BOOK REVIEWS - Analytical Chemistry (ACS Publications)

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of Characterization Organometallic Compounds, Part 1. Minoru Tsutsui, vii + 371 pages. John Editor, Wiley & Sons, Inc., 605 Third Ave., New York, N. Y. 10016. 1969. $15

Reviewed by H. D. Kaesz, Department of Chemistry, University of California, Los Angeles, Calif. 90024

The above-mentioned volume, the first of two planned on the title subject, is an attempt to bring to graduate students and professional chemists a knowledge of the techniques and procedures used in the analysis and identification of organometallic compounds. It is a collection of contributed articles based on lectures presented at an Analytical Symposium on Organometallics (New York Academy of Sciences, November 1966). The literature coverage extends for the most part through 1966 and early 1967 and in this respect the volume was out of date at its appearance in March in 1969. In a few isolated cases, authors have managed to add citations for 1968, but these were invariably for their own publications, inserted no doubt at the last minute. One article carries citations further into 1967 than the others and may have been the last submitted. The gap in time between the first and last submitted articles is often a drawback in contributed volumes. However, delay in publication in this case may also in part be due to the publisher since more than one year has elapsed between the most recent citations and the appearance of the volume in print. The collection is headed by a survey by F. Cartledge and H. Gilman on methods of formation of carbon-metal bonds, intended as an introduction to the field of organometallic chemistry for the nonspecialist. While the approach is an interesting one, I am not convinced it is entirely suitable in a volume such as the present one. In the authors’ own words (preceding the literature citations) “It is obvious that an area as broad as that of organometallic chemistry cannot be adequately introduced in a rather brief chapter.” The second article deals with methods of elemental analysis of organometallic compounds written by the well-known team of analysts, Drs. O. and F. Schwarzkopf. This chapter is quite interesting as it summarizes information that is probably unfamiliar to most ........

We have come to rely so heavily on commercial analytical services that we have lost touch with the actual methods. This chapter serves to correct that situation, and will be especially valuable to chemists who encounter new combinations of elements in their compounds and must take into account whether adequate methods are available to analyze them. The remaining chapters deal with instrumental methods as they apply to the study of organometallic compounds. Infrared spectrometry is covered by K. Nakamoto, using an empirical approach (in the style of Bellamy). The article contains the band assignments and characteristic frequencies which have been reported in the literature since 1960. While this chapter could be of use to a specialist, the lack of a general discussion of principles especially of the limitations of the method, could prove to be a handicap to a nonspecialist for whom the volume is also intended. A chapter on the mass spectrometry of organometallic compounds is contributed by R. W. Kiser. It is well balanced between principles and applications. The same could be said for the chapter on X-ray diffraction by R. Baenziger; however, considering the greater complexity of the latter method, the attempt to present both principles and applications in one chapter can only by considered heroic. Still in 10 pages, the author has given a rather good precis of the principles of X-ray diffraction with graphic representation of terms such as the structure factor, and it was enjoyable to read. A knowledge of vector algebra and fouricr transforms would greatly assist a reader in trying to master this section. Two remaining chapters cover the principles and applications to the study of organometallic compounds of microwave spectrometry (by R. Varma) and Mossbauer spectrometry (by R. H. Herber). These are both valuable contributions to the literature in this field. I believe this book will be of greater use to organometallic chemists than to analytical chemists. The former will be interested in the summaries of data that are contained in the chapters, although there is some duplication of effort. For instance, in a current series of advances in organometallic chemistry there already exist review articles on mass spectra and structural studies of On the organometallic compounds. other hand, the analytical chemist inchemists.

terested in instrumental methods in general will not be satisfied with a discussion of applications restricted to one field alone. Thus, this book tries to do too many things for too many people and, like many works in today’s literature explosion, offers some new items in the midst of some duplication. While this volume could be a useful addition to an institutional library, it is simply not the kind of book I would recommend as a permanent addition to most

personal libraries. Programs for Chemistry. Vols. 1 and 2. DeLos F. DeTar, Editor. xix + 208 pages and xix + 260 pages. W. A. Benjamin, Inc., General Service Operations Center, 250 Hudson St., New York, N. Y. 10013. 1968-69. $14.75 each

Computer

Reviewed by E. Clementi, IBM Research Laboratory, San Jose, Calif. 95114

The two volumes edited by Professor DeLos F. DeTar (Department of Chemistry, Florida State University, Tallahassee, Fla.) represent an attempt to answer the need for documentation and distribution of “Computer Programs for Chemistry.” The two volumes available from W. A. Benjamin, Inc., New York, each at the price of $14.75 (in the cloth bound edition) are very neatly printed and edited. Perhaps this is the most positive accomplishment of this attempt for programming distribution (aside from the good intentions of the Editor and its Board). Unfortunately, the number of shortcomings in the attempt to solve the program distribution problem is rather impressive.

