book reviews Chapters on mass spectrometric apparatus and theories are followed by a very long chapter on structure elucidation. These sections indude good introductory discussions on types of ion sources, energy conversion mechanisms, bond strengths in radical cations, and the dependence of fragmentation patterns on initial energy of the ions. An appendix contains more detailed descriptions of important experimental methods. Sections on the origin and use of metastable ions, cbemical-ionization methods, and instrumental techniques of combined glc-ma are well written and useful. Advanced students may find a number of these sections heloful for reference. Throughout the book, theory and empirical applirnrions RIP diseur~edwrth a goad sense of pempertive. Critical commenrary usually follows presentation of each exp& mental strategy. There is also a good deal of practical advice on how to obtain useful spectra. The author stresses the limitations of our present knowledge of detailed ion-fragmentatian mechanisms. Because the actual structures of both reactant and fragment ions are often unknown except through the assumption of minimum structural change, Dr. Johnstone states that qualitative theories currently used in analyzing mass spectra are not truly predictive hut rest heavily upon analogy. Nevertheless, the hook utilizes fragmentation-product stability and charge localization theories eatensively hecause they are so useful in eorrelating mas8 spectral data. Few typographical errors appear on the books well designed pages. However, some incorrect formulas may confuse the reader: On p. 64 C ~ H I Y should be CaH9., on p. 118 C3H7 should be CIHp and the correct farmula of 2-hexsnone should he given. The relationship of odd mle values to evenelectron ions, stated on p. 53, is of course not valid for ions with odd numbers of nitrogen atoms; this is not pointed out until 50 pages later. In a few eases, the fish-hook convention of electron accounting was puzzling when not all of the necessary electron movements were noted. In summary, I found "Mass Spectrometry for Organic Chemists" helpful in gaining an appreciation of mass spectrometric theories and techniques; however, anyone seekine- an introduction to the oracticnl - interpretation of mass spectra will probably not find this hook adequate. ~
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Jeny R. Mohrig Carktm CoUsgs NorthfleM, Minnesota 55057
rechnlque of Electroorgank Synthesis. Volume V. Part 1 Edited by Norman L. Weinberg, Hooker Chemical and Plastic Corporation, Grand Island, New York. John Wiley and Sons, New York, 1974. viii 917 pp. $47.50.
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This book is directed towards the organic chemist interested in applying electrochemistry to the synthesis of organic comA484 / Journal of ChemicalEducation
pounds by oxidation and is organized acThe Electrochemldry of Metals and cording to the steps that would be followed Semiconductors by a neophyte in this area. The material presented is divided into six chapters: InAshok K. Vijh, Hydro-Quebec Institute troduction, Experimental Methods and of Research. Marcel Dekker, Inc., New Equipment, Principles and Approaches to York, 1973. xiv 297 pp. Figs. and tathe Study of Mechanisms of Organic Elecbles. 16 X 23.5 em. $26.00. trode Reactions, Electrochemical Oxidation of Organic Compounds, Anodic OxidaThose interested in processes involving tion Pathways of Aliphatic and Aiamatic electron transfer, with subsequent chemiFunctions, and Anodic Reactions of Carcal reaction at an interface of a solid and a boxylates, and was contributed by seven phase with high ionic mobility will find this authors. Duplication of material between an informative reference. The author's inthese authors was minimal. rent is to survey areas of electrochemistry The chapter on experimental m e t h d s on which solid s t n v science has an imporand equipment is excellent. A comment ~ ~ ~ in s p t e m ~ t tant bearing. He S I I C C P well should be made, however, about setting up ically covering a broad range of phenomena a dropping mercury electrode. The method connected with electrochemistry in a limitgiven on p. 73 is more complex than what is ed space. The principal value of the volusually used; the capillary is simply atume, however, lies not in elucidation of tached to the reservoir by means of neophysical concepts in solids for the chemist, prene ruhher tubing and mercury is added but in its coverage of recent