In the last ten years Professor Lip- scomh's brilliant X-ray diffraction studies have established not only the structures of the simple boron hydrides discussed by Profemor Starch, these have also been ex- tended to the much more complex neutral and ionic boron hydride species only recently discovered. Their topological and moleculsr orbital treatment of th-

this area. The first chapter is the best summary of

the molecular structures of neutral and ionic boron hydrides, boron halides, borohydrides and carboranes ever written. Chapter 2 describes the three types of "three center bond" for the more open boron hydrides. I t also includes the topological theory of boron hydrides developed by the author. Chapter 3 con- tinues in detail the applic&m of the molecular orbital theory to the structure and relative stabilities of the various molecular conformations of the boron hydrides. Chapter 4 discwe8 the nu- clear magnetic resonance studies reported for these compounds; advantages and pitfalls of these studies are clearly pointed out.

The last chapter summarizes and at- tempts to systematize the chemistry of the various boron hydrides. Much of this is in concise tabular form.

The book includes 339 recent references, some from 1963, and references to eleven review articles written in the last ten years. Two appendixes are attached; the first one on "three center bond" structures of the boron hydride ions; the second on "spherical coordination for boron hydride models."

The book is a joy to read as Profeasor Lipscomb's enthusiasm for this topic permeates i t from cover to cover. This volume is a must for the bookshelves of all inorganic chemists.

HANS B. JONASSEN Tulane Universily

N m Orleans. Louisiana

The Inorganic Chemistry of Nitrogen

Wdliam L. Jolly, University of Cali- fornia, Berkeley. Physical Inorganic Chemistry Series, edited by Robert A. Plane and Michell J. Siako. W. A. Benjamin, Inc., New York, 1964. xi + 124 pp. Figs. and tables. 16 X 23.5 em. $5.75.

The folloving topics are covered in the first six chapters of this book: unique features of nitrogen, elementary nitrogen, ammonia, nitrogen halogen compounds, the hydronitrogens and hydroxylamine, and the nitrogen oxides and oxyacid. The next four chapters cover the com- pounds of nitrogen with sulfur, phospho- rous, carbon, and boron. The final chapter discusses the thermodynamics of nitrogen compounds.

The author points out that the chemical and physical properties of nitrogen com- pounds vary widely and that a large number of strueturea has been established for them. He emphasizes throughout the hook that most nitrogen compounds are

unstable with respect to their elements and that in all these basic reactions which are favored thermodynamirally proceed at a rate which is negligible. This m t - urally makes this field of great interest to scientists to whom numerous pmblems are pointed out which need to be studied.

At the end of each chapter a few general references are listed. These, however, are so general, that in many cases they are of limited usefulness to the reader whose appetite has been whetted by the material in the chapter.

One of the prime purposes of this series as indicated by the editors was to create a series of inexpensive monographs which could be used as supplementary text in advanced treatments of inorganic chem- istry in which a physical chemical ap- proach was strong.

I t was also hoped that these volumes could be used as reference books which would elearly point out meas in which re- search would be fruitful and would con- tribute to the accumulation of fundamental knowledge. Unfortunately this volume is not inexpensive (a. paperback edition would he welcome). I t is also too short to serve as a good reference book.

A few emom have crept in (for example: Fig. 6-1 is not the phase diagram of H20- HNO.)~ -",.

The style of writing, however, is excel- lent and easily understandable. The illustrations are well done, and the paper, type, and binding are of high quality.

HANS B. JONASSEN Tulane University

New Orleans, Louisiana

Physical Chemistry

Gilbert W. Cmaslellan, Catholic Univer- sity of America, Washington, D. C. Addison-Wesley Publishing Co., Inc., Readimg, Massachusetts, 1964. xv f 717 pp. Figs. and tables. 17x24 cm. $12.50.

The author seta the stage for his text in the preface with the comment that "rather than attempt an encyclopedic coverage of the subject and include a paragraph on an- most anything, I have tried to cover fundamentals and some applications in depth," and with a discussion of his aims to cover topics with s. fair amount of mathematical rigor, which is held in most cases to make the subject simpler than the incomplete "simplified" derivations fre- quently encountered in physical chemistry texts. This is done with elementary cdculua including use of partial derive tives; interludes on the uses and manip- ulations of partial derivatives are added where appropriate.

The choice of topiea and relative em- phasis would make this text most appro- priate for a two-semester course in physical chemistry in which the bulk of time is spent on "classical" topics with short treatments of quantum theory with its applications and a moderate amount of time allotted to topics of statistical me- chanics. For such a course this would be the reviewer's choice of the texts available far a degree of sophistication, rigor, and understanding higher than that found in

texts of the level of Maron and Prutton, "Physical Chemidry" and Daniels, el al.

