of the book. The author starts with a brief hktorical review. then quickly shows t,he relationship of photochemistry to spectroscopy and kinetics. The chapter on the absorption process introduces some aspects of both atomic and molecular structure and spectra, including hyhridization, the Frmck-Condon principle and the Jahlonski diagram. The importance of specifying the type of spectral transition, for example n - r * or r - r*,in the understanding of primary processes is emphasized. I t would have been useful to point out that. polyetomio moledeu have many low-lying excited electronic states, and that a given type of absorption is no guarantee that the reacting state has the same orbital occupation as the s t a k formed in absorption. This chapter is the weakest in the book. Some troublesome points are the dim~ssionof eigenfunctions, description of behavior of electrons in antibonding orbitals, and the characterisatinn and illustration of intersystem crossing as an energetically downhill process. I n the next chapter, ultraviolet spectra of organic molecules are discussed in greater detail. There is a verv brief treatment of exneri-
and energy transfer. The arrangement and treatment in the main part of the book make it almost a collection of review articles, permitting quick e n t q into the literature a t any point. These chapters are extensively sub-headed and referenced. There are more than 1000 total references, giving good coverage throngh 1965, with a few dated 1966. In chapter 5 , decomposition reactions are grouped chiefly according to the low molecdar weight, stable fragment eliminated in the photolysis: carbon monoxide, nit,rogen, nitric oxide, sulfur dioxide, or carbon dioxide. This is an effective hut not restrictive classification; for example, the topic, Elimination of Nitric Oxide, is in fact a. concise summary of the photochemistry of organic nitrites emphasizing structural effects, mechanisms, and synthetic possibilities. I n the next chapter addition reactions of excited states are given excellent coverage based on 244 references. Examples are well chosen to illustmte t,he variety and synthetic importance of these processes. Chapter 7 on hydrogen abstraction by excited states describes not only the ketone redoctions but several less familiar eases. Next, rearrangements are covered in a long chapter. The many sub-heads are most helpful in keeping this material sorted out. After short chapters on substitutions and chain reactions initiated by photochemically-generated radicals, the author closes with a chapter on photochemktry and nature. There is an author index and an excellent subject index. This volume will see textbook use in special topics courses on organic photo. chemical reactions. For more general organic photochemistry courses, other sources to supplement the fundamentals will be necessary.
Inorganic Synfheses.
Volume 9
S. Young Tyree, Jr., College of William and Mary, Williamsburg, Virginia, editor-in-chief. McGraw-Hill Book Co., New York, 1967. xiv 241 pp. Figs. and tables. 16 X 23.5 cm. $9.95.
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This "continuing series of elf-contained volumes representing an effort an the part of an outstanding gmup of inorganic chemists to make available detailed and tested methods for the syntheses of inorganic compounds" needs no introduction to readers of T m s JOURNAL.With a few excepbions, theorganisatition conforms to that of previous volumes (See J. CKEM.EDUC., 38, A552 [1961]; 40, A530 L19631; 44, A354 [I9671 for reviews of Volumes 6, 7, and 8). A minor change in format is the fact that the chapters, while still arranged on the basis of periodic group, are no Longer subdivided into A and B subgroups. Beginning with Volume 9, "Inorganic Syntheses" will appear annually, and because of this new yearly publication policy the present volume contains a somewhat smaller number of entries (50 contribw tions describing 94 compounds) than has been customary in the past. For the same reason, contrary to previous practice, no review articles appear in the present volume. Readers of Tms JOURNALwill be interested primarily in the suitability of the procedures for undergraduate and graduate laboratory courses in inorganic chemistry. Most of the syntheses will be challenging toeven themost intrepid student,in fact, many may be too challenging. A number of the products or starting materials are flammable. toxic. shock-sensitive.
