Some Problems in Chemical Kinetics and Reactivity. - ACS Publications

such “magnum opus” should be available, prefer- ably with publication schedules appropriately out of phase. The work under review is accordingly a...
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than twenty-five years, it is highly desirable t h a t more understandable. The author’s boundless enthusiasm for his than one such ‘‘magnum opus” should be available, prefer- subject is evident throughout. I n large measure, this comably with publication schedules appropriately out of phase. pensates for certain interpretations with which others may The work under review is accordingly a welcome addition t o take issue and f u r occasional overly generous statements chemical libraries. Out of twenty Contemplated volumes such as the “millions of known structures with sp3 bonding” this is the fourth t o be published; it hoped to complete the ( p . 71). Quite understandably, the author’s not iiiconsiderseries by 1960 though this is perhaps unwarranted optimism. able contributions to phosphorus chemistry provide the As with Gmelin the obituary crosses in the list of collab- central themes for many of his discussions. orators are silent testimony to the truth of the ancient The text is remarkably free from mechanical errors. saying “Ars longa vita brevis.” Comparisons with Gmelin This and the over-all excellence of printing, binding and preare inevitable. “Pascal” will he a good deal shorter than sentation attest the carefulness with which the manuscript “Gmelin”; if Volume I V is typical, the individual elemelits was handled. Both author and publisher are to be comwill be covered a t lengths ranging from three quarters down 1,limented on a job well done. t o one fifth of t h a t of the corresponding treatment in the The book is strongly recommended both to those specifieighth edition of Gtnelin. The format is satisfactory and cally interested in phosphorus chemistry and to those interthe typography more pleasing than t h a t of Gmelin; on the ested in a significant contribution t o the “renaissance in other hand the French work seems less riclil5- provided with inorganic chemistry.” It is unfortunate t h a t the price is tables and diagrams. so high t h a t many individuals mill find it impossible t o acThe distant contemplation of such a formidable accuniuquire personal copies. lation of experimental fact tends t o be a trifle depressing but i t is impossible t o come to close quarters with a n y S O Y E S CHEMICAL LABORATORY UNIVERSITY OF ILLIXOIS THERALD MOELLER section of the book without encountering intriguing observations and many challenges t o further investigation. It is URBASA,II~LIXOIS probable as a source of references t h a t such works are most useful to the investigator. Here Pascal will be of great value; the deadline for references in each bibliographical Some Problems in Chemical Kinetics and Reactivity. section is clearly indicated and for some elements briiigs the T-olume I. By ? N.i SEMENOV. . Translated by MICHEL literature survey forward some twenty-five years later than BOUDART.Princeton University Press, Princeton, New the corresponding Gmelin volume. I n such cases the value Jersey. 1958. xii 239 pp. 15 X 23 cm. Price, $4.50. of Pascal as a complementary guide t o the more recent This is the second edition of a book which was published literature is self-evident. first in 1954 in a limited edition of the Academy of Sciences DEPARTMEST O F CHEMISTRY of the U.S.S.K. and was written in preparation for a national DARTMOUTH COLLEGE J. H. ~VOLFENDES symposium on Chemical Kinetics and Reactivity. After the discussions of the symposium, the author was asked to HASOVER,S . H. prepare a new edition. This was expanded to include new data from the literature and certain major additions were made to the text of the original. Two English translations, Phosphorus and its Compounds. Volume I : Chemistry. the present one by Roudart and one by Bradley for thc By JOHX R . VANWAZER,Assistant Research Director and Pergamon Press (see review below), have been authorized Senior Scientist, Inorganic Chemicals Division, :\.Ion- as well as a German edition. santo Chemical Company, St. Louis, Missouri. InterThe present volume is the first of two to be issued by the science Publishers, Inc., 250 Fifth Avenue, S e w Uork 1, Princeton Press and comprises the first two of a total of h7.Y. 1958. siii 954 pp. 15.5 X 2 3 . j cm. Price, four parts of this work. These two parts cover Radical $27.50. Reactions (reactions of chain propagation and branching) and Chain Initiation and Termination. The third and In his Preface, tlic author says “tlie purpose of this book fourth parts, on “Kinetics of Chain Reactions” are schedis t o lay the foundation for a new, separate discipline of chemistry-phosphorus chemistry.” However laudable uled to appear in Volume 11. The book was not written as a textbook or treatise, but is such a purpose may be, the creation of a new discipline that can occupy a position of equality among the classical dis- a survey, by a n outstanding scientist in the field, of developciplines of