Chemical Thermodynomicr: lems Approach
A Prob-
Norman 0.Smith, Fardham University, New York. Reinhold Publishing Car278 poration, New York, 1967. x pp. Figs. and tables. l5.S X 23.5 cm. $8.50.
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BOOK
REVIEWS
Introduction to Inorganic Reaction Mechanisms
J . C. Loekharl, University of Newcastlenpon-Tyne, England. D. Van Nost,rand Co., Inc., Prineet,on, New Jersey, 116 pp. $3.95. Paper1966. ix bound.
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Inorganic textbooks tend to neglect problems in reaction mechanisms a t the expense of discussions of synthesis, structure, and bonding. This book, devoted exclusively t,o inorganic mechanisms, is a. welcome supplement to the comprehen~ive textbooks. Some knowledge of thermodynamics and reaction kinetim is necessary to read this book, but upper division undergradnates should have no trouble with it,. As the title indicates, it is an introductory text and is not designed for the specialist in the field of inorganic reaction mechanisms. Superh s t d y problems a p pear a t the end of most chapters. These prnblems are worth the price of the book done. The basic pattern of discussion is to present a chemical reaction and t,hen to discuss all the known lines of evidence that, can be used to develop s. reasonable reaction mechanism. Reactions are divided into the following classes: disnociittionassociation, electron transfer, substitution, redistribution, elimination, chain, and pol,vmerization. Illust,rative examples of each class of reaction are discussed in con-
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siderable detail. The examples cover a wide variety of chemical systems including many nowtransition metalsystems. Original research papers are cited liberally throughout the book. I n the opinion of this reviewer, too much reliance is placed an t.he Ingold-Hughes classification systcm, but this is a subjective view. Occasionally, oversimplification has led to ambiguity as in an attempt to discuss substihttion mechitnisms while considering all reverse reactions to be negligibly slow. I n many respects this book is similar to "Inorganic Reaction Mechsnkms" by John 0. Edwards, (W. A. Benjamin, 1964). One would want both books in tho library, but would choose one or the other as a course textbook. Another book in the same field is "Ligand Substitution Processes" by C. H. Langford and H. B. Gray, (W. A. Benjamin, 1(966), but it is bath more narrow in scope and much more sophisticated. The author has succeeded in showing that the unraveling of rn~chanismproblems in inorganic ehemist,ry is an exciting and challenging business. Without being overwhelmed, the reader is brought to the frontier of chemical research. No higher tribi~tecan be paid to an undergraduate textbook. JAMES E. FIPHOLT Carleta College Northfield, Minnesota
in this Issue
Reviewed in this Issue J . C. Lockhart, Intradoctian to Inorganic Reaction Mechanisms Norman 0.Smith, Chemical Thermodynamics: A Problems Approach P . A . H . I'i'yalt, Energy and Entropy in Chemistry Eugene A . Dauidson, Carbohydrate Chemistry A . N . Nesmeyanov and R. A . Sokolik, Methods of Elementoorganic Chemistry. Volume 1, The 01,gnnic Compounds of Boron, Aluminum, Gallium, Indium and Thallium Kmneth A . Cmnors, A Textbook of Pharmaceutical Analysis H. Geoj%i.ey Bray and Kenneth While, Kinetics and Thermodynamics in Riochemistly lionrnd Kmuskopj, Introduction to Geochemistry Engelbert Broda and Thomas Sehonfeld, The Technical Applications of ITndioactivity. Volume 1 Frederick W . GCibbs, Joseph Priestley Revolutions of the Eighteenth Century E. H . E. Pietsch and the Gmelin Institute, editors, Gmelins Handhoeh der Anorganischen Chemie. 8. Auflage, System Nummer 48, Vanadium. Teil B, Lieferong 2, Verbindungen his Vandium and Wismut E. H . E. Pietsch and the Gmelin Institute, editors, Gmelins Handbuch der Anorganischen Chemio. 8. Auflage, System Nummer 14, Carbon. Teil n, Lieferung I, Das Element Isdope, Atom, Molekeln, Einstoffsystem, I h m p f , Diamxnt
This book of eleven chapters has been carefully compiled for use in presenting chemical thermodynamics a t the intermediate undergraduate level. There is, in each chapter, a sufficient discussion of fundamental thermodynamic theory to make the problems workilble. I n addition to the 108 problems (an average of approximately 10 per chapter) there are nnmerous worked examples throughout the text. One excellent feature of the answels to the problems (given in an appendix) is that full explanation of the method of approach to each problem is given. This is ertremely helpful in self-study, and is one feature which makes the book a very good one to accompany a standard physical chemistry text a t the ilndelgrndunt,e level. A spot check shows that both the thble of contents and index have been casef~dly assembled. Several mnttem of a conceptusl natwe might have been done differently. For example, the term "xork content" in reference to the Helmholtz free energyshould have been avoided. "Work function" is preferable and much less