Chemiostry Sem - 1

ENGINEERING CHEMISTRY
(CH 101 and CH 201)

For B.Tech, BE
As per New Revised Syllabus of MAKAUT
Dr. Pijus Kanti Khatua, M.Sc., Ph.D.

Associate Professor
Department of Applied Science
Haldia Institute of Technology
Haldia, West Bengal
Dr. Dipankar Pramanik, M.Sc., Ph.D.

Assistant Professor
Department of Chemistry
Haldia Govt. College
Haldia, West Bengal
Formerly: Assistant Professor
Deparatment of Applied Sciences
Haldia Institute of Technology
Haldia, West Bengal
2
i
Preface
Purpose and Structure of the Book
This book provides a comprehensive, thorough, and up-to-date application of Theory
Book on CHEMISTRY -I(CH-101 and CH-201) as per WBUT. Endeavour has
made to cover the syllabus exhaustively and present the subject matter in a systematic
and lucid manner. More than 100 Short and long answer type questions have been
incorporated in the text book for better understanding of the students and better
representation during examination. Most of the question has been taken from both
theory and practical related partWBUT, which should take students familiar with
the standard and trend of questions set in the examinations.
General Features of the Book Include:
• Simplicity of presentation of experiments
In teaching-learning process to make the book easily teachable and readiblewhy
choose complicated examples when simple ones are as instructive or even better
• Independence of parts and blocks of chapters

to provide flexibility in tailoring courses to specific needs.
• Self-contained presentation
All formula, structures, grafics, figures are placed where it is exactly needed
would exceed the level of the book and a reference is given instead.
• Contain huge number of question answer

To ensure an enjoyable teaching and learning huge number of question and
answer has included that will help not only for knowledge gathering as well as
for getting idea about the subject also.
Furthermore, we designed the book to be a single, self-contained, authoritative,

and convenient source for studying and teaching engineering chemistry, eliminating
the need for time-consuming searches on the Internet or time-consuming trips to the
library to get a particular reference book.
In written this book we have taken help from several books in the bibliography. So,
we acknowledge them gratefully.
We express our sincerest gratitude and special thanks to our dear colleague Mr. Anu-
pam De, Assistant Professor of Mathematics, Haldia Institute of Technology for his
constant support during writing this book.
We express our sincerest gratitude to our Prof. S.C. Bhattacharya, Jadavpur Univer-
sity, Prof. Pratik Sen, Jadavpur University, Dr. Dipak kumar Jana, Haldia Institute
ii
of Technology for their constant encouragement.
We also thank our collogues: Dr.Sibaprasad Maity, Dr.Gora Das, Dr. Suparna Rana,
Dr. Diptangshu Chakraborty, Dr. Santanu Mishra, Dr. Rajib Kumar Dubey, Dr.
Soumitra Kar and Dr. Rajesh Das for their constant co-operation.
Finally we are thankful to our own family members for their constant inspiration and
support.
We will appreciate any constructive criticisms for the improvement of the book from
the experts as well as the from the learners.
We thank the ....... Publishers ......... for their sincere care in the publication of the
book.
P. K. Khatua
[email protected]
D. Pramanik
[email protected]
iii
Syllabus
Book on Engineering Chemistry
For CH-101(ICE, AEIE, EE, ECE)
and CH-201(ME, PE, CHE, CE, CSE, ITE, BTE FTE)
CONTENTS
Topic:
MODULE 1
1. Chemical Thermodynamics -I, Chemical Thermodynamics -II, Thermochem-
istry
Concept of thermodynamic system: definition with example of diathermal wall, adiabatic
wall, isolated system, closed system, open system, extensive property, intensive property.
Introduction to first law of thermodynamics: different statements, mathematical form. In-
ternal energy: definition, Example, characteristics, physical significance, mathematical ex-
pression for change in internal energy, expression for change in internal energy for ideal
gas. Enthalpy: definition, characteristics, physical significance, mathematical expression
for change in enthalpy, expression for change in enthalpy for ideal gas. Heat capacity: def-
inition, classification of heat capacity (Cp and Cv ): Definition and general expression of
Cp − Cv . Expression of Cp − Cv for ideal gas. Reversible and irreversible processes:
definition, work done in isothermal reversible and isothermal irreversible process for ideal
gas, adiabatic changes: work done in adiabatic process, interrelation between thermody-
namic parameters (P, V and T), slope of P-V curve in adiabatic and isothermal process.
Application of first law of thermodynamics to chemical processes: exothermic, endothermic
processes, law of Lavoisier and Laplace, Hess’s law of constant heat summation, Kirchoff’s
law. 2nd law of thermodynamics: Statement, mathematical form of 2nd law of thermo-
dynamics (Carnot cycle). Joule Thomson effect and throttling processes; Joule Thomson
coefficient for ideal gas, concept of inversion temperature. evaluation of entropy: charac-
teristics and expression, entropy change in irreversible cyclic process, entropy change for
irreversible isothermal expansion of an ideal gas, entropy change of a mixture of gases.
Work function and free energy: definition, characteristics, physical significance, mathemat-
ical expression of ∆A and ∆G for ideal gas, Maxwell’s expression (only the derivation of
4 different forms), Gibbs Helmholtz equation. Condition of spontaneity and equilibrium
reaction.
MODULE 2
2. Reaction Dynamics
Reaction laws: rate and order; molecularity; zero, first and second order kinetics. Pseu-
dounimolecular reaction, Arrhenius equation. Mechanism and theories of reaction rates
iv
(transition state theory, collison theory: ). Catalysis: homogeneous catalysis (definition,

example, mechanism, kinetics) and heterogeneous catalysis(definition, example, mechanism,
kinetics).
3. Solid state Chemistry
Introduction to stoichiometric defects (Schottky and Frenkel) and non - stoichiometric de-
fects (Metal excess and metal deficiency). Role of silicon and germanium in the field of
semiconductor.
MODULE 3
4. Electrochemistry, Electrochemical cell
Conductance, conductance of electrolytic solutions, specific conductance, equivalent con-
ductance, molar conductance and ion conductance, effect of temperature and concentration
(strong and weak electrolyte). Kohlrausch’s law of independent migration of ions, trans-
port numbers and hydration of ions. Conductometric titrations: SA vs SB and SA vs WB;
precipitation titration KCl vs AgNO3 .
Electrochemical cell: cell EMF and thermodynamic derivation of the EMF of a Galvanic cell
(Nernst equation), single electrode potentials, hydrogen half cell, quinhydrone half cell and
calomel half cell (construction, representation, cell reaction, expression of potential, discus-
sion, application). Cell: Primary and secondary cell, storage cell, fuel cell (construction,
representation, cell reaction, expression of potential, discussion, application). Application of
EMF measurement on (a) Ascertain the change in thermodynamic function (∆G, ∆H, ∆S)
(b) ascertain the equilibrium constant of a reversible chemical reaction (c) ascertain the
valency of an ion.
MODULE 4
5. Structure and reactivity of organic molecule
Electronegativity, electron affinity, hybridisation, inductive effect, resonance, hyperconju-
gation, electromeric effect, carbocation, carbanion and free radicals. Brief study of some
addition, eliminations and substitution reactions.
6. Polymerization
Concepts, classifications and industrial applications. Polymer molecular weight (number av-
erage, weight average. viscosity average: Theory and mathematical expression only), Poly
dispersity index (PDI). Polymerization processes (addition and condensation polymeriza-
tion), degree of polymerization, copolymerization, stereo-regularity of polymer, crystallinity
(concept of Tm ) and amorphicity (Concept of Tg ) of polymer. Preparation, structure and
use of some common polymers: plastic (PE: HDPE, LDPE, LLDPE, UHMWPE)), rubber
(natural rubber, SBR, NBR), fibre(nylon 6.6). Vulcanization. Conducting, semi-conducting
polymers and doping.
MODULE 5
7. Industrial Chemistry
Fuel: Primary and secondary fuel, Calorific value of fuels, HCV or GCV and LCV or
v
NCV and their relations, characteristics of fuel. Solid Fuel: Coal, classification of coal,
constituents of coal, carbonization of coal (HTC and LTC), coal analysis: proximate and
ultimate analysis. Liquid fuel: petroleum, classification of petroleum, refining, petroleum
distillation, thermal cracking, octane number, cetane number, aviation fuel (aviation gaso-
line, jet gasoline), bio-diesel. gaseous fuels: natural gas, water gas, coal gas, semi water
gas,bio gas.
MODULE 6
8. Some common and important question and answer
9. Important charts and tables
10. Some important picture of equipments/aperatus
11. References
12. Appendix
vi
Contents
1 THERMODYNAMICS 3
1.1 First law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1 Concept of thermodynamic system . . . . . . . . . . . . . . . . . . . 3
1.1.2 Type of system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.3 Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.4 Steady state and equilibrium . . . . . . . . . . . . . . . . . . . . . . 7
1.1.5 State of a system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.1.6 Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.1.7 Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.1.8 Reversible and irreversible process . . . . . . . . . . . . . . . . . . . 11
1.1.9 First law of thermodynamics . . . . . . . . . . . . . . . . . . . . . . 21
1.1.10 Internal Energy (E/U) . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.1.11 Enthalpy or Heat content (H) . . . . . . . . . . . . . . . . . . . . . . 22
1.1.12 Joule’s Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.1.13 Heat capacity of gases . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.1.14 Value of CP − CV . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.1.15 Joule-Thomson effect . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.1.16 Adiabatic relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.2 Second law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.2.1 Carnot’s Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.2.2 Refrigeration cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1.2.3 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1.2.4 Calculation of entropy change of a system surrounding and universe
during some process . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
1.2.5 Entropy and available work: . . . . . . . . . . . . . . . . . . . . . . . 45
1.2.6 Work function(free energy; Helmholtz’s free energy)[F or A] . . . . . 47
1.2.7 Work function(free energy; Gibb’s free energy; Gibb’s potential; ther-
modynamic potential)[G] . . . . . . . . . . . . . . . . . . . . . . . . 48
1.2.8 TdS relations: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
1.2.9 Gibbs-Helmholtz’s equation: . . . . . . . . . . . . . . . . . . . . . . . 50
1.2.10 Equilibrium and spontaneity from the stand point of ’S’ and ’G’: . . 52
1.2.11 Maxwell relation: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
vii
viii CONTENTS
1.3 Thermochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
1.3.1 Concept of thermochemistry . . . . . . . . . . . . . . . . . . . . . . 58
1.3.2 Heat of reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
1.3.3 Type of reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
1.3.4 Heat of formation(∆Hf ) . . . . . . . . . . . . . . . . . . . . . . . . . 59
1.3.5 Heat of Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
1.3.6 Heat of neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . 60
1.3.7 Heat of Solution (or Dilution) . . . . . . . . . . . . . . . . . . . . . . 61
1.3.8 Integral heat of solution . . . . . . . . . . . . . . . . . . . . . . . . . 61
1.3.9 Laws of Thermochemistry . . . . . . . . . . . . . . . . . . . . . . . . 61
1.3.10 Kirchhoff’s equation . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
1.4 Numerical Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
1.4.1 Example solved question . . . . . . . . . . . . . . . . . . . . . . . . . 63
1.4.2 Objective type question . . . . . . . . . . . . . . . . . . . . . . . . . 70
1.4.3 Short answer type question . . . . . . . . . . . . . . . . . . . . . . . 73
1.4.4 Long answer type question . . . . . . . . . . . . . . . . . . . . . . . 74
2 CHEMICAL KINETICS 77
2.1 Concept of chemical kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2.2 On the basis of speed chemical reactions are three types- . . . . . . . . . . . 77
2.3 Chemical reaction are mainly two types- . . . . . . . . . . . . . . . . . . . . 78
2.4 Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.4.1 Unit of rate of a reaction: . . . . . . . . . . . . . . . . . . . . . . . . 80
2.4.2 The rate of a chemical reaction depends upon this following factors- 80
2.5 Relation of rate with stoichiometry . . . . . . . . . . . . . . . . . . . . . . . 80
2.6 Rate Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.6.1 Calculation of instantaneous rate of a reaction . . . . . . . . . . . . 81
2.6.2 Calculation of average rate of a reaction . . . . . . . . . . . . . . . . 82
2.6.3 Law of mass action : . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.6.4 Order and molecularity of chemical reaction . . . . . . . . . . . . . . 83
2.6.5 Difference between order and molecularity . . . . . . . . . . . . . . . 84
2.7 Rate laws of zero, first and second order reactions . . . . . . . . . . . . . . 85
2.7.1 Zero order reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2.7.2 (A) First order reaction . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.7.3 (A) Second order reaction (initial species are same) . . . . . . . . . . 90
2.8 Pseudo-Unimolecular Reaction or Pseudo-first order Reaction . . . . . . . . 93
2.9 Effect of temperature on reaction rate . . . . . . . . . . . . . . . . . . . . . 93
2.10 Activation Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2.11 Mechanism of Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2.11.1 Postulates of Collision theory . . . . . . . . . . . . . . . . . . . . . . 95
2.11.2 Postulates of transition state theory . . . . . . . . . . . . . . . . . . 96
2.12 Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
CONTENTS ix
2.12.1 Theory of catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

2.13.3 Short answer type question . . . . . . . . . . . . . . . . . . . . . . . 110
2.13.4 Long answer type question . . . . . . . . . . . . . . . . . . . . . . . 111
3 SOLID STATE CHEMISTRY 113

3.1 Concept of solid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
3.2 Defects or imperfection in crystalline solid . . . . . . . . . . . . . . . . . . . 114
3.2.1 Atomic imperfections or Point defect . . . . . . . . . . . . . . . . . . 114
3.3 Impurity Defect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
3.4 Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
3.5 Semiconductor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
3.5.1 Intrinsic Semiconductor . . . . . . . . . . . . . . . . . . . . . . . . . 128
3.5.2 Extrinsic semiconductor due to added impurities . . . . . . . . . . . 129
3.6 Types of semiconductor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
3.7 Numerical Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
3.7.2 Short type question . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
3.7.3 Long type question . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
4 ELECTROCHEMISTRY 135
4.1 Concept of electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
4.2 Conductance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
4.2.1 Specific conductance . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
4.2.2 Equivalent conductance . . . . . . . . . . . . . . . . . . . . . . . . . 136
4.2.3 Molar conductance . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
4.3 Effect of temperature on equivalent conductance . . . . . . . . . . . . . . . 138
4.4 Effect of concentration on equivalent conductance . . . . . . . . . . . . . . . 139
4.5 Transport number and Ionic conductance . . . . . . . . . . . . . . . . . . . 141
4.6 Mobility of H+ and OH− ions in aqueous solution . . . . . . . . . . . . . . . 142
4.7 Kohlrausch’s law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
4.8 Conductometric titration . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
4.8.1 Titration of a strong acid and strong base . . . . . . . . . . . . . . . 144
4.8.2 Titration of a weak acid and strong base . . . . . . . . . . . . . . . . 145
4.8.3 Titration of a strong acid and weak base . . . . . . . . . . . . . . . . 146
4.8.4 Titration of a weak acid and weak base . . . . . . . . . . . . . . . . 147
4.8.5 Precipitation titration of KCl with AgNO3 . . . . . . . . . . . . . . 148
4.9 Electrochemical cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
4.10 Redox reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
4.10.1 Salt bridge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
4.11 General way to represent an electrochemical cell . . . . . . . . . . . . . . . 152
x CONTENTS
4.12 EMF of Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

4.13 Nernst equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
4.14 Single Electrode Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
4.15 Standard half cell reduction potential . . . . . . . . . . . . . . . . . . . . . 155
4.16 Application of Nernst Equation . . . . . . . . . . . . . . . . . . . . . . . . . 156
4.16.1 Measure of pH of a solution by using hydrogen electrode and standard
hydrogen electrode: . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
4.16.2 Determination of valency of an ion which have tendency to reduced
to pure metal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
4.17 Quinhydrone electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.18 Lead Acid storage Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
4.19 Fuel cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
4.20 Determination solubility product of a sparingly soluble salt . . . . . . . . . 161
4.21 Determination of equilibrium constant . . . . . . . . . . . . . . . . . . . . . 162
4.22.3 Short Answer type question . . . . . . . . . . . . . . . . . . . . . . . 171
5 STRUCTURE AND REACTIVITY OF ORGANIC MOLECULES 177

5.1 Electronegativity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
5.2 Inductive effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
5.3 Hyperconjugation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
5.4 Conjugation, Mesomeric effect, Resonance and Aromaticity . . . . . . . . . 179
5.5 Carbocation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
5.6 Carbanion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
5.7 Dipole moment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
5.8 Strength of organic acid base . . . . . . . . . . . . . . . . . . . . . . . . . . 184
5.9 Basicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
5.10 Nucleophilic substitution reaction . . . . . . . . . . . . . . . . . . . . . . . . 190
5.11 SN 1 reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
5.12 SN2 reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
5.13 Elimination reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
5.13.1 1,2-Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
5.13.2 E2 Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
5.14 Aromatic electrophilic substitution . . . . . . . . . . . . . . . . . . . . . . . 196
5.15 Addition Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
5.16.2 Short type question . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
CONTENTS xi
6 POLYMER CHEMISTRY 203

6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
6.2 Monomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
6.3 Degree of polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
6.4 Classification of polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
6.4.1 Classification on the basis of origin . . . . . . . . . . . . . . . . . . . 204
6.4.2 Classification on the basis of used monomer . . . . . . . . . . . . . . 205
6.4.3 Classification on the basis of copolymer structure: . . . . . . . . . . 205
6.4.4 Classification on the basis of chain Growth . . . . . . . . . . . . . . 207
6.4.5 Classification on the basis of mode of polymeric growth . . . . . . . 208
6.4.6 Classification on the basis of tactility . . . . . . . . . . . . . . . . . . 211
6.4.7 Classification on the basis of molecular force . . . . . . . . . . . . . 212
6.5 Preparation of some thermoplastic polymer . . . . . . . . . . . . . . . . . . 213
6.5.1 Low density polythene (LDPE) . . . . . . . . . . . . . . . . . . . . . 213
6.5.2 High density Polythene(HDPE) . . . . . . . . . . . . . . . . . . . . . 214
6.5.3 Linear low density Polythene (LLDPE) . . . . . . . . . . . . . . . . 215
6.5.4 Ultrahigh molecular weight polythene (UHMWPE) . . . . . . . . . . 216
6.5.5 Polyvinyl chloride(PVC) . . . . . . . . . . . . . . . . . . . . . . . . . 216
6.6 Thermosetting plastic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
6.6.1 Phenol-formaldehyde resin . . . . . . . . . . . . . . . . . . . . . . . . 217
6.6.2 Novoloc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
6.6.3 Resol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
6.7 Plasticizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
6.8 Addition polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
6.8.1 Mechanism of addition polymerization . . . . . . . . . . . . . . . . . 220
6.9 Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
6.10 Synthetic rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
6.10.1 Styrene butadiene rubber(SBR) . . . . . . . . . . . . . . . . . . . . . 227
6.10.2 Nitrile rubber (NBR or GR-A or Buna-N) . . . . . . . . . . . . . . . 228
6.10.3 Neoprene rubber(GR-A) . . . . . . . . . . . . . . . . . . . . . . . . . 229
6.11 Biodegradable polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
6.12 Monodisperse and polydisperse polymer . . . . . . . . . . . . . . . . . . . . 231
6.13 Molecular weight of polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
6.13.1 Number average molecular weight . . . . . . . . . . . . . . . . . . . 231
6.13.2 Weight average molecular weight . . . . . . . . . . . . . . . . . . . . 231
6.13.3 Viscosity average molecular weight . . . . . . . . . . . . . . . . . . . 233
6.14 Degree of polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
6.15 Polydisperse Index(PDI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
6.16 Glass transition temperature (TG ) . . . . . . . . . . . . . . . . . . . . . . . 234
6.17 Crystallization temperature(TC ) . . . . . . . . . . . . . . . . . . . . . . . . 235
6.18 Melting temperature(TM ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
6.19 Crystalline, semicrystalline and amorphous polymer . . . . . . . . . . . . . 237
xii CONTENTS
6.19.1 Crystalline polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . 238

6.19.2 Semi-crystalline polymer . . . . . . . . . . . . . . . . . . . . . . . . . 238
6.19.3 Amorphous polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
6.20 Degree of crystallinity: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
6.21 Conducting polymer: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
6.21.1 Semiconductor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
6.21.2 Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
6.22.2 Short Answer question . . . . . . . . . . . . . . . . . . . . . . . . . . 248
6.22.3 Long Answer question . . . . . . . . . . . . . . . . . . . . . . . . . . 249
7 INDUSTRIAL CHEMISTRY: FUEL 251

7.1 Fuel and its classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
7.1.1 Fuels can be classified in two different class depending upon the oc-
currence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
7.1.2 Fuels can be classified in three different class depending upon the
physical state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
7.2 Calorific value of fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
7.2.1 Gross calorific value or higher calorific value (GCV or HCV) . . . . 252
7.2.2 Net calorific value or lower calorific value (NCV or LCV) . . . . . . 252
7.2.3 Net calorific value or lower calorific value (NCV or LCV)with respect
to the constituents in fuel . . . . . . . . . . . . . . . . . . . . . . . . 253
7.3 Characteristics of good fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
7.4 Solid Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
7.4.1 Wood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
7.4.2 Coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
7.4.3 Analysis of coal: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
7.4.4 Proximate analysis: . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
7.4.5 Ultimate Analysis: . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
7.4.6 Carbonization of coal . . . . . . . . . . . . . . . . . . . . . . . . . . 258
7.4.7 High temperature carbonization . . . . . . . . . . . . . . . . . . . . 258
7.4.8 Low temperature carbonization . . . . . . . . . . . . . . . . . . . . . 258
7.5 Liquid Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
7.5.1 Refining of Crude Petroleum . . . . . . . . . . . . . . . . . . . . . . 259
7.6 Petrol or Gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
7.6.1 Knocking and Antiknocking . . . . . . . . . . . . . . . . . . . . . . . 260
7.6.2 Octane number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
7.6.3 Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
7.6.4 Reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
7.7 Knocking in diesel engine . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
7.7.1 Cetane number in Diesel . . . . . . . . . . . . . . . . . . . . . . . . . 262
CONTENTS xiii
7.7.2 A good petrol engine fuel is a bad fuel for diesel engine and vice versa 263
7.8 Aviation Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
7.8.1 Av gas or Aviation gasoline . . . . . . . . . . . . . . . . . . . . . . . 263
7.8.2 Jet fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
7.9 Power Alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
7.10 Bio-diesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
7.10.1 Flash point and ignition temperature . . . . . . . . . . . . . . . . . . 264
7.11 Gaseous Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
7.11.1 Natural gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
7.11.2 Compressed natural gas . . . . . . . . . . . . . . . . . . . . . . . . . 265
7.11.3 Liquified Petroleum Gas . . . . . . . . . . . . . . . . . . . . . . . . . 266
7.12 Synthetic Gaseous Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
7.12.1 Water gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
7.12.2 Producer gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
7.12.3 Coal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
7.12.4 Semi water gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
7.12.5 Carburatted water gas . . . . . . . . . . . . . . . . . . . . . . . . . . 267
7.12.6 Bio gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
7.13.2 Short Answer type question . . . . . . . . . . . . . . . . . . . . . . . 269
7.13.3 Long Answer type question . . . . . . . . . . . . . . . . . . . . . . . 270
xiv CONTENTS
MODULE-I
2 CONTENTS
Chapter 1
THERMODYNAMICS
1.1 First law of Thermodynamics

1.1.1 Concept of thermodynamic system
Thermodynamics: Behind all natural occurring phenomenon starting from eruption of
volcano to earthquake to fountain of a waterfall everywhere in this universe a rule of nature
is being maintained which is unseen in naked eyes. A harmony is maintained throughout
behind all these natural phenomenon. From ancient time human mind tried to offering
explanation behind all these facts and thus with time it is established that all these macro-
scopic phenomenon occurs due to interaction of energy with mass in different mode. Matter
interact with energy in different interconvertible form. This inter-conversion of energy from
one form to another have given birth the concept of thermodynamics. Thermodynamics is
that part of science where we will study the dynamic nature of heat energy. Basically in
thermodynamics we will study the properties of a system at equilibrium not in progress.
Although thermodynamics deals with the inter-conversion of different forms of energy but
mainly it correlates between heat energy and work. Although initial concept of thermo-
dynamics was discovered by Count Ramford but later James Prescott Joule deduced the
relation between work and heat.
Definition: Thermodynamics deals with the inter-conversion of various forms of energy
and also inter conversion of energy and work. It correct name should be energetic.
Scope: Thermodynamical formulations are generally valid in macro-world which says that
in thermodynamics we can study the heat transfer to melt few grams of ice not few molecules
of ice. Laws of thermodynamics can be applicable in ionic equilibrium, homogenous or het-
erogenous equilibrium, electrochemistry, surface tension, metallurgy etc. Energy calculation
in micro-world is generally done by quantum mechanics.
Axiom: Thermodynamics is an axiomatic science, the three laws are the result of human
experience. Some definition connecting thermodynamics are-
System: In our daily life we very often discuss about different things that may be real or
3
4 CHAPTER 1. THERMODYNAMICS
imaginary. The subject of any discussion is the system. So, any part of the universe which
is the subject matter of our studies is called a system. It may be the whole universe or any
small part of it.
Surrounding: Everything except the system of the universe is called surrounding. But
in thermodynamic sense surrounding is the area upto which the influence of the system
reaches. If any light is the system then theoretically the whole universe apart from the light
should be the surrounding but in thermodynamic sense the area upto which the light can
illuminate is the surrounding.
Universe: System + Surrounding = Universe
Let us see an example: a ice cube is added into a beaker of water; the ice will melt after
sometime. Here if we discuss about the melting of ice then the ice cube is the system and
the water of the beaker is the surrounding. On the other hand if take a few ice cube in a
small glass beaker and the beaker is placed inside a large beaker contain some amount of
water. In this case a same thing will happen; the ice cubes in the small beaker will melt
and the temperature of the water in the large beaker will decrease. Now if our discussion
is the cooling of the water in large beaker then it is the system and the ice cube in other
beaker is the surrounding. So, depending upon the interest or our aim of the experiment
the concept of system and surrounding may be reversed.
Wall: The imaginary or real partition between system and surrounding is called wall. If
the wall can pass energy (heat) through it then, it is called diathermal wall. If exchange of
heat is prohibited through it then, it is called adiabatic wall.
1.1.2 Type of system

There are three types of system- 1) Open system 2) Closed system 3) Isolated system
1) Open system: If a system exchanges both mass and energy with surrounding then
the system is called call open system. Example: Boiling of water in a open metal vessel;
any living system including human body is a best example of open system. Our body can
exchange both energy and mass with the nature and hence it is a open system.
Open system
1.1. FIRST LAW OF THERMODYNAMICS 5
2) Closed system: If a system exchanges only energy not the mass with surrounding then
the system is called closed system. Example: Boiling of water in a close metal vessel. There
must be a diathermic wall which basically separates the closed system with the surrounding.
So, diathermic wall and close system is complementary by concept.
Closed system
3) Isolated system: If neither mass nor energy of a system can not exchanged with sur-
rounding then it is called isolated system. Example: boiling of water taken in a thermoflask.
So, there must be an adiabatic wall associated with isolated system. Perfect isolated system
and hence perfect adiabatic wall is an abstract concept.
Isolated system
1.1.3 Process
When some energy change takes place in a system we say a process has occurred.
A) If during the process temperature of a system remains unchanged then, the process is
called isothermal process. Here, dT = 0. Boiling of water at 1 atm. pressure occurs at
constant temperature 100o C and hence it is isothermal process. The most important point
of isothermal process is that as the temperature of the system is constant and hence there
must be an exact and equivalent amount of energy flow between system and surrounding
that any process can be occur at system. So, the systems own energy which is called internal
energy will be unchanged.
B) If during the process there is no flow of heat energy between system and surrounding
then the process is called adiabatic process. Here, dQ = 0. So, in this scenario for the
process to occur the systems own energy will be changed and hence the temperature of the
system will change.
For a multi step process, each small step must be adiabatic for the entire process to be
defined as adiabatic. This means that each small step must not exchange heat energy with
the surrounding. The total heat change of a multi step process might be zero by absorbing
some heat in one step and releasing equivalent amount of heat in another step. But this is
not a adiabatic process as a whole.
In a adiabatic process, the presence of a diathermic wall is not always necessary; sometimes
a open/closed system may provide an adiabatic process. Sudden lowering of pressure of a
gas is associated with fall of temperature of the gas. This process happens so fast that the
gas molecule do not get a chance to absorb heat from the surrounding and hence it absorb
its own heat energy and so the temperature fall.
C) If during the process pressure of a system remains unchanged with surrounding, then
the process is isobaric process. Here, dP = 0.
D) If during the process volume of a system remains unchanged with surrounding, then
the process is isochoric process. Here, dV = 0.
E) If during the process initial and final state of a system is same or remain unchanged
with surrounding
H then, the
H process is cyclic process.
Here, dU = 0. So, dQ = W. In an isothermal process also dQ = W. However, in
isothermal process state changes from (P1 , V1 , T1 ) to (P2 , V2 , T2 ) and in a cyclic process
state remain unchanged. Also in isothermal process W 6= 0 but in cyclic process W may
or may not to be zero depending on whether forward and backward path is same or not.
Intensive and extensive properties: In classical thermodynamics we deal with only
the macroscopic properties of a sytem which include vlume, temperature, pressure, surface
tension, pH, conductance, heat capacity etc. These properties of a system can be devided
in two category: Properties which are independent of amount or mass are called intensive
properties. These are point properties and same at each point of the system and dependent
only on nature of substance. e.g. pressure of a gas,temperature, refractive index, dipole
moment, density etc.
Properties which are dependent on amount or mass are called extensive properties. These
are additive properties and obtained by summing individual point values of the system and
independent on nature of substance. e.g. mass, volume, any form of energy( internal energy,
enthalpy entropy) etc.
Ratio of two extensive properties is always an intensive property. To define a system, we
need both extensive and intensive properties.
1.1.4 Steady state and equilibrium

The terminology steady state and equilibrium are very close but they are quite different in
thermodynamic sense.
i) When a system is in thermal equilibrium, then if we isolate the system from the sur-
rounding then the system restore the equilibrium condition. If the system was in steady
state then after detachment from the surrounding the steady state condition of the system
will be disturbed.
ii) At equilibrium, there is no net driving force acts in the system and hence magnitude of
all properties at equilibrium of the system remain constant. But in steady state there is a
net driving force acting in a particular direction. A definite amount of water in a beaker
having constant mass, temperature, volume etc. are said to be a equilibrium condition; and
hence if the beaker is isolated from the surrounding all properties of the water will remain
same.
On the other hand, say in a beaker some water is flowing to the beaker and in same rate
some water is being going out. This is called steady state condition because if any source
is closed; may the incoming or outgoing; the amount of water will change. So it is a steady
state condition.
1.1.5 State of a system

States of a system are those variables by which energy of a system can be known. For a
real gas in an open system n, P, V and T are states. If it is a closed system then P, V and
T are states. Out of these three states any two can be taken as independent and the rest
becomes dependent.
State function: State functions are those which depend only on initial and final states
are independent of path or previous history. Energy is a state function. Potential energy of
body of mass (m) at a height (h) will be mgh. It does not matter how the body is placed
at that particular height. So potential energy is a state function. Volume, viscosity-co-
efficient, surface tension, vapour pressure, internal energy, enthalpy etc. are state function.
On the other hand those functions have a dependency on path, are called path function.
Heat, work(reversible work is more than irreversible work), heat capacity etc. are path
function.
Mathematical aspect of state function: If, x= f(y), then the rate of change of x with
respect to change of y is represented as δδx
y and is called derivative of x with respect to y.
If z is a property of a system and the value of z is dependent on other state parameter x
and y then, z will be represented as z = f(x,y); and any change of either x or y or both will
change the magnitude of z.

The function z = f(x,y) will be a state function if-
i) z is a single valued function of x and y.
ii) z must
R z be an exact differential and for any change in state,
∆z = zif dz; where zf is the final value of z and zi is the initial value of z.
H
iii) For a cyclic process, the overall change of z will be zero; dz = 0.
iv) The second order differential of z with respect to x and y will be independent of order
differentiation.
δz δz
δz = ( )y δx + ( )x δy
δx δy
δ2z 2
δ z
=
δxδy δyδx
For ideal gas- PV = nRT
nRT
Or, V =
P
δV R
( ) =
δT P P
δ2V R
= − 2
δPδT P
δV RT
Similarly, ( )T = − 2
δP P
δ2V R
= − 2
δTδP P
δ2V δ2V
Hence, =
δPδT δTδP
So, V is a state function and V = f(P,T).

Perfect differential:
Perfect differential
1.1.6 Energy
Energy is something which creates changes in a system when it enters into a system or leaves
the system. Among all forms of energy heat energy has a very unique or peculiar quality.
Any changes created by other energy are purely temporary but any changes created by heat
energy are permanent. It causes a distortion in shape of the system. During conversion of
heat to work the medium expands and so some heat is lost inducing unwanted work. Total
energy of a system is the sum of kinetic energy (Ek ), potential energy (Ep ) and internal
energy (U). When kinetic energy and potential energy are constant then change in total
energy is equal to the change in internal energy. Internal energy is a state function and it
is extensive property. U = f(P,T) or, U = f(V,T) or U = f(P,V).
1.1.7 Work
If any force acts on a system and the manifestation of the acting force is observable in the
surrounding then the effect of the acting force is defined as work. When the leaves of tree
is stand still then it is considered that air pressure is not doing any work; but when there
is undulation of the leaves we say that the air is blowing and some work is done by the air.
So here manifestation of wind is the undulation of leaves. Similarly falling of apple was the
manifestation of gravitational force. Any work is the products of two terms -
i) Intensity factor (I.F. means - amount of opposition) and
ii) Capacity factor (C.F. means - extent by which opposition is overcome).
Some example:
Sl. No. Type of work I.F. C.F. I.F. × C.F.

1. Passage of electricity E Q EQ
Q Coulomb against Volt Coulomb
potential difference or
of E Volt EQ Joule
2. Falling a body of wt. mg h mgh
mg (mass m under
gravitational force g)
through a height h
3. Expansion of a gas (V2 − V1 ) Pext. Pext. (V2 − V1 )
from V1 to V2 against
external pressure Pext.
Depending upon the movement of the boundary work is two type-

i) Internal work
ii) External work
i) Internal work: During expansion of gas, melting of solids molecules separated one from
another by breaking different types interatomic and intermolecular forces. Here although
we can’t see the displacement but some work must be associated here. This type of work
is called internal work.
ii) External work: In thermodynamics we deal with external work mainly where manifesta-
tion of applied force is visible.
a) Work is not a property of any system; it is not present anytime in the system: it involve
only during the change of system through the displacement of boundary.
b) Work is a path function.
c) When the displacement occurs in the direction opposite to the direction of applied force,
then work is said to be done by the system and is given a negative (-Ve) sign and similarly
When the displacement occurs in the same direction of the applied force, then work is said
to be done on the system and is given a positive (+Ve) sign.
d) When work is done either on the system or by the system in a adiabatic condition then
obviously the systems own internal energy will be changed.
Work (W) = Force x displacement of the boundary

= −Popp. × area × displacement
= −Popp. × change in volume
= −Popp. ∆V
So, general expression of work is W = −Popp. ∆V and for any infinitesimal volume change
dw = −Popp. δV = −Pext. dV (opposing pressure can be termed as external pressure).
Change of volume which is finite or infinitesimal (∆V or dV), always refers the difference
between final volume (V2 ) and initial volume (V1 ); ∆V or dV = (V2 - V1 ).
So, during expansion of an ideal gas, the final volume (V2 )is always greater than initial
volume (V1 ); and hence the volume change (V2 - V1 ) is positive and the work (W) is
negative (-Ve). Hence expansion means work is done by the system and it is always negative
sign by convention.
Similarly, during compression of an ideal gas, the final volume (V2 )is always less than
initial volume (V1 ); and hence the volume change (V2 - V1 ) is negative and the work (W)
is positive (+Ve). Hence compression means work is done on the system and it is always
positive sign by convention.
According to new convention the sign is associated with the change of system’s internal
energy. When gas expands or work is done by the system, then internal energy of the
system will decrease and hence a negative sign will be associated with work done by the
system. Similarly when gas compressed or work is done on the system, then internal energy
of the system will increase and hence a positive sign will be associated with work done on
the system.
Now, for a multistep process where volume changes from V1 to V2 to V3 to V4 ........ to
Vn , the total amount of work will be expressed by W = W1 + W2 + W3 + ...... + Wn .
Or, W = [−Pext .(V2 − V1 )] + [−P1ext .(V3 − V2 )] + [−P2ext .(V4 − V3 )] + ..... + [−Pn

ext .(Vn −
Vn−1 )]
1.1.8 Reversible and irreversible process
Reversible process Irreversible process
1. Difference between driving force and 1. Difference between driving force

opposing force is infinitesimally small and opposing force is very large
2. Process is slow 2. Process is quick
3. Intermediate steps are seen 3. Intermediate steps are not seen
4. Equilibrium established 4. Equilibrium does not established
5. Process is gradual 5. Process is sudden
6. Process occurs in both direction 6. Process occurs in one direction
Irreversible process: If during a process difference between driving force and opposing
force is very high then the process occurs in one direction. Such a process occurs very quick,
intermediate steps are not seen and the system is never in equilibrium. The process is called
IRREVERSIBLE process. Example: Expansion of a gas against some constant decreasing
pressure (external) is an example of irreversible process.
Work done in Irreversible process: Let one mole of an ideal gas is taken in a cylinder
fitted with a weightless and friction less piston. The initial state of the gas is P1 , V1 and T1 .
External pressure also P1 . Now pressure is lowered constantly to P2 and kept at P2 , the
gas will expand till its pressure becomes also P2 . Let volume changes from V1 to V2 .
Z V2
WIRREV. = −P2 dV
V1
= −P2 (V2 − V1 )
= −Pext. [Vf − Vi ]
This is the general and most common formula for any irreversible work.
Special case: A) If the process is isothermal and irreversible at the same time .
nRT
V2 =
P2
nRT
and V1 = ; (for n mole gas)
P1
Z V2
So, WIRREV.ISO. = −P2 dV
V1
= −P2 (V2 − V1 )
nRT nRT
= −P2 [ − ]
P2 P1
P2
= −nRT[1 − ]
P1
P2
= −RT[1 − ](for 1 mole ideal gas)
P1
B): If the process is irreversible and at the same time adiabatic.
nRT2
V2 =
P2
nRT1
and V1 = ; (for n mole gas)
P1
Z V2
So, WIRREV.ADIA. = −P2 dV
V1
= −P2 (V2 − V1 )
nRT2 nRT1
= −P2 [ − ]
P2 P1
P2 T1
= −nR[T2 − ]
P1
P2 T1
= −R[T2 − ](for 1 mole ideal gas)
P1
Reversible process: If during a process difference between driving force and opposing
force is infinitesimally then the process occurs in either direction. Such a process occurs
very slow, intermediate steps are seen and the system is in equilibrium. The process is called
REVERSIBLE process. Example: Expansion of a gas against some continuously decreasing
pressure (external) is an example of reversible process.
Work done in Reversible process: Let one mole of an ideal gas is taken in a cylinder
fitted with a weightless and friction less piston. The initial state of the gas is P1 , V1 and T1 .
External pressure also P1 . Now external pressure is lowered infinitesimally small to dP.
now, the pressure of the gas will be (P1 - dP) As a result volume of the gas is increased by
dV
So, here work done
= −(P1 − dP)dV
Again, external pressure is lowered infinitesimally to 2dP and now, the pressure of the gas
will be
= (P1 − 2dP)
As a result volume of the gas is increased by dV. So,
here, work done = −(P1 − 2dP)dV
In this way pressure is ultimately lower to P2 as a result volume increase to V2

This is a reversible process. Now total work done
WREV. = −(P1 − dP)dV + (−)(P1 − 2dP)dV + ........ + (−)P2 V2

PX
2 V2
= − PdV
P1 V1
Z V2
= − PdV
V1
This is the general and most common formula for any reversible work.
Special case: A) If the process is reversible and at the same time isothermal.
nRT
P =
V
Z V2
So, WREV.ISO. = − PdV
V1
Z V2
1
= −nRT dV
V1 V
V2
= −nRTln [As isothermal]
V1
P1
= −nRT
P2
Special case: B) If the process is reversible and at the same time adiabatic.
From 1st law of thermodynamics-
dQ = dU + WREV.ADIA.
Or, 0 = dU + WREV.ADIA.
Or, WREV.ADIA. = − dU
Or, WREV.ADIA. = − CV dT
Or, WREV.ADIA. = − CV (Tf − Ti )
Or, WREV.ADIA. = CV (Ti − Tf )
Comparison of reversible and irreversible work:
Single stage expansion: Isothermal expansion of a ideal gas from a initial stage P1 , V1
to P2 , V2 . Now if Pext < Pint , the piston can be stopped by a set of stoppers at any stage
and when Pext = Pint , the piston will stop automatically.
So, the magnitude of the work done by ideal gas undergoes isothermal expansion at a single
stage-
|W | = Pext (V2 − V1 )
= P2 (V2 − V1 )( after expansion final pressure P2 = external pressure)
= P2 V2 − P2 V1
Work done in REV. and IRREV. system

Two stage expansion: Let us consider an ideal gas expands isothermally from a initial
stage P1 , V1 . to a final stage P2 , V2 through an intermediate stage P, V. So we can rep-
resent the change of state (P1 , V1 )→ (P, V) → (P2 , V2 ). Hence the total amount of work
done by this two stage expansion-
|W | = P(V − V1 ) + P2 (V2 − V)
= PV + P2 V2 − PV1 − P2 V

Infinitesimal multistage stage expansion: Let us consider an ideal gas expands isother-
mally from a initial stage P1 , V1 to a final stage P2 , V2 through an infinitesimal small steps
and during this process before any single infinitesimal small expansion the internal pressure
is just greater than the external pressure after that infinitesimal step the internal pressure
will be equal to the external pressure. So at each step the pressure difference between in-
ternal and external will be minimum (∆P). So the total work is the summation of the small
small work done at each infinitesimal step and hence we can represent the total work done
in an integration form like-
Z V2
|W | = Pext .dV
V1
Now, Pext = Pint − ∆P
Z V2
Or, |W | = (Pint − ∆P).dV
V1
Z V2 Z V2
= (Pint .dV) − ∆P.dV
V1 V1
Z V2
= (Pint .dV)( ∆P & dV very small and their product will be negligible)
V1
Z V2
nRT
= .dV
V1 V
V2
= nRTln
V1

The infinitesimal small step process is called reversible process and in each small steps the
system equilibriate with surroundings. If any step fails to do that the entire process will
be termed as irreversible. In other word, if the steps of a multistep process can be counted
then it is irreversible and if it is uncountable then it is reversible.

So, the area under the graph represents the amount of work (P-V work)associated with the
corresponding process. If we compare the area of these graphs we can see that the magni-
tude of work increases as we increases the steps or work is done by the system in multiple
steps and reaches maximum at infinitesimal steps which is call reversible work. So during
expansion we can say that reversible work is greater than irreversible work.
Single stage compression: Isothermal compression of a ideal gas from a initial stage
P2 , V2 to P1 , V1 . Now if Pext > Pint , the piston can be stopped by a set of stoppers at
any stage and when Pext = Pint , the piston will stop automatically.
So the magnitude of the work done by ideal gas undergoes isothermal compression at a
single stage-
W = − Pext (V1 − V2 )
= P1 (V1 − V2 ) ( after expansion final pressure P1 = external pressure)
= −( P1 V1 + P1 V2 )

Two stage compression: Let us consider an ideal gas expands isothermally from a initial
stage P2 , V2 to a final stage P1 , V1 through an intermediate stage P, V. So we can represent
the change of state P2 , V2 → (P,V) → P1 , V1 . Hence the total amount of work done by
this two stage expansion-
W = − P(V − V2 ) − P1 (V1 − V)
= − PV + PV2 − P1 V1 + P1 V

Infinitesimal multistage stage compression: Similarly, during isothermal compression

by infinitesimal small steps from a initial stage P2 , V2 to a final stage P1 , V1 and during this
process before any single infinitesimal small compression the internal pressure is just less
than the external pressure after that infinitesimal step the internal pressure will be equal to
the external pressure. So at each step the pressure difference between internal and external
will be minimum (∆P). So the total work is the summation of the small small work done
at each infinitesimal step and hence we can represent the total work done in an integration
form like-
Z V1
W = − Pext .dV
V2
Now, Pext = Pint + ∆P
Z V1
Or, W = − (Pint + ∆P).dV
V2
Z V1 Z V1
= − (Pint .dV − ∆P.dV
V2 V2
Z V1
= − (Pint .dV)( ∆P & dV very small, their product will be negligible)
V2
Z V1
nRT
= − .dV
V2 V
V1
= − nRTln
V2

In case of compression the reverse phenomenon happens; work done is maximum in single
step compression and minimizes at infinitesimal steps. So during compression we can say
that irreversible work is greater than reversible work.
When we compare the magnitude of work between expansion and compression work, for
expansion work we will take a modulus value by ommiting the negative sign of the pressure;
but during compression as volume change is negative hence the work will automatically
be a positive value and hence no need to take modulus value. Total work in a isothermal
reversible expansion and compression is (initial and final state is same)-
Total work, W = Wexp. + Wcom.

V2 V1
= − nRTln − nRTln
V1 V2
V1 V1
= nRTln − nRTln
V2 V2
= 0
Hence, in a reversible process Wcycle = 0. Similarly in a irreversible process, if expan-

sion happens from P1 , V1 to P2 , V2 state and compression happens in reverse way, then
expansion and compression work can be written as-
Wexp. = − P2 (V2 − V1 )
Wcom. = − P1 (V1 − V2 )
Wtotal = Wexp. + Wcom.
= − P2 (V2 − V1 ) + (−)P1 (V1 − V2 )
= − P2 (V2 − V1 ) + P1 (V2 − V1 )
= (V2 − V1 )(P1 − P2 )
= + Ve value as V2 > V1 and P1 > P2
From this calculation it is clear that in a same cycle work done is zero if the cycle follow
reversibility but if it is irreversible we get some positive amount of work. So magnitude
of work is very much path dependent (reversible or irreversible) and hence work is a path
function.
Among reversible or irreversible work which work is more? explain:
A) Graphically
Let us consider, A PV Isothermal plot of a gas expands from isothermally and adiabatically
from P1 , V1 to P2 , V2 state. The graph is represented below.
Now, work done isothermally and irreversibly-
|WIRREV. ISO | = P2 (V2 − V1 )

= BC × CD
= Area BCDE
and work done isothermally and reversibly-
Z V2
|WREV. ISO | = PdV
V1
= Area ACDE
Now, difference between work done isothermally-reversibly and work done isothermally-
irreversibly-
|WREV. ISO | − |WIRREV. ISO |

= Area ACDE - Area BCDE
= Positive quantity
From the graphical representation, area of rectangleACDE > area of rectangleBCDE So,
|WREV.ISO | > |WIRREV.ISO |.
So, reversible work is greater than the irreversible work.
B) Mathematically:
If we consider the isothermal expansion work which is often termed as work done by the
system, then we can compare the reversible and irreversible work mathematically also. As
this is expansion work we will take a modulus value.

