Physical Oganic Chemistry complexity; it is not very readable. This appeam to be the m u l t of a number Kenneth B. Wiberg, Yale University, of factors. The very wealth of detail reNew Raven, Connecticut. John Wiley quires compact wilting to meet the d+ and Sons, Inc., New York, 1964. viii mands of limited space. The w15ting 591 pp. Figs. and tables. 15.5 X sometimes seems poorly organized a t the 23.5 cm. $10.75. level of details. Became in some case? full logical exposition is not possible (for The development of physical organic chemistry has been an interesting one. reasons of space or the student's level of preparation), relevant details slip in and Perhaps, as Profemor Wiberg states in his out of the stream of discmion in a manner new "Physical Organic Chemistry," it can bewildering even to the experienced be considered to have come of age with the reader. The derivations, full as they am publication of the 6rst hook published in many ways, sometimes leave a vague under that title by Professor L. P. Hammett, in 1940. On looking again at sense of dissatisfaction because they are that classic text this writer was amazed to not absolutely rigorous. The authors have almost always increased the mathnote just how physical that presentation had been. During the intervening years maticd depth (relative to all other texts) the subject of physical organic chemistry of these derivations, but for reasons of sheer length often stop short of complete would appear to have advanced by twn neas. Since the reader has been atimudivergent paths. One of these, and much lated to higher expectations, this produces the less rtctively followed, developed essenfrustration greater than he receives from tially dong the lines laid down in Hama low-powered approach. It is only from mett's text; i.e., it was actually physicd the good that we demand perfection. chemistry applied to organic systems. The second type of physical organic, which The overall organization of the material might be thought of as having developed deserves comment. This reviewer is prejfrom the studies of the Ingold school, has udiced because of his belief that teaching concentrated on the elucidation of organic thermodynamics well is still the main rereaction mechanisms; the emphasis here of an introductory course in JORN P. CAESI~K sponsibility has been on organic chemistry, with tech~hysicalchemistry, and that this objective Haverford College is served best by placing thermodynamics niques and approaches borrowed from Haverfwd, Pennsylvania physical chemistry used as valuable supfirst and treating the microscopic theory plements. Too often in the past comafterward. The authors present (Chapmunication between these two groups has ters 1-6) a large batch of microscopic been poor and in turn both groups have theory, then thermodynamics, and then Phyricd Chemistry been the poorer for lack of communication. return to microscopic theory and ita adFortunately for a11 who call themselves vanced applications (13-17). While part D. F. Eggers, Jr., N . W . Gregmy, G. D. of the objection to this can be countered physical organic chemists there are a few Halaey, Jr., and B. 8.Rabinantch, all of people, among them Professor Wiberg, hy the observation that the text material the University of Washington, Seattle. can be presented non-seqnentially, the who are able to bridge this gap and to John Wiley and Sons, New York, 1964. amount of cross-referencing between assist the rest of us in bridging this same 784 pp. Figs, and tables. 17 X 24 widely spaced sections on related topics is gap between what might be edled phy~icsl em. $9.95. great enough to make one wish that such organic chemistry on the one hand and organic physical on the other. Viewed rich content were better ordered. from this vantage point ProfessorWiherg's The strongest chaptes in the book are the most ambitious attempt so far to in"Physical Organic Chemistry" is, in our those on chemical kinetics, scattering, opinion, a brilliant success. Seldom, in clude all the basic information pertinent to diffraction and crystal structure, and modem physical chemistry. In this rerecent years, have we experienced the molecular spectra. Those on statistical spect it belongs to the claas of texts of mechaninios are also good. The weakest sheer delight, dimly remembered from which the book by W. J. Moore is the best college days, of having whole new and portions of the text are those dealing with known earlier example. One is unavoidtotally different areas of ideas brought to classical thermodynamics, because the ably inkenced by comparisons, favorable light. And this Wiberg has given us on organization and logical coherence of that and otherwise, between this book and page after page, a t least for this reader. beautiful subject me lost by diffusely Moore's book, now in its third edition. A good treatment ordered In short "Physical Organic Chemistry'' is The authors have succeeded in including of thermodynamics should almost lead the just plain fun-if a bit d i f f i c u l t t o read. substantially more information than is student automatically onward. A large Wiberg has organized his book into available in Moore's book, mostly in the amount of scatter of really closely related three major sections together with nine Line of mathematical details or in dweloptopios is created because the presentation aocompanying appendixes. Part I, ments of special applications, but also a Bonding and Spectra (209 pps.), is essenis dominated by classification according to few sections on recent advances in seientidly a summary of approximate quantum applications. However, this fault a180 tific theory and techniques, mch as magmeehsnical approav,hes to the study of occurs in most other