BOOK
REVIEWS
Thermodynomicr
G. .V. Lewis nnd 31. Randall: Revised hg K. S.Pitzm and L. Bwwer, both of the University of California, 2nd ed. 1fcGraa~-HillBook S e r York, 1961. xii X Figs. :md tnbles. 16 X $12.50.
Berkeley. Co., Inc., 723 pp. 23.5 em.
Prafrnsors Pitser and Bromr aeknawlrdgr their initial doubts regarding the wisdom of revising Lewia and Randall, doubts ns to whether i t might b~ "more nppropriat,~ to leave the masterpiece urichsngrd as a monument to its authors and their em in the development of chemical them~odynilmirs." We ran all be grateful that their doubts vere overcome, for this revision, without losing the flavor and spirit of the original, hrings thc book out of the historical museum and places it onre again on the worktable of the practiring chemist who wants to use thermodynamics. And, since no hook has ever auoroached
~AP. The original was characterized first by n cavalier attitude tmr-ard mathematical rigor and a complete disint~restin the logi~1 structure and beauty of thermodynamics: aecond by n clear and vigorous style; and chiefly by a ronrentration on the use of themlodynamic relations in the pmrtirnl zttnrk on chemical problems,
with a willing.acceptance of arithmetic, graphs, and rough estimates. These characteristics are retained in the revision. With regard to the first, we agree reluctantly that the revisors were wise to keep the unsystematic and ad hoe derivations, even though the typical chemist of 1961 has moro methematical sophistication than his counterpart of 1923; the introduction of elegance would spoil the flavor of Lewis and Randall; and there are other books for those of us who enjoy a systematic logical exposition of the principles Tho revisors have kept the original spirit and style; most of the great passages, such as the chapter on Entropy and Probability, have been kept unchanged and the new material matches the d d in clarity and vigor. What has been eliminated is mainly the final part of the original book in which the thermodynamic data in 1923 were critically reviewed and apsemhled. Today this is both needless and inappropriate; selected tables of representative da.ta for reference and comparison are included in a, few pages of the Appendix. There have also been deletions of some methods of estimation which have been suporseded. There has been a considerable rearrangement of topics in order to include most effectively the new material and the entire text shows small changes and improvements. The chemical potential, and its symbol r , has been admitted on an equal footing with the partial molal free energy; the
G. S. Lrzris and .)I. Randall, Thcmnodyniamirs. Iteviscd by K. S. Pitrer and I,.
symbol z is now used for mole ( n o l o n c ~ r mol) fraction; in the general disrussion of partial mmolal quantities the symbol I' is used for a general extensive proprrty of s solution, rather than the symbol G which has acquired misleading connotations rinee 1923. But no mhior chaners in notation have been introduced: the four state functions appear, as hrfore, E, H, A and F. What has been added? .4 great d d of material representing our increased k n o d edge of old applications, a s in the f i ~ l dof solution thermodynnmies, b0t.h of nonelectrolytic and electrolytic solutions. .4 great deal of material setttng forth the thermodynamically useful result,s of statistical mechanics, in a v ~ r i e t yof specific applications, especially to the thrnnodynamic properties of gasne and t o dilute electrolyte solutions. .4 eonsiderable expansion of the treatment of surfaces and of gravitational and electromagnetic fields, in keeping with increased interest in such systems sinrr 1023. -4 significant addition discussing the new field of irreversible thermodynanlirs. In all of this the revisors have kept the discussion focussed on the application of thermodynamics to chemical prohlems; they have included methods of rducing data, and empirical generalizations which help in estimating needed valurs. There is, for examplq a splendid chapter devoted mtirely to the methods available for estimating entropies. The hook will undouhtrdly resume its place as s. constant guide and reference for chemists using thermodynamics in their research. and as a tenthook and reference for classes in the applmtton of thermodynamics to chemiqtry.
Inorganic Chemistry of Quolitotive Anolysis
Brewrr
8 . F . Cltfford, Pnrdur University, Lafayette, Indiana. Prentice-Hall, Inc., Englewood Cliffs, S e w Jersry, 1961. xvil 515 pp. Figs. and tnhles. 16 X 23 em. $6.95.