Z V2
|WIRREV.ISO | = P2 dV
V1
= P2 (V2 − V1 )
nRT nRT
= P2 [ − ]
P2 P1
P2
= nRT[1 − ]
P1
P1 − P2
= nRT[ ]
P1
Z V2
|WREV.ISO | = PdV
V1
Z V2
1
= nRT dV
V1 V
V2
= nRTln
V1
P1
= nRTln [As isothermal]
P2
P1 − P2
= nRTln(1 − ) ; [As we know ln(1 + X) = X]
P2
P1 − P2
= nRT( )
P2
Now,
|WREV.ISO | − |WIRREV.ISO |
P1 − P2 P1 − P2
= nRT[ ] − nRT[ ]
P2 P1
1 1
= nRT[P1 − P2 ][ − ]
P2 P1
(P1 − P2 )
= nRT(P1 − P2 )[ ]
P1 × P2
1
= nRT(P1 − P2 )2 [ ]
P1 × P2
= Positive quantity
So, from mathematical representation as well as from mathematical explanation the re-
versible work is greater than the irreversible work for isothermal expansion.
1.1.9 First law of thermodynamics

First law of thermodynamics correlates the relationship between heat and work. When some
work is done system exchanges heat energy with surroundings. When a system undergoes
a cyclic changes the sum of heat and work involve in the cycle is zero.
I I
dQ + dW = 0
I
(dQ + dW) = 0
Now, heat (Q) and work (W) is not a state function and hence their cyclic integral individ-
ually can not be zero.
Let,
I
dQ = Q
I
dW = W
So for a cyclic process, Q + W = 0
or, Q = − W
Any of the above equation can be stated as 1st law of thermodynamics. Which implies
that-
i) If Q is positive then W is negative; so if system absorbs heat then an equivalent amount
of work will be done by the system.
ii) On the other hand if q is negative then w is positive; so if some work is done on the
system then an equivalent amount of heat will be released by the system
H at surroundings.
iii) From 1st law the concept of internal energy can de defined. As, (dQ + dW) = 0 and
both heat and energy is not a state function but the cyclic integral of their summation is
zero, then the summation must represent a state function and which is internal energy (U).
So, dU = dQ + dW; and U = f(T, P); U = f(T, V) and U = f(V, P).
Law of conservation of energy: For an isolated system, both q and w is zero and hence,
∆U = 0, so change of internal energy of an isolated system is zero. This is called law of
conservation of energy. In other format this can be stated as-
i) Energy can neither be created nor be destroyed.
ii) When some forms of energy disappear, an exactly equivalent amount of energy of some
other form makes it appearances.
iii) Total energy of the universe is constant.
iv) Energy of an isolated system is constant.
Each of the above statement speaks about the conservation of energy that is why first law
of thermodynamics regarded as law of conservation of energy.
1.1.10 Internal Energy (E/U)

Every system poses a definite amount of energy by virtue of its position, structure and
internal motion. It can do work at the cost of this energy. It is a state function, perfect
differential and extensive properties. It is associated with change in volume.
From the 1st law of thermodynamics we have learned that-
dU = dQ + dW
Or, dU = dQ − P.dV
At constant volume dV = 0
Hence dU = dQV
When a system undergoes any change at constant volume, the heat involve in that process
is the change of its own internal energy.
1.1.11 Enthalpy or Heat content (H)

Enthalpy or heat content is the total energy content of a system by which it can perform
work. It is represented by H. It is associated with change in pressure. For solid and liquid
internal energy and enthalpy are same, i.e. H = U. In solid and liquid change in volume is
really negligible. But for gases
H = U + PV.
Like U, H is a state function, perfect differential and extensive properties. On differentiation-
dH = dU + PdV + VdP
At constant pressure, dHP = dU + PdV
From 1st law, dU = dQ + dW
Or, dU = dQ - P.dV as dW = - P.dV
Or, dU + PdV = dQ
Now, dHP = dQ
So, increase in enthalpy at constant pressure P = heat absorbed at constant pressure P

provided the work is mechanical.
1.1.12 Joule’s Experiment
Joule’ experiment
In Joule’s experiment two interconnected bulbs has been taken with a stopcock attached in
the connecting tube. One of the bulbs is consist of a gas at low pressure (i.e. ideal gas) and
the other bulb is evacuated. The whole set-up is dipped in water taken in a thermostat and
a very sensitive thermometer is placed. The stopcock is now opened and the gas expands
and spreads into the other bulb. This is a expansion against zero opposing pressure. There
is no change in temperature.
Here work done by the gas is ZERO (0), as opposing pressure is ZERO (0). As there is no
change in temperature in thermometer, so we can say that there is no heat transfer between
water and gas bulb. So heat change is also ZERO (0).
Now from the 1st law-
dU = dQ + dW
= 0+0
= 0.
Now internal energy (U) is a state function and U = f(V, T).
So, an exact differential can be written as-
From
dU dU
dU = ( )T dV + ( ) dT
dV dT V
dU dU
0 = ( )T dV + ( ) . 0 ( dT=0 and dU=0)
dV dT V
dU
Or, ( ) dV = 0.
dV T
Now, the gas has expanded and hence there is a certain change is volume or dV 6= 0
hence, ( dU )T = 0.
dV
So, change of internal energy with respect to volume at constant temperature is zero.
1.1.13 Heat capacity of gases

Q
The heat capacity of a system is defined as the limit of ∆T as ∆T → 0 and is expressed
dQ
as ( ). It is expressed as amount of heat required to raise the temperature by ∆T. It is
dT
depend on the mass of the substrate and hence it is an extensive property. On the other
hand specific heat capacity is the heat capacity per unit mass of the substrate and it is
intensive property.
Heat capacity is two type-
dQ
i) Heat capacity at constant volume (CV )= ( V )
dT
dQP
i) Heat capacity at constant pressure (CP )= ( )
dT
Previously we have proved that at constant volume change of heat is equals to change of
internal energy and at constant pressure change of heat is equals to change of enthalpy.
So, (CV )= ( dU )V and (CP )= ( dH )P
dT dT
Expression of internal energy and enthapy:
dU
CV = ( )
dT V
CV . dT = dU
Z T Z
2
CV . dT = dU
T1
∆U = CV .(T2 − T1 )
dH
Again, CP = ( )
dT P
CP . dT = dH
Z T Z
2
CP . dT = dH
T1
∆H = CP .(T2 − T1 )
1.1.14 Value of CP − CV
A) For ideal gas: To find out the relation between CP and CV , we know internal energy
is a state function and we can write -
U = f(T,V) for a closed system
Differentiating partially,
δU δU
dU = ( ) dT + ( )T dV (1.1)
δT V δV
From 1st law, dQ = dU + PdV
Or, dU = dQ - PdV (1.2)
From equation (1.1) & (1.2)
δU δU
dQ - PdV = ( ) dT + ( )T dV (1.3)
δT V δV
Dividing each term of 1.3 by dT at constant pressure(P) and making some rearrangement
dQ dV δU dT δU dV
( )P − P( )P = ( )V ( )P + ( )T ( )
dT dT δT dT δV dT P
dV δU dV
Or, CP − P( ) = CV + ( )T ( )
dT P δV dT P
δU dV
CP − CV = P[1 + ( )T ]( )
δV dT P
This is general relation between CP and CV and it is valid for any gas ideal or real.
i) For Ideal gas:
δU
( ) = 0
δV T
dV
So, CP − CV = P[ 1 + 0 ]( )
dT P
dV
CP − CV = P( )
dT P
We know, PV = RT for one mole ideal gas. Differentiating w.r.to T at const. pressure P
we get-
dV
P( ) = R
dT P
So, CP − CV = R; ( for 1 mole ideal gas)
and CP − CV = nR; ( for n mole ideal gas)
ii) For Real gas:

2a
CP − CV = R(1 + ); ( for 1 mole real gas).
RTV
Where, a is Vander Waals attraction constant.
1.1.15 Joule-Thomson effect

The term throttling means sudden lowering of pressure. Joule and Thomson carried out
experiment on throttling of gases at room temperature. They found all gases excepting
H2 and He show a cooling effect. H2 and He are wormed up. Later experiment revealed
that any gas can be heated, cooled or its temperature remain same or unchanged during
throttling. This change of temperature of the particular gas will depend on experimental
temperature (T).
i) If there is no change of temperature, then the experimental temperature is called inver-
sion temperature(Ti ).
ii) If T < Ti , then there will be cooling effect and
iii) If T > Ti , then there will be heating effect.
PV vs P curve PV vs P curve
Joule and Thomson took a long tube at the middle of which there is a porous plug
pocked with cotton wool. There are two pistons at the two end of the tube. Both end
consists of same gas but different pressure P1 and P2 (P1 > P2 ). The whole experiment
was performed inside a adiabatic jacket (dQ=0).
Joule Thompson throttling

Now a thrust is given on piston P1 and it sweeps a volume V1

so, change of volume is (0 - V1 )= - V1 .
work done on this step = - P1 × - V1

= P1 V1
Same gas is throttled to the other side and pushes the piston by a volume V2 .
so, change of volume is (V2 - 0)= V2 .
work done on this step = −P2 × V2

= −P2 V1
Here, total work done = W
= (- P2 V2 + P1 V1 ).
If, U1 and U2 are internal energies before and after throttling, then,
change in internal energy = (U2 − U1 )
dQ + dW = dU
Here, 0 + (- P2 V2 + P1 V1 ) = (U2 - U1 )
Or, U1 + P1 V1 = U2 + P2 V2
Or, H1 = H2
As enthalpy is not change during throttling so, J-T expansion is ISO-ENTHALPIC in na-
ture though internal energy change.
Joule Thomson co-efficient:

Let in Joule-Thomson expansion dP is the drop in pressure and dT is the change in temper-
ature then the term ( dT )H is called Joule-Thomson co-efficient. It is symbolized as µJ-T .
dP
Therefore,
dT
µJ-T = ( )H .
dP
To find an expression for µJ-T , we write-
H = f(T,P) (for a closed system)
On partial differentiation -
δH δH
dH = ( ) dP + ( )P dT (1.4)
δP T δT
In Joule Thomson expansion -
δH
dH = 0; and also ( ) = CP
δT P
So, equation 1.4 will be
δH
0 = () dP + CP dT
δP T
δH dT
or, 0 = ( )T + CP ( )
δP dP H
dT 1 δH
( )H = − ( )
dP CP δP T
i) For ideal gas-

δH
( ) =0
δP T
So, J-T co-efficient
dT
( ) = 0 (for ideal gas.)
dP H
;
Hence, dT = 0 i.e. T is constant. Thus temperature of ideal will not change by throttling.
ii) For real gas-
δH
µJ-T = ( )T
δP
1 δH
= − ( )
C P δP T
1 2a
= − (b − )
CP RT
1 2a
= ( − b)
CP RT
where b is Vander Waals repulsion constant. This is expression for Joule-Thomson co-
efficient.
Following cases can be considered.
a) When T = (Ti ) = ( 2a ); µJ-T = ( dT )H = 0
Rb dP
so throttling at this temperature will not produce any temperature change. This tempera-
ture is called inversion temperature(Ti). So. Inversion temperature is the temperature at
which J-T co-efficient µJ-T = 0
b) When T > Ti > ( 2a ) i.e. b > ( RT
2a ); µ dT
J-T = ( dP )H = - Ve, but in J-T experiment dP
Rb
is always - Ve, So dT must be + Ve.
So, T will rise. i.e. gas will be wormed.

c) When T < Ti < ( 2a ) i.e. b > ( RT 2a ); µ dT
J-T = ( dP )H = + Ve, but in J-T experiment
Rb
dP is always - Ve, So dT must be - Ve.
So, T will decrease. i.e. gas will be Cooled.
1.1.16 Adiabatic relations

Boyle’s Law; Charle’s law are not valid during adiabatic expansion; as here P, V and T all
are changing.
dQ + dW = dU ; ( for 1 mole gas)

dU = CV dT
for mechanical work, dW = - PdV
Thus for adiabatic expansion-
0 - PdV = CV dT
Here, P = external pressure, if the process is reversible P = internal pressure = external

pressure , So for adiabatic reversible process-
CV dT + PdV = 0
RT
Or, CV dT + dV = 0
V
dV
Or, CV dT + ( CP − CV ) dT = 0
V
Dividing each term by CV T, we get-
dT dV
+ (γ − 1) = 0
T V
Integrating we get,
Z Z
dT dV
+ (γ − 1) = Const
T V
Or, lnT + (γ − 1)lnV = Const
Or, lnTV(γ−1) = Const
Or, TV(γ−1) = Const
(γ−1) (γ−1)
i.e. T1 V1 = T 2 V2 = Const
To obtain a P-V relation we put T = PV

R in equation (I)
PV (γ−1)
V = Const.
R
P
Or, V(γ−1+1) = Const.
R
Or, PVγ = Const.
i.e. P1 Vγ1 = P2 Vγ2 = Const.
To obtain a P-T relation we put V = RT

P in equation
RT γ
P( ) = Const.
P
Or, P1−γ (RT)γ = Const.
1−γ
Or, P γ RT = Const.
1−γ
Or, TP γ = Const.
1−γ 1−γ
γ
i.e. T1 P1 = T2 P2 γ = Const.
All these three relation are valid for ’REVERSIBLE PROCESS’ only.
Prove dY for PV adiabatic are steeper than isothermal:
dX
(A) Grafically:
P vs V curve for isothermal and adiabatic
In PV isothermal expansion:
A) Drop in pressure try to increase in volume.
B) Temperature has no role(as isothermal)
In PV adiabatic expansion:
1.2. SECOND LAW OF THERMODYNAMICS 31
A) Drop in pressure try to increase in volume.

B) Temperature has no role and it falls(as in adiabatic process dq = 0 ; temperature
fall).Now, Decrease in temperature try to decrease in volume So, PV adiabatic always run
below than isothermal.
(B) Mathematically:
For isothermal case-
PV = Const.
Or, PdV + VdP = 0
Or, VdP = −PdV
So,
dY dP P
slope of isothermal = −
dX dV V
For adiabatic case-
PVγ = Const.
= Const.
γ−1 γ
Or, PγV dV + V dP = 0
Or, Vγ dP = − P γ Vγ−1 dV
P
Or, dP = − γ dV
V
dP P
Or, = −γ
dV V
As γ > 1, So slope [ dP ]adiabatic > [ dP ]isothermal

dV dV
So, Adiabatic is steeper than isothermal
1.2 Second law of Thermodynamics

First law of thermodynamics tells us about the law of conservation of energy. It is totally
silent regarding direction of flow of energy. Second law tells us about spontaneity and
the direction of flow of energy. Our experiences is energy flow from down the hill. This
experiences leads second law of thermodynamics which can be stated in many ways.
Some of which are following-
a) Heat flows spontaneously from high to low temperature.
b) According to Clausious: It is impossible for a self acting machine unaided by external
agency to convey heat from low to high temperature.
c) According to Kelvin: It is impossible to cool a body below the coldest of its surroundings.
d) According to Planks: We always require two reservers, if we try to convert heat to work.
The reserver at high temperature called source and the reserver at low temperature called
sink.
All these statements harps in the same tune which is ”ENERGY FLOWS DOWN THE
HILL.”
Engine: engine is a device which converts heat to work. Every engine must work in a cyclic
process. In a cyclic process there are forward and backward path. In forward path engine
does work and work is done on the engine in the backward path. Let an engine absorbs
Q1 heat and does work W1 . Then to take in back to the initial state we are to do some
work(say W2 ) on the engine . Let Q2 heat is rejected by the engine. So,
work obtained per cycle = |W1 − W2 | = |Q1 − Q2 | < Q1 (1.5)
So, second law can also be stated as-
”An engine working in a cyclic process work obtained is always less than heat absorbed per
cycle”.
Q: State second law of thermodynamics in two different forms and prove that
they are of same meaning.
Clausious stated second law as ”heat cannot flow spontaneously from low to high temper-
ature”. Kelvin stated second law as ”heat cannot be completely converted to work in a
cyclic process”. In order to prove that above two statements are same let us consider two
reservoir one at high temperature (T1 ) another at low temperature (T2 ).
Let, our engine obey Kelvin’s statement but disobeys Claudius statement. So, it took Q
heat from HTR and gave less work (W1 ). So, (Q − W1 ) heat is rejected at LTR. The engine
which disobeys Clausius statement can pass this heat from LTR to HTR without requiring
any work. So,
net work obtained per cycle = (W1 + 0) = W1
and
heat loss by source(HTR) = Q − (Q − W1 )
= W1
This is going against Kelvin’s statement. So we see that if Clausius statement is disobeyed,
Kelvin’s statement also disobeyed. Hence the two statements are same.
1.2.1 Carnot’s Cycle

Let an engine absorbed Q heat per cycle and gives W work. The formation of heat converted
to work is . This is called efficiency (η). Carnot considered an imaginary cycle to calculate
maximum efficiency of a reversible engine. Carnot engine is nothing but one mole of an
ideal gas taken in a cylinder fitted with a weightless and friction less piston. There are two
reservoirs. One at high temperature (T1 ), known as source and another at low temperature
(T2 ), known as sink. Now the following reversible cyclic process is carried out.
P vs V curve for Carnot’s cycle
a) Let initial state of the engine is (P1 , V1 , T1 ). It is kept over source at T1 . External
pressure is decreased infinite simmaly small, gas expands. Heat absorbed equivalent to
work done (as it is a case of isothermal dU = 0). The process is repeated till we reach
(P2 , V2 , T1 ). This is an isothermal reversible expansion. If Q1 heat is absorbed from the
source and W1 work done by this engine then-
V2
Q1 = W1 = RT1 ln (1.6)
V1
This is shown by AB portion of the graphical diagram.

b) Now, the engine is taken to the sink at T2 and covered by an adiabatic wall . Here it
does work, temperature falls to T2 . Let it expands from (P2 , V2 , T1 ) to (P3 , V3 , T2 ) .This
is shown the BC portion of the graphical diagram. Work W2 is
W2 = CV (T1 − T2 )
The adiabatic wall is removed. The engine is isothermally reversibly compressed to such a
volume V4 that on subsequent adiabatic reversible compression we can reach initial stage.
Here work done on system is W3 and heat rejected = Q2 .
V4
Q2 = W3 = RT2 ln
V3
This is represented by the CD portion of the graphical diagram.

c) Finally the engine is covered by adiabatic wall and it is adiabatically reversible compressed
to initial state. Work done W4 .
W4 = CV (T2 − T1 )
This is shown by DA curve of the graphical diagram.

Total work obtained per cycle
W = W1 + W2 + W3 + W4
V2 V4
= RT1 ln + CV (T1 − T2 ) + RT2 ln + CV (T2 − T1 )
V1 V3
V2 V4
= (RT1 ln + RT2 ln )
V1 V3
V2 V3
= RT1 ln − RT2 ln
V1 V4
From BC adiabatic,
(γ−1) (γ−1)
T1 V2 = T 2 V3
From AD adiabatic,
(γ−1) (γ−1)
T1 V1 = T 2 V4
Taking ratio of these two equation, we get,

V2 V3
=
V1 V4
Replacing V V1
V3 by V2 in total work expression, we get
4
V2 V1
Wtotal = (RT1 ln − RT2 ln )
V1 V2
V2 V2
= (RT1 ln − RT2 ln )
V1 V1
V2
Wtotal = Rln (T1 − T2 ) (1.7)
V1
So, from equation 1.6 and 1.7 we can write,
Wtotal
efficiency,(η) =
Q1
Rln V
V1 (T1 − T2 )
2
=
RT1 ln V
V
2
1
T 1 − T1
=
T2
T 1 − T2
=
T1
Also,
Wtotal = Qtotal
= (Q1 − Q2 )
W
So, efficiency (η) =
Q1
Q1 − Q2 T1 − T2
= =
Q1 T1
This is expression for a efficiency of Carnot’s engine. So we see that efficiency of an engine
does not depends on engine materials (i.e. the nature of the gas). It simply depends on
temperature difference between source and sink. The greater is the difference greater is
the efficiency. Theoretically an engine will be 100 percent efficient when temperature of
the sink T2 is 0K. But that is never possible. So 100 percent efficient engine can never be
constructed.
1.2.2 Refrigeration cycle

Let, temperature inside the refrigerator(system) = T1
temperature outside the refrigerator(surrounding) = T2
Work done on freeze material = W
Heat extracted from inside(system) = Q1
Heat rejected to outside(surrounding) = Q2
So,
Q2 = Q1 + W
Now,
Heat extracted
efficiency of refrigerator(ψ) =
Work done
Q1 Q1 T1
= =
W Q2 − Q1 T2 − T1
1.2.3 Entropy
(A) Concept of entropy:
Entropy S is mathematically defined as-
Z Z
dQrev.
S = dS =
T
It is a state function extensive property and perfect differential. Calculation shows that
entropy of a system increases during heating, expansion, fusion, sublimation and vaporiza-
tion. Now, heating increases kinetic motion i.e., randomness. Expansion brings indiscipline,
fusion, sublimation and vaporization brings disorder. So entropy measures randomness, in-
discipline or chaos and disorder. Calculation also shows that entropy of the universe is
always increasing. If we look at the nature we shall see that it has a tendency to increase
chaos. Thus if a perfectly cleaned room is kept under lock and key it automatically becomes
uncleaned and dirty. Calculation also shows that increase in entropy decrease efficiency of
an engine. if indiscipline enters a system its work performing ability will decrease. Actually
every substances have some inherent irregularities at any temperature, entropy measures
this. The irregularities increase with temperature and decrease on cooling. A pure sub-
stance becomes perfectly order at absolute zero. So entropy becomes zero at absolute zero.
At TK, if S is the entropy of the substance the unavailable energy is TS. Thus entropy is
best defined as the capacity factor of unavailable energy.
dQrev
(B) dQrev. is path dependent and hence not a state function; but, T is
path independent and hence state function - explain.
From frits law we know that -
dQrev = dU + PdV [P is internal pressure]
for one mole ideal gas -
dV
dQrev = CV dT + RT
V
to understand whether dqrev is path dependent or not, let us we integrate it
Z Z Z
dV
dQrev = CV dT + RT
V
Z Z Z
dV
Or, dQrev. = CV dT + R T
V
Result of the integration of the second term of R.H.S depends on path i.e. whether T is
constant or not.So,dqrev is path dependent and hence it is not a state function. However-
CV dT
Z Z Z
dQrev dV
= + R
T T V
Z Z Z
dQrev dT dV
Or, = CV +R
T T V
Result of the integration of each term of the R.H.S has only one variable and so result
dQ
depends only initial and final state. hence, So, Trev is path independent and state function.
H dQrev
(C) In a cyclic process explain - T =0
Let us consider a carnot’s cycle. In first step Q1 heat is absorbed reversibly by the system
at T1 ; in the second and forth step no heat exchange took place. In third step Q2 heat is
rejected reversibly at T2
So,
XQ Q1 Q
rev = + 0 + (− 2 ) + 0
T T1 T2
Q1 Q2
= −
T1 T2
From carnot’s cycle -
Q1 − Q2 T1 − T2
=
Q1 T1
Q T2
Or, (1 − 2 ) = (1 − )
Q1 T1
Q T2
Or, 2 =
Q1 T1
Q Q1
Or, 2 =
T2 T1
Hence,
XQ
rev = 0
T
so, for a Carnot’s cycle,
I
dQrev
= 0
T
Cyclic process
Any arbitrarily cycle can be broken down to a number of Carnot’s cycle. If for a single
Carnot’s cycle
I
dQrev
= 0
T
So, for any arbitrarily cycle

I
dQrev
= 0
T
dQ
We see that Trev is a state function, perfect differential and extensive properties. hence,
it poses all the properties poses by thermodynamic parameter like U and H. Let us call it
ENTROPY(S). So entropy is mathematically defined as -
Z Z
dQrev
S= dS =
T
During calculation of entropy change we are to ignore the path of transformation, simply
dQrev
we considered initial and final state and find out T ; ASSUMING THE PATH IS
REVERSIBLE.
(D) Entropy change during heating or cooling of a solid or liquid Let m gram of
a solid or liquid of specific heat s is heated from T1 to T2 . The entropy change -
Z S2 Z T2
dQrev
dS =
S1 T1 T
Z T2
msdT
=
T1 T
Z T2
dT
= ms
T1 T
T2
Or, S2 − S1 = ∆S = m.s.ln
T1
During heating,T2 > T1 i.e., ∆S is +ve. So entropy changes(increases)during heating and

entropy changes (decreases) during cooling.
(E) Entropy change during isothermal expansion of a gas Let one mole of an ideal
gas expands isothermally from P1 , V1 to P2 , V2 .The entropy change -
Z
dQrev
dS =
T
dU + PdV
=
T
P = R for one mole ideal gas.

During isothermal change dU = 0 and also T V
Z Z
PdV
dS =
T
Z S2 Z V2
dV
Or, dS = R
S1 V1 V
V2
Or, S2 − S1 = ∆S = Rln
V1
During expansion V2 > V1 .
So, ∆S is +ve. Hence entropy changes(increases)during isothermal expansion of a gas and
entropy changes(decreases)during isothermal compression of a gas
(F) Entropy change during non-isothermal expansion of a gas Let one mole of an
ideal gas expands non-isothermally from P1 , V1 , T1 to P2 , V2 , T2 .The entropy change -
Z
dQrev
dS =
T
dU + PdV
=
T
During isothermal change dU = CV dT and also T P = R for one mole ideal gas.
V
Z Z Z
dT PdV
dS = CV +
T T
Z S2 Z T2 Z V2
dT dV
Or, dS = CV +R
S1 T1 T V1 V
Or, S2 − S1 = ∆S
T2 V2
= CV ln + Rln
T1 V1
T2 T2 P1
= CV ln + Rln
T1 T1 P2
T2 P2
= (CV + R)ln − Rln
T1 P1
T2 P2
= CP ln − Rln
T1 P1
To find out absolute value of entropy we integrate the same equation without limit.
Z
dQrev
dS =
T
dU + PdV
=
Z ZT Z
dT PdV
Or, dS = CV +
T T
Or, S = CV lnT + RlnV + Constant (1.8)
Putting, V = RT
P
RT
= CV lnT + Rln + Constant
P
= CV lnT + RlT + RlnR − RlnP + Constant
= (CV + R)lnT + RlT − RlnP + Constant
= CP lnT − RlnP + Constant (1.9)
Expression (1.8) and (1.9) are for absolute entropy. These expression do not help us to
know ’S’ as we does not know the value of constant. In fact it was one time thought that
absolute entropy can never be known. But now, with the help of statistical thermodynamics
and also from third (3rd) law of thermodynamics absolute entropy has become known.
(G) Entropy change during transition of states Transition(melting, boiling, sublima-
tion, allotropic transformation) occurring at normal temperature are reversible process. So
heat absorbed during such transition
(dT) = Qrev
But here Heat absorbed = latent heat.

Hence, entropy changes/mole-
QLt
∆S =
T
During melting(fusion), boiling(vaporization), sublimation latent heat is absorbed(i.e., en-

dothermic process). So, latent heat(Lt) = ∆H is a positive quantity. So, entropy increases
during melting(fusion), boiling(vaporization), sublimation and decreases during freezing
and condensation.
1.2.4 Calculation of entropy change of a system surrounding

and universe during some process
(A) Reversible cyclic process: Let us considered a system comes from A to B by a
−→ −→
reversible path AB and return back from B to A by a reversible path BA to its original
−→
position. In the forward path AB the system absorbed Q1 heat from surrounding at tem-
−→
perature T1 . In the backward path BA the system rejected Q2 heat to the surrounding at
temperature.
Reversible cyclic process

T2 .
−→
Now, in path AB
Q Q
∆SSystem = + 1 and ∆SSurrounding = − 1
T1 T1
−→
In path BA
Q Q
∆SSystem = − 2 and ∆SSurrounding = + 2
T2 T2
So,
Q Q
Total ∆ SSystem = + 1 − 2 = 0
T1 T2
Q1 Q2
total ∆ SSurrounding = − + =0
T1 T2
∆SUniverse = 0
(B) Irreversible cyclic process: Let us considered a system comes from A to B by
−→ −→
a reversible path AB and return back from B to A by an irreversible path BA to its
−→
original position. In the forward path AB the system absorbed Q1 heat from surrounding at
−−→
temperature T1 . In the backward path BA the system rejected Q∗2 heat to the surrounding
at temperature.
Irreversible cyclic process

T2 . Had backward path ever been reversible; then the system would have rejected Q2 heat.
−→
Now, in path AB
Q Q
∆SSystem = + 1 and ∆SSurrounding = − 1
T1 T1
−→
In path BA
Q Q∗
∆SSystem = − 2 and ∆SSurrounding = + 2
T2 T2
Surrounding is so vast in comparison to system that all changes of surrounding are reversible.
It is a quasi static process.
So, So,
Q Q
Total ∆ SSystem = + 1 − 2 = 0
T1 T2
∗
Q Q
total ∆ SSurrounding = − 1 + 2 = +Ve
T1 T2
∆SUniverse = +Ve
(C) Spontaneous cooling(irreversible) of a hot body: Let m gram of a solid or

liquid of specific heat s is was initially at a very high temperature T1 . It is allowed to cool
spontaneously at room temperature to T2 .
The entropy change of system -
T2
∆SSystem = msln
T1
(T1 − T2 )
= msln[1 − ]
T1
(T1 − T2 )
= −ms
T1
= − ve.
During cooling,
T2 < T 1
Actual heat rejected by system(irreversible) = ms(T1 − T2 )
But, Surrounding is so vast in comparison to system that all changes of surrounding are
reversible and surrounding accept this reversibly.
(T1 − T2 )
∆SSurrounding = ms = +ve.
T2
Now, ∆SUniverse = ∆SSystem + ∆SSurrounding
T 1 − T2 T1 − T2
= − ms + ms
T1 T2
1 1
= ms(T1 − T2 )[ − ]
T 2 T1
ms
= (T1 − T2 )2
T1 T2
= + ve
∆SUniverse = + ve
(D) Free expansion of an ideal gas(irreversible): Let, one mole of an ideal gas
expanded freely(against a zero pressure)from volume V1 to V2 . Such a process is both
isothermal and adiabatic.
V2
∆SSystem = Rln
V1
= + Ve
As, V2 > V1
∆SSurrounding = 0
As the process is adiabatic, surrounding did not change any heat.
∆SUniverse = + ve
(E) Free mixing of gases (irreversible): When two different gases at same initial
pressure mixup then process is called free mixing. Let, nA moles of A gas and nB moles of
B gas both at same initial pressure P are allowed to mix up freely. Also let, in the mixture
there partial pressures are PA and PB respectively.
Before mixing entropies of A and B were-
Free mixing of two gases

-
SA = nA (CP lnT − RlnP + S0A )
SB = nB (CP lnT − RlnP + S0B )
Where, S0A and S0B are constant term.
After mixing entropies of A and B are -
SA (Mix) = nA (CP lnT − RlnPA + S0A )
SB (Mix) = nB (CP lnT − RlnPB + S0B )
So,
Entropy changes, ∆S = [SA (Mix) + SB (Mix)] − [SA + SB ]
PA P
= −nA Rln − nB Rln B
P P
= −nA RlnXA − nB RlnXB
So, entropy changes/mole,
∆S nA nB
= − RlnXA − RlnXB
nA + nB nA + nB nA + nB
= −XA RlnXA − XB RlnXB
X
= − Xi RlnXi
= + ve
As no heat exchange with surrounding took place so,
∆SSurrounding = 0
∆SUniverse = + ve
At a glance-
Process ∆SSystem ∆SSurrounding ∆SUniverse

Rev. cyclic 0 0 0
Irrev. cyclic 0 +ve +ve
Irrev. cooling -ve +ve +ve
Irrev. free expansion +ve 0 +ve
Irrev. free mixing +ve 0 +ve
Above results indicates that in any reversible process entropy of universe increases. Now all
natural process are spontaneous and hence irreversible. So entropy of the universe is always
increasing. Some times first and second laws are jointly stated as - ”while total energy of
the universe is constant, total entropy of the universe is continuously increasing”
1.2.5 Entropy and available work:

Let us considered two source having temperature T1 and T2 and one sink having tempera-
ture T.
Entropy and available work

A Carnot’s engine first works between T1 and T. It takes Q heat and gives W1 work.
So,
T1 − T
W1 = Q
T1
T
= Q(1 − )
T1
The same engine now operates between T2 and T. It takes Q heat and it will gives less W2
work.
So,
T2 − T
W2 = Q
T1
T
= Q(1 − )
T2
Amount of work that becomes unavailable, = W1 − W2
T T
= Q[1 − −1+ ]
T1 T2
T T
= Q[ − ]
T2 T1
1 1
= TQ[ − ]
T2 T1
In case I entropy of engine at source,
Q
=
T1
In case II entropy of engine at source,
Q
T2
Excess entropy in case II,
Q Q
∆S = −
T2 T1
1 1
= Q[ − ]
T2 T1
So,
unavailable work, = T∆S
Since an engine convert 100 percent heat to work at 0K, so at any temperature TK the
amount of unavailable work = (S − S0 )
S is the entropy at TK and, S0 is the entropy at 0K
from 3rd law of thermodynamics we know that S0 = 0 for pure substance in perfectly crys-
talline system. So unavailable work = TS [at TK]
1.2.6 Work function(free energy; Helmholtz’s free energy)[F

or A]
Let, S is the entropy of a system at TK and U is the internal energy. Then, TS amount of
energy is unavailable for work. So,
energy available for work = (U - TS)
This is called work function;free energy or more accurately Helmholtz’s free energy. It is
symbolized as F or A. So-
F = (U - TS)
F is a state function, perfect differential and extensive property. To understand the clear
meaning of F let us differentiate it-
dF = dU - TdS - SdT (1.10)
Now, we know
dQrev. = dU + Wmax.
Or, dU = dQrev. − Wmax. (1.11)
Again,
dQrev.
dS =
T
Or, dQrev. = TdS,
Putting these value in equation 1.11 we get,
dU = TdS − Wmax.
Or, dU − TdS = −Wmax.
dF = −Wmax. − SdT
Or, − dFT = Wmax.
Above equation indicates that decrease in work function at constant temperature gives us
maximum obtainable work from the system. A system may change its state in different
path or many paths. As F is a state function so, -dF is same in each path. However work
obtained will be equal to -dF ONLY WHEN THE PATH IS REVERSIBLE.
1.2.7 Work function(free energy; Gibb’s free energy; Gibb’s

potential; thermodynamic potential)[G]
Let S is the entropy of a system at TK and H is the Enthalpy. Then TS amount of energy
is unavailable for work. So,
energy available for work = (H - TS).
This is called work function;free energy or more accurately Gibb’s free energy. It is sym-
bolized as G. So-
G = (H - TS)
G is a state function, perfect differential and extensive property. To understand the clear
meaning of G let us differentiate it-
dG = dH - TdS - SdT (1.12)
Now, we know
H = U + PV
Or, dH = dU + PdV + VdP
dQrev. = dU + Wmax.
Or, dU = dQrev. − Wmax. (1.13)
Again,
dQrev.
dS =
T
Or, dQrev. = TdS,
dU = TdS − Wmax.
Putting these value in equation 2 we get,
dH = TdS − Wmax. + PdV + VdP
dG = TdS − Wmax. + PdV + VdP − TdS − SdT

= − Wmax. + PdV + VdP − SdT
Or , dGP,T = PdV − Wmax.
Or, − dGP,T = Wmax. − PdV = Wnet.
Now, Wmax. includes all type of reversible work, which may be mechanical, electrical etc.
but PdV is only reversible mechanical work. So, Wmax. − PdV = Wnet. work. Above
equation indicates that decrease in Gibb’s potential at constant pressure and temperature
gives us obtainable net work from the system. A system may change its state in different
path or many paths. As G is a state function so, - dG is same in each path. However work
obtained will be equal to Wmax. ONLY WHEN THE PATH IS REVERSIBLE.
As,
− dFT = − Wmax.
but,
− dGP,T = Wnet.
and we know net work is more important, so G is considered more important.
1.2.8 TdS relations:

From first law we know that
dQ = dU + PdV
for mechanical work,
dQrev. = TdS
Therefore,
dU = TdS - PdV (1.14)
Again,
H = U + PV
Or, dH = dU + PdV + VdP
Or, dH = TdS - PdV + PdV + VdP
Therefore,
dH = TdS + VdP (1.15)
Again,
F = U - TS
Or, dF = dU - TdS - SdT
Or, dF = TdS - PdV - TdS - SdT
Therefore,
dF = - PdV − SdT (1.16)
Again,
G = H - TS
Or, dG = dH - TdS - SdT
Or, dF = TdS + VdP - TdS - SdT
Therefore,
dG = VdP − SdT (1.17)
The equations are considered most important as they have deduced without any precondi-
tion. Hence, they are applicable towards any substance.
So, from equation (1.16),
dF = − PdV − SdT
dF
Or , − = S
dTV
and from equation (1.17),
dG = VdP − SdT
dG
Or , − = S
dTP
So, entropy is the decrease in work function or Gibb’s potential per degree raised in tem-
perature at constant volume or pressure respectively.
1.2.9 Gibbs-Helmholtz’s equation:

Let, ∆H(or ∆U) is the energy change during a process occuring at TK and ∆G or ∆F is the
available energy for work, then relation among them is called Gibbs-Helmholtz’s equation.
To derive this equation let us considered G1 , H1 and S1 are Gibbs potential, enthalpy and
entropy of a system before the process and G2 , H2 and S2 are corresponding those quantities
after the process, Then-
G2 = H2 − TS2
G1 = H1 − TS1
Now,
G2 − G1 = H2 − H1 − (TS2 − TS1 )
Or, ∆G = ∆H − T(S2 − S1 )
dG2 dG1
Or, ∆G = ∆H − T[−( )P + ( ) ]
dT dT P
d
Or, ∆G = ∆H + T [G2 − G1 ]P
dT
d
∆G = ∆H + T [∆G]P (1.18)
dT
Similarly it can be deduced,
d
∆F = ∆U + T [∆F]V (1.19)
dT
Equation (1.18) and (1.19) are called Gibbs-Helmholtz equation. They have a wide appli-
cation.
(A) Gibbs-Helmholtz equation from first principle:
Let us consider a Carnot’s engine working between TK and (T - dT)K. Also let it takes
dQrev. heat from source and gives dWmax. work. Then from Carnot’s cycle-
dWmax. dT
=
dQrev. T
d
Or, dQrev. = T (Wmax. )
dT
Again from first law, dQrev. = dU + dWmax.
d
So, T Wmax. = dU + dWmax.
dT
d
Or, d(−Wmax. ) = dU + T (−Wmax. )
dT
This is the Gibbs-Helmholtz’s equation from first principle.
(B) Integrated from of Gibbs-Helmholtz’s equation:
Gibbs-Helmholtz’s equation is-
d
∆G = ∆H + T [∆G]P
dT
Dividing each term by T2 -
∆G ∆H 1 d
= + [∆G]P
T2 T2 T dT
and making some rearrangement, we get-
∆G 1 d ∆H
− + [∆G]P = − 2
T2 T dT T
d ∆G ∆H
Or, [ ] = − 2
dT T P T
Z ∆G2 Z T2
∆H
= − 2 dT
∆G1 T1 T
Z T2
∆G2 ∆G1 ∆H
− = − 2 dT
T2 T1 T1 T
1.2.10 Equilibrium and spontaneity from the stand point of

’S’ and ’G’:
Let us consider a process in which dS and dS/ are entropy changes of system and surround-
ing. If the process is reversible then,
dS + dS/ = 0
and if If the process is irreversible then,
dS + dS/ > 0
So, for any process
dS + dS/ ≥ 0 (1.20)
Let, during the process system absorbed dQ heat from surrounding at TK. Then we can
always write-
dQ
dS/ = −
T
dQ
So, equation (1.14) will be, dS − ≥ 0
T
Or, TdS − dQ ≥ 0 (1.21)
Again from first law-
dQ = dU + PdV
= CV dT + PdV (1.22)
Putting the value of (1.22)in equation (1.21), we get-

TdS − CV dT − PdV ≥ 0 (1.23)
At constant T and V-
TdST,V ≥ 0
Or, dST,V ≥ 0
So, we see that for irreversible process dST,V > 0. Now all spontaneous process are
irreversible. So in any spontaneous process entropy of system will increase PROVIDED T
and V are constant. A equilibrium process is reversible and dST,V = 0. That is entropy
does not change any more. Before equilibrium, process was irreversible and entropy was
increases, so at equilibrium entropy becomes higher.
we have-
G = H − TS
Or, G = U + PV − TS
Now, dG = dU + PdV + VdP − TdS − SdT
After making rearrangement,
TdS − dU − PdV = − dG + VdP − SdT
Or, TdS − CV dT − PdV = − dG + VdP − SdT ≥ 0 (1.24)

Putting the value of (1.23) in (1.24)
Or, dG − VdP + SdT ≤ 0
Or, dGP,T ≤ 0
So, we see that for any irreversible or spontaneous process dGP,T ≤ 0. So in any spon-
taneous process free energy of system will decrease PROVIDED P and T are constant.
A equilibrium process is reversible and dGP,T = 0. That is free energy does not change
any more. Before equilibrium, process was irreversible and free energy was decreases and
reaches lowest. So. equilibrium is the state with highest entropy and lowest free
energy.
1.2.11 Maxwell relation:

Maxwell gave us four different relations which are often used in solving many thermodynamic
problems.
We know that,
dU = TdS - PdV
So,
δU
( ) = T
δS V
Differentiating with respect to V at constant S we get-
δ δU δT
( ) = ( )S
δV δS δV
δ2U δT
or, = ( )S
δVδS δV
Again-
δU
( ) = −P
δV S
Differentiating with respect to S at constant V we get-
δ δU δP
( ) = −( )V
δS δV δS
δ2U δP
Or, = −( )V
δSδV δS
As U is a perfect differential, so-
δ2U δ2U
=
δVδS δSδV
And hence,
δT δP
( )S = −( )V
δV δS
We Know that,
dH = TdS + VdP
So,
δH
( ) = T
δS P
Differentiating with respect to P at constant S we get-
δ δH δT
( ) = ( )S
δP δS δP
2
δ H δT
Or, = ( )S
δPδS δP
Again-
δH
( ) = −V
δP S
Differentiating with respect to S at constant P we get-
δ δH δV
( ) = ( )P
δS δP δS
2
d H δV
Or, = ( )P
δSδP δS
As H is a perfect differential, so-
δ2H δ2H
=
δPδS δSδP
And hence,
δT δV
( )S = ( )P
δP δS
We know that,
dF = - PdV - SdT
So,
δF
( ) = −P
δV T
Differentiating with respect to T at constant V we get-
δ δF δP
( ) = −( )V
δT δV δT
δ2F δP
Or, = −( )V
δTδV δT
Again-
δF
( ) = −S
δT V
Differentiating with respect to V at constant T we get-
δ δF δS
( ) = −( )T
δV δT δV
d2 F δS
or, = ( )T
δVδT δV
As F is a perfect differential, so-
δ2F d2 F
=
δTδV δVδT
And hence,
δP δS
−( )V = −( )T
δT δV
δP δS
OR, ( )V = ( )T
δT δV
We know that,
dG = VdP - SdT
So,
δG
( ) = −V
δP T
Differentiating with respect to T at constant P we get-
δ δG δV
( ) = ( )P
δT δP δT
2
δ G δV
Or, = −( )P
δTδP δT
Again-
δG
( ) = −S
δT P
Differentiating with respect to P at constant T we get-
δ δG δS
( ) = −( )T
δP δT δP
δ2G δS
Or, = ( )T
δPδT δP
As G is a perfect differential, so-
δ2G δ2G
=
δTδP δPδT
And hence,
δV δS
( ) = −( )T
δT P δP
δT δP
( )S = −( )V (1.25)
δV δS
δT δV
( )S = ( )P (1.26)
δP δS
δP δS
( )V = ( )T (1.27)
δT δV
δV δS
( )P = −( )T (1.28)
δT δP
Maxwell relation with Maxwell equation

1.3 Thermochemistry
1.3.1 Concept of thermochemistry
Thermochemistry deals with heat changes associated with various physical and chemical
transformation. The main aim of study in this chapter is the change of heat energy during
various process.
Thermochemical equation: In a typical thermochemical equation we need to use the physi-
cal states of all reactant and products also.
C(s) + O2 (g) = CO2 (g) + 94.4 K. cal
Here, temperature in 0 C and pressure in atm. is mentioned.
1.3.2 Heat of reaction

According to old definition heat of reaction is defined as the amount of heat evolved or
absorbed during a chemical reaction. In an exothermic reaction heat is evolved and hence
it is given by a +ve sign. In an endothermic reaction heat is absorbed and hence it is given
by a -ve sign. Example are,
C(s) + O2 (g) = CO2 (g) + 94.4 K. cal

1
H2 (s) + O2 (g) = H2 O(l) − 118 K. cal
2
According to modern definition heat of reaction is defined as the difference in total energy
change between product and reactant. In thermodynamics total energy means ”enthalpy”
(H). So, considering enthalpy heat of reaction
X X
HProduct − HReactant = ∆H.
For exothermic reaction

X X
HProduct < HReactant
So, ∆H is -Ve, and for endothermic reaction

X X
HProduct > HReactant
Hence, ∆H is +Ve. So, we can write-
C(s) + O2 (g) = CO2 (g) ; ∆H = −94.4 K. cal

1
H2 (s) + O2 (g) = H2 O(l) ; ∆H = +118 K. cal
2
1.3. THERMOCHEMISTRY 59
1.3.3 Type of reaction

For reaction involved gaseous reactants and product we may have one of heat of reaction
at constant volumes and the other is heat of reaction at constant pressure. Now,
Heat of reaction = Total energy of products - Total energy of reactant
At constant volume; total energy = internal energy(U), as no PV work is done.
So, heat of reaction at constant volume
X X
= UProduct − UReactant
= ∆U.
At constant pressure PV work is done. So, total energy = H.
So heat of reaction at constant pressure
X X
= HProduct − HReactant
= ∆H.
Let us considered, for a reaction
R=P
X X
∆H = HProduct − HReactant
= (UP + PVP ) − (UR + PVR )
= (UP − UR ) + (PVP − PVR )
= ∆U + nP RT − nR RT
= ∆U + (nP − nR )RT
= ∆U + ∆nRT
Where, ∆n = Difference in number of moles of gaseous products and reactants.
I) If, ∆n = 0; ∆H = ∆U
II) If, ∆n > 0; ∆H > ∆U
III) If, ∆n < 0; ∆H < ∆U
1.3.4 Heat of formation(∆Hf )

It is the enthalpy change when ONE MOLE substance is produced from its constituent
element. Some formation reactions are-
1 3
N2 (g) + H2 (g) = NH3 (g)
2 2
1
N2 (g) + O2 (g) = N2 O(g)
2
C(s) + 2H2 (g) = CH4 (g)
Sometimes we defined a term standard heat of formation (∆H0f ). It is the heat of formation
when reactants and products are in their standard states. Standard states indicate that
the substance should at one atmosphere pressure (sometimes partial pressure in case of
mixture); temperature may be anything else. However, when no physical state is mentioned
the temperature is considered 298K by convention. It is arbitrarily assumed that elements
will have zero enthalpy in the standard state. Then
1 3
∆H0f (NH3 ) = H0NH − H0N − H0H
3 2 2 2 2
1
∆H0f (N2 O) = H0N O − H0N − H0O
2 2 2 2
∆H0f (CH4 ) = H0CH − H0C − 2H0H

4 2
Thus standard heat of formation of a substance becomes equal to its standard enthalpy
of products. These values can be used for comparison. Once these values were used to
calculate and bond dissociation and bond energy.
1.3.5 Heat of Combustion

It is the enthalpy change when ONE MOLE of a substance is completely burnt in presence
of oxygen.
3
CH3 OH(g) + O2 (g) = CO2 (g) + H2 O(g)
2
C(s) + O2 (g) = CO2 (g)
Heat of combustion values are utilized to calculated flame temperature and calorific values
of food.
1.3.6 Heat of neutralization

It is the enthalpy change when one equivalent of an acid is exactly neutralized by one equiv-
alent of a base. It is found that for any strong acid and base reaction heat of neutralization
is same (∆H = −13.7 K.Cal) .This can be explained on the basis of ionic reaction.
H+ (aq) + Cl− (aq) + Na+ (aq) + OH− (aq) = Na+ (aq) + Cl− (aq) + H2 O(l)
i.e.
H+ (aq) + OH− (aq) = H2 O(l)
H+ (aq) + NO− + − + −
3 (aq) + K (aq) + OH (aq) = K (aq) + NO3 (aq) + H2 O(l)
i.e.
H+ (aq) + OH− (aq) = H2 O(l)
So, in every case of acid base reaction the enthalpy change (∆H = −13.7 K.Cal) is same.
When either acid or bases are weak or both are week, the value of enthalpy change differ
and this is due to some heat is spent in causing dissociation of weak electrolytes.
1.3. THERMOCHEMISTRY 61
1.3.7 Heat of Solution (or Dilution)

It is the enthalpy change when one mole of a substance is dissolved in a large volume of
solvent and on farther dilution ”no thermal change will occur”.
H2 SO4 (l) + 5H2 O(l) = H2 SO4 , 5H2 O(l) + Q1
H2 SO4 , 5H2 O(l) + 2H2 O(l) = H2 SO4 , 7H2 O(l) + Q2
−−−−−−−−−−− = −−−−−−−−−−−
−−−−−−−−−−− = −−−−−−−−−−−
= Aqueous solution of + no heat (energy) change.
1.3.8 Integral heat of solution

It is the heat of solution when a definite amount of solvent is added to definite amount of
solute.
1.3.9 Laws of Thermochemistry

(A) Law of Lavoisier and Laplace: Heat of formation of any substance is equal in
magnitude with heat of dissociation of same substance.
(B) Hess’s law of constant heat summation: The net heat change of a chemical
reaction is same whether the recation occurs in a single step or multiple steps provided the
initial and final states are same.
Heat change in different path
1
I) C(s) + O2 (g) = CO(g); heat change = ∆H1
2
1
II) CO(g) + O2 (g) = CO2 (g); heat change = ∆H2
2
III) C(s) + O2 = CO2 (g); heat change = ∆H3
So from, Hess’s law of constant heat summation

∆H3 = ∆H1 + ∆H2
These two laws indirectly tell about law of conservation of energy. So, they are regarded as
corollary to the first law of thermodynamics.
1.3.10 Kirchhoff ’s equation

All chemical changes and few physical changes of a reaction are associated with energy that
may be enthalpy change(∆H) or internal energy (∆U). The change of energy is dependent
on temperature. Now this energy change with temperature change can be correlated by
Kirchhoff’s equation.
A+B = C+D
Its heat of reaction-
∆H = HC + HD − HA − HB
To understand how ∆H varies with temperature; we differentiate it with respect to T.
d d d d d
(∆H) = (H ) + (H ) − (H ) − (H )
dT dT C dT D dT A dT B
d
(∆H) = [(CP )C + (CP )D − (CP )A − (CP )B ]
dT
d X X
(∆H) = ( (CP )Product − ( CP )Reactant
dT
= ∆CP
Hence,
d(∆H) = ∆CP dT
If, ∆H1 and ∆H2 are heat of reaction at T1 and T2 temperature, then-
Z ∆ H2 Z T2
d(∆H) = ∆CP dT
∆ H1 T1
Z T2
Or, ∆H2 − ∆H1 = ∆CP dT (1.29)
T1
Similarly, it can be written-
Z T2
∆U2 − ∆U1 = ∆CV dT (1.30)
T1
Equation 1.29 and 1.30 are known as Kirchhoff’s equation. They can be used to determine
heat of reaction at any temperature provided we know it at one temperature.
1.4. NUMERICAL PROBLEMS 63
1.4 Numerical Problems

1.4.1 Example solved question
1.4.1.1. 28 gm of nitrogen gas was expanded isothermally against a constant external pres-
sure from 10 atm to 1 atm pressure at 270 C. Calculate the value of ∆U, ∆H, q
and w. What is the amount of work if the expansion follows a reversible pathway?
(Consider nitrogen as ideal gas)
Ans.
28
The number of moles in 28 gm nitrogen gas =
28
= 1
Initial pressure (P1 )=10 atm and final pressure (P2 ) = 1 atm.
As it is assumed that the gas behaved ideally so at isothermal condition both ∆U
and ∆H is zero.
Work done (Wirr ) = P2 (V2 − V1 )

nRT nRT
= 1( − )
P2 P1
1 × 2 × 300(10 − 1)
= cal
(10 × 1)
= 540 cal
So the amount of work done in irreversible process is 540 cal and amount of heat
transferred = 540 cal. (w = - q)
If it was a reversible process then,
P1
Wrev = − nRTln( )
P2
10
= −1 × 2 × 300 ln ( )
1
= −1381.5 cal
= −1.38 K. cal
So the amount of work done in reversible process is 1.38 Kcal.
1.4.1.2. One mole of a gas expanded against 2 atm constant pressure from 10 lit to 30 lit.
Calculate the amount of work done. (1 lit-atm = 101.3 J)
Ans. Initial volume (V1 ) = 10 lit and the final volume (V2 ) = 30 lit.
So, work done under 2 atm constant pressure will be = 2 × (30 − 10)lit-atm
= 40 lit-atm
= 40 × 101.3J
= 4052 J
= 4.05 KJ
So, the amount of work done in irreversible process is 4.05 KJ.
1.4.1.3. A sample of gas at initial temperature 1000 C expanded from 2 lit to 4 lit in a adi-
abatic reversible manner. Calculate the final temperature when the heat capacity
at constant volume is 5 cal.deg.−1
Ans.
As the heat capacity at constant volume; (CV ) = 5 cal.deg.−1

So, the heat capacity at constant pressure; (CP ) = R + CV
= 2 + 5 cal.deg.−1
= 7 cal.deg.−1
CP 7
Hence,γ, =
CV 5
= 1.4
Initial temperature (T1 )= 1000 C = 373K; Initial volume (V1 )= 2 lit; Final volume
(V2 ) = 4 lit.
For adiabatic process ; T1 Vγ−1

1 = T2 Vγ−1
2
V1 γ−1
T2 = T 1 ( )
V2
2
T2 = 373( )(1.4−1)
4
= 373(0.5)0.4
= 282K
= 500 C
SO the final temperature is 500 C.
1.4.1.4. 10 lit of a gas at initial temperature 00 C compressed from 4 atm to 16 atm in a

adiabatic reversible manner. Calculate the work done when the heat capacity at
constant volume is 5 cal.degree−1

Ans.
As the heat capacity at constant volume; (CV ) = 5 cal.deg.−1

So, the heat capacity at constant pressure; (CP ) = R + CV
= 2 + 5 cal.deg.−1
= 7 cal.deg.−1
CP 7
Hence,γ, =
CV 5
= 1.4
Initial volume (V1 ) = 10 lit; Final volume = V2 .

Initial Pressure (P1 ) = 4 atm; Final pressure (P2 ) = 16 atm.
For adiabatic process ; P1 Vγ1 = P2 Vγ2

4 × 101.4 = 16 × V21.4
107.66 = 16 × V21.4
V21.4 = 6.73
1
V2 = 6.73 1.4
= 3.8 lit.
So the final volume is 3.8 lit.
(P2 V2 − P1 V1 )
Now in a adiabatic reversible process work done ; =
(γ − 1)
(16 × 3.8 − 4 × 10)
=
(1.4 − 1)
20.8
=
0.4
= 52 lit.-atm.
= 52 × 101.3J
= 5.27 KJ
So the work done in the adiabatic process is 5.27 KJ.
1.4.1.5. A heat engine operating in reversible cycle between 2270 C and 270 C absorbs 600
cal. of heat from higher temperature reservoir per cycle. Calculate the amount of
heat rejected at lower temperature reservoir, efficiency of the engine and work done
by the engine.
Ans. T2 = 227 + 273 = 500 K; T1 = 27+273 = 300 K; q2 = 600 cal.
Now from carnot engine’s efficiency expression,
(T2 − T1 ) (q1 + q2 )
=
T2 q2
T1 q
1− = 1+ 1
T2 q2
300 q1
− =
500 600
q1 = −0.6 × 600 cal
= −360 cal
So, 360 cal heat will be rejected at lower temperature reservoir.
(T2 − T1 )
The efficiency of the engine is (η) =
T2
(500 − 300)
=
500
200
=
500
= 0.4
Or, the efficienecy of the engine is 40%.
Total amount of work is = q1 + q2

= - 360 + 600 cal
= 240 cal
So the total amount of work is 240 cal.
1.4.1.6. 64 gm of oxygen gas is heated from 270 C to 3270 C and the volume of the gas is
doubled. Calculate the molar entropy change. What was the value of molar entropy
change if the same expansion happened at i) constant temperature ii) at constant
volume. (CV = 5 cal. deg.−1 )
64
Ans. The number of moles of oxygen gas is = 32 = 2 mole.
T2 = 327 + 273 = 600K; T1 = 27 + 273 = 300K
Now change in entropy;
T2 V2
∆S = nCV ln( ) + nRln( )
T1 V1
600 2V
= 2 × 5 × ln( ) + 2 × 2 × ln( )
300 V
= 10 ln(2) + 4 ln(2)
= 6.93 + 2.772
= 9.7 cal.K−1 .mol−1
−1 −1 −1 −1
So molar entropy change =( 9.7
2 ) cal.K .mol . = 4.85 cal.K .mol .
i) If temperature is constant then
V2
∆ST = nRln( )
V1
2V
= 2 × 2 × ln( )
V
= 4 ln(2)
= 2.72 cal.K−1 .mol−1
ii) If volume is constant then
T2
∆SV = nCV ln( )
T1
600
= 2 × 5 × ln( )
300
= 10 ln(2)
= 6.93 cal.K−1 .mol−1
1.4.1.7. At NTP, 5.6 lit of oxygen gas are mixed with 16.8 lit of nitrogen. Calculate the
entropy change and molar entropy change.
Ans. At N.T.P. 5.6 lit ogygen gas contain 22.45.6 = 0.25 moles of oxygen.
Similarly, 16.8 lit nitrogen gas contain 16.8
22.4 = 0.75 moles of nitrogen.
0.25
Mole fraction of oxygen = (0.25+0.75) = 0.25.
0.75
Mole fraction of nitrogen = (0.25+0.75 = 0.75.
)
Now entropy change for mixing,
∆S = − nRΣ(Xi lnXi )
= −1 × 2 × (0.25 ln0.25 + 0.75 ln0.75)
= −2 × (−0.35 − 0.22)
= 2 × 0.57
= 1.14 cal.deg.−1
So the entropy change for mixing is 1.14 cal.deg.−1
1.4.1.8. Calculate the change in free energy when 10 moles of an ideal gas is compressed
from 1 atm to 0.1 atm at 270 C
Ans.
V2
At constant temperature the entropy change (∆ST ) = nRln( )
V1
0.1
= 10 × 2 × ln( )
1
= - 92.1 cal.K−1 .mol−1
Now, ∆G = ∆H − T∆S
At constant temperature, ∆H = 0
So, ∆G = − T∆S
= - (- 300 x 92.1) cal.mol−1
= 27603 cal
= 27.6 K. cal
So, the change in free energy is 27.6 Kcal.
1.4.1.9. Calculate the equilibrium constant at 270 C of this reaction
1
H2 (g) + O2 (g) = H2 O(l)
2
when, ∆H0 and ∆S0 is 50 KJ. mol−1 and 70 J K−1 mol−1 respectively.
∆G0 = ∆H0 − T∆H0

= 50000 − 300 × 70
= 29000 J. mole−1
Now,∆G0 = - RTlnK (K is the equilibrium constant)
29000
lnK = −
(8.4 × 300)
= −11.5
11.5
Or, logK = −
2.303
= - 4.99 K
= 1.02 × 10−5
So, the equilibrium constant is 1.02 x 10−5 .
1.4.1.10. The enthalpy of formation of NH3 (g) at 270 C is -220 KJ mol−1 . Calculate the ∆Hf
at 770 C. The heat capacity of N2 (g), H2 (g) and NH3 (g) is 35 J K−1 mol−1 , 20 J
K−1 mol−1 and 40 JK−1 mol−1 respectively.
Ans. The balanced chemical equation for formation of ammonia will be
N2 (g) + 3H2 (g) = 2NH3 (g)

So,
1 1
(∆CP ) = CP (NH3 ) − CP (N2 ) − CP (H2 )
2 3
(∆CP ) is change in heat capacity at constant pressure
40 20
(∆CP ) = ( − 35 − )JK−1 mol−1
2 3
= - 21.33 JK−1 mol−1
Now, ∆H0 (300K) = - 220 KJmol−1
According to Kirchoff’s law ∆H2 = ∆H1 + ∆CP (T2 − T1 )
Or, ∆H350 = ∆H300 + ∆CP (350 − 300)
= - 220000 − (21.33 × 50)
= - 221066 Jmol−1
= - 221.1 KJmol−1
So the enthalpy of formation at 770 C will be - 221.1 KJ mol−1 .

