Physical Chemistry
Mmlin Paul, Harpur College, Endicott, New York. D. C. Heath and Co., Boston, 1962. x + 460 pp. Figs. and tables. 16.5 X 24 cm. $8.50.
BOOK
REVIEWS
Elements of Chemical Thermodynamics
L. K. Nash, Harvard University. Addison-We'esley Publishing Co., Inc., Reading, Massachusetts, 1962. ix 118 pp. Figs. and tables. 15 X 23 em. $1.75.
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This hook is intended t o introduce chemical thermodynamics to the student of freshman chemistry. Included are discussions of the three thermodynamic laws and their "ideal" rtpplications t o thermochemistry, phase and chemical equilibria, and colligative properties. Calculus is used sparingly, and the elements of differentiation and integration are discussedin an Appendix. Consequently, the material is appropriate for beginning students who are concurrently enrolled in the first semester calculus course. The subject development follows the usual path found in textbooks of physical chemistry and thermodynamics, hut the material has been carefully simplified and organized so as to be pelittable t o the beginning student. I t is clear that the author has used his sources well. To the initiate the exposition is lucid and smooth, although a t times one wonders if the author's refreshing style doesn't move too fast for the beginner. Fortunately the arguments whieh involve or lead t o chemical appliratitions take precedence over the rather unexciting gas expansions which fill many more advanced texts. It is very important in introducing an abstract subject at thislevel to convince thestudent that the subject is worth learning, and this the author seems t o have ac-
-Reviewed
complished. Less fortunate, in this reviewer's experience and opinion, is the uae of the Carnot cycle as a central pert of the second law development. Nevertheless, the author has been more successful than mast writers in answering the classic student question: What has the Carnot cycle got to do with chemistry? Minimizing and simplifying the mathematics of thermodynamics is s. difficult problem. I n a neat sidestep of the dilemma of explaining exact and inexact differentials, the author uses the same symbol (p) t o stand for both finite and infinitesimal quantities of hest. This works well until the temperature dependence of entropy is discussed and we are presented with the somewhat peculiar relation
require some explanation. The hook is remarkably free from errors; the only one obvious to this reviewer is in Fig. 26, where it is log z and not its negative whieh is plotted. Included are s set of problems which do not require calculus and an ample table of thermodynamic data. The book should he of considerable help in introducing an useful improvement to the b~ginningcourse. BRUCEH. MAHAN Uniuersity of California Berkeley
in This Issue
I,. K . Nash, Elements of Chemical Thermodynamics Martin Paul, Physical Chemistry Erie Hulehinsa, Physical Chemistry George H. Duffey, Physical Chemistry W. T. Elwell and J . A. F. Gidley, Atomic-Ahsorption Speetrophotometry Bdrge Rak, Elementary Introduction t o Molecular Spectra Gmdm M. Bawow, Introduction to Molecular Spectroscopy Gregory R. Choppzn, Experimental Nuclear Chemistry Stamley Raimes, The Wave Mechanics of Electrons in Metals E. G. E. Hawkins, Organic Peroxides: Their Formation and Reactions Cha~lesTanford, Physical Chemistry of Macromolecules Erich Heftmann, editor, Chromatography Joseph 5.Amino, Clinical Chemistry: Principles and Procedures Robert Gould, editor, Borax to Boranes Arthur I. Vogel, A TexGBook of Quantitative Inorganic Analysis Including Element.ary Instrumental Analysis Herhe71 C . B m m , Hydrohoration
To the array of recently published physical chemistry texts, Martin Paul has added a book of modest distinction. It lies between the extremes of rigorous dedication to the modem and the oppasite adherence t o the classical. hut is closer t o the latter. The presentation is fresh and intuitive. Paul's "solution" to the difficult problem of what t o leave out is t o assume that atomic structure, X-ray crystallography, ionic equilibria and nuclear chemistry have now pervaded the introductory course in general chemistry and may appropriately be omitted. His general plan is to demonstrate, whenever possible, the power of the thermodynamic approach. This is done in a pleasingly informal way. Kinetic molecular methods are used frequently, hut these do not reach the "statistical mechanics" level. Thus his second chapter, the Conservation