Physical Chemistry: Thermodynamics (Horia Metiu) - ACS Publications


Physical Chemistry: Thermodynamics (Horia Metiu) - ACS Publicationshttps://pubs.acs.org/doi/full/10.1021/ed085p206Simila...

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Chemical Education Today

Book & Media Reviews Physical Chemistry: Thermodynamics by Horia Metiu Taylor & Francis, New York, London, 2006. 694 pp. ISBN: 978-0815340911 (paper). $49.95

Physical Chemistry: Statistical Mechanics by Horia Metiu Taylor & Francis, New York, London, 2006. 292 pp. ISBN: 978-0815340850 (paper). $44.95

Physical Chemistry: Kinetics by Horia Metiu Taylor & Francis, New York, London, 2006. 169 pp. ISBN: 978-0815340898 (paper). $44.95

Physical Chemistry: Quantum Mechanics by Horia Metiu Taylor & Francis, New York, London, 2006. 481 pp. ISBN: 978-0815340874 (paper). $44.95 reviewed by John Krenos

Horia Metiu has created a significant set of volumes on undergraduate physical chemistry. The integration of Mathematica and Mathcad workbooks into the four texts provides instructors with an attractive new option in teaching. Metiu’s writing style is folksy and the graphics minimal, a refreshing approach. A brief overview of topics and a description of a few software examples form the basis of this review. The four texts are considered in the order provided on the inside cover by the publisher, namely Thermodynamics, Statistical Mechanics, Kinetics, and Quantum Mechanics. Each begins with a preface designed to explain the author’s approach to incorporating Mathematica/Mathcad workbooks into a physical chemistry text, and a preview of the material to be covered. A how-to section follows that elaborates on the use of workbooks, exercises, and problems. The section is worded the same in the four volumes; however, at its end, the author provides a different chapter-by-chapter listing of unsolved exercises, a clearly useful guide for the instructor. The text-specific workbooks are included on a CD-ROM attached to the inside back cover of each text. On each CD, helpful tutorials are also provided for Mathematica and Mathcad. The Mathematica workbooks were created by the author at the University of California Santa Barbara with the use of version

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Jeffrey Kovac University of Tennessee Knoxville, TN 37996-1600

5.1. The Mathcad workbooks were created by Jeffry Madura at Duquesne University. I viewed the workbooks at Rutgers with Mathematica 5.2 (site license) and Mathcad 2001i (personal copy); they performed as advertised. Thermodynamics is the most extensive and impressive. By design, only a few end-of-chapter problems are given. On the other hand, the author embeds numerous examples and exercises in the text. The CD-software workbooks are intended to remove the mathematical simplification and approximation used by necessity in conventional texts; they succeed admirably with calculations of much greater accuracy and application (19 workbook files in Mathematica, a substantial number considering each file typically contains many examples and problems). I particularly like the section on realistic gas laws. An interesting application is the determination of the van der Waals a and b coefficients by fitting actual pressure–temperature data for ethane over a wide range of conditions followed by a comparison to tabular values. This volume also incorporates relevant historical information; for example, insightful and original observations by Daniel Fahrenheit, Joseph Black, and others are presented as supplements. Chapters in Thermodynamics cover the following topics (taken from 29 chapter titles): Temperature, Pressure, Molar Volume, and Equilibrium; The Equation of State; How to Use the Equation of State; Thermodynamic Transformations; Work; Heat; Reversible and Irreversible Transformations; PathDependent and Path-Independent Quantities; First and Second Laws; Helmholtz and Gibbs Free Energies; How to Calculate the Change of Entropy in an Equilibrium Transformation; Thermochemistry; The Change of Chemical Potential During an Equilibrium Transformation; The Chemical Potential of a Compound in a Mixture; Mixtures: Partial Molar Quantities and Activities; Chemical Equilibrium (five chapters); Phase Transitions–Equilibria (four chapters); Vapor–Liquid Equilibrium; Electrolyte Solutions; Electrochemistry (two chapters). All topics are covered in depth. There are nine appendices containing a variety of data. I especially found useful the one in which the author lists thermodynamic properties for 33 compounds at eight different temperatures (298.15 K to 1000 K). One minor issue is the author’s use of lower case symbols for molar volume (υ) and molar entropy (s) contrary to usage found in many physical chemistry texts (Vm and Sm, respectively). Statistical Mechanics and Kinetics are used together in a quarter course at Santa Barbara. The two texts are somewhat integrated in that the last topic in the former, Transition State Theory, has applications to the latter. The 15 chapters in Statistical Mechanics cover the following topics: The Fundamental Equations of Statistical Mechanics; The Physical Interpretation of the Fundamental Equations of Statistical Mechanics; Interpretation of the Thermodynamic Quantities; The Partition Function of a System of Independent Particles; The Partition Function of an