.I. F . ('/ifford, Inorganic Chemistry of Qualitative Analysis Iinlher?p E . l,nwson, Infrared Absorption ot Inorganic Suhstanees E. H. B. Pirtsch and tho ( h e l i n Institute, Gmelins Handhurh der Anorganisrhen Chcmir. 8 Auflago. System 20, Lithium, Supplement E . H . B. Pidsch and the Gmelin Institute, Gmelins Handhurh der Anorganischen Chnnie. 8 -4uflage. Sysbpm 3, Oxygen H . J . E n t e l h mnd .l. G. Sharpe, .4dv:mees in Inorganic Chemistry and Radiochemistry. Volume 2 D. P . G m d h , An Introduction to C ~ o r d i n a t i a nChemistry I. JI. Iiolthoff and Philip J. Eliring, Treat,ise on Analytical Chemistry. Part 2, Anslytical Chemist,ry of the Elements. Volume 5 Isnne ilsimm,, Thc Wellsprings of Lifc George 1,. Clark, Editor, Thp Enryclopedia of iMicrosropy Chnvles C . 1Vindin.g and Gordm D.Hiatt, Polymeric Materials D. R . Laurence and I f . nt'm&m, Clinical Phsrmarology Reuben E. TYood, Basic Mathemstirs of Srienre and Engineering Charles .V. Rsilley, Editor, Advances in Analyt,iral Chemistry and Inetrumentntion. Volume 1 J . W . Mallin, Cryst;tllization E. H.R.Pictsch and the Gmrlin In~tit.utc,Gmelin8 Hi~ndhwhder Anorganisc.hem Chnnie. 8 Anflage. Systrm 34, Mercury Elvin A. Knbat, Expcrimentnl Immunorhemistry Louis h'. Ridenour and Willinnt -4. Nierenbcrg, Editors, Modern Physics for t,he Enpinew. Srrond Series
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I n recent years it has been widely accepted that the teaching of qualitative analysis far its own sake is a waste of time. Courses in this subject still survive, ~ O K ever, with the excuse that they serve as vehicles far teaching the systematirs of inorganic chemistry. Unfortunately hoth the topics studied and the lahorntory o~eratians ~eriormed are uninteresting, s h d students naturally gain the impression that inorganic chemistry is doll. Professor Clifford has tried to avoid this result by including material which goes heyond the usual confines of qualitative anaksis. The subject matter of his book rovers considerably more material than the title might suggest. Themfare, instructors n-ho are looking far a text for an elementary course in inorganic chemistry might well consider this book. ~
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Volume 39, Number I , Jonuory
1962
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53
The book contains sixteen chapters of approximately equal length (eorresponding to a sixteen-week semester). The following selreted chapter headings indicate that some topics are included which are seldom considered a part of qunlitative anelysis: "The Quantized Atom and the Structure of Molecules and Complex Ions," "The Mechanisms of Chemical Reactions," "Apparent Anomalies in t h Periodic ~ Table." Illustrative experiments, which are appended to the appropriate chapters, include not only qualitative analysis schemes (on the drop t o milliliter scale), but also experiments designed to make students think. I t should be pointed out that there are several inaccurate sections in the hook. On pages 4&41 it is argued that, in the B AB followed reaction sequence A 4B C D, the over-all rate is by A proportionnl to [Al'[BI even though the first step is sloa compared to the second step. On pages 88-9, it is stated that, in a solution of 0.01 mole of the "mixed salt" IHgCIlCI04 in one liter of aqueous perchloric acid, the concentrations of CIion and Hg2'- ion are equal. On page 121 i t is implied that the only acid species in aqueous HCI is the OH1+ion. The book is admittedly not a compilation of qualitative analysis methods, but, if erron such as those cited above were eliminated, it would be a very useful text for elmlentary inorganic chemistry.
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Gmelinr Handbuch der Anorgmischen Chemie. 8 Auflage. System Nummer 20, Lithium, Supplement Volume
Edited by the Gmelin Institute under the direction of E. H. B. Pielseh. 8th edition. Verlag Chemie, GMBH., Weinheim, Bergstrasse, 1959. 525 pp. Figs. and tables. 17.5 X 25.5 cm. $77.50. This volume is a supplement t o the 1927 edition. Consequently it,s size (525pages) compared t o the former 254 pages r+ fleets the great amount of research involving the metal between 1926 and 1959. Even in the section on occurrence, the contrast is notable, since the demand for tho metal has exhausted most of the sources described in the former volume. Isotope separation research is discussed. Electroohemical behavior is discussed as a separate topic along with the conventional subjects, physiml properties and chemical reactions. The material on alloys and compounds occupies over half the volume. Typical Gmelin thoroughness is evident---even methods for preparing opbical rrystnla of LiF are included. IT'. F.
R.
Gmelinr Handbuch der Anorganischen
WILLIAML. JOLLY Chamie. 8 Auflage. System Nummer Uniiersity of Colifornin 3, Oxygen Berkeley, California Edited by the Gmelin Institute under the direction of B. H. B. Pietseh. Verlag Chemie, GMBH, Weinheim, Bergstrasse, 1960. 366 pp. Figs. and tables. 17.5 X 25.5 cin. $53. Infrared Absorption of Inorganic Substances
ICelheryn E. h w s o n , Snndia Corp., Albuquerque, S e w Mexico. Reinhold Publishing Corp., New York, 1961. 200 pp. Figs. and tables. 16 X vi 23.5 em. $6.i5.
