John Bockris – författare

This volume presents plenary lectures and invited papers that Were delivered during the Fourth Australian Conference on Electro­ chemistry held at The Flinders University of South Australia, 16-20th February 1976. EZeat~oahemi8try fo~ a Futu~e Soaiety was selected as the Conference theme since the organising committee were mindful of the rapid change in technological perspective which the world now faces. We no longer have a prospect of uncontrolled spontaneous expansion and change as the result of technological enterprise. Rather, we face the task of attempting to reach a state of very restricted growth. In the next few decades special accent must be placed on minimizing pollution and maximizing the efficient utilization of all available energy sources. With this in mind, the Conference organisers considered that a conventional electrochemistry symposium, with its divisions into the various academic aspects, would be less relevant than a meeting devoted to aspects of electrochemistry which may underlie parts of the new and necessary technology for the future state of affairs. What has actually been achieved by the Conference organisers is a balance between the ideals expressed and the resulting response from electrochemists. This response has a bias which reflects the dominance of certain resources, e.g. metallic minerals, within Australia. Consequently, the papers included in T~ends in EZeat~o­ ahemist~ cover subjects which are of both global and local concern.

In this book, the objective has been to set down a number of questions, largely numerical problems, to help the student of electrochemical science. No collection of problems in electrochemistry has previously been published. The challenge which faces the authors of such a book is the breadth of the material in modern electrochemistry, and the diversity of backgrounds and needs of people who may find a "problems book" in electrochemistry to be of use. The general intention for Chapters 2-11 has been to give the first ten questions at a level which can be dealt with by students who are undergoing instruction in the science of electrochemistry, but have not yet reached graduate standard in it. The last two questions in Chapters 2-11 have been chosen at a more advanced standard, corre­ sponding to that expected of someone with knowledge at the level of a Ph.D. degree in electrochemistry.

This volume contains eight chapters covering a wide range of topics: ultrasonic vibration potentials, impedance measurements, photo­ electrochemical kinetics, chlorine production, electrochemical behavior of titanium, structural properties of membranes, bioelec­ troche mistry, and small-particle effects for electrocatalysis. Chapter 1, contributed by Zana and Yeager, discusses the little used but potentially important area of ultrasonic vibration potentials. The authors review the historical literature and the associated theoretical equations. They continue by discussing various aspects of the experimental technique and close with a review of the existing studies. They conclude by noting that vibra­ tion potentials may be useful for determining the effects of various agents on colloidal suspensions found in such important industries as paper production. Chapter 2 is a review of impedance techniques, written by Macdonald and McKubre. The authors include not only derivations of various impedance functions for electrochemical systems but also particularly useful discussions of instrumental methods. The authors close with an interesting claim: "the distribution of current and potential within a porous battery or fuel-cell electrode and within 'flow-through' electrodes is best analyzed in terms of the frequency dispersion of the impedance." Chapter 3, by Khan and Bockris, is a timely review of photo­ electrochemical kinetics and related devices. Their work begins by reviewing critically important papers on photoelectrochemical kinetics. They continue by presenting detailed discussions concern­ ing the conceptual ideas of the semiconductor-solution interface.

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 Pennsylvania. 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 fresh start 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 trans­ portation 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. Corrosion 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.

Of the societal ills which are recognized as present in the Western countries during the 1970's, pollution of air and water is among the first. Whether the breathing of noxious gases acts biochemically as a source of mental irritation is not yet known. But it is not in doubt that reduction of the grime, smog, fouled water, and acrid air would lead to an increase in a feeling of well-being. Nor is it speculative to state that a reversal of the present trend to poison the atmosphere and the water is essential if man is to survive in a technological society. It was partly the lack of realization of the intrinsic nature of over­ potential in electrochemical reactions, * and hence the failure of the early fuel cells to come up to expectations, which led engineers at the turn of the century to rely upon the combustion of oil and coal for the production of energy, with the associated era of increasing atmospheric pollution.

The present decade might be described as one in which man in the affluent countries is finally realizing that there is a bill to pay at the end of the feast-a feast at which he has eaten without inhibition, without knowing there was any need for inhibition. But now, with the situation fully clear, there is a strange non­ plussedness about man's reactions. More oil wells are sought, and clean-up packages are proposed for the same old cars. There is no real awareness yet that this is the end of an era, that quite new technologies have to be built up, and that the time remaining for this is a shatteringly short 15-30 years. However, there are sources of energy other than the fossil fuels. Oil and natural gas will run out (i.e., become too expensive) in any case during the next two or three decades. There seems little point in waiting until fuel is actually rationed and cars can only be used to move from home through smog to work before we change to these new and clean sources. The time to start the change is now, for there is much to be done.

It is now time for a comprehensive treatise to look at the whole field of electrochemistry. The present treatise was conceived in 1974, and the earliest invitations to authors for contributions were made in 1975. The completion of the early volumes has been delayed by various factors. There has been no attempt to make each article emphasize the most recent situation at the expense of an overall statement of the modern view. This treatise is not a collection of articles from Recent Advances in Electrochemistry or Modern Aspects of Electrochemistry. It is an attempt at making a mature statement about the present position in the vast area of what is best looked at as a new interdisciplinary field. Texas A & M University J. O'M. Bockris University of Ottawa B. E. Conway Case Western Reserve University Ernest Yeager & M University Texas A Ralph E. White Preface to Volume 2 This volume brings together some dozen processes well known to the electro­ chemist and treats them according to their various degrees of importance. The production of hydrogen is one of the more important processes, particularly with respect to the prospects of a hydrogen economy. No one would doubt, however, that the most commercially important electrochemical processes at the present time are the production of aluminum and of chlorine. Each of these processes has a separate chapter devoted to it.