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This book by the renowned author Prof. Hrishikesh Chatterjee has been written for those students who will complete the B.Sc. course in three years. The following key features will help the students enjoy going through the book: Presented in a student-friendly format strictly following the syllabi of different universities. Not a single step of theoretical discussion and derivation remains unexplained; A large number of MCQs, short and thought-provoking explanatory questions are included along with answers at the end of each chapter; A large number of worked-out numerical examples and various numerical problems are given in the exercise at the end of each chapter for students' evaluation. This book will help students and readers to appear not only in university examinations but also in various competitive examinations like UPSC, NET, GATE, etc.
1.1 Postulates (Assumption) of kinetic theory; 002
1.2 Consequences of assumptions; 002
1.3
Justification of elastic collision; 003
1.4 Concept of pressure & temperature; 003
1.5
Velocity of molecules; 003
1.6 Derivation of pressure from kinetic theory; 005
1.7 Concept of
temperature from kinetic theory; 006
1.8 Pressure from kinetic equation; 007
1.9 Gas laws from
kinetic theory; 007
1.10 Pattern of distribution of molecular speed; 008
1.11 Assumptions of
molecular speed distribution law; 008
1.12 Maxwell’s law of molecular speed distribution;
009
1.13 Characteristic features of speed distribution law (3-dimension); 011
1.14 Average
properties; 014
1.15 Wall collision frequency; 017
1.16 Application of Wall collision
frequency; 018
1.17 Binary collision frequency(similar gas molecules); 019
1.18 Binary
collision frequency(different gas molecules); 020
1.19 Mean free path; 021
1.20 Effect of
pressure; 022
1.21 Effect of temperature; 022
1.22 Kinetic energy distribution
law(3-dimension); 022
1.23 Fraction of molecules with kinetic energye E/; 024
1.24 Average kinetic energy(3-dimension); 025
1.25 Energy distribution function in two dimension;
025
1.26 Fraction of molecules with kinetic energye E/ in two dimension; 026
1.27 Degrees of
freedom; 026
1.28 Equipartition principle; 028
1.29 Heat capacity from equipartition
principle. 029
REAL GAS 2
2.1 Deviation from ideal behaviour; 045
2.2 Causes of deviation; 048
2.3- van der Waals
equation of state; 048
2.4-A) Volume Correction; 049
2.4-(B) Pressure Correction; 049
2.5
Validity of van der Waals equation; 050
2.5.1 Andrews curve; 050
2.5.2 PV-isotherm of van der
Waals equation; 051
2.6 Critical state of van der Waals equation; 052
2.6.1 Amagat’s
curve from van der Waals equation; 053
2.7 Compressibility factor; 054
2.8 Reduced equation of state. 056
THERMODYNAMICS 3
3.1 Introduction; 061
3.2 Fundamental terms; 062
3.3 Thermodynamic equilibrium state;
065
3.4 State function; 065
3.5 Mathematical aspect of state function; 066
3.6 Work;
068
3.7 Heat; 070
3.8 Internal energy; 070
3.9 dq and dW are not exact differential;
