Elemenls of Slatirlical Thermodynamics
Leonard K . Nash, Harvard University, Cambridge. Addison-Wesley Publishing Ca., Reading, Mass., 1968. viii 128 pp. 52.50.
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Leonard Nash has a remarkable and rare ability to orient his teaching toward a single general and fundamental concept. I n teaching freshman chemistry, this concept is the position of chemical equilibrium. I n "Elements of Chemical Thermodynamics" (ECT), he pared away all the irrelevant and tangential parts of thermodynamics, the elegance of those parts notwithstanding, and led the bright h u t ignorant freshmen as directly as possible from the First and Second Laws of Thermodynamics to the thermodynamic derivation of the equilibrium constant. He did this clearly, gracefully, and with great physical insieht. "Elements of Statistical Thermodynamics" (EST) is the natural successor to ECT. I t goes one step deeper into the problem, to develop an understanding of equilibrium a t a microscopic level. This volume is almost as successful as the earlier text. I felt thst the new hook lacks a little of the grace and elegance of its predecessor. On the other hand, when "Elements of Chemical Thermodynamics" was written, thermodynsmics was already a well-established part of several freshman courses; many of us thought we had a rather clear idea of what was hard and what was easy, of where one could go rapidly and where to be slaw. The natural organization of the material was perhaps becoming clear to us all. Teaching statistical mechanics to freshmen is a. different matter. Very few people have even tried to present it s t the elementary level in any way approaching the depth thst Nash does. He clearly developed his orgsniz* tion during the three years to which his preface refers and found from experience what parts were hard or easy far his students. The result seems to me to be a bit labored in a few spots and perhaps a bit terse in others. Some of the concepts like those of an ensemble, of weak coupling, and of the problem of symmetry in homonuclear diatomics are treated with a bit less precision than the thermodynamic concepts of the first book. On the whole, the new book has the same strong direction and ohemied flavor as ECT. Like its predecessor, it is a pleasure to read. The treatment moves from mathematical tools to physical models and phenomenological equations, then to specific chemical examples and finally to the kind of generalization that we associate with physical insight. The g o d is clear and explicit: why, in terms of the mieroacopic properties of reactants and produck, does a particular chemical equilibrium lie where it does? By taking this viewpoint, rather than simply asking his students to learn how to calculate equilibrium constants from partition functions, Nash does a very important thing. He establishes, a t the freshman leuel, the bridge between the quantum-theoretical treatment of molecular structure that has so dominated high school and first-year college chemistry, and the macroscopic world of descrip-
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Journal of Chemical Education
tive chemistry. The other freshman-level treatments of stat,istical mechanics with which I am familiar (and there are certainly some that I haven't examined) fall far short of making this bridge. They simply don't go deeply enough into the subject to eslabliah the relations between microscopic energy levels and thermodynamic quantities, the state variables and heat capacities. As a result, other treatments cannot get to the calculations and, even more important, to the order-of-magnitude estimates that constitute the connection between the micro and macro worlds. They can only make imprecise qualitative mguments to get these quantities. And i t has been my experience, especially with freshmen, that the greatest source of confusion and misunderstanding among chemistry students is imprecise ideas of fundamental concepts. One needs a treatment a t least rtt the level of "Elements of Statistical Ttiermodynamics" t o show what really makes molecules dissaciate, or how energy and entropy eontribute to an equilibrium constant, how these contributions change with temperature, and how they originate in the properties of molecules. Certain parts of the book particularly pleased me; I liked the discussions of microstate and configuration, and the derivation of the equation of state of the ideal gas. I was sorry there was not more discussion of equat,ions of state and their roles in thermodynamics and statistical mechanics. The problems a t the end of the book are verv much in Naqh's stvle~" ingenious, challenging, and represent,ative of all facets of the material, from derivat,ions to explicit molecular calculations. I would like very much to see serious statistical mechanics incorporated into the earliest parts of the normal chemistry curriculum. American chemists have tended to slight this subject since the days of Gihbs. I n so doing, we avoid a subject that ought to be a keystone in the basic chemical curriculum. The fact that thermodynamics is older or that descriptive chemistry (meaning memorization with the help of the periodic table) is supposed to give us intuition, is no excuse for avoidi n g t h e issue. da dam en tally, to understand chemical phenomena quantitatively in terms of molecular properties, we must use statistical thermodynamics. And "Elements of Statistical Thermodynamics" is a very good place to start.
