Physical Chemistry - ACS Publications


Physical Chemistry - ACS Publicationspubs.acs.org/doi/pdfplus/10.1021/ed048pA222by WF Kieffer - ‎1971Harvad University...

4 downloads 44 Views 8MB Size

book reviews Editor: W . F. KIEFFER College of Woosler Woator, Ohio

Elementary Quantitative Chemistry

E s m m h S . Gilreath, Washington and Lee University, Lexington, Va. W. H. Freeman and Co., S m Francisco, 1969. vii 222 pp. Figs. and tables. 19 X 25 cm. $3.75.

+

According to its preface, this paperback book is designed as a manual for a onesemester course in elementsry quantitative andysis on either the freshman or sophomore level. It is divided into Theoretical Aspects and Experimental Procedures and assumes no background knowledge beyond general chemistry. After some introductory comments on methods and objectives and s. brief chapter on the evaluation of analytical data, one h d s nine more chapters dealing with the elementmy theoretical basis for most classicsl quantitative analysis, although a chapter an calorimetry and spectrophotometry is also included. Five additional chapters of laboratory procedures, again mostly classical, are included in the second section, and the nine appendixes contain a representative selection of data useful in solving the problems at the end of the thporetical chapters together with answers to some of these problems. Unfortunately, while the topics covered are probably quite representative of many elementsry "qurtnt" courses, there seemed to be a great tendency to provide the student with formulas into which he could plug his data and get an answer without really understanding either the basic cone e ~ tor s the dimensions involved. Indeed,

while many approximation formulas are used, the student is not always made aware of the simplifying assumptions. Dimensions, too, are handled in a somewhat haphazard manner as an page 23 where density is defined as the "weight in g r a m of 1 ml of a substance or solution" and then the densities of hydrochloric acid and ammonia are eiven as dimensionless nnmbers in the 5amc paragraph. The d v e d prublem, too, arc rometimes worked without showing all of the dimensions, and this could cause confusion and the mere memorization of mathematical equations. Other confusing and surprising s t a t e ments are sprinkled throughout the text. On page 38, NaCl and KNOs are given as examples of "salts whose solutions are aprotic" when the discussion is concerned with aqueous systems. On page 105 we learn that, "The Ag,CrO, is more soluble because two silver ions occur in the solubility product expression," and in the Mohr method, "The beginning student may have trouble in detecting the end point, but for an experienced analyst this difficulty does not exist." Mention is made of Caldwell and Moyer's ingenious technique of adding nitrobenzene in the Volbard method (p. 106) but no reference is cited. In a casual survey, only nine referenees were noted in the entire text. Most teachers would certainly object to a student being told, "Comet minor errors by neat erasures" (p. 150) in laboratory notebooks. In the experimental section, the instructions are generally adequate for carrying out the usual neutralisation, redox, colori-

D e v i e w e d in this Issue Emarch S. Gilreath, Elementary Quantitative Chemistry

...A205

G e m G. Guilbault and Larry G. Hargts. Instrumental Analysis Manual. hfodern Experiments for the Laboratory

.. .A205

A. R, Knight, Introductory Physical Chemistry

Donald H . Andrewe, Introductory Physical Chemistry Eugene J . Elosenbaum, Physical Chemistry Ernest Rabinowicz, An Introduction to Experimentation Chmles L. Perrin, Mathematics for Chemists Jack Barretl, Introduction to Atomic and Molecular Structure K . T h m s Finley and James WiLsm, Jr., Fundamental Organic Chemistry

...A206 ...A206 ...A211 ...A211 ...A214 ...A216

Richard D. Gilliorn, Introduction to Pbysical Organic Chemistry

. . .A218 . ..A218 . ..A220

Douglas Henderson, editor, Physical Chemistry: An Advanced Treatise. Volume IV, Molecular Properties

... A n 2

C . K . Ingold, Structure and Mechanism in Organic Chemistry

Thazas R . Bhhburn, Equilibrium: A Chemistry of Solutions

New Volumes in Continuing Series

...A224 ...A226

metric, precipitation, and complexation reactions common to most beginning courses. In using the pH meter, this reviewer would have preferred the use of two buffer solutions with different pH values to calibrate the instrument instead of the single buffer solution suggested. On the positive side, there is a rather complete list of common technical errors in spectrophotometric work, although no mention is made of the spectrophotometric error curve showing relative concentration error as s function of transmi& tance or absorbance. One also wonders about the advisability of using 8, glass electrode as a reference electrode in the potentiometric titration of NaCl with AgNOs as suggested on page 194. However in spite of the above criticism, this reviewer feels that there is a very real need for books written to present the fundamentals of a. single area of chemistry in 5 clear and concise manner. Unfortunately, it is the writer's opinion that this book falls somewhat short of this ideal, although it could be useful in those courses designed to provide only a very brief introduction to quantitative analysis and some if its underlying principles.

Indrumental Analysis Manual. Modern Experiments for the Laboratory

George G. Guilbault and Larry G. Hargis, Louisiana State University in New Orleans. Marcel Dekker, Inc., New 444 pp. Figs. and York, 1970. xi tables. 18 X 25.5 em. $7.75.