developments, through the reservoir. with pertinent references. The section an mechanism of electrode The first chapter deals with basic conreactions covers both the kinetics involved cepts in solids. This chapter is presumably and the stereochemistry associated with devised to teach chemists enough about electrode reactions. band theory and chemical binding in solids The fourth chapter deals exhaustively to allow an understanding of the use of with the electrochemical oxidation of all terms such as valence bands, Fermi enerorganic compounds except amines, nitrogies, conduction bands, and similar congen heterocycles (Chap. 5 ) , carboxylic acids cepts. The chapter is in fact somewhat of a (Chap. 6), and organometallic compounds freshman review of cohesive forces, the (Chap. 10, Part 11). and presents a summaBorn-Haher cycle (in which the lack of a ry af the data obtained for each compound consistent sign convention is bothersome) in tables. These tables may be confusing to and correlations between band gaps and the reader since they do not distinguish hecohesive energies in stoichiomeric solid tween isolated compounds and postulated compounds. The important concept of products. Experimental conditions are "density of states," used subsequently in given for a selected number of syntheses in chapter 2, ia neither discussed, nor introthis area. duced in this chapter, so that discussions of The fifth chapter on the oxidation of aliredox reactions on semiconductors in chapphatic and aromatic nitrogen functional ter 2 may be a bit confusing to the uninigroups parallels Chap. 4 in its presentation. tiated. In the discussion of the difference This section has a number of errors in the hetween electrical conductivity in m e w s interpretation of results. The eledrochemiand semiconductors, Ohm's law for metals cal oxidation of aniline to benzoquinone (p. (with na temperature dependence explicit629) proceeds through the loss of four elecly given) is compared to a conductivity for trons and not six. p-Aminophenol does not semiconductors which exponentially varies hydrolyze to benzoquinone (eqn. 5.146) unwith temperature. This again has little less midation occurs. The function of pyrididactic value. Finally statements such as dine was omitted in eqn. 5.155. The forma"The existence of two unbound electrons tion of the triazine from methylenemetbylon the surface of Ge, which are hungry to amine (p. 565) is a resultant of the chemiaccept two more electrons ." in the discal behavior of the latter and is not depencussion of surface states exhibit a lack of dent an electrochemistry. understanding of the quantum mechanics The last chapter on the anodic reactions involved. of earbaaylates is an excellent presentation Subsequent chapters, however, are quite on the Kolbe and related reactions, and bas informative and do not appear to have the tabulated results and experimental condidifficulties of the first. A discussion of gentions for selected preparations. eral principles of electrode reactions on Typographical errors are rare: P h on p. semiconductors is followed by a chapter of 214 should be Ph, amide on p. 376 should specific examples of the use of these princibe amine, and aster on p. 417 is when. The ples on elemental semiconductors, with the terminology used is wrong far a few examknown behavior of germanium and silicon ples; the cyclization of propylene chlorohybeing emphasized. Subsequently, there is a drin with alkali (p. 370) is not saponificachapter on electrode reactions on bulk tion; Et3NfH (p. 565) is not a quaternary compound semiconductors, with the known salt. behavior of GaAs, BaP, and ZnO emphaThis hook will be useful to the organic sized. Particularly welcome here is the secchemist interested in carrying out oxidatian on eleetrocatalysis on hulk compounds tions electrochemically since it offers a very and semiconductors. The next portion of comprehensive treatment of the area. The the book treats anodic oxidations of metals location of specific compounds may involve and semiconductors, with emphasis on kia lengthy perusal of the chapters involved netic descriptions of oxide growth, and a since the index deals only with general discussion of theories of ionic conduction classes. durine - anodic oxidation on metals. This Stanley Wawzonek whjrrr matter 1s npproprmtely fdluwed by me Un,i,m#y of Iowa a chapter on electrude reactnons on mrtalr lowe Ci3: low 52242 covered w ~ t hsurface f~lmn
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