STATISTICAL MECHANICS An Advanced Course with Problems and Solutions RYOGO KUBO University of Tokyo in cooperation with HIROSHI ICHIMURA TSUNEMARU USUI NATSUKI HASHITSUME Tokyo Institute of Technology Kyoto University Ochanomizu University NORTH-HOLLAND AMSTERDAM - OXFORD - NEW YORK - TOKYO.© Elsevier Science Publishers B.V., 1965 A\ll rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission of the publisher, Elsevier Science Publishers B.V. (North- Holland Physics Publishing Division), P.O. Box 103, 1000 AC Amsterdam, The Netherlands. Special regulations for readers in the USA: This publication has been registered with the Copyright Clearance Center Inc. (CCC), Salem, Massachusetts. Information can be obtained from the CCC about conditions under which photocopies of parts of this publication may be made in the USA. All other copyright questions, including photocopying outside of the USA, should be referred to the publisher. ISBN: 0 444 87103 9 Paperback First edition (hardbound) 1965 Second edition (hardbound) 1967 ‘Third edition (hardbound) 1971 Fourth edition (hardbound) 1974 Fifth edition (hardbound) 1978 Sixth edition (hardbound) 1981 Seventh edition (paperback) 1988 Published by: North-Holland Physics Publishing a division of Elsevier Science Publishers BV. P.O. Box 103 1000 AC Amsterdam The Netherlands Sole distributors for the USA and Canada: Elsevier Science Publishing Company, Inc. 52 Vanderbilt Avenue New York, NY 10017 USA ‘North-Holland Personal Library: paperback” Library of Congress Catalog Card Number 67-20003 Printed in The NetherlandsPREFACE TO ENGLISH EDITION The original text of this volume is part of the book “Problems and Solutions in Thermodynamics and Statistical Mechanics”, itself one of the “University Series” published by the Shokabo Publishing Company. At the request of the present publisher, the English edition is being published in two volumes, one on thermodynamics and the other on statistical mechanics. Considering the more urgent interest of university students in statistical mechanics, this Volume has been translated and published first. The volume on thermo- dynamics is expected to be published within a year. The translation was made from the Japanese text by the original authors, together with a few collaborators. As the editor of the original Japanese edition and of the English edition, I wish to express my deep appreciation to Drs. Masaji Kubo, Toshihiko Tsuneto and Satoru Miyake who did the trans- lation work with the authors, and particularly to Professor Donald C. Worth of International Christian University, Tokyo, who kindly took the trouble of helping us with linguistic difficulties. The authors are also indebted to Miss N. Tokuda for the preparation of the manuscript. 1964 RyoGo KusoPREFACE TO JAPANESE EDITION Thermodynamics and statistical mechanics are indispensable tools in studying the physics of the properties of matter. Statistical mechanics, together with quantum mechanics, provides a foundation for modern physics which aims at the thorough understanding of physical phenomena from the microscopic viewpoint of atomic physics. Fundamental knowledge and training in statis- tical mechanics are therefore of vital importance not only for students studying the physical properties of matter but also for those who study nuclear physics or even astrophysics. Outside the realm of physics, its im- portance is rapidly penetrating into chemistry, biology and into those vast areas of technology which owe their growth to the advances in modern physics. Thermodynamics belongs completely to classical physics and is some- times regarded as unimportant by students of physics who are over-occupied in learning modern physics. Even for students in chemistry, the present is different from the time some decades ago when physical chemistry was al- most nothing but chemical thermodynamics. However, it must be stressed here that the usefulness and unique significance of thermodynamics as a fundamental science remain as basic today as they were in the latter half of the last century. Thermodynamics teaches us the value of a phenomenological approach. It avoids explicit use of physical images or models such as atomsand molecules. Instead it deals with relations between somewhat abstract quantities such as energy, entropy, free energy and so forth. Admittedly it does not give intuitive pictures as atomic theories do, which is one of the reasons why students find it difficult to gain sufficient understanding and familiarity to use thermodynamics in real problems. But the simplicity of the logic of thermodynamics sometimes makes us see more clearly into the nature of the basic physics of a given problem from very general principles. This is the great advantage of a phenomenological approach. Obviously, however, it is impossible to explore more deeply the under- lying atomic processes in a given physical phenomenon if we confine our attention to thermodynamics. Such progress is made possible only by quantum mechanics and statistical mechanics. Statistical mechanics providesPREFACE TO JAPANESE EDITION va us with a means to link the physical laws of the microscopic world to those of the macroscopic world. Without close cooperation with statistical mecha- nics, quantum mechanics itself would not be able to represent the physics of the real world. In this sense, statistical mechanics is indispensable as one of the keystones of modern physics. Like any other science, statistical mechanics cannot be mastered easily just by learning its principles once. One has to think by oneself a great deal before one grasps the way in which to use the statistical approach in one’s thin- king, and to apply statistical mechanics to real physical problems. In statis- tical mechanics and in thermodynamics, there are certain aspects which are quite different from other fields of physics. We often meet students who find difficulty in mastering thermodynamics or statistical mechanics, lacking confidence in applying it to real problems, although they know the prin- ciples. Such difficulties are due to insufficient and inadequate training. The purpose of the present book is to provide a guide for students studying and acquiring facility in thermodynamics and statistical mechanics. Thus it contains fundamental topics, examples and a fairly large number of problems with complete solutions. The fundamental topics are rather condensed, but still they cover all of the points which are basic. This book is meant to be read- able without reference to other textbooks. By reading through these topics only, one would be able to obtain fundamental knowledge of thermo- dynamics and statistical mechanics. The examples are partly to supplement the fundamental topics, but they are primarily meant to show the reader how the principles are applied to physical problems. The problems are classified into three groups, A, B and C, in order of in- creasing difficulty. Ifa reader has enough time he may gothroughall problemsin each chapter. But, if not, it is recommended that he studies first the problems in group A throughout the whole book and then later comes back to try Band C. By just finishing group A problems, he will find himself to have obtained a much better understanding of physics. The number of group A problems is fairly large, so that he may even select about half of these and come back later to the other half. The subjects in the fundamental topics and examples which are marked by * are not needed in solving problems in group A. In this book}, thermodynamics and statistical mechanical problems are mostly limited to those of equilibrium states. It might be desirable to include kinetic methods and extensions of thermodynamics and statistical mechanics + The reader is reminded that this text is a translation of the Preface to the original Japanese edition, in which thermodynamics and statistical mechanics are contained in one volume.