+

This book is organized into six parts representing large segments of analytical chemistry such as optical methods, electrochemical methods, separations, and the like. I n turn each of the parts is further broken into chapters devoted to single techniques. In each of the chapters the authors have opened with a cursory ,description of principles underlying the treated method; then experiments follow which are designed to illustrate typical applications. Each experiment features a section devoted to the more specific points of theory and practice pertaining to the procedure to follow. The exercises themselves comprise the procedure, a list of required equipment and materials, an outline far the evduation of experirmun of auestions mental dsta. and B .. designrd to test the atudnn'.i undrr3tandirrg of the experimerrt and it* fwrdumeutal principles. 11, all there are l h chapters containing 49 experiments ranging over almost all types of physieo-chemical analytical method. The only areas totally untreated are those requiring extensive specialized capital equipment Lie neutron activation analysis and X-ray techniques. As one might expect, the most fundsmental weskness of the book lies in the brief introductory sections. Many of these contain such compromising oversimplifications that their real utility is doubtful. Some sections, like those deal-

.

(Continued on page A d W Volume

48, Number 3, March 1971

/

A205

book reviews ing with mass spectrometry and thin layer chromatography, are usefully descriptive, but most are either simplistic or deceptively unclear. One consequently wonders whether this volume would not be stronger if these discussions were omitted and whether the student would not be better served if he were forced to find a, deeper background treatment elsewhere. On the whole, however, the experiments themselves are creditable. They are modern, and they are good a t probing the fundamentals of the techniques. I n addition, they do an excellent job of illustrating areas in which a given method is particularly well-suited. Professors Guilbault and Hargis have written clear procedures which successfully avoid the cookbook style. Among the more novel experiments, Experiment 4, Identification of an Unknown Steroid Using a Computer Search Program; Experiment 6, Measurement of Excited State pK.; and Experiment 47, Analysis of a Mixture at 70 eV (by mass spectrometry) seem particularly interesting. Same of the exercises even border an being "relevant," far example Experiment 43, Separation and Identifies, tion of Pesticides, which is, incidentally, one of the better experiments. Finally, the questions associated with the experiments are particularly noteworthy; virtually none are trivial, all require thought on the student's part, and many will require some library research for proper answers. Chapter 6, Electronics and instruments, tion, authored separately by Dr. Jeffrey Huntington deserves special attention. The chapter comprises an extensive and redable discussion of operational amplifiers and their applications in chemical instrumentation. The treatment begins on a basic level, proceeds through a description of useful circuits, and ends with an examination of some important limitations of operational circuitry. That this chapter is included in the book is gratifying in an era when operational amplifiers are increasingly employed in ~nalyticalinstrumentation. Some notable inconsistencies crop up now and then throughout the hook. Variations in certain numerical quantities like the Faraday and the potential of the saturated oalomel electrode occur oceasionelly. In addition, the suthom have not been wnsistent in their notation regarding elemental oxidation states. I n some areas they have chosen to use the chemicel symbol with Rotoman numerals, but in others they have employed the superscripted signed Arabic number. The hook has heen printed by directly reproducing a typescript copy in an effort to hold down costs. This effort has yielded fairly satisfactory product, but again one notes that certain symbols have been typewritten in some places, but entered in pen and inkin others. In their preface, the authors state that this hook is being released in a preliminary edition to allow a trial period for improvements to be incorporated into the final version. I t is this reviewer's opinion that with s relatively small additional effort directed toward improving the introductory sections and the consistency of the

A206

/

journal of Chemical Education

work, the final edition of this book could be a volume of fairly high quality. Nevertheless, the quality of the experiments included in the present edition is high enough that the book deserves examins, tion for possible use as a laboratory manual or as s laboratory sourcebook.