inorganic, organic, analytical and physical chem- ments in the twenty years or more since his first book on istry is complicated by the twin problems of ample sys- “Chain Reactions’’ was published. It emphasizes radical and radical-chain reactions and there is a frankly personal tematization of fact and principle and of acceptance of such, readers interested the body of information as sufficiently comprehensive and flavor in the discussion of these. varied to permit continued fruitful study. By presenting in chemical kinetics will find it both interesting and rewardphosphorus chemistry as an approach embodying many of ing. The first part of thi, volume includes an extensive disthe principles of structure and homology t h a t distinguish cussion of monoradicals and their reactivity in competitive a i l orderly organic chemistry from a n often much less orderly reactions of addition, decomposition, isomerization, or subinorganic chemistry, the author has done much t o overcomc tlic first complication. By presenting :t massive, but not stitution; the role of polar factors; etc. There is also a c~icyciopedic,array of coordinated informatioii and sug- much briefer discussion of diradicals. Reactions such as gesting innumerable :ireas for expanding research, he has oxidation of hydrocarbons and polymerization are discussed done even more to overcome the second. Whether he has in some detail. In the second part, reactions of chain h i tiation and termination :ire discussed on the h \uccerded in devising a new discipline must be determined geiieous molecular reagents, initiation by io by tlic test of time. However, it cannot be denied that effects . lie has produced a volume that will be both an outstanding This volumc has the miiior teclinical disadvautages reference for all workers in pliosphorus chemistry and :t which are to be expected in such a n edition. I t is a paper.stimulus to continuing research in this fascinating area. This volunie is concerned primarily with the development back edition. There are a fair number of typographical errors, and several instances in which limitations of type o f a set of underlying principles for phosphorus chemistrlarid the implementation of these principles by a thoroughly have resulted in rather odd notations or in the use of a letter or symbol with more than one meaning in a single and Farefully documented body of factual information. The emphasis tliroughout is upon modern interpretation of equation or paragraph. I n :t number of instances new fuudarnental chemistry, Technology and related aspects materials have simply been appended as footnotes rather than actually incorporated into the text. of the chemistry of phosphorus are to be considered in a The author expresses a note of disappointment t h a t 8 0 subsequent companion volume. S o attempt has been made much of the extensive literature which has appeared is cont o cover every subject with absolute completeness. Rather, tile author has attempted t o examine available information cerned with “disjointed observations on this or that reaction and not with a plan of investigation from all sides.” critically and to include only t h a t which has survived his wrutiny. .4lthough some may question his judgment on He notes also that it seems to him t h a t the majority of the xpccific points, none can disagree t h a t his over-all selectioii fundamental problems have not been completely solved as yet. Xonetheless, his book does give a picture which shows is consistently good and t h a t his coverage is excellent. Phr:twology, clarity of expression and style are consider- much accomplished in building u p knowledge of a new group o f substances, such :I\ the f r w radicals represent. The abl\ ;iI)cive :iverage a i i t l rmder the. tcxt lwth readable and

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June 3, 1959

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type of survey of the chemistry of free radicals and the same as in the edition by the Princeton University Press (see review above) except for the addition of a brief but cotechniques of investigation which he has made here should increase the opportunity for other workers to carry out gent section on heterogeneous catalysis in biology. I n adplans of “investigation from all sides” such as he wishes t o dition there is a major section on Kinetics of Chain Reactions, as Part 111. This is a general discussion of systems see. in which chain reactions are competing with reactions of DEPARTMENT OF CHEMISTRY molecules and of the factors which determilie their THEUNIVERSITY OF TEXAS ROBBINC. ANDERSON saturated relative rates. Particular attention is given to the initial AUSTIN12, TEXAS production of free radicals by decomposition reactions and the production of free radicals by reaction between stable molecules is also discussed. Decomposition of alkyl broChemical Transformations by Microorganisms. E. R . mides and chlorides and cracking of hydrocarbons are conSquibb Lectures on Chemistry of Microbial Products a t sidered in some detail. There is an Appendix on the actithe Institute of Microbiology, Rutgers University. By