uf Energy, moves in a natural way to a study of the gaseous statute including the ides, of using spectral information to evaluate energy states. The coverage of gas viscosity and thermal conductivity is relatively complete. Here as elsewhere in this book there are descrip tions of important experimental methods. The problems appear t o be very well chosen. Many of them are tsken directly from the research literature. Ansm-ers are given for representative problems, and important examples are worked in the body of each chapter. The fifth cha,pt,er covers both the liquid and the solid state using the common theme of intermolecular farces. This joint coverage is preferable to the complete omission of thesc topics. Thermochemistry comcs next. The development is rather extensive, including, for example, ionic enthalpies of formation and theoretical flame temperatures. The thermodynamic properties of gases and the second law of thermodynamics are developed concisely without extensive elahoration. Vapor pressure is the theme of the next two chapters ~ h i c h deal with phase transitions and then with properties of solutions. Free energy is introduced a t this point, long after entropy. The chapter on Chemical Equilibrium begins with a conventional "law of mass action" development of the equilibrium constant. Thisis, of course, followed by a more rigorous thermodynamic treatment and ultimately reference is made to the use of molecular statitistics. The coverage of Equilibrium far Nonideal Solutions is adequate, but not extensive. The phase rule is illustrated with numerous systems of practical importance, hut with little use of thermodynamics. The treatment of Rates and Mechanisms of Chemical Reaction is eonventionsl excent for the fsirlv comdete considera-
Volume 40, Number 1 , January 1963
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51
The concluding chapter, Electroehemical Processes, covers both conduction and electromotive force. The hook is outstanding for its concise nesa and freedom from error. It is the feeling of the reviewer that the style, level of presentation and range of topics make this text especially worthy of consideration for a junior or even sophomore level course far students taking another chemistry course simultaneously and having calculus and general physics ss prerequisites. Superior advanced undergraduates, no doubt, would find i t less stimulatine than texts that stress the more
and molecular structure may he its greatest weakness especially for curricula that do not include a course in atomic or modern physics. It is definitely not a text in "mathematical chemistry," but the attention paid t o mathematics is adequate. The author is to be cangratulated for a realistic and workmanlike job of discussing a rather traditional selection of material in an effective manner.
W. H. HALL Bowling Green State University Bowling Gem, Ohio
Physical Chemistry
Eric Hutchinson, Stanford University, Stanford, California. W. B. Saunders 647 pp. Ca., Philadelphia, 1962. x Figs. and tables. 17.5 X 25.5 cm.
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$10.
Another very good entry has been added to the rather rapidly growing field of undergraduate physical chemistry tenthooks. This hook follows the trend, evident in several other recent hooks covering this area, of using a rigorous and sophisticated approach to the subject matter. Particularly noteworthy in this respect is the chapter on liquid solutions in which quantitative development of topics is used to a much greater extent than one is accustomed t o find in undergraduate treatment of solutions. The author does not lose sight of the value of descriptive and interpretive approaches, and prudently intermingles these with the mathematical parts. Furthermore, the experimental side of physical chemistry is presented with detailed descriptions of experimental measurements of many important parameters. Thermodynamics and its application to gases, liquids, solutions, heterogeneous systems, and electrochemical phenomena comprises the bulk of the material in the first half of the hook. Chemical kinetics, atomic and molecular structure, solid state, macromolecules as well as a larger than usual port,ion of colloid and surface chemistry are covered in the latter part of t,he book. The last ehaoter is a brief hut usdul introdurtim t < , t ~ 1 i r t i cmerh.irurs. d S ~ t d l l yb l ~ e r . ~ ain t the i,rmk is a n y twntmcnt i d tlterrnc,ct~t.!ntistn.. S u d w r d w u istry is also not treated.