texta, though to netic resonance. Especially in the secbonding and spectra. Parts I1 and 111 lesser extent. tions dealing with the microscopic theory are entitled Equilibria (95 pps.) and A large part of this reviewer's criticism of matter, derivations tend to be more dewas aroused because the authors' effort Kinetics (136 pps.). Appendixes include This wealth ~ tailed and m o complete. a review of determinants and matrices, evokes a vision of what is perhaps unatof information available in one text is the group character tables, tables of evaluated tainable. It may not yet be to greatest point in its favor. I t should overlap and related integrals, a practical really teach so much to beginning stumake a valuable reference for brief review example of the analysis of an NMR specdents, but tbat is an ambition for many on many topics in physical chemistry. trum, tables of thermodynamic functions teachers, and the book raises that ambiThe student who has used this text in an for a harmonic oscillator, and, interesttion. The information is surely preaent introductory c o m e may find it of greatest ingly, an introduction to computer proin the text; one's only disappointment is value to him some years later. Another gramming. that it has not been as well organized as is important strength is the arrangement of possible. On balance, however, one must Particularly interesting to us, although most physicochemical data in an Appendix this may be merely an accident of our still say that this book is one of the best at the back of the text; the reader need background, were discussions of the pertwo or three in the field. not thumb the book in a vain search for turbation method of approximatian, the WALTERR. THORSON molecular orbital treatment of rtromatic numerical values. Marsochusetts Institute of Technology On the other h d , in my opinion the (Continued on page A806) Camhn'dge, Massachusetts book is hampered by a heavy sense of
chemical kinetics contains an adequste treatment of "absolute" rate theory. The final chapter concludes with considerations of heterogeneous, electrolysis, and photochemical reactions. The material on statistical mechanics and thermodynamics is found in three widely separated parts (Chapters 4,9, and 24) which does not seem to be in keeping with the continuity of development found for other topics. There are some elegant examples chosen and dimussed in detail which illustrate the use of molecular models to obtain observable physical properties. Planck's treae ment of the blackbody radiation problem (in the chapter The Structure of Matter) and the discussion of intermolecular forces and effects of attractive dispersion forces an the equation of state of a gas are particular examples. Questions may always be raised about any text of finite length concerning relative emphasis and coverage of topics; these involve questions of taste in most cases. The reviewer was left with the impreaaion that a valuable addition has been made to the liet of general physical chemistry texts available for capable students.
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BOOK REVIEWS compounds including electron repulsion terms which leads to an introduction to Slater Self-Consistent Field Theory, avery interesting development of symmetry classes and operations and their applications to the analysis of ultraviolet, spectra, an extremely lucid presentation of simple quantum mechanical methods of analyzing NMR spectra, an enlightening, if simplified, development of absolute rate theory, and finally the aforementioned appendix introducing the techniques of computer programming. Other subjects, far too numerous to mention here. msv be somewhat less works in the physical organic library. The subject matter of Part I, in particular, duplicates much of that in Streitwieser's "Molecular Orbital Theory for Organic Chemists." In his preface Professor Wiberg indicates that "Physical Organic Chemistry" is intended as a text "for a one-year graduate course, possibly in conjunction with s. test which mll present the more organic chemictll aspects." I for one will continue t o teach my graduate course with greater emphasis on the more organic chemical aapects; but I shall certainly use Wiberg's book to revise my notes and I shall recommend it, along with several ot,her supplementary texta, t o m y students. Typographical errors dn not appear t o be plentiful and most of them can be corrected on inspection. Our only major criticism of the text is the rather artificial separation of kinetic and equilibrium phenomena into separate rhaptem. We might have preferred, for example, a single discussion of linear free energy relationships, both kinetic and thermodynamic. I n summary Wiberg's "Physical Organir: Chemistry" is, in our opinion, an important addition t o the literature of orgrtnic chemistry ~ n should d do much t o educate students as well as pract,itioners of physical organio chemistry in the more physical aspects of that subject. RICHARD A. SNEEN
Purdue Univemily L q f n y e l l ~ Indiana ,
Spertrometrie Identification of Organic Compounds
Robert M. Silverstein and G. Clayton Bassler, both of the Stanford Research Institute, Menlo Park, California. John Wiley and Sons, Inc., Xew York, 1963. 23.5 X 30 em. l i i pp. Figs. and tables. $8.50. This short text is a welcome addition to the literature concerned with the tnstmmental determination of organic structures. The authon accomplish in good style what they set out to do; namely to compress into one text enough essential information about mass, infrared, nuclear magnetic resonance, and ultraviolet spectrometry so that the advanced under-
(Continued on page A808)
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