Chemical Education Today
Thermodynamics, 2nd ed. N. A. Gocken and R. G. Reddy. Plenum: New York, 1996; ISBN 0-306-45380-0; $59.50 (hb). In Gocken and Reddy’s Thermodynamics, the emphasis is placed firmly on the practical application of thermodynamics to describe real systems. The development of the fundamental principles is done in a traditional style based on ideas of practicality and measurement. The subject material is almost entirely limited to classical thermodynamics, with very little reference to microscopic models or statistical concepts. While this takes away somewhat from the interconnectivity of modern physical chemistry, it keeps the book well focused and allows a considerable amount of detail to be presented without becoming unwieldy. The level of mathematics is kept relatively low, aside from the inevitable differential equations, and a separate chapter summarizes all of the math to be encountered, at a level appropriate for students in a first-year calculus course. Following the first two introductory chapters, roughly one-third of the book is devoted to a standard presentation of the three laws of thermodynamics, definition of the Gibbs and Helmholtz energies, and introduction of the chemical potential. Most of the remaining text is devoted to examples and applications of chemical equilibrium, including discussions of activities and real solutions, colligative properties, chemical reactions, electrolytes and cell reactions, and phase equilibria. This book would be suitable for the thermodynamics component of an introductory physical chemistry course in which more depth is sought than would be typically found in a comprehensive introductory text. At a more advanced level, the lack of statistical models is a limitation; however the material could be useful in a more applied course for students interested in chemical engineering or materials science. The book contains a good selection of problems and examples, and is quite well referenced with numerous footnotes. The strongest element of the book, in my opinion, is a very thorough treatment of phase diagrams, which does a good job of linking the topology to thermodynamic principles (although a more unified discussion of Maxwell construc-
tions and critical points would be welcome). This material includes a good discussion of liquid–vapor curves and partial pressures, and culminates in a large selection of real examples. Another prominent feature of the book is the inclusion of a large number of empirical formulas and approximation schemes, allowing each concept to be immediately extended to describe real systems. But this is also a weakness, since some key ideas can be drowned in a sea of parameters, with no further physical insight being provided. The biggest difficulty, however, stems from the fact that the book’s empirical emphasis is somewhat at odds with the axiomatic approach employed. This can lead to some awkward definitions, which are presented with little justification. For example, temperature is defined as an unspecified function of pressure and volume arising from a constraint on the number of degrees of freedom due to thermal equilibrium. Not only is this not very intuitive, it isn’t even correct since T(P,V) is not a single-valued function. Also, the chemical potential is defined solely as the partial molar Gibbs energy (which in turn is a “purely convenient” function), analogous to other partial molar quantities, rather than as a fundamental intensive variable on an even footing with temperature and pressure. This not only obscures the important role that it plays, but leads to unnecessarily convoluted definitions of chemical equilibrium. As a final note, the book comes equipped with a diskette containing a software package for thermodynamic simulation. The program provides a graphical display of c(sub)p, (Delta)(sub f)H(std), and (Delta)(sub f)G(std) as functions of temperature, using empirical formulas provided in the references. While potentially useful as a database of such information, the software adds very little to the pedagogical value of the book and is unlikely to be of much interest to students. From a practical point of view, the readme.txt file was not in fact readable without additional software, the interactive help is not yet available, and the program crashed several times while being tested. John R. Gunn Department of Chemistry, Université du Montréal Montreal, PQ, Canada email:
[email protected] Vol. 74 No. 8 August 1997 • Journal of Chemical Education
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