1.4.2 Objective type question

1.4.2.1. The living system is thermodynamically an example of(Dec-2014)
A) an isolated system
B)a closed system
C)an adiabatically closed system
D) an open system.
Ans. an open system.
1.4.2.2. At constant pressure the sum of internal energy and pressure-volume product is
called (June-2014)
a) entropy
b) enthalpy
c) heat supplied
d) none of the above.
Ans. enthalpy.
1.4.2.3. For an ideal gas undergoing free expansion(June-2014)

a) ∆T = 0 and ∆S > 0
b) ∆T = 0 and ∆S = 0
c) ∆T < 0 and ∆S > 0
d) ∆T < 0 and ∆S = 0
Ans. ∆T = 0 and ∆S > 0.
1.4.2.4. In which cases reaction is possible at any temperature?(June-2014)

a) ∆H < 0 and ∆S > 0
b) ∆H < 0 and ∆S < 0
c) ∆H > 0 and ∆S > 0
d) none of the above.
Ans. ∆H > 0 and ∆S > 0.
1.4.2.5. In an isothermal process the quantity which remain constant(June-2014)

a) Heat
b) temperature
c) volume
d) none of these
Ans. temperature.
1.4.2.6. For an endothermic reaction. (June-2013)

a) ∆H is positive
b) ∆H is negative
c) ∆H = 0
d) ∆U is negative.
Ans. ∆H is positive.
1.4.2.7. If a system interacts with the surrounding by exchanging energy only, then it is
called as (June-2013)
a) open system
b) closed system
c) isolated system
d) none of these.
Ans. closed system.
1.4.2.8. The sum of internal energy and pressure volume product is called. (Dec-2012)
a) entropy
b) enthalpy
c) heat supplied
d) none of these.
Ans. heat supplied.
1.4.2.9. Entropy of the universe is(Dec-2012)
a) decreasing
b) increasing
c) remaining constant
d) dependent on conditions.
Ans. increasing.
1.4.2.10. Human body is thermodynamically an example of (June-2012)
a) an open system
b) an isolated system
c) a closed system
d)none of these.
Ans. an open system.
1.4.2.11. For a reaction to proceed spontaneously, we must have(June-2012)
a) ∆G < 0
b) ∆G > 0
c) ∆G = 0
d) None of these.
Ans. ∆G < 0.
1.4.2.12. During free mixing, entropy of the surrounding(Dec-2011)
a) remains unchanged
b) increases
c) decreases
d) cannot be predicted.
Ans. unchanged.
1.4.2.13. Which of the following is correct?(June-2011)
a) ( dG )P = - S
dT
b) ( dA )T = P
dV
c) ( dG ) = V d) ( dG )T = V
dT P dT
Ans. ( dG )P = - S.
dT
1.4.2.14. The Joule-Thompson expansion is (June-2011)
a) isoentropic
b) isothermal
c) isoenthalpic
d) isobaric.
Ans. isoenthalpic.
1.4.2.15. The quantity T 4S may be expressed in units of (Dec-2010)

a) J
b) K
c) JK
d)JK−1
Ans. J.
1.4.2.16. A reaction is at equilibrium in a closed rigid vessel at constant temperature when(Dec-

2010)
a) ∆S = 0 b) ∆H = 0 c) ∆U = 0 d) ∆A = 0.
Ans. ∆A = 0.
1.4.2.17. Change of internal energy is equal to heat change in case of(Dec-2010)

a) isochoric process
b) isothermal process
c) isobaric process. d) none of these
Ans. isochoric process.
1.4.2.18. At inversion temperature Joule-Thomson Coefficient is(Dec-2010)

a) zero
b) positive
c) negative
d) all of these.
Ans. zero.
1.4.2.19. When ice melts into water, entropy(Dec-2010)

a) becomes zero
b) remains same
c) increases d) decreases.
Ans. increases.
1.4.2.20. The human body is an example of a(Dec-2010)

a) closed system
b) open system
c) isolated system
d) none of these.
Ans. open system.
1.4.2.21. In the process of melting ice at -150 C(June-2010)
a) ∆G < 0
b) ∆G = 0
c) ∆G 6= 0
d) ∆G > 0
Ans. ∆G > 0
1.4.2.22. One mole of an ideal gas expands isothermaly, until its volume is doubled. What
is the change in Gibbs energy ∆G, for the process?(June-2010)
a) Rln 21
b) Rln2
c) RTln 12
d) RTln2.
Ans. RTln 21 .
1.4.2.23. If the enthalpy of reactant is less than that of product then(June-2010)
a) the reaction is exothermic
b) heat is evolved
c) the reaction is endothermic
d) none of these.
Ans. the reaction is endothermic.
1.4.3 Short answer type question

1.4.3.1. If 50 gm ice, initially at -50 C is heated to water vapour finally at 1270 C, calculate
the entropy change for the entire process. (specific heat of ice and water vapour
are 9.0 and 8 cal/mole respectively)(Dec-2014)
1.4.3.2. What is Kirchhoff’s equation? Deduce it.(Dec-2014)
1.4.3.3. State the difference between endothermic and exothermic reaction. (June-2014)
1.4.3.4. State and explain Hess’s law with example.(June-2014)
1.4.3.5. Define enthalpy. Relate the change in molar enthalpy with the change in molar
internal energy for a given process of an ideal gas system. Justify that the amount
of heat transferred at constant pressure is a measure of the enthalpy change of a
system.(Dec-2012).
1.4.3.6. Prove that for an adiabatic reversible process PVγ = constant. How do you show
that for an ideal gas Cp − Cv = R ?(June-2012)
1.4.3.7. Derive Kirchhoff’s equations.(June-2012).
1.4.3.8. (a) Define Joule-Thomson coefficient and inversion temperature explaining heating
and cooling condition.
(b) Define free-energy[G] and entropy and write their physical significance.(June-
2012).
Cv
1.4.3.9. Define an adiabatic process and show that for a reversible adiabatic process V(T) R
= constant.(June-2011).
1.4.3.10. Prove that maximum work can be obtained from isothermal reversible process.
(b) Prove that adiabatic PV-curve is more steeper than isothermal PV-curve.
1.4.3.11. (a) Prove that for an adiabatic reversible process, PVγ = constant.
b) Show that for an ideal gas Cp − Cv = R , where the notations have their usual
significance.(June-2012).
1.4.3.12. Show that Joule-Thompson effect is an isoenthalpic process. Explain the condition
of heating and cooling.(June-2012).
1.4.4 Long answer type question

1.4.4.1. (a) Show that PdV - VdP is not a perfect differential.
(b) State and explain Hess’s law of thermochemistry. Show that it is a corollary to
the first law of thermodynamics.
(c) Derive Maxwell relation ( dS )T = ( dP )V
dV dT
α2 VT
( d)Derive that Cp −Cv = β , where α is called the thermal expansion coefficient
and β is called compressibility factor.(Dec-2014)
1.4.4.2. Write short note on any three of the following.

(a) Joule-Thomson expansion and inversion temperature.
(b) Clausius-Clapeyron equation
1.4.4.3. (a) One mole of an ideal gas is allowed to expand against a piston that supports
0.4 atm pressure. The gas expands suddenly from the initial pressure of 10 atm to
final pressure of 0.4 atm. The temperature is kept constant at 00 C. Calculate Q,
∆U, ∆H and W.
(b) Show that the work done in isothermal and reversible process is maximum.
(c) Show that the decrease in Gibb’s free energy at constant temperature and pres-
sure is equal to the total work over and above the mechanical work.
(d) Derive Kirchoff’s equation related to variation of enthalpy change with temper-
ature.
1.4.4.4. Prove that for criteria of spontanicity of ∆G should be negative.

1.4.4.5. (a) Prove that Joule-Thomson expansion of gas is isoenthalpic.

(b) Define Joule-Thomson coefficient and inversion temperature. Discuss their
significances.
1.4.4.6. (a) What is enthalpy ? Derive Kirchhoff’s equation.
1.4.4.7. (a) What is a Carnot cycle ? Obtain the expression for the efficiency of a reversible
Carnot engine and starting from this expression state an appropriate statement of
the second law of Thermodynamics.
1.4.4.8. (a) Show that the magnitude of the reversible work done is greater that the mag-
nitude of the irreversible work done during isothermal expansion of an ideal gas.
(b) Calculate the work done when one mole of a real gas at 00 C expands adiabati-
cally and reversibly from 1 Lit to 10 Lit. (Given γ = 53 )
(c) State and explain Hess’s law. (d) Calculate the heat of formation of ammonia.
Given : NH3 + 34 O2 → 21 N2 + 32 O2 ; ∆Hc = −90.6 k. cal mole−1
H2 + 12 O2 → H2 O∆Hc = −68.3 k. cal mole−1
1.4.4.9. Write notes on any three of the following :

(b) Joule-Thomson expansion and inversion Temperature.
(c) Gibbs free energy and its use in denoting the spontaneity of a chemical reaction
(d) Hess law of constant heat summation
1.4.4.10. Write short notes on any three of the following :

(b) Hess law of constant heat summation
(c) Gibbs-Helmholtz equation
1.4.4.11. Write notes on any three of the following : (b) Clausius-Clayperon equation
1.4.4.12. (a) What is a Carnot cycle ? Obtain the expression for the efficiency of a reversible
Carnot engine and starting from this expression state an appropriate statement of
the second law of themodynamics.
(e) What is inversion temperature?
1.4.4.13. (a) For any adiabatic process prove that TVγ−1 = constant.
(c) Drive Kirchhoff’s equation related variation of enthalpy change with tempera-
ture.
1.4.4.14. Write down short notes on any three of the following

(a) Joule-Thompson expansion and inversion temperature.
(d) Gibb’s -Helmholtz equation relating dG and temperature co-efficient.
1.4.4.15. (a) Distinguish between intensive and extensive properties.

(b) Show that Joule-Thomson expansion is an isenthalpic process.
(c) State the significance of Gibbs free energy.

(d) Prove that
α2 VT
Cp − Cv = (Symbols have usual significances ).
β
1.4.4.16. Write short notes on any three of the following : (c) Gibbs-Duhem equation for a
two component system
Chapter 2
CHEMICAL KINETICS
2.1 Concept of chemical kinetics

Chemical kinetics deals with the rate of a chemical reaction, mechanism of a chemical
reaction and external effects like temperature, pressure, catalyst etc on the rate of a chemical
reaction. The rate of a chemical reaction indicates that with time the rate of formation of
product or with time the rate of disappearance of reactant.
2.2 On the basis of speed chemical reactions are

three types-
1) Instantaneous reaction
2) Moderate reaction
3) Very slow reaction.
1) Instantaneous reaction: Those reactions which occur in very very short period of
time (say 10−13 to 10−16 sec) is called instantaneous reaction. Any ionic reactions are the
example of instantaneous reaction.
AgNO3 + NaCl → AgCl ↓ +Na+ + NO−

3
2) Moderate reaction: Those reactions which occur in not so fast or not so slow that
is moderate period of time say some minutes to some hours is called moderate reaction.
Examples are-
1
a) H2 O2 → H2 O + O2
2
b) CH3 COOC2 H5 + H2 O → CH3 COOH + C2 H5 OH
77
78 CHAPTER 2. CHEMICAL KINETICS
3) Very slow reaction These reaction occur with a long period of time, say some years
to few years is called very slow reaction. Examples are- rusting of iron
1
Fe + H2 O2 + CO2 + O2 → Fe(OH)HCO3
2
2.3 Chemical reaction are mainly two types-

1) One directional reaction
2) Reversible reaction
1) One directional reaction: There are some reactions which occur in one direction; that
means reactant converted into product only. In thitype of reaction the concentration of the
reactants gradually decreases with time and the concentration of the product increase with
time and after certain time there will be no reactant in the reaction chamber. Decomposi-
tion of CaCO3 into CaO and CO2 in an open vassel is an example of one directional reaction.
CaCO3 + Heat → CaO + CO2 ↑ ( in a open vassel)
reaction rate change with time for one direction reaction
2) Reversible reaction: There are some reactions which occur in both direction; that
means reactant converted to product and after certain time product converted to reactant
back. At that time the rate of change in concentration of the reactant will equal to the
rate of change in concentration of the product. In this reaction the concentration of the
reactants and product does not change with time but both forward and backward reaction
occurs in same rate. In this state the reaction is called equilibrium reaction. So equilibrium
reaction is dynamic in nature and not static. If the above chemical reaction occur in a close
2.4. RATE 79
vessel, then it will follow a reversible pathway.
CaCO3 + Heat → CaO + CO2 ( in a close vassel)
reaction rate change with time for reversible reaction
2.4 Rate
Thus rate of a chemical reaction is the ratio of change of concentration (∆C) of either
reactant or product with time (∆t).
change in concentration (∆C)

Rate =
change in time (∆t)
So, the rate of reaction can be defined as increased in concentration of product per unit
time or decrease in concentration of reactant per unit time. Hence when we express a
reaction rate with respect to change of concentration of product, we will use a positive sign
as concentration is increasing for product and similarly we will use negative sign for a rate
expression with respect to reactants as the concentration of the reactants decrees with time.
change in concentration of reactant (∆CR )

Rate = (−)
change in concentration of product (∆CP )
Rate = (+)
2.4.1 Unit of rate of a reaction:

Unit of rate of a reaction will be the ratio of unit of concentration with unit of time.
unit of concentration
Thus, unit of rate of reaction =
unit of time
mol.lit−1
=
sec
= mol.lit−1 .sec−1
2.4.2 The rate of a chemical reaction depends upon this fol-

lowing factors-
i) Concentration: Generally reaction rate increases with increasing concentration of re-
actants.
ii) Temperature: For a homogeneous reaction rate of a reaction increases twice to thrice
with every 100 C increase of temperature.
iii) Catalyst: Presence of catalyst can control the rate of a reaction significantly.
iv) Substrate: Generally rate of ionic substrates are fast compared to covalent substrate.
v) Surface area: For solid substrate, rate of reaction increases with increase in surface
area of reactants.
2.5 Relation of rate with stoichiometry

Let us consider a chemical reaction with following balanced equation-
N2 + 3H2 2NH3
So, two molecules of ammonia is formed from one molecule of nitrogen and three molecule
of hydrogen. From this chemical equation we can say that consumption of hydrogen is three
times of nitrogen-
d[H2 ] d[N2 ]
= 3
dt dt
1 d[H2 ] d[N2 ]
=
3 dt dt
Now as both nitrogen and hydrogen are reactants in this reaction and their concentration
is decreasing with time, we will use a negative sign in their rate expression.
1 d[H2 ] d[N2 ]
− = −
3 dt dt
2.6. RATE LAW 81
On the other hand rate of formation of ammonia is twice the rate of consumption of nitrogen.
d[NH3 ] d[N2 ]
= 2
dt dt
1 d[NH3 ] d[N2 ]
= −
2 dt dt
Corelaing both equation we can write
d[N2 ] 1 d[H2 ] 1 d[NH3 ]

− =− =
dt 3 dt 2 dt
So, for a general chemical equation
aA + bB = cC + dD
The rate expression with respect to each substrate will be like this
1 d[A] 1 d[B] 1 d[C] 1 d[D]

− =− = =
a dt b dt c dt d dt
2.6 Rate Law

Rate law is the relation between rate of a reaction with concentration of reactants or prod-
ucts. The effect of stoichiometry of reactants and products are reflected in rate law of a
chemical reaction. In a chemical reaction where more than one substrate are involved, the
rate of the reaction will depend on each substrate but in the rate expression the power of
the concentration of a particular substrate can’t be written from stoichiometric equation of
a reaction; it is purely an experimental fact. Rate of reaction can be calculate in different
ways.
2.6.1 Calculation of instantaneous rate of a reaction

For instantaneous rate measurement of any reaction the small amount of reactants is taken
at any instant after the reaction start and allowed to freeze it for analysis. Freezing is done
for spontaneous stop of the reaction. A straight line graph is plotted with concentration
of reactant or product against different time. Then, concentration of the compound at
different time is plotted. The slope ∆∆Ct of the graph gives us the instantaneous rate of the
reaction. There are so many instruments which can easily measure the instantaneous rate
of any fast reaction.
(a)Measurement of Instantaneous rate (b)Measurement of Instantaneous rate
2.6.2 Calculation of average rate of a reaction

For average rate measurement of any reaction a small amount of reactant is taken at any
instant after the reaction starts and allowed to freeze it for analysis. Again, a small amount
of reactant is taken after some time of the first measurement in the same way. In this way
we get different concentration data at different time . Then, concentration of the compound
at different time is plotted. The ratio of change in concentration with the change in time
at two different time gives us average rate of the reaction.
Measurement of average rate
Let in a chemical reaction, after 5 minutes the concentration of the reactant is 50 ML−1
and after 15 minutes the concentration of the reactant is 30 ML−1 . So, the change in
2.6. RATE LAW 83
concentration with the change in time-

30 − 50
Average rate = M.L−1 minute−1
15 − 5
20
= − M.L−1 minute−1
10
= −2 M.L−1 minute−1
2.6.3 Law of mass action :

The rate of any chemical reaction at any instance is directly proportional to active mass of
the reacting species at that instance. Active mass is the activity of the reacting species and
it is expressed in terms of moles/liter. For a chemical reaction
aA + bB + cC → products
The experimentally derived rate law can be written as,
dc
Rate = (− ) ∝ CpA CqB CrC
dt
dc
(− ) = k.CpA CqB CrC
dt
Where CA , CB and CC are the concentration of substrate A, B and C respectively at a
time t and k is rate constant of the reaction. Now, if the concentration of all reactants are
unity, i.e; 1 mole.lit−1 , then-
Rate = k (rate constant).
So, rate constant is the rate of a reaction where concentration of al reactants are unity.
Though rate of any reaction depend upon many factor but rate constant depends only on
temperature.
2.6.4 Order and molecularity of chemical reaction
For a chemical reaction, aA + bB + cC → products

The experimentally derived rate law can be written as,
dc
Rate(− ) ∝ CpA CqB CrC
dt
dc
(− ) = k.CpA CqB CrC
dt
Where CA , CB and CC are the concentration of substrate A, B and C respectively at a
time t and k is rate constant of the reaction. p, q, and r are power or exponent on the
concentration term in the rate equation and the sum of the power or exponent is called
order of the reaction with respect to A, B and C respectively. The overall order of the
reaction will be expressed as-
order(n) = p + q + r
So overall order of a reaction is the sum of all powers or exponent on the concentrations
term used in a rate expression. Importantly order of a reaction has no relation with the
stoichiometry of the reactants or products of a balanced chemical equation. Order is purely
an experimental fact and it can be zero, any integer, fraction or negative value. Generally
common chemical reactions are zero to third order maximum. Order of a chemical reaction
gives some idea about the reaction mechanism.
Molecularity of a reaction is the sum of the reacting particle take part in the reaction.
Basically the sum of the stoichiometric number of the reactant molecules of a balanced
chemical reaction is called molecularity. It is always a positive integer and never be zero or
fraction. Molecularity do not give any idea about the mechanism of the reaction.
For a chemical reaction like , aA + bB = cC + dD
molecularity = (a + b)
For an elementary reaction order = molecularity but for a complex reaction they differ. For
a multistep reaction, the order of the whole reaction will be the order of the slowest step as
slowest step is the rate determining step.
2HI → H2 + I2
Rate = k[HI]2
For this reaction the order and the molecularity is same.
2N2 O5 → NO2 + O2
Rate = k[N2 O5 ]
For this reaction the order and the molecularity is not same.
2.6.5 Difference between order and molecularity

Order Molecularity
1. It is sum of all powers or 1. It is the sum of the
exponent on the concentrations reacting particle take
term used in a rate expression. part in the reaction.
2. It is purely experimental value. 2. It is purely theoretical value.
3. Value determined from 3. Value determined from
the rate equation. the balance chemical equation.
4. it can be zero, any integer, 4. It is always a positive integer
fraction or negative value. and never be zero or fraction.
5. For a multi step reaction 5. For a multi step reaction
there is only one order each elementary step has
throughout the whole reaction. individual molecularity.
2.7. RATE LAWS OF ZERO, FIRST AND SECOND ORDER REACTIONS 85
2.7 Rate laws of zero, first and second order reac-

tions
2.7.1 Zero order reaction
Let, us consider a reaction: A → Product

If, this reaction follow a zero order rate law, then we can write a rate expression-
dCA
− α C0A
dt
where, CA is the concentration of the reactant A at time t.
dCA
Or, − = kC0A (k is the rate constant)
dt
−dCA = kdt
Z C Z t
A
− = k dt
(C )0 0
A
−[CA − (CA )0 ] = kt
Or, CA = (CA )0 − kt
(CA )0 − CA
Or, k =
t
Hence, from the above equation we can say that unit of a zero order rate constant
unit of concentration
= = mol.lit−1 .sec−1
unit of time
If we plot the rate expression in a graph CA vs t, we will get a straight line with a negative
slope (-k) and it will cut y axis at (CA )0 .
Concentration Vs time for zero order reaction
As the rate for any zero order reaction does not change with change in the concentration
of reactants so, a plot of reaction rate vs time for zero order reaction will be parallel to X
axis.
Rate Vs time for zero order reaction
Half life of a zero order reaction: Half life (t1/2 ) can be defined as the time when then
concentration of a specific substrate of a reaction will be half of it’s initial concentration.
(C )0
So, when t = t1/2 , then CA = A 2
So, the expression of half life will be
(CA )0
= (CA )0 − kt1/2
2
(CA )0
kt1/2 = (CA )0 −
2
(CA )0
t1/2 =
2k
A plot (CA )0 vs t1/2 will give a straight line passing through origin with a slope 1 .
2k
Half life Vs initial concentration for zero order reaction
2.7.2 (A) First order reaction
Let us consider a reaction: A −→ Product

If this reaction follow a first order rate law, then we can write a rate expression-
dCA
− α CA
dt
dCA
− = kCA (k is the rate constant)
dt
dCA
= −kdt
CA
Z C Z t
A dCA
− = k dt
(C )0 CA 0
A
lnCA − ln(CA )0 = −kt
Or, lnCA = ln(CA )0 − kt
If we plot this rate expression in a graph lnCA vs t, we will get a straight line with a
negative slope (-k) and it will cut y axis at-
ln(CA )0
C
or, ln A = −kt
(CA )0
CA
= e−kt
(CA )0
CA = (CA )0 e−kt
If we plot this rate expression in a graph CA vs t, we will get an exponential decay graph
and the graph will touch x axis only when the reaction will complete. From the above
equation we can see that only at t =α, CA will be zero or the reaction will complete.
Hence we can say that first order reaction will never complete or will be completed at
infinite time and hence the decay graph line will never meet x-axis. Rate constant:
We derived the first order rate law and from this rate expression first order rate constant
can be derived.
lnCA − ln(CA )0 = −kt

CA
Or, ln = −kt
(CA )0
1 (CA )0
Or, k = ln
t CA
1
So, unit of k will be =
time
= sec−1
Half life of a first first reaction:

(C
When t = t1/2 ; then, CA = A )0 So, the expression of half life will be
2
(CA )0
ln = ln(CA )0 − kt1/2
2
(C )0
Or, kt1/2 = ln(CA )0 − ln A
2
ln2
Or, t1/2 =
k
0.693
Or, t1/2 =
k
So, from the above equation we can say that half life of a first order reaction is independent
of concentration.
(B)Another expression for first order reaction: Sometimes, the first order rate law
can be expressed in other format where the initial concentration of reactant is ’a mol/litre’
and at any time t, the concentration is (a-x) mol/litre where x is the amount of reactant al-
ready reacted at time t. So, the first order rate law can be written by replacing CA = (a-x)
and (CA )0 = a
ln(a-x) = ln a − kt
a
Or, kt = ln
a-x
1 a
Or, k = ln
t a-x
ln(a - x) Vs time for first order reaction

2.7.3 (A) Second order reaction (initial species are same)

Let us consider a reaction:
2A → Product
If this reaction follow a second order rate law, then we can write a rate expression-
dCA
− α C2A
dt
dCA
Or, − = kC2A (k is the rate constant)
dt
dCA
− 2 = kdt
CA
Z C Z t
A dCA
Or, − 2 = k dt
(C )0 C A 0
A
1 1
Or, − = kt
CA (CA )0
1 1
Or, = + kt
CA (CA )0
If we plot this rate expression in a graph C1 vs t, we will get a straight line graph with a
A
slope (k) and it will cut y axis at (C 1 ) .
A0
Rate constant:
We derived the second order rate law and from this rate expression second order rate
constant can be derived.
(CA )0 − CA
= kt
CA .(CA )0
1 (CA )0 − CA
Or, k =
t CA .(CA )0
So, unit of rate constant k will be-
concentration
unit =
concentration.concentration.time
1
=
concentration.time
= mol−1 .lit.sec−1
Half life of a second order reaction:

(C )0
So, when t = t1/2 , then CA = A 2
So, the expression of half life will be
2 1
− = kt1/2
(CA )0 (CA )0
1
Or, = kt1/2
(CA )0
1
Or, t1/2 =
2.(CA )0
Like the first order rate law, second order rate law can be expressed in other format where
the initial concentration of reactant is ’a mol/litre’ and at any time t, the concentration is
(a-x) mol/litre. Where. x is the amount of reactant already reacted at time t.
So, the first order rate law can be written by replacing CA = (a-x) and (CA )0 = a
1 1
− = kt
a-x a
x
Or, = kt
a(a-x)
1 x
Or, k =
t a(a-x)
(B)Second order reaction (initial species are different) Let us see, another type of
second order reaction:
A + B → Product
The initial concentration of A and B is a and b mol/lit respectively. At any time t, x mol/lit
of each reactant have converted to product. So, at time t, the remaining concentration of
A and B is (a-x) and (b-x) mol/lit respectively. Now with respect to product concentration
(x mol/lit), the second order rate of the above reaction can be written as-
dx
= k(a-x)(b-x)
dt
dx
Or, = kdt
(a-x)(b-x)
Z x Z t
dx
Or, = k dt
o (a-x)(b-x) o
−1 x 1
Z Z t
1
Or, [ − ]dx = k dt
a-b o (a-x) (b-x) o
1
Or, [ln(a-x) − ln(b-x)]x
o = kt
a-b
1
Or, ([ln(a-x) − lna] − [ln(b-x) − lnb]) = kt
a-b
1 (a-x) (b-x)
Or, [ln − ln ] = kt
a-b a b
1 b(a-x)
Or, ln = kt
a-b a(b-x)
1 b(a-x)
Or, k = ln
t(a-b) a(b-x)
ln b(a−x)
a(b−x) Vs initial concentration for second order reaction
2.8. PSEUDO-UNIMOLECULAR REACTION OR PSEUDO-FIRST ORDER REACTION93
2.8 Pseudo-Unimolecular Reaction or Pseudo-first

order Reaction
For a chemical reaction, aA + bB + cC → products. The experimentally derived rate law
can be written as,
dc
(− ) = k.CαA CβB CγC
dt
Where CA , CB and CC are the concentration of substrate A, B and C respectively at time
t and k is rate constant of the reaction. Now overall order of the reaction will be
order(n) = α + β + γ
Now if the concentration of any two reactants among the three reactants are so high that
during the course of reaction their concentration change is negligible, then their concen-
tration will not have any effect to the rate of the reaction. Hence the rate will depend
only upon the concentration of one reactant whose concentration change is significant. This
reaction is called pseudo unimolecular reaction. In the above reaction, let us see that the
concentration of B and C is unaltered during the reaction and hence their concentration
change will be considered as unity. So, the above rate expression will look like
dc
(− ) = k.CαA
dt
This is the unimolecular reaction rate expression. If α = 1, then it will be a pseudo
first order reaction. Example: Acid catalysed hydrolysis of ester in aqueous medium and
decomposition of sucrose in acid medium
CH3 COOEt + H2 O + H+ = CH3 COOH + EtOH

C12 H22 O11 + H2 O + H+ = C6 H12 O6 (glucose) + C6 H12 O6 (fructose)
In both the reaction water is used in large excess and hence it’s concentration change is
negligible. So, these two are pseudo unimolecular reactioN.
2.9 Effect of temperature on reaction rate

Rate of a chemical reaction increases with increase in temperature. But this increase of
reaction rate is not uniform with every same change of temperature. Generally with every
100 C increase in temperature, reaction rate increases by two to three fold. This fold change
of reaction rate is known as temperature co-efficient.
kt+10
Temperature coefficient =
kt
Where, kt and kt+10 is the rate constant of a chemical reaction at t0 C and (t + 10)0 C
respectively. Generally 250 C and 350 C temperature have been selected for this purpose.
Arrhenius proposed an empirical formula that correlates rate constant of a chemical reaction
(k) with temperature at (T) Kelvin also known as Temperature dependent rate equation.
k = A.e−Ea /RT
Where, k is the rate constant of a reaction at T Kelvin; A is a constant called pre-exponential
factor or sometime called frequency factor; Ea is activation energy and R is universal gas
constant. By taking natural logarithm, the above reaction can be written as
Ea
lnk = lnA −
RT
Plot lnk vs 1/T

If we plot this equation (lnk vs 1/T), we will get a straight line with a negative slope
(−Ea /R)and the straight line will cut y axis at lnA point. So, from Arrhenius equation
and corresponding graph we can get the value of pre-exponential factor (A). From the slope
(−Ea /R) of the graph the value of activation energy can be determined. We can also say
that if the value of activation energy (Ea ) increases, the graph will be more steeper and
hence the value of rate constant will decreases. So, activation energy have a direct effect on
rate of a reaction. We can determine the value of activation energy if we know rate constant
of a reaction at two different temperature.
If at T1 and T2 temperature, the rate constant of a chemical reaction is k1 and k2 , then
according to Arrhenius equation, we can write
Ea
lnk2 = lnA −
RT2
Ea
lnk1 = lnA −
RT1
2.10. ACTIVATION ENERGY 95
Or, On substraction of the equation,
k2 Ea 1 1
ln = [ − ]
k1 R T1 T1
From this equation the value of activation energy (Ea ) can be determined.
2.10 Activation Energy

In a chemical reaction reactant molecule does not directly goes to product in terms of
energy; rather there is a high energy state compared to both reactant and product so that
the all the reactant molecule must overcome this hight energy state and then they may be
converted to product. This high energy state is known as transition state and the energy
difference between reactant and transition state is known as activation energy (Ea ). For a
chemical reaction to happen all reactant molecules must cross this energy barrier.
Let us consider for a chemical reaction the average energy of reactant molecules, product
molecules and transition state are ER , EP and EX respective. Now the activation energy
Ea1 will be the energy difference between transition state and reactant and Ea2 is the
energy difference between transition state and product.
Ea1 = EX − ER
and , Ea2 = EX − EP
Now, if Ea1 < Ea2 , then the reaction will be exothermic reaction or heat will be released
during reaction. if Ea1 > Ea2 , then the reaction will be endothermic reaction or heat will
be absorbed during reaction.
2.11 Mechanism of Reaction

2.11.1 Postulates of Collision theory
Reactant molecules must collide with each other for a chemical reaction to happen; without
collision, mixing of reactants does not lead to product formation.
All collision is not effective to transform reactants into products. Only effective collision
transform reactants to products.
Only those collisions are effective where the colliding molecule’s translational kinetic energy
along the center is equal or more than the activation energy of the reaction.
Drawback of collision theory: In collision theory reacting molecules are considered as
hard sphere but this is true only for ideal gas.
The translational energy along the line of collision is considered as activation energy but
the contribution other energy like vibrational or rotational motion have been ignored here.
Effective and ineffective collision
2.11.2 Postulates of transition state theory
Different transition state
According to transition state theory, reacting molecules are transformed into interme-
diate high energy state which is called transition state or activated complex. Now to form
activated complex, reacting molecules must approach each other and during this approach
constant continuous changes happens in bond length, bond angle of the reacting molecules
and hence energy level increases.
The activated complex is a loose association of multiple reacting molecules. In activated
complex both the bond breaking and new bond forming happens simultaneously.
The activated complex is unstable as it is highest energy state in the course of total reaction.
Activated complex finally breaks into products.
2.12. CATALYSIS 97
2.12 Catalysis
Some substrate can change the rate of a chemical reaction but they remain unchanged after
the reaction is known as catalyst and the process is known as catalysis. Catalyst take part
in chemical reaction but their chemical composition remain unchanged after the reaction,
sometimes their physical state may be changed. If a catalyst enhance the rate of a reaction,
is known as positive catalyst and if it retards the rate then it is known as negative catalyst.
Positive catalyst: Potassium chlorate(KClO3 ) liberates oxygen on thermal decomposi-
tion but the reaction rate is slow but in presence of manganese dioxide (MnO2 ) the rate
enhances and hence manganese dioxide acts as a positive catalyst in this particular reaction.
2KClO3 (s) + MnO2 (s) = 2KCl(s) + 3O2 (g) + MnO2 (s)
With and without catalyzed reaction
Negative catalyst: Decomposition of hydrogen peroxide (H2 O2 )is slowed down in pres-
ence of platinum (Pt) or concentrated sulphuric acid and hence platinum or concentrated
sulphuric acid acts as negative catalyst here.
Or, 2H2 O2 → 2H2 O + O2 (g)
Auto catalyst: If the products of a chemical reaction is act as catalyst an it catalyzed the
reaction the the reaction is called auto catalyzed reaction and the produced compound is
called auto catalyst.
2KMnO4 + C2 H2 O4 + 3H2 SO4 = 2MnSO4 + K2 SO4 + 2CO2 + 4H2 O
Homogeneous catalysis: If in a chemical reaction reactants and catalyst present in same

phase, then it is homogeneous catalyst
Oxidation of sulphur dioxide to sulphur trioxide is catalyzed by nitric oxide. Both the
reactant SO2 and O2 are gas and the catalyst nitric oxide (NO) is gas and all are in gaseous
phase. This is homogeneous catalysis.

Gaseous phase; Catalyzed by NO(g)
NO(g)
SO2 (g) + O2 (g ) −−−−−→ SO3 (g)
Gaseous phase; Catalyzed by NO(g)
NO(g)
2CO(g) + O2 (g ) −−−−−→ 2CO2 (g)
Liquid phase; Catalyzed byH2 SO4 (l)
H2 SO4 (l)
CH3 COOC2 H5 (l) + H2 O(l ) −−−−−−−→ CH3 COOH + C2 H5 OH
Heterogeneous catalysis: If in a chemical reaction reactants and catalyst present in

different phase or state, then it will be called heterogeneous catalyst.
2KClO3 (s) + MnO2 (s) = 2KCl(s) + 3O2 (g) + MnO2 (s)
Liquid phase; Catalyzed by Pt(s)
Pt(s)
2H2 O2 −−−−→ 2H2 O + O2 (g)
Gaseous phase; Catalyzed by Pt(s)
Pt(s)
SO2 (g) + O2 (g ) −−−−→ SO3 (g)
Gaseous phase; Catalyzed by Fe(s)
Fe(s)
N2 (g) + 3H2 (g ) −−−−→ NH3 (g)
2.12.1 Theory of catalysis

Let us consider, a uncatalyzed reaction, Reactant → Product.
Let us consider, it is a unimolecular reaction and this reaction will follow a reaction co-
ordinate diagram with a transition state and corresponding activation energy. The rate of
a reaction is slow because of high activation energy and reaction rate is fast because of low
activation energy. Catalyst basically make a intermediate complex with the reactant and
altered the energy of the transition state. It by complexation with catalyst, the activation
energy comes down then the reaction rate will increase (the catalyst will be called positive
catalyst) and if the energy of activation energy increases reaction rate will decrease (the
catalyst will be called negative catalyst).The catalysis reaction is proceeds through two
different way.
2.12. CATALYSIS 99
1) Intermediate complex formation theory

2) Adsorption theory
(A) Intermediate complex formation theory: According to this theory the reactant
and catalyst first react among themselves to form an unstable intermediate which then
react with other reactant converted to product and catalyst in its original form. Kinetics
of homogeneous catalyst:
A general reaction in presence of a catalyst can be written as-
Step 1 R + C k1 I
k−1
k2
Step 2 I −→ P+C
Where, R is reactant, C is catalyst, I is intermediate complex and P is product.

The rate of formation of product = k2 .[I] Now, intermediate forms in forward reaction of
step 1 and hence the rate of intermediate formation will be = k1 .[R][C].
Intermediate decomposition happens in backward reaction of step 1 and in step 2 and hence
the rate of decomposition = k−1 [I] + k2 [I]
At steady state-
k1 .[R].[C] = k−1 [I] + k2 [I]

k1 .[R].[C] = (k−1 + k2 )[I]
k1 .[R].[C]
[I] =
(k−1 + k2 )
Putting this value in rate of product formation we can get, rate
k1 .[R][C]
= k2 .
(k−1 + k2 )
rate = k’[R][C]
k1 k2
where k’ =
(k−1 + k2 )
Here, k’ ia the observed rate constant and which is very high. This high high observed rate
constant indicates that catalyst must involved in the reaction.
(B) Adsorption theory: Adsorption is sticking of solid, liquid or gas on the surface of
solid. As the surface of any solid is not plane surface actually there is some crack corner
ink bottle pores present, any material is adsorbed on the surface either by Van-der-Wall’s
force of attraction or by chemical reaction.
Adsorbate: Substance which adsorbed on the surface of adsorbent is called adsorbate.
Adsorbent: The substance on the surface of which adsorbate is adsorbed is called adsor-
bent. Adsorption is mainly two types-
1) Physical adsorption(Physisorption)
2) Chemical adsorption(Chemisorption)
(1) Physical adsorption(Physisorption): A reversible, multilayered adsorption where
adsorbate is adsorbed on the surface of adsorbent by weak Van-der-Wall’s force of attraction

and the heat of adsorption(20 kJ/mole) is very low is called Physical adsorption. Example
- Chalk(adsorbent) adsorbed ink(adsorbate)
(2) Chemical adsorption(Chemisorption):An irreversible, monolayer adsorption where
adsorbate is adsorbed on the surface of adsorbent by means of chemical bond and the heat
of adsorption is very high(200 kJ/mole or more) is called Physical adsorption.
Example - Hydrogenation of alkene in presence of Ni catalyst. Here, hydrogenation of
alkene in presence of Ni catalyst takes place in two steps-
In the first step gaseous alkene and hydrogen gas is adsorbed in the surface of Ni at hot
condition as there is some unsatisfied valencies like cracks, corner and pores present on
the surface of Ni. Their high concentration in the pores lead to increase the frequency of
collision as well as the rate of reaction. After chemical reaction the saturated hydrocarbon
leaves the surface of the catalyst.
Hydrogenation of alkene in presence of Ni catalyst

Mech. of Hydrogenation of alkene in presence of Ni catalyst

2.13.1.1. The rate of a chemical reaction is 2.5×10−4 mole.lit.−1 min.−1 when the concentra-
tion of reactant is 1.5×10−2 mol.lit−1 . The rate changes to 7.5×10−4 mole.lit. −1 min.−1
when the concentration is 4.5 × 10−2 mol.lit.−1 . Find the order and rate constant
of the reaction.
Ans. Let us consider the order of the reaction is ’n’.
So, Rate = k(Concentration)n ; where k is the rate constant of the reaction. Using
both the values of rate and concentration given, we can write-
2.5 × 10−4 = k(1.5 × 10−2 )n and 7.5 × 10−4 = k(4.5 × 10−2 )n
Taking ratio of these two equation we can write that-
-2
2.5 × 10-4 = k(1.5 ×10 )n
7.5 ×10 -4 k(4.5 ×10-2 )n
Or, 3 = 3n
Or, n = 1.
-4
So it is a first order reaction. Rate constant (k)= 2.5 ×10-2 min−1
1.5 ×10
Or, rate constant is 1.66 × 10−2 min−1
2.13.1.2. A first order reaction is 20% complete in 10 minutes. Calculate the time taken by
the reaction to go to 80% completion.
Ans. The general rate law expression for a first order reaction is CA = CA0 e-kt .
Where CA is the concentration of the reactant at time t and CA0 is the concen-
tration of the reactant at time zero. When the reaction is 20% completed then
80% reactant remain unchanged and hence the concentration of the reactant (CA )
will be 80% of the initial concentration (CA0 );
4
CA = C
5 A0
4
SO, C = CA = CA0 e-kt
5 A0
4
Or, = e-kt
5
5
Or, ln( ) = k.10
4
5
Or, k = (1/10).ln ( ) = 2.23 × 10−2 min.−1
4
Now, when the reaction is 80% completed then 20% of the reaction left; which
indicates that (1/5)CA0 reactant left.
1
So, ( )CA0 = CA0 e-kt
5
1
ln ( ) = −k.t
5
ln 5 = kt
ln 5
Or, t =
(2.23 × CA0 e-kt 10-2
1.61
= min = 72 min.
(2.23 × 10−2 )
2.13.1.3. Show that the reaction time for a first order reaction for 75% conversation is twice
the time for 50% completion.
Let us consider t75 and t50 is the time for 75% and 50% completion of the reaction
respectively. Now, when 75% reaction completed, 25% reaction left and hence the
rate expression is 25%.
C A0 = CA0 .e- kt(75)

1 1
Or, ( ).CA0 = CA0 .e- kt(75) ln( )
4 4
= - kt(75)
Or, ln 4 = kt(75)
1
Or, t(75) = ( )2ln2.
k
Similarly, when 50% reaction completed, .
= CA0 .e- kt(50)

C A0
1 1
Or, .CA0 = CA0 .e- kt(50) ln( )
2 2
Or, ln 2 = kt(50)
1
Or, t(50) = ( )ln2.
k
t(75)
Hence, = 2.
t(50)
2.13.1.4. The half life of a first order reaction is 15 minutes. Calculate the rate constant
and the time taken to complete 80% of the reaction.
The half life (t 1 ) expression of a first order reaction is , t 1 = 0.693 ; where k is the
2 2 k
rate constant.
0.693
k = min−1
15
= 4.62 × 10−2 min−1
(Rate constant) When the reaction is 80% completed, 20% of the reaction is left.
Hence,
C A0 = CA0 .e- kt(80)

1
Or, ( )CA0 = CA0 .e- kt(80)
5
1
Or, ln( ) = - kt
5
Or, ln5 = kt
ln5
Or, t = min.
(4.62 × 10−2 )
1.61
= min. = 35min.
(4.62 × 10−2 )
2.13.1.5. The base catalysed hydrolysis of methyl acetate is 20% completed at 10 minute.
Considering a second order rate law obeying by equimolecular amounts of the es-
ter and base, calculate the half life.
2.13.1.6. Calculate the activation energy of a reaction whose rate constant is doubled when
T is increased from 300 K to 310 K.
The rate of a chemical reaction and temperature is related by the Arrhenius equa-
tion; lnk = lnA − RT Ea , where k is the rate constant, A is frequency factor or
pre-exponential factor, Ea is the activation energy and T is the temperature in
Kelvin. Now, lnk = lnA − Ea Ea
R 300 and ln2k = lnA − R 320 So,
Ea 1 1
ln2k − lnk = ( )[ − ]
R 300 320
Ea 20
Or, ln2 = ( )[ ]
R (300 × 320)
(0.693 × 2 × 300 × 320)
Or, Ea = cal
20
= 13305.6 cal
= 13.3 K.cal.
2.13.1.7. The rate constant of a reaction at 300K and 310K are 4.5 × 10−5 sec−1 and 9 ×
10−5 sec−1 respectively. Evaluate the activation energy and the pre-exponential
factor. What is the order of the reaction?
If, rate constant of a reaction is k1 and k2 at T1 and T2 Kelvin, then-
k2 Ea 1 1
ln( ) = ( )[ − ]
k1 R T1 T2
9.0 × 10−5 Ea 1 1
So, ln( −5
) = ( )[ − ]
4.5 × 10 R 300 310
Ea 10
Or, ln2 = ( )[ ]
R 300 × 310
(0.693 × 2 × 300 × 310)
Or, Ea = cal
10
= 12889.8 cal
= 12.9 K.cal
Ea
Now, ln(4.5 × 10−5 ) = lnA −
300R
Ea
Or, lnA = ln(4.5 × 10−5 ) +
300R
12889.8
= ln(4.5 × 10−5 ) +
(300 × 2)
= 10 + 21.5
= 31.5
Or, A = e31.5
= 4.8 × 1013
2.13.1.8. A first order reaction completed 50% at 40 minute (270 C) and. At 100 C increased
temperature it take 10 minute to complete 50%. Find out the rate constant at
both temperature and the activation energy.
The time taken for 50% reaction completion is the t 1 of the reaction. So, at 270 C
2
0.693
the t 1 is 40 min. Now, for a first order reaction, t 1 = where, k27 is the rate
2 2 k27
constant at 270 C .
0.693
So, k27 =
t1
2
0.693
= min−1
40
= 1.73 × 10−2 min−1
Now, at 100 C elevated temperature (370 C) t 1 is 10 min; hence, rate constant at

2
370 C is ,
0.693
k37 =
t1
2
0.693
= min−1
10
= 6.93 × 10−2 min−1
If the activation energy of this reaction is Ea , then

6.93 × 10−2 Ea 1 1
ln( ) = [ − ]
1.73 × 10−2 R 300 310
(Ea × 10)
ln4 =
(2 × 300 × 310)
(2 × 300 × 310)
Or, Ea = ln4 × cal
10
= 25785 cal
= 25.8 K.cal
Hence, the activation energy is 25.8 Kcal.
2.13.1.9. The half life of a first order reaction is 25 minute. Calculate the rate constant,
fraction of reactant left over after 90 minute and time taken to complete 75% of
the reaction.
The half life of a first order reaction = 25 minute So, rate constant
0.693
k =
t1
2
0.693
= minute−1
25
If, N0 and N are the initial percentage and percentage after 90 minutes then
fraction of reactant left over after 90 minute -
2.303 N0
t = log
k N
2.303 × 25 100
Or, 90 = log
0.693 N
90 × 0.693
Or, = log 100 − log N
2.303 × 25
Or, 1.083 = 2 − log N
Or, − 0.917 = 2 − log N
Or, N = 10−0.917
Or, N = 8.26%
If, N0 = 100% and N = 75% complete then time -
2.303 N0
t = log
k N
2.303 100
Or, t = log
k 25
2.303 × 25
Or, t = log 100 − log 25
0.693
Or, t = 83.08(2 − 1.397)
Or, t = 83.08(0.602)
Or, t = 50.01 minutes
2.13.1.10. The activation energy for a chemical reaction is 120KJ.mol−1 . At 300K, the rate
constant is 10mol−1 .lit.sec−1 . What is the value of rate constant at 400K?
According to Arrhenius equation, lnk = lnA − RT Ea ; where k is the rate constant,
A is pre-exponential factor, Ea is the activation energy and T is the temperature
in Kelvin. So, at 300K we can write,

120000
ln(10) = lnA −
(300 × 8.4)
120000
Or, logA = 1+
(300 × 4.2)
= 47.6
120000
So, at 400K, logk = logA −
(400 × 4.2)
logk = 47.6 − 35.7
Or, logk = 11.9
k = 1011.9 mol−1 .lit.sec−1
2.13.1.11. The half life of given reaction is doubled when the initial concentration is doubled.
What is the order of a reaction.
For an nth order reaction the relationship between half life(t 1 ) and the initial con-
2
K
centration (CA0 ) of reactant is given by- t 1 = (C )(n−1) where K is a constant.
2
A0
If initial concentration is doubled then,
K
2t 1 =
2 [2CA0 ](n−1)
K
2t 1 [2C ](n−1)
2 A 0
Or, =
t1 K
2 [C (n−1)
A0 ]
1
Or, 2 = [ ](n−1)
2
Or, 2(1 − n) = 2
Or, 1 − n = 1
Or, n = 0
So, it is a zero order reaction.
2.13.1.12. In a second order reaction, the initial concentration of the reactant is 2 moles.lit−1 .
The reaction is found to 20% complete at 40 min, Calculate the rate constant of
the reaction, half life and the time required to 80% complete.
The general rate expression of a second order reaction is
1 1
− = kt
C A C A0
where CA is the concentration of the reactant at time t and CA0 is the concen-
tration of the reactant at time zero and k is the rate constant. After 40 mins. the
reaction is 20%complete; hence 80%is incomplete. So, CA = 80%C0A = 45 C0A

1 1
4 C A0 − C 0 = k40
5 A
5 1
Or, CA0 − = k40
4 C A0
1
Or, CA0 = k40
4
1
Or, k = mole−1 .lit.min−1
4 × 2 × 40
= 2 × 10−3 mole−1 .lit.min−1
So, the rate constant of the reaction is 2 × 10−3 mole−1 .lit.min−1 . Half life t 1 of a
2
second order reaction
1
=
k.CA0
1
Or, t 1 = min = 250 min.
2 2 × 2 × 10−3
So, the half life of the reaction is 250 min. The time to complete 80% of the
reaction
80% complete; hence 20% is incomplete. So, CA=20%CA0=(1/5) CA0
1 1
1 C A0 − = kt80
5
C A0
5 1
Or, − = kt80
C A0 C A0
4
Or, = kt80
C A0
4
Or, 80t = min.
2 × 2 × 10−3
= 1000 min.
So, the rate constant of the reaction is 2 × 10−3 mole−1 .lit.min−1 . Half life t 1 of a
2
second order reaction
1
=
k.CA0
1
Or, t 1 = min. = 250 min.
2 2 × 2 × 10−3
So, the half life of the reaction is 250 min.

So, at 1000 min 80% of the reaction will be completed.
2.13.1.13. For a reaction 2A+B → Product, it was found that doubling the concentration
of both reactant increases the reaction rate by sixteen fold. But on doubling the
concentration of B alone, the reaction rate increases by four fold. What is the
order of the reaction with respect to A?
Let us consider, the order of the reaction with respect to A and B is m and n
respectively. So, we can write
Rate = k[A]m [B]n
When the concentration of both A and B doubled then,
16 × Rate = k[2A]m [2B]n
When the concentration of B doubled then
4 × Rate = k[A]m [2B]n

(16 × Rate) k[2A]m [2B]n
So, =
(4 × Rate) k[A]m [2B]n
Or, 4 = 2 m
Or, m = 2
So, it is second order reaction with respect to A.

