book reviews Editor: W.
F. KIEFFER
College of Wooster Woater, Ohio
The book can be recommended t o undergraduate students to provide a proper perspective on those aspects of chemistry which transcend the solely scientific ones. I commend the editor and publisher for the swiftness with whieh this well-designed hook has been made available a t a reasonable price. James A. Goldman New Yorh City Community College Broohlyo, New York 11201
Science, Scientists and Society
William Beronek, Jr., editor, California Institute of Technology. Bagden & Quigley, Ine., Publishers, Tarrytown-onHudson, New York, 1972. vii + 199 pp. Figs. and tables. 22.5 X 15 cm. $2.95. This volume is the published record of the "Chemistry and Society" series of lectures whieh took place during the winter quarter of 1971 a t the California Institute of Technology. Accompanying some of the lectures are portions of the subsequent discussions where the audience had an opportunity to probe further the implications of the prepared remarks of the speakers, the majority of whom were Caltech faculty members. Basically, there are two different types of articles. One kind consists of sociological, philosophical comments. The other type resembles many Sigma Xi Lectures as they appear in the American Scientist. Moderately technical information about some aspects of science or technology is followed by a section pointing out general implications and consequences. Of this latter genre there are four articles dealing, respectively, with fa) air pollution and conservation, ( b ) energy-environment interaction, ( e ) trace metal contamination, and id) the development of a gasoline detergent. In eaeh case there is some historical narrative that amply demonstrates the impact upon society of scientific and technological research. The other type of article is more speculative and philosophical in nature. Far example, in "Homo Scientificus According to Beckett," Max Delbnick contends that for an individual the motivation for scientific research is obsessive, compulsive, willful "playing", i.e., experimenting, for its own sake, very much in the sense meant by Jacques Barzun when he used the title "Science: The Glorious Entertainment."
Delbnick admits that science is potentially harmful because the ultimate implications of such compulsive playing can never be completely anticipated. In another article, George Hammand, elaborating on Thomas Kuhn's seminal work, argues that scientists in general retain more tenaciously than do other scholars their fundamental principles of knowledge. While this may be debatable, more significant is the suggestion that to be effective in contemporary science, a person must possess the ability to be comfortable with ambiguity and a lack of definite answers. Lee DuBridge presents a brief history of the relation of science to politics as illustrated in the establishment of NSF, AEC, NIH, and NASA, and alludes to the well known increases in governmental funding of research until the 1967-68 period. Complementing DuBridge's lecture is the opening essay by David J. Kevles, a Caltech history professor, in which are recounted the changes that have occurred in the relationship between scientists and society, particularly with respect to moral dilemmas such as, for example, whether or not to work an a militarily related project. The focus on the future is more extensively discussed in the concluding panel discussion: "Future of Chemistry." George Hammond foresees more chemical research in government laboratories; more diversification in educational methods and an orientation perhaps less directed to the intellectual elite; and more realistic self appraisal. Norman Davidson considers chemistry to he a mature science in that no great conceptual revolutions are foreseen. Far him the purpose of modern science is for it to be useful. Harry Drickamer further comments that he is critical of the current trend toward increasing so~histicatianabout relatively simple systems. Drickamer. as Davidson. areues for more diversity and individuality.
William Beronek, Jr., editor, Science, Scientists and Society
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Treuor H. Leuere, Affinity and Matter: Elements of Chemical Philosophy 1800-1865
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Gregogv C. Demitros, Charles R. Russ, JamesF. Salmon, James H. Weber, and Gerald S. Weiss, Inorganic Chemistry
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JohnR. Dyer, Organic Spectral Problems G. N Sehrourer, editor, Transition Metals in Homogeneous Catalysis New Volumes in Continuing Series
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~tiin'tyand Matier: Elements of Chemical Philosophy 1800-1865
Trevor H. Leoere. Clarendan Press, Oxford, 1971. xvii + 230 pp. Figs. 24.2 X 16 cm. $14.50. John Dalton entitled his major work "A New System of Chemical Philosophy" and Levere's bwk traces chemical philosophy as it pertains to chemistry's central problem, namely that of affinity from Dalton's time to the dawn of "modern" chemistry or a t least of classical physical chemistry. It is not a n easy book to read hut that is partly because it abundantly demonstrates that chemistry deals with profound questions not easily answered. Newton had established the existence of universal gravitational attraction. But how does that help us understand selective affinity and limited affinity, those properties of matter that make the universe interesting? Why does oxygen react explosively with hydrogen and only slowly with iron and with eaeh only up to a point? Was Berzelius' electrical dualism enough or was it even helpful? Was geometrical pattern, as Mitscherlich and Laurent were implying, more important perhaps than electrical character? Does a numerical valence give us any hint as to the nature of valence? If Dalton's atoms are merely round bodies differing only in mass, how then account for compound formation a t all? This book