Introduction

Electrochemistry is an old science: There is good archaeological evidence that an electrolytic cell was used by the Parthans (250 B.C. to 250 A.D.), probably for electroplating, though a proper scientific investigation of electrochemical phenomena did not start before the experiments of Volta and Galvani. The meaning and scope of electrochemical science has varied throughout the ages: For a long time it was little more than a special branch of thermodynamics; later attention turned to electrochemical kinetics. During recent decades, with the application of various surface-sensitive techniques to electrochemical systems, it has become a science of interfaces, and this, we think, is where its future lies. So in this book we use as a working definition: . . . Electrochemistry is the study of structures and processes at the interface between an electronic conductor (the electrode) and an ionic conductor (the electrolyte) or at the interface between two electrolytes. . . This definition requires some explanation. (1) By interface we denote those regions of the two adjoining phases whose properties differ significantly from those of the bulk. These interfacial regions can be quite extended, particularly in those cases where a metal or semiconducting electrode is covered by a thin film. Sometimes the term interphase is used to indicate the spatial extention. (2) It would have been more natural to restrict the definition to the interface between an electronic and an ionic conductor only, and, indeed, this is generally what we mean by the term electrochemical interface. However, the study of the interface between two immiscible electrolyte solutions is so similar that it is natural to include it under the scope of electrochemistry. Metals and semiconductors are common examples of electronic conductors, and under certain circumstances even insulators can be made electronically conducting, for example by photoexcitation. Electrolyte solutions, molten salts, and solid electrolytes are ionic conductors. Some materials have appreciable electronic and ionic conductivities, and depending on the circumstances one or the other or both may be important.