book reviews Modern Aspects of Inorganic Chemistry. Fourth Edition
H. J. EmeUus and A. G. Shorpe, University of Cambridge. A Halsted Press Book, John Wiley & Sons, New York, 1973. av 677 pp. Figs. and tables. 14.5 X 22.5 cm. $15.50.
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Two books which were to have a profound effect upon the teaching of inorganic chemistry appeared in 1938. The first of these was Linus Pauling's "The Nature of the Chemical Bond" which quickly established itself among that handful of texts which have changed the course of chemical history. The second, EmelCus and Anderson's "Modem Aspects of Inorganic Chemistry," while more modest in its achievement, was equally vivid, readable, and exciting, particularly when compared to the conventional wisdom of the standard inorganic texts then available. The inorganic chemistry of Ephraim and of Partington was indeed desperately in need of the putative renaissance of the 1950's but the inorganic chemistry of Emelbus and Anderson had merely been interrupted by the more pressing matters of World War 11. New editions of Emelbus and Anderson appeared in 1952 and 1960 but they bad little of the impact of the first. The same fate even befell the third edition of Pauling's classic which came out in 1960. The reasons were similar in the two cases. Contemporary needs and contemporary fashions (which owed so much to the originals) had rendered the later editions out-of-joint with the times. We now have a completely rewritten entry from the Emelbus stable, this time with A. G. Sharp as coauthor, and we must try to decide how this will trot against the current field, in particular the formidable mount of that well known Texas hone fancier F. Albert Cotton and the equitable if not equine Geoffrey Wilkinson. The new book displays the virtues of its predecessors. It is unusually readable, it does not overwhelm with detailed fact or over-ramified theory, and it gives a remarkably even-handed contemporary account of the whole range of traditional inorganic chemistry. The departure of J . S . Anderson as coauthor has perhaps led to the deletion of the chapters on "Metals and Intermetallic Compounds" and on "Interstitial and Non-Stoichiometric Compounds" hut some of this material has been interposed elsewhere. The attractive chapter on "Organometallic Compounds" is rather brief and selective and there is virtually no mention of bioinorganic chemistry. Chapter 2 is undoubtedly the weakest in the book telling an average U S student less than he already knows about nmr spectroscopy and far less than he needs to know about the other physical methods. However, even though many structures are presented throughout the book the physical measurements on which they are based are rarely emphasized or discussed. In particular vibrational spectroscopy is seldom invoked. Indeed there is relatively little formal treatment of bondA60
/ Journal of Chemical Educahon
ing theory in the book. Presumably in the British scheme of things this is taken care of elsewhere. There are no problems and the references are mainly to review articles and other texts. Where might this text fit in present chemical curricula? It would serve as an admirable complement to more theoretically inclined books such as Day and Selbin or Cartmell and Fowles. It would usefully supplement books such as Huheey or Douglas and MeDaniel which are rather selective in their treatment of descriptive chemistry. As a graduate text, however, it cannot complete with Phillips and Williams to say nothing of Cotton and Wilkinson. And if the already announced "Son of Cotton and Wilkinson" lives up to expectations, one fears that it will not be able to challenge successfully a t the undergaduate level either. Derek A. Davenport Purdue University West Latayette, Indiana 47907
Modern Electrochemistry
John O'M. Bockris, University af Pennsylvania and Arnulyo K. N. Reddv, Indian Institute of Science. PlenumfRosetta Edition, Plenum Publishing Corp., New Yark, 1973. Volume 1: Ix + 622 pp. Vol. 2: Ivi 1432 pp. Fig. and tables. 15 X 22 cm. $8.95each volume.
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John O'Mara Backris has taken i t upon himself to wage a personal crusade to lead electrochemistry into the space age. As a n educational contribution ta this end, the two volumes under review are a flattering overview of general electrochemistry and should be considered as the currently definitive text on this subject. (Bockris and Reddy present much more of a general textbook than the only other comparable set, the quality two-volume contribution to the Academic Press series "An Advanced Treatise an Physical Chemistry" edited by Eyring, Jast, and Henderson.) The statement is made, and then firmly substantiated, that there was a "Great Nernstian Hiatus" in electrochemistry following the work of the great nineteenth century electrochemist. Scientists seemed to be so hypnotized by the elegant simplicity of the Nernst equation (1891). that for half a century equilibrium electrical potential theory was felt to be the key to explaining electrical effects due t o currents. The Tafel equation, proposed in 1905, tried to establish current as the dependent variable generated by overvoltage hut could not make significant headway against the impressive Nernst formalism. In 1923, Debye and Hiiekel managed to introduce a second model to electrochemistry, but not until the late 1940's did electrochemists adopt the current-centric approach to ionic phenomena. Around 1950 much international emphasis switched from electrochemistry as an equilibrium emf situation to electrochemistry as a kinetic process. Time became a more fundamental independent variable and diffusion processes and electrode kinetics were recognized as the very important mechanisms
for electrochemical reactions. Starting with these basic principles, these volumes develop an alternative structure for electrochemistry. Without denying thermodynamics, the interpretation of dynamic phenomena is no longer attempted with a theory of equilibrium balance. The "impure" observables of polarization and overvoltage can be seen a s natural driving forces in establishing and maintaining currents. The Tafel equation evolves into the sophisticated Butler-Volmer equation which can be used to explain a wealth of experimental facts and trends. Thermodynamics is then introduced in a secandary relationship and put to excellent use when appropriate. The subject matter of these volumes is partitioned into ionics and eleetrodies which bear a superficial resemblance to classical ionic conductance processes and galvanic cell theory. Volume I covers the topics of ionics and stresses the derivation of the Debye-Hiiekel theory with refinements and applications. Protonic conduction is also discussed as is the nature of ionic liquids. The authors proclaim "one theory per phenomena;" hence some pet theoretical developments are bound to be missing from the text, but the authors have attempted to be critical in selecting the best theory available. The second volume is devoted to electrodics and it is here that the distinction between, e.g., Glasstone's approach to electrochemistry and Bockris' becomes most apparent. The present treatment strongly emphasizes electrode kinetics to the virtual exclusion of the standard presentation of half-cell and battery potentials. There are many fine features to these volumes. Although there are occasional lapses into awkward and forced grammatical constructions. in eeneral these books
loid science, quantum mechanics, much classical electrical field theory, and much solid state physics. Widely varying examples are presented from biophysics, industrial technology, and such developments as fuel cells and space age energy sources. There is a commendable emphasis on potential-pH diagrams and their metallurgical usage. Applications far technological purposes in the final chapter are excellent as glimpses into state-of-the-art electrochemical technology. The mathematics is extensive, yet quite completely developed in each context, hence eminently instructive. The graphs, tables, and diagrams are dentiful and usuallv. verv . clear and heloiul. I believe that anyone teaching physical chemistry should be familiar with the content and viewpoint represented by these volumes, since most physical chemistry textbooks still dwell upon the thermodynamic approach. These books should be recommended to students and used as course textbooks, since they do reflect the deserved revitalization of the field of eketrochemistry. E. Miller Layton. Jr. Iowa State University Arnes, iowa 50010
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