is a very scholarly tracing of the history of ideas of affinity which served as a central concept within chemistry and as a unifying concept between chemistry and physics. And affinity ideas constantly demanded greater clarity as to the nature of matter, whether it was in fact composed of mass particles or whether atoms were simply centers of forces. The book centers an the major figures in the developing arguments, Newton's legacy, the contributions of such men as Davy, Faraday, Amphre. Oersted, Berzelius and the ideas stemming from organic chemistry through Dumas, Laurent and Gerhardt. The last chapter deals with ideas of matter and affinity as revealed in chemical mechanics and dynamics, Berthollet, Hess, Joule and Berthelot being the major protagonists. Perhaps all this is philosophy of science and not an integral part of chemistry, but a t least we should know enough of it not to claim that what we normally present as the nineteenth century hackground t o modern chemistry was childishly simple. Perhaps the reason our students don't "catch on" as quickly to what we teach (Continued on page A2441 Volume 50, Number 4, April 1973
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book reviews them as we would like, is because they ask the kinds of questions this book grapples with. They are questions to which we still don't have easy answers. Otto Theodor Benfey Earlham College Richmond, iodiana 47374
Inorganic Chemistry
Gregory C. Demitras, La S a l k College, Charles R. Russ, University of Maine, James F. Salmon, Loyala College, James H. We-ber, University of New Hampshire, and Gerold S. Weiss, Millersville State College. Prentice-Hall, Inc., New .Jersey, 1972. x + 556 pp. Figs. and tables. 16.5 X 24.0 cm. $15.95. Many instructors, including this reviewer, have long felt the need for a text written specifically for the so-called advanced inorganic chemistry course a t the undergraduate level. T h e hook by Demitras, et al.. is designed to fulfill this need, and on casual inspection it appears to be quite appealing. The text is divided into three parts: T h e Atom, Bonded Atoms, and The Behavior of Atoms and Molecules. The first two parts include the customary discussions of structure and bonding, and
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also present chapters on the inorganic solid state and bonding in metals. The third part is divided into two sections. The first section contains chapters on aeidbase systems, non-aqueous solvents, coordination chemistry, electrode potentials, reaction mechanisms, and the isaelectranic principle. The second section presents a n6vel approach to descriptive chemistry. Rather than the more traditional group organization, this material is covered in four chapters discussing the chemistry of the hydrides, oxygen and the oxides, the halogens, and organometallic chemistry. The choice of topics and the length of the hook are appropriate for a one semester course. Each chapter is supplemented with many study questions, some of which are quite challenging. Unfortunately, a closer inspection of this book reveals serious deficiencies. All of the problems that multiple authorship can create are found in Demitras, et al. Different styles and aproaehes fail to blend into a smoothly flowing text that develops eoncepts in logical progression. In spite of crass references, each chapter seems to stand alone and sometimes does not appear in its most appropriate position. Far example, atomic parameters in covalent bonds are discussed in Chapter 2, although bonding parameters and the nature of the covalent bond are not discussed until Chapters 3 and 4. Some topics, such as symmetry natation, are presented and not effectively used in later chapters. Other topics, such as bonding in hexacoordinated complexes, are covered somewhat
.reduidintly in separate chapters. T h e level of treatment is inconsistent throughout, varying from sketchy reviews to appropriately advanced surveys; e.g., Chapters 1 and 6, respectively. Consequently, the student has not always been adequately prepared for a true understanding of later material. These editorial problems might be talerable if the individual chapters were lucid and well organized. However, in too many places the discussions are disjointed and confusing. The chapter on banding in metals is particularly weak in this respect. At many points concepts are not carefully presented, and this imprecision leads to misconceptions. For example, E" is confused with E,,H in the discussion of electrode potentials and free energy (p. 333 f f and thus the expression, IG' = -nFE", seems to imply that all half-reactions with positive potentials proceed spontaneously. Later in the same discussion, inconsistent conventions are used for free energy of hydration. Similar examples can be cited throughout the book. Some chapters over-emphasize systems for elassifying properties, at the expense of a real understanding of the chemistry involved. Other chapters treat the material so superficially that the student is unlikely to gain much insight. The book is further weakened by many misprints and minor factual errors. The figures and tables are often unclear, incorrect, or absent when needed. In conclusion, the weaknesses of this book are serious and numerous enough to raise doubts
about its desirability as a text for undergraduate advanced inorganic chemistry, in spite of any attractive features it may have. Roben L. Carter University of Massachossm Boston, 02116
Organic Spectral Problems
