Thermodynamics of solids (Swalin, Richard A.)

From now on, the infidels can be referred to this inexpensive paperback for additional reading. The system of atomic weights is dis- cussed in some de...
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is currently a matter of argument between the reviewer and the author. It is my opinion that it cannot be so corrected. The above comments are meant as description, not criticism, for I believe that the author's aim of producing a text has been well executed. Many problems are given which will increase the usefulness of JAMES W. COBBLE the book for self study. I recommend the P u ~ d u eUniversity book highly, both for this purpose, and as Lafayette, Indiana a text.

a dictionary can be used intelligently by a non-reader. Certainly research workers in the topics covered will find this volume useful, and it will be a useful addition to even modest libraries. I t is, in many ways, the inorganic equivalent to the Annual Reviews of Physical Chemistry.

ROBERTM. MAZO California Institute of Technology Pasadena Nonequilibrium Thermodynamics: A Phenomenological Theory of l r r a versible Processes in Fluid Systems

Donald D. Fitts, University of Pennsylvania, Philadelphia. McGraw-Hill Book Co., Inc., New York, 1962. xviii 173 pp. 16 X 24 cm. 57.95.

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The modern developments in irreversible thermodynamics date from the fundamental papers of Onsager in 1931, and the subject emerged as a coherent discipline in the dissertation of Prigogine, which was published as a book in 1947. Several other monographs have since a p peared, and chapters on irreversible thermodynamics have heen incorporated into recent editions of several well-known texts on clsasical thermodynamics. The subject is of great importance for physical chemistry and related disciplines. Yet it is rarely taught in universities. Perhaps one reason for this is that none of the existing literature is really suitahle for use as a text. The volume under review is a successful attempt to deviate this situation. The subject matter is the phenomenological macroscopic theory of thermal conduction, diffusion, thermal diffusion, electrokinetic phenomena, chemical reactions, etc. in fluid systems. The field of thermalelectric-magnetic effects in solids is com~ l e t e l y omitted. Although irreversible thermodynamics has had its most striking successes in this field, its omission is not of too much conssquence for chemists. On the other hand, the study of chemical reactions by the methods of irreversible thermodynamics yields only very meagre results. The subject is developed in a rather formal manner, with heavy emphasis being given to the mathemstical manipulations necessary to go from equation (N) to equation ( N + l ) ; this should enhance the book's value rts a. text. Brief mention of experimental results is made throughout the book, but only in connection with isathermal diffusion is a detailed discussion of experiments given. The connection of the phenomenological theory (a jargon term common in the literature of the subject) with the microscopic molecular processes which underlie irreversible phenomena. is only mentioned in passing. A good understanding of equilibrium thermodynamics is desirable before undertaking the study of this volume. The theory is carefully and thoroughly worked out. The only exception to this is Section 6 2 , dealing with the rate of cooling of a fluid in a magnetic field, which contains, at the least, a serious mathematical error. Whether this error can be corrected in such a way as to obtain a proper theory

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Journal o f Chemical Education

The Mole Concept in Chemistry

William F. Kieffm, College of Wooster, Wooster, Ohio. Selected Topics in Modern Chemistry Series. Reinhold Publishimg C o p , New York, 1962. ix 118 pp. 13 X 19 cm. $1.95.

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The third volume in the new paperback series, "Selected Topics in Modem Chemistry," puts together and organizes as much information as possible under one unifying theme, the mole concept. Nine chapters, averaging 13 pages each, examine from many angles the central idea that "the male is Avogadro's Number of chemical units being eonsidered." Avogadro's Number of molecules is a mole of molecules, Avogadro's Number of atoms is a mole of atoms, and Avogadro's Number of ions is a m d e of ions. The student who thoughtfully reads Kieffer's little hook will be thinking of the faraday as a mole of electrons and of the einstein as a mole of quanta. What is Avogadro's Number? Kieffer begins at the beginning and discusses the concept of atomic weights. Untold thousands of freshmen have had it said to them thrtt if the weight of atom A is twice thrtt of atom B, then two pounds of A will contain the same number of atoms as one pound of B, two grams of A will contain the same number of atoms as one gram of B, and so on. Some of them never got the message. From now on, the infidels can be referred to this inexpensive paperback for additional reading. The system of atomic weights is discussed in some detail, from the first scale proposed by ~ a l t o nto the one adopted by international agreement in 1961. The magnitude of Avogadro's Number depends not only on the choice of atomic weight scale but also on the choice of weight units. "Convention has established the gram as the unit of weight for molar amounts." Except for merely mentioning that chemical engineers frequently use the poundmole, Kieffer gives no ground and redefines the mole as the amount of substanoe containing the same number of chemical units as there me atom8 in exactly 12 grams of lac. The connection between the properties of gases and numbers of molecules dates back to Avogadro's explanstion (1811) of Gay Lussac's Law of Combining Gas Volumes. The kinetic-molecular

