> AGUIDE mie) Bases Chapman and Hall i EaA Guide to Thermodynamics J.A. RAMSAY Fellow of Queens? College, Professor of Comparative Physiology in the University of Cambridge CHAPMAN AND HALL LTD AND SCIENCE PAPERBACKS 11 NEW FETTER LANE LONDON EC4First published 1971 by Chapman and Hall Ltd., 11 New Fetter Lane, London EC4P 4EE Set in cold type by E.W.C. Wilkins and Associates Ltd., Printed in Great Britain by T. & A. Constable Ltd., Edinburgh. SBN 412 10590 X cased edition PRE 1974 - RE-CIRC SBN 412 20770 2 Science Paperback edition © 1971 J.A. Ramsay - BL All rights reserved. No part of this publication may be produced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher. w/sh This title is available in both hardback and paperback editions. The paperback edition is sold subject to the condition that it shall not, by way of trade or otherwise, be lent, re-sold, hired out, or otherwise circulated without the publisher's prior consent in any form of binding or cover other than that in which it is published and without a similar condition including this, condition being imposed on the subsequent purchaser.Contents Preface. Part 1 COInnaAwWN 10 11 Part 2 be 14 Hh 16 17 18 {Ideal Systems The Scope of Thermodynamics The Terminology of Thermodynamics Simple Mathematics in Thermodynamics The Fist Law of Thermodynamics The Thermodynamic Behaviour of an Ideal Gas The Second Law of Thermodynamics Entropy Open Systems Free Energy Equilibrium Chemical Potentials ll Real Systems The Problems of Real Systems Partial Differential Equations Scales of Temperature Maxwell’s Equations Applications in Engineering Applications in Chemistry Applications in Physics Epilogue Appendix. The Methods and Uses of Calculus Index vi 121 ab] 129 137 153 165 175 185 191 209Preface Thave already written two books and I am quite ready to admit that there was more than an element of opportunism about both of them. In the first case I had prepared, and had for some years delivered, a course of lectures on the subject. In the second case Thad to prepare myself for a drastic revision of the whole approach to the teaching of biology in Cambridge. These books were in a sense by-products of other activities and I wrote them because I thought they might sell. But this book is different. I have written it for my own fun, and as I now sit down to write this preface I have no idea whether the book will ever be published or not; and I don’t really mind if it isn’t. It came about this way. Take any textbook of biochemistry and you will find somewhere in it the equation AG = AH - TAS. Sometimes the equation is simply written down as though it were a fact that every schoolboy knows. Sometimes an attempt is made to explain the meaning of its terms; entropy is said to be a measure of the randomness of the system, and so on. Sometimes other equations are brought in to amplify and extend its meaning. But within my own experience of such books I never felt that I knew what it was all about; and eventually in some irritation I decided I must get to the bottom of it. That must have been over ten years ago. In the odd moments which I have been able to spare I have read the first few chapters of quite a number of textbooks of thermodynamics, some elementary, some a little more advanced. This was an immensely interesting and stimulating experience, but it did not at once remove the source of my irritation. Only very gradually did I perceive that there were two main ways in viPREFACE vii which the subject could be introduced: either from the observation of the natural world, leading to the formulation of the laws in mathematical terms; or by the creation, by means of definitions made meaningful by operations, of a mathematical structure which was later shown to have relevance to practical problems. It did not make it any easier for me that most textbooks seemed to make use of both lines of approach, changing at convenience from the one to the other. Being accustomed to think in concrete rather than abstract terms I found the first approach — from perpetual motion machines, cylinders and pistons, and the like —-very much more satisfactory; and, accordingly, I set myself the task of getting the subject organized consistently along these lines. Tam a great believer in the old saying that the way to discover whether you understand something is to try to explain it to someone else. So I started to write it all down in my own words, as though it was for someone else to read. I enjoyed doing this, though it brought me many humbling and chastening experiences. And then it quite suddenly occurred to me that pethaps I was not the only person who had come up against these difficulties, that perhaps there were others who had felt the same unease as I had and who might even find some comfort in reading what I had written. So this book. What, then are the sims of this book? First of all, it aims to Present the subject in a way which might appeal to the non- mathematically minded student who prefers the concrete to the abstract approach. I have tried as far as possible to introduce each new concept by means of some operation which can be visualised, by some experiment which can be carried out with a cylinder and piston or an electric cell or a van t’Hoff box, by something which can be described in words. Having first put forward the idea in words, and in a context which should be familiar, I have then sought to give it greater generality and precision by putting it into the language of mathematics. But at the same time I do not want the original operation to be lost sight of in the mathematics, and that is why I have introduced all the important concepts in the context of ideal systems. The kind of mathematical language which is adequate to describePREFACE ideal systems is not difficult to read and not difficult to translate back into words. This approach to thermodynamics is not approved of by modern authorities on the subject; by focusing attention upon ideal systems, they say, it implants misleading ideas in the mind of the student. But I am not in sympathy with the attitude towards teaching which this view implies. If one’s aim is to present the general principles of any subject to elementary students then I hold it to be not only justifiable but positively a virtue to accept the risk that the student may later have to unlearn some part of what he thinks he knows if thereby he is enabled more quickly and more easily to come to terms with what really matters. Too often the message is allowed to become obscured by that meticulous attention to strict accuracy which the writer feels is necessary to placate his own colleagues, where a straight- forward, though possibly unguarded, statement would reach the student more effectively. It is with just such a purpose in mind that I have postponed consideration of scales of temperature to Part II of the book instead of taking it up at the beginning, as is traditional; if the student thinks of temperature as no more than a reading on the scale of a mercury-in-glass thermometer let him continue in this simple faith while he takes in the new ideas of system, state and properties. One of the first discoveries that I made in my attempts to learn about this subject is that there is not one thermodynamics, but three. For physicists, for chemists and for engineers, for each there exists a special kind of thermodynamics, and with a little experience it is possible, merely by flipping over the pages of a book, to discover for which public it is intended. Once in a while one comes across a book which is intended for biologists. But I have yet to find a conveniently small book which is just about thermodynamics wherein one can discover what thermo- dynamics, per se, is about. A second aim, then, of this book is to provide an account of thermodynamics which is short, simple and general, giving some indication of the importance of thermodynamics in the main fields of science but not addressed to the devotees of any one scientific discipline. I should hasten to make it clear, however, that I have never