Free-radical substitution reactions. Bimolecular homolytic substitutions

Free-radical substitution reactions. Bimolecular homolytic substitutions (SH2 reactions) at saturated multivalent atoms (Ingold, K. U.). A. R. Abramov...
0 downloads 0 Views 4MB Size
book reviews Editor: W. F. KIEFFER College of Woorter Wooslsr, Ohio

Replenish the Earth: A Primer in Human Ecology

G. Tyler Miller, Jr., Wadsworth Puhlishing Co., Inc., Belmont, California, 1972. 199 p. $2.95 (softback). As a biologist who teaches a course in human ecology, I have tended to become more than a little skeptical about the recent plethora of paperbacks written about the subject. Only rarely does one find one of these books that he would do more than glance through, t o say nothing of use as a text in his coqrse. "Replenish the Earth" is one of those rare exceptions. I t is a high quality text, and I intend to use it when my course is offered again. The hook opens with a n introduction to the population-consumption problem. After discussing the parameters of population growth, the author launches into a discussion of the First (you can't get something for nothing) and Second (if you think things are mixed up now-just wait) Laws of Thermodynamics. These laws provide the framework within whieh the remainder of the topics are covered. These include such diverse but interrelated themes as ecosystems and biogeochemical cycles, cybernetics, land use, world hunger, and resource depletion. The book concludes with an honest evaluation of what needs to be, and can be done individually and collectively to help in the solution of what Miller refers to as the "overpopullution" problem. While the non-major student may encounter some difficulty in understanding the relevance of the principles of thermodynamics at their first mention in the tent, he will became familiar with the Intent of the author by the end of his reading. The author has a way of presenting material in such a way that even fairly complex concepts become clear. The text is well supplemented by supportive figures, graphs, and tables. Each is carefully identified as to source and date for ease of confirmation. Particularly helpful, for example, are the figures taken from "World Dynamics" by J. W. Forrest-

-Reviewed

er whieh represent the projections for world population growth, resource depletion, and pollution if one assumes that one of these factors varies while the others remain fixed. A great help to the student, t w , is the selected bibliography which fallows the text. The student is given ample resource material to support each chapter of the book. By far the biggest compliment that can he paid the author is that he has accomplished the very difficult task of keeping his opinions separate from the facts. The single greatest problem one encounters in such books is that they are overemotional and it is often difficult to believe even the valid portions for fear they have been twisted by the well-meaning predisposition of the author. This book does not suffer from that difficulty. "Replenish the Earth" would be an excellent text to use in either a college level or an advanced secondary level course in human ecology. I recommend it with enthusiasm. James E. Perley Department of Biology The College of Wooster Woaster. Ohio

General Chemistry Gordon M. Barrow. Wadsworth Publishing Company, Inc. Belmont, California, 1972. 757 pp. Figs. and tables. 18.5 X 26 cm. $12.95. It is almost a truism that textbooks for non-science majors should emphasize material that is interesting and directly applicable to systems with whieh they are familiar. Science majors, on the other hand, are supposed to take their principles straight, although nowadays usually with chasers showing how they could be related to the students' everyday experience. Bar-

in this k s & ?

G. Tyler Miller, Jr., Replenish the Earth: A Primer in Human Ecology Gordon M. Barrou, General Chemistry James A. Hall andDonald A. Keyworth, Brief Chemistry of the Elements George S. Hammond, Janet Osteryoung, Thomas H. Crawford, and Harry B. Gray, Models in Chemical Science: An Introduction to General Chemistry Philip S. Chen, Handbook of Chemistry for High School Students K. U Ingold andB. P. Roberts, Free-Radical Substitution Reactions. Bimolecular Homolytie Substitutions (SH2Reactions) at Saturated Multivalent Atoms New Volumes in Continuing Series

