XOV.
5. 1964
BOOKREVIEW’S
wise “Thermodynamik der Irreversiblen Prozesse” is a book t h a t this reviewer wishes he could have written himself. Haase is a master teacher who has given the physical chemist a first-rate introduction t o the thermodynamics of irreversible processes. I t is t o be hoped t h a t the linguistic laziness of the English-speaking world will not impede this book in achieving t h e high reputation it truly deserves. DEPARTMENT OF CHEMISTRY UXIVERSITY O F KANSAS LAXREKCE,KASSAS
RICHARD J. BEARMAN
The Chemistry of Cationic Polymerization. Edited by P . H . PLESCH. Pergamon Press, T h e Macmillan Co., 60 Fifth Xve., New York 11, S . P. 1964. 728 pp. 16 X 24 c m . Price, $30.00. T h e concepts and experimental information available for cationic-catalyzed polymerization have increased in a spectacular fashion in t h e past twenty years. h specialized book of this kind, consisting of contributed chapters amounting t o 712 pages, is a n indication of the interest in this general subject. There is considerable overlap in many of the chapters which t h e editor has clearly recognized, and rather than disrupt the flavor of a chapter by a n expert, he has chosen to allow some duplication and insert comments and cross-references. One could always quarrel with the verbosity of some of the chapters, b u t it is inevitable in a specialized book of this type. There are two groups of people t o whom this book will be very useful: ( 1 ) macromolecular chemists who are interested both in synthesizing large molecules a n d mechanisms of polymerization; a n d ( 2 ) a small “hard-core” of researchers throughout the world working on the details of mechanisms of catalyzed-cationic polymerization. T h e first two chapters I. “Carbonium Ions,” by M . L. Burstall (Battersea College of Technology, London) and F. E . Treloar (University of Malaya) 11. “Organic Reactions Related t o Cationic Polymerization,” by M . L . Burstall are background material t o review the chemistry of ion pairs in solution. T h i s may have seemed advisable, b u t this reviewer rather questions whether it has been worthwhile, because by necessity these chapters cover details of intermediates and transition states, etc., which are also discussed by authors in individual chapters. Perhaps this repetition may be helpful t o some readers. T h e third to eighteenth chapters are listed here for information: 111. “A Comparison of the Radical, Cationic a n d Anionic Mechanisms of Addition Polymerization,” by P. E. M. Allen (University of Birmingham) and P . H . Plesch (University of Keele) I V . “Isobutene,” by P . H. Plesch V . “Aliphatic Mono-olefins Other T h a n Isobutene,” by C . M . Fontana (Celanese Corporation of .4merica) V I . “Styrene,” by Professor A . R . Mathieson (University of S o r t h e r n Nigeria) 1-11. “Aryl Olefins Other T h a n Styrene,” by S. Bywater (National Research Council, O t t a w a ) V I I I . “Polyenes,” by U‘.Cooper (Dunlop Rubber C o . ) IX. “17iny1 Ethers,” by Professor D . D . Eley (University of Nottingham) X . “Epoxides,” by A. M . Eastham (National Research Council, O t t a w a ) X I . “Cyclic Oxygen Compounds Other T h a n Epoxides,” by J . B . Rose ( I . C . I . Plastics Division) X I I . “Miscellaneous Oxygen Compounds,” by A . Schrage (Rexall Chemical Co.) X I I I . “Sulphur Compounds,” by J . La1 (Goodyear Tire and Rubber C o . ) XI1.. “Nitrogen Compounds,” by G . D . Jones ( D o w Chemical Co.) X1.. “Co-polymerization,” by R . B . Cundall (University of Sottingham) X V I . “Cationic Reactions of Polymers and Cationic Graft Polymerization,” by Professor G . Smets and M . van Beylen (University of Louvain) X1’II. “Cationic Polymerizations Induced by High Energy Radiation,” by S. H . Pinner ( B X Plastic L t d . )
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XI-111. “Experimental Techniques,” by P . H. Plesch This reviewer would disagree occasionally with points of view raised, b u t in a book of this sort this would be unavoidable. Research workers in specific areas of cationic polymerization will want this book as part of their personal library; certainly every macromolecular chemist will need this book for reference referral. T h e editor is to be complimented for completion of a difficult task. OFFICE O F THE DEAN O F S C I E N C E ISSTITUTE OF BROOKLYN POLYTECHSIC SEW 1 - 0 ~11201 ~ BROOKLYS,
C . G . OVERBERCER
The Rare-Earth Elements. By D. S . TRIFONOV, Institute of the History of Sciences and Technology of t h e Academy of The Macmillan Co., 60 Fifth Ave., Sciences of the U.S.S.R. 128 pp. 14.5 X 22 cm. New York, N. Y . 1963. xv Price, $3.50.