useful and interesting lecture maierial. Entropy is introduced through a well written discussion of spontaneous processes and randomness, although the approach is not statistical. There is no mention of heat engines, but the defining entropy equation is reasonably justified by the author. A number of equations LARRYR. FAULKNER throughout the book am not rigorously Harvad University derived, hut m e justified in the discussion. Cambridge, Mass. 02158 The treatment of kinetics is adequate. There is no development of the kinetic theory of gases which leaves discussion of the collision theory a bit unsupported and perhaps a bit lean. Transition state Introductory Physical Chemistry theory is included in the obapter in more d e t d as is enzyme catalysis. A . R. Knight, University of SaskatcheAppendices explain the use of logarithm wan, Saskatoon, Canada. Prenticeand graphs. Each chapter is followed by Hall, Inc., Englewood Cliffs, New Jer10-20 problems, no answers given. The 344 pp. Figs. and sey, 1970. xiii problems appear reasonable and on a level tables. 16 X 23 cm. $10.95. consktent with the author's treatment. The author states in his preface that his The printing and figures me reasonable, hook is designed for a one semester course and there appear to be a minimum of for pre-medical student.% and other life typographical errors. science majors. It appears to be a'fine PETERM. J E P ~ I S book for its intended purpose, hut should State University College not be mistaken as a, text for chemistry Col-tland.New Ywk majors in physical chemistry. The choice of topics reflects the interests of one studying the life sciences, while the level of Introductory Physical Chemistry coverage makes very small demands for previous or extensive knowledge of calDonnld H. Andrews, Florida Atlantic culus. Calculus is used in the developUniversity, Boca Raton. McGraw ment, hut it is fully explained as it is inHill Book Co., New York, 1970. 689 troduced. I t is an interesting hook hepp. Figs. and tables. 19 X 24 cm. cause of its unusual (for chemists) em$14.50. phasis. "Introductory Physical Chemistry" The hook begins with thermodynan~ics: represents an attempt to apply two princithe first law, thermochemistry, seeond and ples to the make-up of a one year underthird laws, free energy. Equilibrium graduate physical chemistry course: first, wnstants and their calculation, and secthatthe material should he presented in a tions an acid-base equilibria and ion acway that helps the student intuitively see tivities follow. Next is a chapter on chemical kinetics, with the remainder of "the basic pattern of relationships," to the hook devoted to applications, of therquote the preface; and second, that right modynamics: electrochemistry, phase now the use of biological examples and equilibria, non-electrolyte and electrolyte applications is an excellent way to keep the interest of the typical student in solutions, and mxromolecular systems. physical chemistry. The treatment is such tbat it should be In line with the first of the above principossible to cover the entire book in one ples, the author often applies new ideas semester, especially considering the abfirst to simple physical systems before sence of such topics as gases, kinetic theory, statistics and statistical thermataking up chemical applications. Thus, dynamics, quantum mechanics, structure, the first eight pages of the chapter on and the solid state. chemical kinetics are devoted ta diffiusian The text has some features worth menof a gas between reservoirs in a gravitational field, while the introduction to tioning. Most important is the fact tbat quantum theory is made via s. fairly exthe lighter than usual dependence on tensive discussion of classicd wavesmathem&ical manipulations and techessentially a somewhat diluted version of niques is compensated hy a more extensive than usual exposition of the source and Kauzmann's treatment in "Quantum significance of the thermodynamic results. Chemistry." Plenty of numerical eexamples are inserted in the text immediately The careful explanations should give followingthe material to which they apply. students a greater feeling of security than Also, derivations are kept to a. bare minithey might find in mathematics which is mum. perhaps beyond their grasp. Such Except for the last segment of the text, thoughts suggest that the book might be the organization is not unusual. Three a very useful supplement for students in chapters on gases and a brief chapter on an ordinary physical chemistry course, or condensed phases are followed by five it might he a suitable text for some adchapters on thermodynmnics and five vanced freshman sections. chapbersof applieationsaf thermodynamics There are numerous worked problem throughout the book. These e x a m p l e to equilibria, solutions, and electrochemistry. A discussion of kinetics is next, complement the discussion and again followed by six chapters on quantum should impart to the student a. sense of theory and its application to atomio and greater familiarity and comfort. Many molecular structure and spectra, and of the problems and other illustrative photochemistry. One chapter discusses examples have biological implications and instructors should find among them some (Continued a page A t l o )

+

I book reviews I

types of solid states and one deals with surface chemistry. Throughout the book applications to biology and biological examples are diacussed wherever possible. The final four chapters, entitled Macromolecules, Entropy and Informstion, Bioirreversibility, and Biocvbernetics discuss in some detail several applications of physical ohemistry to biological systems. Much of the material in these chapters is not to be found in any other physical chemistry text. The chapter an macromolecules discusses the structures of DNA and RNA, DNA replication, and RNA and protein synthesis. Entropy and Information quantifies the idea of information and its relation to entropy, and discusses, among other things, the information content of DNA. Bioirreversibility discusses steady state kinetim, and applies the Onsager relations to coupled reactions. The find chapter, Biocybernetics, compares the thermodynamic and cybernetic descriptions of a system and its interactions with its surroundings, and discusses the application of cybernetics to some biochemical systems. Although the author indicates his intent to stick to relatively few hesic principles, curtailing his treet,ment of "far-flung applications," the book contains at least some mention of most topics the reviewer looked for. Two exoeptions are the total absence of nuclear and radiation chemistry, and the lack of any discussion of the methods of studying fast reactions, or indeed of any modern aspects of kinetics. A few comments about the physical layout of the book follow: I t contain^ around 260,000 words-about 10% more than Daniels and Alberty's 3rd edition. The legibility is good, although the type is small. The margins are too narrow for notes. A cunory reading revealed six typographicd errors. There are a great many illustrations-perhaps too many. While in many sections the illustrations complement the text very well, in others they sometimes senre no obvious purpose. For instance, it seems wasteful to devote almost half of p. 4 to a drawing of a mercury thermometer. The problem sets are ample. The author also includes well selected sets of references after each chappter, containing titles up to 1968. The index is not ss complete as it might be. For instance, several pages of the chapter on Mt~cromoleculesare devoted to enzyme kinetics, but the only index reference to this section seems to he in the name index under Michwlis (for MichaelisMenten mechanism). I n most respects this book would not stand out above the excellent texts already available for the one year physical chemistry course. The emphasis on biochemical applications is very timely, however, and in my opinion sufficiently important t~ warrant careful consideration of this text for use with "average" physical chemistry students.

DANIEL B. HOWELL Nebraska W e s l e y m Universitz~ Ltmoln, Nebraska 68504 A210

/

Journal of Chemical Education

book reviews

I

Physical Chemistry

Eugae J . Rosenbaum, Drexel University, Philadelphia. Appleton-Century681 pp. Crofts, New York, 1970. x Figs. and tables. 17 X 24 cm. $12.95.

