BOOK REVIEWS Chemistry in NobAqueour Solvents
Hany H. Sisln; University of Florida, Gainesville. Selected Topics in Modern Chemistry Series. Reinhold Publishing Corp., New York, 1961. vii 119 pp. Figs. and tables. 13 X 18.5 cm. $1.95.
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The first two volumes in the new paperback series, Selected Topics in Modern Chemistry, came off the press in December. One is Sisler's "Chemistry in NonAqueous Solvents," the other is VanderWerf's "Acids, Bases, and the Chemistry of the Covalent Bond." The series, edited by Sisler and VsnderWerf, is intended to provide supplementary textual materials for general chemistry teachers and the abler students of general chemistry. Sisler's book deals with chemical reactions in solvents other than water, and it thereby leads its readers to a better understanding of reaotions taking place in water at the same time that it liberates them f ~ o mtheir aqueous provincialism. This is accomplished in five chapters averaging 22 pages each. The first chapter discusses the role of the solvent in chemical reactions taking place in solution. The effect of solubility relationships is illustrated by the reaction between aqueous silver nitrate and a q u e ous barium chloride precipitating silver chloride in contrast with the reaction between liquid ammonia solutions of silver chloride and barium nitrate to produce a precipitate of barium chloride.
The importance of the physical properties of the solvent is discussed, such as the effect of dielectric constant on solubility of ionic compounds and of viscosity on electrolytic conductance. The effect of chemical properties of the solvent is discussed a t some length. Assuming that the reader is acquainted with the Br$nsted and Lewis definitions of acids and bases, Sisler discusses the leveling effect of the solvent with admirable clarity. In the second chapter, chemistry in liquid ammonia is discussed to the degree of completeness appropriate to readers of this series. I t is pointed out thst liquid ammonia was the first non-aqueous solvent to receive systematic investigation, due credit being given to Franklin, Kraus and Cady for their work begun more than a half-century ago. This work not only advanced the knowledge of nitrogen compounds hut established the value of liquid ammonia as a solvent in many types of organic and inorganic syntheses. In the third chapter sulfuric acid as solvent is discussed, credit being given to the pioneer work of Hantzsch, the investigations of Hammett in the 1930's and the more recent work by Gillespie. Here the reader should pause to reflect thst the strongest acids possible in water, ammonia, and sulfuric acid are hydronium ion, ammonium ion and HsSOlt ion, respeotively; and that the strongest, bases possible in these respective solvents are hydroxyl ion, amido ion and HSOIion.
Hamy H. Sisler, Chemistry in Non-Aqueous Solvents Calvin A. Vande~Werf,Acids, Bases, and the Chemistry of the Covalent Bond Robert R. H e i h and Roland W . Ure, Jr., Thermoelectricity: Science and Engineering Henry Eying, C . J . Christensen, and H. S. Johnston, editors, Annual Review of Physical Chemistry. Volume 12, 1961 Eugen Medocher, Quantum Mechanics G. Porter, editor, Progress in Reaction Kinetics. Volume 1 The Chemistry of Natural Products, (IUPAC Symposium) John R. Catch, Carbon-14 Compounds Jacob C m q , Semimicro Qualitative Analysis: A Non-Hydrogen Sulfide System G o s t a Charlot, Les MBthodes de la Chimie Analytipe: Analyse QuantiBtive MinBrale. Brian A. Foz and Allan G. C a m e ~ aA, Chemicd Approach to Foodand Nutrition M. C. Cobb, The Scientific Approach to Career Planning Waller J . Gensler and Kinereth D. Gender, Writing Guide for Chemists J . T k l i s , R. C. Gloss, D. J . Hughes, and A. R . Meetham, editors, Encyclopaedic Dictionary of Physics. Volume 1, A to Compensated Bars V e n a H. Cheldelin, Metabolic Pathways in Microorganisms
In Chapter 4 the author shifts from amphiprotic to aprotio solvents and usea the Lewis definitions of acids and bases in discussing chemical reactions occurring in liquid dinitrogen tetroxide and in liquid sulfur dioxide. The final chapter attempts to give Bome indication of the great variety of solvents available to the chemist and mentions a few pertinent facts about several basic solvents, a few neutral solvents, and some scidio solvents--especially acetic acid. Any student or teacher reading this little book will be reminded that mcst reactions occur in solution-often in aqueous aolntion. The fact that water served as the solvent medium in so many of the reaotions carried nut by chemists up to the turn of the century obscured the profound influence of the solvent on the course of chemical reactions. Obviously the only reagents available for use in a given solvent are those that can exist for an appropriate length of time in that solvent. This book discusses not only the leveling effect of the solvent but also the effects of oxidizing and reducing characteristics. Solvolysis and solvation are illustrated with numerous examples. This hook is highly recommended to the audience for which it was written. Good diagrams and a good index add to its value. LAWRENCE P. EBLIN Ohio University Athens
Acids, Bares, and the Chemistry of the Covalent Bond
Calvin A. Va'anderWerf, University of Kansas, Lawrence. Selected Topics in Modern Chemistry Series. Reinhold Publishing Corp., New York, 1961. ix 117 pp. Figs. and tables. 13 X 19 cm. Paperbound. $1.95.