2.13.2.1. When rate constant K has the unit moles litre−1 sec−1 the order of the reaction is
(Dec-2014)
A)0 B)1 C) 2 D) 3
Ans.A)0
2.13.2.2. The half life of a first order reaction is 20 minutes. The time required for 75%
completion of the reaction is(June-2014)
a) 30 minutes b) 40 minutes c) 50 minutes d) 60 minutes.
Ans.d) 60 minutes
2.13.2.3. Hydrolysis of ethyl acetate in presence of excess water follows(June-2013)

a) 2nd order kinetics b) 1st order kinetics c) zero order kinetics d) pseudo-1st
order kinetics.
Ans.d) pseudo-1st order kinetics.
2.13.2.4. For a reaction A−→B, both change in enthalpy (∆H ) and change in entropy (∆S
) are positive. The most favourable condition for the reaction is (Dec-2011)
a) low pressure b) high pressure c) low temperature d) high temperature.
Ans.d) high temperature.
2.13.2.5. If infinite time is required for completion of a chemical reaction, then order of the
reaction is
a) zero b) first c) second d) third.
Ans.b) first
2.13.2.6. The minimum amount of energy possessed by the reacting molecules to produce
effective collisions is called
a) threshold energy b) internal energy c) activation energy d) kinetic energy.
Ans.c) activation energy
2.13.2.7. The half-life period of a reaction is found to be directly proportional to the initial
concentration. The order of the reaction is( Dec-2010)
a) zero b) one c) two d) three.
Ans.a) zero
2.13.2.8. If the rate of a reaction becomes twice for every 100 C rise in temperature, by what
factor does the rate of the reaction increase when temperature is raised from 300 C
to 800 C ?
a) 16 b) 32 c) 64 d) 128.
Ans.b) 32
2.13.2.9. The half-life period of a reaction is found to be directly proportional to the intial
concentration. The order of reaction(June-2010) is
a) zero b) one c) two d) three.
Ans.a) zero
2.13.2.10. The dimension of rate constant of a second order rate equation is (June-2012)
a) mole litres−1 b) molelitres−1 s−1 c)mole−1 litress−1 d) mole−1 litres−1 .
Ans.mole−1 litress−1
2.13.3 Short answer type question

2.13.3.1. (a) What is activation energy of a reaction? What is meant by activated com-
plex? (b) Draw relevant diagram showing the variation of energy with respect to
reaction co-ordinate for exothermic and endothermic reaction.1+1+3 (June-2014)
2.13.3.2. (a)Write down the Arrhenius equation for the temperature dependence of specific
rate and explain the term used. (b)What is the unit of frrquency factor for a first
order reaction? (c) Plot k vs 1/T and explain the significance of the slope of the
plot. (June-2013)
2.13.3.3. State and explain Arrhenius equation. What is the significance of activation en-
ergy ? How can it be determined ? 2 + 2 + 1(June-2013)
2.13.3.4. (a)What is pseudo-unimolecular reaction ? Give one example. (b) Deduce the ex-
pression for the rate constant of a first order reaction. Show that half-life period
of a first order reaction is independent of the initial concentration.2 + 3(June-2012)
2.13.3.5. Write notes on: (a) Homogeneous catalysis

2.13.3.6. Distinguish between the following: (a) Order and molecularity of a reaction.(June-
2011)
2.13.3.7. What is catalysis ? Derive the kinetic expression of ’homogeneous catalysis’ with
example.1 + 4(Dec-2010)
2.13.4 Long answer type question

2.13.4.1. Explain the transition state theory for a reaction.(Dec-2014)
2.13.4.2. (a) State the difference between order and molecularity of a reaction.(b) A first
order reactionhas rate constant equal to 1.25 × 10−4 sec−1 at 298 K and 8.5 ×
10−4 sec−1 at 318 K. Calculate the activation energy of the reaction. (c) State the
assumption of collision theory reaction rate. 3+4+4(June-2014)
2.13.4.3. What are the basic postulates of transition state theory ? 3( June-2013)
2.13.4.4. Why is first order reaction never complete ? 2( June-2013)
2.13.4.5. Write short notes on: (c) Homogeneous catalysis
2.13.4.6. (a) What do you mean by the activation energy of a reaction ? How does the rate
constant of a chemical reaction depend on the temperature ? (b) Calculate the
activation energy of a reaction whose rate constant is doubled when temperature is
increased from 200 K to 300 K.(c) Show the influence of a positive catalyst on the
activation energy of a reaction in the energy profile diagram. 3 + 4 + 3(Dec-2012)
2.13.4.7. Write notes on any three of the following :(f) Order and Molecularity of the reac-
tion.
2.13.4.8. Write down Arrhenius equation for the activation energy of a reaction. Plot lnk
vs 1/T and write the significance of the slope. 3(June-2012)
2.13.4.9. Write notes on any three of the following : (f) Homogenous catalyst. 5(Dec-2011)
2.13.4.10. Deduce the expression for the rate constant of a second order reaction where the
initial concentrations of the two reactants are same. 5
2.13.4.11. (b) Write down Arrhenius equation for the temperature dependence of specific
rate and explain the terms used. 5( June-2011)
2.13.4.12. (c) What is meant by pseudo-first order reaction ? Show how can you arrive at
the rate equation for a pseudo first-order reaction as a special case of second-order
reaction kinetics. 2+3
2.13.4.13. (a) Distinguish between Order and Molecularity. (b) A first order reaction is never
complete. Justify. (c) What is activation energy ? Write down its physical sig-
nificance. (d) Write the main features of Transition State theory.(e) Write down
Arrhenius equation for the temperature dependent on specific rate. Plot log K
vs 1/T and explain the significance of the slope of the plot. 2 + 3 + 3 + 4 +
3(Dec-2010)
2.13.4.14. Consider a 1st order reaction A → B, where A is reactant and B is product. As-
suming a is the initial concentration of the reactant and x is the concentration of
the product after time t, show that half-life decomposition period of the reaction
is independent of a. 4
2.13.4.15. State the differences between molecularity and order of a chemical reaction.3
2.13.4.16. The half-life period of the decomposition of a compound is 5 min. If the initial
concentration is halved, the halflife period is reduced to 25 min. Find the order
of reaction. 4
Chapter 3
SOLID STATE CHEMISTRY
3.1 Concept of solid
Solid compounds have different characteristic in shape and size from liquid or gas. Solids are
rigid, malleable, incompressible due to the absence of translational and rotational motion
of the atoms, molecules and ions.They have definite malting point. On heating, the kinetic
energy of the constituent starts vibrate on the equilibrium or mean position and after
a certain limit the vibration energy becomes more than the binding energy among the
constituents, as a result the solids get melt. The melting point of ionic solids are higher
than amorphous solids due to strong electrostatic force of attraction among the opposite
ions in case of ionic solids. So solids are generally two types-
1) Crystalline solid
2) Amorphous solid
1) Crystalline solid:The main criteria of a solid to be crystalline is, ion constituents are
arranged in a regular three dimension fashion to get a particular geometry. It have sharp
melting point and called anisotropic solid. But, due to presence of thermal vibration of
the constituent in the crystalline solid the arrangement pattern of the constituent is seldom
perfect. Due to presence of thermal vibration of the constituents, some impurities and
defects in crystalline solid influence different chemical properties of solids.
2) Amorphous solid: An amorphous solid is any noncrystalline solid in which the atoms
and molecules are not organized in a definite lattice pattern. Such solids include glass,
plastic, and gel. An amorphous does not have a definite geometric or crystalline shape. It
is a solid in which there is no long-term order in the positions of the atoms. Most classes of
solid materials can be found or prepared in an amorphous form. Solids and liquids are both
forms of condensed matter; both are composed of atoms in close proximity to each other.
113
114 CHAPTER 3. SOLID STATE CHEMISTRY
3.2 Defects or imperfection in crystalline solid

In a crystalline solid, the constituent particles, ions are arranged in regular fashion. But,
this arrangement is completely perfect at 0K temperature. Above this temperature the
arrangement of constituents are imperfect or defective from their intrinsic arrangement.
Again defects or imperfect arrangements can be introduced in the crystal purposefully by
adding some impurity from outside into the crystal lattice. Due to presence of defects in
the crystal, solids changes their chemical properties (like colour, electrical conductivity and
mechanical properties) as well as produce some new properties also.
Defects or imperfectness of crystal: Any deviation of arrangement of the constituent
atoms or molecules from their regular three dimension particular intrinsic geometry is called
defect or imperfectness of crystal.
In crystal three types of defects are found. These are-
1) Atomic imperfection or Point defects
2) Line defects and
3) Plane defects.
3.2.1 Atomic imperfections or Point defect

The defects in crystal is due to i) the missing of constituent atoms or molecules from their
normal crystal point or ii) constituent atoms or molecules leave from their intrinsic/own
crystal point and shifted to interstitial position in the crystal lattice or iii) shifting of any
foreign particle in the crystal point or interstitial position in the crystal.
Point defects or atomic imperfections are three types
i) Stoichiometric defect
ii) Non-stoichiometric defect
iii) Impurity defect
3.2.1.1. Stoichiometric defect
The point defect in crystal occurs due to i) the missing of constituent atoms or molecules
from their normal crystal point or ii) constituent atoms or molecules leave from their intrin-
sic/own crystal point and shifted to interstitial position in the crystal lattice. Stoichiometric
number ratio of constituent atoms or molecules are in same ratio is called Stoichiometric
defects.
Such type of defect is also called intrinsic defect. Some times this type of defect is called
thermodynamic defect as it depends on temperature. Stoichiometric defects are two types-
i) Vacancy defect
ii) Interstitial defect
3.2.1.1.1. Vacancy defect: The vacancy defect in crystal occurs due to the missing of
constituent atoms or molecules from their normal crystal point.
As some constituent atoms or molecules are missing from their crystal point density of
solid decreases due to such type of vacancy defect.
3.2. DEFECTS OR IMPERFECTION IN CRYSTALLINE SOLID 115
Vacancy defect
3.2.1.1.2. Interstitial defect: The interstitial defect in crystal occurs due to missing of
constituent atoms or molecules from their intrinsic/own crystal point and shifted to inter-
stitial position in the crystal lattice.
The void space present in between the crystal points in the crystal is called interstitial po-
sition. As some extra constituent atoms or molecules are present in the interstitial position
in the crystal the density of solid increases due to such type of interstitial defect.
Interstitial defect
The above all defects are found in case of non-ionic crystalline solid.
Presence of stoichiometric defects in ionic crystal but electrical neutrality is present are
mainly two types-
i) Schottky defect
ii) Frenkel defect
3.2.1.1.A. Schottky defect:This type of crystal defect was discovered by German scien-
tist Schottky in 1930. This is basically vacancy defect and it is found mainly in MX type
(as NaCl) of ionic crystal. If any number of cations are missing from the cationic point and
to maintain the electrical neutrality same number of anions are missing from the anionic
point in ionic crystal lattice, then Schottky defect arises. The missing ion pairs are found
on the crystal surface. Such type of missing of pair of opposite ions create holes in crystal
lattice.
The electrical neutrality as well as stoichiometric ratio is maintained in such type of defect.
Due to missing of ion pairs from the crystal lattice (actually present at the outer surface of
the crystal) the density of Schottky defected crystal always less than the ideal crystal.
The schottky defect is found in those ionic crystals which have-
i) High coordination number ii) size of cation and anion are approximately same. Examples:
NaCl, KCl, CsCl, KBr etc.
Schottky defect
The number of schottky defect (NS ) present per cc is given by-
WS
−
NS = N × e 2KT
Where, N is the number of vacant site per cc

WS is the required work to form Scottky defect.
K is the gas constant

T is the absolute temperature.
3.2.1.1.B. Frenkel defect:indexFrenkel defectsThis defect was discovered by Russian sci-
entist Frenkel in 1926. This defect is basically another type of vacancy defect and it is found
mainly in MX type (as AgBr) of ionic crystal. If any cation is missing from the cationic
point and the missing ions are occupied in the interstitial site then Frankel defect arises.
The electrical neutrality as well as the stoichiometric ratio are maintained in such type of
defect. Due to presence of cation at interstitial site in crystal lattice the mass and density
of Frenkel defected crystal always same as the ideal crystal.
The Frenkel defect is found in those ionic crystals which have-
i) low coordination number ii) the size of cation is less than counter anion. Examples: Agcl,
AgBr, AgI, Zns etc.
Frenkel defect
The number of Frenkel defect (NF ) present per cc is given by-
WF
/ 1 −
NF = (NN ) × e 2KT2
Where, N is the number of site vacant per cc

N/ is the number of alternative interstitial site per cc
WF is the required work to form Frenkel defect.
K is the gas constant
T is the absolute temperature. Consequences of Schottky and Frenkel defects:
i) Presence of defect in the crystal leads to increase in electrical conductivity. When a
potential is applied an ion moves from its lattice site and occupy a nearby and creates a
new hole another nearby ions moves in to it.The process is continuing and hole moves from
one end to another end as a result the electricity is conducted throughout the crystal.
ii) The dielectric constant of the crystal increases as in Frenkel defect the cation occupy the
interstitial site causing closeness of similar charge.
Difference between Schottky defect and Frenkel defect
3.2.1.2.Non-stoichiometric defect:The point defect in ionic crystal is due to i) the
Schottky defect Frenkel defect

1. Schottky defects occur due 1. Frenkel defects occur due
to migration of equal number of to migration of cation from its
cation and anion from a lattice lattice point to the interstitial
site to the surface of the crystal site of the crystal
2. In Schottky defected crystal 2. In Frenkel defected crystal
the dielectric constant of the dielectric constant of
the crystal remain unchanged the crystal increses
3. Due to missing of ion pairs from 3. Due to missing of cations from
their original crystal point to the their original crystal point to the
outer surface the mass and density interstitial site, the mass and density
of Schottky defected crystal decreases of Frenkel defected crystal remain same
4.Schottky defect is found in those 4. Frenkel defect is found in those
ionic crystal having high coordination ionic crystal having low coordination
number and almost similar size number and cation size is
of both cation and anion much smaller than anion size
5. Examples: NaCl, KCl, CsCl, KBr etc. 5. Examples: Agcl, AgBr, AgI, ZnS etc.
change in stoichiometric ratio from their normal crystal geometry or ii) the ratio of cation
and anion in the crystal is differ from the ratio directed by the chemical formula of the
compound is called non-stoichiometric defects.
Due to such defect though there is difference in the number of cation and the anion but the
crystal carry electrical neutrality. Some times this type of compound is called Barthollied
(by the name of scientist Barthollet) compound. Examples:
Fe0.88 O, Cu1.87 S, Fe0.88 O
Non-stoichiometric defects is found in ionic crystal due to excess or deficiency of metal ions.
Non-stoichiometric defects are two types-
1) Metal excess defects
2) Metal deficiency defects
1) Metal excess defect: The metal excess defect arises due to two following:
3.2.1.2.1.A. Anion vacancies or F centers: When any constituent anion is missing
from its own lattice point of an ionic crystal and to maintain the electrical neutrality the
vacancy of the lattice point is filled up by an electron then the defect is called anion vacancy
or F center.
Metal excess defect due to anion missing

From the figure it is clear that though the crystal is electrically neutral, there is excess of
metal ion. Such type of metal excess defect (due to anion vacancy) is found in those ionic
crystal which show the Schottky defects. Examples: Alkali metals halide like NaCl, KCl,
CsCl, KBr etc. The anion vacancies are produced when these halides are heated with excess
of their constituent metal vapour. The metal atom get deposited on the surface of the alkali
halide crystal. The halide ions now move into the surface and combine with metal atom
form MX leaving e− . as-
M + X− → M+ X− + e−
Anion vacancy also called F-center because F is taken from the German word Fabre which
means colour. These F-center are associated with the colour of the compound and the
intensity of the colour increases with greater f-center. F-center crystals are paramagnetic in
nature due to presence of unpaired electron in the vacant site. When any light fall on the
F-center it absorb light energy and the electron promoted from valence band to conduction
band becomes photo conductors actually it is n-type semiconductor. Again, any heat fall
on the F-center it absorb heat energy and it becomes thermal conductor.
Question: The colour of NaCl is white, it becomes yellow when heated with Na
vapour. Why?
The metal Na atom get deposited on the surface of the NaCl crystal . The Cl− ions now
move into the surface and combine with metal atom form NaCl leaving e− as-
Na + Cl− → Na+ Cl− + e−

The electron in the F-center absorb light fallen on it and get excited. During transition of
electron from higher level to the ground level it radiate energy and we see the complemen-
tary yellow colour.
Question: The colour of KCl is white, it becomes lilac when heated. Why?
Excess cation occupying interstitial sites. Sometimes the constituent anion converted
to gas by leaving electron and the electron occupy the interstitial site of the crystal. These
type of formation of gas by constituent anion and hence excess of cation which occupy the
interstitial site of the crystal causing the constituent cation excess in the crystal is called
metal excess defect. In this case the electrical neutrality of the crystal is maintained also.
Metal excess defect due to interstitial cation

Such type of metal excess defect (due to cation in the interstitial site) is found in those
ionic crystal which show the Frenkel defects. Examples: ZnO, CdO, Fe2 O3 , Cr2 O3 etc.
Question: When ZnO is heated some amount of O2 is liberated and the colour
of ZnO is transformed from white to yellow as well as its electrical conductivity
increases. Why?
ZnO is white in colour. When ZnO is heated it undergoes chemical reaction by releasing
electrons.
ZnO(s) → Zn++ + 21 O2 (g) + 2e−
As a result some amount of O2 is liberated from ZnO and Zn+2 ion is produced which
is trapped in the interstitial site of the crystal. Here non-stoichiometric ZnO is formed
and the electron in the interstitial site absorb light fallen on it and get excited. During
transition of electron from higher level to the ground level it radiate energy and we see the
complementary yellow colour as well as enhanced electrical conductivity.
Question: Metal excess defected ZnO (due to excess cation occupying intersti-
tial sites)is heated in dioxygen and cooled to room temperature, the electrical
conductivity decreases. Why?

Zn++ + 12 O2 (g) + 2e− → ZnO(s)
Actually, some electrons from interstitial site are added to O2 and converted to O2− ions
and these O2− combine with Zn+2 ions to form ZnO. As a result of removal of electrons
from interstitial site electrical conductivity decrease.
Importance of Metal excess defects:
i)Crystal with metal excess defect are normally coloured due to presence of free electrons
either in lattice point or interstitial position. When any light fall on the F-center it absorb
light energy and the electron promoted to the higher energy levels giving the absorption
band as a result they are coloured. ii)Crystal with metal excess defect are normally conduct
electricity and heat due to presence of free electrons either in lattice point or interstitial po-
sition. When any light fall on the F-center it absorb light energy and the electron promoted
from valence band to conduction band becomes photo conductors actually it is n-type semi-
conductor because the number of defects is very small. Again, any heat fall on the F-center
it absorb heat energy and it becomes thermal conductor.
3.2.1.2.2. Metal deficiency defect When any constituent cation is missing from its own
lattice point of an ionic crystal and create a cationic vacant there or extra anions or negative
charges occupy in the interstitial site and to maintain the electrical neutrality the nearest
neighbour cation reached to higher oxidation state by gaining excess positive charge then
the defect is called metal deficiency defect.
Metal deficiency defect due to cation missing
From the figure it is clear that though the crystal is electrically neutral, there is number
of cation less than anion. Such type of metal deficiency defect(due to cation vacancy) is
found in those ionic crystal which have different oxidation state. Examples are FeO, NiO,
FeS etc.
Metal deficiency defect are two types:

3.2.1.2.2.A.Cation vacancies: In such type of metal deficiency defect the constituent
cation is missing from its own lattice point of an ionic crystal and create a cationic vacant
there and to maintain the electrical neutrality the nearest neighbour cation reached to higher
oxidation state by gaining excess positive charge then the defect is called metal deficiency
defect.
Metal deficiency defect due to cation missing
found in those ionic crystal which have different oxidation state. Examples are FeO, NiO,
FeS etc.
Extra anion in the interstitial site In such type of metal deficiency defect extra anions
or negative charges occupy in the interstitial site and to maintain the electrical neutrality
the nearest neighbour cation reached to higher oxidation state by gaining excess positive
charge then the defect is called metal deficiency defect. Normally, due to large size of anion
or negatively charged ion, it is very difficult to fit them in the interstitial site in ionic crystal.
found in those ionic crystal which have different oxidation state. There is no example of
such compound.
Importance of Metal deficiency defects:
i) Due to absence of cation in the crystal or cation vacancy provide positive hole. Due
to presence of these holes an electron may be transferred in a particular direction in the
structure at the same time the positive hole migrate to the opposite direction of the electron
flow produce p-type semiconductor.
ii) Due to absence of cation on the surface or cation vacancy provide the characteristic to
3.3. IMPURITY DEFECT 123
the compound to acts as catalyst.

iii) Due to absence of cation on the surface or cation vacancy provide the characteristic of
metallic luster in compound like FeS.
3.3 Impurity Defect

Some time some small amount of foreign materials are present in pure crystal as impurities
and brings defect in crystal called impurity Defect.
3.4 Doping
The process by which small amount of foreign materials are introduced in pure crystal as
impurities to brings defect in crystal called doping.
The small amount of foreign materials are called substitutional impurity which (atoms or
ions) are introduced in pure crystal and they replace the atoms or ions from their lattice
point the foreign impurities .
On the other hand the impurity (atoms or ions) which occupy the interstitial site in crys-
tal, are called interstitial impurity and the solid crystal is called interstitial solid solution.
Examples are:
i) Na+ ion is replaced by Sr+2 if small amount of SrCl2 is added in molten NaCl is and
allowed to crystallization. In this case to get electrical neutrality each two Na+ ion is re-
placed by one Sr+2 ion from the crystal. In the crystal one Sr+2 ion occupy the lattice
point of one Na+ ion and lattice point for other Na+ ion is vacant. So cation vacancy in
the crystal is equal to the doped Sr+2 ion.
ii)Ag+ ion is replace by Cd+2 if small amount of CdCl2 is added in molten AgCl is and
allowed to crystallization. In this case to get electrical neutrality each two Ag+ ion is re-
placed by one Cd+2 ion from the crystal. In the crystal one Cd+2 ion occupy the lattice
point of one Ag+ ion and lattice point for other Ag+ ion is vacant.So cation vacancy in the
crystal is equal to the doped Cd+2 ion.
Electrical property of solid: On the basis of electrical conduction solid can be divided
in to three category-
i) Conductors
ii) Semiconductors and
iii) Insulator
i) Conductors: The solid materials through which electricity can pass easily are called
conductors. Metals are very good conductor of electricity. Silver metal is the best con-
ductor among the metals. The free electrons present in the metal are responsible for the
conduction. For this reason metals are also called electronic conductor. Copper(Cu), Alu-
minium(Al), Platinum(Pt), Gold(Au) etc.areexamples of conducting materials. The normal
value of electrical conduction of the metals are in the order of 108 ohm−1 .m−1 .
ii) Semiconductors:The solid materials through which electricity do not pass easily are
called semiconductors. Their electrical conducting power in between good conductors and
insulator. These materials are called semiconductor. Germanium(Ge), Silicon(Si) met-
als and some other metal oxides like Cu2 O, CuO, Fe2 O3 , FeO and Cr2 O3 are examples
of semiconductors. The normal value of conductivity of semiconductors are in the order
104 ohm−1 .m−1 .
iii) Insulator: The solid materials through which electricity do not pass are called insu-
lator. Their electrical conducting power is really zero. Wood, bricks, some plastics, rubber
and Mica etc. are examples of insulators. The normal value of conductivity of insulators
are less than 10−20 ohm−1 .m−1 .
Band theory: Metals are usually crystalline with common coordination number twelve
(12). Actually the metals atoms are linked by a special type of bonds known as metallic
bond. In metal the atoms loose the valence shell electrons and become positive charge. The
released electrons are not bound up with any particular metal ion, means the matrix of
positive ions remains embedded in a sea of mobile electrons. The band theory explains the
position of these mobile electrons and the process of electrical conduction. In crystal, when
they occupy a definite positions, the electrons are subjected to a non-uniform electric field.
The electrons may now take position in the band.The band however non-continuous, but
separated by forbidden zones.
Molecular orbital picture of H2
In metals, due to high coordination number, valence shell electrons are not sufficient for
pairing with all surrounding atoms to form covalent bonding. Hence, the lower bands are
filled up first but the upper band are farthest from from the nucleolus and they are empty
or partially filled due to insufficient electrons. The lower energy band is called valence band
3.4. DOPING 125
and the upper energy band is called conduction band. The metallic bond structure can be
explain by the help of molecular orbital theory. In case of metallic compound molecular
theory is called band theory. According to molecular orbital theory, two molecular orbital
are formed by the combination of two atomic orbital. Out of these two molecular orbital
the energy of one orbital is lower than the energy of each atomic orbital, which is called
bonding molecular orbital. The other molecular orbital have higher energy than the atomic
orbital and called antibonding molecular orbital.
Electrical conduction of metal with the help of band theory
The electrical conduction in metals will takes place when the valence shell is partly full,
or the valence and conduction bands are overlap. In case of valence shell is completely
filled and there is overlap between valence band and conduction band on application of a
potential, the valence band electron will not move and acceptance of electrons will also be
forbidden. In such case the partially filled or unfilled electrons in the conduction band may
shift to a slightly higher level in the same band. Thus there becomes a possibility of the
transfer of electrons from one atom to another atom, which will lead to electrical conduction.
Band theory for conduction of current
Metals are good conductor electricity and the electrical conduction of the metals are in the
order of 108 ohm−1 .m−1 .
In case of insulator every atoms is covalently linked with the nearest surrounding atoms and
hence the valence band is completely filled and perturbation within the band are imposable
with an appreciable difference in energy gap (band gap) between the valence and conduction
band.
3.5. SEMICONDUCTOR 127
Band theory in case of insulator
Electrons therefore cannot be promoted and if very high electrical potential be applied
there will be rupture of the crystal instead of conduction. The normal value of conductivity
are in the order 10−22 ohm− .m− .
In case of semiconductor a small amount of electric current can flow at room temperature
and the normal value of conductivity of semiconductors are in the order 102 to10−9 ohm−1 .m−1 .
With rise in temperature the electrical conduction of semiconductor increases due to tran-
sition of electron from valence band to the conduction band.
3.5 Semiconductor
Semi-conductors are solid metal having electrical conducting power in between metal con-
ductors and insulator.
Band theory in case of semiconductor

In semiconductors such as silicon and germanium, valence band is also filled. However, the
band gap between the filled up valence band and the nearest conduction band is small. At
room temperature, kinetic energy associated with electrons is sufficient to promote some
electrons to the conduction band and a small degree of electrical conductivity is shown
by the semi conductor. Electrical conductivity of semiconductors increase with increase in
temperature, since more electron can jump to the conduction band. Examples are Ger-
manium(Ge), Silicon(Si) metals and some metal oxides.. On the basis of mechanism of
conduction semiconductors are two types-
i) Intrinsic semiconductor
ii) Extrinsic semiconductor
3.5.1 Intrinsic Semiconductor

Semiconductors are the solids which are perfect insulators at absolute zero. However they
conduct electric current at room temperature in pure state. Silicon(Si) and Germanium(Ge)
are important two examples of semiconductors. Pure Silicon and germanium crystallizes
with similar pattern like diamond in which each atom is bonded to four other atoms. At
room temperature the conductivity of either silicon or germanium is extremely low, since
there is no free or conducting electrons in metals. However, at higher temperatures, the
crystal bonding breaks down, electrons are ejected and are able to move through the crystal
structure. Hence the conductivity increases. The materials which show such type of semi
3.6. TYPES OF SEMICONDUCTOR 129
conduction without any external materials called intrinsic semiconductor. This type of con-
duction is called intrinsic conduction as it can be introduced in the crystal with out adding
any external materials. Conductivity of intrinsic semiconductors being very low, they have
no practical use. However their conductivity can be increased by adding an appropriate
amount of impurity.
3.5.2 Extrinsic semiconductor due to added impurities

Silicon and germanium (group 14 elements) in pure state have very low electrical conduc-
tivity. However, the electrical conductivity of those elements can be improved by adding
small amount of impurities (mainly elements of group 13 or group 15). These impurities
are called doping agent or dopant. Appropriate doping agent increase the conductivity of
semiconductors upto 104 times. Doping enhances the conductivity of semiconductor and
called extrinsic semiconductor. The increase in conduction is due to participation of impu-
rity elements in between the valence band and conduction band and thus making a bridge
through which electrons can jump easily from the valence band to the conduction band.
For example, addition of boron to silicon at the rate of one atom per million of silicon
atoms, increase the conductivity by a factor of approximately one hundred thousand (from
4 × 108 ohm−1 cm−1 to 0.8 ohm−1 cm−1 at room temperature). Semiconductors are used in
transistors, photoelectric devices and rectifiers.
3.6 Types of semiconductor

There are two types of semiconductor-
i) n-type semiconductor
ii) p-type semiconductor
3.6.1. n-type semiconductor: Here n stands for negative. n-type semiconductors are
obtained due to metal excess defect or by adding trace amount of group 15 elements
[like phosphorous(P), Arsenic(As), Antimony(Sb)] having electronic configuration
ns2 np3 to extremely pure silicon or germanium by doping. The valency of Germa-
nium(Ge), Silicon(Si) is 4. Each Germanium(Ge), Silicon(Si) atom in the crystal is
attached with 4 atom of respective metal by 4 covalent bond. When an element of
group 15 (let As) is added to germanium (group 14) crystal, keeping the same crys-
tal structure, some of the atoms of germanium are replaced by arsenic. In such case
four electrons out of 5 valence electrons of impurity element (let P) is used in form-
ing covalent bonds to 4 atoms of germanium while the fifth electrons remains unused.
n-Type semiconductor semiconductor
This extra electron can serve to conduct electricity as in case of metals. Here group
15 element (P, As, Sb, Bi) is called donor. As a result germanium containing im-
purities of arsenic, it is arsenic doped germanium which exhibit fairly high electrical
conductivity. Silicon doped with a group 15 element (P, As, Sb, Bi) is called an
n-type semiconductor. Here n standing for negative since electrons are used for the
conduction of electricity.
3.6.2. p-type semiconductor: Here p stands for positive. p-type semiconductors are ob-
tained due to metal deficiency defect or by doping with impurity atoms containing
less electron (element of group 13) than the parent insulator to the lattice of an in-
sulator. On adding trace amount of group 13 elements [like boron(B), gallium(Ga)
or indium(In)] having electronic configuration ns2 np1 to extremely pure Silicon or
germanium by doping. The valency of Germanium(Ge), Silicon(Si) is 4. Each Ger-
manium(Ge), Silicon(Si)atom in the crystal is attached with 4 atom of respective
metal by 4 covalent bond. When an element of group 13 (let In) is used in forming
covalent bonds to 3 atoms of germanium while there is a short of electron to form
4th bond to the neighbour germanium indium atoms are not able to fully satisfy the
tetra valency of germanium because they have one electron less than germanium.
p-Type semiconductor semiconductor

3.7. NUMERICAL PROBLEM 131
Hence some of the sites which were normally occupied by the electrons, will be left un-
occupied. This gives rise to electron vacancies, commonly known as positive holes, because
the net charge at these site is positive. On application of the electric field, electrons from
adjacent sites move into the positive holes resulting in the formation of new positive holes
and thus this phenomenon continues and current is carried through out the crystal lattice.
Here group 13 element (B, Al, Ga, In) is called acceptor. Thus doping of germanium crystal
with boron, indium and Gallium increase the conductivity of germanium. Since the current
in this case is carried due to the migration of positive holes, this type of conduction is called
p-type semiconductor..
Difference between p-type and n-type semiconductor:
p-type semiconductor n-type semiconductor
1. These are the intrinsic 1. These are the intrinsic
semiconductors which or pure crystalline which
have been doped by a have been doped by a
trivalent element like Boron trivalent element like arsenic
2. In these semiconductors, 2. In these semiconductors,
conduction is mostly conduction is mostly
by transfer of positive hole by transfer of free electrons
3. Such type of 3. Such type of
semiconductors is produced semiconductors is produced
due to metal deficiency defect due to metal excess defect
4. In these semiconductors, 4. In these semiconductors,
there is excess of electrons 4. there is excess of holes
5. In these semiconductors, conduction 5. In these semiconductors, conduction
is due to positive electric charge is due to negative electric charge
6. In these semiconductors, conduction 6. In these semiconductors, conduction
is increase with rise in temperature is increase with rise in temperature
3.7 Numerical Problem

3.21.1.1. On adding little indium to germanium metal, we get(Dec-2014)
A) rectifier B)insulator C) n-type semiconductor D) p-type semiconductor.
Ans. D) p-type semiconductor.
3.21.1.2. Which of the following defects arise due to misplacement of ions in a crystal lattice?
A) Schottkey defect B)Frankel defect C) Metal excess defect D) non-stoichiometric
defect
Ans. A) Schottkey defect
3.21.1.3. Arsenic dopped silicon is an example of- (June-2014)
a) p-n-type semiconductor b) n-type semiconductor c) p-type semiconductor d)
n-p-type semiconductor.
Ans.b) n-type semiconductor
3.21.1.4. F-centers are found in some crystals due to a) electron trapped in cation vacancy
b) electron trapped in anion vacancy c) presence of interstitial cation d) none of
these.
Ans.b) electron trapped in anion vacancy
3.21.1.5. A metal deficient ionic compound acts as (June-2013)

a) n-type semiconductor b) p-type semiconductor c) intrinsic semiconductor d)
none of these.
Ans.b) p-type semiconductor
3.21.1.6. Germanium is an example of (Dec-2012)

a) intrinsic semiconductor b) n-type semiconductor c) p-type semiconductor d)
insulator.
Ans.a) intrinsic semiconductor
3.21.1.7. Schottky defect is due to

a) missing of anion from a lattice b) missing of cation from a lattice c) missing of
cation and anion both from a lattice d) none of these.
Ans.c) missing of cation and anion both from a lattice
3.21.1.8. Which of the following metal containing compounds can show metal deficiency
defects ?
a) Sodium b) Silver c) Calcium d) Copper.
Ans.a) Sodium
3.21.1.9. Which defect causes decrease of density of crystal ? (June-2012)

a) Interstitial Defect b) Schottky Defect c) Frenkel Defect d) F-centre Defect.
Ans.b) Schottky Defect
3.21.1.10. Germanium is an example of a) intrinsic semiconductor b) n-type semiconductor

c) p-type semiconductor d) an insulator.
Ans.a) intrinsic semiconductor
3.21.1.11. ZnO is white when cold and yellow when hot, because of
a) charge transfer b) d-d transfer c) metal excess defect d) none of these.
Ans.c) metal excess defect
3.21.1.12. Schottky defect is found in (Dec-2011)

a) NaCl b) ZnO c) AgCl d) FeO.
Ans.a) NaCl
3.21.1.13. With the increase in temperature, conductivity of p-type semiconductor a) in-

creases b) decreases c) is changed but the direction of change cannot be predicted
3.7. NUMERICAL PROBLEM 133
d) does not change.

Ans.a) increases
3.21.1.14. Indium dopped silicon is a (June-2011)

a) p-type semiconductor b) n-type semiconductor c) p-n-type semiconductor d)
none of these
Ans.a) p-type semiconductor
3.21.1.15. Schottky defects consist of

a) anion vacancy and cation vacancy b) only cation vacancy c) only anion vacancy
d) excess cation in the interstitisl position.
Ans.a) anion vacancy and cation vacancy
3.21.1.16. ZnO is white when cold and yellow when hot. This is due to (Dec-2010)
a) charge transfer b) d-d transition c) metal excess defect d) Schottky defect.
Ans.c) metal excess defect
3.21.1.17. The electrons trapped in anion vacancies in metal excess defects are known as
(June-2010)
a) valence electrons b) F-centres c) mobile electrons d) trapped electrons.
Ans. F-centres
3.21.1.18. The material used in the solar cell contains

a) Cs b) Si c) Sn d) Ti.
Ans. Si
3.7.2 Short type question

3.21.2.1. Write down the difference between Schottky defect and Frenkel defect. (Dec-2014)
3.21.2.2. Distinguish between p-type and n-type semiconductor?
3.21.2.3. Explain why the colour of ZnO is white when hot and yellow when cold. 3+2
(June-2014)
3.21.2.4. What is the difference between n-type and p-type semiconductors ?
3.21.2.5. What do you mean by pseudounimolecular reaction ? Give an example. 2 +

3(Dec-2011)
3.7.3 Long type question

3.21.3.1. Give example of n-type and p-type dopent. 2.5(Dec-2014)
3.21.3.2. Write down a short note on Schottky defect. 3(June-2014)

3.21.3.3. Discuss the defect encountered in ZnO.
3.21.3.4. Why does NaCl when heated in presence of Na vapour turn yellow ? 3 + 3(June-
2013)
3.21.3.5. Write short notes the following :

d) Schottky and Frenkel defects.
3.21.3.6. Distinguish between p-type and n-type semiconductors. Give two important kinds
of example of semiconductors. 5(Dec-2012)
3.21.3.7. Write notes on any three of the following:

e) Schottky defect and Frenkel defect (June-2012) 10.
3.21.3.8. Differentiate between Schottky and Frenkel defects with the help of diagram. 5
3.21.3.9. What is colour centre generator ? Explain with example. 3(Dec-2011)
3.21.3.10. Distinguish between Frenkel and Schottky defect. 3
3.21.3.11. What is p-type semiconductor? Give an example. 5 (June-2011)
3.21.3.12. What is stoichiometric and non-stoichiometric defects? Explain with example. 2
3.21.3.13. Write short notes (Dec-2010)

e) Role of germanium as semiconductor
3.21.3.14. What are the differences between p-type and n-type semiconductors ? 3(June-
2010)
3.21.3.15. CdCl2 will induce Schottky defect if added to AgCl crystal. 3

Chapter 4
ELECTROCHEMISTRY
4.1 Concept of electrochemistry

Electrochemistry is a branch of chemistry where we will study how chemical energy can be
transformed into electrical energy and vice versa. Substances which conduct electricity or
current are termed as conductors. Metals and electrolytes are good conductor of electric-
ity; metal carries current by flow of electron where no matter is being transported during
current flow whereas in case of electrolytes, movement of ions (matter) is responsible for
electricity flow. During current flow an internal force of the conductor resist the flow of
current through it which is known as resistance of the conductor.
4.2 Conductance
According to Ohm’s law, resistance (R) of any conductor is directly proportional to its
length (l) and inversely proportional to its area of cross section (a). Ohm’s law can be
expressed as:
l
R = ρ
a
; where is specific resistance or resistivity. When l=1 cm and a=1 cm2 then ρ will be equal
to R. Hence specific resistance or resistivity of a conductor can be defined as the resistance
of the conductor having 1 cm length and 1 cm2 area of cross section.
Unit of resistance is ”ohm” and unit of specific resistance can be determined as:
l
R = ρ
a
l
or, ρ = R
a
135
136 CHAPTER 4. ELECTROCHEMISTRY
Unit of specific resistance

ohm.cm.cm
=
cm
= ohm.cm
Conductance (Λ) can be defined as reciprocal of resistance.
4.2.1 Specific conductance

specific conductance (κ) can be defined as reciprocal of specific resistance. Conductance
is basically the ease of current flow through a liquid conductor. specific conducatance is
defined by the conductance of a solution of the dissolved electryle and the whole solution
is being placed between two electrode of 1 sq. cm area and 1 cm. Unit of conductance will
simply be reciprocal of unit of resistance i.e.,
1
= ohm−1 = mho.
ohm
Unit of specific conductance =
1
= mho.cm−1
ohm.cm
4.2.2 Equivalent conductance

Form the expression of conductance, we know that
1
Λ =
R
1a
=
ρl
1al
=
ρll
V
= κ 2;
l
where V = volume of the solution = area × length= a × l
Equivalent conductance is defined by the conductance of a solution containing 1 gm-
equivalent of the dissolved electrolyte and the whole solution is being placed between two
electrode of 1 sq. cm area and 1 cm apart.
Thus equivalent conductance
(Λ) = κV
4.2. CONDUCTANCE 137
(as l = 1 cm2 )
Now, say Ceq gm-equivalent dissolved in 1000 cc of solution
So, 1 gm-equivalent will be present in
1000
cc solution.
Ceq
So, equivalent conductance
1000κ
(Λ) =
Ceq
cm3
Unit of equivalent conductance = mho.cm−1 × .
gm-equivalent
mho.cm2
=
gm-equivalent
= mho.cm2 .gm-equivalent−1
4.2.3 Molar conductance

Molar conductance is defined by the conductance of a solution containing 1 gm-mole of the
dissolved electrolyte and the whole solution is being placed between two electrode 1 cm
apart.
Molar conductance
(Λm ) = κV
(V = volume of a solution containing 1 gm-mole dissolved electrolyte)

Now, say CM gm-mole dissolved in 1000 cc of solution
So, 1 gm-mole will be present in
1000
cc solution.
CM
So, equivalent conductance
1000κ
(Λ) =
CM
cm3
Unit of molar conductance = mho.cm−1 × .
gm-mole
mho.cm2
=
gm-mole
= mho.cm2 .gm-mole−1
Relation between equivalent conductance and molar conductance Let us consider

an electrolyte (molecular weight M) having weight W gm taken in between two electrode
(in the cubic core);p and q are the valency and number of cations are respectively.
M
Now, equivalent weight of the electrolyte is; E =
pq
W
C gm equivalent equivalent =
E
W
= m
pq
W × pq
=
M
1000κ
Now, equivalent conductance = Λ =
c
1000κ
=
W×pq
M
1000κ
=
M gram mole × pq
Λm
=
pq
So,
Λm = Λ × pq
4.3 Effect of temperature on equivalent conduc-

tance
In general equivalent conductance should increase with temperature as with increased tem-
perature, the dissociation of electrolyte and ionic mobility of ions incresaes. Conductance
4.4. EFFECT OF CONCENTRATION ON EQUIVALENT CONDUCTANCE 139
and temperature are corelated by this equation:
Λ0T = Λ0 0 [1 + α(T − 250 C];

25 C
where Λ0T and Λ0 0 are the equivalent conductance at T0 C and 250 C respectively; α is
25 C
the temperature coefficient.
4.4 Effect of concentration on equivalent conduc-

tance
Conductance of an electrolyte depends on the number of ions present in the solution and the
speed of the ions which is known as ionic mobility. As strong electrolyte already completely
dissociated in solution hence number of ions do not changes with dilution. Therefore, the
conductance of a strong electrolyte depends upon only the ionic mobility of the ions present
in solution. In a concentrated solution, the density of ions are high as the the attraction
between ions are high. According to Debye and Huckel, at high concentration a particu-
lar type of ion is surrounded by the opposite charged ions and thus a ionic cloud is being
created. A cationic cloud formed on an anion and vice versa. These ionic clouds are gen-
erally spherical when no electric fields is present. But in presence of an external electrical
field these ionic spheres get distorted. As the extend of ionic cloud distortion increases
the the ionic mobility decreases. This is commonly known as relaxation effect. As dilution
increases, the extend of this distortion decreases or the attraction between ions decreases;
as a result the ionic mobility or the conductance of the solution increases. With increase
in concentration, the equivalent conductance of any electrolyte decreases but the pattern
of the graph is different for strong and weak electrolyte. Conductance generally depends
upon the number of ions and speed of ions (ionic mobility).
Strong electrolytes are completely dissociated in solution and hence decrease in concentra-
tion or increase in dilution will increase the ionic mobility only. Hence the with dilution
equivalent conductance will increase slightly in a regular straight line. At infinite dilution
this value will reach at its maximum which is termed as limiting equivalent conductance
(Λ0 ). Example of strong electrolytes are NaCl, KCl, K2 SO4 ,HCl, H2 SO4 , HNO3 , NaOH,
KOH etc.
Equivalent conductance vs concentration for strong electrolyte

The relationship between concentration of any electrolyte and its equivalent conductance is
given by Debye-Huckel-Onsagar equation:
√
Λeqv. = Λ0 − b c;
where b is a constant and its value depends upon stoichiometry of the electrolyte of interest,
c is the concentration of the electrolyte in gm-eqv./L.
Weak electrolytes are partially dissociated in solution and hence with increase in dilution
or decrease in concentration both the dissociation of electrolytes and the number of ions
increases. These two combine effect increases equivalent conductance exponentially and
becomes almost equal parrallel to y-axis.
Equivalent conductance vs concentration for weak electrolyte

Thus at infinite dilution, the equivalent conductance of a weak electrolyte can not be deter-
mined. But from Kohlrausch’s law, indirectly we can calculate that. So for weak electrolyte
4.5. TRANSPORT NUMBER AND IONIC CONDUCTANCE 141
when equivalent conductance reaches maximum at almost complete dissociation, i.e.; disso-
ciation constant (α) is close to unity. α can be expressed as a ratio of equivalent conductance
at a certain concentration of a electrolyte(Λ) with equivalent conductance at infinite dilu-
tion Λ0 of same electrolyte.
4.5 Transport number and Ionic conductance

Transport number can be defined as fraction of current transported by a particular type of
ion in a solution of electrolyte.
So, transport number for cation
I+
t+ =
I
and transport number for aniion
I−
t− = ;
I
where I+ is the amount of current carried by cation and I− is the amount of current carried
by anion. Current carried by any type of ion depends upon speed of ions (u), charge of the
ions (c) and valency of ion (z). Thus
I+ ∝ u+ c+ z+
and
I− ∝ u− c− z−
Hence,
u+ c+ z+
t+ =
(u+ c+ z+ ) + (u− c− z− )
and
u− c− z−
t− =
(u+ c+ z+ ) + (u− c− z− )
Thus,
u+
t+ =
(u+ ) + (u− )
and
u−
t− =
(u+ ) + (u− )
Let us consider at infinite dilution the ionic conductance of cation is λc and ionic conduc-
tance of anion is λa . Now as ionic conductance varies directly proportional to speed of that
particular type of ion-
u+ ∝ λc and u− ∝ λa
Thus,
λc λa
t+ = and t− =
(λc + λa ) (λc + λa )
λc λa
or, t+ = and t− =
Λ0 Λ0
So, transport number of a particular type of ion can be expressed as fraction of conductance
at infinite dilution offered by that particular type of ion.
Transport number by Hittroff’s method
4.6 Mobility of H+ and OH− ions in aqueous solu-

tion
The ionic mobility and hence the conductance value of both H+ and OH− ion is very
high. The conductance value of H+ and OH− ions are 350 mho.cm2 .mole−1 and 200
mho.cm2 .mole−1 respectively.
Earlier it was considered that high charge density of both the ion is responsible for this
abnormal high conductance. But in aqueous solution the H+ ion basically exists as a
hydroxonium ion H3 O+ . The high mobility can be explained by the fact that from hydrox-
onium ion the H+ ion migrates to neighboring water molecule and thus the proton molecule
is transported from one molecule to other molecule of water. Thus in presence of an external
field water molecule migrates from one molecule to another molecule. A proton does not
travel an entire distance up to the electrode rather it only travels the distance between two
water molecule. This mechanism is known as Grotthus-type mechanism.
4.7. KOHLRAUSCH’S LAW 143
Hydroxyl ion are getting transported in similar manner. The major difference is that in
proton transfer proton transported from hydroxonium ion to water molecule but in case for
hydroxide ion transport proton transported from water to adjacent hydroxide ion.
4.7 Kohlrausch’s law

Kohlrausch observed that the difference in equivalent conductance of a pair of electrolyte
is same when the pair of electrolyte consists of same counter ion at same temperature and
when same solvent is being used.
Thus from the table we can see that difference in equivalent conductance at infinite
dilution between K and Li salt is always almost same as the anion counter part is same
for the pair. This can be explained as at infinite dilution, there exists no other attraction
between ions, the conductance of any particular ion of different electrolyte will be same.
The ionic conductance of chloride ion will be same for a sodium chloride solution as well as
for a potassium chloride solution at infinite dilution. Hence the difference of conductance
between NaCl and KCl will be the difference between Na+ and K+ as the value of chloride
ion will cancel out. Thus it can be said that the attraction among ions at infinite dilution
will be almost negligible.
The equivalent conductance of an electrolyte will be equal to the sum of the ionic conduc-
tances of the corresponding ions created by that electrolyte at infinite dilution.
If equivalent conductance of an electrolyte at infinite dilution is Λ0 and ion conductance of
cation and anion are λ0c and λ0a respectively then according Kohlrausch’s law-
Λ0 = nc λ0c + na λ0a
; where nc and na are number of cation and anion respectively. Thus according to this law
the equivalent conductance of Λ0 Ca (PO ) at infine dilution will be
3 42
Λ0 Ca (PO ) = 3λ0 +2 + 2λ0

3 42 Ca PO4 -3
By using Kohlrausch’s law, we can determine the equivalent conductance of an weak

electrolyte at infinite dilution which can not be determined experimentally. If we need to
determine the equivalent conductance of benzoic acid (an weak electrolyte) at infinite dilu-
tion then we can write logically that-
Λ0(PhCOONa) = Λ0 + + Λ0
Na PhCOO−
Λ0( NaCl) = Λ0 + + Λ0 −
Na Cl
0 0
Λ (HCl) = Λ + + Λ −0
H Cl
0 0 0 0
Λ (PhCOONa) + Λ (HCl) − Λ (NaCl) = Λ + + Λ0 + Λ0 + + Λ0 − − Λ0 + − Λ0 −
Na PhCOO− H Cl Na Cl
= Λ 0 0
+Λ +
PhCOO− H
0
= Λ (PhCOOH)
4.8 Conductometric titration
Conductance is being measured in this type of titration method, a graph is generally plot-
ted (conductance vs titrant) and from graph we generally determine the equivalent point of
the titration. No indicator needed in these type of titrations; the plotted graph itself will
indicate the end point of the reaction. Depending upon the dissociation in aqueous solution
and ionic mobility, the nature of different conductometric titration graph can be predicted.
Generally an acid is being titrated against a base
4.8.1 Titration of a strong acid and strong base
An example of a strong acid and strong base are HCl and NaOH respectively as they
dissociate completely in aqueous medium. Generally an acid is being titrated against a
base and hence acid solution is taken in a beaker and the base is taken in burette. As the
acid is a strong acid it will dissociate into H+ and OH− ion completely and hence number of
ions will be maximum in the solution. Furthermore as H+ ion has very large ionic mobility
and hence ionic conductance, the solution will show high conductance.
4.8. CONDUCTOMETRIC TITRATION 145
Titration curve: Strong acid vs strong base
Now as we add base drop by drop from burette, acid-base reaction will take place. As the
base is strong one also, it will also dissociate into Na+ and OH− ion completely. During the
acid-base reaction, the OH− ion will consume H+ to form water. So, we can say as drops
of NaOH will be added, H+ ion will be consumed by OH− and Na+ ion will be added in
solution. So, we can say that as titration will proceed each Na+ is being replaced by Na+ .
Now ionic conductance of Na+ is less compared to H+ and hence conductance will decrease
as the titration will proceed.
After reaching equivalent point when all the H+ ion is consumed, additional addition of
NaOH will simply add more Na+ and OH− in solution and hence conductance will increase
again. If will plot a conductance vs drops of base, we will get a graph like this. Now in first
half the decrease of conductance is due to removal of H+ and in second half of the graph
the increase of graph is due to addition of OH− . As ionic conductance of H+ is higher than
OH− , the rate of decrease will be more faster than the rate of increase or the decrease line
will be much more steeper than the increase line.
H+ + Cl− + Na+ + OH− = Na+ + Cl− + H2 O
4.8.2 Titration of a weak acid and strong base

An example of a weak acid and strong base are CH3 COOH and NaOH respectively. As
the acid is a weak acid it will dissociate partially into H+ and CH3 COO− ions and hence
number of ions will be few in the solution and hence the solution will show low conductance
value. Now as we add few drops of base from burette, acid-base reaction will take place.
Titration curve: Weak acid vs strong base
As the base is strong one also, it will also dissociate into Na+ and OH− ion completely.
During the acid-base reaction, the OH− ion will consume H+ to form water. So, we can
say by addition of few drops of base at first conductance will decrease slightly. Now as we
move further wilh addition of more drops of base, all H+ will be consumed and hence the
dissociation of the weak acid will increase which will be reflected by gradual increase in
conductance value.
Beyond the equivalent point when all the H+ ion is consumed, additional addition of
NaOH will simply add more Na+ and OH− in solution and hence conductance will increase
again sharply. If will plot a conductance vs drops of base, we will get a graph like this.
Now in first half the increase of conductance is due to more dissociation of acetic acid and
in second half of the graph the increase of graph is due to addition of OH− .
CH3 COOH + Na+ + OH− = CH3 COO− + Na+ + H2 O
4.8.3 Titration of a strong acid and weak base
An example of a strong acid and weak base are HCl and NH4 OH respectively. As the acid
is a strong acid it will dissociate into H+ and OH− ion completely and hence number of
ions will be maximum in the solution. Furthermore as H+ ion has very large ionic mobility
and hence ionic conductance, the solution will show high conductance.
4.8. CONDUCTOMETRIC TITRATION 147
Titration curve: Strong acid vs weak base
Now as we add base drop by drop from burette, acid-base reaction will take place. During
the acid-base reaction, the OH− ion will consume H+ to form water. So, we can say as
drops of NH4 OH will be added, H+ ion will be consumed by OH− and NH+ 4 ion will be
added in solution. So, we can say that as titration will proceed each Na+ is being replaced
by NH+ + +
4 . Now ionic conductance of NH4 is less compared to H and hence conductance
will decrease as the titration will proceed.
After reaching equivalent point when all the H+ ion is consumed, additional addition of
NH4 OH will have no effect. This is due to the fact that NH4 OH will not dissociated fur-
ther as it is weak base and due to common ion effect. So, the conductance value will be
unchanged or we will get a parallel line to X-axis.
H+ + Cl− + (NH+ + + −
4 + OH ) = NH4 + Cl + H2 O
4.8.4 Titration of a weak acid and weak base
An example of a weak acid and strong base are CH3 COOH and NH4 OH respectively. As
the acid is a weak acid it will dissociate partially into H+ and CH3 COO− ions and hence
number of ions will be few in the solution and hence the solution will show low conductance
value.
Titration curve: Weak acid vs weak base
Now, as we add few drops of base from burette, acid-base reaction will take place. During
the acid-base reaction, the OH− ion will consume H+ to form water. So, we can say by addi-
tion of few drops of base at first conductance will decrease slightly. Now as we move further
with addition of more drops of base, all H+ will be consumed and hence the dissociation of
the weak acid will increase which will be reflected by gradual increase in conductance value.
After reaching equivalent point when all the H+ ion is consumed, additional addition
of NH4 OH will have no effect. This is due to the fact that NH4 OH will not dissociated
further as it is weak base and due to common ion effect. So, the conductance value will be
unchanged or we will get a parallel line to X-axis.
CH3 COOH + (NH4 OH) = CH3 COO− + NH+

4 + H2 O
4.8.5 Precipitation titration of KCl with AgNO3
KCl and AgNO3 both are strong electrolyte and hence they dissociate completely in aqueous
medium. KCl is being titrated against AgNO3 and hence KCl solution is taken in a beaker
and AgNO3 is taken in burette.
4.9. ELECTROCHEMICAL CELL 149
Titration curve: Precipitation titration
As KCl is strong electrolyte it will dissociate into K+ and NO−

3 ion completely and hence
number of ions will be maximum in the solution and hence the solution will show high
conductance. Now as we add AgNO3 drop by drop from burette, a precipitation of AgCl
will occur.
K+ + Cl− + Ag+ + NO−

3 = AgCl ⇓ +K+ + NO−
3
Now, as AgCl precipitated, chloride ion is removed from the solution and nitrate ion is
introduced in the solution. So, we can say that as titration will proceed each chloride is
being replaced by a nitrate ion. The ionic conductance value of chloride and nitrate is
comparable and hence there will not be any effective change of conductance.
After reaching equivalent point when all the Cl− ion is consumed, additional addition of
AgNO3 will simply add more Ag+ and NO− 3 in solution and hence conductance will increase
again. If will plot a conductance vs drops of base, we will get a graph like this. Now in
first half there will be no change in conductance and hence we will observed a straight line
parallel to X-axis and then in the second half an increase of conductance will be observed.
The point where two line intersect will be the equivalent point.
4.9 Electrochemical cell

Chemical reaction can take place by passing electrical energy under suitable condition. This
is commonly known as electrolysis. The device, where this transformation may take place
is known as electrolytic cell.
In case of reverse electrolysis, spontaneous chemical reaction generates electrical energy and
the device where this phenomenon happens is known as electrochemical cell or galvanic cell.
An example of electrochemical cell is Daniel cell. In this section we will discuss details of
electrochemical cells and how some physical parameters of a solution can be determined
from from it.
4.10 Redox reaction

If in a chemical reaction oxidation and reduction happens simultaneously, then the reaction
is known as redox reaction. In this section we will emphasize on that type of oxidation-
reduction reaction which happens by electron transfer only.
Generally loos of electron is known as oxidation and gain of electron by another species is
known as reduction.
M → M+n + ne 99K oxidation
M+n + ne → M 99K reduction

