The mechanism of an elementary act is undoubtedly one of the most fundamental problems of chemical and, in particular, electro chemical kinetics. Although this problem has fascinated scientists for quite a long time, it was only in the late fifties and early sixties that it began to be actively investigated for charge transfer reactions. Owing to the development of new methods in the analysis of this problem, significant advancements were made in theoretical as well as experimental studies. These investigations showed that the physical mechanism of charge transfer in all processes including heterogeneous electrochemical and homogeneous chemical and bio chemical processes is basically the same. Hence, the results ob tained in the field of electrochemical kinetics are relevant to the understanding of homogeneous chemical reactions as well. This book endeavors to summarize the results of investigations carried out during the last two decades. It is based on the author's monograph "Electrode Reactions: The Mechanism of an Elementary Act" (Nauka, 1979). As compared to the first version, the book has been considerably revised and enlarged not only to include a large body of data published between 1978 and 1982, but also to analyze in detail the links between electrochemical and homogeneous, in particular enzymatic, kinetics. As a result, a new chapter has been added to the book. The change in the title reflects the fact that the material contained in the book is not restricted to an investigation of purely electrochemical problems."

This volume contains five chapters covering four topics of current research interest: splitting of water, lithium batteries, intercalation, and fundamental aspects of electrode processes. Two chapters are devoted to splitting of water. The first chapter, by Gutmann and Murphy, presents a comprehensive review of the classical methods of splitting water by electrolysis and also presents some novel techniques for splitting water. Chapter 2, by Gratzel, surveys the current research being done on water splitting using visible light. Two chapters are included that deal with the timely topics of lithium batteries and intercalation. The first, Chapter 3 by Marincic, presents a practical guide to the recent development of lithium batteries, while the second, Chapter 4 by McKinnon and Haering, presents and discusses various theoretical approaches to inter calation. The last chapter in the book, Chapter 5 by Khan, presents a survey of many of the fundamental concepts and misconceptions of electrode kinetics as applied to semiconductors in particular."

This book has been planned and written by Dr. Hine with his knowledge and experience in electrochemical science and engineering for over thirty years since he joined with me at Kyoto University in 1948. This book is unique and is useful for engineers as well as scientists who are going to work in any interdisciplinary field connected with elec trochemistry. Science is sure to clarify the truth of nature as well as bring prosperity and an improvement to the welfare of human beings. The origin of the word "science" is the same as of "conscience," which means the truth of our heart. When we consider a scientific and technological subject, first we classify it into the components and/or factors involved, and then we clarify them individually. Second, we combine them to grasp the whole meaning and feature of the subject under discussion. Computers may help us greatly, but how to establish the software that will be most desirable for our purposes is of great importance. We need to make these efforts ourselves, and not decorate with borrowed plumes. With this concept in mind, this book is attractive because the author describes the basic science in electrochemistry and practice, and discusses the electrochemical engineering applications as a combination of science and technology."

This volume contains the papers presented at the UNESCO Scientific Forum on Chemistry in the Service of Mankind - Electrochemistry in Research and Development, held in Paris, June 4-6, 1984. Electrochemistry is concerned with the way electricity produces chemical changes and in turn chemical changes result in the production of electricity. This interaction forms the basis for an enormous variety of processes ranging from heavy industry through batteries to biological phenomena. Although there are many established applications, modern research has led to a great expansion in the possibilities for using electrochemistry in exciting future developments. To encourage this progress, UNESCO has set up an Expert Committee on Electrochemistry and its Applications in the European and North American region, which has already held a number of meetings devoted to specific topics. To achieve a synthesis of the main directions of development and to demonstrate the importance of these for the needs of our modern society, the Expert Committee organized a Forum on Electrochemistry in Research and Development. The object of this was to assess the future trends in research and development and to establish a dialogue between experts in electrochemistry and their colleagues in the many other disciplines which can make use of electrochemistry. The Forum was also intended to present electrochemistry and its applications in a form accessible to non-specialists so that science policy-makers will be aware of the potentialities of this subject for the future needs of mankind.

