book reviews quent psragraphs. In Chapter 11, which is entitled The Second Law, A Criterion for Reversibility, the diligent student will doubtless he plagued by the fact thrtt the definition of the essential concept of "reversibility" is diffused over two ehslpters. If he succeeds in working his way through the Carnot cycle argument, he learns thst entropy changes can be calculated only along reversible paths, which is true enough, and then that equality between T A S (= qrcv) and q (or a zero value for the Gibbs free energy) is the "criterion of revemibility." But, how can he confidently use the entropy change or AG as s. criterion for reversibility in an arbitrary process when heis not sure what constitutes a reversible path along which to calculate AS in the first place? There are also difficulties for the beginner a t the level of applications. I n sum, two chapters are devoted to phase equilibria with the last chapter being s. discussion of anumber of solid-liquid phase diagrams. Yet, in connection with a n earlier example of freezing point lowering, the student is led to believe that an ethylene glycol-water mixture will freeze solid a t s temperature just below that a t which ice begins to. form. I n another place he reads that the maximum work available from a, reversible electrochemical cell is the "bond energy," presumably the enthdpy change. Had a discussion of the contributions of AH and AS to AG been included somewhere this slip would probably have been avoided. Given the emphasis placed an numerical problems, the hook has surprisingly limited tables of thermodynamic data. The appendix listing the standard data compilations is not a n adequate solution of this problem for students in large introductory clhsses. The authors report that advanced chemistry students have found this text useful for quick reviews of chemical thermodynamics. This may well be a use to which it is best suited. NORMAN C. CRAIR Oberlin College Obedin, Ohio 44074
The hook consists of a comprehensive table in which heats of metal-ligands interactions in solution, AH, are summarized. The published literature has been covered from the years of 1909 up to mid1969. Values for 97 different metal ions together with 517 ligands are listed. Included also are the related thermodynamic quantities, log K and AS, and the AC,, values where available. I n addition, the following information is also included in the table: the appropriate resetion, temperature, method, conditions of measurement of AH, original and additional literature references, and pertinent supplemental information. I n order to have a convenient and proper use of the book, Professors Christensen and Ieatt have given a, brief hut clear illustration of the "Use of the Table and Indexes" in the very beginning of the book. There are five excellent IndexesAuthor, Empirical Formula, Element, Synonym, and Reference. The Author Index lists each author alphabetically together with the reference and ligand or ligands investigated. The Empirical Formula. Index contains the empiricsl formula, name, and synonym(s) of each ligand together with the locrttion of the ligand in the table. The Element Index contains an alphabetical listing of d l elements appearing in the Metal Ion column of the table together with their valence states and locations in the table. The Synonym Index is a n alphhetioal listing of the common synonyms of the ligands appearing in the table together with their names and locations in the table. The Reference Index includes B year-byyear alphabetical listing of all cited references. I n summary, this hook represents the first attempt to summarize the large amount of literature on heats of metalligand interactions in solutions. The authors have done an excellent job summarizing and compiling such a great number of A H vdues together with the related thermodynamic quantities and necessary pertinent information. I t is a vduable reference source for either practical or re~ e a r c hscientists in both physical and hiological sciences. GEORGEW. C. HUNG The University of Tennessee Medical Unils M a p h i s , Tennessee 58103
Handbook of Metal Ligand Heats and Related Thermodynamic Quantities
James J. C h ~ i s h s e nand Reed M . Izatt, R i c h a m Youne Universitv. Provo. Ut&. Marcel ljkkker, Ine., ~ e ~wo r k ; 1970. vii 324 pp. Table. 18.5 X 26 cm. $14.50.
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This book is intended t o be s, general reference source for workers in the areas of thermochemistry and thermodynamics of metal-ligands interaction, including those in such fields as chemistry, physics, bacteriology, engineering, microbiology, and medicine. I t is especially helpful for those workers in the fields of solution chemist,ry and coordination chemistry.
A190
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Journol of Chemical Educafion
The Hydrated Electron
Edwin J . Hart, Argonne National Lahoratory, Argonne, Illinois, and Michael Anbar, Stanford Research Institute, Menlo Park, California. John Wiley & Sons, Inc., New York, 1970. xiii 267 pp. Figs. and tables. 23.5 X 15.5 om. $12.95.
