II is True; Statement-II: positively charged at pH = 7.0? [JEE 2012 P-I]
is correct explanation for Statement-I ⊕
b. statement-I is True, Statement-II: is True; statement-II H 3 N − CH − CO − NH − CH − CO − NH − CH − CO − NH − CH − CO O

| | | |
is not a correct explanation for statement-I H R1 R2 H
c. statement-I is True, statement-II is False ⊙
H N − CH − CO − NH − CH − CO − NH − CH − CO − NH − CH − CO O
d. statement-I is False, statement-II is True | | | |
H R R H
Integer and Subjective Peptide R1 R2
25. Which of the following disaccharide will not reduce I H H
Tollen’s reagent? [JEE 2005] II H CH3
CH2OH CH2OH III CH2COOH H
HO O H H O OH IV CH 2 CONH 2 (CH 2 ) 4 NH 2
Structure (Q) H HO H OH V CH 2 CONH 2 CH2CONH2
H O H VI (CH 2 ) 4 NH 2 (CH 2 ) 4 NH 2
OH H OH H VII CH2COOH CH2CONH2
HOH2C CH2OH VIII CH2OH (CH 2 ) 4 NH 2
OH O H H O OH IX (CH 2 ) 4 NH 2 CH3
Structure (P) H HO OH H
30. A tetrapeptide has – COOH group on alanine. This
H O H
produces glycine (Gly), valine (Val), phenyl alanine (Phe)
OH H H OH and alanine (Ala), on complete hydrolysis. For this

tetrapeptide, the number of possible sequences (primary COOH
structures) with − NH 2 group attached to a chiral center HS
NH 2
is_____. [JEE Adv. 2013 P-I]
Thiol group (SH) is present in cysteine.
31. The total number of lone-pairs of electrons in melamine is
_____. [JEE Adv. 2013 P-I] O
||
32. The total number of distinct naturally occurring amino CH 3 — S — CH 2 — CH 2 — CH — C — OH
acids obtained by complete acidic hydrolysis of the |
NH 2
peptide shown below is_____. [JEE Adv. 2014 P-I]
O
Methionine
H NH 2
O O H O H O N
| | N N
N N N N N
N CH 2 O
| |
CH 2 O
Cytosine
H H O H O N
O |
H
33. The total number of lone pairs of electrons in N2 O3 is
10. (b) Ester in presence of aqueous KOH solution gives
[JEE Adv. 2015 P-I]
SNAE reaction so, following reaction takes place
ANSWERS and SOLUTIONS HOH2C O CH2OH HOCH2 O CH2OH

(a) As in cellulose β 1− 4 glycosidic linkage is present. O
1. || 
Aq. KOH
SNAE
→
O − C − Me OΘ
2. (d) As chain of natural rubber involves weak van der
OH OH
Waal force of interaction.
O HOCH2 OΘ CH2OH
3. (b, c) ||
+ Me − C − OΘ  →
Hemiketal
Ring opening O
4. (a)
OH
5. (b)
→ ⊕ ve silver mirror test
Tollen 's
Reagent
6. (d) C6 H12 O6 + 36ADP + 36H3 PO 4 + 6O 2 

→ In above compound reaction takes place in presence of
6CO 2 + 36ATP + 42H 2 O Aq. KOH (SNAE) and ∝-Hydroxy carbonyl compound
is formed which give ⊕ ve Tollen’s test so this
7. (d) R − I + AgF 
→ R − F + AgI (Swarts Reaction) compound will behave as reducing sugar in an aqueous
8. (a) KOH solution.
CHO CHO Aexperimental
H OH HO H 11. (a, d) Steric factor =
Acalculated
HO H H HO
Steric factor = 4.5
H OH HO H
H OH HO H It means Aexperimental > Acalculated
CH 2 OH CH 2 OH [This seems that reaction occurs more quickly than particles
D(+) glucose L(−) glucose collide, this concept of steric factor was introduced].
NH 2 CHO
9. (c) HO |
S COOH HI∆
12. (b) (CH − OH)4  →CH3 − CH2 − CH2 − CH2 − CH2 − CH3
C S n −Hexane
|| |
O NH 2 CH2 − OH
Biomolecules 257
13. (d) Structure of β -L-Glucopyranose is 21. (a) A→3; B→2; C→4
H (Mixture) (Separation method)
O H2O : Sugar ⇒ Recrystallization
HO CH2OH H H2O : Aniline ⇒ Steam distillation
OH H2O : Toluene ⇒ Differential extraction

H H OH
22. (b) A→3; B→4; C→1; D→2
OH H
(A) Wilkinson catalyst : RhCl(PPh3)3
14. (b) CH2OH CH2OH (B) Chlorophyll : C55H72O5N4Mg
O O (C) Vitamin B12 (also known as cyanocobalamin) contain
H H H H cobalt.
H H
(D) Carbonic anhydrase contains a zinc ion.
OH H O OH H
OH OH 23. (d) A→3; B→1; C→2; D→4
H OH H OH 24. (c) C6 H12 O6 +Fehling’s solution

Maltose
→ (C 6 H 11O 7 ) − + Cu
 O↓
Cu22O Ø
+ (Red ppt)
H 3O
25. In structure (P) both the rings are present in acetyl form
2 D-glucose therefore it will not hydrolyse in solution that’s why
Fehling solution cannot react with this. In structure (Q)
15. (b) cis–[PtCl2(NH3)2] is used in chemotherapy to inhibit
one ring present in the form of hemiacetal. This will
the growth of tumors.
hydrolyse in solution and it can reduce Fehling solution.
16. (d) Seliwanoff's test is used to distinguish aldose and
O
ketose groups. ||
26. (2) —C — O − and — NH 2 are basic groups in lysine.
17. (a) moles of C57 H110 O6 (s)
27. (6) Let number of glycine units = n
445
= = 0.5 Mass of decapeptide = 796
890
Mass of H 2 O needed = 162 g,
2C57 H110 O6 (s) + 163O2 (g) 
→ 114CO2 (g) + 110 H2 O(l )
Total mass = 958 g
110 55 47
n H2 O = = 958 × = 75 × n
4 2 100
55 958 × 47
m H2 O = × 18 =495 g ∴ n= ≈6
2 100 × 75
18 (d) Haemoglobin 
→ positively charged sol CH 2 OH
O OH
Ag –sol 
→ negatively charged sol 28. (8) H HO
H
H
19. (c) For the given structure 'uracil' is found in RNA. OH H
Total No. of stereoisomers = 24 = 16 which contain 8D –
O Configuration and 8L– Configuration.
NH 29. (4) Presence of –NH2 group containing substituent for R1

and R2 would be positively charged at pH = 7.0. Peptides
N O IV, VI, VIII and IX contain – NH2 group.
|
H 30. (4) Because –COOH group of tetrapeptide is intact on
alanine, its NH 2 must be participating in condensation.
20. (a) All the three statements are correct a/c to NCERT
∴ Alanine is at one terminus, – – – A.
(s-block) Elements.

To fill the 3 blanks, possible options are: O
(i) When NH2 group attached to non-chiral carbon
(2) OH — C NH 3
G V P
G P V CH 2
(ii) When NH 2 group attached to chiral carbon
V G P P V G
V P G P G V O
Where, Glycine (G) (3) HO C
Valine (V) NH 2
Phenyl alanine (P)
O
Alanine (A)
O C OH
So the number of possible sequences is 4.
31. Lone pairs = 6 (4) HO C NH
ɺɺ
ɺɺ
N ɺɺ
NH 2 NH 2 CH 2
N N
ɺɺ ɺɺ
Only glycine is naturally occurring amino acid. So, no. of
NH 2
ɺɺ
Melamine
distinct naturally occurring amino acids is 1.
33. (8)
32. This peptide on complete hydrolysis produces 4 distinct
ɺɺ :
O
amino acids which are given below: ɺɺ == N
:O ɺɺ ɺɺ == O
N ɺɺ +
O ɺɺ ɺɺ ɺɺ == N
:O ɺɺ –– N
O
ɺɺ :O:−
(1) H 2 N — CH 2 — C — OH Total no. of lone pairs = 8
ɺɺ
Glycine (natural)
Environmental Chemistry &

Environmental Chemistry & Chemistry in Everyday Life 259
25 Chemistry in Everyday Life

QUICK LOOK The plants grow in total darkness are called etiolated (Long,
thin, weak and yellow in colours).
The environment is the aggregate of all those things and set of Temperature: Temperature influences every reaction and
conditions which directly or indirectly influence not only the life activity of organisms. Temperature shows daily as well as
of organisms but also the communities at a particular place. Any annual variations. The phenomenon of change of temperature
external force or influence, which surrounds and affects the life between day and night and in different seasons of the year is
of a plant in any way, becomes a factor of its environment. These called thermoperiodicity. It is of two types, diurnal (or daily)
factors are called environmental factors and may be living and seasonal (or annual). Thermoperiodicity determines
(biotic) as well as non-living (abiotic). The abiotic factors affect periodical phenomena like seed germination, stem growth,
the structure, life history, physiology and behaviour of flower formation, fruiting, dispersal, maturation of gonads,
organisms. The biotic factors mostly influence growth and breeding, egg laying, etc. Low night temperature is suitable for
reproduction. The environmental conditions which influence the seed germination in many plants, e.g., Rumex, Asclepias.
life and development of plants, each part of the environment is Cooler nights also help in increasing size of tuber in Potato and
called ecological factor. Ecological factors are grouped into four fruit setting in Tomato. Organisms adapted to live at relatively
main classes (ecological factors) which are as follows: constant temperature during the whole year are known as
stenothermal, e.g., many palms, corals, snakes and some fishes.
Climatic factors: The study of climatic factors is known as The organisms which can tolerate large changes of temperature
climatology. The chief climatic factors are: are called eurythermal, e.g., Artemesia, Cyclops, Toad, Wall
Lizard.
Water: Rainfall is the chief source of soil moisture. Water
exchange between earth surface and atmosphere is called
On the basis of temperature the plants are classified as below:
hydrological cycle. Humidity of the air is expressed in terms of
Megatherms or Climate or Tropical: The vegetation
relative humidity. It is measured by hygrometer (Psychrometer).
growing in the condition in which high temperature prevails
Epiphytes and cryptogamic plants grow in those regions where
throughout the year (30–40°C). The dominant vegetation is
relative humidity is high.
tropical rain forest.
Light: Light (solar radiations) is a very important ecological Mesotherms: Climate-subtropical, the high and low
factor as it is the source of energy to the whole biosphere. It temperature alternates. The dominant vegetation is tropical
enters the biosphere through the process of photosynthesis decidous forest type. Those plants in which leaf fall takes
performed by green plants and other autotrophs. Here organic place once in a year are called deciduous plants e.g., Ficus
food is manufactured from inorganic raw materials. Solar energy religiosa (Sacred tree).
is changed into chemical energy of food. The radiant energy of Microtherms: The vegetation growing in the low
sunlight carries out all important functions, without this life temperature (10–20°C) condition. (The temperature remains
except few bacteria would disappear. On this basis of relative low throughout the year). The vegetation is mixed
light requirements and the effect of light on the overall vegetative coniferous forests type (Taiga).
development, plants are classified ecologically into following Hekistotherms: The vegetation growing in the very low
categories: temperature (0–10°C) conditions. The dominant vegetation
Heliophytes are popularly called sun plants because they is Alpine vegetation (Tundra).
grow in open in full sunlight. The plants growing at very low temperature are called
Sciophytes are shade plants which grow in areas having cryophytes or psychrophytes.
moderate to low intensity light, as below the shade of other
plants. Optimum growth occurs with light of 10–30% of full Wind: High wind velocity causes soil erosion, breakage and
sunlight. uprooting of trees. Most of the pollutants are dispersed through

the medium of air. Wind do harm in blossom trees because it Mesosphere: Next 40 km zone above stratosphere is called
prevents working of insects. Wind modifies the humidity. Dry mesosphere. Last limit of mesosphere is called mesopause.
winds cause dwarfing of plants. Wind helps in pollination, Ionosphere: Uppermost zone of atmosphere is ionosphere
dispersal of fruits and seeds and prevents frost damage. If the and in this zone all the gases are in ionised form.
areas are subjected to strong winds, the leaves of plants become
Fire: Fire may be man caused or natural. It is basically of three
small and rolled and these plants develop an overall shape that
types:
offer resistance to wind. Sometimes, shrubs and trees are
(i) Surface fire (ii) Ground fire (iii) Crown fire
planted to protect the field against wind. Such structures are
Such plants which grow well in fire burnt condition are called
known as wind breaks or shelter belts. These plants (Trees) are
pyrophytes or fire loving plants.
planted at 90° to the wind velocity.
Topographic or Geographic Factor: Topographic factors are
Atmospheric Humidity: Moisture in the form of invisible
concerned with the physical geography of the earth in an area.
vapours in atmosphere is called humidity. Atmospheric
The chief topographic factors are as follows:
humidity is generally expressed in terms of relative humidity
Micro climate refers to local combinations of factors such as
(R.H.) which is defined as, "amount of vapours in atmosphere
wind, rate of evaporation, humidity, temperature which differ
as the percentage of total amount which the air or atmosphere
from regional climate.
can hold at the existing temperature." Rate of transpiration is
inversely related to relative humidity. Area having high Altitude: Height of mountain chains. About 300 feet rise in
humidity have dense vegetation due to lower rate of altitude decreases temperature by 1°F. There is also increase in
transpiration. The areas with low relative humidity are dry. humidity and wind velocity. Slope winds are local wind
They produce sparse vegetation due to high rate of movements which are uphill during the daytime and downhill at
transpiration. R.H. is influenced by environmental conditions night. Shade caused by mountains reduces the total sunlight
like solar radiation, temperature, wind, etc. If temperature is falling on an area. Sunlight has more of ultraviolet rays. In high
high, R.H. is low and if temperature is low, R.H. is high. mountains situated in tropical areas, all the vegetation zones are
Atmosphere: Gaseous cover over the earth surface is called found – tropical, subtropical, temperate and alpine. With the
atmosphere. Earth's atmosphere is about upto height of 300 km, increase in altitude climate changed as decrease in temperature,
out of which 95% of gases is upto height of 20 km and rest 5% increase in humidity, increase in precipitation and increase in
in next 280 km. wind velocity.
Generally the vegetation that develops on base of mountain to
Earth's atmosphere is having a mixture of gases out of which top is Tropical → Temperate → Taiga → Tundra. Species
important ones are: diversity generally increases as one proceeds from high altitude
Table 25.1: Mixture of Gases in Atmosphere to low altitude and from high latitude to low latitude.
(1) Nitrogen 78.08% (by volume)
Steepness of the Slopes: Steep slopes cause fast running of
(2) Oxygen 20.84% (by volume)
water which result in erosion and do not permit the
(3) Argon 0.93% (by volume)
accumulation of humus so the soil becomes denuded. In such
(4) CO2 0.03% (300 ppm)
soil plants cannot grow properly and vegetation changes to
xerophytic plants.
Earth's atmosphere is divided into four different zones from
Exposure of Slopes: Exposure of slope to sun and wind affects
below to above:
very much the kind of plants growing there. Generally the slopes
Troposphere: First 20 km of earth's atmosphere is called
exposed to sun and wind supports vegetation. That’s why green
troposphere in which different physical phenomena, i.e.,
houses and hot beds are always built in a way to face sun or
lightening, thundering and cloud formation occur.
southern slopes which receive greater amount of solar energy.
Stratosphere: About 30 km zone over troposphere is called
stratosphere. Direction of Mountains Chain: Mountains steer or deflect
Temperature increases in this zone (upto 90ºC) due to ozone winds into different directions. Outer Himalayas show frequent
formation. In this zone under the influence of ultra-violet rains with luxuriant vegetations while the middle and inner
rays, this ozone layer is formed, which prevents entry of Himalayas are dry with poor vegetation. The southern slopes of
harmful UV-rays to reach the earth surface. Himalayas e.g., Kullu valley are directly exposed to sunlight

and has luxuriant mesophilous vegetation due to monsoon ownership. (grazing
Plantations, grounds, burial
wind. Whereas Northern slopes of Himalayas e.g., Lahul valley
pasture lands, grounds,
are exposed to weak light and strong dry wind, thus have ponds, water in village pond
xerophilous vegetation. wells etc are etc) public
some of the park, picnic
Edaphic Factor: The study of soil is called edaphology or examples of spots, play
pedology. The soil can be defined as “the upper crust of earth resources. In grounds in
surface in which plants roots are anchored.” The term soil is cities, people cities are
have plot, accessible to
derived from the Greek word, solum. houses and other all people
Table 25.2: Natural Resources (on the Basis of Exhaustibility) properties. living there.
Renewable Non-Renewable
Resources which can be used again Resources which can be used only Table 25.4: On the Basis of the Status of Development
and again once Potential Developed Stock Reserves
They can be reproduced, Once used they can not be Resources These are the Materials in the These are the
replenished and renewed reproduced, replenished or renewed. which are found resources which environment resources which
They take million of years in their in a region, but are available in which have the can be put into
formation have not been the country and potential to use with the
These are also called as These are also called exhaustible utilized human being satisfy human help of existing
inexhaustible resources. resources has been using needs but technical
them for a long human beings knowledge but
These includes solar energy, water These includes minerals of all types
time. do not have the their use has not
resources, geothermal energy, wind including energy minerals, coal,
appropriate been started.
energy, soil, forests and wild life petroleum, natural uranium,
technology to
resources thorium, iron ore etc.
access them.
Ex. Rajasthan E.g., E.g., Water is a E.g., River water
Table 25.3: On the Basis of Origin and Gujarat Agricultural and compound of can be used for
Biotic Abiotic have enormous Industrial two inflammable generating power
All living elements of the They comprises all non-living potential for the resources gases, hydrogen but presently it is
environment are included in biotic elements of environment development of and oxygen being utilised
resources. wind and solar which can be only to a limited
They go on reproducing or They are of both type—exhaustible energy, but used as a rich extent.
regenerating till favourable and inexhaustible these have not source of energy
conditions are available in the been developed but we do not
environment so for. know how to use
Eg. Crops, grass, animals, fish, Exhaustible— All types of minerals them.
forest, livestock and man himself. and conventional power resources
Inexhaustible– Water, air, solar Hazards of Mining: Mining is a hazardous industry; both for
energy etc. the workers and for the residents. The miners have to work
On the Basis of Ownership under tough conditions where no natural light is available.
Individual Community National International There is always a risk of collapse of mine roof, inundation with
resources owned Resources water and fire. The areas around mines face the problem of too
These are These are All the minerals, The oceanic
much dust from the mines. Slurry from mines damages the
owned privately accessible to water resources, resources
by individuals all the forests, wildlife, beyond 200 km roads and the farmland. Houses and clothes become dirty more
members of land within the of Exclusive often than in other areas. Miners are at great risk of getting
the political boundaries Economic zone afflicted with pulmonary disorders. Cases of respiratory tract
community and oceanic area belong to open diseases are very high in mining areas.
upto 12 nautical ocean and no
miles [Unit used to individual Conservation of Minerals: It takes millions of years for the
measure distances country can formation of minerals. Compared to the present rate of
at sea], (19.2km) utilise these
consumption, the replenishment rate of minerals is very slow.
from the coast without the
termed as territorial agreement of Hence, mineral resources are finite and non-renewable. Due to
water and resources international this, it is important that we conserve the mineral resources.
belong to the nation institutions
In villages, Village Petroleum: Petroleum is a major source of fuel for various
people have land commons uses. Petroleum also provides raw materials for various

manufacturing industries; like plastic, textiles, pharmaceuticals, Classification of Alluvial Soil
etc. Most of the petroleum in India is found in anticlines and On the basis of size of their grains: Duars, Chos and Terai
fault traps in the rock formations of the tertiary age. The oil On the basis of age: Bangar (old Alluvial)
bearing layer is a porous limestone or sandstone through which Khadar (New Alluvial)- More fine particles and more fertile
oil may flow. The intervening non-porous layers prevent the oil than Bangar.
from rising or sinking. Petroleum is also found in fault traps
Black Soil: These soils are black in colour and they are
between porous and non-porous rocks. Gas usually remains
eminently suitable for the cultivation of cotton. In some areas
above the oil because it is lighter than oil.
they are also called regur. They are sticky when wet and
Natural Gas: Natural gas is found along with or without develop deep wide cracks on drying which helps in the process
petroleum. It is used as fuel and also as industrial raw material. of self-aeration and absorption of nitrogen from the
Natural gas is mainly used by the fertiliser and power atmosphere. They have the capacity to hold moisture.
industries. Nowadays, use of CNG (Compressed Natural Gas)
Formation: Climatic conditions along with the parent rock
is increasing as vehicle fuel in the country.
materials are the important factors for the formation of black
Electricity: Electricity is generated mainly by two methods; by soil. The black colour is due to the presence of compounds of
running water which drives hydro turbines and by burning other iron and aluminium. They are rich in soil nutrients, such as
fuels like coal, petroleum and natural gas to drive turbines. calcium carbonate, magnesium, potash and lime and known for
its fertility. Cotton, cereals, oilseeds and many kinds of
Soil: Soil is one of the most important natural resources. Soil
vegetables are well suited to black soils.
supports the growth of plants. Soil is the natural home of many
living organisms, such as ants, rats, snakes, and many insects. Red and Yellow Soils: These soils comprising red loams and
Soils are derived largely from rocks and minerals broken down yellow earths are derived from crystalline igneous and
by weathering. It takes millions of soil up to a few cm in depth. metamorphic rocks rich in ferromagnetism minerals. It looks
Various Physical, Chemical and Biological processes help in yellow when it occurs in hydrated form.
formation of soil:
Laterite Soil: Soil develops in areas with high temperature and
Physical Processes: Rocks expanding and contracting in hot heavy rainfall. This is the result of intense leaching due to
sun and cold rain cracks and chips. Wind wears the rock away heavy rains. Humus content of the soil is low because most of
into tiny bits and water trapped in cracks expands when freezes, the microorganisms, particularly the decomposers, like bacteria,
splitting and breaking the rock. Running water usually carries gets destroyed due to high temperature. Laterite soils are poor
sand and gravel. in nitrogen, phosphoric acid, potash, lime and magnesia. They
are suitable for cultivation with adequate dose of manures and
Chemical Action: Oxygen and CO2 in the air and water
fertilisers. This soil is useful for growing tea, coffee and
combine with substances in the rock to alter it. Weak acid in
cashew nut.
rain attack the rock, some of the rocks dissolve; some softens
and in the end crumbles. Arid Soil: These soils are formed under arid and semiarid
conditions in the northwestern part of the country. These soils
Biological Processes: When plants die, they are decomposed
range from red to brown in colour. They are generally sandy in
by the microorganisms. Decomposed plants and animal
texture and saline in nature. These soils have a high soluble salt
material, called humus is an important addition to the
content and a low to very low humus content. They are rich in
developing soil. Animals also help by digging burrows and
phosphate but poor in nitrogen.
mixing the soil, improving its ability to hold air and moisture
Forest Soils: These soils are found in the hilly and
Alluvial Soil: These soils contain adequate proportion of mountainous areas. These forest soils are characterised by the
potash, phosphoric acid and lime which are ideal for the growth deposition of organic matter derived from forest growth.
Humus predominates in all forest soils. The soil is loamy and
of sugarcane, paddy, wheat, vegetables and other cereal and
silly in valley sides and coarse grained in upper slopes.
pulse crops. It is the most widely spread and important soil of
Soil Erosion: It is the removal of soil by the forces of nature
India. It covers about 24% of the country’s total land surface.
like wind and water. Generally there is a balance between soil
These soils are generally deficient in nitrogen and humus.
forming process and erosion process. Sometimes, this balance

is disturbed due to human activities like deforestation, On the basis of source of pollution, it can be of various
overgrazing, construction and mining etc. types:
Types of Soil Erosion Air Pollution

Water Erosion: Water is a powerful agent of soil erosion. Air or atmospheric pollution is the addition of materials or
Major types of erosion caused by water are: chemicals into atmosphere in such concentration that they begin
Sheet Erosion: When the top layer of the soil is removed over to exert adverse effect on human beings, other desirable species,
a large area by running water, it is called sheet erosion. It is human assets and resources. Total amount of air pollutants is
harmful because it removes the top layer which is finer and estimated to be 1×1012 tonnes, out of which pollutants added by
fertile. human activities are only 5 × 108 tonnes or 0.05%.
Gully Erosion: If erosion continues unchecked for sufficient Air Pollutants: The common air pollutants are : Dust, Smoke,
time, small finger shaped grooves develop on the landscape, Carbon monoxide (CO), Ammonia (NH3), Sulphur dioxide
called Rill Erosion, with further erosion of the soil, the rills may (SO2), Hydrogen sulphide (H2S), Nitrogen dioxide (NO2),
deepen and become enlarged and are ultimately turned into Hydrogen cyanide, Hydrogen fluorides, Chlorines, Phosgenes,
gullies. The main cause of gully erosion is the removal of Arsines, Aldehydes, Ozone, Ionising and radiations. CO2 is not
vegetation. Gullies cut up agricultural land and the entire area a normal air pollutant. There is 0.03% CO2 in the air and its
may be tuned into bad land. higher percentage is the cause of greenhouse effect.
Wind Erosion: Wind is a powerful agent of erosion in arid
and semi arid lands with little rainfall. Wind can lift the Types of Air Pollutants: It is of two types:
valuable topsoil from one area and deposit in another area. It
Primary Air Pollutants: Air is polluted by poisonous gases
is very dangerous type of erosion because due to wind most
and undesirable substances. They are released by burning fossil
of the deserts of the world are expanding.
fuels. These substances are called primary air pollutants. The
Soil Conservation: It includes all those measures, which help
primary air pollutants are the following:
in protecting the soil from erosion and exhaustion. Protective
soil ensures progress in agriculture; industrial development, Soot released from unburned fuel
economic betterment and a high standard of living so there is Sulphur dioxide (SO2)
urgent need to conserve soil. Benzopyrene (hydrocarbon) released from cigarette smoke
Afforestation: It means increase area under forest. Ammonia (NH3)
Indiscriminate felling of trees should be stopped and efforts Oxides of nitrogen
should be made to plant trees in new areas. Carbon monoxide (CO)
Lead (Pb)
Crop rotation: Terracing and contour ploughing across the hill
slopes is a very effective and one of the oldest methods of soil Secondary Air Pollutants: Secondary air pollutants are
conservation. Shelter belts (the rows of trees) can also reduce poisonous substances formed from primary air pollutants. In
soil erosion because these break the force of wind and water. bright sunlight nitrogen, nitrogen oxides, hydrocarbons and O2
Strip cropping (growing strips of grass between the crops) can interact to produce more powerful photochemical oxidants like
break up the force of wind and reduce erosion. ozone (O3), peroxyacetyl nitrate (PAN), aldehydes, sulphuric
acid, peroxides, etc. All these constitute photochemical smog,
Natural Pollution: It is pollution caused by natural sources,
which retard photosynthesis in plants.
e.g., volcanic eruptions, release of methane by paddy fields and
Causes of Air Pollution
cattle, release of carbon monoxide by plants and animals,
Agriculture: Hydrocarbons released by plants, pollen
emission of natural gas, ozone, nitrogen oxides, soil erosion,
grains, insecticides etc. cause air pollution.
dust storms, cosmic rays, ultraviolet rays, etc.
Dust: Dust in the air is increased by dust storms wind,
Anthropogenic or Man-made Pollution: It is pollution caused by volcanoes, automobiles, etc.
human activities like noise, automobiles, industries, smoking, Industries: Combustion of fossil fuels like coal, petroleum,
pesticides etc. Anthropogenic pollution is often quite small in etc. Industrial smoke is the main source of pollution.
quantity as compared to natural pollution. Example, 0.05% of Automobiles: The combustion of petrol and diesel in
atmospheric pollution is man-made while 99.95% is natural automobiles releases harmful gases into the air. They
pollution. also produce dust.

Ionising radiations: Ionizing radiations include alpha Respiratory disorders: Excessive ethylene accelerates
particles, beta particles and gamma rays. They are released respiration causing premature senescence (old age) and
into the air on testing atomic weapons. abscission (accumulation of yellow fluid (pus) in the body).
Freons: Use of freons and other chlorofluorocarbon Aldehydes irritate nasal and respiratory tracts. Chlorine and
compounds in refrigerants, coolants and as filling agents in phosgenes (carbonyl chloride) cause pulmonary oedema.
aerosol also cause pollution. Bronchitis is another bad effect of air pollution.
Aerosols: Aerosols are small particles of all sorts of solid or Nausea: H 2S smells like rotten eggs and causes nausea.
liquid substances suspended in the air. They block the Vomiting: SO 2 causes vomiting.
stomata of plants and prevent the gaseous exchanges Jaundice: Arsines induce RBC breakdown and jaundice.
between plants and atmosphere. They may also change the Oxygen carrying capacity: CO reduces O 2 carrying
climate of an area. capacity of RBC by its permanent combination with
haemoglobin.
Biological Indicators: Some plants are sensitive to certain air Coughing: Coughing is induced by phosgenes (carbonyl
pollutants. These plants are used to indicate the presence of these chloride).
substances. These plants are called biological indicators. e.g., Headache: SO 2 causes headache.
The tissues present in the tip of dasheri mango turns black
Cancer: Cancer is caused by air pollutants like ash, soot,
when they are exposed to sulphur dioxide (SO 2 ) fumes.
smoke, chromium, nickel and radioactive elements.
Pinto beans and Petunias are used to indicate the presence Mutation: Radioactive elements produce mutation. Ozone
of peroxy acetyl nitrate (PAN). produces chromosomal aberrations.
Tobacco and annual blue–grass plants are used to show the
Cardiac diseases: Cadmium causes high blood pressure
presence of ozone (O3 ). Lichens are biological indicators and heart diseases.
of air pollution caused by SO 2 . Pneumonia: Pneumonia is caused by breathing in too much
of manganese particles.
Ecological Effects of Air Pollution Depletion of ozone umbrella: In the atmosphere, about 30
Death: When air is polluted with poisonous gases, death km above the surface of the earth, the ozone molecules (O3)
comes as a result immediately. Bhopal episode is a good form an umbrella. It prevents the penetration of harmful
example. Bhopal episode – On 2nd December 1984 about ultra violet radiation from the sun and thus protects the life
3000 human beings died, due to the leakage of methyl of the earth. It is now feared that there is danger of
isocyanate (toxic gas) into the air from an insecticide plant depletion of the ozone umbrella, which may occur by the
managed by Union Carbide Corporation. use of freons and other CFC-compounds in refrigerants,
Chlorosis: The disappearance of chlorophyll is called coolants in domestic refrigerators and cold storage facilities,
chlorosis. It is caused by SO 2 , nitrogen dioxide, ozone and and as filling agents in the form of plastics and in aerosol
fluorides. packages. On reaching the ozone umbrella, they destroy
Necrosis: The breakdown of cells is called necrosis. It is ozone molecules as a result of photochemical reactions.
caused by SO 2 , nitrogen dioxide, ozone and fluorides. Over the past 16 years, the density of the ozone layer has
Greenhouse effect: CO 2 is released into the air by the been diminishing at an average rate of 3%. It is calculated
combustion of fuels. It is estimated that CO 2 content of that the depletion of ozone layer by 1% results in an
increase in the incidence of skin cancer by 5% to 7%. A
the air is increasing at the rate of 0.4% per annum. This
will result in an appreciable warming up of the earth. hole in O3 layer has been discovered over Antarctica.
This is called greenhouse effect. Acid rain: One of the major environmental issues facing
Crop losses: Heavy loss of crop is caused by smog. Smog human society at the national and international level is the
denotes a combination of smoke and fog. The important problem of rain water having low pH. The rainwater is
components of smog are ozone and PAN (peroxy acetyl always slightly acidic as CO2 in the atmosphere gets
nitrate). They damage leafy vegetables, cereals, textile dissolved in it. However during recent years, it has been
crops, ornamental plants, fruits and forest trees. noted a further lowering of pH of rain water often as low as
2.4. This lowering of pH is due to the dissolution of acids in

the rain water. Precipitation of oxides of sulphur and Causes of Water Pollution
nitrogen with rain is termed acid rain. Acid rain is caused Domestic sewage: Domestic sewage consists of human
by air pollution. When atmospheric air contains sulphur faeces, urine, and the dirty used–up water in houses. It
dioxide (SO2) and oxides of nitrogen such as nitrous oxide contains a large number of bacteria and virus. The sewage is
(N2O) and nitric oxide (NO), they dissolve in rain water released into the rivers on the banks of which most of the
forming sulphuric acid and nitric acid. The rain water falls cities are situated.
Industrial effluents: All industrial plants produce some
as acid rain.
organic and inorganic chemical wastes. Those nonusable
Acid rain affects both materials and organisms. It attacks
chemicals are dumped in water as a means of getting rid of
building materials principally sandstone, limestone, marble,
them. The industrial wastes include heavy metals (Hg, Cu,
steel and nickel. In plants, it leads to chlorosis (gradual
lead, zinc etc), Detergents, Petroleum, Acids, Alkalies,
yellowing in which the chlorophyll making mechanism is Phenols, Carbonates, Alcohol, Cyanides, Arsenic, Chlorine,
impeded) or depigmentation of leaves. etc.
Acid rain increases the acidity of lakes and rivers. Vast Thermal pollution: Hot effluents and hot water (e.g.,
tracts of forests and lakes in Europe and North America thermal plants/atomic reactors) bring about rise in water
have been destroyed by acid rain. Acidity kills fish, bacteria temperature. Warm water contains less oxygen, has lower
and algae and the aquatic ecosystem collapses into sterility rate of putrescibility resulting in increased organic loading,
leaving a crystal clear but ultimately a dead lake. replacement of green algae by blue-green ones. Many
animals fail to reproduce e.g., Trout, Salmon.
Control of Air Pollution
The emission of exhaust from automobiles can be reduced Noise Pollution
by devices such as positive crankcase ventilation valve and Noise is unwanted annoying sound of generally 80 dB and
above. It is a physical non-persistent pollution which affects the
catalytic converter.
receiver directly. Upto a certain limit, the effect depends upon
Electrostatic precipitators can reduce smoke and dust from
the mood and upbringing of the person.
industries.
Gaseous pollutants arising from industries can be removed Frequency: Frequency of sound is measured in cycles per
by differential solubility of gases in water. second called Hertz or Hz. Human hearing lies within the
A finepray of water is the device called scrubber can frequency of 50-15,000 Hz. Below 50 Hz is infrasound while
separate many gases like NH3, SO2, etc. from the emitted above 15,000 Hz is ultrasound. Infrasonic sound or infrasound
exhaust. waves cannot be listened but certain body parts resonate at this
frequency. Therefore, they can be felt. Infrasound can damage
Vehicles based on compressed natural gas (CNG) should be
the body parts. Ultrasonic vibrations or ultra sound waves are
introduced.
employed in imaging, cleaning, drilling, cutting, welding and
sealing packages.
Water Pollution
Water pollution is degradation of quality of water due to Loudness: Loudness of sound intensity is measured in decibels
addition of substances (e.g., silt), chemicals (e.g., metals, or dB.
inorganic and organic chemicals) or factors (e.g., heat) and Some Boom: It is a series of shock waves left behind by a
supersonic jet flying at a speed of more than one Mach (speed
deprivation that makes it a health hazard, unfit for human use,
of sound). It produces sudden rattling of windows and doors.
use by animals and industries as well as growth of aquatic
Buildings may develop cracks. Startle reaction may appear in
biota. Water pollutants belong to three categories – biological,
human beings and animals.
chemical and physical.
Sources of Noise Pollution: Natural sources of noise pollution
are rare (e.g., thunder of clouds). Man-made noise pollution is
Water pollutants: The common water pollutants are: Domestic
also a recent phenomenon. The important sources are as
sewage, Industrial effluents, Pesticides, Herbicides, Fertilisers,
follows:
Bacteria and Viruses, Plankton blooms and Heavy metals like
Loudspeakers
Mercury, Temperature, Silt, Radioactivity, Oils etc. Commercial establishments

Builders elements: oxygen, carbon, hydrogen, nitrogen, calcium, and
Defence equipment phosphorus. Every organic molecule contains carbon. Since 65-
Agricultural machines 90% of each body cell consists of water (by weight), it isn't
Industries surprising that oxygen and hydrogen are major components of
Crackers the body. So is your dog. So is your desk. So is the sun. Drugs
Transport vehicles are chemicals. Food is made from chemicals.
Effects: Noise brings about :

Dyes: These are coloured chemical substances capable of
Damage to ear drum and impairment of hearing (a ten year
imparting colours to the textiles, food stuff, leather, paper,
exposure to 80 dB impairs hearing by 15 dB).
cosmetics etc. Dyes can be classified on the basis of chemical
Interference in conversation and hearing.
composition and their applications:
Emotional disturbance, development of anxiety and stress
Direct dyes: These dyes stick to the fibre through hydrogen
(first effect).
bonding. They belong to the class of azo dyes. They are
Damage to eye sight, colour perception, night vision, etc.
used to dye the fabric directly by placing it in hot aqueous
Hypertension, changes in peripheral circulation and
solution of the dye. Some common examples are Martius
breathing pattern, decreased heart output and gastric
yellow, Congo red etc.
problems.
Acid dyes: They are characterised by the presence of
Headache, sleeplessness, annoyance and irritability.
Reduced productive performance. −COOH, − SO3H or phenolic group. They are applied in
the presence of acidic solutions. They are usually applied to
Control of Noise Pollution: Noise pollution can be controlled
wool, silk, nylon. They do not have affinity for cotton.
through three methods:
Common examples are orange-I, orange-II, methyl red,
Reduction at source
methyl orange, etc.
Protection of receiver
Basic dyes: These dyes contain – NH2 or – NR2 group as
Interruption in transmission
The various methods of controlling noise pollution are as follows: colour bearing groups or colour enhancing groups. They are
Sound Absorption: The sound entering residential areas and generally used for wool, cotton, leather, paper, polyester,
dwelling units should be reduced. Acoustic furnishing should nylon etc. Some common examples are aniline yellow,
be undertaken to absorb sound and reduce noise pollution. chrysoidine G, butter yellow, etc.
Disperse dyes: They are usually applied in the form of
Sound Diversion: High intensity sound should be deflected dispersion of finely divided dye in a soap solution in the
away from residential areas. presence of phenol, cresol, benzoic acid, etc. They are
mainly used to dye dacron, nylon and other synthetic fibres.
Quieter Machines: Efforts should be made to develop quieter
Celliton fast pink B and Celliton fast blue B are common
machines.
examples.
Loudspeakers: Their use should be restricted. Under no Vat dyes: These dyes are insoluble compounds which upon
condition the sound level be raised above 90 dB during the day reduction give soluble (leuco form) product. The reduced
and 60 dB during the night. product is generally colourless and has affinity for specific
Occupational Exposures: In case a person works in industry fabrics. Indigo is one such dye.
producing high intensity sound, ear plugs and ear muffs should Mordant dyes: A mordant is any substance which can be
be used for protection of ears. fixed to the fibre and which can be dyes later on. Mostly
hydroxides or basic salts of chromium, aluminium and
Traffic: Highway traffic is not allowed to pass through towns iron are used as mordants. A dye which imparts different
and cities. It is diverted throughby passes and over-bridges. colours in the presence of different mordants is referred to
Pressure horns are not allowed inside towns and cities. as mordant dye. For example, alzarin is a mordant dye.
When mordanted with aluminium salt solution, it imparts
Chemistry in Everyday Life rose-red colour to fabric but the same fabric is dyed blue
Everything is made of chemicals. You are made of chemicals when it is mordanted with barium salt. With ferric salts, it
99% of the mass of the human body is made up of only six dyes violet.

Cosmetics: The word cosmetics is derived from Greek word, with care to prevent inhalation of the fine particles which
kosmetikos. It means decorating or beautifying or improving irritate the lungs.
complexion of skin. Some of the cosmetics which find use in
daily life are discussed below: Deodorants: As the name suggests, deodorants are applied
primary to mask the body odour. The body odour results from
Creams: Creams are used for facial make-up. These are often
the bacterial action following perspiration. A deodorant must
classified as: Clearing creams, cold creams, vanishing cream,
therefore, possess antibacterial properties. Aluminium salts
sunburn creams and bleach creams.
have been found to possess excellent antibacterial properties. In
Cleansing creams: Remove facial make up, surface grime,
lipstick and oil.
addition to aluminium salts, ZnO and ( C17 H35COO )2 Zn also
Cold creams: Lubricate the skin and prevent roughness and find use in deodorants preparation because they are astringents
chaffing. as well as antiseptics.
Vanishing creams: Keep the skin cool and oily.
Sunburn creams: Save the skin from sunburn in summer. Chemicals in Medicine and Health Care
Bleach creams: Exert a bleaching effect on dark skin. Chemotherapy: Chemical substances of natural or synthetic
origin which are used for curing diseases and reducing
Perfumes: Perfumes are the materials used to provide
suffering from pain are called medicines or drugs. The branch
fragrance. Several requirements have to be fulfilled to make a
of science which deals with the treatment of diseases using
good perfume and any material, which just gives good smell,
suitable chemicals is known as chemotherapy.
may not be a perfume.
A perfume invariably consists of three ingredients: a vehicle, Drugs and Medicines: A medicine is a chemical substance
fixative and odour producing substance. which cure the disease, is safe to use, has negligible toxicity
Vehicle or solvent: The role of the solvent is to keep the odour and does not cause addiction. In contrast, a drug is a chemical
producing substances in solution. Ethanol and water mixture is substance which also cures the diseases but habit forming
the most common vehicle used in perfumery. causes addiction and serious side effects.
Fixative: The function of the fixative is to equalise the rate of
Classification of Medicines: Medicines are generally
evaporation of various odoriferous components of the perfume
classified according to the purpose for which they are used. The
by suitably adjusting their volatility. Sandal wood oil finds use
different terms thus used along with examples are given below:
as fixative. Other substances used as fixative are benzoin,
glyceryl diacetate and esters of cinnamyl alcohol.
Analgesics: Medicines used for getting relief from pain are
Odoriferous Substance: Both natural and synthetic
called analgesics. These are of two types:
substances are used to impart odour to a perfume. For
example: terpenoids like linalool which occur in essential (i) Narcotics: Drugs which produce sleep and unconsciousness
oils are natural odour producing compounds while are called narcotics.
anisaldehyde (p-methoxy-benzal-dehyde) is a synthetic e.g. Morphine, codeine, marijuana etc.
odour producing compound.
(ii) Non-narcotics: Aspirin (2-acetoxybenzoic acid) is the most
Talcum Powder: Talcum powder is used to reduce irritation of
commonly used analgesic with antipyretic (temperature
the skin. Talcum powder, like face powders, contain talk
lowering) properties.
[Mg
(Mg33 (OH) 2 Si 4 O10 ].
) Chalk, zinc oxide, zinc sterate and suitable
perfume act as the other main constituents of talcum powder. Nowadays because of its antiblood clotting action, aspirin is
Often specific ingredients like antiseptic and cooling agents are widely used to prevent heart attacks. Other examples are
added. The role of the talk is to act as a powder base and to Ibuprofen, Naproxen etc.
make skin smooth. Chalk absorbs secretion (perspiration)
without showing any evidence of such absorption. Zinc oxide OCOCH3 CH 3
|
masks enlarged pores and mirror blemishes, whereas zinc COOH CH — COOH
makes powder adhere to skin. Baby talcum powder contain
considerable amounts of zinc sterate for adhesiveness and boric H 3C
2-Acetoxybenzoic acid (acetoxybenzoic acid) Naproxen
acid, for antiseptic purposes. Talcum powders need to be dusted or acetylasalycylic acid (aspirin)

Salol (Phenyl Salicylate): Salol is used as an
H 3C — CH — CH 2 — —CH — COOH intestinal antiseptic for throat ailments.
| |
CH3 CH Mercurochrome Solution (2–5%): Mercurochrome
Ibuprofen 3
solution is used as an antiseptic for skin, mucous
Tranquillizers or Hypnotics: The drugs which act on the surfaces and wounds.
central nervous system (CNS) and help in reducing stress and Cresols (Lysol): A solution of cresols (i.e. m and p-
fatigue by inducing a sense of well being are called methyl phenols) in soapy water in called lysol and is
tranquillizers. used as disinfectant.
The most commonly used tranquillizers are barbituric acid and Antimicrobials: Drugs used to cure diseases caused by
its 5, 5-disubstituted derivatives such as veronal, luminal, microbes or microorganisms such as bacteria, viruses, fungi etc.
seconal, amytal and nembutal. are called antimicrobials. These include antibacterial,
Chlordiazepoxide and meprobamate are relatively mild antifungal and antiviral agents.
tranquillizers and hence are used for relieving tension. Equanil
Control of Microbial Diseases: All the microbial diseases are
is used for reducing depression and hypertension.
controlled by the following three methods:
Reserpine isolated from the Indian plant Rauvolfia serpentina is By using the bactericidal drug, i.e. a drug which kills the
also a powerful tranquillizer. It also slows down the pulse rate organisms in the body.
and lowers the blood pressure. By using the bacteriostatic drugs i.e. a drug which inhibits
or arrests the growth of the organism.
Antiseptics and Disinfectants
By increasing the immunity and resistance of the body of
Antiseptics: Antiseptics are the chemical substances which
infection.
prevent the growth of microorganisms and may even kill them.
Some important antimicrobial drugs are:
Disinfectants: Disinfectants are chemical substances which kill (i) Antibiotics (ii) Sulpha drugs
microorganisms but are not safe to be applied to the living
Antibiotics: Antibiotics are now defined as chemical
tissues. They are generally used to kill the microorganisms
substances (produced wholly or partially by chemical
present in drains, toilets, floors etc.
synthesis), which in low concentration, either kill or inhibit the
A few examples of disinfectants and antiseptics used in growth of microorganisms by intervening in their metabolic
everyday life are given below: processes.
Chlorine: A low concentration of chlorine i.e. 0.2 to 0.4 Example: (i) First antibiotic, penicillin (ii) Chrysogenum
parts per million (ppm) is used for sterilisation of water to
Types of Antibiotics: The antibiotics can be either bacterial or
make it fit for drinking purposes.
bacteriostatic.
Dettol: Antiseptic is a mixture of chloroxylenol and
Terpineol in a suitable solvent. Bactericidal Bacteriostatic
Bithional: It is added to good quality soaps to reduce the Penicillin Erythromycin
odours produced by bacterial decomposition of organic Aminoglycosiders Tetracyline
matter on the skin. Ofloxacin Chloramphenicol
Iodine: Iodine is a powerful antiseptic, it is used as tincture Broad Spectrum Antibiotics: The full range of micro-
of iodine (which is 2–3% solution of iodine in alcohol and organisms attacked by an antibiotic is called its spectrum.
water). Broad spectrum antibiotics are effective against several
Iodoform (CHI 3 ) : It produces iodine on coming in different types of harmful bacteria.
contact with skin and is used as antiseptic powder for Example: Tetracyline, Vancomycin and ofloxacin and a
wounds. mixture of potent antibiotics, chloramphenicol.
Boric acid: Boric acid in the form of dilute aqueous Sulpha Drugs: A group of drugs which are derivatives of
solution is a mild antiseptic and used for eye wash. It sulphanilamide are called sulpha drugs.
also forms part of antiseptic baby powders.
Hydrogen Peroxide: Hydrogen peroxide is also used H2N — —SO 2 NH 2
as an antiseptic under the name perhydrol for washing (Sulphanilamide)
wounds, teeth and ears. (p-amino benzene sulphonamide)

N H 2 C — OH
Sulphadiazine H 2 N — —SO 2 — NH —
N
Sulphadiazine + 3NaOH 
→ HC – OH + 3C15 H 31COONa
Soap
(Sodium palmitate )
Sulphapyridine H 2 N — —SO 2 — NH — H 2 C — OH
N Glycerol
Sulphapyridine
NH Non-soapy Detergent or Synthetic Detergents: This is the

Sulphaguanidine H 2 N — —SO 2 — NH — C
NH 2 sodium salt of a long chain benzene sulphuric acid or the
Sulphaguanidine
sodium salt of a long chain alkyl hydrogen sulphate. Synthetic
Antihistamines: These drugs are also anti allergic drugs since detergents are prepared by reacting hydrocarbons from
they are used to treat allergy i.e. skin rashes, inflammation of petroleum with concentrated sulphuric acid and converting the
tissues, asthma (Breathing difficulties) and itching of hives. product into its sodium salts e.g.,
Since allergy is caused due to release of histamine in the body, Anionic detergents
therefore these drugs are also called antihistamines. Example:
+
Diphenhydramine, cetrizine, chlorpheniramine, promethazine C12 H 25 — —SO3 N a
etc.
Sodium p-dodecyl
Benzene sulphonate
Antacids: Substances which neutralise the acid and raise the +
pH to an appropriate level in stomach are called antacids. The C12 H 25 — O — SO 2 — O N a
most commonly used antacids are: magnesium hydroxide,
Sodium lauryl sulphate
magnesium carbonate, magnesium trisilicate, aluminium
hydroxide gel, sodium bicarbonate and aluminium phosphate. Cationic detergents
+
 CH 3 
Detergents: Detergents are substances which remove the dirt  | 
 H 3C ( H 2 C )15 − N − CH 3  Cl−
and have cleansing action in water. There are two types of  | 
detergents:  CH 3 
Cetyltrimethyl ammonium chloride
Soap: A soap is a sodium or potassium salt of some long chain

Non-ionic Detergent CH 3 (CH 2 )16 COO(CH 3 O)n⋅ CH 2 CH 2 OH
carboxylic acids (fatty acids). Sodium salts of fatty acids are
known as hard soaps and potassium salts of fatty acids are Advantages of Synthetic Detergents over Soaps
known as soft soaps. Hard soaps are used for washing purpose Synthetic detergents can be used even in hard water
and soft soaps are used as toilet soaps, shaving creams and whereas some of the soaps gets wasted if water is hard.
shampoos. Some examples of soap are sodium stearate, Synthetic detergents have a strong cleansing action than
C17 H35 COO − Na + , sodium palmitate, C15 H 31COO − Na + and soaps.
sodium oleate. C17 H33 COO − Na + . Soap is prepared by heating

oil or fat of vegetable or animal origin with concentrated
sodium hydroxide solution.
1. Which of the vitamins given below is water soluble?
O
|| [JEE Main 2015]
H 2 C — O — C — C15 H 35 a. Vitamin C b. Vitamin D
O c. Vitamin E d. Vitamin K
||
HC — O — C — C15 H 35 + 3NaOH 
→
2. Which of the following compounds is not an antacid?
O
|| [JEE Main 2015]
H 2 C — O — C— C15 H 35 a. Aluminium hydroxide b. Cimetidine
( Tripalmitin )
fat or oil c. Phenelzine d. Ranitidine

3. The concentration of fluoride, lead, nitrate and iron in a 10. Which of the following conditions in drinking water
water sample from an underground lake was found to be causes methemoglobinemia ?
1000 ppb, 40 ppb, 100 ppm and 0.2 ppm, respectively. a. > 50 ppm of lead b. > 100 ppm of sulphate
This water is unsuitable for drinking due to high c. > 50 ppm of chloride d. > 50 ppm of nitrate
concentration of: [JEE Main 2016]
11. The temporary hardness of water is due to:-
a. Fluoride b. Lead
[JEE Main 2019]
c. Nitrate d. Iron
a. Ca(HCO3)2 b. NaCl
4. Which of the following is an anionic detergent? c. Na2SO4 d. CaCl2
a. Sodium stearate [JEE Main 2016]
b. Sodium lauryl sulphate 12. Water filled in two glasses A and B have BOD values of
c. Cetyltrimethyl ammonium bromide 10 and 20, respectively. The correct statement regarding
d. Glyceryl oleate them is: [JEE Main 2019]
a. A is more polluted than B
5. The distillation technique most suited for separating
glycerol from spent-lye in the soap industry is: b. A is suitable for drinking, whereas B is not
a. Simple distillation [JEE Main 2016] c. B is more polluted than A
b. Fractional distillation d. Both A and B are suitable for drinking
c. Steam distillation 13. The reaction that is NOT involved in the ozone layer
d. Distillation under reduced pressure depletion mechanism is the stratosphere is:
6. A water sample has ppm level concentration of following [JEE Main 2019]
anions F– = 10, SO24− = 100 , NO3− = 50 . The anion/anions i i
a. HOCl(g) →OH(g) Cl(g)
ho
that make/makes the water sample unsuitable for drinking

i i
is/are b. CF2Cl2 (g) →Cl(g) CF2Cl(g)
uv
a. only SO 24− b. only NO3−

c. CH 4 + 2O3 
→ 3CH 2 = O + 3H 2 O
c. both SO 24− and NO3− d. Only F− i i
d. ClO(g)+O(g) 
→Cl(g) O2 (g)
7. The recommended concentration of fluoride ion in
drinking water is up to 1 ppm as fluoride ion is required to 14. A 10 mg effervescent tablet containing sodium
make teeth enamel harder by converting [3Ca3 (PO4)2. bicarbonate and oxalic acid releases 0.25 ml of CO2 at T =
Ca(OH)2] to [JEE Main 2018] 298.15 K and p = 1 bar. If molar volume of CO2 is 25.0 L
a. [3{Ca3(OH)2}.CaF2] under such condition, what is the percentage of sodium
b. [CaF2] bicarbonate in each tablet? [Molar mass of NaHCO3 = 84
c. [3(CaF2).Ca(OH)2] g mol–1] [JEE Main 2019]
d. [3Ca3(PO4)2.CaF2]
a. 16.8 b. 8.4 c. 0.84 d. 33.6
8. Which is wrong with respect to our responsibility as a human
15. An example of solid sol is: [JEE Main 2019]
being to protect our environment? [JEE Main 2019]
a. Butter b. Gem stones
a. Avoiding the use of floodlighted facilities
c. Paint d. Hair cream
b. Restricting the use of vehicles
c. Using plastic bags 16. Peroxyacetyl nitrate (PAN), an eye irritant is produced by:
d. Setting up compost tin in gardens [JEE Main 2019]
a. Acid rain b. Photochemical smog
9. A water sample has ppm level concentration of the
c. Classical smog d. Organic waste
following metals: Fe = 0.2; Mn = 5.0; Cu = 3.0; Zn = 5.0.
The metal that makes the water sample unsuitable for 17. Taj Mahal is being slowly disfigured and discoloured.
drinking is: [JEE Main 2019] This is primarily due to:- [JEE Main 2019]
a. Zn b. Fe a. Water pollution b. Global warming
c. Mn d. Cu c. Soil pollution d. Acid rain

18. The higher concentration of which gas in air can cause 5. (d) Glycerol is high liquid with B.P. 290ºC. It can be
stiffness of flower buds? [JEE Main 2019] separated from spent-lye b distillation under reduced
a. SO2 b. NO2 pressure. Liquid is made to boil at lower temperature than
c. CO2 d. CO normal temperature by lowering pressure on its surface, so
19. Water samples with BOD values of 4 ppm and 18ppm, external pressure is reduced and B.P. of liquid is lowered
respectively, are: [JEE Main 2019] hence glycerol is obtained without decomposition at high
a. Highly polluted and Clean temperature.
b. Highly polluted and Highly polluted
c. Clean and Highly polluted 6. (d) NO3− : The maximum limit of nitrate in drinking water
d. Clean and Clean is 50 ppm. Excess nitrate in drinking water can cause
disease, such as methemoglobinemia.
SO24− : above 500 ppm of SO 24− ion in drinking water
20. The correct match between Column I and Column II is: causes laxative effect otherwise, at moderate levels it is
[JEE Main 2019]
harmless.
Column I Column II
F–: Above 2 ppm concentration of F– in drinking water
A. Norethindrone 1. Antibiotic
causes brown mottling of teeth.
B. Ofloxacin 2. Anti-fertility
∴ The concentration given in question of SO 24− and NO3−
C. Equanil 3. Hypertension
in water is suitable for drinking but the concentration of
4. Analgesics F– (i.e 10 ppm) make water unsuitable for drinking
a. A→2; B→3; C→4 purpose.
b. A→2; B→1; C→3
7. (c) F– ions make the teeth enamel harder by converting
c. A→4; B→3; C→1
[3(CaF2).Ca(OH)2]
d. A→2; B→3; C→1
[3Ca 3 (PO 4 ).Ca(OH) 2 ] to[3Ca 3 (PO 4 ) 2 .CaF2 ]
Hydorxyapathe Fluorapatite
[JEE Main 2019] 8. (c)
Column I Column II
A. Ester test 1. Tyr
9. (c) (i) Zn = 2.0 (ii) Fe = 0.2
(iii) Mn =5.0 (iv) Cu =3.0
B. Carbylamine test 2. Asp
C. Phthalein dye test 3. Ser 10. (d) Concentration of nitrate >50 ppm in drinking water
4. Lys causes methemoglobinemia.
a. A→2; B→4; C→1 11. (a) Ca(HCO3)2 is reponsible for temporary hardness of water.
b. A→3; B→2; C→1
12. (c) Two glasses "A" and "B" have BOD values 10 and
c. A→2; B→4; C→3
d. A→3; B→4; C→2 "20", respectively.
Hence, glass "B" is more polluted than glass "A".
ANSWERS and SOLUTIONS 13. (c)
1. (a) Vitamin ‘B’ and ‘C’ are water soluble. 14. (a)
2. (c) Phenelzine is antidepressant drug.

