Huque and Nawab

Principles of
Physical . Chemistry
•1'

Fully Revised by
Dr. Muhammad Mahbubul Huque
Dr. Muhammad Yousuf Ali MoIlah
Brothers' Publications
Huque and Nawab

Principles of Physical
Chemistry

i Revised by
mmad Mahbubul Huque
Mohammad Yousuf A. Mollab

Brothers' Publication
3/5, Rafine Plaza January, 2009
Mirpur Road, Dhaka-1205
Published by
Brothers' Publication
3/5, Rafine Plaza
Mirpur Road, Dhaka-1205

First Edition: 1968

Second Edition: 1971
Fully Revised Edition : 2009 \
Fully Revised Edition-2

[All rights reserved, no part of this publication can be reproduced in any form
without the prior permission of the authors.)

Composed by
Alka Computer
Ban glabazar, Dhaka-1 100

Price 300/-
Muhammad Mahbubul Huque
M.Sc. (Dhaka), Ph. D. (McGill, Canada)
Former Professor
Department of Chemistry
Dhaka University, Dhaka
and
Founding Chairman
Department of Chemistry
Jahangirnagar University
Savar, Dhaka

Mohammad Yousuf All Mollah

M.Sc. (Dhaka), Ph. D. (Macquarie, Australia)
Professor
Department of Chemistry
Dhaka University, Dhaka
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 Dedicated to the memory of

• Late Professor M. Ali Nawab

Professor Al. A. Nawab was the senior author of the First Edition of
the book. He was Proftssor of the Department of Chemistry of Dhaka
Universit. Late Professor Nawab was the Chairman of the
Department of Chenstrof Dhaka University during 1973-1976.
Professor Nawab expired on 23 April 1993.
0

I. •
- '.•rn

0
 (vi)

PREFACE TO THE REVISED EDITION

The first edition of 'Principles of Physical Chemistry' was published in 1968 and the third edition came in
1974. The authors did not make attempts to bring out further editions of the book aS at ih.. time science
text books written in Bengali were preferred by the students. We had forgotten about the hook. Professor
M. A. Nawab, the senior author expired in 1993. Then about three years back a former student of mine who
was doing undergraduate studies in Pharmac y in a Private University in Dhaka showed me a photocopy of
the original third edition of the book which was being used as a text book. This was described as a 'full),
revised edition'. A survey revealed that a large number of students in different universities and colleges in
Bangladesh ere using this 'fully revised edition' as a text hook of Physical Chemistry. As mentioned this
was not a Revised Edition as the authors did not make any revision after the third edition. Professor M.
Yousuf A. Mollah. Professor of Physical Chemistry at the Dhaka University. persuaded me to prepare a
revised edition, I agreed on condition that he will be a co-author. The book on Physical Chemistry being
presented with the same title as the original one is the result of joint efforts of Prof. M. Yousuf A. Mollah
and me. We traced the printing house which had been marketing the photocopies as 'fully revised edition'.
They apologized for their action and agreed to publish the edition we have prepared.

This is a Fulls' Revised Edition with major changes. While rewriting this hook we focused on the syllabti of
undergraduate courses on Physical Chemistry of Public. Private Universities and University Colleges in
Bangladesh. The students of Pharmacy. Biochemistry and Engineering will also be benefited from this
book. All through the book SI units have been used. Many chapters have been rewritten with additional
materials. A number of chapters have been divided into smaller chapters for the convenience of the
students: For example. Thermodynamics has been presented in three chapters with titles: Thermodynamics
I: the First Law, Thermochemistry, Thermodynamics H: the Second and the Third Law. The chapter on
Solution has been divided into Solution and Dilute Solution. Electrochemistry has been divided into two
chapters: Electrol y tic Conduction and Electrolysis, Electrochemical cells. The chapter on Reaction Kinetics
has been presented completely in a new format. Acids and Bases have been presented as a separate chapter.
Solubility and Solubility Product form a new chapter. As the material presented in the chapter on Surface
Chemistry and Colloids in the third edition is considerable, this has been split into two chapters: Surface
Chemistry and Colloidal State. In many chapters topics have been rewritten with the inclusion of new
materials and presented in a better way: Brief discussion of mass spectra. I.R and N.M.R. spectra and their
applications are included in the chapter on Physical Properties and Molecular Structure. End of Chapter
Questions and Problems have been revised, many new questions and problems with answers have been
incorporated. The format of the book has also been changed.