If a zinc rod is dipped in a blue coloured copper sulphate solution, mettalic zinc will be
oxidised by loosing electron and zinc cation will come into solution whereas copper cation
will be reduced by accepting electron to brown coloured metallic copper and will be de-
posited on zinc rod. Thus with time we will notice the disappearance of blue colour of the
solution and overgrowth of brown copper on zinc rod. This oxidation-reduction (redox) can
be expressed as-
Zn(s) + Cu+2 (aq) → Zn+2 (aq) + Cu(s)

The above stated reaction and the principle can be used to form a galvanic cell which is
known as Daniel Cell.
Galvanic cell
4.10. REDOX REACTION 151
A zinc rod is dipped in a zinc sulphate solution and a copper rod is dipped in a copper
sulphate solution separately. Now if we connect the two rod by an external circuit and an
ammeter is placed in parallel to the circuit.
4.10.1 Salt bridge

Two end of an inverted U-tube is dipped into two beaker containing solution. Both end of
the U-tube is plugged by cotton or wool so that any direct contact of electrolyte solution
and the salt inside salt bridge can be avoided. This U-tube is known as salt bridge and is
filled with electrolyte like KCl, KNO3 or NH4 NO3 etc.
As soon as the external circuit is completed, a flow of electricity will be observed as de-
flection in ammeter will be noticed. This is due to the flow of electron from zinc rod to
copper rod. These rods are termed as electrodes; the zinc rod will be called as ANODE and
the copper will be called as CATHODE. As the electron flows from zinc (Anode) to copper
(Cathode), the zinc rod must be rich of electron and there must be demand for electron at
copper rod. This indicate that electron loss reaction (oxidation) is happening at anode and
electron consumption reaction (reduction) is happening at cathode. The chemical reaction
that is responsible for the generation of electricity will be like this-
At anode
Zn(s) → Zn+2 (aq) + 2e− ( Oxidation)
At cathode
Cu+2 (aq) + 2e− → Cu(s)( Reduction)
Overall reaction
Zn(s) + Cu+2 (aq) → Zn+2 (aq) + Cu(s)
As the negative charged electron flows from zinc rod (anode) to copper rod (cathode),
conventionally the current will flow in opposite direction.
Function of salt bridge: Salt bridge mainly helps in maintaining the electrical neutrality
of both the electrolytic solution used in a Daniel cell. When the redox reaction happens
in a Daniel cell, from anode metallic zinc is converted to zinc cation and comes to solution
hence the solution is enriching with positive charge. To neutralize this positive charge,
negative charged ions like chloride anion etc comes out from the salt bridge and goes into
anode solution. Similarly, at cathode positively charged cations are reduced and hence the
electrolyte solution have a shortening of positive charge. To neutralize this, salt bridge
provide the cations like potassium cation etc.
4.11 General way to represent an electrochemical

cell
Generally ANODE is represented at left hand side and CATHODE is represented at right
hand side and both side is separated by salt bridge. Anode is represented by writing the
metallic electrode first followed by a single bar vertically and then the electrolyte solu-
tion. For cathode, the electrolyte solution is written first followed by the vertical bar and
the metallic electrode. The physical states of both the electrolytic solution and the elec-
trode written in first bracket sometimes. Now in between cathode and and anode a double
vertical bar placed as a symbol for salt bridge. Thus the above Daniel cell be represented as-
Zn(s) | ZnSO4 (aq) k CuSO4 (aq) | Cu(s)
where, the first part is anode and the second part is cathode.
Anode:
Zn(s) | ZnSO4 (aq)
and Cathode:
CuSO4 (aq) | Cu(s)
Sometimes a single electrolyte solution and two electrode used in a galvanic cell. In that
case to represent the cell, no vertical bar is used for salt bridge and the cell is represented as-
Pt (s), H2 ((g)1 atm); HCl((aq)a=1); Cl2(g) ; Pt(s)
4.12 EMF of Cell

In a general galvanic cell electron flow from anode to cathode; this implies that the anode
is rich of electron and cathode have a demand for electron. In very crude scence greater
the difference of electron density in between this two electrode, higher will be the potential
difference between the two half cell. This potential difference basically controls the flow of
electricity in a galvanic cell circuit. The difference in potential between two electrode is
known as electromotive force (EMF). Now, as in anode oxidation takes place so potential
of anode is known as oxidation potential. Similarly the potential of cathode is known as
reduction potential. Electromotive force (EMF) of a cell will be defined as a force which
drives the negatively charged electrons from anode to cathode and hence the electricity flow
from cathode to anode.
Standard EMF or Potential (E0 ): Standard EMF or standard potential of a cell is defined as
the EMF of an electrode when all the component of the cell are in standard state, i.e., solutes
4.13. NERNST EQUATION 153
are at 1M concentration, gaseous components are in 1 atm pressure, solid components are
at their pure state and temperature of the system is at 250 C. EMF of a cell is generally
expressed as Ecell .
The EMF of a cell will be the sum of the two electrode potential;
Ecell = Eanode (oxidation) + Ecathode (reduction)
where Eanode is the oxidation potential of anode and Ecathode is the reduction potential
of cathode.
Now, conventionally cell emf can be written in reduction format, i.e., both the cathode and
anode emf should be expressed in reduction form. The cathode was already in reduction
format and hence we need to change the anode expression from oxidation format to a re-
duction format. Generally a change in sign will do this job.
Ecell = Ecathode (reduction) − Eanode (reduction)
Thermodynamic significance of EMF: As both emf (E) of a cell and Gibbs free energy (∆G)
related to spontaneity of a chemical reaction, hence both can be correlated by an equation-
∆G = − nFE
where n is the number of electron involve in the reaction and F denotes Faraday (96500
coulomb/mole).
As both n and F is positive valued for a chemical reaction, then EMF (E) of a reaction must
be positive for spontaneity of the chemical reaction as in that case ∆G will be negative.
So, for a spontaneous chemical reaction E must be positive and for a non-spontaneous
reaction E will ne negative. For a equilibrium reaction E will be zero.
4.13 Nernst equation

The Nernst equation represents a relationship between cell potential and the concentration
of the reactant and product present in that chemical cell.
Let us consider a chemical reaction-
aA + bB = cC + dD
where a mole A reacts with b mole B and gives c mole C and d mole D as product. Now
change in Gibbs free energy of this chemical reaction can be written as-
∆G = ∆G0 + RTlnQ
where Q is known as reaction quoscent which is very similar to equilibrium constant (K)
and ∆G0 is called as standard change of Gibbs free energy.
Where Q can be expressed as-
[C]c [D]d
Q =
[A]a [B]b
As we know that-
∆G = − nFE
∆G0 = − nFE0
− nFE = − nFE 0 + RTlnQ
RT
E = E0 − lnQ
nF
0.0591
E = E0 − logQ
n
This is Nernst equation which shows how emf of a cell changes with the change of concen-
tration of both reactant and product.
4.14 Single Electrode Potential

The standard potential of a galvanic cell can be expressed as-
E0cell = E0cathode/reduction + E0anode/oxidation

E0cell = E0cathode/reduction − E0anode/reduction
Where E0 is the standard reduction potential of the cathode half cell and
cathode/reduction
0
E is the standard oxidation potential of the anode half cell. The standard
anode/oxidation
potential of any half cell or any one electrode can not be determined directly. We can only
measure the difference in emf between two electrode by constructing cell. In this case if we
can use one standard electrode or reference electrode whose standard potential is zero, then
we can measure the difference or the the standard potential of the other half cell.
Standard hydrogen electrode can solve this problem as the standard potential of hydrogen
electrode is zero. This electrode can be formed by immersing a platinum wire (electrode) in
a acid solution of strength 1(M). Interesting point is that this hydrogen electrode can serve
either as cathode or anode depending upon the nature of other half cell electrode.
As anode: The hydrogen electrode can be used as anode and in that case pure H2 gas is
passed into solution and it is oxides to hydrogen ion (cation) by releasing electron at Pt
electrode. In this case, the other half cell will act as cathode and electron will be transported
from hydrogen electrode to cathode where selective reduction will happen. Any half cell
4.15. STANDARD HALF CELL REDUCTION POTENTIAL 155
electrode whose standard reduction potential is positive can serve as cathode with hydro-
gen electrode as anode to complete a full electrochemical cell where spontaneous chemical
reaction will generate electrical energy.
As cathode:Similarly, the hydrogen electrode can be used as cathode and in that case H+
ion will be reduced to hydrogen gas by accepting electron. In this case, the other half
cell will act as anoode and electron will be transported to hydrogen electrode from anoode
where selective oxidation will happen. Any half cell electrode whose standard reduction
potential is negative can serve as anoode with hydrogen electrode as cathode to complete a
full electrochemical cell where spontaneous chemical reaction will generate electrical energy.
Standard hydrogen electrode (SHE) can be expressed as-
Pt(s) | H2 (g, 1 atm) | H+ (aq, 1 M)

Anode half cell reaction:
1
H2 (g, 1 atm) = H+ (aq, 1 M) + e
2
The reverse will be for cathode half cell reaction. Now for both cases the electrode potential
will be 0 V at 250 C.
4.15 Standard half cell reduction potential

Let us consider to determine the M+n | M half cell standard reduction potential. In this case
we will make a electrochemical cell with this half cell with a standard hydrogen electrode.
If by the completion of external circuit, hydrogen gas bubbling is observed at hydrogen
electrode then hydrogen electrode is acting as cathode. If we observed that hydrogen gas
is consumed at hydrogen electrode, then hydrogen electrode is acting as anode.
If hydrogen electrode acts as cathode, then-
E0cell = E0 + − E0 +n
H |H2 M |M
E0cell 0
= 0 − E +n
M |M
E0 +n 0
= − Ecell
M |M
If hydrogen electrode acts as anode, then-
E0cell = E0 +n − E0 +
M |M H | H2
E0cell = E0 +n − 0
M |M
0 0
E +n = Ecell
M |M
A list of standard reduction potential of some half cell electrode is given here from
higher positive value to lower value. The value of standard reduction potential indicates
the tendency of a species of higher oxidation state to go to a lower oxidation (reduction)
state. If two half cell electrode combine and form a electrochemical cell, that electrode will
act as cathode preferentially with relatively higher standard reduction potential. Now if we
look the standard reduction potential of these two electrode-
E0 +2 = +0.34 V
Cu |Cu
E0 +2 = −0.76 V
Zn |Zn
This value indicates that Cu+2 will preferentially reduced to metallic Cu at cathode and at
anode Zn will be oxidised to Zn+2 as standard reduction potential value of copper system is
higher than zinc system. Point to mention that if we use silver system instead of copper sys-
tem, then Ag+ preferentially reduced to silver at cathode and Cu will be oxidised to Cu+2
at anode as standard reduction potential value of silver system is higher than copper system.
E0 + = +0.80 V
Ag |Ag
4.16 Application of Nernst Equation

4.16.1 Measure of pH of a solution by using hydrogen elec-
trode and standard hydrogen electrode:
An electrochemical cell can be constructed by using standard hydrogen electrode (SHE)
(a=1; acid strength is 1M) and a hydrogen electrode (a=x; acid strength is unknown).
Pt(s) | H2 (g, 1 atm) | H+ (aq, a = 1 M) k H+ (aq, a = x) | H2 (g, 1 atm) | Pt(s)
Here the standard hydrogen electrode acts as anode and hydrogen electrode acts as cathode.
The half cell potential value of standard hydrogen electrode is zero.
The cell potetial of the above cell can be expressed as-
Ecell = Ecathode − Eanode

Ecell = EH+ |H − ESHE
2
Ecell = EH+ |H − 0
2
Ecell = EH+ |H
2
4.16. APPLICATION OF NERNST EQUATION 157
Now the half cell reaction at cathode is-
1
H+ + e = H2
2
So,EH+ |H = E0 + − 0.0591
2 H | H2
So, the Nernst equation for above half cell will be-
1
0 0.0591 [H2 ] 2
EH+ |H = E + − log +
2 H | H2 1 H
1
EH+ |H = 0 − 0.0591log +
2 H
EH+ |H = −0.0591pH
2
Replacing this value in above equation-
Ecell = −0.0591pH
Ecell
pH =
−0.0591
Thus pH of a solution can be determined from observed value of an properly constructed
electrochemical cell.
Measure of pH of a solution by using standard hydrogen electrode and a calomel electrode:
Calomel electrode is a half cell electrode which can be used as a reference electrode. In
combination of calomel electrode and another unknown electrode, the potential of the later
can be calculated from observed cell potential value. Calomel electrode can be constructed
by using mercury, mercurous chloride, and KCl solution in a glass tube. As depicted in
the picture, mercury (Hg) is taken in the glass tube and on top of this a paste of mercury
and mercurous chloride (Hg2 Cl2 ) is placed. Finally a known concentration of KCl solution
placed on top of the paste in such a way that no mixing happens. A Pt wire is attached to
mercury layer only which is connected to electrical circuit.
An electrochemical cell can be constructed by using standard hydrogen electrode as anode
and calomel electrode as cathode-
Pt(s) | H2 (g, 1 atm) | H+ (aq, a = 1 M) k Hg(l) | Hg2 Cl2 (s) | Cl− (aq)
The cathode half cell reaction for calomel electrode will be-
Hg2 Cl2 + 2e → 2Hg(l) + 2Cl− (aq)

We can express the cell potential for this half cell by using Nernst equation-
0.0591 2
EHg Cl2 |Hg = E0Hg Cl |Hg − log[Cl− ]
2 2 2 2
EHg Cl2 |Hg = 0.27 − 0.0591 log[Cl− ]; (E0Hg Cl |Hg = 0.27V)
2 2 2
From the above equation we can say that the value of calomel half cell potential depends
on chloride ion concentration. If we can fix the concentration of KCl or the chloride ion
concentration of a calomel electrode, the half cell potential can be determined. In reality
three varieties of calomel electrode available depending upon KCl concentration.
Now, the cell potential of this electrochemical cell can be expressed as-
Ecell = Ecathode − Eanode

Ecell = EHg Cl2 |Hg − EH+ |H
2 2
Ecell = EHg Cl2 |Hg − (−0.00591pH)

2
Ecell = EH+ |H + 0.0591pH
2
Ecell − EHg Cl2 |Hg

2
pH = [ at 298K]
0.0591
The value of proper calomel electrode potentail is available in literature depending upon
chloride ion concentration and the observed value for cell potential can be determined from
experiment. Hence we can calculate the pH of a acidic solution.
4.16.2 Determination of valency of an ion which have ten-

dency to reduced to pure metal.
Let us consider a metal (M) and its salt (MA) having M+n oxidation state. Now the metal
ion can be reduced to metal or the metal can be oxidised to M+n and hence the valency
of the metal will be n. Now an unknown concentration (a) of salt solution prepared for
a ) prepared for anode.
cathode and exactly 10 fold diluted solution ( 10
So, the concentration of M+n at cathode and anode is a and ( 10 a ) respectively. If we con-
struct a cell from this two solution using M as electrode, then the cell representation and
the reaction at cathode and anode will look like-
a
M | M+n ( ) k M+n (a) | M
10
a
M → M+n ( ) + ne(Anode reaction)
10
+n
M (a) + ne = M(Cathode reaction)
a
M+n (a) = M+n ( )
10
4.17. QUINHYDRONE ELECTRODE 159
The half cell potential of both electrode will be as-

For cathode:
0.0591 1
E +n = E0 +n − log
M |M(cathode) M |M n a
For Anode:
0.0591 1
E +n = E0 +n − log a
M |M(anode) M |M n ( 10 )
Now the expression of complete cell EMF will look like-
Ecell = E +n − E +n
M |M(cathode) M |M(anode)
0.0591 1 0.0591 1
Ecell = E0 +n − log − E0 +n + log a
M |M n a M |M n ( 10 )
0.0591 1 0.0591 1
Ecell = − log + log a
n a n ( 10 )
0.0591 10 0.0591 1
Ecell = log − log
n a n a
0.0591
Ecell = log10
n
0.0591
Ecell =
n
0.0591
n =
Ecell
Thus from the above equation we can determine the valency of the metal (n) just from the
observed emf value of the electrochemical cell.
4.17 Quinhydrone electrode

It is a redox electrode where oxidation and reduction happens on organic substrate quinone
and hydroquinone. An equimolar solution of quinone and hydroquinone is used here and
the platinum wire of the calomel elctrode is attached to it.
The Nernst equation for this half cell reaction will be like-
Q + 2H+ + 2e → H2 Q
0.0591 [H2 Q]
EQ|H2 Q = E0Q|H Q − log
2 2 [Q][H+ ]2
0.0591
EQ|H2 Q = E0Q|H Q − log[H+ ]2
2 2
0.0591
EQ|H2 Q = E0Q|H Q + log[H+ ]2
2 2
EQ|H2 Q = E0Q|H Q + 0.0591log[H+ ]
2
0
EQ|H2 Q = EQ|H Q − 0.0591pH
2
0
EQ|H Q − EQ|H2 Q
2
pH =
0.0591
Thus pH can be determined by using quinhydron electrode.
4.18 Lead Acid storage Cell

Storage cell is a type of electrochemical cell that produces electrical energy during discharg-
ing and again by using electrical energy the cell can be restored. Thus it acts in a reversible
manner. It is used in automobile to start the engine, it enlightens interior and exterior of a
car and used in household as emergency light during load shading. The most widely used
storage cell is lead-acid storage cell. It contain six small similar cells which are connected in
series. This type of cell can provide maximum potential about 12V. A lead-antimony alloy
coated with lead dioxide acts as cathode and sponge lead acts as anode. Both the electrode
dipped in sulphuric acid solution. During discharging the cell provide current and the cell
reaction is-
Pb (s) → Pb+2 (aq) + 2e (Anode reaction)

+ +2
PbO2 (s) + 4H (aq) + 2e → Pb (s) + 2H2 O (aq) (Cathode reaction)
+
Pb(s) + PbO2 (s) + 4H (aq) → 2 Pb+2 (aq) + 2H2 O (aq)( during discharging)
So, during discharging at both electrode Pb+2 (aq) produced and which precipitated as lead
sulphate as sulphate ion present in solution. During discharging water molecule is produced
as by product. During charging the reverse reaction takes place. Lead sulphate dispropor-
tioned between metallic Pb (s) and Pb+4 (aq) and water is consumed during charging. That
is why water needs to be added in storage cell if the cell dried due to evaporation.
4.19. FUEL CELL 161
4.19 Fuel cell

Fuel cell is a type of electrochemical cell where reactants molecules are supplied from ex-
ternal source as needed and the reaction byproducts are removed as the reaction proceeds.
Hydrogen-Oxygen fuel cell: In a Hydrogen-Oxygen fuel cell, hydrogen and oxygen gas com-
bines to produce water and electricity.
Fuel cell
Here in cathode oxygen gas supplied and in anode hydrogen gas supplied. A porous graphite
block with some catalytic platinum or palladium is used as electrode at both electrode. At
cathode oxygen accept electron from electrode and reduced to OH− (aq) ion by the help of
water. This OH− (aq) migrates to anode by porous tube and oxidise hydrogen to water.
O2 (g) + 2H2 O (aq) + 4e → OH− (aq); (at anode)

(H2 (g) + 2OH− (aq) → 2H2 O (aq) + 2e) × 2; ( at cathode)
2H2 (g) + O2 (g) → 2H2 O (aq) (overall cell reaction).
The standard cell potential of this hydrogen-oxygen fuel cell is 1.229V. The efficiency of the
cell can be increased by controlling the pressure of the reacting gases, rate of diffusion of
the gases inside the electrode and proper catalyst.
Application of fuel cell: This type of small electrochemical cell can be used in portable
instruments like laptops, camera’s, cell-phones etc and as well as in pacemaker, hearing aid
etc. It is used in space craft, submarines, military vehicle etc.
4.20 Determination solubility product of a spar-

ingly soluble salt
Let us consider a sparingly soluble salt PbSO4 and hence solubility product of this salt will
be-
Ksp = [Pb+2 (aq)][SO−2

4 (aq)]
This can be correlated with the equilibrium constant of a reaction like-
PbSO4 (s) Pb+2 (aq) + SO−2

4 (aq)
So, to evaluate the value of Ks we need to construct a electrochemical cell where a net above
reaction happens-
Pb (s) | PbNO3 (aq) k K2 SO4 (aq), PbSO4 (s) | Pb (s)

Pb (s) → Pb+2 (aq) + 2e(Anode )
PbSO4 (s) + 2e = Pb(s) + SO−2
4 (aq)(Cathode)
PbSO4 (s) + 2e = Pb+2 (aq) + SO−2
4 (aq)
Now standard EMF of the cell will be-
E0cell = E0cathode − E0anode

E0cell = E0 +2 − E0PbSO |Pb
Pb |Pb 4
As this is a precipitation reaction, observed cell potential will be zero. Hence we can write
a Nernst equation for the whole cell reaction like this-
0.0591
E0cell = E0cell − logPb+2 SO−2
4
2
0.0591
0 = E0cell − logKs
2
2E0cell
logKs =
0.0591
Thus from the above equation solubility product Ks can be determined.
4.21 Determination of equilibrium constant

For this chemical equation we have established the Nernst equation like this-
aA + bB = cC + dD
0.0591
E = E0 − logQ
n
Now at equilibrium point Q=K (equilibrium constant) and cell potential will be zero as
rate of forward recation will be equal to rate of backward rcation. So, the above equation
can be written as-
0.0591
0 = E0 − logK
n
nE0
logK =
0.0591
nE0
K = 10 0.0591
Thus equilibrium constant (K) can be determined from Nernst equation.

4.23.1.1. What is electrochemistry?
Ans. Electrochemistry is a branch of chemistry where we will study how chemical
energy can be transformed into electical energy and vice versa. Substances which
conduct electricity or current are termed as conductors. Metals and electrolytes
are good conductor of electricity; metal carries current by flow of electron where
no matter is being transported during current flow whereas in case of electrolytes,
movement of ions (matter) is responsible of electricity flow. During current flow
an internal force of the conductor resist the flow of current through it which is
known as resistance of the conductor.
4.23.1.2. Construct a galvanic cell and calculate the cell emf-

Ans.
Pb (s) | PbNO3 aq(1M) k Hg2 Cl2 (l), Cl− aq(0.1M) | Hg (s)

E0 +2 = −0.13V
Pb |Pb
E0Hg Cl | Cl− = −0.28V
2 2
4.23.1.3. The resistance of a KCl solution is 250 ohm and equivalent conductance is 20 mho.cm−2 .
What is the concentration of the solution when electrodes are 5 cm apart and hav-
ing area of section about 10 cm2 ?
Ans.Cell constant ( al ) = 10
5
= 0.5 cm−1
According to Ohm’s law Resistance = Sp. Resistance × cell constant
So, Sp. Resistance = resistance = 250 0.5 = 500 ohm.cm
cell constant
1
Specific conductance = 500 mho.cm−1 = 2 × 10 − 3 mho.cm−1
Now, equivalent conductance
(1000 × sp. conductance)
=
concentration
(1000 × sp.conductance)
Or, concentration =
equivalent conductance
(1000 × 2 × 10−3 )
=
20
= 0.1(N)
So the concentration of the KCl solution is 0.1 (N).
4.23.1.4. A weak acid of having strength 0.01 (N) is showing specific conductance 7.5 ×
10−4 ohm−1 .cm−1 . If the degree of dissociation of this acid is 0.025, find out the
value of conductance at infinite dilution.
Ans.
(1000 × specific conductance)
Equivalent conductance of the acid =
concentration
(1000 × 7.5 × 10−4 )
=
0.01
= 75 mho. cm2 equiv.−1
(Equivalent conductance)
Now, degree of dissociation(α) =
(conductance at infinite dilution)
(Equivalent conductance)
Hence,conductance at infinite dilution =
(degree of dissociation)
75
=
0.025
= 3 × 103 mho. cm−1
4.23.1.5. Equivalent conductance of acetic acid is 15.8 mho.cm2 .equiv−1 at room tempera-
ture. The ionic conductance of acetate anion and hydrogen ion is 35.5 and 349.8
respectively. Calculate the degree of dissociation.
Ans.The equivalent conductance at infinite dilution of acetic acid;
Λ0 = l0 + + l0
H CH3 COO−
= (35.5 + 349.8)mho.cm2 .equiv−1
= 85 mho.cm2 .equiv−1
Equiv. conductance of acetic acid
So, degree of dissociation =
Eqiv. conductance of acetic acid at infinite dilution
15.8
=
385.3
= 0.041
So the degree of dissociation is 4.1%.
4.23.1.6. The equivalent conductance at infinite dilution for sodium benzoate, HCl and
NaCl is 80, 390 and 110 mho.cm2 .equiv−1 respectively. What is the equivalent
conductance of benzoic acid?
Ans. According to Kohlrausch’s law equivalent conductance at infinite dilution
Λ0 = Λ0c + Λ0a ; where Λ0c and Λ0a are ionic conductance of cation and anion at
infinite dilution respectively). Hence, Λ0 (PhCOONa)= Λ0 + + Λ0 =
Na PhCOO−
2 −1
80 mho.cm equiv
Λ0 (NaCl)= Λ0 + + Λ0 − = 110 mho.cm2 equiv−1
Na Cl
Λ0 (HCl) = Λ0 + + Λ0 − = 390 mho.cm2 equiv−1
H Cl
Now, Λ0 (PhCOONa) + Λ0 (HCl) - Λ0 (NaCl) = (80 + 390 − 110) mho.cm2 equiv−1
Or,Λ0 + + Λ0 + Λ0 + + ΛΛ0 − − Λ0 + − Λ0 − = 360 mho.cm2 equiv−1
Na PhCOO− H Cl Na Cl
Or, Λ0 + Λ 0 = 360 mho.cm 2 equiv−1
PhCOO− H+
Or, Λ0 (PhCOONH) = 360 mho.cm2 equiv−1
So, the equivalent conductance of benzoic acid at infinite dilution is 360 mho.cm2 equiv−1 .
4.23.1.7. In a conductivity cell, a 0.01(N) solution of NaCl and KCl shows specific resistance
250 ohm and 200 ohm respectively. Specific conductance of NaCl is 1.6 × 10−3
mho.cm−1 . Calculate the specific conductance and equivalent conductance of KCl
solution.
Ans.For fixed cell, the cell constant ( al )will be constant
l
From Ohm’s law resistant(R) = Sp. resistance(σ) × ( )
a
1 l
Or, 1/R = ( ).( )
σ a
l
For, NaCl solution, (1/250) = (1.5 × 10−3 ) × ( )
a
l
Or, cell constant( ) = 1.6 × 10−3 × 250
a
= 0.4
For KCl solution in the same cell,
l
Resistant (R) = Specific resistance(ρ) × ( )
a
a
Or, Specific resistance(ρ) = Resistant(R) × ( )
l
200
=
0.4
= 500 ohm.cm
1
Hence Specific conductance (1/ρ) = mho.cm−1
500
= 2 × 10−3 mho.cm−1
(1000 × specific conductance)
Now, equivalent conductance of KCl =
concentration
(1000 × 2 × 10−3 )
=
0.01
= 2 × 102 mho. cm2 equiv−1
So, the specific conductance and equivalent conductance of KCl is 2 x 10−3

mho.cm−1 and 2 x 102 mho.cm2 .equiv−1 . respectively.
4.23.1.8. The speed ratio of potassium and chloride ion in a aqueous solution is 0.8. Cal-
culate the transport number of each ion.
Ans. Let us consider the speed of K+ and Cl− is u and v respectively.
Hence, u/v = 0.8

Or, t+ /t− = 0.8; (t+ and t− are transport number of cation and anion)
Or, t+ /(1 − t+ ) = 0.8
Or, t+ = 0.8 − 0.8t+
Or,1.8t+ = 0.8
Or,t+ = 0.8/1.8
= 0.44
Hence, t− = 1 − t+
= 1 − 0.44
= 0.56
So the transport number of cation and anion is 0.44 and 0.56 respectively.
4.23.1.9. The dimension of an electrode pair is 5 cm2 area and they are 1 cm apart. When an
electrolytic cell fitted with this electrode having a NaCl solution of 29.25 gm.lit.−1
showing a resistance 10 ohm. Calculate equivalent conductance.
Ans.
l 1
Cell constant( ) =
a 5
= 0.2 cm−1
Concentration of NaCl = 29.25 gm.lit.−1
29.25
= ( N)
58.5
= 0.5( N)
According to Ohm’s law Resistance = Sp. Resistance × cell constant
resistance
So, Sp. Resistance =
cell constant
10
=
0.2
= 50 ohm.cm
1
Specific conductance = mho.cm−1
50
= 2 × 10−2 mho.cm−1
(1000 × sp.conductance)
Now, equivalent conductance =
concentration
(1000 × 2 × 10−2 )
=
0.5
= 40 mho.cm2 .equiv−1
So the equivalent conductance NaCl solution is 40 mho.cm2 .equiv−1 .
4.23.1.10. Calculate standrad emf of the cell Zn | Zn+2 k CuSO+2 | Cu; when-
E0 +2 = +0.34V
Cu |Cu
E0 +2 = −0.76V
Zn |Zn
Ans. Here Zinc electrode is anode and copper electrode is cathode. The standard
emf of the cell is
E0Cathode − E0Anode = E0 +2 | Cu − E0 +2 | Zn
Cu Zn
= +0.34 V − (−0.76 V)
= +0.34V + 0.76V
= +1.1V
So the standard emf of the cell is + 1.1V.
4.23.1.11. Calculate pH of a solution used in hydrogen electrode when the oxidation elec-
trode potential is + 0.25V.
Ans. A half cell reaction for hydrogen electrode as oxidation electrode (at anode)
will be
1 +
2 H2 → H + e
The half cell reaction for this electrode will be
0.0591 H+
EH |H+ = E0 − log
2 H2 | H+ 1 [H2 ]1/2
0.25 = 0 − 0.0591 logH+
0.25 = 0.0591 pH
0.25
pH =
0.0591
= 4.23
So, the pH of the solution is 4.23.
4.23.1.12. The standard reduction potential for a electrode E0 +4 +2 is 0.16V and that for
Sn |Sn
E0 +3 +2 is 0.77V. Write a cell reaction and calculate the value of equilibrium
Fe |Fe
constant at room temperature.
Ans. As the standard reduction potential of iron (Fe) electrode is greater than
tin (Sn) electrode, Fe+3 will be preferencially reduced to Fe+2 and hence it will
act as cathode and tin will act as anode.
So, the cell reaction will be
Fe+3 + Sn+2 → Fe+2 + Sn+4
E0Cell = E0Cathode − E0Anode

= E0 +3 +2 − E0 +4 +2
Fe |Fe Sn |Sn
= (0.77 − 0.16)V
= 0.61V
0.0591 [Sn+4 ][Fe+2 ]
ECell = E0Cell − log +2
2 [Sn ][Fe+3 ]
+4 +2
At Equilibrium, K = [Sn+2 ][Fe+3 ] ; ECell = 0
[Sn ][Fe ]
0.0591
0 = 0.61 − logK
2
1.21
logK =
0.0591
K = 1020
So the equilibrium constant is 1020
4.23.1.13. The standard potential for a electrode E0 + is +0.80V and that for E0
Ag |Ag Zn|Zn+2
is -0.76V. The concentration of zinc ion is 0.01(M) and the observed cell emf is
zero. What is the concentration of silver ion?
Ans. Standard reduction potential E0 + = + 0.80V
Ag |Ag
0
Standard reduction potential E +2 = + 0.76V So, Silver electrode will act as
Zn |Zn
cathode and Ag+ will preferencially be reduced.
E0Cell = E0Cathode − E0Anode

= E0 + − E0 +2
Ag |Ag Zn |Zn
= 0.80 V − 0.76V
= 0.04 V
The cell reaction can be written as

2Ag+ + Zn → Zn+2 + 2Ag
0.0591 [Ag]2 [Zn+2 ]

ECell = E0Cell − log
2 [Zn][Ag+ ]2
0.0591 [Zn+2 ]
0 = 0.04 − log
2 [Ag+ ]2
[Zn+2 ]
log = 1.35
[Ag+ ]2
log[Zn+2 ] − log[Ag+ ]2 = 1.35
log[0.01] − 2log[Ag+ ] = 1.35
−2 − 2log[Ag+ ] = 1.35
log[Ag+ ] = −1.68
Concentration of [Ag+ ] = 0.021(M)
So, the concentration of silver ion is 0.021(M).

4.23.1.14. The emf of a electrochemical cell corresponds to the reaction Zn(s) + 2H+ →
Zn+2 (0.1M) + H2 (g, 1 atm) is 0.30V at 250 C. Calculate the pH of the solution
used at hydrogen electrode. (E0 +2 = −0.76 V)
Zn |Zn
Ans.The Nernst equation for this electrochemical reaction can be written as
0.0591 [Zn+2 ][H2 ]

ECell = E0Cell − log
n [Zn][H+ ]2
0.0591 [Zn+2 ]
0.30 = (E0Cathode − E0anode ) − log + 2
2 [H ]
[Zn+2 ]
Or,0.30 = (0 + 0.76V) − (0.0295)log
[H+ ]2
[Zn+2 ]
Or, − 0.46 = −(0.0295)log
[H+ ]2
Or, 15.6 = log[0.1] − log[H+ ]2
Or, 15.6 = −1 + 2pH
16.6
pH =
2
= 8.3
So, the pH is 8.3.

1.23.2.1. The unit of ionic mobility is(Dec-2014)
A) cm2 volt. sec−1 B)cm2 volt−1 sec−1 C) cm−2 volt. sec D) none of these.
Ans. Cm2 volt−1 sec−1
1.23.2.2. The conductance of an ion in aqueous solution depends on its

A) Charge only B) speed only C) Charge and speed D) charge, speed and hydra-
tion.
Ans. Charge, speed and hydration.
1.23.2.3. The electrode potential of a standard hydrogen electrode is

A) 0.1 volt B)1 volt C) 0.01 volt D) 0 volt.
Ans.0 volt.
1.23.2.4. Which of the following is true for a galvanic cell?(June-2014)

a) the cell potential is always positive b) the products are less stable than the
reactants c) ∆G for the cell reaction is positive d) the cell potential is always
negative
Ans. The cell potential is always positive
1.23.2.5. The ion conductance of an ion depends on its (June-2013)

a) charge only b) speed only c) charge and speed d) charge, speed and hydration.
Ans. Charge, speed and hydration.
4.22.3 Short Answer type question

1.23.3.1. Draw the conductometric titration curve of strong acid vs weak base and explain
the salient features of the curve.( June-2013) 1 + 4
1.23.3.2. Draw the conductometric titration curve for HCl vs NaOH and explain the fea-
tures of the curve. How does the nature of curve change, if pure water is used
intead of NaOH ?(Dec-2012) 3 + 2
1.23.3.3. Write down the electrode reactions and over all reaction of the following cells: (i)
zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu(s)
(ii) Pt(s) | H2 (g) | H+ (aq) || Ag+ (aq) | Ag(s) (June-2012)
1.23.3.4. What is single electrode protential ? Derive the pH of an electrochemical cell with
the help of Nernst equation. 2 + 3
1.23.3.5. (a) What is equivalent conductance and what is its unit (b) What is the law of
independent imigration of ions ??(Dec-2011)
1.23.3.6. Draw the conductometric titration curve of acetic acid vs. sodium hydroxide and
explain the salient features of the curve. (June-2011)3
1.23.3.7. Define ionic mobility and equivalent conductance with their units. How does
equivalent conductance vary with concentration for both strong and weak elec-
trolytes? (Dec-2010) 2 + 3

4.24.1.1. (a) Draw the conductometric titration curve for the titration of HCl vs NaOH and
explain the salient features in the curve.
(b) What is Kohlrausch’s Law? If the ionic conductance at infinite dilution of
NaCl, HCl and CH3COONa are 126.45, 426.16 and 91.0 respectively, what will
be the equivalent conductance of acetic acid?
(c) Discuss the physiochemical principle involved in the measurement of pH of an

aqueous solution by hydrogen electrode method.(Dec-2014)
( 4+2+3+6)
4.24.1.2. Write short note on any three of the following. (5 each) (d) reference electrode
4.24.1.3. (a) How does equivalent conductance changes with concentration for weak and
strong electrolyte? Explain with suitable curve.
(b) Deduce Nernst’s equation.(June-2014) 3+5
4.24.1.4. State and explain Kohlrausch’s law of indipendant migration of ions. With the
help of this determine the equivalent conductance of acetic acid.(June-2013) 3+3
4.24.1.5. (a) What is meant by transport number of an ion ? How is it related with ionic
conductance ?
(b) ”H+ and OH? ions show very high ionic mobility in aqueous medium.”? ex-
plain with mechanism.
(c) What is calomel electrode ? How can we measure the pH of a solution using
calomel electrode ? (Dec-2012) 3 + 3 + 6
4.24.1.6. (a) Explain Kohlrausch’s law. Discuss two applications of it.

(b) Explain how ionic mobility varies with (i) size, (ii) temperature.( June-2012)(
2+4)+4
4.24.1.7. Explain the variation of equivalent conductance of strong and weak electrolytes
with concentration. 4
4.24.1.8. Write short notes on any three of the following :(e) Hydrogen electrode
(f) Conductometric titration. (Dec-2011)
4.24.1.9. Write notes on any three of the following : (d) Calomel electrode
4.24.1.10. (a) Discuss the physicochemical principle involved in the measurement of pH of

an aqueous solution by Hydrogen electrode method. 6
June-2011
4.24.1.11. (a) What is reference electrode? Explain the working principle of one reference
electrode. 5
4.24.1.12. What is storage cell? What do you mean by changing cycles? 5
4.24.1.13. Write down short notes on any three of the following
4.24.1.14. Determination of transference number using moving boundary method 5
4.24.1.15. Write short notes

(b) Reference electrode
(c) Storage cell(Dec-2010)
4.24.1.16. What is reference electrode ? Explain the working principle of one reference
electrode.(June-2010) 5
4.24.1.17. The resistance of a KCl solution is 250 ohm and equivalent conductance is 20
mho.cm2. What is the concentration of the solution when electrodes are 5 cm
apart and having area of section about 10 cm2 .
4.24.1.18. A weak acid of having strength 0.01(N) is showing specific conductance 5.8 ×
10−4 ohm− 1.cm− 1. If the degree of dissociation of this acid is 0.025, find out the
value of conductance at infinite dilution.
4.24.1.19. Equivalent conductance of acetic acid is 15.8 mho.cm2 .equiv−1 at room temp. The
ionic conductance of acetate anion and hydrogen ion is 35.5 and 349.8. Calculate
the degree of dissociation.
4.24.1.20. The quivalent conductance at infinite dilution for soudium benzoate, HCl and
NaCl is 80, 390 and 110 respectively. What is the equivalent conductance of ben-
zoic acid.
4.24.1.21. In a conductivity cell, a 0.001(N)solution of NaCl and KCl shows specific resis-
tance 250 ohm and 200 ohm respectively. Specific conductance of NaCl solution is
1.5 x 10−3 mho.cm.−1 Calculate the specific conductance and equivalent conduc-
tance of KCl solution.
4.24.1.22. Calculate standrad emf of the cell Zn | Zn+2 k CuSO+2 | Cu; when-
E0 +2 = +0.34V
Cu |Cu
E0 +2 = −0.76V
Zn |Zn
4.24.1.23. Write a spontaneous cell presentation with these values-
E0 +4 +2 = +0.15V
Sn |Sn
E0 = −0.76V
Zn|Zn+2
Calculate the equilibrium constant of the reaction.
4.24.1.24. The emf of a electrochemical cell corresponds to the reaction is
Mg(s) + 2H+ → Mg+2 (0.1M) + H2 (g, 1 atm)

where, E0 +2 = −2.36V
Mg |Mg
2.80 V at 25oC. Calculate the pH of the solution used at hydrogen electrode.
4.24.1.25. Calculate pH of a solution used in hydrogen electrode when the oxidation elec-
trode potential is + 0.25 V.
4.24.1.26. The dimension of an electrode pair is 4 sq cm area and they are 2 cm apart.
When an electrolytic cell fitted with this electrodes and filled with NaCl solution
of strength 29.25 gm/lit. It is showing a resistance 10 ohm. Calculate the equiv-
alent conductance.
4.24.1.27. The speed ration of potassium and chloride ion in a aqueous solution is 0.8. Cal-
culate the transport number of each ion.
4.24.1.28. The concentration of zinc ion is 0.01M and the observed cell emf is zero. What is
the concentration of silver ion?
4.24.1.29. The standard reduction potential for a electrode Sn+4 /Sn+2 is 0.16 V and that for
Fe+3 /Fe+2 is 0.77 V. Write a cell reaction and calculate the value of equilibrium
constant at room temperature.
4.24.1.30. The standard potential of the following half cell is-
E0 + = +0.80V
Ag |Ag
E0 = −0.76V
Zn|Zn+2
The concentration of zinc ion is 0.01M and the observed cell emf is zero. What is
the concentration of silver ion?
4.24.1.31. Construct a galvanic cell and calculate the cell emf-
Pb | PbNO3 (1M) k Hg2 Cl2 (l), Cl− (0.1M) | Hg

E0 +2 = −0.13V
Pb |Pb
E0Hg Cl | Cl− = −0.28V
2 2
Chapter 5
STRUCTURE AND
REACTIVITY OF ORGANIC
MOLECULES
5.1 Electronegativity
The electron cloud of a chemical bond formed by two different atom is not shared equally
by both the atom. The electron cloud electron is distorted to any one atom depending upon
the relative attraction force of the two atom. This attraction force is known as electroneg-
ativity. In periodic table, the electronegativity generally decreases along in a group. The
upper right corner atoms of periodic table are most electronegative and left lower corner
atoms are least electronegative. So, fluorine (F) is the highest electronegative atom and ce-
sium (Cs) is the least electronegative atom. Based on bond energies of diatomic molecules,
the quantitative value of electronegativity of individual atom is calculated by Pauling.
Pauling assigned the electronegativity of fluorine 4.0 and then from this value, the elec-
tronegativity of other atoms have been calculated.
5.2 Inductive effect

A chemical bond in a molecule formed by two different atom is polarized due to difference
of electronegativity of the two atom. The more electronegative atom shared the electron
cloud more and hence it gets partial negative charge and the other atom experience partial
positive charge. This polarization of a bond will induce secondary polarization to the adja-
cent bond. This effect is called inductive effect. In ethyl chloride molecule, the C-Cl bond is
polarized by getting partial negative charge on chlorine atom and partial positive charge on
C-1 carbon atom. The C-2 carbon atom will try to compensate the positive charge slightly
on C-1 atom and hence the C-C bond will also be polarized.
177
178CHAPTER 5. STRUCTURE AND REACTIVITY OF ORGANIC MOLECULES
Inductive effect
This is called inductive effect. This effect operates through sigma bond and gets weaker as
we moves away from electronegative atom. Sometimes this effect operates through space or
through solvent and then it is called field effect.
Inductive effect is generally expressed by I and can be classified in two group, namely +I
effect and -I effect.Those atoms or groups draw the electron pair towards itself compared
to hydrogen, are designated groups having -I effects
-NR+ + +
3 , -SR2 , -NH3 , -NO2 , -SO2 R, -CN, -COOH, -F, -Cl, -Br, -I, -OAr, -COOR, -OR, -CORetc.
Similarly those groups pushes the electron pair away from them are called groups having
+I effect (alkyl groups). Among alkyl groups, tertiary alkyl group have highest +I effect
followed by secondary, primary and methyl group. A atom with sp hybridization have
higher electron withdrawing effect compared to sp2 hybridized atom which is higher than
sp3 hybridized atom attached in a bonding. Generally with distance, the inductive effect
or field effect reduces.
Inductive effect occurs through sigma bond.
It is irreversible and permanent.
This effect is additive in nature. More than one electronegative atom attached to a carbon
atom will produce greater bond polarization compared to single electronegative atom.
Inductive effect in benzene ring

5.3. HYPERCONJUGATION 179
5.3 Hyperconjugation
A positive charge on a carbon or a C=C double bond may be get stabilized by adjacent β
C-H sigma bond. This is known as hyper conjugation.
Hyper conjugative structure

The theory of hyperconjugation is that the C-H bond breaks and makes a new C=C double
bond and the produced proton do not leaves the space rather it always get attached with
the π cloud of the double bond. A more molecular orbital based explanation is that the
C-H sigma bond overlap with the vacant p-orbital of the adjacent carbon or with the π
cloud of the double bond and hence it is stabilised. More the number of β C-H bond, more
is the the stability of the positive charge or double bond.
5.4 Conjugation, Mesomeric effect, Resonance and

Aromaticity
Compounds contain more than one multiple bonds can be classified in two part; the com-
pounds where multiple bonds are located in conjugation and compounds where multiple
bonds are present in isolated state. The compounds where multiple bonds are present in
conjugation (e.g. dienes) are more stable compared to the isolated multiple bond contain-
ing molecules. Obviously these extra thermodynamic stability of conjugated compounds
are supported by lower heat of combustion and lower heat of hydrogenation. It has been
observed that isolated double bonds migrates under suitable condition to conjugated double
bond and thus offer more stability to the compounds. Not only C=C double bonds but
C=O, C=NH etc bonds can make conjugation with other multiple bonds.
In conjugated system redistribution of electrons take place along the multiple bonds through
π electron cloud. Mesomeric effect is shown by few groups adjacent to this groups which
take part in this redistribution by donating it’s unshared electron pair or by attracting elec-
trons from adjacent π electron cloud. This redistribution of electron offers extra stability
to the molecule.
A positive or negatively charged molecule can be stabilised by the delocalization of π elec-
tron cloud. Phenoxide anion gets stabilized by delocalizing the negative charge in the
benzene nucleus through π electron delocalization. Similarly benzylic cation is stabilised by

the delocalization of π electron cloud of the benzene ring to the vacant p-orbital of benzylic
carbon.
Mesomeric effect and inductive effect both creates permanent polarization in a molecule
and thus effects the physical properties of molecules. Mesomeric effect operates in unsatu-
rated compounds and more in conjugated compounds but inductive effect operates both in
saturated and unsaturated compounds. π electrons involve in case of mesomeric effect but
for inductive effect only σ electrons involve. Inductive effects transmitted only in a short
distance through σ bond and dye away but mesomeric effect can transmitted through quite
a long distance of a molecule provided conjugation is available till end.
All properties of certain molecules can not be explained by a single structure of a molecule
and hence the molecule is represented by several structure. Among these structures, no
single structure can explain all the properties of the molecule. The actual structure is
the hybrid structure of all these and this phenomenon is called resonance. All the single
structures are called resonating structures. The resonating structures do not contribute
equally to the main structure rather the main structure is the population percentage of
the all structures depending upon their relative stability. Most stable resonating structure
contribute more to the main structure.
Let us consider the structure of acetate anion. Acetate anion can have two equivalent res-
onating structure and hence they contribute equally to the actual structure. The carbon
oxygen bond order will be 1.5.
Due to resonance, molecules attain some extra stability and this extra energy is called
resonance energy. For benzene molecule resonance energy is 36 kcal/mole.
5.5 Carbocation
Any species with a positive charge on carbon atom are generally called carbocation. Car-
bocation may be two type: one with pentavalent carbon (carbonium ion) and other type
is trivalent carbon (carbenium ion). The former type is rare and generally cabenium ion is
known as carbocation.
Stability of carbo cation(carbenium ion)
A carbocation is trivalent species with a positive charge on carbon. The hybridization of

carbon in a carbocation is sp2 and hence it is planer structure with a vacant p orbital per-
pendicular to the plane of three ligand. The positive charge is due to the vacant p orbital
5.5. CARBOCATION 181
and hence the stability of carbocation will depend on the stability of the positive charge.
Stability of carbocation: A carbocation is get stabilised by number of factors-
a) Any group adjacent to the carbocation having positive inductive effect (+I effect) sta-
bilizes the carbocation by pushing σ electron pair to the vanact p orbital. So, a tertiary
carbocation will be more stable compared to secondary one and which is more stable than
primary carbocation as the number of + I effect showing alkyl group substituent decreases
from tertiary to secondary to primary carbocation.
b) Hyperconjugation stabilizes a carbocation and hence more the number of hyprconju-
gating β hydrogen present in a carbocation, the carbocation will be more stable. Tertiary
butyl carbocation has nine hyperconjugating β hydrogen whereas secondary butyl carboca-
tion have five hyperconjugating β hydrogen and hence tertiary butyl carbocation is more
stable than secondary butyl isomer. As we have described that hyperconjugation is due to
the overlap of adjacent β C-H bond with the vacant p orbital hence replacement of C-H
bond by C-D bond will reduce the hyperconjugation as C-D bond is more stronger than
C-H bond.
c) Conjugation effect greatly stabilizes carbocation. Any heteroatom adjacent to a car-
bocation centre can stabilize the carbocation by the involvement of the unshared pair of
electron of the heteroatom with the vacant p orbital of the carbocation. Any conjugated π
system like C=C to the carbocation can stabilize the positive charge of the carbocation.
d) Lastly resonance effect stabilizes carbocation mostly. Benzyl carbocation is highly stable
due to resonace of π cloud of ring which overlap with the vacant p orbital.
1. Let us compare the stability of these carbocation.
The stability of carbocation depends mainly on hyperconjugation and resonance. In this
series there are two allyl carbocation and hence resonance effect offer them more stability
compared to the other two. Among these two allyl carbocation, one is secondary and an-
other is primary carbocation and hence obviously the secondary allyl carbocation will be
more stable than primary allyl carbocation
The other two carbocation are tertiary and primary having nine and zero hyperconjugating
hydrogen respectively and hence the tertiary carbocation is more sbale than the primary.
Thus the increasing order of stability of these carbocations is
2. Arrange the stability of these carbocatons.
At first we must look at the hybridization status of the carbocations to compare the stabil-
ity. Carbocations are generally sp2 hybridized and hence they must be planner in geometry.
The tertiaty butyl carbocation can easily adopt this geometry and hence it is stable. But
when we look the structure of the other two, the positive charge is on bridgehead carbon
atom. Now to get stability, the bridgehead carbon must be planner in geometry which is
very tough and hence these carbocations are very unstable. Now if we compare the relative
stability of this two bridgehead carbocations, in former these is only one bridging carbon
but in later case there is two bridging carbon. When carbocations will try to attain the
planarity by distortion of bonds, more distortion possible where these is two carbon bridge
present. Hence relative stability of the following carbocations are like this
3. Which carbocation is more stable?
In this case both carbocation are allylic in nature but the first one is much more stable
compared to the second one as the first carbocation is stabilisd by lone pair of electron
present on oxygen atom. In second carbocation the methoxy group is involved in cross
conjugation and hence cannot stabilize the carbocation.
4. Which carbocation is more stable?