071
3.10 Zeroth law of thermodynamics; 071
3.11 1st law of thermodynamics; 072
3.12 Importance of thermostat; 074
3.13 Ways of transformation of state; 074
3.14 In isothermal
expansion |Wrev | > |Wirrev |; 078
3.15 Joule’s Experiment; 079
3.16 Enthalpy(H);
3.16.1-Enthalpy for an ideal gas; 079
3.17 Heat Capacity(C); 080
3.18.1 Relation between Cp
and Cv; 081
3.18.2 Cp – Cvfor different cases; 082
3.19 Adiabatic Change. 083
THERMOCHEMISTRY 4
4.1 Introduction; 091
4.2 Laws of thermochemistry; 092
4.3 Hess’s law from 1st law;
094
4.4 Heat of formation; 094
4.5 Heat of combustion; 095
4.6 Temperature dependence of
Heat of reaction; 095
4.7 Heat of solution; 096
4.8 Heat of neutralisation. 097
THERMODYNAMICS 5
5.1 Need for Second law; 109
5.2 Conversion of heat into work; 110
5.3 Carnot Cycle;
5.4-Conclusion from Carnot Cycle; 112
5.4.1 Refrigerator; 115
5.5 Kelvin-Planck and Clausius
statements are equal; 116
5.6 Carnot Theorem; 117
5.7 Clausius Inequality; 118
5.8
Entropy; 119
5.9 Calculation of ΔS For Reversible Processes; 123
5.10 Entropy Change for
Irreversible Processes; 127
5.10.1 Entropy and unavailable work; 132
5.10.2 T-S Diagram of
Carnot Cycle; 133
5.11 Free energy; 134
5.12 Criteria of spontaneity and equilibrium; 135
5.13 Lowering of Gibbs
Free Energy and Entropy of universe; 137
5.14 Properties of G; 137
5.15 Variation of G with
Pressure; 138
5.16 Gibbs-Helmholtz Equation; 139
5.17 Application of G-H Equation;
141
5.18 Maxwell Relations; 142
5.19 Heat Capacity Relations; 144
5.20 Joule-Thomson
Expansion; 146
5.21 J-T Experiment; Isenthalpic Process; 147
5.22 Derivation of μJ,T.
148
CHEMICAL KINETICS 6
6.1 Introduction; 165
6.2 Rate of reaction; 166
6.3 Rate law and rate constant; 167
6.4
Order and Molecularity; 168
6.5 Integrated rate law for isolated reactions; 169
6.6
Determination of order of reaction; 179
6.7 Opposing Reaction; 181
6.8 Consecutive reaction;
183
6.9 Application of steady-state approximation; 186
6.10 Concept of pre-equilibrium step;
187
6.11 Parallel reaction; 188
6.12 Temperature dependence of reaction; 189
6.13
Thermodynamically controlled and kinetically controlled reactions; 192
6.14 Catalytic reaction;
193
6.14.1 Introduction; 193
6.14.2 Catalyst increases rates of both forward and backward
reactions equally; 194
6.14.3 Classification of catalytic reaction; 195
6.14.4 Mechanism of
homogeneous catalysis; 195
6.14.5 Pre-equilibrium treatment; 196
6.14.6 Mechanism of acid-base catalysis; 197
6.14.7 Acid Catalysed reaction; 197
6.14.8
Protolytic Mechanism; 198
6.14.9 Prototropic Mechanism; 199
6.14.10 Enzyme Catalysis.
200
THERMODYNAMICS OF SYSTEM OF VARIABLE COMPOSITION 7
7.1 Systems with variable compositions; 215
7.2 Partial molar properties; 216
7.3 Lowering of
μi; 219
7.4 Chemical potential(μi); 220
7.5 Gibbs-Duhem equation; 221
7.6
Condition of spontaneity and equilibrium; 222
7.7 Variation of μi with pressure; 222
7.8
Free energy change of mixing; 224
7.9 Thermodynamic criteria of ideal solution; 225
7.10
Fugacity; 226
7.11 Activity and activity coefficient. 227
CHEMICAL EQUILIBRIUM 8
8.1 Introduction; 237
8.2 Variation of Free energy with advancement of reaction; 237
8.3
Equilibrium Constant and ΔrG; 239
8.4 Different aspects of Kp, Kc, Kx; 241
8.5 Reaction
Isotherm; 244
8.6 Van’t Hoff Equation; 246
8.7 Effect of pressure on equilibrium
composition; 247
8.8 Le Chatelier’s principle of mobile equilibrium; 248
8.9 Effect of
addition of a constituent; 249
8.10 Effect of addition of inert gas; 250
8.11 Distribution
law; 253
8.11.1 Dimerisation of benzoic acid; 254
8.11.2 Solvent Extraction. 256
IONIC EQUILIBRIUM 9
9.1 Ionic Equilibrium; 273
9.2 Ionic Product of water; 275
9.3 True Dissociation Constant of
weak acid; 276
9.4 pH; 276
9.5 Ionisation of monoprotic acid; 277
9.6 Hydrolysis of salt;
278
9.7 Buffer Solution; 282
9.8 Mechanism of buffer action; 282
9.9 pH of buffer
