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.

We enthusiastically welcome this opportunity to introduce this major work of Gurevich, Pleskov, and Rotenberg to English-speaking readers since photoelectrochemistry has, in recent years, become very significant for modern energy transfer and energy conversion phenomena. While having its roots in early electrochemistry, this field, in its modern aspects, has had an important impact on knowledge of the production and state of solvated electrons and on photoassisted electrolysis at semiconductors. Photoeffects resulting in electron emission into solution have also given rise to new ways of understanding double-layer structure and measuring potentials of zero charge. Electrochemical photoemission studies have added to and comple- mented the literature of solvated electron chemistry arising from experiments with high-energy radiation. The authors' treatment of photoelectron emission phenomena at metal/ solution interfaces is thorough and quantitative and, we believe, will con- stitute a landmark in the development of this fundamentally interesting and practically important area of electrochemistry and photophysics. H. Wroblowa B. E. Conway v Foreword A characteristic feature of modern electrochemistry is the continually broadening utilization of nontraditional methods and development of new directions of research. A number of such approaches are based on illumina- tion techniques. First, irradiation is used in electrochemistry mainly as a research tool. Mention should be made here of methods such as electro- reflection, ellipsometry, internal reflection spectroscopy, interferometry of surface layers, and other techniques firmly established in experimental electrochemistry. Second, light directly affects electrode processes. In- vestigation of the latter phenomenon is the subject of photoelectrochemistry.

The idea of an "Advanced Study Institute" on the theme of electrode reactions on solid electrolytes was put forward by Dr. J. Dupuy at the meeting of the International Society for Electrochemistry in Eindhoven in September 1973. Through Dr. Dupuy, the Solid State Physics Department of Lyons University offered the Institute possibilities of accommodation in Corsica that seemed particularly tempting. The subject matter appealed to a number of people for a variety of reasons. A great deal of development work on applications comes up against interface phenomena which appreciably reduce anticipated performances. Numerous potential applications of specific electrodes or gauges appear that would benefit from a more systematic approach. From a more fundamental viewpoint, interface phenomena on ionic crystals are the subject of indepen dent investigations in quite distinct research fields such as solid state physics and electrochemistry. The choice of an interpretation from among the different models available is very often not a straightforward matter, and an attempt to promote a synthesis by bringing together the proponents of the various "schools" could not fail to be rewarding.

The storage of electroenergy is an essential feature of modem energy technologies. Unfortunately, no economical and technically feasible method for the solution of this severe problem is presently available. But electrochemistry is a favourite candidate from an engineering point of view. It promises the highest energy densities of all possible alternatives. If this is true, there will be a proportionality between the amount of electricity to be stored and the possible voltage, together with the mass of materials which make this storage possible. Insofar it is a matter of material science to develop adequate systems. Electricity is by far the most important secondary energy source. The present production rate, mainly in the thermal electric power stations, is in the order of 1.3 TW. Rechargeable batteries (RB) are of widespread use in practice for electroenergy storage and supply. The total capacity of primary and rechargeable batteries being exploited is the same as that of the world electric power stations. However, the important goal in the light of modem energy technology, namely the economical storage of large amounts of electricity for electric vehicles, electric route transport, load levelling, solar energy utilization, civil video & audio devices, earth and spatial communications, etc. will not be met by the presently available systems. Unless some of the new emerging electrochemical systems are established up to date, RB's based on aqueous acidic or alkali accumulators are mainly produced today.

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 field of Supramolecular chemistry has reached a high level of sophistication and maturity, especially in the last 5-10 years. The sophistication is primarily evident in the highly complex chemical architectures that have been synthesized to accomplish specific functions such as selective binding and transport of substrates, in catalysis, and for the formation of assemblies, to name just a few of the applications. Many other molecular structures have been synthesized to form unusual materials with interesting and/or useful properties. From this point of view, the field is mature, as would have been anticipated from its historical development, starting in 1967 with Pedersen and the crown ethers. Since that time, the field has evolved mainly from a synthetic organic perspective. There are notable exceptions to this statement, but in general it holds true that the major advances were made in the laboratories of organic chemists with considerable topological insight. by The design and synthesis of the molecules was also partly guided physical insight provided by measurements and calculations done by physical chemists. As a consequence, many chemical systems were synthesized in relatively small amounts to afford their full characterization but not in large enough quantities to fully explore their intended properties or structures. Thus in the decades of the 70's and 80's physical chemists played an important role in guiding the future directions in the field, providing needed structural and energetic information and providing improved experimental designs.