Nearly 200 pages of the 468 pages for the two volumes are devoted to listing of the programs. The remaining is distributed between flow charts, discussion on the use of programs, discussion on how to transfer a program from computer of one manufacturer to a different, one, and corrections to the program listing in Volume 1 (available in Volume 2). The first volume is clearly addressed to nmr practitioners rather than experts. Indeed, by now, any expert can obtain (independently from the knowledge of the existence of this volume) the routines described in Volume 1. However, the practitioner will find the theoretical exposition most insufficient and the amount of programming documentation exceedingly long.

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The second volume is devoted to computer programs for reaction mechanism “of virtually any complexity.” (Well, this is a rather bold statement in view of the fact that the best chemist would agree that we do not understand at present even the reaction mechanism of extreme simplicity.) One of the programs deals with two reactants and two products. The second is capable of tackling problems involving up to 150 compounds. The main criticism is that the Editor fails to cope with the fact that computer programs are necessarily dynamic in nature. The writer of the program continues to change the program; the computer industry makes a computer obsolete within five years or so. In addition, no large program can guarantee to be fully and totally absent of programming errors. Thus, the two volumes document in full detail programs for IBM 7094, whereas for the past few years nearly every user has gone to IBM System 360 (and the two are incompatible). The largest per cent of the programs are for the CDC 6400, therefore they are of no immediate use for the CDC 3600 or CDC 7600. In summary, whereas most wines improve with aging, most programs go The two volumes are the start sour. of a wine cellar stacked with nicely labeled bottles containing, by 1969 or 1970, sour wine. Still, Professor DeTar should be congratulated for his attempt and so the program contributors. It takes much effort to get such volumes neatly organized. Perhaps the avenue of Quantum Chemistry Program Exchange (University of Indiana, Bloomington, Ind.) or of Computer Physics Communications (Queen’s University of Belfast, England—North Holland Publishing Co., Amsterdam), or of the Journal of Computational Physics (Academic Press, New York) indicates more awareness of the dynamic aspect inherent in programming and in program

distribution.

Ion Exchange and Solvent Extraction of Metal Complexes. Y. Marcus and ix + 1037 pages. A. S. Kertes. John Wiley & Sons, Inc., 605 Third Ave., New York, N. Y. 19916. 1969.

$44.95 Reviewed by Fletcher L. Moore, Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tenn. 37830. Operated by the Union Carbide Corp. for the U. S. Atomic Energy Commission.

This book is written for practicing chemists, both those who study metal complex formation in solution and those 132 A

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who apply ion exchange and solvent extraction techniques in analysis, radiochemistry, and preparative work. Graduate students also will profit from the fundamental discussion of solution chemistry and separation methods. The book is divided into three convenient sections. In the first part the authors discuss the theory of electrolyte solutions and the chemistry of metal complex formation, both in aqueous and organic solutions. After treatment of the basic principles of ionic equilibria, quantitative discussions of distribution equilibria in ion exchange and solvent extraction are presented in subsequent sections. The second section is devoted to a detailed discussion of ion exchangers and methods of calculation of stability of metal complexes from distribution data using ion exchangers. The important case of the distribution of metal ions between anion exchange resins and anhydrous or partially nonaqueous solvents is critically reviewed. The third section deals with the basic chemistry of solvent extraction. Excellent detailed treatments of extraction by compound formation, solvation, ion-pairing, and synergism are presented. Several applications of distribution methods to the study of metal complex formation are discussed in the final

chapter.