The present volume is comprised of six chapters covering topics having both fundamental and substantial applied significance in electrochemistry: ion-exchange membrane behavior, corrosion and metal deposition, semiconductor charge injection, and the electro- catalytic properties of carbon. In the first chapter, Verbrugge and Pintauro examine transport models for ion-exchange membranes using approaches from the direction of electrochemical thermodynamics of irreversible proces- ses and others. The properties ofth~ models are examined quantita- tively in some mathematical detail. Drazic, in Chapter 2, gives an up-to-date account of advances in our knowledge of the "active" dissolution of iron in corrosion processes and the accompanying processes of H2 evolution and H sorption. The important process of O reduction in iron corrosion 2 is also considered, together with the more controllable aspect of anodic dissolution and cathodic deposition, as well as the influence of anions on the dissolution kinetics of iron in aqueous medium. An important aspect of metal plating technology is the use of a modulated or pulsed-current regime to provide better control over deposit morphology. In two chapters, one by Popov and Mak- simovic and the other by Pesco and Cheh, complementary aspects of this important technique are examined in detail: from the theo- retical electrode-kinetic direction, taking into account the important nonsteady diffusion situation, and from the practical direction of examining the morphologies of electrodeposits generated under various AC modulated or pulsed-current regimes.

As stated by Buckminster Fuller in Operation Manual for Spaceship Earth, "Synergy is the behavior of whole systems unpredicted by separately observed behaviors of any of the system's separate parts." In a similar vein, one might define an intellectual synergy as "an improvement in our understanding of the behavior of a system unpredicted by separately acquired viewpoints of the activities of such a system." Such considerations underlie, and provide a motivation for, an interdisciplinary approach to the problem of unraveling the deeper mysteries of cellular metabolism and organization, and have led a number of pioneering spirits, many represen ted in the pages which follow, to consider biological systems from an elec trochemical standpoint. is itself, of course, an interdisciplinary branch of Now electrochemistry science, and there is no doubt that many were introduced to it via Bockris and Reddy's outstanding, wide-ranging and celebrated textbook Modern Electrochemistry. If I am to stick my neck out, and seek to define bioelec trochemistry, I would take it to refer to "the study of the mutual interac tions of electrical fields and biological materials, including living systems.""

The present volume is the second in a two-volume set dealing with modelling and numerical simulations in electrochemistry. Emphasis is placed on the aspect of nanoelectrochemical issues. It seems appropriate at this juncture to mention the n- growing body of opinion in some circles that George Box was right when he stated, three decades ago, that "All models are wrong, but some are useful." Actually, when the statement itself was made it would have been more appropriate to say that "All models are inaccurate but most are useful nonetheless." At present, however, the statement, as it was made, is far more appropriate and closer to the facts than ever before. Currently, we are in the midst of the age of massively abundant data. Today's philosophy seems to be that we do not need to know why one piece of information is better than another except through the statistics of incoming and outgoing links between information and this is good enough. It is why, both in principle and in practice, one can translate between two languages, without knowledge of either. While none of this can be ignored, and it may even be true that "All models are wrong and increasingly you can succeed without them" the traditional approach of scienti?c modelling is still the order of the day. That approach may be stated as hypothesize - measure - model - test. It is in this light that the present volume should be viewed.

The intention of this monograph has been to assimilate key practical and theoretical aspects of those spectroelectrochemical techniques likely to become routine aids to electrochemical research and analysis. Many new methods for interphasial studies have been and are being developed. Accordingly, this book is restricted in scope primarily to in situ methods for studying metal! electrolyte or semiconductor! electrolyte systems; moreover, it is far from inclusive of the spectroelectrochemical techniques that have been devised. However, it is hoped that the practical descriptions provided are sufficiently explicit to encourage and enable the newcomer to establish the experimental facilities needed for a particular problem. The chapters in this text have been written by international authorities in their particular specialties. Each chapter is broadly organized to review the origins and historical background of the field, to provide sufficiently detailed theory for graduate student comprehension, to describe the practical design and experimental methodology, and to detail some representative application examples. Since publication of Volume 9 of the Advances in Electrochemistry and Electrochemical Engineering series (1973), a volume devoted specifically to spectroelectrochemistry, there has been unabated growth of these fields. A number of international symposia-such as those held at Snowmass, Colorado, in 1978, the proceedings of which were published by North-Holland (1980); at Logan, Utah in 1982, published by Elsevier (1983); or at the Fritz Haber Institute in 1986-have served as forums for the discussion of nontraditional methods to study interphases and as means for the dissemination of a diversity of specialist research papers.