15. (b)
3. (c) Highest concentration is of nitrate (100 pm)
16. (b) Photochemical smog produce chemicals such as
4. (b) Sodium lauryl sulphate = detergent, anionic formaldehyde, acrolein and peroxyacetyl nitrate (PAN).
Cetyltrimethyl ammonium bromide = detergent, cationic
17. (d) Taj Mahal is slowly disfigured and discoloured due to
Glyceryl oleate = detergent, non-ionic
acid rain.
Sodium stearate = soap, anionic

18. (a) Due to acid rain high concentration of SO2 makes in (B) Aspartic (Asp)
plants the flower buds stiff and makes them fall. O NH 2 O
|| | ||
19. (c) Clean water would have BOD value of less than 5 ppm H — O — C — CH 2 — CH — C — OH
whereas highly polluted water could have a BOD value of
17 ppm or more. NH2
(C) Serine (Ser) HO — CH 2 — CH
20. (b) A→2; B→1; C→3 COOH
(A) Norethindrone – Antifertility
(D) Lysine (Lys)
(B) Ofloxacin – Antibiotic
NH2
(C) Equanil – Hypertension (tranquillizer) NH 2 — CH 2 — CH 2 — CH 2 — CH 2 — CH
COOH
21. (a) A→2; B→4; C→1
A. Ester test 2. Aspartic acid (Acidic amino acid)
(A) Tyrosine (Tyr)
NH 2 O B. Carbylamine 4. Lysine (NH2 group present)
| || C. Phthalein dye 1. Tyrosine (Phenolic group present)
OH CH 2 — CH — C — OH
Chemical Periodicity 273
26 Chemical Periodicity
QUICK LOOK The decrease in size along a period is due to the effect of
successive increasing nuclear charge without addition of a new
Periodic properties are directly or indirectly related to their shell, i.e., in each element of a given period a new electron is
electronic configuration and show a regular gradation on added in the same principal quantum number.
moving from left to right in a period or from top to bottom in a In the second period the nuclear charge increases from + 3 in Li
group. Some important periodic properties are : oxidation to + 9 in F. The increased nuclear charge attracts the electrons
number, shielding effect, atomic radii, ionisation energy, more strongly to the nucleus and thus decreases the size of the
electron affinity, electro-negativity, valency, density, m.pt. atom. In case of noble gases, the atomic radii are only the van
and b.pt. der Waal's radii which are naturally higher than the covalent
The radius of an atom is the distance between the centre of radii of other elements.
its nucleus and electrons in the last orbit. However, In a given group, atomic radius generally increases as one moves
according to quantum mechanics, there is no certainty about from top to bottom, e.g., in group 1 atomic size increases steadily
the exact position of electrons at any time. Theoretically, an from lithium to caesium, i.e. rCs > rRb > rK > rNa > rLi
electron, at one time, may be very close to the nucleus while The increase in size on descending a group is due to addition of
at other time it may be far away from the nucleus. In spite of extra shell which outweighs the effect of increased nuclear
these limitations we need to have some operational charge. Remember that He and Fr are smallest and largest atom
definitions of the term atomic radius. There are three respectively.
operational concepts of atomic radius.
(2) Ionic Radius: It is the effective distance from the nucleus
(1) Covalent Radius: It is half of the distance between the of an ion upto which it has its influence on its electron cloud.
nuclei of two like atoms bonded together by a single bond. Thus A cation is always much smaller than the corresponding atom.
covalent radius of carbon in a compound having C — C single Further, more the number of electrons removed, smaller will
bond can be determined by dividing the bond length by 2, i.e., be the size of the resulting positive ion.
C−C rFe > rFe2+ > rFe3+ .

rc = ∴ C − C = 2rc or rc + rc 1.26 0.76 0.64
2
where, rc is the single bond covalent radii (SBCR) of carbon. This is due to following two factors:
A cation formed by the loss of electrons may result in the
However, if atoms forming the covalent bond are different i.e.,
complete disappearance of the outer shell and since the
one is more electronegative than the other. Then the atomic
remaining inner shells do not extend so far in space, the
radius is determined by the relation
cation is much smaller than the metal atom.
A − B = rA + rB − 0.009 ( χ A − χ B )
Sodium atom (Na) → Sodium ion (Na+)
where χ A and χ B are electronegativities of the atoms A and B
(2, 8, 1) (2, 8)
respectively. This relation was given by Stevenson in 1941. Whenever a cation is formed, the ratio of nuclear charge to
In a given period, atomic radius generally decreases from left to the number of electrons (Z/e ratio) is increased with the
right and thus in any period, alkali metal is the largest and result the effective nuclear charge is increased and the electrons
halogen is the smallest atom. are pulled towards the nucleus. Consequently, the cation
In second period elements the covalent radii decrease from Li becomes smaller. An anion is always larger than the
to F. corresponding atom.
3Li 4Be 5B 6C 7N 8O 9F 10Ne Atomic radius of I = 1.23; Ionic radii of I– = 2.16
1.23 0.89 0.80 0.77 0.74 0.74 0.72 1.6 This is again due to following two factors: (a) Since in the

formation of an anion, one or more electrons are added, the calories per gram atom. In an atom, the energy required to
electron cloud expands and the ionic size increases. (b) In the remove first electron from a gaseous atom is called first
formation of anion, the effective nuclear charge decreases with ionisation energy. The energy required to remove one electron
the result the electrons get away from the nucleus and thus the from a unipositive ion to form a bipositive ion is called second
anion becomes larger than the corresponding atom. ionisation energy. Second ionisation energy is higher than the
In any particular group, the ions of elements increase in size on first. The reason is that in unipositive ion, left after the removal
moving from top to bottom. of one electron from the atom, the electrons are more firmly
In case of isoelectronic ions (ions having same number of bound to the nucleus than in the atom. Hence, more energy is
electrons but different nuclear charge); the greater the nuclear needed to remove the second electron.
charge, the greater is the attraction for electrons and smaller is A → A+ + e−1 (First I.E.)
ionic radius. Hence size of such ions decreases, which is as
A+ → A+2 + e−1 (Second I.E.)
follows
C−4 > N−3 > O−2 > F−1 > Ne > Na+ > Mg+2 > Al+3 A+2 → A+3 + e−1 (Third I.E.)
> Si+4 > P+5 > S+6 > Cl+7 Similarly, third ionisation energy is even more than second
Size of ions (in decreasing order) ionisation energy.
(1) Variation of Ionisation Energy in Periodic Table

(3) van der Waal's Radius: It is one-half of the distance Ionisation energy decreases in a group as the atomic number
between the nuclei of two adjacent atoms belonging to two increases. It is based on the fact that as we move down a
neighbouring molecules of an element in the solid state. group, the size of atom increases, and the outer electrons
The covalent radius is always smaller than the corresponding become farther away from the nucleus thus reducing the
van der Waal's radius. This is because of the fact that in the force of attraction and hence ionisation energy decreases.
formation of a chemical bond, the two atoms have to come Li Na K Rb Cs
closer to each other. This also explains why covalent bonds are 5.4 eV 1.0 eV 4.3 eV 4.2 eV 3.9eV
much stronger than the van der Waal's forces. It is important to Ionisation energy increases along a period with increase in
note that since the noble gases ordinarily do not form any atomic number. This is due to the size of atom since it
covalent bond, in crystals of noble gases, no chemical forces decreases along a period and outer electrons are most
are operating between the atoms. Hence the van der Waal's strongly attracted by the nucleus and hence more energy is
forces are the only attractive forces in these cases. In other required to remove the electron.
words, the van der Waal's radii constitute the atomic radii of Li Be B C N O F Ne
noble gases and since van der Waal's radii are larger than 5.4 9.3 8.3 11.3 14.6 13.6 17.0 21.6
covalent radii, atomic radii of noble gases are largest in their eV eV eV eV eV eV eV eV
respective periods (anomaly). The ionisation energies of inert gases are greater than that of
their immediate neighbour. It is due to their complete octet
Ionisation Potential or Ionisation Energy: The electrons in ns2p6 configuration which is highly stable. Therefore, it is
an atom are attracted by the nucleus. When an electron is to be very difficult to remove an electron from the outermost orbit
removed then work is done against this nuclear attraction. In of an inert gas.
other words, energy is required to remove an electron from an
atom. To understand the details of chemical behaviour of an (2) Factors Affecting the Value of Ionisation Energy
element we must have an indication of the energy with which Size of atom: With an increase in atomic size, the
an atom binds its electrons. This is obtained by the ionisation potential is reduced, since the distance of the
measurement of ionisation potential or ionisation energy. It outermost electron from the nucleus increases and hence the
may be defined as the energy required to remove an electron force of attraction decreases.
from the outermost orbit of an isolated gaseous atom in its The charge on the nucleus: With an increase in the nuclear
ground state. It is expressed in electron volts (eV) or kilo charge, there is an increase in force of attraction of nucleus

for electrons making the removal of the electrons more IE1 : Na < Al < Mg < Si < S < P < Cl < Ar
difficult. Thus an increase in nuclear charge increases the IE2 : Mg < Si < Al < P < S < Cl < Ar < Na
ionisation potential. IE1 of elements with very high values
The shielding or screening effect of inner shells: The Cl < H < O < Kr < N < Ar < F < Ne < He
valence electrons in a multi-electron atom are pulled by the
nucleus but are repelled by the electrons of the inner shells. (4) Importance of Ionisation Energy
The valence electrons, therefore, do not experience the total Lower is the ionisation potential of an element, more would
pull of the nucleus. Instead the total pull of the nucleus is be its reducing power and also reactivity.
reduced by the electrons in inner shells. This effect of It gives rough estimate about the basic character of the
reducing the force of attraction of nucleus by the inner elements.
shells is called screening effect. This effect is exhibited The relative values of ionisation potential and electron
maximum by s2p6 (the most stable) shell. Therefore, the affinity of two elements are related to the nature of bond
ionisation energy of K is much less than Cu, however, both formed during their combination.
have one electron in their fourth shell. The ionisation potentials provide an indication about the
number of valence electron (s) in an atom; the abnormally
K19 = 1s2 , 2s2 p6 ,3s2 p6 , 4s1
high value indicates that the electron removed is other than
Cu 29 = 1s2 , 2s2 p6 ,3s2 p6 d10 , 4s1 the valence electron.
The ionisation energy of K is 4.33 eV while that of Cu is IE1, IE2 and IE3 values are 5.39, 75.62 and 122.42 eV. Since
7.72 eV. This is due to a large screening effect of s2 p6 , the values shows sudden jump, it indicates that the number
of valence electron in its atom is one. Similarly, values of
penultimate orbit in K while s2 p6 d10 , penultimate orbit in
IE1, IE2 and IE3 as 9.32, 18.21 and 153.85 eV indicate that
Cu which exhibit little screening effect. the number of valence electrons in its atom is two.
Type of electrons involved: Ionisation energy also depends
upon the type, i.e., s, p, d or f, electrons which are to be
Electron Affinity
removed, s-electrons are closer to the nucleus and are more Those atoms whose nuclear forces are not completely screened
tightly held as compared to p, d or f electrons. Hence, by electronic shells, offer attraction for electrons. Such atoms
ionisation energy decreases in the order of s > p > d > f capture electrons if these are available within their effective
orbitals. fields to neutralise the electrostatic forces of the nucleus.
Completely filled or half filled sub-shells: According to Energy is always liberated whenever there is a force of
Hund's rule, completely filled or half filled orbitals are more attraction offered by an atom or ion, and this energy is called
stable. Therefore, it is comparatively difficult to remove the electron affinity. This may be defined as, ''the energy released
electrons from these shells. The ionisation energy of Be (9.3 when an extra electron is added to a neutral gaseous atom''.
eV) is more than B (8.3 eV) because Be has 2s2 When first electron is added in a neutral atom then some energy
configuration of the outermost orbit which is fully filled. is released that is called first electron affinity but in case of
Similarly, nitrogen (14.6 eV) has more ionisation energy second electron affinity energy will be absorbed due to
than oxygen (13.6 eV) because nitrogen has outermost shell electronic repulsion. Example as
configuration as 2s2p3 in which p shell is half filled and is
(a) O ( g ) + e − → O −( g ) + E1 ( ∆H = − ve, Exoenergic)
more stable. Similarly, ionisation energy of Mg is more than
Al and that of P is more than S. (b) O (−g ) + e − → O −2 + E 2 (∆H = + ve, Endoenergic)
Thus, higher the energy released in the process of taking up an
(3) Relative Ionisation Energies extra electron, the higher will be the electron affinity. Higher the
IE1 and IE2 of the 2nd period elements value of electron affinity of an atom, the more is its tendency to
IE1 : Li < B < Be < C < O < N < F < Ne change into anion. It is very difficult to determine the electron
IE2 : Be < C < B < N < F < O < Ne < Li affinity experimentally. The values have been calculated on the
IE1 and IE2 of the 3rd period elements basis of thermodynamic concepts. It is expressed in electron

volts. The values of inert gases are assumed to be zero because group and (→ ) represents a period.
they have stable ns2p6 configuration and unable to accept any Metallic Non-Metallic
electron. The values for alkali metals are between zero and one.
Metallic Decreases Non-Metallic Increases
The electron affinities of Be, Mg are zero since they have
(Electro +Ve) (Electro –Ve)
complete ns2 configuration which cannot accommodate extra
Increases Decreases
electron. Similarly, the values for N and P are very low because
they also have completely half-filled p orbitals (ns2p3) and are (b) Reducing nature decreases in a period while oxidising
more stable. nature increases. The reducing nature increases in a group
(1) Factors Affecting the Value of Electron Affinity while oxidising nature decreases.
Atomic size: The value of electron affinity decreases with the Reducing nature Oxidising nature
increase in the size of atom since the nuclear attraction
decreases down a group as the atomic number increases. Its Reducing Decreases Oxidising Increases
nature nature
value increases as we move along a period since the size of
Increases Decreases
atoms decreases along a period. The lower value of F than Cl
is due to the very small size of F in which negative charge is
(c) Stability of metal increases while activity of the metal
highly concentrated and repels the incoming electron thereby
decreases in a period and in a group stability decreases while
reducing the force of attraction of the nucleus towards the
activity increases.
adding electron and hence decreasing the electron affinity.
Thus, chlorine has a highest value of electron affinity. Stability of the metal
Nuclear Charge: The value of electron affinity increases
with increasing nuclear charge. Thus, its value increases Stability of Increases
the metal
with increase in nuclear charge along a period.
Decreases
Screening or Shielding Effect: The value of electron
affinity increases with the decrease in shielding effect of This trend is observed especially in IA, IIA and IIIA elements.
inner electrons. Besides, the value of electron affinity also (d) The basic nature of the oxides decreases in a period while
depends to some extent upon the type of orbital in which acidic nature increases. In a group, basic nature increases while
electron is added. The value is greater when electron enters acidic nature decreases.
's' orbital and decreases successively for p, d and f orbitals.
Basic nature of oxides Acidic nature of oxides
(2) Importance of Electron Affinity: Certain properties of the
elements are predicted on the basis of values of electron Basic nature Decreases Acidic nature Increases
of oxides of oxides
affinity.
Increases Decreases
The elements having high values of electron affinity are
capable of accepting electron easily. They form anions and
electrovalent compounds. These elements are electro- Electronegativity
negative in nature. The tendency of an atom in a compound to attract a pair of
The elements having high values of electron affinity act as bonded electrons towards itself is known as electronegativity of
strong oxidising agents, for example, F, Cl, Br, O,S, etc. the atom. It is important to note that electron affinity and
electronegativity both measure the electrons attracting power
On the basis of the general trend of ionisation potential and but the former refers to an isolated gaseous atom while the
electron affinity, the following properties can be predicted, latter to an atom in a compound. Thus electron affinity is
(a) Metallic nature decreases in a period while nonmetallic attraction for a single electron while electronegativity is for a
nature increases. Metallic nature increases in a group while pair of bonded electrons. Further electron affinity is energy
non-metallic nature decreases. The arrow (↓) represents a while electronegativity is a tendency.

Activity of the metal electronegativities of the atoms A and B respectively, the
factor 0.208 arises from the conversion of kcal to electron
Activity of Decreases
the metal volt (1 eV = 23.0 kcal/mole), while
Increases ∆E = Actual bond energy − (E A − A × E B− B )
(1) Factors Affecting the Value of Electronegativity
Pauling and Mulliken values of electronegativities are related
The size of the atom.
as: χ (Pauling) = 0.34 χ (Mulliken) – 0.2
Electronic configuration. Small atoms attract electrons more
than the larger one and are therefore more electronegative.
(4) Importance of Electronegativity: The following predictions
Secondly, atoms with nearly filled shell of electrons, will
can be made from value of electronegativity:
tend to have higher electronegativity than those sparsely
Nature of the bond between two atoms can be predicted from
occupied ones.
the eelctronegativity difference of the two atoms.
(2) Variation of Electronegativity in the Periodic Table (a) The difference X A − X B = 0, i.e., X A = X B the bond is
In a period, electronegativity increases from left to right. This purely covalent.
is due to decrease in size and increase in nuclear charge. Thus (b) The difference X A − X B is small, i.e., X A > X B , the
the alkali metals possess the lowest value, while the halogens bond is polar covalent.
have the highest. Inert gases have zero electronegativity. (c) The difference X A − X B is 1.7, the bond is 50%
In a group, electronegativity decreases from top to bottom.
covalent and 50% ionic.
This is due to increase in atomic size.
(d) The difference X A − X B is very high, the bond is more
If an element exhibits various oxidation states, the atom in the ionic and less covalent. The molecule will be represented in
higher oxidation state will be more negative due to greater such case as BA (B+ A − ) . Percentage ionic character may
attraction for the electron, e.g., Sn II (1.30) and Sn IV (1.90).
be calculated as,
(3) Electronegativity may be expressed on the following three Percentage of ionic character = 16(XA − XB ) + 3.5(XA − XB )2
scales: where X A and X B represents electronegativity of bonded
1. Mulliken's Scale: Mulliken regarded electronegativity as atoms A and B.
the average value of ionisation potential and electron This relation was given by A.L. Allerd (1961).
affinity of an atom. Greater the value of difference (X A − X B ), more stable will
Ionisation potential + Electron affinity be the bond.
Electronegativity =
2 H–F H – Cl H – Br H–I
2. Allred-Rochow Scale: Allred and Rochow defined electro- XA − XB 1.9 0.9 0.7 0.4
negativity as the electrostatic force exerted by the nucleus on
Stability decreases
0.359 Z
the valence electrons. Thus χ = + 0.744 where Z is Stability of compounds in which X A − X B is very small are
r2
the effective nuclear charge and r is the covalent radius of the unstable in nature, SiH 4 (0.3), NCl3 (0.0) , PH 3 (0),
atom in Å. AsH 3 (0.1) are unstable.
3. Pauling Scale: Pauling’s scale of electronegativity is the
(X O − X A ) difference predicts the nature of the oxides formed
most widely used. It is based on excess bond energies. He
determined electronegativity difference between the two by the element A. X O is the electronegativity of oxygen.
atoms and then by assigning arbitrary values to few XO − XA is large, the oxide shows basic nature, (e.g., Na 2O ).
elements (e.g. 4.00 to fluorine, 2.5 to carbon and 2.1 to XO − XA is small, the oxide shows acidic nature, (e.g., SO 2 ).
hydrogen), he calculated the electronegativity of the other
Ionic compounds having percentage ionic character less
elements. χ A − χ B = 0.208 ∆E where χ A and χ B are than 20% were found coloured, e.g.,

AgCl AgBr AgI Ag2S 2. Identify the least stable ion amongst the following
22% 18% 11% 8% a. Li + b. Be − c. B − d. C−
White Light yellow Dark yellow Black
3. Which of the following represent the correct order of
Lesser the percentage ionic character, darker will be the colour.
increasing first ionization enthalpy for Ca, Ba, S, Se and
Ar?
Elements of second period are known as Bridge elements.
a. Ca < S < Ba < Se < Ar b. S < Se < Ca < Ba < Ar
Their properties resemble with the properties of diagonal
c. Ba < Ca < Se < S < Ar d. Ca < Ba < S < Se < Ar
elements of third period.
For isoelectronic ions the size depends on the nuclear 4. The first ionisation potential of Na is 5.1 eV. The value of
charge. Greater is the nuclear charge, smaller is the size. electron gain enthalpy of Na + will be
The increase in magnitude of radii is more in the beginning a. −2.55 eV b. −5.1 eV
of a group because the difference in energy between energy c. −10.2 eV d. +2.55 eV
shells is more.
5. The group having isoelectronic species is
The ionisation potentials provide an indication about the
[JEE Main 2017]
number of valence electron (s) in an atom e.g., Na has IE2
>>> IE1 (because it has one valence electron) while Mg has a. O − , F − , Na + , Mg 2+
IE3 >>> IE2 > IE1 because it has two valence electrons and b. O 2 − , F − , Na + , Mg 2 +
attains noble gas configuration after losing 2 electrons. c. O − , F − , Na, Mg +
The highest I.E. in a period is shown by noble gas.
d. O 2− , F − , Na, Mg 2 +
The electronegativity of a series of transition metals is
almost similar. The electronegativity of all lanthanide’s are 6. Based on the compounds of group 15 elements, the correct
identical (≈1.1). statement(s) is (are) [JEE Adv. 2018 P-I]
The most electronegative element is Fluorine (value is 4.0 a. Bi 2 O 5 is more basic than N 2 O 5
on the Pauling scale). The least electronegative elements is b. NF3 is more covalent than BiF3
Cs and Fr with a value of 0.700. c. PH 3 boils at lower temperature than NH3
The electron affinity of exactly half-filled configuration is d. The N–N single bond is stronger than the P–P single
approximately zero and exactly zero for fully filled bond
configuration.
7. In general, the properties that decrease and increase down
The electron affinities of gaseous anions are always negative.
a group in the periodic table respectively, are:
Some of the polar crystals when heated produce electric
a. electronegativity and electron gain enthalpy.
current. This phenomena is termed as piezoelectric effect.
b. electronegativity and atomic radius.
All the elements of f- block (4f series – Lanthanides and
c. atomic radius and electronegativity.
5f series – Actinides) are placed in 3rd group (IIIB) and d. electron gain enthalpy and electronegativity.
form a separate block at the bottom of the periodic table.
8. The electronegativity of aluminium is similar to:
[JEE Main 2019]
a. Boron b. Carbon
One and More than One Correct c. Lithium d. Beryllium
1. The set representing the correct order of first ionization 9. The correct order of the atomic radii of C, Cs, Al and S is:
potential is [JEE Main 2019]
a. K > Na > Li a. S < C < Al < Cs
b. Be > Mg > Ca b. S < C < Cs < Al
c. B > C > N c. C < S < Cs < Al
d. Ge > Si > C d. C < S < Al < Cs

− 2 2
10. The correct option with respect to the Pauling electro- 2. (b) Be is the least stable ion, Be (1s 2s ) has stable
negativity values of the elements is [JEE Main 2019] electronic configuration, addition of electron decreases
a. Ga < Ge b. Si < Al stability.
c. P > S d. Te > Se
3. (c) Ionisation energy increases along a period from left to
11. The element with Z = 120 (not yet discovered) will be right and decreases down a group. The position of given
an/a : [JEE Main 2019] elements in the periodic table is as
a. transition metal b. inner-transition metal
c. alkaline earth metal d. alkali metal Group No. 2 16 18
Ca S Ar
12. The effect of lanthanoid contraction in the lanthanoid
Ba Se
series of elements by and large means: [JEE Main 2019]
This, the order of increasing ∆H IE1 is
a. decrease in both atomic and ionic radii
b. increase in atomic radii and decrease in ionic radii Ba < Ca < Se < S < Ar
c. increase in both atomic and ionic radii 4. → Na + + e − First IE
(b) Na 
d. decrease in atomic radii and increase in ionic radii
Na + + e − 
→ Na
13. The correct order of atomic radii is: [JEE Main 2019] Electron gain enthalpy of Na + is reverse of (ionisation
a. Ce > Eu > Ho > N b. N > Ce > Eu > Ho energy) because reaction is reverse so
c. Eu > Ce > Ho > N d. Ho > N > Eu > Ce
∆H(eq) = −5.1 eV.
Statement/Assertion and Reason 5. (b) Ions O 2− F− Na + Mg +2

14. Statement I: Band gap in germanium is small. And Atomic number = 8 9 11 12
–
Statement II: The energy spread of each germanium Number of e = 10 10 10 10
2− − + 2+
atomic energy level is infinitesimally small. Therefore O , F , Na , Mg are isoelectronic.
a. Statement-I: is True, Statement-II is True; Statement-II:
6. (a, b, c) Basic character of oxide decreases as we move
down the group.
b. Statement-I is True, Statement-II: is True; Statement-II
∴ Bi 2 O 5 is more basic than N 2 O 5 .
Covalent nature depends on the electronegativity
difference between bonded atoms.
NF3 is more covalent than BiF3 .
15. Statement I: Pb4+ compounds are stronger oxidizing
Boiling point of NH3 is more (due to H-bonding) than
agents than Sn4+ compounds. And
Statement II: The higher oxidation states for the group PH 3 .
14 elements are more stable for the heavier members of P–P single bond is stronger than N–N single bond (as in
the group due to ‘inert pair effect’. N, due to smaller size of atoms lone pair-lone pair
a. Statement-I: is True, Statement-II is True; Statement-II: repulsion will be more).
is correct explanation for Statement-I 7. (b) Electronegativity decreases as we go down the group
b. Statement-I is True, Statement-II: is True; Statement-II and atomic radius increases as we go down the group.
is not a correct explanation for Statement-I 8. (d) E.N. of Al = (1.5) ≈ Be (1.5)
c. Statement-I is True, Statement-II is False In a period
AR ↓
9. (d)
In a group (AR-Atomic radius)

1. (b) In a group, ionisation energy decreases down the
AR ↑
group Be > Mg > Ca

Atomic radii order : C < S < Al < Cs
Atomic radius of C : 170 pm 13. (c) Eu
Yb
Atomic radius of S : 180 pm size
Atomic radius of Al : 184 pm
Atomic radius of Cs : 300 pm
z
10. (a) B C Eu > Ce > Ho > N
Al Si
14. (c) Both statements I and II are true and II is correct
Ga < Ge
explanation of I.
Along the period electronegativity increases.
15. (c) Statement I is true. Stronger oxidizing agent is one
11. (c) Z = 120 which itself can easily by reduced. Pb4+ is unstable, due to
Its general electronic configuration may be represented as inert pair effect, can easily be reduced to stable Pb2+,
[Nobal gas] ns2 , like other alkaline earth metals. hence a stronger oxidising agent than Sn4+.
Statement II is false. Due to inert pair effect, the higher
12. (a) Due to Lanthanoid contraction both atomic radii and oxidation states of group 14 elements become less stable
ionic radii decreases gradually in the lanthanoid series. for heavier member.
Representative Elements: s- and p-Blocks Representative Elements: 281
27 s- and p-Blocks
QUICK LOOK water to produce corresponding hydroxides which are
strong alkalies e.g.,
The elements in the long form of the periodic table has been 2Na + 2H 2O 
→ 2NaOH + H 2
divided into four blocks, namely s, p, d and f blocks. The
elements of group I and II receive their last electron in Na 2 O + 2H 2 O 
→ 2NaOH
s-orbital. So they are called as s-block elements. The first Na 2 O 2 + 2H 2 O 
→ 2NaOH + H 2 O 2
element of a group differs considerably from the rest of the
elements of the same group. This anomalous behaviour is due to 2KO 2 + 2H 2 O 
→ 2KOH + H 2O 2 + O 2
Smaller size of their atoms Thus peroxides and superoxides also act as oxidising agents
Their higher ionisation energies since they react with H 2 O forming H 2 O 2 and O 2
Their higher electronegativites
respectively. The hydroxides of all the alkali metals are
Absence of vacant d-orbitals in their valence shell
white crystalline solids. They are strongest of all base and
High polarising power of its cation.
readily dissolve in water with the evolution of much heat.
Thus Li differs from the rest of alkali metals (Na, K, Rb and
Basic strength: The basic strength of these hydroxides
Cs) and Be differs from rest of the alkaline earth metals (Mg,
increases as we move down the group, Li to Cs. The
Ca, Sr and Ba).
hydroxides of alkali metals behave as strong bases due to
their low ionisation energies which decrease down the
Diagonal Relationship: On moving diagonally some members
group. The decrease in ionisation energies leads to
show similar properties with the members of next higher group
weakening of the bond between metal and hydroxide ion
which is particularly seen in the elements of second and third
and M – O bond in M – O – H can easily break giving M +
periods of the periodic table. However, the similarities shown
and OH − ⋅ This results in the increased concentration of
are far less pronounced than the similarities within a group.
hydroxyl ions in the solution i.e. increased basic characters.
Table 27.1: Diagonal Relationship Solubility and stability: All these hydroxides are highly
Group 1 Group 2 Group 13 Group 14 soluble in water and thermally stable except lithium
Period-2 Li Be B hydroxide.
∆
2LiOH  → Li 2 O + H 2 O
Period-3 Mg Al Si Formation of salts with acids: Alkali metals, hydroxides
The main reasons for the diagonal relationship are being strongly basic react with all acids forming salts.
Similarity in electropositive character NaOH + HCl 
→ NaCl + H 2 O
Similarity in polarising power
2NaOH + H 2SO 4 
→ Na 2SO 4 + 2H 2 O
Similarity in atomic or ionic radii
Halides: The alkali metals combine directly with halogens
Alkali Metals: The group I comprising Li, Na, K, Rb, Cs and under appropriate conditions forming halides of general
Fr are commonly called alkali metals. Francium is radioactive formula MX. These halides can also be prepared by the
action of aqueous halogen acids (HX) on metals, oxides,
and has a very short life (half life of 21 minutes), therefore very
hydroxides or carbonates.
little is known about it.
M 2 O + 2HX 
→ 2MX + H 2 O
General Characteristics of the Compounds of the Alkali MOH + HX 

→ MX + H 2 O
Metals M 2 CO3 + 2HX 
→ 2MX + CO 2 + H 2 O (M = Li, Na, K,
Oxides and Hydroxides: All the alkali metals, their
Rb or Cs)
oxides, peroxides and superoxides readily dissolve in
(X = F, Cl, Br or I)

Polarisation Effect: Minerals
When a cation approaches an anion, the electron cloud of the Be – Beryl (Be 3 Al 2Si 6 O18 ) and Phenacite (Be 2SiO 4 )
anion is attracted towards the cation and hence gets distorted. Mg – Magnesite MgCO 3 , Dolomite CaMg(CO 3 ) 2 , Epsomite
This effect is called polarisation. The power of the cation to MgSO 4 and H 2 O
polarise the anion is called its polarising power and the Ca–Limestone (CaCO 3 ), Fluoropatite [3(Ca 3 (PO 4 ) 3 ⋅ CaF2 )]
tendency of the anion to get polarised is called its polarisability.
Gypsum (CaSO 4 ⋅ 2H 2 O), Anhydrite (CaSO 4 )
The greater the polarisation produced more is the concentration
Sr – Celestite (SrSO 4 ), Strontianite (SrCO3 )
of the electrons between the two atoms thereby decreasing the
Br – Barytes (BaSO 4 )
ionic character or increasing the covalent character.
Electronic Configuration: The general electronic

configuration of alkaline earth metals is ns2.
Be – 1s2 2s2 Mg – 1s 2 2s2 sp 6 3s 2
Ca – 1s2 2s 2 2p6 3s 2 3p 6 4s2 Sr – [Kr]5s 2
Polarising Polarised Unpolarised
cation anion anion Ba – [Xe]6s 2 Ra – [Rn]7s 2
Figure: 27.1
Nature of metallic bonding in alkaline earth metals: In
alkali metal two electrons are involved in the metallic
Anomalous Behaviour of Lithium and its Diagonal
bonding. Moreover, sizes of alkaline earth metal ions are
Relationship with Magnesium
smaller than those of alkali metal ions. Consequently,
The properties of lithium are quite different from the properties
stronger metallic bonds are formed which result in the close
of other alkali metals. On the other hand, it shows greater packing of the atoms. Due to the presence of stronger
resemblance with magnesium, which is diagonally opposite metallic bonds, alkaline earth metals have
element of it. The main reasons for the anomalous behaviour of (1) Higher melting points
lithium as compared to other alkali metals are (2) Higher boiling points
The extremely small size of lithium atom and its ion. (3) higher densities
(4) Harder than the corresponding alkali metals.
Greater polarising power of lithium ion (Li + ), due to its
small size which results in the covalent character in its Density: The alkaline earth metals are denser and harder
compounds. than the corresponding alkali metals. The atoms of alkaline
Least electropositive character and highest ionisation energy earth metals have smaller size and are hence held by
as compared to other alkali metals. stronger metallic bonds, as compared to alkali metals.
Therefore, they are more closely packed in their crystal
Non-availability of vacant d-orbitals in the valence shell.
lattice which accounts for high density and increased
hardness of these elements.
Alkaline Earth Metals
The group 2 of the periodic table consists of six metallic Characteristic flame colouration: Except Be and Mg (due
elements. They are Beryllium (Be), Magnesium (Mg), to high ionization energy), the alkaline earth metals impart
Calcium (Ca), Strontium (Sr), Barium (Ba) and Radium (Ra). characteristic colours when introduced to flame of a burner.
This property is due to the ease of excitation of their
The name alkaline earth metals was given to magnesium,
valence electrons. When elements or their compounds are
calcium, barium and strontium since their oxides were
introduced to flame, the electrons absorb energy from the
alkaline in nature and these oxides remained unaffected by
flame and gets excited to higher energy levels. When these
heat or fire and existed in earth.
electrons return to their ground state, they emit absorbed
energy in the form of visible light having characteristic
Occurrence: Like alkali metals, alkaline earth metals are also
wavelengths. Depending upon the wavelength of light
highly reactive and hence do not occur in the free state but are emitted, different colours are imparted to the flame. Salts
likely distributed in nature in the combined state as silicates, (generally chlorides) impart characteristic colours to the
carbonates, sulphates and phosphates. Bunsen flame.
Representative Elements: s- and p-Blocks 283

Table 27.2: Ion and Colour Calcium 4.15%, 5th CaCO3.2H2O As an alloying
Ion Colour most a obtained in pure agent for hardness
Ca2+ Brick-red bundant form in 1808, in aluminium
Sr2+ Crimson element in calcium is derived compounds.
Ba2+ Apple green earth’s crust. from Latin word Calcium is the
Ra2+ Carmine-red calx, meaning “lime” primary constituent
of teeth and bones.
Electropositive or Metallic Character: The alkaline earth Strontium 0.038% Discovered in 1787 SrCO3 is used for
metals are highly electropositive and hence metallic and their and named after the the manufacture of
small town of glass for colour
electropositive or metallic character increases down the group.
Strontian (Scotland) TV picture tubes.
However, they are less electropositive or metallic than the Barium 0.042% Found in minerals BaSO4 is used in
alkali metals. It is due to smaller size and higher ionisation with erite (BaCO3) medicine as a
energies as compared to alkali metals, hence have less tendency and barite (BaSO4) contrast medium
to lose electrons than those of alkali metals (Group I). after which it is for stomach and
named. intestine X – rays
Like the alkali metals they also form predominantly ionic
Radium Traces Isolated as chloride Used in cancer
compounds but tendency of covalency is greater, particularly in 1898 from the radiotherapy
with Be and Mg because of their smaller atomic and ionic radii. mineral pitchblende
Be forms compounds which are essentially covalent.
Group IIA (Alkaline earth metals) and Group IIB (Zn, Cd, Hg)
Melting and Boiling Points: The alkaline earth metals have Mg acts as a bridge element between IIA and IIB.
higher melting and boiling points as compared to those of alkali Ca Sr Ba Ra IIA(2)
metals which is attributed to their small size and more close 20 38 56 88
packed crystal lattice as compared to alkali metals and presence Be Mg
12
of two valence electrons. 4
Zn Cd Hg IIB (14)
Heat of Hydration 30 48 80
The heats of hydration of M2+ decreases with an increase in Bridge Element
their ionic size and their values are greater than that of Figure: 27.2
alkali metal ions. Table 27.4: Properties of IIA and IIB Groups
Alkaline earth metal ions, because of their larger charge to S. Properties IIA(Be, Mg, Ca, IIB (Zn, Cd, Hg)
size ratio, exert a much stronger electrostatic attraction on No. Sr, Ba, Ra)
the oxygen of water molecule surrounding them. 1 Electronic [Inert gas] ns 2 [Inert gas]
Since the alkaline earth metals (except Be) tend to lose their configuration (n − 1)d10ns2
valence electrons readily, they act as strong reducing agents 2. Block s–block d – block
as indicated by E0red values. The particularly less negative 3. Oxidation state +2 +2, mercury also forms
value for Be arises from the large hydration energy dimeric Hg 22 −
associated with the small size of Be2+ and the relatively 4. Nature of oxide BeO is amphoteric, ZnO is amphoteric,
large value of heat of sublimation. other oxides are CdO and MgO are
basic. basic
Table 27.3: Occurrence and Uses of Alkaline Earth Metals 5. Nature of Electron–deficient ZnCl2, CdCl2 are ionic
Elements Abundance Main Minerals Uses Halides BeX2, others (MX2) but less than IIA,
Beryllium 2.8 × 10−3% First detected in Used in corrosion are ionic: HgCl2 is covalent.
1798 in the resistant alloys. MgCl2 < CaCl2 <
gemstone beryl and SrCl2 < BaCl2
emerald 6. Nature of Less soluble in More soluble than IIA
(Be2Al2Si6O18) sulphates water and solubility
Magnesium 2.33%,7th Pure Mg first prepared When alloyed decreases down the
most abundant in 1800, named after with Al, Mg is group BeSO4 >
element in the Magnesia district widely used as MgSO4 > CaSO4 >
earth’s crust in Thessaly, Greece structural material SrSO4 > BaSO4
where large deposits because of its high 7. Nature of Solubility of Solubility of
of the mineral are strength, low hydroxides hydroxides hydroxides decreases
found density and ease increases as we as we move down the
in machining. move down the group.
group.

8. Nature of Soluble ZnS, CdS, HgS 13. Reducing Weaker as ionisation Stronger as ionisation
sulphides insoluble and precipitate power potential values are high potential values are
in salt analysis. and oxidation potential low and oxidation
9. Reactivity Increases as we Decreases as we move values are low. potential values are
move down the down the group Zn > high.
group Be < Mg < Cd > Hg
Ca < Sr < Ba
General Characteristics of Compounds of the Alkaline
Earth Metals
Difference between Alkaline Earth Metals and Alkali Oxides: The oxides MO are obtained either by heating the
Metals: Both alkaline earth metals and alkali metals are s-block
metals in oxygen or by thermal decomposition of their
elements as the last electron enters the ns-orbital. They
carbonates.
resemble with each other in some respects but still there are ∆
2M + O2  → 2MO (M = Be, Mg, Ca)
certain dissimilarities in their properties on account of different
∆
number of electrons in the valence shell, smaller atomic radii, MCO3 
→ MO + CO 2 (M = Be, Mg, Ca, Sr, Ba)
high ionisation potential, higher electronegativity etc. Expect BeO all other oxides are extremely stable ionic
solids due to their high lattice energies.
Table 27.5: Properties of Alkaline Earth Metals and Alkali Metals
They have high melting point, have very low vapour pressure,
Properties Alkaline earth metals Alkali metals
1. Electronic Two electrons are present One electron is present are very good conductons of heat, are chemically inert and act
configuration in the valence shall. The in the valence shell. as electrical insulators. Therefore, these oxides are used for
configuration is ns2 The configuration is ns1 lining furnaces and hence used as refractory materials.
(bivalent) (monovalent) more
Due to small size of beryllium ion, BeO is covalent but still
electropositive
2. Valency Bivalent Monovalent
has high melting point because of its polymeric nature.
3. Electropositive Less electropositive More electropositive
Hydroxides: The hydroxides of Ca, Sr and Ba are obtained
nature
either by treating the metal with cold water or by reacting
4. Hydroxides Weak bases, less soluble Strong bases, highly
and decompose on soluble and stable the corresponding oxides with water. The reaction of these
heating. towards heat. oxides with H2O is also sometimes called as slaking.
5. Bicarbonates These are not known in These are known in
M + 2H 2O 
→ M(OH)2 + H 2 (M = Ca, Sr, Ba)
free state. Exist only in solid state.
solution. M + 2H 2O 
→ M(OH)2 + H 2 (M = Ca, Sr, Ba)
6. Carbonates Insoluble in water. Soluble in water. Do
Decompose on heating. not decompose on
MO + H 2 O 
→ M(OH) 2 (M = Ca, Sr, Ba)
heating (LiCO3 is an Ba(OH)2 and Mg(OH)2 being insoluble are obtained from
exception)
7. Action of Directly combine with Do not directly suitable metal ion solutions by precipitation with OH − ions.
nitrogen nitrogen and form combine with nitrogen BeCl 2 + 2NaOH 
→ Be(OH) 2 ↓ +2NaCl
nitrides except lithium
8. Action of Directly combine with Do not directly MgSO 4 + 2NaOH 
→ Mg(OH) 2 ↓ + Na 2SO4
carbon carbon and form carbides combine with carbon
9. Nitrates Decompose on heating Decompose on
Uses
evolving a mixture of heating evolving only
NO2 and oxygen oxygen Calcium fluoride or fluorospar (CaF2 ) is by far the most
10. Solubility of Sulphates, phosphates Sulphates, important of all the fluorides of the alkaline earth metals
salts fluorides, chromates, phosphates, fluorides, since it is the only large scale source of fluorine.
oxalates etc are insoluble chromates, oxides etc
in water are soluble in water. CaCl 2 is widely used for melting ice on roads, particularly in
11. Physical Comparatively harder. Soft, low melting very cold countries because 30% eutectic mixture of CaCl 2
properties High melting points. points paramagnetic.
Diamagnetic.
/ice freezes at 218 K as compared to NaCl /ice at 255K.
12. Hydration of The compounds are The compounds are CaCl 2 is also used as a desiccant (drying agent) in the
compounds extensively hydrated. less hydrated. NaCl, laboratory.
MgCl2.6H2O, KCl, RbCl form non –
CaCl2.6H2O, BaCl2.2H2O hydrated chlorides
Anhydrous MgCl 2 is used in the electrolytic extraction of
are hydrated chlorides. magnesium.

Resemblance of Beryllium with Aluminium (Diagonal Oxidation state: The p-block elements show variety of
Relationship) oxidation states both positive and negative. Some of the p-
The following points illustrate the anomalous behaviour of Be block elements show different oxidation states due to inert -
and its resemblance with Al. pair effect, where their lower oxidation states is more
Unlike Groups 2 elements but like aluminium, beryllium predominant.
forms covalent compounds. Diagonal relationship: On moving diagonally across the
the hydroxides of Be, [Be(OH)2 ] and aluminium periodic table the elements show certain similarities
[Al(OH)3 ] are amphoteric in nature, whereas those of other Li Be B C
elements of Group-2 are basic in nature.

Na Mg Al Si
the oxides of both Be and Al i.e. BeO and Al 2 O3 are high
melting insoluble solids. Note
BeCl 2 and AlCl3 have bridged chloride polymeric structure. Elements of 2nd period differ from their own group elements.
Cl Cl Cl Cl This is due to the following reasons:
Cl — Be Be — Cl Al Al
Cl Cl Cl Cl Properties
Small size
The salts of beryllium as well as aluminium are extensively
Absence of vacant d-orbital
hydrolysed.
High IP
p-block Elements
Table 27.6: Some Important Characteristics of p-block in Tabular form
The right side of the periodic table having group number 13, S. No. Property Along period (left Along group (top
14, 15, 16, 17 and 18 are known as p-block elements. These to right) to bottom)
elements have 3, 4, 5, 6, 7 and 8 electrons in their outermost 1. Atomic radii Decreases Increases
shell, respectively. The last electron of these groups’ elements 2. Ionisation potential Increases Decreases
occupies the position in p-sub shell that is why these elements 3. Electron affinity Increases Decreases
are called as p-block elements. Their general electronic 4. Electronegativity Increases Decreases
2 1− 6 5. Metallic character Decreases Increases
configuration is ns np .
6. Oxidising property Increases Decreases
7. Reducing property Decreases Increases
Some Important Properties of p-block Elements
Electron affinity: Electron affinity increases from left to Boron Family: Group 13 elements are boron (2), aluminium
right along the period amongst the p-block elements and it (Al), Gallium (Ga), Indium (In) and thallium (Tl).
decreases from top to bottom. But group 15 is having Boron is the only non-metal in this group and others are metal.
exceptionally low values of electron affinity and is due to Non-metallic character of boron is due to its small size and high
extra stability of exactly half filled orbitals in their valence ionisation energy. The general valence shell electronic
shell. Similarly, elements of group 18 (noble gases) have
configuration of these elements is ns 2 np1 .
zero affinities due to presence of complete octet which
provides them stability.
Boron: The name boron comes from the Arabic and Persian
Metallic character: The metallic character is governed by words for borax, its principal ore. It was first isolated in 1808
Size of atoms and by Gay-Lussac and Thenard and independently by Sir
Ionisation energy Humphry Davy.
The elements having bigger size and low ionisation energy The pure element is shiny and black. It is very hard and
has a greater metallic character. After combining both the extremely pure form it is nearly as hard as diamond, but too
above mentioned factors we observe that the elements with much brittle for practical use. At high temperatures it is a good
above two properties are located in left corner of p-block conductor but at room temperature and below, it is an insulator.
and strong non-metallic elements are located at right corner
and a diagonal strip of elements separates this two, having Aluminium: Aluminium ranks third on the list of the ten
in between properties are called as metalloids. most abundant elements in the earth’s crust, while its oxide is

fourth among the ten most common compounds in the crust. It 4. First 801 578 579 558 589
ionisation
is the most abundant metal on the planet. Its name is taken
energy
from the Latin alumen, for alum. It is soft, light weight and (KJ/mol)
silvery, its existence was proposed by Lavoisier in 1787, and 5. Electro- 2.0 1.5 1.6 1.7 1.8
it was named by Davy in 1807 and finally isolated by Orsted negativity
in 1825.
In its purest form the metal is bluish-white and very ductile. It Density: Generally increases down the group but
is an excellent conductor of heat and electricity and finds use in aluminium has an exceptionally low density.
some wiring. When pure it is too soft for construction purposes Melting point and Boiling point: B to Ga decreases then
but addition of small amounts of silicon and iron hardened it Ga to Tl increases. Ga has lowest M.P. (29.8°C) and
significantly. Aluminium is the most abundant element in earth therefore liquid at room temperature.
crust among this family. Atomic radii and Ionic radii: On moving from B to Tl the
size increases due to addition of new energy shells at each
Gallium: Gallium is one of the elements originally predicted step down the group but Ga is smaller than Al.
by Mendeleev in 1871 as aluminium, indicating that it should Ionisation Energy: Generally IE decreases down the group
have the properties similar to aluminium. The actual metal was but Ga has higher IE than Al exceptionally due to smaller in
isolated and named by Paul-Emile Lecoq de Boisbaudran in size as compared to Al.
1875. Metallic character: Electropositive character increases
down the group hence metallic character also increases
At room temperature gallium is soft as lead and can be cut with down the group but aluminium is having high metallic
a knife. Its melting point is abnormally low and it will begin to character than Gallium due to low IE than Ga.
melt in the palm of a warm hand. Gallium is from one of the Oxidation state: The elements of B group have three
small numbers of metals that expands on freezing. valence electrons i.e., two in s-subshell. The most oxidation
state should be +3 but due to small size of boron it cannot
Indium: The element indium (Latin indicum, for the colour
lose its valence electrons to B3+ ion, and combines with
indigo) was discovered in 1863 by Reich and Richter. It is a
other atoms through covalent bonds. Except boron, other
rare metal, with an abundance similar to that of silver. It is
elements also exhibit +1 oxidation state and down the group
generally found in deposits with zinc and refineries which
+1 state becomes more stable.
produce this more common metal often sell indium as well.
Reducing property: Down the group the reducing property
The pure metal is so soft that you can “wipe” it onto other
decreases.
material in much the same way as lead. It is corrosion resistant.
Al > Ga > In > Tl
Thallium: Sir William Crookes discovered thallium in 1861,
positively identifying it by a green line in its spectrum (hence Group Trends in Chemical Properties
the name, which is from the Greek, thallos for “green twig”) Hydrides: None of the elements from Group 13 reacts
Thallium compounds are quite toxic and some have been used directly to hydrogen. However a number of hydrides of
as rat poisons. A few compounds are used in glasses for special these elements have been prepared by indirect methods.
infrared lenses. Boron hydrides are called boranes.
Two types of boranes:
Table 27.7: General Trends in Physical Properties B n H n + 4 , called nidoboranes
S. Property Boron Aluminium Gallium Indium Thallium
B n H n + 6 , called arachnoboranes
No.
1. Configur- [He] [Ne] [Ar] [Kr] [Xe] The simplest borone is diborane B2 H 6
ation 2s 2 2p 2 3s 2 sp 2 4s2 4p2 5s 2 5p 2 6s 2 6p 2
2BF3 ( g ) + 6LiH ( s ) 
450K
→ B2 H 6 ( g ) + 6LiF ( s )
2. Common +3 +3 +3 +3 +3, +1 Other elements of this group forms only a few stable
oxidation hydrides of NH3 types. AlH3 is colourless polymeric solid
state
of formula (AlH3)x and contains Al  H  Al bridges. A
3. Atomic 83 143 135 167 170
radius complex hydride of aluminium is a very good reducing
(pm) agent and used as a reagent in lab as Li[AlH4], Lithium

aluminium hydrides. It is a white crystalline solid. Silicon is a crystalline semi-metal or metalloid. One of its
ether
4LiH + AlCl 3  → Li[AlCl 4 ] + 3LiCl forms is shiny, grey and very brittle. In another allotropic form
silicon is a brown amorphous powder most familiar in “dirty”
Gallium also form Li[GaH 4 ] .
beach sand.
Oxides and hydroxides: The Group 13 elements forms
oxides and hydroxides of composition M2O3 and M(OH)3 Germanium (Ge): Like silicon, germanium is used in the
respectively. As we move down the group the acidic manufacture of semi-conductor devices. But unlike silicon, it is
character in oxides and hydroxides decreases and basic rather rare. It was also predicted by Mendeleev in 1871
character increases due to decrease in strength of M  O (ekasilicon) to fill out his periodic table and was discovered in
bond due to which basicity increases. 1886 by Winkler. It is generally extracted from the by products
B2 O3 > Al 2 O3 > Ga 2 O3 > In 2O 3 > Tl 2 O3 of zinc-refining.
B(OH)3 > Al(OH)3 > Ga(OH)3 > In(OH)3 > Tl(OH)3
Tin (Sn): It is one of the major elements along with copper
Trend in acidity
used in bronze. It was named after the Etruscan god Tinia, the
Basic character increases
chemical symbols for it is taken from Latin Stannum. The metal
Oxides and hydroxides of Al and Ga shows amphoteric
is silvery white and very soft when pure. It has the look of
nature.
freshly cut aluminium but the feel of lead. Polished tin is
2Al(OH)3 (s) + 3H 2SO4 (aq) 
→ Al 2 (SO4 )3 (aq) + 6H 2 O(l )
slightly bluish. It has been used for many years in the coating of
Al(OH)3 (s) + NaOH(aq) 
→ Na[Al(OH) 4 ](aq) steel cans for food because it is more resistant to corrosion than
iron. It is chiefly used in solders. SnF2 is found in fluoride
Carbon Family: The carbon family or Group 14 consists of toothpastes.
Carbon (3), Silicon (Si), Germanium (Ge), Tin (Sn) and Lead (Pb).
Carbon and silicon are non metals; germanium is a semi-metal or Lead (Pb): Its symbol came from ‘plumber’ word because
metalloid whereas tin and lead are metals. All the elements of since old plumbing was done with lead pipes. Although lead is
Group 14 have four electrons in their valence shells. Their general not very common in earth’s crust, what is there is readily
electronic configuration is ns2np2. Carbon and silicon are the most available and easy to refine. Its chief use today is in lead-acid
abundant elements in the group in earth crust. storage batteries such as those used in automobiles.
In pure form it is too soft to be used for much else. Lead has
Carbon: Carbon is the sixth most abundant element in the
a blue-white colour when first cut but quickly dulls on
known universe but not nearly as common on the earth, despite
exposure to air forming Pb2O. Various isotopes of lead come
the fact the living organisms contain significant amounts of the
at the end of the natural decay series of elements like
elements. Carbon commonly occurs in environment as methane
uranium, thorium and actinium. These are Pb – 206, Pb –
(CH4) and carbon dioxide (CO2). Carbon exists in several forms
207 and Pb – 208.
called allotropes. Diamond is one of very strong crystal lattice,
known as a precious gem. Graphite is another allotrope in Table: 27.8 Physical Properties
which carbon atoms are arranged in planes which are loosely Sr. Property Carbon Silicon Germanium Tin Lead
attached to one another (hence used as lubricant). The recently No.
discovered fullerenes are yet other form of carbon. Carbon has 1. Configur- [He] [Ne] [Ar] [Kr] [Xe]
ation 2s 2 2p 2 3s 2 3p 2 4s 2 4 p 2 5s 2 5p2 6s 2 6p 2
a very high melting and boiling point and rapidly combines
with oxygen at elevated temperature. An important (but rare) 2. Common +4 +4 +4 +4, +4,
radioactive isotope of carbon, C – 14 is used to date ancient oxidation +2 +2
state
objects of organic origin. Atomic 77 117 122 140 175
3.
radius
Silicon: The name silicon is taken from Latin silex, which (pm)
means “flint”. The element is on second position in abundance 4. First 1086 786 762 709 716
ionisation
in the earth’s crust after oxygen, was discovered by Berzelius in
energy
1824. (KJ/mol)
The most common compound of silicon, SiO2 is the most 5. Electrone- 2.5 1.8 1.8 1.8 1.9
abundant chemical compound in the earth’s crust. gativity

Catenation: A remarkable property of carbon is its ability to Multiple Choice Questions
form compounds in which carbon atoms are linked to one One and More than One Correct
another in chains or rings. This property of forming chains and 1. The species present in solution when CO 2 is dissolved in
rings is known as catenation. On going down the group,
water are [JEE Main 2006]
tendency of catenation decreases. C >> Si > Ge ≈ Sn >> Pb
a. CO2 , H 2CO3 , HCO , CO −
3
2−
3 b. H 2 CO3 , CO32−
Due to high tendency of catenation carbon forms bonds with
other carbon atoms and forms so many compounds which are c. CO32− , HCO3− d. CO 2 , H 2 CO3
studied in organic chemistry. 2. MgSO 4 on reaction with NH 4 OH and Na 2 HOP4 forms a
white crystalline precipitate. What is its formula?
Allotropy: A characteristic property of the elements of carbon
[JEE Main 2006]
family is that these show allotropy. Example: carbon has two
a. Mg(NH 4 )PO 4 b. Mg 3 (PO 4 ) 2
important allotropic forms i.e. diamond and graphite. Allotropy
c. MgCl 2 ⋅ MgSO 4 d. MgSO 4
is the existence of an element in two or more forms, which are
significantly different in physical properties but have similar 3. Among the following, the paramagnetic compound is
3
chemical properties. In diamond carbon is sp hybridised and [JEE 2007 P-I]
has four tetrahedral bonds with adjacent carbon atoms. In a. Na2O2 b. O3 c. N2O d. KO2
graphite carbon is sp2 hybridised. The three covalent bonds 4. The percentage of p-character in the orbitals forming
form hexagonal layers and fourth unhybridised p-electron of P — P bonds in P4 is [JEE 2007 P-I]
each carbon forms an extended delocalised π-bonding with a. 25 b. 33 c. 50 d. 75
carbon atoms of adjacent layers. Due to this free electron 5. Aqueous solutions of Na2S2O3 on reaction with Cl2 gives
graphite is electric conductor while diamond is not. Also due to [JEE 2008 P-I]
sliding property of graphite it has been using as a lubricant. a. Na 2S4O6 b. NaHSO 4
c. NaCl d. NaOH
Silica (SiO 2 ) : Silicon is unable to form pπ − pπ bond with
6. The reaction of P4 with X leads selectively to P4O6.The X
oxygen atom due to its relatively large size. Thus it satisfies it’s
is [JEE 2009 P-I]
all four valencies with four oxygen atoms and constitutes three
a. Dry O2
- dimensional network. In this structure each oxygen atom is
b. A mixture of O 2 and N 2
shared by two silicon atoms. Three crystalline modifications of
c. Moist O2
SiO 2 are quartz, cristobalite and tridymite of which quartz and
d. O2 in the presence of aqueous NaOH
cristobalite are important. (N2 is used to retard the further oxidation.)
| | | 7. The compound(s) formed upon combustion of sodium
—Si — O — Si — O — Si —
| | | metal in excess air is(are) [JEE 2009 P-I]
O O O a. Na2O2 b. Na2O
| | |
—Si — O — Si — O — Si — c. NaO2 d. NaOH
| | |
O O O 8. The nitrogen oxide(s) that contain(s) N−N bond(s) is(are)
| | | [JEE 2009 P-II]
—Si — O — Si — O — Si — a. N2O b. N2O3
| | |
c. N2O4 d. N2O5
Quartz (rock crystal) is the purest form of silica. It is used in 9. In the reaction 2X + B2 H 6 → [BH 2 (X) 2 ]+ [BH 4 ]− the
preparation of costly glasses and lenses. It is also used as amine (s) X is (are) [JEE 2009 P-II]
piezoelectric material (crystal oscillators and transducers). a. NH 3 b. CH3 NH 2
Several amorphous forms of silica such as silica gel and fumed
c. (CH 3 ) 2 NH d. (CH 3 )3 N
silica are known. Silica gel is made by acidification of sodium
silicate and when dehydrated, is extensively used as a drying 10. The reagent(s) used for softening the temporary hardness
agent in chromatographic and catalyst support. of water is(are) [JEE 2010 P-I]

a. Ca 3 (PO 4 ) 2 b. Ca(OH) 2 18. Which of the following exists as covalent crystals in the
c. Na 2CO3 d. NaOCl solid state? [JEE Main 2013]
a. Iodine b. Silicon
11. Extraction of metal from the ore cassiterite involves c. Sulphur d. Phosphorus
[JEE 2011 P-I]
19. Concentrated nitric acid, upon long standing, turns
a. carbon reduction of an oxide ore
yellow-brown due to the formation of
b. self-reduction of a sulphide ore
[JEE Adv. 2013 P-I]
c. removal of copper impurity
a. NO b. NO2 c. N2O d. N2O4
d. removal of iron impurity
20. The carbon-based reduction method is NOT used for the
12. Extra pure N2 can be obtained by heating
extraction of [JEE Adv. 2013 P-II]
[JEE 2011 P-I]
a. tin from SnO2
a. NH 3 with CuO b. NH 4 NO3
b. iron from Fe2O3
c. (NH 4 ) 2 Cr2 O7 d. Ba(N 3 ) 2 c. aluminium from Al2O3
13. Which ordering of compounds is according to the d. magnesium from MgCO3.CaCO3
decreasing order of the oxidation state of nitrogen? 21. The correct statement(s) for orthoboric acid is/are
[JEE 2012 P-I] [JEE Adv. 2014 P-I]
a. HNO3 , NO, NH 4 Cl, N 2 a. It behaves as a weak acid in water due to self ionization
b. HNO3 , NO, N 2 ,NH
NH4 Cl b. Acidity of its aqueous solution increases upon addition
4Cl
of ethylene glycol
c. HNO3 , NH 4 Cl, NO, N 2
c. It has a three dimensional structure due to hydrogen
d. NO, HNO3 NH 4 Cl, N 2 bonding.
d. It is a weak electrolyte in water
14. With respect to graphite and diamond, which of the
statement(s) given below is (are) correct? 22. The pair(s) of reagents that yield paramagnetic species
[JEE 2012 P-II] is/are [JEE Adv. 2014 P-I]
a. Graphite is harder than diamond a. Na and excess of NH3
b. Graphite has higher electrical conductivity than diamond b. K and excess of O2
c. Graphite has higher thermal conductivity than diamond
c. Cu and dilute HNO3
d. Graphite has higher C–C bond order than diamond
d. O2 and 2-ethylanthraquinol
15. The reaction of white phosphorus with aqueous NaOH
gives phosphine along with another phosphorus 23. Under ambient conditions, the total number of gases
containing compound. The reaction type; the oxidation released as products in the final step of the reaction
states of phosphorus in phosphine and the other product scheme shown below is [JEE Adv. 2014 P-II]
Complete OH − / H 2 O slow disproportionatio
are respectively XeF6 →
Hydrolysis
P + other product  → Q 
a. redox reaction; –3 and –5
Complete slow disproportionation
b. redox reaction; +3 and +5 XeF → P + other product  → Q  → Products
Products
in OH − / H 2 O
c. disproportionation reaction; –3 and +5 a. 0 b. 1 c. 2 d. 3

d. disproportionation reaction; –3 and +3
24. The product formed in the reaction of SOCl2 with white
16. The shape of XeO 2 F2 molecule is [JEE 2012 P-II]
phosphorous is [JEE Adv. 2014 P-II]
a. trigonal bipyramidal b. square planar
a. PCl3 b. SO2Cl2 c. SCl2 d. POCl3
c. tetrahedral d. see-saw
17. The correct statement(s) about O3 is(are) 25. Hydrogen peroxide in its reaction with KIO4 and NH2OH
[JEE Adv. 2013 P-II] respectively, is acting as a [JEE Adv. 2014 P-II]
a. O–O bond lengths are equal. a. reducing agent, oxidising agent
b. Thermal decomposition of O3 is endothermic. b. reducing agent, reducing agent
c. O3 is diamagnetic in nature. c. oxidising agent, oxidising agent
d. O3 has a bent structure. d. oxidising agent, reducing agent