in the number of preparations that are short, simple, and safe enough for use in general or inorganic chemistry laboratory courses and a corresponding increase in the number of cpmplicated preparations requiring elaborate equipment and safety precautions as well as excessive expenditures of time. Emphasis has shifted from relatively stable ionic compounds of the metals to more unstable orgsnome:allics and covalent eompounds of the nonmetals. "Inorganic Syntheses," in its last half dozen volumes, has faithfully reflected this trend. I n the vernscular, the series shows "where the action is." Consequently, instructors of lower level courses with iqexperieneed students and limited facilities should he warned that they will not fin3 here many experiments suitable for their needs. I n line with the increasing complexity mentioned above, the starting materials for a. number of the ~ r e ~ a r a t , i o nins this volume are rtctuallv
involve elaborate apparatus, and the praductr or starting materials are toxic, corrosive, flammable, explosive, p y r y phoric, hygroscopic, or sensitive t o aw or moisture (safet,y precautions, as in previous volumes, are prominently provided). Inasmuch as "Inorganic Syntheses" is not intended primarily for instructional use, these deficiencies should not be construed as criticism of what is undoubtedly a. significant contribution to a most useful series. The present volume contains 42 contribution~ which describe 92 diversified compounds. The general organization of the series is discussed in previous reviews [See 3. CHGM.EDUC.,38, A552 (1961); 40, A530 (1963); 44, A354, 624 (1967); 45, A436 (1968)l. The former pract,ice of dividing the book into chapters hased upon the Mendeleev periodic elapsification has been abandoned. Volume 11 consists of six chapters dealing with areas of considerable current research interest. The first and shortest chapter (14 pp.) is devoted to the high-temperature syndhesis of very pure solid-state compounds, which are becoming increasingly important for theoretical studies and industrial applications. The technique of high temperature chemical t,ransport is employed to prepare single crystals of CdG a A and Fer04, but few students would R. STEPHENBERRY be patient enough to wait the ten days University of Chicago required t,o grow crystals of the lst,ter Chicago, Illinois compound. As in Volumes 9 and 10, an entire section (Chapter 2, 30 pp.) is allot,ted to boron-hydrogen compounds. The third and longest chapter (64 pp.), Inorganic Syntheses, Volume 11 the one which includes mast of the preparations simple enough for instructional William L. Jolly, Editor-in-Chief, Uniuse, describes those perennial favorites versity of California, Berkeley. McGraw-Hill Book Co., New York, 1968. of the inorganic laboratory course-the coordination compounds. Several of 231 pp. Figs. 16 X 23.5 cm. xii these compounds, e.g., [Cr(en)s] [Ni$10.50. (CN)sI and K,[Mo(CN)sI, exhibit unI n the last few decades, synthetic inusual coordination numbers. I n this organic chemistry, like the world in which sect,ion also, ruthenium, the last of the it functions, is becoming more complex, platinum metals to be included in "Insophisticated, and dangerous. Comparorganic Syntheses,'' makes its debut with ison of the latest volume in this wella versatile intermediate, K,[Ru2Cho].known series withvolumes publi~hedin the H,O. 1930's and 1940's reveals a sharp decrease (Continued on page A 4 4 ~
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book reviews
trainine of ahemists has heen deficient
The fourth chapter (17 pp.), entirely the contribution of Editor-in-Chief William L. Jolly, presents a new general procedure for a simplified approach t,o organometallic synthesis based upon the deprotonation of weak acids by pot&+ sium hydroxide. The fifth (25 pp.) and sixth (56 pp.) chapters deal with fluorine compounds and miscellaneous nonmetallic compounds, respectively. The latter includes two compounds of the noble (formerly inert) g.as xenon. I n keeping with the emphasis on syntheses that are "applieahle to s. variety of related compounds," an unusually large number of general methods are given. Preparations possibly simple enough for use in undergraduate courses might include lattice-stabilized complex ions, K4[Mo(CN)8], K3Mn04 ("magnetically pure" and free of COS), "cohaloximes," hexacoordinate complexes of bis(2,4pentanedionato)cobalt(II), ferrocene, nickelocene, and square planar dichloropalladium(I1) complexes. Unusual oxidation states, which can always be depended upon to add spice to inorganic laboratory courses, are well represented. A variety of preparative techniques are employed, such as the use of nonaqueous solvents; gas, thin-layer, and column chromatography; ion exchange; sealed tubes; vacuum systems; dry boxes; controlled inert atmospheres; low or high temperatnres; powerful reducing agents; high pl.essure fluorination; halide exchange reactions; high temperature chemical transport. reactions; and the Grignard reaction. A change in policy that t,his reviewer has called for in previous reviews has been made, but. it may not be obvious to the casual reader. Contributors and checkers are now provided with proofs of their contributions, a procedure that should go a long way toward reducing errors that have occasiandly crept into earlier volumes. Unfortunat,ely, although the series is considered a journal in book form, reprints a t r e still not provided. h i d e from this minor complaint, the volume is highly recommended as providing reproducible methods far the synthesis of a large number of interesting compounds. Dr. Jolly deserves our spccia1 thanks for his yeoman service as contributor and checker a3 well Editorin-Chief.
