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64029 PREFACE The object of the present book is to provide an introduction to the principles and applications of thermodynamics for students of chemistry and chemical engineering. All too often it appears that such students tend to regard the subject as an academic and burdensome discipline, only to discover at a later date that it is a highly important tool of great prac tical value. The writers purpose has been to explain the general structure of thermodynamics, and to give some indication of how it may be used to yield results having a direct bearing on the work of the chemist. More than one hundred illustrative numerical problems are worked out in the text, and a total of about three hundred and sixty exercises of a variety of types have been included for solution by the reader. In the hope of imparting the whole subject with an aspect of reality, much of the material for this purpose has been taken from the chemical literature, to which references are given. In order to economize space, and at the same time to test the readers grasp of thermodynamics, the derivations of a number of interesting results have been set as exercises. To this extent, at least, the exercises are to be considered as part of the text, although their solution should in any event be regarded as essential to any adequate course in chemical thermodynamics. In treating the various topics in this book the particular method em ployed has been determined in each case by considerations of simplicity, usefulness and logical development. In some instances the classical, his torical approach has been preferred, but in others the discussion follows more modern lines. Whenever feasible the generalized procedures, involv ing reduced temperatures and pressures, which have been evolved in recent years chiefly by chemical engineers, are introduced. As regards statistical methods, the author feels that the time has come for them to take their place as an essential part of chemical thermodynamics. Consequently, the applications of partition functions to the determination of heat capaci ties, entropies, free energies, equilibrium constants, etc., have been intro duced into the text in the appropriate places where it is hoped their value will be appreciated. The symbols and nomenclature are essentially those which have been widely adopted in the American chemical literature however, for reasons given in the text, and in accordance with a modern trend, the Gibbs symbol M and the shorter term chemical potential are employed for the partial molar free energy. Because atmospheric pressure is postulated for the conventional standard state of a liquid, some confusion has resulted from the use of the same symbol for the standard state as for the liquid at an arbitrary pressure. Hence, the former state is indicated in the text in VI PREFAOB the usual manner, by a zero or circle, but the latter is distinguished by a small square as superscript. The writer would like to take this opportunity to acknowledge his in debtedness to certain books, namely, F. H. Macdougall, Thermodynamics and Chemistry L. E. Steiner, Introduction to Chemical Thermody namics B. F. Dodge, Chemical Engineering Thermodynamics and, in particular, G. N. Lewis and M. Randall, Thermodynamics and the Free Energy of Chemical Substances. He is also sincerely grateful to Dr. Allen E. Steam, University of Missouri, and Dr. Roy F. Newton, Purdue I diversity, for reading the manuscript of this book and for making numerous suggestions which have helped materially to clarify and improve the treat ment. Finally, the author wishes to express his thanks to his wife for reading the proofs, and for her continued aid and encouragement. SAMUEL GLASSTONE BERKELEY, CALJF. November 1946 CONTENTS CHAPTER PACE PREFACE v I. HEAT, WORK AND ENERGY 1 1. Introduction, 1 2. Temperature, 2 3. Work, Energy and Heat, 5. II. PROPERTIES OF THERMODYNAMIC SYSTEMS 14 4. Thermodynamic Systems, 14 5. Equations of State, 18. HI...