John R. Dyer, Georgia Institute of Technology. Prentice-Hall, Inc., Englewood Cliffs, New Jersey, 1972. x + 207 pp. Figs. and tables. 19.3 x 23.5cm. $5.95. Tbis book consists of 95 problems for which spectral data only are given. Full infrared and proton magnetic resonance spectra are displayed whilethe ultraviolet data are given in the form Am..'"""'"' nm. The mass spectra, as recorded by a flatbed recorder, are given in addition to a table of m / e and relative intensity data. The problems are divided into three sections: 45 problems which can be solved by an undergraduate with the background normally gained in an introductory course; 50 problems in two sections of 25 whicb require the understanding gained from a course with an emphasis on spectral identification. Throughout the sections the pmblems increase in difficulty. The author bas written a brief but instructive introduction to the solving of a structural problem using spectral data and illustrates general approaches by providing detailed answers to the first four problems in sections one and two. To find the answers to the problems the student must consult a key in the rear of the book which directs him to standard reference books, handbooks and chemical catalogs, or, for same problems, to a literature citation. The primary aim of the book is to provide a number of spectral problems which an undergraduate or beginning graduate student can work on his own. The student must, however, rely on other books for standard reference tables of spectral data. Tbis book joins other books on thd market which have nearly the same format. Tbis one can be commended for its very clear reproduction of spectra and its keyed answers, a feature whicb the student engaged in self-study will appreciate. LeRoy W . Haynes The College of Wooster Woosfer. Ohio
Transition Metals in Homogeneous Catalysis
Edited by G. N. Sehmuzer, University of California, San Diego. Marcel Dekker, Inc., New York, 1971. ix + 415 pp. Figs. and tables. 23.5 X 16 em. $32.50. This book of about 400 pages consists of seven chapters written by experts in each respective area. Seven of the nine authors are members of industrial laboratories (Continued on page A246J Volume 50, Number 4, April 1973
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book reviews from which outstanding contributions have originated. All aspects of homogenwus catalysis could not be covered hut those selected for review are the most important and best understood. In Chapter 1, Professor Schrauzer has redefined the nature of catalytic phenomena in new terms of (1) quantum mechanical selection rules of spin and angular momentum, (2) the proximity effect and (3) the introduction of efficient alternate reaction paths due t o interaction with the substrate. Chapter 2 by J. Kwiatek discusses hydrogenation and dehydrogenaiion. After a discussion of the similarities of the elements of the hydrogenation cycle of hydrogen activation, substrate activation, hydride transfer and product formation the author describes for group VIII elements the various ways in which the catalytic cycle can be completed and the correlations which can be shown to exist between selectivity and catalyst structure. In Chapter 3, Dr. W. Keim first elaborates o n the uses of soluble r ally1 complexes in various oligomerization and eooligomerization reactions for alkenes, alkynes and dienes to give novel cyclic and open chain compounds. He next describes their telomerization reactions in the presence of nucleaphiles such as alcohols, acids, and amines. After a discussion of their reaction mechanisms the chapter ends with a discussion of the catalysis of hydrogenation, isomerization and polymerization by ally1 complexes.
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Eric W. Stern has written the fourth chapter on Oxidation. He emphasizes the mechanistic aspects of homolytic and heterolytic processes and is concerned with both the organic and inorganic moiety in the reaction. The fifth chapter authored by D. T. Thompson and R. Whyman discusses carhonyl&an and hydrogormylation reactions. This p o s t versatile activation of a functional group by transition metals is reviewed both for catalytic metal carhonyls and for the recently developed stoichiometric reaction involving carbonylation of organoboran derivatives, a very efficent, low temperature, low pressure reaction. In the sixth chapter, F. D. Mango and J. H. Schactschneider discuss Catalysis of Symmetry Forbidden Reactions and show the critical role orbital symmetry plays in bond transformations. They apply the concept of orbital symmetry to both the organic transformations as well as the rearrangements of ligands coordinated to transition metals. The authors are primarily concerned with reactions which would he symmetry forbidden were it not far the presence af metals. The chapter includes a MO treatment of the [1,3] sigmatropic transformation with two appendices of iterative extended Hiickel calculations, as an aid in applying orbital symmetry rules to transition metal catalysis as demonstrated in six model compounds involving a propylene-iron complex. The last chapter on Electron Transfer Catalysis by R. G. Link considers only a few selected processes which illustrate in aqueous solution particular catalytic
mechanisms in detail. All the chapters present excellent but not necessarily comprehensive reviews of their areas. They are written clearly and concisely and presented in an up-to-date, sophisticated fashion. This book is a much needed, most valuable addition t o the bookshelf of the research scientist interested in homogeneous catalysis. It is unfortunate that its price ($32.50) is so high. Hans B. JOnaSSen Tolane University New Orleans. La. 70118
New Volumes in Continuing Series The following titles are those of volumes zn continuing series. Many of these series are familiar to readers who are bed serued by pmrnpt announcement a j the appearance of the new titles. The policy of THIS JOURNAL will be to publish full reuiews onlg of inaugural oolumes in new series
Methods in Carbohydrate Chemistry. Volume VI: General Carbohydrate Methods
Edited by Roy L Whistler, Purdue University, and James N. BeMiller, Southem Illinois University. Academic Press, New Yark, 1972. xxvii 603 pp. Figs. and tables. 23.5 x 15.5 cm. $27.50.
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