Modern Aspects of Electrochemistry

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 theor

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LIST OF CONTRIBUTORS THOMAS Z. FAHIDY Department of Chemical Engineering University of Waterloo Waterloo, Ontario, Canada, N2L 3G1

VIJAY MODI Department of Mechanical Engineering Columbia University New York, New York 10027

KATHARINA KRISCHER Abt. Physikalische Chemie Fritz-Haber-Institut der Max-PlanckGesellschaft Berlin, Germany D-14195

ASHOK K. VIJH Electrochemistry Section Hydro-Quebec Research Institute Varennes, Quebec, Canada J3X 1S1

ANDRZEJ LASIA Department of Chemistry University of Sherbrooke Sherbrooke, Quebec, Canada J1K 2R1 MARK C. LEFEBVRE Department of Chemistry University of Ottawa Ottawa, Ontario, Canada K1N 6N5

ALAN C. WEST Department of Chemical Engineering and Applied Chemistry Columbia University New York, New York 10027 J. DELIANG YANG Department of Chemical Engineering and Applied Chemistry Columbia University New York, New York 10027

A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher.

MODERN ASPECTS OF ELECTROCHEMISTRY No. 32 Edited by

B. E. CONWAY University of Ottawa Ottawa, Ontario, Canada

J. O’M. BOCKRIS Molecular Green Technology College Station, Texas

and

RALPH E. WHITE University of South Carolina, Columbia Columbia, South Carolina

KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW

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0-306-45964-7

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Preface This volume is composed of six chapters covering both fundamental and applied electrochemistry, as in previous monographs in this series. The first chapter, by Krischer, provides a detailed analysis of oscillatory processes that arise in the kinetics of certain electrode processes, for example, in active to passive transitions involving oxide films and in H 2 and small organic molecule oxidations. The origin of such periodic phenomena in electrochemistry has remained obscure for some time. (Why are steady states not simply attained?) The author gives a thorough and mathematical treatment of the conditions required for onset of oscillations, including, it is important to note, coupling with resistive elements of experimental circuits and diffusion. Her review encompasses broader aspects of periodic phenomena such as those currently being considered in theories of transition between “order” and “chaos,” part of a new paradigm in biology and cosmology. Lasia, in the second chapter, offers a much-needed comprehensive treatment of ac impedance (“impedance spectroscopy”) as applied to the study of ki