AN INTRODUCTION TO ELECTROCHEMISTRY by SAMUEL GLASSTONE. PREFACE: The object of this book is to provide an introduction to electro chemistry in its present state of development. An attempt has been made to explain the fundamentals of the subject as it stands today, de voting little or no space to the consideration of theories and arguments that have been discarded or greatly modified. In this way it is hoped that the reader will acquire the modern point of view in electrochemistry without being burdened by much that is obsolete. In the opinion of the writer, there have been four developments in the past two decades that have had an important influence on electrochemistry. They are the ac tivity concept, the interionic attraction theory, the proton-transfer theory of acids and bases, and the consideration of electrode reactions as rate processes. These ideas have been incorporated into the structure of the book, with consequent simplification and clarification in the treatment of many aspects of electrochemistry. This book differs from the au thors earlier work, The Electrochem istry of Solutions in being less comprehensive and in giving less detail. While the latter is primarily a work of reference, the present book is more suited to the needs of students of physical chemistry, and to those of chemists, physicists and physiologists whose work brings them in con tact with a variety of electrochemical problems. As the title implies, the book should also serve as an introductory text for those who in tend to specialize in either the theoretical or practical applications of electrochemistry. In spite of some lack of detail, the main aspects of the subject have been covered, it is hopedimpartially and adequately. There has been some tendency in recent electrochemical texts to pay scant attention to the phenomena at active electrodes, such as ovcrvoltage, passivity, cor rosion, deposition of metals, and so on. These topics, vihich are of importance in applied electrochemistry, are treated here at Mich length as seems reasonable. In addition, in view of tho growing interest in electrophoresis, and its general acceptance as a branch of electrochem istry, a chapter on clectrokinetic phenomena has boon included. No claim is made to anything approaching completeness in the matter of references to the scientific literature. Such reformers as arc given arc generally to the more recent publications, to review articles, and to papers that may, for one reason or another, have some special interest. References are also frequently included to indicate the sources from which data have been obtained for many of the diagrams and tables. Since no effort was made to be exhaustive in this connection, it was felt that an author index would be misleading...

Dr. Samuel Glasstone, the senior author of the previous editions of this book, was anxious to live until his ninetieth birthday, but passed away in 1986, a few months short of this milestone. I am grateful for the many years of stimulation received during our association, and in preparing this edition have attempted to maintain his approach. Previous editions of this book were intended to serve as a text for students and a reference for practicing engineers. Emphasis was given to the broad perspective, particularly for topics important to reactor design and oper ation, with basic coverage provided in such supporting areas as neutronics, thermal-hydraulics, and materials. This, the Fourth Edition, was prepared with these same general objectives in mind. However, during the past three decades, the nuclear industry and university educational programs have matured considerably, presenting some challenges in meeting the objec tives of this book. Nuclear power reactors have become much more complex, with an ac companying growth in supporting technology. University programs now offer separate courses covering such basic topics as reactor physics, thermal hydraulics, and materials. Finally, the general availability of inexpensive xv xvi Preface powerful micro-and minicomputers has transformed design and analysis procedures so that sophisticated methods are now commonly used instead of earlier, more approximate approaches."

Dr. Samuel Glasstone, the senior author of the previous editions of this book, was anxious to live until his ninetieth birthday, but passed away in 1986, a few months short of this milestone. I am grateful for the many years of stimulation received during our association, and in preparing this edition have attempted to maintain his approach. Previous editions of this book were intended to serve as a text for students and a reference for practicing engineers. Emphasis was given to the broad perspective, particularly for topics important to reactor design and oper ation, with basic coverage provided in such supporting areas as neutronics, thermal-hydraulics, and materials. This, the Fourth Edition, was prepared with these same general objectives in mind. However, during the past three decades, the nuclear industry and university educational programs have matured considerably, presenting some challenges in meeting the objec tives of this book. Nuclear power reactors have become much more complex, with an ac companying growth in supporting technology. University programs now offer separate courses covering such basic topics as reactor physics, thermal hydraulics, and materials. Finally, the general availability of inexpensive xiii xiv Preface powerful micro- and minicomputers has transformed design and analysis procedures so that sophisticated methods are now commonly used instead of earlier, more approximate approaches.