26. In the context of the Hall-Heroult process for the 35. The pair in which phosphorous atoms have a formal
extraction of Aℓ, which of the following statements is oxidation state of +3 is: [JEE Main 2016]
false? [JEE Main 2015] a. Orthophosphorous and pyrophosphorous acids
a. CO and CO2 are produced in this process b. Pyrophosphorous and hypophosphoric acids
b. Aℓ 2O3 is mixed with CaF2 which lowers the melting c. Orthophosphorous and hypophosphoric acids
point of the mixture and brings conductivity d. Pyrophosphorous and pyrophosphoric acids
c. Aℓ3+ is reduced at the cathode to form Aℓ 36. The increasing order of atomic radii of the following
d. Na 3 AℓF6 serves as the electrolyte Group 13 elements is [JEE Adv. 2016 P-I]
a. Al < Ga < In < Tl b. Ga < Al < In < Tl
27. Which one of the following alkaline earth metal sulphates
c. Al < In < Ga < Tl d. Al < Ga < Tl < In
has its hydration enthalpy greater than its lattice enthalpy?
[JEE Main 2015] 37. The crystalline form of borax has [JEE Adv. 2016 P-I]
2−
a. CaSO 4 b. BeSO 4 a. tetranuclear [B 4 O 5 (OH) 4 ] unit
c. BaSO 4 d. SrSO4 b. all boron atoms in the same plane
28. Which among the following is the most reactive? c. equal number of sp 2 and sp3 hybridized boron atoms
[JEE Main 2015] d. one terminal hydroxide per boron atom
a. Cl2 b. Br2 c. I2 d. ICl 38. The products obtained when chlorine gas reacts with cold
29. Which one has the highest boiling point? and dilute aqueous NaOH are [JEE Main 2017]
− −
[JEE Main 2015] a. Cl and ClO −2 b. ClO and ClO 3−
a. He b. Ne c. Kr d. Xe − −
c. ClO −2 and ClO 3− d. Cl and ClO
30. The correct statement(s) regarding, (i) HClO, (ii) HClO2 ,
39. Both lithium and magnesium display several similar
(iii) HClO3 and (iv) HClO4 , is (are)
properties due to the diagonal relationship; however, the
[JEE Adv. 2015 P-II] one which is incorrect, is [JEE Main 2017]
a. The number of Cl = O bonds in (ii) and (iii) together is two a. Nitrates of both Li and Mg yield NO2 and O2 on heating
b. The number of lone pairs of electrons on Cl in (ii) and b. Both form basic carbonates
(iii) together is three c. Both form soluble bicarbonates
c. The hybridization of Cl in (iv) is sp3 d. Both form nitrides
d. Amongst (i) to (iv), the strongest acid is (i) 40. The colour of the X2 molecules of group 17 elements
31. The species in which the N atom is in a state of sp changes gradually from yellow to violet down the group.
hybridization is [JEE Main 2016] This is due to [JEE Adv. 2017 P-I]
a. NO +2 b. NO −2 c. NO3− d. NO 2 a. The physical state of X2 at room temperature changes
from gas to solid down the group
32. Which one of the following ores is best, concentrated by
b. decrease in HOMO-LUMO gap down the group
froth floatation method? [JEE Main 2016]
a. Magnetite b. Siderite c. decrease in π* − σ* gap down the group
c. Galena d. Malachite d. decrease in ionization energy down the group
33. The reaction of zinc with dilute and concentrated nitric 41. The correct statement(s) about the oxoacids, HClO 4 and
acid, respectively, produces [JEE Main 2016]
HClO, is(are) [JEE Adv. 2017 P-I]
a. N 2 O and NO 2 b. NO 2 and NO
a. The conjugate base of HClO 4 is weaker base than H 2O
c. NO and N 2 O d. NO 2 and N 2 O
b. The central atom in both HClO 4 and HClO is sp3
34. The main oxides formed on combustion of Li, Na and K hybridized
in excess of air are, respectively [JEE Main 2016]
c. HClO 4 is formed in the reaction between Cl 2 and H 2O
a. Li 2 O, Na 2 O and KO 2 b. LiO 2 , Na 2 O 2 and K 2 O
d. HClO 4 is more acidic than HClO because of the
c. Li 2 O 2 , Na 2 O 2 and KO 2 d. Li 2 O, Na 2 O 2 and KO 2
resonance stabilization of its anion

42. Which of the following combination will produce H 2 gas? a. At 800°C, Cu can be used for the extraction of Zn from
[JEE Adv. 2017 P-II] ZnO
a. Au metal and NaCN(aq) in the presence of air b. At 500ºC, coke can be used for the extraction of Zn
b. Zn metal and NaOH(aq) from ZnO
c. Fe metal and conc. HNO3 c. Coke cannot be used for the extraction of Cu from Ca2O.
d. At 1400°C, Al can be used for the extraction of Zn
d. Cu metal and conc. HNO3
from ZnO
43. Among the following, the correct statement(s) is(are) 49. Hall-Heroult's process is given by [JEE Main 2019]
a. Cr2 O3 + 2Al 
→ Al2 O3 + 2Cr
a. AlCl3 has the three-centre two-electron bonds in its
b. Cu 2+ (aq.) + H 2 (g) 
→ Cu(s) + 2H + (aq)
dimeric structure
b. BH3 has the three-centre two-electron bonds in its c. ZnO + C 
Coke, 1673K
→ Zn + CO
dimeric structure d. 2Al2 O3 + 3C 
→ 4Al + 3CO2
c. Al(CH3)3 has the three-centre two-electron bonds in its 50. Sodium metal on dissolution in liquid ammonia gives a
dimeric structure deep blue solution due to the formation of:
d. The Lewis acidity of BCl3 is greater than that of AlCl3
[JEE Main 2019]
44. The covalent alkaline earth metal halide (X = Cl, Br, I) is: a. sodium ion-ammonia complex
[JEE Main 2019] b. sodamide
a. CaX2 b. SrX2 c. sodium-ammonia complex
c. BeX2 d. MgX2 d. ammoniated electrons
45. The Mond process is used for the [JEE Main 2019] 51. The amphoteric hydroxide is: [JEE Main 2019]
a. Extraction of Mo a. Ca(OH)2 b. Be(OH)2
b. Purification of Ni c. Sr(OH)2 d. Mg(OH)2
c. Purification of Zr and Ti
52. The correct option with respect to the Pauling electro-
d. Extraction of Zn
negativity values of the elements is: [JEE Main 2019]
46. The alkaline earth metal nitrate that does not crystallise a. Ga < Ge b. Si < Al
with water molecules, is [JEE Main 2019] c. P > S d. Te > Se
a. Sr(NO3)2 b. Mg(NO3)2
53. The reaction that does NOT define calcination is:
c. Ca(NO3)2 d. Ba(NO3)2
[JEE Main 2019]
47. Aluminum is usually found in +3 oxidation state. In ∆
a. ZnCO3  → ZnO + CO2
contarast, thallium exists in +1 and +3 oxidation states ∆
b. Fe2O3·XH2O  →Fe2O3 + XH2O
this is due to: [JEE Main 2019]
∆
a. lanthanoid contraction b. lattice effect c. CaCO3·MgCO3  →CaO + MgO + 2CO2
c. diagonal relationship d. inert pair effect ∆
d. 2Cu 2 S + 3O2  → 2Cu 2 O + 2SO2
48. The correct statement regarding the given Ellingham
diagram is: [JEE Main 2019] 54. A 
4 KOH, O2
→ 2B + 2 H2O
(Green)
4Cu + O2 → 2Cu2O
3 B 
→ 2C + MnO2 + 2H2 O
4HCl
(Purple)
–300
2 B  
H2O, KI
→ 2 A + 2KOH + D
∆Gº (kJ/mol)
2C + O 2 → 2CO
–600 2Zn + O 2 → 2ZnO In the above sequence of reactions,

A and D respectively, are :-
4 2
–1050 3
Al + O2 → Al2O3
3
a. KIO3 and MnO2 b. KI and K2MnO4
500ºC Temp.(ºC) 2000ºC
c. MnO2 and KIO3 d. KI and KMnO4

55. A metal on combustion in excess air forms X, X upon a. A→ 1; B→ 3; C→ 4; D→ 2
hydrolysis with water yields H2O2 and O2 along with b. A→ 1; B→ 2; C→ 3; D→ 4
another product. The metal is: [JEE Main 2019] c. A→ 3; B→ 1; C→ 2; D→ 4
a. Rb b. Na c. Mg d. Li d. A→ 3; B→ 4; C→ 2; D→ 1
56. The element that does NOT show catenation is: 61. Match the conversions in Column I with the type(s) of
[JEE Main 2019] reaction(s) given in Column II. [JEE 2008 P-II]
a. Sn b. Ge c. Si d. Pb Column I Column II
(A) PbS → PbO 1. roasting
57 Which of the following are true [JEE Adv. 2019 P-I]
a. Manosaccharides can not be hydrolysed to give poly- (B) CaCO3 → CaO 2. calcinations
hydeoxy aldehydes and ketones. (C) ZnS → Zn 3. Carbon reduction

b. Hydroolysis of sucrose gives dextrorotatory glucose (D) Cu 2S → Cu 4. self reduction
and laevorotatory fructose. a. A→ 1, 3, 4; B→ 1,3; C→ 3,4; D→ 1,2
c. Oxidation of glucose with bromine water gives b. A→ 1, 2; B→ 1, 2; C→ 3,4; D→ 1,2,3,4
glutamic acid. c. A → 1; B → 2; C → 1, 3; D → 1, 4
d. The two six membered hemiacetal form of (+) glucose d. A→ 1, 3; B→ 1,2,3,4; C→ 2,1; D→ 1,2
are anomers.
62. All the compounds listed in Column I react with water.
58. In the Mac. Arthur process of extraction Match the result of the respective reactions with the
NaCN + Q
Au  → R 
extracted
with Y
→Z [JEE Adv. 2019 P-II] appropriate options listed in Column II.
a. R is R is [Au(CN 4 )]⊙ b. Z is [Zn(CN) 4 ]2 − [JEE 2010 P-II]
Column I Column II
c. Q is O 2 d. Y is Zn
(A) (CH 3 ) 2 SiCl2 1. Hydrogen halide
formation
(B) XeF4 2. Redox reaction
59. Match the extraction processes listed in Column I with 3. Reacts with glass
(C) Cl2
metals listed in Column II: [JEE 2006]
(D) VCl5 4. Polymerization
Column I Column II
(A) Self reduction 1. Lead 5. O2 formation
(B) Carbon reduction 2. Silver a. A→ 1,2,3; B→ 1,3; C→ 1,2,3,4; D→ 1,2
(C) Complex formation and 3. Copper b. A→ 1, 4; B → 1, 2, 3, 5; C → 1, 2, 3; D → 1
displacement by metal c. A→ 1,3; B→ 1,2,3,4; C→ 1,2,3; D→ 1,2,4
(D) Decomposition of iodide 4. Boron d. A→ 1,2,3,4; B→ 2,3,4; C→ 2,3; D→ 1,2,3,4,5
a. A→1, 3; B → 1, 3; C → 2; D → 4 63. The unbalanced chemical reactions given in Column I

b. A→ 1,2; B→ 1,2; C→ 1,2,3; D→ 1,2,4 show missing reagent or condition (?) which are provided
c. A→ 1,2,3; B→ 1,2; C→ 1,2,3; D→ 1,2,3,4 in Column II. [JEE Adv. 2013 P-II]
d. A→ 1,2,3; B→ 1,2,4; C→ 1,3,2; D→ 1,2,3 Column I Column II
60. Match the following: [JEE 2006]
(A) PbO2 + H2SO4 
→ PbSO4 + O2 +
? 1. NO
Column I Column II
other product
(A) Bi3+ 
→ (BiO) + 1. Heat
(B) Na 2S2O3 + H2 O 
?
→ NaHSO4 + 2. I 2
(B) [AlO 2 ]− 
→ Al(OH)3 2. Hydrolysis
other product
(C) SiO 44− 
→ Si 2 O67− 3. Acidification
(C) N 2 H 4 
?
→ N 2 + other product 3. Warm
2−
(D) (B4O ) 
→[B(OH)3 ] 4. Dilution by water
7
(D) XeF2 
?
→ Xe + other product 4. Cl 2

a. A→ 1; B→ 3; C→ 4; D→ 2 c. statement-I is True, statement-II is False
b. A→ 3; B → 4; C → 2; D→1 d. statement-I is False, statement-II is True
c. A→ 3; B→ 1; C→ 2; D→ 4 68. Statement-I: Pb 4 + compounds are stronger oxidizing
d. A→ 3; B→ 4; C→ 1; D→ 2
agents than Sn 4 + compounds. And
Statement-II: The higher oxidation states for the group
[JEE Main 2019]
14 elements are more stable for the heavier members of
Column I (Ores) Column II ( Metals)
the group due to ‘inert pair effect’. [JEE 2008 P-I]
(A) Siderite 1. Zinc
(B) Kaolinite 2. Copper is correct explanation for Statement-I
(C) Malachite 3. Ferric chloride test b. statement-I is True, Statement-II: is True; statement-II
(D) Penicillin 4. Bayer’s test is not a correct explanation for statement-I
a. A→2; B→1; C→4; D→3
b. A→3; B→1; C→4; D→2
c. A→3; B→4; C→2; D→1 69. Statement-I: Nitrogen and Oxygen are the main
components in the atmosphere but these do not react to
d. A→2; B→4; C→1; D→3
form oxides of nitrogen.
Statement-II: The reaction between nitrogen and oxygen
Statement/Assertion and Reason
requires high temperature. [JEE Main 2015]
65. Statement-I: Boron always forms covalent bond. And
Statement-II: The small size of B 3 + favours formation of is correct explanation for Statement-I
covalent bond. [JEE 2007 P-I] b. statement-I is True, Statement-II: is True; statement-II
is not a correct explanation for statement-I
Paragraph
66. Statement-I: In water, orthoboric acid behaves as a weak
monobasic acid. And The noble gases have closed-shell electronic configuration and are
Statement-II: In water, orthoboric acid acts as a proton monoatomic gases under normal conditions. The low boiling
points of the lighter noble gases are due to weak dispersion forces
donor. [JEE 2007 P-I]
between the atoms and the absence of other interatomic
interactions. The direct reaction of xenon with fluorine leads to a
series of compounds with oxidation numbers +2, +4 and +6. XeF4
reacts violently with water to give XeO3. The compounds of xenon
exhibit rich stereochemistry and their geometries can be deduced
considering the total number of electron pairs in the valence shell.
[JEE 2007 P-I]
67. Statement-I: Alkali metals dissolve in liquid ammonia to
70. Argon is used in arc welding because of its
give blue solution. And
a. low reactivity with metal
Statement-II: Alkali metals in liquid ammonia give
b. ability to lower the melting point of metal
[ M(NH3 )n ]
+
solvated species of the type (M = alkali c. flammability
metals). [JEE 2007 P-II] d. high calorific value
71. The structure of XeO3 is
a. linear b. planar
c. pyramidal d. T-shaped

72. XeF4 and XeF6 are expected to be 76. 25 mL of household bleach solution was mixed with
a. oxidizing b. reducing 30 mL of 0.50 M KI and 10 mL of 4 N acetic acid. In the
c. unreactive d. strongly basic titration of the liberated iodine, 48 mL of 0.25 N Na2S2O3
was used to reach the end point. The molarity of the
Paragraph for Question Nos. 73 to 75 household bleach solution is
There are some deposits of nitrates and phosphates in earth’s a. 0.48 M b. 0.96 M
crust. Nitrates are more soluble in water. Nitrates are difficult c. 0.24 M d. 0.024 M
to reduce under the laboratory conditions but microbes do it 77. Bleaching powder contains a salt of an oxoacid as one of
easily. Ammonia forms large number of complexes with its components. The anhydride of that oxoacid is
transition metal ions. Hybridization easily explains the ease of
a. Cl 2 O b. Cl2 O7
sigma donation capability of NH3 and PH3. Phosphine is a
flammable gas and is prepared from white phosphorus. c. ClO 2 d. Cl 2 O6
[JEE 2008 P-I]
73. Among the following, the correct statement is Paragraph for Question Nos. 78 and 79
a. Phosphates have no biological significance in humans The reactions of Cl 2 gas with cold-dilute and hot-concentrated
b. Between nitrates and phosphates, phosphates are less
NaOH in water give sodium salts of two (different) oxoacids of
abundant in earth’s crust
chlorine, P and Q, respectively. The Cl 2 gas reacts with SO 2
c. Between nitrates and phosphates, nitrates are less
abundant in earth’s crust gas, in presence of charcoal, to give a product R. R reacts with
d. Oxidation of nitrates is possible in soil white phosphorus to give a compound S. On hydrolysis, S gives
an oxoacid of phosphorus, T. [JEE Adv. 2013 P-II]
74. Among the following, the correct statement is
78. P and Q, respectively, are the sodium salts of
a. Between NH3 and PH3, NH3 is better electron donor
a. hypochlorus and chloric acids
because the lone pair of electrons occupies spherical ‘s’
b. hypochlorus and chlorus acids
orbital and is less directional
c. chloric and perchloric acids
b. Between NH3 and PH3, NH3is better electron donor
d. chloric and hypochlorus acids
because the lone pair of electrons occupies sp3 orbital
79. R, S and T, respectively, are
and is more directional
c. Between NH3 and PH3, NH3 is a better electron donor a. SO 2 Cl 2 , PCl5 and H 3 PO 4
because the lone pair of electrons occupies sp3 orbital b. SO 2 Cl 2 , PCl3 and H 3 PO 3
and is more directional c. SOCl2 , PCl3 and H 3 PO 2
d. Between NH 3 and PH3, NH3 is better electron donor d. SOCl2 , PCl5 and H 3 PO 4
because the lone pair of electrons occupies spherical ‘s’
orbital and is less directional Paragraph for Question Nos. 80 and 81
75. White phosphorus on reaction with NaOH gives PH3, as Upon heating KClO 3 in the presence of catalytic amount of
one of the products. This is a MnO2 , a gas W is formed. Excess amount of W reacts with
a. dimerization reaction white phosphorus to give X. The reaction of X with pure gives
b. disproportionation reaction Y and Z. [JEE Adv. 2017 P-II]
c. condensation reaction
d. precipitation reaction 80. W and X are, respectively
a. O 3 and P4 O 6 b. O 2 and P4 O 6
Paragraph for Question Nos. 76 and 77 c. O 2 and P4 O10 d. O 3 and P4 O10
Bleaching powder and bleach solution are produced on a large
81. Y and Z are, respectively
scale and used in several household products. The effectiveness
a. N 2 O 5 and HPO3 b. N 2 O 3 and H 3 PO 4
of bleach solution is often measured by iodometry.
[JEE 2012 P-II] c. N 2 O 4 and HPO3 d. N 2 O 4 and H 3 PO 3

+2
Integer and Subjective Mg + NH 4OH + Na 2 HPO 4  → Mg(NH 4 )PO 4
82. The coordination number of Al in the crystalline state of
AlCl3 is_______ [JEE 2009 P-II] 3. (d) O22− = σ 1s 2σ *1s 2 ,σ 2s 2σ *2s 2 , σ 2p 2z , π 2p 2x = π 2p 2y , π * 2p 2x = π *
O 22 = σ 1s 2σ *1s 2 , σ 2s 2σ *2s 2 , σ 2p z2 , π 2p 2x = π 2p 2y , π * 2p x2 = π * 2p 2y
83. The value of n in the molecular formula Be n Al2Si 6O18 is
Number of unpaired electrons = 0.
_______ [JEE 2010 P-I]
N = N  → O number of unpaired electrons = 0
84. The total number of diprotic acids among the following is ⊕ Θ
_______ [JEE 2010 P-II] O == O— O ← → O == O 
→ O Number of unpaired
H 3 PO 4 H 2SO 4 H 3 PO3 H 2 CO3 H 2S2 O 7 electrons = 0
H3 BO3 H 3 PO 2 H 2CrO4 H 2SO 3 O−2 = σ 1s 2σ *1s 2 σ 2s2 , σ *2s 2 , σ 2p 2z , π 2p 2x = π 2p 2y , π * 2p 2x = π * 2p1y
O = σ 1s 2σ *1s 2 σ 2s 2 , σ *2s 2 , σ 2p 2 , π 2p 2 = π 2p 2y , π * 2p 2x = π * 2p1y
85. Reaction of Br2 with2 Na 2 CO 3 in aqueous solution z givesx
Number of unpaired electrons = 1
sodium bromide and sodium, bromated with evolution of
CO gas. The number of sodium bromide molecules Thus O −2 is paramagnetic.
2
involved in the balanced chemical equation is _______ Hence, (d) is correct.

[JEE 2011 Paper -I] 3
4. (d) P is sp hybridised in P4.
86. The difference in the oxidation numbers of the two types P
of sulphur atoms in Na 2S4 O6 is_______ [JEE 2011 P-I]
P P
87. Among the following, the number of compounds than can
react with PCl5 to give POCl3 is _______ P
(O2, CO2, SO2, H2O, H2SO4, P4O10) [JEE 2011 P-II] Hence (d) is correct.
88. A list of species having the formula XZ4 is given below. 5. (b) Na 2S2O3 + 4Cl 2 + 5H 2O 
→ 2 NaHSO 4 + 3HCl
2+
XeF4 , SF4 , SiF4 , BF4− , BrF4− ,  Cu ( NH 3 )4  , [ FeCl 4 ] , CoCl6.
2− 2− 2−
and
(b) PPtCl
4 + 3O 2 → P4 O 6 (exclusively)
N2
4 4
, [ CoCl4 ] and [ PtCl 4 ]

2− 2− 2−
, FeCl4 7. (a, b) In dry air
Defining shape on the basis of the location of X and Z 8. (a, b, c)
atoms, the total number of species having a square planar N 2O N ≡≡ N → O,
shape is_______ [JEE Adv. 2014 P-I] O
89. Three moles of B2H6 are completely reacted with N—O—N O == N — N
N 2 O3 :
methanol. The number of moles of boron containing O O O
product formed is_______ [JEE Adv. 2015 P-II]
O O
90. (a) Calculate the amount of Calcium oxide required when O O
↑ ↑
N 2O 4 : N—N N 2 O5 : N— O — N
it reacts with 852 gm of P4 O10 . [JEE 2005]
(b) Write the structure of P4 O10 . O O O O
91. Predict whether the following molecules are isostructural 9. (a, b, c) Due to bulkiness of trimethylamine, it does not
or not. Justify your answer. (i) NMe3 ; (ii) N(SiMe3 )3 react.
[JEE 2005] 10. (b, c, d)
Ca(HCO3 ) 2 + Ca(OH) 2 
→ 2CaCO3 ↓ +2H 2 O
ANSWERS and SOLUTIONS [Clarke 's method]
1. (a)
NaOCl + H 2O ↽ ⇀ HOCl + NaOH
CO2 + H 2O ↽ ⇀ H 2CO3 ↽ ⇀ H + + HCO3− ↽ ⇀ H + + CO3−2
OH − + HCO3− 
→ CO32− + H 2 O
2. (a) Test of Mg +2 ion Ca(HCO3 ) 2 + NaCO3 
→ CaCO3 ↓ +2NaHCO3

11. (a, d) Cassiterite contains impurity of FeWO4
H O
(SnO 2 ) O H
H O O H
SnO 2 + 2C 
→ Sn + 2CO
B
∆
12. (d) Ba(N 3 )2 
→ Ba + 3N 2
H O O H
13. (b) HNO3 
→+5 H O
O H
NO 
→ +2, N 2 = 0
NH 4 Cl 
→−3 –
O O
14. (b, c, d) Graphite is sp 2 hybridized and contains van der B + 4H2 O
3
waal’s force. While diamond is sp hybridised. O
O
15. None of these P4 (white) + NaOH + 3H 2 O 
→ (stable complex)
PH 3 + 3NaH 2 PO 2 (C) It has a planar sheet like structure due to hydrogen
PH 3 has –3 and NaH 2 PO3 has + 1 O.N. bonding.
(D) H 3 BO3 is a weak electrolyte in water.
16. (d) Shape of XeO 2 F2 is
22. (a, b, c)
(a) Sodium (Na) when dissolved in excess liquid
Xe ammonia, forms a blue coloured paramagnetic solution.
F (see − saw)
(b) K + O 2 
→ KO 2
O O (potassiumsuperoxide)
1 and KO2 is paramagnetic.

Hybridisation H = V+M−C+A
2
(c) 3Cu + 8 HNO3 
→ 3Cu(NO3 ) 2 + 2 NO + 4H 2 O
1 (dilute)
= 8 + 2 − 0 + 0 = 5(sp3d)
2 Where “NO” is paramagnetic:
17. (a, c, d) OH
CH 2 − CH 3
1.21Å
(d) + O 2 (air) →
117°
OH
(2 − ethyl anthraquinol)
18. (b) Silicon exists as covalent crystals in the solid state.
O
19. (b) 4HNO3 
→ 2H 2 O + 4NO 2 + O 2
CH 2 − CH 3
NO 2 remains dissolved in nitric acid colouring it yellow + H 2O 2
or even red at higher temperature.
20. (c, d) Fe2O3 and SnO2 undergoes C reduction. Hence (c) O
and (d) are correct. Where "H 2 O2 " is diamagnetic.
21. (b, d) (A) H 3 BO3 is a weak monobasic Lewis acid. −
− +
23. (c) XeF6 + 3H 2 O  OH
→ XeO3 + 3H 2 F2  → HXeO 4−
H 3 BO3 + H − OH ↽ ⇀ B(OH) + H 4 . . .(i)
−
→ XeO64 − (s) + Xe
OH / H 2 O
(B) Equilibrium (i) is shifted in forward direction by the 
(disproportionation) (g) ++H
Xe(g) H22O
O( ) )++O
( ℓ O2(g)
2 (g)
addition of syn-diols like ethylene glycol which forms a

24. (a) P4 (s) + 8SOCl 2 (ℓ) Æ 4PCl3 (ℓ) + 4SO2 (g) + 2S2 Cl 2 (g)
stable complex with B(OH)−4 .
25. (a) KIO 4 + H 2 O 2 

→ KIO3 + H 2 O + O 2 Correct Order : Ga < Al < In < Tl
Data Reference : NCERT
NH 2 OH + 3H 2 O 2 
→ HNO3 + 4H 2 O
37. (a, c, d) Structure of Borax
26. (d) O
HO
27. (b) BaSO 4 is least soluble. Θ
sp3
B OH
BeSO 4 is most soluble.
O O B
28. (d) The interhalogen compounds are generally more sp 2
reactive than halogens (except F2). B O B
Θ
HO O
2
29. (d) Xe has the highest boiling point. sp OH sp3
30. (b, c) H — O — Cl (I) Correct formula of borax is Na 2 [B4 O5 (OH)4 ].8H 2 O
..
(a) Borax has tetranuclear (B 4 O 5 (OH) 4 ) 2 – unit
. . == O (II)
H — O — Cl
(b) Only two ‘B’ atoms lie in the same plane
..
H — O — Cl == O (III) (c) Two Boron atoms are sp 2 and two are sp3 hybridised.
||
O (d) One terminal hydroxide per boron atom
O 38. (d) Cl2 + 2OH − 
→ Cl− + ClO− + H 2O
|| [cold and dilute]
H — O — Cl == O (IV)
|| 39. (d) Mg can form basic carbonate like
O
5Mg +2 + 6CO32− + 7H 2 O 
→
31. (a) NO −2 = sp 2
4MgCO3 ⋅ Mg(OH) 2 ⋅ 5H2 O ↓ 2HCO3−
NO3− = sp 2
While Li can form only carbonate (Li2CO3) not basic
NO 2 = sp 2
carbonate.
NO+2 = sp
40. (b, c) HOMO = π * , LUMO = σ *
32. (c) Galena = PbS As we move down the group, the energy difference
For sulphur ores froth flotation is carried out. between π* and σ * decreases, the higher wavelength
33. (a) Zn + HNO3 (dil.) 
→ Zn(NO3 )2 (aq) + N 2 O + H 2 O radiations are absorbed and their complimentary colours
are observed.
Zn + HNO3 (conc.) 
→ Zn(NO3 ) 2 + NO 2 + H 2 O
41. (a, b, d)
34. (d) Li + O 2 (g) 
→ Li 2 O
(excess) (a) HClO4 > H2O Acidic character
Na + O 2 (g) 
→ Na 2 O 2 ClO 4− < OH − Conjugate Base
(excess)
(b) Both HClO 4 and HClO central atom is sp3 hybridised.
K + O 2 (g) 
→ KO 2
(excess) (d) HClO 4 > HClO (Acidic strength)
+3
→ H + + ClO −4
HClO 4 
35. (a) Orthophosphorous acid  H 3 P O3 
  → H + + ClO −
HClO 
+3
Pyrophosphorous acid  H 2 P2 O 5  O− O− O O
  | || || ||
Cl == O Cl == O Cl Cl
36. (b) r < rAl (because of poor shielding of nuclear || | || −
Ga
(135 pm) (143 pm) O O O− O O O− O O O O
charge by 3d e− ) In ClO −4 , negative charge is dispersed on four oxygen
In and Tl follows regular trend [radii increases on moving atoms, so better resonance stabilised.
down the group]

42. (b) Zn + 2NaOH 
→ Na 2 ZnO 2 + H 2 54. (c) MnO2 (A) 
2
→ 2K2 MnO4 (B) + 2H2O
4KOH,O
(Green)
Iron become passive with conc. HNO3 .
3K 2 MnO4 (B) 
→ 2KMnO4 (C) + 2H2 O
4HCl
Copper liberate NO 2 with HNO 3 . (Purple)
43. (b, c, d) 2KMnO4 (C)  

H2 O, KI
→ 2MnO2 (A) + 2 KOH +KIO3 (D)
H e– H e
–
H A 
→MnO2
B e– – B It has two 3c-2e bonds.
e D 
→ KIO3
H H H
Cl Cl Cl 55. (a) Rb + O 2 (excess) 
→ RbO 2
2AlC3  → Al Al No 3c-2e bond
2RbO 2 + 2H 2 O 
→ 2RbOH + H 2 O 2 + O 2
Cl Cl Cl
CH3 CH3 56. (d) Catenation is not shown by lead.
CH3
Al Al 57. (a, b, d)
Has two 3c-2e bonds.
H2O
CH3 CH3 CH3 Sucrose 
hydrolysis
→ D(+ )Glu cos e+ D ( + ) Fructose
[ Dextrorotatory] [ Laevorotatory]
Also, BCl3 is stronger lewis acid than AlCl3.
44. (c) All halides of Be are predominantly covalent in nature. 6CH2OH 6CH2OH
H 5 OH H 5 O OH
45. (b) Mond's process is used for the purification of Nickel. 4 HOH 1 4 HOH H
OH H OH H 1
46. (d) Smaller is the size of central atoms, more water OH
HO 2 OH
O OH
HO 2 HO
3 3
molecules will crystallise hence Ba(NO3)2 is answer due HOHOH HOHOH
to its largest size of ‘+ve’ ion. α o = (112 o ) α o = (19 o )
47. (d) Inert pair effect is prominent character of p-block α − D − Glucopyranose β − D − Glucopyranose
elements. NaCN + O2
58. (b, c, d) Au  →[Au(CN4 )]⊙ 
Zn
→[Zn(CN)4 ]2− + Au
48. (d) According to the given diagram Al can reduce ZnO.
59. (a) A→1, 3; B → 1, 3; C → 2; D → 4
3ZnO + 2Al 
→ 3Zn + Al2 O3
60. (d) A→ 2; B → 3; C → 1; D → 2, 3
49. (d) Hall-Heroult's process is given by
61. (c) A → 1; B → 2; C → 1, 3; D → 1, 4
2Al2 O3 + 3C 
→ 4Al + 3CO2
62. (b) A→ 1, 4; B → 1, 2, 3, 5; C → 1, 2, 3; D → 1
2Al 2 O3 (ℓ) ↽ ⇀ 4Al3+ (ℓ) + 6O 2Θ (ℓ)
(A) (CH 3 ) 2SiCl2 + 2H 2 O → (CH 3 ) 2 Si(OH) 2 + 2HCl
At cathode:- 4Al3(ℓ+) + 12eΘ 
→ 4Al(ℓ) (CH 3 ) 2 Si(OH) 2 can undergo polymerisation to form
2Θ Θ
At Anode : 6O (ℓ ) → 3O2 (g) + 12e
 silicones.
1
3C+3O2 
→ 3CO2 ( ↑ ) (B) 3XeF4 + 6H 2O → XeO3 + 2Xe + 12HF + 1 O 2
2
50. (d) 1
(C) Cl 2 + H 2 O → 2HCl + O 2
51. (b) Be(OH)2 is amphoteric in nature while other alkaline 2
earth metal hydroxides are basic in nature. (D) VCl5 + H 2 O → VOCl3 + 2HCl
52. (a) B C 63. (b) A→3; B→ 4; C→ 2; D→1

Al Si ∆ 1
(A) PbO 2 + H 2SO 4  → PbSO 4 + H 2 O + O 2
Ga < Ge 2
Along the period electronegativity increases. (B) 2Na 2S2 O3 + Cl2 + 2H2 O 
→ 2NaCl + 2NaHSO4 + 2S
53. (d) Calcination in carried out for carbonates and oxide (C) N 2 H 4 + 2I 2 
→ N 2 + 4HI
ores in absence of oxygen. Roasting is carried out mainly
(D) XeF2 + 2NO 
→ Xe + 2NOF
for sulphide ores in presence of excess of oxygen.

64. (c) A→3; B→4; C→2; D→1 1
= × (0.25 × 48 ×10−3 ) = 6 ×10−3
(A) Siderite : FeCO3 2
(B) Kaolinite : Al2(OH)4Si2O5 Molarity ¥×25 × 10−3 = 6 × 10−3
(C) Malachite : Cu(OH)2.CuCO3
6
(D) Calamine : ZnCO3 Molarity of bleach solution = = 0.24 M
25
65. (a) According to Fajan’s rule, small cations having high 77. (a) Bleaching powder contains salt of HCl.
charge density always have tendency to form covalent It is obtained by adding H 2 O to Cl2 O.
bond.
Thus option (a) is correct.
66. (c) H 3BO3 (orthoboric acid) is a weak lewis acid. For Question Nos. 78 to 79
2NaOH + Cl 2 
→ NaCl + NaClO+ H 2 O
H 3 BO3 + H 2 O ↽ ⇀ B(OH) −4 + H + (Cold + dil) P
It does not donate proton rather it accepts O H − from 6NaOH + 3Cl2 

→ 5NaCl + NaClO3 + 3H 2 O
(Hot + conc.) Q
water.
Charcoal
Hence (c) is correct. SO 2 + Cl 2  → SO 2 Cl 2
R
67. (b) Blue colour is due to solvated electrons.
SO 2 Cl2 + P4 
→ PCl5 + SO 2
S
68. (c) The lower oxidation states for the group 14 elements
are more stable for the heavier member of the group due PCl5 + H 2 O 
→ H 3 PO 4 + HCl
T
to inert pair effect.
78. (a)
69. (a) 79. (a)
For Question Nos. 70 to 72 For Question Nos. 80 to 81
[MnO2 ]
70. (a) Argon is used mainly to provide an inert atmosphere in 2KClO3 → 2KCl + 3O 2
(W)
high temperature metallurgical (arc welding of
metals/alloys) extraction. 5O 2 + P4 
→ P4O10
(X)
Xe P4 O10 + 4HNO3 
→ 2N 2 O 5 + 4HPO3
(X ) ( Z)
71. (c)
O O
O 80. (c)
3
sp hybridised pyramidal structure. 81. (a)
Hence (c) is correct. 82. Coordination number of Al is 6. It exists in ccp lattice
with 6 coordinate layer structure.
72. (a) 6XeF4 + 12H 2 O 
→ 4Xe + 2XeO3 + 24HF + 3O 2
83. Be3Al 2Si 6 O18 (Bery1) (according to charge balance in a
XeF64 + 3H 2 O 
XeF → XeO3 + 6HF
molecule)
2n + 6 + 24 − 36 = 0 fi n=3
73. (c) 84. Six dipotic acids: H 2SO 4 , H 2 CO3 , H 2S2 O7 , H 2 CrO 4 , H3PO3, H 2SO3
74. (c) On going from top to bottom in nitrogen group the H 3 PO3 , H 2SO3
bond angle decreases due to more p-character in the bond
85. 3Br2 + 3CO32 − 
→ 5Br − + BrO3− + 3CO 2
pair and subsequently more s-character in lone pair
orbital. No. of sodium bromide molecules = 5
75. (b) P4 + 3NaOH + 3H 2 O 
→ 3NaH 2 PO 2 + PH 3 O O
+ +
86. ɺɺ − ɺɺ
N aO − S +−5 S S−S− O Na
For Question Nos. 76 to 77 ɺɺ0 ɺɺ0 +5
O O
76. (c) No. of moles of bleach solution
1 Difference in oxidation nos. = 5
= × No. of moles of Na 2S2 O3
2 87. Five compounds

88. XeF4 → Square planar Moles of CaO = 3 × 6 = 18
−
BrF → Square planar Wt. of CaO = 18 × 56 = 100 gm
4
2+ O
 Cu ( NH 3 )4  → Square planar
P
[ Pt Cl4 ]
2−
→ Square planar (b) O
O
SF4 → See–saw O
O
SiF4 → Tetrahedral O P P O
BF4− → Tetrahedral O O
2−
[FeCl4 ] → Tetrahedral P
[CoCl4 ]2− → Tetrahedral O

No. of species having a square planar shape is 4. 91. N(Me)3 and N(SiMe 3 )3 are not isostructural. N(Me)3 is
89. B2 H 6 + 6MeOH 
→ 2B(OMe)3 + 6H2 trigonal pyramidal while N(SiMe3 )3 is trigonal planar due
1 mole of B2H6 reacts with 6 moles of MeOH to give 2 to back bonding.
moles of B(OMe)3
3 moles of B2H6 will react with 18 moles of MeOH to Si(Me)3
give 6 moles of B(OMe)3 .
N N
90. (a) 6CaO + P4O10 
→ 2Ca 3 (PO4 )2
852 Me Me Si(Me)3
Moles of P4 O10 = =3 (Me)3Si
Me
284
Transition Elements: d- and f-Blocks 301
28 Transition Elements: d- and f-Blocks

QUICK LOOK Ionisation energy: The ionization energy (IE) of transition
elements are higher than those of s-block elements but
The series of elements, that are formed by filling the 3d, 4d and lower than p-block elements. In a particular transition
5d shells of electrons, comprise the d-block elements. They are series, ionization energy although increases gradually as we
often called as transition elements because their position in the move from left to right but this increase is not appreciable.
periodic table is between s-block and p-block elements.
The increase in ionisation energy is due to increase in
nuclear charge, the effect of increase in nuclear charge is
Electronic Configuration: The general electronic
partly balanced by the increase in screening effect.
configuration is (n − 1)1−10 ns1−2 where n is the outermost shell.
Consequently, the increase in ionisation energy along the
The number of electrons in their outermost subshell remains
period of d-block elements is very small.
two while their penultimate shell of electrons expands from 8 to
Variable oxidation states: Transition elements usually
18 electrons.
exist in several different oxidation states and the oxidation
Electronic configuration of 3d series states changes in units of one, e.g., Fe2+ and Fe+3 , Cu+1
Sc Ti V Cr Mn and Cu +2 .
1 2 2 2 3 2 5 1 5 2
3d 4s 3d 4s 3d 4s 3d 4s 3d 4s Scandium can have an oxidation number of (+II) if both s
Fe CO Ni Cu Zn electrons are used for bonding and (+III) when two s and
3d6 4s2 3d 7 4s 2 3d8 4s 2 3d10 4s1 3d10 4s 2 one d electrons are involved. Similarly, all the elements
Anamolous configuration of Cu and Cr: Copper and show variable oxidation states depending upon the number
chromium have a single electron in 4s-orbital. This is due to of electrons available for bonding in their s and d sub-shells.
the gain of additional stability by the atom having either Complexes and their properties: The transition elements
half-filled (5 electrons) or completely filled (10 electrons) have an unparalleled tendency to form coordination
d-shell. compounds with the Lewis bases, which are called as ligands.
3+
→  CO ( NH 3 )6 
CO 3+ + 6NH 3 
General Characteristics of Transition Elements
4−
Except for mercury, which is a liquid at room temperature →  Fe ( CN )6 
Fe 2 + + 6CN − 
all other elements are solid metals exhibiting all the
s and p-block elements form very few complexes. The
characteristics of a metal.
They show variable oxidation states unlike s and p block reason of transition elements are so good at forming
elements. complex is that they have small, highly charged ions and
They, and some of their compounds, show catalytic have vacant low energy orbitals to accept lone pairs of
properties. electrons donated by ligands.
Their compounds are coloured. Size of atoms and ions: The covalent radii of the elements
They have great tendency to form complex compounds. decrease from left to right across a row in the transition
They form alloys and interstitial compounds. series. This is because of the poor screening by the d
Conductivity: All the transition metals are good conductors electrons due to which, the nuclear charge attracts all of the
of heat and electricity. Silver is the best conductor of electrons more strongly, hence a contraction in size occurs.
electricity. The elements in the first group in the d-block show the
excepted increase (due to the addition of extra shell) in size
Density: Because of small size of their atoms and strong
Sc → Y  → La. However in the subsequent groups
metallic bonding the density and hardness of transition
elements are high. there is an increase between first and second members,

but hardly any increase between second and third elements. Alloy formation: Alloys are homogeneous solid solutions
This is due to lanthanide contraction (discussed in f-block of two or more metals obtained by melting the components
elements). and then cooling the melt. These are formed by metals
Colour: Many compounds of transition elements are whose atomic radii differ by not more than 15% so that the
coloured in contrasts to those of s and p block elements. In atoms of one metal can easily take up the positions in the
compound state due to the surrounding groups (ligands), the crystal lattice of the other. Since transition metals have
d-orbitals of transition elements are not degenerated but similar atomic radii, they form alloys very readily.
split into two groups of different energy. Thus it is possible
to promote electrons from one group to another group. This f-block Elements
corresponds to fairly small amount of energy difference and The elements in which the differentiating electron enters the
so light is absorbed in visible region. Some compounds of anti penultimate energy level i.e. (n – 2) f, are called f-block
transition metals are white, for example ZnSO 4 and TiO 2 . elements. These are often called as inner transition elements or
In these compounds it is not possible to promote the rare earth elements. The differentiating electron in transition
electrons within the d-level. elements may enter either 4f or 5f orbitals based upon which
Magnetic properties: On the basis of behaviour in a they are differentiated into lanthanides and actinides.
magnetic field, substances are classified as paramagnetic,
diamagnetic and ferromagnetic. Those substances which are Lanthanides: In lanthanides the differentiating electron enters
attracted by the applied magnetic field are called 4f orbital. These are cerium to lutetium. The name lanthanides
paramagnetic whereas those which are repelled by the is because they come immediately after lanthanum.
magnetic field are called diamagnetic. Substances which are
very strongly attracted by the applied field are called Actinides: In actinides the differentiating electron enters 5f
ferromagnetic. orbitals. These are thorium to lawrencium. These elements
Paramagnetism is a property due to the presence of unpaired come immediately after actinium.
electrons. Thus most of the transition metals are Electronic configuration: General electronic configuration
paramagnetic. As the number of unpaired electrons of f- block elements is (n − 2)f 1−14 (n − 1)d 0−1ns 2
increases, the paramagnetic character also increases. Lanthanides [ Xe] 4f 1−14 5d 0−1 6s 2
The magnetic moment is calculated from the following
Actinides [ Rn ] 5f 1−14 6d 0−1 7s 2
formula µ = n ( n + 2 ) B.M . Where n is the number of
unpaired electrons and B. M. stands for Bohr Magneton. Characteristics of Lanthanides
Catalytic properties: Many transition metals and their Oxidation states: Lanthanides show only one stable
compounds have catalytic properties. For e.g., oxidation state, which is not in the case of actinides. The
V2 O5 , Fe,FeCl3 , Ni,Pd etc. typical oxidation state of lanthanides is +3. Some elements
This property of transition elements is due to their variable show +2 and +4 also, when they lead to
oxidation states. In some cases the transition metals with (a) a noble gas configuration e.g., Ce 4+ (f 0 )
their variable valency may form variable unstable
(b) a half filled f shell e.g., Eu 2+ (f 7 )
intermediate compounds. In other cases the transition metal
provides a suitable reaction surface. (c) a completely filled f shell e.g., Yb 22+ (f 14 )
Non-stoichiometry: Another feature of the transition Lanthanide contraction: In lanthanide series with
elements is that they sometimes form non stoichiometry increasing atomic number there is a progressive decrease in
compounds. These are compounds of indefinite structure the atomic as well as ionic radii. This regular decrease is
and proportions. known as lanthanide contraction. This is due to the poor
Example: Fe0.94O. It is mostly due to the variable valency shielding of f orbitals, which are unable to counterbalance
of transition elements. Sometimes, non stoichiometry is the effect of increasing nuclear charge. Net result is
caused by defects in the solid structures. contraction in size.

Consequences of lanthanide contraction: Since the change in Multiple Choice Questions
ionic radii in lanthanides is very small (only 15 pm from One and More than One Correct
3+ 3+
Ce to Cu ), their chemical properties are similar. This 1. A solution when diluted with H 2 O and boiled, it gives a
makes the separation of the elements in pure state very difficult. white precipitate. On addition of excess NH 4 Cl / NH 4 OH,
Due to lanthanide contraction, the difference in size between the volume of precipitate decreases leaving behind a white
second (4d) and third (5d) is very small. As the size of the gelatinous precipitate. Identify the precipitate which
lanthanide ions decreases from La+3 to Lu+3 the covalent dissolves in NH 4 OH / NH 4 Cl. [JEE 2006]
character of the hydroxides increases and hence the basic a. Zn(OH) 2 b. Al(OH) 3
strength decreases. Thus La(OH)3 is most basic whereas Lu c. Mg(OH) 2 d. Ca(OH) 2
(OH)3 is least basic.
2. Extraction of zinc from zinc blende is achieved by
Complex formation: The lanthanides do not have much
[JEE 2007 P-I]
tendency to form complexes due to low charge density
a. electrolytic reduction
because of their size. However, the tendency to form complex
b. roasting followed by reduction with carbon
and their stability increases with increasing atomic number.
c. roasting followed by reduction with another metal
Chemical behaviour: The first few members of the series d. roasting followed by self-reduction
are quite reactive like calcium. However with increasing
3. Native silver metal forms a water soluble complex with a
atomic number, their behaviour becomes similar to that of
dilute aqueous solution of NaCN in the presence of
aluminium.
[JEE 2008 P-I]
They combine with H 2 on gentle heating. When heated with a. nitrogen b. oxygen
carbon, they form carbides. On burning in the presence of c. carbon dioxide d. argon
halogens, they form halides. 4. Among the following the coloured compound is
They react with dilute acids to liberate H2. [JEE 2008 P-II]
They form oxides and hydroxides of the type N2O3 and a. CuCl b. K 3 [Cu(CN) 4 ]
M(OH)3 which are basic alkaline earth metal oxides and c. CuF2 d. [Cu(CH 3 CN) 4 ]BF4
hydroxides.
5. Oxidation states of the metal in the minerals haematite
and magnetite, respectively, are [JEE 2011 P-II]
General Characteristics of Actinides
a. II, III in haematite and III in magnetite
Oxidation states: The dominant oxidation state of these
b. II, III in haematite and II in magnetite
elements is +3 (similar to lanthanides). Besides +3 state, c. II in haematite and II, III in magnetite
they also exhibit +4 oxidation state. Some actinides show d. III in haematite and II, III in magnetite
still higher oxidation states. The maximum oxidation state
6. The colour of light absorbed by an aqueous solution of
first increases upto the middle of the series and then
CuSO 4 is [JEE 2012 P-I]
decreases i.e. it increases from +4 for Th to +5, +6 and +7
a. orange –red b. blue –green
for Pa, V and Np but decreases in the succeeding elements. c. yellow d. violet
Chemical behaviour: The ability of actinides to exist in
7. Which of the following hydrogen halides react(s) with
different oxidation states has made their chemistry more
AgNO3 (aq) to given a precipitate that dissolves in
complex. Moreover, most of these elements are radioactive
and the study of their chemistry in the laboratory is difficult. Na 2S2 O3 (aq)? [JEE 2012 P-I]
They react with boiling water to give a mixture of oxide and a. HCl b. HF
hydride. c. HBr d. HI
All these metals are attacked by HCl but the effect of HNO3 8. In the cyanide extraction process of silver from argentite
is very small due to the formation of a protective oxide ore, the oxidizing and reducing agents used are.
layer on their surface. [JEE 2012 P-II]

a. O 2 and CO respectively c. Both Cr 2 + and Mn3+ exhibit d 4 electronic configuration
b. O 2 and Zn dust respectively d. When Cr 2 + is used as a reducing agent, the chromium
c. HNO3 and Zn dust respectively ion attains d 5 electronic configuration
d. HNO3 and CO respectively 16. Copper is purified by electrolytic refining of blister
copper. The correct statement(s) about this process is(are)
9. Which of the following arrangements does not represent
[JEE Adv. 2015 P-I]
the correct of the property state against it?
a. Impure Cu strip is used as cathode
[JEE Main 2013]
b. Acidified aqueous CuSO 4 is used as electrolyte
a. V 2+ < Cr 2+ < Mn 2+ < Fe2+ : paramagnetic behaviour
c. Pure Cu deposits at cathode
b. Ni 2+ < Co2+ < Fe2+ < Mn 2+ : ionic size
d. Impurities settle as anode – mud
c. Co3+ < Fe3+ < Cr3+ < Sc3+ : stability in aqueous solution
17. Fe3+ is reduced to Fe 2 + by using [JEE Adv. 2015 P-I]
d. Sc < Ti < Cr < Mn : number of oxidation states
a. H 2 O 2 in presence of NaOH
10. Four successive members of the first row transition
b. Na 2 O 2 in water
elements are listed below with atomic numbers. Which
one of them is expected to have the highest E 0M3+ / M2+ c. H 2 O 2 in presence of H 2SO 4
d. Na 2 O 2 in presence of H 2SO 4
value? [JEE Main 2013]
a. Cr(Z = 24) b. Mn(Z = 25) 18. Galvanization is applying a coating of [JEE Main 2016]
c. Fe(Z = 26) d. Co(Z = 27) a. Pb b. Cr c. Cu d. Zn
19. Which of the following compounds is metallic and
11. Experimentally it was found that a metal oxide has
ferromagnetic? [JEE Main 2016]
formula M 0.98O. Metal M, is present as M 2+ and M 3+ in
a. TiO 2 b. CrO 2 c. VO 2 d. MnO 2
its oxide. Fraction of the metal which exists as M3+
would be [JEE Main 2013] 20. In the following reactions, ZnO is respectively acting as
a. 7.01 % b. 4.08 % c. 6.05% d. 5.08% a/an [JEE Main 2017]
(A) ZnO + Na 2 O 
→ Na 2 ZnO 2
12. Sulfide ores are common for the metals
[JEE Adv. 2013 P-I] (B) ZnO + CO 2 
→ ZnCO3
a. Ag, Cu and Pb b. Ag, Cu and Sn a. acid and base b. base and acid
c. Ag, Mg and Pb d. Al, Cu and Pb c. base and base d. acid and acid
13. Upon heating with Cu 2S the reagent(s) that give copper 21. The option(s) with only amphoteric oxides is(are)
metal is/are [JEE Adv. 2014 P-I] [JEE Adv. 2017 P-II]
a. CuFeS2 b. CuO a. ZnO, Al 2 O3 , PbO, PbO 2 b. Cr2 O3 , CrO, SnO, PbO
c. Cu 2 O d. CuSO 4 c. Cr2O3 , BeO, SnO, SnO 2 d. NO, B2 O3 , PbO, SnO 2
14. The color of KMnO 4 is due to [JEE Main 2015] 22. With respect to an ore, Ellingham diagram helps to predict
a. M → L charge transfer transition the feasibility of its – [JEE Main 2019]
a. Vapour phase refining b. Zone refining
b. d − d transition
c. Electrolysis d. Thermal reduction
c. L → M charge transfer transition
23. The ore that contains both iron and copper is:
d. σ − σ * transition
[JEE Main 2019]
15. The correct statement(s) about Cr 2 + and Mn3+ is(are) a. Malachite b. Dolomite
[Atomic numbers of Cr = 24 and Mn = 25] c. Azurite d. Copper pyrites
[JEE Adv. 2015 P-I]
24. The 71st electron of an element X with an atomic number
2+
a. Cr is a reducing agent of 71 enters into the orbital: [JEE Main 2019]
b. Mn3+ is an oxidizing agent a. 4f b. 6p c. 6s d. 5d

25. The metal d-orbitals that are directly facing the ligands in 29. Match each of the reactions given in Column I with the
K3[Co(CN)6] are : [JEE Main 2019] corresponding product(s) given in Column II.
a. dxz, dyz and d z 2 b. dxy, dxz and dyz [JEE 2009 P-II]
c. dxy and d x 2 −y 2 d. d x 2 −y 2 and d z 2 Column I Column II