This book consists of contributions by participants in the Symposium "Spectroscopic and Electrochemical Characterizat.ion of Solute Species in Non~Aqueous Solvents" which took place at the American Chemical Society Meeting, Division of Analytical Chemistry, August 31 and September I, 1976, San Francisco, California. The manuscripts were submitted to the editor during the first half of 1977 and, in most cases, represent reviews of selected research topics in the broad area of characterization of solute species in non~aqueous solvents. In organizing this Symposium, I attempted to bring together a significantly large group of research workers involved in spectro scopic and electrochemical studies in the three large classes of non-aqueous solvents ~ organic solvents, covalent inorganic sol vents and molten salts. The experimental apprcaches and problems, such as avoidance of traces of moisture and oxygen, are frequently similar for all types of non-aqueous solvents. It is hoped that this volume will be useful to all concerned with chemistry in non-aqueous solvents. Gleb l>lamantov , Contents 1. IDENTIFICATION AND SYSTEMIZATION OF SOLVENT PROPERTIES INVOLVED IN THE LIGAND SUBSTITUTION KINETICS OF LABILE COMPLEXES OF NICKEL(II) J. F. Coetzee, D. Frollini, C. G. Karakatsanis, E. J.

1.1. Definition of Terms-Thrombosis, Thromboembolic Disease, Atherosclerosis, and Blood Clotting The terms heart attack or myocardial infarction are more commonly used than thrombosis. The infarct-muscle destruction is simply the end result and thrombosis is the real cause of the heart attack. Thrombosis may be defined as the process of formation of a coalescent or agglutinated solid mass of blood components in the blood stream. Thrombi formed in either arteries or veins often cause occlusion in the vascular system and prevent blood flow. Obstruc to the blood vessel usually occurs at the site where the thrombi deposit. tion Furthermore, thrombi may break loose, travel through the circulating blood stream, and cause obstruction at some distal point of narrowing elsewhere. The mass or thrombus that moves is referred to as an "embolus." The two phenomena are lumped together under the term thromboembolic disease. Thrombosis that reduces blood supply to the heart is the primary factor in heart attacks."

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."

Recent progress in the synthesis of nanomaterials and our fundamental understanding of their properties has led to significant advances in nanomaterial-based gas, chemical and biological sensors. Leading experts around the world highlight the latest findings on a wide range of nanomaterials including nanoparticles, quantum dots, carbon nanotubes, molecularly imprinted nanostructures or plastibodies, nanometals, DNA-based structures, smart nanomaterials, nanoprobes, magnetic nanomaterials, organic molecules like phthalocyanines and porphyrins, and the most amazing novel nanomaterial, called graphene. Various sensing techniques such as nanoscaled electrochemical detection, functional nanomaterial-amplified optical assays, colorimetry, fluorescence and electrochemiluminescence, as well as biomedical diagnosis applications, e.g. for cancer and bone disease, are thoroughly reviewed and explained in detail. This volume will provide an invaluable source of information for scientists working in the field of nanomaterial-based technology as well as for advanced students in analytical chemistry, biochemistry, electrochemistry, material science, micro- and nanotechnology.

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

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."

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.""

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."

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.

All-solid-state batteries have gained much attention as the next-generation batteries. This book is about various Li ion ceramic electrolytes and their applications to all-solid-state battery. It contains a wide range of topics from history of ceramic electrolytes and ion conduction mechanisms to recent research achievements. Here oxide-type and sulfide-type ceramic electrolytes are described in detail. Additionally, their applications to all-solid-state batteries, including Li-air battery and Li-S battery, are reviewed.Consisting of fundamentals and advanced technology, this book would be suitable for beginners in the research of ceramic electrolytes; it can also be used by scientists and research engineers for more advanced development.

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.

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.

The objective of the present volume is to develop the theory and practice of nonmetal electrochemistry from first principles, emphasizing energy level models, in particular the fluctuating energy level model of Marcus and Gerischer. A single volume emphasizing these models. and the in terpretation of experiments based on these models, has not been available. Yet this area of electrochemical technology, where the use of such models is required, has developed a great deal of interest. This is not only because of the interest in photoelectrochemical solar cells, but also because of the importance of the concepts in corrosion, sensors, coated metal electrodes, and, indeed, to the general theory of electrode reactions. This book is an attempt to fill the void-to develop in a single volume the basic description of electrode reactions on nonmetallic electrodes and oxide-covered metal electrodes. The development of the fluctuating energy level model to describe electrode reactions on nonmetals (as described in Chapters I through 3) has permitted a significant forward step in the understanding of such re actions. The power of the model is illustrated by the simple methods available to determine the energy levels of interest-the conduction and valence bands of the nonmetals (Chapter 5), and their relation to the energy levels of oxidizing or reducing agents in solution. In Chapter 6, we illustrate the ability of the simple models. based on these parameters, to describe successfully electrode reactions at an inert electrode."