+

This text will seem comfortable and vaguely familiar to any physical chemistry instructor. It begins with several chapters devoted to classical thermodynamics and gas theory, moves on through quantum mechanics and bonding theory to s brief survey of physical methods used in structure determination, and in the last half deals with statistical mechanics, reaction kinetics, electrochemistry, liquids, solids, and multiphase equilibria. The arrangement and choice of topics is very reasonable and very, conventional. I think that students will find the writing in this text to be unusually clear and easy to comprehend. The author has been very successful in treading the narrow path between over simplification and over involvement in minor detsils. I was unhappy about several aspects of the book. The problems are almost all of the type that require little more than plugging a few pieces of data into the ap~ r o ~ r i aequation. te Some chapters, such as those on bonding and statistical mechrtnics, have too few problems of any kind to allow a student to get a. firm grasp of the mst,erid. There is no hint anv-

relate physicd chemistry to other areas of science, or even other ireas of chemistry. There is very little that is novel in this book, topic after topic is presented in s tried and true manner resembling a sort of composite of d l the popular views of the past 20 years. In short, this book is a good, gray product which does its job, hut wd1 never cause much of a stir.

JAMESE. FINHOLT Carldon College Northfield, Minnesota 66057

An Introduction to Exparimenlation

Ernest Rabinowin, Massachusetts Institute of Technology. Addison-Wesley Publishing Co., Reading, Massachu124 pp. Figs. and setts, 1970. viii tables. 15.5 X 23 cm. Softbound $3.25.

+

This paperback edition presente a cis+ fication and expansion of the earlier chapters which appeared in the book "Physiod Measurements and Analysis" by N. H. Cook and E. Rahinowics (Addison-Wesley 1963). In attempting to emphasize the conditions under which the normal distribution does or does not apply to experimental work, the author presents chapters which discuss: the quditative evaluation of exp+ximents, errors of measurement, evaluation of functional relation-

Volume 48, Number 3, March 1971

/

A21 1

book reviews ships, and the preparation of a. technical report in that order. From the viewpoint of the chemist, it is unfortunate that the terminology and symbolism used 1s not that which is common to chemistry. For example, the term "resolution" is defined as the smallest quentity that an instrument will detect, i.e., "detection limit" in chemistry. The author also uses internal and external estimates of error in place of the more common random and systematic differentiation, respectively. I t is quite certain that most statisticians would approve of the concise discussion of measurement accuracy presented in Chap. 1, but would criticize the fact that there is no mention of the relationship and/or distinction hetween precision and accuracy until much later in the book. For the chemist, there is a good discussion of the principles of the analytical balance and errors which may he associated with weighing; a well written chapter on curve fitting thrtt presents practical means for treating scattered data; and some very useful suggestions on the best means for presenting data in a technical report. While the book will find broad use for supplemental reading, its brevity will preclude its adoption as a text.

Mathematics for Chemists

Charles L. Pewin, University of California. La Jolla. Wilev-Interscience. New YO;~,. 1970. xii 253 pp. ~ i ~and i . tables. 15 X 23.5 om. $11.95.

+

Applied mathematics courses for chemists have been taught by chemists in many schools for almost a decade. However, there are still very few texts written for such wwses. The present volume attempts to 6 U in this gsp. The basic concepts of elementary calculus are reviewed in the first two chapters of the book. Some specisl functions (such as error functions, Gamma functions, the Delta function, Bessel functions, Legendre polynomials, eto.), solution of differential equations by power-series expansion, the eigenvalue-eigenfunction problem, Fourier series, etc., are treated superficially in s terse style in chapters three, four, and five. Chapter 6 concerns probability and statistics, while veotors me discussed in chapter seven. Following this, matrices, vectors and functions, operators, the general formulation of quantum mechanics, the variational principle, linear variation principle, perturbation theory, etc., are treated. Finally in Chapter 10, group theory is introduced. Overall, the organization of materid and presentstion are poor. For many importsnt concepts, the .author merely R. K. SKOGERBOE states the definitions (sometimes ambigColorado State Unbersity uously) without further explanation or Fott Collins, Colwado 80521 pointing out the important physical impli-

A214

/

Journal o f Chemical Education

cation. If the author would organize the material in a better order and discuss the concept of linear vector space before the hmis set, completeness, operator, etc., were introduced, he might explain these important concepts more clearly once and for all. Besides, the author fails to explain why operators in quantum mechanics have to he linear and hermitian and what is the physical implication of a basis set being complete. It appears that the natural way to introduce the Dirac delta. function would he to start from the Laplace transformation instead of just stating the definition and listing some of the rules for mrtnipulsting this function. In many cases, the author treate some elementary topics in a relatively detailed manner while discussing some new, important or advanced topics in a terse style. The choice of topics for the present hook is also questionable. Topics range from use of desk cdculation to digital and analog computers, and from the definition of differentiation to the general formulation of quantum mechanics. However,. many important topics such as functions of complex variables, integral transformrmtion (some are presented in exercises in the present hook, but not enough) hypergeometric functions, etc., are not included. Group theory is usually discussed in most quantum chemistry courses or treated in an independent course. It would be much more beneficial to students for the space devoted to group theory in this hook to be (Cmztinued on page A218)

book reviews devoted to same other important topics such as a more complete and logical treatment of special functions and linear algebra. than that in Chapters 3, 4, 5, 7,8,and 9. The many exercises that demonstrate spplications of mathematics to quantum mechanics, molecular structure, spectroscopy, equilibrium-constant problems, statistical mechanics, etc., are a goad feature of the present book. However, I do not believe that the present book can provide a sound mathematical background for modern chemistry to students who are for modern chemistry to students who are doing graduate work in any field of chemistry except organic chemistry. Even for organic chemists I would recommend other more readable books such as M. L. Boas' "Mathematical Methods in the Physical Sciences" (Wiley, New York 1966). YUHKANGPAN Boslon College Chestnut Hill, Massachusetts 06187

Introduction to Atomic and Molecular Structure

Jack Barrett, London University, England. John Wiley & Sons, Inc., New 327 pp. Figs. and York, 1970. xvi tables. 15.5 X 23.5 cm. $12.50.

