Chemical Education Today
Modern Electrochemistry, Volume 1: Ionics
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John O’M. Bockris and Amulya K. N. Reddy. Plenum: New York, 1998. xxxvii + 769 pp. 15.7 × 23.5 cm. Hardbound: ISBN 0-306-45554-4, $95.00. Paperback: ISBN 0-30645555-2, $49.50.
The first edition of Modern Electrochemistry, a two-volume set published in 1970, is familiar as a classic work to those who teach and practice electrochemistry. The second edition of Volume 1 here reviewed is a worthy successor, containing nearly all the original material, updated with the results of two and one-half decades of additional research, as well as a large amount of new material. For those unfamiliar with the original work, this is not a treatment of applied analytical methods such as classical polarography and cyclic voltammetry. Rather, it seeks to gather together the most current thought regarding the theoretical underpinnings of all electrochemical phenomena. As such it is more appropriately regarded as a textbook in physical rather than analytical electrochemistry. Investigators seeking descriptions of the latest tricks for lowering the detection limits of their favorite techniques should look elsewhere. The second edition of Volume 1, like the original, is devoted to a study of ionics, the physical electrochemistry of solutions—primarily, but not exclusively, those prepared with water. The original Volume 2 is a treatment of electrodics, the physical chemistry of heterogeneous phenomena observed at the solution– electrode interface. This book begins with a brief survey of electrochemistry, a virtually complete revision of the original reflecting modern concerns. Chapter 2 describes the physical nature of solvents, particularly water, and ion–solvent interactions, and contains a detailed analysis of the properties of solvents and ions at the atomic level. This chapter is also a significant rewrite of the original, including all the material on ion–solvent interactions, solvation number and dielectric constant, plus additional treatments of the thermodynamics of hydration, modern theories based on simulation, and phenomena relating to biological systems. Ion–ion interactions with particular attention to activity coefficients are dealt with in the third chapter, including a critical analysis of the Debye–Hückel theory and a multitude of improvements thereupon. The content is similar to that of the original edition, again with the addition of some modern theories based upon computational methods, including simulation. Chapter 4 covers ion transport, focusing almost exclusively on the processes of diffusion and electrostatic migration. Added in the second
edition is an updated version of material on proton transport found in Chapter 5 of the original. The remainder of the original Chapter 5, regarding proton transfer reactions, appears to have been eliminated from the second edition. Volume 1 concludes with a new Chapter 5, which incorporates the material from Chapter 6 of the first edition on ionic liquids, including properties and models of transport phenomena in pure molten salts and mixtures of salts. Descriptions of current models based on simulation and a short treatment of room-temperature liquid electrolytes are added. The authors claim to have prepared this work as a textbook for undergraduates. A sizable collection of problems has been included at the end of each chapter, with a few “micro research” problems that reward a somewhat greater amount of effort with a significant result. Although the authors have done an admirable job of beginning each idea at a very basic level and building from there, the buildup is quite rapid as textbooks go and liberally sprinkled with mathematics and its attendant condensation of information, so the reading is challenging. Additionally, the authors are not bashful about invoking the calculus when it is appropriate. On the basis of the level of treatment and the sheer volume of material, this volume would be most appropriate as a textbook for an advanced course (post physical chemistry) in physical electrochemistry. It seems eminently suitable as a source of supplemental reading for students in a variety of upper-level courses, including physical chemistry. As a reference for the practicing electrochemist it shines because of its thorough coverage of the discipline, its excellent index, and its easyto-use system of paragraph headings, each of which includes sufficient detail to enable the researcher to confidently identify the relevant portion of text. In view of the challenge presented in reading this text, I (who consider myself an applied analytical chemist) confess significant surprise in finding that the volume is relatively difficult to put down. The authors have managed to include more than their fair share of the “So that’s why that happens!” factor. Assuming that the successor to Volume 2 of this work reflects revision similar to that of Volume 1, this set is a musthave for any technical college or university library, especially if it was not acquired in its original edition. While its utility as an undergraduate textbook appears limited in view of its rigor and the frequency with which advanced courses devoted to electrochemistry are offered at the undergraduate level, it will certainly provide an intellectual treat for the motivated student with the patience to absorb it. David L. Langhus Department of Chemistry Moravian College Bethlehem, PA 18018-6650
JChemEd.chem.wisc.edu • Vol. 76 No. 8 August 1999 • Journal of Chemical Education
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