Journal of Chemical Education  •  Vol. 85  No. 2  February 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education 

Chemical Education Today

Book & Media Reviews Ideal Gas of Atoms; The Thermodynamic Functions of an Ideal Gas of Atoms; The Thermodynamics Properties of an Ideal Gas for which Electronic and Nuclear Contributions are Negligible; A Test of the Theory for a Gas for which Electronic and Nuclear Degrees of Freedom Matter; The Statistical Mechanics of a Gas of Diatomic Molecules; A Gas of Diatomic Molecules: Comparison with Experiment; Chemical Equilibrium; Transition State Theory (four chapters). Polyatomic molecules are not included in the discussion, a topic that many physical chemistry texts consider in detail. An ample number of workbooks (11) and exercises are included. One topic with clear and thorough explanations is the development of the properties of ortho- and para-hydrogen. The accompanying workbook calculations of heat capacity against temperature are informative. Kinetics is the smallest and least developed volume. Basic kinetics, however, is treated well and workbooks with powerful differential equation solving power offer great utility (eight workbooks are included). The nine chapters in Kinetics cover these topics: Generalities about the Rates of Chemical Reactions; Irreversible First-Order Reactions; The Temperature Dependence of the Rate Constant: the Arrhenius Formula; Irreversible Second-Order Reactions; Reversible First-Order Reactions; Reversible Second-Order Reactions; Coupled Reactions; An Example of a Complex Reaction: Chain Reactions; Enzyme Kinetics. Missing topics include collision theory, Lindemann theory, RRKM theory, termolecular reactions, transport processes, and molecular reaction dynamics (although a discussion of potential energy surfaces relating to some chemical reactions is given in Statistical Mechanics). Quantum Mechanics is a volume I especially like. The approach is to begin with physical observables and classical mechanics, leading to the introduction of mathematical operators and the transformations required for the wave treatment. The 21 chapters in Quantum Mechanics cover: Why Quantum Mechanics?; Dynamical Variables and Operators; The Eigenvalue Problem; What Do We Measure When We Study Quantum Systems; Some Results are Certain, Most are Just Probable; The Physical Interpretation of the Wavefunction; Tunneling; Particle in a Box; Light Emission and Absorption: the Phenomena; Light Emission and Absorption: Einstein’s Phenomenological Theory; Light Absorption: A Result of Quantum Theory; Light Emission and Absorption by a Particle in a Box and a Harmonic Oscillator; Two-Particle Systems; Angular Momentum; Two-Particle Systems: The Radial and Angular Schrödinger Equation; The Energy Eigenstates of a Diatomic Molecule; Diatomic Molecule: Its Spectroscopy; Hydrogen

Atom: the Eigenstates; The Spin of the Electron and Its Role in Spectroscopy; The Hydrogen Molecule; Nuclear Magnetic Resonance and Electron Spin Resonance. Most chapters have workbooks, a total of 17. The section on NMR is of particular note because most chemists are familiar with this technique and accurate calculations are possible with less effort. Symmetry is not covered, because, in the words of the author, “to do it right would take too much time” and, in addition, “doing it briefly leads to a presentation devoid of content.” As in Statistical Mechanics, polyatomic molecules are not treated. The author uses the symbol ħ for the Planck constant and the symbol Ω for the photon frequency in both Statistical Mechanics and Quantum Mechanics (Ephoton = ħΩ). In Chapter 9 of Quantum Mechanics, he introduces the “old” Planck constant h, the “old” frequency v, and the latter’s mathematical relationship to Ω. The term “old” refers to the old quantum theory. The symbol ħ is then referred to as the “new” Planck constant and Ω the “new” photon frequency. In Chapter 21, the “old” constant and frequency are used in the treatment of NMR. In that chapter, the author reveals for the first time that Ω is called the angular frequency. Taken as a whole, the four volumes on physical chemistry by Metiu are impressive, particularly Thermodynamics and Quantum Mechanics. The texts may be used with or without the math software, but teaching will be most effective if workbooks are used. The two-semester physical chemistry sequence at Rutgers covers the topics of quantum chemistry and spectroscopy in the first semester; thermodynamics, statistical mechanics, and kinetics in the second. One of our instructors has the goal of incorporating Mathematica workbooks into our first semester course and is currently evaluating Quantum Mechanics. Without a doubt, the four textbooks provide essential materials of great utility to physical chemistry instructors. The bottom line is that the set of four volumes is a must have—a keeper—as a novel resource or invaluable classroom tool. Supporting JCE Online Material

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John Krenos is a member of the Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road, Piscataway, NJ 08854-8087; krenos@ rutgers.edu.

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