+

I

The author of this book has attempted to present what is essentially a, qualitative introduction to quantum chemistry for undergraduate science students. As experienced workers in this area me well aware, a meaningful nan-mathematical approach to quantum mechanics is far more difficult to accomplish than an effective mathematical one. The more qualitative the presentation, the more knowledgeable the author must be to avoid misleading or incorrect statements, and the more skill is required to insure that the subject material is instructive as well as accurate. Unfortunately, tbis hook does not exhibit the requisite skill and understanding for a successful qualitative treatment. For example, a wave packet of finite width in coordinate space is used to represent "an electron whose position is known exactly" on p. 44, and an p. 69 it is asserted that a linear combination of any two eigenfunctions is again an eigenfunction. Other misinterpretations and misstatements abound throughout the book. The discussions and explanations are neither especially interesting nor instructive. A student attempting to learn from this book would at best achieve a superficial knowledge of the subject, dong with some serious misunderstandings. In view of the existence of a number of good mtroductory books in quantum .: chemmtry, it is d~fficultto recommend tbis book to anyone.

:

DONALD R. WHITMAN Case Western Reserve University Cleveland, Ohio 441 06 (Continued on page Ad181

A216

/

Journal o f Chemical Education

book reviews Fundamental Organic Chemistry

K . Thomas Finley, Eastman Kadak Co., and James Wilson, Jr., Rochester Institute of Technology, Rochester, New York. Prentioe-Hall, Inc., Englewaod 429 Cliffs, New Jersey, 1970. xviii pp. Figs. and tables. 17 X 24.5 cm. $9.95.

+

This small b w k is designed apparently for a. terminal one-semester or two-quarter murse for non-maiors. There are twelve chspterj of rcxr awl thrw xppmdims. A ficwral bibliography, xniaem ro pmlrlrm*, a glcmary and index romplere the honk. Each chapter closes with a summary which, while being helpful to the student, has the common failing of being too brief at times. Reading references are given for each chapter also, and there is an abundance of problems which seem ta be excellent and varied in nature. The 16page Appendix I1 is especially vrtlu~ble. It deals with modern spectroscopic methods of mdysis: mass, infrared, ultraviolet, and nuclear magnetic resonance. Aliphatic and aromatic compounds are treated together. Most of the chapters are adequate in coverage, and even remarkably complete for this type of course. The m$n difficulty is that there are just not enough of them. This leads to the serious neglect of some phases-a, point recognized by the authors who consciously made their choices. They have "favored

A21 8 / Journal of Chemical Education

a. more detailed examination of a few topies" and even eliminated certain functional groups from consideration. For example, reaction mechanisms receive more consideration than might be expected in such a short treatment of organic chemistry, while the reviewer would not be reconciled to the negligible mention of phenols, and diilsotisittion was not noted at all. The material is "packed in" solidly, and explrtnstions are severely limited. For example, several illustrations of molecular structure using the "stick models" are misleading if far no other reason than that they attempt to show unshared pairs of electrons and/or carbonyl groups without adequate interpretation. The reviewer does recommend that this text be given serious consideration by anyone who wishes to teach such a course, with heavy emphsis on drill and/or quiz sections, with problem solving.

subject had been accomplished, and the work of consolidation and development, by a vastly increased number of workers, Clearly, was only just beginning . Ingold has taken a dim view of progress in physical organic chemistry since 1950. Accordingly, the new generation of ehemists who have made their contributions after 1950 will enjoy two acerbic comments in J. D. Robert's review of the first edition ( J . Amer. Chem. Sac., 75, 6355 (1953)) and feel that they are again applicable. These are: "Despite the broad title, the work is largely devoted to the contributions of the author and his coworkers.. . . '(Not only is the current status of each of these topies presented but also the line of historicd development is traced. These discussions will be valuable for orientation of future research workers in the fields except where the emphasis on the author's own idem and experiments is such as to give an incomplete if not distorted perJOHN W. CAITTUM spective." The College of Wwster Nevertheless, the book has many virtues Wwster, Ohio and would be required reading for anyone preparing a course on mechanisms or on Structure and Mechanism in Organic physical organic chemistry. The sections Chernirtty on the benzidine rearrangement and aromatic rearrangements are each as fine C. K . Ingold, University of London. 2nd a review of these topies as is available. ed. Cornell University Press, Ithsea, The chapter on cerboxyl and phosphate New York, 1969. ix 1266 pp. Figs. reactions reflect Ingold's deep interest. and tables. 16.5 X 24.5 cm. $32.50. Aliphatic substitution, aromatic snhstitution, and saturated rearrangements conThe tone of this hook is set by the tain an unpa~alleled assemblage of the preface: "The first edition of "Struccritical data with a perceptive analysis. ture and Mechanism" was written in 1950-51, when the formation of the (Cmuinued on page A2O)

+

. .."

