BOOK REVIEWS Valence
C . A. Coulsm, University of Oxford, England. 2nd ed. Oxford University 404 pp. Press, Oxford, 1961. ix Figs. and tables. 14.5 X 22.5 cm. $6.
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Approximately ten years have passed since the first edition of this book was printed. The reviewer of that edition (J. CHEM.EDUC.,29, 532 [19521) pointed out that much of the discussion involved mathem&ctical equations, which for most chemists would require some effort t o follow. For the non-mathematicallyminded chemist, the same may he said of the second edition. For the most part, the chapters and their arrangement are the same as in the first edition. However, clarifying alterations appear in numerous instances, e.g., rewording, expansion of discussion, addition of a half-dozen figures, and additional equations t o reduce gaps in following the mathematical developments. The chapters on theories of valence, wax-mechanieal principles, molecular orbital theory, valence-bond theory, and nonmetallic solids remain virtually unchanged. Slightly greater expansion was made in the chapters on the campadson of molecular orbital and valence-bond theories, polyatomic moleonles, conjugated and aromatic molecules, metals, and atomic orbitals. In the last, the change involves
-Reviewed
an expansion of about two pages on the topic of d-orbitals, and the discussion is shifted to the end of that chapter. There has been appreciable rewriting of the chapter on hybridization. The most extensive change has been made in the last chapter, namely, the hydrogen bond and other miscellaneous topics. This chapter, which has been expanded by about 50% in the number of pages, includes such topics as hyperconjugation, hindered rotation around a single bond, electron-deficient molecules, boron hybrides, theoretical interpretation of bridge structure, inorganic r-electron rings (new in the second edition), and mesoionic compounds. It is the opinion of this reviewer that cursory coverage of such complex topics which, in some cases, are still unresolved detracts from the merits of the book. The uninitiated reader may feel he has been exposed to these topics, but he is not likely to feel sufficiently secure to apply this exposure. The major change in the second edition is the introduction of an entire chapter on ligand-field theory. This chapter is primarily descriptive and a large part of the discussion can be followed by most readers. In certain sections, however, i t is likely that the person who has had no prior contact with ligand-6eld theory will find some di5culty in keeping track of the terminology and in following the discussion involving symmetry considerations.
in this Issue
C . A . Coulsm, Valence Philip John Durrant and Belyl Durrant, Introduction to Advanced Inorganic Chemistry A . I . Dahl, editor, Temperature: Its Measurement and Control in Science and Industry. Volume 3, Part 2, Applied Methods and Instruments H. W . Thompson, editor, Advances in Spectrosoopy. Volume 2 E. H. E. Pietsch, editor, Gmelins Handbuch der Anorganischen Chemie, 8. Auflage, System-Nummer 28, Calcium. Part B, Section 3 E. H. E. Pietsch, Gmelins Handhuch der Anorganischen Chemie, 8. AuEage, Svstem-Nommer 52. Chromium. Part A. Section 1 ~ & c e T.Eidmon, ~cientists: Their ~syehologiralWorld Chem Sourees,4th ed. Harold A. Seheraga, ProteinStructure Edward M . Kosozuer, Molecular Biochemistry Mzehael Kasha and Bernard Pullman, editors, Horizons in Biochemistry: Albert SeeneGyiirgyi Dedicatory Volume F. G.A . Stone, Hydrogen Compounds of the Group IV Elements Sister Ma~tinetteHagen, Clathrate Inclusion Compounds Peter Sykes, A Guidebook to Mechanismin Organic Chemistry William A. Pryor, Mechanismof Sulfur Reactions Marcel Florkin and Elme? H . Stotz, editors, Comprehensive Biochemistry. Volume 2, Organic and Physical Chemistry E. L. Gefter, Organophosphom Monomers and Polymers Russell L. Ackoff in collahoration with S. K. Gupta. and J. S. Minas, Scientific Method: Optimieing Applied Research Decisions F~iedrichKlafes, Lehrbuch der Orgttnischen Chemie, Band 2 Norman Kharaseh and Walter Wolf, compilers and editors, Index to Reviews, Symposia Volumes and Monographs in Organic Chemistry for the Period 1940-1960 H. J . Emdleus and A . G. Sharpe, editors, Advances in Inorganic Chemistry and Radiochemistry, Volume 4
There are several excellent features of this book, written by a recognized authority in the field. Physical interpretations frequently accompany the mathematical equ&ons, and figures and graphs clarify mathematical aspects which otherwise might he obscure. In brief statements throughout the hook, the author cautions the reader about misinterpretation of concepts such as those pertaining t o resonance, hybridization, electronegativity, and bond additivity. Many of the concepts, however, are so widely utilized that someone glancing a t selected sections and not reading the full text carefully may miss these very important remarks. The reader who is willing to take a little time Kill gain some acquaintance with the ideas and terminology which are so prevalent in current chemical literature, although in some sections both the ideas and terminology may seem rather strange, e.g., " L i atoms" and "negatively hicovnlent ions" (p. 334). I n addition to the above changes, many numerical values have been brought up to date, as evidenced by the many changes in the discussion and in tables. Two items which apparently slipped by the updating process are the reference (p. 235) t o the existence of OsF8, which recently has been shown to be OsFs, and the reference (p. 138) to CsF as being the moat polar of all molecules, which is not in accord with evidence based on measurement of dipole moment and internuclenr distance. MILTON TAMRES Uniuersity of Michigan Ann .47h0r
