Modern Electrochemistry, Vol 2A : Fundamentals of Electrodics, 2nd edition

817 Pages·2000·18.47 MB·English

by  John O'M. Bockris

VOLUME 2A
MODERN
ELECTROCHEMISTRY
SECOND EDITION
Fundamentals of
Electrodics
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To J. A. V. Butler and Max Volmer
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VOLUME 2A
MODERN
ELECTROCHEMISTRY
SECOND EDITION
Fundamentals of
Electrodics
John O’M Bockris
Molecular Green Technology
College Station, Texas
Amulya K. N. Reddy
President
International Energy Initiative
Bangalore, India
and
Maria Gamboa-Aldeco
Texas A&M University
College Station, Texas
KLUWER ACADEMIC PUBLISHERS
NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW
eBookISBN: 0-306-47605-3
Print ISBN: 0-306-46166-8
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PREFACE TO THE FIRST EDITION
This book had its nucleus in some lectures given by one of us (J.O’M.B.) in a course
on electrochemistry to students of energy conversion at the University of Pennsylva-
nia. It was there that he met a number of people trained in chemistry, physics, biology,
metallurgy, and materials science, all of whom wanted to know something about
electrochemistry. The concept of writing a book about electrochemistry which could
be understood by people with very varied backgrounds was thereby engendered. The
lectures were recorded and written up by Dr. Klaus Muller as a 293-page manuscript.
At a later stage, A.K.N.R. joined the effort; it was decided to make a freshstart and
to write a much more comprehensive text.
Of methods for direct energy conversion, the electrochemical one is the most
advanced and seems the most likely to become of considerable practical importance.
Thus, conversion to electrochemically powered transportation systems appears to be
an important step by means of which the difficulties of air pollution and the effects of
an increasing concentration in the atmosphere of carbon dioxide may be met. Corro-
sion is recognized as having an electrochemical basis. The synthesis of nylon now
contains an important electrochemical stage. Some central biological mechanisms
have been shown to take place by means of electrochemical reactions. A number of
American organizations have recently recommended greatly increased activity in
training and research in electrochemistry at universities in the United States. Three
new international journals of fundamental electrochemical research were established
between 1955 and 1965.
In contrast to this, physical chemists in U.S. universities seem—perhaps partly
because of the absence of a modern textbook in English—out of touch with the
revolution in fundamental interfacial electrochemistry which has occurred since 1950.
The fragments of electrochemistry which are taught in many U.S. universities belong
not to the space age of electrochemically powered vehicles, but to the age of
vii
viii PREFACE TO THE FIRST EDITION
thermodynamics and the horseless carriage; they oftenconsist of Nernst’s theory of
galvanic cells (1891) together with the theory of Debye and Hückel (1923).
Electrochemistry at present needs several kinds of books. For example, it needs
a textbook in which the whole field is discussed at a strong theoretical level. The most
pressing need, however, is for a book which outlines the field at a level which can be
understood by people entering it from different disciplines who have no previous
background in the field but who wish to use modern electrochemical concepts and
ideas as a basis for their own work. It is this need which the authors have tried to meet.
The book’s aims determine its priorities. In order, these are:
1. Lucidity. The authors have found students who understand advanced courses
in quantum mechanics but find difficulty in comprehending a field at whose center
lies the quantummechanics of electron transitions across interfaces. The difficulty is
associated, perhaps, with the interdisciplinary character of the material: a background
knowledge of physical chemistry is not enough. Material has therefore sometimes
been presented in several ways and occasionally the same explanations are repeated
in different parts of the book. The language has been made informal and highly
explanatory. It retains, sometimes, the lecture style. In this respect, the authors have
been influenced by The Feynman Lectures on Physics.
2. Honesty. The authors have sufferedmuch themselves from books in which
proofs and presentations are not complete. An attempt has been made to include most
of the necessary material. Appendices havebeen oftenused for the presentation of
mathematical derivations which would obtrude too much in the text.