solution; 283
9.10 Buffer Capacity; 283
9.11 Acid-Base Indicator. 285
LIQUID 10
10.1 Introduction of Surface tension; 295
10.2 Surface of a liquid; 295
10.3 Surface Free
Energy; 296
10.4 Surface tension; 297
10.5 Contact angle; 298
10.6 Excess pressure within
a curved membrane; 299
10.7 Temperature dependence of surface tension; 300
10.8 Variation of
surface tension with concentration; 300
10.9 Determination of surface tension; 302
10.10
Introduction of Viscosity; 307
10.11 Streamline Flow; 308
10.12 Turbulent Flow; 308
10.13
Viscosity; 308
10.14 Viscosity coefficient; 308
10.15 Critical Velocity; 309
10.16
Poisueille’s Equation; 310
10.17 Error in the determination of η largely depends on
radius; 312
10.18 Temperature dependence of η; 312
10.19 Determination of η.
313
COLLIGATIVE PROPERTIES 11
11.1 Solution; 321
11.2 Ideal Solution; 322
11.3 Raoult’s Law; 323
11.4 Colligative
Properties; 324
11.5 Elevation of boiling point; 325
11.6 Depression of freezing point;
327
11.7 Osmosis and Osmotic pressure; 330
11.8 Relation between different colligative
properties; 331
11.9 Deviation from ideal behaviour; 332
11.10 Van’t Hoff factor (i);
333
11.11 Ideal dilute solution; 333
11.12 Measurement of molecular weight from colligative
properties. 334
SOLID 12
12.1 Introduction; 347
12.2 Laws of Crystallography; 349
12.3 Crystal system; 354
12.4
Crystal lattice; 355
12.5 Interplanar separation; 356
12.6 X-ray diffraction by crystal;
358
12.7 Diffraction by atoms; 359
12.8 Bragg’s Law. 360
CONDUCTANCE 13
13.1 Introduction; 371
13.2 Conduction of electricity by electrolytic solution; 372
13.3 Moving
boundary method; 375
13.4 Conductance; 376
13.5 Equivalence conductance; 379
13.6
Measurement of conductivity; 381
13.7 Debye-Huckel-Onsager Theory; 382
13.8 Temperature dependence of ionic conductance; 384
13.9 Variation of specific conductance with
dilution; 384
13.10 Variation of equivalent conductance with dilution; 384
13.11
Kohlrausch’s law of independent migration of ions; 385
13.12 Ostwald Dilution Law;
386
13.13 Application of conductance measurement; 387
13.14 Ionic strength; 392
13.15
Debye-Huckel Limiting law; 393
13.16 Effect of dielectric constant on activity coefficient.
394
HETEROGENEOUS EQUILIBRIUM 14
14.1 Henry’s Law; 409
14.2 Distribution law; 410
14.3 Solvent Extraction; 412
14.4
Phase Rule; 413
14.4.5 One component system; 419
14.5 Two component system; 422
14.5.1
Liquid-liquid system; 422
14.5.2 Liquid-vapour system. 425
QUANTUM CHEMISTRY 15
15.1 Waves and classical wave equation; 439
15.2 Debroglie’s Hypothesis; 441
15.3
Particle in a box in the light of Debroglie’s Hypothesis; 443
15.4 Matter wave-what it is?
446
15.5 Schrodinger time -independent wave equation; 447
15.6 Well behaved function;
449
15.7 Operator; 450
15.8 Operator in Quantum mechanics; 454
15.9 Postulates of Quantum
mechanics; 455
15.10 Free particle moving along axis; 457
15.11 Particle in one dimensional
potential box; 458
15.11.1 Wave function for the particle; 460
15.11.2 Plotting of wave
function and probability density at different quantum levels. 460
MOLECULAR SPECTROSCOPY 16
16.1 Introduction; 463
16.2 Characterisation of electromagnetic radiation; 464
16.3 Interaction
of radiation with molecule; 464
16.4.1 Rigid diatomic molecule and its rotation; 468
16.4.2
Selection rules for rotational spectra; 470
16.4.3 Appearance of rotational spectra; 470
16.5
Rotation-Vibration spectra; 472
16.5.1 Vibration of a diatomic molecule; 472
16.5.2 Selection
rule for vibrational spectra; 474
16.5.3 Anharmonic oscillation; 474
16.5.4 Vibration-rotation
transition. 477
ELECTROCHEMICAL CELL 17
17.1 Introduction; 487
17.2 Conversion of chaotic dispersal of energy to ordered dispersal;
487
17.3 Reversible cell and irreversible cell; 489
17.4 Principle of determination of E.m.f
of cell; 489
17.5 Electrochemical potential; 490