This volume aims at bringing together the results of extensive research done during the last fifteen years on the interfacial photoelectronic properties of the inorganic layered semiconducting materials, mainly in relation to solar energy conversion. Significant contributions have been made both on the fundamental aspects of interface characteristics and on the suitability of the layered materials in photoelectrochemical (semiconductor/electrolyte junctions) and in solid state photovoltaic(Schottky and p-n junctions) cells. New insights into the physical and chemical characteristics of the contact surfaces have been gained and many new applications of these materials have been revealed. In particular, the basal plane surface of the layered materials shows low chemical reactivity and specific electronic behaviour with respect to isotropic solids. In electrochemical systems, the inert nature of these surfaces characterized by saturated chemical bonds has been recognized from studies on charge transfer reactions and catalysis. In addition, studies on the role of the d-band electronic transitions and the dynamics of the photogene rated charge carriers in the relative stability of the photoelectrodes of the transition metal dichalcogenides have deepened the understanding of the interfacial photoreactions. Transition metal layered compounds are also recognized as ideal model compounds for the studies Involving surfaces: photoreactions, adsorption phenomena and catalysis, scanning tunneling microscopy and spectroscopy and epitaxial growth of thin films. Recently, quantum size effects have been investigated in layered semiconductor colloids.

The current volume covers a host of topics in organic synthesis, photo- / radiation-chemistry, electron donor-acceptor interaction, supramolecular chemistry and photovoltaics. It provides a unique forum for expounding and discussing the latest developments in these important disciplines of "Fullerene Research." The selected examples, described in this comprehensive and one-of-a-kind resource, will illustrate the continuing interest and potential of fullerenes as multifunctional moieties in well-ordered multicomponent composites. In view of the novelty and the various areas involved, the composed monographs are of interest for condensed matter physicists; materials scientists; electrochemists; biochemists; solid-state, physical, organic, inorganic, and theoretical chemists; chemical, electrical, and optical engineers; and upper-level undergraduate and graduate students in these disciplines.

This volume documents the scientific events of the NATO Advanced Research Workshop (ARW) on The Preparation of Nanoparticles in Solutions and in Solids. The ARW was held in the second largest city in Hungary, Szeged, truthfully referred to as "the city of sunshine," from March 8 to March 13, 1996. The seventy-seven participants, including seventeen students, came from twentyone different countries. Housing all participants together and arranging a number of social activities fostered lively discussions both inside and outside of formal sessions. Twenty-one key lectures were presented in five sessions. Each session was followed by a fortyfive minutes of general discussion. One evening was devoted to the presentation of fifty-five posters. Thirty-two contribution were submitted and accepted for publication in the present volume. The volume also contains the minutes of the discussions, and a summary of the conclusions of the working groups. The ARW was organized under the auspices and financial support of NATO, City of Szeged, European Research Office of the US Army, Hungarian Academy of Sciences, Hungarian National Committee for Technological Development (OMBF), International Association of Colloid and Interface Scientists IACIS, and National Science Foundation (NSF). Both the organizers and participants gratefully acknowledge the generous support of the agencies. The Editors also thank the high quality and creative contributions of the participants. It is they who made this volume a reality. Janos H. fendler Irnre Dekany ix Glossary of Some Names and Acronyms Advanced Materials Man-made materials having superior mechanical, thennal, electrical, optical, and other desirable properties.

This NATO Advanced Research Workshop was devoted to a specialized topic in molten salt chemistry and was held in an exotic location (as far as Westerners were concerned) well within the Arctic Circle. It nevertheless facilitated a fruitful week, both ofscience and ofhuman contacts. The 42 oral presentations and posters from nine countries enabled the 59 participants to learn a great deal about many areas of recent research in the molten salt chemistry of refractory metals, while making new contacts as well as renewing old friendships. The time ofinformal contact ledto the beginningofa numberofnew research cooperations with interchangeofpersonnel. Thus the twin aimsofadvancing science and improving East-West understanding were both amply fulfilled. Indeed a warm and happy family atmosphere was very tangible doth during the scientific sessions and the social events, which participants, accompanying persons and local staffall enjoyed. This opportunity of living for a short time within the Arctic Circle was a novelty for most Westerners, who generally appreciated the very warm weather (the hottest for 20 years according to some residents), as well as the beautiful surroundings ofvery green birch/pine forest, rushing rivers, vast lakes and rounded mountains, frequently illuminated by wonderful sunsets. The evening barbeque beside Lake Imandra (100 km long) and the coach tour beside the beautiful White Sea dotted with islands in the Kandalaksha Recreational Area (National Park), to sample Pomor culture, dancing and fresh salmon soup, were high spots ofthe social programm