The Principles of Electrochemistry

Abstract

"This book has been written with the idea of furnishing an account of theoretical electrochemistry as it is today, and to satisfy an inner urge of the author to see the subject he is interested in as B logical, connected whole." In these words. Dr. MacInnes gives the key to the plan of his book and the motive that guarantees good work. Considering that fifteen years were spent in preparation and that the author has had extensive practical experience with many of the subjects discussed, it is not surprising that the finished product is one of the most satisfying treatments of the field in many years. The style is rigorous, clear, and concise. The attention given to the different subjects is such as to produce an unusually well-balanced book. True to his purpose, the author has refrained from discussing most of the speculative in electrochemistry and has confined himself to real accomplishment. So well has he hacked theory with experimental data, that one has the feeling whatever is found therein is dependable and authoritative. Such strict hewing to the line has even forbidden inclusion of the modern theory of acids and bases. The omission will be regretted by some, but twenty-four well-packed chapters covering practically the whole of the electrochemistry of solutions should offset any regrets. Some subjects not commonly discussed are "The Effects of Gravity and Centrifugal Force on the Electromotive Force of Galvanic Cells"; "The Determination of Thermodynamic Ionization Constants from the Potentials of Cells without Liquid Junctions"; "Thermodynamic Studies of Non-Aqueous Solutions"; and "Electrokinetic Phenomena: Electro-osmosis, Electrophoresis, and Streaming Potential." To name chapters of outstanding excellence is difficult, but transference. Debye-Hueckel theory, liquid junctions, the meaning of pH, interionic attraction and conductance, and the effect of structure and substitution on ionization constants are discussed unusually well. A hit on indicators and solubility products might well have been included to make a more complete work, the former because of its bearing on pH values and the latter because of its use in determining activity coefficients and standard potentials. An unusual feature is the extensive amount of data incorporated-there are ninety-eight tables and especially the critical evaluation of much of it, e.g., activities and standard potentials. In some cases the values have even been recalculated. This same precision extends to the text. Symbols are clearly defined and the real meaning of equations set forth. All equations are derived "from the ground up" with exception of the Poisson equation, the Gronwall-LaMer-Sandved extension and the Onsager conductance equation. Even Planck's equation for liquid junctions is derived in the appendix. The literature references are exceedingly abundant, and there are many explanatory footnotes. A list of symbols in the front of the book is very helpful. It is unfortunate that multiplicity of quantities has caused a shortage of suitable symbols. The use of small capitals and large capitals is especially bad as it necessitates closest observation in reading. An obvious error in this list is the definition of γ. This should be "Activity coefficient on molal, m, basis" instead of "molar." Most to be criticized, in the reviewer's opinion, is the almost complete omission of any conventions interrelating the signs of cell and half-cell potentials and the chemical reactions producing such potentials. On page 110 there is one convention governing signs, but nothing approaching in completeness such rules as are found in, say, the Getman-Daniels "Physical Chemistry" and MacDougall "Physical Chemistry." To the expert such conventions are, perhaps, unnecessary, but they are extremely valuable to the novice and timesavers to all. Regrettable also is the use of plus for the base metal potentials and minus for the noble metal potentials, F for the Helmholtz free energy and Z for the Gibbs free energy. There seems to be no real advantage in departing from the conventions and symbols most widely used in this country. Fomat, typing, and indexing leave nothing to be desired. This outstanding work is recommended unreservedly to electrochemists, advanced students, and teachers. The lack of problems somewhat diminishes its value as a text. Finally, many thanks to prof. Luigi Pavilpsano for having scanned and published this book to LibGen.