We hope that the Revised Edition of the book with its new look will receive the same acceptance by the
students and teachers as the earlier editions.

Printing of this book has been an arduous task. The publishers are not well acquainted with printing a book
on science with a lot of figures and formulae. They have, however, made great efforts to keep.the book free
of printing mistakes. We thank the publishers for their valiant efforts. In spite of their best intentions you
will find some errors. We hope to eliminate these in the future edition.

January, 2009 M. M. Huque
 (vii)

PREFACE TO THE SECOND EDITION

We are gratified to see that the first edition of the book has been well accepted by the students and teachers
in spite of the numerous printing errors. In the preparation of second edition attempt has been made to
increase the clarity of the presentation at several places. The number of numerical examples at the end of
the chapters has been considerably increased. Apart from these changes little has been altered in the
arrangement of the material and the get up. We have also tried hard to keep the printing errors at the
minimum.
We are indebted to many of our colleagues in the universities and colleges who have kindly sent their
criticisms and pointed out the shortcomings of the first edition. These have been of great help in making
improvement in the clarity of representation.
We are sorry, we could not make the book completely free of mistakes in spite of our best wishes.

January. 1971 M. M. Huque

Dhdka M. A. Nawab
 (viii)
PREFACE TO THE FIRST EDITION

Printing of an object by a hundred painters, or writing of a hundred poetry ()it same subject need no
explanation, but writing on a book on a subject like Physical Chemistry calls for an explanation specially
when excellent books in English are available. During the last many years of teaching Physical Chemistr)
to the undergraduate students, we have alwa ys felt the necessity of explaining the fundamental concepts.
We believe that once the basic principles have been understood by the students, more than half the battle is
won. In this respect, there is a need for a book on Physical Chemistry for our students whose background is
different from those for whom the available books are meant. Many of these hooks cover Fields wider and
deeper than what is needed for our undergraduates at the B. Sc. (Pass) level. We, therefore, felt the
necessit y of writing a book o n Physical Chemistry that would fully meet the requirements of the B. Sc.
(Pass) students and at the same time help in building a sound background for the Honours students. We
always tried, while writing the hook. to explain the basic principles as clearl y and elaborately as possible. It
is upto the teachers who teach the suhjc.t and the students who would read to judge whether our aims have
been fulfilled.
In the book most portions deal with the kinetic theory, thermodynamics and chemical kinetics. We have
used some final results and equations of Quantum Chemistry and did not go anywhere beyond it because
we thought that Quantum Chemistr y and Statistical Mechanics should be treated at a higher level. Although
the approach his been basically classical attempts have been made to acquaint the students with
thermodynamic approach. In many places both kinetic and thermodynamic treatment have been used to
show that identical results can be obtained. Only the methodology and physical concept are different.
Quantum mechanical approach has been kept to minimum, only flashes appear here and there.
In several places we have gone a little beyond than what is expected to form the syllabus of Pakistani
Universities. The idea is to point to the fact that improvements need he made as is constanil being done in
western countries. This is further meant to pros ide the mental food for the more serious and above average
students. The average students may leave out these portions on advanced treatment.
Contrary to common practice we have not included a chapter on atomic structure and radioactivity. These
two topics generally form a part of Inorganir Chemistry syllabus in our country and excellent treatment is
available in text books of Inorganic Chemisti-v. We therefore, thought it wise to leave out the branches from
the present volume. This has considerably reduced the size of the book.
We express our thanks to a number of our colleagues who always inspired us during the writing of the
book. Thanks are specially due to Prof. M. H. Khundkar, I-lead of the Department of Chemistry. University
of Dhaka. for his encouragement at various stages. Mr. A. J. Mahmood, Senior Lecturer in Chemistry.
University of Dhaka, deserves special thanks for kindly going thr'ough a large portion of the manuscript and
making valuable suggestions. Thanks are also due to Mr. A. N. M. Akhter, a student of the Dhaka College.
for drawing a number of original sketches and helping in making the design of the dust cover. We are
indebted to Mr. Mesbahul Haque for preparing the index. We must also thank Mr. Sycd Md. Faziul Huq of
the Students' Publications for taking the task of publishing the book. Mr. A. K. M. Raja Meah deserves
special mention for his untiring efforts and hard work in the printing of the book.
Good printing is a challenging task and in spite of our best efforts some mistakes are still there. We
apologise for this and hope to improve in the next edition. We shall appreciate receiving comments from
those who use the book, so that improvements can be made in future.