many safety precautions, the instructor will still be left with a variet,y of experiments that illustrate synthetic techniques and compound types of great utility in contemporary inorganic chemistry. Techniques that are employed include the use of non-aqueous solvents, vacuum systems, dry box snd cont,rolled atmospheres, gas phase reactions, low or high temperatures, remote control manipulation, resolution of optical isomers by diastereoisomer format,ion, and fluorimtion by means of ant,imony and arsenic fluorides. I n keeping with the emphasis on syntheses that are "applicable to a variety of related compounds," a number of general methods are given (organometallic chelate compounds, fluorophosphoranes, sulfamides, tetrahalo complexes of dipositive met,als in the first transition series, and anhydrous metal chlorides by reaction of metal oxides with thionyl chloride or hrxaahloroorooene). The line of demarcation between inorganic and organio chem~stryhas of late become nebulous, and several syntheses in this volume employ the Grignard reaction (trimethylphosphine, trimethylantimony dihdides, and substituted sdfamides). I t is implicit in the concept of scientific progress that much work rapidly becomes obsolete. Accordingly, not all the G. R. M C M ~ A N syntheses are new; some constitute improvements upon syntheses published earCase Western Reserve University lier in the series (anhydrous metal ehloCleoeland, Ohio
624
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Journal of Chemical Educotion
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rideu, TiBrc NhC4, S4N4,SOP9,and ICI). Coordination compounds, because of their color and ease of preparation, are perennial favorites of instructors and students alike. A sizable selection of such compounds is given; they range from the long known and thoroughly familiar [Co(NH,)&I]CI% to recently discovered and still unfamiliar compounds such as perchloratonickel(I1) complexes. Preparations of starting materials and intermediates of interest to the coordination chemist include KICo(NHa)~ NOS)^], (NH&PtCle, and Re(V) complexes. Unnsnal oxidation states, always to be relied upon to provide an exotic flavor to m y inorganic laboratory course, me well represented by C,H,MO(CO)~ C1NOs, ICI, and [(RO)sPIaNi),and the preparation of metal iron(II1) oxides will be of interest to industrial chemists because of the important electronic applications of the ferrospinels. My previous objections to the series (J. CHEM.EDUC.,44, A354 [19671), via., the failure to submit galley and page proofs to contributors for correction and the lack of reprints, require reiteration here. Aside from theseminor comnlaints. thevolume is
GEORGEB. KAUPFMAN
California Slate College Fresno
Chromatographic Methods
R. Stock, Regional College of Technology, Nottingham, and C . R. F . Rire. Regional College of Technology, Liverpool, England. 2nd ed. Chapman and Hall (distribut,ed in the U.S. by Barnes and Noble, New York, 1067). viii 256pp. Figs. and tablea. 13.5 X 21..5 em. Clothbound, $7.50; paperbound,
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54. This is a second edition of this book. which originally appeared in 1963. After an Introduction elassifvine chromatoerachromatography and zone electrophoresis, gas chromatogrrtphy, thin-layer chromatography and model experiments in ehromatographic techniques. Compared with the first edition, which was .50 pages shorter. the chanter on thin-laver chrosieve chromatography are new. These additions are certainly warranted by the recent activity in these fields. Some timely additions have been made to the section on ion exchange. Additions have made the bibliography more current. No ehanees were made in the other material. ters were not revised in the new edition. For example, it is incorrectly inferred that Tswett separated only colored s o h stances in his original work with chromatography (p. 1). I t is not true that chromatoeraoh was lareelv unused between 1903
(Continued on page A912)
BOOK REVIEWS mentioned. The statement that "The number of applications of ion-exchange paper sheets so far reported is not large.. ." (p. 97) is not accurate. And column chromatography is not slower than thin-layer chromatography (p. 171) if suction is employed. Despite these and some other similar minor shortcomings, this is a. valuable, inexpensive, largely-accurate introduction to chromatography for the novice. Each individual technique is adequately and and concisely described, and the chapten are linked so that bhey compare and contrast the various methods. The recipetype model experiments, illust,rat,ing inorganic, organic and biochemical applications, allow a beginner to get started in the laboratory on his own. The chapter on gas ehmmstography is the only olle stressing theory. and it is the best introdoction to this topic ever encountered. The new edition would have been impmved had the authors decided to revise and u p d a t e esch chapter. Even so, it is a book which should be tlaed widely by stodents in both secondary schools and universities ss reqrdred reading in courses including the introd~~etion of chromatography or as an aid for individual study.
J ~ S E PSHERMI H I.afagetle College Easlon. Pennsylvania 18042 Thin-Layer Chromatography
Kurt Randeralh, Ilarvard University. Translated by D. D. Libman. 2nd revised and enlarged. Academic Press, Inc., New Ywk, 1966. xiii 285 pp. Figs. and tables. 17.5 X 24.5 cm. 89.50.
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This edit,ion of Dr. Knnderath's hook represents an expansion and updating of the previous one. An attempt has been made to be selective in the use of reference material, emphasis being placed on those sources that give ns*sanahle amount of discussion of experimental technique. The book is written in a clear and concise manner and phobographs and illustrations of good quality are used intelligent,ly throughout. A number of 1964 references are included. The iallawing topics are discussed in the first section of the hook: historical introduction; general technique of thinlayer ehrvmatography (an introdnction to the method); and technique of thinlayer chromatography (e.g., the preparation of layers; sdsohents and other c o a t ing m a t e d s ; methods of d e t e h o n ; qualitative and quantitative methods; thin-layer ehromslography using radioactive isot,opes; t,hiwlayerelect rophoresis; recording ihi~l-layerchromatograms; and preparative thim-layer chromatography). Although this section is wd-executed, oeeasionslly unbalanced treatment of snbjects is encountered. For example, four and a half pages are dedicated t,a "applying the substances," a matter that has heen iha~.oughlyexploited in previous hooks on thin-layer ehrametography, whereas less than two pages are devoted
A912 / Journal o f Chemical Education