Carbocation is an electron deficient species and hence any electron donating group adjacent
to it will stabilize carbocation whereas on the other hand electron withdrawing group will
destabilize a carbocation. Ester group (-COOEt) is an electron withdrawing group and
hence it will destabilize carbocation. Now in second compound the ester group is directly
attached to carbocation centre whereas in first compound the ester group is separated from
positice charge bearing carbon by one methylene group and hence the first carbocation more
stable than the second.
5. Which carbocation is more stable and why?
The first (para-methoxy benzylic) carbocation is more stable than the second (para-nitro
benzylic) carbocation as in first cae the lone pair of oxygen can take part into resonance
(+R effect) and hence stabilize the carbocation. Actually this effect is exhibited by princi-
ple of vinyology which is operating through the benzene ring. In later case the nitro group
have -R effect and hence it will destabilize the carbocation rather.
6. C-C bond length in CF2 = CF2 is shorter than CH2 = CH2 explain.
The structure of both the molecule is-
In case of CF2 = CF2 the strong electronegative atom fluorine uses more p-character
to form C-F bon and hence the carbon atom uses more s-character to make C-C bond. As
with increasing s-character the relative overlap increases hence, the bond length decreases.
7. The bond dissociation energy of C-H bond in cyclopropane is less than n-
propane.
Genearlly sp3 , sp2 and sp hybridized carbons have 1090 , 1200 and 1800 bond angle re-
spectively. So, we can say that with increasing bond angle s-character increases or with
decreasing bond angle p-character increases. Now in case of cyclopropane all three carbon
atom is sp3 hybridized and the inner bond angle is 600 which is far less than normal sp3
bond angle. Hence carbon must used more p character to form the inner bonds which is
the C-C bond. So, carbon must used more s-character to form the outer C-H bond. As
more s-charcter used in making C-H bond and s-orbital can hold electron more tightly, so
the bond must be weak or bond dissociation energy must be low.
8. Whether both the C-N bond in these compound will have similar bond
length?
1st compound: Nitro substituents in a benzene ring generally show -R effect and thus draw
the electron towards it. Now if we see the resoanating canonical forms, we will observe that
C-N bond getting double bond character in resonance and hence they have partial dou-
ble bond character and shorter bond length. In this particular compound one nitro group
beautifully take part into resonance and thus the C-N (a) bond will be stronger and bond
5.6. CARBANION 183
length will be shorter. But another nitro group is flanked by two ortho methyul group and
hence due to steric inhibition of resonance, the nitro group is out of plane from the benzene
ring and so the resonance phenomenon is absent here. So, the C-N (b) bond length will be
a normal character in nature.
2nd compound: In this compound we will observe the same phenomenon. Due to very large
size of iodide atom, both the adjacent nitro group is partially out of plane from benzene
ring and hence the extend of resonance is less here. As a consequence the C-N bond length
will be norma in nature wherea the other C-N bond length will be shorter due to proper
resonance.
5.6 Carbanion
A trivalent carbon centre having an unshared pair of electron is called carbanion. The
stability of carbanion depends on electron density on the carbon atom. Higher the electron
density higher is the reactivity and hence lower is the stability and vice versa. Hence the
general order of carbanion stability will be methyl > primary > secondary > tertiary. This
is due to the fact that in tertiary carbanion, three +I effect showing alkyl group is attached
with the negatively charged carbon centre which increases the electron density on carbon
atom mostly and hence least is the stability. As we move to left in the above series, the
number of alkyl group decreases and hence +I effect decreases and hence stability increases.
5.7 Dipole moment

The electron pair of a covalent bond formed by two identical atom is symmetrically aligned
between two atom but when a covalent bond is formed between two atom having different
electronegativity, the electron pair of the bond shifted towards the more electronegative
atom. Thus the covalent bond will carry partial ionic character. Like a magnet, we can say
that this charge separation will create a dipole in the bond and hence in the molecule. The
product of the charge (e) and the distance (d) between the charge is called dipole moment
(µ); µ = e × d. Generally the value of e is of the order of 10−10 e.s.u. and the value of
d is of the order of 10−8 cm and hence the value of µ will be in the order of 10−18 which
is called Debye (D). Dipole moment is a vector quantity and its direction is indicated by
arrow directing towards the more electronegative atom or towards net negative end. The
dipole moment of a bond is called bond moment and for the molecule it is called dipole
moment. Let us compare the dipole moment of few molecules.
In between carbon dioxide and sulphur dioxide the dipole moment of the former is zero
whereas the later have a positive dipole moment value. CO2 is a linear molecule and hence
the bond moment of two C=O bond acts in opposite direction and hence net dipole moment
of the compound is zero. Whereas SO2 is a bent molecule and hence the bond moment of
two S=O bond give a finite dipole moment value for the molecule.
When we will look at the both isomer of 1,2-dichloroethene, there is net dipole moment of
the cis isomer whereas the trans isomer have almost zero dipole moment. In case of trans
isomer, the bond moment of two C-Cl bond acts in opposite direction and hence net dipole
moment of the molecule tends to zero. Whereas in case of cis isomer, the two C-Cl bond
moment contribute a significant value towards the net dipole moment of the molecule.
In between chloroform and chloromethane, chloroform have low dipole moment compare to
chloromethane. In case of chloroform three C-Cl bond canceal some bond moment of each
other and hence the net bond moment of C-Cl bond decreases. But in chloromethane there
is only one C-Cl bond and hence the bond moment of C-Cl bond in chloromethane will be
higher compared to C-Cl bond moment in chloroform ans so the dipole moment.
NF3 have a dipole moment 0.24 D whereas NH3 have 1.46 D. In case of ammonia the lone
pair of electron on nitrogen atom decides the value and direction of dipole moment. But
when NF3 molecule is concern, three strong electronegative fluorine replace the hydrogen.
So the bond moment of C-F bond will be towards more electronegative fluorine atom. But
the bond moment of the lone pair of nitrogen acts opposite to the bond moment of C-F
bond. Hence the net dipole moment of the molecule is low.
In between para-diacetyl benzene or para-dicyano benzene para-dicyano benzene is a linear
molecule as the cyano group is sp hybridized. Hence the bond moment of two para cyano
groups acts in opposite direction hence overall the dipole moment of the molecule is zero.
Whereas para-diacetyl benzene can have two conformer-cis and trans. The trans conformer
do not have any dipole moment as the both bond moments acts in opposite direction but
the cis isomer contribute some dipole moment value and hence overall there is some dipole
moment value for the para-diacetyl benzene.
In between ethyl cyanide and ethyl isocyanide in ethyl cyanide (any cyanide), there exists
only one resonating structure where the bond moment or dipole moment acts towards
the more electronegative nitrogen atom. But in case of isocyanide there two resonating
structures exists. In one form the dipole moment acts towards negatively charged carbon
from positively charged tetra valent nitrogen but in other resonating structure the dipole
moment acts towards more electronegative nitrogen from electron deficient carbon atom.
Hence the net dipole moment of isocyanides is generally low.
Dipole moment of CH3 F (1.56D) and CH3 Cl (1.51D) are similar even though fluorine is
considerably more electronegative than chlorine. Dipole moment value depends on two
factors - amount of charge separation and distance between the two opposite charge. Here
although charge separation is higher in case of fluoromethane due to large electronegativity
but due to higher atomic radius of chlorine distance between the charge will be greater in
chloromethane compared to fluoromethane. This two combine effect plays role and as a
consequence these two molecule have almost similar dipole moment value.
5.8 Strength of organic acid base

Relative strength of acid and bases can be defined by many theories available in organic
chemistry. According to Arrhenius, acids are defined as compounds capable of producing
proton (H+ ion) and bases are capable of producing hydroxide ion (HO− ion). This def-
5.8. STRENGTH OF ORGANIC ACID BASE 185
inition holds true only in aqueous solution but acid base relationship have a wide range
application. So more generalised Bronsted definition of acids are proton donor and bases
are proton acceptors. Sulphuric acid in water medium will donate proton to water molecule
and water molecule will be converted to its conjugate acid hydronium ion (H3 O+ ) and sul-
phuric acid will be converted to its conjugate base HSO−4 . Here sulphuric acid is acid and
water is the base. Later a more generalised concept of acid-base was provided by Lewis.
Molecules or ions which can co-ordinate with unshared pair of electrons are called acid and
molecules or ions which have unshared pair of electrons are called bases.
Any acid HA when dissociates in water it will liberate proton and its conjugate base A− is
produced. The equilibrium constant Ka of the dissociation will be given by
HA = H+ + A−
[A− ][H+ ]
Ka =
[HA]
A−
logKa = logH+ + log
HA
A−
pKa = pH − log
HA
Here the strength of acid can be expressed by pKa scale where pKa = log[H+ ]. As strength
of acidity depends the number of dissociated hydrogen ion, hence higher the value of disso-
ciation constant (Ka ) greater is the acidity. So lower the value of pKa higher is the acidity.
Genrally pKa above 16 do not show acid character in water.
The strength of HA acid depends on the stability of its conjugate base A− , electronegativity
of A, nature of solvent.
Let us discuss the relative acidity strength o some compounds.
1. Compare the acidity between formic acid and acetic acid.
To compare the acidity among carboxylic acids, we must consider the stability of the corre-
sponding conjugate bases. Let us look the structure of conjugate bases The conjugate base
of acetic acid is less stable compared to the conjugate base of formic acid as the electron
density increases in conjugate base of acetic acid due to the +I effect of methyl group.So,
the dissociation of acetic acid will be less compared to formic acid and hence its acidity will
be less compared to formic acid.
2. Explain the difference in pKa values of the following carboxylic acid
Let us have a close look on the conjugate bass of these three carboxylic acids. Relative sta-
bility of conjugate base increases Acidity increases (pKa decreases) The carboxylate anion
is attached to a sp3 , sp2 and sp carbon respectively. As’s’ character increases from sp3 to
sp; the relative ability to hold the electron pair increases. So the relative stability of the
conjugate base increases and hence acidity increases or pKa value decreases.
3. Compare the acidity of the following carboxylic acids:
The structure of corresponding conjugate bases of these carboxylic acids are like this If
we move along the series from left to right the electronegativity of the substituent halogen
decreases and hence the relative electron density on carboxylate anion will comparatively
increase. So, the stability of conjugate base will decrease and the acidity will decrease along
the series.
4. Explain the increase of pKa values in the following series of carboxylic acids
To compare the pKa values of these carboxylic acids, we must consider the stability of the
conjugate bases of these compounds. The conjugate bases will be stabilized by the -I effect
of chlorine atom. Now as we move from left to right the electronegative chlorine atom is
shifting away its location from negatively charged carboxylate ion and thus the stability of
the corresponding conjugate bases are decreasing from left to right and hence the acidity
decreases or pKa value increases.
5. Explain the difference in pKa values of the following phenolic compounds
Unlike carboxylic acid, the acidity of phenolic compounds are offered by H+ ion from pheno-
lic -OH group. To understand the difference in acidity among different phenolic compounds
we must consider the stability of corresponding conjugate base after dissociation of a pro-
ton, which are phenoxide ions. Let us see the structure and stability of the corresponding
conjugate bases of these substituted phenols. A nitro group is attached at ortho, meta and
para position respectively. Nitro group have both -R and -I effect which can stabilize the
negative charge of phenoxide and hence nitro phenols are more acidic than phenols or they
have less pKa values compared to phenol. When we compare among ortho, meta and para
nitro phenol; if we look the stability of their corresponding conjugate bases. The conjugate
base of ortho and para isomers are stabilized by extended resonance of the nitro group but
no such extended resonance is possible when nitro group present at meta position. Hence
the meta-nitro phenol is less acidic than either ortho or para isomer. Here point to mention
that at ortho or para position the nitro group shows both its -R and -I effect whereas at
meta position it shows only -I effect which is very less effective compared to resonance effect.
A small difference in pKa values between the ortho and para isomer can be explained by
the fact that the conjugate base of para-nitro phenol is more stable compared to the ortho
isomer as in para-nitro phenoxide both the negative charge (on phenoxide oxygen and on
nitro oxygen) are far apart from each other and thus minimize the dipolar repulsion. So
the increasing order of acidity will be phenol, meta-nitro phenol, ortho-nitro phenol and
para-nitro phenol. N.B.: Here important point to mention that with increasing number of
nitro substituents at ortho and para position the effective stability of phenoxide ion will
increase and hence acidity of the corresponding compound will increase or pKa value will
decrease. Thus the pKa values of the corresponding compounds are like this. 2,4,6-trinitro
phenol (picric acid)will be more acidic than 2,4-dinitro phenol and which will be more acidic
than nitro-phenol 6. Explain the difference between pKa values of formic acid (3.77) and
oxalic acid (1.23). Formic acid is a monocarboxylic acid but oxalic acid is a dicarboxylic
acid. The conjugate base of formic acid is formate anion but in case of oxalic acid, here we
consider the first dissociation pKa 1 and hence in conjugate base of oxalic acid there exists
an undissociated carboxylic acid group and a carboxylate anion which can form intramolec-
ular hydrogen bonding and hence are highly stabilized. That is why the pKa value of oxalic
acid is much less than formic acid or in other words oxalic acid is much more acidic than
5.8. STRENGTH OF ORGANIC ACID BASE 187
formic acid.
6. Discuss the effect of halogen, OH and OMe groups on the acidity on substi-
tuted benzoic acid.
The presence of halogens, OH and OMe groups have interesting effect on pKa value of
benzoic acid. These groups have electron withdrawing -I effect as well as electron donat-
ing +R effect. In case of ortho substitution the -I effect predominates and the pKa value
goes down to the unsubstituted benzoic acid. But in para isomer, the +R effect plays the
role and hence para isomer is weaker acid than ortho isomer. Sometimes the +R effect is
so prominent that the para hydroxyl and paramethoxy benzoic acid is weaker acid than
benzoic acid. The acidity of meta substituted benzoic acid remain in between of ortho and
para isomer.
7. Compare the acidity of 2-hydroxy benzoic acid, 4-hydroxy benzoic acid

and 2,6-dihydroxy benzoic acid.
If we compare the stability of their corresponding conjugate bases, the stability of 2-hydroxyl
benzoates and 2,6-dihydroxy benzoates are more stable than 4-hydroxy benzoate anion due
to formation of intramolecular hydrogen bong in case of first two compounds. When we
compare the stability of 2-hydroxy benzoate and 2,6-dihydroxy benzoate, obviously the later
is more stable as the negative carboxylate anion is stabilized by both ortho hydroxyl groups.
So the increasing order of acidity will be 4-hydroxy benzoic acid, 2-hydroxy benzoic acid
and 2,6-dihydroxy benzoic acid.
8. Compare the acidity between maleic acid and fumeric acid.
Maleic acid and fumeric acid is the trade name of cis-trans isomer of butenedioic acid
respectively. As these compounds posses two carboxylic acid then we must consider the
dissociation of both proton by comparing pKa1 (first dissociation) and pKa2 (second dis-
sociation). When we compare the first dissociation, the conjugate base of maleic acid (cis
isomer) is more stable than the fumerate (trans isomer) by making intramolecular hydrogen
bond. Hence we have the pKa1 values like this: maleic acid (1.92) and fumeric acid (3.02).
But when we compare the pKa2 then we must dissociation of second hydrogen and this
dissociation will be comparatively harder for cis isomer compare to the trans isomer as the
hydrogen is in a part of stable ring now.
9. Compare the acidity of the following two compounds
To compare the acidity of these two compounds, we must compare the stability of their
corresponding conjugate bases. Both the conjugate bases will rearrange their ?-bonds to
gain aromaticity for all the ring present in the molecule. To attain this aromaticity the
rearrangement of the 1st conjugate base leads to a charge development in such a way that
the two adjacent 5 membered ring gets a negative charge each whereas the 7 membered rings
gets a positive charge. So two negative charged rings are separated by a positive charged
ring and hence the structure is stabilized. But the conjugate base of second compound gets
two ngatively charged 5 membered ring side by side and the positively charged 7 membered
ring are located at one side and hence the conjugate base is relatively less stable due to
charge repulsion.
So compound one is more acidic than compound two.
10. Arrange the pKa values-
pKa 1 (malonic acid), pKa (acetic acid), pKa 2 (malonic acid)
Let us see the structure of malonic acid and acetic acid first and then the ionization pattern
of these acids and the stability of corresponding conjugate bases. Malonic acid is dibasic
acid and hence it will have two pKa (pKa 1 and pKa 2) corresponding to two ionizations.
The first ionization will be easy as after first ionization the conjugate base (1) will be highly
stabilized by intramolecular hydrogen bonding and due to the same reason second ionization
will be much harder. Whereas the ionization of acetic acid will follow a normal pathway.
Hence the increasing order of pKa values will be like pKa 1 (malonic acid), pKa (acetic acid),
pKa 2 (malonic acid).
5.9 Basicity
Any organic base is represented by B− having an unshared pair of electron and hence the
strength of any base will be determined by how fast it can donate its unshared electron to a
proton. In other word basicity of any substrate will be determined by the ability to attract
proton; higher the attraction towards proton higher is the basicity. The protonated base is
called conjugate acid of the corresponding base. In analogy with acid strength, higher the
stability of a conjugate acid of a base greater is the basicity.
If we consider the reversible reaction; i.e.;
BH = B− + H+
[B− ][H+ ]
Ka =
[BH]
B−
logKa = logH+ + log
BH
B−
pKa = pH − log
BH
Hence, in this case higher the dissociation constant, lower is the basicity and vice versa. In
other word lower the pKa , lower is the basicity and higher the pKa higher is the basicity.
Let us discuss the relative acidity strength o some compounds.

1. Compare the basicity of the following bases
The basicity of organic compounds mainly depends upon the availability of lone pair of
electron and its density on nitrogen atom. Generally any electron donating substituents at-
tached to nitrogen atom increases the electron density and any electron withdrawing group
decreases the electron density on nitrogen atom and hence the basicity increases or decreases
respectively. In this series of organic bases as we move from left to right number of alkyl
5.9. BASICITY 189
group substituent is increasing and thus electron density on nitrogen atom is increasing as
alkyl groups have +I effect. So the basicity increases from left to right.
The above explanation holds true when no other effect is acting or in other words in gas
phase or in non-polar phase like in hexane or pentane solvent. But in aqueous solvent we
must consider the effect of water which basically stabilizes the positively charged conjugate
acid of a bases by forming hydrogen bond. As the number of hydrogen bond increases the
stability of the corresponding conjugate acid increases. A primary amine after protonation
can make three hydrogen bong with its three hydrogen atom attached to nitrogen whereas
secondary amine can form two and tertiary amine can form one hydrogen bond after proto-
nation in aqueous medium. Thus stability of conjugate acid increases from tertiary amine
to secondary amine to primary amine. These two effects play a combine role in determining
the strength of amine bases in aqueous medium. Experimental data shows that when alkyl
group is methyl then the order of basicity is 2. Compare the basicity of ethyl amine,
ethanamidine and guanidine.
To explain the strenth of basicity of these organic compounds we must consider the stability
of their corresponding conjugate acids. The conjugate acid of guanidine is resonacestabilised
by both the other amine group present. The conjugate acid of ethamidine is stabilised by
only one adjacent amine group whereas there is no such resonance stabilitization possible in
case of conjugate acid of ethyl amine. So the order of increasing stability of corresponding
conjugate acids will be ethyl amine, ethamidine and guanidine and hence this will be the
increasing order of basicity.
3. Compare the basicity of aniline and nitro-anilines.
The basicity of aromatic amines depends upon the availability of lone pair of electron on
amine group as the lone pair can take part into resonce into the benzene ring. In nitro-
aniline compounds nitro group show both the -R and -I effect and due to both effect electron
can flow towards the nitro group from amine group. Hence nitro-anilines are less basic than
aniline. Now among the nitro-anilines, meta isomer shows only -I effect not the -R effect
but ortho and para-nitro aniline shows both -R and -I effect. We know that -I effect is less
powerfull than -R effect, so meta-nitro aniline is more basic than ortho and para isomer.
Now in case of ortho and para-nitro aniline the lone pair of amine group is delocalised intro
nitro group through resonance but the -I effect is more active in ortho isomer as the nitro
group is more close to the amine group. Hence para nitro aniline will be more basic than
ortho isomer. The increasing order of basicity will be o-nitro aniline, p-nitro aniline, m-nitro
aniline and aniline.
4. Explain the fact that 2,4,6-trinitro-N,N-dimethyl aniline is 40000 times more
basic than 2,4,6-trinitro aniline.
In case of 2,4,6-trinitro aniline the lone pair of amine group take part into resonance with the
para nitro and both ortho nitro group and hence available electron density on amine group
drastically reduced and hence the compound show very poor basicity. On the other hand
bulky N,N-dimethyl amine group faces severe steric repulsion by two ortho nitro group.
Due to this interaction the N,N-dimethyl amine group goes out of plane from the plane of
benzene ring and hence the lone pair of amine group can’t take part in resonance with the
benzene ring. As a consequence the lone pair is highly available for donation and so the
basicity is significantly high. This phenomenon is called steric inhibition of resonance.
5. Explain why these amines behave as strong base.
These aromatic amines resemble in structural similarity in such a way that lone pair of the
amine group’s faces severe dipolar interaction. Once the amine group is protonated, the
dipolar strain is released and hence the conjugate acid is highly stabilized. Here point to
mention that lone pair of one amine group is protonated and that hydrogen make a hydro-
gen bond with the other nitrogen.
6. Explain the fact that 2,6-di-tertiarybutyl pyridine is a weaker base compared
to either pyridine or 2,6-di-methyl pyridine.
The basicity of these types of compounds depends upon the relative stability of correspond-
ing conjugate acids. The protonated version of 2,6-di-tertiarybutyl pyridine is unstable
in aqueous medium as water molecule cannot make hydrogen bonding with the conjugate
acid. The presence of two bulkier tertiary butyl groups restricts the rotation of the hy-
drogen bond between the water molecule and the protonated amine and hence makes the
bond very weak. On the other hand in case of pyridine or 2,6-di-methyl pyridine, this type
of destabilization do not occur as there is no such bulky ortho substituent or less bulkier
methyl group present.
7. Arrange the following compounds in increasing order of basicity.
First of all in this series of compounds, we must compare the stability of the negative charge
present in the molecule to compare the extend of basicity. In all compounds there exists
a second canonical resonating structure by which the negative charge gets stabilized. In
one of two canonical forms the negative charge is on less electronegative nitrogen atom and
hence this molecule is comparatively less stables than the other two and hence it is most
basic. When we compare the rest of the two molecule’s basicity; the negative charge of the
third compound is comparatively more stable due to the presence of electron withdrawing
NH+ 3 group. Hence the increasing order of basicity is
5.10 Nucleophilic substitution reaction

The displacement of a functional group attached to a carbon atom by another functional
group is known as substitution reaction. The functional group which leaves from a carbon
centre is known as leaving group and the group entered is known as nucleophile. A well
studied substitution reaction is the conversion of alkyl halide to alcohol by aqueous base.
R-X + OH− = R-OH + X−
Kinetic study of the above reaction shows that the rate of the reaction may or may not be
depend upon the concentration of the nucleophile [Nu:] which is aqueous base here.
5.11. SN 1 REACTION 191
Rate = k1 [R-X]
or, Rate = k2 [R-X][Nu:]
Those reaction follow the former rate law are termed as Substitution Nucleophilic Unimolec-
ular SN 1 reaction and those follow the later rate law are termed Substitution Nucleophilic
Bimolecular SN 2 reaction.
5.11 SN1 reaction

In a typical SN 1 reaction, substitution happened in a two step process.
SN1 reaction
In first step a heterolytic bond cleavage occur and hence a carbocation is formed. In
the second step the nucleophile attached with the positively charged carbocation and the
product formed. The first step is slow and is the rate determining step. As in the first step
only alkyl halide involved so the rate of the reaction depend only on the concentration of
alkyl halide.
R-X → (slow/rds )R+ + X−

R+ + Nu− = R-Nu
The carbocation formed in the first step is called intermediate. Let us see a energy profile
diagram of SN1 reaction.
Energy profile diagram in SN1 reaction
From the energy profile diagram we can see that in the first step (which is the slowest
step and rate determining step), the R-X bond breaks and hence the reaction goes through
a high energy state to intermediate carbocation. This high energy state is called transition
state (T.S.). The energy difference between the reactant and the T.S. is called activation
energy (Eact ). Any reaction must attain the activation energy in order to go to the product.
So, we can say that lower the activation energy higher is the rate of a reaction and vice
versa. Now to increase the rate of a chemical reaction we need to minimize the activation
energy either by raising the energy of reactant or by lowering the energy of T.S. down.
Let us closely look the structure of T.S. of a SN1 reaction. It is the mid way of the alkyl
halide and carbocation and hence we can say that T.S. should be a state where partial R-X
bond breaking happens and hence X got slightly negative charge and R got slightly positive
charge. As δ+ charge generated on alkyl group, we can say that carbocation character is
forming here and this is termed as incipient carbocation. The characteristics of incipient
carbocation follows the characteristics of carbocation. In order to increase reaction rate we
should find the ways to stabilize this incipient carbocation as T.S. stabilization will decrease
activation energy.
Nature of substrate: Like carbocation, incipient carbocation will be stabilized by resonance
or mesomeric effect, conjugation by adjacent π electron cloud or unshared pair of electron
of a heteroatom, hyperconjugation and +I effect of alkyl group.
Benzyl halide, allyl halide, alpha alkoxy methyl halide, tertiary butyl halide types of sub-
strate are good choice for SN1 reaction. In each case the T.S. which is incipient carbocation
will be stabilize by either by resonance or conjugation of by hyperconjugation. In substi-
tuted benzyl halide, any electron releasing substituent at ortho or para position will enhance
the SN1 reaction more as T.S. will be much more stabilize by extended conjugation.
In simple alkyl halide series the reaction rate decreases as we move from tertiary butyl
halide to secondary butyl halide to primary halide to methyl halide as the stability of cor-
5.12. SN2 REACTION 193
responding T.S. decreases.

Nature of leaving group: In the first step the leaving group leaves from the alkyl center and
hence a stable leaving group will easily depart from alkyl center. In a alkyl halide series,
the reactivity of alkyl iodide will be fast, followed by alkyl bromide, chloride and fluoride as
the stability of the leaving group decreases along the series. The stability of iodide anion is
highest due to larger size of iodine atom which can disperse the negative charge in its large
size. So, in the bromide, chloride and flouride series as the size of atom decreases so the
stability of their corresponding anion decreases. Generally tosylate, brosylate, sulphonate,
iodide, acetyl, azide etc are good leaving group.
Effect of solvent: The substrate of SN 1 reaction is alkyl halide which is neutral molecule
but the T.S. is incipient carbocation and hence it is a charged species. So, a polar solvent
will stabilize the charged T.S. more and hence the activation energy will decrease or the
rate of the reaction will increase. In example, solvolysis of a alkyl halide will be more faster
in 80% ethanol compared to 100% ethanol as the former solvent system is more polar.
Optical activity: If the substrate is a optically pure substrate, then in a pure SN1 reaction
we will get a racemic mixture of product. Let us see a pure chiral substrate where the
carbon atom to which the leaving group is attached is asymmetric. In the first step, we
will get intermediate the carbocation which is sp2 hybridized and planar molecule with a
vacant p orbital perpendicular of the plane containing the three ligand. Now in the second
step, the negatively charged nucleophile have the equal probability to attack the positively
charged carbocation from both lobe of the vacant p orbital. Attachment of nucleophile from
either lobe of the p orbital will lead to a pair of enantiomer or racemic mixture.
5.12 SN2 reaction

In a typical SN2 reaction substitution happened in a single step.
SN2 reaction
In this method the reacting nucleophile will attack from the back side of the leaving group
at the carbon centre. As it is a one step reaction hence this step will be the rate determining
step and in r.d.s. the concentration of both alkyl halide and nucleophile involve and so it
is bimolecular reaction.
R-X + Nu− = Nu-R + X−

Rate = k2 [R-X][X− ]
If we draw the energy profile diagram of this reaction we will get this plot.
The reactant goes into product directly via transition state. The reacting centre is sp3
hybridised tetrahedral geometry. At transition state both the carbon-leaving group bond
breaking and carbon-nucleophile bond making happen simultaneously. So, the T.S. is a
trigonal pipyramidal pentavalent structure where the main three ligand of carbon makes
the trigonal and the leaving group and the nucleophile is above and below the trigonal in
opposite direction.
The rate of a SN2 reaction can be enhanced by these methods.
Structure of reactant: In a SN2 reaction the T.S. is pentavalent whereas the reactant is
tetravalent and hence we can say that T.S. is more crowded than the reactant. More
crowded T.S. will increase its energy and hence activation energy will increase. So, in a less
hindered carbon centre the back side attack of the nucleophile occurs with low energy T.S.
In a series of alkyl halide, as branching increases at the reacting centre the reaction rate
decreases. Among methyl halide, ethyl halide, isopropyl halide and tertiary butyl halide
the rate of SN2 reaction decreases from left to right as the steric hinderance of the reacting
carbon centre increases.
In case of allyl halide or benzyl halide, the rate of SN2 reaction is very high. This is due
the fact that in the T.S. of these system, the p orbital which holds both the leaving group
and nucleophile in its two lobe is at same plane of the π cloud of allyl or benzene system
and hence overlap happens which gives the T.S. stability.
Effect of solvent: In a SN2 reaction the nucleophile is negatively charged and the T.S.
have slightly negatively charged so charge density of T.S. is lower than the reactant. More
polar solvent will stabilize the reactant more compare to the T.S. So, theoretically reaction
rate should decreases with increase in solvent polarity. In reality solvent polarity change
have little effect on the rate of SN2 reaction.
If we use a polar aprotic solvent like DMF (Dimethyl formamide) or DMSO (Dimethyl
sulphoxide) in a SN2 reaction, the reaction rate increases compared to use of polar protic
solvent. This is due the fact that polar protic solvent can solvate both cation and anion
and hence solvated anions which is a nucleophile, lost its activity to some extend. But
polar aprotic solvent can solvate only cation not anion. So, the nucleophiles or the anions
are free to attack from back side. The rate of nucleophilic substitution of methyl iodide
with sodium azide increases 106 fold by changing the polar protic methanol solvent to polar
aprotic DMF solvent.
5.13. ELIMINATION REACTION 195
Stereochemistry in SN2 reaction
Stereochemistry: As in a SN2 reaction, the attack happens from back side so, inversion
of the reaction centre happens. If the carbon centre is chiral then inversion of configura-
tion happen; from an optically pure isomeric substrate we got pure isomeric product with
inverted configuration.
5.13 Elimination reaction

In a typical elimination reaction two atoms or groups are being eliminated from a molecule.
Generally this two atoms of groups are eliminated from two adjacent carbon atom but
examples are there where groups or atoms are eliminated from other centre other than
carbon. When both the eliminating groups are eliminated from adjacent carbon atom,
the process is called 1,2-elimination or β elimination. However examples are there for 1,4-
elimination, 1,5- or 1,6-elimination reaction. We will discuss mostly the 1,2-elimination
reaction.
5.13.1 1,2-Elimination
In a 1,2 elimination reaction a leaving group (Y) and a hydrogen atom (H) are being
eliminated from α and β carbon respectively and as a result a carbon-carbon double bond
formed. In presence of base this elimination takes place and generally an halide from α
position and a hydrogen from β position is eliminated. This is called base induced 1,2-
elimination reaction. In other format alcohols form alkene by dehydration in presence of
acid. Quarternery ammonium hydroxide salts on heating produce alkene by 1,2-elimination
method. Other leaving groups like −OSO2 Ar , − OAc, − SR2 etc are also take part in 1,2-
elimination reaction.
1,2-elimination reaction can be classified in three different category depending upon the
mechanism of the reaction.
E1 mechanism: In E1 reaction, the leaving group Y leaves first and generate a crabocation.
This step is exactly similar like SN1 reaction. The carbocation transformed into alkene by
loss of a proton. This is two step process and the reaction kinetics is unimolecular. The
energy profile diagram is like a SN1 reaction. As the first step, where carbocation former is
the slowest step or rate determining step hence the rate of the reaction will depend upon the
stability of the incipient carbocation which is the T.S. of the reaction. That is why tertiary
butyl bromide affords isobutene at faster rate than the rate of elimination for secondary
butyl bromide.
If the carbocation intermediate have more than one type of hydrogen for elimination, we
will get multiple elimination product. Now the ratio of all alkene will not be same. The
more substituted alkene will be the major product as more substituted alkene is more stable
by hyperconjugation. Thus the E1 elimination of 3-methyl-2-bromo-butane can lead to 2-
methyl-2- butene and 3-methyl-2-butene as product but the former will be predominant as
it is more stable by the hyperconjugation effect of 9 β hydrogen where the later product
have only one β hydrogen. The more substituted alkene is called as Saytzeff product and
the less substituted alkene is called Hoffman product.
5.13.2 E2 Elimination
This reaction happens in a single step. The base abstract the β hydrogen and the leaving
group Y leaves from the adjacent carbon simultaneously. The energy profile diagram looks
like a SN2 reaction. In the transition state the C-H bond and the C-Y bond partially breaks
whereas a partial double bond character is formed between two carbon atom and hence the
T.S. is an incipient alkene which have similar characters like alkene. So, T.S. (the incipient
alkene ) will be stabilised by presence of hyperconjugating β hydrogen. In the rate expres-
sion both the substrate and the base concentration is involve and hence it is bimolecular
reaction.
Stereochemically E2 reaction is very important as the orientation of the abstracted hydrogen
and the leaving group must be anti to each other. This stereochemical criteria makes E2
reaction stereospecific. An partucular stereoisomer will afford an particular steroisomeric
product due the mechanistic pathway of the reaction. If in the substrate more than one
beta position and hence more than one beta hydrogen present, E2 elimination will occur
by abstracting that beta hydrogen which will lead to more substituted alkene as the corre-
sponding T.S. will be more stable due to hyperconjugation and hence activation energy will
be low or reaction rate will be fast. Thus 2-bromo-butane will give but-2-ene as predominat
product as the corresponding T.S. will be more stable due to presence of 6 hyperconjugating
hydrogen. Whereas the minor product will be 1-butene as the corresponding T.S. is less
stable due to the presence of only 2 hyperconjugating β hydrogen.
E1 CB Mechanism: In a E1 CB pathway, the C-H bond breaking precedes over C-Y bond
breaking. This happens because the leaving group is poor like -SMe2 . As a result in first
step at beta position carbanion formed and in the consecutive next step the carbanion force
the leaving group to leave and a carbon carbon double bond formed.
5.14 Aromatic electrophilic substitution

In a simple aromatic compound like benzene, a π electron cloud present and hence it is an
electron rich species. Any electron deficient species (electrophile; E+ ) can make a complex
with the aromatic ring and subsequently the electrophile can make a bond with the ben-
zene by replacing a hydrogen from it. This is one type of substitution reaction and as it
happens on aromatic system it is called aromatic electrophilic substitution. It is obvious
5.15. ADDITION REACTION 197
that in this substitution process hydrogen ion (H+ ) acts as a leaving group. The rate of
the reaction depends on the electron density of the aromatic ring and the electrophilicity of
the electrophile. A strong electrophile can react with relatively less active aromatic nucleus
and a en electron rich nucleus can react with poor electrophile.
The mechanism of the aromatic electrophilic substitution is multistep. At first the elec-
trophile sit on the π cloud of the aromatic ring and form π-complex. In the second step
the electrophile make a sigma bond with a carbon atom by breaking a double bond of the
aromatic ring. As a result the aromaticity of the ring is lost and hence this step associated
with high energy. The adjacent carbon gets positive charge due to this carbon-electrophile
sigma bond formation. In the last step the hydrogen attached to the carbon containing
electrophile stabilises the adjacent positive charge by breaking this C-H bond and the com-
pound regains its aromaticity.
Nitration of benzene: Nitration of benzene by mixed acid is an example of aromatic elec-
trophilic substitution. Here the mixed acid produces strong electrophile nitronium ion. The
mixture of concentrated sulphuric acid and concentrated nitric acid is called nitrating mix-
ture or mixed acid. Strong concentrated sulphuric acid react on nitric acid and eliminate
water to produce nitronium ion. This nitronium ion makes π complex followed by sigma
complex and at last nitrobenzene as product.
5.15 Addition Reaction

Addition reaction includes addition of electrophiles to carbon-carbon multiple bond. Addi-
tion of halogen, hydrogen halides, water (via sulphonation, via oxymercuration-demercuration,
borohydride addition), dihydroxylation, epoxide formation, ozonolysis etc. We will discuss
addition of HX to carbon-carbon double bond.
HX dissociates to H+ and X− . The proton adds to one carbon containing the double bond
and the X− adds to the other carbon. For a symmetrical alkene like ethylene, cycloxexene
etc no question raised about the regioselectivity. But for an asymmetric alkene like propene
we could get two product, 1-halo propane or 2-halo-propane. The major product will be the
later and the former will be the minor product. This can be explained by details mechanism
of the reaction. At first step the proton have the both choice to bind with carbon and hence
the other arbon of the double bond will get positive charge or a carbocation centre will be
formed. Now if proton adds to C-1 carbon then a 20 carbocation formed and if proton adds
to C-2 carbon then a 10 carbocation formed. As 20 carbocaton is more stable compared to
10 carbocation, the proton will add to C-1 carbon predominatly and hence the negatively
charged X- will add to 20 carbocation centre and thus 2-halo propane is the major product.
This can be expressed by Markownikov rule which tells that when a hydrogen halide adds
to an unsymmetrical alkene the negatively charged halogen adds to the more substituted
carbon atom.
If the addition is carried out in presence of peroxide the reverse result is obtained. In pres-
ence of peroxide 1-propane is the major product and this is Anti-Markownikov’s addition.
If we look the mechanism of the addition in presence of peroxide, we will observed that the
reaction mechanism pathway changes from ionic mechanism to a free radical mechanism
where peroxide acts as a free radical initiator. The initiator molecule first abstract a hy-
drogen free radical and thus form halogen free radical to react. The halogen free radical
will add to the carbon-carbon double bond. For an unsymmetrical alkene the halogen free
radical adds to the carbon at less hindered side and produce a more stable secondary free
radical. If the halogen free radical adds to more substituted carbon then we would reach
to less stable primary free radical. So the secondary free radical which is predominant and
more stable now take a hydrogen radical and the initiator halogen free radical is reproduced.
Now the halogen free radical will carry the reaction again in chain loop.
Point to note that the Merkownikov and Anti-Merkownikov rule only works in unsymmet-
rical alkene. The peroxide effects only acts particularly in HBr addition because in HBr
addition by a free radical pathway both the step is exothermic but for all other haloacid
either or both steps are endothermic.

5.17.1.1. But-2-ene is more stable than But-1-ene due to (Dec-2014)
A) Inductive effect B)resonance effect C) Hyperconjugative effect D) electromeric
effect.
Ans. Hyperconjugative effect
5.17.1.2. Which one is more nucleophilic species?

A) H2 O B) -OH C)-OCH3 D) NH3 .
Ans. -OH
5.17.1.3. The most stable carbonium ion is (June-2014)

a) (CH3)2 CH+ b) Ph3 C+ c) CH3 CH+ +
2 d) CH2 = CH − CH2 .
+
Ans. Ph3 C
5.17.1.4. Which one of the following has the least bond angle ?(June-2013)
a) NH3 b) BeF2 c) H2 O d) CH4 .
Ans. H2 O
5.17.1.5. Anti-Markownikoff’s addition of HBr is not observed in (June-2012)

a) pentene b) 2-butene c) butene d) propene.
Ans. 2-butene
5.17.1.6. Which of the following carboxylic acids will have the lagest Ka value ?
a) CH3 − CH2 − COOH b) Cl − CH2 − COOH c) Ph − COOH d) F3 C − COOH.
Ans. F3 C − COOH
5.17.1.7. Which of the following carbonium ions will be the most stable ?
a) Ph3 C+ b) H3 C − CH+ +
2 c) H2 C = CH − CH2 d) (CH3)2 − CH .
+
Ans. Ph3 C+
5.17.1.8. The half-life of a first order reaction is 20 minutes. The time required for 75%
completion of the reaction is
a) 30 minutes b) 40 minutes c) 50 minutes d) 60 minutes.
Ans. 40 minutes
5.17.1.9. The most stable carbanion is(Dec-2011)

a)Ph3 C− b) (C6 H11 )3 C− c) (C3 H5 )3 C− d) (CH3 )3 C− .
Ans. Ph3 C−
5.17.1.10. The boiling point of p-nitrophenol is greater than o-nitrophenol because of(June-
2010)
a) ionic bonding b) intermolecular H-bonding c) van der Waals attractive forces
d) intramolecular H-bonding.
Ans. Intermolecular H-bonding
5.17.1.11. The ligand that can act as a flexidentate ligand is

a) OH− b)Ethylene diamine c) NO− 2−
2 d) SO4 .
Ans. Ethylene diamine
5.17.1.12. Which of the following has the least bond angle ?

a) NH3 b)H2 O c) CH4 d) BeF2 .
Ans. H2 O
5.16.2 Short type question

5.17.2.1. Give one example of nucleophile. Give reaction and mechanism of nitration in
benzene ring. Write note on electromeric effect.(Dec-2014)
5.17.2.2. (a) Aniline is a weaker base than methyl amine. Why? (June-2011) 2
5.17.2.3. (a) Explain that alcohols are weaker acids than phenols but are stronger nucle-
ophiles. (Dec-2010)3

5.17.3.1. Write comparative short note on Substitution nucleophlic unimolecular and bi-
molecular reaction covering (i) rate equation (ii) mechanism (iii) potential energy
diagram and (iv) implication of stereochemistry if any. (Dec-2014)
5.17.3.2. Explain the order of acid strength HCOOH > CH3 COOH > Phenol > Ethanol
5.17.3.3. Write down the product of the following reaction with mechanism
(CH3 )3 C − CH2 OH + Conc. H2 SO4 4+4+4
5.17.3.4. Discuss about SN1 and SN2 with example.(June-2014) 4
5.17.3.5. State Markonikov’s rule. Explain Markonikov and anti-Markonikov addition of

the HBr to propane.( June-2013)5
5.17.3.6. Write short notes each (a) Inductive effect (b) Carbocation
5.17.3.7. Compare the C-Cl bond lengths in CH2 = CH−Cl and CH3 −CH2 −Cl(Dec-2012)
5.17.3.8. Arrange the molecules in their increasing acidity order : Phenol, 2,6-dimethyl-4-
nitrophenol, 3,5-dimethyl- 4-nitrophenol
5.17.3.9. Predict all possible products of neopentyl bromide that undergo solvolysis in aque-
ous alkali medium.
5.17.3.10. Distinguish with example : (i) Carbonium ion and carbenium ion (ii) Addition
reaction and substitution reaction
5.17.3.11. Write notes on any three of the following: Anti-Markownikov’s rule
5.17.3.12. Write notes on any two of the following : (i) Resonance (June-2012)
5.17.3.13. Explain why p-nitrophenol has much higher boiling point than o-nitrophenol al-
though both have same molecular weight
5.17.3.14. What do you mean by hybridization ? How is it related to structure and acidity
of ethane, ethylene and acetylene
5.17.3.15. Which one of the following is more acidic and why ?(i) CCl3 COOH and (ii)
CH3 COOH.
5.17.3.16. Differentiate between the following : Addition polymerisation and condensation

polymerisation.
5.17.3.17. Write short notes on any three of the following : (d) E1 and E2 reaction (d)
Compare the acidic characters of formic acid, acetic acid and phenol.
5.17.3.18. Write notes on any three of the following :(e) Mesomeric effect (Dec-2011)
5.17.3.19. Arrange the following in increasing acidity :(i) Phenol(ii) 2,6-Dimethyl-4-nitrophenol(iii)

3,5-Dimethyl-4-nitrophenol.
5.17.3.20. Give an example of hyperconjugation with explanation.
5.17.3.21. Distinguish between the following with example : (i) Carbonium ion and carbanion
(ii) Addition reaction and substitution reaction.
5.17.3.22. Discuss the role of solvents in SN1 reaction.
5.17.3.23. Write down short notes on any three of the following (f) Markonokov’s and anti-
Markonikov’s rule.(June-2011)
5.17.3.24. What is solvolysis reaction? What will be the product when solvent is methanol?
5.17.3.25. Write the stability order of carbocation with examples
5.17.3.26. Explain the order of acid strength

HCOOH > Cl-CH2 COOH > CH3 COOH > Phenol > Ethanol(Dec-2010)
5.17.3.27. Distinguish between SN1 and SN2 reactions giving examples.
5.17.3.28. Explain why benzoic acid is weaker than formic acid.
5.17.3.29. Write down the products of the following reaction with mechanism : CH3 CH =
−−−−−−−−−−−−−−→
CH2 + HBr(Benzoyl peroxide)
5.17.3.30. Write short notes (d) Resonance and Hypercojugation
5.17.3.31. Explain why :(a) Phenol is more easily nitrated than benzene. (June-2010)
5.17.3.32. Explain Mesomeric Effect with example.
5.17.3.33. Why does benzene undergo electrophilic substitution rather than addition reaction
?
5.17.3.34. Write short notes on any three of the following : (a) Hyperconjugation (f) Hydro-
gen bonding and its effect on properties of compounds.
Chapter 6
POLYMER CHEMISTRY
6.1 Introduction
The Natural giant molecules DNA which contains all the genetic information from gener-
ation to generation is a macromolecule. Similarly biomolecules like starch, cellulose, pro-
teins, enzymes etc. and synthetic compunds like polythene, polyvinyl chloride are also class
of macromolecules. Among these macromolecules some macromolecules have large num-
ber (Hundred to ten thousand or more) of repeating simple monomer unit joint together
through covalent bonds which is called polymer and the process of formation of polymer
from the simple starting molecules is called polymerization.
The word ”Polymer” have been taken from greek word ”Poly”, which means many and
”meros” which means part or unit. Polymers have very high molecular weight. Polymers
are macromolecules but chlorophyll, butter, Tween 20, Tween 60, Tween 80, Sodium do-
decyl sulphonates (SDS), Cetyl trimethyl ammonium bromide(CTAB) are macromolecule
due to their giant structure but having no repeating unit of monomer that is why they are
not polymer.
6.2 Monomer
The smallest unit or part which combine togetherrepeatedly to form polymers is called
monomers. Polythene is a polymer which is formed by the combination (addition) of ETHY-
LENE monomer unit.
nC2 H4 → (C2 H4 )n .
6.3 Degree of polymerization

The number of monomer unit present in a polymer is called degree of polymerization.
Synthetic polymer are mainly prepared from organic compounds having long chain molecules
203
204 CHAPTER 6. POLYMER CHEMISTRY
but there are so many polymer which are mainly prepared from inorganic compounds like
metaphosphoric acid (HPO3 )n , silicates (SiO2 )n , asbestos fiber.
6.4 Classification of polymers

Polymer can be classifieon different basis.
1. Classification On the basis of origin
2. Classification On the basis of used monomer
3. Classification On the basis of copolymer structure
4. Classification on the basis of chain growth
5. Classification on the basis of mode of polymeric growth
6. Classification on the basis of tactility
7. Classification on the basis of molecular force.
6.4.1 Classification on the basis of origin

On the basis of origin polymer can be divided into two categories:
a) Natural polymer
b) Synthetic polymer
c) Semi-synthetic polymer
Natural polymer: Complex compound which obtained from natural resources having
high molecular mass and weak molecular forces are called natural polymer. Natural rub-
ber, protein,starch, cellulose, gum resin silk and wool are example of natural polymer.
Natural rubber is a sappy material obtained from latex of rubber tree (plant in the tropical
zone) is a polymer of cis poly isoprene (cis-2 − methyle − 1, 3 − butadiene) having average
molecular weight about one million.
Proteins are the large polymer of different amino acid (contain −NH2 and − COOH) having
amide linkage by the condensation (removal of one molecule of water) of one −NH2 and −
COOH.
Starch and cellulose are polymers made from monosaccharide (α − D -glucose) and (β − D
-glucose) respectively.
Synthetic polymer: Depending on demand and supply there are variety of artificially syn-
thetic polymer which is obtained from chemical resources having high molecular mass and
weak molecular forces. Synthetic polymers can be made to achieve such properties which
cannot be achieved with natural polymer. They can withstand very high temperature and
resistance to many chemicals. Synthetic rubber (Styrenebutadiene rubber or Buna-S,nitrile
rubber or Buna-N), Polyvinylchloride(PVC), Bakelite, Teflon, nylon etc. are examples of
synthetic polymer.
Semi-synthetic polymer: To increase the different properties of natural polymers they
are treated by some chemical which are called semi synthetic polymer. Vulcanised rubber,
nitrocellulose, cellulose acetate etc. are examples of semi-synthetic polymer.
6.4. CLASSIFICATION OF POLYMERS 205
6.4.2 Classification on the basis of used monomer

On the basis of used monomer polymer can be divided into two categories:
a) Homopolymer
b) Copolymer
Homopolymer: Polymer obtained from only one type of monomer unit is called ho-
mopolymer. Polyethylene, polyvinylchloride, polystyrene, polybutadiene, polyacrylonitrile,
polypropylene etc. are examples of homopolymer.
Homopolymer - PVC
Copolymer: Polymer obtained by the simple addition of more than one monomer unit or
condensation(release of material during reaction) of more than one type of monomer unit
having bi or more functional group is called copolymer. Styrene butadiene rubber(SBR or
Buna-S), Nitrile rubber(NBR or Buna-N rubber), nylon-66 etc. are examples of copolymer.
Copolymer - Nylon6,6
Polyester, phenol formaldehyde resin, melamine formaldehyde resin.
6.4.3 Classification on the basis of copolymer structure:

On the basis of copolymer structure polymer can be divided into two categories:
a) Block copolymer
b) Graft copolymer
a) Block copolymer: A linear chain copolymer in which one monomer unit is blocked by
other monomer unit in various manner are called block copolymer. Suppose A and B are
two monomers. One monomer is blocked in different way like-
i) ABABABABABA
ii) ABBABBABBABBA
iii) ABBBABBBABBBA etc.
Example: Styrenebutadiene(SBR)
Block copolymer - SBR. Normally use as Shoe sole
b) Graft copolymer: A branched chain copolymer in which one monomer unit form the
main or long backbone chain and branches attached to it are made by other monomer
is called graft copolymer. Example: High Impact Polystyrene (HIPS) consists of the
polystyrene backbone with polybutadiene chains branching from it in each direction.
Graft copolymer - SBR. Normally use as CD case.