The text opens with faur chapters (70 pages) on the physical properties of gases and the kinetic theory of gases. Some derivations, e.g., pressure of a gas, are covered using average molecular speeds, and then the Maxwell distribution func- tion is presented and a variety of averages and properties are derived from this. A short chapter on the bulk properties of solids and liquids is then followed by a de- velopment of the laws of thermodynamics, overing 110 pages, which NnS through conditions for equilibrium and properties of the free energy functions. This de- velopment follows an outline somewhat similar to that of the first eight chap- ters of Klotz, "Chemical Thermody- namics!' The discussion is begun with a careful consideration of the concept of temperature and the definition of tem- perature scdeles with the use of the "zeroth law!' The treatment of the first law, which probably introduces and applies the bulk of the mathematical apparatus and approach of thermodynamics as well as the thermochemicd applications, takes about 50 pages of this block of material. After this general treatment follow four chapters (120 pages) on the applietttions of thermo- dynamics to systems of variable composi- tion, phase equilibria, and ideal solutions and colligative ~ r o ~ e r t i e s of solutions. This is done with full use of the chemical potential and its properties in the derive tians. Two chapters on equilibria in non- ideal systems and in electrochemical cells, with a later chapter on electrical conduc- tion, mostly of electrolyte solutions, pro- vide 80 pages of material on electrochem- istry. Quantum theory is treated in three chapters on the structure of matter, mod- ern theory of the atom, and the covalent bond. An argument is presented for the SchrBdinger equation and the formalism of modern quantum mechanics is sum- marized. The problems of the free par- ticle and the particle in a. one dimensional box with infinite walls are solved care- fully, and the results of the one electron hydrogen atom problem are presented and used in the usual "aufbau" discussion of electronic configurations of polyelectronic atom. A description of chemical bonding in the valence bond and molecular orbital approaches precedes a qualitative disous- sion of the hondimg of the first row ele- ments in t e r m of hybrid orbitals and sigma and pi honding. Solutions for the energy levels of the rigid rotor and har- monic oscillator are given with a very brief oonsideration of molecular spectra. Chapters of approximately 20-page length are found on the structure of solids and liquids, statistical thermodynamics, sur- face phenomena, and tranaport properties. An 80-page, three-chapter unit, discussing various aspects of chemical kinetics, con- cludes the book. Sufficient, hut not ex- cessive, time is spent on the integration of ~imnle rate laws. The Lindemann mech- ~~~~ r ~ - ~ ~~ ~~ ~

aniwl fur a unimolrrulxr rrartion is form- u l ~ r ~ d i~ an e m m p l ~ ui a irwdel far a reac- rim mechanism, und s trearmeut of mnlri- step chain reactions includes the hydrogen- bromine reaction and the Rice-Herefeld mechanism for the decomposition of ethane as the principal examples. The chapter on the theoretical aspects of

Volume 41, Number 10, October 1964 / 577

chemical kinetics contains an adequste treatment of "absolute" rate theory. The final chapter concludes with con- siderations 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 observa- ble physical properties. Planck's treae ment of the blackbody radiation problem (in the chapter The Structure of Mat- ter) 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.

JORN P. CAESI~K Haverford College

Haverfwd, Pennsylvania

Phyricd Chemistry

D. F. Eggers, Jr., N . W . Gregmy, G. D. Halaey, Jr., and B. 8. Rabinantch, all of the University of Washington, Seattle. John Wiley and Sons, New York, 1964. 784 pp. Figs, and tables. 17 X 24 em. $9.95.

the most ambitious attempt so far to in- clude all the basic information pertinent to modem physical chemistry. In this re- spect i t belongs to the claas of texts of which the book by W. J. Moore is the best known earlier example. One is unavoid- ably inkenced by comparisons, favorable and otherwise, between this book and Moore's book, now in its third edition.

The authors have succeeded in including substantially more information than is available in Moore's book, mostly in the Line of mathematical details or in dwelop- ments of special applications, but also a few sections on recent advances in seien- tific theory and techniques, mch as mag- netic resonance. Especially in the sec- tions dealing with the microscopic theory of matter, derivations tend to be more de- tailed and m o ~ complete. This wealth of information available in one text is the greatest point in its favor. I t should make a valuable reference for brief review on many topics in physical chemistry. The student who has used this text in an introductory come may find it of greatest value to him some years later. Another important strength is the arrangement of most physicochemical data in an Appendix at the back of the text; the reader need not thumb the book in a vain search for numerical values.