Department of Chemistry M. NI. Huque

University of Dhaka Ni. A. Nawab
Januam5i. 1968


(ix)
CONTENTS
Page
STATE OF AGGREGATION OF MATTER INTERMOLECULAR FORCES . -11

1.1 Matter: States of Aggregation

4
1.2 Intermolecular Forces
8
1.3 Hydrogen bondi
11
QUESTIONS AND PROBLEMS

12-76
2 THE GASEOUS STATE
12
2.1 Ideal Gases: The Gas Laws
12
2.2 Bo y le's Law
15
2.3 Charles Law or Gay-Lussacs Law
17
2.4 The Absolute Zero of Temperature
17
2.5 Avogadros Law
18
2.6 The Ideal Gas Equation
18
2.7 The Significance of R
19
2.8 The Numerical Value of R
The Use of the Gas Equation in Calculations Involving Gases 20
2.9
21
2.10 Diffusion and Effusion: Graham's Law of Diffusion
2.11 Equttion of State of a Gas Mixture: Dalton's Law of Partial Pressure 22
24
2.12 The Kinetic Theory of Gases
25
2.13 Root-mean-square (r.m.s.) Velocity
25
2.14 Derivation of the Kinetic Equation
27
2.15 Deduction of the Gas Laws from the Kinetic Equation
29
2.16 Molecular Velocities
30
2.17 Distribution of Velocities
31
2.18 Average Velocity. r.m.s. Velocity and Most Probable Velocity
32
2.19 .MeanFree Path
33
2.20 Viscosity of Gases
33
2.21 Molecular Diameter
34
2.22 Frequency of Collisions of Gas Molecules
35
2.23 Number of Molecules Striking a Surface
35
2.24 Avogadro Number
36
2.25 The Kinetic Theory - a review: Brownian Movement
37
2.26 Behaviour of Real Gases: The Arnagats Curves
38
2.27 Modification of the Ideal Gas Equation: van der Waals Equation of State
41
2.28 Significance and Limitations of van der Waals Equation
43
2.29 Other Equations of State
43
2.30 Change of State: Gas-Liquid Transition
44
2.31 Andrews' Experiments with CO2
 (x)

2.32 Determination of Critical Constants 46

2.33 'an der Waals Equation and the Critical Phenomena 48

2.34 Continuity of State 50

2.35 The Equation of The Corresponding States 51

2.36 Liquefaction of Gases - the Basic Principles 52

2.37 Methods of Attaining Low Temperature 53

2.38 Uses of Liquefied Gases 57

2.39 Density of Gases and Molecular Mass 57

2.40 Abnormal Densities of Gases: Molecular Association and Dissociation 64

2.41 Heat Capacities of Gases: Definitions 68

2.42 Heat Capacity and Kinetic Theory 68

2.43 Experimental Determination of y of a 70

2.44 The Principle of Equipartition of Energy 72

QUESTIONS AND PROBLEMS 74

3 THE LIQUID STATE 77-93
3.1
Vapour Pressure of Liquids 77

3.2 . Kinetic Theory of Vapour Pressure 78
3.3
Vapour Pressure and Temperature 79
3.4
Boiling Point of a Liquid: Enthalpy of Vaporization 80

