Chemical Education Today
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book & media reviews
Edward J. Walsh Allegheny College Meadville, PA 16335
Reaction Kinetics Michael J. Pilling and Paul W. Seakins. Oxford University: New York, 1995. xiii + 305 pp. Figs. and tables. $29.95 (paperback). This first-edition text aims to give advanced undergraduates a broad overview of reaction kinetics. It begins with a review of the fundamentals of rate equations and coefficients. The authors assume, at least implicitly, that the reader has had some previous exposure to chemical kinetics, so this initial review is brief. The first new material that undergraduate students are likely to encounter is in Chapter 2, which presents a fairly comprehensive overview of experimental techniques used to study reaction kinetics in the gas and liquid phases. The rest of the book is divided into three sections. The first, Chapters 3 through 5, presents an indepth look at reaction kinetics and dynamics in the gas phase. Rate theories for activated bimolecular reactions are discussed at a relatively sophisticated level (although the overview of variational transition state theory is somewhat muddy) and are compared with experimental results. The authors discuss both bulb methods and molecular beam techniques for the experimental study of reaction dynamics and show how experimental results can shed light on the atomiclevel mechanisms of elementary reactions. Unimolecular reactions are treated within the context of RRKM theory, and association reactions are touched on briefly. The book’s second section (Chapters 6 and 7) examines, in less detail, the kinetics of elementary reactions in solution and at surfaces. The third section (Chapters 8 through 11) considers systems of elementary reactions, including chain reactions, explosions, and oscillatory reactions. This section points out the importance of kinetics in studies of combustion, polymerization, and atmospheric chemistry, giving these chapters an applied flavor that nicely complements the fundamental viewpoint of Chapters 3 through 7. The book concludes with a brief discussion of photochemical kinetics in Chapter 12. The book is well laid out and attractively typeset. Each chapter features a number of shaded “boxes” containing supplementary material or mathematical derivations that can be omitted on a first reading (e.g., the mechanism by which lasers operate, or the use of numerical methods to integrate complex rate equations). A large number of figures supplement the text. For the most part, these are well-designed and easy to understand;
however, a few figures have defects that I hope will be corrected in subsequent editions. For instance, a poorly placed (and superfluous) legend rendered Figure 2.18 nearly unintelligible to me on the first (and second!) reading. The ordinate of Figure 11.2(b) is unlabeled, and the shaded background of Figure 12.6 makes it hard to read. One aspect of the book’s design that I found particularly appealing is the wealth of “study notes”, which are summaries of recent and ongoing research in reaction kinetics and dynamics, and which include references to journal articles that have appeared in the last 10 to 15 years. A variety of topics are covered in these study notes, ranging from the role of intramolecular vibrational energy redistribution in RRKM theory to the photodissociation of molecules embedded in clusters. The study notes convey the sense that reaction kinetics is a thriving and wide-ranging subfield of chemistry. Of course, no first edition text is without its minor errors. For instance, in-text citations of the references listed at the end of each chapter are sometimes a bit sloppy. Also, although partition functions are described in Chapter 3 as weighted sums of quantum states, the translational partition function in Table 3.3 is not dimensionless, but has units of volume. My main substantive complaint is that the book omits any discussion of gas phase ion–molecule reactions, or other gas phase reactions which take place on barrierless potential surfaces. Because of their importance in interstellar chemistry, these reactions have been the focus of many lowtemperature experimental studies, and a variety of elegant “capture” theories have been advanced to explain the unusual kinetic behavior they exhibit. The text would be suitable for use in a survey-style course in chemical kinetics for advanced undergraduates who have already taken a standard physical chemistry course. A few homework problems accompany each chapter. The text is written at a level somewhat below that of K. J. Laidler’s Chemical Kinetics, but instructors who use Laidler’s book in an introductory graduate-level course may wish to consult the “study notes” provided by Pilling and Seakins for hints on connecting Laidler’s text to the modern research literature. Robert J. Hinde Department of Chemistry, University of Tennessee Knoxville, TN 37996-1600
Vol. 74 No. 6 June 1997 • Journal of Chemical Education
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