The descriptions of the

care-

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selected examples are sufficiently lucid to be valuable aids to chemists

involved in this area. The authors have authoritatively evaluated the tremendous volume of recent literature and have skillfully developed an integrated picture of the present state of each subject. Expert appraisals are offered throughout the book, and controversial points of view presented impartially. The subject matter is presented in The an organized and logical manner. format is excellent. A few' typographical errors were noted but they were not Numerous well-selected misleading. references are listed at the end of each chapter. The appendices contain a wealth of information, including a compilation of the activities of electrolytes on a molar concentration basis, physical properties of ion exchangers and solvents, and a valuable collection of distribution charts. The authors have accomplished their purpose “to provide a physico-chemical monograph in which the theoretical framework of the title subject is elaborated, general relationships are derived, and experimental material is presented in a systematic way.” They are to be commended for an exceptionally good contribution. In spite of the high

arc

ANALYTICAL CHEMISTRY, VOL. 42, NO. 2, FEBRUARY 1970

price, this book will become a welcome addition to the libraries of the many chemists interested in ion exchange and solvent extraction of metal complexes.

Reflexionsspektroskopie: Grundlagen, Methodik, Anwendungen. Gustav Kortüm. viii + 378 pages. SpringerVerlag, 1 Berlin 33, Heidelberger Platz 3, Germany. 1969. $21.50 (Reflectance Spectroscopy; Principles, Methods, Applications. Gustav Kortüm. James E. Lohr, translator, vi + 366 pages. Springer-Verlag New York Inc., 175 Fifth Ave., New York, N. Y. 10010, USA. 1969. $19.50) Reviewed by Harry G. Hecht, University of California, Los Alamos Scientific Laboratory, Los Alamos, N. M. 87544

Although the review copy of the above book sent was the German edition, an English edition has likewise been published. This is indeed fortunate. Much of the work in this field has been developed by German workers, and there are few places where the technique is discussed in depth in

English. Thus, Prof. Kortiim’s book will certainly be a welcome addition to the literature in the field of reflectance spectroscopy. Reflectance spectroscopy is not a new technique, but it has only been in recent years that the power of the method has begun to be recognized. The number of papers which report its use for such studies as adsorption, catalysis, molecular structure, ligand field theory, and photolysis has increased greatly. Prof. Kortiim’s book is intended to investigate theoretically and demonstrate by means of experimental results, the capabilities of diffuse and internal reflectance spectroscopic techniques. Following a brief and conventional treatment of reflection phenomena, such as the derivation of Fresnel reflection larvs, etc., a number of classic experiments are discussed which clearly show that both diffuse and regular reflection components must be considered in any real case. A treatment of multiple scattering leads into considerations of radiative transfer theory. The treatment is not theoretically oriented, but contains just enough of the mathematical development to make one appreciate the simpler approximate solutions, such as that of Kubelka and Munk on which the remainder of the book is largely based. An exhaustive discussion is given of the verification of the theory in various experimental situations, and chapters on techniques and applications are also included. The emphasis of the book is in the field of diffuse reflectance, with

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fewer than 30 pages devoted to attenuated total reflection. Prof. Kortüm has done more than any other single person to show the power of the reflectance method by his numerous researches of the past several years, and the book summarizes the “state of the art” very well. The work of others is given adequate treatment, and it must be said that the book as a whole fulfills its intended purpose admirably. One might have hoped that in translation most of the typographical errors would have been caught, so that the English edition of the book might be more like that expected for a second edition, but unfortunately, quite a number of errors remain in the English version. Furthermore, the translation in many places leaves something to be desired. For example, the sentence, “Since it is a question of half-quantitative consideration, the «-values can be excepted from great exactitude” (page 45 in the English) is all but meaningless until one consults the German to find that what was being said was, “Da es sich um eine halb-qiiantitative Betrachtung handelt, kann auf grosse Genauigkeit dor «-Werte verzichtet werden.” Some other particularly poor choices of words in translation which alter or color the intended meaning are “resolution” (page 119) when re-solving is intended, “derivations” (page 211) for derivatives, and “fugative” (page 332) components for those evolved during pyrolysis. I have admittedly picked out the most glaring examples, and do not wish to imply that the meaning is often vague. On the contrary, other than the occasional preservation of the Germantype sentence structure, which in English becomes rather awkward, the book is quite readable, and should prove to be a valuable reference book for those who must resort to reflectance spectroscopy to obtain optical data.

