July 20, 1958
BOOKREVIEWS
3805
Walling goes on to discuss Free Radical Polymerizations equilibria have cast light on t h e mechanisms involved and in the next three chapters which are called, respectively, have expedited the exploitation of sorption and elution Free Radical Polymerizations; The Kinetics of Radical processes b y industry. Uses of ion-exchange resins are beChain Processes (Chapter 3); Copolymerization, Chain coming so numerous and in some instances are so elegant Transfer, and Inhibition in Polymerization (Chapter 4); t h a t i t behooves the chemist and chemical engineer to acSome Further Characteristics of Radical Polymerizations quaint himself with t h e fundamental principles involved in (Chapter 5). These are superb accounts of the whole field ion-exchange processes. of free radical polymerizations. The treatment is very deKitchener has not tried t o justify all the theories concerntailed, b u t most lucid. All the important work in this vast ing ion exchange, but instead has attempted to sift out the field is summarized succinctly and the reference coverage is main, well established principles from those which are controversial in a formidable amount of original literature. Conremarkable for its inclusiveness. There are excellent compilations of data in tabular form. Here great care has ob- sidering the versatility and complexity of the process, he viously been taken in selecting reliable information and in has done a n excellent job of organizing and condensing the assembling i t in a manner as to make it easily accessible. pertinent details into a minimum number of pages. Hcre again I felt compelled to compare Professor Walling’s The book is interesting and written in such a manner t h a t account with that given in a standard work, namely, “The anyone with a rudimentary knowledge of physical chemisMechanism of Polymer Reactions” by G. M. Burnett, t r y can understand its contents. It appears t h a t the inforand this certainly indicates just how thorough and up-tomation contained would be valuable supplementary matedate is the account of this field which Professor Walling has rial for a standard course in physical chemistry and should given. by all means be included in the course on unit processes ofS f t e r this very excellent and complete account of free fered to chemical engineers. radical polymerizations, Professor Walling proceeds t o disOnly one discrepancy is apparent in the entire book. It cuss in turn Radical Addition Reactions Yielding Small occurs in the elution sequence for divalent ions on page 29. Molecules (Chapter 6); Radical Addition Reactions In- The appearance of B a + + as the first and last member of the volving Atoms Other than Carbon (Chapter 7); and Halosequence will cause some consternation among those who gen Substitution Reactions (Chapter 8). I n these the same read the book. high standard is maintained and important stereochemical The author has covered the important applications of ion aspects of free radical reactions are stressed throughout. exchange rather well, in genera1,hxcept t h a t he has apparKinetic details of the various reactions are also carefully and ently not kept up with the most recent developments in the critically discussed. separation of rare earths by this method. The most recent The book then continues with a really outstandingly well- reference cited on this subject is more than ten years old written and complete account of Autoxidations (Chapter 9). and citric acid is not the complexing agent used for the I n the reviewer’s opinion, this is by far the best review of the commercial production of pure rare earths. Citric acid has chemistry of autoxidation which has appeared in the litera- been replaced by the more efficient chelating agents such as ture. The literature coverage is excellent and the subject ethylenediaminetetraacetic acid and ~ - h v d r o x y e t l i y l e t l i ~ l matter most judiciously selected. There then follow two enediaminetriacetic acid. very good chapters on Radical Formation by Thermal CleavAMES LABORATORY age of Covalent Bonds (Chapter 10) and Radical Production JACKE. POWELL Box 14-$, STATION A by Photochemical, High-Energy Radiation, and OxidaARIES,IOWA tion-Reduction Processes. Throughout the book the literature seems to be very completely covered right up to about the middle of 1956. It is also pleasing t o note t h a t Professor Walling has included a The Physical Chemistry of Electrolytic Solutions. Third large number of references to important relevant Russian Edition. ACS Monograph No. 137. By HERBERTS. work. The book has two good indexes, and it is interesting HARSED, Professor of Chemistry, Yale University to note t h a t the Author Index is twice as large as the SubEmeritus, and BESTONB. OWEX,Professor of Chemistry, ject Index; this is an indication of how extensively the literaYale University. Reinhold Publishing Corporation, ture has been covered. 430 Park Avenue, New York 22, New York, 1958. xxxiii This then is a major work of scholarship and i t will ob803 pp. 16.5 X 23.5 cm. Price, $20.00. viously be the standard monograph on the Chemistry of Free Radicals in Solution for some considerable time. It Although not truly “a drastic revision,” the Third Ediwill appeal to all chemists, and no physical or physical- tion of Harned and Owen’s “The Physical Chemistry of organic chemist who wishes to keep informed of the advances Electrolytic Solutions” is much bigger and better than the in free radical chemistry can afford to be without a copy. earlier editions. This book has grown from 643 pages in I n closing, one might note t h a t the book is dedicated to 1943 and 681 in 1950 to 836 pages in 1958. hlorris S. Kharasch and Frank R . Mago, pioneers of free The numerical values in Chapter Y and iri the equations radical chemistry, who first aroused and then maintained throughout the book are now up-to-date except that 1.858 Professor Walling’s interest in the subject. Regrettably, instead of 1.860 persists for the freezing point constant of Professor Kharasch died recently. This book would be a water. Of course the authors have not revised all the exfitting memorial to this great chemist who laid the foundaperimental results which depend upon these values because tions of much of the work described in its pages. they are mortal and have only tn-o lives to give to their science. Otherwise the first edition is reprinted almost DEPARTMEST OF CHEMISTRY USIVERSITY O F BRITISHCOLUhlBIA C. A. MCDOWELL unchanged except that the material in the 37 pages of Appendix B of the second edition and much new material is 8, B. C., CANADA VASCOUVER incorporated a t the ends of the appropriate sections or as new sections a t the ends of the appropriate chapters. The first five theoretical chapters have been increased by GO Ion-Exchange Resins. By J. A. KITCHESER, University Reader in Physical Chemistry, Imperial College of Sci- pages, and the experimental chapters and appendix by 120 pages. ence and Technology, University of London. John Wiley The important additions arc discussions of “Irreversible and Sons, Inc., 440 Fourth Avenue, New York 16, N. Y. Thermodynamics” (25 pages), of the Fuoss-Onsager treat109 pp. 11 X 17 cm. Price, $2.00. vii ment of the conductarice of moderately concentrated solu.%lthough the ion-exchange process was discovered more tions ( 2 5 pages), of the Onsager-Kim treatment of the \ I k n than a hundred years ago, synthetic organic ion-exchange effect, the effect of high field strengths on conductance (10 materials were not invented until 1935. As a matter of pages), of the Mayer treatment of chemical potentials ( 3 fact, the currently popular sulfonated styrene-clivinylberipages), of the Glueckauf-McKay cross-diff erentiatio!i zeiie catioti-exchange copolymers did not make an appearniethods (10 pages), and the presentation of new experlatice until 19-14 and the strongly basic quaternary aminonium mental material (about 100 pagesj. The authiirs have type anion-exchange resins were unknown until 1948. made a noble effort to give clear discussioiis, but the nature U‘ith the advent of stable, high capacity ion-exchangers of the material iiecessarily makes the readiiig of the first which possessed a single functional group, i t became possible four chapters eveti more difficult than before, and puslies to uiiderstand the behavior and properties of ion-exchange the first presentation of an experimental result back tu page media. Many t h r o u g h investigations of ion-exchange 197.
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