Electrochemistry Volume 5

Electrochemistry plays a key role in a broad range of research and applied areas including the exploration of new inorganic and organic compounds, biochemical and biological systems, corrosion, energy applications involving fuel cells and solar cells, and nanoscale investigations. The Handbook of Electrochemistry serves as a source of electrochemical information, providing details of experimental considerations, representative calculations, and illustrations of the possibilities available in electrochemical experimentation. The book is divided into five parts: Fundamentals, Laboratory Practical, Techniques, Applications, and Data. The first section covers the fundamentals of electrochemistry which are essential for everyone working in the field, presenting an overview of electrochemical conventions, terminology, fundamental equations, and electrochemical cells, experiments, literature, textbooks, and specialized books. Part 2 focuses on the different laboratory aspects of electrochemistry which is followed by a review of the various electrochemical techniques ranging from classical experiments to scanning electrochemical microscopy, electrogenerated chemiluminesence and spectroelectrochemistry. Applications of electrochemistry include electrode kinetic determinations, unique aspects of metal deposition, and electrochemistry in small places and at novel interfaces and these are detailed in Part 4. The remaining three chapters provide useful electrochemical data and information involving electrode potentials, diffusion coefficients, and methods used in measuring liquid junction potentials. * serves as a source of electrochemical information * includes useful electrochemical data and information involving electrode potentials, diffusion coefficients, and methods used in measuring liquid junction potentials * reviews electrochemical techniques (incl. scanning electrochemical microscopy, electrogenerated chemiluminesence and spectroelectrochemistry)

Annotation. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued.

It is now time for a comprehensive treatise to look at the whole field of electrochemistry. The present treatise was conceived in 1974, and the earliest invitations to authors for contributions were made in 1975. The completion of the early volumes has been delayed by various factors. There has been no attempt to make each article emphasize the most recent situation at the expense of an overall statement of the modern view. This treatise is not a collection of articles from Recent Advances in Electro chemistry or Modern Aspects of Electrochemistry. It is an attempt at making a mature statement about the present position in the vast area of what is best looked at as a new interdisciplinary field. Texas A & M University John O'M. Bockris University of Ottawa Brian E. Conway Case Western Reserve University Ernest B. Yeager Texas A & M University Ralph E. White Preface to VoluIJJe 8 The past three decades have seen the rapid evolution of the transport aspects of electrochemical engineering into a formal part of electrochemistry as well as chemical engineering. With minor exceptions, however, this subject has not been systematically covered in any treatise or recent electrochemical text. The editors believe that the treatment in this volume will serve the function.

This series, formerly edited by Heinz Gerischer and Charls V. Tobias, now edited by Richard C. Alkire and Dieter M. Kolb, has been warmly welcomed by scientists world-wide which is reflected in the reviews of the previous volumes: "This is an essential book for researchers in electrochemistry; it covers areas of both fundamental and practical importance, with reviews of high quality. The material is very well presented and the choice of topics reflects a balanced editorial policy that is welcomed." —The Analyst "All the contributions in this volume are well up to the standard of this excellent series and will be of great value to electrochemists.... The editors again deserve to be congratulated on this fine collection of reviews." —Journal of Electroanalytical Chemistry and Interfacial Chemistry "...competently and clearly written." —Berichte der Bunsen- Gesellschaft für Physikalische Chemie

7 The Electrified Interface.- 7.1 Electrification of an Interface.- 7.1.1 The Electrode-Electrolyte Interface: The Basis of Electrodics.- 7.1.2 New Forces at the Boundary of an Electrolyte.- 7.1.3 The Interphase Region Has New Properties and New Structures.- 7.1.4 An Electrode Is Like a Giant Central Ion.- 7.1.5 The Consequences of Compromise Arrangements: The Electrolyte Side of the Boundary Acquires a Charge.- 7.1.6 Both Sides of the Interface Become Electrified: The So-Called "Electrical Double Layer"--7.1.7 Double Layers Are Characteristic of All Phase Boundaries.- 7.1.8 A Look into an El.

This book is based on the George Fisher Baker Lecture given by Jean-Michel Savéant at Cornell University in Fall 2002. * The first book focusing on molecular electrochemistry * Relates to other fields, including photochemistry and biochemistry * Outlines clearly the connection between concepts, experimental illustrations, proofs and supporting methods * Appendixes to provide rigorous demonstrations to prevent an overload of algebra in the main text * Applications-oriented, focused on analyzing the results obtained rather than the methodology

The objective of this second edition remains the discussion of the many diverse roles of electrochemical technology in industry. Throughout the book, the intention is to emphasize that the applications, though extremely diverse, all are on the same principles of electrochemistry and electrochemical engineer based ing. Those familiar with the first edition will note a significant increase in the number of pages. The most obvious addition is the separate chapter on electrochemical sensors but, in fact, all chapters have been reviewed thoroughly and many have been altered substantially. These changes to the book partly reflect the different view of a second author as well as comments from students and friends. Also, they arise inevitably from the vitality and strength of electrochemical technology; in addition to important improvements in tech nology, new electrolytic processes and electrochemical devices continue to be reported. In the preface to the first edition it was stated: . . . the future for electrochemical technology is bright and there is a general expectation that new applications of electrochemistry will become economic as the world responds to the challenge of more expensive energy, of the need to develop new materials and to exploit different chemical feedstocks and of the necessity to protect the environment. The preparation of this second edition, seven years after these words were written, provided an occasion to review the progress of industrial electro chemistry.