Some time ago a group of present and former collaborators of Professor John O'M. Bock ris, following a suggestion by Professor J. D. Mackenzie (Los Angeles), conceived the idea of an International Symposium devoted to reviewing the active and developing aspects of the science of electrochemistry. From this beginning has sprung the "Electrochemistry Symposium-The Past Thirty and the Next Thirty Years," which took place at Imperial College, London, from April 3-6, 1975. The plan for this symposium is unusual, since it features pairs of invited addresses, one to summarize the "state of the art" and the other to suggest directions for future re search in particular aspects of electrochemistry. This volume of proceedings gives these papers in their fmal, considered, and fully referenced form, arranged in the sequence of their delivery at the symposium. Also in cluded are introductory addresses given by Professor Ubbelohde, Professor Frumkin, Dr. Egan, and Dr. Inman. Both aspects of nearly every topic, plus the discussions, are integrated in a Report or Summary. A synopsis of the matters raised at the symposium and prepared by Professor John O'M. Bockris closes this volume. The cooperation of Plenum Press, New York, is gratefully acknowledged.

This volume contains selected presentations of the IUTAM Symposium on Combustion in Supersonic Flows' held in Poitiers at the Ecole Nationale Superieure de Mecanique et d'Aerotechnique (ENSMA) from 2 to 6 October 1995. The presentations focus on four main topics related to combustion in supersonic streams and practical issues relevant to the development of new propulsion systems: fundamental studies of premixed and unpremixed combustion, fluid dynamics aspects of supersonic combustion, practical systems including Scramjet, Ramaccelerators and Pulsed Detonation Engines, and the application of detonation to propulsion. Important progress has been made in the understanding of local mechanisms which allow combustion to be stabilized in a supersonic flow; in particular, various mechanisms controlled by mixing, chemical kinetics, viscous heating and shock waves are now well identified. Despite the difficulty of developing experimental work on supersonic combustion, a good set of experimental data is now available, allowing validation of theoretical analysis and models. The main aspects of modelling of turbulent combustion in high speed flows were discussed, including the influence of turbulent fluctuations on the chemistry-controlled phase of combustion and the applicability of flamelet models to high speed flows. The full range of numerical approaches is covered including Direct Numerical Simulation, Large Eddy Simulation, k-epsilon and shock tracking methods. A considerable effort has been made to generalize these methods to the treatment of supersonic reactive flows and to develop new numerical methods taking into account the most recent theoretical work and a better understanding of the underlying physics."

Electrified interfaces span from metaVsemiconductor and metaVelectrolyte interfaces to disperse systems and biological membranes, and are notably important in so many physical, chemical and biological systems that their study has been tackled by researchers with different scientific backgrounds using different methodological approaches. The various electrified interfaces have several common features. The equilibrium distribution of positive and negative ions in an electrolytic solution is governed by the same Poisson-Boltzmann equation independent of whether the solution comes into contact with a metal, a colloidal particle or a biomembrane, and the same is true for the equilibrium distribution of free electrons and holes of a semiconductor in contact with a different conducting phase. Evaluation of electric potential differences across biomembranes is based on the same identity of electrochemical potentials which holds for a glass electrode and which yields the Nernst equation when applied to a metal/solution interface. The theory of thermally activated electron tunneling, which was developed by Marcus, Levich, Dogonadze and others to account for electron transfer across metaVelectrolyte interfaces, is also applied to light induced charge separation and proton translocation reactions across intercellular membranes. From an experimental viewpoint, the same electrochemical and in situ spectroscopic techniques can equally well be employed for the study of apparently quite different electrified interfaces.

