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Chemical Thermodynamics: Basic Theory and Methods, 6th Edition by Irving M. Klotz and Robert M. Rosenberg Wiley: New York, 2000. xxi + 556 pp. Figs. and tables. 16.4 × 24.2 cm. ISBN 0471331074. $89.95.
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reviewed by Frank L. Somer Jr.
This new “millennium” edition represents the latest refinement of a text that first appeared more than 50 years ago. It is not the sort of sweeping overhaul that we saw in the fifth edition, but the changes are significant and generally serve to improve the exposition of the subject matter—classical thermodynamics. In fact, in its strict adherence to a macroscopic, operational viewpoint, this book bucks the current trend of trying to meld thermodynamics and statistical mechanics into a single subject. In doing so, it fills an important niche, demonstrating the unique power of thermodynamic reasoning— its independence from any underlying mechanical model— to an audience (students of chemistry, biology, and geology, for example) interested more in applications of thermodynamics than in the details of its logical foundations. The main criteria for additions to the text seem to have been breadth of applicability and experimental accessibility, in line with the authors’ stated goal of training students to apply thermodynamics to practical problems. One prominent addition is a detailed consideration of Planck’s thermodynamic potential (Y = ᎑G/T ) as applied to phase and chemical equilibria. This function is nice in that its temperature dependence is congruent with that of the equilibrium constant (e.g. a maximum in Y implies a maximum in K ), and its various applications illustrate to students the important fact that there are useful potentials for describing constant-temperature systems (the Massieu function is also briefly addressed), other than the usual free-energy functions (which are, of course, still given adequate treatment). Another important addition is the expanded coverage of excess thermodynamic functions, the standard means for quantifying non-ideality in solutions, which were given only cursory treatment in previous editions. The current edition remedies this situation by adding two new sections on experimental determination of excess functions, as well as a new subsection describing a scheme for representing the excess free energy of mixing as a function of composition, application of which gives information about the energies of interaction between the components of a solution. Other additions are analytical calculation of the fugacity coefficient of real gases using the Redlich–Kwong equation of state, and a more detailed justification of the Lewis and Randall rule for estimating fugacities in mixtures of real gases. Material removed in the transition from the previous edition is relatively minor and includes sections on the “∆G
Jeffrey Kovac University of Tennessee Knoxville, TN 37996-1600
version of Hess’ law” and the unattainability of absolute zero. The coverage of apparent molar quantities (in which thermodynamic changes in formation of solutions are assigned entirely to the solute) has also been cut back, presumably in favor of the increased focus on the more widely encountered excess molar quantities. Not surprisingly, then, the sixth edition has grown slightly larger than the fifth, but it remains well within what can be reasonably well covered in a onesemester course. Aside from these changes to the main body of the text, this new edition also benefits from several auxiliary additions. For students, the most welcome of these will probably be the Companion to Thermodynamics, a separate manual containing clear and detailed solutions to the even-numbered exercises. A number of new exercises have appeared, most of which correspond to the increased emphasis on the Planck function, excess functions, and the Redlich–Kwong equation. Many exercises make use of the expanded and reorganized (according to source) tables of thermodynamic data and Web-based databases, which are also referenced regularly throughout the text. This is a very good book, in terms of both conception and execution. I have only a few complaints, one of which is that the enthalpy and free-energy functions are introduced as a priori definitions, rather than derived as Legendre transformations of the energy. I would also prefer to see the chemical potential introduced before—and then used in a more unified development of—phase and chemical equilibria. Of course, these sorts of issues are understandable in light of the book’s applications-oriented nature. Overall, the fundamental concepts are covered in enough detail to provide a solid foundation, yet concisely enough to leave plenty of time for applications to practical problems. The derivations are extremely clear and complete, and the presentation has a nice flow, with numerous examples interspersed throughout. It seems to me that this text is best suited to a first graduate course or an advanced undergraduate course in thermodynamics. I have used it in a master’s-level course, where it was quite well received by the students. I also regularly refer my undergraduate physical chemistry students to this book when they ask for a more detailed discussion of certain topics than is given their “p-chem” text or are looking for some additional practice problems, and they seem to find it very accessible. This book does not assume any previous exposure to thermodynamics, and so could presumably be used for the relevant parts of an introductory course in physical chemistry. It is not quite as pedantic as the usual physical chemistry tomes, though, so in this case the instructor should be careful to provide adequate context for the excellent formal development provided in this text. Frank Somer teaches at St. John’s University, Jamaica, NY 11439;
[email protected].
JChemEd.chem.wisc.edu • Vol. 78 No. 6 June 2001 • Journal of Chemical Education
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