. . .A413 . . A413 . . A414

. . A414 . . . A414

. . A415 . . . A415

row has attempted a combination, a textbook for science majors that develops chemical principles within a framework of systems that are familiar to, if not understood by, most students: the atmosphere, the solid earth, natural waters, energy resources, synthetics, and life processes. This is an important teat both when it succeeds and when it does not. Attempts at curriculum and syllabus revision have usually taken the form of restringing those pearls of wisdom we are convinced students must learn (rarely losing pearls in the process, hut often introducing newly cultured ones, mare advanced topics). Barrow discards essentially none of the pearls, but he has redesigned the string 'so there are loops and branches we have usually avoided. For example, carbon dating is discussed in Chapter 4 (interaction of radiation with the atmosphere) before kinetics is formally introduced in the context of the usual mechanistic arguments, Chapters 19 and 22. Barrow's approach is to introduce whatever concepts are necessary at the point where they become essential to explain the system of interest, but not to interrupt the flow of a discussion to elabarate them if this is to be done in a different context. There are a number of explicit statements like, "No argument will be offered here as to why these should be adopted, hut with these statements you are led to many other compounds that actually occur. Later you will see some of the reasons behind them." Assuming many instructors will wish to approach the text nan-linearly and put topics together in mare familiar ways, Barrow provides in the Preface and Appendices suggestions for alternative ordering of material on stoichiometry, atomic and molecular strueture, kinetics, and thermodynamics. As aids to students there are flaw diagrams (not too helpful) and summaries before each chapter and "concepts to master and facts to know," "operations to be able to perform," and a good set of problems at the end. The "operations" are like performance objectives, but are too broad to be useful for self-study without assigned problems. Enrichment material appears in marginal nates; occasionally this supplementary matter is used later as though it was originally a part of the main text. The development of most topics fallows standard patterns a t the level of other current textbooks that do not depend upon a knowledge of calculus. The atomic and molecular structure material contains a good constrained-wave, particle-in-a-box introduction to wave mechanics and discussion of different electron-pair-band models that gives a taste of the vitality of the field without being confusing. After the usual introduction to equilibria neglecting activity effects, there is a fine section on sea water and, later, living tissues showing haw important activity coefficients can be. The traditional final chapter an nuclear chemistry (here divided among several earlier chapters as the ideas are needed) has been replaced by two chapters on biochemistry. This material is far less sketchy than most first level presentations because organic functional groups and polymers are introduced in a prevmus section on synthesis. The empha(Continued on page A414J Volume 50, Number 8. August 7973

/

A413

book reviews sis of these syntheses (both inorganic and organic) is on consumer products; systematic organic chemistry (but little inorganic), reaction kinetics, and properties of surfactant and eomplexing molecules are imbedded within this context, an example of the exploitation of previous interest to introduce chemical concepts. My criticisms are not focussed on this approach hut on specifics. The layout is confusing, with figures and art work not well-separated from the textual material and also sometimes misplaced. The author comes off most poorly when he tries to give the barest essentials, e.g., of MO theory, symmetry, and X-ray diffraction, because they are usually too bare. The sections on MO's, 7.8 and 11.7 particularly, seem gratuitous. The emphasis in much of the acid-base chemistry is on neutralization rather than equivalence; this can lead to misunderstanding of the properties of weak acid-base solutions. The staichiometry stresses too much equation balancing rather than matter conservation and the mole concept: this is surprising in view of the emphasis on material flow in technical processes. The writing is sometimes uneven and choppy, especially in sections like that an technology and consumer products, perhaps difficult to integrate with more conventional material. Unqualified value judgments are made which students may not be able to discern as sueh: for example, "The only foreseeable solution [to the energy crisis] is the use of nuclear energy." Simply neglecting other energy sources (solar, geothermal) is misleading and obscures a problem in need of solution, just exactly what Barrow does not wish to do. How does this new approach fare overall? I believe it is worth very serious consideration hy all instructors of relatively heterogeneous general chemistry courses. High level courses populated by strongly motivated science students are probably better sewed by the mathematically more sophisticated texts available. Barrow's approach and mathematical sophistication are not, however, mutually exclusive; I hope that the two will soon be wed so this alternative approach will he available for all levels of general chemistry. Barrow helps students see why we find chemistry such a fascinating field and may provide reasons for joining us, if only for the duration of a course, as partners in the search for better understanding of the world around us. Jerry A. Bell Simmons Coiiege BOS~OO. MBSSaChu~etts

Brief Chemistry of the Elements

James L. Hall, Benjamin Writing Center, and Donald A. Keyworth, Tenneco Chemical, Inc. W.A. Benjamin, Inc., Menlo Park, 1971. x 246 pp. Figs. and tables. 23.5 X 16 em. $3.95, paper.

