A Textbook of Physical Chemistry: Dynamics of Chemical Reactions, Statistical Thermodynamics and Macromolecules (SI Unit), 3e, Volume 5

559 Pages·2015·40.007 MB·English

by  K. L. Kapoor

A Textbook of
Physical Chemistry
Volume V
A Textbook of Physical Chemistry
Volume I : States of Matter and Ions in Solution
Volume II : Thermodynamics and Chemical Equilibrium
Volume III : Applications of Thermodynamics
Volume IV : Quantum Chemistry and Molecular Spectroscopy
Volume V : Dynamics of Chemical Reactions, Statistical Thermodynamics, Macromolecules, and
Irreversible Processes
Volume VI : Computational Aspects in Physical Chemistry
A Textbook of
Physical Chemistry
Volume V
(SI Units)
Dynamics of Chemical Reactions, Statistical Thermodynamics,
Macromolecules and Irreversible Processes
Third Edition
k l kAPoor
Former Associate Professor
Hindu College
University of Delhi
New Delhi
McGraw Hill Education (India) Private Limited
New Delhi
McGraw Hill Education Offices
New Delhi New York St louis San Francisco Auckland Bogotá Caracas
Kuala lumpur lisbon london Madrid Mexico City Milan Montreal
San Juan Santiago Singapore Sydney Tokyo Toronto
Published by McGraw Hill Education (India) Private Limited,
P-24, Green Park Extension, New Delhi 110 016.
A Textbook of Physical Chemistry, Vol V
Copyright © 2015 by McGraw Hill Education (India) Private Limited.
No part of this publication may be reproduced or distributed in any form or by any means, electronic, mechanical, pho-
tocopying, recording, or otherwise or stored in a database or retrieval system without the prior written permission of the
publishers. The program listings (if any) may be entered, stored and executed in a computer system, but they may not be
reproduced for publication.
This edition can be exported from India only by the publishers,
McGraw Hill Education (India) Private Limited.
Print Edition
ISBN (13): 978-93-39204-31-0
ISBN (10): 93-39204-31-X
E-book Edition
ISBN (13): 978-93-392-0432-7
ISBN (10): 93-392-0432-8
Managing Director: Kaushik Bellani
Head—Higher Education (Publishing and Marketing): Vibha Mahajan
Senior Publishing Manager (SEM & Tech. Ed.): Shalini Jha
Associate Sponsoring Editor: Smruti Snigdha
Senior Editorial Researcher: Amiya Mahapatra
Senior Development Editor: Renu Upadhyay
Manager—Production Systems: Satinder S Baveja
Assistant Manager—Editorial Services : Sohini Mukherjee
Assistant General Manager (Marketing)—Higher Education: Vijay Sarathi
Senior Graphic Designer—Cover: Meenu Raghav
General Manager—Production: Rajender P Ghansela
Manager—Production: Reji Kumar
Information contained in this work has been obtained by McGraw Hill Education (India), from sources believed to
be reliable. However, neither McGraw Hill Education (India) nor its authors guarantee the accuracy or completeness
of any information published herein, and neither McGraw Hill Education (India) nor its authors shall be responsible
for any errors, omissions, or damages arising out of use of this information. This work is published with the
understanding that McGraw Hill Education (India) and its authors are supplying information but are not attempting
to render engineering or other professional services. If such services are required, the assistance of an appropriate
professional should be sought.
Typeset at Script Makers, 19, A1-B, DDA Market, Paschim Vihar, New Delhi 110 063, and text printed at
To the Memory of My Parnets