3.5 Trouton's Rule 80

3.6 Measurement of Vapour Pressure 81

3.7 Surface Tension 83
3.8
Adhesion and Cohesion 85

3.9 Measurement of Surface Tension 85

3.10 Surface Tension and Temperature 89

3.11 The Viscosity of Liquids 89

3.12 The Poiseuille Equation 89

3.13 Measurement of Viscosity 90

114 Viscosity and Temperature 92

3.15 Viscosity and Its Importance 92

3.16 Structure of Liquids 92

QUESTIONS AND PROBLEMS 93

4 THE SOLID STATE 94-119

4.1 Preparation of Crystals 94
4.2 Bonding in Crystals and their Characteristic 96
4.3 Internal Structure of a Crystal 97
4.4 Symmetry in Crystals 101
4.5 The Crystal Systems 102


(xi)

4.6 X-rays and Diffraction of X-rays by Crystals 103

4.7 Cubic Lattices 105

4,8 The Structure of Sodium Chloride Crystals 108

4.9 The Powder Method 108
4.10 Application of X-ray Diffraction 109
4.11 Conductors, Insulators and Semiconductors 109
4.12 Defects in Solids 113

4.14 Liquid Crystals 'IS

4.15 The Specific Heats of Solids 17

4.16 Isomorphism [8
QUESTIONS AND PROBLEMS [19

5 THERMODYNAMICS I: THE FIRST LAW 120-142

5.1 The Nature of Thermodynamics 120
Important Concepts in Thermodynamics 121
5.2
The First Law of Thermodynamics 125
5.3
5.4 Mathematical Formulation of the First Law 126
5.5 Thermodynamic Processes 127
129
5.6 Work of Expansion
5.7 Isothermal Reversible Expansion of an Ideal Gas: Maximum Work
129
5.8 Constant Volume Processes [32

5.9 Partial Differential Notation 132

5.10 Constant Pressure Processes and Enthalpy 132
133
5.11 Relationship between U and H
5.12 Heat Capacity and Molar Heat Capacity 134
138
5.13 The Internal Energy of an Ideal Gas: Joule's Experiments
Joule-Thomson Porous Plug Experiments 138
5.14
Adiabatic Processes 141
5.15
QUESTIONS AND PROBLEMS 142

6 THERMOCHEMISTRY 143-170
Heat of Reaction or Enthalpy of Reaction 143
6 .1
144
6.2 Conventions
6.3 Heat of Reaction at Constant Pressure and at Constant Volume 145
6.4 The Determination of Heats of Reaction: Calorimetry 146
146
6.5 Enthalpy of Combustion: Bomb Calorimeter
149
6.6 Laws of Thermochemistry
153
6.7 Heat of Formation
6.8 Effect of Temperature on Heat of Reaction: The Kirchhoff Equation 155
156
6.9 Enthalpy of Solution


(xii)

6.10 Heat of Neutralization 158

6.11 Enthalpy Change during Phase Change 160
6.12 Calculation of Heat of Reaction: Bond Energy 160
6.13 Enthalpy of Ionization or Ionization energy 164
6.14 Electron Affinity 165
6.14 The Lattice Enthalpy (L,E.) 165
QUESTIONS AND PROBLEMS 168

7 THERMODYNAMICS II: SECOND AND THIRD LAWS 171-201

7.1 Necessity of the Second Law 171
7.2 Spontaneous and Non- spontaneous Processes 171
7,3 Heat Engine 172
7.4 Statement of the Second Law 173
7.5 The Carnot Cycle 174
7.6 Entropy - A New Thermodynamic State Function 177
7.7 Entropy and equilibrium 182
7.8 Entropy Change of an Ideal Gas 182
7.9 Calculation of AS for Physical Processes 184
7.10 The Third Law of Thermodynamics 187
7.11 Entropy and Molecular Chaos 188
7.12 The Free Energy and the Work Function 190
7.13 Gibbs-Helmholtz Equation 196
7.14 Equilibrium between Phases : The Clapeyron Equation 197
7.15 The Clausius-Clapeyron Equation 199
QUESTIONS AND PROBLEMS 201

