Modern Electrochemistry Vol.1

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Modern Electrochemistry Vol.1
Modern Electrochemistry Vol.1
J. O. Bockris, A. Reddy
27,9 Мб

The textbook Modern Electrochemistry by Bockris and Reddy originated in the needs of students at the Energy Conversion Institute of the University of Pennsylvania in the late 1960s. People trained in variousdisciplines from mathematics to biology wanted to understand the new high-energy-density storage batteries and the doubling of the efficiency of energy conversion offered by fuel cells over heat engines. The task was to take a group that seemed to be above average in initiative and present electrochem istry well enough to meet their needs.

The book turned out to be a great success. Its most marked characteristic was—is—lucidity. The method used was to start off at low level and then move up in a series of very small steps. Repetition is part of the technique and does not offend, for the lesson given each time is the same but is taught differently.

The use of the book spread rapidly beyond the confines of energy conversion groups. It led to the recognition of physical electrochemistry—the electrochemical discipline seen from its roots in physics and physical chemistry, and not as a path to superior chemical analysis. The book outlined electrochemical science for the first time in a molecular way, paying due heed to thermodynamics as bedrock but keeping it as background. The success of the effort has been measured not only by the total sales but by the fact that another reprinting had to be made in 1995, 25 years after the first one. The average sales rate of the first edition is even now a dozen copies a month! Given this background, the challenge of writing a revised edition has been a memorable one. The changes in the state of electrochemical science in the quarter century of the book’s life have been broad and deep. Techniques such as scanning tunneling microscopy enable us to see atoms on electrodes. Computers have allowed a widespread development of molecular dynamics (MD) calculations and changed the balance between informed guesses and the timely adjustment of parameters in force laws to enable MD calculations to lead to experimental values. The long-postponed introduction of commercial electric cars in the United States has been realized and is the beginning of a great step toward a healthier environment. The use of the new room-temperature molten salts has made it possible to exploit the advantage of working with pure liquid electrolytes—no solvent—without the rigors of working at 1000 °C.

All the great challenges of electrochemistry at 2000 A.D. do not have to be addressed in this second edition for this is an undergraduate text, stressing the teaching of fundamentals with an occasional preview of the advancing frontier.

The basic attributes of the book are unchanged: lucidity comes first. Since the text is not a graduate text, there is no confusing balancing of the merits of one model against those of another; the most probable model at the time of writing is described. Throughout it is recognized that theoretical concepts rise and fall; a theory that lasts a generation is doing well. These philosophies have been the source of some of the choices made when balancing what should be retained and what rewritten. The result is quite heterogeneous. Chapters 1 and 2 are completely new. The contributions from neutron diffraction measurements in solutions and those from other spectroscopic methods have torn away many of the veils covering knowledge of the first 1–2 layers of solvent around an ion.

Chapter 3 also contains much new material. Debye and Huckel’s famous calculation is two generations old and it is surely time to move toward new ideas. Chapter 4, on the other hand, presents much material on transport that is phenomenological-material so basic that it must be presented but shows little variation with time. The last chapter, which is on ionic liquids, describes the continuing evolution that is the result of the development of low-temperature molten salts and the contributions of computer modeling. The description of models of molten silicates contains much of the original material in the first edition, for the models described there are those still used today.

A new feature is the liberal supply of problems for student solution—about 50 per chapter. This idea has been purloined from the excellent physical chemistry textbook by Peter Atkins (W. H. Freeman). There are exercises, practice in the use of the chapter’s equations; problems (the chapter’s material related to actual situations); and finally, a few much more difficult tasks which are called “microresearch problems,” each one of which may take some hours to solve. The authors have not hesitated to call on colleagues for help in understanding new material and in deciding what is vital and what can be left for the literature. The authors would particularly like to thank John Enderby (University of Bristol) for his review of Chapter 2; Tony Haymet (University of Sydney) for advice on the weight to be given to various developments that followed Debye and Huckel’s ground-breaking work and for tutoring us on computational advances in respect to electrolytic ion pairs. Michael Lyons (University of Dublin) is to be thanked for allowing the present authors use of an advanced chapter on transport phenomena in electrolytes written by him. Austin Angell (Arizona State University of Tempe) in particular and DouglasInman (Imperial College) have both contributed by means of criticisms (not always heeded) in respect to the way to present the material on structure in pure electrolytes. Many other electrochemists have helped by replying to written inquiries. Dr. Maria Gamboa is to be thanked for extensive editorial work, Ms. Diane Dowdell for her help with information retrieval, and Mrs. Janie Leighman for her excellence in typing the many drafts. Finally, the authors wish to thank Ms. Amelia McNamara and Mr. Ken Howell of Plenum Publishing for their advice, encouragement, and patience.