17.6 Electrode potential; 491
17.7 Cell
construction, its E.m.f. and Nernst equation; 492
17.8 Types of electrodes and expression of
electrode potential; 494
17.9 Standard Hydrogen Electrode and standard electrode potential;
497
17.10 Secondary standard electrodes; 499
17.11 Thermodynamics of electrochemical cells;
499
17.12 Concentration cell with transference; 501
17.13 Concentration cell with transference
with cation reversible electrodes; 502
17.14 Liquid junction potential; 504
17.15
Concentration cell without transference; 506
17.16 Application of E.m.f. measurement. 508
Elementary Physical Chemistry (For Minor and Generic courses) is published in one volume for all the semesters of Three-year B.Sc. (Minor) and B.Sc. (Generic) courses. The book is a result of my long teaching experience of forty years at the undergraduate (Honors) and post-graduate levels at RAMAKRISHNA MISSION RESIDENTIAL COLLEGE, NARENDRAPUR, WEST BENGAL. My interaction with the students and their reciprocal interaction helped me a lot to write this book lucidly, explaining each step of the theoretical matter where students may face difficulty during study. Moreover, I have tried my level best to avoid unnecessary portions so that students within these three years may have time to prepare for examinations like IIT Jam, NET, GATE, CSIR and other exams for higher studies or service. After the theoretical discussion of each chapter, a large number of numerical problems have been solved as worked-out examples, mentioning the formulae and using units of all the terms for a better understanding of theory and the chemistry associated with the problems. For the self-assessment of the students, quite a large number of numerical problems have been set in the exercise. A large number of MCQS, Short questions, descriptive and explanatory questions are given at the end of each chapter so that the students can self-check their level of understanding of the subject and this will help them in future examinations for higher studies. While writing the book, I always kept in mind the advice of the legendary professor of physical chemistry, late Dr. (Prof) P. C. Rakshit who always encouraged and advised me to write a student-friendly Physical Chemistry book not only for information but also for understanding, in a simple language and lucid manner so that the students may develop an interest in physical chemistry. I followed Prof. Rakshit’s advice throughout the book and hope that students will not find any difficulty in understanding the course matter of the subject while preparing for the examinations. I believe this book will be of lot of help for the students. I expect advice from any well-wishers regarding upgrading and betterment of the book. Students finding any difficulty may contact me if needed, through the publisher.
-Hrishikesh Chatterjee
This textbook is written in one volume strictly to cover the whole semester-based undergraduate syllabi of Indian universities following the new syllabus for B.Sc. (minor) and B.Sc. (generic) courses and also universities of neighbouring countries, maintaining the lucidity of expression and explanation. Emphasis has been given to solving both theoretical questions and numerical problems based on the topics discussed. The book contains chapters on kinetic theory; gaseous state; liquid state( surface tension and viscosity); solid state; thermodynamics (I); thermochemistry; thermodynamics( Il); open system of variable composition; colligative properties; ionic equilibrium; chemical equilibrium; chemical kinetics; catalytic reactions and enzyme catalysis; conductance; electrochemical cells; spectroscopy and quantum mechanics. . The book will be compatible with the likings of the students for thorough, as well as easy understanding of the subject.
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Prashant Kumar Mishra