This book had its nucleus in some lectures given by one ofus (J. O'M. B. ) in a course on electrochemistry to students of energy conversion at the Vniversity of Pennsylvania. It was there that he met a number of people trained in chemistry, physics, biology, metallurgy, and materials science, all ofwhom wanted to know something about electrochemistry. The concept of writing a book about electrochemistry wh ich 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 importanee. 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 effeets of an increasing concentration in the atmosphere of carbon dioxide may be met. Corrosion is recognized as having an electroehemical basis. The synthesis of nylon now contains an important electroehemical stage. Some central biological mechanisms have been shown to take place by means of electrochemical reactions. A number of Ameriean organizations have recently recommended greatly increased activity in training and research in electrochemistry at universities in the Vnited States."

In Number 20 of Modern Aspects of Electrochemistry, we present chapters whose organization is typical for the series: They start with the most fundamental aspects and then work to the more complex. Thus, Jerry Goodisman gives us an interesting contribution on a subject in which he is one of the pioneers, the electron overlap contribution to the double layer potential difference. Closely related to this theme, but not always imbued with knowledge ofit, is the electron transfertheory, treated in this volume by the experienced author A. M. Kuznetsov ofthe Frumkin Institute. H. P. Agarwal is a well-known figure in the field of faradaic rectification, which he originated, and he now teils us about the more recent thinking in the field. On the other hand, Hector D. Abruna comes relatively new to us, and his field, that of X-ray interactions with electrodes, is new, too, but probably augers the trend for the future. The photoelectrochemical reduction of CO2 , described here by Isao Taniguchi from Kumamoto University, is a subject which will have much practical importance as the greenhouse effect continues. Finally, alu mi nu m in aqueous solutions and the physics of its anodic oxide is a subject which seems ever with us, and is described in its latest guise by Aleksandar Despie and Vitaly P. Parkhutik.

Recognized experts present incisive analysis of both fundamental and applied problems in this continuation of a highly acclaimed series. Topics discussed include: * A review of the literature on the potential-of-zero charge by Trasatti and Lust. * A thorough review and discussion of nonequilibrium fluctuations in corrosion processes. * A wide-ranging discussion of conducting polymers, electrochemistry, and biomimicking processes. * Microwave (photo)electrochemistry, from its origins to today's research opportunities, including its relation to electrochemistry. * New fluorine cell design, from model development through preliminary engineering modeling, laboratory tests, and pilot plant tests. * A comprehensive account of the major and rapidly developing field of the electrochemistry of electronically conducting polymers and their applications. These authoritative studies will be invaluable for researchers in engineering, electrochemistry, analytical chemistry, materials science, physical chemistry, and corrosion science.

Recognized experts present incisive analysis of both fundamental and applied problems in this continuation of a highly-acclaimed series. Topics discussed include: * The way in which electrochemical systems may function as on a single electrode; * The foundational area of voltaic measurements at liquid interfaces; * Direct methanol fuel cells, which would avoid the unpleasant necessity faced by the current general of fuel cells - namely, using hydrogen; * Dynamic processes in molten salts; * Electrochemical techniques and Microbial Induced Corrosion (MIC).

Covering both the theoretical and applied aspects of electrochemistry, this well-known monograph series presents a review of the latest advances in the field.

Number 25 of this acclaimed series breaks new ground with articles on charge transfer across liquid-liquid interfaces, electrochemical techniques to study hydrogen ingress in metals, and electrical breakdown of liquids. Also included are articles on the measurement of corrosion and ellipsometry, bringing these older subjects up to date.

Integrating both theoretical and applied aspects of electrochemistry, this acclaimed monograph series presents a review of the latest advances in the field. The current volume includes chapters on the mechanism of nerve excitation from an electrochemical standpoint, the electronic factor in the kinetics of charge-transfer reaction, and five other subjects.

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.

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.

The present volume contains five chapters covering areas of contemporary interest in the fields of electrolyte solutions, the state of solvent molecules at electrode surfaces, charged colloid interfaces, surface chemistry of oxide electrodes and electro chemistry, and bioelectrochemistry of charge transfer complexes. The first chapter, by Barthel, Wachter, and Gores, covers the topic of conductance of nonaqueous pro tic and aprotic electro lyte solutions. This field is not only of intrinsic interest in itself, illustrating the important departures of ion-transport behavior in organic solvents from that, more well known, in water, but the information and extensive new data presented in this chapter will be of interest to those working with nonaqueous alkali-metal batteries where the conductivity and ion-association behavior of electrolytes in various solvents other than water is of great importance. The second chapter is devoted to a very fundamental and ubiquitous aspect of electrochemistry of electrodes: the state of solvent molecules, adsorbed and oriented, at their surfaces. The role of solvent adsorption and orientation in double-layer proper ties, it will be recalled, remained poorly understood until the early 1960s. This chapter, by Trasatti, gives a thorough account of the present state of knowledge of solvent orientation at electrode interfaces and of the unsuspected (until recent years) role it plays in properties of the double layer and in determining the potential profile at charged metal surfaces in solution."