vated complex, written by M . I. Temkin, with some inFRASKH. STODOLA, Korthern Utilization Research and teresting comments on the question of “equilibrium” of Development Division, Agricultural Research Service, this complex with the reagent molecules. -2 second apU. S. Department of Agriculture, Peoria, Illinois. John pendix, written by Semenov and N. 0. Sokolov, discusses Wiley and Sons, Inc., 440 Fourth Avenue, Xew York quantum-mechanical calculation of activation energies134 pp. 12.5 X 19 cm. Price, with the conclusion that “theoretical calculation of activa16, N. Y. 1958. ix $4.25. tion energies in quantitative terms for gas-phase bimolecular This is the second book in the series of the E. K . Squibb reactions remains completely impracticable.” As noted in the former review, the book is not a conipreLectures on Chemistry of Microbial Products. The lechensive textbook or treatise, but it is an interesting and tures are delivered annually a t the Institute of Microbiology, Rutgers, The State University of Kew Jersey, by prominent stimulating discussion by an outstanding scientist in the investigators. I n three chapters, this little treatise high- field of the present status of our knowledge of chemical lights the (1) chemical composition, (2) type reactions and kinetics and chain reactions involving free radicals. (3) synthetic powers of selected microorganisms. It is DEPARTMENT O F CHEMISTRY pleasingly written and each chapter is headed by quotations THEUNIVERSITY OF TEXAS ROBBINC. ANDERSON relevant t o the subjects discussed. T o the chemist and AUSTIN12, TEXAS microbiologist alike, chapter 2 should be of definite value, for it lists the types of reactions that are brought about by microorganisms: oxidation, reduction, hydrolysis, decarboxylation, deamination, amination, phosphorylation, dehydration, condensation, methylation, dismutation, amidation, esterification, acylation and transglycosylation. The discussion on the formation of a-ketoglutaric acid and L-glutamic acid could have been included here rather than in BOOKS RECEIVED chapter 3, where the biosyntheses of a few pigments and gibberellins are discussed. April 10, 1959-May 10, 1959 h-aturally, in a limited number of lectures such as these, PHILIP H. ABELSOS, Edited by. “Researches in Ceoit is impossible to discuss all microbial transformations and chemistry.” John Wiley and Sons, Inc., 440 Fourth important related subjects. Consequently, the biospnAvenue, h‘ew York 16, S. Y. 1959. 511 pp. $11.00. theses of compounds like proteins, vitamins and enzymes were omitted and others such as nucleic acids, antibiotics ERNSTBAYER. H. MAYER-KAUPP,Edited by. “Anleiand cell wall studies, were mentioned only in passing. I n tungen fur die Chemische Laboratoriumspraxis.” Band spite of this, the book should furnish important references X. “Gaschromatographie.” Springer-\.erlag, Heidelberand inspiration for further reading in microbial chemistry. ger Platz 3, Berlin-Wilrnersdorf, Germany. 1959. 163 pp. D M . 39.60. RESEARCH LABORATORIES THEUPJOHNCOMPANY DUREYH . PETERSOS ~ V A L T E RJ. HAMER,Edited by. “The Structure of ElectroKALAMAZOO, MICHIGAN OLDRICH K. SEBEK lytic Solutions,” John IViley and Sons, Inc., 440 Fourth Avenue, New York 16, Iz’.Y . 1959. 441 pp. $18.50. C. A . JACOBSON,,, Compiled by. CLIFFORDA. HAMPEL, Some Problems of Chemical Kinetics and Reactivity. Edited by. Encyclopedia of Chemical Reactions.” Volume I . By N. AT. SEMENOV, Institute of Chemical \-ohme VIII. “Tungsten. Uranium. Vanadium Physics, Academy of Sciences of the U.S.S.R. TransYtterbium. Yttrium. Zinc. Zirconium. Addenda.” B.Sc., Ph.D. Pergamon Press, lated by J . E. S. BRADLEY, Reinhold Publishing Corporation, 430 Park Avenue, Sew Inc., 122 East 55th Street, S e w York 22, X Y . 1959. York 22, N. Y. 1969. 533 pp. $614.00. x 305 pp. 15 X 22 cm. Price, $7.50. AXD TARA PRASADDAS. “Theory a i d This is one of two English translations of the second edi- ~ J I TKUMARSAHA lpplications of Nuclear Induction.” Saha Institute o f tion of the book by Semenov, the other translation having Suclear Physics, 92, Upper Circular Road, Calcutta 9, been made by M. Boudart for the Princeton University India. 1957. 516 pp. $6.00. Press (see above). The first edition was a limited one published in 1954 by the Academy of Sciences of the A. J. C. WILSON,General Editor. N. C. BAENZICEK and U.S.S.R. C. S. BARRETT(Metals), J. M. RIJVOETA N D J. WYART This volume is a hard-cover edition and is well-bound and (Inorganic Compounds), AND J. MONTEATH ROBERTSOX well-printed. It is listed as Volume I on the title page, but (Organic Compounds), Section Editors. 0. EISSER, As110 indication is given as to what Volume I1 may be. A sistant Editor. “Structure Reports.” Supplementary Name Index and a brief Subject Index have been provided. \’olurnc and Cumulative Index for 1940-1950. Volunie Part I of the present volume, on radical reactions, and 14. S . V . -4. Oosthoek’s Uitgevers Mij., I h n s t r a a t 1-:I. Part 11, on initiation and termination of reactions, are the Utrecht, The Setherlands. 1959. 215 pp. $9.50.

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