On the other h d , in my opinion the book is hampered by a heavy sense of

complexity; it is not very readable. This appeam to be the m u l t of a number of factors. The very wealth of detail re- quires compact wilting to meet the d+ mands of limited space. The w15ting sometimes seems poorly organized a t the level of details. Became in some case? full logical exposition is not possible (for reasons of space or the student's level of preparation), relevant details slip in and out of the stream of discmion in a manner bewildering even to the experienced reader. The derivations, full as they am in many ways, sometimes leave a vague sense of dissatisfaction because they are not absolutely rigorous. The authors have almost always increased the math- maticd depth (relative to all other texts) of these derivations, but for reasons of sheer length often stop short of complete neas. Since the reader has been atimu- lated to higher expectations, this produces frustration greater than he receives from a low-powered approach. It is only from the good that we demand perfection.

The overall organization of the material deserves comment. This reviewer is prej- udiced because of his belief that teaching thermodynamics well is still the main re- sponsibility of an introductory course in ~hysical chemistry, and that this objective is served best by placing thermodynamics first and treating the microscopic theory afterward. The authors present (Chap- ters 1-6) a large batch of microscopic theory, then thermodynamics, and then return to microscopic theory and ita ad- vanced applications (13-17). While part of the objection to this can be countered hy the observation that the text material can be presented non-seqnentially, the amount of cross-referencing between widely spaced sections on related topics is great enough to make one wish that such rich content were better ordered.

The strongest chaptes in the book are those on chemical kinetics, scattering, diffraction and crystal structure, and molecular spectra. Those on statistical mechaninios are also good. The weakest portions of the text are those dealing with classical thermodynamics, because the organization and logical coherence of that beautiful subject me lost by diffusely ordered A good treatment of thermodynamics should almost lead the student automatically onward. A large amount of scatter of really closely related topios is created because the presentation is dominated by classification according to applications. However, this fault a180 occurs in most other texta, though to lesser extent.

A large part of this reviewer's criticism was aroused because the authors' effort evokes a vision of what is perhaps unat- tainable. It may not yet be to really teach so much to beginning stu- dents, but tbat is an ambition for many teachers, and the book raises that ambi- tion. The information is surely preaent in the text; one's only disappointment is that it has not been as well organized as is possible. On balance, however, one must still say that this book is one of the best two or three in the field.

WALTER R. THORSON Marsochusetts Institute of Technology

Camhn'dge, Massachusetts

Physical Oganic Chemistry

Kenneth B. Wiberg, Yale University, New Raven, Connecticut. John Wiley and Sons, Inc., New York, 1964. viii + 591 pp. Figs. and tables. 15.5 X 23.5 cm. $10.75.

The development of physical organic chemistry has been an interesting one. Perhaps, as Profemor Wiberg states in his new "Physical Organic Chemistry," i t can be considered to have come of age with the publication of the 6rst hook published under that title by Professor L. P. Hammett, in 1940. On looking again at that classic text this writer was amazed to note just how physical that presentation had been. During the intervening years the subject of physical organic chemistry would appear to have advanced by twn divergent paths. One of these, and much the less rtctively followed, developed essen- tially dong the lines laid down in Ham- mett's text; i.e., i t was actually physicd chemistry applied to organic systems. The second type of physical organic, which might be thought of as having developed from the studies of the Ingold school, has concentrated on the elucidation of organic reaction mechanisms; the emphasis here has been on organic chemistry, with tech- niques and approaches borrowed from physical chemistry used as valuable sup- plements. Too often in the past com- munication between these two groups has been poor and in turn both groups have been the poorer for lack of communication.

Fortunately for a11 who call themselves physical organic chemists there are a few people, among them Professor Wiberg, who are able to bridge this gap and to assist the rest of us in bridging this same gap between what might be edled phy~icsl organic chemistry on the one hand and organic physical on the other. Viewed from this vantage point Professor Wiherg's "Physical Organic Chemistry" is, in our opinion, a brilliant success. Seldom, in recent years, have we experienced the sheer delight, dimly remembered from college days, of having whole new and totally different areas of ideas brought to light. And this Wiberg has given us on page after page, a t least for this reader. In short "Physical Organic Chemistry'' is just plain fun-if a bit d i f f icu l t to read.

Wiberg has organized his book into three major sections together with nine aocompanying appendixes. Part I, Bonding and Spectra (209 pps.), is essen- tidly a summary of approximate quantum meehsnical approav,hes to the study of bonding and spectra. Parts I1 and 111 are entitled Equilibria (95 pps.) and Kinetics (136 pps.). Appendixes include a review of determinants and matrices, group character tables, tables of evaluated overlap and related integrals, a practical example of the analysis of an NMR spec- trum, tables of thermodynamic functions for a harmonic oscillator, and, interest- ingly, an introduction to computer pro- gramming.

Particularly interesting to us, although this may be merely an accident of our background, were discussions of the per- turbation method of approximatian, the molecular orbital treatment of rtromatic

(Continued on page A806)

578 / Journal of Chemical Education