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."

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.

This monograph is an attempt to present in a concise manner those aspects of the electrolytic growth of crystals considered to be of basic mechanistic significance. The accent has been put consistently on the understanding of the physical models of the processes discussed. Out of the extensive amount of information in this field, the authors have tried to abstract those systems which can be considered central, and which can, therefore, be related to the basic concepts connected with the electrodeposition of metals. In particular, stress has been laid upon consideration of atomic movements -of ions and molecules in solution, of adsorbed substances on the surface of metals, of steps on a growing crystal. Although the main stress is upon the physical picture, a number of derivations have been presented in detail. It is assumed that the reader is familiar to some degree with the concepts of electrodics; in particular, frequent reference is made to models of the electrical double layer at the metal solution interface and the transfer of charged species across it."

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.

It gives us pleasure in writing the Preface to this volume, in which we tried to bring together a number of stimulating and interesting people discussing physical electrochemistry. The first chapter, by Ashok Vijh, gives a remarkable account of electrochemistry as looked at from a physicist's point of view. Among the revelations of the chapter is that in a recent survey of leading areas in Science, two out of fifteen areas chosen were electrochemical and these two were the only chemical subjects chosen. In Mikhail Vorotyntsev's chapter, one finds a very modern study of the double layer, but tenuously connected with the simpler studies made in the safe harbor of mercury. In the pioneering chapter by Pons et al., one is looking at a cutting edge of electrochemistry at this time-the use of IR spectros copy in modes which allow the first practical determinations of the spectra of adsorbed species at the interface-an area pioneered by Pons himself. In Chapter 4, we have reached photoelectrochemistry once more, but now Tributsch speaks about what has rapidly become the major area of that topic, photoelectrocatalysis. Close to this chapter, and indeed intellectually connected with it, is that by Schmickler and Schultze about electron transfer reac tions at oxide-covered metal electrodes in which theories which are still relatively dubious for metal-solution surfaces are applied to complex systems involving oxides."

No. 29 offers new insights into the energies of activation of electrode reactions and the interfacial behavior of proteins.

Integrating both theoretical and applied aspects of electrochemistry, this acclaimed monograph series presents a review of the latest advances in the field. The current volume covers ion and electron transfer across monolayers of organic surfactants, determination of current distributions governed by Laplace's equation, and three other subjects.

Prof. Jerzy Sobkowski starts off this 31st volume of Modern Aspects of Electrochemistry with a far-ranging discussion of experimental results from the past 10 years of interfacial studies. It forms a good background for the two succeeding chapters. The second chapter is by S. U. M. Khan on quantum mechanical treatment of electrode processes. Dr. Khan's experience in this area is a good basis for this chapter, the contents of which will surprise some, but which as been well refereed. Molecular dynamic simulation is now a much-used technique in physical electrochemistry and in the third chapter Ilan Benjamin has written an account that brings together information from many recent publications, sometimes confirming earlier modeling approaches and sometimes breaking new territory. In Chapter 4, Akiko Aramata's experience in researching single crystals is put to good advantage in her authoritative article on under- tential deposition. Finally, in Chapter 5, the applied side of electrochemistry is served by Bech-Neilsen et al. in the review of recent techniques for automated measurement of corrosion. J. O'M. Bockris, Texas A&M University B. E. Conway, University of Ottawa R. E. White, University of South Carolina Contents Chapter 1 METAL/SOLUTION INTERFACE: AN EXPERIMENTAL APPROACH Jerzy Sobkowski and Maria Jurkiewicz-Herbich I. Introduction.............................................. 1 II. Molecular Approach to the Metal/Solution Interface............. 3 1. Double-Layer Structure: General Considerations .......... 3 2. Solid Metal/Electrolyte Interface.......................... 8 3. Methods Used to Study Properties ofthe Metal/Solution Interface: Role of the Solvent and the Metal............. 15 The Thermodynamic Approach to the Metal/Solution Interface 35 III.

This long-awaited and thoroughly updated version of the classic text (Plenum Press, 1970) explains the subject of electrochemistry in clear, straightforward language for undergraduates and mature scientists who want to understand solutions. Like its predecessor, the new text presents the electrochemistry of solutions at the molecular level. The Second Edition takes full advantage of the advances in microscopy, computing power, and industrial applications in the quarter century since the publication of the First Edition. Such new techniques include scanning-tunneling microscopy, which enables us to see atoms on electrodes; and new computers capable of molecular dynamics calculations that are used in arriving at experimental values. A description of the electrochemical stage - the high field region near the interface - is the topic of Chapter 6 and involves a complete rewrite of the corresponding chapter in the First Edition, particularly the various happenings which occur with organic molecules which approach surfaces in solution. The chapter on electrode kinetics retains material describing the Butler-Volmer equation from the First Edition, but then turns to many new areas, including electrochemical theories of potential-dependent gas catalysis. Chapter 8 is a new one devoted to explaining how electrochemists deal with the fast-changing nature of the electrode surface. Quantum Mechanics as the basis to electrode kinetics is given an entirely new look - up to and including considerations of bond-breaking reactions.