+

Great hooks create a market, good books satisfy a market, and poor books are a A41 4

/

Journal ot Chemical Education

drug on the market. "A Brief Chemistry of the Elements" falls with a resounding thud into the third category. The authors' putative purpose is set out in the first paragraph of their preface: "This is a brief account of descriptive inorganic chemistry with qualitative analysis. We wrote the h w k to supplement general chemistry texts, particularly 'Models in Chemicol Science' by Hammond. O s t e ~ o u n e . Crawford. . . and Grav. .. and ' ~ h e m i c k~;ineiples' by Dickerson, Gray, and Haight." The two in-house books specifically referred to are of very different characters: the latter a fairly rigorous presentation for majors, the former a much more gentle, though by no means trivial, introduction. Neither has chapter-by-chapter coverage of descriptive chemistry and the present bwk is intended ta supply these deficiencies. Even for this limited purpose it does not serve. The trestment, though extensive, is pedestrian, poorly organized, inconsistent, strangely old-fashioned (or at least not in key with the two books it is trying to complement) and, at times, quite simply wrong. Let me briefly itemize: Item, page 9. "Electrons simply do their natural thing" (Certain things electrons are claimed to do should not he allowed even in private between consenting atoms). Item, page 31. ". .. the molar heat of vaporization of water (539.55 kcal mol-1) . . ." (When citing data to five significant figures take care not to confuse kilocalories with calories and moles with grams.) Item, page 52. "Some of the metals, however, are quite unreactive because of their relatively low electrode potentials." (Ah, so that's the reason!) Item, page 111. "But in most mercury(1) compounds, the element has a formal oxidation state of +2 because the mercury(1) ion usually exists as the dimer ." (As someone in Alice (alas, not the Mad Hatter) said "what's one and one and one and one . . .?) Item, page 137. "The N=N bond energy is 170 keal mole-'; the carbon-carbon single hond energy is 58.6 keal male-', and the carbon-carbon triple hond energy is 123 kcal molrl." (Help!) Item, page 157. "Water solutions of hydrogen peroxide are used as a bleach because oxygen is liberated . . (Surely that should he "nascent oxygen".) A final word must he reserved for the references. These are fewer than ten in number: two are to the 1931 edition of Treadwell and Hall's "Analytical Chemistry" which could possibly be exhumed from most libraries, one each to Mikroehimica Acta (1954) and to Philosophical Transactions, London (1884) which would be somewhat harder to find and two more to different editions of "Spot Tests" by Feigl and Vesper (sic) which would he impossible to locate under its stated co-authorship. One can of course protest too much about poor hooks but unfortunately sueh bwks tend to drive out good ones since they have a habit of ending up on library shelves. Libraries are presently searching for ways to economize: not buying this b w k would he a small beginning.

..

."

Derek A. Davenport P w d w University Lafayette, Indiana 47907

Models in Chemical Science: An lntroductlonto General Chemistry

George S. Hammond, California Institute of Technology, Janet Osterydung, Colorado State University, Thomas H. Crawford, University of Louisville, and Harry B. Gray, California Institute of Technology. W. A. Benjamin, Ine., Menlo Park, Calif., 1971. xiii 422 pp. Figs. and tables. 25 x 19em. $10.95

+

With the publication of "Models in Chemical Science: an Introduction to General Chemistry" by Hammond, Osteryoung, Crawford, and Gray, we are vouchsafed a further glimpse of the coming apocalypse in chemical education as envisioned bv the kminenees erises of Pasadena. Unhke its immediate predecessor, "Chemical Dynamics" by Dence, Gray, and Hammond, this book is relatively unexceptionable but, in contrast to the earlier "Basic Principles of Chemistry" by Gray and Haight and "Elements of Chemical Bonding" by Gray, it is in no way erceptional either. The title and the preface both suggest an emphasis on "the role of models in stimulating interplay between theory and experiment" and to a certain degree this object is achieved though not as well as in Pimentel a n d Spratley and by no means at their exalted level of sophistication. The interplay is not so much between theory and described experiment, however, as between theory and dogmatic, or a t least merely stated, fact. There is no descriptive chemistry to speak of and the one chapter which suggests it (Structures and Reactions of Compounds of Carbon and Silicon) leans toward the mechanistic. What are the virtues of the book? It is a sound, compact, and engaging introduction to modem chemical principles. As such it would serve as an admirable refresher for those whose chemistry was taken some years ago, as a suitable corrective for that diminishing breed whose high school chemistry is overly factual and, in conjunction with a suitable supplement in descriptive chemistry (but see following review), as an attractive alternate to the more traditional middle-level texts presently available. The style teeters on the edge of trendiness (The Relevance of Molecular Structure, How Little Can We See on a Clear Day?, Eileen and George hatting tennis balls at each other instead of shovelling coal) hut far more than most the authors' have the flair and lucidity to bring it off. This trendiness extends to the make-up and to the illustrations. Most of the time this leads to an unusually attractive hook but a few diagrams (e.g., 5-1, 5-2, 5-5, 6 1 , 6 3 , page 155, 8-2, 8-14, 9-2) should either be redram (or reeonsidered) in future editions. Derek A. Davenport Purdue University Latayette, Indiana 47907