52
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Journal of Chemical Education
An undergraduate physical chemistry textbook is, by necessity, an abridgement of the important developments of classical and modern physico-chemical research. This reviewer feels, however, that the omission of certain topics, such as thermochemistry, is unfortunate. In the chapter on the shape and size of molecules no mention is made of the important contributions of NMR to this srea. The difference between path-dependent functions and point functions is another topic, well worth mentioning, which is excluded. The virtual absence of references in this hook accents these omissions. The problems a t the end of each chapter are good and, in certain instances, quite challenging. An instructor's guide is furnished; i t gives answers to problems m d the method of solution for some. Several of the sets have many problems taken from the literature, an important factor in ~ravidinga sense of reality for the person attempting them. Very few example problems are worked out in the text. This will likely create difficulties for an average student, for the gap betwcen some of thwabstract sections of the text and the problema is wide indeed. The illustrations and figures are done with precision and clarity throughout this work. They complement the material in the tentvery well. Errors in the hook are infrequent. Care should be exercised, as with any other hook, in taking d l equations a t face value. Far example, the kinetic theory i s an apformulaon page 49 far n ~ > ~ . only proximation as one can see by integration of the equation preceding i t in the text. The a.pproximation voiced by this equation is valid for Eo>>nRB (note also the omission of no from the numerator of the equation and the omission of the subscript from the E's). This equation may confuse some users of the hook because its approximate nature is overlooked. This is s. hook well worth an examin* tion by a. teacher of physical chemistry. Despite some omissions and a few uneven spots, itis avery good textbook.
treatment the courae begins with a study of quantum mechanics, molecular structure, etc., and then develops and rationalizes macroscopic physical chemistry on the basis of the mirroscopic properties of matter. As one of the first American texts t o use this %on-classical" approach this book is most welcome. The hook starts with a discussion of the structure of crystals and then follow ehapters on atomic and subatomic particles, wave theory and its application t o quantum mechanics, vibrational and rotational energy levels in molecules, electronic states in atoms, and basic valence theory. After this, the classical subjects of thermadynamics, chemical and physical equilihrium, activity concepts, and electrochemistry are treated. Finally the book closes with a discussion of kinetics, catalysis, and photochemistry. The organization of the hook is good with subjects following in a logical and very "presentable" order. The only exception that this reviewer would make is that statistical mechanics should he treated in a separate chapter instead of being divided between Chapters 7 and 9. This hook has the advantages of the %an-classical approach" in that macroscopic properties of matter can be related to molecular and atomic properties without the background digressions necessary in the "classical" approach. Further, the undergraduate is quickly brought to the point where he can read modern phydieal chemical research results with some understanding. Strong points in the hook that merit special mention are: the inclusion in Chapter 1 of s section on vector analysis, the treatment of the harmonic oscillator and the descriptian of vibration-rotation spectra, the discussion of the properties of condensed phases, and the treatment of chemical kinetics. The greatest weakness of the hook is in its approach t o quantum meehrtnics. The author develops quantum mechanics from wave theory, that is, the quantum mechani d wave function for a hound article is
MORLEYRUSSELL Michigan State Universitg East Lansing
Physical Chemistry George H. Duffeg, South Dakota State College, Broakings. McGraw-Hill Book Co., Inc., New York, 1962. x 527 pp. Figs. and tables. 16 X 23.5 em. $5.75.
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It is inevitable that the next few years will see much discussion by teachers of undergraduate physical chemistry about how this course should be taught. The "classicd" approach t o this subject has usually begun with thermodynamics and other macroscopic properties of matter and has treated quantum mechanics, molecular structure, spectroscopy, and s t a t i s t i d mechanics a t the end of the course as time Mare recently, however, permitted. physical chemists have been experimenting with a %on-classical" approach. I n this
A better approach might he the postula tional approach in which the fundamental ideas of quantum mechanics are introduced as a series of postulates. Analogies can still be drawn fmm wave theory, hut conceptually difficult discussions like the treatment of selection rules in rotation and vibration spectra in Chapter 4 could he avoided. In the absence of a lot of explanatory materid in lecture, this reviewer feels that the averaee undereradu-
I n summary, this reviewer feels that this hook would make a good, hut difficult, text in an undergraduate physical chemistry course for instructor8 who want t o exoeriment with the %on-clessicd" ao-
(Continued on page A64)