theory developed in the nineteenth century to the point that Avogdro's brilliant guess was confirmed by deduction. Two useful results are discussed here: the estimation of the weight of one mole of gas from PVT data; and the identification of per cent by volume with mole per cent in gaseous mixtures, which puts meat on the bones of Dalton's Law of Partial Pressures. The nineteenth century chaos with regard to atomic weights ended with the acceptance of Cannizzaro's Principle. The book shows how correct atomic weights lead to correct empirical formulas and how knowledge of the weight of a mole of a substance Leads to its molecular formula. For solving problems based on chemical equations, the author makes a pitch for the mole approach. The student whp plugs numbers into an "is-to" proportion "owes himself the full understanding of why he seta up the numbers he does." Raoult's Law is applied to dilute solutions containing non-volstile solutes, and then colli~ative~ronerties andmolalitv . . are discussed: The discussion of chemical equivalence makes a good ease for abandoning the conventional designation of "gram equivalent weight" and the correlated "normality" scale of concentration. The coefficients for any reaction must be established by experiment, not by mere inepeotion of formulas. Ambiguity is avoided by referring to moles and molarity. An equally good case is made for using the term "molar conductance" rather than "equivalent conductance!' A separate chapter is devoted to a discussion of four methods for determining Avogadro's Number, chosen for their simplicity and directness. In the h a 1 chapter the author deals with "moleculm" quantities: the volume of a single atom, the number of molecules in 1.MX) cm5, etc. This book contains 61 exceptiondy well-chosen problems. Most of them are solved. Many of them contain original data, with literature citations. There are numerous other references to journal articles suitable far freshman redera. Most of the material in this book is so important that it ought not be omitted from textboob. Since much of it is not found where it ought to be, this book should be welcomed as a useful supplement to many freshman texts. LAWRENCE P. EBLIN Ohio University Athens, Ohio

Thermodynamics of Solids

Richard A. Swalin, University of Minnesota, Minneapolis. John Wiley & Sons, Inc., New York, 1962. ix 343 pp. Figs. and tables. 15.5 X 23.5 em. $12.50.

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According to the author this book has evolvedfrom "lectures presented to under(Continued a page A6841

BOOK REVIEWS graduate and graduate students in t h e arcs of material science," and has heen "written for t h e reader who has had exposure t o a formal course in thermodynamics." The first third of t h e hook is used for a review of basic chemical thermodynamics. This material is eonsiderod partly from bhr statistical point of view. Most of i t can be found in clearer form clscwhere, hut it is a useful collection of topics. While much elementary thcrmodynamics is repeated, important applications t o solids are not given. For example, what do the thermodynamic equations look like when applied t o nonisotropic solids7 The second third of the book deals

mostly with t h e thrrmod,ynamics of solid ~olutions. Effective use is made of t h e "quasichemical model," i s . , neighboring a t o m form bonds. Somp of this material would be uscful for a teacher of physical chemistry who is looking for unusual and practical examples of thermodynamic methods. There is s. 3:3-p,age chaptw on the thermodynamics of interfaces which mentions a variety of topics. The (:ihbs equation is derived but no use is found Ear i t and i t is not mentioned in th? indrx. A good selection of numerical d8t.a on interfacial energies is provided. In this chapter also, however, important t,opics have heen omitted, e. g., methods for experimentally messuring the surfncc t ~ n s i a nof a solid. The last third of t,he haok cliscnsses point

defects in clcmontd crystals and in 1,innry compounds. This material comprises a worthwhile introduction t o the subject, but i t is not always presented in the clearwt fashion. I t is encouraging t o see notation of t h a t t h e author adopts t h ~ Krogrr and Vink, hut he does not explain with examples the natation for charged defects, often a source of difficulty t,o the heginner. Diffusion in oxidea is discussed but t h e aut,hor sometimes confuses chemical diffusion with tracer diffusion, and misses t h r opportunity of exploring bhis import,ant distinction. My conchmion is t h a t this hook a d d he of nse in a course similar t o t h a t irom which i t arose, with an experienced teacher on hand toexplain and amplify the difficult points. I t is less soitshlp for self study hy sn undergraduate or beginning graduate student, because few topics are developed with really adequate care and detail. A library copy would he ~vorthwhile for teachers and students of chemist r y a t t h e undergraduate and graduate level. The hook would not serve as a reference n a r k on "Thermodynamics of Solidsn-a work which is still lacking in any language.

WALTER J. >'I.IOORE Indiana University Rloorninglon

Introduction t o Chemical Instrumentation: Electronic a n d Operotions

Signals

Edward J . Bair, Indiana University, Rloomington. McGraw-Hill Book Co., Inc., New York, 1963. viii :34O pp. Figs. and tables. 16 X 24 cm. $10.75.

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This book would be an excellent text for a course in chemical instrumentation nt the senior level in collcge or graduate school. The sub-title, "Electronic Signals and Operations," is perhaps more descriptive of the author's purpose. The aext is woven about the hasis for all instrumcntation, the signal. The haok begins x i t h a short, descripbive chapter on the mathematical analysis of s signal. This appears a t first to be a lonely chapter hut i t is used later in the book. I n the next rather long chapter ( 1 18 pages) the author treats the sources of chemical signals. This is quite extensive including all varieties of radiation from nuclear magnetic resonsnee t o radioactivity and clectrochernistry, irom dielectric measurements t o polarography. The third chapter explains the operation of the components which are basic t o electronic instrumentation. Resistance, capacitance, reactance, vacuum tubes, gas filled tuhes and semieond,rctor dcvices are covered. As a specific applicatian and review of Chapter Three, Chapter Four is ashort chapter devoted to the pract,ical theory of the oscilloscope. The next chapter is devoted to circuits \$-hieh will form pulses, trigger, clip, and gate which are called nonlinear operations. These techniques were new t o this reviewer and the concluding portion oi the chapt,er which suggests nay8 for using these dwiers for chemical measurements was most, intriguing. The sixth chapter introducrs tho more common or small signal trmt.

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Journal o f Chemical Education