This volume contains ?ve chapters. The topics covered are the cathodic reduction of nitrate, for which the key issues are pr- uct selectivity and current ef?ciency; a discussion of ionic l- uids known as molten or fused salts in key industrial processes; the properties of nanowires made of metals and semiconductors by means of electrodeposition into porous templates and template synthesis; and an overview of a range of alloys used in elect- plating, and trends in ammonium electrolysis. Also, included is a review of the applications of synchroton x-ray scattering to the electrochemical interphase. Chapter 1 by Celia Milhano and Derek Pletcher reviews the cathodic reduction of nitrate as a "truly fascinating reaction" since processes for nitrate removal from drinking water and effluents and reducing nitrates in nuclear waste is an essential step in n- lear waste disposal. The authors also review electrochemical membrane technology not involving the cathodic reduction of - trate. In Chapter 2, the authors discuss substances called ionic l- uids, and the fact that this is really a new more modern term for molten or fused salts. However, the label of ionic liquids is usu- ly applied to the liquid state of salts at or near room temperature, which is a way to differentiate low-melting salts from higher me- ing cousins. These molten or fused salts form the basis of several key industrial processes, and this chapter is primarily devoted to the non-haloaluminate ionic liquids as reviewed by Tetsuya Tsuda and Charles L. Hussey.

This volume of Modern Aspects covers a wide spread of topics presented in an authoritative, informative and instructive manner by some internationally renowned specialists. Professors Politzer and Dr. Murray provide a comprehensive description of the various theoretical treatments of solute-solvent interactions, including ion-solvent interactions. Both continuum and discrete molecular models for the solvent molecules are discussed, including Monte Carlo and molecular dynamics simulations. The advantages and drawbacks of the resulting models and computational approaches are discussed and the impressive progress made in predicting the properties of molecular and ionic solutions is surveyed. The fundamental and applied electrochemistry of the silicon/electrolyte interface is presented in an authoritative review by Dr. Gregory Zhang, with emphasis in the preparation of porous silicon, a material of significant technological interest, via anodic dissolution of monocrystalline Si. The chapter shows eloquently how fundamental electrokinetic principles can be utilized to obtain the desired product morphology. Markov chains theory provides a powerful tool for modeling several important processes in electrochemistry and electrochemical engineering, including electrode kinetics, anodic deposit formation and deposit dissolution processes, electrolyzer and electrochemical reactors performance and even reliability of warning devices and repair of failed cells. The way this can be done using the elegant Markov chains theory is described in lucid manner by Professor Thomas Fahidy in a concise chapter which gives to the reader only the absolutely necessary mathematics and is rich in practical examples.

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).

This volume of Modern Aspects contains seven chapters. The major topics covered in the first six chapters of this volume include fundamentals of solid state electrochemistry; kinetics of electrochemical hydrogen entry into metals and alloys; oxidation of organics; fuel cells; electrode kinetics of trace-anion catalysis; nano structural analysis. The last chapter is a corrected version of chapter four from Volume 35. Faisal M. AI-faqeer and Howard W. Pickering begin the first chapter by going back to 1864 and Cailletet who found that some hydrogen evolved and was absorbed by iron when it was immersed in dilute sulfuric acid. The absorption of hydrogen into metals and alloys can lead to catastrophic failures of structures. They discuss the kinetics of electrochemical hydrogen entry into metals and alloys. In chapter three, Clyde L. Briant reviews the electrochemistry, corrosion and hydrogen embrittlement of unalloyed titanium. He begins by reviewing the basic electrochemistry and general corrosion of titanium. He also discusses pitting and galvanostatic corrosion followed by a review of hydrogen embrittlement emphasizing the formation of hydrides and the effect of these on titanium's mechanical properties. Christos Comninellis and Gy6rgy F6ti discuss the oxidative electrochemical processes of organics in chapter three. They begin by defining direct and indirect electrochemical oxidation of organics. They introduce a model that allows them to distinguish between active (strong) and non-active (weak) anodes. Different classes of organic compounds are used for kinetic models of organic oxidation at active and non-active type anodes.

