BOOK
REVIEWS
Ionic Reactions and Equilibria
O m r Robbina, Jr., Eastern Michigan University, Ypsilanti. Mamillan Co., New York, 1967. xiv 370 pp. Figs. and tables. 15 X 23 cm. Paperbound. $3.95.
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A more accurate hut less concise title for this hook would be: "The Application of Basic Thermodynamic Principles to Chemical Systems!' Little mathematical preparation on the part of the reader isassumed, although simple manipulations involving calculus are used. Apparently, the book has been used as the basic text for the second term of beginning chemistry for the science major at the author's school. The book consists of four major parts, each having several chapters. Ample exercises are provided at the end of each chapter and answers to the even-numbered numerical problems are given in an appendix. Part I is titled, Reactions of Substances, m d is a brief treatment of acid-base concepts, primarily from the BrBnsted-Lowry and the Lewis points of view; oxidationreduction reactions; and coordination compounds. These topics are covered rapidly at a level typical of the "average" general chemistry course. Part 11, Chemical Thermodynamim, shifts the emphasis to the prinoipal subject under consider* tion. Concepts of heat end work are presented in a clear, exact way. Reversible expansion work is developed using a graphical integration argument without the
-Reviewed
necessity of calculus. The analytic expression is, however, also introduced. The First Law and its application to thermochemical considerations is also treated with minimum use of calculus. The convention followed is that work done by the system is positive. The entropy concept is approached in a postulatory fashion rather thsn through a consideration of the Carnot cycle. The practical need far the Gibhs free energy function is demonstrated very clearly. Part 111 is called, Properties of Solutions, and considers deviations from ideality and the need for activities. Colligalive properties, phase equilibria, and conductance are treated at roughly the level of Maran and Prutton's "Principles of Physical Chemistry," 3rd ed. Part IV, Chemical Equilibrium, occw pies nearly half of the book. Chemical kinetics is treated in ten pages-just to the extent sufficient to enable the author to point out the fallacy in the usual develop ment of equilibrium concepts from kinetic arguments. Thereafter, equilibrium is considered solely from 8. thermodynamic point of view. Electroehemical cells are thoroughly treated in a chapter which discu88eS various experimental methods far the determination of equilibrium constants. The last three chapters in this seetion consider buffers and polyprotic acids and bases, solubility produot, and stepwise complex-ion equilibria. These topics are dealt with in a manner reminiscent of J. N. Butler's "Ionic Equilibrium!' How-
in this Issue
Omer Robbins, Jr., Ionic Reectians and Equilibria Douglas C . Neekers, Mechanistic Organic Photochemistry S. Young T y e e , Jr., editor-in-chief, Inorgsnic Synthesis. Volume 9 R. Sloek and C. B. F. Rice, Chromatographic Methods Kurt Randemth, Thin-Layer Chromatography Sadler Research Laboratories, Inc., NMR Chemical Shift Index E. H. E. Pietseh and the Gmelin Institute, editors, Gmelins Handbuch der Anorganischen Chemie. 8. Auflage, System Nummer 21, Natrium. Lieferung 4, Verbindungen von Natrium und Kohlenstoff (zh Natriomcyrtnid) bis Natrium and Wismut
E. H . E. Pietsch and the Gmelin Institute, editors Gmelins Handbuch der Anorganischen Chemie. 8. Auflage, System Nummer 57, Nickel. Teil A 2, Lieferung 1, Physikalische Eigenschdten des Elements New Volumes in Continuing Series
ever, Professor Robbins constantly bases his treatment explicitly on the thermodynamic principles underlying these phenomena. It is doubtful that many instructors of beginning chemistry courses will wish to delve into thermodynamics in their classes to the extent found in t.his hook. Discriptive chemistry of the elements is almost totally lacking. In his preface, the author st,ates that the hook attempts to answer three questions with respect to reactions in squeous medium: (1) How do suhstances react? (2) Why do substances react? (3) How completely do substances react? Part I of the hook is designed to provide some answers to the first question. In the opinion of this reviewer, this question is rather inadequately answered. To the extent that classical thermodynamics can answer the second question, this book provides a meaningful answer, and abundant examples of the answer to the third question are presented. The hook is obviously written to students. In view of its attractive price, many students and instructors alike will no doubt fine this clear and understandable treament of elementary thermodynamics a useful supplement to their personal libraries. University of South Florida Tampa
Mechanislie Organic Photochemistry
Dmglas C . Neekers, Hope College, Holland, Michigan. Reinhold Publishing 320 pp. Corp., New York, 1967. xii Figs. and tables. 16 X 23.5 cm. $14.75.