6.4.4 Classification on the basis of chain Growth

On the basis of chain growth polymer can be divided into to three parts:
a) Linear chain polymer
b) Branched chain polymer
c) Cross linked polymer
Linear, branched and cross linked polymer
a)Linear chain polymer: Polymer in which single monomer (incase of homo poly-
mer) or more than one monomer (incase of copolymer) units are linked together to form only
long chain or straight chain linear polymer called linear chain polymer. Due to their lin-
ear structure the different polymeric backbone chain these chains are well fitted to each
other, having high density and high melting point. Example: High density polyethy-
lene(HDPE) Polyvinylchloride(PVC) Polystyrene(PS) Polybutadiene etc.(homopolymer);
Nylon-66 Styrene butadiene polyester(copolymer)etc.
b) Branched chain polymer: Polymer in which single monomer unit (incase of homo
polymer) or more than one monomer (incase of copolymer) units are linked together to form
long chain with long or short branch throughout the long backbone chain is called branched
chain polymer. Due to presence of branch throughout the polymeric backbone chain these
chains are not well fitted to each other and hence they are low density polymer with high
melting point. Example: Low density polyethylene(LDPE) Glycogen etc. (homopolymer:)
c) Cross linked polymer: Polymer in which normally more than one monomer (incase
of copolymer) units are linked together to form long chain and different long backbone
chains are randomly cross linked resulting in the three dimensional network structure called
branched chain polymer. Due to presence of three dimensional cross link throughout the
different polymeric backbone chain with a giant molecular structure and make the structure
rigid hard and brittle. Example: Homo polymer: Vulcanized rubber Bakelite (PF) resin
Urea formaldehyde(UF) resin Melamine formaldehyde(MF) resin etc.
6.4.5 Classification on the basis of mode of polymeric growth

a) Addition polymerization
b) Condensation polymerization
a) Addition polymerization :
Addition polymerization
During the process of polymeric chain growth if there is only addition of monomers with out
any loss of small molecules like H2 O, NH3 , alcohol etc. and the polymer is an exact multiple
of used monomer unit then the polymerization process is called addition polymerization.
Example of addition polymers are PE PVC, PP etc.
b) Condensation polymerization:
Condensation polymerization
During the process of polymeric chain growth if chemical reaction takes place between
different functional group of single monomer or different monomers with the loss of com-
pound like HCl, H2 O or other compounds and the polymer is not an exact multiple of used
monomer unit then the polymerization process is called condensation polymer polymeriza-
tion. Example of condensation polymers are PF, UF, MF, Nylon, PET etc.
Different between addition and condensation polymerization:
Addition polymerization Condensation polymerization

A) This type of polymerization A) This type of polymerization
occur by the addition of occur by the condensation of
single monomer unit. occur by single monomer unit.
B) Generally the used monomer have B) Generally the used monomer have
no functional group. Two or more functional group.
C) Empirical formula of the polymer C) Empirical formula of the polymer
is same as molecular formula and is not same as molecular formula
molecular formula is an integral and molecular formula is not an
multiple of empirical formula integral multiple of empirical formula
D) Polymerization takes place without D) Polymerization takes place with
loss of any compound. loss of compound.
E) Polymerization takes places by E) Polymerization takes places by
linear or branch polymerization. cross linked polymerization polymer
J) Example of these these polymers J) Example of these these
are polymers are PVC,PE, are Nylon6,6, PF , MF, UF resin,
PP Epoxy rein,Polyester resin etc.
Preparation of some important condensation polymer:

1) Nylon-6,6
2) Nylon-6
3) polyester or poly ethylene teriphthalate
1) Nylon-6,6:
Nilon-6,6
Nylon-6,6 is a polymer having poly amide group (-CONH-) in a long back bone chain. It
is a thin and trade type polymer and capable of forming fiber. Nylon-6,6 is prepared from
equimolar ratio of hexamethylene diamine and adipic acid at a temperature 900 C. The
number 6,6 indicate the carbon atoms. It is an example of copolymer ans linear polymer
same time. The preparation method of nylon-6,6 is condensation polymerization process.
2) Nylon-6:
Nilon-6 from caprolactum
Nilon-6 from caproic acid
Nylon-6 is a polymer having poly amide group (-CONH-) in a long back bone chain. It
is a thin and trade type polymer and capable of forming fiber. Nylon-6 is prepared from
ε-amino caproic acid by self condensation at a temperature 900 C. The number 6 indicate
the carbon atoms present in monomer unit. Unlike nylon-6,6, nynol-6 is a homopolymer.
3) polyester or poly ethylene terephthalate(PET): Polyester is a polymer having
poly ester group(-COOC-)in long back bone chain. It is a thin and trade type polymer and
capable of forming fiber. The important polyester is poly ethylene terephthalate (PET). It
is prepared from equimolar ratio of ethylene glycol and terephthalic acid at a temperature
140 − 1900 C.
PET
Characteristics of polyester or poly ethylene terephthalate (PET):

a) Polyester is colour less odour less polymer soluble in ester amyl acetate
b) It is a condensation polymer .
c) Resistance to insect, heat and moisture also.
d) Chemically inert, nonpolar, moisture resistance and highly resistance to any acid base.
e) Produce fine highly tough wrinkle free but flexible fiber.
f) Resistance to any acid base except HNO3 .
Uses of polyester
a) As produce high quality fiber like dacron, terylene they normally used for the preparation
of clothes.
b) These are used for the preparation of high quality magnetic recording tape.
c) Fir thin and thread type having high tensile strength they are used as curtain, fishing
line.
6.4.6 Classification on the basis of tactility

On the basis of orientation of functional group or side groups throughout the long backbone
chain of any polymer polymer can be divided into to three parts:
i) Isotactic polymer
ii) Syndiotactic polymer
iii) Atactic polymer
i) Isotactic polymer:
Isotactic polymer
Polymer in which orientation of functional group or side groups are at the same side through-
out the main or long backbone chain are called isotactic polymer. Due to presence of
functional group or side groups same side throughout the polymeric backbone chain these
polymer cis polymer. Example: Cis polyisoprene (Natural Rubber).
ii) Syndiotactic polymer:
Syndiotactic polymer
Polymer in which orientation of functional group or side groups are arrange in the alternate
fashion throughout the main or long backbone chain are called syndiotactic polymer. Due
to presence of functional group or side groups alternate fashion throughout the polymeric
backbone chain these polymer also are trans polymer. Example: Trans polyisoprene (Gut-
taparcha) polypropylene.
iii) Atactic polymer:
Atactic polymer
Polymer in which orientation of functional group or side groups are arrange in the
Random or haphazard fashion throughout the main or long backbone chain are called
atactic polymer. Example: Polypropylene.
6.4.7 Classification on the basis of molecular force

The quality of polymer can be characterized by their different mechanical properties like
tensile strength modulus of rupture, modulus of elasticity, elongation at break, flexural
strength, impact indentation strength, abrasion test, tearing strength etc. These mechan-
ical properties are depending upon intermolecular forces like Vander Walls forces, dipole-
dipole interaction etc. among the polymeric backbone chain and hydrogen bonding. These
molecular forces are very much dependent on the functional group in the backbone chain
and the size of the polymer molecule. On the basis of molecular forces polymer can be
divided into to five parts:
i) Elastomer
ii) Fiber
iii) Thermoplastic
iv) Thermosetting plastic
i) Elastomer: The polymers in which the molecular forces like Vander Walls forces dipole-
dipole interaction among the polymeric backbone chain and hydrogen bondings are very
weak resulting the weak mechanical properties like tensile strength modulus of ruptured
modulus of elasticity elongation at break flexural strength impact indentation strength
abrasion test tearing strength etc. These polymers are stretched over a long range during
application of stress and when stress is removed they return back to their original shape.
This is the main and important properties of elastomer. Elastomers are mainly having long
chain in coiled form with some inter linking among the long chain. During application of
stretching force these coils get straight towards the direction of applied force and when
the force is withdrawal the interlinking helps to return back to its original form of coiling.
Examples: Natural rubber.
ii) Fiber: The polymers which have higher inter molecular forces like Vander Walls forces
dipole-dipole interaction among the polymeric backbone chain and hydrogen bondings
than elastomers and fiber resulting comparatively strong mechanical properties like tensile
strength modulus of ruptured modulus of elasticity elongation at break flexural strength
impact indentation strength abrasion test tearing strength etc. These polymers are thin
and thread type. Due to flexible nature these polymer can be woven. Examples: Nylon66
6.5. PREPARATION OF SOME THERMOPLASTIC POLYMER 213
Terylene Dacron Polyester Orlon Acrilon.

iii) Thermoplastic: The polymers which have intermediate inter molecular forces like
Vander Walls forces dipole-dipole interaction among the polymeric backbone chain and
hydrogen bondings in between elastomers and fiber resulting comparatively strong mechan-
ical properties like tensile strength modulus of ruptured modulus of elasticity elongation
at break flexural strength impact indentation strength abrasion test tearing strength etc.
higher than elastomer but lower than fiber.It have normally linear polymeric chain some-
times cross linking between chains. The main property of thermoplastics is these are hard
at room temperature and on application of heat the polymer become soft and fluid like
but when heat source is removed again it become hard. Depending on this characteristic
of thermoplastics they can moulded any desire shape after melting. Due to presence of
no or few cross linking the polymer chains are slide over other on heating. So thermo-
plastics polymers are reversible and recyclable. Examples: polyethylene, polyvinylchloride,
polypropylene etc.
6.5 Preparation of some thermoplastic polymer
A)Polythene(polyethelene): The monomer of polythene is ethylene. Polythene is pre-

pared by the addition polymerization of monomer ethylene in presence of heat catalyst
produce either linear or branch or semi branch polymer. Depending up on the density
ethylene polymer is divided into -
1) Low density polythene (LDPE)
2) High density polythene (HDPE)
3) Linear low density polythene (LLDPE)
4) Ultrahigh molecular weight polythene (UHMWPE)
6.5.1 Low density polythene (LDPE)
Low density polythene is prepared by a number of methods. The common method for
the preparation of LDPE is polymerization of ethylene monomer at high pressure (1000 -
4000 atm) and temperature (2500 C) in presence of oxygen peroxide hydro peroxide( free
radical generator). In this process huge branched chains are formed through out every long
back bone chain. The presence of branches repel each other and the long chains are not
well fitted to each other having some gap produce low density (0.91 to 0.925 gm/cc) polymer.
Low density polyethylene

Characteristics of low density polythene:
a) Low density polyethylene have density is low (0.91 to 0.925 gm/cc).
b) It is branched chain addition polymer.
c) Semi crystalline polymer having crystallinity 45-50 percent.
d) Chemically inert, nonpolar and having dielectric property zero.
e) Tough but flexible.
f) Melting point 105 − 1100 C.
Uses of low density polythene:
a) As LDPE is a good insulator they normally used for the preparation of electrical wires
and cables.
b) Pouch pack, squeeze bottles, delivery pipes are prepared from LDPE.
c) Toys, refill for ball pen and ball pen also prepared from LDPE.
6.5.2 High density Polythene(HDPE)

The common method for the preparation of HDPE is by the polymerization of ethylene
monomer at high pressure (30 - 35 atm) and temperature (70 − 2000 C) in presence of metal
oxide catalyst like CrO3 on silica alumina.
High density polythene can be prepared by the polymerization of ethylene monomer at low
pressure (5 - 7 atm) and temperature (60 − 700 C) in presence of Zieglar Natta catalyst like
triethyl aluminum and titanium tetrachloride. In this process of polymerization as there is
absence of branch through out the long chain back bone, the chains are well fitted to each
other which makes the polymer a high density (0.95 to 0.97 gm/cc) polymer.
High density polyethylene

Characteristics of high density polythene:
a) High density polyethylene have high density (0.95 to 0.97 gm/cc).
6.5. PREPARATION OF SOME THERMOPLASTIC POLYMER 215
b) It is less branched.
c) Highly crystalline polymer having crystallinity 80-90 percent.
e) Highly tough but flexible.
Uses of high density polythene:
a) As HDPE is a good insulator they normally used for the preparation of high performance
electrical cables.
b) Bucket, cup, toys are prepared from LDPE.
c) Due to inertness it is used for the storage of H2 SO4 , pipes for LPG gas and water reserver
also.
6.5.3 Linear low density Polythene (LLDPE)

LLDPE can be prepared by the polymerization of ethylene monomer at 2500 C temperature
and low pressure with alpha olefin (butadiene hexene or octene) in presence of Philips or
Zieglar Natta catalyst like triethyl aluminum and titanium tetrachloride. The polymeriza-
tion between ethylene and butane or hexene occur in gaseous phase and octene in solution
phase. In this process the short branched chains are formed through out every long back
bone chain. Due to presence of very short branches, density of the polymer lies in between
LDPE and LLDPE (0.92 gm/cc) polymer.
Linear low density polyethylene
Characteristics of linear low density density polythene:

a) Linear low density polyethylene have density in between low and high density polythene
(0.92 to 0.925 gm/cc).
b) It is linear chain addition polymer with short branch.
c) Moderate crystalline polymer having crystallinity 70-75 percent.
e) Moderately tough but flexibility more than LDPE.
Uses of low density polythene:
a) As HDPE is a good insulator they normally used for the preparation of covering electrical
wires and cables.
b) Bag, polyethylene sheet, toys are prepared from LDPE.

c) Pouch bag pipes, bucket mug and flexible tube are prepared from LLDPE.
6.5.4 Ultrahigh molecular weight polythene (UHMWPE)

Ultra high molecular Weight polyethylene is prepared from ethylene monomer by using of
compression moulding followed by ram extrusion gel spinning and by Kneading. Ultimately
annealing of the polymer is done by heating the material at 1350 C temperature and cool-
ing down at 50 C temperature per hour up to 650 C. Then the material is covered by heat
insulating blanket for a day to bring down the temperature to room temperature.
Ultra high molecular weight polyethylene
Characteristics of ultra high molecular weight polythene:

a) High density polyethylene have density is low (0.95 to 0.97 gm/cc).
b) Long back bone linear chain addition polymer having molecular weight 2 to 5 million or
more.
c) Highly crystalline polymer having crystallinity 80-90 percent.
e) Highly tough, enormous tensile strength due to long back bone chain.
f) Highly resistance to abrasion and ultra violet radiation.
Uses of ultra high molecular weight polythene:
a) As ultra high molecular weight poly ethylene have enormous tensile strength due to
long back bone chain they are normally used for the heavy duty gloves, armor for vehicle,
preparation of high performance electrical cables.
b) String for high performance bow.
c) As rope for climbing, suspension rope in parachutes.
6.5.5 Polyvinyl chloride(PVC)

Depending upon the characteristic polyvinyl chloride are two types-
1) Rigid polyvinyl chloride
6.6. THERMOSETTING PLASTIC 217
2) Plasticised/flexible polyvinyl chloride

1) Rigid polyvinyl chloride: Rigid polyvinyl chloride is a homopolymer which is pre-
pared from gaseous vinyl chloride (monomer) in water emulsion at a temperature 30−450 C,
and a pressure 1-5 atm. in presence of benzoyl peroxide or cumene hydro peroxide catalyst.
2) Plasticised/flexible polyvinyl chloride: Plasticised/flexible polyvinyl chloride is pre-
pared by exactly same process as described above and additionally some plsticizer molecule
like dioctyl phthalate, dibutyl phthalate etc. are being added.
Characteristics of Polyvinyl chloride:
a) Polyvinyl chloride is colour less, odour less, fire retardant polymer.
b) It is an addition polymer .
c) Low crystalline polymer having crystallinity 30-50 percent.
d) Chemically inert, nonpolar, moisture resistance and highly resistance to any acid base.
e) Highly tough but flexible.
Uses of Polyvinyl chloride:
a) As PVC is a good insulator they normally used for the preparation of insulating materials
in electrical wire.
b) Bucket, sheet for flooring, plate are prepared from PP.
c) PP is used for preparation of bathroom door, storage tank for fruit juice, oil etc.
6.6 Thermosetting plastic

The polymers which have strongest inter molecular forces like Van der Walls forces dipole-
dipole interaction among the polymeric backbone chain and hydrogen bonding than elas-
tomers thermoplastic and fiber resulting comparatively strongest mechanical properties like
tensile strength modulus of ruptured modulus of elasticity elongation at break flexural
strength impact indentation strength abrasion test tearing strength etc. due to presence
of three dimensional cross linking among the polymeric chains. The main property of
thermosetting plastics is these are hard at room temperature due to presence of three di-
mensional network cross linking on application of heat the polymer become more hard as
farther cross linking takes place and ultimately gets burnt but never melt. Depending on
this characteristic of thermosetting plastics cannot moulded again are not reversible and
recyclable. Examples: Bakelite(PF resin), Melamin formaldehyde resin(MF) Urea formalde-
hyde resin(UF)
Different thermosetting polymer:
6.6.1 Phenol-formaldehyde resin

Phenol formaldehyde is an important polymer in making different composite materials as
well plywood. It is a brown black color viscous liquid prepared from phenol and formalde-
hyde at a temperature 140 − 1450 C in presence of catalyst called resol. At high temperature
poly condensation takes place and it becomes three dimensional cross linked, brittle and
hard mass solid called BAKELITE. Bakelite is formed through methylol(-CH2 OH for-
mation which ultimately converted to methylene(-CH2 −) by removal of water molecule.
Generally,phenol-formaldehyde polymer are two types-
1) Novoloc
2) Resol
6.6.2 Novoloc
When phenol and formadehyde ratio greater than one (normally, phenol : formaldehyde
=1: 1.5-1.8) in presence of acid catalyst (normally oxalic or acetic acid) only linear long
chain polymer is formed having methylene linkage and some ether is also formed. This
polymer is mainly used for the preparation of laminates. Novoloc also can be converted to
bakelite by the addition of Hexamethylene tetramine (commercially called Hexa which on
hydrolysis produce formaldehyde) heated at 140 − 1450 C, poly condensation take place and
it becomes three dimensional cross ling, brittle and hard mass solid.
Phenol-formaldehyde(NOVOLOK) polymer
6.6.3 Resol
When phenol and formadehyde ratio is less than one (normally, phenol : formaldehyde =
1: 1.5-1.8) in presence of alkali catalyst (normally NaOH) linear long chain as well as some
cross linked polymer among the polymeric methylene linkage also formed.
6.7. PLASTICIZER 219
Phenol-formaldehyde(resol) polymer
Resol is mainly used for the preparation of marine grade plywood composite board etc.
When resol is heated at a temperature 140 − 1450 C poly condensation take place and it be-
comes three dimensional cross linked, brittle hard mass solid polymer called BAKELITE.
Bakelite is formed through methylol (-CH2 OH formation which is ultimately converted to
methylene (-CH2 −) by removal of water molecule.
Phenol-formaldehyde(bakelite) polymer
Properties of bakelite:
a) It is high thermal and electrical resistance. b) It is hard rigid and scratch proof. c) It is
resistant to many inorganic and base.
Use of bakelite:
a) Novoloc is used for the preparation of laminates.
b) Resol is used for preparation of comb, P.O. Box, marine grade, shutter grade, Boilling
water proff ply board, block board, flush door etc..
c) Resol is used for preparation of electrical board, switch etc.
6.7 Plasticizer
There are certain plastics which are not soft sufficiently on heating; and during the plastic
properties (soft,flexibility, less brittleness etc.) are lost. To improve these plastic properties,
some organic compounds are added to these plastic material which make the plastic mate-
rials soften. These external organic compounds are called plasticizer. For example: PVC
is extremely hard and brittle but it can be converted to highly flexible PVC by addition
of small amount dioctyl phthalate or n-butyl phthalate. Other examples of plasticizer are
Dibutyl phthalate, cresyl phthalate, Dialkyl phthalate etc.
Difference between thermoplastic and thermosetting plastic polymer
Thermoplastic Thermosetting plastic
A) Maximum thermoplastic polymer are A) Thermosetting plastic polymer
formed by addition polymerization in are formed by only
few cases condensation polymerization. condensation polymerization.
B) The molecular forces are B) The molecular forces are
normally weak. tremendously strong.
C) Polymer backbone chains are C) Polymer backbone chains are
connected together by Van der Wall’s connected together by
or dipole-dipole attraction or H-bonding. strong covalent bond.
D) These polymers are normally D) These polymers are normally
soft and flexible. hard and brittle.
E) These polymers are normally E) These polymers are normally
linear or branch cross linked polymer
F) On application of heat these F) On application of heat the these
polymers become soft and again polymers become more hard
become hard on cooling. due to farther cross linking.
G) On continuous heating these G) On continuous heating these
polymer get melt. polymers get burnt.
H) These polymers are recyclable. H) These polymers are not recyclable.
I) These polymers soluble in I) These polymers insoluble
many organic solvent. in organic solvent.
J) Example of these J)Example of these polymers
polymers are PVC, PE, are PF resin(Bakelite), MF resin,
PP UF resin Epoxy rein, Polyester resin etc.
6.8 Addition polymerization

During the process of polymeric chain growth if there is only addition of monomers with
out the loss of any small molecule and the polymer is an exact multiple of used monomer
unit is called addition polymerization. Example of addition polymers are PE PVC, PP etc.
6.8.1 Mechanism of addition polymerization

Addition polymerization proceed through two types of mechanism
A) Free radical mechanism
B) Ionic mechanism. A) Ionic mechanism are two type-
6.8. ADDITION POLYMERIZATION 221
i) Cationic mechanism
ii)) Anionic mechanism
Every polymerization reaction proceeds through three steps-
1) Chain initiation
2) Chain propagation
3) Chain termination
1) Chain initiation: This is the first step of polymerization reaction where initiator acti-
vate the monomer unit resulting in the formation of active center in monomer unit.
As-
M(Monomer) + I(Initiator) = M∗ (Active center in monomer unit)
I (Free radical, heat, pressure, catalyst etc.)
2) Chain propagation: This is the second step of polymerization reaction where second
third forth ...... monomer units are added with activated monomer unit consecutively re-
sulting in the formation of large chain unit.
As-
M∗ (active center in monomer) + M(Monomer) = M − M∗

M − M∗ + M(Monomer) = M − M − M∗
M − M − M∗ + M(Monomer) = M − M − M − M∗
−−−−−−−−−−−−−−−−−−− −−−−−−
−−−−−−−−−−−−−−−−−−− −−−−−−
= (M)n − M∗
3) Chain termination: This is the third and final step of polymerization reaction where
termination of active center is removed by the following possible way
a) Recombination of two smaller activated monomers
b) Recombination of two larger activated polymeric chain
c) Recombination of one smaller activated monomer with a larger activated monomer
d) Disproportion(Simultaneous oxidation and reduction of two activated monomers)
A) Free radical mechanism: It is the way of polymerization where the initiator of the
reaction is a free radical. This initiator free radical is produced by many way but one of
the important way is decomposition of the compound by sun light, heat, catalyst etc. As
example peroxide, hydroperoxide, peracid are very useful initiator in organic polymerization
reaction.
Benzoyl peroxide
Decomposition of benzoyl peroxide in presence of sun light or heat form free radical as
initiator-
Now, the following three common steps of free radical polymerization reaction are
1) Chain initiation: This is the first step of polymerization reaction where initiator is
added to the monomer unit resulting in the formation of free radical center in monomer
unit.
As-
Free radical chain initiation of vinyl chloride

2) Chain propagation: This is the second rapid step of polymerization reaction where
second third forth ...... monomer units are added with generated free radical monomer unit
consecutively resulting in the formation of large chain radical.
As-
Free radical chain prpagation of vinyl chloride

termination of free radical after long propagation is takes place by the following possible way
Free radical chain termination of vinyl chloride

A) Recombination of two smaller free radicals:
B)Recombination of two larger polymeric free radical chain:
C) Recombination of one smaller free radical monomer with a larger free radi-
cal:
D) Disproportion:(Simultaneous oxidation and reduction of activated long chain free rad-
ical)
In this process any one free radical centered carbon atom abstracted hydrogen free radi-
cal(reduction) from other(oxidation) free radical and thereby chain termination takes place.
One important think is one of the products is unsaturated as below.
Other important way of chain termination is-
1) Inhibitor reaction: The process of termination is done by inhibitor, a compound
which inhibit the growth of polymerization reaction by termination. This termination is
done when inhibitor combine with generated free radical and give comparatively stable
product. Oxygen, Nitrobenzene, Dinitrobenzene and phenolic materials are act as inhibitor
in many organic polymerization reaction.
Example of polymers formed by free radical mechanism are polyethylene, polypropylene,
styrene, styrene butadiene etc.
B) Ionic polymerization:It is the way of polymerization where the initiator of the re-
action is an ion. This initiator ion is formed from specific Lewis acid or base produce
cation(carbonium ion) or anion(carbanion)on the monomer unit. Depending up on this
cation and or anion formation ionic polymerization is devided into two parts -
i) Cationic mechanism: It is the way of polymerization where the initiator of the reaction
is formed by the combination of Lewis acid(AlCl3 , FeCl3 , BF3 ) used as catalyst with a co
catalyst like water.
1)Chain initiation: This is the first step of cationic polymerization reaction where initia-
tor is added to the monomer unit resulting in the formation of cation center(carbinium ion)
in monomer unit.
As-
Cationic chain initiation of vinyl chloride
2) Chain propagation: This is the second rapid step of cationic polymerization reac-
tion where second third forth ......monomer units are added with generated cation cen-
ter(carbinium ion) in monomer unit consecutively resulting in the formation of large chain
cation.
Cationic chain propagation of vinyl chloride

termination of cation after long propagation is takes place by
a) Proton release
b) or by combination with any part of initiator
Cationic chain termination of vinyl chloride

a) Proton release: It is the way of long chain termination of cationic polymerization by
release of proton from carbonium ion chain to the counter ion attached consequently form
unsaturated compound. b) combination with any part of initiator: It is the way of
long chain termination of cationic polymerization by the formation of covalent bond by the
combination of carbonium ion with negative part of initiator.
Example of polymers formed by cationic mechanism are Vinyl ethers, Styrene Isobutylene
etc.
ii) Anionic mechanism: It is the way of polymerization where the initiator of the reaction
is formed by the combination of any Lewis base (n-BuLi, Alkyl-Na) alkali meal amide etc.
)used as catalyst
Chain initiation: This is the first step of anionic polymerization reaction where initiator
is added to the monomer unit resulting in the formation of anion center(carbanion) in
monomer unit.
As-
Anionic chain initiation of vinyl chloride

2) Chain propagation: This is the second rapid step of anionic polymerization reac-
tion where second third forth ......monomer units are added with generated anion cen-
ter(carbanion) in monomer unit consecutively resulting in the formation of large chain
anion. As-
Anionic chain propagation of vinyl chloride

termination of anion after long propagation is takes place by the combination with any
foreign compound(such as CH3 OH, H2 O, CO2 ) added from outside. With out the addition
of foreign compound the termination of anionic polymerization is not possible
Anionic chain termination of vinyl chloride

Electron withdrawing group like -CN, -COOH, -CHO stabilized the carbanion and hence
boost up the anionic polymerization reaction. Example of polymers formed by anionic
mechanism are Styrene, Isoprene, butadiene etc.
Condensation polymerization: During the process of polymeric chain growth if there
is reaction takes place between different functional group of single monomer or different
monomers with the loss or elimination of compound like HCl , H2 0 or other compound and
the polymer is not an exact multiple of used monomer unit is called condensation polymer
polymerization. Example of condensation polymer are PF UF, MF, Nylon PET etc.
Coordination polymerization:Organometallic compound has a great role in many chem-
ical reaction as well as polymerization reaction also. When Organometallic compound act as
initiator in Polymerization reaction is called coordination polymerization reaction. Zieglar
and Natta first prepared polymer by coordination polymerization halide of Ti V, Zr, Cr,
Wand Mo.The coordination polymerization can be done by the combination of halide of
different transition metal like TiCl2 , TiCl3 , TiCl4 etc. and organometallic compound such
as trialkyl(Trimethyl, Triethyl) aluminium. The most common and useful catalyst is the
combination of triethyl aluminium with titanium trichloride. These catalysts are hetero-
geneous catalyst. The monomer catalyst complex involves coordination between a carbon
atom of a monomer and a metal atom of the catalyst. In this polymerization the triethyl
aluminium act as electron donor and and meal halide acts as an electron acceptor. The dif-
ferent catalysts for coordination polymerization reaction. Mechanism of coordination
polymerization: 1) Chain initiation: This is the first step of coordination polymer-
ization reaction where complex catalyst is added to the monomer unit resulting in the
formation of metal-carbon bond in monomer unit.
2) Chain propagation: This is the second rapid step of coordination polymerization reac-
tion where second third forth ...... monomer units are added with generated metal-carbon
bond in monomer unit, consecutively resulting in the formation of large chain metal-carbon
bond.
3) Chain termination: This is the third and final step of coordination polymerization
reaction where termination of large chain metal-carbon is terminated by the transfer of
hydrogen atom from monomer or from active hydrogen containing compound.
Importance of coordination polymerization:
1) Normal free radical polymerization involves atactic polymer whereas coordination poly-
merization isotactic polymer. That means stereospecific polymer can be prepared by this
coordination polymerization. Using this process(Zeiglar-Natta catalyst) of polymerization
isoprene produces only stereospecific Cis-1,4-polyisoprene
2) Coordination polymerization always involves mainly linear polymer hence highly crys-
talline in nature.
6.9 Rubber
Rubber is a natural elastomeric polymer whose monomer unit is cis-2-methyle-1,3-butadiene.
Raw rubber material is extracted from rubber plant which is milk like sappy and negatively
charged colloid, get polymerized bio chemically. The main source of natural rubber is rub-
ber tree (scientific name: Hevea Basiliensis.)
Cis polyisoprene(natural rubber)
Rubber tree is found mainly in tropical countries like southern part of India, Srilanka,
Malaysia, Thailand, South America. Solid rubber is white brownish amorphous solid which
is soluble in petrol/carbon disulphide. The main compositions of latex which is extracted
from rubber plant are -
6.10. SYNTHETIC RUBBER 227
Water - 55-60 percent

Rubber (cis isoprene) - 32-35 percent
Protein - 02-03 percent
Fatty acid - 01 percent
Soluble salt - 01 percent
Ash - 0.03 percent
The approximate molecular weight of rubber polymer is 100000- 160000. Due to its cis con-
figuration, natural rubber is well packed and they held together by Van-der Waals force of
attraction. That is why natural rubber has weak molecular force and it is called elastomer.
To increase the elastic properties of rubber during rubber preparation the extracted latex
is treated with sunlight/heat/chemicals (mainly sulpher or hydrogen sulphide etc). The
function of sulpher is breaking of pi electron in rubber and make three dimensional cross
linking between double bonded carbon atom by sulpher bridge. This is called vulcanization
of rubber. In this way natural rubber becomes very strong highly elastic low abrasion re-
sistance towards many chemicals and hard.
Trans polyisoprene(Gutta percha)

The Trans isomer of 2-methyle-13-butadiene is known as Gutta Percha obtained from the
tree named Dischopsis Gutta and Palagum Gutta.
6.10 Synthetic rubber

Synthetic rubbers are:
1) Styrene butadiene rubber(SBR)
2) Neoprene rubber
3) Butyl rubber
4) Nitrile rubber
5) Polysulphide rubber
6.10.1 Styrene butadiene rubber(SBR)

Buna-S rubber is a copolymer obtained by the addition of butadiene and styrene at a ratio
3:1 in a emulsion system in presence of free radical initiator like benzoyl peroxide or cumene
hydro peroxide with support of dextrose.
Styrene butadiene rubber(Buna-S)
The produced rubber is called cold rubber as the polymerization carried at temperature
-150 C to 50 C. At this temperature the chain length can be controlled. If the reaction tem-
perature is 500 C then he rubber is called hot rubber and in this case the chain can not be
controlled.
Such types of synthetic rubbers are more efficient than natural rubber. These rubber
have high tensile strength, low abrasion oxidation and resistance to weather oil and acid
base.
6.10.2 Nitrile rubber (NBR or GR-A or Buna-N)

Buna -N rubber is a copolymer obtained by the addition of butadiene and acrylonitrile at
a ratio 3:1 in a emulsion system in presence of free radical initiator like benzoyl peroxide
or cumene hydro peroxide. Synthetic rubbers can be vulcanized as there is weak pi bond
present in the long back bone polymeric chain.
6.11. BIODEGRADABLE POLYMER 229
Nitrile butadiene rubber(Buna-N)

Such types of synthetic rubbers are more efficient than natural rubber. These rubber have
high tensile strength low abrasion oxidation and resistance to weather oil and acid base.
Due to presence of -CN group this is less resistance towards base.
6.10.3 Neoprene rubber(GR-A)

Neoprene rubber is also called polychloroprene or duprene. Neoprene rubber is a copolymer
obtained by the addition of monomer chloroprene (2-chloro-13-butadiene). Chloroprene is
prepared by dimerisation of acetylene by passing through aqueous solution of ammonium
chloride (NH4 Cl) and cuprous chloride(Cu2 Cl2 )at a temperature 700 C. HCl is added finally.
Free radical initiators like benzoyl peroxide or cumene hydro peroxide or oxygen enhance
the polymerization of chloroprene to neoprene.
Polychloroprene(Neoprene)
6.11 Biodegradable polymer

The higher weather stability of polymer is economically profitable and scientists are con-
tinuously trying to make the polymeric substance durable. But some polymers are not
biodegradable. That means micro organism cannot decompose them and the major prob-
lem is after use the polymeric products are thrown hare and there which makes layers on
the earth and water cannot penetrate to the under ground in rainy season. To overcome
the disposal problem few thermoplastic polymer are recycled. But during every recycling
the plastic properties of the polymers are gradually decreased. The thermosetting polymers
are not recyclable. Therefore they cause major problem for our ecosystem. This problem
are solved by preparing plastics which get degrade spontaneously after certain period of
time (require for use). Such polymers which are biodegradable by chemical oxidation or
by micro organism are called biodegradable polymers. He the carbon-carbon bond in poly-
mers is inert due to non-polarity and cannot break by means of natural micro organism or
by chemical treatment. To make the polymers biodegradable it is needed to incorporate
some reactive functional group in the carbon-carbon bond of the polymer. Mainly used
such type functional group is ester(-COOR) where the carbon-carbon bond is not directly
linked but linked by (-O-). Due to the incorporation of ester functional group in between
carbon-carbon bond the polymer become biodegradable.When these polymer is buried as
waste they will be degraded by microorganism through enzymatic catalysis.
The beat examples of bio degradable polymers are-
Poly-hydroxy butyrate valerate(PHBV)
Poly-hydroxy butyrate (PHB)
Polyglycolic acid(PGA)
Polylactic acid(PLA)
Poly-hydroxy butyrate valerate(PHBV): It is a co-polymer. This type of bio-degradable
polymer is prepared from 3-Hydroxybutanoic acid and 3-Hydroxypentanoic acid. It is nor-
mally used in the preparation of packaging materials for orthopedic device. The main
drawback of these polymers is very costly.
Poly-hydroxy butyrate valerate(PHBV)
The presence of ester linkage is responsible to bio-degradation by microorganism through

enzymatic catalysis. Use of such copolymers:
1. Preparation of packaging materials for orthopedic device.
2. Preparation of film.
3. Preparation of molded items.
6.12. MONODISPERSE AND POLYDISPERSE POLYMER 231
6.12 Monodisperse and polydisperse polymer

Polymers which have molecular weight equal to an integral multiple of the molar mass of
any chain due to presence of equal chain length in the polymer called monodisperse poly-
mer.
Examples are Protein Starch Polymers which have molecular weight are not equal to an
integral multiple of the molar mass of any chain due to presence of mixture of different
chain length in the polymer called polydisperse polymers. The main reason is that the
polymerization occurs through random collision of the molecules and the termination of
chains can occur with different length or different size.
Examples are mainly synthetic polymer like polyester phenol formaldehyde resin urea
formaldehyde resin melamine formaldehyde resin etc. The molecular weight of such poly-
mer is not fixed and varies in between certain range. In case of such polymer the molecular
weight is average molecular weight.
6.13 Molecular weight of polymer

There are three types of molecular weight-
a) Number average molecular weight
b) Weight average molecular weight
c) Viscosity average molecular weight
6.13.1 Number average molecular weight

Number average molecular weight is determined by the total weight of the all different
molecules of different chain length divided by the total number of molecules present. Num-
ber average molecular weight can be determined by colligative property measurement. If
a polymer sample have N1 N2 N3 Nn number of molecules according to the chain length and
the molecular masses are M1 M2 M3 Mn respectively. The number average molecular weight
(MN )can be determined as-
Total mass of the polymer

MN =
Total number of molecules in polymer
N1 M1 + N2 M2 + N3 M3 + ......... + Nn Mn
=
N1 + N2 + N3 + ......... + Nn
P
NM
= Pi i
Ni
6.13.2 Weight average molecular weight

Weight average molecular weight is determined by the total of different weight fractions
(individual weight of any chain or molecule divided by total molecular weight of the polymer)
of the polymer multiplied by their respective molecular weight. Weight average molecular
weight can be determined by light scattering measurement method. If a polymer sample
have N1 , N2 , N3 , Nn number of molecules according to the chain length and the molecular
masses are M1 , M2 , M3 , Mn respectively then the weight fraction of different polymeric
chains will be W1 , W2 , W3 , Wn respectively.
Now-
Total mass of the 1st species
W1 =
N1 M1
=
N1 M1 + N2 M2 + N3 M3 + − − − − − − − − +Nn Mn
N M
= P1 1
Ni Mi
Total mass of the 2nd species
W2 =
N2 M2
=
N1 M1 + N2 M2 + N3 M3 + ......... + Nn Mn
N M
= P2 2
Ni Mi
− − − − −− −−−−−−−−
− − − − −− −−−−−−−−
and
Total mass of the i-th species
Wi =
Ni Mi
=
N1 M1 + N2 M2 + N3 M3 + ......... + Nn Mn
NM
= Pi i
Ni Mi
Then the Weight average molecular weight,(MW ) can be determined as

MW = W1 M1 + W2 M2 + W3 M3 + − − − − − − +Wn Mn
X
= Wi Mi
N1 M1 N2 M2 N3 M3 Nn Mn
= (P )M1 + ( P )M2 + ( P )M3 + − − − − +( P )Mn
Ni Mi Ni Mi Ni Mi Ni Mi
N1 M21 N2 M22 N3 M23 Nn M2n
= P +P +P + − − − − +P
NM Ni Mi Ni Mi Ni Mi
P i i2
Ni Mi
= P
Ni Mi
6.13. MOLECULAR WEIGHT OF POLYMER 233
6.13.3 Viscosity average molecular weight

The viscosity average molecular weight MV of the polymer can be determined from the
intrinsic viscosity([η])
η − η Solvent
[η] = [ Solution ]
η Solvent
= η Specific
For this purpose different concentration(let 20/40/60/80 percent) of a polymer is prepared

in non-reacting solvent and the viscosity as well as specific viscosity is measured. A straight
line graph with positive slope has been plotted for specific viscosity against the concentration
of the polymer. By extrapolating the line on Y axis and where is touches the Y axis that
point is the intrinsic viscosity([η]) of the polymer.
Fig.
Then using the famous equation of Mark-Kuhn-Houwink i.e.
a
[η] = KMV
we will get the viscosity average molecular weight of the polymer. Where K and a are
constant for specific pair of polymer and solvent and obtained from the literature. It is
observed that the value of a vary in the range 0.5 to 0.9 .
Now
a
[η] = KMV
a
log[η] = log(MV )
log[η] = logK + alogMV
Putting the respective value of two constant K and a and [η] we will get the value of MV .
Different molecular mass distribution in polymer

It is important to remember that for monodisperse(Polymers which have molecular

weight equal to an integral multiple of the molar mass of any chain due to presence of equal
chain length in the polymer) polymer
MW = MN
The normal range of a vary from 0.5 to 0.9 and in such case viscosity average molecular
weight (MV ) always less than weight average molecular weight(MW ).
When the value of constant a becomes unity the viscosity average molecular weight (MV )
= Weight average molecular weight (MW ).
6.14 Degree of polymerization

It is the number of monomer units present in a polymer. It can be expressed in two way
1) Number average degree of polymerization(DMN )
2) Weight average degree of polymerization(DMW )
Number average degree of polymerization
MN
(DMN ) =
MO
and weight average degree of polymerization
MW
(DMW ) =
MO
where MO is the molecular weight of monomer unit.
6.15 Polydisperse Index(PDI)

The Ratio of weight average molecular weight (MW ) with respect to number average molec-
ular weight (MN ) is called poly disperse indec(PDI)
MW
(PDI) =
MN
6.16 Glass transition temperature (TG)

. The glass is said to be a supercooled, liuid, hard, brittle, amorphous substance having
variable melting point and very high viscosity(1013 Poise or more). The glass transition
temperature of any amorphous polymer is the temperature where it undergo transition
6.17. CRYSTALLIZATION TEMPERATURE(TC ) 235
from rubbery (soft and called viscoelastic state) to glassy (hard and rigid) solid or vice-
versa. This can be done by heating the solid polymer to melt and allow to cool gradually.
The viscosity of liqid gradually increses and it will converted to rubber like material. On
farther cooling at a particular temperature the rubber form transformed to rigid form. This
temperature is called glass transition temperature. The term glass transition temperature
is only applicable for thermoplastic polymer not for thermosetting polymer. The molecu-
lar force of polymer very much depend on glass transition temperature. Glass transition
temperature of few amorphous polymers are-
Amorphous polymer T0G C
Polyvinyl Chloride(PVC) 80
Polytetrafluoroethylene(Teflon) 115
Polypropylene(PP) 5
Polyethylene(PE) -20
Glass transition temperature depends on following factor:

1) It increases with increase in molecular weight of polymer.
2) It increases with increase in branch in polymeric backbone chain.
3)It increase with increase in large group in polymeric backbone chain.
6.17 Crystallization temperature(TC)
In case of crystalline polymer and amorphous polymer, above the glass transition a state
will arrive where molecules moved into ordered arrangement with a very stable crystalline
structure by gaining of energy and there by given off energy called crystalline temperature
(TC ). TC can be measured by differential calorimetry(DSC)
Specific volume Vs temperature

Glass transition temperature(TG ),
Crystallization temperature(TC )
Melting temperature(TM )
Heat flow Vs temperature

Glass transition temperature(TG ),
Crystallization temperature(TC )
Melting temperature(TM )
Crystallization temperature depends on following factor:

1) It increase with increase in molecular weight of polymer.
6.18. MELTING TEMPERATURE(TM ) 237
2) It increase with decrease the branch in polymeric backbone chain.

3)It increase with decrease the large group in polymeric backbone chain.
6.18 Melting temperature(TM)

In case of both amorphous and crystalline polymer a point above crystallization tempera-
ture another thermal transition state will arrive where by gaining of energy the molecules
moved into a disordered arrangement with a very unstable structure and get melts called
melting temperature(TM ). Reaching this temperature(TM ) where melting starts the the
temperature remain unchanged until whole polymer get melts. Melting temperature of few
polymers are-
Amorphous polymer T0M C
Polyvinyl Chloride(PVC) 212

Polystyrene(PS) 240
Polypropylene(PP) 175
High density polyethylene(HDPE) 115
Low density polyethylene(LDPE) 135
Melting temperature depends on following factor:

1) It increase with in crease in aromatic part in polymer.
2) It increase with in crease in molecular weight of polymer.
3)It increase with in crease the large group and polar in polymeric backbone chain.
6.19 Crystalline, semicrystalline and amorphous

polymer
The polymer is made of large number of repeating monomer unit varying from 100 to lacks
or more and consequently their respective molecular weights are also high. In polymer the
molecules are held together by van der Waals force or by hydrogen bonding. In polymer
the molecules are arranged in well packed form or haphazardly oriented in one dimensional
or linear, two dimension or sheet, three dimensional or cross linked network structure. Due
to presence of giant structure and curing conditions the molecules of polymers are arrange
in different fashion called crystalline, semi-crystalline or amorphous polymer. and their
crystallinity may vary from 0 to 99%.
6.19.1 Crystalline polymer

In polymer the molecules are arranged in regular fashion and thereby well packed in the
form of crystal having a thickness about 10 to 18 nm with parallel long backbone chain
perpendicular to the surface of the polymer plate is called crystalline polymer. The crys-
tallinity about 95 to 99%. Example of crystalline polymers are Polyethylene, polyester,
polyethylene terephthalate etc.
Properties of crystalline polymer:
Crystalline polymers have the following properties-
1. Rigid and strong
2.having high melting point
3.high molecular forces
4.less effected by solvents
6.19.2 Semi-crystalline polymer

In polymer the molecules are arranged in regular closed pack as well as haphazard fashion
and thereby polymer have both crystalline and amorphous portion is called semi-crystalline
polymer. The crystallinity in semi-crystalline polymer about 50 to 75%. Example of crys-
talline polymers are Polyvinyl alcohol(both PVA hot and PVA cold), polyester, polyethylene
terephthalate etc.
Properties of Semi-crystalline polymer:
1. soft and weak
2.having low melting point
3.low molecular forces
4.highly sensitive towards solvents
6.19.3 Amorphous polymer

In polymer the molecules are arranged in irregular and disorder fashion and thereby polymer
have low molecular force, melting point is called semi-crystalline polymer. The crystallinity
in semi-crystalline polymer about 20 to 50%. Example of amorphous polymers are Polyvinyl
acetate(fevicol), polystyrene, poly methyl methacrylate (PMMA) etc.
Properties of amorphous polymer:
1. very soft and weak
2.having low melting point
3.low molecular forces
4.highly sensitive towards solvents
6.20. DEGREE OF CRYSTALLINITY: 239
6.20 Degree of crystallinity:

Polymer having different strength due to presence of different percentage of crystallinity.
Polymer crystallinity is also called degree of crystallinity is the ratio of polymer of the
crystalline part of the polymer to the rest amorphous polymer.
Mathematically represented as-
ρPolymer − ρAmorphous
ρCrystalline − ρAmorphous
Where, ρPolymer, ρAmorphous and ρCrystalline are densities of whole polymer, amor-
phous part and crystalline part of polymer respectively.
6.21 Conducting polymer:

Polymer made from natural sources or from artificially they are normally bad conductor or
poor conductor of electricity. Conducting polymer are those which conduct electricity. We
know all metals are good conductor of electricity but when a polymer conduct electricity we
called it conducting polymer or intrinsic conducting polymer or simply synthetic metal. We
know metals have free electron which moves and current flows but how does the electricity or
current flows through some polymers. The main cause of conducting current by a polymer
is presence of conjugated Π electrons in the backbone chain. Here the conduction takes
place by overlapping of orbital of conjugated Π electrons in the polymer chain., due to
high coordination number, valence shell electrons are not sufficient for pairing with all
surrounding atoms to form covalent bonding. Hence, the lower bands are filled up first but
the upper band are farthest from from the nucleolus and they are empty or partially filled
due to insufficient electrons.
Band theory (valence band and conduction band)

The lower energy band is called valence band and the upper energy band is called conduction
band. The band theory explains the position of these mobile electrons and the process of
electrical conduction. In polymer, when they occupy a definite positions, the electrons are
subjected to a non-uniform electric field. The electrons may now take position in the band.
The band however non-continuous, but separated by forbidden zones.
Molecular orbital picture of H2
If the energy gap between the valence band and conduction band(band gap) are large then
the polymer is called electrically insulator.
6.21. CONDUCTING POLYMER: 241
Band theory in case of insulator
In case of semiconductor a small amount of electric current can flow at room temperature
and the normal value of conductivity of semiconductors are in the order 102 to10−10 ohm−1 .m−1 .
6.21.1 Semiconductor
Semi-conducting polymers are having the energy gap between the valence band and con-
duction band(band gap) are not so large and not so small. They have low conductivity.
Band theory in case of semiconductor
Examples are poly acetylene1.7 × 10−9 ohm−1 .m−1 and polyaniline10−10 ohm−1 .m−1 .
Delocalisation of electron in a conjugated system)
Due to this low conductivity these are not used in practical field. The conductivity of these
semiconductor however enhance by many ways-
1. Doping
2. Filled with conducting polymer
3. Blending with conducting polymer
6.21.2 Doping
The conduction power of semiconductor can be enhanced by input some foreign material or
impurities. These impurities are called doping agent or dopant. Appropriate doping agent
increase the conductivity of semiconductors upto 104 times. Doping enhances the conduc-
tivity of semiconductor and called extrinsic semiconductor. The increase in conduction is
due to participation of impurity elements in between the valence band and conduction band
and thus making a bridge through which electrons can jump easily from the valence band to
the conduction band.Actually the conjugated Π electrons have very low ionisation potential
and high electron affinities the foreign materials develop positive or negative charge through
oxidation or reduction of the semiconductor. Doping are mainly two type.
i) p-type doping through oxidation of materials: In this type of doping some elec-
trons from the conjugated Π bonds are removes through oxidation creating a positive hole
called polaron inside the polymer. The positive hole or polaron can move throughout the
polymeric chain and make it conducting polymer.
p-type doping creates positive hole
Lewis acids(FeCl3 , AlCl3 ) are generally use as doping agent.

ii) n-type through reduction of materials: In this type of doping some electrons are
introduced to the conjugated Π bonds through reduction creating a negative hole or charge
inside the polymer. The negative hole or charge can move throughout the polymeric chain
and make it conducting polymer.
n-type doping creates positive hole
Lewis bases(Na+ C10 H− + −

8 , K C10 H8 ) are generally use as doping agent.
2. Filled with conducting polymer:The conduction power of semiconductor can be
enhanced by input some foreign conducting material or good conductor in powder(carbon
dust) form or granule from(metallic fibers). The role of polymer is to bind the conducting
materials. The minimum concentration of conducting filler required to start the conduction
is called percolation threshold.
3. Blending with conducting polymer:The conduction power of semiconductor can
be enhanced by input some foreign conducting polymer material. During such type of
blending we should alert about the compatibility of those polymer. In such cases the
strength properties of the blend polymer also enhanced.
Another application of conducting polymer Due to light weight low cost than metal
semiconductor and easy to preparation conducting polymers have diversified application.
a. Rechargeable light weight batteries
b. Optical display device
c. Solar cell
d. telecommunication system
e. electronic toys
f. As analytical sensor.
Some common important monomer and polymer of addition polymer:
Some common important monomers and polymer of condensation polymer:

Sl. Name of structure Name of polymer structure commercial Uses

No. monomer of monomer Name of polymer of polymer Name Uses
1. Ethylene CH2 = CH2 Polythene −[CH2 − CH2 ]− Polythene Bag,

/Ethene Packing
materials
2. Propene CH(CH3 ) = CH2 Polypropene −[CH(CH3 )− PP Seat covers,
Polypropene CH2 ]− ropes,
carpet
fiber
3. 1,3-Butadiene CH2 = CH Polybutadiene −[CH2 − CH Polybutadiene Tyres,
−CH = CH2 = CH − CH2 ]− shoe
soles
4. Styrene CH(C6 H5 ) = CH2 Polystryne −[CH(C6 H5 ) − CH2 ]− Polystryne Refrizerator
linings,
toy, cup
5. Vinyl chloride CH(Cl) = CH2 Polyvinyl −[CH(Cl) − CH2 ]− PVC Gramaphone
chloride records,
electrical
insulator
6. Isoprene CH2 = C(CH3 ) Cis −[CH2 − C(CH3 ) Natural Tyres,
−CH = CH2 Polyisoprene = CH − CH2 ]− rubber tubes
7. Chloroprene CH2 = C(Cl) Neoprene −[CH2 − C(Cl) Synthetic Container
−CH = CH2 rubber = CH − CH2 ]− Rubber for oil,
Pipe for
petrol
8. Acrylonitrile CH(CN) = CH2 polyacrylo −[CH(CN) PAN Blankets,
CH(CN) = CH2 nitrile −CH2 ]− Carpets,
sweater
9. Methyl C(COOCH3 ) Polymethyle −[C(COOCH3 ) PMMA Lenses,
methacrylate (CH3 ) = CH2 methacrylate (CH3 ) − CH2 ]− Aircraft
window
10. Tetrafluoro CF2 = CF2 Polytetra −[CF2 − CF2 ]− Teflon Non stick
ethylene fluoroethylene Teflon frying
pan,
gaskaets
11. Monochloro CClF = CF2 PolyMonochloro −[CClF − CF2 ]− PCTFE Valves,
trifloroethylene trifloroethylene gaskaets
12. Ethyl CH(COOCH3 ) Polyethyle −[CH(COOCH3 ) PEA Blankets,
acrylate = CH2 methacrylate −CH2 ]− Cloths
13. Butadiene CH(C6 H5 ) = CH2 Styrene −[CH(C6 H5 ) SBR Shoes sole,
styrene + CH2 = CH butadiene −CH2 − CH2 SBR Tyres
−CH = CH2 rubber −CH = CH − CH2 ]−
14. Butadiene CH2 = CH − CH Polybutadiene −[CH2 − CH = Polybutadiene Carpets,
acrylonitrile = CH2 + CH acrylonitrile CH − CH2 ]− acrylonitrile sweater
(CN) = CH2 −CH(CN) − CH2 ]−
15. Vinyledene CH2 = CCl2 + Polyvinyl −[CH2 − CCl2− Swaran electrical
chloride CH2 = CH(Cl) chloride CH2 − CH(Cl)]− Warp insulator
+ Vinyl
chloride
Sl. Name of structure of Name of structure commercial Uses

No. monomer monomer polymer of polymer Name Uses
1. Ethylene HOCH2 − CH2 OH + Polyethylene −[OCH2 − CH2 OOC Terylene Seat belts,
glycol + HOOC − C6 H4 − COOH terephthalate −C6 H4 − CO]− or Decron ropes,
Terephthalic (PET) nets,
acid magnetic
tapes
2. Ethylene HOCH2 − CH2 OH Polyethylene −[OCH2 − CH2 OOC Glyptal Paints,
glycol + + C6 H4 − (COOH)2 terephthalate −C6 H4 − CO]− lacquers
Phthalic + (PET)
acid +
3. Caprolactum (−CH2 )5 CONH− Polyamide −[NH Nylon-6 Ropes,
(CH2 )5 CO]− tyre cords
thrade,
fabris
4. ε-Amino NH2 − (CH2 )5 − NH2 Polyamide −[NH(CH2 )5 CO]− Nylon-6 Ropes,
caproic tyre cords,
acid thrade,
fabris
5. Hexamethylene NH2 − (CH2 )6 NH2 + Polyamide −[NH − (CH2 )6 Nylon-6,6 Fabrics
diamine + HOOC− NHOC − (CH2 )4 for textile,
Adipic (CH2 )4 − COOH −CO]− bristles
acid for brushes
6. Ethylene HOCH2 − CH2 OH + Polyethylene −[OCH2 − CH2 O Terylene Seat
glycol + CH3 O − OC − C6 H4 terephthalate −OC − C6 H4 or belts,
Dimethyl −CO − OCH3 −CO − O]− Decron ropes, nets,
terephthalic magnetic
acid tapes
7. Phenol + C6 H5 − OH Poly Three Novoloc or Wood adhesive,
Formaldehyde + HCHO phenol dimensional resol Electrical
formaldehyde cross linking (Phenoplast) equipments
network PF (PO box)
structure resin pressure
(see p.-) cooker
handle
8. Melamine + C3 N6 H6 Poly Three dimensional (Aminoplast) plywood
Formaldehyde + HCHO melamine cross linking network MF adhesive,Cup
formaldehyde structure(see p.-) resin plate, dish
structure(see page-) plate, dish
9. Urea + NH2 − CO − NH2 Poly Three dimensional (Aminoplast) MR grade
Formaldehyde + HCHO urea crosslinking network UF plywood
formaldehyde structure(see p.-) resin adhesive
structure(see p.-) adhesive

6.24.1.1. A conducting polymer is (June-2014)
a) polyethylene b) polypropylene c) polyaniline d) bakelite
Ans. Polyaniline
6.24.1.2. An example of thermosetting polymer is
a) PVC b) Nylon c) polyethylene d) Bakelite.
Ans. Bakelite
6.24.1.3. Bakelite is an example of(June-2013)
a) metal b) thermoplastic c) rubber d) thermoset.
Ans. Thermoset
6.24.1.4. Example of thermosetting plastic is (Dec-2012)
a) PVC b) Nylon c) Polythene d) Bakelite.
Ans. Bakelite
6.24.1.5. A conductive polymer is
a) Polyethylene b) Polypropene c) Polysulprurnitride d) Bakelite.
Ans. Polysulprurnitride
6.24.1.6. Which of the following is a macromolecule but not polymer ?
a) Nylon-66 b) Bakelite c) Polyester d) Chlorophyll.
Ans. Chlorophyll
6.24.1.7. Caprolatum is monomer of
a) Bakelite b) PVC c) Nylon-6,6 d) Nylon-6.
Ans. Nylon-6
6.24.1.8. Proteins are biopolymers. The monomer unit present in them is(June-2012)
a) amino acid b) carbohydrate c) fatty acid d) alkene.
Ans. Amino acid
6.24.1.9. Tetrafluoroethylene is the monomer of(Dec-2011)
a) Polyethylene b) Nylon 6 c) Polyvinyl chloride d) Teflon.
Ans. Teflon
6.24.1.10. Strachs are biopolymers. The monomer units present in them are
a) alkene b) amino acid c) fatty acid d) carbohydrate.
Ans. Carbohydrate
6.24.1.11. Which of the following is not a polymer?(June-2011)
a) Silk b) DNA c) TNT d) Starch
Ans. TNT
6.24.1.12. Monomer unit present in natural rubber is

a) 1,3-butadiene b) 2-methyl-1,3-butadiene c) 2-ethyl-1,3-butadiene d) 2-chloro-
1,3-butadiene.
Ans. 2-Methyl-1,3-butadiene
6.24.1.13. Phenol formaldehyde is an example of

a) addition polymer b) isotactic polymer c) thermoplastic polymer d) thermoset-
ting polymer.
Ans. Thermosetting polymer
6.24.1.14. An example of step-growth polymer i(Dec-2010)

a) PVC b) Teflon c) Bakelite d) Poly-butadiene.
Ans. Bakelite
6.24.1.15. A conducting polymer is (June-2010)

a) Polacetylene b) Polypropylene c) Bakelite d) Poly-butadiene.
Ans. Polacetylene
6.22.2 Short Answer question

6.24.2.1. What do you understand by polymerization? Write down the structure and use
of Nylon-6,6 and PVC.( Dec-2014)
6.24.2.2. (a) What is polydispersity index of a polymer(June-2014 )
6.24.2.3. (a) What is calorific value of a fuel ?

(b) How can you account for different properties of two samples of a polymer
having the same number-average molecular weight. (2 + 3)
6.24.2.4. Explain the number average and weight molecular mass of polymer. Which one
is greater and why ?(Dec-2012)( 3 + 2)
6.24.2.5. (b)Define number average molecular weight of a polymer.(Dec-2011) (1+1)
6.24.2.6. (c) What is glass transition temperature of a polymer ?(2)
6.24.2.7. What is tacticity? Draw the structures of isotactic, syndiotactic and atactic poly-
mers with structures.( June-2011)(2+3)
6.24.2.8. Give the outline of preparation, structure and uses of SBR. How is HDPE manu-
factured ? What are its uses ?(Dec-2010)(3 + 2)
6.24.2.9. (b) The degree of polymerization of polyethylene is 1000. Find the molecular
weight of polyethylene. 2
6.24.2.10. Write down the structure and use of Nylon-66 and PVC.(Dec-2010)
6.22.3 Long Answer question

6.24.3.1. Differentiate between addition and condensation polymerisation.
6.24.3.2. What is glass transition temperature?
6.24.3.3. Name monomers of the following polymers

(i) PVC
(ii) Teflon
(iii) Nylon-6
(iv) Bakelite (Dec-2014)
6.24.3.4. Equal number of polymer molecules with M1 = 100000 and M2 = 10000 are mixed.
Calculate MN and Mw.
What do you mean by degree of polymerization.
6.24.3.5. (a) Write down the difference between thermoplastic and thermosetting resin with
example.
(b) Explain addition and condensation polymerization with example.
(c) Classify polymers on the basis of tacticity. (June-2014)(3 + 4 + 3 )
6.24.3.6. (a) Discuss essential structural criteria for electrical conductivity, environmental
stability and melt-and solution processibility in conducting polymers with suitable
example.( 4)
6.24.3.7. (b) What is plastic ? Distinguish between thermoplastics and thermosetting poly-
mer.( June-2013)(5)
6.24.3.8. Write short notes(e) Conducting polymer.
6.24.3.9. Discuss the difference among isotactic, syndiotactic and atactic polymers.(Dec-
2012) (3)
6.24.3.10. Write notes the following :

(a) Conducting polymer.
6.24.3.11. Write short notes on (a) Vulcanization(June-2012)
6.24.3.12. (a) Discuss the essential structural criteria for conductivity, environmental stabil-
ity and process ability in conducting polymers with suitable examples (6)
6.24.3.13. Write notes on any three of the following :(a) Biodegradable polymer(Dec-2011)
6.24.3.14. Write notes on any three of the following : (c) Vulcanization of rubber
6.24.3.15. Write about the synthesis and uses of the following :

(i) HDPE
(ii) Buna-S-Rubber.
6.24.3.16. (c)What are the difference between thermoplastic and thermosetting resins?(June-
2011)
6.24.3.17. Write down short notes on any three of the following(b) Vulcanization of rubber
6.24.3.18. What is conducting polymer? Give an example.( 2)
6.24.3.19. Write the chemical structures of the repeat units of Nylon 6, 6 and Nylon 6. Why
are they so named ? ( Dec-2010) (4)
6.24.3.20. (a) Define condensation polymerization with suitable example.

