BOOK REVIEWS phatic hydrocarbons; oxygenated aromatic hydrocarhons; oxygenated polymethylene hydroearhons; heterocyrlic oxygen compounds; s ~ ~ g a r smixed ; oxyhalogenated hydrocarbons; nitrogenated aliphatic hydrorarhons; nitrogenated cyclic hydrocarbons; mixed oxygen-nitrogen derivatives of hydrocmhons; mixed h e b gen-nitrogen derivatives of hydrocarbons: sulfur derivatives of hydrocarhons; derivatives of hydrocarbons wit,h ot,her elements. The reviewer noted that sn incorrect reference in given on page 145 for the viscosity of n-butylcyclopent,ane. The reviewer recommends to Professor Timmermans that in a future volume he give consideration to the following points: (1) Have the publishers arrange to condense the presentation of the data so that only about half the number of pages will be required to present the same material; (2) Omit presentation of all data already presented in the tables of the American Petroleum Institute Research Project 44 and the tables of the Manufacturing Chemists Association Research Project, which are available in mast of the departments of chemistry in universities throughout the world; (3) Critically appraise the data and with appropriate weighting present selected vslue.9; (4) Where possible, give equations yielding values over the range of the independent variable. Because of the high cost, $28.50, of this volume, it is quite unlikely that individ~~alswill want to have s. copy. But each scientific library will probably wish to have a copy for reference by scientists interested in t,hese fields.
FREDERICK D. ROSSINI University of Notre Dame Notre Dame, Indiana
Fundamentals of Carbanion Chemistry
Donald J . Cram, University of California, Los Angeles. Academic Press, Inc., New York, 1965. Volume 4 of "Oreanir Chemistrv" series. viii 289bp. F l p . and'tahlm. 16 X 23.5 nn. $9.50.
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Most physical organic chemistry texts devote little at,tent,ion to "carbanions"including such relatives as enolate ions and organomet,allic compounds-in spite of the great. synthetic importance of sueh speries. Furthermore, despite extensive treatments of SN reactions a t saturated carbon, SE reactions in which carbanions are potential intermediates are frequently ignored in courses in advanced organic chemistry. This book is intended to help fill the gap. The first chapter is a. compilation of the kinetic and equilibrium acidities of varioun typw of C-H bonds, toget,her wi1.h a disc,wsion of the methods of obtaining such data; in Chapter 2 these results are interpreted in structural terms. Chapter 3 is a general discussion of the stereochemktry of electrophilic wbstitu-
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tions and carbanion processes, while Chapter 4 summarizes the detailed studies of Cram and his group on the stereochemical effects of varying the leaving group snd the medium. The fifth chapter deals with the chemistry of allylic anions, involved in base-catalyzed olefin is* merieations, and Chapter 6 concerns miscellaneous molecular rearrangements in which carhanions are putat,ive intermediates. Among the excellent features of this book are numerous tables, mostly original compilations of hitherto scattered data. Extensive references, and clear critical discussions of such complex stories as stereochemical retention during deuterium exchange, help the reader to obtain an appreciation of the state of modern research in this field. Furthermore, this is a very personal account in which Cram does not hesitate t o express his own opinions about the interpret,ation of some piece of data, even if this interpret,at,ion is a t variance with that of the original author. Unfortunately the original interpretation is sometimes not even presented, and this leads to a lack of balance when questions in active dispute are discussed. The strongest part of the hook is that in which Cram's own very important studies are summarised and interpreted. If there is a. flaw, it is that everything is "explained" even when the data are not sufficient, so that open questions tend to he covered up. The printing job is clean and readable, although some of the illustrations are difficult to decipher (e.g., p. 178 B). The unfortunate use of dotted lines instead of single resonance forms can lead students (and even authors, as the "phenanions" on pages 237 and 242 illustrate) into trouble. Except in the illustrations, there are remarkably few errors, either typographicd or factual. Curiously, however, "SE," and "SN," are used throughout instead of the universally accepted " S d " and " S N ~ " ; also, inverse isotope effects are cdled "negative" effects. I n summary, this is a n important contribution to the chemical literature. While it is perhaps too personal an account to make it a completely satisfactory textbook, it should stimulate research and serve as a useful reference for advanced students, teachers, and chemical investigatoa. RONALDBEESLOW Columbia Uniuersily New York, N m York
Chemical Energy
Laurence E. Strong and Wilrner J . Slmtton, both of Earlham College, Richmond, Indiana. Reinhold Puhlishing Corp., New York, 1965. Selected Topics in Modern Chemistry. x 115 pp. Figs. and tables. 12.5 X 18.5 em. $1.95.
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Thermodynamics has a. reputation far abstruseness which tends to incnlcate in a beginning student the conviction that he will never be able to understand it.