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This is a useful addition to the recent crop of hooks which reflect the current popularity of photochemistry. The work is intended for organic chemists and biochemists who are not primarily in the area. of photochemistry and for students at the senior or first year graduate level. I t is therefore similar in purpose to Kan's "Organic Photochemistry." The similarity extends to content; both provide valuable reviews of the current (1965-66) state of qualitative organic photochemistry. The fint fonr chapters (52 pages) are devoted to the concepts of photochemktry. In the remaining 153 pages the different types of photochemical reactions are reviewed in turn. A section on concepts in a hook of this design must introduce the principles used in subsequent discussion, hut if the length is to remain within hounds, it can be little more than an outline. Since the fondamentals of photochemistry are relatively incompressible, several confusing and arguable statements creep in. It is perhaps a commentary on the state of development of this field that any difficultiev here detract very little from the main part
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of the book. The author starts with a brief hktorical review. then quickly shows t,he relationship of photochemistry to spectroscopy and kinetics. The chapter on the absorption process introduces some aspects of both atomic and molecular structure and spectra, including hyhridization, the Frmck-Condon principle and the Jahlonski diagram. The importance of specifying the type of spectral transition, for example n - r * or r - r*,in the understanding of primary processes is emphasized. I t would have been useful to point out that. polyetomio moledeu have many low-lying excited electronic states, and that a given type of absorption is no guarantee that the reacting state has the same orbital occupation as the s t a k formed in absorption. This chapter is the weakest in the book. Some troublesome points are the dim~ssionof eigenfunctions, description of behavior of electrons in antibonding orbitals, and the characterisatinn and illustration of intersystem crossing as an energetically downhill process. I n the next chapter, ultraviolet spectra of organic molecules are discussed in greater detail. There is a verv brief treatment of exneri-
and energy transfer. The arrangement and treatment in the main part of the book make it almost a collection of review articles, permitting quick e n t q into the literature a t any point. These chapters are extensively sub-headed and referenced. There are more than 1000 total references, giving good coverage throngh 1965, with a few dated 1966. In chapter 5 , decomposition reactions are grouped chiefly according to the low molecdar weight, stable fragment eliminated in the photolysis: carbon monoxide, nit,rogen, nitric oxide, sulfur dioxide, or carbon dioxide. This is an effective hut not restrictive classification; for example, the topic, Elimination of Nitric Oxide, is in fact a. concise summary of the photochemistry of organic nitrites emphasizing structural effects, mechanisms, and synthetic possibilities. I n the next chapter addition reactions of excited states are given excellent coverage based on 244 references. Examples are well chosen to illustmte t,he variety and synthetic importance of these processes. Chapter 7 on hydrogen abstraction by excited states describes not only the ketone redoctions but several less familiar eases. Next, rearrangements are covered in a long chapter. The many sub-heads are most helpful in keeping this material sorted out. After short chapters on substitutions and chain reactions initiated by photochemically-generated radicals, the author closes with a chapter on photochemktry and nature. There is an author index and an excellent subject index. This volume will see textbook use in special topics courses on organic photo. chemical reactions. For more general organic photochemistry courses, other sources to supplement the fundamentals will be necessary.
Inorganic Synfheses.
Volume 9
S. Young Tyree, Jr., College of William and Mary, Williamsburg, Virginia, editor-in-chief. McGraw-Hill Book Co., New York, 1967. xiv 241 pp. Figs. and tables. 16 X 23.5 cm. $9.95.