psendo-scientific models whenever an explanation is needed t o account for some magnetic property. To get out of the "dark ages" has usually required more physics m d exposure t o qoantnm mechanics than the average chemist has been willing to invest in. Dr. McMillan has written a book intended to fill t,his deficiency with ease and mbstance. A trinitsrian division is used to present the theory, the measurement of magnetic susceptibilities and electron paramagnetic resonance. I n the theory section magnetic polarization, vector models of atoms and molecules, the theory of magnetic ~usceptibilities,thermodynamics of magnetism~,and the symmetry of molecules and cry&& is offered in n hundred pages. I t is obvious that brevity is needed, and mrgery is required to nccomplish t,he task. To this reviewer, it is clear that the author has accomplished his goal t,o write a hook "not intended for specialists"; hut "for chemists doing research in other fields and for chemistry students." The sections on magnetic susceptibility and electron paramagnetic resonance measurements are presented with an emphnsis on solid^. Much detail is given and even hint,s on techniques based on the a.ut,hor's experience are given. The hook concludes with a number of appendices containing the tahles usually expected in this type of hook such as atom configurations and terms, magnet,ir moment,s and the inevitable character tables of the single groups. The drawings arc clear and well done and contribute to the presentation. Cert,ainly this book ought t o be considered as part of m y advanced inol; ganir chemistry course a?a source texr. PAULB. DOHAIN Bmndeis TJnivprsity Wallham, Mass. 09164 Practical Inorganic Chemistry G. Pass and H . Sutcliffe, both of the University of Salford, England. Barnes & Noble, Inc., New York, 1968. xvi +225 pp. Figs. and tables. 15 X 22 cm. $6.50.
At double the price this book represents money well spent by any practicing inorganic chemist or student of chemistry. The authors have succeeded in their stated g o d (the preface): ". . . we have attempted to emphasize the relationship G e o ~ ~B.l i KAUFFMAN between theory and practice." Physically California Slate College the hook is well illustrated and well built. h a n o , Calif. 93788 This is a n excellent hook for use in a senior or beginning graduate level course in Inorganic Preparations. It can also be Electron Paramagnetism used by the professional chemist as a day-to-day reference to relate theoretical Juan A . McMillan, Argonne National and laboratory discussions in comparative Laboratory. Reinhold Book Carp. (a chemistry. The student will not be oversubsidiary of Chapman-Reinhold, Inc.), helped if i t he used in a preparations 228 New York, March, 1968. xi course, and the professional chemist will pp. Figs. and tables. 15.5 X 23.5 be greatly aided by the suggestions and em. $14.50. the continuity which he will find thereinespecially if he is dealing with an unEvery modern chemist regardless of familiar area or with an ares he may have field is a t one time or another in the course brushed only lightly during his own trainof research interested in the magnetic ing. properties of molecules. Generally the
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A44
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Journal o f Chemical Education
The format of this hook operates smoothly from a discussion of typical elements in s, comparative standpoint in Chapter 1 through a series of preparations and practical laboratory work to suggested instrumental and andlytical work. More specifically, the oxo-acids and 0x0-acid salts and high temperature reactions are treated in Chapters 2 and 3. Next, the elements of the first transition series are treated, then some special compounds: coordination, clathrate; double salts. Then, stabilization of oxidation states is treated, electrochemical oxidation-reduction, stereochemistry (including optical phenomena); catalysis, nonaqueous systems, inorganic polymers, high vacuum techniques, inert atmosphere techniques, spectroscopic techniques, conductance measurements, gas chromrttography, magnetic measurements, and finslly potentiometric methods. Throughout the discnssions in these specific areas are: (1) preparative directions with references, (2) specific questions that stimulate further experimentation and observation, (3) cautions a n potentisl hazardous operations, (4) suggested analyses and instrumenlal met,hods, and (5) discussions on the fundamentals of what, is happening (e.g., there is a brief, hut leading discussion on thermodynamics of reactions, elect,rochemical equations and idem of significance, kinetic effects, and an introductory explanation of standard instrument operation and theory). An introductiou is also given in the use and general interpretation of spectra. For student. use the book will, of course, need supplementing by lectures and other references. The latter point is made clear by the authors. However, these authors have tucked neatly int,o 225 pages one of the mast outst,anding practical books that h a appeared in many years. I t is unique; i t is not just preparations, not just theory, not just a series of experiments and exercises, but it does, very succinctly emphasize the relation between theory and practical laboratory work. DWIGHTA. PAYNE Tulane University New Orleans, Lozlisiana 70118 X-Ray Structure Determination: A Practical Guide George H . Slout, and Lyle H . Jensen, both of the University of Washington. The Macmillan Co., New York, 1968. 467 pp. Figs. and tables. 16 xi X 24 cm. $16.95.
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Elements of X-Ray Crystallography Leonid V . Aiaroff,Institute of Materials Science, University of Connecticut. McGraw-Hill Book Co., New York, 1968. xvi 610 pp. Figs. and tables. 17.6 X 23.5 em. $15.75.
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Until recently, the application of X-ray diffraction techniques to the solution of crystal 8tructures was restricted to professional crystallographers willing to devote many months to the tedious work of collecting and analyzing data. I n the (Continued on page 4 4 6 )