New Books Advances in Optical and Electron Microscopy, Vol. 3. R. Barer and V. E. Cosslett, Editors, xii + 286 pages. Fifth Ave., Academic Press, Inc., Ill New York, N. Y. 10003. 1969. 100/-

The present volume in this series continues along the same lines as the previous two volumes, presenting articles on both optical and electron microscopy. The two articles on optical microscopy reflect the growing interest in variable magnification and in quantitative measurement, respectively. The one on zoom systems in microscopy presents a comprehensive account of the design and operation of various types of zoom systems, many of them previously described only in the patent 134 A

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literature. Another chapter on mensuration methods in optical microscopy describes in similar detail some techniques of stereology, particle size measurement and related topics. In electron microscopy there is a timely review of the promising techniques for localization of the mineral content of tissues by microincineration. Another chapter describes the potentialities of the new procedures for carrying out small angle electron diffraction in the electron microscope, equally applicable to the study of magnetic domains and of long spacings in macromolecules. The final article discusses the adaptation of autoradiographic procedures to the special conditions of electron microscopy, emphasizing the precautions necessary if meaningful results are to be obtained. There is a cumulative index of authors, one of titles, and a subject index. Advanced Physical Chemistry: A Survey of Modern Theoretical Principles. S. M. Blinder, xvii + 554 pages. The Macmillan Co., 866 Third Ave., New York, N. Y. 10022. 1969.

$13.95 The author has based this book on in physical chemistry for honors undergraduates and advanced physical chemistry for first-year graduate students which he has taught at the University of Michigan. The emphasis is somewhat theoretical and mathematical. The intended purpose of the book has been to survey the more important theoretical principles of modern physical chemistry and, as such, emphasis has been relatively heavy on derivations, light on applications. A selection of problems and exercises is given at the end of the text. There are 23 chapters, six appendices, and a subject index. courses

The Photographic Action of Ionizing Radiations in Dosimetry and Medical, Industrial, Neutron, Auto- and Microradiography. R. H. Herz. xviii + 629 pages. John Wiley & Sons, Inc., 605 Third Ave., New York, N. Y. 10016. 1969. $22.50

The purpose of this book is to fill the need of those in several disciplines— e.g., science, medicine, biology, tech-

nology, and engineering—for detection and recording of images by photoTheir success depends graphic means. largely on the correct and efficient use of photographic techniques and this, in turn, depends on the understanding of the photographic action involved. The first chapter of the book deals briefly with some of the physical principles of ionizing radiations, with particular emphasis on absorption processes, because the photographic action naturally de-

ANALYTICAL CHEMISTRY, VOL. 42, NO. 2, FEBRUARY 1970

on the energy absorbed in the photographic layer. This is intended mainly as an introduction to the subionization ject. Other chapters are: measurements and units; the photographic process; the direct photographic response to X- and gammarays ; the photographic response to particles; photographic dosimetry, fundamentals of radiography; medical radiography; the processing of radiographs; industrial radiography; neutron radiography ; autoradiography; microradiography. A subject index and several appendices are included.

pends

Hackh's Chemical Dictionary, 4th rev. ed. Julius Grant, Editor, xi + 738 pages. McGraw-Hill Book Co., 330 West 42nd St., New York, N. Y. 10036. 1969. $29.50

This 4th edition has been updated and revised, reflecting the great advances in chemistry since the previous edition. It covers all important aspects of modern chemistry today and makes apparent the growing interconnection of chemistry with other sciences. There entries than the preare 23,000 more vious edition and the total number of words now defined has risen to 80,000. Definitions were reworded more precisely, relatively unimportant matter was deleted, and a more concise presentation was effected. The dictionary puts foremost accuracy, current usage, and conciseness. As closely as possible it adheres to current procedures and to international standards where they exist and are accepted—and to cus-

tomary usage. Biological and Biochemical Applications of Electron Spin Resonance. D. J. E. Ingram, x + 311 pages. Plenum Publishing Corp., 227 West 17th St., New York, N. Y. 10011. 1969. $20

The story of the biological and biochemical applications of ESR up to the present time is presented. Included are chapters on such subjects as radiation effects, enzyme interaction, the triplet state, and metallo-organic compounds. There is an introductory chapter on basic principles, and two chapters summarizing the techniques that are employed, including the spectrometers The last chapter sumthemselves. marizes some of the latest techniques and developments and attempts to make some predictions of the way in which future work may progress. There is emphasis here on the power of simultaneous studies with electron resonance and other techniques—such as X-ray crystallography or Mossbauer experiments. There are author and subject indices at the end of the book.