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This research monograph has its origins in two diverse areas af physical science which, in recent years, have been the object of a. number of moderately suc-
cessful attempts a t unification. On the one hand there are the clttssio studies of metal-ammonia solutions going back to the early work of Weyl and to the work of Kraus snd his colleagues after the turn of the century. These solutions represent systems in which the electron is relatively stable. Kraus recognized and suggested that the blue color of these solutions might he attributed to solvated electrons, and i t is somewhat'regrettable that the authors have not devoted a little more attention to this earlier groundwork. On the other hand there is the more recent work on the radiation chemistry of water (to which the monograph is speeifioally directed) and of other polar liquids from the studies of which there has come such a wealth of information about the optical properties and the chemical reactivity of excess electrons in polar liquids. These are systems in which the electron is relatively unstable. The authors trace the developments in the experimental work on irradiated aqueous solutions which led to the understanding that the primary reducing species was the hydrated electron: the observation that the reactivity of the reducing species showed a pH-dependence, and the classic experiments of Czapski and Schwarz which showed, from the kinetic salt effect, thst the reducing species had unit negative charge. These observations, together with the primitive theories about the optioal properties of the solvated electron, and the newly-developed technique of pulse radiolysis, led to the spectraphot.ographic detection of the absorption spectrum of the hydrated electron in Boag's lahoretory. Some authors have referred t o the hydrated electron as the simplest of chemical species, a. naive response to the symThe structure of solvated bolism e.,-. electrons is a complex matter which is by no means fully understood. The chapter on Physical Properties contains a brief description of the cavity-continuum model along with a. useful compilation of those physical properties which have been studied. Although we may not yet know precisely what the hydrated electron is, we certainly know a large part of what there is to know ahout what i t does. The codification of its reactivity, which has been so successfully studied by the pulse radiolysis method, is the major substance of this monograph. The hydrated electron is a powerful reducing agent. There are separate chapters on its reaction with water, with inorganic compounds, with orgsnio compounds and with molecules of biological interest. The last will be particularly useful to radiation biologists. The data. on unusual valence states and the data on electron transfer are of interest in other areas of chemistry. The book deals with an interesting and important chemical species-not quite as important as the authors, in an obvious flush of enthusiasm, suggest in the opening lines of the Preface-which may play a role in a variety of chemical reactions. I t represents a further example of data evolving from fast-reaction studies in (Continued on page A19B)
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and confusing to the student. Professor Buerger has compiled a, volume which should be required reading for such authors. He has succeeded in doing what radiation chemistry which are of primary he set out to do, namely, to create s o m e significance in other areas of chemistry. thing useful and understandable for stuLEONM. DORFMAN dents in chemistry, physics, mineralogy, Ohio State Uniuersity rnetsllorgy, and biology. I especially Columbus, Ohio 43U0 like the lavish use of figures. This hook will not he suitable for use as a principal text by all instructors, because, ideally, they should have more insight from prsetical use into this subject. I t should be owned, and read, by everyone who Introduction to Crystal Geometry considers himself a. crystallographer, and by everyone who makes use of the results Marlin J . Buerger, Massachusetts Inof X-ray crystallographers. stituteof Technology,Cambr.idge, Mass., On the minus side, the author displays and University of Connecticut,, Storrs, an undue emphasis on the nomenclatural Conn. MoGraw-Hill Book Co., Inc., aspects of his snbject. These include a New York, 1971. xii f 204 pp. Pigs. preference for the 1st setting (which no and tables. 23.5 X 16 cm. 812.50. one uses) in the monocliniesystem, rehashing the hexagonal-trigonel-rhombohedra1 According to its introduction "most of hessel, use of "isometric" instead of the the information conlained in this hook has more economical (and nnembiguons) been available since 1801, when the theory "cubic," and axid labeling in the orthoof space groups was first publiahed." rhombic system including 8. lengthy exWhy, then, this book? Well, for one position of whet happens to t,he space t of fundamental, thing, it puts a g r e ~deal group symbol when the axes are permuted. t,hough elementary, material between the same net of covers. More important, An eleven page table of the equivalent positions and their multiplicities for all however, is the antidotal elTect one hopes 230 space groups seems unnecessary. The t,his book will have against the mounds only misprint noted in this carefully of garbage which have been produced on produced work is an obvious one on p. 154. this subject since 1891: any author writing a text book of physical chemistry J ~ R DONOHUE Y feels qualified to write {.heususl obligatory Uniuersil?,qf Pennsylvania chapter(s) un crystallography and symPhiladelphia metry, and tho resulting jargon is useless
book reviews
A 192 / Journal o f Chemical Education
McGraw-Hill Yearbook of Science a n d Technology. 1971
Daniel N . Lapedes, Editor in Chief. MrGraw-Hill Inc.. New York. 1971. and tables. 28.5 X 22 4 8 1 ~ ~Figs. . cm. $27.50. This newest in the oldest series of science yearbooks is a worthy companion to the new 15-volume McGraw-Hill Encyclopedia. of Science and Technology. The bulk of the volume is devoted to 1970 developments from "absolute zero" to "xylem." I n these days when it is impossible to keep even with the frontiers of knowledge in any but narrow fields of specialby, the need for an authoritatively writt,en sommary of recent advances is experienced by everyone. This volume meets that need. I n addition, 10-page essays preview 1971 advances in each of six fields. Chemists will be glad to find those on origin of life and on computecassisted rtnalytical chemistry, a t l e a d The book is further made a visual pleasure by the inclusion of 8. collection of excellent photographs of scientific importance. WFK
Absolute Configuration of Metal Complexes
Cli$'ord J . Hawkins, University of Queensland. A Volume hl the Interscience Monographs on Chemist~y, (Conlinued on page A194)
