Molecular Thermodynamics (McQuarrie, Donald A.; Simon, John D.)

Jan 1, 2000 - in Molecular Thermodynamics give an immediate sense of its organization as ... Second Law of Thermodynamics; Entropy and the Third Law...
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Chemical Education Today

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Edward J. Walsh Allegheny College Meadville, PA 16335

Molecular Thermodynamics by Donald A. McQuarrie and John D. Simon University Science Books: Sausalito, CA, 1999. ISBN 1-891389-05-X. $78. reviewed by Norman C. Craig

As the title implies, this new physical chemistry textbook interweaves the statistical–molecular view with classical thermodynamics. For the most part this book is extracted from the 31 chapters of a recent comprehensive physical chemistry text by the same authors. Titles of the 14 chapters in Molecular Thermodynamics give an immediate sense of its organization as well as its content: The Energy Levels of Atoms and Molecules; The Properties of Gases; The Boltzmann Factor and Partition Functions; Partition Functions and Ideal Gases; The First Law of Thermodynamics; Entropy and the Second Law of Thermodynamics; Entropy and the Third Law of Thermodynamics; Helmholtz and Gibbs Energies; Phase Equilibria; Solutions I: Liquid–Liquid Solutions; Solutions II: Solid–Liquid Solutions; Chemical Equilibrium; Thermodynamics of Electrochemical Cells; and Nonequilibrium Thermodynamics. The chapter on nonequilibrium thermodynamics is an exceptional resource in a non-monograph. Interspersed with the first six numbered chapters are five lettered “Math Chapters” that provide essential mathematical material. This book effectively develops statistical thermodynamic ideas and equations in an accessible way and then uses them to reinforce and deepen the presentation of thermodynamics. Another notable feature of the book, as in its longer source book, is the frontispiece for each chapter, which is a photograph of a famous contributor to thermodynamics, such as Planck, Clausius, Gibbs, Helmholtz, Lewis, and Onsager, and a vignette about the person’s principal contribution and life. An abundance of worked and end-of-chapter problems is another strong feature, as is the near absence of errors, a sine qua non for a useful physical chemistry text. The tone of the writing is friendly and accessible. A manual with solutions to all the problems is available.

What is the audience for this text? In the preface the authors indicate that this book is suitable for an undergraduate physical chemistry course, presumably for a one-semester presentation since no development of kinetic processes, of the principles of quantum mechanics or of spectroscopy is included. Using the book in this way would be a strenuous undertaking and, even then, would require a careful selection of material. For an undergraduate physical chemistry course, I find two features missing that are important in my opinion. No figures or descriptions tell how experimental measurements are made even though many data are cited and used. With a very few exceptions the book contains no citations of the sources of data, of other texts, or of the literature. Consequently, students have no leads to supplementary material and may conclude that physical chemistry is a settled, classical subject. There are other disappointments. The zeroth law is not mentioned. Thus, the operational definition of temperature through experimental measurements is not well grounded or fully explained. The authors make a point of taking the modernizing step of using IUPAC units and symbols throughout the book, a choice that I applaud. Regrettably, they have not taken the same forward step with respect to “heat”. In the development of the first law, heat is carefully defined as a particular process by which energy is transferred. Elsewhere, however, “heat” is often used as though it were an energy content, as in “heat of reaction” and “heat bath”. The explanation of quantities like ∆ rH ° is inconsistent with IUPAC usage. We read that “∆ rH is an extensive quantity, whereas ∆ rH ° is an intensive quantity.” The “°” standard state designation does not confer such a per-mol distinction. We also read that ∆ rH ° “refers to the enthalpy change associated with one mole of a specified reagent.” The “°” does not confer this distinction either. In the IUPAC recommendations, the extent of reaction variable, ξ, carries units of mol. Thus, the per-mol aspect of ∆ rH ° or ∆ rH refers to any reaction as written, even to those with no unit stoichiometric coefficient. A ∆ rH ° or a similar quantity only has full meaning when a state-specific chemical equation is clearly associated with it. Norman C. Craig is in the Department of Chemistry, Oberlin College, Oberlin, OH 44074. • Vol. 77 No. 1 January 2000 • Journal of Chemical Education