misleading. The definition of adiabatic pracess shoidd be in t e m i of rly = 0, not, q = 0, since the latter statement ii; ambiguo~ts. There is a section of Chapter 3 entitled Visual Comparison of Entropies, which might well have been st,rengthened by mention of the Sacknr-Tetrode eqnstion; also, this reviewer is not happy with the choice of the ward "visual" in this conk x t ; perhaps "qualitative" might have been a better word. The matter is minor, however. There are a few typographical errors, e.g., equations 4.24, 4.26, and 4% are i w correct. This s i t u ~ t i o nis almost inevitable in the first printing of a book of technical nature, and merely represents entropy which surely will be pumped o ~ r t in subsequent printings. I n summary, the book would be an esd e n t problem text to accompany any of the modern physical chemistry texts which tend to shy more and more away from the~madynamicsin favor of stntisticnl and quantum mechanics, kinetics, structure, and spectroscopy. Further, it n-onld serve very well as the principal text in an intermediate course-ne semester or one or two qusrters-in chemical thermodynamics. F R ~ R.K ~ I E E K S University of Cincinnati Cincinnati, Ohio 46881
Energy a n d Entropy in Chemistry
P . A . H . Wyatt, The University of Sheffield. St. Martin's Press, New York, 1967. ix 192 pp. Figs. and tableq. 14.5 X 22.5 cm. $6.
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The author says in his preface, "In this book I have tried to shorten the path to Volume 45, Number I , January 1968
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chemical thermodynamics for beginners by building upon ideas acquired a t school in elementary physics and chemistry." On the hook jacket the publisher states, "Subtleties of definition and queetions of rigour are avoided since the author believes them to be bewildering to t,he average student a t the beginning.. ." In this spirit the author begins his development with potential energy and its extension to the idea of chemical potentials. Free energy and its application to chemical equilibrium is introduced. After free energy is introduced enthslpy and internal energy (the author calls it tats1 energy) are discussed only to be rejected as inadequate to deal with the interpretation of reaction spontaneity and equilibrium. Considerable space ia devoted to describing relationships between thermodynrsmic properties and a statistical mechanics interpretation. The book concludes with n brief chapter on thermodynamics and kinetics. To shorten the path and avoidsubtleties, the author has resorted to a, good many dogmatic assertions. Healsomakes rather frequent use of the word this without much clarity as to what is intended. By and large little use is made of calculus to present the analysis of relationships. Relatively little data for substances or their reactions is presented. Only in the next to the last chapter is a table of data presented. and this table comorise~electrode potentials for jort r l g h r half-cell rrsctiow. Or.edntn tnhk m a ) . o m - t m w a n,conl for u presc,.tntion ref thcrmdy,.arnivi! I n developing a relation between free energy change and the equilibrium constant the aubhor leads himself to conclude that the equilibrium constant has units. When he applies his ideas (p. 26) to the ammonia synthesis reaction with a standard free energy change of -16,350 joule mole-' he feels obliged to say that @ J w i e . J ~ 6 X ~ Q a must .a have units of stm-'. How it is possible for an exponential to have units the author apparently leaves as one of the mysteriesor subtleties. T h e d i s cussion of calorimetry includes (p. 36) the statement t,hat temperature changes can be kept small by using smnll amounts of react,ing substances. However, the temperat,nre change far the mixing of, say, aqueous sodium hydroxide and aqueous hydrogen chloride is quite independent of the total amount used provided the calorimeter can he treated as havingzero heat capacity. The idea. of number of degrees of freedom is introduced (p. 80) as the minimum number of such quantities as U , H, G, V, S, P, and T required to fix the state of a system completely. However, this definition of degrees of freedom runs into trouble when applied to phase equilibrium in Chapter 8. Thus a, two phaseone component system is said to be univariant and the author states (p. 124) that addition of heat increases temperature and pressure together. Actually the addition of heat shifts the enthalpy of the system and the relative amounts of the two ohases in equilibrium, but does not alter temperature or prevsure so long as phme equilibrium is maintained. Each chapter of the book concludes with from two to seven problems. Answers to,
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lournol o f Chemical Education
and discussion of, the problem8 form an appendix to the book. L.~URENCE E. STKONG Earham College Richmond, Indiana
Carbohydrate Chemistry
Eugme A. Davidson, Duke University. Holt, Rinehart and Winston, Inc., New York, 1967. vi 441 pp. Figs. and tables. 16 X 25 cm. $11.95.