Dr. Samuel Glasstone, the senior author of the previous editions of this book, was anxious to live until his ninetieth birthday, but passed away in 1986, a few months short of this milestone. I am grateful for the many years of stimulation received during our association, and in preparing this edition have attempted to maintain his approach. Previous editions of this book were intended to serve as a text for students and a reference for practicing engineers. Emphasis was given to the broad perspective, particularly for topics important to reactor design and oper ation, with basic coverage provided in such supporting areas as neutronics, thermal-hydraulics, and materials. This, the Fourth Edition, was prepared with these same general objectives in mind. However, during the past three decades, the nuclear industry and university educational programs have matured considerably, presenting some challenges in meeting the objec tives of this book. Nuclear power reactors have become much more complex, with an ac companying growth in supporting technology. University programs now offer separate courses covering such basic topics as reactor physics, thermal hydraulics, and materials. Finally, the general availability of inexpensive xv xvi Preface powerful micro-and minicomputers has transformed design and analysis procedures so that sophisticated methods are now commonly used instead of earlier, more approximate approaches."

Das vorliegende Buch ist als Einfiihrung in das Ge biet der Kernreaktortheorie fiir Physiker, Ingenieure und aIle jene gedacht, die zum erstenmal mit Reaktor .. problemen in Beriihrung kommen. Da die Leser ganz verschiedene Voraus- setzungen mitbringen, ist hier ein ziemlich weiter Spielraum im Hinblick auf den Umfang und die Schwierigkeit desStoffes geboten. Einige Leser werdendaher gewisse Kapitel beiseite lassen wollen; das ist oft moglich, ohne die grund- satzliche Entwicklung des Stoffes zu beeintrachtigen. Die gegenwartige Form ist die Umarbeitung eines Entwurfes, der im Jahre 1950 herausgebracht wurde und sich aus den Vorlesungen entwickelt hat, die M. C. EDLUND an der Schule fiir Reaktortheorie in Oak Ridge gehalten- hat. Die Autoren beniitzen diese Gelegenheit, um ihre Dankbarkeit vielen Wissen- schaftlern gegeniiber zum Ausdruck zu bringen, deren gemeinsames Bemiihen in Verbindung mit dem Manhattan-Projekt zur Entwicklung der Ideen gefiihrt hat, die in diesem Buche diskutiert werden. 1m besonderen sollen die Beitrage von R. F. CHRISTY, C. ECKART, E. FERMI, F. L. FRIEDMAN, L. W. NORDHEIM, P. MORRISON, . G. PLACZEK, L. SZILARD, E. TELLER, A. M. WEINBilJRG, J. A. WHEELER, E. P. WIGNER und G. YOUNG erwahnt werden. Der Dank der Autoren gebiihrt auch einer Anzahl von Kollegen, die- den vorlaufigen Entwurf gelesen haben, besonders A. M. WEINBERG fiir seinen helfenden Rat und seine wertvolle Kritik.

AN INTRODUCTION TO ELECTROCHEMISTRY BY SAMUEL GLASSTONE, PREFACE The object of this book is to provide an introduction to electro chemistry in its present state of development. An attempt has been made to explain the fundamentals of the subject as it stands today, de voting little or no space to the consideration of theories and arguments that have been discarded or greatly modified. In this way it is hoped that the reader will acquire the modern point of view in electrochemistry without being burdened by much that is obsolete. In the opinion of the writer, there have been four developments in the past two decades that have had an important influence on electrochemistry. They are the ac tivity concept, the interionic attraction theory, the proton-transfer theory of acids and bases, and the consideration of electrode reactions as rate processes. These ideas have been incorporated into the structure of the book, with consequent simplification and clarification in the treatment of many aspects of electrochemistry. This book differs from the au thors earlier work, The Electrochem istry of Solutions in being less comprehensive and in giving less detail. While the latter is primarily a work of reference, the present book is more suited to the needs of students of physical chemistry, and to those of chemists, physicists and physiologists whose work brings them in con tact with a variety of electrochemical problems. As the title implies, the book should also serve as an introductory text for those who in tend to specialize in either the theoretical or practical applications of electrochemistry. In spite of some lack of detail, the main aspects of the subject have been covered, it is hopedimpartially and adequately. There has been some tendency in recent electrochemical texts to pay scant attention to the phenomena at active electrodes, such as ovcrvoltage, passivity, cor rosion, deposition of metals, and so on. These topics, vihich are of importance in applied electrochemistry, are treated here at Mich length as seems reasonable. In addition, in view of tho growing interest in electrophoresis, and its general acceptance as a branch of electrochem istry, a chapter on clectrokinetic phenomena has boon included. No claim is made to anything approaching completeness in the matter of references to the scientific literature. Such reformers as arc given arc generally to the more recent publications, to review articles, and to papers that may, for one reason or another, have some special interest. References are also frequently included to indicate the sources from which data have been obtained for many of the diagrams and tables. Since no effort was made to be exhaustive in this connection, it was felt that an author index would be misleading...

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, involving 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 Idiversity, 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...