(A) Cu + dil HNO3 1. NO
26. The pair that does NOT require calcination is:
(B) Cu + conc HNO3 2. NO 2
[JEE Main 2019]
a. ZnO and MgO (C) Zn + dil HNO3 3. N 2 O
b. Fe2O3 and CaCO3.MgCO3 (D) Zn + conc HNO3 4. Cu(NO3 )2
c. ZnO and Fe2O3.xH2O
5. Zn(NO3 )2
d. ZnCO3 and CaO
a. A→ 1,2; B→ 1,3; C→ 3,4; D→ 2
Matrix Match/Column Match b. A→ 1,4; B→ 2,4; C→ 3,5; D→ 2,5
c. A→ 3,4; B→ 1,2; C→ 1,2; D→ 2,4
27. Match the extraction processes listed in Column I with
d. A→ 1,2,3; B→4,5; C→ 1,2; D→ 1
metals listed in Column II: [JEE 2006]
Column I Column II 30. Match the statement of Column I with those in Column II:
(A) Self reduction 1. Lead [JEE Main 2015]
(B) Carbon reduction 2. Silver Column I (Catalyst) Column II (Process)
(C) Complex formation 3. Copper (A) TiCl3 1. Wacker process
and displacement by (B) PdCl2 2. Ziegler-Natta
metal polymerization
(D) Decomposition of 4. Boron (C) CuCl2 3. Contact process
iodide
(D) V2 O 5 4. Deacon’s process
a. A→ 1,3; B→ 1,3; C→ 2; D→ 4
b. A→ 1,2; B→ 2,3; C→ 1,3; D→ 4 a. A→ 2; B→ 1; C→ 4; D→ 3
c. A→ 1,2,3; B→ 1,2; C→ 1,2; D→ 4 b. A→ 1; B→ 2; C→ 3; D→ 4
c. A→ 3; B→ 1; C→ 2; D→ 4
d. A→ 1,2,3,4; B→ 4; C→ 2; D→ 1
d. A→ 3; B→ 4; C→ 2; D→ 1
28. Match the reactions in Column I with nature of the
31. Match the following items in column I with the
reactions/type of the products in Column II.
corresponding items in column II. [JEE Main 2019]
[ JEE 2007 P-II]
Column I Column II
Column I Column II
(A) Na2CO3·10 H2O (1) Portland cement ingredient
(A) O −2  → O 2 + O 22− 1. redox reaction
(B) Mg(HCO3)2 (2) Castner-Kellner process
(B) CrO24− + H + 
→ 2. one of the (C) NaOH (3) Solvay process
products has
(D) Ca3Al2O6 (4) Temporary hardness
trigonal planar
structure
a. A→1; B→3; C→4; D→2
(C) MnO −4 + NO −2 + H + 
→ 3. dimeric bridged
tetrahedral metal b. A→3; B→4; C→2; D→1
ion c. A→1; B→3; C→2; D→4
(D) NO3− + H2SO4 + Fe2+ 
→ 4. disproportionation d. A→3; B→1; C→2; D→4
a. A→ 1,2; B→ 1,3; C→ 2, 4; D→ 2 Paragraph

b. A→ 1,4; B→ 3; C→ 1,2; D→ 1 Paragraph for Question Nos. 32 to 34
c. A→ 1,3; B→ 1,2; C→ 2; D→ 1,2,3,4
Copper is the most noble of the first row transition metals and
d. A→ 1,2,3; B→ 1,4; C→ 1, 2; D→ 1
occurs in small deposits in several countries. Ores of copper

include chalcanthite (CuSO4 ⋅ 5H 2O), atacamite (Cu 2Cl(OH)3 ), 39. Fe3+ 
−
SCN (excess)
→ blood red (A) 
F (excess) −
→ colourless (B)
cuprite (Cu 2 O), copper glance (Cu 2S) and malachite Identify A and B.
(Cu 2 (OH)2 CO3 ). However, 80% of the world copper (a) Write IUPAC name of A and B.
(b) Find out spin only magnetic moment of B.
production comes from the ore of chalcopyrite (CuFeS2 ).
[JEE 2005]
The extraction of copper from chalcopyrite involves partial
roasting, removal of iron and self-reduction. 40. (B) ←
Moist air
 MCl 4 
Zn
→ (A)
white fumes having (M = transtitionelement
(M)=transition element (purple color)
pungent smell colourless)
[JEE 2010 P-I] colourless
32. Partial roasting of chalcopyrite produces Identify the metal M and hence MCl 4 . Explain the
a. Cu 2S and FeO b. Cu 2O and FeO difference in colours of A and MCl 4 . [JEE 2005]
c. CuS and Fe 2 O3 d. Cu 2O and Fe 2O3 41. The oxidation number of Mn in the product of alkaline
33. Iron is removed from chalcopyrite as oxidative fusion of Mn O 2 is_____ [JEE 2009 P- II]
a. FeO b. FeS 42. The number of water molecule(s) directly bonded to the
c. Fe 2O 2 d. FeSiO3 metal centre in CuSO 4 ⋅ 5H 2 O is_____ [JEE 2009 P-II]
34. In self- reduction, the reducing species is
a. S b. O2− ANSWERS and SOLUTIONS
2−
c. S d. SO2 1. (a) Due to formation of tetraammine zinc (II) complex
Zn +2 + NH 4 OH 
→ [Zn(NH 3 )4 ]+2
When a metal rod M is dipped into an aqueous colourless 2. (b) Option (B) is correct.
concentrated solution of compound N, the solution turns light 3. (b) Ag dissociates in a solution of NaCN in the presence
blue. Addition of aqueous NaCl to the blue solution gives a of air, forms sodium argentocyanide.
white precipitate O. Addition of aqueous NH 3 dissolves O and 4Ag + 8NaCN + 2H 2 O + O 2 
→ 4 Na[Ag(CN) 2 ] + 4NaOH
gives an intense blue solution. [JEE 2011 P-I] 4Ag + 8NaCN + 2H 2 O + O 2 
→ 4 Na[Ag(CN) 2 ] + 4NaOH
35. The metal rod M is 4. (c) In the crystalline form CuF2 is blue colored.
a. Fe b. Cu
c. Ni d. CO 5. (d) Haematite: Fe 2 O3 : 2x + 3 × (−2) = 0
36. The compound N is x=3
a. AgNO3 b. Zn(NO 3 ) 2 Magnetite: Fe3 O 4 [an equimolar mixture of FeO and
c. Al(NO3 )3 d. Pb(NO3 )2 Fe 2 O3 ]
FeO : x − 2 = 0 ⇒ x = 2
37. The final solution contains
Fe 2 O3 : x = 3
a. [Pb(NH3 )4 ]2 + and [CoCl 4 ]2 −
b. [Al(NH 3 ) 4 ]3+ and [Cu(NH3 )4 ]2+ 6. (a) The CuSO 4 solution is blue. The colour that is
absorbed complementary to the colour that is observed.
c. [Ag(NH 3 ) 2 ]+ and [Cu(NH3 )4 ]2+
7. (a, c, d) HCl, HBr, HI gives AgCl, AgBr, AgI, ppt. HF
d. [Ag(NH 3 ) 2 ]+ and [Ni(NH 3 )6 ]2 +
does not react with HF.
Ag + forms a water soluble [Ag(S2 O3 ) 2 ]3− ion.
38. Write balanced chemical equation for developing a black 8. (b) Ag 2S + 4NaCN ↽ ⇀ 2NaAg(CN) 2 + Na 2S
and white photographic film. Also give reason why the 0
solution of sodium thiosulphate on acidification turns 4Na 2S + 5O 2 + 2H 2O 

→ 2Na 2SO 4 
→ 4NaOH + 2S
ox
milky white and give balance equation of this reaction.
+1 0
[JEE 2005] 2Na Ag(CN) 2 + Zn 
→ NaZn(CN) 4 + 2A g

− 2+ +2 NO is neutral oxide. CrO is basic oxide. B2O3 is acidic
9. (a) Number of unpaired e in Fe is less than Mn .
oxide.
10. (d) Factual
22. (d) Ellingham diagram helps in predicting the feasibility
11. (b) 3x + 2 (0.98 − x) = 2
of thermal reduction of ores.
x + 1.96 = 2 , x = 0.04
23. (d) Copper pyrites CuFeS2 :
0.04
+3
% of M = ×100 = 4.08% Malachite : Cu(OH)2 ⋅ CuCO3
0.98
Azurite Cu(OH)2 ⋅ 2CuCO3
12. (a) Sulfide ore of Ag → Argentite (Ag 2S), Pb → Galena
Dolomite CaCO3 ⋅ MgCO 3
(PbS), Cu → Copper glance (Cu2S). Hence (A) is correct.
13. (a, c, d) 24. (a)
∆
(A) 2CuFeS2 + O 2 
→ Cu 2S + 2FeS + SO 2 25. (d) K3[Co(CN)6]
1100° C
(B) 4CuO  → 2Cu 2 O + O 2 Co +3 
→[Ar]18 3d 6
∆ eg
2Cu 2O + Cu 2S  → 6Cu + SO 2
dx2y2
∆
(C) Cu 2S + 2Cu 2 O  → 6Cu + SO 2 t2g
1 dxy dyz dxz
720° C
(D) CuSO 4  → CuO + SO 2 + O 2
2 26. (a) ZnO and MgO both are in oxide form therefore no
1100° C
4CuO → 2Cu 2 O + O 2 , change on calcination.
∆
2Cu 2 O + Cu 2S  → 6Cu + SO 2 27. (a) A→ 1,3; B→ 1,3; C→ 2; D→ 4
14. (c) 28. (b) A→ 1,4; B→ 3; C→ 1,2; D→ 1
15. (a, b, c) 29. (b) A→ 1,4; B→ 2,4; C→ 3,5; D→ 2,5

(A) Cr 2 + is a reducing agent because Cr 3+ is more stable. 3Cu + dil.8HNO3 → 3Cu(NO3 ) 2 + 4H 2 O + 2NO
(B) Mn 3+ is an oxidising agent because Mn 2 + is more stable. Cu + conc.4HNO3 → Cu(NO3 ) 2 + 2H 2 O + 2NO 2
(C) Cr 2 + and Mn 3+ exhibit d 4 electronic configuration. 4Zn + dil.10HNO3 → 4Zn(NO3 ) 2 + 5H 2 O + N 2 O

Zn + conc.4HNO3 → Zn(NO3 )2 + 2H 2O + 2NO 2
16. (b, c, d)
(B) Impure Cu strip is used as anode and impurities settle 30. (a) A→ 2; B→ 1; C→ 4; D→ 3
as anode mud. TiCl3 = Ziegler-Natta polymerisation, PdCl2 = Wacker
(C) Pure Cu deposits at cathode. process
(D) Acidified aqueous CuSO 4 is used as electrolyte. CuCl2 = Deacon’s process, V2O5 = Contact process
17. (a, b) 2Fe +3 + H 2 O 2 + 2OH − 

→ 2Fe +2 + 2H 2 O + O 2 31. (b) A→3; B→4; C→2; D→1
Na 2CO3 .10H2 O 
→ Solvay process
Na 2 O 2 + H 2 O 
→ H 2 O 2 + NaOH
Mg(HCO3 )2 
→ Temporary hardness
18. (a) Galvanization is applying a coating of Zn.
NaOH 
→ Castner–Kellner cell
19. (b) NCERT based (Solid state).
Ca 3 Al2 O6 
→ Portland cement
20. (a) Although ZnO is an amphoteric oxide but in given
reaction For Question Nos. 32 to 34
(A) ZnO + Na 2 O 
→ Na 2 ZnO 2 32. (b) 2CuFeS2 + O 2 → Cu 2S + 2Fes + SO 2 ↑
acid base salt
2CuS + 3O 2 → 2Cu 2 O + 2SO 2 ↑
(B) ZnO + CO 2 
→ ZnCO 3
base acid salt 2FeS + 3O 2 → 2FeO + 2SO 2 ↑
21. (a, c) ZnO,Al 2O3 , PbO, PbO 2 ,Cr2 O3 , BeO,SnO and SnO2
33. (d) FeO + SiO 2 → FeSiO3
are amphoteric oxides. (slag )

34. (c) Cu 2S + 2Cu 2 O → 6Cu + SO 2 ↑
[ Fe(SCN)(H 2O)5 ]
2+
(Blister copper ) 39. Fe3+ + SCN − →
aqueous
(excess)
(A) (blood red)
S2− → S4+ is oxidation, i.e., S2− is reducing agent.
[ Fe (SCN)(H 2O)5 ] 2+
+ 6F− →
aqueous
(excess)
Fe F6
3−
+ SCN − + 5H 2O
(A) (blood red) (B) (blood red)
[ Fe F6 ]
2+ 3−
35. (b) Fe (SCN)(H 2 O)5 + 6F− → + SCN − + 5H 2 O
(A) (blood red) (B) (blood red )
(colourless)
36. (a) (a) Pentaaquathiocyanato iron (III) ion, hexafluroferrate
37. (c) 2AgNO3 + Cu 
→ Cu(NO3 ) 2 + 2Ag (III)
N M Light blue
(b) Magnetic moment = n(n + 2) = 35 = 5.92 B.M.,
AgNO3 + NaCl 
→ AgCl + NaNO3
White ppt O where n = number of unpaired electrons.
Cu 2 + + 4NH 3 
→ [Cu(NH 3 ) 4 ]2 +
M = Ti, A = [ Ti(H 2 O)6 ] , B = TiO 2
3−
40.
+ −
AgCl + 2NH 3 
→ [Ag(NH 3 ) 2 ] Cl
Ti ( + IV) ion contains no d-electrons, while d–d transition
38. (a) Reactions used in developing the photographic film of single electron of Ti (+ III) will cause colour change.
2AgBr + C6 H 4 (OH) 4 
→ 2Ag + 2HBr + C6 H 4 O 2
Hydroquinone
(developer )
(back silver
(black silver
particles)
particles)
quinone
41. 2MnO 2 + 4KOH + O 2 → 2K 2 MnO 4 + 2H 2 O
(Potassiummanganate)
(Potassium manganate)
AgBr → Na 3 [ Ag(S2 O3 ) 2 ] + NaBr
+ 2Na 2S2 O3 
(sensitive un
on exposed
exposed Hypo solution
O.S. of Mn = +6 in K 2 MnO 4
emulsion )
emulsion)
42. CuSO 4 ⋅ 5H 2 O → [Cu(H 2 O)4 ]SO 4 ⋅ H 2 O
(b) Na 2S2O3 + 2H + 
→ 2Na + + H 2SO3 + S↓
colloidal sulphur
So, water molecules directly attached to Cu are 4.
Coordination Compounds 309
29 Coordination Compounds
QUICK LOOK solution are called co-ordination compounds. For example,
when KCN solution is added to Fe(CN) 2 solution, the
Molecular or addition compounds are formed when species formed, no longer gives tests of Fe 2+ and CN − .
stoichiometric amounts of two or more stable compounds join
Fe(CN2 ) + 4KCN 
→ Fe(CN).4KCN or
together. These fall into two categories:
(a) Those which lose their identity in solution. K 4 [Fe(CN)6 (aq.) ↽ ⇀ 4K + (aq.) + [Fe(CN 6 )(aq)]
4:1 complex
(b) Those which retain their identity in solution.
An aqueous solution of carnallite shows the properties of Other examples are, [Cu(NH 3 )4 ]SO 4 (aq.) ↽ ⇀
K + , Mg 2+ and Cl− ions. Potassium alum solutions similarly [Cu(NH 3 ) 4 ]2 + (aq.) + SO 24 − (aq.) K 2 [Zn(CN 4 )](aq.)
1:1 complex
show the properties of K + , Al3+ and SO 24− ions. They are called
+ 2−
double salts and exist only in the crystalline state. The other ↽ ⇀ 2K (aq.) + [Zn(CN) 4 ] (aq.)
2 :1 complex
two examples of addition compounds behave in a very different
Also, coordination compound is defined as species in which
way from the double salts. When dissolved they do not form
metal atom or ion is attached to group of neutral
2+ −
Cu 2 − , or Fe and CN ions, but instead give more complicated molecules/ions by coordinate covalent bonds.
structures—the cuproammonium ion [Cu(H 2 O) 2 (NH3 )4 ]2+ and Ligand: It is an ion or molecule capable of donating a pair
of electrons to the central atom via a donor atom. The
the ferrocyanide ion [Fe(CN)6 ]4− . These are complex ions and
neutral molecules, anions or cations which are directly lined
exist are a single entity. Complex ions are indicated by square with central metal atom or ion in the coordination entity are
brackets. Molecular compounds of this type are called co-
called ligands. Ligands may be simple ions such as Br − ,
ordination compounds. Coordination compounds are the
compounds in which the central metal atom is linked to ions or small molecules such as H 2O or NH3 , larger molecules
2+ such as H 2 NCH 2 CH 2 NH 2 or N(CH 2 CH 2 NH 2 )3 or even
neutral molecules by coordinate bonds, e.g. Cr ( H 2O )5 Cl  .
macromolecules such as proteins.
If the species thus formed as given above carries positive
When a ligand is attached to a metal ion through a single donor
charge, it is called a complex ion.
atom, as with Cl − ,H 2 O or NH3 , the ligand is said to be
Double salts: Those addition compounds which lose their
identity in solution are called double salts. For example, unidenate. Similarly when a ligand is bond through two dononr
when K 2SO 4 solution is added to Al 2 (SO 4 )3 solution, atoms, as in H 2 NCH 2 CH 2 NH 2 (ethane-1, 2-diamine) or
species formed gives tests of K + , Al3+ and SO24− ions. C 2 O 42− (oxalate), the ligand is said to be bidentate and when
several donor atoms are present in a single ligand as in
K2SO4 + Al2 (SO4 )3 + 24H2O 
→K2SO4 .Al2 (SO4 )3.24H2O
N(CH 2 CH 2 NH 2 )3 or ethylene-diaminetetraacetic acid
↽
(aq.)
⇀ (aq.) + 2Al+3 (aq). + 4SO24− (aq.) (EDTA), the ligand is said to be polydentate.
Other Examples Classification of Ligands: There are several ways to

Ferric alum: K 2SO 4 .Fe 2 (SO 4 )3 .24H 2 O classify ligands and these are discussed as under:
Chrome alum: K 2SO 4 .Cr2 (SO 4 )3 .24H 2O Based upon charges
Carnallite: KCl.MgCl2 .6H 2O (a) Neutral ligands: H 2 O, NO,CO,C6 H 6 , etc.
+ +
Mohr’s salt: (NH 4 ) 2 SO 4 .FeSO 4 6H 2 O (b) Positive ligands: N O and NH 2 − N H 3
Tutton salt: M 2SO 4 ,CuSO 4 .6H 2 O [M = Na, K]
(c) Negative ligands: Cl− , NO2− ,CN− ,OH−
Coordination compounds: Those addition compounds
Based upon denticity of the ligand: The number of
which retain their identity (i.e., doesn’t lose their identity) in
donations accepted by a central atoms from a particular

ligand is known as the denticity of the ligand. Ligands may central atom but also accept the electron cloud from the
be classified as follows based on their denticity: central atom in their low-lying vacant orbitals. This kind of
Monodentate: Only one donation is accepted from the back donation is known as ‘synergic effect’ or ‘synergic
ligand. bonding’.
Example: H 2 O, NO, CO, NH 3 , CO32− ,Cl− , etc. Example: Co, CN, NO, PF3 , PR 3 (R = H, Et, Ph...),
Bidentate: Ligands with two donor atoms, e.g. ethyl- C2 H 4 , C2 H 4 , CO 2 , etc.
2−
enediamine, C2O (oxalate ion) etc. Two donations are
4
(a) In case of CO, the back donation to the π* orbital of
accepted from the ligand. central atom may be depicted as:
Chelating ligand: Multidentate ligand simultaneously co- π*
ordinating to a metal ion through more than one site, a : C≡ M=C=O
M
ligand that can form a ring structure with the central atom is
called a chelating ligand. All polydentate ligands are the π*
Figure: 29.1
example of chelating ligands. Chelated complexes are more
stable than similar complexes with monodentate ligands as By valence bond or molecular orbital theory, it is well
dissociation of the complex involves breaking two bonds understood that the bond order of C—O bond decreases but
rather than one. However, it must be noted that NH 2 NH 2 the C—O bond length must increase due to synergic effect.
+
and N ( CH 2 − CH 2 )3 N cannot act as chelating ligands due Similarly, as CN and N O are isoelectronic with CO, so
to the formation of three membered ring and locked back donation takes place in these species also in the π *
structure, respectively. orbitals and the same conclusion can be drawn for the bond
ɺɺ order and bond lengths.
H 2 C — NH 2 O == C — O −:
Example: | | (b) In case of PR3, the back donation may be depicted as:
ɺɺ
H 2 C — NH 2 O == C — O −: Vacant 3d orbital accepts
Ethylene diamine Oxalateion
the back donation
Ambidentate ligand: A ligand that may have more than
one kind of donor sites but at a time only one kind of donor M : P
site is utilised for donation is called as ambidentate ligand.
Ligands which can ligate through two different atoms Figure: 29.2
−
present in it. Examples of such ligands are the NO and 2
(c) In case of C2H4, the back donation may be depicted
− using the example of Zeise’s salt.
SCN − ions. NO2 ion can coordinate through either the
H
nitrogen or the oxygen atoms to a central metals atom/ion. *
Similarly, SCN − ion can coordinate through the sulphur or Cl Cl π C H

Pt
nitrogen atom. Such possibilities give rise to linkage
Cl H
isomerism in coordination compounds. For example, π* C
O
M ← N nitrito-N H
O Figure: 29.3
M ←
 O — N == O nitrito-O Here the back donation is accepted in the π* orbitals of C—C
M ←
 SCN thiocyanato or thiocyanato-S bond. Hence, the bond order of C—C bond decreases and the
M ←  NCS isothiocyanato or thiocyanato-N bond length increases as compared to free C2H4 molecule. Due
Based upon bonding interaction between the ligand and to back bonding C2H4 molecule loses its planarity. Similarly,
the central atoms C2H2 molecules loses its linearity not the planarity.
(a) Classical or simple donor ligand: These ligands only
IUPAC Nomenclature of complex compounds: In order
donate the lone pair of electrons to the central atom. For
to name complex compounds certain rules have been
example, O2− ,OH− ,F− , NH2− , NH3 , N3− ,etc. framed by IUPAC. These are as follows:
(b) Non-classical or π-acid or π-acceptor ligand: These The positive part of a coordination compound is named first
ligands not only donate the lone pair of electrons to the and is followed by the name of negative part.

The ligands are named first followed by the central metal. [(CO)3 Fe(CO)3 Fe(CO)3 ]
tri- µ carbonylbis [tricarbonyliron (0)]
The prefixes di-, tri-, tetra-, etc., are used to indicate the
number of each kind of ligand present. The prefixes bis [Be O(CH COO) ]
4 3 6
hexa -µ -acetato(O,O')-µ4oxotetraberyllium(II)
(two ligands), tris (three ligands), etc., are used when the
If any lattice component such as water or solvent of
ligands includ a number e.g., dipyridyl, bis
crystallisation are present, these follow the name and are
(ehylenediamine).
preceded by the number of these groups (molecules of
In polynuclear complexes, the bridging group is indicated in
the formula of the complex by separating it from the rest of solvent of crystallisation) in Arabic numerals.
the complex by hyphens. In polynuclear complexes (a [Cu(H 2O)4 ]SO 4 .H 2 O
Tetraaquacopper(II)sulphate1− water
complex with two or more metal atoms), bridging ligand
[Cr(H O) Cl ]Cl.2H O
(which links two metal atoms) is denoted by the prefix µ 2 4 2 2
tetraaquadichlorochromium (III( chloride 2-water
before its name. Following punctuation rules should also be followed while
Naming of ligands: The different types of ligands i.e. writing the name of the complex compounds. The name of the
neutral, negative or positive are named differently in a complete compound should not start with a capital letter, e.g.,
complex compound. When a complex species has negative [Cu(NH ) ]SO 3 4 4
charge, the name of the central metal ends in – ate. For Tetraamminecopper (II) sulphate (Correct)
Tetraamminecopper (II) sulphate (Incorrect)
some elements, the ion name is based on the Latin name of The full name of the complex ion should be written as one
the metal (for example, argentate for silver). Some such
word without any gap. There should be a gap between the
Latin names used (with the suffix – ate) are given below:
cation and anion in case of ionic complexes. The full name
Fe Ferrate Cu Cuperate of non-ionic complexes should be written as one word
Ag Argentate Au Aurate without any gap.
Sn Stannate Pb Plumbate Drawbacks of valence bond theory
(a) The classification of complexes as ionic or outer orbital
Point of attachment in case unidentate ligands with and covalent or inner orbital is arbitrary. It could not
more than coordinating atoms (ambidentate ligands) : explain why some complexes of metal ion use inner orbitals
The point of attachment in case of unidentate ligands with (d 2sp3 , low spin complexes) whereas some other make
more than one coordinating atom is either indicated by high spin complexes (sp 3 d 2 ).
using different names for the ligands (e.g, thiocyanato and
(b) The explanation offered in the VBT for many complexes
isothiocyanato) or by placing the symbol of the donor
of Cu(II) involving promotion of a 3d electron to a 4p
atom attached, the name of the ligand separated by a
orbital was unsatisfactory, as explained earlier. It can’t
hypen.
predict effectively whether a four coordinated complex is
(NH ) [Cr(SCN) ]
4 3 6 (NH ) [Pt(NCS) ]
4 2 6 tetragonal or square planar e.g., [Cu(NH 3 ) 4 ]2 + is suggested
Ammonium hexathioxyanato -S-chromate (III) Ammonium hexathiocyanato -N-platinate (IV)
or or
Ammonium hexathiocyanatochromate (III) Ammonium hexaisothiocyanatoplatinate (IV) to have sp3 configuration by Valence Bond. Theory, but X-
Name of the bridging groups: If a complex contains two rays study shows its geometry as square planar, i.e., dsp 2 .
or more central metal atoms or ions, it is termed as
(c) It doesn’t explain the variation of magnetic properties of
polynuclear. In certain polynuclear complexes, ligands may
complex with temperature.
link the two metal atoms or ions. Such ligands which link
(d) It doesn’t explain or predicted any distortion in symmetrical
the two metal atoms or ions in polynuclear complexes are
complexes. A number of assumptions are involved.
termed as bridge ligands. These bridge ligands are separated
(e) There is no quantitative interpretation of magnetic data.
from the rest of the complex by hyphens and denoted by the
(f) It has nothing to say about the spectral properties of
prefix µ . If there are two or more bridging groups of the
coordination compounds.
same kind, this is indicated by di- µ−, tri −µ −, etc.
(g) It does not give a quantitative interpretation of the
[(NH 3 )]5 Co − NH 2 − Co(NH 3 )5 ](NO3 )5 thermodynamic or kinetic stabilities of coordination
µ -amidobis [pentaamminecobalt (III)] nitrate
compounds.
[(NH 3 )5 Co − OH − Co(NH 3 )5 ]Cl5
µ - hydroxobis [pentaamminecobalt (III) ] chloride (h) It does not distinguish between strong and weak ligand.

Crystal field theory: The crystal field theory, first proposed Thus these latter two orbitals have no independent
by Hand Bethe in 1929 to explain the colour and magnetic existence, but the d z 2 can be thought of as having the
properties of some solid crystalline salts of metals. It was average properties of the two shown in figure 29.4.
also applied to interpret the electronic spectra of transition Therefore, since both have high electron density along the
metal complexes. The principal qualitative aspects of the
z-axis, the d z 2 orbital has a large fraction of its electron
crystal field theory (CFT) may be summarized as follows.
(a) It is a hypothetical modal in which the ligands are density concentrated along the same axis. Also, since one of
imagined to be point negative charges (either from the net the component wave function (d z 2 − x 2 ) has lobes the x-axis
negative charge on the ligand or from the negative end of and the other (d z 2 − y2 ) along the y-axis, the resultant d z 2
the ligand dipole arising from the lone pair of electrons on
orbital has a tours of electron density in the xy plane, which
its donor atom). the ionic ligands (e.g., F–,Cl– etc.) are
is often referred to as “doughnut or collar”. It will be better
regarded as negative point charges, while neutral ligands
to divide the set of d orbitals in two groups:
(e.g., H2O,NH3 etc) are regarded as dipoles. z
(b) The bonding between the central metal cation and
ligands is purely electrostatic or coulombic in nature. The
theory now considers only the electrostatics interaction dz2 −x2 x
z
between a metal and the ligands. This may be considered in
two steps: (a) electrostatics attraction between the positive
z x
nucleus of the metal and the negatively charged electrons of
the ligands (imagined as point charges): (b) electrostatic y
repulsion force between the electrons in the valence shell of
the metal and the ligand electrons.
(c) The arrangement of the ligands around the central metal dy2−z2
y
ion is such that the repulsion between these negative points
Figure: 29.4
is minimum.
(d) Splitting of d-orbital energies: The five d-orbitals in an (a) The orbitals in which lobes lie along the axes (dx2 − y2 .dz2 ) :
isolated gaseous metal atom/ion are degenerate i.e., they reffered to as "e g " orbitals in Octahedral symmetry and “e”
have equal energy. If a spherically symmetric field of
orbitals in Tetrahedral symmetry. (Also called as doubly
negative charges is placed around the metal, the orbitals will
degenerate orbitals).
remain degenerate, but all of them will be raised in energy
(b) The orbitals in which lobes lies in between the axes
as a result of repulsion between the negative field and the
(d xy ,d yz ,d zx ) : reffered to as "t 2g " orbitals in Octahedral
negative electrons in the orbitals. If the field results from
the influence of real ligands (either anions or the negative symmetry and "t 2 " orbitals in Tetrahedral symmetry. (Also
ends of dipolar ligands, such as NH 3 or H 2 O), the called triply degenerate orbitals.)
symmetry of the field will be less than spherical and the Crystal field splitting of d-orbitals in octahedral
degeneracy of the d-orbitals will be removed. It is this complexes: Assume six ligands symmetrically positioned
splitting of d orbital energies and its effects that form the along the Cartesian axes, with metal atom at origin as
basis of crystal field theory. shown in the figure 29.5.
+z
Geometrical relationship of the d-orbitals: There is no
unique way of representing the five d-orbitals, but the most
convenient representations are shown in figure 29.4. In fact, –y
there are six wave functions but can be written for orbitals –x
having the typical four-lobed form (d xy and d x 2 − y2 , for +x
example), but there can be only five d-orbitals having any

physical reality, therefore, one of them the "d z2 " orbital is
+y
conventionally regarded as a linear combinations of two
–z
others, the d z 2 − y2 and d z2 − x 2.
Figure: 29.5

Now there will be repulsion between the electrons of many ways. The number of isomers depend on the
ligands and that present in the d orbitals and consequently coordination number of the metal and the geometry adopted
the energy of the d orbitals will be raised. However this by it and also on the nature of the ligand. In one respect such
raise in energy will not be same for every d orbital and it isomerism differs from the isomerism observed in carbon
can be clearly seen that the "eg " orbtials will be raised compounds. Actually, the stereochemistry of coordination
compounds is more varied since metals involve much larger
more in energy due to stronger repulsions than the "t 2g "
number of orbitals (s, p and d) whose energy and spatial
orbitals. To understand this splitting more clearly we can distribution are widely different. The main types within each
assume it to be a two step process as shown in figure. category may be further classified as follows:
d x 2 −y2 , d z 2
eg Isomerism
0.6∆ o
Energy
∆o Constitutional Isomerism Stereoisomerism

Average energy level 1. Geometrical
1. Ionisation
0.4∆ o (Bary-centre)
2. Hydrate 2. Optical
t2g
3. Coordinate
d xy ,d yz ,d xz 4. Linkage
step I step II 5. Polymerisation
d orbitals in free ion 6. Ligand
Figure: 29.6
Names of Ligands
Step (i): Average energy of the d-orbitals of metal atom/ion (a) Names of anionic ligands (both organic and inorganic) end
in a hypothetical spherical crystal field. in –o. The anion names are usually changed accordingly:
Step (ii): Splitting of d-orbitals of metal atom/ion in
—ide 
→ ido; —ite 
→ ito; —ate 
→1to.
ito.
octahedral crystal field. In the first step, the ligands
Exceptions are halides (halo), hydroxides (hydroxo),
approach the central metal, producing a hypothetical
peroxides (peroxo) etc.
spherical field which repels all of the d-orbitals to the same
(b) Names of neutral and cationic ligands are used without
extent. In the second, the ligands exert an octahedral field,
modification and placed within enclosing mark except for
which splits the orbital degeneracy. In going from the first
to the second step, average energy (the bary centre, or aqua, ammine carbonyl and nitrosyl.
“center of gravity”) of the orbitals must remain constant and
it is necessary for the two e g orbitals to be the further
repelled by 0.6 ∆ 0 while the three t 2g orbitals are stabilized
1. If the bond length of CO bond in carbon monoxide is
to an extent of 0.4 ∆ 0 as shown in figure. This constancy of 1.128 Å, then what is the value of CO bond length in
the bary centre of the d-orbitals holds for all complexes, Fe(CO) 5 ? [JEE 2006]
regardless of geometry. So a. 1.15 Å b. 1.128 Å
C.F.S.E. = [−0.4(n)t 2g + 0.6(n ')eg ]∆ o + np c. 1.72 Å d. 1.118 Å
2. Among the following metal carbonyls, the C-----O bond
Where n & n’ are number of electron(s) in t 2g & eg orbitals
order is lowest in [JEE 2007 P-II]
respectively and ∆ o crystal field splitting energy for a. [Mn(CO) 6 ]+ b. [Fe(CO)5 ]
octahedral complex. n represents the number of extra c. [Cr (CO)6 ] d. [V (CO)6 ]−
electron pairs formed because of the ligands in comparison
to normal degenerate configuration. 3. Both [Ni(CO)4 ] and [Ni(CN) 4 ]2− are diamagnetic. The
Isomerism among Coordination Compounds: When the hybridization of nickel in these complexes, respectively,
same empirical formula applies to two or more complexes are [JEE 2008 P-II]
having different structures, either in atom connectivity or in a. sp 3 , sp 3 b. sp 3 , dsp 2
the orientation of atoms in space, the compounds are referred
c. dsp 2 , sp3 d. dsp 2 , dsp 2
to as isomers. Isomerism in complex compounds may arise in

4. The spin only magnetic moment value (in Bohr magneton 10. NiCl2 {P(C2H5 )2 (C6H5 )}2 exhibits temperature dependent
units) of Cr(CO) 6 is [JEE 2009 P-II] magnetic behavior (paramagnetic / diamagnetic). The
a. 0 b. 2.84 coordination geometries of Ni2+ in the paramagnetic and
c. 4.90 d. 5.92 diamagnetic states are respectively. [JEE 2012 P-II]
5. The correct structure of ethylenediaminetetraacetic acid a. tetrahedral and tetrahedral
(EDTA) is [JEE 2010 P-I] b. square planar and square planar
c. tetrahedral and square planar
HOOC— CH 2 CH 2 — COOH
a. N – CH = CH –N d. square planar and tetrahedral
HOOC— CH 2 CH 2 — COOH 11. Consider the following complex ions, P, Q and R
HOOC COOH P = [FeF6 ]3− , Q = [V(H2O)6 ]2 + and R = [Fe(H2 O)6 ]2+ . The
b. N − CH 2 − CH 2 − N
HOOC COOH correct order of the complex ions, according to their spin-
HOOC — CH2 only magnetic moment values (in B.M.) is
CH2 — COOH
c. N − CH2 − CH2 − N [JEE Adv. 2013 P-I]
HOOC — CH2 CH2 — COOH a. R < Q < P b. Q < R < P
COOH c. R < P < Q d. Q < P > R
CH 2 12. Which of the following complex species is not expected to

d. HOOC — CH 2 | H exhibit optical isomerism? [JEE Main 2013]
NHC — CH − N
H | a. [Co(en 3 )]3+ b. [Co(en) 2 Cl 2 ]+
CH 2 — COOH
CH 2 +
HOOC c. [Co(NH 3 )3 Cl3 ] d. [Co(en)(NH3 )2 Cl2 ]
13 The number of geometric isomers that can exist for square

6. The ionization isomer of [Cr(H 2O) 4 Cl(NO 2 )]Cl is
+
planar [Pt(Cl)(py) (NH3 )(NH2OH)] is (py = pyridine):
[JEE 2010 P-I]
a. [Cr(H 2 O) 4 (O 2 N)]Cl 2 b. [Cr(H 2 O) 4 Cl2 ](NO 2 ) [JEE Main 2015]
a. 2 b. 3 c. 4 d. 6
c. [Cr(H 2O) 4 Cl(ONO)]Cl d. [Cr(H 2O)4Cl2 (NO2 )]H 2O
14. The pair having the same magnetic moment is:
7. The complex showing a spin-only magnetic moment of [At. No.: Cr = 24, Mn = 25, Fe = 26, Co = 27]
2.82 B.M. is [JEE 2010 P-II] [JEE Main 2016]
a. Ni(CO)4 b. [NiCl 4 ]2 − a. [Cr(H 2 O) 6 ]2 + and [CoCl4 ]2 −
c. Ni(PPh 3 ) 4 d. [Ni(CN) 4 ]2 − b. [Cr(H 2 O)6 ]2 + and [Fe(H 2 O) 6 ]2 +

c. [Mn(H 2 O)6 ]2 + and [Cr(H 2 O) 6 ]2 +
8. Geometrical shapes of the complexes formed by the
d. [CoCl 4 ]2 − and [Fe(H 2 O)6 ]2 +
reaction of Ni 2 + with Cl − , CN − and H 2 O, respectively,
are [JEE 2011 P-I] 15. Which one of the following complexes shows optical
a. octahedral, tetrahedral and square planar isomerism? [JEE Main 2016]
b. tetrahedral, square planar and octahedral a. [Co(NH 3 )3 Cl3 ]
c. square planar, tetrahedral and octahedral b. cis[Co(en) 2 Cl2 ]Cl
d. octahedral, square planar and octahedral c. trans[Co(en)2 Cl 2 ]Cl (en = ethylenediamine)
9. Among the following complexes (K–P) d. [Co(NH 3 )4 Cl 2 ]Cl
K 3 [Fe(CN)6 ] (K ), [Co(NH 3 )6 ]Cl3 (L),
16. Among [Ni(CO)4 ], [NiCl 4 ]2 − , [Co(NH3 )4 Cl2 ]Cl, Na3[CoF6 ],
Na 3 [Co(oxalate)3 ] (M ), [Ni(H 2 O)6 ]Cl2 (N), Na 2 O2 and CsO2 the total number of paramagnetic
K 2 [Pt(CN) 4 ] (O) and [Zn(H 2 O)6 ] (NO 3 ) 2 (P )
compounds is [JEE Adv. 2016 P-I]
Following compounds are diamagnetic. a. 2 b. 3 c. 4 d. 5
[JEE 2011 P-II]
17. The geometries of the ammonia complexes of Ni 2+ , Pt 2+ &
a. K, L, M N b. K, M, O, P
c. L, M, O, P d. L, M, N, O Zn2+ , respectively, are [JEE Adv. 2016 P-II]

a. octahedral, square planar and tetrahedral a. H2O and (H2O + OH–)
b. square planar, octahedral and tetrahedral b. (H2O + O2) and H2O
c. tetrahedral, square planar and octahedral c. (H2O + O2) and (H2O + OH–)
d. octahedral, tetrahedral and square planar d. H2O and (H2O +O2)
18. The compound(s) that exhibit(s) geometrical isomerism 23. Diborane (B2H6) reacts independently with O2 and H2O to
is(are) [JEE 2009 P-I] produce, respectively [JEE Main 2019]
a. [Pt(en)Cl2 ] b. [Pt(en)2 ]Cl 2 a. HBO2 and H3BO3 b. H3BO3 and B2O3
c. B2O3 and H3BO3 d. B2O3 and [BH4]–
c. [Pt(en)2 Cl2 ]Cl 2 d. [Pt(NH3 )2 Cl2 ]
24. The correct order of the spin-only magnetic moment of
19. The pair(s) of coordination complexes/ions exhibiting the metal ions in the following low spin complexes,
same kind of isomerism is(are) [JEE Adv. 2013 P-I] [V(CN)6]4–, [Fe(CN)6]4–, [Ru (NH3)6]3+, and [Cr(NH3)6]2+,
a. [Cr(NH 3 )5 Cl]Cl 2 and [Cr(NH 3 ) 4 Cl 2 ]Cl is : [JEE Main 2019]
b. [Co(NH3 )4 Cl2 ]+ and [Pt(NH3 )2 (H 2 O)Cl]+ a. V2+ > Cr2+ > Ru3+ > Fe2+
b. V2+ > Ru3+ > Cr2+ > Fe2+
c. [CoBr2Cl2 ]2− and [PtBr2Cl2 ]2− c. Cr2+ > V2+ > Ru3+ > Fe2+
d. [Pt(NH3 )3 (NO3 )]Cl and [Pt(NH3 )3 Cl]Br d. Cr2+ > Ru3+ > Fe2+ > V2+
20. On treatment of 100 mL of 0.1 M solution of 25. The ion that has sp3d2 hybridization for the central atom,
CoCl3 ⋅ 6H 2 O with excess AgNO3 1.2 × 1022 ions are is : [JEE Main 2019]
– – –
a. [ICl2] b. [IF6] c. [ICl4] d. [BrF2]–
precipitated. The complex is [JEE Main 2017]
a. [Co(H 2 O)5 Cl]Cl2 ⋅ H 2O 26. The calculated spin-only magnetic moments (BM) of the
anionic and cationic species of [Fe(H2O)6]2 and [Fe(CN)6],
b. [Co(H 2 O) 4 Cl 2 ]Cl 2 ⋅ 2H 2 O
respectively, are : [JEE Main 2019]
c. [Co(H 2 O)3 Cl3 ] ⋅ 3H 2 O a. 4.9 and 0 b. 2.84 and 5.92
d. [Co(H 2 O)6 ] Cl3 c. 0 and 4.9 d. 0 and 5.92
21. Addition of excess aqueous ammonia to a pink coloured 27. Among the following molecules / ions, C 22 − , N 22 − , O 22 − , O 2
aqueous solution of MCl2 ⋅ 6H 2 O ( X ) and NH 4 Cl gives which one is diamagnetic and has the shortest bond
length? [JEE Main 2019]
an octahedral complex Y in the presence of air. In
a. C 22 − b. N 22 − c. O2 d. O 22 −
aqueous solution, complex Y behaves as 1 : 3 electrolyte.
The reaction of X with excess HCl at room temperature 28. The correct statement about ICl5 and ICl −4 is
results in the formation of a blue coloured complex Z. The [JEE Main 2019]
calculated spin only magnetic moment of X and Z is 3.87 −
a. ICl5 is trigonal bipyramidal and ICl is tetrahedral.
4
B.M., whereas it is zero for complex Y. Among the
b. ICl5 is square pyramidal and ICl −4 is tetrahedral.
following options, which statement(s) is(are) correct?
c. ICl5 is square pyramidal and ICl −4 is square planar.
[JEE Adv. 2017 P-I]
d. Both are is ostructural.
a. The hybridization of the central metal ion in Y is d 2sp3
b. When X and Z are in equilibrium at 0°C, the colour of 29. Two complexes [Cr(H 2 O6 )Cl3 ] (A) and [Cr(NH3 )6 ]Cl3
the solution is pink (B) are violet and yellow coloured, respectively. The
c. Z is a tetrahedral complex incorrect statement regarding them is: [JEE Main 2019]
d. Addition of silver nitrate to Y gives only two equi- a. ∆0 value of (A) is less than that (B).
valents of silver chloride b. ∆0 value of (A) and (B) are calculated from the energies
4–
22. Hydrogen peroxide oxidises [Fe(CN)6] to [Fe(CN)6] in 3– of violet and yellow light, respectively.
acidic medium but reduces [Fe(CN)6]3– to [Fe(CN)6]4– in c. Both absorb energies corresponding to their comple-
alkaline medium. The other products formed are, mentary colors.
d. Both are paramagnetic with three unpaired electrons.
respectively. [JEE Main 2018]

30. The complex that has highest cry splitting energy (∆), is a. Mn —Mn bond b. Mn — C bond
[JEE Main 2019] c. Mn —O bond d. C — O bond
a. K3[CO(CN)6] b. [CO(NH3)5(H2O)]Cl3
41. The pair of metal ions that can give a spinonly magnetic
c. K2[COCl4] d. [CO(NH3)5Cl]Cl2
moment of 3.9 BM for the complex [M(H2O)6]Cl2, is :
31. The metal that form nitride by reacting directly with N2 of [JEE Main 2019]
air, is [JEE Main 2019] 2+
a. Cr and Mn 2+
b. V and Co2+
2+
a. K b. Cs c. Li d. Rb 2+
c. V and Fe 2+
d. Co2+ and Fe2+
32. Homoleptic octahedral complexes of a metalion 'M3+' with
42. The magnetic moment of an octahedral homoleptic
three monodentate ligands and L1, L2, L3 absorb wavelengths
Mn(II) complex is 5.9 BM. The suitable ligand for this
in the region of green, blue and red respectively. The
complex is : [JEE Main 2019]
increasing order of the ligand strength is: – –
a. CN b. NCS
[JEE Main 2019]
c. CO d. ethylenediamine
a. L2 < L1 < L3 b. L3 < L2 < L1
c. L3 < L1 <L2 d. L1 < L2 < L3 43. Which of the following set represent correct formula for
Malachinte, Magnetite, Calamine & Cryolite?
33. Wilkinson catalyst is: [JEE Main 2019]
[JEE Adv. 2019 P-I]
a. [(Ph3P)3RhCl] (Et = C2H5)
a. CuCO3,Fe2O3, ZnO, Al2O3
b. [(Et3P)3IrCl]
b. CuCO3. Cu(OH)2, Fe3O4, ZnCO3, Na3AlF6
c. [(Et3P)3RhCl]
c. CuCO3, Fe3O4, ZnCO3 Al2O3
d. [(Ph3P)3IrCl]
d. CuCO3. Cu(OH)2, Fe2O3, ZnCO3, Na3AlF6
34. The type of hybridisation and number of lone pair(s) of
44. Identify the option where all four molecules possess
electrons of Xe in XeOF4, respectively, are:
permanent dipole moment at room temperature.
[JEE Main 2019]
a. BF3, O3, SF6, XeF6 [JEE Adv. 2019 P-I]
a. sp3d and 1 b. sp3d and 2
b. BeCl2, CO2, BCl3, CHCl3
c. sp3d2 and 1 d. sp3d2 and 2
c. SO2, C6H5Cl, H2Se, BrF5
35. The difference in the number of unpaired electrons of a d. NO2, NH3, POCl3, CH3Cl
metal ion in its high-spin and low-spin octahedral
complexes is two. The metal ion is: [JEE Main 2019] Matrix Match/Column Match
2+ 2+ 2+
a. Fe b. Co c. Mn d. Ni2+
45. Match the complexes in Column I with their properties
36. Which of the following tests cannot be used for listed in Column II. [JEE 2007 P-I]
identifying amino acids? [JEE Main 2019] Column I Column II
a. Biuret test b. Xanthoproteic test
(A) [Co(NH3 )4 (H2O)2 ]Cl2 1. geometrical isomers
c. Barfoed test d. Ninhydrin test
(B) [Pt(NH3 )2 Cl2 ] 2. paramagnetic
37. The number of bridging CO ligand (s) and CO-CO bond
(s) in CO2(CO)g, respectively are :- [JEE Main 2019] (C) [Co(H 2 O)5 Cl]Cl 3. diamagnetic
a. 0 and 2 b. 2 and 0 (D) [Ni(H 2 O)6 ]Cl2 4. metal ion with +2
` c. 4 and 0 d. 2 and 1 oxidation state
a. A→ 1,2,4; B→ 1,3,4; C→ 2,4; D→ 2,4
38. The hydride that is NOT electron deficient is:-
b. A→ 1,3,4; B→ 1,2,4; C→ 2,4; D→ 2,3
[JEE Main 2019]
c. A→ 1,2,4; B→ 1,2,3; C→ 2,3; D→ 1,2
a. B2H6 b. AlH3
d. A→ 1,2,4; B→ 1,3,4; C→ 1,2,3,4; D→ 2
c. SiH4 d. GaH3
39. The coordination number of Th in K4[Th(C2O4]4(OH2)2] 46. Match each coordination compound in Column-I with an
is:- ( C2O4 = Oxalato)
2-
[JEE Main 2019] appropriate pair of characteristics from Column-II.
{en = H 2 NCH 2 CH 2 NH 2 ;
a. 6 b. 10 c. 14 d. 18
atomic numbers : Ti = 22, Cr = 24, Co = 27, Pt = 78}
40. Mn2(CO)10 is an organometallic compound due to the
presence of : [JEE Main 2019]

Column I Column II c. A is diamagnetic and B is paramagnetic with two
(A) [Cr(NH 3 ) 4 Cl 2 ]Cl 1. Paramagnetic and unpaired electrons
exhibits ionization d. Both are paramagnetic
isomerism 50. The hybridization of A and B are
(B) [Ti(H 2 O)5 Cl](NO 3 ) 2 2. Diamagnetic and a. dsp2, sp3 b. sp3, sp3
exhibits cis-trans
c. dsp 2 , dsp 2 d. sp3d 2 , d 2sp3
isomerism
(C) [Pt(en)(NH 3 )Cl]NO3 3. Paramagnetic and Paragraph for Question Nos. 51 and 52
exhibits cis-trans
An aqueous solution of metal ion M1 reacts separately with
isomerism
reagents Q and R in excess to give tetrahedral and square planar
(D) [Co(NH3)4 (NO3)2 ]NO3 4. Diamagnetic and
complexes, respectively. An aqueous solution of another metal
exhibits ionization
ion M2 always form tetrahedral complexes with these reagents.
isomerism
Aqueous solution of M2 on reaction with reagent S gives white
a. A→ 1; B→ 3; C→ 4; D→ 2
precipitate which dissolves in excess of S. The reactions are
b. A→ 3; B→ 1; C→ 4; D→ 2
summarized in the scheme given below.
c. A→ 1; B→ 2; C→ 3; D→ 4
Scheme: [JEE Adv. 2014 P-II]
d. A→ 2; B→ 3; C→ 4; D→ 1
Q R
Tetrahedral ←
excess
M1 
excess
→ Square planar
Statement/Assertion and Reason Q
Tetrahedral ← M2 R
→ Tetrahedral
excess excess
47. Statement-I: [Fe(H 2 O)5 NO]SO4 is paramagnetic. And S,
S, stoichiometric amount
stoichiometricamount
Statement-II: The Fe in [Fe(H 2 O)5 NO]SO 4 has three
White S Precipitate
unpaired electrons. [JEE 2008 P-II] 
excess →
Precipitate dissolves
is correct explanation for Statement-I 51. M1, Q and R, respectively are
b. statement-I is True, Statement-II: is True; statement-II a. Zn 2+ , KCN and HCl b. Ni 2+ , HCl and KCN
is not a correct explanation for statement-I c. Cd 2+ , KCN and HCl d. Co 2+ , HCl and KCN
d. statement-I is False, statement-II is True 52. Reagent S is
a. K 4 [Fe(CN)6 ] b. Na 2 HPO 4
Paragraph c. K 2 CrO 4 d. KOH
The coordination number of Ni 2+ is 4 Integer and Subjective
NiCl 2 + KCN (excess) 
→ A (cyano complex) 53. Total number of geometrical isomers for the complex
NiCl 2 + Conc. HCl (excess) 
→ B (chloro complex) [RhCl(CO)(PPh 3 )(NH3 )] is________ [JEE 2010 P-II]
[JEE 2006]
54. EDTA 4 − is ethylenediaminetetra acetate ion. The total
48. The IUPAC name of A and B are 1–
a. Potassium tetracyanonickelate (II), potassium tetra- number of N – Co – O bond angles in [Co(EDTA)]
chloronickelate (II) complex ion is ________ [JEE Adv. 2013 P-I]
b. Tetracyanopotassiumnickelate (II), teterachlorpotassi- 55. If the freezing point of a 0.01 molal aqueous solution of a
umnickelate (II) cobalt (III) chloride-ammonia complex (which behaves as
c. Tetracyanornickel (II), tetrachloronickel (II)
a strong electrolyte) is −0.0558°C, the number of
d. Potassium tetracyanonickel (II), potassium tetra-
chloride(s) in the coordination sphere of the complex is
chloronickel (II)
[ K f of water = 1.86 K kg mol–1] [JEE Adv. 2015 P-I]
49. Predict the magnetic nature of A and B.
a. Both are diamagnetic 56. For the octahedral complexes of Fe 3 + in SCN −
b. A is diamagnetic and B is paramagnetic with one (thiocyanato-S) and in CN − ligand environments, the
unpaired electron. difference between the spin-only magnetic moments in

Bohr magnetons (When approximated to the nearest (d) V − = 3d 4 4s 2 effective configuration = 3d 6 ; three lone
integer) is [Atomic number of Fe = 26] ________ pair for back bonding with CO. Maximum back bonding is
[JEE Adv. 2015 P-I] present in Fe(CO)5 therefore CO bond order is lowest here.
57. In the complex acetylbromidodicarbonylbis (triethyl-
3. (b) Ni(CO) 4 = sp 3 ; [Ni(CN) 4 ]2 − = dsp 2
phosphine)iron(II), the number of Fe–C bond(s) is______
[JEE Adv. 2015 P-II] 4. (a) [Cr(CO)6 ] , Cr(24) = [Ar]3d 5 4s1
58. Among the complex ions, [Co(NH2 − CH2 − CH2 − NH2 )2 Since (CO) is strong legand, in Cr(CO)6 no unpaired
electron is present. So ‘spin only’ magnetic moment is
Cl 2 ]+ , [CrCl2 (C 2 O 4 ) 2 ]3− , [Fe(H2O)4 (OH)2 ]+ , [Co(NH 2 −
zero.
CH 2 − CH 2 − NH 2 ) 2 (NH 3 )Cl]2 + [Fe(NH 3 ) 2 (CN)4 ]− , and
5. (c)
[Co(NH 3 ) 4 (H 2 O)Cl]2+ , the number of complex ion(s)
6. (b) Cl – is replaced by NO 2– in ionization sphere.
that show(s) cis-trans isomerism is________
[JEE Adv. 2015 P-II] 7. (b) [NiCl4 ]–2 , O.S. of Ni = +2
59. The number of geometric isomers for the complex Ni(28) = 3d 8 4s 2
[CoL2 Cl2 ]− (L = H2 NCH2 CH2 O− ) is________ Ni+2 = 3d8
[JEE Adv. 2016 P-I] 3d 4s 4p
60. Among the species given below, the total number of

Cl – being weak ligand
diamagnetic species is ____. H atom, NO2 monomer, O −2
3d 4s 4p
(superoxide), dimeric sulphur in vapour phase, Mn 3 O4 ,
(NH 4 )2 [FeCl 4 ], (NH 4 )2 [NiCl 4 ], K 2 MnO 4 , K 2 CrO4
sp2
[JEE Adv. 2018 P-I]
No. of unpaired electrons = 2
61. The ammonia prepared by treating ammonium sulphate
Magnetic moment µ = 2.82 BM.
with calcium hydroxide is completely used by
NiCl 2 .6H 2 O to form a stable coordination compound. 8. (b) [NiCl 4 ]2 − – Tetrahedral
Assume that both the reactions are 100% complete. If [Ni(CN) 4 ]2 − – Square planar
1584 g of ammonium sulphate and 952 g of NiCl 2 .6H 2 O [Ni(H 2 O)6 ]2 + – Octahedral
are used in the preparation, the combined weight (in
grams) of gypsum and the nickel-ammonia coordination 9. (c) L :[Co(NH 3 )6 ]Cl3 M : Na 3 [Co(Ox)3 ]
compound thus produced is_____. (Atomic weights in g O : K 2 [Pt(CN) 4 ] P :[Zn(H 2 O)6 ] (NO3 ) 2
mol–1 : H = 1, N = 14, O = 16, S = 32, Cl = 35.5, Ca = 40,
10. (c) [NiCl2 P(C 2 H 5 ) 2 (C6 H 5 ) 2 ]+2
Ni = 59) [JEE Adv. 2018 P-I]
Ni +2 (28) :[Ar]4s°3d8
In strong ligand 3d8
1. (a) Due to synergic bond formation between metal and
CO, the bond order of CO decreases.
2. (a) Hybridisation is dsp2 (diamagnetic)
(a) Mn + = 3d 5 4s1 in presence of CO; effective;

Square planar
configuration = 3d 4s . Three lone pairs for back bonding
6 0
with vacant orbital of C in CO.

