Practical chemical thermodynamics for geoscientists, edited by B. Fegley, Jr. with contributions by R. Osborne. Amsterdam: Academic Press (Elsevier), 2013, 674 p, hardcover (ISBN #9780122511004).

Authors


image

Bruce Fegley has scripted a comprehensive text in classical phenomenological thermodynamics. Someone must perform this task every so often! Fegley explains fundamental principles in a lucid, easy-to-read manner, with abundant solved example problems, data tables, and problem sets for which a solutions manual is available. I recommend this book as a text for advanced undergraduate students. It also has a place with research scientists who may wish to refresh their understanding of a particular topic. Although digital versions of the text are available, I am happy to have this book on my shelf next to Nordstrom and Munoz's Geochemical thermodynamics (1994), Anderson and Crerar's Thermodynamics in geochemistry (1993), DeHeer's Phenomenological thermodynamics (1986), Kern and Weisbrod's Thermodynamics for geologists (1967), and Denbigh's The principles of chemical equilibrium (1955).

The practical aspects of this book lie in the many worked examples, and the condensed tables of standard thermodynamic properties and heat capacity regressions for a wide range of materials (appendices 1 and 2). While these data are no substitute for Chase et al.'s JANAF tables, or for self-consistent geoscience databases, they are useful for quick calculations. The worked examples, tested in the author's courses, make the copious equations accessible to the student. They often build on earlier examples through the text. An additional practical aspect is the extensive discussion of measurement techniques. Thus, we have a schematic of the electrochemical cell used by Wachter and Hildebrand in 1930, and separate sections on the calorimetry of pure substances and of reactions. Fegley reveals his deep interest in the sources and usefulness of thermodynamic data again in his in-depth discussion of reference states (ch. 5). The tables in the text are also quite practical, including mineral heat capacities, energy conversion factors, and Bridgman's formulas.

This hefty volume is peppered with images and short biographies of many scientists who contributed to the field. The juxtaposed visages of Carnot and Clausius (pp. 176–177) offer an amusing contrast. These, and frequent narratives about the development of key ideas, provide quite an engaging context for the subject matter, in contrast to the axiomatic treatment (e.g., Denbigh 1955). They are an aid for learning. For example, the third law is introduced through the historical development of the Nernst heat theorem, humanized with a bio of Hermann Walther Nernst (1864–1841). History is also given voice in the author's frequent use of non-SI units, giving the student valuable experience and the facility to appreciate older literature.

Another strength is the layout of topics. Fegley follows the first law with 100 pages on the thermal properties of pure substances, and thermochemistry. The second law is then presented, with a clear explanation of simple statistics and Stirling's approximation, and a short (incomplete) history of Maxwell's demon. Then 150 pages on phase equilibria of pure materials, and equations of state, precede the third law, which introduces chemical equilibria, solutions, and binary systems. Appendices, a 20-page bibliography, and a comprehensive index round out the volume. The author frequently refers the student back to earlier sections to review topics.

While the author covers a great many topics in excellent detail, he has drawn clear boundaries for the scope of this volume. Kinetic theory is dismissed early, and statistical thermodynamics is introduced only obliquely through the Boltzmann-Planck equation. On the other hand, Fegley dives deeply into models for heat capacities near absolute zero. The book finishes with binary solutions and phase diagrams. The student will have to go elsewhere for more advanced topics such as Schreinemaker's rules, the Darken equation, activity–activity diagrams, or Pourbaix (EH-pH) diagrams. Topics chosen for worked examples and discussion tend toward those aligning with the author's research expertise, in particular cosmochemistry, meteoritics, and gaseous systems. This is in contrast, for example, to Kern and Weisbrod's focus on solid earth examples. In a similar manner, the bibliography lacks reference to first authored works by a great number of modern contributors to the thermodynamics of solid planetary bodies. A welcome addition would be a short section guiding the student to the next level of study. But these are all minor weaknesses.

The greatest strength of this volume is its attention to the needs of the student. I hope its greatest value will be in drawing a new generation to apply classical thermodynamics in the geosciences with intellectual rigor. Given the rarity of Anderson and Crerar's hardcover edition, I urge colleagues to purchase this edition while it is still in print. I have found it a pleasure to review this excellent addition to the thermodynamics literature.

Ancillary