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This hook is the first attempt to compile the work done in a relatively new fieldInorganic Infrared Spectroscopy Since 1952, tremendous interest in this field has developed, as evidenced by the 1171 references the book reports in this period. The author has divided the book into three parts. The first part deals with the techniques available and the applications of infrared spectroscopy for inorganic comnounds. The second art nrescnts
This fourth section devoted to the el+ ment oxygen contains three chapters, Air (157 pages), a brief bpage .4rtive Oxygen, and over 200 pages on Ozone. The comprehensive compilation of the physical properties of air includes solubility, adsorption data. as well as those narmdly referred to as mechanical, thermal, acoustical, and electrical. The ozone chapter points out the ohsaleseence of murh previous literature data. The material here included deals almost exclusively with topics of concern to prepnration and examination on n l;~horntoryrather than industrial scale.
\V. F. X
Advances in inorganic Chemistry and Radiochemistry, Volume 2
glossary of spectroscopic terms is p r e sentrd. The third part include an extensive bibliography covering the period Januar5-, 1952, through April, 1960. The book r i l l serve as a vduable reference book for people working in this field, and should be an excellent starting point for those people just becoming interested.
Edited by H . J. Emeldus and A. CI. Sharpe, University Chemical L a b o r s tory, Cambridge, England. Academic 3Y2 Press, New York, 1960. viii pp. Figs. and tables. 16 X 23.5 cm. $12.
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I n 1959, the first volume of this series of reviews appeared wherein editors Emelbus and Shilrpe suggested that a JOHN R. FERFURO "world-mide interest in inorganic ehemAlgonne N a l i m l Laboratmy istry and radiochemistry has created A ~ g a n eIllinois , which r+ a keen demand for articles .
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54 / Journal of Chemical Education
view t,he fields of current interest t o . and . . . inform the research workers non-specialist of recent progress." Since this first volume has not been reviemd in THIS JOURNAL, perhaps s word or two about it is not out of place. Volume I covers such tapirs as Mechansims of Redox Reactions of Simple Chemistry (Taube), Compounds of Aromatic Ring Systems and Metals (E. 0. Fischer and Fritz), Recent Studies of the Boron Hydrides (Lipscomh), Lat,tice Energies and thoir Significance in Inorganic Chemistry (T. C. Rhddington), Graphite Intercalation Compounds (Riidorff), Srilsrd-Chdmers React,ion in Solids (Harbottle and Sutin), Artiv&m Analysis (Atkins and Smales), Phosphonitrilic Halides and their Derivatives (Paddock and Searle) and The Sulfuric Acid Solvent System (Gillespie and E. .4. Robinson). I believe that on t,he rhole both the editors and authors did an admirable job. The presentat,ions of Taube and Waddington are excellent, although some of t h e cobwebs should have been removed from the lattice energy discussions. The second volume continues in t h e style of the first, and contains the following: Stcreorhemistry of Ionic Solids (Dunit. and Orgel), Organometsllic Compounds (Eisch and Gilmanj, FluorineContaining Compounds of Sulfur (Cady), Amides and h i d e s oi the Oxyacids of Sulfur (Berke-Goehring), Halides of the Actinide Elements (lintz and Sheft), Structures of Con~pounds Containing Chains af Sulfur Atoms (Foss), Chemical Reactivity of the Boron Hydrides and Related Topics (Stone), and Mass Spectrometry in Nuclear Chemistry (Thode, McMullen, and Fritze). This revieuer's penlssl of the volume indirates that the presentations continue on the high level of competence and authoritativeness thst characterized the first volume. Several drtails are of particular note: Dunitz and Orgels' discussion of Ionic Solids is outstanding. I t should be t,he required reading of all of 11s who attempt. to keep up on modern developments. The three rhapt,ers on sulfur rhemistn. (RS veil as the one in Volume I) may convinr~those people who wonder if it is still profitable to lecture on the chemistry of Group VI in undergraduate courses that there is a tremendous and interesting field here not limited t,o the mmufaetnre of sulfuric acid. (Several omissions in the chapter on Fluorine Containing Compounds of Sulfur are inevitable, but. i t is too had that the n e n methods of preparztion of SF4and its widespread synthetic possibilities as a fluorinating agent are not adequately discussed; the same can be said of the somewhat scanty references to the impact of hydroboration on synthetic organic chemistry in the two places in this volume where it could have been discussed.) It is clear that many chemists uill have inkrest in these volumes; they will be quite usehll in many graduate and nndwgradunte courses in inorganic chemistry. J A ~W.SCOBBLE Pirrdue Universily I,afauetle, Indiana
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(Conlinrred on page A521
