BOOKS
Descriptive Approach to Nonstoichiometric Compounds Nonstoichiometric Compounds. No. 39, Advances in Chemistry, vii + 253 pages. Special Issues Sales, American Chemical Society, 1155 Sixteenth St., N.W., Washington, D.C. 20036. 1963. $7.00. Re viewed by Dr. A. R. Ubbelohde, F.R.S. Dr. Ubbelohde is professor of thermo dynamics and head of the department of chemical engineering and chemical technology, Imperial Col lege, London, England. This symposium has descriptive inor ganic chemistry as a prominent basis of its arrangement. Papers comprise a quite wide range of information about oxides, hydrides, intermetallic compounds, chalcogenides, clathrates, and bronzes. General reasons under lying the stability of crystal compounds of nonstoichiometric compositions are not well brought out by this descriptive kind of classification. In particular, modes of cooperative interaction in a solid, whose correlation with defect structures is not yet fully elucidated, do not receive full critical treatment which could stimulate fresh research. One introductory problem that might well have received fuller dis cussion is agreement on the best de scriptive symbolism for defects. Ex perts do not agree on how to sym bolize even isolated defects in crystals. A second group of problems raised by several authors involves micro-hetero geneity, domain structures, partial segregation or clustering of defects, and microphases in nonstoichiometric solids. λΙοΓβ explicit discussion seems desirable about ways in which bound ary effects may be stabilizing such heterogeneities. Explanations based on short-range interaction forces stress ways in which cooperative defects which break up the crystal into a net work involve much less formation en ergy per lattice site than isolated de fects. A quite different explanation for micro-heterogeneity stresses its possible role in modifying cooperative electronic energy by affecting forbid den energies in the band of values up to the Fermi level. Yet another ex planation, possibly applicable to re 64
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markable out-of-step micro-heterogene ity of structure in some oxides, could depend on consequent modifications of the vibrational free energy of the solid. Although these general prob lems are touched on, they do not emerge with sufficient clarity. Again, reference to some of the newer techniques of study is made too much in passing to exert maximum stimulus on new research. For ex ample, in dealing with hydrides, sur prisingly little reference is made to the information obtainable from vari ous kinds of isotope effect, which can become quite large as a result of co operative action in crystals. Again, the electronic significance of the in tense absorption produced, when the same atom is present with more than one valency in a crystal, is insufficiently clarified. Effects of hydrostatic pres sure on nonstoichiometric equilibrium are not dealt with, though some strik ing and sensitive dependences of vapor pressures on defect structures are presented. In all, this collection is valuable and stimulating; but it needs considerable digging to bring to the surface the most suggestive and most stimulating information leading to future work.
Electrochemistry of Hydrocarbons Ions
in
Hydrocarbons. ANDREW viii + 261 pages. John Wiley & Sons, Inc., 440 Park Ave. South, New York 16, NT. 1.962. $12.50. Reviewed by Dr. R. A. Friedel. GEMANT.
Dr. Friedel is spectrometry project co ordinator of the Pittsburgh Coal Re search Center, U.S. Bureau of Mines. The opening sentence in the pre face states "Whereas most treatises dealing with the electrical properties of hydrocarbons, particularly electrical conductivity, assume a phenomenological and physical standpoint, this mono graph gives prominence to the chemi cal aspects of the topic by examining chemical structures of the various ions that may occur in liquid hydrocar bons." The book is offered as an original contribution in a compara tively new field; it is concerned in
large measure with the work of the author, but not exclusively so. The book is a very good introduction into the field. It covers a tremendous range of topics involved in the electro chemistry of hydrocarbons and accord ingly does not, in its 261 pages of text, cover these subjects with thor oughness. It is not apparent from the title that the book deals with electrochem istry. The unwary might expect that the book is -at least partly concerned with electron paramagnetic resonance (EPR) investigations of aromatic radical ions. More space could have been devoted profitably to EPR; de scriptions of some of the new electro chemical techniques now used in con junction with EPR would have been worthwhile. The book serves a use ful purpose to beginners as well as to the aqueous electrochemist by in troducing many suggestions for needed research in the field. There are, in fact, so many notations of work that needs to be done, or redone pre cisely, that one might easily gain the impression that little precise knowl edge has been developed in the field. In some cases the recommendation of more precise investigation of prob lems implies lack of adequate experi mentation. For example, a reference to the fact that work at temperatures slightly above ambient would yield valuable information leads one to won der why the higher temperature work wasn't carried out. Photochemical effects were examined by using a sun lamp; the point was made that prob ably "ultraviolet light was most effec tive in the reaction." The reader wonders why this was not checked, or why an ultraviolet lamp or a mono chromatic source was not used initially. There are a few points with regard to spectroscopy which should be men tioned. The presence of o-phthalic aldehyde in a sample was indicated by its ultraviolet spectrum. As this compound has a rather nonspecific ultraviolet spectrum, an additional spectral technique such as infrared should have been used. In another experiment rather definite conclu sions did not seem justified in view of the lack of spectral information avail able on the substances involved. There are other indications that the author has not had too great a famili arity with some of the techniques that he has used in his researches. This is understandable, as a wide range of techniques has been covered.
The book is recommended as a good introduction to the subject as well as a state-of-the-art treatment and an indicator of research to be done in the field. There are eight main parts with a total of 30 chapters, for an average of eight pages per chapter. Titles for the eight parts are: I. Correlations with Other Fields II. Hydrogen Ions III. Ions in Amine-Aliphatic Acid Solu tions IV. Ions from Oxidation of OrthoSubstituted Aromatics V. Ions from Ozonolysis of Aromatics VI. Metal-Complex Ions VII. Electron Transfer Ions VIII. Radiolytic Ions
Technical Books for Developing Countries A program for the distribution of U.S. scientific and technical books in coun tries asking for help in "catching u p " technologically has been inaugurated by the Agency for International Devel opment (AID) and the National Academy of Sciences. A number of U.S. publishers are cooperating to fur nish books at a substantial discount. According to Dr. Leona Baumgartner, AID assistant administrator for human resources and social develop ment, and Dr. Harrison Brown, foreign secretary of Ν AS, the pilot stage of the program will be in operation by late fall. AID funds will permit dis tribution of approximately 4000 vol umes to each of 13 participating na tions or areas over an 18-month pe riod. Beginning participants, chosen on the basis of need and interest, are Ethiopia, Nigeria, Iran, Turkey, Indo nesia, Korea, Brazil, Guatemala, Hon duras, El Salvador, Costa Rica, Nica ragua, and Panama. Foreign institutions of higher learn ing requesting the books will pay only a small, fixed percentage of the origi nal list price. Only individual, Eng lish-language books in fields of natural and social sciences, published in the U.S., are eligible for distribution. Textbooks in multiple copies for class use will not be provided, although AID is studying means of meeting this need. The project is part of a broad effort by AID to make U.S. science and technology more widely available in those parts of the world where devel opment is hampered by the lack of adequate source materials. Hereto fore, the high cost of such literature, plus currency exchange difficulties, has made such distribution impracticable.
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