Handbook of Chemistry for High School Students

Philip S. Chen, Atlantic Union College. Chemical Elements Publishing Co., Camarillo, Calif., 1972. viii 233 pp. Figs. and tables. 23 x 15.5 cm. $5.95.

+

High school chemistry students who have received quality instruction are aware that the school's adopted text is not the sole source of chemical information. They have been taught to use a wide range of reference materials. Among these appear various handbook publications which are tome-like, expansively comprehensive, prohibitively expensive to the student, and often figuratively anchored to the teacher's desk. The "Handbook of Chemistry for High School Students" attempts to remedy the situation. Sturdily bound between 6 x 9 hard, red covers, the Handbook contains 233 off-white pages of assorted tables and information. These, with an index, divide into five sections listed as fallows: Section I. Mathematical Tables and Formulas, includes some instruction on the use of logarithms and log tables, conversion factors, defining formulas, quadratic formula, fundamental physical constants, and some other items of lesser importance; Section 11. The Chemical Elements, contains 28 items or tables. The more important among these are atomic radii, gram-atomie volumes, first ionization potentials, electronegativities, bond energies, activity series, and ionic radii; Section III. Inorganic Compounds, includes 15 items. The items of importance are physical constants for approximately 125 compounds, oxidation potentials, oxidation numbers of elements, common ions and their charges, solubility product constants for 87 compounds, 36 ionization constants for weak acids and bases, and a vapor pressure table for water; Section IV. Organic Compounds, displays four main headings. One of these, however, has 25 sub-headings dealing with important physical constants for a like number of classes of organic compounds. A tahle of 21 acid-base indicators appears among the four principal items; and Section V. Chemical Pastime and Miscellaneoos, encompasses 12 items. Mast of these qualify as fun or pastime items which possess some substance for learning. Two important items deal with (1) Latin and Greek roots in chemical terminology, and (2) s glossary of 265 chemical terms. Finally, this Handbook could and would be helpful to high school students especially to serious students who desire to prepare well. As to how many copies should be made available, or whether or not students should buy their own remains a problem of local concern. Charles W nenorcrron Soader neqhrs n,gn Scooo O e . e a o d Ohm d n 7 2 4

Free-Radical Substitution Reactions. Bimolecular Homolqtic Substitutions (SH2 Reactions) at Saturated Multivalent Atoms K. U.Ingold, National Research Council of Canada, and B. P. Roberts, University College London. Wiley-Interscience, New York, 1971. viii + 245 pp. Figs. and tables. 23.8 X 16.2 cm. $11.95. This is a stimulating monograph on a very rapidly developing field of chemistry,

