Electrochemistry is one of the oldest branches of Physical Chemistry. Having its foundations in the work of Faraday, Arrhenius and others, it evolved from the study of transport in electrolyte solutions to that of electrode kinetics. Kinetic methods are inherently unable to identify unequivocally the species involved in a reaction. Therefore, beginning in the 70s many spectroscopic and diffraction techniques were applied to the study of the electrode-electrolyte interface, in order to identify intermediary reaction species, and even the spatial arrangement of atoms or molecules at the interface. In order to disseminate these techniques, a NATO Advanced Sutdy Institute was held at Puerto de la Cruz, Tenerife (Canary Islands, Spain) from July 2 to 15, 1988. The Institute consisted of tutorial type lecutures, poster sessions, and round-table discussions. It was attended by over 65 participants from NATO-member countries, and others from Argentina and Japan. In the present volume most of the lectures presented at the Institute have been collected. At least one chapter is devoted to each technique. Emphasis has been made on case studies, rather than theory, which can be found in textbooks and other publications. Our purpose in this book is to help the electrochemists uninitiated in spectroscopic methods to decide which techniques would be suitable for application to their particular problems. We thank all the lecturers who contributed to this volume, and even those UHPs (Unrepentant Habitual Procrastinators) who did not in spite of our urgings to do so.

This ninth volume in the series concentrates on in situ spectroscopic methods and combines a balanced mixture of theory and applications, making it highly readable for chemists and physicists, as well as for materials scientists and engineers. As with the previous volumes, all the chapters continue the high standards of this series, containing numerous references to further reading and the original literature, for easy access to this new field. The editors have succeeded in selecting highly topical areas of research and in presenting authors who are leaders in their fields, covering such diverse topics as diffraction studies of the electrode-solution interface, thin organic films at electrode surfaces, linear and non-linear spectroscopy as well as sum frequency generation studies of the electrified solid-solution interface, plus quantitative SNIFTIRS and PM-IRRAS. Special attention is paid to recent advances and developments, which are critically and thoroughly discussed. The result is a compelling set of reviews, serving equally well as an excellent and up-to-date source of information for experienced researchers in the field, as well as as an introduction for newcomers.

Proceedings of the NATO Advanced Research Workshop, Funchal, Madeira, Portugal, December 14--18, 1992

It is hard to overstate the importance of electrochemistry in the modern world: the ramifications of the subject extend into areas as diverse as batteries, fuel cells, effluent remediation and re-cycling, clean technology, elect- synthesis of organic and inorganic compounds, conversion and storage of solar energy, semiconductor processing, material corrosion, biological electron transfer processes and a wide range of highly specific analytical techniques. The impact of electrochemistry on the lives of all of us has increased immeas- ably, even in recent years, but this increase has not been reflected in the level or content of courses taught at universities, many of which portray the subject as a collection of arcane recipes and poorly understood formulae of marginal importance to the mainstream of chemistry. This approach reached its nadir with the recent extraordinary furore surrounding the purported discovery of cold fusion, where two electrochemists claimed to have shown that the fusion of deuterium nuclei could be effected under ambient conditions by the electrochemically induced intercalation of deuterium atoms into palladium. Whatever the truth behind such claims, their discussion revealed a lamentable lack of knowledge of modern elect- chemistry, not only among science writers for the popular press, but among many professional chemists and physicists whose acquaintance with the subject seems, for the most part, to have stopped somewhere about the time of Nernst. In a year in which Professor R.

"Provide comprehensive, authoritative reviews on recent developments and applications of well-established techniques in field of modern electro-and electroanalytical chemistry, defined in its broadest sense. "

This volume maintains the series’ high standards, containing chapters covering topics such as the cathodic reduction of nitrate, and including discussion of product selectivity, current efficiency, and the thermodynamics and kinetics for the reactions studied.

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.

A broad, almost encyclopedic overview of spectroscopic and other analytical techniques useful for investigations of phase boundaries in electrochemistry is presented. The analysis of electrochemical interfaces and interphases on a microscopic, even molecular level, is of central importance for an improved understanding of the structure and dynamics of these phase boundaries. The gained knowledge will be needed for improvements of methods and applications reaching from electrocatalysis, electrochemical energy conversion, biocompatibility of metals, corrosion protection to galvanic surface treatment and finishing. The book provides an overview as complete as possible and enables the reader to choose methods most suitable for tackling his particular task. It is nevertheless compact and does not flood the reader with the details of review papers.

This volume provides a practical, intuitive approach to electroanalytical chemistry, presenting fundamental concepts and experimental techniques without the use of technical jargon or unnecessarily extensive mathematics. This edition offers new material on ways of preparing and using microelectrodes, the processes that govern the voltammetric behavior of microelectrodes, methods for characterizing chemically modified electrodes, electrochemical studies at reduced temperatures, and more. The authors cover such topics as analog instrumentation, overcoming solution resistance with stability and grace in potentiostatic circuits, conductivity and conductometry, electrochemical cells, carbon electrodes, film electrodes, microelectrodes, chemically modified electrodes, mercury electrodes, and solvents and supporting electrolytes.

This volume provides a practical, intuitive approach to electroanalytical chemistry, presenting fundamental concepts and experimental techniques without the use of technical jargon or unnecessarily extensive mathematics. This edition offers new material on ways of preparing and using microelectrodes, the processes that govern the voltammetric behavior of microelectrodes, methods for characterizing chemically modified electrodes, electrochemical studies at reduced temperatures, and more. The authors cover such topics as analog instrumentation, overcoming solution resistance with stability and grace in potentiostatic circuits, conductivity and conductometry, electrochemical cells, carbon electrodes, film electrodes, microelectrodes, chemically modified electrodes, mercury electrodes, and solvents and supporting electrolytes.