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This "continuing series of elf-contained volumes representing an effort an the part of an outstanding gmup of inorganic chemists to make available detailed and tested methods for the syntheses of inorganic compounds" needs no introduction to readers of T m s JOURNAL.With a few excepbions, theorganisatition conforms to that of previous volumes (See J. CKEM.EDUC., 38, A552 [1961]; 40, A530 L19631; 44, A354 [I9671 for reviews of Volumes 6, 7, and 8). A minor change in format is the fact that the chapters, while still arranged on the basis of periodic group, are no Longer subdivided into A and B subgroups. Beginning with Volume 9, "Inorganic Syntheses" will appear annually, and because of this new yearly publication policy the present volume contains a somewhat smaller number of entries (50 contribw tions describing 94 compounds) than has been customary in the past. For the same reason, contrary to previous practice, no review articles appear in the present volume. Readers of Tms JOURNALwill be interested primarily in the suitability of the procedures for undergraduate and graduate laboratory courses in inorganic chemistry. Most of the syntheses will be challenging toeven themost intrepid student,in fact, many may be too challenging. A number of the products or starting materials are flammable. toxic. shock-sensitive.
many safety precautions, the instructor will still be left with a variet,y of experiments that illustrate synthetic techniques and compound types of great utility in contemporary inorganic chemistry. Techniques that are employed include the use of non-aqueous solvents, vacuum systems, dry box snd cont,rolled atmospheres, gas phase reactions, low or high temperatures, remote control manipulation, resolution of optical isomers by diastereoisomer format,ion, and fluorimtion by means of ant,imony and arsenic fluorides. I n keeping with the emphasis on syntheses that are "applicable to a variety of related compounds," a number of general methods are given (organometallic chelate compounds, fluorophosphoranes, sulfamides, tetrahalo complexes of dipositive met,als in the first transition series, and anhydrous metal chlorides by reaction of metal oxides with thionyl chloride or hrxaahloroorooene). The line of demarcation between inorganic and organio chem~stryhas of late become nebulous, and several syntheses in this volume employ the Grignard reaction (trimethylphosphine, trimethylantimony dihdides, and substituted sdfamides). I t is implicit in the concept of scientific progress that much work rapidly becomes obsolete. Accordingly, not all the G. R. M C M ~ A N syntheses are new; some constitute improvements upon syntheses published earCase Western Reserve University lier in the series (anhydrous metal ehloCleoeland, Ohio
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Journal of Chemical Educotion
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rideu, TiBrc NhC4, S4N4,SOP9,and ICI). Coordination compounds, because of their color and ease of preparation, are perennial favorites of instructors and students alike. A sizable selection of such compounds is given; they range from the long known and thoroughly familiar [Co(NH,)&I]CI% to recently discovered and still unfamiliar compounds such as perchloratonickel(I1) complexes. Preparations of starting materials and intermediates of interest to the coordination chemist include KICo(NHa)~ NOS)^], (NH&PtCle, and Re(V) complexes. Unnsnal oxidation states, always to be relied upon to provide an exotic flavor to m y inorganic laboratory course, me well represented by C,H,MO(CO)~ C1NOs, ICI, and [(RO)sPIaNi),and the preparation of metal iron(II1) oxides will be of interest to industrial chemists because of the important electronic applications of the ferrospinels. My previous objections to the series (J. CHEM.EDUC.,44, A354 [19671), via., the failure to submit galley and page proofs to contributors for correction and the lack of reprints, require reiteration here. Aside from theseminor comnlaints. thevolume is
GEORGEB. KAUPFMAN
California Slate College Fresno
Chromatographic Methods
R. Stock, Regional College of Technology, Nottingham, and C . R. F . Rire. Regional College of Technology, Liverpool, England. 2nd ed. Chapman and Hall (distribut,ed in the U.S. by Barnes and Noble, New York, 1067). viii 256pp. Figs. and tablea. 13.5 X 21..5 em. Clothbound, $7.50; paperbound,
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54. This is a second edition of this book. which originally appeared in 1963. After an Introduction elassifvine chromatoerachromatography and zone electrophoresis, gas chromatogrrtphy, thin-layer chromatography and model experiments in ehromatographic techniques. Compared with the first edition, which was .50 pages shorter. the chanter on thin-laver chrosieve chromatography are new. These additions are certainly warranted by the recent activity in these fields. Some timely additions have been made to the section on ion exchange. Additions have made the bibliography more current. No ehanees were made in the other material. ters were not revised in the new edition. For example, it is incorrectly inferred that Tswett separated only colored s o h stances in his original work with chromatography (p. 1). I t is not true that chromatoeraoh was lareelv unused between 1903
(Continued on page A912)