The omission of the word from the title of this hook may he helpful in this respect. More importantly, the development of the subject without the use of the calculus makes possible its comprehension by the average freshman student, who is not a n extinct species (see review by 43, Derek Davenport, J. CREM. EDUC., 56 [19661). Despite its title this little hook zs a book on thermodynamics, which the authors call "an elegantly logical subject" in their preface. The real concern of the hook is "the formulation of the energetics of chemical reaction system?." Some of the general features of energy are pointed out before the discussion is focused on its chemical aspects. This is done in the first chapter, which considers temperature-changing capacity, capacity to produce electricity, capacity to lift masses. caoacitv to oroduce lieht. the interconnection of changes, the concept of energy, and some units of energy. I n the second chapter the authors introduce sueh basic concepts as system, state, adiabatic and isothermal processes, the First Law, internal energy, and enthalpy. The development of chemical energy concepts is then interrupted for brief discussions of calorimetry and the molecular interpretation of internd energy. In the third chapter the authors return ta "the arithmetic of energy" and cansider such topics as thermachemical equations, Hess's Law, enthalpy of formation, and the variation of AH with temperature. The knowledge developed in the preceding chapters is applied in the fourth chapter to selected chemieal systems. Lattice enthalpies and the Born-Haber cycle are discussed, and likewise the calculation of covalent bond enthalpies by analogous energy cycles. The aut,hors show how hydration enthalpies can he calculsted from lattice and solution enthalpies, and how the energetics of electrode reactions can he interpreted in t e r m of differences in sublimation enthalpies or hydration enthdpies. The crux of thermadynamies is in the fifth chapter. It is decidedly more abstract than the preceding material, being concerned with "the direction of change." Order and disorder, reversible and irreversible processes, entropy, free energy, the Second Law, all are here. Some of the far-reaching implications of the concepts of entropy and free energy are then considered in the sixth chapter. Here are discussed the free energy of mixing in relation to concentration ratio, the relationship of standmd free energy chanee to the eauilihrium constant. the erni it equation; the Third ~ a w , and ' absolute entropies. I n the final chapter the free energy changes that govern the direction of spontaneous change are related to the structures of the reacting substances. I t is pointed out that there are processes for which, essentially, A H = 0 so that AG = -TAS; examples are the mixing of gases and the operation of electrochemical concentration cells. On the other hand, attention is given to equilibrium phase changes, sueh as melting, for which AG =
. . " .
- .
(Continued on pare A468)
BOOK R E V I E W S = TaS. Trouton's rule is ~resented, together with a discussion of the abnormally high entropy of vaporization of water. Chemical interpretations are also offered far the free energies of formation of water, ammonia, methane, the hydrogen halides, and aliphatic hydrocarbons; and for the increase in entropy that accompanies the formation of water molecules and certain insoluble compounds from their ions. Finally, there is an examination of the effect which variations in temperatme have on reaction feasibility in terms of the separate effects of the enthalpy and entropy terms. Teachers already know--or should know-the previously issued paperbacks on thermodynamics (Nash, reviewed in THIS JOURNAL 40, 51 [19631, and Mahan, 41, 56 [1964]). reviewed in THIS JOURNAL These books accomplish all that one could expect in a poekei4eed volume on thermodynamics for firsbyear students who are competent in the elementary operations of the calculus. I n writing "Chemical Energy," Strong and Stratton have demonstrated that it is possible to develop meaningful thermodynamic thinking with only a. knowledge of algebra.
0 so that AH
LAWRENCE P. EBLIN Ohio University Athens
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Laboratory Chemistry
Therald MoeUer, University of Illinois, Urbans, and Dean F. Marlin, University of South Florida, Tampa. D. C. Heath and Co., Boston, 1965. viii + 279 pp. Figs. and tahles. 21 x 28 em. $4.50. Few chemistry teachers w o d d disagree with the authors' t h ~ e s ,stated in the preface, that laboratory instruction is a significant part of the total instruction in chemistry, and that the introduction to the laboratory should come when the student begins his study of chemistry. The authors also feel that the experiments should he "primarily instructive, interesting, and challenging," a worthy aim whieh the present manual seems to fulfill reasonably well. Thifi laboratory manual is designed to accompany the textbook, "University Chemistry," by Bailar, Moeller, and Kleinherg, or any general chemistry text which covers the usual area,? of general chemistry. For those who are seeking a manual which departs redioelly from the traditional, or which encourages the student to devise his own methods and procedures, the search must turn elsewhere. "Laboratory Chemistry" offers a conservative set of experiments with principles and instructions outlined in considerable detail and, for the most part, with clarity. This reviewer recalls the laboratory manual of Professor B. Smith Hopkins whieh was widely used thirty years or so
ago. Many of the experiments of Hopkind book were uniquely effective in cl~allenging t h e freshman ntndcnts' interest. The present book is quite obviously a modified descendant of the older manual, far far more than a faint family resemblance is readily discerned in both the organization and the content of the experiments. A comparison of the present manual with another direct descendant of Hopkina' originsl book, i.e., "Laboratory and Classroom Exercises in General Chemistry" (sixth edition) by Hopkins, Moeller, and Tamres, shows that most of the experiment3 areessentially the same even to detail? oi wording. However, the material has been cansiderahly reorganieed and some new experiments have been added. The 110 short experimenbs in Hopkins, Moeller, and Tamres have been consolidated into 34. Each experiment k preceded by a brief statement of the principle involved, and appropriate thaught-provoking q u e s tions have been added. Tear-out report sheets, perforated for a ring binder, accompany each experiment. The 34 experiments are grouped under six headings (the number of experiments in each category k indicated): Basic Techniques and Concepts ( 9 ) ; The States of Matter (5); The Chemistry of Selected Nonmetals (7); Catalysis, Rate and Equilibrium (4); The Chemistry of Selected Metals (6); Preparative Inorganic Chemistry (3). (Continued o n page A468)
