Statistical mechanics, second edition (Mayer, Joseph Edward)

primarily on transition state theory treat- ments are offered for estimating the A-factor. A new discussion of activation energies is included which p...
4 downloads 0 Views 2MB Size
book reviews primarily on transition state theory treatments are offered for estimating the A-factor. A new discussion of activation energies is included which provides some suggestions for qualitatively estimating this parameter in selected himolecular reactions. Regrettably, activation energies continue to resist quantitative generalization for reactions involving four - - - - or more reaction centers although Professor Benson has made a laudable start in the right direction. The final section is addressed to several complex reaction systems. While the cases discussed are of considerable interest and illustrate interesting applications, they are by no means inclusive. Since each complex system. cases not men~ -includine ~ ~ numerous ~ , twnrd, rends ro exhihir IW own ehnracrrristic pnrpertirs, n general methodolwy i\ all but impusuible to dewlop. F~nally,thenumeroustablc~ presented in thr aawndix omvide quwk awrss tan a wealth of infannation useful t o anyone interested in atomic and molecular ~raoerties and reac. . tiuw including thcrmcrhcm~raldatat'oruomr gas phase free md~rals.11 - h d d also he noted that SI unirsare not "3rd nnd all nwrpy data are based on the calorie. Currently a sizable amount of information on specific reacting systems is known, but unifying themes and generalities suitable for eatendine these data to uncharacterized aysrems remaill smrcr. It is in rhia very dif. fictrlr nrea that I'rot'e.sur Hrnscm ha* made asi@i~+nt cuntribut~on.In sum, thisedition of i n important boak continues to provide valuable reference information both for use in the classroom and in research. It should prove to be a welcome addition t o any personal or departmental chemistry library. ~~

~

~

~

~

Leonard D. Spicer Universlfy of Utah

san Lake Ci3: Utah 84112

Statistical Mechanics. Second Ediilon

Joseph Edward Mayer, University of California, San Diego-La Jolla, and the late Maria Goeppert Mayer. John Wiley & Sons, New York, 1977. xv 491 pages. Figs. and tables. 16 X 23.5 cm. $23.50.

+

The first edition afthis book has long been regarded as a classic in the field of equilihrium statistical mechanics. Thus, after 37 years a new edition is indeed welcome. The present book is the same length as the first edition, but has been completely rewritten. The revisions are largely in the organization and the manner of development rather than in the introduction of new or updated material. More attention has been given to the logic and fundamental structure, making this edition mathematically more abstract than the first. The book is divided into three parts. Part I rives a verv brief historical prespective, a . short account of prohnhility theory, and a disctssiun of kinetic theory ofgases. Part 11 cmtaitu the atatiurical-m~rhanirnl formalism ~

A248 / Journal of Chemical Education

and the derivations of the ensemble distrihutians. Part 111 is devoted t o applications: perfect gases, dense gases, liquids, crystalline solids, Bose-Einstein and Fermi-Dirac perfect gases, systems in electric and magnetic fields, and the density matrix. The chapters and even some sections are intended to be self-contained, so that the reader can study various parts of the formal theory or the applications without reference to other chapters. The authors have succeeded quite well in this attempt. I found the presentation of the basic theory in Part I1 to be the most valuable part of this hook. The logical structure of statistical mechanics is beautifully and elegantly displayed. The various ensembles are introduced in a unified way so as to emphasize their inherent similarities. In the development of the formalism, classical and quantum systems are treated in parallel, so that again the inherent similarities are evident. My only criticism here is that Planck's constant is introduced into classical phase space by means of an ad hoe application of the uncertainty principle rather than by the more rigorous WignerKirkwoad expansion. In the chapters on applications, the emphasis is on the mathematical structure rather than on the physical problems. In fact, the chapter on liquids invokes such mathematical abstraction that it puts even Munster [A. Miinster, "Statistical Thermodynamics"] to shame. Although these chapters in this new edition have been completely rewritten, they still deal for the most part with material contained in the first edition. No recent applications are included. For example, such recent and important developments in the theory of liquids as Percus-Yevick, hypernetted chain, and perturbation theories are barely mentioned in the 44-page chapter on liquids. Devotees of the first edition will be happy to find that the chapter on dense gases still contains an extensive treatment of clusters, a technique pioneered by one of the authors. The book is clearly written with detailed discussions. The level of presentation, however, is fairly advanced and the treatment is largely abstract and mathematical. This approach is not particularly suitable for a first exposure t o statistical mechanics. The mathematical background that the reader should have is modest, with many mathematical topics outlined in the appendices. In addition to the normally expected acquaintance with quantum theory, the reader is also assumed to be familiar with the Hamiltonian formulation of classical mechanics. In contrast to the first edition, there are no prohlems or exercises. Thus, this book is not a good choice for a senior or first-year graduate course in statistical mechanics, especially since D. McQumie's "Statistical Mechanics" is available. For the serious student of statistical mechanics, however, this hook provides a unique insight into the foundations and logical structure. It is destined t o attain the same reputation as a classic as did the first edition. Donald D. Fins Universtly of Pennsylvania Philadelphia.Pennsylvania 19104

Fundamentals of Electrochemical Analysis

Zbigniew Golus, Warsaw University, with translation by G. F. Reynolds, University of Reading. John Wiley % Sons, New York, 1976. xviii 520 pages. Figs. and tables. 16 X 23.5 cm. $49., cloth.

+

The author presents a logical and clear development of the theory and application of polarography, chronopotentiometry, stationary electrode voltammetry with linearly changing potential, and the rotating disc method. I t is the author's ooinian that "an -~~ ~mderatnndineof the theor;tieal orincinles ~

~

~

The first six chapters treat the electrical double layer structure, rates of electrode processes, diffusion, diffusion controlled electrode processes, charge transfer controlled processes, and the application of each of these topics t o the four techniques listed above. The seventh chapter presents the theoretical equations which describe each of these techniques under reversible and irreversible conditions and a description of the extractable kinetic oarameters. The first 254 pages of the book-are comprised of these chapters. The next six chapters treat electrode processes which involve complicated chemical reactions involving preceding and following first-order chemical reactions, catalytic reactions, higher-order reactions, dimerization, and disproportionation. Chapter 14 describes the aoolication of the four emohasized techniques tu thr study of