namely that of bimolecular free-radical substitutions a t saturated multivalent atoms in which radical attack on an atom not part of a multiply-bonded system of the molecule brings about replacement of a second radical originally bound to the atom. Excluded from the present treatment are bimolecular homolytic suhstitutions at univalent atoms (atom abstraction reactions), S-1 reactions (involving rate-determining homolysis of AB followed by radical combination), homolytic aromatic substitutions and attack a t other unsaturated centers, and hot atom substitutions. In the light of this, then, the title of the hook is misleading and one has to go to the subtitle to find out what it is exactly that the book treats. The book is divided into chapters that correspond to the groups in the Periodic Table. Thus, S,2 reactions at IA, II, IIIA, N A , VA, W A , Transition, and Group 0 elements are presented in that order. The authors state that this arrangement obviates the need of a subject index, which is indeed the case if one is already familiar with the book or is interested in reading all about the reactions at a given group of elements. On the other hand, the student or research worker who is only interested in looking up a given reaction or eompound will find it much more difficult to do so without the suhject index. Perhaps the greatest value of this book, in addition to making available an excellent summary of the work carried out on this subject, is that it will no doubt stimulate a great deal of research in this area. The authors have collected a large number of interesting reactions for whieh no mechanism bas heen proposed, or for whieh a non-SH2 mechanism has been suggested and have reinterpreted them. These new suggested mechanisms will undoubtedly serve as springboards for further investigations of the transformations in question. The current interest in this field of endeavor is evident from the fact that the majority of the references quoted are of work carried out since 1960. Many 1970 references are also included. and the authors RIP LO he commended for hrmgmg us a readable, up to date and ehallenamg re view of the subject R. A. Abrarnovitch University of Alabama University. Alabama 35486

York, 1972. x + 460 pp. Figs. and tables. 23.5 X 15.5 cm. $21.50. Contributors: M. Hancock: M. N. Levy; M. Twutsui; 0. A. Reutov; 0. A. Ptitsyna; E. G. Perevalova; T. B. Nikitina. Publications of the National Bureau of Standards 1971 Catalog. A Compilation of Abstracts and Key Word and Author Indexes. National Bureau of Standards Special Publication 305 Supplement 3 Betty L. Oberholtzer. Superintendent of Documents, U. S. Government Printing Office, Washington, D. C. 20402, July, 1972. iii 338 pp. 26 X 20 cm. $3.

+

NMR. Basic Principles and Progress. Grundlagen und Fortschritte. Vol. 7 Edited by P. Diehl, E. Fluck, and R. Kosfeld. Springer-Verlag. New York, 1972. 153 pp. Figs. and tables. 25.5 i 17 cm. $24.80. ~ d v a n c e in s Inorganic Chemistry and Radiochemistry. Voi. 1 4 Edited by H. J. Emeleus and A. G. Sharpe, University Chemical Laboratory, Cambridge, England. Academic Press, New York, 1972. vii + 435 pp. Figs. and tables. 23.5 X 16cm. $19.50. Contributors: N. A. Bell; M. Bermann; 0. Glemser; W. Levason: C. A. MeAuliffe: R. Mews; P. L. Timms. Absorption Spectra in the Ultraviolet and Visible Region. Vol. XVI Edited by L. Lang. Callaharators: A. Barteehi, G. Horuath J. Szoke, and G. Varsanyi. Academic Press, Inc., New York, 1972. 399 pp. Figs. and tables. 25.5 X 20 cm. Organic Electronic Spectral Data. Vol. VIII, 1966 Edited by John P. Phillips, Henry Feuer, and B. S. Thyagarajan. Interscience Publishers, New York, 1972. xiii 782 pp. 23.5 X 15.5 cm. $34.95.

+

New Volumes in Continuing Series The following titles a m those of volumes in continuing series. Many of these series are familiar to readers who are best served by prompt announcement of the appearance of the new titles. The policy of T H I S JOURNAL will be to publish full reviews only of inaugural volumes i n new series.

Contributors: J. C. Craig; H. Feuer; L. D. Freedman; K. Genest; M. K. Hrenoff; P. M. Laughton; C. M. Martini; F. C. Nachod; J. P. Phillips; B. S. Thyagarajan; 0. H. Wheeler. Techniques of Electrochemistry. Vol. 1 Edited by Ernest Yeager, Case Western Reserve Univ., and Aluin J. Salkind, Rutgers Medical School. Wiley-lnter581 pp. science, New York, 1972. ix Figs. and tables. 23.5 X 15.5 em. $27.95.

+

Organometaliic Reactions. Vol. 4 Edited by Ernest I. Becker, Univ. of Mass., and Minoru Tsutsui, Texas A & M University. Wiley-Interscience, New

Contributors: Roger G. Bates; B. E. Conway; Jaroslav Kuta; Richard Payne; Alvin J. Salkind; Ernest Yeager. Volume 50. Number 8, August 1973

/

A415