Theory of Unimolecular Reactions (Slater, Noel B.) - ACS Publications

A Short Account of RRKM Theory of Unimolecular Reactions and of Marcus Theory of Electron Transfer in a Historical ... Journal of Chemical Education...
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Physical Methods of Organic Chemistry. Part 1

Edited by Arnold Weissbwger, Research Laboratories, Eastman Kodak Co., Rochester, New York. 3rd edition. Interscience Publishers, Inc., New York, 1959. xii 918 pp. Figs. and tables. 16 X 23.5 em. $24.50.

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The latest revision of "Weissberger" lives up to the deserved reputation of its predecessors. This volume contains the following sections: l . * Automatic Control, Julian M. Sturtevant; 2.* Autamatic Recording, D. R. Simonsen; 3.. Weighing, Alsoph H. Corwin; 4. Determination of Density, Norman Bauer and S. Z. Lewin*; 5.* Determination of Particle Size and Molecular Weight, George L. Beyer; 6. Temperature Measurement, Julisn M. Sturtevant; 7. Determination of Melting and Freezing Temperatures, E v d d L. Skau, J e t t C. Arthur, Jr.,' and Helmut Wakeham; 8. Determination of Boiling and Condensation Temperatures, W. Swietoslawski and John R. Anderson; 9. Determination of Vapor Pressure, George W. Thamson; 10. Calorimetry, Julirtn M. Sturtevant; 11. Determination of Solubility, W. J . Mader,* R. D. Vold, and M. J . Vald; 12. Determination of Viscosity, B. F. Swindells,* R. Ullman; and H. Mark; 13. Determination of Properties of Insoluble Monolayers a t Mobile Interface6 A. E. Alexander*; 14. Determination of Surface and Interfacial Tension, by the late William D. Harkins, revised by A. E. Alexander*; 15. Determination of Osmotic Pressure, R. H. Wagner and L. D. Moore, Jr.* The asterisked sections are new in this edition. The new authors are also asterisked. The writing is not alwaya as succinct and clear as might be desired hut the coverage is goad and generally authoritative. Departmental libraries will find this one of their more used volumes.

Thus large molecules me less dependent on collisions to maintain the equilibrium population whieh is being continually depleted by decomposition. Tho larger the molecule the lower the pressure a t which the high pressure rate falls off. In transition state theory the activated complex is specified as the configuration of no return. This critical configuration varies slightly -5th the rotational state but this does not cause serious difficulty. Slilter considers various alternative models. In one the molecule is assumed to decompose when the critical bond exceeds a certain length. This oversimplifies the activated complex model but is near enough for the results to be inatruetive. So far it is difficult to marshall the available experimental evidence or design new experiments to distinguish sharply between the earlier models proposed by Rice and by Kassell and later ones developed by Slster. Mass spectrography with electron beams having definite energies provides positive ions which subsequently unimolecularly decompose. Such data e m provide critical tests of unimolecular decomposition theories. Slater mentions only briefly this growing field but his book is an extremely valuable contribution to the unfinished field of unimolecull~r reactions and anyone seriously interested in such reactions must connult this excellent book. HENRYEYRING Universit~lof Utah Salt Lake City

Organic Chemistry

Robert Thunton Momison and Robert Neilson Boyd, both of New York University. Allyn and Bacon, Inc., Boston, 1959. xiv 948 pp. 16 X 24 rm. $10.75.

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This is a very remarkable book written with considerable care and skill. There J. A. CAMPBELL are, for instance, simple explanations left out of the text because they are presented Harvey Mudd College as questions a t the end of the chapter. Clmemonf, California The o~ganirationof the book follows a conventional integrated pattern as indicated by the early chapter headings: Theory of Unimolervlar Reactions Structure & Properties; Methane; Alkanes; Alkenes I ; Alkenes 11; Alkynes; Noel B . Slaler, Baker Lecturer, Cornell Dienes; Cyclic Aliphatic Hydrocarbons; University, Ithaca, New York. CorBenzene; Resonance; etc. The authors nell University Press, Ithaoil, New have deliberately chosen t o remain within York, 1959. xi 230 pp. 15 X 23.5 this framework because the traditional cm. $4.75. organization by family emphasizes the Slrater hs9 undertaken ken general hisdependence of properties on molecular torical development of the Theory of structure. Unimoleculm Reactions in whieh he has Once beyond the Table of Contents, fitted in his own very interesting contrithe novelty of approach becomes immebutions. He develops the consequences diately evident. A serious attempt is of Lindeman's pioneering suggestion that made to relate every fact of organic chemin thermal decamoosition. molecules are istry mentioned in its pages to theoretical principles. These latter are introduced as soon as needed. They are, in general, dealt with in a remarkably lucid manner. view has completely replaced the untenThere is something about the style that able rdistion hypothesis of F. Perrin is most refreshing; somehow the reader which held that absorption of radiation is taken t o the inside of a chemist's way was the important energizing factor. The of thinking. The authors do not fear to prater the number of deerees of freedom charaeteriee certain ideas as probable rather than certain. When the evidence for a mechanism is too complex t o be

included, the authors say so. In the authors' words: "A ehsnge is long overdue. The science of organic chemistry has come of age and needs to be taught on that basis." The book discusses conformational analysis in detail beginning in the chapter on alkanes; the stereochemistry of water and ammonia follows the most recent ideas of a tetrahedral distribution of four electron pairs whether shared or unshared; energy of activation and rate of reaction are defined in the alkane chapter also, and the increase in number of activated collisions with increasing temperature is ably explained. "Wherever feasible we have used actual experimental data as the basis for problems." There are around a thousand problems a t the ends of chapters, and more are interspersed in the text. Answers are included a t the end of the book. The book contains excellent discussions on the relation of structure to physical properties. Methods of preparation and reactions are set out in tables before they are discussed, thus giving a. useful overview of the types of reactions characteristic of a class of compounds. Formulas and diagrams are well set out and used liberally. The book ends with an excellent six-page list of advanced readings arranged by topics rather than chapter headings. The index covers 41 pages. Some topics this reviewer would have liked to see developed differently. No justification for the variations among atomic electronegativities could be found. The authors continue the pattern of introducing stereoisomerism due to molecular asymmetry by introducing a further new concept, that of polarized light. The subject can be introdueed in terms familiar to the student by pointing to the freezing point depression generally produced on each other by enantiomorphs. The book contains more material than is likely to be covered in a one-year course in organic chemistry, hut its use in such a course should fascinate rather than discourage the student. The book is probably not suitable for freshman organic courses, though the ablest freshmen ought to be encouraged to grapple with it. Of the recent spate of unconventional organic texts, the reviewer would rank this one as the best.

0. T. BENFEY Earlham College Richmond. Indiana

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Toxic Aliphatic Fluorine Compounds

F . L. M . Pattison, University of Western Ontario, London, Ontario, Canada. Elsevier Publishing Co., Amsterdam, 1959, distributed in U. S. by D. Van Nostrand Co., Inc., Princeton, New Jersey. xi 227pp. Figs. and tables. 13 X 19 em. Paperbound. $3.50.

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This book is one of a series of monographs on industrial toxic agents. Actually, however, it goes far beyond this limitation and discusses in smrtll space some of the most important problems of modern biochemistry. (Continued on page 8688)