Preface
in recent years, the teaching curriculum of Physical Chemistry in many indian
universities has been restructured with a greater emphasis on a theoretical and
conceptual methodology and the applications of the underlying basic concepts and
principles. This shift in the emphasis, as i have observed, has unduly frightened
undergraduates whose performance in Physical Chemistry has been otherwise
generally far from satisfactory. This poor performance is partly because of the
non-availability of a comprehensive textbook which also lays adequate stress on
the logical deduction and solution of numericals and related problems. Naturally,
the students find themselves unduly constrained when they are forced to refer to
various books to collect the necessary reading material.
it is primarily to help these students that i have ventured to present a textbook
which provides a systematic and comprehensive coverage of the theory as well as
of the illustration of the applications thereof.
The present volumes grew out of more than a decade of classroom teaching
through lecture notes and assignments prepared for my students of BSc (General)
and BSc (honours). The schematic structure of the book is assigned to cover
the major topics of Physical Chemistry in six different volumes. Volume I
discusses the states of matter and ions in solutions. It comprises five chapters
on the gaseous state, physical properties of liquids, solid state, ionic equilibria
and conductance. Volume II describes the basic principles of thermodynamics
and chemical equilibrium in seven chapters, viz., introduction and mathematical
background, zeroth and first laws of thermodynamics, thermochemistry, second
law of thermodynamics, criteria for equilibrium and A and G functions, systems
of variable composition, and thermodynamics of chemical reactions. Volume III
seeks to present the applications of thermodynamics to the equilibria between
phases, colligative properties, phase rule, solutions, phase diagrams of one-,
two- and three-component systems, and electrochemical cells. Volume IV deals
with quantum chemistry, molecular spectroscopy and applications of molecular
symmetry. it focuses on atomic structure, chemical bonding, electrical and
magnetic properties, molecular spectroscopy and applications of molecular
symmetry. Volume V covers dynamics of chemical reactions, statistical and
irreversible thermodynamics, and macromolecules in six chapters, viz., adsorption,
chemical kinetics, photochemistry, statistical thermodynamics, macromolecules
and introduction to irreversible processes. Volume VI describes computational
aspects in physical chemistry in three chapters, viz., synopsis of commonly used
statements in BASiC language, list of programs, and projects.
The study of Physical Chemistry is incomplete if students confine themselves
to the ambit of theoretical discussions of the subject. They must grasp the practical
significance of the basic theory in all its ramifications and develop a clear
perspective to appreciate various problems and how they can be solved.
it is here that these volumes merit mention. Apart from having a lucid style
and simplicity of expression, each has a wealth of carefully selected examples and
solved illustrations. Further, three types of problems with different objectives in
view are listed at the end of each chapter: (1) Revisionary Problems, (2) Try Yourself
Problems, and (3) Numerical Problems. Under Revisionary Problems, only those
problems pertaining to the text are included which should afford an opportunity to
the students in self-evaluation. in Try Yourself Problems, the problems related to
the text but not highlighted therein are provided. Such problems will help students
extend their knowledge of the chapter to closely related problems. Finally, unsolved
Numerical Problems are pieced together for students to practice.
Though the volumes are written on the basis of the syllabi prescribed for
undergraduate courses of the University of Delhi, they will also prove useful to
students of other universities, since the content of physical chemistry remains the
same everywhere. in general, the Si units (Systeme International d’ unite’s), along
with some of the common non-Si units such as atm, mmhg, etc., have been used
in the books.
Salient Features
∑ Comprehensive coverage to adsorption, chemical kinetics, photochemistry,
statistical thermodynamics, macromolecules
∑ emphasis given to applications and principles

∑ explanation of equations in the form of solved problems and numericals
∑ iUPAC recommendations and Si units have been adopted throughout.
∑ Rich and illustrious pedagogy
Acknowledgements
i wish to acknowledge my greatest indebtedness to my teacher, late Prof. R P
Mitra, who instilled in me the spirit of scientific inquiry. I also record my sense
of appreciation to my students and colleagues at hindu College, University of
Delhi, for their comments, constructive criticism and valuable suggestions
towards improvement of the book. i am grateful to late Dr Mohan Katyal (St.
Stephen’s College), and late Prof. V R Shastri (Ujjain University) for the numerous
suggestions in improving the book. i would like to thank Sh. M M Jain, hans Raj
College, for his encouragement during the course of publication of the book.
i wish to extend my appreciation to the students and teachers of Delhi
University for the constructive suggestions in bringing out this edition of the book.
i also wish to thank my children, Saurabh-Urvashi and Surabhi-Jugnu, for many
useful suggestions in improving the presentation of the book.
Finally, my special thanks go to my wife, Pratima, for her encouragement,
patience and understanding.
Feedback Request
The author takes the entire responsibility for any error or ambiguity, in fact or
opinion, that may have found its way into this book. Comments and criticism
from readers will, therefore, be highly appreciated and incorporated in subsequent
editions.
K L Kapoor
Publisher’s Note
McGraw-hill education (india) invites suggestions and comments from you, all
of which can be sent to [email protected] (kindly mention the title and
author name in the subject line).
Piracy-related issues may also be reported.