8 SOLUTIONS 202-225
8.1 Types of Solutions 203
8.2 Units of Concentration 203
8.3 Solution of Gas in Liquids 205
8.4 Effect of Temperature 206
8.5 Influence of Pressure 206
8.6 Validit y and Limitations of Henrys Law 208
8.7 Solution of Gas in Solid 208
8.8 Liquid - Liquid Solution: The Solution Process 209
8.9 Ideal and Non - ideal Solutions 211
8.10 Solid - Liquid Solution; The Solution Process 211
8.11 Solubility 213
8.12 Effect of Temperature on Solubility 214
8.13 Distribution of a Solid between Two Immiscible Liquids: The Distribution Law 216
 (xiii)

217
8.14 Deviations from Distribution Law
220
8.15 Applications of Distribution Law
222
8.16 Solvent Extraction
225
QUESTIONS AND PROBLEMS

226-254
9 DILUTE SOLUTIONS COLLIGATIVE PROPERTIES
226
9.1 Lowering of Vapour Pressure
228
9.2 Ideal Solution
228
9.3 Molecular Mass from Lowering of Vapour Pressure
229
9.4 Derivation of Raoults Law
229
95 Measurement of Loweringof Vapour pressure
231
9.6 Elevation of Boiling Point
233
9.7 Thermodynamic Derivation of Boiling Point Elevation
Determination of Molecular Mass from Boiling Point Elevation 235
9.8
237
9.9 Depression of Freezing Point
238
9.10 Thermodynamic Derivation of the Freezing Point Depression
240
9.11 Measurement of Depression of Freezing Point
241
9.12 Osmosis and Osmotic Pressure
242
9.13 Semi-permeable Membrane
243
9.14 Determination of Osmotic Pressure
245
9.15 Vant Hoff s Laws of Osmotic Pressure
246
9.16 Determination of Molecular Mass from Osmotic Pressure Measurements
247
9,17 Thermodynamic Derivation of Osmotic Pressure Laws
248
9.18 Relative Osmotic Pressure
249
9.19 Interrelation between the Colligative Properties
250
9.20 Abnormal Molecular Masses from Colligative Properties
252
9.21 Importance of Osmosis Phenomenon
252
QUESTIONS AND PROBLEMS

255.283
10 CHEMICAL EQUILIBRIUM
255
10.1 Reversible Reactions
257
10.2 The Equilibrium Law; the Equilibrium Constant
260
10.3 Gaseous Equilibria
261
10.4 Relation between K and K,
262
10.5 Determination of Equilibrium Constants
262
10.6 Criteria of Chemical Equilibrium
263
10.7 Activity and Activity Co-efficient
264
10.8 Calculations involving Chemical Equilibrium
264
10.9 Homogeneous Equilibria
269
10.10 Equilibria in Solution
 (xiv)

10.11 Heterogeneous Equilibria 270

10.12 Factuis Influencing Equilibrium: The Principle of Le Chatelier 271
10.13 Applicatiorts of the Principles of Chemical Equilibrium to

Reactions of Industrial Importance 276

10.14 Free Energy Change and Equilibrium Constant 278

10.15 Influence olTemperature on Equilibrium Constant : Thermodynamic Derivation 280

QUESTIONS AND PROBLEMS 282

11 PHASE EQUILIBRIA 284-308

11.1 Definition of Terms 285
11.2 Deduction of the Phase Rule 287
.11.3 Water System 288
11.4. The Sulphur System 290
11.5 Phosphorus System 292
11.6 Sublimation and Triple Point 293
11.7 Solid-liquid Equilibria: Eutectic Point 294
11.8 Liquid-Liquid Systems 299
11.9 Fractionating Column 301
11.10 Completely Misiblc Liquid Pairs Showing Deviation from Raoults Law 302
11.1 l'Distillation of Non-ideal Solutions: Azeotropic Mixture 302
11.12 Liquid—Liquid Equilibria in Partly Miscible Systems
Critical Solution Temperature (CST) 303
11.13 Immiscible Liquid Pairs: Steam Distillation 306
QUESTIONS AND PROBLEMS 308