Recognized experts present incisive analyses of both fundamental and applied problems in this continuation of a highly acclaimed series. Topics in Number 35 include: * Impedance spectroscopy with specific applications to electrode processes involving hydrogen; * Fundamentals and contemporary applications of electroless metal deposition; * The development of computational electrochemistry and its application to electrochemical kinetics; * Analysis of electrolyte solutions at high concentrations; * Applications of the Born theory to solvent polarization by ions and its extensions to treatment of kinetics of ionic reactions. GBP/LISTGBP

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.

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

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.

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.

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

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."

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.

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.

This volume of Modern Aspects contains a remarkable spread of topics covered in an authoritative manner by some internationally renowned specialists. In a seminal chapter Drs. Babu, Oldfield and Wieckowski demonstrate eloquently the strength of electrochemical nuclear magnetic resonance (EC-NMR) to study in situ both sides of the electrochemical interface via the simultaneous use of and This powerful non-invasive technique brings new insights to both fundamental and practical key aspects of electrocatalysis, including the design of better anodes for PEM fuel cells. The recent impressive advances in the use of rigorous ab initio quantum chemical calculations in electrochemistry are described in a remarkable chapter by Marc Koper, one of the leading protagonists in this fascinating area. This lucid chapter is addressed to all electrochemists, including those with very little prior exposure to quantum chemistry, and demonstrates the usefulness of ab initio calculations, including density functional theory (DFT) methods, to understand several key aspects of fuel cell electrocatalysis at the molecular level. The most important macroscopic and statistical thermodynamic models developed to describe adsorption phenomena on electrodes are presented critically in a concise and authoritative chapter by Panos Nikitas. The reader is guided through the seminal contributions of Frumkin, Butler, Bockris, Guidelli and others, to the current state of the art adsorption isotherms, which are both rigorous, and in good agreement with experiment.

This volume in the acclaimed series Modern Aspects of Electrochemistry starts with a dedication to the late Professor Brian Conway who for 50 years helped to guide this series to its current prominence. The remainder of the volume is then devoted to the following topics: PEM fuel cells; the use of graphs in electrochemical reaction newtworks; nanomaterials in Lithium-ion batteries; direct methanolf fuel cells (two chapters); fuel cell catalyst layers. The book is for electrochemists, electrochemical engineers, fuel cell workers and energy generation workers.

This volume analyzes and summarizes recent developments in several key interfacial electrochemical systems in the areas of fuel cell electrocatatalysis, electrosynthesis and electrodeposition. The six Chapters are written by internationally recognized experts in these areas and address both fundamental and practical aspects of several existing or emerging key electrochemical technologies. The Chapter by R. Adzic, N. Marinkovic and M. Vukmirovic provides a lucid and authoritative treatment of the electrochemistry and electrocatalysis of Ruthenium, a key element for the devel- ment of efficient electrodes for polymer electrolyte (PEM) fuel cells. Starting from fundamental surface science studies and interfacial considerations, this up-to-date review by some of the pioneers in this field, provides a deep insight in the complex catalytic-electrocatalytic phenomena occurring at the interfaces of PEM fuel cell electrodes and a comprehensive treatment of recent developments in this extremely important field. Several recent breakthroughs in the design of solid oxide fuel cell (SOFC) anodes and cathodes are described in the Chapter of H. Uchida and M. Watanabe. The authors, who have pioneered several of these developments, provide a lucid presentation d- cribing how careful fundamental investigations of interfacial electrocatalytic anode and cathode phenomena lead to novel electrode compositions and microstructures and to significant practical advances of SOFC anode and cathode stability and enhanced electrocatalysis.

This volume in the acclaimed series Modern Aspects of Electrochemistry starts with a dedication to the late Professor Brian Conway who for 50 years helped to guide this series to its current prominence. The remainder of the volume is then devoted to the following topics: PEM fuel cells; the use of graphs in electrochemical reaction newtworks; nanomaterials in Lithium-ion batteries; direct methanolf fuel cells (two chapters); fuel cell catalyst layers. The book is for electrochemists, electrochemical engineers, fuel cell workers and energy generation workers.

