BOOK REVIEWS Chapter 6 concludes the hook with a presentation of the mechanical theory of chemical reactions. The various theories as to how 8. particle escapes from a potcntial minimum including the "shuttling action" of Brownian motion and the transition state approach are discussed. Then a classical approach, which adopts the quantum mechanical conoept of phonons, is presented. The case of the particle moving in n potential field with two minima, is also discussed. Using his theory the author estimates the rate constant for a simplified model of a chemical reaction. EDWARD 8. AMIB University of Arkansas Fayetfeville
Techniques of Polymer Characterization
Edited by P. W. A l l a . Academic Press, Inc., New York, 1959. xiv 256 pp. Figs. and table^. 15 X 22.5 cm. $9.50.
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The field of polymer chemistry has expanded so rapidly over such a short time that it is a characteristic of many workers in it that they have little or no formal training in their specialty. Rather, they have either picked it up as an apprentice by working in a polymer research laboratory or have developed their techniques by themselves with the help of the literature. "Techniques of Polymer Characterization" is directed primarily toward this lest group. As the title indicates, it is devoted to the study of the properties of high polymers as they show up in dilute solutions.
These are the properties af the polymer molecules themselves and not, in general, cooperative properties such as one finds, e.g., in crystallites in solid polymers. The subjects covered are: fraotionation, osmometry, miscellsneous number average molecular weight determinations, light scattering, viscometry, end-group analysis, and bbek and graft copolymer characterization. The approach is a practical one. The theom for each section is sketched enough to indicate the background for the metho>, hut no attemot is made to eive - fine details. On thr othrr 1l:tnd the twhuiquts them~ r l v r as n di?cursrd rxtr.nsivvlv itwl pnvlic~ ul.tr cure is t n k v ~to point mtt p l . c w wlwm one might make errors inadvertently and where especial pains must he taken. One often feels that the attitude is that of s. master talking to his apprentice. In addition, there is copious reference to the original literature. Since each chapter is written by a different author there is some variation in the approach hut none of the chapten could he called inadequate. From the point of view of subject matter, one might wish that somewhat more sprtce had been spent on light mattering, that polyelectrolyte behavior had been included to a greater extent, and that the small section on the effect of rate of shear on viscosity measurements had been expanded. From the point of view of approach, occasionally the experts were a little overenthusiastic. For example, after indicating that one cannot obtain homogeneous fractions from a heterogenous polymer, the author speaks (p. 58) of cases where nearly homogeneous fractions may be used to establish a molecular weight distribution curve. These are all relatively minor objections, however, and should not conceal the fact that this will he a. very useful hook, bath for the novice who wants to got a start in the field and for the old hand who wants to brush up on recent developments. The present hook is complemented in some respects by the recently published "Number Average Molecular Weights" hy Bonnar, Dimhst, and Stross (Interscience, 1958). In that hook considerable detail is given in showing how actual calculations w e carried out to convert experimental data into molecular charaoteristics. The present work however is muoh more com~letein its discussion of the exverirncnrnl nwthodu t11t.unn~lvt~s :xrd, oir,wrcc.. also covers inethod5 m l n,lntwl u, nl~n,lwr :xvrmyr rnc~lrcul:rrwrightc. ~
T n o ~ h E. s FERINQTON The College of Wooster Woosler,Ohio Liquids and Liquid Mixtures
J. S. Rowlinsa, Senior Lecturer in Chemistry, The University of Mancheater. Butterworths Scientifio Publications. Academic Press. Inc.. New York. 1959.' ix 360 pp. Figs. and tahles: 15 22 cm. $12.
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In the past the theoretical and experimental study of the thermodynamic hehavior of liquid mixtures has often been separated from the study of pure liquids. (Continued a page A854)
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lournal of Chemical Education
BOOK REVIEWS There have existed also artificial internal divisions in each of these fields of study. This hook undertakes the task of bringing together these previously separated fields and presenting a unified discussion of the thermodynemie properties of liquids. The first part (241 pp.) of the hook (360 pp.) describes the equilibrium properties of pure liquids and liquid mixtures. Colligative properties of the ideal dilute solution, polymer solutions, or liquid surfaces are not covered. The description makes use of clsssical thermodynamics together with a critical disouasion of experimental data and methods for determining and calculating thefie dsts. The last part (107 up.) of the hook is a n account of the statistical thermodynamics of fluids and fluid mixtures; the experimental rcsults in the first part of the book are interpreted in so far as pos~iblea t present hv molecular t,heory. The first t,hroe chapters are devoted to pore liquids. Chapter 1 defines in general terms what is meant hy the expression "liquid state." Chapter 2 describes the thermodynamic properties of pure liquids; thermodynamic formulas, experimental methods, and experimental data for the thermodynamic properties are presented in this description. Experimental results and thennodynamic theory far the critical state are discussed in Chapter 3. The next three chapters present thermodynamic theory and selected experimental data for binary liquid mixtures. Chapter 1 discusses binary mixtures of "~implc" liquids (liquids composed of molecules of such type that the intermolecular forces do not depart greatly from spherical symmetry). Chapter 5 consider8 binary mixtures of "eomplex" liquids. Chapter 6 is s n interesting presentationofthethermodynamic behavior of hinary liquid mixtures a t high pressure; aseotropy and c r i e iesl points of mixtures are the principal suhjects of discussion. The last three chapters of the baok describe the application of molceular t h e o ~ to the equilibrium properties of liquids. Intcrmolcculnr forces are discussed in Chsptor 7. Chapters 8 and !I present tho recent developments which unite the statistical thermodynamic treatment of pure fluids and fluid mixtures. Of particular value in these two chapters is the disoussion of the prineipleofcorrespondingstates. The literature is fillcd with erroneous a& tempts st the application of this principle to pure suhstnnce~andmixt~~res; itishoped that the lucid presentation in thifi baok will receive the attention deserved. It is evident that care has been used in preparing tables of experimental data. in this hook; the author states that most of the tables were calculated anew from the original literature. A large list of references is given a t the end of each ohaptpter.
JAMES R. BROCR The University of Tezas Asstin
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Journal o f Chemical Education