The origin of this book lies in a time before one of the authors (J. O'M. B.) left the University of Pennsylvania bound for the Flinders University. His collaboration with Dennis Matthews at the University of Pennsylvania had contributed a singular experimental datum to the quantum theory of elec trode processes: the variation of the separation factor with potential, which could only be interpreted in terms of a quantum theory of electrode kinetics. The authors came together as a result of grad~ate work of one of them (S. U. M. K.) on the quantum mechanics and photo aspects of elec trode processes, and this book was written during a postdoctoral fellowship held by him at the Flinders University. Having stated the book's origin, it is worthwhile stating the rational izations the authors had for writing it. Historically, quantization in elec trochemistry began very early (1931) in the applications of the quantum theory to chemistry. (See the historical table on pages xviii-xix.) There was thereafter a cessation of work on the quantum theory in electrochemistry until a continuum dielectric viewpoint, based on Born's equation for solvation energy, began to be developed in the 1950s and snowballed during the 1960s.

There is no doubt that the field of artificial membrane transport using synthetic ionophores has advanced remarkably in the past 15 years due primarily to the synthesis of new ionophores. Even though the theoretical framework substantially predated this activity, the merging of theory with transport experiment has often been sketchy. The purpose of this outline has been to examine key examples to illustrate the underlying principles and to suggest how experimental variables dominate the results obtained. To a very good approximation the assumption of a "diffusion" regime is often justified, is easily confirmed experimentally and provides a clear framework for exploitation of the inherent selectivity of a given ionophore. Thus for synthetic chemists who wish a "quick and nasty" experiment to examine the question of selectivity, the recipe is clear: a mixture containing all ions of interest in a standard experiment for each ligand of interest using a moderately stirred (100-200 rpm) cell and analysis of the mixture produced on the OUT side of the cell at a fixed, small extent of transport. Together with duplicates and controls, this modest set of experiments will place the results on an unambiguous footing from which clear conclusions about each ionophore's characteristics are readily obtained. For those with more detailed interests in the transport process the demands are correspondingly higher.

This book originated out of the papers presented at the special symposium, "Electrochemistry in Transition-From the 20th to the 21st Century," scheduled by the Division of Colloid and Surface Science during the American Chemical Society meeting in Toronto. The symposium was in honor of Professor J. O'M. Bockris, who received the ACS award on "The Chemistry of Contemporary Technological Problems" (sponsored by Mobay Corporation) during this meeting and who also reached his 65th birthday in the same year. The symposium was of a multidisciplinary nature and encompassed the fields of theoretical and experimental elec trochemistry, surface science, spectroscopy, and electrochemical technology. The symposium also had an international flavor in that the participants represented several countries Australia, Belgium, Canada, Chile, England, Japan, Korea, the Netherlands, Poland, Switzer land, Venezuela, Yugoslavia, and the United States. The symposium was graciously sponsored by the ACS (Petroleum Research Fund and Division of Colloid and Surface Science), Alcan International, Dow Chemical Company, EG&G, Electrolyzer Corporation, Exxon, General Electric Company, IBM, Institute of Gas Technology, International Association of Hydrogen Energy, Johnson Matthey, Inc., Kerr-McGee Corporation, Medtronics, and Texas A&M University (Center for Electrochemical Systems and Hydrogen Research and the Hampton Robinson Fund). The "theme" of the papers presented at the symposium covered not only significant contributions made to electrochemistry in the twentieth century, but also "New Horizons in Electrochemistry" for the twenty-first century. Thus, the scientists who presented papers were invited to contribute chapters to this book, having the same titles as the symposium."

The necessity for a better understanding of the basic processes that determine the operation of fuel cells became evident during the devel opment of practical units in the last three decades. The search for efficient electrocatalysts in low-temperature fuel cells intensified the general study of the nature and the role of the electrode material. Re search on the complex mechanisms of the anodic oxidation of different fuels and of the reduction of molecular oxygen on solid electrodes was stimulated, and the strong influence of adsorbed species on the electrode reaction in question was investigated. Suitable electrolytes had to be found for the high-temperature fuel cells. The use of electrodes with large internal surface lead to the development of models of porous electrode. structures and to the mathematical analysis of the operation of these models under certain conditions. While the chapters I to III introduce the reader to the general field offuel cells, the progress made in the understanding of the basic problems in the electrochemistry of fuel cells since the end of the second world war is reviewed in chapters IV to XVI of this monograph. In contrast, the technological aspects necessary for the development of practical units are not covered here. The open literature published as books or as papers in scientific journals has been considered up to the time of the writing of the final draft of the specific chapter, at least till the end of 1967."