Introduction Chemistry
to Advanced Inorganic
Philip John Durrant, Cambridge University, and Beryl Durrant, University of London. John Wiley and Sans, Inc., New York, 1962. xv 1171 pp. Figs. and tables. 17 X 25.5 cm. $15.50
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The Durrants, a n experienced team of textbook writers a t the University of Cambridge, have produced a camprehensive inorganic source hook which their British publisher Longmans, Green and Company is able to sell a t a bargain price in this country ($15.50). The book fallows the usual format of theoretical followed by descriptive chemistry and takes its place beside (but dwarfs in size) Moeller, Partingtan, Heslop and Robinson, Cotton and Wilkinson, etc. Like all the above, except the last, the ratio of pages is such that the transition elements get relatively short shrift. The only reason for writing another inorganic text is that the authors have a different point of view to present. In this case the Dmrants discard the app o a c h based on accessibility and familiarity of compounds in favor of a systematic treatment based on theoretical principles. Questions of whether chemistry is yet ready far this aside, the logical extention of the scheme would be t o make the book s, catalog of undiscovered compounds. Happily, a masterful compromise is a t hand, and a system haeed on Volume 40, Number 3, March 1963
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modes of hybridi~ationfrom valence bond theory is used to classify the compounds of each element. Oxidation state is used in the usual way for the transition elements. The book opens with a sound and advanced treatment of quantum theory and valenlency. Valence bond and molecular orbital theories are discussed and compared. This is followed by excellent discussions of spectroscopic methods, with summsries of results and information which can be derived from each method. The theoretical section concludes by considering bond lengths, dipole moments, bond energies and the determination of crystal structures. A novel method for calculating band lengths from other data is presented. This section is longer and on a higher level than each of two theoretical inorganic textbooks recently published in this country. The descriptive chemistry is presented with the same high level of sophistication. The chemical elioh6 is carefully avoided and many new and interesting interpretations are offered. Unfortunately, some of these confuse rather than enlighten as when we are told that hydrogen is not a reducing agent or that nitrogen and phosphorus exhibit the same oxidation state in all compounds,(especially in light of the subsequent discussion of the oxidation of ammonia and P C I d In the transition series, the normal prehybridization electron configurations are given in most cases as including np' electrons. No reason is given. Nomenclature is occasionally annoying as with the silanes and it is also annoying to read that lithium, beryllium and boron a t o m are electron deficient. Other minor points include an incorrect statement of the boiling points of fluommethanes and a puzzling one to the effeot that aromatic compounds with fluorine atoms in the side chain behave as aliphatic. More serious is that HBr is stronger, not weaker than HC1 and this argument cannot be used to explain the hydrolysis of metal bromides. The structure of SIN, given in two places with N-N bonds is wrong and in discussing the acceptor properties of boranes, AH values are more significant than temperatures of dissociation. It is not true that P and S exert more than four a bonds only in combination with fluorine. It is surprising to read that FeO, FezOs and FeaO, are not chemical compounds (nowhere defined) but not very surprising thst monomeric carbonyls are more volatile than others. Finally, typographical errors are to be expected in the first edition of so large a work and a modest number are found ( e.g., pp. 383, 467, 590,262, 648, 663, 681,772,813, 896., 961., 1030. and 1084). The lack of references to k e y ~oint's is, however,
regrettable. On the bdance, the Durrants have an encyclopedic work of great sophistication and originality. The method of classi6cation according to hybridization states of the elements offers great advantage over other classifications hased on binmy compounds with various elements, oxidation states, or on historical, geologiesl or industrial interest, and is in keeping with the direction of progress in the science. Orbital diagrams of a novel
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Journal of Chemical Education