This long-awaited and thoroughly updated version of the classic text (Plenum Press, 1970) explains the subject of electrochemistry in clear, straightforward language for undergraduates and mature scientists who want to understand solutions. Like its predecessor, the new text presents the electrochemistry of solutions at the molecular level. The Second Edition takes full advantage of the advances in microscopy, computing power, and industrial applications in the quarter century since the publication of the First Edition. Such new techniques include scanning-tunneling microscopy, which enables us to see atoms on electrodes; and new computers capable of molecular dynamics calculations that are used in arriving at experimental values. A description of the electrochemical stage - the high field region near the interface - is the topic of Chapter 6 and involves a complete rewrite of the corresponding chapter in the First Edition, particularly the various happenings which occur with organic molecules which approach surfaces in solution. The chapter on electrode kinetics retains material describing the Butler-Volmer equation from the First Edition, but then turns to many new areas, including electrochemical theories of potential-dependent gas catalysis. Chapter 8 is a new one devoted to explaining how electrochemists deal with the fast-changing nature of the electrode surface. Quantum Mechanics as the basis to electrode kinetics is given an entirely new look - up to and including considerations of bond-breaking reactions.

Recognized experts present incisive analysis of both fundamental and applied problems in this continuation of a highly acclaimed series. Topics discussed include: A review of the literature on the potential-of-zero charge by Trasatti and Lust. A thorough review and discussion of nonequilibrium fluctuations in corrosion processes. A wide-ranging discussion of conducting polymers, electrochemistry, and biomimicking processes. Microwave (photo)electrochemistry, from its origins to today's research opportunities, including its relation to electrochemistry. New fluorine cell design, from model development through preliminary engineering modeling, laboratory tests, and pilot plant tests. A comprehensive account of the major and rapidly developing field of the electrochemistry of electronically conducting polymers and their applications. These authoritative studies will be invaluable for researchers in engineering, electrochemistry, analytical chemistry, materials science, physical chemistry, and corrosion science.

Recognized experts present incisive analysis of both fundamental and applied problems in this continuation of a highly acclaimed series. Topics discussed include: A thorough and mathematical treatment of periodic phenomena, with consideration of new theories about the transition between `order' and `chaos'; Impedance spectroscopy as applied to the study of kinetics and mechanisms of electrode processes; The use of stoichiometric numbers in mechanism analysis; The electro-osmotic dewatering of clays with important implications for the processing of industrial waste and geotechnical; stabilization; Magnetic effects in electrolytic processes and the electrolytic Hall effect; and The computer analysis and modeling of mass transfer and fluid flow. These authoritative studies will be invaluable for researchers in engineering, electrochemistry, analytical chemistry, materials science, physical chemistry, and corrosion science.

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 Pennsyl- 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 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 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. Cor- 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.

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 Pennsyl- 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 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 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. Cor- 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.

Prof. Jerzy Sobkowski starts off this 31st volume of Modern Aspects of Electrochemistry with a far-ranging discussion of experimental results from the past 10 years of interfacial studies. It forms a good background for the two succeeding chapters. The second chapter is by S. U. M. Khan on quantum mechanical treatment of electrode processes. Dr. Khan's experience in this area is a good basis for this chapter, the contents of which will surprise some, but which as been well refereed. Molecular dynamic simulation is now a much-used technique in physical electrochemistry and in the third chapter Ilan Benjamin has written an account that brings together information from many recent publications, sometimes confirming earlier modeling approaches and sometimes breaking new territory. In Chapter 4, Akiko Aramata's experience in researching single crystals is put to good advantage in her authoritative article on under- tential deposition. Finally, in Chapter 5, the applied side of electrochemistry is served by Bech-Neilsen et al. in the review of recent techniques for automated measurement of corrosion. J. O'M. Bockris, Texas A&M University B. E. Conway, University of Ottawa R. E. White, University of South Carolina Contents Chapter 1 METAL/SOLUTION INTERFACE: AN EXPERIMENTAL APPROACH Jerzy Sobkowski and Maria Jurkiewicz-Herbich I. Introduction.............................................. 1 II. Molecular Approach to the Metal/Solution Interface............. 3 1. Double-Layer Structure: General Considerations .......... 3 2. Solid Metal/Electrolyte Interface.......................... 8 3. Methods Used to Study Properties ofthe Metal/Solution Interface: Role of the Solvent and the Metal............. 15 The Thermodynamic Approach to the Metal/Solution Interface 35 III.