In weak ligand 3d8
(b) Fe = 3d 4s in presence of CO; effective; con-
0 6 2
figuration = 3d 8 four lone pairs for back bonding with CO. Hybridisation is sp3 (paramagnetic)
(c) Cr = 3d 4s . Effective configuration
0 5 1
= 3d . Three
6
lone pair for back bonding with CO. tetrahedral


−
11. (b) R=Fe (no. of unpaired e = 5)
+3 20. (a) Moles of complex
Molarity × y volume (ml)
Q = V+2 (no. of unpaired e − = 3) =
1000
R = Fe+2 (no. of unpaired e − = 4)
100 × 0.1
As all ligands are weak field, hence the no. of unpaired = = 0.01 mole
1000
electrons remains same in the complex ion. Moles of ions precipitated with excess of
µ = n(n + 2) B.M. Hence (B) is correct. 1.2 × 10 22
AgNO 3 = = 0.02 moles
12. (c) [Co(NH3)3Cl3] will not exhibit optical isomerism due 6.02 × 10 23
to presence of plane of symmetry. Number of Cl– present in ionisation sphere
Mole of ion precipitated with excess AgNO3
13. (b) No. of Geometrical isomers of [Pt(Cl)(py)(NH3) =
(NH2OH)]+ =3 mole of complex
14. (b) Each [Cr(H2O2)6]2+ and [Fe(H2O)6]2+ contain 4 unpaired 0.02

= =2
electrons. 0.01
15. (b) With coordination number six, if two bidentate ligands It means 2Cl − ions are present in ionisation sphere.
in cis-position are present, then it is optically active. ∴ Complex is [Co(H 2 O)5 Cl]Cl 2 ⋅ H 2 O
16. (b) [Ni(CO) 4 ] 3d10 , sp3 0 unpaired electron 21. (a, b, c)

O
[NiCl4 ]2– 3d8 , sp3 2 unpaired electron [Co(H 2 O)6 ]Cl2 + NH3 →
2
[Co(NH 3 )6 ]Cl3
Pink [Y]
[ X]
[Co(NH 3 ) 4 Cl2 ]Cl 3d6 , d2sp3 0 unpaired electron
Na 3 [CoF6 ] 3d6 , sp3d2 4 unpaired electron [Co(H 2O) 6 ]Cl2 + HCl ↽ ⇀ [CoCl4 ]2−
Blue
[ X] [Z]
Na 2 O2 O 22 − 0 unpaired electron
hybridisation of Co in Y is d 2sp3. Z is tetrahedral.
CsO2 O−21 1 unpaired electron
At. 0ºC, equilibrium favours X, so the colour of the
17. (a) Ni2+ with NH 3 shows CN = 6 forming [Ni(NH3)6]2+ solution is pink.
(Octahedral). Pt2+ with NH3 shows CN = 4 forming 1
→ [Fe(CN) 6 ]3− + H 2O
22. (d) [Fe(CN)6 ]4− + H 2 O 2 + H + 
[Pt(NH3)4]2+ (5d series CMA, square planner). Zn 2+ with 2
NH 3 shows CN = 4 forming [Zn(NH3 )4 ]2+ (3d10 1 1
[Fe(CN)6 ]3− + H 2O2 + OHΘ 
→ [Fe(CN) 6 ]4 − + H 2 O + O 2 .
configuration, tetrahedral). 2 2
Cl Cl 23. (c) B 2 H 6 + 3H 2 O 
→ 2H 3 BO 3 + 3H 2
18. (c, d)
Cl B2 H 6 + 3O 2 
→ B2 O 3 + 3H 2 O
en Pt 4+ en Pt 4+ en 24. (a) According to question all the complexes are low spin.
Complex Configuration No. of unpaired
en electrons
Cl
cis-form trans-form [V(CN)6]4– t 3e0 3
2g g
Cl NH 3 Cl Cl [Cr(NH3)6]2+ t 4 0
e 2
2g g
Pt Pt [Ru(NH3)6]3+ t 2g 5e0g 1
NH 3 Cl NH 3 NH 3 [Fe(CN)6]4– t 2g 6e0g 0
Trans Cis
25. (c)
19. (b, d) [Co(NH3 )4 Cl2 ]+ (an octahedral complex) and Chemical species Hybridisation of central atom
[Pt(NH 3 ) 2 (H 2 O)Cl] +
(a square planar complex) will ICl −
2
sp3d
show geometrical isomerism. IF6− sp3d3
[Pt(NH 3 )3 (NO 3 )]Cl and [Pt(NH 3 ) 3 Cl]Br will show ICl −4 sp3d2
ionization isomerism. BrF2− sp3d

26. (c) Complex is [Fe (H2O)6]2 [Fe(CN)6] 35. (b)
Complex Configuration No. of Magnetic 36. (b)
ion unpaired moment
electrons CO CO
37. (d) CO
[Fe(H2O)6]2+ t 4 e 2 4 4.9 BM CO Co Co CO
2g g
[Fe(CN)6] 4–
0 0 CO CO
t 2g6 eg0 CO
Bridging CO are 2 and Co – Co bond is 1.
27. (a)
Chemical species Bond order Magnetic behaviour 38. (c)
2−
C 2
3 diamagnetic (1) B2H6 : Electron deficient
N 22 − 2 paramagnetic (2) AlH3 : Electron deficient
O2 2 paramagnetic (3) SiH4 : Electron precise
O 2−
2 diamagnetic (4) GaH3 : Electron deficient
2
1 2-
B.O. ∝ 39. (b) C2O4 (oxalato) : bidentate
bond length H2O (aqua) : Monodentate
28. (c)
40. (b) Compounds having at least one bond between carbon
Chemical species Hybridisation Shape
and metal are known as organometallic compounds.
ICl5 sp3d2 Square pyramidal
CO CO CO CO
ICl −4 sp3d2 Square planar
ICl5 ICl −4 OC Mn Mn CO
Cl Cl Cl Cl
CO CO CO CO
I I 41. (b) V 2 + 
→[V(H 2 O) 6 ]Cl 2 ; [Ar]18
3d3
Cl Cl Cl Cl
–
3 unpaired e , spin only
Cl
magnetic moment= 3.89 B.M.
29. (b) ∆0 order will be compared by spectro chemical series Co 2 + 
→[Co(H 2 O) 6 ]Cl 2 ;[Ar]18
not by energies of violet & yellow light so ∆0 order is 3d7
–
[Cr(H 2 O)6 ]Cl3 < [Cr(NH 3 )6 ]Cl3 3 unpaired e , spin only
magnetic moment= 3.89 B.M.
30. (a) As complex K3[CO(CN)6]have CN − ligand which is
strongfield ligand amongst the given ligands in other 42. (b) µ = 5.9 BM ∴n (no of unpaired.e–) = 5
complexes. Cation MnII – 3d5 configration only possible for relatively
weak ligand.
31. (c) Out of alkali metals only Li reacts directly with N2.
∴ NCS–
6Li + N 2 
→ 2Li 3 N
43. (b) Malachite, CuCO3, Cu(OH)2
32. (c) Order of λ abs − L3 > L1 >L 2 Magnetite, Fe3O4
1 Calamine, ZnCO3
So ∆ O order will be L 2 > L1 > L3 (as ∆ O ∝ ) Cryolite, Na3AlF6
λ abs
44. (c, d)
So order of ligand strength will be L 2 < L1 < L3
Cl
33. (a) Wilkinson catalyst is [(ph3P)3RhCl] (c) ..
SO2 sp2(2+1) ; S C6H5Cl ;
O
O O
F F
..
34. (c) Xe sp3d2⇒[5σ-bond +1 l.p.] H2Se; H — Se:
e
F F
H

O Cl For Question Nos. 48 to 50
(d) + N 48. (a)
P C
N
H H Cl H H 49. (c)
O Cl
O H Cl H
45. (a) A→ 1,2,4; B→ 1,3,4; C→ 2,4; D→ 2,4 50. (a)
OH2 2+ NH3 2+ For Question Nos. 51 to 52
H 3N NH3 H 2O OH2 51. (b)
(A) Co Co 52. (d)
H 3N NH3 H 3N NH3 HCl(Q)
[NiCl4 ]2 − ← KCN(R )
 Ni 2 +  → [Ni(CN) 4 ]2 −
excess excess
(M1 )
OH2 OH2 Tetrahedral square planar
(trans (cis)
HCl(Q) KCN(R )
Co 2 + 7 )
= 3d (Paramagnetic) [ZnCl4 ]2− ←
excess
 Zn 2 + 
excess
→ [Zn(CN)4 ]2−
Tetrahedral (M 2 ) square planar
(B) [Pt(NH3 ) 2 Cl2 ] is square planar.
HOH
H 3N Cl H 3N Cl (S)
2+ 2+
Pt Pt → [Zn(OH) 4 ]2 −
Zn(OH)2 
White ppt. Soluble
H 3N Cl Cl NH3
(cis) (trans) 53. (c)
2+ 8 0
Pt = 5d 4s (diamagnetic)
54. Total no. of N – Co – O bond angles is 8.
OH2 +
H 2O OH2 O
(C) Co
H 2O OH2 O
O
Cl
2+ 7 N O
Co = 3d (paramagnetic)
Co
OH2 2+ N O
H 2O OH2
(D) O O
Co
H 2O OH2
O
OH2
Ni 2 + = 3d 8 (weak field ligand, paramagnetic) 55. ∆Tf = iK f m
46. (b) A→ 3; B→ 1; C→ 4; D→ 2 0.0558 = i × 1.86 × 0.01
(A) [Cr(NH 3 )4 Cl2 ]Cl 
→ i=3
Paramagnetic and exhibits cis-trans isomerism ∴ Complex is [Co(NH 3 )5 Cl]Cl2. The no. of chloride is 1.
(B) [Ti(H 2 O)5 Cl](NO3 )2 
→ 56. [Fe(SCN)6 ]3− and [Fe(CN)6 ]3−
Paramagnetic and exhibits ionisation isomerism In both the cases the electronic configuration of Fe3+ will be
(C) [Pt(en)(NH3 )Cl]NO3 
→ 1s 2 , 2s 2 , 2p6 ,3s 2 ,3p 6 ,3d 5
Diamagnetic and exhibits ionisation isomerism Since SCN is a weak field ligand and CN is a strong field
(D) [Co(NH3 ) 4 (NO3 )2 ]NO3 
→ ligand, the pairing will occur only in case of [Fe(CN)6 ]3−
Diamagnetic and exhibits cis-trans isomerism (high spin)
Case-1 3d 5
47 (a) [Fe(H 2 O)5 NO]SO 4 Here Fe has +1 oxidation state. (no pairing)
Fe + = 3d 6 4s1 in presence of NO + 4s1 electron are paired

(low spin)
in 3d sub shell. Case-2 (pairing)
So electronic configuration of Fe + is
3d

Case – 1 µ = n(n + 2) = 5(5 + 2) = 35 = 5.91 BM O 2 − (Superoxide) :- σ 1s 2 , σ *1s 2 , σ 2s 2 , σ * 2s 2 , σ 2p z2 ,
Case – 2 µ = n(n + 2) = 1(1 + 2) = 3 = 1.73 BM π 2p2x π *2px2

Difference in spin only magnetic moment π 2p2y π *2p1y
= 5.91 − 1.73 = 4.18 ≈ 4
One unpaired electron is present in either π * 2p x or
PEt 3 O|| π * 2p y . So it is paramagnetic in nature. Dimeric sulphur
57. Et 3 P C CH 3
in vapour phase:- It is similar as O 2 in vapor state,
Fe
paramagnetic in nature.
OC Br
CO Mn 3 O 4 : − It is combined form of MnO and Mn 2 O3 .
The number of Fe – C bonds is 3. Mn +2 has 5 unpaired electrons (d5 electronic
+
58. [Co(en) 2 Cl 2 ] 
→ will show cis-trans isomerism configuration).
Mn +3 has 4 unpaired electrons (d4 electronic
[CrCl2 (C 2 O 4 ) 2 ]3− 
→ will show cis-trans isomerism
configuration).
[Fe(H 2O) 4 (OH) 2 ]+ 
→ will show cis-trans isomerism So it is paramagnetic in nature.
[Fe(CN) 4 (NH3 ) 2 ]  −
→ will show cis-trans isomerism (NH 4 )2 [FeCl4 ] : − Consist [Fe +2 Cl 4 ]−2 ion.
[Co(en) 2 (NH 3 )Cl]2+ 

→ will show cis-trans isomerism [FeCl 4 ]−2 tetrahedral, sp3 Hybridized, has configuration
eg3, t2g3. (Paramagnetic in nature)
[Co(NH 3 ) 4 (H 2 O)Cl]2+ 
→ will not show cis-trans
(NH 4 )2 [NiCl4 ] : − Consist [ Ni +2 Cl 4 ]−2 ion.
isomerism (although it will show geometrical isomerism)
[NiCl 4 ]−2 : − tetrahedral, sp3 Hybridized, has
No. of complex ions that shows cis-trans isomerism is five.
4 3
59. [CoL 2 Cl 2 ]– (L = H 2 NCH 2 CH 2 O – ) configuration eg , t2g . (Paramagnetic in nature)
K 2 MnO 4 : − Mn +6 is present in compound which has one
L is unsymmetrical bidentate ligand
So it is equivalent to [M(AB) 2 a 2 ] . Possible G.I. are unpaired electron in 3d subshell. Mn+6 - [Ar]3d1
Paramagnetic in nature
a a
+6
A B A A K 2 CrO 4 : − Cr is present in compound which has zero
M M
unpaired electron, diamagnetic in nature.
B A B B
a a
a a a 61. 12(NH 4 ) 2 SO 4 + 12Ca(OH) 2 + 4NiCl2 .6H 2 O
A a B a A a
M M M ↓
B A A B B a 12CaSO 4 ⋅ 2H 2 O + 4[Nio(NH 3 )6 ]Cl2 + 24H 2 O
B A a
No. of geometric isomers = 5. 952
n NiCl2 .6 H 2 O = = 4 mol
238
60. H atom :- 1 - Paramagnetic
1s1 Mass = 12 × M CaSO4 .2 H 2 O + 4M[ Ni ( NH3 )6 ]Cl2
NO2 Monomer - N Paramagnetic = (12 × 172) + (4 × 232) = 2992g

C
O
Analytical Chemistry and Experimental Skills Analytical Chemistry and 323
30 Experimental Skills
QUICK LOOK dissolves in water to give NH 4 OH, which being basic,
turns red litmus blue,
In qualitative inorganic analysis, the given compound is
→ NH 4 OH ↽ ⇀ NH 4+ + OH − .
NH 3 + H 2 O 
analysed for the basic and acid radicals (i.e., the cations and the
Tests for HCl gas: It is colourless gas with a pungent
anions), that it contains. For example, zinc blende is analysed
irritating smell. It turns moist blue litmus paper red i.e., it is
for the Zn 2+ and S2 − ions that it contains.
acidic in nature. It gives white ppt. with AgNO 3 solution.
Test for Different Gases This white ppt. is soluble in NH 4 OH.
Colourless Gases HCl + AgNO3 

→ AgCl + HNO3
White ppt.
Tests for CO2: It is colourless and odourless gas. It gives
AgCl + 2NH 4 OH 
→ [Ag(NH 3 ) 2 ] + 2H 2 O.
white ppt. with lime water which dissolves on passing Soluble
excess of CO 2 . Test for CH 3 COOH vapours: These vapours are

Ca(OH) 2 + CO 2 
→ CaCO3 ↓ + H 2 O; colourless with a vinegar like smell.
Lime water White ppt.
CaCO3 + CO2 + H 2 O 
→ Ca(HCO3 ) 2 Coloured Gases
White ppt. Excess So lub le
Soluble
Test for Cl 2 : It is a greenish yellow gas with a pungent
Test for CO: It is colourless and odourless gas. It burns
smell. In small quantity it appears almost colourless. It
with a blue flame. 2CO + O 2 
→ 2CO 2
bleaches a moist litmus paper.
CO is highly poisonous gas.
Cl22 + H 2O 
→ 2HCl + [O]; Colour + [O] 
→ Colourless.
Test for O 2 : It is colourless and odourless gas. It rekindles
Blue litmus paper first turns red and then becomes
a glowing splinter.
colourless.
Test for H 2 S : It is a colourless gas with a smell of rotten Test for Br2 : Brown vapours with a pungent smell. It turns
eggs. It turns moist lead acetate paper black. moist starch paper yellow.
(CH 3 COO) 2 Pb + H 2S 
→ 2CH 3 COOH + PbS Test for I 2 : Violet vapours with a pungent smell. It turns
Black
Test for SO2 : It is a colourless gas with a suffocating moist starch paper blue.
Tests for NO 2 : Brown coloured pungent smelling gas. It
odour of burning sulphur. It turns acidified K 2 Cr2 O7
turns moist starch KI paper blue.
solution green.
2KI + 2NO 2 
→ 2KNO2 + I2 ; I 2 + Starch 
→ Blue
3SO 2 + K 2 Cr2 O 7 + H 2SO 4 
→ K 2SO 4 + Cr2 (SO 4 )3 + H 2 O
Green colour. It turns ferrous sulphate solution black,
Test for NH 3 : It is a colourless gas with a characteristic 3FeSO 4 + NO 2 + H 2SO 4 
→ Fe 2 (SO 4 )3 + FeSO 4 . NO + H 2 O
ammonical smell. It gives white fumes of NH 4 Cl with 3FeSO 4 + NO 2 + H 2SO 4 
→ Fe2 (SO 4 )3 + FeSO 4 . NO + H 2 O
Black brown
HCl, NH 3 + HCl 
→ NH 4 Cl . With Nessler’s reagents, it
White fumes Systematic Procedure for Qualitative Analysis of Inorganic
gives brown ppt. Salts
2K 2 [HgI4 ] + NH3 + KOH 
→ NH 2 HgOHgI + 7KI + 2H 2 O It involves the following steps:
Nessler 's reagent Iodine of Millon 's base
( Brown ppt ) Preliminary Tests
It gives deep blue colour with Cu SO 4 solution, Physical examination: It involves the study of colour,
smell, density etc.
CuSO 4 + 4NH 3 
→ [ Cu(NH3 )4 ] SO4 ⋅ NH3 Dry heating: Substance is heated in a dry test tube.
Deep blue

Table 30.1: Qualitative Analysis of Inorganic Salts Borax Bead Test: The transparent glassy bead (NaBO2 + B2O3)
Observation Result
when heated with inorganic salt and the colour produced gives
(a) A gas or vapour is evolved. Compounds with water of
crystallisation
some idea of cation present in it.
Vapour evolved, test with litmus Ammonium salts, acid salts, and
paper. hydroxides. (usually accompanied by Table 30.2: Borax Bead Test
change of colour) Colour of bead in oxidising Colour of bead in Basic radical
The vapour is alkaline. Ammonium salts. flame reducing flame present
The vapour is acidic. Readily decomposable salts of strong Greenish when hot, blue in Red and opaque Cu
acids. cold.
Oxygen is evolved Nitrates,chlorates and certain oxides. Dark green in hot and cold Same Cr
Dinitrogen oxide Ammonium nitrate or nitrate mixed
Deep – blue Deep blue Co
with an ammonium salt.
Dark-brown or reddish fumes Nitrates and nitrites of heavy metals. Yellow when hot Green Fe
(oxides of nitrogen), acidic in Violet in hot and cold Colourless Mn
reaction. Brown in cold Grey or black or opaque Ni
CO2 is evolved, lime water Carbonates
becomes turbid. or hydrogen carbonates.
Microcosmic Salt Bead Test: Microcosmic salt, Na(NH4)
NH3 is evolved which turns red Ammonium salts.
litmus blue. HPO4 .4H2O is also used to identify certain cations just like
SO2 is evolved, which turns Sulphates and thiosulphates. borax. When microcosmic salt is heated in a loop of platinum
acidified K2Cr2O7 green, decolo- wire, a colourless transparent bead of sodium metaphosphate is
urises fuschin colour.
formed.
H2S is evolved, turns lead acetate Hydrates, sulphides in the prescnce of
paper black, or cadmium acetate water. Na (NH 4 )HPO 4 .4H 2 O 
→ Na(NH 4 )HPO 4 + 4H 2 O
yellow.
Cl2 is evolved, yellowish green gas, Unstable chlorides e.g., copper Na(NH 4 )HPO 4 
→ NaPO3 + NH 3 + H 2 O
bleaches litmus paper, turns KI – chlorides in the presence of oxidising
Now NaPO3 reacts with metallic oxides to give coloured
starch blue, poisonous. agents.
Br2 is evolved (reddish brown, Bromides in the presence of oxidising orthophosphates.
agents. NaPO3 + CuO 
→ NaCuPO 4 (Blue)
turns fluorescent paper red).
I is evolved, violet vapours Free iodine and certain iodides
2 NaPO3 + CoO 
→ NaCoPO 4 (Blue)
condensing to black crystals
(b) A sublimate is formed Ammonium and mercury salts. NaPO3 + Cr2 O3 
→ NaPO3 .Cr
◊Cr22O 33 (Green)
White sublimate As2 O3 ,Sb2 O3
Table 30.3: Charcoal Cavity Test
Grey sublimate Hg
Nature and colour of bead Cation
Steel grey, garlic odour As
Yellow, brittle bead Bi3+
Yellow sublimate S, As2S3 ,HgI
HgI2 (Re d)
2 (Red)
Yellow, soft bead which marks on Pb 2+
paper
Flame Test: Characteristic flame colour : Certain metals and White, brittle Sb3+
their salts impart specific colours to Bunsen burner flame. White yellow when hot ZnO
Pb imparts pale greenish colour to the flame. White garlic odour As 2 O3
Cu and Cu salts impart blue or green colour to the flame. Brown CdO
Borates also impart green colour to the flame. Grey metallic particles attracted Fe, Ni, CO
Ba and its salts impart apple green colour to the flame. by magnet
Sr imparts crimsen red colour to the flame. Maleable beads Ag and Sn (White),Cu (Red flakes)
Ca imparts brick red colour to the flame.
Na imparts yellow colour to the flame. Table 30.4: Cobalt Nitrate Test
K imparts pink-violet (Lilac) colour to the flame. Colour Composition Result
Blue residue CoO.Al2 O3 Al
Li imparts crimsen-red, Rb imparts violet and Cs imparts
violet colours to the flame. Green residue CoO.ZnO ZnO
Livid-blue flame is given by As, Sb and Bi. Pink dirty residue CoO.MgO MgO
Blue residue NaCoPO4 PO34− in absence of Al.

Analytical Chemistry and Experimental Skills 325

Wet Tests for Acid Radicals: Salt or mixture is treated with White or yellowish S2 O 2−
3 Aq. Solution + AgNO3 → white
dil. H2SO4 and also with conc. H2SO4 separately and by white turbidity on
warming (thiosulphate) ppt. changing to black (viii) on
observing the types of gases evolved. Confirmatory tests of warming,
anions are performed. Na 2 S2 O3 + 2AgNO3 
→
Table 30.5: Observations with Dilute H2SO4 Ag 2 S2 O3 + 2NaNO3 ;

white ppt.
Observations Acid Radical Confirmatory test
Brisk effervescence Gas turns lime water milky but Ag2S2O3 + H2O 
→ Ag2S + H2SO4
CO32− black ppt.
with evolution of milkyness disappears on passing
colourless and (carbonate) gas in excess, ;
odourless gas. Na 2 CO3 + H 2 SO4 
→ Table 30.6: Observations with Concentrated H2SO4
Na 2 SO 4 + H 2 O + CO 2 Observation Acid Radical Confirmatory Test
Colourless C l − (chloride) Add MnO2 in the same test tube
Ca(OH)2 + CO2 
→ CaCO3 + H2O
lime water milky pungent gas
giving white and heat–pale green Cl2 gas (i)
CaCO3 + H 2 O + CO 2 
→
Ca(HCO3 )2
fumes with aq. S.E.+ HNO3 + AgNO3 solution –
soluble NH 4 OH
white ppt. soluble in aq. NH3 (ii)
Brown fumes NO−2 Add KI and starch solution blue
colour Chromyl chloride test (iii)
(Nitrite)
2NaNO3 + H 2 SO 4 
→ Reddish brown −
Br (bromide) Add Mn 2O and heat –yellowish
Na 2 SO 4 + 2HNO 2 fumes
brown Br2 gas (iv)
HNO 2 
→ NO (colourless);
S.E.+ HNO3 + AgNO3 solution –
2NO + O2 (air) 
→ 2NO2
pale yellow ppt. partially soluble
(brown);
aq. NH3 (v)
2KI + H 2 SO 4 + 2NHO 2 
→
Layer test (vi)
K 2 SO 4 + 2H 2 O + 2NO + I 2 ;
Violet pungent −
I (iodide) S.E.+ HNO3 + AgNO3 →
I2 + starch 
→ blue colour vapours turning
Smell of rotten eggs S2− Gas turn lead acetate paper black starch paper blue. yellow ppt. insoluble in aq. NH3
(H2S smell) on (sulphide) Sodium carbonate extract (SE)* + (vii) Layer test (viii)
heating sodium nitroprusside – purple Brown pungent −
NO (nitrate) Ring test (viii)
3
colour, fumes intensified
Na 2S + H2SO4 
→ H2S + Na 2SO4 ; by the addition of
Cu- turnings.
H 2 S + (CH3 COO)2 Pb 
→
Colourless gases C 2 O 42− Acidified KMnO4 solution is
PbS + 2CH 3 COOH; turning lime water decolorised (ix)
(black)
(oxalate)
milky and burning S.E. + CH3COOH + CaCl2
Na 2 S + Na[Fe(CN)5 NO] 
→
sodium nitroprusside
with blue flame.
solution–white ppt. decolorising
Na 4 [Fe(CN)5 NOS] acidified KMnO 4 solution (x)
(purple)
Colourless gas with SO32− Gas turns acidified K2Cr2O7

pungent smell of solution green [different from Table 30.7: Wet Tests for Basic Radicals
burning sulphur (sulphite)
CO32− ] since gas also turns lime Group Group Basic Composition and colour of the
water milky reagent radical precipitate
∆ I Dilute Ag + AgCl :white  Chloride
Na 2 SO3 + H 2 SO4  →
HCl 
Pb 2+ PbCl 2 :white  insouble
insoluble
Na 2 SO 4 + H 2 O + SO 2 ;  cold dilute HCl
HgCl :white 
2− Hg2+ 2
Cr2 O 7 + 3SO2 + 2H + 
→
II H2S in Hg2+ HgS :black 
2Cr 3+ + 3SO 24 + H 2 O ; presence 
(green)
Pb 2+ PbS:black 
of dilute 
Ca(OH) 2 + SO 2 
→ CaSO 3 Bi 2S3 :black
(milky)
HCl Bi 3+ 
CuS :black  Sulphides
Solution gives smell Cu 2 + 
CH 3 COO − Aq. Solution + neutral FeCl3 → CdS :yellow  insoluble in
of vinegar Cd 2 +
(acetate) blood red colour As 2S3 :yellow  dilute HCl

3CH3 COONa + FeCl2 
→ As 3+ Sb2S3 :orange 
neutral
Sb 3+ 
SnS : brown 
Fe(CH3 COO)3 + 3NaCl Sn 2+
(red) SnS2 : yellow 

III NH4OH Fe 3+
Fe(OH)3 :  5. Passing H2S gas into a mixture of Mn2+, Ni2+, Cu2+ and
in 
Cr3+ reddish brown  Hg2+ ions in an acidified aqueous solution precipitates
presence 
Cr(OH)3 : green 
of NH4Cl Al3+ [JEE 2011 P-II]
Al(OH3 : white 
a. CuS and HgS b. MnS and CuS
Hydroxides are insoluble in
c. MnS and NiS d. NiS and HgS
NH 4 OH
IV H2S in Zn 2+ ZnS :  6. For the given aqueous reactions, which of the statement(s)
presence 2+  is (are) true?
Mn greenish white 
of 
Co 2+ MnS: buff 
NH4OH  excess KI + K3[Fe(CN)6 ] 
dilute H2SO4
→ brownish-yellow solution
2+ CoS: black
Ni 
NiS : black  excess KI + K [Fe(CN) ] 
→ brownish-yellow solution
Sulphides are insoluble in
ZnSO4
NH 4 OH
V H2S in Ba 2+ BaCO3 :white white precipitate + brownish-yellow filtrate
presence 2+ 
Sr SrCO3 :white  Carbonates are insoluble
of
Ca 2+ CaCO3 :white
NH4OH Na 2S2O3
VI NaHPO4 Mg 2+ Mg (NH4 )PO4 : White colourless solution

VII NaOH NH +4 Ammonia gas is evolved [JEE 2012 P-II]
a. The first reaction is a redox reaction
Multiple Choice Questions b. White precipitate is Zn 3 [Fe(ON) 6 ]2
One and More than One Correct c. Addition of filtrate to starch solution gives blue colour
1. Consider a titration of potassium dichromate solution with d. White precipitate is soluble in NaOH solution
acidified Mohr’s salt solution using diphenylamine as
7. Upon treatment with ammoniacal H 2S, the metal ion that
indicator. The number of moles of Mohr’s salt required
precipitates as a sulfide is [JEE Adv. 2013 P-I]
per mole of dichromate is [JEE 2007 P- II]
a. Fe(III) b. Al(III) c. Mg(I) d. Zn(II)
a. 3 b. 4 c. 5 d. 6
8. The molarity of a solution obtained by mixing 750 mL of
2. A solution of metal ion when treated with KI gives a red 0.5(M)HCl with 250 mL of 2(M)HCl will be
precipitate which dissolves in excess KI to give a [JEE Main 2013]
colourless solution. Moreover, the solution of metal ion on a. 0.875 M b. 1.00 M
treatment with a solution of cobalt(II) thiocyanate gives c. 1.75 M d. 0.975 M
rise to a deep blue crystalline precipitate. The metal ion is
9. Consider the following reaction xMnO4− + yC2 O42 − + zH +
[JEE 2007 P- II]
a. Pd2+ b. Hg2+ z
 → xMn 2+ + 2yCO 2 + H 2 O. The values of x, y and z
c. Cu2+ d. Co2+ 2
in the reaction are respectively [JEE Main 2013]
3. A solution of colourless salt H on boiling with excess
a. 5, 2 and 16 b. 2, 5 and 8
NaOH produces a non-flammable gas. The gas evolution
c. 2, 5 and 16 d. 5, 2 and 8
ceases after sometime. Upon addition of Zn dust to the
same solution, the gas evolution restarts. The colourless 10. How many litres of water must be added to 1 litre of an
salt (s) H is (are) [JEE 2008 P-I] aqueous solution of HCl with a pH of 1 to create an
a. NH4NO3 b.NH4NO2 aqueous solution with pH of 2? [JEE Main 2013]
c. NH4Cl d. (NH4)2SO4 a. 0.1 L b. 0.9 L c. 2.0 L d. 9.0 L
4. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water 11. In Carius method of estimation of halogens, 250 mg of an
gave a solution of density 1.15 g/mL. The molarity of the organic compound gave 141 mg of AgBr. The percentage
solution is [JEE 2011 P-I] of bromine in the compound is:
a. 1.78 M b. 2.00 M (Atomic mass Ag = 108, Br = 80) [JEE Main 2015]
c. 2.05 M d. 2.22 M a. 24 b. 36 c. 48 d. 60

12. Which of the following compounds is not colored yellow? 19. The following ligand is [JEE Main 2019]
[JEE Main 2015]
NEt2
a. Zn 2 [Fe(CN) 6 ] b. K 3[Co(NO2 )6 ] N
c. (NH 4 )3 [As(Mo3O10 ) 4 ] d. BaCrO 4
O– –O
13. The pair(s) of ions where BOTH the ions are precipitated
upon passing H 2S gas in presence of dilute HCl, is(are) a. Bidentate b. Hexadentate
[JEE Adv. 2015 P-II] c. Tetradentate d. Tridentate
a. Ba 2+ , Zn 2+ b. Bi3+ , Fe3+ 20. 100 mL of a water sample contains 0.81 g of calcium
c. Cu 2+ , Pb 2+ d. Hg 2+ , Bi 3+ bicarbonate and 0.73 of magnesium bicarbonate. The
hardness of this water sample expressed in terms of
14. The hottest region of Bunsen flame shown in the figure
equivalents of CaCO3 is: (molar mass of calcium
below is: [JEE Main 2016]
bicarbonate is 162 g mol–1 and magnesium bicarbonate is
region 4
region 3 146 gmol–1) [JEE Main 2019]
region 2 a. 1,000 ppm b. 10,000 ppm
c. 100 ppm d. 5,000 ppm
region 1
21. The tests performed on compound X and their inferences are:
[JEE Main 2019]
Test Inference
a. region 1 b. region 2 c. region 3 d. region 4 (A) 2,4-DNP test Coloured precipitate
(B) Iodoform test Yellow precipitate
15. The reagent(s) that can selectively precipitate S2 − from a
(C) Azo-dye test No dye formantion
mixture of S2 − and SO24− in aqueous solution is(are)
Compound ‘X’ is:
[JEE Adv. 2016 P-I] H 3C CH3
NH2 OH
a. CuCl2 b. BaCl2 N
c. Pb(OOCCH 3 ) 2 d. Na 2 [Fe(CN)5 NO] a. CH3 b. COCH3
16. Sodium salt of an organic acid 'X' produces effervescence
with conc. H2SO4. 'X' reacts with the acidified aqueous H 3C CH3
NH2 N
CaCl2 solution to give a white precipitate which
decolourises acidic solution of KMnO4. 'X' is CHO CHO
c. d.
[JEE Main 2017]
a. Na 2 C 2 O 4 b. C6H5COONa
22. In the reaction of oxalate with permanganate in acidic
c. HCOONa d. CH3COONa
medium, the number of electrons involved in producing
17. The correct option(s) to distinguish nitrate salts of Mn2+ one molecule of CO2 is : [JEE Main 2019]
and Cu2+ taken separately is (are) [JEE Adv. 2018 P-II] a. 10 b. 2 c. 1 d. 5
a. Mn2+ shows the characteristic green colour in the flame
23. A compound 'X' on treatment with Br2/NaOH, provided
test
C3H9N, which gives positive carbylamine test. Compound
b. Only Cu2+ shows the formation of precipitate by
'X' is :- [JEE Main 2019]
passing H2S in acidic medium
a. CH3COCH2NHCH3
c. Only Mn2+ shows the formation of precipitate by
b. CH3CH2COCH2NH2
passing H2S in faintly basic medium
d. Cu2+/Cu has higher reduction potential than Mn2+/Mn c. CH3CH2CH2CONH2
(measured under similar conditions) d. CH3CON(CH3)2
18. The lanthanide ion that would show colour is- 24. Which of the following compounds reacts with
[JEE Main 2019] ethylmagnesium bromide and also decolourizes bromine
a. Sm 3+
b. La 3+
c. Lu3+
d. Gd3+ water solution: [JEE Main 2019]

CN O CN a. R is a V-shaped molecule
CH2 —CO2CH3 b. Z is dirty white in colour
a. b. c. Bond order of Q is 1 in its ground state
d. The oxidation state of Zn in T is + 1.
OCH3 OH
CN
c. CH2 d.
31. Match the anionic species given in Column I that are
present in the ore(s) given in Column II is:
25. The hardness of a water sample (in terms of equivalents of
[JEE Adv. 2015 P -I]
CaCO3) containing 10–3 M CaSO4 is:
Column I Column II
(molar mass of CaSO4 = 136 g mol–1) [JEE Main 2019]
(A) Carbonate 1. Siderite
a. 100 ppm b. 50 ppm
c. 10 ppm d. 90 ppm (B) Sulphide 2. Malachite
(C) Hydroxide 3. Bauxite
26. Chlorine on reaction with hot and concentrated sodium
(D) Oxide 4. Calamine
hydroxide gives: [JEE Main 2019]
5. Argentite
a. Cl− and ClO−2 b. Cl− and ClO3−
a. A→ 1,3,4; B→ 5; C→ 2,3; D→ 3
c. Cl− and ClO − d. Cl3− and ClO−2
b. A→ 1,2; B→ 2,4; C→ 2,3; D→ 4
27. Fusion of MnO2 along with KOH and O2 forma X. c. A→ 2,3; B→ 1,2; C→ 2,3; D→ 4
Electrolytic oxidation of X yields Y. X undergoes d. A→ 3; B→ 3,4; C→ 4; D→ 1,2,3
disproportionation in acidic medium to MnO2 and Y. The
Manganese in X and Y is in the form W & Z respectively,
[JEE Main 2019]
then [JEE Adv. 2019 P-I]
Column - I (drug) Column – II (test)
a. W & Z are coloured
(A) Chloroxylenol 1. Carbylamine Test
b. W is diamagnetic
c. Both W & Z are tetrahedral in shape (B) Norethindron 2. Sodium Hydrogen
d. Both W & Z invole pπ–dπ bonding for π bond Carbonate Test
28. Which green coloured compound of chromium is formed (C) Sulphapyridine 3. Ferric chloride test
in borax bead test ? [JEE Adv. 2019 P-I] (D) Penicillin 4. Bayer’s test
(a) Cr(BO2)3 (b) Cr2O3
a. A→2; B→1; C→4; D→3
(C) CrB (d) CrBO3
b. A→3; B→1; C→4; D→2
29. With reference to aqua regia, choose the correct option(s):
c. A→3; B→4; C→1; D→2
[JEE Adv. 2019 Paper -II]
d. A→2; B→4; C→1; D→3
a. Aqua regia is prepared by mixing conc. HCl and conc.
HNO 3 in 3:1 molar ratio.
Paragraph
b. Reaction of gold with aqua regia produces an anion
having Au in +3 oxidation state. Paragraph for Questions Nos. 33 to 35
c. Reaction of gold with aquaregia produces NO 2 in the p-Amino-N, N-dimethylaniline is added to a strongly acidic
absence of air solution of X. The resulting solution is treated with a few drops
d. The yellow colour of aqua regia is due to the presence of aqueous solution of Y to yield blue coloration due to the
of NOCl and Cl2. formation of methylene blue. Treatment of the aqueous solution
30. Consider the following reaction (unbalanced) of Y with the reagent potassium hexacyanoferrate (II) leads to
the formation of an intense blue precipitate. The precipitate
Zn + Hot conc. H 2SO4 
→G + R + X
dissolves on excess addition of the reagent. Similarly, treatment
Zn + conc. NaOH 
→T + Q
of the solution of Y with the solution of potassium
G + H2S + NH3 (aq) 
→ Z(precipitate) + X + Y hexacyanoferrate (III) leads to a brown coloration due to the
Choose the correct option(s) [JEE Adv. 2019 P-II] formation of Z. [JEE 2009 P-I]

33. The compound X is Integer and Subjective
a. NaNO3 b. NaCl 40. A student performs a titration with different burettes and
c. Na 2SO 4 d. Na 2S finds titre values of 25.2 mL, 25.25 mL and 25.0 mL. The
number of significant figures in the average titre value
34. The compound Y is is________ [JEE 2010 P-I]
a. MgCl2 b. FeCl2
41. The concentration of R in the reaction R→P was
c. FeCl3 d. ZnCl2 measured as a function of time and the following data is
35. The compound Z is obtained:
[R] (molar) 1.0 0.75 0.40 0.10
a. Mg 2 [Fe(CN)6 ] b. Fe[(CN)6 ]
t (min). 0.0 0.05 0.12 0.18
c. Fe 4 [Fe(CN)6 ]3 d. K 2 Zn[Fe(CN)6 ]2 The order of the reaction is________ [JEE 2010 P-I]
42. The volume (in mL) of 0.1 M AgNO3 required for
Paragraph for Question Nos. 36 to 37 complete precipitation of chloride ions present in 30 mL
Bleaching powder and bleach solution are produced on a large of 0.01 M solution of [Cr(H2O)5Cl]Cl2, as silver chloride
scale and used in several household products. The effectiveness is close to________ [JEE 2011 P-II]
of bleach solution is often measured by iodometry. 43. In 1L saturated solution of AgCl [Ksp (AgCl) = 1.6 ×10−10 ],
[JEE 2012 P-II] 0.1 mol of CuCl [K sp (CuCl) = 1.0 ×10−6 ] is added. The
36. 25 mL of household bleach solution was mixed with 30
resultant concentration of Ag + in the solution is 1.6 ×10− x.
mL of 0.50 M KI and 10 mL of 4 N acetic acid. In the
titration of the liberated iodine, 48 mL of 0.25 N The value of “x” is________ [JEE 2011 P-II]
44. 29.2% (w/w) HCl stock solution has a density of 1.25 g
Na 2S2 O3 was used to reach the end point. The molarity
mL−1. The molecular weight of HCl is 36.5 g mol−1. The
of the household bleach solution is
volume (mL) of stock solution required to prepare a 200
a. 0.48 M b. 0.96 M
mL solution of 0.4 M HCl is________ [JEE 2012 P-I]
c. 0.24 M d. 0.024 M
45. Consider the following list of reagents:
37. Bleaching powder contains a salt of an oxoacid as one of K2Cr2O7, alkaline KMnO4 ,CuSO4 , H2 O2 ,Cl2 ,O3 , FeCl3 ,
its components. The anhydride of that oxoacid is HNO3 and Na2S2O3. The total number of reagents that can
a. Cl 2 O b. Cl2 O7 c. ClO 2 d. Cl 2 O 6
oxidise aqueous iodide to iodine is________
[JEE Adv. 2014 P-I]
Paragraph for Question Nos. 38 to 39 46. Among Pbs, CuS, HgS, MnS, Ag2S, NiS, CoS, Bi2S3 and
An An aqueous solution of a mixture of two inorganic salts, SnS2, the total number of black coloured sulphides is____
when treated with dilute HCl, gave a precipitate (P) and a [JEE Adv. 2014 P-I]
filtrate (Q). The precipitate P was found to dissolve in hot
water. The filtrate (Q) remained unchanged, when treated with ANSWERS and SOLUTIONS
H2S in a dilute mineral acid medium. However, it gave a 1. (d) Cr2 O 72− + Fe 2+  Fe33++ ++Cr
→ Fe Cr33++
precipitate (R) with H2S in an ammoniacal medium. The n factor of Cr2 O72− = 6 ,
precipitate R gave a coloured solution (S), when treated with
n factor of Fe2+ = 1
H2O2 in an aqueous NaOH medium.
So, to reduce one mole of dichromate 6 moles of
38. The precipitate P contains
Fe2+ are required.
Hence (d) is correct.
a. Pb 2 + b. Hg 22 +
2. (b) Hg 2+ + KI 
→ HgI2
c. Ag + d. Hg 2 +
(Red ppt.)
39. The coloured solution S contains HgI 2 + KI 
→ K 2 HgI4
(excess) soluble
a. Fe 2 (SO 4 )3 b. CuSO 4
2+
HgI + Co(SCN) 2 
→ Hg(SCN) 2
c. ZnSO 4 d. Na 2 CrO4 bluecrystalline
Blue crystalline precipitates
precipiates

3. (a, b) NH 4 NO3 + NaOH 
→ NH 3 + NaNO3 + H 2 O (a) Cu 2 + + S 2 − 
→ CuS ↓ .
Black ppt
7NaOH + NaNO3 + 4Zn 

→ 4Na 2 ZnO 2 + NH 3 + 2H 2 O 2+ 2−
Cu + SO 4 → No. ppt.

NH 4 NO 2 + NaOH 
→ NaNO 2 + NH 3 + H 2 O
(b) Ba 2 + + S2 − 
→ No. ppt.
3Zn + 5NaOH + NaNO 2 
→ 3Na 2 ZnO 2 + NH 3 + H 2 O
Ba 2+ + SO42 − 
→ BaSO4 ↓ .
4. (c) Total mass of the solution = 1000 + 120 = 1120 g White ppt
1120 120 (c) Pb 2+

+S 2−
→ PbS ↓ .

V= = 0.973 L , n urea = = 2 mol , Black ppt
1.15 60
−28
K sp (PbS) = 10
2
M= = 2.05 M
0.973 Pb 2+ + SO42− 
→ PbSO4 .
Black ppt
5. (a) H 2S in presence of aqueous acidified solution
K sp (PbSO 4 ) = 1.6 ×10−8
precipitates as sulphide of Cu and Hg apart from
(d) No ion is precipitated.
Pb +2 , Bi +3 , Cd +2 , As +3 , Sb +3 and Sn +2 .
So, Ans is (a) & (c) or (a).
6. (a, c, d) ** In option (c)
KI(excess) + [K3 Fe(CN)6 ] + H2SO4 
→ as the difference in Ksp of PbS & PbSO4 is large.
so only PbS is selectively precipitated.
K 4 [Fe(CN)6 ] + I 2 + KOH
(Brownish – Yellow solution) 16. (a) Na 2 C 2 O 4 + H 2 SO 4 
→
conc.
KOH + I 2 + K 4 [Fe(CN)6 ] + ZnSO 4 → Zn(OH) 2 + I2
Na 2SO4 + CO ↑ + CO2 ↑ + H 2 O
(Brown-Yellow Filterate)
Na 2 C2 O4 + CaCl2 
→
I 2 + Starch → Blue colour
Zn(OH)2 + NaOH (Excess)
æææææ → NaÆZnO
(Na22 ZnO 2 ) CaC2 O4 ↓ + 2NaCl
(Excess) 2 (white ppt.)
(soluble in alkaline medium) 5CaC 2 O 4 ↓ + 2KMnO 4 + 8 H 2SO 4 

→
(purple)
3+ 3+ 2+ 2+
7. (d) Among Fe , Al , Mg , Zn
K 2SO4 + 5CaSO4 + 2MnSO4 + 10CO2 + 8H 2O
only Zn 2 + is precipitated with ammonical H 2S as ZnS. (colourless)
0.5 × 750 + 250 × 2 17. (b, d) (a) Manganese show pale purple colour in flame
8. (a) (Molarity) Mix = = 0.875 M test.
1000
(b) Cu +2 
H2S
→ CuS ↓
9. (c) 2MnO −4 + 5C 2 O 24 − + 16H + 
→2Mn +2 + 10CO 2 + 8H 2 O HCl Black ppt.
O 2−
4
+
+ 16H 
→2Mn +2
+ 10CO 2 + 8H 2 O (c) Both Cu +2
and Mn +2 form precipitate with H 2S in
basic medium.
10. (d) 0.1× 1 = (1 + v) × 0.01
(d) Eº Cu +2 / Cu = +0.34
⇒ 1 + v = 0.1 ⇒ 1 + v = 10
0.01 Eº Mn 2+ / Mn = −1.18 V
⇒ v = 10 − 1 = 9L
18. (a) Sm3+ (4f 5) = yellow colour
80 141 mg
11. (a) % of Bromine = × × 100 = 24% 19. (c) Donating atoms are both nitrogen and oxygen.
188 250 mg
20. (b) n eq .CaCO3 = n eq Ca(HCO3 ) 2 + n eq Mg(HCO3 ) 2
12. (a) Zn 2 [Fe(CN) 6 ] is bluish white ppt. W 0.81 0.73
or, ×2 = ×2+ ×2
2+ 2+ 2+ 3+ 100 162 146
13. (c, d) Cu , Pb , Hg , Bi
∴ W = 1.0
give ppt with H 2S in presence of dilute HCl.
1.0
∴ Hardness = × 10 6 =10,000 ppm
14. (b) It is fact 100
15. (a or a, c) 21. (d) →2, 4 - DNP test is given by aldehyde on ketone.

→ Iodoform test is given by compound having 31. (a) A→ 1,3,4; B→ 5; C→ 2,3; D→ 3
CH3 — C — Group Siderite FeCO3
||
O Malachite CuCO3 .Cu(OH)2
Bauxite AlO x (OH)3.2x ; 0 < | x < 1
+7 +2
(c) 2MnO4 + 5C2O4 +16H 
→ 2Mn2+ +10CO2 + 8H2O
2– +
22. Calamine ZnCO3
10 e– transfer for 10 molecules of CO2 so per molecule of Argentite Ag 2S
CO2 transfer of e– is '1'.
32. (c) A→3; B→4; C→1; D→2
Br2 CHCl3
[X] → C3 H 9 N → CH 3 CH 2 CH 2 —NC Me
23. (c) NAOH KOH
Hoffmann's Carbylamine Cl
Bromamide Reaction (A) Chloroxylenol
degradation FeCl3 test
Thus [X] must be aride with one carbon more than amine. HO Me
Thus [X] is CH3CH2CH2CONH2. OH
C≡CH
24. (d) OH OMgBr
(B) Norethindron

EtMgBr
→ + CH3 — CH3
O
decolourises Bromine water
Bayer’s test
25. (a) ppm of CaCO3 SO2

(C) Sulphapyridine
(10–3 × 103) × 100 = 100 ppm NH N
H2 N
26. (b) 3Cl2 + 6OH – 
→ 5Cl – +ClO3– + 3H 2 O
Carbylamine test
27. (a,c,d) (D) Penicillin
KOH electrolytic
MnO 2 
O2
→ MnO 24 − 
Oxidation
→ MnO 4− NH S
(W) (Z)
H2 N N
O
acidic COOH
Sodium hydrogen carbonate test
MnO 2 + MnO4
∆ ∆
28. (a) Na2B4O7. 10H2O  → Na2B4O7  → NaBO2 +B2O3 33 (d)
∆
Cr2 O 3 + B 2 O 3 
→ Cr(BO 2 ) 3 34. (c)
Green
29. (a, b, d) 35. (b) Na 2S+ 2H + 

→ H 2S + 2Na +
(X)
Au + 4H + + NO3− + 4Cl− 
→[AuCl4 ]− + NO + 2H 2 O
N(CH 3 ) 2 N(CH 3 ) 2
(a) Fact.
(b) [AuCl4 ]− gets formed; Au(+3). + H 2S + + 6Fe3+ 
→ 6Fe 2+ + NH + + 4H +
(c) NOCl/NO is formed. (Y)
(d) Fact. NH 2 NH 2
30. (a,b,c) Zn + H2SO4 
→ ZnSO4 + SO2 + H2 O + 6Fe 3+
→ 6Fe 2+ + NH +4 + 4H + + Methylene Blue

(Hot & conc.) (G) (R ) (X)
 II 
Zn + conc. NaOH 
→ Na 2 ZnO2 + H2 4FeCl33 ++ 3K
4FeCl Fe(CN)66  
3K44  Fe(CN) → Fe44 [Fe(CN)
→ Fe
 Fe(CN)66 ]3 ++ 2KCl
2KCl
(T) (Q)   Intense blue
ZnSO4 + H2S + NH3 (aq) 

→ ZnS ↓ + (NH4 )2 SO4 + H2 O
(Z)
FeCl K33[ Fe(CN)
FeCl33 ++K Fe(CN)66] 
→
 Fe [Fe(CN)
→Fe Fe(CN)66 ]++3KCl
3KCl
(G) (Y) (X) Brown coloration

(X) − Na 2S CuCl ↽ ⇀ Cu + + Cl−
y y
(Y) − FeCl3
(Z) − Fe[Fe(CN)6 ] ∴ K sp of AgCl = [Ag ] [Cl −1 ]
+
For Question Nos. 36 to 37 1.6 ×10 −10 = x(x + y) . . .(i)

+ −
1 Similarly K sp of CuCl = [Cu ] [Cl ]
36. (c) = × No. of moles of Na 2S2 O3
2 1.6 ×10 −6 = y(x + y) . . .(ii)
1
= × (0.25 × 48 ×10−3 ) On solving (i) and (ii) [Ag + ] = 1.6 × 10−7
2
∴ x=7
= 6 ×10−3
n W W × d sol W 100 d
Molarity ×25 ×10−3 = 6 ×10−3 44. Molarity = = = = × ×
V M w × v M w × Wsol Wsol M w × 100
6
Molarity of bleach solution = = 0.24 M W
25 % × d × 10
n W W d sol W 100 × d so ln W
=
37. (a) Bleaching powder contains salt of HCl. = = = × × 1000 =
V It Mis obtained
w ×v M w × Wsol Wsol M w × 100 Mw
by adding H 2 O to Cl 2 O. Thus option (a) is correct.
29.2 ×1.25 ×10
= = 10 M
For Question Nos. 38 to 39 36.5
38. (a) ⇒ M1V1 = M 2 V2 ⇒ 10 × V1 = 0.4 × 200
39. (d) Pb +2 + 2HCl 

2 Hot
→ PbCl22 
Water →
Hot soluble 0.4 × 200
⇒ V= == 88ml
ml
10
Cr +3 
H2S
→ Cr(OH)3 ↓
ammonical 45. Total no. of reagents are 7. K 2 Cr2 O7 , CuSO 4 , H 2 O 2 , Cl2 , O3 , FeC
Cr(OH)3 
NaOH
H 2 O2
→ Na 2 CrO 4 K 2 Cr2 O7 , CuSO 4 , H 2 O 2 , Cl2 , O3 , FeCl3 , HNO 3
Yellow solution
40. (3) K 2 Cr2 O7 , 7H 2SO 4 + 6KI 

→
4K 2SO 4 + Cr2 (SO 4 )3 + 3I 2 + 7H 2 O
41. From two data, (for zero order kinetics)
x 0.25 x 0.60 2CuSO 4 + 4KI 
→ Cu 2 I2 + I 2 + 2K 2SO 4
KI = = = 5 ⇒ K II = = =5
t 0.05 t 0.12 H2 O2 + 2KI 
→ I2 + 2KOH
−
42. Number of ionisable Cl in Cl2 + 2KI 
→ 2KCl + I 2
[Cr(H 2 O)5 Cl]Cl 2 is 2
O3 + 2KI + H 2 O 
→ 2KOH + I 2 + O 2
∴ Millimoles of Cl − = 30 × 0.01× 2 = 0.6
2FeCl3 + 2KI 
→ 2FeCl 2 + I 2 + 2KCl
∴ Millimoles of Ag + required = 0.6
∴ 0.6 = 0.1 V ⇒ V = 6 ml 8HNO3 + 6KI 
→ 6KNO3 + 2NO + 4H 2 O + 3I 2
2KMnO 4 + KI + H 2 O 
→ KIO3 + 2MnO 2 + 2KOH
43. Let the solubility of AgCl is x mol litre −1
46. No. of black coloured sulphides {PbS, CuS, HgS, Ag2S,
AgCl ↽ ⇀ Ag + + Cl− NiS, CoS}= 6
x x
* Bi2S3 in its crystalline form is dark brown but Bi 2S3
and that of CuCl is y mol litre−1
precipitate obtained is black in colour.
Mock Test-1
Test Booklet code
333
A Mock Test 1 “JEE-Main”

Do not open this Test Booklet until you are asked to do so.
Read carefully the Instructions on the Back Cover of this Test Booklet.
Important Instructions:
1. Immediately fill in the particulars on this page of the Test Booklet with Blue/Black Ball Point Pen. Use of pencil is strictly
prohibited.
2. The Answer Sheet is kept inside this Test Booklet. When you are directed to open the Test Booklet, take out the Answer
Sheet and fill in the particulars carefully.
3. The test is of 3 hours duration.
4. The Test Booklet consists of 90 questions. The maximum marks are 360.
5. There are three parts in the question paper A, B, C consisting of, Physics, Chemistry and Mathematics having 30
questions in each part of equal weightage. Each question is allotted 4 (four) marks for each correct response.
6. Candidates will be awarded marks as stated above in instruction No. 5 for correct response of each question. 1/4 (one
fourth) marks will be deducted for indicating incorrect response of each question. No deduction from the total score will
be made if no response is indicated for an item in the answer sheet.
7. There is only one correct response for each question. Filling up more than one response in each question will be treated as
wrong response and marks for wrong response will be deducted accordingly as per instruction 6 above.
8. Use Blue/Black Ball Point Pen only for writing particulars/ marking responses on Side-1 and Side-2 of the Answer Sheet.
Use of pencil is strictly prohibited.
9. No candidates is allowed to carry any textual material, printed or written, bits of papers, pager, mobile phone, any
electronic device, etc., except the Admit Card inside the examination hall/room.
10. Rough work is to be done on the space provided for this purpose in the Test Booklet only. This space is given at the
bottom of each page and at the end of the booklet.
11. On completion of the test, the candidate must hand over the Answer Sheet to the Invigilator on duty in the Room / Hall.
However, the candidates are allowed to take away this Test Booklet with them.
12. The CODE for this Booklet is A. Make sure that the CODE printed on Side-2 of the Answer Sheet and also tally the serial
number of the Test Booklet and Answer Sheet are the same as that on this booklet. In case of discrepancy, the candidate
should immediately report the matter to the invigilator for replacement of both the Test Booklet and the Answer Sheet.
13. Do not fold or make any stray marks on the Answer Sheet.
Name of the Candidate (in Capital letters):

Roll Number : in figures
in words
Examination Centre Number:
Name of Examination Centre (in Capital letters):
Candidate’s Signature: Invigilator’s Signature:

Read the following instructions carefully:
1. The candidates should fill in the required particulars on the Test Booklet and Answer Sheet (Side-1) with
Blue/Black Ball Point Pen.
2. For writing/marking particulars on Side-2 of the Answer Sheet, use Blue/Black Ball Point Pen only.
3. The candidates should not write their Roll Numbers anywhere else (except in the specified space) on the Test
Booklet/Answer Sheet.
4. Out of the four options given for each question, only one option is the correct answer.
5. For each incorrect response, one-fourth (¼) of the total marks allotted to the question would be deducted from
the total score. No deduction from the total score, however, will be made if no response is indicated for an item
in the Answer Sheet.
6. Handle the Test Booklet and Answer Sheet with care, as under no circumstances (except for discrepancy in
Test Booklet Code and Answer Sheet Code), another set will be provided.
7. The candidates are not allowed to do any rough work or writing work on the Answer Sheet. All
calculations/writing work are to be done in the space provided for this purpose in the Test Booklet itself,
marked ‘Space for Rough Work’. This space is given at the bottom of each page and at the end of the booklet.
8. On completion of the test, the candidates must hand over the Answer Sheet to the Invigilator on duty in the
Room/Hall. However, the candidates are allowed to take away this Test Booklet with them.
9. Each candidate must show on demand his/her Admit Card to the Invigilator.
10. No candidate, without special permission of the Superintendent or Invigilator, should leave his/her seat.
11. The candidates should not leave the Examination Hall without handing over their Answer Sheet to the
Invigilator on duty and sign the Attendance Sheet again. Cases where a candidate has not signed the Attendance
Sheet a second time will be deemed not to have handed over the Answer Sheet and dealt with as an unfair
means case. The candidates are also required to put their left hand THUMB impression in the space
provided in the Attendance Sheet.
12. Use of Electronic/Manual Calculator and any Electronic Item like mobile phone, pager etc. is prohibited
13. The candidates are governed by all Rules and Regulations of the JAB/Board with regard to their conduct in the
Examination Hall. All cases of unfair means will be dealt with as per Rules and Regulations of the JAB/Board.
14. No part of the Test Booklet and Answer Sheet shall be detached under any circumstances.
15. Candidates are not allowed to carry any textual material, printed or written, bits of papers, pager,
mobile phone, electronic device or any other material except the Admit Card inside the examination
hall/room.
Mock Test-1 335
JEE-MAIN: CHEMISTRY MOCK TEST-1

1. In a galvanic cell, the salt bridge a. forward direction because Q > K c
a. does not participate chemically in the cell reaction. b. reverse direction because Q > K c
b. stops the diffusion of ions from one electrode to another.
c. forward direction because Q < K c
c. is necessary for the occurrence of the cell reaction
d. ensures mixing of the two electrolytic solutions d. reverse direction because Q < K c
2. Sodium metal crystallizes in a body centred cubic lattice 8. Two Faraday of electricity is passed through a solution of
with a unit cell edge of 4.29 Å. The radius of sodium atom CuSO4. The mass of copper deposited at the cathode is:
is approximately a. 0 g b. 63.5 g
a. 1.86 Å b. 3.22 Å c. 2 g d. 127 g
c. 5.72 Å d. 0.93 Å 9. What is the half life period of a radioactive substance if
3. Which of the following is the energy of a possible excited 87.5% of any given amount of the substance disintegrates
state of hydrogen? in 40 minutes?
a. +13.6 eV b. − 6.8 eV a. 160 min b. 10 min
c. 20 min d. 13 min 20 sec
c. − 3.4 eV d. + 6.8 eV
10. 3 g of activated charcoal was added to 50 mL of acetic
4. The number of atoms in 100 g of an fcc crystal with
acid solution (0.06 N) in a flask. After an hour it was
–3
density =10.0 g cm and cell edge equal to 200 pm is filtered and the strength of the filtrate was found to be
equal to 0.042 N. The amount of acetic acid adsorbed (per gram of
a. 5 × 10 24 b. 5 × 10 25 c. 6 × 10 23 d. 2 × 10 25 charcoal) is :
a. 18 mg b. 36 mg
5. The following reaction is performed at 298 K.
c. 42 mg d. 54 mg
2NO(g) + O2 (g) ↽ ⇀ 2NO2 (g)
11. The ionic radii (in Å) of N 3− , O 2 − and F− are respectively:
The standard free energy of formation of NO (g) is 86.6
a. 1.36, 1.40 and 1.71 b. 1.36, 1.71 and 1.40
kJ/mol at 298 K. What is the standard free energy of
c. 1.71, 1.40 and 1.36 d. 1.71, 1.36 and 1.40
formation of NO 2 (g) at 298 K? (Kp = 1.6 ×10 )
12
12. In the context of the Hall-Heroult process for the
a. R (298)ℓn (1.6 × 10 ) − 86600
12 extraction of Aℓ, which of the following statements is
b. 86600 + R(298) ℓn (1.6 × 1012 ) false?
a. CO and CO 2 are produced in this process
ℓn (1.6 × 1012 )
c. 86600 − b. Aℓ 2 O3 is mixed with CaF2 which lowers the melting
R(298)
point of the mixture and brings conductivity
d. 0.5[2 × 86600 − R(298) ℓn (1.6 ×1012 )]
c. Aℓ 3+ is reduced at the cathode to form Aℓ
6. The vapour pressure of acetone at 20°C is 185 torr. When d. Na 3 AℓF6 serves as the electrolyte
1.2 g of a non-volatile substance was dissolved in 100 g of
13. From the following statements regarding H 2 O 2 , choose
acetone at 20 ° C, its vapour pressure was 183 torr. The
the incorrect statement
molar mass (g mol–1) of the substance is:
a. It can act only as an oxidising agent
a. 32 b. 64 b. It decomposes on exposure to light
c. 128 d. 488 c. It has to be stored in plastic or wax lined glass bottles in
7. The standard Gibbs energy change at 300 K for the dark
d. It has to be kept away from dust
reaction 2A ↽ ⇀ B + C is 2494.2 J. At a given time, the
14. Which one of the following alkaline earth metal sulphates
composition of the reaction mixture is [A] = 12 , [B] = 2 and
has its hydration enthalpy greater than its lattice enthalpy?
[C] = 12 . The reaction proceeds in the: a. CaSO 4 b. BeSO 4
[ R = 8.314 J / K / mol, e = 2718 ] c. BaSO 4 d. SrSO 4