12 KINETICS OF CHEMICAL CHANGE 309-365

12.1 The Definition of Rate of Reaction 309
12.2 Experimental Determination of the Rate of a Reaction 311
12.3 Factors Affecting the Rates of Reaction 312
12.4 Dependence of Rate on Concentration: The Rate Law 313
12.5 Units of Rate Constants 314
12.6 Determination of the Rate Law: Determination of Order of Reactions 315
12.7 Some Typical Reactions 328
12.8 Complex Reactions 334
12.9 Influcuce of Temperature on Reaction Rates 337
12.10 Collision Theory of Reaction Rates 339
12.11 Transition State Theory 34c
12.12 The Rate Law and Mechanism of Reaction
12.13 Molecularity and Order of Reactions
12.14 Unimolecular Reaction: Lindemanns Mechanism
 (xv)
347
12. 15 Theory of Absolute Reaction Rate 349
12.16. Hydrogen-Chlorine Reaction 350
12.17 Branching Chains: Explosive Reactions 350
12.18 HydrogenOXYgefl Reaction 352
12.19 Absorption of Light: Beer-Lambe rt Law 354
12.20 Consequences of the Absorption of Light 355
12.21 Luminescence 356
12.22 The Laws of Photochemistry 358
12.23 Determination of Quantum Yield 359
12.24 Photosensitized Reaction 360
12.25 Photosynthesis 360
12.26 Radiation Chemistry 361
12.27 Gas Solid Systems: Reactions Involving One Gas
362
12,28 Gas-Solid Systems: Reactions Involving Several Gases 363
12.29 Heterogeneous Reactions in Solution 363
QUESTIONS AND PROBLEMS

366.378
13 CATALYSIS 366
13.1 Definition 366
13.2 Types of Catalysis 368
13.3 Characteristics of Catalysts 370
13.4 Energy Changes in Catalytic Reactions 371
13.5 promoters and Catalytic Poisons 371
13.6 Theories of Mechanism of Catalysis 375
13. Acid-lLtse Catalysis 375
13.8 Mechanism of Acid-Base Catalysis 376
13.9 Enzyme Catalysis 377
13.10 Mechanism of Enzyme Catalysis 378
QUESTIONS AND PROBLEMS
379-409
AND ELECTROLYSIS
14 ELECTRICAL CONDUCTANC E 379
14.1 Electrolyti c ConLluctiofl 379
14.2 Metallic and Electrolytic Conduction 380
14.3 Electrolysis 381
14.4 The Mechanism of Electrolytic CnduCtiOn 381
14.5 Faraday's Laws of Electrolysis 384
14.6 Faraday and Sig ificance f the Faraday's Laws 385
14.7 The Conductance of Electrol y tIc Solutions 387
14.8 Experimental DeterrnhrliItiOil of Conductance 389
14.9 Conductance Cell: Cell Colishult
 (xvi)

14.10 Conductivity Water 390

14.11 Conductance and Electrolyte Concentration 391

14.12 The Conductance Ratio 392

14,13 Debye-Huckel- Onsagcr Theory 393

14.14 Independent Migration of Ions; Kohlrauscli s Law 395

14.15 Absolute Velocity of Ions; ionic Mobility 397

14.16 Applications of Conductance Measurements 399

14.17 Transport Number (or Transference Number) 402

14.18 Measurement of Transport Number 405

14.19 Factors Affecting Transport Numbers 408

QUESTIONS AND PROBLEMS 408

15 ELECTROCHEMICAL CELL 410-452

15.1 Galvanic Cells 410
15.2 The Origin of E.M.F. at Metal-Solution Interface 411
15.3 Reversible and Irreversible Cells . 412
15.4 Measurement of E.M.F of Electrochemical Cells 413
15.5 Weston Standard Cell 414
15.6 Types of Half-Cells 415
15.7 Sinle Electrode Potential; Standard Hydrogen Electrode 417
15.8 Secondary Standard Electrodes . 419
15.9 Electrochemical Cells; Notations and Sign Convention 419
15.10 Determiiation of Standard Electrode Potential (SEP) 421
15.11 Values of Standard Electrode Potentials - 422
15.12 Uses of Standard Potential Values 424
15.13Effect of Concentration and Temperature on Electrode Potential; The Nernst Equ'ation 426
15.14 Determination of pH of a Solution 430
15.15 Thermodynamics and E.M.F. of Cells 433
15.16 Liquid Junction Potential; Salt Bridge 439
15.17 Types of Galvanic Cell 439
15.18 Application of E.M.F. Measurements 443
15.19 Lead Storage Cell 447
15.20 LecLanches Dry Cell 447
15.21 Fuel Cell 447
15.22 Polarization and Overvoltage 449
15.23 The Polarograph . 450
QUESTIONS AND PROBLEMS 451