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 Texas A & M University Ralph E. White Preface to Volume 8 Experimental methods in electrochemistry are becoming more diverse. This volume describes many of the new techniques that are being used as well as some of the well-established techniques. It begins with two chapters (1 and 2) on electronic instrumentation and methods for utilization of microcomputers for experimental data acquisition and reduction. Next, two chapters (3 and 4) on classical methods of electrochemical analysis are presented: ion selective electrodes and polarography.

This volume is concerned with methods that are available for the calculation of for mation constants, in particular computational procedures. Although graphical meth ods have considerable value in the exploration of primary (raw) data they have been overtaken by computational methods, which, for the most part, take primary data and return the refined formation constants. Graphical methods are now considered com plementary to these general computational procedures. This volume brings together programs that span the lifetime of computer-assisted determination of formation constants. On one hand the reader will find listings of programs that are derived from LETAGROP (b.l961) and the GAUSS-G/SCOGS (b. 1962) families. On the other hand programs are presented that are the newest mem bers of the SCOGS lineage and from the on-going MINIQUAD series. One program is presented that describes a computational approach to the classical Hedstrom Osterberg methods; another that takes care of electrode calibration in a simple yet rigorous manner. Potentiometry and spectrophotometry are the most popular experimental tech niques for equilibrium studies, and the programs in this volume reflect this. Four programs handle potentiometric data, two will process spectrophotometric data, and one makes use of both types of data separately or in combination."

Mechanism of charge transport in organic solids has been an issue of intensive interests and debates for over 50 years, not only because of the applications in printing electronics, but also because of the great challenges in understanding the electronic processes in complex systems. With the fast developments of both electronic structure theory and the computational technology, the dream of predicting the charge mobility is now gradually becoming a reality. This volume describes recent progresses in Prof. Shuai's group in developing computational tools to assess the intrinsic carrier mobility for organic and carbon materials at the first-principles level. According to the electron-phonon coupling strength, the charge transport mechanism is classified into three different categories, namely, the localized hopping model, the extended band model, and the polaron model. For each of them, a corresponding theoretical approach is developed and implemented into typical examples.

Soot Formation in Combustion represents an up-to-date overview. The contributions trace back to the 1991 Heidelberg symposium entitled "Mechanism and Models of Soot Formation" and have all been reedited by Prof. Bockhorn in close contact with the original authors. The book gives an easy introduction to the field for newcomers, and provides detailed treatments for the specialists. The following list of contents illustrates the topics under review:

This is a book about things in magnetism that interest me. I think that these are important things which will interest a number of other chemists. The restriction is important, because it is difficult to write well about those things which are less familiar to an author. In general, the chemistry and physics of coordination compounds are what this book is about. Magnetochemistry is the study of the ground states of metal ions. When the ions are not interacting, then the study of single-ion phenomena is called paramagnetism. When the metal ions interact, then we are concerned with collective phenomena such as occur in long-range ordering. Several years ago, Hans van Duyneveldt and I published a book that explored these subjects in detail. Since that time, the field has grown tremendously, and there has been a need to bring the book up to date. Furthermore, I have felt that it would be useful to include more subsidiary material to make the work more useful as a textbook. This book is the result of those feelings of mine.