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I t is indeed unfortunate, a s t h e author states, t h a t “the number of review articles and books on the rare-earth elements in Russian is very small.” This circumstance has led him to prepare a little volume of facts gleaned from out-of-date Russian works and some, but obviously not all, of t h e English language reviews of t h e subject. His intent was to furnish t h e Russian student of chemistry with “an account which is lively, easilyintelligible and informative, of t h e long and extremely involved story of the discovery of these elements, their properties, the methods for their separation, t h e present state of problems regarding them, a n d some prospects of future developments in this branch of chemistry.” T h e result of Trifonov’s abbreviated and cursory interpretation of existing accounts, and a detectable amount of Russian bias in assessing t h e contributions of the various workers whose names are cited, is extremely disappointing-in t h a t he has fallen miserably short of his stated goal. Only the history of their discovery and t h e early chemistry of t h e rare earths have been treated adequately. Modern ionexchange methods for separating rare earths have been passed over lightly, and solvent extraction techniques have not been discussed a t all. Interpretation and translation of English works t o Russian, and literal retranslation of the result to English by a n Indian translator, with inadequate final editing, have contributed t o t h e inclusion of a n appalling number of typographical errors, obvious mistakes, and garblings of radiochemical symbols. Owing t o t h e many mistakes, various omissions, perpetuation of many common misconceptions ( t h a t t h e ion-exchange method is unsuitable for producing large quantities of pure rare earth materials, t h a t rare earth elements a r e extremely difiicult t o obtain in the metallic state, t h a t t h e cost of rare earth oxides and metals is prohibitive, t h a t dilute nitric acid acts only on metallic cerium, e t c . ) , and a complete lack of specific references to the source of d a t a cited, this book is not to be recomniendedeither to the student, whom it will confuse, or t o t h e expert, whom it will disappoint.
IOWA STATE L T AMES,I O U A50012
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Consecutive Chemical Reactions. By S . M . RODIGUINand E . N . RODIGUINA.Translated from the Russian b y Scripta Technica, Inc. D. Van S o s t r a n d Co., Inc., 120 Alexander S t . , Princeton, S . J . 1964. i x 136 pp. 15.5 X 2 3 . 5 cm. Price, %c5.00.
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One day last March, I ( = this reviewer) received from M o u n t Olympus a curiously composed proposal t h a t I review a small book on the mathematical theory of chemical reaction kineticsby D r . and M r s . Rodiguin of Russia-for the American Chemical Society’s most celebrated Journal. T o have rejected the proposal on a n y grounds whatever-ideological, temperamental, or financial-would have invited certain persecution by all the gods and the Society too. T h e last time I was persecuted by the XCS was when I was falsely accused of having taken advantage of one of their “inexperienced” employees, a very pretty Chinese girl, in San Francisco. (She didn’t even give me a second look.) T o avoid another such experience, here I a m . S o t having ever been much corrupted by Aristotle, Gibbon, F r e u d , M a r s , or the ACS, I can hope to give a pleasantly objective estimate of the book’s virtues and sins.