This volume of Modern Aspects covers a wide spread of topics presented in an authoritative, informative and instructive manner by some internationally renowned specialists. Professors Politzer and Dr. Murray provide a comprehensive description of the various theoretical treatments of solute-solvent interactions, including ion-solvent interactions. Both continuum and discrete molecular models for the solvent molecules are discussed, including Monte Carlo and molecular dynamics simulations. The advantages and drawbacks of the resulting models and computational approaches are discussed and the impressive progress made in predicting the properties of molecular and ionic solutions is surveyed. The fundamental and applied electrochemistry of the silicon/electrolyte interface is presented in an authoritative review by Dr. Gregory Zhang, with emphasis in the preparation of porous silicon, a material of significant technological interest, via anodic dissolution of monocrystalline Si. The chapter shows eloquently how fundamental electrokinetic principles can be utilized to obtain the desired product morphology. Markov chains theory provides a powerful tool for modeling several important processes in electrochemistry and electrochemical engineering, including electrode kinetics, anodic deposit formation and deposit dissolution processes, electrolyzer and electrochemical reactors performance and even reliability of warning devices and repair of failed cells. The way this can be done using the elegant Markov chains theory is described in lucid manner by Professor Thomas Fahidy in a concise chapter which gives to the reader only the absolutely necessary mathematics and is rich in practical examples.

This volume of Modern Aspects contains seven chapters. The major topics covered in the first six chapters of this volume include fundamentals of solid state electrochemistry; kinetics of electrochemical hydrogen entry into metals and alloys; oxidation of organics; fuel cells; electrode kinetics of trace-anion catalysis; nano structural analysis. The last chapter is a corrected version of chapter four from Volume 35. Faisal M. AI-faqeer and Howard W. Pickering begin the first chapter by going back to 1864 and Cailletet who found that some hydrogen evolved and was absorbed by iron when it was immersed in dilute sulfuric acid. The absorption of hydrogen into metals and alloys can lead to catastrophic failures of structures. They discuss the kinetics of electrochemical hydrogen entry into metals and alloys. In chapter three, Clyde L. Briant reviews the electrochemistry, corrosion and hydrogen embrittlement of unalloyed titanium. He begins by reviewing the basic electrochemistry and general corrosion of titanium. He also discusses pitting and galvanostatic corrosion followed by a review of hydrogen embrittlement emphasizing the formation of hydrides and the effect of these on titanium's mechanical properties. Christos Comninellis and Gy6rgy F6ti discuss the oxidative electrochemical processes of organics in chapter three. They begin by defining direct and indirect electrochemical oxidation of organics. They introduce a model that allows them to distinguish between active (strong) and non-active (weak) anodes. Different classes of organic compounds are used for kinetic models of organic oxidation at active and non-active type anodes.

This volume of Modern Aspects contains a remarkable spread of topics covered in an authoritative manner by some internationally renowned specialists. In a seminal chapter Drs. Babu, Oldfield and Wieckowski demonstrate eloquently the strength of electrochemical nuclear magnetic resonance (EC-NMR) to study in situ both sides of the electrochemical interface via the simultaneous use of and This powerful non-invasive technique brings new insights to both fundamental and practical key aspects of electrocatalysis, including the design of better anodes for PEM fuel cells. The recent impressive advances in the use of rigorous ab initio quantum chemical calculations in electrochemistry are described in a remarkable chapter by Marc Koper, one of the leading protagonists in this fascinating area. This lucid chapter is addressed to all electrochemists, including those with very little prior exposure to quantum chemistry, and demonstrates the usefulness of ab initio calculations, including density functional theory (DFT) methods, to understand several key aspects of fuel cell electrocatalysis at the molecular level. The most important macroscopic and statistical thermodynamic models developed to describe adsorption phenomena on electrodes are presented critically in a concise and authoritative chapter by Panos Nikitas. The reader is guided through the seminal contributions of Frumkin, Butler, Bockris, Guidelli and others, to the current state of the art adsorption isotherms, which are both rigorous, and in good agreement with experiment.

Recognized experts present incisive analyses of both fundamental and applied problems in this continuation of a highly acclaimed series. Topics in Number 35 include: Impedance spectroscopy with specific applications to electrode processes involving hydrogen; Fundamentals and contemporary applications of electroless metal deposition; The development of computational electrochemistry and its application to electrochemical kinetics; Analysis of electrolyte solutions at high concentrations; Applications of the Born theory to solvent polarization by ions and its extensions to treatment of kinetics of ionic reactions. GBP/LISTGBP

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.