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This book, one of the two v & n e s first issued in the new paperback series, Selected Topics in Modern Chemistry, deals with the making and breaking of bonds. The book consists of six chapters averaging 19 pages each. In the first chapter the reactions of covalent compounds are classified as (1) free radical reactions, in which electrons are paired or unpaired, and (2) polar reactions, in which electron pairs are shared or unshared. The polar reactions, which involve electron-pair donors and electron-pair acceptors, are the ones with tihid. tl& hruk is conrcrnrd. 11)the wrmd chnpwr, the r ~ a d r ris I d frbm the early cxncrirnrr~tnldcfirlirionr of acids and b&es -through the Arrhenius theory of 1887 to the Br$nsted-Lowry concept of 1923. Topics discussed include conjugate acid-base pairs, relative strengths of acids and bases, amphiprotic substances, the leveling effect of solvents, the types of neutralization reaction typical of protonic solvents, the preparation of weak acids and weak bases by protolytic rertctions, and the hydrolysis of anions and hydrated cations. In Chapter 3 VanderWerf probes the question, "What structural features confer Volume
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proton-donating and proton-accepting tendencies?" He discusses the relationship of acidity and basicity to charge, to relative eloetronegativities, and to ion size. In connection with electronegativity he considers the relative acidities of some .
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the role of resonance. In Chapter 4 the Lewis definitions for acids and bases are presented as logical oonceptual extensions of the Br$nsted definitions. It is shown how the Lewis definitions unleashed the acid-base concept from its dependence upon hydrogen, how the fundamental acid-base reaction hecomes the formation of an sdduct made up of an acid portion and a base portion, and how the Lewis concent has revolutionized the theory and praeiice of acid catalysis. Chapter 5 is conoerned with basedisplacement resctions. As an organic ohemist, the author is concerned with the worth of the base-displacement viewpoint, which is that it provides the intellectual link between Br$nsted acid-base reactions and the many base-displacement reactions that make up a large part of organic chemistry. Nucleophilic substitutions, elimination, and nucleophilic additions are considered here. The final chapter is concerned with the less numerous displacements of one Lewis acid by another. Eleetrophilie displacements and additions are discussed here. VanderWerf brings his little book to a close by revealing that one of his aims has been to help those who are planning the study of organic chemistry to appreciate "the compelling beauty and iascinrttion of the well-developed intellectual framework upon which modern organic chemistry is based." The two types of reeders for whom this entire book will be most useful are: (1) atudents just beginning a course in organic chemistry who feel that there is a wide gap between whet thev know and what thev would like to L a w about electron;^ structure and whet might be called "chemical personality"; and (2) chemists in other areas of specislizatian to whom organic chemistry just didn't make sense when they were students. The 6rst three chapters, and most of the fourth, provide excellent supplementary reading for all the ~ h l e rstudents in eeneral chemistrv. ", regardless of their organic chemical ootmtial. The value of this well-written book is enhanced by good diagrams and a complete index. LAWRENCE P. EBLIN Ohio University Athm Thermoelectricity: Engineering
Sciance and
Ro6erf R. He& and Roland W. Um, JI., both of Westinghouse Research Laboratories, Pitt~burgh,Pennsylvania. Interscience Publishers, Inc., New York, 1961. xi 576 pp. Figs. and tables. 16.5 X 23.5 em. $18.50.