15. Which among the following is the most reactive? 21. Which compound would give 5-keto-2-methyl hexanal
a. Cl 2 b. Br2 c. I 2 d. ICl upon ozonolysis?
CH3
16. Which one has the highest boiling point?
a. He b. Ne c. Kr d. Xe CH3
a. CH3 b.
17. The number of geometric isomers that can exist for square
+ CH3
planar [Pt(Cl)(py) (NH 3 )(NH 2 OH)] is (py = pyridine):
a. 2 b. 3 c. 4 d. 6 CH3
CH3
18. The color of KMnO 4 is due to
a. M → L charge transfer transition c. d. H 3C
CH3
b. d − d transition
c. L → M charge transfer transition 22. The synthesis of alkyl fluorides is best accomplished by :
d. σ − σ * transition a. Free radical fluorination
19. In Carius method of estimation of halogens, 250 mg of an b. Sandmeyer’s reaction
organic compound gave 141 mg of AgBr. The percentage c. Finkelstein reaction
of bromine in the compound is: (Atomic mass d. Swarts reaction
Ag = 108, Br = 80) 23. In the following sequence of reactions:
a. 24 b. 36 c. 48 d. 60 Toluene →
KMnO 2
A 
SOCl 2
→ B 
H 2 / Pd
→ C, the product
BaSO 4
20. In the reaction shown below, the major product(s) formed C is:
is/are
a. C 6 H 5COOH b. C6 H 5CH 3
H
|
N CH3 c. C6 H 5CH 2 OH d. C 6 H 5CHO
O 24. In the reaction

NH3
a.
NH 2

NaNO2 / HCl
0 − 5°C
→ D 
CuCN / KCN
∆
→ E + N2 The product E
O
NH 2 CH3
is
H
b. |
N CH 3 + CH 3 COOH
COOH
O O
H CH3
| a. b.
N CH 3
O CH3
H CN
| + H 2O
c. N CH 3
c.
O O
d.
⊕ H3 CH
N H 3CH 3COO − CH3
25. Which polymer is used in the manufacture of paints and

H lacquers?
| + H 2O
d. N CH 3 a. Bakelite b. Glyptal
c. Polypropene d. Poly vinyl chloride
O O
Mock Test-1 337

26. Which of the vitamins given below is water soluble? Assertion and Reason
a. Vitamin C b. Vitamin D
c. Vitamin E d. Vitamin K Note: Read the Assertion (A) and Reason (R) carefully to mark
27. Which of the following compounds is not colored yellow? the correct option out of the options given below:
a. Zn 2 [Fe(CN)6 ] b. K 3 [Co(NO 2 )6 ] a. If both assertion and reason are true and the reason is the
c. (NH 4 )3 [As(Mo3O10 )4 ] d. BaCrO 4 correct explanation of the assertion.
b. If both assertion and reason are true but reason is not the
28. Match the statement of Column with those in Column II:
Column I Column II correct explanation of the assertion.
c. If assertion is true but reason is false.
H+
(A) C12 H 22 O11 + H 2 O → 1. Pseudo first
order d. If the assertion and reason both are false.
C 6 H12 O 6 +C 6 H12 O 6 e. If assertion is false but reason is true
(B) CH 3 COOC 2 H 5 HOH
H + or OH −
→ 2. Zero order 29. Assertion: Enthalpy and entropy of any elementary
CH 3 COOH + C 2 H 5 OH substance in the standard state are taken as zero.
Reason: At zero degree absolute, the constituent particles
(C) H 2 + Cl 2 
hv
→ 2HCl 3. Second order
become completely motionless.
(D) CH3 Cl + OH− 
→ CH3 OH + Cl− 4. First order
30. Assertion: Molecularity has no meaning for a complex
a. A→1; B→3, 4; C→2; D→3 reaction.
b. A→2; B→4; C→3; D→1
Reason: The overall molecularity of a complex reaction is
c. A→1; B→3, 2; C→2; D→4
equal to the molecularity of the slowest step.
d. A→4; B→1; C→3; D→2
Space for rough work

JEE ADVANCE PAPER-I
Time 3 Hours. Max. Marks 264 (88 for Chemistry)

Read The Instructions Carefully
Question Paper Format and Marking Scheme:

1. The question paper has three parts: Physics, Chemistry and Mathematics. Each part has three sections.
2. Section 1 contains 8 questions. The answer to each question is a single digit integer ranging from 0 to 9 (both inclusive).
Marking Scheme: +4 for correct answer and 0 in all other cases.
3. Section 2 contains 10 multiple choice questions with one or more than one correct option.
Marking Scheme: +4 for correct answer, 0 if not attempted and –2 in all other cases.
4. Section 3 contains 2 “match the following” type questions and you will have to match entries in Column I with the entries
in Column II.
Marking Scheme: for each entry in Column I, +2 for correct answer, 0 if not attempted and – 1 in all other cases.
NOTE: It’s the mock test as per previous year’s papers but sometimes IIT changes the test paper pattern and
marking scheme too.
SECTION 1 (Maximum Marks: 32) 4. The total number of lone pairs of electrons in N 2 O 3 is
This section contains EIGHT questions.
5. For the octahedral complexes of Fe3+ in SCN −
The answer to each question is a SINGLE DIGIT INTEGER
ranging from 0 to 9, both inclusive. (thiocyanato-S) and in CN − ligand environments, the
For each question, darken the bubble corresponding to the correct difference between the spin-only magnetic moments in
integer in the ORS. Bohr magnetons (When approximated to the nearest
Marking scheme: integer) is [Atomic number of Fe = 26]
+4 If the bubble corresponding to the answer is darkened.
0 In all other cases.
6. Among the triatomic molecules/ions, BeCl 2 , N 3− , N 2 O,
NO +2 , O 3 ,SCl 2 , ICl −2 , I3− and XeF2 , the total number of
1. If the freezing point of a 0.01 molal aqueous solution of a
linear molecule(s)/ion(s) where the hybridization of the
cobalt (III) chloride-ammonia complex (which behaves as
central atom does not have contribution from the d-
a strong electrolyte) is −0.0558°C, the number of
orbital(s) is
[Atomic number: S = 16, Cl = 17, I = 53 and Xe = 54]
[ K f of water = 1.86 K kg mol–1]
7. Not considering the electronic spin, the degeneracy of the
2. The total number of stereoisomers that can exist for M is
second excited state (n = 3) of H atom is 9, while the
H 3C CH 3
degeneracy of the second excited state of H − is
8. All the energy released from the reaction X → Y. ∆ r G 0

H 3C + 3+
M
O = −193 kJ mol −1 is used for oxidizing M + as M → M
3. The number of resonance structures for N is +2e − , E 0 = −0.25V. Under standard conditions, the
OH
NaOH number of moles of M + oxidized when one mole of X is
→ N
converted to Y is [F = 96500 C mol –1 ]
Mock Test-1 339

SECTION 2 (Maximum Marks: 40) CH 3 CH 3
This section contains TEN questions. c. d.
H 3C Br H 3C Br
Each question has FOUR options (a), (b), (c) and (d). ONE OR
MORE THAN ONE of these four option(s) is (are) correct. 13. The correct statement(s) for orthoboric acid is/are
For each question, darken the bubble(s) corresponding to all the a. It behaves as a weak acid in water due to self ionisation
correct option(s) in the ORS.
b. Acidity of its aqueous solution increases upon addition
Marking scheme:
of ethylene glycol
+4 If only the bubble(s) corresponding to all the correct
c. It has a three dimensional structure due to hydrogen
option(s) is(are) darkened.
bonding.
0 If none of the bubbles is darkened
–2 In all other cases
d. It is a weak electrolyte in water
14. The major product of the reaction is
− − − H 3C
9. For the reaction: I + ClO + H 2SO 4 
→ HSO + I 2
3 4
CO 2 H
The correct statement(s) in the balanced equation is/are →
NaNO2 , aqueous HCl
0° C
−
a. Stoichiometric coefficient of HSO4 is 6 CH 3 NH 2
b. Iodide is oxidised H 3C NH 2 H3C CO2 H

c. Sulphur is reduced a. b.
d. H 2 O is one of the products. CH 3 OH CH3 OH
H 3C CO 2 H H 3C NH 2
10. Compound(s) that on hydrogenation produce(s) optically
inactive compound(s) is (are) c. d.
CH 3 OH CH 3 OH
H Br
H Br 15. The reactivity of compound Z with different halogens
a. H3C CH3 b. H 2 C CH 3
under appropriate conditions is given below:
H Br OH mono halo substituted derivative when X 2 = I 2
H 3C X2
di halo substituted derivative when X 2 = Br2
CH 3 Br H
c. CH 3 d. H 3C CH 3 tri halo substituted derivative when X 2 = Cl2
C(CH 3 )3
Z
11. The major product of the following reaction is The observed pattern of electrophilic substitution can be
O explained by
a. the steric effect of the halogen
C H 3 i. + 
KOH , H O
2
ii. H , heat
→ b. the steric effect of the tert-butyl group
O c. the electronic effect of the phenolic group
CH 3 CH 3
d. the electronic effect of the tert-butyl group
O O
a. b. 16. An ideal gas in thermally insulated vessel at internal
pressure = P1 , volume = V1 and absolute temperature
= T1 expands irreversibly against zero external presssure,
O O
CH 3 as shown in the diagram. The final internal pressure,
c. CH 3 d. volume and absolute temperature of the gas are P2 , V2
and T2 , respectively. For this expansion.
12. In the following reaction, the major product is
CH 3
CH 2 
1 equivalent HBr
→
H 3C Pext = 0 Pext = 0
CH 3 P1 ,V2 ,T2
CH 3 P1 ,V2 ,T2
CH 3
a. H 3C b. H C
3
Br Br Thermal insulation

a. q = 0 b. T2 = T1 For each entry in Column I, darken the bubbles of all the
matching entries. For example, if entry (A) in Column I, matches
c. P2 V2 = P1V1 d. P2 V2γ = P1V1γ
with entries (2), (3) and (4), then darken these three bubbles in the
17. Fe3+ is reduced to Fe2+ by using ORS. Similarly, for entries (B), (C) and (D).
a. H 2 O2 in presence of NaOH Marking scheme:
For each entry in Column I
b. Na 2 O 2 in water
+2 If only the bubble(s) corresponding to all the correct match(es)
c. H 2 O2 in presence of H 2SO 4 is(are) darkened
d. Na 2 O 2 in presence of H 2SO 4 0 If none of the bubbles is darkened
–1 In all other cases
18. The % yield of ammonia as a function of time in the
19. Different possible thermal decomposition pathways for
reaction N 2 (g) + 3H 2 (g) ↽ ⇀ 2NH 3 (g), ∆H < 0 at (P, T1 )
peroxyesters are shown below. Match each pathway from
is given below: Column -I with an appropriate structure from Column –II is:
P

− CO ↑
→ R i + R ′Oi
T1 1
O
 Q
− CO1 ↑
→ R i + R ′Oi 
→ R i + Xi + carbonyl c
O
R → ROi + R Oi R
 i i
′ → R + X + carbonyl compound ↑
time
(Peroxyester)
 R
→ RCO2i + R ′Oi  → R i + Xi + ca
If this reaction is conducted at (P,T2 ), with T2 > T1 , the 1 − CO ↑ 1 − CO ↑
→ RCO i + R Oi → R i + X i + carbonyl compound ↑
% yield of ammonia as a function of time is represented S
 → RCO 2i + R ′Oi  → R i + R ′Oi
by
T
→ RCO + R ′O 
i i
− CO ↑
→ R + R ′O
i i
2 1
T1 T1
% Yield % Yield
a. b. Column I Column II
(A) Pathway A 1. O
time time O
C6 H 5 CH 2 O CH3
T1 T2
% Yield T2 % Yield T1 O
(B) Pathway B 2.
c. d. O
C6 H 5 O CH3
time time
(C) Pathway C 3. O
O CH3
SECTION 3 (Maximum Marks: 16)
C6 H 5 CH 2 O
This section contains TWO questions. CH 2 C6 H 5 CH3
Each question contains two columns, Column I and Column II
Column I has four entries (A), (B), (C) and (D) (D) Pathway D 4. O
O CH3
Column II has five entries (1), (2), (3), (4) and (5)
C6 H 5 O
Match the entries in Column I with the entries in Column II C6 H 5 CH3
One or more entries in Column I may match with one or more
entries in Column II a. Α→1; B→3; C→4; D→2
The ORS contains a 4 × 5 matrix whose layout will be similar to b. Α→2; B→4; C→4; D→1
the one shown below: c. Α→1; B→1; C→2; D→4
(A) (1) (2) (3) (4) (5) d. Α→3.; B→2; C→1; D→3
(B) (1) (2) (3) (4) (5)
20. Match the orbital overlap figures shown in Column -I with
(C) (1) (2) (3) (4) (5)
the description given in Column -II and select the correct
(D) (1) (2) (3) (4) (5)
Mock Test-1 341

answer using the code given below the lists. 3. p-d π bonding
(en = H 2 NCH 2 CH 2 NH 2 ; atomic numbers :
(C)
Ti = 22, Cr = 24, Co = 27; Pt = 78)
Column I Column II
4. d-d σ antibonding
1. p-d π antibonding
(A) (D)
a. Α→2; B→3; C→1; D→4

2. d-d σ bonding b. Α→2; B→4; C→4; D→1
(B) c. Α→1; B→1; C→2; D→4
d. Α→3.; B→2; C→1; D→3

JEE ADVANCE PAPER-II
Time 3 Hours. Max. Marks 240 (80 for Chemistry)

Read The Instructions Carefully
Question Paper Format and Marking Scheme:

1. The question paper has three parts: Physics, Chemistry and Mathematics. Each part has three sections.
2. Section 1 contains 8 questions. The answer to each question is a single digit integer ranging from 0 to 9 (both inclusive).
Marking Scheme: +4 for correct answer and 0 in all other cases.
3. Section 2 contains 8 multiple choice questions with one or more than one correct option.
Marking Scheme: +4 for correct answer, 0 if not attempted and –2 in all other cases..
4. Section 3 contains 2 “paragraph” type questions. Each paragraph describes an experiment, a situation or a problem. Two
multiple choice questions will be asked based on this paragraph. One or more than one option can be correct.
Marking Scheme: +4 for correct answer, 0 if not attempted and – 2 in all other cases.
NOTE: It’s the mock test as per previous year’s papers but sometimes IIT changes the test paper pattern and
marking scheme too.
SECTION 1 (Maximum Marks: 32) CHCl2

II H2O
 →
This section contains EIGHT questions. 100° C
The answer to each question is a SINGLE DIGIT INTEGER

COCl
ranging from 0 to 9, both inclusive. III  H 2
Pd − BaSO
→
For each question, darken the bubble corresponding to the correct 4
integer in the ORS.

Marking scheme: CO 2 Me
IV
+4 If the bubble corresponding to the answer is darkened. DIBAL-H
→
0 In all other cases.
1. In dilute aqueous H 2SO 4 , the complex diaquodioxalato- 4. The crystal of a solid is square packing of identical
spheres in each layer and spheres of one layer are placed
ferrate (II) is oxidized by MnO −4 . For this reaction, the
just above the voids made by spheres in previous layer.
ratio of the rate of change of [H + ] to the rate of change of The packing efficiency of such crystal (in %) is
[MnO −4 ] is [π = 3.15, 2 = 1.4]
2. The number of hydroxyl group(s) in Q is
+
H 
H

heat
→P 
0°C
→Q
HO
H 3C CH3 5. Among the complex ions, [Co(NH 2 - CH 2 - CH 2 -NH2)2
3. Among the following, the number of reaction(s) that Cl 2 ]+ , [CrCl 2 (C 2 O 4 ) 2 ]3– , [Fe(H 2 O) 4 (OH) 2 ]+ , [Fe(NH3)2]
produce(s) benzaldehyde is
(CN) 4 ]− , [Co(NH 2 − CH 2 − CH 2 − NH 2 ) 2 (NH 3 )Cl]2 + and
[Co(NH 3 ) 4 (H 2 O)Cl]2 + , the number of complex ion(s) that
I CO, HCl
→
show(s) cis-trans isomerism is
Mock Test-1 343

6. Three moles of B2 H 6 are completely reacted with H
|
methanol. The number of moles of boron containing O
O
product formed is H 3C CH3
CH3 O
7. The molar conductivity of a solution of a weak acid HX O H
a. b.
(0.01 M) is 10 times smaller than the molar conductivity
of a solution of a weak acid HY (0.10 M). If λX0 − ≈ λY0 − , H
|
the difference in their pK a values, pK a (HX) pK a (HY), O
O CH2
is (consider degree of ionisation of both acids to be << 1)
CH2 O H
8. A closed vessel with rigid walls contains 1 mol of 238
U c. d. H
92
and 1 mol of air at 298 K. Considering complete decay of

238 206
92 U to 82 Pb, the ratio of the final pressure to the initial 12. In the following reactions, the major product W is
OH
pressure of the system at 298 K is NH2 NaOH
 
NaNO 2 , HCl
0° C
→ V 
→W
SECTION 2 (Maximum Marks: 32)
This section contains EIGHT questions.
Each question has FOUR options (a), (b), (c) and (d). ONE OR
MORE THAN ONE of these four option(s) is (are) correct. a.
For each question, darken the bubble(s) corresponding to all the N= N OH
correct option(s) in the ORS.
Marking scheme:
+4 If only the bubble(s) corresponding to all the correct option(s)
is(are) darkened. OH
0 If none of the bubbles is darkened b.
–2 In all other cases N=N
9. Which of the following compounds will exhibit
geometrical isomerism?
a. 1-Phenyl-2-butene c.
b. 3-Phenyl-1-butene OH
N=N
c. 2-Phenyl-1-butene
d. 1,1-Diphenyl-2-propane
10. In the following reactions, the product S is
OH
d.
H 3C
 i. O3
ii. Zn ,H2 O
→ R 
NH3
→S
N=N
H 3C H 3C N
N
a. b.
13. The correct statement(s) regarding, (i) HClO, (ii) HClO 2 ,
N (iii) HClO3 and (iv) HClO 4 , is (are)
N
c. d. a. The number of Cl = O bonds in (ii) and (iii) together is
H 3C H 3C two
b. The number of lone pairs of electrons on Cl in (ii) and
11. The major product U in the following reactions is (iii) together is three
+
CH2 = CH − CH3 , H radical initiator, O2 c. The hybridisation of Cl in (iv) is sp3

high pressure, heat
→ T  →U
d. Amongst (i) to (iv), the strongest acid is (i)

14. The pair(s) of ions where BOTH the ions are precipitated undergoes transition to a state S2 . The state S2 has one radial
upon passing H 2S gas in presence of dilute HCl, is(are) node and its energy is equal to the ground state energy of the
2+ 2+ 3+ 3+ hydrogen atom.
a. Ba , Zn b. Bi , Fe
2+ 2+
c. Cu , Pb d. Hg 2+ , Bi 3+ 17. Energy of the state S1 in units of the hydrogen atom
15. Under hydrolytic conditions, the compounds used for ground state energy is :
preparation of linear polymer and for chain termination, a. 0.75 b. 1.50
respectively, are c. 2.25 d. 4.50
18. The orbital angular momentum quantum number of the
a. CH 3SiCl3 and Si(CH 3 ) 4
state S2 is :
b. (CH 3 ) 2 SiCl2 and (CH 3 )3 SiCl
a. 0 b. 1
c. (CH 3 ) 2 SiCl2 and (CH 3 )3 SiCl3 c. 2 d. 3
d. SiCl 4 and (CH 3 )3 SiCl
Paragraph for Question No. 19 to 20
16. When O 2 is adsorbed on a metallic surface, electron In the following reactions
transfer occurs from the metal to O 2 . The TRUE Pd − BaSO4
C8H 6  → C8H8 → i. B2 H 2
X
H2 ii. H 2O2 . NaOH, H 2O
statement(s) regarding this adsorption is(are)
H2O
a. O 2 is physisorbed HgSO 4 , H 2SO 4
b. heat is released
C8 H8 O 
i. EtMgBr, H 2 O
ii. H + , heat
→Y
c. occupancy of π 2p
*
of O 2 is increased
19. Compound X is
d. bond length of O 2 is increased O OH
SECTION 3 (Maximum Marks: 16) CH3 CH3

a. b.
This section contains TWO questions.
Based on each paragraph, there will be TWO questions OH
Each question has FOUR options (A), (B), (C) and (D). ONE OR CHO
c. d.
MORE THAN ONE of these four option(s) is(are) correct.
For each question, darken the bubble(s) corresponding to all the
correct option(s) in the ORS. 20. The major compound Y is
Marking scheme:
+4 If only the bubble(s) corresponding to all the correct option(s) a. CH3 b. CH3
is(are) darkened.
0 If none of the bubbles is darkened CH3
–2 In all other cases CH2
CH3
CH3
The hydrogen-like species Li 2+ is in a spherically symmetric c. d.
state S1 with one radial node. Upon absorbing light the ion

Mock Test-1 345

+2 −
ANSWER and SOLUTIONS 8. (b) Cu + 2e 
→ Cu (s)
JEE-Main 2 mol 1 mol = 63.5
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 9. (d) t = 40 min
a a c a d b b b d a
2.303 a
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. k= log
t a−x
c d a b d d b c a a
2.303 a
21. 22. 23. 24. 25. 26. 27. 28. 29. 30. k= log
b d d c b a a a c b
40 a − 0.875 a
2.303 a
1. (a) = log
40 0.125 a
2. (a) For BCC unit 6 cell, 3 a = 4r 2.303
= log 8 = 0.051 min
3 3 40
r= a= × 4.29 Å = 1.85 Å
4 4 0.693 0.693
t1/ 2 = = = 13.58 min
k 0.051
3. (c) Energy in 1st excited state = −3.4 eV
10. (a) Amount of acetic acid adsorbed
Z × Mw
4. (a) ρ = 3 eff −30 [For fcc, Zeff = 4 unit cell] (0.06 − 0.042) × 50 ×10−3 × 60
a × 10 × N A = = 16 ×10−3 = 18 mg
3
ρ × a 3 × 10−30 × N A
∴ Mw = 11. (c) Ionic Radii order: N3− > O 2− > F−
Zeff
(10.0 g cm –3 × (200 pm)3 × 10−30 cm 3 × 6 × 1023 atoms) 12. (d)
=
4 13. (a) It can act as an oxidising as well as reducing agent.
−1
Thus, 12gmol contains = N A atoms = 6 × 10 atoms 23
14. (b) BaSO 4 is least soluble, BeSO 4 is most soluble.
6 × 10 23 15. (d) The interhalogen compounds are generally more reactive
∴ 100 g contains = × 100 = 5 × 10 24 atoms
12 than halogens (except F2).
5. (d) ∆GRx n = 2∆GNO2 − 2∆G NO 16. (d) Xe has the highest boiling point.
∆G NO2 = ∆G NO + 12 ∆G Rx 17. (b) No. of Geometrical isomers of

[Pt(Cl)(py)(NH 3 )(NH 2 OH)]+ = 3
= ∆G NO + 12 (− RT ln e K p )
18. (c)
= 0.5[2 × 86600 − R (298) ℓn (1.6 × 1012 )]
80 141 mg
P0 − P n1 19. (a) % of Bromine = × ×100 = 24%
6. (b) = Xsolute = 188 250 mg
P 0
n1 + n 2
20. (a) Only amines undergo acetylation and not acid amides.
185 − 183 2 1.2 / M
= = O
185 185 1.2 + 100
NH C CH 3
M 58
NH 2
⇒ M = 64 O O
C C + CH 3 COOH
7. (b) ∆G = −RT ln e K c H3C O OH
C NH 2
2494.2 = 8.314 × 300 ln e K c ⇒ K c = e −1 C NH 2 O
1 21. (b)
K c = e−1 = = 0.36
2.718 CH3 CH3
(B)(C) 2 × 12
Q= = =4 O
[A]2 [1/ 2]2 O3
Zn / H 2 O
→ CHO
Q > K c , i.e. backward reaction. CH3 CH3
5-keto-2-methyl hexanal

Total no. of stereoisomers of M = 2
22. (d) R − I + AgF 
→ R − F + AgI (Swarts Reaction)
H 3C CH 3
23. (d) CH 3 COOH
→
KMnO 2

SOCl2
→
H 3C O
Toluene Benzoic acid
COCl CHO 3. (9)

HO

H 2 / Pd
BaSO4
→ 
NaOH
→N
Benzoyl chloride Benzaldehyde
O–
24. (c)
+
NH3 N Cl − CN N is
O– O O

→
NaNO2 / HCl
0− 5° C
→
CuCN / KCN
∆
+ N2
1 2 3
CH3 CH3 CH3 O O –
O
25. (b) Glyptal is used in the manufacture of paints and
lacquers. 4 5 6
26. (a) Vitamin ‘B’ and ‘C’ are water soluble. O O O–
27. (a) Zn 2 [Fe(CN)6 ] is bluish white ppt.

7 8 9
28. (a) A→1; B→3, 4; C→2; D→3
ɺɺ :
O
(A) Inversion of cane sugar is pseudo first order reaction. +
(B) Hydrolysis of ester in the presence of acid is first order 4. ɺɺ == N
(8) :O ɺɺ ɺɺ
ɺɺ == O
N ɺɺ == N
:O ɺɺ –– N
ɺɺ
O ɺɺ
while in the presence of base is second order reaction. :O:−
ɺɺ ɺɺ
(C) Photochemical reactions are of zero order. Total no. of lone pairs = 8
(D) SN2 reactions are of second order.
5. (4) [Fe(SCN) 6 ]3 − and [Fe(CN) 6 ]3 −
29. (c) Enthalpy is zero but entropy is not zero. Vibrational
In both the cases the electronic configuration of Fe3+ will
motion exists even at absolute zero.
be 1s 2 , 2s 2 , 2p 6 , 3s 2 , 3p 6 , 3d 5 .
30. (b) Molecularity of a reaction can be defined only for an
elementary reaction because complex reaction does not Since SCN is a weak field ligand and CN is a strong field
take place in one single step and it is almost impossible ligand, the pairing will occur only in case of [Fe(CN) 6 ]3 − .
for all the total molecules of the reactants to be in a state
of encounter simultaneously. (high spin)
Case-1 3d 5
(no pairing)
JEE Advance Paper -I
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. (low spin)
Case-2 (pairing)
1 2 9 8 4 4 3 4 a,b,d b,d
11. 12. 13. 14. 15. 16. 17. 18. 19. 20.
a d b,d c a,b,c a,b,c a,b b a a Case – 1 µ = n (n + 2) = 5(5 + 2) = 35 = 5.91 BM
Case – 2 µ = n (n + 2) = 1(1 + 2) = 3 = 1.73 BM
1. (1) ∆T f = iK f m
Difference in spin only magnetic moment
0.0558 = i × 1.86 × 0.01 ⇒ i = 3
= 5.91 − 1.73 = 4.18 ≈ 4
∴ Complex is [Co(NH 3 )5 Cl]Cl2 .
6. (4) BeCl 2 , N 3− , N 2 O, NO +2 , O 3 ,SCl 2 , ICl −2 , I3− , XeF2
2. (2) Bridging does not allow the other 2 variants to exist.
Mock Test-1 347

BeC 2 
→ sp 
→ linear (2) H 3 C == CH — C — CH 2 — CH 3 
→ H3 C — CH — C — CH
H 2 /Pt
−
N 
→ sp 
3 → linear H Br
H 3 C == CH — C — CH 2 — CH3 
→ H3 C — CH — C — CH 2 — CH3
N 2 O 
→ sp 
→ linear
⊕
H Br
NO 2 
→ sp 
→ linear Optically inactive
O 3 
→ sp 2 
→ linear
(3) H 2 C == C — C — CH 3  → H 3 C — C — C — CH3
H 2 /Pt
SCl 2 
→ sp 3 
→ linear
H2C H Br H
I 3− 
→ sp 3 d 
→ linear
H 2 C C — C — CH 3 H 3 C — C — C — CH3
ICl −2 
→ sp 3 d 
→ linear
H2C H Br
XeF2 
→ sp 3d 
→ linear Optically inactive
So, among the following only four (4) has linear shape and no
d-orbital is involved in hybridization.
(4) H2C == CH —C — CH2 —CH3  → H3C — CH2 — C— CH2 —CH
H2 /Pt
7. (3) Single electron species don’t follow the (n + ℓ) rule but H 
H2C == CH —C — CH2 —CH Br → H C — CH — C—CH —CH
3 3 2 2 3
multi electron species do. H Br

Ground state of H− = 1s2 Optically inactive
First excited state of H − = 1s1 , 2s1 O

11. (a) ɺɺ Θ
:OH
Second excited state of H − = 1s1 , 2s 0 , 2p1 →
CH 2
CH3
O O
Px Py Pz HO
→
2
(3 degenerate orbitals) Θ
CH CH
3
8. (4) X 
→ Y ∆ r G = −193KJ / mol
0
O
→ M 3 + + 2e − E = −0.25V
M + 
0
CH3 CH3
OH
∆G for the this reaction is
0
O O
H+ ,H2O/∆
∆G = − nFE = −2 × ( −0.25) × 96500 = 48250 J / mol
0 0 ← 
48.25 KJ/mol
So the number of moles of M + oxidized using CH 3 3
12. (d) | H + + Br Θ
|
X  → Y will be H 2 C == C — CH == CH 2  → H 3 C — C — CH == CH 2 
→
193
= = 4 moles
48.25
3 CH 3
− − | |
9. (a, b, d) 6I + ClO + 6H2SO4 
3 → H C == C — CH == CH 2 
→ H 3 C — C — CH == CH 2 
→
Cl − + 6HSO 4− + 3I 2 + 3H 2 O
H3C Θ Θ H3C
C == CH — CH2  →
Br :
10. (b, d) C == CH — CH2 — Br
H3C H3C
CH 3
(1) H 3C — CH == CH — C 
→ H3C — CH 2 — CH13.
2—C (b, d) (a) H 3 BO 3 is a weak monobasic Lewis acid.
H Br CH 3 H3 BO3 + H − OH ↽ ⇀ B(OH) −4 + H + . . .(i)
H 3C — CH == CH — C 
→ H3C — CH 2 — CH 2 — C
H2 /Pt
(b) Equilibrium (i) is shifted in forward direction by the
H Br addition of syn-diols like ethylene glycol which forms a
Optically active stable complex with B(OH) −4 .

forward reaction would be greater than at lower temperature
H O that is why the percentage yield of NH3 too would be more
O H O H
H O initially.
B 19. (a) Α→1; B→3; C→4; D→2
O H
O
H O O
H O
O H
(A) H5C6CH2 O CH3
– i
O i
O C6 H5 − CH2 + CO2 + CH2O
B + 4H 2 O O CH3
O O CH3
O
(B) H 5 C6 CH 2 O
(stable complex) CH 2 C6 H 5
(c) It has a planar sheet like structure due to hydrogen
i
bonding. O
i |
(d) H3BO3 is a weak electrolyte in water. C6 H 5 — C H 2 + CO 2 + Ph — CH 2 — C — CH 3
|
14. (c) OH ɺɺ
:OH
| |
CH3
H3C C == O H3C C == O
CH —CH2 —CH  
NaNO2 / HCl
→ CH —CH2 —HC i
H3C H3C
⊕

→ Ph — C H 2 + CH3 — CO — CH3
NH2 N N
O CH3
H3C H3C
⊕
O
H O CH3
CH —CH2 —CH —COOH ← 
H3C
H2O
H3C
CH —CH2 —HC C == O (C) C6 H 5 O
OH C6 H 5
i
15. (a, b, c) OH O
i |
I C6 H 5 — CO 2 + CH3 + C — CH 3
→ I2 |
Rxn(i)
CH3
CMe 3
OH OH i i

→ Ph + CH3 — CO — Ph + CH 3
Br

Br2
→ O
Rxn(ii)
O
CMe 3 CMe 3
O CH3
Br (D) C6 H 5
i
OH C6 H 5 − CO 2 + CH3Oi 
→ C6 H 5i + CO2
Cl Cl
→
Cl 2 20. (a) Α→2; B→3; C→1; D→4
Rxn(iii)
CMe 3
Cl
(A) 
→ d-d σ bonding
16. (a, b, c) Since container is thermally insulated so, q = 0,
and it is a case of free expansion therefore W = 0 and
∆E = 0. So, T1 = T2 . Also, P1 V1 = P2 V2 .
(B) 
→ p-d π bonding
+3 − +2
17. (a, b) 2Fe + H 2 O 2 + 2OH 
→ 2Fe + 2H2 O + O2
Na 2 O 2 + H 2 O 
→ H 2 O 2 + NaOH
(C) 
→ p-d π antibonding
18. (b) N 2 (g) + 2H 2 (g)
N 2 (g) + 2H 2 (g) ↽ ⇀ 2NH 3 (g); ∆H < 0
Increasing the temperature lowers equilibrium yield of (D) 
→ d-d σ antibonding
ammonia. However, at higher temperature the initial rate of
Mock Test-1 349

JEE Advance Paper-II 1
Z = 1 [ th is shared in first layer and
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 8
8 4 4 75 5 6 3 9 a a 1
is shared in second layer
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 2
1
b a b,c c,d b b,c,d a b c d ∴ Z = × 4 + 0.5 = 1
8
1. (8) [Fe(C 2 O 4 )(H 2 O)]2 − + MnO 24 − + 8H + 
→ (2r 2 ) = h2 + x 2 fi h = 2r
Mn 2 + + Fe 3 + + 4CO 2 + 6H 2 O Area = 4r 2 [∵ a 2 = (2r )2 fi a = 2r ]
So, the ratio of rate of change of
+
Vol = 4r 2 × 2r = 4 2r 3
[H ] to that of rate of change of [MnO 4 ] is 8.
4
1× π r 3
2. (4) 3 π
D= 3
= = 0.75 = 75%
4 2r 3 2
+ 5. (5) [Co(en) 2 Cl2 ]+ 
H 
H
∆
→
+ [CrCl 2 (C 2 O 4 ) 2 ]3− 
HO
[Fe(H 2 O) 4 (OH) 2 ]+ 

→
[Fe(CN) 4 (NH 3 ) 2 ]− 
[Co(en) 2 (NH 3 )Cl]2 + 
(P)
aqueous dilute KMnO 4 [Co(NH 3 ) 4 (H 2 O)Cl]2 + 
→ will not show cis-trans
(excess) 0°C
isomerism (although it will show geometrical isomerism)
OH
6. (6) B 2 H 6 + 6MeOH 
→ 2B(OMe)3 + 6H 2
1 mole of B2 H 6 reacts with 6 moles of MeOH to give 2
HO OH moles of B(OMe)3
HO (Q)
3 moles of B2 H 6 will react with 18 moles of MeOH to
give 6 moles of B(OMe)3 .
3. (4)
[H + ] [X − ]
CHO 7. (3) HX ↽ ⇀ H + + X − Ka =
I CO, HCl
→ [HX]
[H + ] [Y − ]
HY ↽ ⇀ H + + Y − Ka =
CHCl2 CHO [HY]
II  
→ H2O
100 ° C Λ m for HX = Λ m1 Λ m for HY = Λ m 2
COCl CHO 1
III Λ m1 = Λm Ka = Cα 2
 H2
Pd − BaSO 4
→ 10 2
2
 Λm 
IV CO 2 Me CHO Ka1 = C1 ×  0 1 
BIBAL − H

→  Λm1 
2
 Λm 
Ka 2 = C2 ×  0 2 
4. (75)  Λ m2 
2r
2
h Ka1 C1  Λm1 
= × 
Ka 2 C2  Λm 2 
x
2
0.01  1 
= × = 0.001
0.1  10 
pKa1 − pKa 2 = 3

8. (9) In conversion of 238
92 U to 206
82 Pb, 8α - 12. (a) NH 2
+ –
N2 Cl
particles and 6β particles are ejected. −Napthol/NaOH
N →
aNO3,HCl
0°C
β  →
The number of gaseous moles initially = 1 mol
The number of gaseous moles finally = 1 + 8 mol; (1 mol (V)
from air and 8 mol of 2 He 4 ) So the ratio = 9 /1 = 9 N = N − Ph
OH
9. (a) Ph − CH 2 CH3 Ph − CH H
C == C 2
C == C
H H H CH3
cis trans
(W)
10. (a)
O 13. (b, c) H — O — Cl
||
H 3C H 3C C—H .. ..
. . == O
(I) H — O — Cl (II) H — O — Cl == O
 (i) O3
(ii) Zn.H2 O
→ ||
CH 2 — C — H
R || O
O
O
||
O (III) H — O — Cl == O (IV)
|| ||
H 3C C—H O
ɺɺ
→ NH 3
+ 14. (c, d) Cu 2 + , Pb 2 + , Hg 2 + , Bi 3+ give ppt. with H 2S in presence
CH 2 — CH — NH3
|| of dilute HCl.
O−
CH3 CH3
| |
15. (b) Cl — Si — Cl 
H O
→ HO — Si — OH 
→
O−
2
OH
+
| |
H 3C NH
H 3C NH2 CH3 CH3
OH CH CH3 CH3
CH 2 OH | |
−2H 2 O H — O — Si — O — Si ——O — H
| |
CH3 CH3 n
H 3C
N
Me3SiCl, H 2O
(S) CH 3 CH3
Me | | Me
O
|| Me Si — O — Si — O — Si ——O — Si Me
H 3C C—H Me | | Me
CH 3 CH3 n
..
CH 2 — CH — NH 2
|| 16. (b, c, d) * Adsorption of O 2 on metal surface is
OH
exothermic.
11. (b) + * During electron transfer from metal to O 2 electron
+ H3C — CH — CH3 
→ →
occupies π 2p
*
orbital of O2 .
CH 3
| * Due to electron transfer to O 2 the bond order of O 2
C — CH 3 decreases hence bond length increases.

→ 
O2
→ |
O
O For Question Nos. 17 to 18
U
CH H E1H × 32 9
H 3C CH3 17. (c) E S1 = = = 2.25 × E1H .
22 4
T
Mock Test-1 351

18. (b) S2 is 3p ∴ l = 1 O
||
For Question Nos. 19 to 20 C — CH3 CH2 − CH2 − OH
C 8 H 6 
→ = double bond equivalent
6 (i) EtMgBr (X)
= 8 +1− =6 (ii) H 2 O
2
C ≡ CH CH = CH 2 OH CH3
| +
|
Ph — C — CH 3 
H / heat
→ Ph — C == CH — CH 3
| (Y)
(1) B2 H8
Et
HgSO 4 , H 2SO 4 , H 2O (2) H 2O 2 , NaOH, H 2O
19. (c)
20. (d)

1. 2 g of oxygen contain same number of atoms as contained a. More cis-2-pentene is formed
by b. Equilibrium is shifted in the forward direction
a. 0.5 g hydrogen b. 4.0 g sulphur c. Equilibrium remains unaffected
c. 7.0 g nitrogen d. 2.3 g sodium d. Additional trans-2-pentene is formed
2. The axial angles in triclinic crystal system are 10. The dissociation constant of CH 3 COOH is 1.8 ×10−5.
a. α = β = γ = 90° b. α = γ = 90°, β ≠ 90°
The hydrolysis constant for 0.1 M sodium acetate is
c. α ≠ β ≠ γ ≠ 90° d. α = β = γ ≠ 90°
a. 5.56 × 10 4 b. 5.56 ×10−10
3. A sample of drinking water was found to be severely c. 1.8 × 10−5 d. 1.8 × 109
contaminated with chloroform CHCl3 , supposed to be a
11. The half-life of a first order reaction having rate constant
carcinogen. The level of contamination was 15 ppm (by
mass). Determine the molality of chloroform in the water K = 1.7 ×10−5 s−1 is
sample. a. 12.1 h b. 9.7 h
a. 2.12 × 10 −4 mol kg −1 b. 1.26 × 10 −4 mol kg −1 c. 11.3 h d. 1.8 h
c. 0.12 × 10 −4 mol kg −1 d. 5.36 × 10 −4 mol kg −1 12. Which characteristic is true in respect of colloidal particle
a. They always have two phases
4. The temperature at which hydrogen molecules will have b. They are only in liquid state
the same root mean square velocity as oxygen molecules c. They can't be electrolysed
have at 27°C is d. They are only hydrophilic
a. 25°C b. 7.93°C
13. The heat of transition (∆H t ) of graphite into diamond
c. −248°C d. 127°C
would be, where
5. An electron makes a transition from orbit n = 4 to the C(graphite) + O 2 (g) 
→ CO 2 (g); ∆H = x kJ
orbit n = 2 of a hydrogen atom. The wave number of the
emitted radiations (R = Rydberg's constant) will be C(diamond) + C 2 (g) 
→ CO 2 (g) ; ∆H = y kJ
16 2R 3R 4R a. (x + y) kJ mol −1 b. (x − y) kJ mol−1
a. b. c. d.
3R 16 16 16 c. (y − x) kJ mol−1 d. None of these
6. Select the compound in which chlorine is assigned the 14. All the nuclei from the initial element to the final element
oxidation number +5 constitute a series which is called
a. HClO 4 b. HClO 2 a. g-series b. b-series
c. HClO3 d. HCl c. b-g series d. Disintegration series
7. The molar conductivity is maximum for the solution of 15. The following compound will undergo electrophilic
concentration substitution more readily than benzene
a. 0.001 M b. 0.005 M a. Nitrobenzene b. Benzoic acid
c. 0.002 M d. 0.004 M c. Benzaldehyde d. Phenol
8. The number and type of bonds between two carbon atoms 16. Cis and trans 2-butene are
in calcium carbide are a. Conformational isomers
a. One sigma, one pi b. One sigma, two pi b. Optical isomers
c.Two sigma, one pi d. Two singma, two pi c. Position isomers
d. Geometrical isomers
9. The standard state gibbs free energy change for the given
17. Electrolysis of a concentrated solution of sodium fumarate
isomerization reaction cis-2-pentene ↽ ⇀ trans-2-pentene gives
is –3.67 kJ / mol at 400K. If more trans-2-pentene is added a. Ethylene b. Ethane
to the reaction vessel, then c. Acetylene d. Vinyl alcohol
Mock Test-2 353

18. Identify X and Y in the following sequence 24. The correct statement in respect of protein haemoglobin is
C 2 H 5 Br 
X
→ product 
Y
→ C3 H 7 NH 2 that it
a. Acts as an oxygen carrier in the blood
a. X = KCN, Y = LiAlH 4
b. Forms antibodies and offers resistance to diseases
b. X = KCN, Y = H 3O + c. Functions as a catalyst for biological reactions
c. X = CH 3Cl,Y = AlCl3 / HCl d. Maintains blood sugar level
d. X = CH 3 NH 2 , Y = HNO 2 25. Which one of the following is known as broad spectrum
antibiotics
19. Consider the following alcohols
a. Streptomycine b. Ampicillin
(i) 1-Phenyl-1-propanol c. Chloramphenicol d. Penicillin G
(ii) 3-Phenyl-1-propanol
26. The element or elements whose position is anomalous in
(iii) 1-Phenyl-2-propanol
the periodic table is
The correct sequence of increasing order of reactivity of
a. Halogens b. Fe, Co and Ni
these alcohol in their reaction with HBr is
a. (i), (ii), (iii) b. (ii), (i), (iii) c. Inert gases d. Hydrogen
c. (i), (iii), (ii) d. (ii), (iii), (i) 27. Flux added in the extraction of iron is
20. Reaction between diethyl cadmium and acetyl chloride a. Silica b. Felspar
leads to the formation of c. Limestone d. Flint
a. dimethyl ketone b. ethylmethyl ketone 28. The correct order of the increasing ionic character is
c. diethyl ketone d. acetaldehyde a. BeCl 2 < MgCl 2 < CaCl 2 < BaCl 2
21. Which of the following is basic? b. BeCl 2 < MgCl 2 < BaCl 2 < CaCl 2
a. CH 3CH 2 OH b. H 2 O2 c. BeCl 2 < BaCl 2 < MgCl 2 < CaCl 2
c. HOCH 2 CH 2 OH d. CH 3COOH d. BaCl 2 < CaCl 2 < MgCl 2 < BeCl 2
29. Nesseler's reagent is

22. CH3CN 
Na, C2 H5OH
→ X. The compound X is:
a. K 2 HgI 4 b. K 2 HgI 4 + KOH
a. CH 3CH 2 NO 2 b. CH 3CH 2COOH
c. K 2 HgI 2 + KOH d. K 2 HgI 4 + Hg
c. C6 H 5 N(CH 3 )2 d. C6 H 5CONH 2
30. The primary valence of the metal ion in the co-ordination
23. Which of the following is a synthetic polymer
compound K 2  Ni ( CN )4  is
a. Rubber b. Perspex
c. Protein d. Cellulose a. Four b. Zero c. Two d. Six


JEE ADVANCE PAPER-I
SECTION 1 Contains 8 Questions SECTION 2 Contains 10 Multiple Choice Questions
The answer to each question is a single digit integer ranging from 0 to With one or more than one correct option
9 (both inclusive). 9. Sodium metal crystallises in a body centred cubic lattice
1. At 400 K, the root mean square (rms) speed of a gas X with a unit cell edge of 4.29 Å. The radius of sodium atom
(molecular weight = 40) is equal to the most probable speed is approximately
a. 1.86 Å b. 3.22 Å c. 5.72 Å d. 0.93 Å
of gas Y at 60 K. The molecular weight of the gas Y is
10. 18 g glucose (C6 H I2 P6 ) is added to 178.2 g water. The vapor
2. Based on VSEPR theory, the number of 90 degree
pressure of water (in torr) for this aqueous solution is :
F−Br−F angles in BrF5 is
a. 7.6 b. 76.0 c. 752.4 d. 759.0
3. 20% surface sites have adsorbed N2 . On heating N 2 gas 11. For one mole of a van der Waals gas when b = 0 and T =
evolved from sites and were collected at 0.001 atm and 300 K, the PV vs. 1/V plot is shown below. The value of
298 K in a container of volume is 2.46 cm3. Density of the van der Waals constant a (atm. liter2 mol2) is.
surface sites is 6.023 ×1014 / cm2 and surface area is 1000
PV (liter-atm mol–1)
24.6 (Graph not to scale)
cm2, find out the no. of surface sites occupied per 23.1
21.6
molecule of N2 . 20.1
4. The total number of contributing structure showing
1
hyperconjugation (involving C–H bonds) for the 0 2.0 3.0
following carbocation is 1
(mol liter −1 )
V
H 3C ⊕ CH 2 CH 3
a. 1.0 b. 4.5 c. 1.5 d. 3.0
12. A piston filled with 0.04 mol of an ideal gas expands

reversibly from 50.0 mL to 375 mL at a constant
temperature of 37.0°C. As it does so, it absorbs 208 J of
5. The volume (in mL) of 0.1 M AgNO3 required for heat. The values of q and w for the process will be
complete precipitation of chloride ions present in 30 mL (R = 8.314 J / mol K) (ln 7.5 = 2.01)
of 0.01 M solution of [Cr(H 2 O)5 Cl]Cl 2 , as silver chloride a. q = +208 J, w = −208 J b. q = −208 J, w = −208 J
is close to c. q = −208 J, w = +208 J d. q = +208 J, w = +208 J
6. Among PbS, CuS, HgS, MnS, Ag 2S, NiS, CoS, Bi 2S3 and 13. The first ionisation potential of Na is 5.1 eV. The value of
electron gain enthalpy of Na + will be
SnS2 , the total number of black coloured sulphides is
a. –2.55 eV b. −5.1 eV
7. 29.2% (w/w) HCl stock solution has a density of 1.25 g c. −10.2 eV d. +2.55 eV
−1 −1
mL . The molecular weight of HCl is 36.5 g mol . The
14. In a galvanic cell, the salt bridge
volume (mL) of stock solution required to prepare a 200 a. does not participate chemically in the cell reaction.
mL solution of 0.4 M HCl is b. stops the diffusion of ions from one electrode to another.
8. The maximum number of isomers (including c. is necessary for the occurrence of the cell reaction
d. ensures mixing of the two electrolytic solutions
stereoisomers) that are possible on monochlorination of
the following compound is 15. Stability of the species of Li 2 , Li 2− and Li+2 increase in
CH 3 the order of
C a. Li 2 < Li +2 < Li −2 b. Li −2 < Li +2 < Li 2
CH 3 CH 2
H
CH 2 CH3 c. Li 2 < Li −2 < Li +2 d. Li −2 < Li 2 < Li +2
Mock Test-2 355

16. How many litres of water must be added to 1 litre of an (C) CO 2 (P = 1 atm, T = 273K) 3. P = nRT
aqueous solution of HCl with a pH of 1 to create an
(D) Real gas with very large 4. P(V − nb) = nRT
aqueous solution with pH of 2?
molar volume
a. 0.1 L b. 0.9 L c. 2.0 L d. 9.0 L
a. A → 2; B → 3; C → 2; D → 1, 4
17. NiCl2 {P(C2 H 5 ) 2 (C6 H 5 )}2 exhibits temperature dependent
b. A → 1, 3; B → 1; C → 2; D → 4
magnetic behavior (paramagnetic / diamagnetic). The c. A → 3; B → 4; C → 3, 4; D → 1, 2
coordination geometries of Ni2+ in the paramagnetic and
d. A → 1, 2; B → 3; C → 1, 2; D → 1, 4
diamagnetic states are respectively.
a. tetrahedral and tetrahedral 20. The standard reduction potential data at 25ºC is given
b. square planar and square planar below:
c. tetrahedral and square planar E °(Fe 3 + , Fe 2 + ) = + 0.77 V; E °(Fe 2 + , Fe) = − 0.44V
d. square planar and tetrahedral
E °(Cu 2 + , Cu) = + 0.34V; E °(Cu + , Cu) = + 0.52V
18. Four successive members of the first row transition elements
E°[O 2 (g) + 4H + + 4e − 
→ 2H 2 O] = + 1.23V;
are listed below with atomic numbers. Which one of them is
expected to have the highest E 0M3+ / M2+ value? E°[O 2 (g) + 2H 2 O + 4e − 
→ 4OH − ] = + 0.40V
a. Cr(Z = 24) b. Mn(Z = 25) E °(Cr 3 + , Cr) = − 0.74V; E °(Cr 2 + , Cr) = − 0.91 V
c. Fe(Z = 26) d. Co(Z = 27) Match E° of the redox pair in Column I with the values
given in Column II.
SECTION 3 Contains 2 Match The Following Type Questions Column I Column II
3+
You will have to match entries in Column I with the entries in (A) E °(Fe , Fe) 1. – 0.18 V
Column II.
(B) E °(4H 2 O ↽ ⇀ 4+ + 4OH − ) 2. – 0.4 V
19. Match gases under specified conditions listed in Column-I
with their properties/laws in Column-II. (C) E °(Cu 2 + + Cu 
→ 2Cu + ) 3. – 0.04 V
Column I Column II (D) E °(Cr 3 + , Cr 2 + ) 4. – 0.83 V
(A) Hydrogen gas (P = 200 atm, 1. Compressibility
a. A → 2; B → 3; C → 1; D → 4
T = 273K) factor ≠ 1
b. A → 1; B → 2; C → 3; D → 4
(B) Hydrogen gas (P ∼ 0, 2. Attractive forces
c. A → 3; B → 4 ; C → 1; D → 2
(P 0, T = 273K) are dominant
d. A → 2; B → 3; C → 1; D → 4

SECTION 1 Contains 8 Questions.
10. Mixture(s) showing positive deviation from Raoult’s law
The answer to each question is a single digit integer ranging from 0 to at 35ºC is(are)
9 (both inclusive). a. carbon, tetrahedral + methanol
1. The maximum number of electrons that can have principal b. carbon disulphide + acetone
quantum number, n = 3, and spin quantum number, c. benzene + toluene
1 d. phenol + aniline
ms = − , is
2 11. For a gaseous state, if most probable speed is denoted by
2. The dissociation constant of a substituted benzoic acid at C*, average speed by C and mean square speed by C,
25ºC is 1.0 × 10–4. The pH of a 0.01M solution of its then for a large number of molecules the ratio of these
sodium salt is speeds are
3. The total number of cyclic structural as well as stereo a. C* : C : C = 1.225 :1.128 :1
isomers possible for a compound with the molecular b. C* : C : C = 1.128 :1.1225 :1
formula C 5 H10 is c. C* : C : C = 1:1.228 :1.225
d. C* : C : C = 1:1.225 :1.128
4. To an evacuated vessel with movable piston under
external pressure of 1 atm, 0.1 mol of He and 1.0 mol. of 12. The species having bond order different from that in CO is
an unknown compound (vapour pressure 0.68 atm. At a. NO– b. NO+ c. CN– d. N2
0ºC) are introduced. Considering the ideal gas behaviour, 13. Which of the following is the wrong statement?
the total volume (in litre) of the gases at 0ºC is close to a. ONCF and ONO − are not isoelectronic
5. The coordination number of Al in the crystalline state of b. O3 molecules is bent
AlCl3 is c. Ozone is violet–black in solid state
6. Among the following, the number of compounds than can d. Ozone is diamagnetic gas
react with PCl5 to give POCl3 is 14. The qualitative sketches I, II and III given below show the
variation of surface tension with molar concentration of
O 2 , CO 2 , SO 2 , H 2 O, H 2SO 4 , P4 O10
three different aqueous solutions of KCl, CH 3 OH and
7. If the freezing point of a 0.01 molal aqueous solution of a
CH 3 (CH 2 )11 OSO 3− Na + at room temperature. The correct
cobalt (III) chloride-ammonia complex (which behaves as
assignment of the sketches is
a strong electrolyte) is –0.0558ºC, the number of
[Kf of water = 1.86 K kg mol–1]
Surface tension
Surface tension
II III
Surface tension
I
8. A student performs a titration with different burettes and
finds titre values of 25.2 mL, 25.25 mL and 25.0 mL. The
number of significant figures in the average titer value is
SECTION 2 Contains 8 Multiple Choice Questions Concentration Concentration Concentration

With one or more than one correct option
9. The correct statement(s) regarding defects in solids is(are) a. I : KCl II : CH 3 OH III : CH 3 (CH 2 )11 OSO 3− Na +
a. Frenkel defect is usually favoured by a very small b. I : CH 3 (CH 2 )11 OSO 3− Na + II : CH 3 OH III : KCl
difference in the sizes of cation and anion c. I : KCl II : CH 3 (CH 2 )11 OSO 3− Na + III : CH 3 OH
b. Frenkel defect is a dislocation defect
d. I : CH 3 OH II : KCl III: CH 3 (CH 2 )11 OSO 3− Na +
c. Trapping of an electron in the lattice leads to the
formation of F-centre 15. Using the data provided, calculate the multiple bond
d. Schottky defects have no effect on the physical energy (kJ mol–1) of C≡C bond in C2H2. That energy is
properties of solids (take the bond energy of a C—H bond as 350 kJ mol–1)
Mock Test-2 357

−1 −9
→ C 2 H 2 (g); ∆ H = 225 kJ mol
3
2C(s) (g) 
+ H 2 2(g)
2C(s)H 18. The solubility product (K sp ; mol dm ) of MX2 at 298 K
2C(s) 
→ 2C(g) based on the information available for the given
∆H = 1410 kJ mol −1 concentration cell is (take 2.303 × R × 298 / F = 0.059 V)
H 2 (g) 
→ 2H(g) a. 1×10−15 b. 4 × 10−15
∆ H = 330 kJ mol −1
c. 1× 10−12 d. 4 × 10−12
a. 1165 b. 837
c. 865 d. 815
Chemical reactions involve interaction of atoms and molecules.
16. A solution of (–)-1-chloro-1-phenylethane in toluene A large number of atoms/molecules (approximately
racemises slowly in the presence of a small amount of
6.023 × 10 23 ) are present in a few grams of any chemical
SbCl5 , due to the formation of
compound varying with their atomic/molecular masses. To
a. carbanion b. carbene
handle such large numbers conveniently, the mole concept was
c. carbocation d. free radical
introduced. This concept has implications in diverse areas such
SECTION 3 Contains 2 Paragraph Type Questions as analytical chemistry, biochemistry, electrochemistry and
Each paragraph describes an experiment, a situation or a problem. radiochemistry. The following example illustrates a typical
Two multiple choice questions will be asked based on this paragraph. case, involving chemical/electrochemical reaction, which
One or more than one option can be correct. requires a clear understanding of the mole concept.
Paragraph for Question No. 17 to 18 A 4.0 molar aqueous solution of NaCl is prepared and 500mL
of this solution is electrolysed. This leads to the evolution of
The electrochemical cell shown below is a concentration cell.
chlorine gas at one of the electrodes (atomic mass:
M|M 2 + (saturated solution of sparingly soluble salt, Na = 23, Hg = 200, 1 Faraday = 96500 coulombs)
2+ −3
MX 2 ) || M (0.001 mol dm ) | M.
M The emf of the cell depends
19. The total number of moles of chlorine gas evolved is
on the difference in concentration of M 2 + ions at the two a. 0.5 b. 1.0
electrodes. The emf of the cell at 298 K is 0.059 V. c. 2.0 d. 3.0
17. The value of ∆ G (kJ mol −1 ) for the given cell is
20. If the cathode is a Hg electrode, the maximum weight (g)
(take 1 F = 96500 C mol −1 ) of amalgam formed from this solution is
a. –5.7 b. 5.7 a. 200 b. 225
c. 11.4 d. –11.4 c. 400 d. 446


