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Chemical Thermodynamics Vol. I: Principles and Applications Vol. II: Advanced Applications by J. Bevan Ott and Juliana Boerio-Goates Academic Press: New York, 2000. Vol. I: 664 pp. ISBN 0-12530990-2. $80. Vol. II: 438 pp. ISBN 0-12-530985-6. $56. reviewed by Robert G. Mortimer
Eighty years ago, most research in physical chemistry involved thermodynamics or reaction kinetics. However, research in thermodynamics has now become unfashionable. The authors of this work, which is a two-volume textbook for seniors and beginning graduate students in chemistry, have had the courage to devote their careers to this field. They obviously care deeply about thermodynamics, which they call a “preeminent example of an exact science”, and probably have had the desire to write these volumes for many years. Both volumes are written in a clear and unpretentious style and are easy to read. The first volume of Ott and Boerio-Goates’s Chemical Thermodynamics is subtitled Principles and Applications. Most of the presentation of the principles of thermodynamics is at the level of a physical chemistry course, which the members of the intended audience have already taken. This repetition is not bad, since most people have to be exposed to thermodynamics more than once to appreciate and understand the subject. However, as one reads along in the book, thinking that everything should be familiar to the student, one occasionally arrives at a nice exposition at a higher level. Examples of higher-level presentations are a clear discussion of the Joule–Thomson expansion, Caratheodory’s proof that dqrev possesses an integrating factor, and a very nice presentation of applications of the third law of thermodynamics, including adiabatic demagnetization and laser cooling. The authors include an interesting anecdote about W. F. Giauque, who finally succeeded in crystallizing glycerol by canvassing many firms that stored large quantities of glycerol and obtaining seed crystals from a firm in Manoose Bay, British Columbia. There is also a derivation of the Debye– Hückel limiting law. The final chapter of the first volume treats statistical thermodynamics. It adequately covers the physical basis of statistical thermodynamics, but does not go beyond the level of a physical chemistry course. It treats only dilute gases and crystal models with independent degrees of freedom, and omits any mention of ensembles. The system partition function is not referred to as a canonical partition function, and is arrived at by constructing the partition function of a pair of independent molecules from that of a single molecule and extending this treatment to the case of many molecules.
Jeffrey Kovac University of Tennessee Knoxville, TN 37996-1600
Fermion and boson distribution functions are not discussed. However, both the Einstein model and the Debye model of crystal vibrations are presented in some detail. This is probably the least successful chapter in the volume, and some instructors will want to supplement it with other sources. The second volume is subtitled Advanced Applications. The first chapter is a summary of the thermodynamic principles discussed in the first volume, so that this volume can be used without the first. The other chapters prove that thermodynamics is alive and well and is making important contributions to modern research. One example is a thorough discussion of the thermodynamics of metabolism, muscle action, and other biological processes. Molecular information is integrated into the discussions, and the reader is shown that thermodynamics can provide molecular information. There are two chapters on phase equilibrium, which include numerous phase diagrams. Modern topics, such as the transition to the superconducting state and critical exponents, are included. Other chapters provide detailed discussions of nonelectrolyte and electrolyte solutions and also discuss industrially important chemical processes. The second volume is very well done and is very informative, even to an instructor. Volume I contains several appendixes, which include a clear and carefully done description of the International Temperature Scale of 1990 and a description of various equations of state. Both volumes provide problems at the end of each chapter. Volume I also contains exercises, which are slightly simpler than the problems. Most of the exercises and problems are based on actual data and seem to be well chosen. However, most chapters in Volume I have only from 5 to 15 exercises and 2 to 10 problems. Most chapters in Volume II have from 5 to 10 problems. There are relatively few typographical errors in the two volumes. There are a few conceptual errors. For example, it is stated that dq possesses an integrating factor without restricting dq to reversible processes. It is stated that the Clausius statement of the second law (that heat cannot be transferred from a cooler to a hotter object without something else happening) is restricted to cyclic processes. It is also stated that in the polynomial representation of a heat capacity, the constant term alone can be used as an approximation. This is not necessarily correct near room temperature if the polynomial is in terms of the Kelvin temperature. Such errors are not very serious, although every instructor would like to find that nonexistent error-free textbook. Instructors of chemical thermodynamics courses will certainly want to consider this text for adoption. The authors apparently teach a one-semester course from each volume, and the second semester should be especially exciting and informative for the students (and also the instructor). Robert G. Mortimer is in the Chemistry Department, Rhodes College, Memphis, TN 38112;
[email protected].
JChemEd.chem.wisc.edu • Vol. 78 No. 5 May 2001 • Journal of Chemical Education
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