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Not-so-very-oldtimers can r e e d the day when thermoelectricity was used only
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for measuring and controlling temperature: as a means of Dower neneration it \$:IS gvnwdly ronceded IA I,? irwonsrrluenrinl. Tlw modrrn prrowupstion with thc i u w w g y conusc of tlwrmo~le~tri~~ity version and refrigeration is now so complete that this latest hook on the subject mentions thermometry only once, quite casually, and mentions temperature control not at all. The hook should appeal chiefly to scientista and engineers concerned with the design of thermoelectric devices or to the chemist charged with the development of thermoelectric materials. Its distinguishing characteristic is the wealth of detailed theory given connecting the electrical and thermal transport properties of semiconductors with their use in energy converters or cooling devices. Bibliographies a t the end of the chapters are voluminous and include references through 1959 in most instances. For 8. less intensive and more general introduction, one might do better to read Ioffe's little hook, or selected papers in the book recently edited by Xgli (see TAIS J~UUNAL, 38, 534 [19611). The theory includes a treatment of thermal conduction, an irreversible effect, using the Onsager reciprocal relations, and points out the connection between the more complete theory and Kelvin's theory in which the reversible effets were treated separately. The theoretical parts of the book are separated into sections of increasing degree of specialization, This organieation leads to considerable repetition, and the reviewer was left with the feeling that some condensation might have been achieved without loss of clarity. Chemists will take most interest in chapters on diffusion, crystal growth, and the chemistry of mixed valence materiala. The first of them includes, in addition to a standard discussion of Fiek's Law, concise treatment of the Soret diffusion. The connection between thermoelectricity and diffusionis the following: due to the presence of temperature gradients or concentration gradients, the composition and properties of thermoelectric materials may change with time. Unfortunately, the experimental data on diffusion in thermoelectric materials are so scarce that no useful quantitative examples have been provided. Fifty-two pages are devoted to mixed valence semiconductors; however, the reader will be disappointed to l e a n in a later chapter that these materids, along with electrolytically conducti~gsolids(for which the Seebeck coefficient may he as high as 1 mV deg-1) and liquids, hold little promise for use in practical devices. The length and cost of the book could have been substantially reduced by eliminating or condensing some of t h w topiw, adequately covered in other monographs, which prove, by the authors' own analysis, to be of minor present concern. Heikes and Ure were assisted by a. group of 14 eollaborstors; of the 17 chapters, the principal authors wrote or co-authored 8. The difficult job of editing for uniformity of nomenclsture and symbolism has been, with minor exceptions, well done, but the literary style is variable. Numerous typographical errors and one mist h e in indexing were found. While such evidences of carelessness probably will
not detract from the utility of the book for the specialist, it definitely reduces the pleasure s. more general reader would find in studying this hook. ALLENB. SCOTT Oregon State University Corvallis
Annual Review of Physical Chemistry. Volume 12,1961 Edited by Henry Eyring, and C . J . Christensen, both of the University of Utah, Salt Lake City, and H. S . Johnston, University of California, Berkeley. Annual Reviews, Inc., Pa10 Alto, Cal514 pp. Tables. ifornia, 1961. vii 16 X 23 cm. 87.
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Volume 12 of this well-known series lives up to the high standards of previous volumes. Nineteen fields of ohvsical chemistry are covered. Most of these are coveted regularly but s. few are new or occssionally-reported areas. The topics covered and the authors are as follows: Physical Organic Chemistry, A. N. Bourns and E. Buncel; Marine Geochemistry, E. D. Goldberg; Physical Properties of High Polymers, I