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BOOKSRECEIVED
Son let's look a t t h e book! I t contains, in a clearly expressed way, the mathernatical anall-sis of t h e kinetics of consecutive chemical reactions of t h e t y p e A = B = C. . ., a n d therefore similar to radioactive decay series rnother --t daughter + grandaughter, e t c . , except t h a t i i i chemistry one or in 're steps m a y be reversible, or one or tilore steps m a y be crccompatiied by branching of one kirid or another, including chain reactions. uniption t h a t all steps in a series are effectively first order, the rate equations consist ( i f a set of TI sitnultaiieous linear differential equations of t h e first order i l l n dependent one iuvariables-the concentrations C,, Cn, . . ,, C,,-antl dependent variable, the time 1 . For reactions such a s .I 2! = B = etc., it is assumed t h a t the coticetitration of 2! is large and doesn't change much. T h e authors present a considerable n u n ber of explicit cases for n = 2, 3 , . . ., and give t h e solutions of the rate equations in detail as linear functions of esponentials, exp( - A t ) , in t h e time. T h e method used by tlie authors for the solutions of the rate equations is made t o depend 011 Laplace-Carson transfornis in which d/dt is replaced b y t h e operator P ,which is then treated much like a noncommuting algebraic entity. Xfter some algebra, the final solutions a r e found t o depend on t h e solution of a simple integral equation. In additioii t o the treatment of explicit examples i n t h e main body of tlie book, t h e authors give, in appendices, a good discussion of the Laplace-Carson method a s well a s a n extensive table of transforms and what they call "originals." T h e authors helpfully discuss niaxiina and minima in t h e concentrations C i , b u t are silent about what happens when tWCJ or more rate constants are equal. I t is of interest t o comparc t h e authors' treatnient with tlie classical one given b y H . Bateinan ( P i o r . Cumbridge Phi[. S o r . , 15, 123 (1910)) in his much cited b u t apparently little read paper on the radioactivity case (sly dig here a t t h e book by Friedlander and Kennedy). Bateinan multiplied all t h e rate equations by e x p ( - s t l and integrated with respect t o t froin 0 t o m . In two Or three pages he arrives a t tlie solution of t h e general case including tlie solution of t h e simple iutegral equation. I t seems to this reviewer t h a t t h e matrix method provides a still simpler niearis of solving t h e rate equations ( r f . L . Mirsky, "Introduction t o Linear Algebra, " Oxford University Press, Loiid011, 1955, p . 317). 'Thus if C = [C,, c2,. . ., C,]?' is t h e column concentration vector atid K = [ k , j ] is t h e n X n quite general rate conitniits matrix, then the n rate equations a r e included in the sitnplc expression dC/dt = K C . T h e solution is clearly C = ( e x p X t l G , where cnis the value of C a t t = (3, say. For most practical cases, A-can be diagonalized with a properly chosen matrix S. I n two or tliree lines it is elementary t o show that C = SIl.C-1C,, where 11 = jSij exp(X,t)]. T h e n numbers A , , A?, , , _,A,. a r e the characteristic roots of t h e K matrix. So now the chemists have a K matrix t o exhibit alongside the physicists' S. matrix, which t h e latter are currently YO passionately fond of. I t m a y now be rightly asked if t h e book under review coritributes anything fundamentally new or useful t o science, t o chemical engineering or to o u r over-all culture. Since ktiown principles atid r u l e were used t o solve tlefiiiite problems without uncovering anything truly uiiexpectetl, the auswer t o t h e first question is probably no. Chemical eiiginecrs and their hand-
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maidens, t h e organic chemists, may well find t lie I X N J ~ very useful, which answers the second question. .As for culturc, the book is not only well written b u t deserves tlie w r i i i t r i a t tention of those distinguished liurrianists who deplrire scieiitiits' efforts t o express all manner of things in predictive f i 1 r i i i i i l : i h ; sometimes we can. Beauty takes more t l i : t I i O I I C ~ f < l r i i i , For those cornballs who believe t h a t a woman's place is i i i ii i l i i l l ' ~ house, barefoot, t h e book shows t h a t we have a t least O I i C \ v l i [ i can do higher algebra too. T h e two equations at t h e bottom of page 4 d i i l i ' t seein t o I)e correct; tlie editor of this Etiglisli edition appareiitly ,lipprd t i l ) there. In the last two pages t h e authors give their collcrtctl references, aud here they may be accused of beiiig pri~viiici:i!: if t h e Russians would only learn t o write in Basque, (;reek, Spanish, or better still, English, t h e provi1ici:rl traitx iiiiglit vanish with t h e wild winds. But why split hairs. This reviewer hopes tliat the Roiliguiiiy collect enough i u royalties on their book so tliat the Suiora c i i i i have a mink coat and a Rolls-Royce. CALIFORSIA INSTITUTE O F TECHXOLOGY PASADENA, C.4LIFORNI.4
I ) o s hI. YOST
BOOKS RECEIVED September, 1961 Institute for Scientific Information. "Sciencc Citatirm Intlcx An International Interdisciplinary Index til tlic Literature of Science Source Index." Institute for Scientific Iiiformation, 325 Chestnut St., Philadelphia, P a . 19106. 1961, 158 pp. 31250 per year, educational orgaiiizations: 811150 per year, industrial organizations. Institute for Scieutific Information. "Science Citaticjti Index. An International Interdisciplinary Index t o the Literaturc of Science. Citation Indexes." Institute for Scieiitific Inforination, 325 Chestnut St., Philadelphia, P a . 191O(i 1964. 263 pp. $1250 per year, educational org:inizations: 51950 per year, industrial organizations.
H. H . MITCHELL. "Comparative Sutrition of Man anti 1)omeitic hnitnals." Voluine 11. ;\cademic Press In?., 111 Fiftli Ave., S e w York 3, S.Y. 1964. 840 pp. $28.00.