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Electrochemical Processes in Fuel Cells. Manfred W. Breiter. xi + 274 pages. Springer-Verlag, New York, Inc., 175 Fifth Ave., New York, N. Y. 10010. 1969. $12 In the last few decades, development of different types of fuel cells has stimulated research into basic processes occurring in these cells. Chapters I to III introduce the reader to the general field of fuel cells. The progress made in the understanding of the basic problems in the electrochemistry of fuel cells since the end of World War II is reviewed in In contrast, the Chapters IV to . technological aspects necessary for the development of practical units are not covered here. The open literature published as books or as papers in journals has been considered at least until the end of 1967. It is the purpose of this monograph to describe and discuss the progress made in the understanding of electrochemical processes. Ultra Micro Weight Determination in Controlled Environments. S. P. Wolsky and E. J. Zdanuk, Editors, ix 4 511 pages. John Wiley & Sons, Inc., 605 Third Ave., New York, N. Y. 10016. 1969. $19.95

The rising interest in ultramicromass determination inspired the preparation of this book. The microbalance field has developed dynamically in recent years, and the concept of microweighing has been widened markedly by the recognition of the potential of the quartz crystal oscillator. Because the microbalance has been applied so broadly, details of theory, design, and utilization are scattered throughout many publications. The prime objective of this volume, therefore, is to provide a single effective source of information on the theory, design, applications, and commercial availability of conventional and quartz oscillator microbalanccs. Max S. Matheson Pulse Radiolysis. x + 202 and Leon M. Dorfman. MIT Press, 50 Ames St., pages. 1969. Cambridge, Mass. 02142.

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$11.75 This book is the first volume in a new Research Monograph Series in Radiation Chemistry. As a general technique for the study of fast reactions, the pulse radiolysis method has extensive applicability in radiation chemistry. In another scientific area it is also a powerful tool inasmuch as it is applicable to the study of chemical kinetics and general studies of the nature of transient molecular species, particularly with regard to reactions in solution. The monograph is designed to integrate both aspects of pulse radiolysis.

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ANALYTICAL CHEMISTRY, VOL. 42, NO. 2, FEBRUARY 1970

The various reactions of short-lived intermediates studied here have, in the author’s words, “been presented in the context of their significance to radiation chemistry. Yet these studies involve the observation of a broad variety of transient intermediates, such as excited singlet and triplet molecules, free radicals, organic radical ions, solvated electrons, and metal ions of unstable valency, whose properties and reactivities should be of general interest. The critical compendium of reactions is, therefore, presented in a format which, it is hoped, will also be useful to kineticists who have little interest in the special field of radiation chemistry, but who share a common interest in the reactivity of particular intermediate species.” Advances in Chromatography, Vol. 8. J. Calvin Biddings and Roy A. Keller, Editors, xvi + 400 pages. Marcel Dekker, Inc., 95 Madison Ave., New York, N. Y. 10016. 1969. $18.75

The latest volume of this series presents critical and current surveys of the most important advances in the re-

of chromatography. spective areas Noted authors were asked to separate the hard-core advances from the overwhelming mass of supporting evidence and data. They have summarized and developed in single papers their own ideas and expressed opinions of various facets or trends in research, putting their subject matter in perspective. Controversy has been encouraged. The series is intended to promote information flow from countrj· to country as well as among the specialists in the different branches of chromatography. There are author and subject indices. Physiological Chemistry of Proteins and Nucleic Acids in Mammals. George xii + 221 pages. W. B. Kaldor. Saunders Co., West Washington Square, Pa. 19105. 1969. $9.00 This book is the second in a series of five monographs designed not only to introduce the student to the fundamentals of biochemistry but also to show the student how these biochemical principles apply to various areas of mammalian physiology and pathology. It is intended to acquaint the reader with some of the important physiological functions of proteins and nucleic acids. First presented is the chemical basis of their macromolecular structure. This is followed by a brief description of some of the important physiological functions of these macromolecules— e.g., antigen and antibody structure and interactions, coagulation of blood, and the mechanochemistry of muscular contraction. A subject index is included.