book reviews Chemists will he much indebted to the author for these exkensive reviews. Ingold enjoys the interplay of ideas in the development of s. field. This style will appeal to the scholar of chemistry and such developments of the line of thought are not readily avsilable elsewhere. However, student*, anxious to reach the frontiers as frst as possible, may not appreciate the intricate treatme&. Related to the above, many chemists will feel that the ext,ensive evidence presented to demonstrate & I , zt E, and *A4 effects may be outdated. Such symbols are used with decreasing frequency, and the trend is to express such effects in terms of Hsmmett's c p theory and other quantitative and more thermodynamic frames of reference. Ingold hay attempted to recogniee these more thermodynamic approaches by including sections on acidity functions and crp theory (notable ommissions from the first edition). However, he is on less familiar ground and i t is here that the writing, though sometimes perceptive, hocomes the most suhject,ive. An example is the attempt to convert "Hammett i r p theory" to "Hammete Burkhmdt relation." Ingold, as much as anyone, should know that credit largely goes to the one whose eloquent exposition s ~ a r k sand ins~iresthe following neness, - tion. Despite the title of the hook, structure is largely confined to rotational energy

A220

/

Circle No. ID(

01

harriers and conformationd effects in cyclohexanen. Omitted are the nmr and esr structural studies of reactive intermediates (carbmions, cmhonium ions, carbenes and methylenes, triplet stat,es, and cation and anion radicals) which has been such a'feature of the past decade. As for mechanism, the elegant develapment of photochemistry, the contribnt,ions of MO theory, enzyme models, biological pathways, genetic coding (is this not a. problem in structure and mechanism), pH rate profiles, orgmometallics of transition metals, and many other fields of current interest go unnoticed. This hook is R. testament to the many contributions of the English school and to the singular energies and perception of the man ithat led it. I t is an updating of these contributions and 8. tracing of the linw of thought in their development,. I t also trace4 the development of several other selected fields in a most valuable manner.

N. C. DENO The Pennsylvania State University University Park, 16802 lnlroduclion l o Physical Organic Chemistry

Richard D. Gilliom, Southwestern a t Memphis, Tennessee. Addison-Wesley Publishing Co., Reading, Massachusetts, 342 pp. Figs. and tables. 1970. vii 17 X 34 cm. $13.50.

+

"Introduction t o Physical Organic Chemistry," according to the author's

R e a l m ' S e n i n Carl

Journal of Chemicol Education

preface, "evolved from an attemp% to teach physical organic chemistry to undergraduate seniors a t a comprehensible level without covering only familiar ground." The result is a hook intentionally limited in scope compared to others in the broad area of advanced organio chemistry (such as March's "Advanced Organic Chemistry: Reactions, Mechanisms, and Structure," reviewed in J. CHEM.EDUC., 46, 537 (1969)). The text that comes the closest to providing the same coverage is "An Introduction to Physical Organic Chemistry" by Kosower (reviewed in J. CHEM.EDUC. 46, A192 (1969)). The outline of the hook is potentially a. stmng paint in the light of its design far a one-semester course. Its contents may he divided roughly into three parts: a review of fundamentds of atomic structure and chemical bonding (2 chaps, 20 pp.), a fairly systematic development of principles and techniques utilized by physical organic chemists (9 chaps., 207 pp.), and finally, in-depth illustrations of these precepts in the study of two major rertotion mechanisms (2 chaps, 88 pp.). The author suggests in his preface that the introductory review chapters need not he covered in class, a valid suggestion considering their relatively low level of sophistication. However, their usefulness to students could he considerably enhanced by some references to suggested readings (as done adequately on the whole a t the end of later chapters) especially with regard to resonance theory. Molecular orbital theory is the first % 2' (Continued on page )A

Circle No. 143 m Raadsrr' Senice Card

book reviews basic tool of physical organic chemistry to be developed in depth. This is done with some rigor, but unfortunately this portion comprises the least readable section of the text, and for students naive in the subject, Lebedes "Introduction to Mbleeular Or.bjtal Theory" (reviewed in J. C a m . E k c . , 44, 117 (1967)) is superior. A discusZion of application of the WoodwardHoffmann rules for electrocyclic resetions in Gilliom's text is well done, but no mention is made of sigmatropic reactions. Seniors as well as many beginning graduate students will appreciate the attention to chemical kinetics presented in the next several chapters. One on experimental methods emphasiaing "tricks of the trade" is particularly well done. Much of this material will be review for students having completed physical ehemistry; however, it is concisely done in a well integrated attempt to give practical information for someone interested in applying kinetic theory to setualproblems. In a. chapter on theories of chemical kinetics, collision and transition state theories sre lucidly presented. Subsequently a chapter on kinetic isotope effects yields a clear description of the primary effect; discussion of secondary isotope effects is less satisfying. Two unrelated chapters, one covering linear free energy relationships which %mounts to a catalogue of the various Hammett type equations, and another on acids, bases, and solutions, complete

A222

/

Journal o f Chemical Education

the coverage of fundamental techniques and principles. The former especially will he useful to those who have difficulty in keeping the many equations and their respective pammeters categorized. A general discussion of fundament,al approaches to mechanism studies (kinetic and nonkinetic) is given in a short chapter preceding the last two chapters of the hook in which principles previously developed are applied to mechanistic studies of electrophilic aromatic substitution and to nucleophilic substitution and elimination a t saturated carbon. These are most suitable m a s for detailed study in view of the tremendous amount of attention physical organic chemists have paid to them. On the whole, coverage is eomprehensive enough to not only illustrate use of principles hut also to yieldpenetrating insights into just how complicated a subject mtty become if it is studied thoroughly. Unfortunately, the text a9 a, whole contains too many errors, not only of the obvious typographical variety but also at least eight which would seriously confuse if not mislead a naive student. In several places impressions exactly counter to those intended are rendered due to poor composition. In terms of rigor, generally for an undergraduate course, choice of a text may result in one of two extremes: either the instructor may iind a hook so readable as to provide a backbone from which he may launch his discourses, canfident that students can fall back on the text to achieve a. firmfoundtltion, or it may he sufficiently rigorous that most lecture

material must be drawn from it. For those students well founded in modern physical chemistry, "Introduction to Physical Organic Chemistry" might serve in an intermediate capacity, between the above extremes but closer to the latter.