16 ACED-BASE EQUILIBRIA 453-493

16.1 Acids and Bases:. the Arrhenius concept 453

16.2 B ronsted-Lovry concept 4i4
 (xvii)

16.3 The Lewis Concept 456

16.4 Self-Ionization (or auto ionization) of Water 457
16.5 Hydrogen ion concentration —The pH Scale 458
16.6 Some useful relationship 461
16.7 Measurement of pH 462
16.8 Dissociation of weak acids and weak bases: Ostwalds Dilution Law 465
16.9 Dissociation constants of weak acids and weak bases 466
16.10 pH of solutions of very weak acids 467
16.11 pH of solutions of very weak bases 469
16,12 The Common Ion Effect 471
16.13 Indicators in Acid - Base Titration.s 472
16.14 Acid -Base Titrations; Choice of Indicator for Titrations 474
16.15 Titration of a Strong Acid with a Strong Base 475
16.16 Titration of a Weak Acid with a Strong Base 416
16.17 Buffer Solutions 478
1618 Salt Hydrlysis 484
16.19 The pH of Salt Solutions 485
16.20 Amphoteric Electrolytes: Zwitter Ions 491
QUESTIONS AND PROBLEMS 491

17 SOLUBILITY AND COMPLEX-ION EQUILIBRIA

17,1 Solubility and Solubility Product 494
17.2 Solubility and Common Ion Effect 498
17.3 Effect of p11 on Solubility 500
17.3 Predicting Precipitation 501
17.4 Applications of Solubility Product Principle 502
17.5 Equilibria of Complex Ions 503
QUESTIONS AND PROBLEMS 505

Ni.22,
18 SURFACE CHEMISTRY
18.1 The Nature of Surfaces
507
18.2 Definition of Terms
508
18.3 Nature of Adsorption
310
18.4 Gas-Solid Systems: Langmuir Isotherm
513
18.5 Deviations froLit 1nmii isc.Thcrm
514
18.6 BET (Brunauer, Fniniet and Teller) Isotherm
515
18.7 Gas-Liquid interface; Surface Film and Surface Pressure
517
I8.8 Gibhs Adsorption Equation
518
18.9 Adsorption from Solution
 (xviii)

18.10 Freundlich Isotherm 519

18.11 Langmuir Isotherm for Solid-Liquid Adsorption 519
18.12 Chromatography 520
QUESTIONS AND PROBLEMS 522

19 COLLOIDS AND EMULSION 523.541

19.1 Crystalloids and Colloids 523
19.2 Disperse Phase and Dispersion Medium 524
19.3 Types of Colloids 524
19.4 Sol and its Preparation 525
19.5 Purification of Colloids: Dialysis and Electrodialysis 528
19.6 Lyophobic and Lyophilic Sols 529
19.7 Properties of Colloids 531
19.8 Stability of Colloids 536
1'.9 Peptization 537
19.10 Gel 537
19.11 Syneresis 537
19.12 Imbibition and Swelling 538
19.13 Foam 538
19.14 Colloidal electrolyte 538
19.15 Emulsion 539
19.16 Importance of Colloids 540
QUESTIONS AND PROBLEMS 541

20 PHYSICAL PROPERTIES AND MOLECULAR STRUCTURE 542-568

20.1 Molar Volume 542
20.2 Parachor 543
2 0.5 Refractive Index and Molar Refraction 545
20.4 Optical Activity 546
20.5 Dipole Moment and Molecular Structure 549
20.6 Spectroscopy and Molecular Structure 552
QUESTIONS AND PROBLEMS 568

INDEX 569-574