3. Modernity. There developed during the 1950’s a great change in emphasis in
electrochemistry away from a subject which dealt largely with solutions to one in
which the treatment at a molecular level of charge transfer across interfaces dominates.
This is the “new electrochemistry,” the essentials of which, at an elementary level, the
authors have tried to present.
4. Sharp variation is standard. The objective of the authors has been to begin each
chapter at a very simple level and to increase the level to one which allows a connecting
up to the standard of the specialized monograph. The standard at which subjects are
presented has been intentionally variable, depending particularly on the degree to
which knowledge of the material appears to be widespread.
5. One theory per phenomenon. The authors intend a teaching book, which acts
as an introduction to graduate studies. They have tried to present, with due admission
of the existing imperfections, a simple version of that model which seemed to them
at the time of writing to reproduce the facts most consistently. They have for the most
partrefrainedfrompresenting the detailed pros and cons of competing models in areas
in which the theory is still quite mobile.
In respect to references and furtherreading: no detailed references to the literature
have been presented, in view of the elementary character of the book’s contents, and
the corresponding fact that it is an introductory book, largely for beginners. In the
PREFACE TO THE FIRST EDITION ix
“further reading” lists, the policy is to cite papers which are classics in the development
of the subject, together withpapers of particular interest concerning recent develop-
ments, and in particular, reviews of the last few years.
It is hoped that this book will not only be useful to those who wish to work with
modern electrochemical ideas in chemistry, physics, biology, materials science, etc.,
but also to those who wish to begin research on electron transfer at interfaces and
associated topics.
The book was written mainly at the Electrochemistry Laboratory in the University
of Pennsylvania, and partly at the Indian Institute of Science in Bangalore. Students
in the Electrochemistry Laboratory at the University of Pennsylvania were kind
enough to give guidance frequently on how they reacted to the clarity of sections
written in various experimental styles and approaches. For the last four years, the
evolving versions of sections of the book have been used as a partial basis for
undergraduate, and some graduate, lectures in electrochemistry in the Chemistry
Department of the University.
The authors’ acknowledgment and thanks must go first to Mr. Ernst Cohn of the
National Aeronautics and Space Administration. Without his frequent stimulation,
including very frank expressions of criticism, the book might well never have emerged
from the Electrochemistry Laboratory.
Thereafter, thanks must go to Professor B. E. Conway, University ofOttawa, who
gave several weeks of his time to making a detailed review of the material. Plentiful
help in editing chapters and effecting revisions designed by the authors was given by
the following: Chapters IV and V, Dr. H. Wroblowa (Pennsylvania); Chapter VI, Dr.
C. Solomons (Pennsylvania) and Dr. T. Emi (Hokkaido); Chapter VII, Dr. E. Gileadi
(Tel-Aviv); Chapters VIII and IX, Prof. A. Despic (Belgrade), Dr. H. Wroblowa, and
Mr. J. Diggle (Pennsylvania); Chapter X, Mr. J. Diggle; Chapter XI, Dr. D. Cipris
(Pennsylvania). Dr. H. Wroblowa has to be particularly thanked for essential contributions
to the composition of the Appendix on the measurement of Volta potential differences.
Constructive reactions to the text were given by Messers. G. Razumney, B. Rubin,
and G. Stoner of the Electrochemistry Laboratory. Advice was often sought and
accepted from Dr. B. Chandrasekaran (Pennsylvania), Dr. S. Srinivasan (New York),
and Mr. R. Rangarajan (Bangalore).
Comments on late drafts of chapters were made by a number of the authors’
colleagues, particularly Dr. W. McCoy (Office of Saline Water), Chapter II; Prof. R.
M. Fuoss (Yale), Chapter III; Prof. R. Stokes (Armidale), Chapter IV; Dr. R. Parsons
(Bristol), Chapter VII; Prof. A. N. Frumkin (Moscow), Chapter VIII; Dr. H. Wrob-
lowa, Chapter X; Prof. R. Staehle (Ohio State), Chapter XI. One of the authors
(A.K.N.R.) wishes to acknowledge his gratitude to the authorities of the Council of
Scientific and Industrial Research, India, and the Indian Institute of Science, Banga-
lore, India, for various facilities, not the least of which were extended leaves of
absence. He wishes also to thank his wife and children for sacrificing many precious
hours which rightfully belonged to them.