G. LANDOLT ROBERT Muskingum College New Caeord, Ohio Physical Chemistry: An Advanced Treatise. Volume IV, Molecular Propelties

Edited by Dough Henderson, IBM Research Laboratories, San Jose, California. Academic Press, Inc., New 832 pp. Figs. and York, 1970. x k tables. 23.5 X 16 c a $39.

+

This volume follows the pattern of previous parts of the treatise. "Distinguished investigators have contributed chapters in the field of their special competence!' The bulk of the discussions treat the theoretical interpretation of data. to learn ahout the structure of single molecules. There is some mention of experimental methods, e.g., measuring dipole moments, esr spectrtt, Mossbauer spectra, and malecular beam techniques. The suthors are selective in their choice of material to illustrate general principles. Each chapter is provided with a list of general as well ss special references to compensate for the non-encyclopedic coverage of the topic. Chapters cover rotational and vibrational (Continued on page ASS4

book reviews spectra, electric moments, nmr-, esr-, nuclear quadrupole resonance-, Mossbauer-, moliecular beam-spectroscopy and electron diffrsction by gases.

/

i

1

Equilibrium: A Chemistry of Solutions

Thomas R. Blackbum, Hobart m d William Smith Colleges, New York. Halt. Rinehart and Winston. Inc.. New ix 220 pp.' F& and ~ o r k 1969. , tables. 15.3 X 22.8 cm. $3.50 paperback; 55.50 clothbound.

+

This book is designed for use in a one term course devoted to the study of equilibrium. Studentsare assumed to have bad an introductory course in chemistry and to possess a working knowledge of high school mathematics. Initial chapters are concerned with a simple and qualitative discussion of the meaning and importance of entropy in the real world, definitions of equilibrium quotients and their temperature dependence, the hydration of ions and the ealculation of the pH of solutions of simple and polyprotie weak acids and bases. Subsequent chapters deal with coordination equilibria, solubility, liquid-liquid distribution and its application to counter current separation prockses, and oxidation-reduction svstems. Avvendiies r* view the fuudsmentnl marhernatiml rods and discu~rthe thennodytlamir basis of equilibrium. I t is obvious that the author is familiar with his subject and enjoys teaching it. Attempts are made to demonstrate its importance and relevance to the understanding of natural pbenomona in general. A few examples of topics which are mentioned as illustrative material in the appropriate places are the relationship between pH and the solubility of COI in biological fluids; the process by which limestone caves are famed; snd the use of chelons in treating heavy metal poisoning. Of timely interest is a short discussion of ion-exchmge electmdes. The author stresses the importance of setting up the proper mass balmce equations in solving equilibrium problems. An intuitive rather than rigorow approach for deriving proton balance expressions in some of the examples tends to detract slightly from the clarity, however. There are a few other inevitable minor points upon which critical comment can he made, but a major shortcoming of the book, in this reviewer's opinion, is the heavy emphasis on graphical solutions to equilibrium problems. I n fact, on p. 48 it is stated, "Graphical trestments of acid-base equilibria are convenient, and often the only possible solution to complex problems." There is no doubt that distribution diagrams are valuable in showing bow the relative proportions of various species in a system may vary with cbanging pH and the text abounds with these diagrams. On the other hand, the functions (Catznued a page A 8 6 )

..

A224

/

Journol of Chemical Education

book reviews whlich must be platted in arriving at a grr~phicalsolution yield no more informa t10n than is embodied in the original e q u a t10ns which describe a system, and unless grt:at pains and time are taken, the grapbicslI solutions yield considerably less precise r eiults than numerical solutions. I t is aho a fact that the equations for a polyP" >ticacid system, citing just one example, ctuIbe derived and solved using the numr!rical Newton-Raphson method fairly quickly having only a slide rule and pencil an d paper at hand. Furthermore, in this day and age of ready access in most labonitories to mini- and midi-digital comPuters, it would be folly not to devote some POrtion of a full term course on equilibria to the application of these valuable tools. A1,xorithms for use of highspeed computers arta remarkably straightforward and reduce to trivial proportions many problems wtlich are well beyond the scope of graphicalI methods. In spite of this shortcoming, the book does merit serious consideration for use in an elementary course an equilibrium. M m y different types of equilibrium situs, tioIns are described, and an instructor can en,ploy numerical solutions in class, if he SO desires.

DANIEL L. LEUSSING Ohio State University Columbus

The following titles are those of volumes in continuing series. Many of these series are fmilior to readers who are best served by prompt announennmt of the appearance of the new titles. The policy of THIS JOURNAJ, will be to publish full revinus only of inaugural volumes in nnu series.

welopmenlr in Applied ertrorcopy. Volume 78

Edited by E. L. Grove, Illinois Institute of Technology, Chicago, and Alfred J . Perkina, University of Illinois, Chicago. Plenum Press, New York, 1970. S e lected papers from the Seventh National Meeting of the Society for Applied Spectroscopy, held in Chicago, May 13-17, 1968. xi 291 pp. Figs. and tables. 16 X 23.5 cm. $12.50.