ANSWER and SOLUTIONS T 400
⇒ =
JEE-Main 2 32
400 × 2
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. ∴ T= = 25 K or T = 25 − 273 = −248°C
b c b c c c a b a b 32
11. 12. 13. 14. 15. 16. 17. 18. 19. 20.
1 1 1  1 1  3R
c a b d d d c a d b 5. (c) Wave number =R 2 − 2  =R −  =
λ  n1 n 2   4 16  16
21. 22. 23. 24. 25. 26. 27. 28. 29. 30.
a a b a c d c a b c ∗
6. (c) HClO3
⇒ 1 + x − 2 × 3 = 0 ; x = 6 − 1 = +5
2 × 6 × 1023
1. (b) Number of atoms in 2 g of oxygen = 1
16 7. (a) Since molar conductance ∝
Molarity
(1) 6 ×10 × 0.5 = 3×10
23 23
8. (b) 1σ and 2π
6 ×1023 × 4
(2) = 7.5 ×1022
32 9. (a) Equilibrium shifts backward by Le-chatelier’s
principle.
6 ×1023 × 7
(3) = 1.5 ×1023
28 K w 1× 10−14
10. (b) K b = = = 5.56 × 10−10
6 ×10 × 2.3
23 K a 1.8 × 10−5
(4) = 6 ×1022
23
11. (c) K = 1.7 ×10−5 s−1
∴ The correct answer is (b).
0.693 0.693
t1/ 2 = = × 105 = 11.32h
2. (c) The axial angles in triclinic crystal system are different K 1.7
and none is perpendicular to any of the others i.e.,
12. (a) Dispersion medium and dispersed phase are phases of
α ≠ β ≠ γ ≠ 90°.
colloid.
3. (b) Level of contamination = 15 ppm
13. (b) Graphite → diamond ∆H t = ( x − y ) kJ mol −1 .
= 15 parts in 106 parts Mass % of CHCl3
14. (d) Definition of disintegration series.
15 15. (d) Phenol will undergo electrophilic substitution more
= 6 ×100 = 1.5 ×10−3
10 readily than benzene.
Thus, the water sample contains 16. (d) Cis and trans 2-butene are geometrical isomers.
1.5 × 10−3% (by mass) of CHCl3 CHCOONa CH
17. (c) || + 2H 2 O 
Electrolysis
→ |||
15g CHCOONa CH
Amount of CHCl3 = = 0.126mol
119.5g mol−1 Acetylene
Mass of water (solvent) = 10 6 g = 10 3 kg + 2CO 2 + 2KOH + H 2
So, molality of CHCl3 in solution 18. (a) C2 H5 Br 

KCN(X)
→ C2 H5CN 
LiAlH4 (Y)
→
0.126 mol C2 H5CH 2 NH 2 (C3H 7 NH 2 )
= = 1.26 × 10 −4 mol kg −1 X = KCN,Y = LiAlH 4
103 kg
19. (d) HBr reacts with alcohols through the formation of
3RT carbocation. The stable is the carbocation formed, more is
4. (c) r.m.s. (H 2 ) = the reactivity of alcohol with HBr. The carbocation
2
formed are
3R × 400 CH+CH 2CH3
r.m.s. (O 2 ) =
32 CH2CH2CH+2
( T = 273 + 127 = 400 K) CH2 − CH+ − CH3
3 RT 3R × 300
=
2 32 (1) (2) (3)
Mock Test-2 359

CH 2CH 3 2. (0)
20. (b) Cd + 2CH3COCl 
→ 2CH3COCH2CH3 + CaCl2
CH 2CH 3
H3COCl 
→ 2CH3COCH2CH3 + CaCl2 Br
F F
21. (a) Ethanol is the weakest acid among these, hence it is F F

most basic. F
All four planar bonds (F−Br−F) will reduce from 90° to
22. (a) CH3CN + 4H 
Na, C2H5OH
→ CH3CH 2 NH 2 (X)
84.8° after ℓp − bp repulsion.
23. (b) Perspex is a synthesised polymer. So among the following only four (4) has linear shape and
2+ no d-orbital is involved in hybridization.
24. (a) Four Fe ions of each haemoglobin can bind with 4
molecules of O 2 and it is carried as oxyhaemoglobin. 3. (2) PN2 = 0.001 atm, T = 298 K, V = 2.46 cm2
Hb 4 + 4O 2 
→ Hb 4 O8 By ideal gas, PV = nRT
PV 0.001× 2.46 ×10−3
25. (c) Chloramphenicol is broad spectrum antibiotic used in n N2 = = = 1.0 × 10−7
RT 0.0821× 298
the treatment of typhoid, dysentry, acute fever.
Now molecules of
26. (d) It shows similarities with both alkali metals as well as
N 2 = 6.023 × 1023 × 1× 10−7 = 6.023 × 1016
halogens.
Now total surface sites available
27. (c) Impurities of SiO 2 is present in iron ore so basic flux
= 6.023 ×1014 ×1000 = 6.023 ×1017
CaCO3 is added. ∴ Surface site used to adsorb
CaO + SiO2 
→ CaSiO3 N2 =
20
× 6.023 × 1017 = 12.04 × 1016
Flux Impurity Slag 100
∴ Sites occupied per molecule of
28. (a) BeCl 2 < MgCl 2 < CaCl 2 < BaCl2
12.04 × 1016
As we go down the group I.E. decreases. Hence ionic N2 = =2
character increases. 6.02 ×1016
29. (b) 2KI + HgI 2 

→ K 2 Hgl4 + KOH 4. (6) 6 × H − atoms are there
(6) Number of ionisable Cl− in [Cr(H 2 O)5 Cl]Cl 2 is 2

Nessler's reagent
5.
30. (c) Primary valencies are also known as oxidation state.
∴ Millimoles of
K 2 [ Ni (CN)4 ], 2 + x − 4 = 0 ⇒ x = +2
Cl− = 30 × 0.01× 2 = 0.6
∴ Millimoles of Ag + required = 0.6
JEE Advance Paper -I
∴ 0.6 = 0.1 V
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
⇒ V = 6 ml
4 0 2 6 6 6 8 8 a c
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 6. (6) Black coloured sulphides
c a b a b d c d d c {PbS, CuS, HgS, Ag 2S, NiS, CoS}
1. (4) Vrms ( Xgas )( 400K ) = Vmp ( Ygas)(60 K ) * Bi2S3 in its crystalline form is dark brown but Bi 2S3
M.W.(X gas) = 40; M.W.(Ygas) = x precipitate obtained is black in colour.
3RT1 2RT1 7. (8) Molarity

=
M1 M2
n W W × d sol W 100 × d so ln
= = = = × ×1000
400 × 3 2 × 60 V M w × v M w × Wsol Wsol M w × 100
=
40 x W
% × d ×10
120 =W
⇒ 30 = , x=4
x Mw

29.2 × 1.25 × 10 1
= = 10 M M1V1 = M 2 V2 PV = −a ×   + RT
36.5 V
⇒ 10 × V1 = 0.4 × 200 y = mx + C fi Slope = – a
0.4 × 200 y2 − y1 20.1 − 21.6
⇒ V= = 8ml Slope = = 1.5
10 x 2 − x1 3−2
Cl 12. (a) q = + 208 J, (as it absorb heat)
Br CH 3 v 
8 (8) w Re w = −2.303 nRT log10  2 
Br Cl  v1 
CH 3  375 
= −2.303 × (0.04 × 8.314 × (310) log10   = −208 J
CH 3  50 
13. (b) E.A = Ionisation potential
CH 3 CH 2 C*− CHCH 3 Two Enantiomeric pairs = 4
* ∴ EA of Na + = −5.1eV
H
14. (a)
CH 3
15. (b) B.O. of Li +2 = 0.5 , B.O. of Li −2 = 0.5
CH 3 CH 2 C − CH 2 CH 3 1
Hence stability order = Li −2 < Li +2 < Li 2
H
0.1
CH 2 Cl 16. (d) 0.1× 1 = (1 + v) × 0.01 ⇒ 1 + v =
0.01
CH 3 CH 2 C*− CH 2 CH 3 1 ⇒ 1 + v = 10 ⇒ v = 10 − 1 = 9L
H 17. (c) [NiCl2 P(C 2 H 5 ) 2 (C6 H 5 ) 2 ]+2

Total = 2 + 4 + 1 + 1 = 8 Ni +2 (28) : [Ar]4s°3d 8
9. (a) For BCC 6 unit cell, 3a = 4r
In strong ligand 3d8
3 3
r= a= × 4.29 Å = 1.85 Å
4 4
18
10. (c) Moles of glucose = = 0.1
180 In weak ligand 3d8
178.2
Moles of water = = 9.9
18 Hybridisation is dsp2 (diamagnetic)
⇒ n Total = 10
Square planar
∆P 0.1
⇒ =
P° 10
Hybridisation is sp3 (paramagnetic)
⇒ ∆P = 0.01P°
= 0.01× 760 = 7.6 torr tetrahedral
PS = 760 − 7.6 = 752.4 torr 18. (d) Factual
11. (c) b = 0, T = 300 K, n = 1
19. (d) A → 1, 2 ; B → 3 ; C → 1, 2 ; D → 1, 4
 an 2 
P + 2  (V − nb) = RT (A) Z =
PVm
at high pressure and low temperature.
 V  RT
 a   an 2 
 P + 2  (V) = RT Equation  P + 2  (V − nb) = nRT reduces to
 V   V 
a P(V − nb) = nRT.
⇒ PV + = RT
V
Mock Test-2 361

(B) For hydrogen gas value of Z = 1 at P = 0 and it increases 3. (7) Cyclic C5 H10
continuously on increasing pressure.
(C) CO2 molecules have larger attractive forces, under normal
conditions.
PVm For 3rd structure 2 cis-trans and 1 optical isomer are
(D) Z = , at very large molar volume Z ≠ 1.
RT possible. Total 7 isomers.
20. (c) A → 3; B → 4 ; C → 1 ; D → 2 4. (7) Let unknown is X.

p He = p total − Px = (1 − 0.68) atm = 0.32 atm
(A) ∆G oFe3+ / Fe = ∆G oFe3+ / Fe2+ + ∆G oFe2+ / Fe
RT
⇒ −3 × FE o(Fe+3 / Fe) = − 1× FE o(Fe+3 / Fe+2 ) + (−2 × FEoFe+2 / Fe ) Now p He = n He
V
⇒ E oFe+3 / Fe = − 0.04 V RT 0.10 × 0.082 × 273
∴ v= = =7
p He 0.32
(B) O 2 (g) + 2H 2 O + 4e − 
→ 4OH E ° = 0.40 V . . .(i)
→ O 2 (g) + 4H + + 4e − E ° = − 1.23 V . . .(ii)
2H 2 O  5. (6) Coordination number of Al is 6. It exists in ccp lattice
with 6 coordinate layer structure.
So 4H 2 O ↽ ⇀ 4H + + 4OH . . .(iii)
rd
6. (5)
E° For III reduction = 0.40 − 1.23 = − 0.83 V.
7. (1) ∆Tf = iK f m
(C) ∆G o(Cu+2 / Cu) = −1× FE oCu+2 / Cu+ + (−1× F × EoCu+ / Cu )
0.0558 = i × 1.86 × 0.01
−2 × FE oCu +2 / Cu = − 1× FE oCu +2 / Cu + + (−1× F × E oCu + / Cu ) i=3
⇒ E o
= − 0.18 V. ∴ Complex is [Co(NH3 )5 Cl]Cl2
Cu +2 / Cu
(D) ∆G oCr +3 / Cr +2 = ∆G oCr +3 / Cr + ∆G oCr / Cr +2 8. (3)
−1× F × E Cr
o
= −3 × F × E oCr +3 / Cr + (−2 × F × E oCr / Cr +2 ) 9. (b, c)
+3
/ Cr +2
10. (a, b)
⇒ E oCr+3 / Cr +2 = − 0.4 V.
(a) CCl 4 + CH 3 OH ⇒ Positive deviation from Raoult’s
law
JEE Advance Paper -II O
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
9 8 7 7 6 5 1 3 b, c a, b C
11. 12. 13. 14. 15. 16. 17. 18. 19. 20.
(b) CS2 + CH 3 CH 3
c a a d d c d b b d
⇒ Positive deviation from Raoult’s law
1. (9) Number of orbital for n = 3 is = n = 9 2
(c) C 6 H 6 + C 7 H 8 ⇒ Ideal solution
1
Number of electrons for n = 3 and ms = − =9 OH NH 2
2
2. × 10–4
(8) K a (C6 H 5COOH) =11 10
(d) +
pH of 0.01M C6 H5COONa
C6 H5COO− + H 2 ↽ ⇀ C6 H5COOH + OH −1 ⇒ Negative deviation from Raoult’s law.
0.01(1− h) 0.01h 0.01h
2RT 8RT 3RT

K w 0.01h 2 11. (c) C*: C : C = = =
Kh = = M πM M
Ka 1− h
8
10−14 10−2 h 2 2: = 3
= − (1–h ≃ 1) 3.14
10−4 1− h
1 : 1.128 : 1.225
[OH − ] = 0.01h = 0.01× 10−4 = 10−6
12. (a) N O − (16 electron system)
[H + ] = 10 −8 pH = 8
Bond order =2.

+ − 16. (c) Racemises slowly due to formation of intermediate
NO , CN and N2 are isoelectronic with CO therefore all
have same bond order (=3). carbocation.
13. (a) ONCF and ONO– are isoelectronic in nature. For Question Nos. 17 to 18
17. (d) ∆G = −nFE cell
14. (d) Impurities affect surface tension appreciably. It is
= −2 × 96500 × 0.059
observed that impurities which tend to concentrate on
surface of liquids, compared to its bulk lower the surface = −11.387 kJ mol −1
tension. = −11.4 kJ
Substances like detergents, soaps [CH 3 (CH 2 )11 SO 3− Na + ] −0.0591 C
18. (b) E = log10 −3
decreases the surface tension sharply. 2 10
Those like alcohol (e.g., –CH 3 OH, C 2 H 5 OH) lower the −0.0591  C 
0.059 = log10  −3 
surface tension slightly. This can also be related to the fact 2  10 
that CH 3 OH has smaller dielectric constant. Dielectric C
10 −2 = C = [M 2 + ] = 10 −5 M.
constant is directly proportional to surface tension. So, on 10 −3
adding CH 3 OH in water, overall dielectric constant K sp = [M +2 ] [X − ]2 = 4s3 = 4(40-−55))33 == 44 ¥
= 4(10 ×10−-15
decreases and surface tension decreases.
Inorganic impurities present in bulk of a liquid such as
→ Na + + Cl−
19. (b) NaCl 
KCl tend to increase the surface tension of water.
At anode: 2Cl − 
→ Cl 2
15. (d) 2C(s) + H 2 (g) 
→ C 2 H 2 (g) (H − C ≡ C − H)
Moles of Cl − = 2 in 500 ml.
⇒ B⋅E(H2) + ∆B⋅E(H2) + ∆Hsub (C) – B⋅E (C – H) × 2 +
Therefore 1 mole of Cl2 evolves.
B⋅E(C ≡ C ) ∆Hrxn
⇒ 330 + 1410 − [350 × 2 + x] = 225 ⇒ x= 815 20. (d) Na—Hg (amalgam) formed = 2 moles at cathode.
Mock Test-3 363

1. The volume of 1.0 g of hydrogen in litres at N.T.P. is 10. Ammonium cyanide is salt of NH4OH(Kb = 1.8 × 10–5)
a. 2.24 b. 22.4 c. 1.12 d. 11.2 and HCN (Kb = 4.0 × 10–10). The hydrolysis constant of
2. Which set of characteristics of ZnS crystal is correct? 0.1 M NH 4 CN at 25ºC is
a. Coordination number (4: 4) : ccp; Zn2+ ion in the alternate a. 1.4 b. 7.2 × 10 −15
tetrahedral voids
b. Coordination number (6: 6); hcp; Zn2+ ion in all tetrahedral c. 7.2 ×10 −1 d. 1.4 ×10−6
voids
11. For the reaction A + B → C it is found that doubling the
c. Coordination number (6: 4) : hcp; Zn2+ ion in all octahedral
concentration of A increases the rate by 4 times, and
voids
doubling the concentration of B doubles the reaction rate.
d. Coordination number (4: 4); ccp; Zn2+ ion in all tetrahedral
voids What is the overall order of the reaction?
a. 4 b. 3/2
3. PtCl4.6H2O can exist as a hydrated complex. 1 molal
c. 3 d. 1
aqueous solution has depression in freezing point of 3.72º
Assume 100% ionisation and K f (H 2 O) = 1.86° mol−1 kg, 12. The coagulation power of an electrolyte for arsenious
then complex is sulphide decreases in the order
a. [Pt(H 2O)6 ]Cl4 b. [Pt(H 2O)4 Cl2 ]Cl 2 2H 2 O a. Na + , Al+3 , Ba +2 b. PO4-3 , SO4-2 , Cl -
c. [Pt(H 2O)3 Cl3 ],Cl.3H 2O d. [Pt(H 2 O 4 )Cl 4 ]4H 2 O c. Al+3 , Ba +2 , Na + d. None of these
4. A weather balloon filled with hydrogen gas at 1 atm and 13. Correct relationship between heat of fusion (∆H fus ), heat
27ºC has volume equal to 12000 litres. On ascending, it
of vaporisation ( ∆H vap ) and heat of sublimation (∆Hsub ) is
reaches a place where temperature is –23ºC and pressure
0.5 atm. The volume of the balloon is a. ∆H fus = ∆H vap + ∆H sub
a. 24000 L b. 12000 L
b. ∆H vap = ∆H fus + ∆H sub
c. 10000 L d. 20000 L
c. ∆H sub = ∆H vap + ∆H fus
5. In Bohr model of the hydrogen atom, the lowest orbit
corresponds to d. ∆H sub = ∆H vap − ∆H fus
a. Infinite energy b. The maximum energy
14. The number of neutrons in the parent nucleus which gives
c. The minimum energy d. Zero energy
N14 on β- emission is
6. When KMnO 4 is reduced with oxalic acid in acidic
a. 7 b. 14 c. 6 d. 8
solution, the oxidation number of M n changes from
a. 7 to 4 b. 6 to 4 15. Which represents nucleophilic aromatic substitution
c. 7 to 2 d. 4 to 2 reaction?
7. The unit of molar conductivity is a. Reaction of benzene with Cl 2 in sunlight
a. Ω–1cm–2 mol–1 b. Ω cm–2 mol–1 b. Benzyl bromide hydrolysis
c. Ω–1cm2 mol–1 d. Ω cm2 mol–1 c. Reaction of NaOH with dinitrofluorobenzene
8. In a double bond connecting two atoms, there is a sharing of d. Sulphonation of benzene
a. 2 electrons b. 1 electron
16. Which one of the following is the chiral molecule?
c. 4 electrons d. All electrons
a. CH 3 Cl b. CH 2 Cl 2
9. In a reversible reaction, the catalyst
c. CHBr3 d. CHClBrI
a. Increases the activation energy of the backward reaction
b. Increases the activation energy of the forward reaction 17. n-Propyl chloride and benzene react in the presence of
c. Decreases the activation energy of both, forward and anhydrous AlCl3 to form
backward reaction a. ethyl benzene b. methyl benzene
d. Decreases the activation energy of forward reaction
c. n-propyl benzene d. iso-propyl benzene

18. 1-chlorobutane reacts with alcoholic KOH to form 24. The waxes are long chain compounds of fatty acids, which
a. 1-butene b. 2-butane belong to the class of
c. 1-butanol d. 2-butanol a. Esters b. Ethers
19. An alcohol having molecular formula C5H11OH on c. Alcohols d. Acetic acid
dehydration gives an alkene, which on oxidation yield a 25. Which of the following is a local anaesthetic?
mixture of ketone and an acid. The alcohol is a. Diazepam b. Procaine
a. CH3CH2CH(OH)CH 2CH3 b. CH 3CHCH 2 CH 2 CH 3 c. Mescaline d. None of these
|
OH 26. The electronic configuration of the element which is just
c. (CH3 )2 CHCH(OH)CH3 d. (CH3 )2 CCH2OH above the element with atomic number 43 in the same
periodic group is
20. m-chlorobenzaldehyde on reaction with conc. KOH at
a. 1s 2 2s 2 2p 6 3s 2 3p 6 3d 5 4s 2
room temperature gives
a. potassium m-chlorobenzate and m-chlorobenzyl alcohol b. 1s 2 2s 2 2p 6 3s 2 3p 6 3d10 4s 2 4p 5
b. m-hydroxy benzaldehyde and m-chlorobenzyle alcohol c. 1s 2 2s 2 2p 6 3s 2 3p 6 3d 6 4s1
c. m-chlorobenzyl alcohol and m-hydroxy benzyle alcohol
d. 1s 2 2s 2 2p 6 3s 2 3p 6 3d10 4s1 4p 6
d. potassium m-chlorobenzoate and m-hydroxy bezaldehyde
21. Acetamide is treated separately with the following 27. Complex is formed in the extraction of
reagents. Which one of these would give methyl amine? a. Na b. Cu c. Ag d. Fe
a. PCl5 b. NaOH + Br2 28. MgCl 2 .6H 2O when heated gives
c. Sodalime d. Hot conc. H 2SO 4 a. Magnesium oxychloride b. Magnesium dichloride
22. On treating aniline with nitrous acid and HCl at 0–5ºC c. Magnesium oxide d. Magnesium chloride
gives 29. Acidified potassium dichromate on reacting with a
a. An alcohol sulphite is reduced to
b. Diazonium salt a. CrO 2 Cl 2 b. CrO 24 −
c. Nitro aniline
c. Cr 3+ d. Cr 2+
d. Aniline hydrogen chloride
23. ‘Rayon’ is 30. In the extraction of which of the following, complex ion
a. Natural silk b. Artificial silk forms?
c. Natural plastic or rubber d. Synthetic plastic a. Cu b. Ag c. Fe d. Na

Mock Test-3 365

JEE ADVANCE PAPER-I
SECTION 1 Contains 8 Questions occupied by aluminium ions and n fraction of tetrahedral
The answer to each question is a single digit integer ranging from 0 to holes occupied by magnesium ions, m and n, respectively,
9 (both inclusive). are
1. The molar conductivity of a solution of a weak acid HX 1 1 1
a. , b. 1,
(0.01 M) is 10 times smaller than the molar conductivity 2 8 4
of a solution of a weak acid HY (0.10 M). If λ X0 ≈ λ Y0 , − − 1 1 1 1
c. , d. ,
the difference in their pK a values, pK a (HX) pK a (HY), 2 2 4 8
is (consider degree of ionization of both acids to be << 1) 10. A monatomic ideal gas undergoes a process in which the
ratio of P to V at any instant is constant and equals to 1.
2. The total number of α and β particles emitted in the What is the molar heat capacity of the gas?
nuclear reaction 238
92 U → 82
214
Pb is 4R 3R 5R
a. b. c. d. 0
3. The number of hydroxyl group(s) in Q is 2 2 2
+
11. The given graphrepresents the variation of Z
H 
H

heat
→ P 
0° C
→Q PV
(compressibility factor = ) versus P, for three real
HO nRT
H 3C CH3 gases A, B and C. Identify the only incorrect statement.
C
4. The total number of basic groups in the following form of A
A
lysine is Ideal gas
⊕ B
1
H 3 N − CH 2 − CH 2 − CH 2 − CH 2 O C
CH − C Z
B
H2 N O−
0 P (atm)
5. In 1 L saturated solution of AgCl [Ksp(AgCl)=1.6×10–10],
0.1 mol of CuCl [K sp (CuCl) = 1.0 × 10−6 ] is added. The a. For the gas A, a = 0 and its dependence on P is linear at
all pressure
resultant concentration of Ag + in the solution is b. For the gas B, b = 0 and its dependence on P is linear at
1.6 ×10− x. The value of “x” is all pressure
c. For the gas C, which is typical real gas for which
6. EDTA4– is ethylenediaminetetraacetate ion. The total
number of N – Co – O bond angles in [Co(EDTA)1–] neither a nor b = 0. By knowing the minima and the
complex ion is point of intersection, with Z = 1, a and b can be
7. Reaction of Br2 with Na2CO3 in aqueous solution gives calculated
sodium bromide and sodium bromated with evolution of d. At high pressure, the slope is positive for all real gases
CO2 gas. The number of sodium bromide molecules 12. For the reaction: I − + ClO3− + H 2SO4 
→ Cl− + HSO4− + I2
involved in the balanced chemical equation is The correct statement(s) in the balanced equation is/are
8. A decapeptide (Mol. Wt. 796) on complete hydrolysis a. Stoichiometric coefficient of HSO −4 is 6
gives glycine (Mol. Wt.75), alanine and phenylanine. b. Iodide is oxidised
Glycine contributes 47.0% to the total weight of the c. Sulphur is reduced
hydrolysed products. The number of glycine units present d. H2O is one of the products.
in the decapeptide is 13. The rate of a reaction doubles when its temperature
changes from 300 K to 310 K. Activation of such a
SECTION 2 Contains 10 Multiple Choice Questions reaction will be (R = 8.314 JK −1 and log 2 = 0.301)
a. 53.6 kJ mol−1 b. 48.6 kJ mol −1
9. If the unit cell of a mineral has cubic close packed (ccp) array
c. 58.6 kJ mol−1 d. 60.5 kJ mol−1
of oxygen atoms with m fraction of octahedral holes

14. The freezing point (in ºC) of a solution containing 0.1 g of Match the following:
K3[Fe(CN)6](Mol. Wt. 329) in 100 g of water (Kf = 1.86K Column I Column II
kg mol–1) is (A) Vn/Kn = ? 1. 0
a. −2.3 × 10−2 b. −5.7 × 10−2 (B) If radius of nth orbit 2. –1
c. −5.7 × 10−3 d. −1.2 × 10−2 ∝E ,x=?
x
n
15. The carboxyl functional group (—COOH) is present in (C) Angular momentum in 3. –2
a. picric acid b. barbituric acid lowest orbital
c. ascorbic acid d. aspirin 1 4. 1
(D) ∝ Zy , y = ?
16. Which compound would give 5-keto-2-methyl hexanal rn
upon ozonolysis? a. A → 3 ; B → 2 ; C → 1 ; D → 4
CH3 b. A → 1 ; B → 2 ; C → 3 ; D → 4
CH3 c. A → 4 ; B → 2 ; C → 1 ; D → 3
a. b.
CH3 d. A → 3 ; B → 4 ; C → 1 ; D → 2
CH3 20. An aqueous solution of X is added slowly to an aqueous
CH3 solution of Y as shown in Column - I. The variation in
CH3
conductivity of these reactions in Column - II.
c. d. H 3C
. Column I Column II
CH3
(A) (C2 H 5 )3 N + CH 3 COOH 1. Conductivity
X Y
decreases and
17. For the process H 2 O(ℓ) 
→ H 2 O(g) at T=100ºC and 1
then increases
atmosphere pressure, the correct choice is
(B) KI(0.1M)+ AgNO3 (0.01 M) 2. Conductivity
a. ∆Ssystem > 0 and ∆Ssurrounding > 0 X Y
decreases and
b. ∆Ssystem > 0 and ∆Ssurrounding < 0 then does not
c. ∆Ssystem < 0 and ∆Ssurrounding > 0 change much
(C) CH 3 COOH + KOH 3. Conductivity
d. ∆Ssystem < 0 and ∆Ssurrounding < 0 X Y
increases and
18. Which of the following exists as covalent crystals in the then does not
solid state? change much
a. Iodine b. Silicon (D) NaOH + HI 4. Conductivity
X Y
c. Sulphur d. Phosphorus does not
change much
SECTION 3 Contains 2 Match The Following Type Questions
and then
You will have to match entries in Column I with the entries in increases
Column II.
a. A → 1 ; B → 2 ; C → 3 ; D → 4
19. According to Bohr’s theory,
b. A → 2 ; B → 4 ; C → 3 ; D → 1
E n = Total energy K n = Kinetic energy
c. A → 3 ; B → 4 ; C → 2 ; D → 1
Vn = Potential energy rn = Radius of nth orbit
d. A → 3 ; B → 4 ; D → 1 ; D → 2
Mock Test-3 367

SECTION 1 Contains 8 Questions a. The number of the nearest neighbours of an atom
The answer to each question is a single digit integer ranging from 0 to present in the topmost layer is 12
9 (both inclusive). b. The efficiency of atom packing is 74%
1. Amongst the following, the total number of compounds c. The number of octahedral and tetrahedral voids per
whose aqueous solution turns red litmus paper blue is atom are 1 and 2, respectively
KCN K 2SO 4 (NH 4 ) 2 C 2 O 4 d. The unit cell edge length is 2 2 times the radius of the
NaCl Zn(NO3 ) 2 FeCl3 atom
K 2 CO3 NH 4 NO3 LiCN 10. The standard Gibbs energy change at 300 K for the
2. When the following aldohexose exists in its D– reaction 2A ↽ ⇀ B + C is 2494.2 J. At a given time, the
configuration, the total number of stereoisomers in its composition of the reaction mixture is [A] = 12 , [B] = 2 and
pyranose form is
[C] = 12 . The reaction proceeds in the:
CHO
| [ R = 8.314 J / K / mol, e = 2718 ]
CH 2
| a. forward direction because Q > K c
CHOH
| b. reverse direction because Q > K c
CHOH
| c. forward direction because Q < K c
CHOH d. reverse direction because Q < K c
|
CH 2OH 11. A compound MpXq has cubic close packing (ccp)
3. The number of resonance structures for N is arrangement of X. Its unit cell structure is shown below.
The empirical formula of the compound is
4. The concentration of R in the reaction R→P was
measured as a function of time and the following data is
obtained:
[R] (molar) 1.0 0.75 0.40 0.10 M=
X=
t (min). 0.0 0.05 0.12 0.18
The order of the reaction is
5. The oxidation number of Mn in the product of alkaline
oxidative fusion of MnO2 is
a. MX b. MX 2
6. The total number of diprotic acids among the following is
H 3 PO 4 H 2SO 4 H 3 PO 3 H 2CO3 H 2S2 O 7 c. M 2 X d. M 5 X14
H3 BO3 H 3 PO 2 H 2 CrO 4 H 2SO 3 12. Which of the following is the energy of a possible excited
7. The number of neutrons emitted when 235
U undergoes state of hydrogen?
92
142 90
a. +13.6 eV b. − 6.8 eV
controlled nuclear fission to 54 Xe and 38 Sr is
c. − 3.4 eV d. + 6.8 eV
8. In dilute aqueous H 2SO 4 , the complex diaquodioxa-
13. Assuming 2s-2p mixing is not operative, the paramagnetic
latoferrate (II) is oxidised by MnO −4 . For this reaction,
species among the following is
the ratio of the rate of change of [H + ] to the rate of a. Be2 b. B2
change of [MnO −4 ] is c. C2 d. N2+
14. In allene(C3H4), the type(s) of hybridization of the carbon
SECTION 2 Contains 8 Multiple Choice Questions
atoms is (are)
a. sp and sp 3 b. sp and sp 2
9. The correct statement(s) for cubic close packed (cep) three
dimensional structure is (are) c. only sp 2 d. sp 2 and sp3

15. Isomers of hexane, based on their branching, can be L = 24 cm
divided into three distinct classes as shown in the figure
I. and Cotton wool d Initial formation of Cotton wool

Soaked in X The product Soaked in Y
and 17. The value of d in cm (shown in the figure), as estimated

II.
from Graham’s law, is
a. 8 b. 12 c. 16 d. 20
II. 18. The experimental value of d is found to be smaller than
the estimate obtained using Graham’s law. This is due to
The correct order of their boiling point is a. larger mean free path for X as compared to that of Y
a. I > II > III b. III > II > I b. larger mean free path for Y as compared to that of X
c. II > III > I d. III > I > II c. increased collision frequency of Y with the inert gas as
CH3 compared to that of X with the inert gas
d. increased collision frequency of X with the inert gas as
16. H3C  → N (isomeric products)
Cl 2 , h v
compared to that of Y with the inert gas
CH3 Paragraph for Question Nos. 19 to 20

Cl → M(isomeric products)
CC5HH11Cl fractional distillation
When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M
What are N and M ? NaOH in an insulated beaker at constant pressure, a
a. 6, 6 b. 6, 4 temperature increase of 5.7ºC was measured for the beaker and
c. 4, 4 d. 3, 3 its contents (Expt. 1). Because the enthalpy of neutralization of
SECTION 3 Contains 2 Paragraph Type Questions a strong acid with a strong base is a constant (–57.0 kJ mol −1 ),
Each paragraph describes an experiment, a situation or a problem. this experiment could be used to measure the calorimeter
Two multiple choice questions will be asked based on this paragraph. constant. In a second experiment (Expt. 2), 100 mL of 2.0 M
One or more than one option can be correct. acetic acid (K a = 2.0 × 10 −5 ) was mixed with 100 mL of 1.0 M
Paragraph for Question Nos. 17 to 18 NaOH (under identical conditions to Expt. 1) where a
X and Y are two volatile liquids with molar weights of 10g temperature rise of 5.6°C was measured. (Consider heat
mol–1 and 40g mol–1 respectively. Two cotton plugs, one capacity of all solutions as 4.2 J g −1 K −1 and density of all
soaked in X and the other soaked in Y, are simultaneously
solutions as 1.0 g mL−1 )
placed at the ends of a tube of length L = 24 cm, as shown in
the figure. The tube is filled with an inert gas at 1 atmosphere 19. Enthalpy of dissociation (in kJ mol −1 ) of acetic acid
pressure and a temperature of 300 K. Vapours of X and Y react obtained from the Expt. 2 is
to form a product which is first observed at a distance d cm a. 1.0 b. 10.0 c. 24.5 d. 51.4
from the plug soaked in X. Take X and Y to have equal 20. The pH of the solution after Expt. 2 is
molecular diameters and assume ideal behaviour for the inert a. 2.8 b. 4.7 c. 5.0 d. 7.0
gas and the two vapours.
Mock Test-3 369

ANSWER and SOLUTIONS 8. (c) In a double bond connecting two atoms sharing of 4
JEE-Main electrons take place as in H2C = CH2.
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 9. (c) Decreases the activation energy of both forward and

d a c d c c c c c b backward reaction.
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. KW
c c c d b,c d c a c a
10. (b) K h =
Ka × Kb
21. 22. 23. 24. 25. 26. 27. 28. 29. 30.
1 × 10 −4
b d b a b a c c c b = = 1.4
4.0 × 10 −4 × 1.8 ×10 −5
1. (d) 2 g of hydrogen occupy volume = 22.4 L
11. (c) A + B → C On doubling the concentration of A rate of
22.4 ×1
1 g of hydrogen occupies volume = = 11.2 L reaction increases by four times. Rate ∝[A]2. However on
2
doubling the concentration of B, rate of reaction increases
2. (a) ZnS has zinc blende type structure (i.e., ccp structure). two times. Rate ∝[B]
The S2– ions are present at the corners of the cube and at the Thus, overall order of reaction = 2 + 1 = 3
centre of each face. Zinc ions occupy half of the tetrahedral
12. (c) According to Hardy-Schulze rule.
sites. Each zinc ion is surrounded by four sulphide ions
which are disposed towards the corner of regular tetrahedral. 13. (c) Heats of combustion are always exothermic except
Similarly, S2– ions surrounded by four Zn2+ ions. oxidation of N as,
3. (c) (∆Tf )cal = K f × m → N 2 O ; ∆H = + ve
N 2 + 12 O 2 
(∆Tf )cal = 1.86 ×1 = 1.86 → 2NO ; ∆H = + ve

N 2 + O 2 
(∆Tf )obs 3.72 β

14. (d) 6 X14  → 6+1 N14
i= = = 2 = 1 + (n − 1)α .
(∆Tf )cal 1.86
in 6 X14 no. of neutrons 14 – 6 = 8.
Hence,α = 1,∴ n = 2
∴ Two species will be produced from single species which 15. (b, c)
Cl3H22OO
is only possible for [Pt(H 2 O)3 Cl3 ],Cl3H NO F O2 OH
OH − +

→ Na +
4. (d) P1 = 1 atm, V1 = 12000 L,
T1 = 27 + 273 = 300K NO NO
Di nitro phenol
phenol
Di nitro fluoro benzene
Dinitrofluorobenzene Dinitro
P2 = 0.5 atm, V2 = ?
H
T2 = −23 + 273 = 250K |
16. (d) I — C* — Br
P1 V1 P2 V2 |
=
T1 T2 Cl
P1 V1 T2 1 × 12000 × 250 A carbon atom which is attached to four different atoms
or V2 = = = 20, 000 L or groups is called a chiral or asymmetric carbon atom.
P2 T1 0.5 × 300
such a carbon atom is often marked by an asterisk.
5. (c) In hydrogen atom, the lowest orbit (n = 1) corresponds
CH 2 CH 2CH 3
to minimum energy (– 13.6 eV).
+2
COOH +7 17. (c) + CH 3 CH 3 CH 2 Cl 
AlCl3
→
6. (c)5 | + 2KMnO4 + 3H2SO4  → K2SO4 + 2MnSO4 +10CO2 + 8H2O
COOH
18. (a) CH 3CH 2 CH 2CH 2 − Cl + KOH(alc.)  →
K 2SO 4 + 2MnSO 4 + 10CO 2 + 8H 2 O
CH 3CH 2 − CH = CH 2 + KCl + H 2 O
In this reaction oxidation state of Mn change from +7 to +2. 1-butene
1
7. (c) Molar conductivity = CH 3 — CH — CH — CH 3
ρM 19. (c) | | 
Dehydration
→
So, its unit will be Ω–1cm2 mol–1 CH 3 OH
CH 3 — C == CH — CH 3 
→ CH 3 — C == O
Oxidation heat
28. (c) MgCl 2 .6H 2O  → MgO + 5H 2 O + 2HCl
| |
CH 3 CH 3
29. (c) Cr2 O72− + 8H + + 2SO32− 
→ 2Cr +3 + 3SO42− + 4H 2O
+ O == C — CH 3
| 30. (b) Ag 2S + 4NaCN ↽ ⇀ 2Na  Ag ( CN )2  + Na 2S
OH
Sodium dicyno argentate
20. (a)
2Na[Ag(CN) 2 ] + Zn 
→ Na 2 [Zn (CN) 4 ] + 2Ag ↓
Cl Cl Cl Sodium tetracynozincate (ppt)
+ KOH 
→ + JEE Advance Paper-I
CHO COOK CH 2OH 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
Cannizzaro's
reaction 3 8 4 2 7 8 5 6 a a
− 11. 12. 13. 14. 15. 16. 17. 18. 19. 20.
O O
|| | b a, b, d a a d b b b a c
Ph — C — H + HO − 
→ Ph — C — H
| [H + ][X − ]
OH 1. (3) HX ↽ ⇀ H + + X − Ka =
[HX]
I
[H + ][Y − ]
O HY ↽ ⇀ H + + Y − Ka =
|| [HY]
21. (b) CH 3 — C — NH 2 + Br2 + NaOH 
→ CH 3 NH 2
Λ m for HX = Λ m1 Λ m for HY = Λ m2
“Hofmann’s bromamide reaction”
1
22. (d) Λ m1 = Λm Ka = Cα 2
NH2 N 2+ Cl− 10 2
2 2
 Λm   Λm 
+ HONO  
HCl
→ Ka1 = C1 ×  0 1  Ka 2 = C2 ×  0 2 
 Λ m1   Λ m2 
2
NH2 Ka1 C1  Λm1 
= × 
Ka 2 C2  Λm 2 
ææ
Æ O O
2
0.01  1 
= × = 0.001 ⇒ pKa1 − pKa 2 = 3
23. (b) ‘Rayon’ is man-made fibre which consists of purified 0.1  10 
cellulose in the form of long threads. Rayon resembles −6α −2 β
2. (8) 92 U 238  → 80 X 214  → 82 Pb 214
silk in appearance. Hence called as artificial silk.
(6α ,2 β ), total 8 particles.
24. (a) Waxes are esters of higher fatty acids.
25. (b) The anaesthetics produce temporary insensitibility to 3. (4)
the vital function of all type of cells, specially of nervous +
H 
H
∆
→
system and are used during surgical operations. +
These are classified as HO
(a) General anasthetic – produces unconsciousness all over 
→
the body e.g. N 2 O, Cyclopropane, chloroform
(b) Local anasthetic – affect only the part of body e.g.
(P)
Xylocaine, Procain etc.
aqueous dilute KMnO4
(excess) 0°C
25 Mn − 3d 4s .
5 2
26. (a)
OH
27. (c) Hydrometallurgy
Ag 2S + 4NaCN 
→ 2Na[Ag(CN) 2 ] + Na 2S HO OH
2Na[Ag(CN) 2 ] + Zn 
→ Na 2 [Zn(CN) 4 ] + 2Ag HO (Q)
Mock Test-3 371

O 10. (a)
|| −
4. (2) —C — O and — NH 2 are basic groups in lysine. 11. (b)
5. (7) Let the solubility of AgCl is x mol litre−1 12. (a, b, d) ClO3− + 6I− + 6H 2SO4 
→ 3I2 + Cl− + 6HSO−4 + 3H 2O
AgCl ↽ ⇀ Ag + + Cl− and that of CuCl is y mol litre−1 ClO3− + 6I− + 6H2SO4 
→ 3I2 + Cl− + 6HSO−4 + 3H 2O
x x
CuCl ↽ ⇀ Cu + + Cl− Ea  T2 − T1 
y y 13. (a) 0.3010 =  
2.303R  T1T2 
∴ K sp of AgCl = [Ag + ] [Cl −1 ]
Ea  310 − 300 
⇒ 0.3010 =  
1.6 × 10−10 = x(x + y) . . .(i) 2.303 × 8.314 × 10 −3  310 × 300 
Similarly K sp of CuCl = [Cu + ] [Cl− ] E a = 53.6 kJ mol
1.6 × 10−6 = y(x + y) . . .(ii) → 3K + + [Fe(CN)6 ]3− , i = 4
14. (a) K 3 [Fe(CN)6 ] 
On solving (i) and (ii) [Ag + ] = 1.6 × 10−7 m 1000 0.1 1000
∆Tf = K f × i × × = 1.86 × 4 × × = 2.3 × 10
∴ x=7 M W 329 100
6. (8) Total no. of N – Co – O bond angles
m 1000is 8. 0.1 1000
∆T = K × i × × = 1.86 × 4 × × = 2.3 × 10−2 fi Tf′ = −2.3 × 10−2
O M W 329 100
15. (d) O
||
O O — C — CH 3
O
COOH
N O
Co (Aspirin)
N O
16. (b) CH3 CH3
O O
O
O3
Zn / H 2 O
→ CHO
O
CH3 CH3
7. (5) 3Br2 + 3CO32 − 
→ 5Br − + BrO3− + 3CO 2 5-keto-2-methyl hexanal
17. (b) At 100°C and 1 atmosphere pressure

8. (6) Let number of glycine units = n
Mass of decaeptide = 796 H 2 O( ℓ ) ↽ ⇀ H 2 O(g) is at equilibrium. For equilibrium
Mass of H 2 O needed = 162 g, Total mass = 958 g ∆Stotal = 0 and ∆Ssystem + ∆Ssurrounding = 0
47
∴
∆Ssystem > 0 and ∆Ssurrounding < 0
958 × = 75 × n
100
18. (b) Silicon exists as covalent crystal in the solid state.
958 × 47
∴ n= ≈6 19. (a) A → 3; B → 2; C → 1; D → 4
100 × 75
9. (a) In ccp lattice: 20. (c) A → 3; B → 4; C → 2; D → 1
Number of O atoms 
→4 (A) → (C2 H5 )3 NH + CH3 COO−
(C2 H5 )3 + N + CH3 COOH 
X Y
Number of Octahedral voids 

→4 Initially conductivity increases due to ion formation after
that it becomes practically constant because X alone
Number of tetrahedral voids 
→8
cannot form ions. Hence (3) is the correct match.
Number of Al3+ = 4 × m (B) KI(0.1 M)+ A gNO3 (0.01 M) 
→ AgI ↓ + KNO3
Number of Mg 2 + = 8 × n X Y
Number of ions in the solution remains constant until all

Due to charge neutrality 4(−2) + 4m(+3) + 8n(+2) = 0
the AgNO3 precipitated as AgI. Thereafter conductance
1 1 increases due to increase in number of ions. Hence (4) is
∴ m= and n =
2 8 the correct match.

(C) Initially conductance decreases due to the decrease in the 5. (6) 2MnO2 + 4KOH + O2 → 2K 2 MnO4 + 2H 2O O.S. of Mn = +6i
(Potassiummanganate)
number of OH ions thereafter it slowly increases due to
the increase in number of H2 ++ions.
2MnO 4KOH + O2 (2)
Hence → is2K
the2 MnO 4 + 2H 2 O
correct O.S. of Mn = +6in K 2 MnO4
match.
6. (6) H 2SO 4 , H 2 CO3 , H 2S2 O7 , H 2 CrO 4 , H3PO3,
H 3 PO3 , H
H22SO
SO33
(D) Initially it decreases due to decrease in H+ ions and then
increases due to the increase in OH ions. Hence (1) is the 7. (3) 92 U 235 → 54 Xe142 + 38Sr 90 + 30 n1
correct match.
 
2.303 Ê a0 ˆ 2.303  a 
JEE Advance Paper -II 8. (9) K = log Á ˜ , K= log  0 
t Ë a0 - x ¯ t1/8  1 a0 
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 8 
3 8 9 5 6 6 3 9 b,c,d b
11. 12. 13. 14. 15. 16. 17. 18. 19. 20.
9. (b, c, d) (a) For any atom in topmost layer, coordination
b c c b b b c d a b number is not 12 since there is no layer above topmost
layer, (b) Fact, (c) Fact, (D) 2 a = 4R
1. (3) K CN , K 2CO3 ,- LiCN are basic in nature and their
aqueous solution turns red litmus paper blue. So, a = 2 2 R
2. (8) 10. (b) ∆G = − RT ln e K c
CH 2 OH
2494.2 = 8.314 × 300 ln e K c
O OH
H
H HO ⇒ K c = e−1
H
OH H 1
K c = e −1 = = 0.36
2.718
Total No. of stereoisomers = 24 = 16 which contains 8D –
(B)(C) 2 × 12
Configuration and 8 – L Configuration. Q= 2
= =4
[A] [1/ 2]2
3. (9) OH
NaOH
→ N Q > K c , i.e. backward reaction.
1 1
HO 11. (b) X : 8 × + 6 × =4

→NNaOH 8 2
1
N is M= × 4 + 1 = 2; M 2 X 4 = MX 2
4
O–
12. (c) Energy in 1st excited state = −3.4 eV
13. (c) Assuming that no 2s-2p mixing takes place

O– O O
(a) Be 2 → σ 1s 2 , σ *1s 2 , σ 2s 2 , σ * 2s 2 (diamagnetic)
(b) B2 → σ 1s 2 , σ *1s 2 , σ 2s 2 , σ * 2s 2 , σ 2p z2 , ππ 2p
0
1 2 3
x
2p 0
(diamagnetic)
y
O O– O (diamagnetic)
2 π 2p π *2p 1 0
(c) C2 → σ 1s , σ *1s , σ 2s , σ * 2s , σ 2p z , π 2p1x , π *2p0x , σ * 2p z (param
2 2 2 2 0
y y
4 5 6
π 2p1x π *2p 0x
σ 1s 2 , σ *1s 2 , σ 2s 2 , σO* 2s 2 , σ 2p z2 , , σ * 2p 0z (paramagnetic)
–
O C2 O ,
π 2p1y π *2p 0y
7 8 9
(d) N 2 → σ 1s 2 , σ *1s 2 , σ 2s 2 , σ * 2s 2 , σ 2p z2 , π ,π , σ * 2p 0z (diam
π π
, σ *1s 2 , σ 2s 2 , σ * 2s 2 , σ 2p z2 , ππ 22 pp x2 , π *2 p 0x
2
4.(5) From two data, (for Nzero order
σ 1s kinetics)
2
,σ * 2p 0z (diamagnetic)
2 π *2 p 0y
x 0.25 y
KI = = =5
t 0.05 H H
x 0.60 14. (b) C == C == C (allene)
⇒ K II = = =5 H sp 2 sp sp 2 H
t 0.12
Mock Test-3 373

15. (b) III > II > I More the branching in an alkane, lesser Energy evolved due to neutralization of HCl and NaOH
will be the surface area, lesser will be the boiling point. = 0.1× 57 = 5.7 kJ = 5700 Joule
CH3 CH3 Energy used to increase temperature of solution
16. (b)
Cl = 200 × 4.2 × 5.7 = 4788 Joule
* *
H 3C H 3 C
CH3 Energy used to increase temperature of calorimeter
CH3 1,d
1,d = 5700 − 4788 = 912 Joule
CH3 CH3
ms. ∆t = 912
CH3 m.s × 5.7 = 912
H3C Cl H 3C
CH2Cl ms = 160 Joule / °C [Calorimeter constant]
M→d, 1 cannot be separated by fractional distillation. Energy evolved by neutralization of CH 3COOH and
For Question Nos. 17 to 18 NaOH = 200 × 4.2 × 5.6 + 160 × 5.6 = 5600 Joule
rX d 40 So energy used in dissociation of 0.1 mole
17. (c) = = =2
rY 24 − d 10 CH 3COOH = 5700 − 5600 = 100 Joule
d = 48 − 2d Enthalpy of dissociation = 1 kJ / mole
3d = 48 1× 100 1
⇒ d = 16 cm 20. (b) CH3COOH = =
200 2
18. (d) As the collision frequency increases then molecular 1× 100 1
CH 3CONa = =
speed decreases than that expected. 200 2
[salt]
For Question Nos. 19 to 20 pH = pK a + log
[acid]
19. (a) HCl + NaOH 
→ NaCl + H 2 O
1/ 2
n = 100 × 1 = 100 m mole = 0.1 mole pH = 5 − log 2 + log ⇒ pH= 4.7
1/ 2

1. The number of moles of SO 2 Cl 2 in 13.5 g is a. 1.0 ×10−4 b. 1.0 ×10−10
a. 0.1 b. 0.2 c. 1.0 ×1010 d. 1.0 ×1014
c. 0.3 d. 0.4 11. According to Arrhenius theory, the activation energy is
2. Arrangement of sulphide ions in zinc blende is a. The energy it should possess so that it can enter into an
a. simple cubic b. hcp effective collision
c. bcc d. fcc b. The energy which the molecule should possess in order
to undergo reaction
3. A pressure cooker reduces cooking is increased
c. The energy it has to acquire further so that it can enter
a. Heat is more evenly distributed
into a effective collison
b. Boiling point of water inside the cooker is increased
d. The energy gained by the molecules on colliding with
c. The high pressure tenderizes the food another molecule
d. All of the above
12. Which of the following is property of colloid?
4. Two flasks of equal volume contains SO 2 and CO 2 a. Scattering of light b. They show attraction
respectively at 25 °C and 2 atm pressure. Which of the c. Dialysis d. Emulsion
following is equal in them ? 13. Which of the following is an example of endothermic
a. masses of the two gas b. number of molecules reaction?
c. rates of effusion d. molecular structure a. C 2 H 2 + 2H 2 
→ C 2 H 6 ; ∆E = −314.0 kJ
5. The ratio of the kinetic energy to the total energy of an
b. C + O 2 
→ CO 2 ; ∆E = −393.5 kJ
electron in a Bohr orbit is
a. –1 b. 2 c. N 2 + O 2 
→ 2NO; ∆E − 180.5kJ
c. 1 : 2 d. None of these d. 2H 2 + O 2 
→ 2H 2 O; ∆E + 571.8 kJ
6. Oxygen has oxidation states of +2 in the 14. The nuclear binding energy for Ar (39.962384 amu) is:
a. H2O2 b. CO 2 (given mass of proton and neutron are 1.007825 amu and
c. H 2O d. OF2 1.008665 amu respectively)
a. 343.81 MeV b. 0.369096 MeV
7. Given l / a = 0.5 cm −1 , R = 50 ohm, N = 1.0. The equivalent c. 931 MeV d. None of these
conductance of the electrolytic cell is
15. Which is an electrophile?
a. 10 ohm −1 cm −2 gm eq −1 b. 20 ohm −1 cm 2 gm eq −1
a. AlCl3 b. CN − c. NH 3 d. CH 3OH
c. 300 ohm −1 cm 2 gm eq −1 d. 100 ohm −1 cm 2 gm eq −1
16. Cyanide and isocyanide are isomers of type
8. In N 2 molecule, the atoms are bonded by a. Positional b. Functional
a. One σ, Two π b. One σ, One π c. Tautomer d. Structural
c. Two σ, One π d. Three σ bonds 17. Acetone will be formed by the ozonolysis of
a. Butene-1 b. Butene-2
9. For the reaction H 2 (g) + I 2 (g) ↽ ⇀ 2HI(g), the c. Isobutene d. Butyne-2
equilibrium constant changes with 18. Which of the following reactions gives
a. Total pressure
H 2 C = C = C = CH 2 ?
b. Catalyst
Zn /CH3 OH
c. The amounts of H 2 and I 2 taken a. CH 2 Br − CBr = CH 2 
ææææ →Æ
d. Temperature b. HC ≡ C − CH 2 − COOH 

Aq.K 2 CO 3
o
→
40 C
10. A certain weak acid has a dissociation constant of c. CH 2 Br − C ≡ C − CH 2 Br →

Zn
Heat
−4
1.0 ×10 . The equilibrium constant for its reaction with a d. 2CH2 = CH − CH2 I 
→
strong base is.
Mock Test-4 375

19. Which of the following does not form phenol or 25. Which of the following is molecular disease?
phenoxide? a. Allergy b. Cancer
a. C6 H5Cl b. C 6 H 5 COOH c. German measeles d. Sickel-cell-anaemia
c. C6 H5 N 2 Cl d. C 6 H 5SO 3 Na 26. Hydrogen can be put in halogen group because
20. Identify the final product (Z) in the following sequence of a. It has deuterium and tritium as isotopes
reactions: b. It forms hydrides like chlorides
+
Me2 C = O + HCN 
→ X 
H 3O
→ Y 
H 2SO4
→ Z; c. It contains one electron only
Heat
d. It is light
a. (CH 3 ) 2 C(OH)COOH b. CH 2 = C(CH 3 )COOH
27. Which of the following metal is extracted by
c. HOCH 2 CH(CH 3 )COOH d. CH 3CH = CHCOOH
amalgamation process?
21. When propionic acid is treated with aqueous sodium a. Tin b. Silver
bicarbonate, CO 2 is liberated. The C of CO 2 comes from? c. Copper d. Zinc
a. methyl group b. carboxylic acid group 28. Which of the following hydroxide is insoluble in water?
c. methylene group d. bicarbonate group
a. Be(OH)2 b. Mg(OH)2
22. Aniline undergoes condensation to form Schiff base on
c. Ca(OH)2 d. Ba(OH)2
reacting with
a. Acetyl chloride b. Ammonia 29. The product of oxidation of I− ion by MnO−4 in alkaline
c. Acetone d. Benzaldehyde medium is
23. The mass average molecular mass and number average a. I2 b. IO3−
molecular mass of a polymer are respectively 40,000 and
c. IO−4 d. I3−
30,000. The polydispersity index of polymer will be
a. < 1 b. > 1 c. 1 d. 0 30. Potassium ferrocyanide is a
24. Hardening of oils is caused by a. Normal salt b. Mixed salt
a. H 2 b. N 2 c. O 2 d. CO 2 c. Double salt d. Complex salt

JEE ADVANCE PAPER-I

SECTION 1 Contains 8 Questions 6. CH 3 — CH 2 — CH 2 — CH 2 OH
The answer to each question is a single digit integer ranging from 0 to CH 3 — CH 2 — CH — CH3
9 (both inclusive). |
OH
1. HCl gas is passed into water, yielding a solution of enantiomeric ( ± )
−1 OH
density 1.095g mL and containing 30% HCl by weight.
|
Calculate the molarity of the solution. CH3 — C — CH3 ; CH 3 — CH — CH 2 OH
| |
2. A sample contains a mixture of NaHCO 3 and Na 2 CO 3 . CH3 CH 3
HCl is added to 15.0 g of the sample, yielding 11.0 g of Total number of isomers (including stereoisomers) is
NaCl. What percent of the sample is Na 2 CO 3 ? 7. Total number of isomers
Reactions are: CH3 CH 2 CH 3 CH3 CH3
 Na 2 CO3 + 2HCl 
→ 2NaCl + CO 2 + H 2 O 
 
 NaHCO 3 + HCl → NaCl + CO 2 + H 2 O 
Mw of NaCl = 58.5, Mw of NaHCO3 = 84, Mw of CH3 CH3 H CH3 Mirror CH3 H
Na 2 CO3 = 106g mol−1
H H CH3 H H CH3
3. Amongst the following, the total number of compounds
meso Pair of enantiomers
soluble in aqueous NaOH is
H 3C CH3 8. In the scheme given below, the total number of

N COOH NO 2 OH
intramolecular aldol condensation products formed from
‘Y’ is
1. O3
2. Zn, H2O
→ Y 
1. NaOH(aq)
2. heat

→
N
H 3C CH3
OCH 2 CH3 OH
CH 2OH
9. For a dilute solution containing 2.5 g of a non-volatile
CH 2 CH 3 COOH non-electrolyte solute in 100 g of water, the elevation in
CH 2 CH 3 boiling point at 1 atm pressure is Assuming concentration
of solute is 2°C. Assuming concentration of solute is
much lower than the concentration of solvent, the vapour
pressure (mm of Hg) of the solution is (take
4. The total number of contributing structures showing K b = 0.76 K kg mol −1 )
hyperconjugation (involving C—H bonds) for the
a. 724 b. 740
following carbocation is.
c. 736 d. 718
5. The total number(s) of stable conformers with non-zero 10. Two closed bulbs of equal volume (V) containing an ideal
dipole moment for the following compound is (are) gas initially at pressure pi and temperature T1 are
connected through a narrow tube of negligible volume as
shown in the figure below. The temperature of one of the
Cl
bulbs is then I raised to T2. The final pressure pf is:
Br CH3
T1 T1 T1 T2
Br Cl Pi , V Pi , V ⇒ Pf ,V Pf ,V
CH3
Mock Test-4 377

 TT   T1  17. The number of structural isomers for C6H14 is
a. p i  1 2  b. 2pi  
 T1 + T2   T1 + T2  a. 3 b. 4
c. 5 d. 6
 T2   TT 
c. 2pi   d. 2pi  1 2 
18. Amongst the given options, the compound(s) in which all
 T1 + T2   T1 + T2 
the atoms are in one plane in all the possible
11. A stream of electrons from a heated filament was passed
conformations (if any), is (are)
between two charged plates kept at a potential difference
H H
V esu. If e and m are charge and mass of an electron, C−C H
a. b. H − C ≡ C — C
respectively, then the value of h/λ (where λ is wavelength H2C CH 2 CH 2
associated with electron wave) is given by:
c. H 2 C = C = O d. H 2 C = C = CH 2
a. meV b. 2 meV
c. meV d. 2 meV
SECTION 3 Contains 2 Matches The Following Type Questions
12. Reduction of the metal centre in aqueous permanganate You will have to match entries in Column I with the entries in
ion involves Column II.
a. 3 electrons in neutral medium
19. According to Bohr’s theory,
b. 5 electrons in neutral medium
c. 3 electrons in alkaline medium E n = Total energy K n = Kinetic energy
d. 5 electrons in acidic medium Vn = Potential energy rn = Radius of nth orbit
13. For the following electrochemical cell at 298 K, Match the following:
+ 4+ 2+
Pt(s) | H 2 (g, 1 bar) H (aq, 1 M) || M (aq), M (aq) | Pt(s) Column I Column II
2+
[M (aq)] (A) Vn / K n = ? 1. 0
E cell = 0.092 V when = 10 x.
[M 4 + (aq)] (B) If radius on nth orbit 2. –1
RT ∝ E nx , x = ?
Given: E 0M4+ / M2+ = 0.151 V; 2.303 = 0.059 V
F (C) Angular momentum in 3. –2
The value of x is
lowest orbital
a. –2 b. –1
1 4. 1
c. 1 d. 2 (D) ∝ Zy , y = ?
rn
14. Which one of the following molecules is expected
a. A → 3; B → 2; C → 4; D → 1
diamagnetic behaviour?
b. A → 1; B → 2; C → 3; D → 4
a. C2 b. N2
c. O2 d. S2 c. A → 3; B → 1; C → 2; D → 4
d. A → 3; B → 2; C →1; D → 4
15. Aqueous solutions of HNO3, KOH, CH3COOH and
CH3COONa of identical concentrations are provided. The 20. Match the thermodynamic processes given under Column
pair (s) of solutions which form a buffer upon mixing is I with the expression given under Column II:
(are) Column I Column II
a. HNO3 and CH 3COOH (A) Freezing of water at 1. q = 0
b. KOH and CH 3COONa 273 K and 1 atm
c. HNO3 and CH 3COONa (B) Expansion of 1 mol of 2. w = 0
d. CH 3COOH and CH 3COONa an ideal gas into a
vacuum under
16. The value of log10K for a reaction A ↽ ⇀ B is
isolated conditions
−1 −1 −1
(Given ∆ r H o
298K = −54.07 kJ mol , ∆ S o
r 298K = 10 JK mol (C) Mixing of equal 3. ∆Ssys < 0
−1 −1
and R = 8.314 JK mol ; 2.303 × 8.314 × 298 = 5705 ) volumes of two ideal
a. 5 b. 10 c. 95 d. 100 gases at constant

temperature and cooling to 300 K at 1
pressure in an isolated atm
container 5. ∆G = 0
(D) Reversible heating of 4. ∆U = 0 a. A → 3,5; B → 1,2,4 ; C → 1,2,4; D → 1,2,4,5
H 2 (g) at 1 atm from b. A → 1,2,4; B → 1,2,4,5; C → 3,4; D → 1,2,4
300 K to 600 K, c. A → 3,5; B → 1,2,4; C → 1,2,4,5; D → 1,2,4
followed by reversible d. A → 1,2,4; B → 3,5; C → 1, 4,5; D → 1,2,4

Mock Test-4 379

SECTION 1 Contains 8 Questions h2 h2
a. b.
The answer to each question is a single digit integer ranging from 0 to 4π 2 ma 02 16π 2 ma 02
9 (both inclusive).
h2 h2
0.45 g of an acid (mol wt. = 90) required 20 ml of 0.5 N c. d.
1. 32π 2 ma 02 64π 2 ma 02
KOH for complete neutralization. Basicity of acid is
12. The equilibrium 2Cu I ↽ ⇀ Cu° + Cu II in aqueous
2. The co-ordination number of copper in cuprammonium
medium at 25ºC shifts towards the left in the presence of
sulphate is
a. NO 3− b. Cl− c. SCN − d. CN −
3. The co-ordination number of cobalt in the complex
[Co(en) 2 Br2 ]Cl 2 is 13. The bond energy (in kcal mol–1) of C – C single bond is
approximately
4. The primary valence of the metal ion in the co-ordination a. 1 b. 10 c. 100 d. 1000
compoun K 2 [Ni ( CN )4 ] is
14. N 2 + 3H 2 ↽ ⇀ 2NH 3 Which is correct statement if N 2
5. The oxidation number of Cr in [Cr(NH 3 )6 ]Cl3 is is added at equilibrium condition?
6. The number of equivalent Cr − O bonds in CrO 24 − is. a. The equilibrium will shift to forward direction because
according to IInd law of thermodynamics the entropy must
7. The number of the following reagents that produce ppt. increases in the direction of spontaneous reaction
with ZnSO4 solution is. b. The condition for equilibrium is G N2 + 3G H2 = 2G NH3
NaOH, N 2 CO3 , NaCl, Na 2 HPO 4 , Na 2S, CH 3CO3 Na where G is Gibbs free energy per mole of the gaseous
species measured at that partial pressure. The condition of
8. The change in the magnetic moment value when
equilibrium is unaffected by the use of catalyst, which
2+ 2+
Cu ( H 2O )4  is converted to Cu ( NH3 )4  is. increases the rate of both the forward and backward
reactions to the same extent
c. The catalyst will increase the rate of forward reaction
by α and that of backward reaction by β .
d. Catalyst will not alter the rate of either of the reaction
9. A gas described by van der Waal’s equation
a. behaves similar to an ideal gas in the limit of large 15. For a first order reaction A→P, the temperature (T)
molar volumes dependent rate constant (k) was found to follow the
b. behaves similar to an ideal gas in the limit of large 1
equation log k = −(2000) + 6.0. The pre-exponential
pressures T
factor A and the activation energy Ea, respectively, are
c. is characterized by van der Waal’s coefficients that are
dependent on the identity of the gas but are independent of a. 1.0 ×106 s−1 and 9.2 kJmol −1
the temperature b. 6.0s−1 and 16.6 kJmol −1
d. has the pressure that is lower than the pressure exerted
c. 1.0 ×106 s−1 and 16.6 kJmol −1
by the same gas behaving ideally
d. 1.0 ×106 s−1 and 38.3 kJmol −1
10. Assuming that Hund’s rule is violated, the bond order and
magnetic nature of the diatomic molecule B 2 is 16. The initial rate of hydrolysis of methyl acetate (1 M) by a
weak acid (HA, 1M) is 1/100th of that of a strong acid
a. 1 and diamagnetic b. 0 and diamagnetic
(HX, 1M), at 25ºC. The Ka of HA is
c. 1 and paramagnetic d. 0 and paramagnetic
−4 −5
a. 1×10 b. 1×10
11. The kinetic energy of an electron in the second Bohr orbit
c. 1×10−6 d. 1×10−3
of a hydrogen atom is [a0 is Bohr radius].