The major problem facing new energy conversion and storage technologies remains device ef?ciency. Projects based on nanostructured materials can yield improved performance in devices involving electrochemical reactions and heterogeneous catalysis, such as fuel and solar cells, batteries, etc. Nanoscale structures drama- cally alter the surface reaction rates and electrical transport throughout the material, causing a dramatic improvement in energy storage, conversion, and generation. Furthermore, the design of nanoscale materials to be applied in alternative energy devices is a predictable way to develop a wide range of new technologies for a more sustainable future. Therefore, the goal of this book is to present basic fundamentals and the most relevant properties of nanostructured materials in order to improve alternative energy devices. This book begins with a chapter by Gratzel .. summarizing the use of mesoscopic thin ?lms and hybrid materials in the development of new kinds of regenerative photoelectrochemical devices. Applications include high-ef?ciency solar cells. In chapter two, Ribeiro and Leite describe assembly and properties of nanop- ticles. The chapter presents a review on the properties and main features of nanoscale materials, emphasizing the dependence of key properties on size for energy purposes. A general description is also given of nanoparticle synthesi- tion methods (mainly oxides), focusing on advances in tailoring controlled shape nanostructures.

Bioenergetics, the topic of volume 5 of this Series, is concerned with the energetics, the kinetics, and the mechanisms of energy conversion in biological systems. This phenomenon can be investigated on diffe rent levels of complexity. On a global level the role of biological pro cesses for the steady state of our enviroment is considered. At the physiological level, the relation between energy input and the physiolo gical state of an organism is of interest, while at the cellular level the biochemical pathways for degradation and synthesis of all relevant substrates is investigated. At present the majority of bioenergetic stu dies pertain to the molecular level. The processes in a cell are cataly zed by a large number of proteins called enzymes. The enzymes in volved in energy transduction can be considered as molecular ma chines which transform energy from one form into another, or transfer energy from one process to another. Living systems operate far from equilibrium and are open in the ther modynamic sense, i. e. they exchange energy and matter with the sur roundings. Chapter 1 presents the principles of non equilibrium thermo dynamics applied to biological systems. About 0. 05% of the energy from the sunlight which reaches the surface of the earth is used by plants and algae as well as some bacteria to synthesize organic com pounds, and thus supplies all organisms with the energy necessary for life."

This volume of Modern Aspects of Electrochemistry contains six chapters. The first four chapters are about phenomena of interest at the microscopic level and the last two are on phenomena at the macroscopic level. In the first chapter, Uosaki and Kita review various theoretical models that have been presented to describe the phenomena that occur at an electrolyte/ semiconductor interface under illumination. In the second chapter, Orazem and Newman discuss the same phenomena from a different point of view. In Chapter 3, Bogus lavsky presents state-of-the-art considerations of transmembrane potentials and other aspects of active transport in biological systems. Next, Burke and Lyons present a survey of both the theoretical and the experimental work that has been done on hydrous oxide films on several metals. The last two chapters cover the topics of the production of chlorine and caustic and the phenomena of electrolytic gas evol ution. In Chapter 5, Hine et al. describe the engineering aspects of the three processes used in the chi or-alkali industry, and in Chapter 6, Sides reviews the macroscopic phenomena of nucleation, growth, and detachment of bubbles, and the effect of bubbles on the conduc tivity of and mass transfer in electrolytes.

The holding of an Advanced Study Institute on the topic of "Solid State Batteries" at this time represented a logical progression in a series of NATO-sponsored events. Summer Schools at Belgerati, Italy in 1972 and Ajaccio, Corsica in 1975 on the topic of "Solid -State IOllics" dealt with fundamental aspects of solid-state electro chemistry and materials science. The application of specific solid ionic conductors played a significant role in the Science Committee Institute on "Materials for Advanced Batteries" held at Aussois, France in 1979. Interest in these and related fields has grown substantially over this period, and is sustained today. Research and development programmes exist within universities, governmental research laboratories and industry, worldwide and a series of international conferences and collaborations have been set up. Advanced batteries, both secondary and primary, have a potentially important role o play in the development of many areas of tech nology in the late 20th century and beyond. Applications include stationary storage, vehicle traction and remote power sources, as well as industrial and domestic cordless products and consumer and military electronics. The concept of an all-so lid-state battery is not new but, until recently, their performance has precluded their use in other than specialist low power, primary, applications. Recent materials' developments, however, make the solid-state battery a real possibility in all of the application sectors mentioned above. Further, such cells offer many attractive features over alternative present-day and advanced systems."