+

Contributors: Racquel 2. LeGeros, hn P. LeGeros, Otto R. Trautz, and Iward Klein; Conrad M. Phillippi; B. D. Brier; W. R. Feairheller and W. J. wiford; C . N. R. Rao and A. S. N. urthy; J. A. Koningstein; Dorothy S. tin and Albert B. Harvey; D. F. Burow; hn W. Cessels and Paul A. Wilks, Jr.; S. Herwnn, R. L. Levy, L. J. Leng, ~dA. A. Post; P. D. Klimstra and R. H. ble Jr.; Deniel A. Netsel; Milton I. %enberg; George Slomp; Robert T. Connor; Elizabeth R. McCdl; Braham orwick; P. A. Wilks, Jr., and J . W. ~ssels. (Continued on page A 8 8 )

A226

/

Journal o f Chemical Education

book reviews Applied Spectroscopy Reviews. Volume 3

Edited by Edward G. Brame Jr., E. I. du Pant de Nemours and Co., Wilmington, Delaware. Marcel Dekker, Inc., New York, 1970. xii 345 pp. Figs. and tables. 16 X 23.5 em. $17.50.

+

Catrihtors: K. R. Bhaskar; M. V. George; V. Kalysnaraman; C. Merritt, Jr.; Samuel Natelson; Frank S. Parker; John A. Perry; C. N. R. Rao; Masamichi Tsuboi: Anna M. Yoekum. Chemistry and Physics of Carbon. Volume 6

Edited by Philip L. Walker, Jr., Pennsylvania State University, University Park. Maroel Dekker, Inc., New York, 1970. x 354 pp. Figs. and tables. 16 X 23.5 cm. $23.50.

+

Catributors: N. N. Avgul; A. V. Kiselev; D. E. Kline; Jacques Maire; Jacques MBring; B. R. Puri; R. E. Taylor. The Determination of Organic Peroxides

R. M. Johnsa, Borough Polytechnic, London, and I. W. Siddipi, St. Mary's Hospitsl, London. Volume 4 of "Monographs in Organic Function$ Group Analysis." Pergmnon Press, Inc., New York, 1970. ix 119 pp. Figs. and tables. 16 X 21.5 cm. $6.75.

+

A228

/

lourno1 of Chemical Education

Electroanalylical Chemistry. Volume 4

MSssbauer Effect Mefhodology. Volume 5

Edited by Irwin J. Gwennan, New England Nuclear Corp., Boston. Plenum Press, New York, 1970. viii 278 pp. Figs. and tables. 16 X 23.5 om. $19.50.

+

Contributors: H. A. StAckler and H. Sano; J. G. Stevens snd L. H. Bowen; S. Chandrs and R. H. Herber; G. W. Dulaney and A. F. Clifford; G. K. Shenoy and S. L. Ruby; R. T. Mullen; R. M. Housley; T. A. Kitchens, P. P. Craig, and R. D. Taylor; D. Schroeer; A. Nath, M. P. Klein, W. Kiindig, and D. Lichtenstein; A. J. F. Boyle and G. J. Perlow; J. G. Mullen and R. C. Knsuer; C. L. Herzenberg; G. M. Kalvius, T. E. Katils, and 0. V. Lounasmaa. Kinetic Data on Gar Phase Unimolecular Reactons

Sidney W. Bason, Stanford Research Institute, Stanford, Cali., and H. Edward O'Neal, San Diego State College, California. National Bureau of Standards Publication NSRDS-NBS 21, issued February 1970. 645 pp. $7. (Order from the Superintendent of Documents, U.S. Government Printing Office, Washington, D. C. 20402, or loed U.S. Department of Commerce Field Offices ss SD Catalog No. Cl3.48:21; or from the Clearinghouse for Federal Scientific and Technical Information, Springfield, Va. 22151 as NSRDSNBS 29.)

Edited by Albn J. Bard, University of Texas, Austin. Marcel Dekker, Inc., New York, 1970. xii 327 pp. Figs. and tables. 16 X 23.5 cm. $18.75.

+

Contributors: F. C. Anson; Allen J. Bmd: A. T. Hubbard: K. S. V. Santhanrtm;'~anH. ~ l u ~ t e rMargaretha si Sluyters-Rebbach.

Advances in Physical Organic Chemistry. Volume 8

Edited by V.Gold, University of London Ac~demicPress, Inc., New York, 1970. x 425 pp. Figs. and tables. 16 X 23.5 om. 135s.

+

Catributors: J. E. Bennett; T. W. Bentley; Fulvio Cacace; Eleanor J. Fendler; J. H. Fendler; R. A. W. Johnstone; B. Mile; A. Thomas; B. Ward.

Advancer in Macromolecular Chemistry. Volume 2

Edited by Wallaee M. Pasika, Texas A and M University, College Station. Academic Press, Inc., New York, 1970. x 267 pp. Figs. and tables. 16 X 23.5 cm. 100s.

+

Contributors: J. C. Arthur, Jr.; A. Blumstein; B. Chu; H. L. Frisch; D. Klempner; M. M. Koton.