SECTION 3 Contains 2 Paragraph Type Questions b. At the start of the reaction, dissociation of gaseous X 2
Each paragraph describes an experiment, a situation or a problem. takes place spontaneously
Two multiple choice questions will be asked based on this paragraph. c. β equlibrium = 0.7
One or more than one option can be correct.
d. K C < 1
Thermal decomposition of gaseous X 2 to gaseous X at 298 K
takes place according to the following equation: Tollen’s reagent is used for the detection of aldehyde when a
X 2 (g) ↽ ⇀ 2X(g) solution of AgNO 3 is added to glucose with NH 4 OH then
gluconic acid is formed
The standard reaction Gibbs energy, ∆r G° of this reaction is
Ag + + e − 
→ Ag ; Eored = 0.8 V
positive. At the start of the reaction, there is one mole of X 2
C6 H12 O 6 + H 2 O 
→ Gluconic acid
and no X. As the reaction proceeds, the number of moles of X
formed is given by β . Thus β equilibrium is the number of moles of (C6 H12 O7 ) + 2H + + 2e− ; E ooxd = − 0.05 V
X formed at equilibrium. The reaction is carried out at a Ag(NH3 ) 2+ + e − 
→ Ag (s) + 2NH3 ; E ooxd = 0.337 V
constant total pressure of 2 bar. Consider the gases to behave RT F
[Use 2.303 × = 0.0592 and = 38.92 at 298 K
ideally. (Given: R = 0.083 L bar K −1 mol −1 ) F RT
17. The equilibrium constant K p for this reaction at 298 K, in 19. 2Ag − + C6 H12 O6 + H 2 O 
→ 2Ag (s) + C6 H12 O7 + 2H +
terms of β equilibrium , is Find ln K of this reaction.

a. 66.13 b. 58.38
8βequilibrium
2
8βequilibrium
2
c. 28.30 d. 46.29
a. b.
2 − βequilibrium 4 − βequilibrium
2
20. When ammonia is added to the solution, pH is raised to
4β 2
equilibrium 4β 2
equilibrium
11. Which half-cell reaction is affected by pH and by how
c. d. much?
2 − βequilibrium 4−β 2
equilibrium
a. E oxd will increase by a factor of 0.65 from Eooxd
b. E oxd will decrease by a factor of 0.65 from Eooxd
reaction, is
a. Decrease in the total pressure will result in formation of c. E red will increase by a factor of 0.65 from E ored
more moles of gaseous X d. E red will decrease by a factor of 0.65 from E ored

Mock Test-4 381

ANSWER and SOLUTIONS 13. (a) For exothermic reactions H p < H R .
JEE-Main For endothermic reactions H p > H R .
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
a d b b a d a a d c 14. (a) 18 Ar 40 Total no of protons = 18
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. Total no of neutrons = 22
c a a a a b c c b c
Mass defect = [m × p + m × n] − 39.962384
21. 22. 23. 24. 25. 26. 27. 28. 29. 30.
d d b a b b b a b d
= [1.007825 ×18 + 1.008665 × 22] − 39.962384
= [18.14085 + 22.19063] − 39.962384 = 0.369
1. (a) Molecular mass of
SO 2 Cl 2 = 32 + 2 × 16 + 35.5 × 2 = 135 Binding energy = mass defect × 931
13.5 = 0.369 × 931 = 343.62MeV

Moles = = 0.1
135 15. (a) AlCl3 is lewis acid i.e., electron deficient compound.
2−
2. (d) Arrangement of sulphide ions (S ) in zinc blende So it is electrophile.
2+
(ZnS) is fcc while Zn ions occupy alternate tetrahedral 16. (b) R — C ≡≡ N and R — N = C are functional isomers.
Cyanide Isocyanide
voids.
3. (b) The temperature at which a liquid boils increases with CH 3C == O
17. (c) CH 3 — C == CH 2 |
increase in pressure. | CH 3
CH 3 
O3
H2O, Zn
→ Acetone
4. (b) Equal volumes of all gases under similar conditions of
18. (c) CH2Br − C ≡ C − CH2Br → CH 2 = C = C = CH 2
Zn
temperature and pressure contain equal number of
∆
molecules.
19. (b) Benzoic acid.
5. (a) K.E. = – (T.E.)
OH
6. (d) Oxygen have + 2 oxidation state in OF2 . | H3O+
20. (b) Me2C = O + HCN 
→ CH 3 — C — CN  →
−1 |
7. (a) l / a = 0.5 cm , R = 50 ohm CH 3
(X )
Ra 50
p= = = 100
l 0.5 OH
|
1000 1 1000 1 1000 CH 3 — C — COOH 
H2SO4
→ CH 2 == CCOOH
Λ = k× = × = × = 10 ohm−1 cm2 gm eq−1 | |
N p N 100 1 CH3
CH 3
(Y ) (Z)
π σ
*
8. (a) N N 21. (d) CH 3 — CH 2 — COOH + Na H CO3 
→ CH 3CH 2 COONa + H 2 O
π CH 3 — CH 2 — COOH + Na H CO 3 
*
→ CH 3CH 2 COONa + H 2 O + C O 2
*
9. (d) Equilibrium constant changes with temperature,

22. (d) C6H5NH2 + O = CHC6H5 
→C6H5 − N = CHC6H5 + H2O
pressure and the concentration of either reactant or Schiff 's base
product.
23. (b) Average number molecular weight Mn = 30,000
10. (c) HA : K a = 10−4
Average mass molecular weight M w = 40,000
HA + NaOH ↽ ⇀ NaA + H 2O
Clearly, the reverse reaction is the hydrolysis reaction. M w 40,000
Polydispersity index (PDI) = = = 1.33
1 K 10−4 Mn 30,000
⇒ K Required = = a = −14 = 1010
K h K w 10
24. (a) Oil (unsaturated) + H 2 
Ni
→ Fat (saturated)
11. (c) The definition of activation energy.
25. (b) "Cancer" is known as molecular disease.
12. (a) Scattering of light is a property of colloid.

26. (b) Hydrogen, forms hydrides like halides, e.g. HCl. 4. (6) These are total 6α — H to sp 2 carbon and they all can
27. (b) Cu 2 Cl 2 + Ag 2S 
→ Cu 2 S + 2AgCl participate in hyperconjugation.
2AgCl + Hg 
→ Hg 2 Cl 2 + 2Ag H+ H+
+
H+
AgCl + Hg 
→ Ag + HgCl

→ + +
28. (a) The solubility of hydroxides of alkaline earth metals in
water increases on moving down the group. Three structures Two structures
− + − +2
29. (b) KI + MnO 
→ K IO + Mn
4 3
5. (3)
6. (5)
30. (d) In K 4 Fe(CN) 6 , the species retains its identity in solid
7. (7)
as well as in solution state.
8. (1)
JEE Advance Paper -I Ws
9. (a) ∆TL = k b × m = k b ×
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. M s × Wsolution
9 9 4 6 3 5 7 1 a c 2.5 × 1000 0.76 × 2.5 × 1000
2 = 0.76 × Ms = = 9.5
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. Ms ×100 100 × 2
d a, d d c c. d b c b, c d a
Ws
% by weight × 10 × d 30 × 10 × 1.095 760 − x ns Ws 2.5 × 18
1. (9) M = = = 9M = Xs = = = = 36.0
Mw2 36.5 760 n solution Wsolv 9.5 × 100
M solv
2. (9) Let x be the percentage of Na 2 CO3 . Then, weight of
x = 760 − 36 = 724
NaHCO 3 = (15 − x)g
10. (c) Initial moles = final moles
11.0 g
Moles of NaCl produced = = 0.18 mol Pi × V Pi × V Pf × V Pf × V
58.5g + = +
RT1 RT1 RT2 RT1
 x 
The NaCl is produced by the reaction of   mol of Pi Pi Pf Pf 2Pi 1 1
 106  + = + = Pf  + 
T1 T1 T2 T1 T1  T2 T1 
(15 − x)
Na 2 CO 3 and mol of NaHCO 3 . Each mol of 2Pi  T + T2   T2 
84 = Pf  1  Pf = 2Pi ×  
Na 2 CO 3 produces 2 mol of NaCl.
T1  T1T2   T1 + T2 
2 x 15 − x 11. (d) K.E. = eV

∴ + = 0.188 Solve x : = 13.5 g Na 2 CO 3 ,
106 84 h h
λ= ⇒ = 2meV
NaHCO3 = (15 − 1.35) = 13.6 g 2meV λ
1.35
% Na 2 CO3 = ×100 = 9.0% Na 2 CO3 12. (a, d) In acidic medium
15
MnO 4− + 8H + + 5e − 
→ Mn 2 + + 4H 2 O
3. (4) Aromatic alcohols and carboxylic acids form salt with
In neutral medium,
NaOH, will dissolve in aqueous NaOH.
MnO 4− + 2H 2 O + 3e − 
→ MnO 2 + 4OH −
H 3C ⊕ CH 2 CH 3
Hence, number of electrons loose in acidic and neutral
medium are 5 and 3 respectively.
0.059 [M 2 + ][H + ]2
COOH 13. (d) E cell = E cell
o
− log10
COOH OH OH 2 [M 4 + ]pH 2
0.059
0.092 = 0.151 = log10 10x
N 2
H 3C CH 3 ∴ x=2
Mock Test-4 383

14. (c) O2 is expected to be diamagnetic in nature but actually +1× number of monodentate ligand = 2 × 2 + 1× 2 = 6.
it is paramagnetic.
4. (2) Primary valencies are also known as oxidation state.
15. (c, d) In option (c), if HNO3 is present in limiting amount K 2 [ Ni (CN) 4 ], 2 + x − 4 = 0 ⇒ x = +2
then this mixture will be a buffer and the mixture given in
option (d), contains a weak acid (CH3COOH) and its salt 5. (3) x + 6 × (0) + 3 × (−1) = 0
with strong base NaOH, i.e. CH3COONa. x – 3 = 0, x + 3, Oxidation number of Cr is = +3
16. (b) ∆G ° = ∆H° − T∆S° = −54.07 × 1000 − 298 × 10 6. (4)
7. (4)
= −57050 J mol−1 − 57050 = −5705log10 K
8. (0)
log10 K = 10
Hence (b) is correct.  n 2a 
9. (a, c, d)  P + 2  (V − nb) = nRT
 V 
17. (c) C6 H14
At low pressure, when the sample occupies a large
H 3C — CH 2 — CH 2 — CH 2 — CH 2 — CH 3
volume, the molecules are so far apart for most of the time
H 3 C — CH — CH 2 — CH 2 — CH 3
| that the intermolecular forces play no significant role, and
CH 3 the gas behaves virtually perfectly.
H 3C — CH — CH — CH 2 — CH 3 a and b are characteristic of a gas and are independent of
|
CH 3  n2a 
temperature. The term  P + 2  represents the pressure
 V 
H 3C — CH — CH — CH 3
| | exerted by an ideal gas while P represents the pressure
CH 3 CH 3 exerted by a real gas.
CH3
10. (a) B2 (10) = σ1s2 σ 1s2σ 2s2σ 2s2 π 2p2
* *
| x
H 3C — C — CH 2 — CH 3 , Hence (c) is correct
| 6−4
CH 3 Bond order = = 1 (nature is diamagnetic as no
2
18. (b, c) unpaired electron)
19. (d) A → 3; B → 2; C →1; D →4 nh mv2 e2

11. (c) mvr = and = 2 ⇒ mv2 r = e2
20. (a) A → 3,5; B → 1,2,4; C → 1,2,4; D → 1,2,4,4 2π r r
e2 × 2π nh
⇒ v= ∴ (mvr = )
JEE Advance Paper -II nh 2π
1 4
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
me × 4π 2
1 2
2 4 6 2 3 4 4 0 a, c, d a ⇒ K.E. = mv = 2
. . .(i)
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 2 n 2h 2
c b,c,d c b d a b c b a h2
Expression for a 0 =
4π 2 me2
WB × 1000
1. (2) Normality = N = h2
Eq.wt × V ⇒ me2 = . . .(ii)
4π 2a 0
0.45 × 1000
∴ Eq. Wt = = 45
0.5 × 20 h2 1
⇒ K.E. = × . . .(iii)
Molec. Wt 90 8ma 02π 2 n 2
∴ Basicity = = =2
Eq. Wt 45 h2
For n = 2 K.E. =
2. (4) In Cuprammonium sulphate [Cu(NH3 )4 ]SO4 co- 32π 2 ma 02
ordination no. of Cu is 4. 12. (c, d) Cu2+ ions will react with CN– and SCN– forming
3. (6) [Co(en)2 Br2 ]Cl2 [Cu(CN) 4 ]3 − and [Cu(SCN) 4 ]3− leading the reaction in
C.N.of Co = 2 × number of bidentate ligand the backward direction.
Cu 2 + + 2CN − 
→ Cu(CN) 2  
 βeq   2βeq 
2Cu(CN) 2 
→ 2CuCN + (CN) 2 Px(g) = Ptotal  =  Ptotal 
1 + βeq   2 + βeq 
CuCN + 3CN − 
→ [Cu(CN) 4 ]3−  2 

Cu 2 + + 4SCN − 
→ [Cu(SCN) 4 ]3−  2β eq. 
2
 × Ptotal 
Cu 2 + also combines with CuCl2 which reacts with Cu to (Px) 2  2 + β eq. 
So Kp = =
produce CuCl pushing the reaction in the backward (Px 2 )  2 − β eq. 
 × Ptotal 
direction.
 (2 + β eq ) 
CuCl2 + Cu 
→ 2CuCl ↓
4βeq.
2
 8βeq2 
⇒ Kp = × P =  2 
13. (c) 4 − βeq.  4 − βeq 
2 total
14. (b)
18. (c) (a) Correct statement. As one decrease in pressure
2000
15. (d) Given, log K = 6 − reaction will move in the direction where no. of gaseous
T molecules increases.
Ea
Since, log K = log A − (b) Correct statement
2.303RT
At the start of reaction Qp < K p so dissociation of X 2 take
So, A = 106 sec−1
place spontaneously.
Ea = 38.3kJ / mole
and Ea (c) Incorrect statement as
1 8β eq2 8 × (0.7)2
16. (a) Rate in weak acid = (rate in strong acid) Kp = = > 1, but
100 4 − β eq2 4 − (0.7) 2
1
∴ [H + ]weak acid = [H + ]strong acid (d) Correct statement.
100
As ∆G° > 0 & ∆G° = −RTℓ n Kp
1
∴ +
[H ]weak acid = M = 10 −2 M ∆G° > 1, so K p should be less than 1.
100
∴ Cα = 10−2 So K <1
K p − K c (RT) ∆ng. (RT > 1)
∴ K a = 10−4
Kp
For Question Nos. 17 to 18 Kc = ⇒ Kc < Kp
RT
17. (b) Paragraph-1 X 2 (g) ↽ ⇀ 2X(g)
So Kc < 1
Initial mole 1 0
t = t eq. (1 − α ) 2α
RT
βequilibrium 19. (b) E ocell = ln K
Given 2α = β equilibrium So, α = nF
2 1 0.0592
(0.8 − 0.05) = × ln K
 β eq  2 2.303
Total mole at equilibrium = (1 + α ) = (1 +  
 2  (0.8 − 0.05) × 22.303
ln k = = 58.38
0.0592
 β eq. 
1 − 
Px 2 =  2 P  =  2 − β eq P  =  2 − β eq P  20. (a) On increasing concentration of NH3 the concentration
 total   total 
of H+ ion decreases. Therefore, Ered increases.
1 + β eq.   2 + β eq   2 + β eq
total

 2 
Mock Test-5 385

1. One mole of potassium dichromate completely oxidises 9. The formation of nitric oxide by contact process
the following number of moles of ferrous sulphate in N 2 + O 2 ↽ ⇀ 2NO. ∆H = 43.200 kcal is favoured by
acidic medium
a. Low temperature and low pressure
a. 1 b. 3
b. Low temperature and high pressure
c. 5 d. 6
c. High temperature and high pressure
2. In a solid lattice, the cation has left a lattice site and is d. High temperature and excess reactants concentration
located at an interstitial position, the lattice defect is
a. Frenkel defect 10. The pH of an aqueous solution Mg ( OH )2 is 9.0. If the
b. Schottky defect solubility product of Mg ( OH )2 is 1 × 10 −11 , what is [ Mg 2 + ] ?
c. F-centre defect
a. 1 × 10 −5 b. 1.0 × 10 −4
d. Valency defect
c. 1×10−2 d. 0.1
3. At 300 K, the vapour pressure of an ideal solution containing
3 mole of A and 2 mole of B is 600 torr. At the same 11. If ‘I’ is the intensity of absorbed light and C is the
temperature, if 1.5 mole of A and 0.5 mole of C (non- concentration of AB for the photochemical process
volatile) are added to this solution the vapour pressure of AB + hv → AB*, the rate of formation of AB* is directly
solution increases by 30 torr. What is the value of PBo ? proportional to
a. 940 b. 405 a. C b. I
c. 90 d. None of these c. I 2 d. C.I
12. Gold number is maximum for the lyophilic sol is
4. If the root mean square speed of helium is 4.75 m s–1 at
a. Gelatin b. Haemoglobin
25°C, then its speed will become 9.50 m s–1 at
c. Sodium oleate d. Potato starch
a. 100°C b. 323°C
13. For the allotropic change represented by equation
c. 919°C d. 1192°C
C(diamond) → C(graphite); the enthalpy change is
5. Which electronic level would allow the hydrogen atom to ∆H = −1.89 kJ. If 6 g of diamond and 6 g of graphite are
absorb a photon but not to emit a photon?
separately burnt to yield carbon dioxide, the heat liberated
a. 3s b. 2p in the first case is
c. 2s d. 1s a. Less than in the second case by 1.89 kJ
6. The product of oxidation of I − with M nO −4 in alkaline b. More than in the second case by 1.89 kJ
medium is c. Less than in the second case by 11.34 kJ

a. IO 3− b. I 2 d. More than in the second case by 0.945 kJ
− −
c. IO d. IO 4 14. The half-life of 6 C14 if its K or λ is 2.31 × 10 −4 is
7. The standard reduction electrode potentials of four a. 2 × 10 2 yrs b. 3 × 10 3 yrs
elements are A = − 0.250 V, B = − 0.136 V, C = − 0.126 V
c. 3.5 × 10 4 yrs d. 4 × 10 3 yrs
and D = − 0.402 V. The element that displaces A from its
15. Most stable carbonium ion is
compounds is
+ +
a. B b. C a. C 2 H 5 b. (CH 3 )3 C
c. D d. None of these + +
c. (C 6 H 5 )3C d. C 6 H 5CH 2
8. The bond angle in carbon tetrachloride is approximately
a. 90 ° 16. Which of the following compounds will exhibit cis-trans
b. 109° isomerism
c. 120° a. 2-butene b. 2-butyne
d. 180° c. 2-butanol d. Butanone

17. Acetylene gas is obtained by the electrolysis of 24. The base present in DNA, but not in RNA is
a. Sodium fumarate a. Guanine b. Adenine
b. Sodium succinate c. Uracil d. Thymine
c. Sodium maleate
25. Which of the following is an antidiabatic drug
d. Both (a) and (c)
a. Insulin b. Penicillin
18. The compound added to prevent chloroform to form
c. Chloroquine d. Aspirin
phosgene gas is
a. C2 H5OH 26. The correct sequence of elements in decreasing order of
first ionisation energy is
b. CH3COOH
a. Na > Mg > Al b. Mg > Na > Al
c. CH 3 COCH 3
c. Al > Mg > Na d. Mg > Al > Na
d. CH 3 OH
19. Epoxides are 27. In the metallurgical extraction of zinc from ZnO the
a. Cyclic ethers reducing agent used is
b. Not ethers a. Carbon monoxide b. Sulphur dioxide
c. Aryl-alkyl ethers c. Carbon dioxide d. Nitric oxide
d. Ethers with another functional group
28. In the lime (kiln), the reaction CaCO3 (s) 
→ CO2 (g)
20. NaOH / H + reacts with
goes to completion because
a. C6 H 5OCH3 b. CH 3 OH
a. Of high temperature
O b. CaO is more stable than CaCO3
||
c. CH 3 — C — CH 3 d. C2 H5OH
c. CO2 escapes simultaneously
∆
21. In the reaction C8 H 6 O 4 
→ X 
→ NH3
d. CaO is not dissociated
The compound X is
a. Phthalic anhydride b. Phthalic acid 29. Amalgams are
c. o-xylene d. Benzoic acid a. Highly coloured alloys
b. Always solid
22. In the reaction CH 3 (CH 2 ) 4 CN  → A 
Zn , HCl
→ B 
HONO O
→C
c. Alloys which contain mercury as one of the contents
) CN  → A 
Zn , HCl
→ B 
HONO O
→ C ; C is d. Alloys which have great resistance to abrasion
a. Pentanal b. Pentanone
30. Generally, a group of atoms can function as a ligand if
c. 2-Hexanone d. Hexanal
a. They are positively charged ions
23. A polymer containing nitrogen is b. They are free radicals
a. Bakelite b. Dacron c. They are either neutral molecules or negatively charged ions
c. Rubber d. Nylon-66 d. None of these

Mock Test-5 387

JEE ADVANCE PAPER-I
SECTION 1 Contains 8 Questions 8. Hydrolysis of an alkyl halide (RX) by dilute alkali [OH − ]
The answer to each question is a single digit integer ranging from 0 to takes place simultaneously by SN 2 and SN1 pathways. A
9 (both inclusive).
1 d[R − X]
plot of − vs. [OH − ] is a straight line of
1. The change in the number of unpaired electrons when [RX] dt
2+ 4−
 Fe ( H 2 O )6  is changed into  Fe ( CN )6  is the slope equal to 2 × 103 mol −1 L h −1 and intercept equal to
1×102 h −1. Calculate the initial rate (more
(mol L−1 min −1 ) of
2. A compound of mol. wt. 180 is acetylated to give a consumption of RX when the reaction is carried out taking
compound of mol. wt. 390. The number of amino groups
1mol L−1 of RX and 0.1 mol L−1 of [OH − ] ions.
in the initial compound is?
3. Specific rotations of α-anomer of glucose is + 112 ° and SECTION 2 Contains 10 Multiple Choice Questions
for β-anomer is + 19 ° . Specific rotation of equilibrium With one or more than one correct option
mixture is 52.6 ° . Calculate % composition of α-and β-
anomers in the equilibrium mixture. 9. The ionic radii (in Å) of N3− , O2− and F− are
respectively:
4. Consider all possible isomeric ketones including
a. 1.36, 1.40 and 1.71
stereoisomers of MW = 100. All these isomers are
b. 1.36, 1.71 and 1.40
independently reacted with NaBH 4 (Note: Stereoisomers
c. 1.71, 1.40 and 1.36
are also reacted separately). The total number of ketones
that give a racemic product(s) is/are d. 1.71, 1.36 and 1.40
5. Amongst the following, the total number of compounds 10. From the following statements regarding H 2O 2 , choose
soluble in aqueous NaOH is the incorrect statement
a. It can act only as an oxidizing agent
H 3C CH3 b. It decomposes on exposure to light
N COOH OCH2CH3 OH c. It has to be stored in plastic or wax lined glass bottles in
CH2OH3 dark
d. It has to be kept away from dust
11. AgNO3 (aq.) was added to an aqueous KCl solution
OH CH2CH3
NO2 gradually and the conductivity of the solution was
CH2OH3 COOH
measured. The plot of conductance (^) versus the volume
of AgNO3 is
N
H 3C CH3 + +
+ + +
a. Λ + ++ b. Λ +
6. The half-life period of a radioactive substance is 2 min. +
+ +
The time taken for 1 g of the substance to reduce to 0.25 g
volume volume
will be (a) (b)
7. ∆ f H − of hypothetical MgCl is −125 kJ mol−1 and for +

+
+
MgCl 2 is −642 kJ mol−1 . The enthalpy of c. Λ ++ + + + + + + d. Λ + + + +
disproportionation of MgCl is –49x. Find the value of x.

volume volume
(c) (d)

12. The intermolecular interaction that is dependent on the –1300 kJ/mol, respectively. The standard enthalpy of
inverse cube of distance between the molecules is: combustion per gram of glucose at 25°C is
a. ion-ion interaction b. ion-dipole interaction a. + 2900 kJ b. – 2900 kJ
c. London force d. hydrogen bond c. – 16.11 kJ d. +16.11 kJ
13. According to Molecular Orbital Theory 18. Which of the following compounds is not colored yellow?
a. C 22 − is expected to be diamagnetic a. Zn 2 [Fe(CN) 6 ]
b. O 22 + is expected to have a longer bond length than O2 b. K 3[Co(NO2 )6 ]
+ −
c. N and N have the same bond order
2 2
c. (NH 4 )3 [As(Mo3O10 ) 4 ]
d. He +2 has the same energy as two isolated He atoms d. BaCrO 4
14. For the first order reaction

SECTION 3 Contains 2 Match The Following Type Questions
2N 2 O5 (g) 
→ 4NO 2 (g) + O 2 (g)
You will have to match entries in Column I with the entries in
a. the concentration of the reactant decreases exponent- Column II.
tially with time
19. Match each of the diatomic molecules in Column I with
b. the half-life of the reaction decreases with increasing
its property/properties in Column II.
temperature
Column - I Column – II
c. the half-life of the reaction depends on the initial
(A) B2 1. Paramagnetic
concentration of the reactant
d. the reaction proceeds to 99.6% completion in eight (B) N 2 2. Undergoes oxidation
half-life duration (C) O −2 3. Undergoes reduction
15. In the reaction, P + Q 
→ R + S the time taken for 75% (D) O2 4. Bond order ≥ 2
reaction of P is twice the time taken for 50% reaction of P. 5. Mixing of ‘s’ and ‘p’
The concentration of Q varies with reaction time as shown orbitals
in the figure. The overall order of the reaction is a. A → 5, 3, 1, B → 5, 4, C → 2, 1, D → 4, 1, 2
b. A → 1, 3, 5, B → 1, 2, 4 C → 3, 2, D → 1, 2,
[Q]0 c. A → 1, 3, B → 1, 2, 4 C → 1, 2, 3 D → 4, 5,
[Q] d. A→1, 3, 5, B→4, 5, C→1, 2, D→1, 2, 4
[According to MOT]
20. Match the compounds/ions in Column I with their
Time properties/reactions in Column II.
a. 2 b. 3 c. 0 d. 1 Column I Column II
16. Choose the correct reason(s) for the stability of the (A) C6H5CHO 1. gives precipitate with
lyophobic colloidal particles. 2, 4-dinitrophenyl-
a. Preferential adsorption of ions on their surface from the hydrazine
solution (B) CH3C ≡ CH 2. gives precipitate with
b. Preferential adsorption of solvent on their surface from AgNO3
the solution (C) CN − 3. is a nucleophile
c. Attraction between different particles having opposite
charges on their surface (D) I − 4. is involved in cyano-
hydrin formation
d. Potential difference between the fixed layer and the
diffused layer of opposite charges around the colloidal
a. A → 1, 2, 3, B → 2, C → 1, 3, 4, D → 2, 3
particles
b. A → 1, 3, 4, B → 2, 3 C → 1, 2, 3, D → 2
17. The standard enthalpies of formation of CO 2 (g), H2O(l ) c. A → 1, 3, B → 1, 4, C → 1, 3, D → 2, 3
and glucose(s) at 25°C are –400 kJ/mol, –300 kJ/mol and d. A → 2, 3, B → 1, 2, C → 1, 3, D → 1, 2
Mock Test-5 389

SECTION 1 Contains 8 Questions 10. Among the electrolytes Na 2SO4 , CaCl2 , Al2 (SO 4 )3 and
The answer to each question is a single digit integer ranging from 0 to NH4Cl, the most effective coagulating agent for Sb 2S3
9 (both inclusive).
sol is
2−
1. The number of rings formed in  Ca ( EDTA )  is a. Na 2SO4 b. CaCl2 c. Al2 (SO 4 )3 d. NH4Cl
…………… 11. The compound(s) with TWO lone pairs of electrons on the
2. The number of equivalent Cl − O bonds in Cl2 O7 is central atom is(are)
a. BrF5 b. ClF3
……………
c. XeF4 d. SF4
3. In fructose, the possible optical isomers are……………
4. Oxidation of glucose is one of the most important 12. Solubility product constant (K sp ) of salts of types
reactions in a living cell. What is the number of ATP MX, MX 2 and M 3X at temperature ‘T’ are
molecules generated in cells from one molecule of
4.0 ×10 −8 , 3.2 × 10 −14 and 2.7 × 10−15 , respectively.
glucose?
−3
Solubilities (mole dm ) of the salts at temperature ‘T’
5. 10 gm of a mixture of hexane and ethanol reacts with
are in the order
sodium to give 200 ml. of H 2 at 27 °C and 760 mm
a. MX > MX 2 > M 3 X b. M 3 X > MX 2 > MX
pressure. The percentage of ethanol is……………
c. MX 2 > M 3 X > MX d. MX > M 3 X > MX 2
6. The polymerisation of propene to linear polypene is
represented by the reaction 13. According to the Arrhenius equation
 CH3  a. a high activation energy usually implies a fast reaction
 CH 3 
|  |  b. rate constant increases with increase in temperature.
n  CH == CH 2  → — CH — CH 2— 
n This is due to a greater number of collisions whose energy
Where n has large integral value, the average enthalpies of exceeds the activation energy
bond dissociation for (C == C) and (C −− C) at 298 K c. higher the magnitude of activation energy, stronger is
are +590 and +331kJ mol −1 , respectively. The enthalpy the temperature dependence of the rate constant
d. the pre-exponential factor is a measure of the rate at
of polymerization is −360 kJ mol −1 . Find the value of n. which collisions occur, irrespective of their energy
7. In the case of a first order reaction, the time required for 14. For a linear plot of log (x/m) versus log p in a Freundlich
93.75% of reaction to take place is x times that required adsorption isotherm, which of the following statements is
for half of the reaction. Find the value of x. correct?
8. In 1 L saturated solution of AgCl (K sp of AgCl a. Both k and 1/n appear in the slope term
b. 1/n appears as the intercept
gCl(K of AgCl) = 1.6 × 10 −10 ), 0.1mol of CuCl (Ksp CuCl = 1.0 ×10−6 ) is c. Only 1/n appears as the slope
added. The resultant concentration of Ag + in the solution d. log (1/n) appears as the intercept.
is 1.6 ×10− x. Calculate the value of x. 15. When O2 is adsorbed on a metallic surface, electron
transfer occurs from the metal to O2 . The TRUE
SECTION 2 Contains 8 Multiple Choice Questions statement(s) regarding this adsorption is(are)
With one or more than one correct option a. O2 is physisorbed
9. Which of the following atoms has the highest first b. heat is released
ionization energy? c. occupancy of π 2p
*
of O2 is increased
a. Rb b. Na d. bond length of O2 is increased
c. K d. Sc

16. Methylene blue, from its aqueous solution, is adsorbed on b. Carbon dating can be used to find out the age of earth
activated charcoal at 25 °C. For this process, the correct crust and rocks
statement is c. Radioactive absorption due to cosmic radiation is equal to
a. The adsorption requires activation at 25 ° C the rate of radioactive decay, hence the carbon content
b. The adsorption is accompanied by a decrease in remains constant in living organism
enthalpy d. Carbon dating cannot be used to determine concen-
c. The adsorption increases with increase of temperature tration of 14 C in dead beings
d. The adsorption is irreversible
18. What should be the age of fossil for meaningful
SECTION 3 Contains 2 Paragraph Type Questions determination of its age?
a. 6 years
Each paragraph describes an experiment, a situation or a problem.
Two multiple choice questions will be asked based on this paragraph. b. 6000 years
One or more than one option can be correct. c. 60,000 years
d. It can be used to calculate any age
Carbon–14 is used to determine the age of organic material. Paragraph for Question Nos. 19 to 20
The procedure is based on the formation of 14 C by neutron Rocket propellants consist of rocket engines powered by
capture in the upper atmosphere propellants. These are used both in space vehicles as well as in
14
7 N + 0 n1 
→ 14
6 C + 1n
1
offensive weapons such as missiles. The propellants are
14
C is absorbed by living organisms during photosynthesis. chemical substances which on ignition provide thrust for the
The 14 C content is constant in living organism once the plant or rocket to move forward. These substances are called rocket
animal dies, the uptake of carbon dioxide by it ceases and the propellants. A propellant is a combination of an oxidiser and a
level of 14 C in the dead being, falls due to the decay which fuel which when ignited undergoes combustion to release large
C 14 undergoes quantities of hot gases. The passage of hot gases through the
nozzle of the rocket motor provides the necessary thrust for the
7 N + β
−
14
6 C 
→ 14
rocket to move forward according to Newton's third law of
The half life period of 14 C is 5770 years. The decay constant
motion.
(λ ) can be calculated by using the following formula
19. A biliquid propellant contains
0.693 a. Liquid hydrazine
λ= . The comparison of the β - activity of the dead
t1/ 2 b. A mixture of liquid fuel and a liquid oxidiser
matter with that of the carbon still in circulation enables c. A solid rocket fuel
measurement of the period of the isolation of the material from d. A liquid fuel which can also act as an oxidiser
the living cycle. The method however, ceases to be accurate
20. A hybrid rocket propellant uses
over periods longer than 30,000 years. The proportion of 14 C
a. A liquid oxidiser and a solid fuel
12 12
to C in living matter is 1 : 10 . b. A composite solid propellant
17. Which of the following option is correct? c. A biliquid propellant
a. In living organisms, circulation of 14 C from atmosphere d. A solid, liquid and gas as a propellant
is high so the carbon content is constant in organism
Mock Test-5 391

ANSWER and SOLUTIONS 11. (b) In photochemical reaction the rate of formation of
JEE-Main product is directly proportional to the intensity of
absorbed light.
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
d a c c d a c b d d 12. (d) Gold number shows the protective power of a
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. lyophilic solution. Lesser the gold number, greater will be
b d d b c a d a a c the protecting power of that colloid. Gelatin is one of the
21. 22. 23. 24. 25. 26. 27. 28. 29. 30. best protective colloid. Among the given colloids, potato
a d d d a d a d c c starch has maximum gold number.
13. (d) C(graphite) 

→ C(diamond ) , ∆H = 1.9 kJ
1. (d) Cr2 O7−− → Cr 3+ ; Fe ++ → Fe+++
n=1 C(graphite) + O 2 
→ CO 2 , ∆H = −∆H1
n=6
eq. of K2 Cr2 O7 = eq. of FeSO 4 1× 6 = x × 1 C(diamond) + O 2 
→ CO 2 , ∆H = −∆H 2
2. (a) When an ion (generally cation due to its small size) is ( − ∆H1 ) − ( − ∆H 2 ) = 1.9 kJ or ∆H 2 = ∆H1 + 1.9
missing from its normal position and occpy an interstitial
For combustion of 6g, ∆H 2 > ∆H1 by 1.9 / 2 = 0.95 kJ.
site between the lattice points, the lattice defect obtained
0.693 0.693
is known as Frenkel defect. 14. (b) t1/ 2 = = = 0.3 ×104 yrs = 3.0 × 10 3 yrs.
k 2.31× 10−4
3. (c) P = PAo x A + PBo x B 15. (c) In the triphenyl methyl carbonium ion the π electrons
 3  o 2  o of all the three benzene rings are delocalised with the
600 = PAo   + PB   ;3PA + 2PB = 3000
o
 3 + 2   2 + 3  vacant p-orbital of central carbon atom. So, it is resonance

 4.5  o 2  stabilised. It is the most stable of all the carbonium ions
630 = PAo   + PB  ;4.5PA + 2PB = 4410
o o
given
 4.5 + 2 + 0.5   4.5 + 2 + 0.5 
CH3
1.5PAo = 1410; PAo = 940 and PBo = 90
|
The ion CH 3 — C+ is stabilised by hyperconjugation, a
4. (c) r.m.s. speed ∝ T |
2 CH3
4.75 298  4.75  298
= or   = second order resonance.
9.50 T  9.50  T
or T = 1192 K or T = 1192 − 273 = 919°C 16. (a)
CH 3 CH 3 CH 3 H
5. (d) When electron jumps to lower orbit photons are C == C C == C
emitted while photons are absorbed when electron jumps H H H CH 3
Cis 2 butene Trans 2 butene
to higher orbit, 1s orbital is the lower most, electron in
Cis-trans isomerism shown by compound which have double
this orbital can absorb photons but cannot emit.
or triple bond by which they restrict their rotation, since 2
6. (a) 6MnO 4− + I − + 6OH − 
→ 6MnO 24− + IO 3− + 3H 2 O butyne have no hydrogen on triple bonded carbon.
7. (c) A is displace from D because D have a E° = −0.402 V CH 3 — C ≡≡ C — CH 3 [It does not show cis-trans]
2 butyne
8. (b) CCl4 is sp3 hybridised so bond angle will be
CH — COONa CH COO−
approximately 109 ° . 17. (d) || 
→ || −
+ 2Na +
CH — COONa CH COO
9. (d) High temperature and excess concentration of the
reactant concentration. Sodium salt of maleic acid or fumaric acid
1× 10−14 CH COO− CH
10. (d) pH = 9 ∴ [H ] = 10 [OH ] = +
= 10−5
−9 − || 
→ ||| + 2CO 2 + 2e −
10 −9
CH COO− CH
Acetylene
Mg(OH) 2 ↽ ⇀ Mg 2 + + 2OH −
18. (a) Because it float over chloroform and prevent its
K sp = [Mg 2 + ][OH − ]2 ⇒ 1 ×10 −11 = [Mg 2 + ][10 −5 ]2 oxidation.
1× 10−11 19. (a) Cyclic ethers are called epoxies. CH 2 — CH 2
⇒ [Mg 2 + ] = = 10−1 = 0.1
(10−5 )2 O

20. (c) 2CH 3 − CO − CH 3  
dil NaOH
→ 3. The α-anomer of D-glucose has a specific rotation of +112
OH O degrees in water. The β-anomer of D-glucose has a specific
| || rotation of + 19 degrees (18.7 actually, but rounding up to 19).
CH 3 — C — CH 2 — C — CH 3
| (Diacetone alchol) If the fraction of glucose present as the α-anomer is xand
CH 3
the fraction present as the β-anomer is y, and the rotation of
21. (a) the mixture is +52.6 degree, we have
O X (+112.2 degree) + y(18.7) = 52.6 degree ……..(i)
||
C There is a very little of the open chain form present, so the
COOH
→ fraction present as the α-anomer (x) plus the fraction present
COOH as the β-anomer (y) should account for all the glucose, i.e.,
C
|| x + y = 1 or y = 1 – x.
O
CONH 2 Putting value of y in equation (i), we get
+ NH 3  →
COOH
x (+112.2 degree) + (1 – x)(18.7) = 52.6 degree ……..(ii)
Solving equation (ii) for (x), we have, x = 0.36 or 36%. Thus
22. (d) CH 3 (CH 2 ) 4 CN  → CH 3 (CH 2 ) 4 CH 2 NH 2  →
Zn , HCl HONO
(y) must be (1 – 0.36) = 0.64 or 64%.

4 CN  →
Zn , HCl
CH 3 (CH )
2 4 CH 2 NH 2  HONO
 → So, percentage composition of α- and β-anomers in the
CH 3 (CH 2 )4 CH 2 OH  O
→ CH 3 (CH 2 ) 4 CHO equilibrium mixture is 36% and 64% respectively.
Hexanal
4. (5)
23. (d) Nylon-66- It is a polymer containing nitrogen
5. (4)
 H H O 
 | | ||  H 3C CH3
 — N — (CH 2 ) 6 — N — C — (CH 2 ) 4 — C —  N OH OH COOH
 || 
 O n
Nylon-66
24. (d) Thymine is present in DNA while in RNA there is

Uracil.
N
25. (a) Insulin is an antidiabatic drug.
26. (d) Mg > Al > Na. This is due to the presence of fully H 3C CH3
filled s-orbital in Mg. 6. (2) 1g →
t1/ 2
0 ⋅ 5g →
t1/ 2
0 ⋅ 25g t 25% = 4min
27. (a) ZnO + CO   → CO 2 + Zn
28. (d) Lime stone – CaCO3, Clay – silica and alumina 7. (8) 2MgCl 
→ Mg + MgCl 2 ∆H = ?
Gypsum – CaSO
CaSO44 .2H 2O → MgCl ; ∆H1 = −125 kJ mol −1
Mg(s) + 1/ 2Cl 2 (g) 
29. (c) Amalgams are alloys which contain mercury as one of → MgCl2 ; ∆H 2 = −642 kJ mol −1
Mg(s) + Cl2 (g) 
the contents.
∆H = ∆H 2 − 2∆H1 = −642 − (2 × −125) = −392 kJ mol −1
30. (c) Ligand must have capacity to donate lone pair of
∴ −49 x = −392 ⇒ x=8
electrons to form coordinate bond.
−d[RX]
JEE Advance Paper -I 8. (5) = k 2 [RX][OH − ] (by SN 2 pathway)
dt
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
k 2 = rate constant of SN2 reaction
4 5 2 5 4 2 8 5 c a
−d[RX]
11. 12. 13. 14. 15. 16. 17. 18. 19. 20. = k 2 [RX][OH − ] + k1[RX]
d b a, c c b,c,d b c b b a dt
1 d[RX]
1. (4) − = k 2 [OH − ] + k1
[RX] dt
2. (5) Difference in mass of compound 1 d[RX]
= 390 – 180 = 210 This is the equation of a straight line for −
[RX] dt
wt. of CH 3 CO – group is = 43
vs [OH − ] plot with slope equal to k 2 and intercept equal
210
Therefore no. of − NH 2 group = = 4.88 = 5 . to k1 .
43
Mock Test-5 393

−1
From question: k 2 = 2 × 10 mol L hr , k1 = 1× 10 hr
3 −1 2 −1
∆H combustion = (6 × ∆H f CO 2 + 6 × ∆H f H 2 O) − ∆H f C6 H12 O 6
[RX] = 1.0 M and [OH ] = 0.1M −
= (6 × −400 + 6 × −300) − (−1300)
−d[RX] = −2900 kJ / mol
Hence, = 2 × 103 × 1 × 0.1 + 1× 10 2 × 1
dt = −2900 /180 kJ / g
= 300 mol L−1 hr −1 = 5 mol L−1 min −1
= −16.11 kJ / g
3− 2− −
9. (c) Ionic Radii order: N > O > F 18. (a) Zn 2 [Fe(CN) 6 ] is bluish white ppt.
10. (a) It can act as an oxidising as well as reducing agent. 19. (d) A → 1, 3, 5, B → 4, 5, C → 1, 2, D → 1, 2, 4
[According to MOT]
+
+
Λ + 20. (a) A → 1, 2, 3, B → 2, C → 1, 3, 4, D → 2, 3
+++ +
11. (d) (Note: Assuming AgNO3 is ammonical)
Volume NO2
12. (b) Ion-dipole interaction
(a) PhCHO + O 2 N NH − NH 2 
→
13. (a,c) (a) C 22 − Total no. of electrons = 14 so it is
O 2N
diamagnetic
(b) O 22 + Bond order = 3; O2 Bond order = 2 PhHC = N − NH NO2
(ppt.)
∴ Bond length in O 22 + is less than bond length in O2 .

PhCHO + Ag 2O 
NH3
→ PhCOO − + Ag ↓
+ +
(c) Bond order of N = 2.5 ; Bond order of He = 1/ 2
2 2
(whiteppt )
CN
∴ Some energy is released during the formation of He +2 from |
two isolated He atoms. → Ph — C — O−
PhCHO  KCN
|
14. (a, b, d) For first order reaction [A] = [A]0 e− kt H
Hence concentration of [NO2 ] decreases exponentially, (b) CH3C ≡ CH 

ammonical AgNO3
→ CH3 − C ≡ C− Ag + ↓
(White ppt )
0.693
Also, t1/ 2 = ,. which is independent of concentration CN
|
K (c) PhCHO 
KCN
→ Ph — C — O − ;
and t1/ 2 decreases with the increase of temperature. |
H
2.303  100  AgNO3 + CN − 
→ AgCN ↓
t 99.6 = log  
K  0.4 
(d) AgNO3 + I − 
→ AgI ↓
2.303 0.693
t 99.6 = (2.4) = 8 × = 8 t1/ 2
K K
JEE Advance Paper –II
15. (d) Overall order of reaction can be decided by the data
given t 75% = 2t 50% 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
5 6 8 38 10 5 4 7 d c
∴ It is a first order reaction with respect to P.
11. 12. 13. 14. 15. 16. 17. 18. 19. 20.
From graph [Q] is linearly decreasing with time, i.e., order
b, c d b,c,d b,c,d b b c b 2 1
of reaction with respect to Q is zero and the rate
expression is r = k[P]1[Q]0 . 1. (5)
16. (a, d) (a) Preferential adsorption of ions on surface from 2. (6)
the solution 3. (8) Fructose has three chiral centres and hence 23 = 8
(c) Attraction between particles having same charges on optical isomers are possible.
their surface accounts for the Brownian motion. 4. (38) C 6 H12 O 6 + 6O 2 → 6CO 2 + 6H 2 O + 38ATP
(d) Definition of Zeta Potential.
5. (10) 22400 ml of H 2 is produced by 46 gms of ethanol.
17. (c) Combustion of glucose
46 × 200 23
C6 H12 O6 + 6O2 
→ 6CO2 + 6H 2 O 200 ml of H 2 is produced by =
22400 56

23 → Square planar
Percentage of C 2 H 5 OH = × 100 = 9.6% ≃ 10%
56 × 10 → Two lone pair on central atom (Xe) → One lone pair
6. (5) Energy released = Energy due to formation of two on central atom (S)
single bonds = 2 × 331 = 662 kJ mol−1 of propene Only, ClF3 & XeF4 contains two lone pair of electrons on
∆H polymerisation/mol = 590 − 662 = −72 kJ mol−1 central atom.
∆H polymerisation = −72 × n = −360 ⇒ n = 5 12. (d) Solubility of
0.0693
7. (4) t1/ 2 = (MX) = 4 ×10−8 = 2 ×10−4
k1
Solubility of (MX 2 ) = 8 × 10 −5
2.303 100 2.303 100
Also, t 93.75 = log = log Solubility of (M3 X) = 1× 10−4
k1 100 − 93.75 k1 6.25
2.303 4 × 2.303× log 2 4 × 0.693 ∴ MX > M 3 X > MX 2 .
= log 24 = = = 4t1/ 2
k1 k1 k1 13. (b, c, d) K = A e − Ea / RT
+
8. (7) AgCl ↽ ⇀ Ag + Cl − (K sp = 1.6 ×10 −10 ) dk Ea
(S′+ x )
S′ =K
+ dT RT 2
CuCl ↽ ⇀ Cu + Cl− (K sp = 1 × 10−6 )
( x +S′ )
x
dk
∝ Ea
∴ S′(S′ + x) = 1.6 ×10 −10
; x(x + S′) = 10 −6
dT
S′ A → Frequency factor
= 1.6 × 10 −4
x = No of collisions per unit time per unit volume.
∴ S′ = (1.6 × 10−4 )x. ⇒ x(x + 1.6 × 10−4 x) = 10−6
14. (c) According to the Freundlich adsorption isotherm
⇒ x = 10−3 x x 1
= kP1/ n log = log K + log P
∴ S′ = 1.6 ×10−7 = 1.6 ×10− x The value of =
(Thevlueofx x 7)
=7 m m n
9. (d) I. P1 = Sc > Na > K > Rb 15. (b, c, d) Adsorption of O2 on metal surface is exothermic.
During electron transfer from metal to O2 electron
10. (c) As Sb2S3 is a negative sol, so, Al2 (SO 4 )3 will be the
occupies π 2p
*
orbital of O2 .
most effective coagulant due to higher charge density on
Al3+ in accordance with Hardy-Schulze rule. Due to electron transfer to O2 the bond order of O2
Order of effectiveness of cations: decreases hence bond length increases.
Al3+ > Ca ++ > Na + > NH 4+ 16. (b) Adsorption of methylene blue on activated charcoal is
physical adsorption hence it is characterised by decrease
11. (b, c)
in enthalpy.
F
F
F 17. (c) Radioactive absorption due to cosmic radiation is equal to
Br Cl the rate of radioactive decay, hence the carbon content
F F F F remains constant in living organism
F 18. (b) 6000 years
(Square Shape) (T-Shape)
→ One lone pair on central atom (Br) → Two lone pair 19. (b) Biliquid Propellant – A double base propellant is a
on central atom (Cl) high strength, high modulus gel of cellulose nitrate (gun
F cotton) in glyceryl trinitrate or a similar solvent.
F
F F 20. (a) Hybrid Propellant – A hybrid propellant consists of a
S solid fuel and liquid oxidiser to provide propulsion energy
Xe
F F F and working substance e.g., Solid acrylic rubber and
F liquid N 2 O 4 .
(See-Saw Shape)

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JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

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JEE MAIN AND Advanced EXAM PATTERN

JEE Advanced Exam Pattern

JEE Advanced Exam Pattern - Paper II

An Analysis of the IIT-JEE

Class Physics Chemistry Math Total

Questions Toughness Level Percentage wise:

The problems and examinations in the chemistry

IIT-JEE Syllabus: Chemistry

Section-C: Organic Chemistry Alkynes: Acidic character; Addition of hydrogen,

Biological functions of nucleic acids. (Insoluble salts excluded).

18. Alkyl and Aryl Halides.......................................................................................................................... 167–178

2 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

7. Given that the abundances of isotopes 54Fe, 56Fe, and 57Fe,

4 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

[Co(NH 3 )5 SO 4 ]NO 3 + AgBr

[Co(NH3 )5 Br]Cl2 + BaSO4

6 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

Millimole of CH 3COOH remaining after adsorption  225 

⇒ Number of molecules of CH 3COOH adsorbed ∴ m moles of MnCl 2 = 1 mg of

1 MnCl2 = (55 + 71) = 126 mg

= 6.023 × 1014 × 1000 = 6.023 × 1017 27. Be n Al 2Si 6 O18

8 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

 3 N ×10−8 Silver atoms present in 10−12 m 2 .

10.5 31. Number of electron in one molecule of H 2 O is

10 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

Table: 2. 4 Bravais Lattices

+ n 2 b + n 3 c where a, b, c are primitives and n i are any Figure: 2.5

integers and a i are known as the primitive vectors which lie in nA

atoms/cell υ = volume occupied per cell, V = volume of β γ

Atomic Atoms London Noble Soft Poor

12 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

14 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

16 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

18 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

pressure. For example, dimethyl ether has greater vapour

20 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

22 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

24 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

Whitegelatinous ppt. Sodium meta

14. (b) Liquid solution = −11.387 kJ mol −1

26 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

PBº + (PAº − PBº )x A = 22.5  50 

28 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

 M 2 2  − Mv 2  proportional to its absolute temperature, i.e.,

Diatomic f = 5 (3 translatory and 2 rotatory e.g.: H 2 , O 2 etc. ) T2

30 Multiple Choice Questions

30 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

24.6 (Graph not to scale)

expands irreversibly against zero external pressure, as

32 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

X and Y are two volatile liquids with molar weights of 10 g

34 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

2RT 8RT 3RT 3 3RT

Pi Pi Pf Pf For Question Nos. 20 to 21

(b) Correct statement: As the start of reaction Q p < K p so T T

36 JEE-Main & Advanced Chapter-wise Solved Papers: Chemistry

unpaired electron/s are present or diamagnetic if all the π (2Px ) π (2Py )