(b) Explain mathematically Weight Average Molecular Weight.
( c) What are raw rubber and vulcanized rubber ?(June-2010)(5+4+4)
Chapter 7
INDUSTRIAL CHEMISTRY:
FUEL
7.1 Fuel and its classification

Fuels are substrates which liberates heat energy on heating or combustion. Combustion is
a type of oxidation process which undergoes in presence of oxygen. So fuels are store house
of heat energy which can be used for different household or industrial purpose when needed.
The fuels available in the world are mainly fossil fuel which is limited and not renewable.
So use of nuclear fuel as an alternative fuel is of immence importance.
7.1.1 Fuels can be classified in two different class depending

upon the occurrence
a) Fuels which are available naturally and used directly in their crude form without any
further process are called natural fuel or primary fuel like-wood, crude oil, natural gas etc.
b) Fuels are are derived from by transformation of natural fuel are called derived fuel
or secondary fuel like-coke, charcoal, petrol, diesel,kerosine, coal gas, biogas, water gas,
producer gas etc.
7.1.2 Fuels can be classified in three different class depending

upon the physical state
a) Sild Fuel
b) liquid fuel
c) Gaseous fuel.
a) Fuels which are available naturally and used directly in their crude form without any
further process are called natural fuel or primary fuel. fuel like-wood (solid), crude oil
(liquid), natural gas (gaseous) etc.
251
252 CHAPTER 7. INDUSTRIAL CHEMISTRY: FUEL
b) Fuels are are derived from by transformation of natural fuel are called derived fuel or
secondary fuel like-coke, charcoal (solid), petrol, diesel, kerosine (liquid), coal gas, biogas,
water gas, producer gas (gaseous) etc.
7.2 Calorific value of fuel

Calorific value of a fuel is the total amount of heat liberated by complete combustion of a
unit mass or unit volume of fuel in presence of oxygen or air at normal temperature and
pressure.
Units of calorific value: The units of calorific value are cal, K.cal or B.Th.U (British
thermal unit). 1 calorie can be defined as the amount of heat needed to raise the tempera-
ture of 1 gm of water from 14.50 C to 15.50 C
Calorific value of solid are expressed by cal/gm., K.cal/gm., K.cal/kg., B.Th.U./ft3 and
for liquid fuels cal/m3 ., K.cal/m3 , K.cal/kg., B.Th.U./lb. Calorific value of solid and non-
volatile liquid fuels are determined by bomb calorimeter and gaseous fuels are determined
by Boy’s gas calorimeter and for liquid fuel both calorimeter are used. Basically calorific
value are measure by two way-
a) Gross calorific value or higher calorific value (GCV or HCV)
b) Net calorific value or lower calorific value (NCV or LCV)
7.2.1 Gross calorific value or higher calorific value (GCV or

HCV)
GCV is the total amount of heat evolved during combustion of unit quantity of fuel and the
combustion producta are allowed to cool to room temperature. The steam produced during
combustion is transformed into water during cooling and remains in liquid state. Most of
the fuel content hydrogen either as their chemical component and during full combustion the
hydrogen is converted into water vapour. If the water vapour is condensed into liquid state
then the latent heat is liberated and this extra heat is added in calorific value. Generally
Bomb calorimeter is used to determine GCV.
7.2.2 Net calorific value or lower calorific value (NCV or

LCV)
NCV is the total amount of heat evolved during combustion of unit quantity of fuel and
the combustion products are allowed to escape. Thus water produced during combustion
remains in gaseous state. In this case the water vapour is allowed to escape. From the
above difference it is clear that the amount of heat as GCV for a particular amount of fuel
will be more compared to NCV as latent heat is added with the former.
So, NCV = GCV - Latent heat of water vapour.
Since 2 gm of hydrogen upon complete combustion give 18 gm of water-
7.3. CHARACTERISTICS OF GOOD FUEL 253
or, 1 gm of hydrogen upon complete combustion give 9 gm of water-
NCV = GCV − ( Weight of hydrogen × 9 × Latent heat of water vapour)

Or,NCV = GCV − (Weight of hydrogen × 9 × 587)
as Latent heat of water vapour = 587 cal/gm

If percentage of hydrogen present be H% then, NCV
H
NCV = GCV − ( × 9 × 587)
100
NCV = GCV − (0.09H × 587)Cal
7.2.3 Net calorific value or lower calorific value (NCV or

LCV)with respect to the constituents in fuel
We know the calorific values of H, C and S are 34500, 8080 and 2240 K. cal/kg. respectively.
Again it is assumed the hydrogen present in fuel is not completely available for combustion.
Oxygen present with hydrogen in the from of water. That hydrogen is called fixed hydrogen.
So, hydrogen available for combustion = total hydrogen - fixed hydrogen.
Since 2 gm of hydrogen upon complete combustion with 16 gm oxygen give 18 gm of water-
or, 1 gm of hydrogen upon complete combustion with 8 gm oxygen give 9 gm of water-
Now, 8 gm of oxygen combine with 1 gm of hydrogen and get fixed.
So, 1 gm of oxygen combine with 18 gm of hydrogen and get fixed.
So, 80 gm(let) of oxygen combine with 81 × 80 gm of fixed hydrogen = 10 part = 81 gm of
total oxygen
So, fixed hydrogen = 18 gm of total oxygen
So, hydrogen available for combustion = total hydrogen - fixed hydrogen.
So, hydrogen available for combustion = total hydrogen - 18 gm of total oxygen
Now, GCV = H% × 34500 + C% × 8080 + S% × 2240K. cal

H × 34500 + C × 8080 + S × 2240
= K.cal
100
NCV = GCV − (0.09H × 587)K.Cal
7.3 Characteristics of good fuel

The following factors are taken into consideration when fuel has been selected for any
purpose-
a) Suitability
b) Easy availability
c) Low cost
d) High purity
e) Higher calorific value

f) Moderate ignition temperature
g) Moderate velocity of combustion
h) Low smoke
i) Control over combustion
j) Easy transportable
k)Low harmful product
l) Low moisture content.
7.4 Solid Fuel

7.4.1 Wood
Wood is commonly used as domestic fuel. The main chemical component of fuel is cellulose.
Dry wood offers approximately 3500 to 4000 kcal/kg calorific value and this varies a lot
depending upon nature of wood. The average chemical composition is roughly 50 carbon,
35 oxygen and others.
7.4.2 Coal
Coal is the fossilized version of animals and plants. It is highly rich with carbon and other
impurities like water, sulphur, nitrogen, mud and others. Depending upon percentage of
coal and hence the calorific value, coals are classified in four groups-anthracite, bituminous,
lignite and peat. The formation of cellulosic vegetables to coal under the earth is associated
with long chemical process. In the initial stage the cellulosic materials attacked by some
anaerobic micro organism and at a particular temperature it is converted to low graded,
soft coal peat. Then at higher temperature and pressure and with a long period of time it is
converted to comparatively better quality coal named as lignite. Depending on the quality,
this soft, high moisture content low calorific value peat and lignite coal is called low rank
coal. Again for a long period of time low graded lignite coal by removal of volatile materials,
converted to hard, more porous, spongy, high carbon contain high graded bituminous coal
and anthracite coal. Depending on the quality, this Hard, brittle, extremely low volatile
matter content, high calorific value bituminous and anthracite coal is called high rank coal.
Some solid fuels and their characteristics
Solid fuel C% H% O% N% Moisture% Calorific value(k.cal/kg)

Wood 40 - 40 5-7 22 - 40 2-7 70 - 95 3500 - 4000
Peat 50 -60 4-8 22 - 44 1-3 70 - 90 4000 - 5000
Lignite 70 -70 5-7 20 - 35 1-3 35 - 50 5000 - 7500
Bituminous 70 - 85 4-7 20 - 25 1-2 10 - 20 6500 - 8800
Anthracite 85 - 95 4 -5 2-5 0.3 - 2 2-4 8000 - 8800
7.4. SOLID FUEL 255
7.4.3 Analysis of coal:

Raw coals or industrial grade coals are analysed for percentage of carbon, hydrogen, mois-
ture, oxygen etc. This analysis helps to classify the coals in its utility for specialized purpose.
The analysis of coal can be done in two method-one is called Proximate analysis and another
is called Ultimate analysis.
7.4.4 Proximate analysis:

In this method percentage of volatile matter, ash content, moisture content and fixed carbon
is determined in a rough method. In this method no wet chemical reaction is involved.
i) Volatile matter: In a muffle furnace a known quantity of moisture free coal (W1 gm)
is heated at 950 ± 200 C for 7 min in absence of air (presence of air will oxidise carbon and
other element present). The final weight of the coal is (W2 ).
So the weight of the volatile matter will be (W1 − W2 ) gm.
Hence percentage of volatile matter
(W1 − W2 )100
=
W1
ii) Ash Content: The left over material of complete combustion of coal is known as ash
content. This is mainly consists of mud, inorganic carbonates, slate, clay, metal oxides etc.
A certain quantity of air dried coal (W1 gm) is heated in a muffle furnace at 7500 C in
presence of air. After complete combustion W3 gm of ash is left. Hence the percentage of
ash content
(W3 )100
=
W1
iii) Moisture Content: Coal sample contain some amount of moisture. During air drying
some moisture content of the coal is lost by evaporation and some part of moisture is still
remained inside coal. This remaining moisture after air drying is called inherent moisture.
This inherent moisture can be removed by heating at 105 - 1100 C.
A certain quantity of air dried coal on a silica or porcelain crucible of weight (W1 gm) is
heated at 105 - 1100 C for 1 hour. After heating the weight of the coal with the crucible
is W4 gm. So the weight of moisture content will be (W1 − W4 ) gm and the percentage of
the moisture will be-
(W1 − W4 )100
=
W1
iv) Fixed Carbon: Percentage of fixed carbon will be = 100 - (Volatile matter% + Ash
content% + Moisture content%)
7.4.5 Ultimate Analysis:

Ultimate analysis is carried out to determine the percentage of carbon, hydrogen, oxygen,
nitrogen, sulphur by chemical method and thus classification of coal is carried out depending
upon this data. Pricing of coal is also determined out depending upon the ultimate analysis
data.
i) Percentage of carbon and hydrogen: A certain amount of coal is combusted in
presence of pyre and excess oxygen (free from moisture and CO2 )(g). The C and H present
in coal sample are converted into CO2 and H2 O(g) respectively. This combustion products
are passed through pre-weighed CaCl2 chember (absorb H2 O) and KOH chember (absorb
CO2 ) respectively. Now the increased weight of these two chember is the weight of H2 O
and CO2 respectively. From this data, percentage of H and C can be calculated.
Let us consider W1 gm of coal sample was taken and after all the above process, increased
weight of water and carbon dioxide absorbing chember is M1 and M2 gm respectively.
1
H2 (2gm) + O2 = H2 O(18gm)
2
CaCl2 + 7H2 O = CaCl2 .7H2 O
From the 1st reaction we can say that 18 gm of water can be obtained from 2 gm of hydrogen.
Hence M1 gm of water will come from M1 (2/18) gm of hydrogen.
2 × (M1 ) × 100
Percentage of H =
18 × (W1 )
C(12gm) + O2 = CO2 (44gm)

2KOH + CO2 = K2 CO3 + H2 O
From the 1st reaction we can say that 44 gm of carbon dioxide can be obtained from 12 gm
of carbon.
Hence M2 gm of carbon dioxide will come from M2(12/44) gm of carbon.
12 × (M2 ) × 100
Percentage of C =
44 × (W1 )
ii) Percentage of sulphur: A certain amount of finely powdered coal is fused with Eschka
nixture (2:1 mixture of MgO and Na2 CO3 ) in presence of air. The sulphur content of the
coal sample is oxidised to SO2 and which is convered to sulphite salts by Eschka mixture.
S + O2 = SO2
MgO + SO2 = MgSO3
Na2 CO3 + SO2 = Na2 SO3 + CO2
7.4. SOLID FUEL 257
The sulphites are oxidised to sulphates by bromine water oxidation.
SO−2 −2 +
3 + Br2 + H2 O = SO4 + 2H + 2Br
−
The oxidised sulphate salts are soluble in water and by adding barium salts they are pre-
cipitated. The precipitate is filtered, washed and dried. From the weight of precipitate, the
percentage of sulphur is calculated.
SO−2
4 + BaCl2 = BaSO4 ↓ +2Cl
−
Now, molecular weight of barium sulphate (BaSO4 ) is 233 and atomic weight of S is 32.
Hence, we can say that 233 gm of BaSO4 can be obtained from 32 gm of S. If W1 gm of
coal was taken and M3 gm of BaSO4 is obtained, then percentage of sulphur will be
32(M3 )100
=
233(W1 )
iii) Percentage of nitrogen: Kjeldahl method is used to determine the percentage of

nitrogen. A known quantity of finely powdered coal sample is digested with H2 SO4 in pres-
ence of concentrated K2 SO4 and HgSO4 . In this process all nitrogen present in the coal
sample will be converted to (N H4 )2 SO4 .
N + H2 SO4 → (NH4 )2 SO4
The digestion mixture is neutralized by KOH and then heated with excess KOH to liberate
NH3 gas from ammonium salt.
(NH4 )2 SO4 + 2KOH = 2NH3 + K2 SO4 + 2H2 O
This ammonia gas is abosorbed into a known volume of standardized sulphuric acid. The
excess acid is back titrated against standard NaOH solution.
Let us consider both the sulphric acid and NaOH have the same strength = (N/10) and
V1 ml of slphuric acid was taken and V2 ml of NaOH was consumed for back titration. So,
(V1 − V2 ) ml of (N/10) sulphuric acid equivalent ammonia was produced.
Now,
1000 ml of (1N) ammonia = 17 gm ammonia.

17 × (V1 − V2 ) × 0.1(N)
(V1 − V2 ) ml of 0.1(N) ammonia = gm ammonia.
1000
17 gm. NH3 contain = 14 gm. N2

17 × (V1 − V2 ) × 0.1(N) 14 × 17 × (V1 − V2 ) × 0.1(N)
or, gm. NH3 contain = gm. N2
1000 1000 × 17
1.4 × ×(V1 − V2 ) × 0.1(N)

SO, percentage of N2 = gm N2
×W
iv) ASh Content: As mentioned in proximate analysis.

v) Percentage of oxygen: = 100 - percentage of (C + H + S + N + ash content).
7.4.6 Carbonization of coal

The conversion of coal into coke is known as carbonization. In this method in absence of air
coal is heated at high temperature so that the volatile matters of the coal is escaped out;
porous and carbon enriched residue is left which is called coke. The coals which contains
less than 20-30 volatile matter can be used to make coke. Only bituminous coal fit for
corbonization process.
Those coals which upon heating softens and swells and on cooling form porous solid mass
are called caking coal. The left over residue after this heating process is known as coke.
If the coke is hard, porous and strong compared to the coal, it is known as coking coal.
Depending upon temperature and rate of carbonization, the process is classified in two part-
i) Low Temperature Carbonization (LTC) and
ii)High Temperature Carbonization (HTC).
7.4.7 High temperature carbonization

a) High temperature carbonization is carried out at 900 − 12000 C.
b) The coke product in this process contain 1-3 volatile matter.
c) Yield of coke in this method is 65-75.
d) The quality of product coke is hard.
e) Higher amount of gas is produced as byproduct (300 − 390 m3 /tonne).
f) The product coke is used for metallurgical industry.
7.4.8 Low temperature carbonization

a) Low temperature carbonization is carried out at 500 − 7000 C.
b) The coke product in this process contain 5-12 volatile matter.
c) Yield of coke in this method is 75-80.
d) The quality of product coke is soft.
e) Higher amount of gas is produced as byproduct (130 − 150 m3 /tonne).
f) The product coke is used as domestic fuel.
7.5. LIQUID FUEL 259
7.5 Liquid Fuel

Crude petroleum is the largest source of liquid fuel. Crude petroleum is a mixture of all
liquid fuels we used in different area and it consists of various alkanes ( having carbon chain
C1 − C40 ), cycloalkanes, aromatic hydrocarbons and some quantities of sulphur, nitrogen,
oxygen etc. As boiling point of various hydrocarbon depends upon the molecular weight
and size, liquid fuel are purified by fractional distillation method by refining of crude oil.
Our major oil industries like Indian Oil Corporations, Hindustan Petroleum, Reliance etc
are doing this purification in their oil industry.
7.5.1 Refining of Crude Petroleum

The crude petroleum obtained from petroleum mining is a dark coloured viscous liquid. It
contains sand, mud, water, minerals, sulphur etc along with the mixture of all possible hy-
drocarbons. At first this sand, mud etc impurities are separated from the crude oil mixture
and then depending upon the difference in boiling point individual liquid fuel components
are purified by fractional distillation.
i) Separation of water: Crude petroleum is an emulsion of oil and sea water (salt wa-
ter). A normal water wash at 70 − 800 C remove the salt from this emulsion. Now, as
fuels are hydrocarbons and hence posses minimum charge and hence this emulsion is passed
through electrodes which pass the uncharged hydrocarbons easily and polar waters which
was present as micro droplets mixture in emulsion are separated by forming large droplets.
ii) Removal of sulphur: Treatment of copper oxide separates the sulphur as copper sul-
phide precipitate.
iii) Fractional Distillation of Petroleum: In a fractionating column, separation of dif-
ferent liquid fuel is done at different temperature. Basically the crude oil is heated above
4000 C, so that all component of the crude oil is converted to vapour phase. Now this hot
vapour mixture is passed into the fraction column. The column is designed with many
stages coupled with thermostat of desired temperature. The upper side of the column is
cooler and the lower side is hotter. When the crude vapour mixture enters into column,
the fuel with higher boiling point condensed first and transformed into pure liquid. The
corresponding stage is fitted with a drainage outlet and hence the liquid can be drainage
out. Similarly at the next stage the liquid with comparatively lower boiling point will be
condensed. Gradually at the top the liquid with least boiling point will be condensed. Thus
in the fraction column the liquids with different boiling point can be separated. At the top
the petroleum gas will be collected and at the end the residue containing lubricating oil,
paraffin wax etc will be obtained. The name of the liquid fuel with corresponding boiling
point range and chemical composition are listed in this table.
Refining of crude petroleum
Name of C distillation End Calorific value

refine materials present temperature uses K.cal/kg
Uncondensed C1 − C 5 < 350 C LPG gas for 25000 -
petroleum gas domestic purpose 29000
Petroleum C5 − C 7 35 − 700 C Solvent for the separation 11000 -
ether of oil and fats 11500
Gasoline C5 − C 9 40 − 1200 C Motor fuel 11000 -
or petrol in IC engine 12000
Solvent spirit C9 − C10 120 − 1800 C Solvent for 11000 -
or naphtha varnish and paints 12000
Kerosine C10 − C16 180 − 2500 C Jet, racing car engine fuel 11000 -
fuel for illumination in village 11500
Diesel C10 − C18 250 − 3200 C Fuel for Diesel 11500 -
engine, boiler 12000
Heavy C17 − C35 320 − 4000 C Fuel for ship, oil 12000 -
oil for Hydraulic press 12500
Residue > C35 > 4000 C Fuel for -
metallurgical purpose
7.6 Petrol or Gasoline

The fractional distillation part of crude oil that is obtained by condensing at 40 − 1200 C is
known as petrol or gasoline. The chemical composition of petrol is C5 − C9 hydrocarbon.
It also contain some aromatic hydrocarbon. Petrol is primarily used as combustion fuel of
internal engine.
7.6.1 Knocking and Antiknocking

Knocking is an unwanted metallic sound just like the rattling of hammer produced in in-
ternal combustion engine due to immature ignition of air petrol mixture. In a combustion
engine, petrol vapour and air mixed and then ignition happened by electric spark from
battery. This phenomenon moves the piston of the engine and thus the engine works. If
before proper mixing of air and petrol vapour, ignition happens (premature ignition) then
explosion happens in the engine which is known as knocking. As incomplete combustion
happens due to knocking so, efficiency of engine will be lost or more fuel will be consumed.
Knocking depends upon chemical composition of fuel or more precisely on chemical struc-
ture. Generally straight chain hydrocarbons are poor for combustion and branch chain
hydrocarbons are good substrate for combustion. Hence, branch chain hydrocarbons pro-
duce less knocking compared to straight chain hydrocarbon. The knocking property of fuel
is generally expressed by a scale called octane number.The efficiency of engine decrease
with knocking which depends on the nature of the gasoline. The knocking of fuel increase
according to the following order-
7.6. PETROL OR GASOLINE 261
a) Aromatic < cycloparaffin < olefin < branched chain paraffin < straight chain paraffin
b) n-butane < n-pentane < n-hexane < n-heptane < n-octane
c) n-heptane < 2-methyl hexane < 2,2-dimethyl pentane.
7.6.2 Octane number

Octane number is a property of petrol only. It is defined as the percetange of iso-octane in
a mixture of iso-octane and n-heptane pesent in a petrol sample. n-heptane is a straight
chain hydrocarbon and a component of petrol. It has lowest octane number zero (0).
Hence n-heptane will have maximum knocking property. On the other hand iso-octane
(2,2,4-trimethyl pentane) is a branch chain hydrocarbon and a component of petrol. It
has highest octane number hundred (100). Hence iso-octane will have minimum knocking
property.
Octane number of a sample of petrol 70 indicates that in that sample percentage of iso-
octane is 70% and percentage of n-heptane is 30%. Similarly if a petrol consists of only
n-heptane then it’s octane number is zero and if some petrol sample consists of only iso-
octane then it’s octane number is hundred. So, higher the octane number of a fuel, it will
be a better choice. So, hydrocarbon with more branching will act as good fuel.
Antiknocking Knocking phenomenon is associated with straight chain hydrocarbon rich
fuel. Hence the process by which the knocking can be minimized is called anti-knocking
and the substrate that can reduce knocking is known as antiknocking agent. Tetraethyl
lead [Pb(C2 H5 )4 ] or TEL is known as a good antiknocking agent. This substrate basically
isomerizes the straight chain hydrocarbon into branch one and hence octane number of the
petrol is increased. Previously TEL was mixed with petrol and hence all petrol pumps
was marked with leaded petrol as TEL mixed petrol will emit lead in environment with
the smoke. As lead is toxic to living organism and environment hazard TEL mixed petrol
or leaded petrol was replaced later. Now a days other anti-knocking agents is mixed with
petrol like methyl tertiary butyl ether (MTBE)[CH3 − O − C(CH3 )3 ]. Hence all
petrol stations are now-a-days marked with unleaded petrol.
7.6.3 Cracking
Ease of combustion of a liquid fuel depends upon it’s volatility. Hydrocarbons with higher
molecular weight are less volatile and hydrocarbons with low molecular weight are more
volatile. So, to achieve complete combustion and hence to achieve good calorific value,
high molecular weight hydrocarbons are broken into low molecular weight hydrocarbons.
This phenomenon is called cracking. Two types of cracking process is generally carried
out-thermal cracking and catalytic cracking.
Thermal cracking: In this method cracking is carried out at 450 − 5500 C temperature and
1-7 atm. pressure without presence of any catalyst.
Catalytic cracking: Catalytic cracking is carried out at low temperature and pressure in
presence of synthetic alumina as catalyst.
C14 H30 (Tetradecane) → C7 H16 (Heptane) + C7 H14 (Heptene)

C14 H30 (Tetradecane) → C7 H16 (Heptane) + C6 H14 (Hexane) + C(carbon)
7.6.4 Reforming
Reforming is a process by which the octane number of a petrol sample is increased by altering
it’s chemical composition. This is also known as aromatization. Reforming is carried out
at high temperature (450 − 5500 C), pressure (20-50 atm) and sometimes Cr2 O3 or V2 O5 is
used as catalyst. Generally in this process cyclohexane and it’s derivatives are aromatizes
to benzene and it’s derivative. Linear chain hydrocarbons are converted to cyclohexane
derivatives. Straight chain hydrocarbons are isomerizes to branch chain hydrocarbon. By
all this method octane number of a petrol sample is increased.
7.7 Knocking in diesel engine

An efficient diesel engine is one where ignition takes place immediate just after compression
due to sudden raise in temperature. Depending upon the diesel quality the combustion in
diesel engine does not occur just immediately after compression and there is some time lag.
Between these two operation (compression and ignition). This time lag is called ignition
delay. The ignition delay depends upon the following factor-
a) nature of the fuel
b) Engine disign
c) Time for compression
d) Proper mixing of oxygen with diesel.
In case of long ignition delay the vapour of the fuel gets accumulate in the cylinder before
combustion causing un-uniform violent burning, known as knocking.
7.7.1 Cetane number in Diesel

During fractional distillation, the 250 − 3200 C distillate fraction is known as diesel and it is
used mainly in vehicle engine. The carbon number present in diesel sample is in the range
of C10 − C18 . Like octane number of petrol, cetane number is the parameter for diesel oil
quality in terms of calorific value. Cetane or α-methyl naphthalene have the highest com-
bustion rate and n-hexadecane have lowest combustion rate. So, cetane number is defined as
the percentage of cetane or α-methyl naphthalene in a mixture of cetane and n-hexadecane.
Higher the cetane number means ease of combustion, better is the diesel ignition.
Cetane number of a diesel fuel indicate the percentage of cetane (hexadecane, having very
short ignition delay) mixed with α-methyl naphthalene (having longer ignition delay) which
will have the same ignition property of the said diesel fuel. If a diesel consists of only
7.8. AVIATION FUEL 263
n-hexadecane then it’s cetane number is 100 and a diesel consists of only α-methyl naph-
thalene, cetane number is zero. Cetane number of a sample of diesel 80 indicates that it
has same ignition property as that of a mixture of diesel having cetane is 80% and 20%n-
hexadecane. The order of increase cetane number is in the following -
a) Aromatic < branched alkane < alkene < naphthalene < n-alkane
b) n-butane < n-pentane < n-hexane < n-heptane < n-octane
c) n-heptane < 2-methyl hexane < 2,2-dimethyl pentane
So, higher the octane number of a fuel, it will be a better choice.
7.7.2 A good petrol engine fuel is a bad fuel for diesel engine
and vice versa
A good petrol engine fuel consist of maximum number of branched chain hydrocarbon and
aromatic hydrocarbon where as a good diesel engine fuel consist of straight hydrocarbon
chain with minimum number of branch and aromatic hydrocarbon. Thus the condition of
petrol engine knocking is just opposite to the diesel engine. In petrol engine, pre-ignition
by compression leads to knocking so to minimize the knock we needs fuel with
higher ignition temperature. A branched chain hydrocarbon and aromatic hydrocarbon
have High ignition temperature. On the other hand in Diesel engine, ignition delay is
the main cause of knocking. So to minimize the knocking we need fuel with low
ignition temperature. A straight chain hydrocarbons with minimum number of branch
and aromatic hydrocarbon have low ignition temperature. For this reason it is called ”A
good petrol engine fuel is a bad fuel for diesel engine and vice versa”
7.8 Aviation Fuel

The fuels used in aviation sector to fly aircrafts are known as aviation fuel. Aviation fuel
have hight octane rating and it is consists of n-octane and iso-octane. Aviation fuels are
classified in two part-
7.8.1 Av gas or Aviation gasoline

This type of gasoline is comparatively less volatile than common gasoline used in motor
engine. This is the unique property of avgas as at high altitude less volatile fuel has
advantage.
7.8.2 Jet fuel

Jet fuel is a mixture of kerocene and naphtha or gasoline. In this blend the percentage of
aromatic content donot increases 25%. This kerocene-gasoline blend is mixed with air and
then injected in combustion chamber. This have low sulphur content.
7.9 Power Alcohol

Ethyl alcohol (ethanol) has very high octane number. So, anhydrous alcohol (99.9% v/v)
can be a good alternative for fuel. But pure ethanol is not used as fuel rather a blending
of ethanol-petrol at a ratio 1:4 with a trace amount benzene or ether is used sometimes in
motor engine. This mixture of petrol and ethyl alcohol is called power alcohol or gasohol.
Depending upon different cases upto 25% ethanol blend can be used. Ethnol blending
increases the octane number of the fuel. It reduces starting difficulties as it’s flash point is
low and having calorific value 7000K.Cal/kg (approx.)
7.10 Bio-diesel
Petroleum is not a renewable energy source and it’s stock is limited. It is immense important
to search for alternative fuel source otherwise in next 20-30 years this world will come to a
halt as source of petroleum will be over. Bio-diesel can be a good alternative of petroleum.
Bio-diesel can be generated from vegetable oil or from animal fat. Jatropa seeds are good
source of bio-diesel. The triglycerides from the jatropa seed extract are trans-esterified in
presence of catalyst and alcohol (methanol or ethanol).
Fig.
Bio-diesel blends with petroleum diesel are represented as BXX where XX represented the
percentage of bio-diesel in the mixture. B100 represent the pure bio-diesel where as B60
represent 60% bio-diesel and 40 % petroleum diesel There are several similarities of bio-
diesel and normal diesel-
a) The specific gravity of bio-diesel is more than normal diesel.
b) The cetane number of bio-diesel is higher than normal diesel.
c) The flash point of bio-diesel is higher than normal diesel and hence bio-diesel is more
safer.
Advantage of Bio-diesel:
a) Bio-diesel have high flash point.
b) Bio-diesel is biodegradable, non-toxic.
c) It can be used in normal diesel engine as pure form or as a blend.
d) It reduces greenhouse effect.
e) Bio-diesel has low emission of carbon monoxide or carbon-di-oxide.
7.10.1 Flash point and ignition temperature

Flash point
Liquid fuels are evaporate continuously and the rate of evaporation increases with temper-
ature. The emitted vapour does not catch the fire at any temperature in presence of any
external source of flame or spark. The minimum temperature at which emitted vapour of
liquid fuel catch fire in presence of any external source of flame or spark is called flash point.
Ignition temperature
7.11. GASEOUS FUEL 265
Liquid fuels are evaporate continuously and the rate of evaporation increases with tem-
perature.The emitted vapour does not catch the fire at any temperature on application of
pressure on it. The minimum temperature at which emitted vapour of liquid fuel undergo
compression with raise in temperature and on application of pressure catch fire with out
any external source of flame or spark is called ignition temperature.
7.11 Gaseous Fuel

Gaseous fuels genearlly have very high calorific value and hence used in most industrial as
well as in domestic purpose. Some common advantage and disadvantage of gaseous fuels
are-
Advantage: i) Gaseous fuel do not produce ash and smoke.
ii) It has high calorific value.
iii) Gaseous fuels are easy to handle.
iv) In gaseous fuel homogeneous heating is possible.
v) Gas presuure can be controlled and hence rate of combustion can be controlled.
Disadvantage: i) Large container needed to store the gas.
ii)Possibility of fire related hazard is much more here.
iii) Gaseous fuel is much more expensive than solid or liquid fuel.
7.11.1 Natural gas

Gaseous fuels those are available in coal mines and oil mines are called natural gas. The
main chemical composition of natural gases are methane, ethane, propane, butane etc which
are small chain hydrocarbons. Among these methane is the main component of natural gas.
The calorific value of natural gas is 10000-14000 k.cal/m3 .
7.11.2 Compressed natural gas

When natural gas is kept under high pressure, it remain at a compressed stage which is
called comprssed natural gas or CNG. This is a non-corrisive odourless gas. CNG is lighter
than air and hence it quickly diffuses in air. CNG is stored in special designed tank which
can hold the pressure of the gas. CNG is combustible at only 5-15% mixture with air. At
low composition, it is non combustible and at higher percentage due to lack of sufficient
oxygen it is non-combustible.
The advantage of CNG is-
i) Environment friendly: Maximum public transport at metropoliton cities like Delhi and
Bangalore are run by CNG and hence the city pollution has significantly decreases.
ii) Cost: CNG is much cheaper than other fuels and hence it is popular where it is available.
iii) Ease of transportation: CNG can be carried by proper pipe line and hence it is convenient
to transport the gas from one source to another.
iv) High calorific value: The calorific value of CNG is higher than other liquid or gaseous
fuels.
7.11.3 Liquified Petroleum Gas

Liquified petroleum gas is commonly known as LPG. The main component of LPG is three
or four carbon hydrocarbon. Propane (C3 H8 ) and butane (C4 H10 ) is the main chemical
component of LPG; both are colourless and odourless gases. To detect the leakage of LPG
a small percentage of foul smelling CH3 SH is added to LPG. LPG is mainly used as domestic
fuel.
7.12 Synthetic Gaseous Fuel

7.12.1 Water gas
Water is a mixture of carbon monoxide (41%) and hydrogen (51%). Sometimes water gas is
called blue gas as it burns with blue flame. The calorific value of water gas is 2800 kcal/m3
Water gas is prepared by passing steam on red hot coal at 900 − 10000 C.
C + H2 O(steam) = CO + H2
Use: i) Good source of hydrogen gas.

ii) Reducing agent in metallurgical industry.
iii) A good raw material for synthetic petrol by Fischer-Tropsch method.
7.12.2 Producer gas

Water is a mixture of carbon monoxide (20-30%), nitrogen (50-55%), hydrogen (10-12%)
and some carbon dioxide. The calorific value of water gas is 900-1300 kcal/m3
Water gas is prepared by passing air on red hot coal at 11000 C.
C + [N2 + O2 ](air) = CO + N2 + H2
Use: i) It is used as fuel in some industry.

ii) Reducing agent in metallurgical industry.
7.12.3 Coal gas

During carbonization coal, the gases are condensed and used as fuel. This is known as
coal gas. The calorific value is high-4900 k.cal/m3 . Actually during carbonization the gas
evolved is a mixture of various impurities which are purified later by several process to get
coal gas. Coal gas is colourless but have some characteristic odour and it burns with long
flame.
Coal → Coke + Coal gas

The main component of coal gas is H2 (40%), CH4 (32%), CO(3%), and some CO2 , N2 etc.
Uses: i) It is mainly used as illuminating gas.
ii) Sometimes it is used as reducing agent at metallurgical industry.
7.12.4 Semi water gas

A mixture of water gas and producer gas is called semi water gas. The calorific value of
semi water gas is 1700 kcal/m3 It is used by passing steam and air on red hot coke.
C + H2 O(steam) + [N2 + O2 ](air) = CO + N2 + H2 + CO
Use: Semi water gas is mainly used as raw material to prepare ammonia by Haber method.
7.12.5 Carburatted water gas

Water gas can be used as illuminating agent but it have low calorific value 2800kcal/m3 .
To increase th calorific value, some oil gas is mixed with water gas ans hence it’s calorific
value increases to 4500k.cal/m3 . It is used as a good source of illuminating agent.
7.12.6 Bio gas

Biogas is prepared by uncontrolled anaerobic decomposition of organic waste material
like cattle manure (cow dung), landfill waste, sewage extraction, vegatable etc. Biogas
is methane enriched gas.
Use: Biogas is mainly used as a good alternating source of fuel.

7.13.1.1. Which of the following possess an octane rating of 100? (Dec-2014)
a) petrol
b)LPG
c) CNG
d) iso-octane.
Ans. Iso-octane
7.13.1.2. Producer gas is amixture of
a) Carbon monoxide and hydrogen
b)carbon monoxide and nitrogen
c) Carbon dioxide and hydrogen
d) carbon dioxide and nitrogen.
Ans. Carbon monoxide and nitrogen
7.13.1.3. The calorific value is highest for( June-2013)

a) water gas
b) LPG
c) producer gas
d) carburated water gas.
Ans. LPG
7.13.1.4. The compound with antiknock value of zero is( Dec-2012)

a) n-pentane
b) n-butane
c) n-hexane
d) n-heptane.
Ans. n-heptane
7.13.1.5. Fuel used in jet plane is(June-2012)

a) aviation gasoline
b) 995% ethyl alcohol
c) alcohol with diesel
d) alcohol with petrol.
Ans. Aviation gasoline
7.13.1.6. Water gas is a mixture of(June-2011)

a) carbon monoxide and hydrogen
b) carbon monoxide and nitrogen
c) carbon dioxide and hydrogen
d) carbon dioxide and nitrogen.
Ans. Carbon monoxide and hydrogen
7.13.1.7. Which of the following is used as anti-knocking agent?

a) Nickel tetracarbonyl
b) Nickel tetracarbonyl
c) Tetraethyl lead
d) Tetraethyl silane.
Ans. Tetraethyl lead
7.13.1.8. Octane number of isooctane is

a) 100
b) zero
c) 50
d) None of these.
Ans. 100
7.13.1.9. Which of the following is used as fuel in jet engine ?(Dec-2010)

a) Petrol
b) Diesel
c) Kerosene
d) Power alcohol.
Ans. Kerosene
7.13.1.10. Which one of the following is not a primary fuel ? a) Wood
b) Natural gas
c) Coke
d) Crude oil.
Ans. Coke
7.13.1.11. The highest ranking coal is( June-2010)
a) Anthracite
b) Bituminous
c) Lignite
d) Peat.
Ans. Anthracite
7.13.2 Short Answer type question

7.13.2.1. (a) Distinguish between HTC and LTC of coal. (b) What is aviation fuel?(Dec-
2014)
7.13.2.2. Write a technical note on octane number and name the unleaded additive that
improves octane value.( June-2013) 4+1
7.13.2.3. (a) What is calorific value of a fuel ? (b) Distinguish between Higher or Gross
Calorific Value ( HCV ) and Lower or Net Calorific Value ( LCV ). 2 + 3
7.13.2.4. (a) What is CNG and write its advantage over other fuels ? b) What is octane
number of a fuel ? How can the octane number be improved ?(Dec-2012) 3 + 2
7.13.2.5. What is LPG ? Why is it used as a domestic fuel ? Define octane number of a
fuel. How octane number can be improved ? (June-2012)1 + 1 + 3
7.13.2.6. (a) What is the calorific value of a fuel ? 2 (b) Distinguish between GCV and
NCV. (Dec-20113) 3
7.13.2.7. (a) Write a short note on bio-diesel. 3
7.13.2.8. What do you understand by HTC and LTC of coal? Write down the usefulness of
each process.(June-2011) 2+3
7.13.2.9. Distinguish between the following: (a) Thermal and catalytic cracking 2
7.13.2.10. (a) What is CNG and what is its composition ? (b) What are the advantages of
CNG over other fuels ?(Dec-2010) 2 + 3
7.13.2.11. Explain octane number and cetane number with their significanes.(June-2010)
7.13.3 Long Answer type question

7.13.3.1. Write short note on any three of the following.(Dec-2014 )(5 each)
a) Why a good motor engine fuel is not good diesel engine fuel or vice versa?
c) Octane number and Cetane number.
e) Biodiesel.
7.13.3.2. State and explain the basic features of high and low temperature carbonization
of coal. Write the usefulness of both the processes. Define gross and net calorific
value of a fuel. What are proximate and ultimate analysis of coal?(June-2014) 7
+2+2+4
7.13.3.3. (d) Write down the difference between HTC and LTC with example. (e) What is
TEL?. 4 + 1
7.13.3.4. (b) What is spontaneous ignition temperature of a fuel? (c) Define octane number
and cetane number of a fuel. (d) State the reason that led to replacement of
conventional gasoline with unleaded gasoline. (e) Which type of hydrocarbons
are suitable as components unleaded gasoline and diesel? Explain with suitable
reason.(June-2014) 2+4+3
7.13.3.5. (d) What is CNG ? What are the advantages of CNG ? Mention two uses of CNG.
(June-2013) 4
7.13.3.6. Write notes on any two of the following :

( c) Bio-diesel. (Dec-2012)
7.13.3.7. (b) What is proximate analysis of coal and what is its significance ? (c) Indicate the
major fractionation products along with their boiling range and uses obtainable
from atmospheric distillation of crude oil.(June-2012) 4 + 6
7.13.3.8. (b) What is spontaneous ignition temperature of a fuel ? (c) What is the impor-
tance of unleaded gasoline ? Which type of hydrocarbons is suitable as components
of unleaded gasoline and why ? 2+ 5
7.13.3.9. (a) What are water gas and semi-water gas ?

(b) How do gasoline and diesel differ in chemical composition ?(Dec-2011) 3+3
7.13.3.10. (a) Define octane number and cetane number with their significance.(June-2011)
7.13.3.11. Write short note- (e) Knocking and anti-knocking. 5
7.13.3.12. (a) What is meant by proximate analysis of coal and what is it’s significance?
(b) Indicate major fractionation products along with their boiling range and uses
obtainable from atmospheric distillation of crude oil. (c) Calculate the weight and
volume (at NTP) of air required for combustion of 1 kg of carbon. (Air content
is 21% by volume and 23% by weight of oxygen). 4+6+5
7.13.3.13. (c) How can biofuel be an ideal substitute of fossil fuel in solving the global energy
crisis? 5
7.13.3.14. Write short notes on any three of the following : (a) Bio-diesel
(b) Carbonisation of coal and its utility.
(d) Explain Octane Number and Cetane Number with their significances.(Dec-
2010) 5+5+5
7.13.3.15. (a) What do you understand by HTC and LTC of a coal ? Write down the
usefulness of each process.
7.13.3.16. (b) What are the important products formed from the atmospheric distillation of
crude oil ? (June-2010)4
7.13.3.17. (a) What is anti-knocking compound ? Discuss the function of TEL as anti-
knocking agent. What is unleaded petrol ? Write its significance.6
7.13.3.18. Write short notes on any three of the following : (b) Proximate analysis of coal 5
Bibliography
[1] Complex Variables, Stephen D. Fisher, Dover Publications, Mineola, Newyork.
[2] Alan Jeffrey, Advanced Engneering Mathematics, Harcourt/Academic Press, Burling-

ton.
[3] Ruel V. Churchill, Jambs W. Brown, Roger F. Verhey, Complex Variables and Appli-
cations, Tata Mc.GrawHill.
[4] S.Lipchutz, Probability, Schaum’s outline.
[5] S.C. Gupta and V.K.Kapoor, Fundamentals of Mathematical Statistics, S Chand and
Sons.
[6] Dr. Arup Mukherjee, Probability and Statistics.
273
Index
∆H = ∆U + ∆nRT, 59 Block copolymer, 206

CP − CV , 24 Branched chain polymer, 207
E2 Elimination, 196 Buna-N rubber, 228
SN2 reaction, 193 Buna-S rubber, 227
SN 1 reaction, 191
(GCV or HCV), 252 Calorific value of fuel, 252
(NCV or LCV), 252 Carbanion, 183
1,2-Elimination, 195 Carbocation, 180
Carbonization of coal, 258
Vacancy defect, 114 Carburatted water gas, 267
Carnot’s cycle, 32
Addition polymerization, 208, 220
Catalysis, 97
Addition Reaction, 197
Catalytic cracking, 261
Adiabatic process, 6
Cation vacancies, 122
Adiabatic relations, 29
Cetane number, 262
Adiabatic wall, 4
Amorphous polymer, 238 Characteristics of good fuel, 253
Analysis of coal, 255 Closed system, 5
Anion in the interstitial site, 122 CNG, 265
Anion vacancies or F centers, 118 Coal, 254
Antiknocking, 261 Coal gas, 266
Atactic polymer, 211 Collision theory, 95
Auto catalyst, 97 Concentration and equivalent conductance,
Av gasoline, 263 139
Average rate, 82 Condensation polymerization, 208
Aviation Fuel, 263 Conducting polymer, 239
Axiom, 3 Conductometric titration, 144
Conductors, 123
Bakelite, 218, 219 Copolymer, 205
Band gap, 242 Cracking, 261
Band gap, 126, 240 Cross linked polymer, 207
Band theory, 124 Crystalline polymer, 238
Basicity, 188 Crystalline solid, 113
Bio-diesel, 264 Crystallization temperature (TC ), 235
Biodegradable polymer, 229 Cyclic process, 6
274
INDEX 275
Degree of crystallinity, 239 Equilibrium constant, 162

Degree of polymerization, 203 Equivalent conductance, 136
Diathermal wall, 4 Extrinsic Semiconductor, 129
Difference between order and molecular-
ity, 84 Fiber, 212
Difference, Schottky and Frenkel defect, First law of thermodynamics, 21
118 First order reaction, 87
Dipole moment, 183 Flash point, 264
Doping, 123 Fuel, 251
Fuel cell, 161
Efficiency in refrigerator, 35 Function of salt bridge, 151
Efficiency of Carnot’s engine, 35
Elastomer, 212 Gaseous Fuel, 265
Electrochemical cell, 149 Gibb’s free energy, 48
Electrochemistry, 135 Gibbs-Helmholtz’s equation, 50
Electronegativity, 177 Gibbs-Helmholtz’s equationfrom first prin-
Electrophilic Substitution, 196 ciple, 51
Elimination reaction, 195 Glass transition temperature (TG ), 234
EMF, 152 Graft copolymer, 206
Energetic, 3
Energy, 9 Heat capacity, 24
Engine, 32 Heat of combustion, 60
Enthalpy or heat content (H), 22 Heat of formation, 59
Entropy, 35 Heat of neutralization, 60
Entropy and available work, 45 Heat of reaction, 58
Entropy change during heating, 38 Heat of solution, 61
Entropy change during isothermal expan- Helmholtz’s free energy, 47
sion of a gas, 38 Hess’s law, 61
Entropy change during non-isothermal ex- Heterogeneous catalysis, 100
pansion of a gas, 39 Heterogeneous catalyst, 98
Entropy change during transition, 40 High density Polythene(HDPE), 214
Entropy change in free expansion gas, 43 High temperature carbonization, 258
Entropy change in free mixing gas, 43 Homogeneous catalysis, 97
Entropy change in irreversible cooling, 42 Homopolymer, 205
Entropy change in irreversible cyclic pro- Hyperconjugation, 179
cess, 41
Entropy change in reversible cyclic pro- Ignition temperature, 264
cess, 40 Imperfectness of crystal, 114
Entropy in a cyclic process, 36 Inductive effect, 177
Entropy is not a state function, 36 Instantaneous rate, 81
Entropy is path dependent, 36 Instantaneous reaction, 77
Equilibrium and spontaneity from entropy, Insulator, 124
52 Integral heat of solution, 61
276 INDEX
Integrated from of Gibbs-Helmholtz’s equa- Monodisperse polymer, 231

tion, 51 Monomer, 203
Intensive properties, 6
Internal energy (E/U), 22 n-type semiconductor, 129
Interstitial defects, 115 Natural fuel, 251
Intrinsic defects, 114 Natural gas, 265
Intrinsic Semiconductor, 128 Natural polymer, 204
Irreversible process, 11 Negative catalyst, 97
Isobaric process, 6 Neoprene rubber(GR-A), 229
Isochoric process, 6 Nernst equation, 153
Isolated system, 5 Non-stoichiometric defect, 118
Isotactic polymer, 211 Novoloc, 218
Isothermal process, 6 Nucleophilic substitution reaction, 190
Number average molecular weight, 231
Jet fuel, 263 Nylon-6, 209
Joule’s experiment, 23 Nylon6,6, 209
Joule-Thomson co-efficient, 27
Octane number, 261
Joule-Thomson effect, 25
Open system, 4
Kirchhoff’s equation, 62 Order of a reaction, 84
Knocking, 260 p-type semiconductor, 130
Knocking in diesel engine, 262 Perfect differential, 8
Kohlrausch’s law, 143 Petrol, 260
Phenol-formaldehyde resin, 217
Law of Lavoisier and Laplace, 61
Point defect, 114
Law of mass action, 83
poly ethylene terephthalate(PET), 210
Linear chain polymer, 207
Polydisperse Index(PDI), 234
Linear low density Polythene (LLDPE),
Polydisperse polymer, 231
215
Polythene, 213
Low density polythene (LDPE), 213
Positive catalyst, 97
Low temperature carbonization, 258
Power Alcohol, 264
LPG, 266
Precipitation titration, 148
Maxwell relation, 53 Process, 5
Measurement of pH, 156 Producer gas, 266
Proximate analysis, 255
Measurement of valency of an ion, 158
Pseudo-1st order Reaction, 93
Melting temperature(TM ), 237
PV adiabatic and isothermal, 30
Mesomeric effect, 180
PVC, 216
Metal deficiency defect, 121
Metal excess defect, 118 Quinhydrone electrode, 159
Moderate reaction, 77
Molar conductance, 137 Rate, 79
Molecularity of a reaction, 84 Redox reaction, 150
INDEX 277
Refining of Crude Petroleum, 259 Ultimate analysis, 256

Reforming, 262 Ultrahigh molecular weight polythene (UHMWPE),
Relation of rate with stoichiometry, 80 216
Represent an electrochemical cell, 152 Unit of rate, 80
Resol, 218 Units of calorific value, 252
Reversible process, 12 Universe, 4
Rubber, 226
Very slow reaction reaction, 78
Salt bridge, 151 Viscosity average molecular weight, 233
Schottky defects, 116 Water gas, 266
Second law of thermodynamics, 31 Weight average molecular weight, 231
Second order reaction, 90 Wood, 254
Secondary cell, 160 Work, 9
Secondary fuel, 252
Semi water gas, 267 Zero order reaction, 85
Semi-synthetic polymer, 204
Semiconductors, 124
Semicrystalline polymer, 238
Solubility product, 161
Specific conductance, 136
State function, 7
State of a system, 7
Stoichiometric defects, 114
Strength of organic acid base, 184
Surrounding, 4
Syndiotactic polymer, 211
Synthetic polymer, 204
Synthetic rubber, 227
System, 4
TdS relations, 49
TdS relations with free energy, 50
Temperature and equivalent conductance,
138
Temperature dependent rate equation, 94
Theory of catalysis, 98
Thermoplastic, 213
Thermoplastic and thermosetting plastic
polymer, 220
Thermosetting plastic, 217
Transition state theory, 96
Transport number, 141

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ENGINEERING CHEMISTRY

(CH 101 and CH 201)

As per New Revised Syllabus of MAKAUT

Dr. Pijus Kanti Khatua, M.Sc., Ph.D.

Dr. Dipankar Pramanik, M.Sc., Ph.D.

• Independence of parts and blocks of chapters

• Contain huge number of question answer

Furthermore, we designed the book to be a single, self-contained, authoritative,

of Technology for their constant encouragement.

(transition state theory, collison theory: ). Catalysis: homogeneous catalysis (definition,

2.12.1 Theory of catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

3 SOLID STATE CHEMISTRY 113

4.12 EMF of Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

5 STRUCTURE AND REACTIVITY OF ORGANIC MOLECULES 177

6 POLYMER CHEMISTRY 203

6.19.1 Crystalline polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . 238

7 INDUSTRIAL CHEMISTRY: FUEL 251

1.1 First law of Thermodynamics

1.1.2 Type of system

1.1.4 Steady state and equilibrium

1.1.5 State of a system

change the magnitude of z.

So, V is a state function and V = f(P,T).

Sl. No. Type of work I.F. C.F. I.F. × C.F.

Depending upon the movement of the boundary work is two type-

Work (W) = Force x displacement of the boundary

Or, W = [−Pext .(V2 − V1 )] + [−P1ext .(V3 − V2 )] + [−P2ext .(V4 − V3 )] + ..... + [−Pn

1.1.8 Reversible and irreversible process

Reversible process Irreversible process

1. Difference between driving force and 1. Difference between driving force

As a result volume of the gas is increased by dV. So,

here, work done = −(P1 − 2dP)dV

In this way pressure is ultimately lower to P2 as a result volume increase to V2

WREV. = −(P1 − dP)dV + (−)(P1 − 2dP)dV + ........ + (−)P2 V2

Work done in REV. and IRREV. system

Work done in REV. and IRREV. system

Work done in REV. and IRREV. system

then it is irreversible and if it is uncountable then it is reversible.

Work done in REV. and IRREV. system

Work done in REV. and IRREV. system

Infinitesimal multistage stage compression: Similarly, during isothermal compression

Work done in REV. and IRREV. system

Total work, W = Wexp. + Wcom.

Hence, in a reversible process Wcycle = 0. Similarly in a irreversible process, if expan-

Work done in REV. and IRREV. system

Now, work done isothermally and irreversibly-

|WIRREV. ISO | = P2 (V2 − V1 )

and work done isothermally and reversibly-

|WREV. ISO | − |WIRREV. ISO |

this is expansion work we will take a modulus value.

1.1.9 First law of thermodynamics

1.1.10 Internal Energy (E/U)

1.1.11 Enthalpy or Heat content (H)

Like U, H is a state function, perfect differential and extensive properties. On differentiation-

So, increase in enthalpy at constant pressure P = heat absorbed at constant pressure P

1.1.12 Joule’s Experiment

1.1.13 Heat capacity of gases

U = f(T,V) for a closed system

From 1st law, dQ = dU + PdV