of experimental conditions is thoroughly type are intelligently used to clarify treated in a number of significant papers. bonding situations for the reader. It is A h , the great pprogresrr in automation regretted (but understandable) that kiinvolving temperature and temperature netics, thermodynamics and nuclear cbemcontrol is evident if one compares the istry could not 6nd their place in this aections dealing with this subject in volume. The book is already the most Volume 1 published in 1941 and the comprehensive on the subject since present Volume 3 published in 1962. Sidgwick and its unique method of clasOn the whole, the papers are well sification makes it an excellent reference written and contain many useful tables, volume. J. J. Z U C K E ~ M A Ngraphs and drawings. Most of the papers have complete bibliographies, and there Conell Uniuersity fore will simplify the procedure of obtainIthaca, New Yolk ing more detailed information on subject mstter where desired. Author and suhject indices are provided. Temperature: Its Measurement and In make-up and emphasis the present Control in Science and Industry. book resembles Volume 1 of the series Volume 3, Part 2, Applied Methods and much more closely than Volume 2. Instruments Needless to say, it will be found to be an extremely useful reference aource for any Edited by A. I. Dahl, General Electric one interested in the practical and enCo., Schenectady, New York. Charles gineering aspects of temperature and M. Hmfeld, Bureau of Standards, temperature control. Washington, D. C., editor-inshief. The one disadvantageous feature apReinhold Publishing Carp., New York, pears to be the large size (over 1000 pages, 1962. xiv 1094 pp. Figs. and 7 in. X 10 in.) and the correspondingly tables. 18.5 X 26 em. 529.50 high cost. When this is combined with the fact that it is only one book of three It is necessary to refa ace our remarks comprising Volume 3, it can only mean on the book being reviewed here with the that it will have fewer owners and users explanation that the proceedings of the than would otherwise be the case. PerFourth Symposium on Temperature held haps the answer lies in minimizing overlap in 1961 me being published in Volume 3 of topics within the various parts of the under a. title used for two previous symvolume, screening out papers not preposia-Temperature, Its Measurement senting significantly new subject matter and Control in Science and Industry. etc. in order to keep the size within The proceedings of the Second Symposium manageable limits. Otherwise, the prewere published in 1941 in Volume 1 and diction one can make is that the seriousthose of the Third Symposium in 1955 in ness of the problem of the s i ~ of e the volVolume 2. Volume 3 differsfrom Volumes umes will increase with future symposia. 1 and 2 in that it will be published in three parts, i.e. three separate books, under the E. L. PACE headings: Part 1, Basic Standardds, Western Reserve Uniuersity Concepts and Methods; Part 2, Applied Cleveland. Ohio Methods and Instruments; and Part 3,
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Zoology and Medicine. Part 2, which is being considered here, contains the papers presented a t the Fourth Symposium which were grouped under the following section headings: Section I, Thermoelectric Thermometry; Section 11, Resistance Thermometry; Section 111, Radiation Thermometry; Section IV, Dynamic Temperature Measurements; Section V, Automatic Methods of Temperature and Control; Section VI, Miscellaneous Temperature Methods and Techniques; and Section VII, Temperature Sources and Thermal Imaging Techniques. The present volume serves the pnrpoae of bringing up to date a number of topics which appeared in Volume 1 but were largely omitted in Volume 2. Hence, in Volume 3 such topics as automatic temperature regulation, radiation pyrometry, thermoelectric thermometry are again covered thoroughly and include the advances achieved in the interim between the Second and Fourth Symposium. Thermoelectric thermometry remain8 tho moat important aingle topic. This is reflected in the fact that fully onequarter of the book is devoted to it alone. Papers on the physical properties and application of many new thermocouple materials are included with particular emphasis on the high temperature range. The subject of dynamic and transient temperature measurement under a variety
Avdmces in Spectroscopy.
Volume 2
Edited by H. W . Thompson, St. John's College, Oxford, England. Interscience Publishers, Inc., 1961. xi 483 pp. Figs. and tables. $13.
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The appearance of the second volume of this "Advances . . ." series provides a welcome addition to the chemist's and chemistry teacher's reference shelf. Professor Thompson has kept admirably to his declared aim to provide "authoritative surveys on recent progress in different fields (of spectroscopy) written by experts who themselves contributed to it." The choice of topics and authors is quite timely and appropriate. They include: Applicstion of Atomic Absorption Spectra to Chemical Analysis (A. Walsb); Spectra of Flames (A. G. Gaydon); X-Ray Spectroscopy (Herbert Friedman); Nuclear Magnetic Resonance (R. E. Richards); Infra-Red Spectra of Crystals (W. Vedder and D. F. Hornig); Refraction of Gases in the Infr*Red (J. H. Jaffe);Infra-Red Spectra of Micro-organisms (K. P. Norris); The UltreViolet Absorption Spectra of Proteina and Related Compounds; (G. H. Bemen); Some Recent Developments in the Theory of Molecular Energy Levels (H. C. LongueGHiggins). The authors of the various chapters are indeed contrihue