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This book is offered as a remedy for "the failure of books on carbohydrate chemistry to apply modern organic chemical developments to discussions of reactions," and to counteract the "neglect" by most organic texts of modern carbohydrate chemistry. Broadly divided into sections entitled Structural Analysis and Reactions, the first seclion includes chapters on general stereochemistry and conformation, and on structure, stereoohemistry, and conformation of sugrtrs, together with discussions of physical tools such as infrared and nmr spectroscopy, and optical rotatory measurements, in relation to structure. The second section sets out with a survey of the reactions of various functional groups, in chapters entitled Cerbohydrate Reactions a t Carbon 1, and Reactions af Chain Hydroxyls. Glycol-cleavage reactions and methylation of hydroxyl groups are related to standard procedures for structure determinstion with polysaccharides. The biological role of sugar derivatives is emohasised in discussions of amino soaars, ph&phstes and sulfstes of sugars, &co: peptides, and glywlipids. The b~osynthesis of polysaecharides is mentioned. Other chapters deal with analytical methodology, synthesis of isotopically labeled sugars, and the separation and physieo-chemical characterization of polysaccht~rides. Appendixes give an abbreviated version of the Definitive Rules of Carbohydrate Nomenclature and the algebraic derivation, from sedimentation data, of molecular-weight distributions. Lists of general references for each chapter are followed by specific literature references for citations in the text: a totalof about 370 references is given. I n a book of this type, the reader has a rinht to exoeet that factual statements.
erences are given, the information given is expected to be that of the authors cited. The reader of the Dresent book can make neither of these a&nptions. To document fully every error in this book would require a review longer than the book itself. I n scores of instances the author makes statements, purported to be facts, t h s t have absolutely no documentary foundation in the literature. Worse still, there are numerous exzmples where respected authorities in the field are credited with facts and interpretations that are
completely a t variance with the material in their cited publications. This is especially disconcerting in view of the numerous "interpretations" offered in the book for experimental observations recorded by othen. I n some cases the content, of the text corresponds with the references cited, but in many cases i t does not. This reviewer spot-checked some of the references and was amazed to find thst, in one chapter alone, not a single one of 10 consecutive references bore any relation whatsoever to the subject material a t the point of citation in the text. The index is woefully inadequate; for example, there is no mention of any dkaccharide, not even sncrose, although there is considerable discussion of disaecharides in the text. Major errors are far too numerous to list individually, hut, for example, on page 25.5 it is stated that methyl 4,6-0-benzylidene-a-n-glueopyranoside-a classic example used to demonstrate cleavage of glycols by periodate-is not oxidized by periodate. Emil Fischer's procedure for synthesis of glyeasides is credited on page 163 to a. completely unrelated article published in 1963, and s. grossly incorrect mechanistic rationale is given for the glycosidation reaction. On page 154 it is implied that glywsyl halides normally react by way of open cmbonium ions, despite the abundant experimental evidence that supports the conventional mechanism by way of closed-ion intermediates. Throughout the baok the 1,6-anhydrohexopyranose ring-system is depicted with a bridge between equatorial atoms at C-l and C-5 of the tetrahydropyritn ring-a stereochemically impossible form. A particularly horrendoos "mechanism" is given on page 118. A large proportion of the structural formulas have errors such as bivalent hydrogen or nitrogen atoms, trivalent oxygen atoms, and di-, tri-, penta- or hexavalent carbon atoms, and an unusual spiro epoxide formolation is depioted for many of the cyclic acetal structures. Such errors were present in almost every formula sequence examined in chapter 6. Despite inclusion of an Appendix dealing with nomenclature, the nomenclature used throughollt t,he baok is in s. confused and garbled state. The treatment of subject material is uneven in depth. Optical .rotatory d i s persion, a. technique whose contributions to carbohydrate chemistry to date have been small compared with monoehromatic polarimetry, is treated in excessive detail. Information given on the rapidly advancing fields of nmr spectroscopy and quanbitative canformational analysis, as applied to carbohydrates, is superficial and not up to date. The reader who is not already wellversed in the classic and contemporary literature on carbohydrate chemistry will be grossly misled bv this baok. The book has shorb comings that are so serious that it can in no way be recommended as a class text, and certainly not as a source of reference.
DEKEKHORTON The Ohio Slate University Columbus, Ohio 45H0 (Continued a page A64)
