MARCH, 1848
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method of determination for which each reagent has been reported. References to the original literature are listed after each reagent. The arrangement and style of treatment in Volume I11 are the same as in the preceding volumes. Far reviews of 24, 364, 519 (1947). Volumes I and 11, see THISJOURNAL, Volume 111contains 19 chapters, covering the following topics: pyridine and its derivatives (Chapter I, 48 pages), quinoline and quinoline derivatives (Chapter 11, 15 pages), dipyridvl and related compounds (Chapter 111, 41 pages), pyrazolone derivatives (Chapter IV, 12 pages), miscellaneaus heterocyclic nitrogen compounds (Chapter V, 37 pages), the dioximes (Chapter VI, 80 pages), acyloin oximes (Chapter VII, 15 pages), hydroxyoximes (Chapter VIII, 20 pages), monoximes of diketones (Chapter IX, 5 pages), isonitroso compounds (Chapter X, 13 pages), isonitroso phenols (Chapter XI, 49 pages), miscellaneous oximes (Chapter XII, 16 pages), cupferron and neocupferron (Chapter XIII, 49 pages), uitroso amines (Chapter XIV, 8 pages), rhodanine and its derivatives (ChapterXV, 15pages), osrbaeides, thiocarbadiaes, and semicrtrbadizes (Chapter XVI, 24 pages), carba~ones(Chapter XVII, 9 psges), thiocsrbeeones (Chapter XVIII, 90 pages), and miscellaneous imino compounds (Chapter XIX, 25 pages). The volume conoludes with an index of names and synonyms of the organic reagents treated in the text, and one on their uses, the oompounds being listed alphabetically under the element or radical for which they are employed in analytical procedures. Volume 111, together with the three others in the series, will make a useful reference source for all who have occasion to make chemical analyses. JOHN R. YOE Umv~asmror Vmazm* Ca*monmvlL=m Vraorlrrn
SMALL WONDER-THE
since 1923; and we, in this country, have issued the Colloid Symposium Monographs annually since 1923. Since the author mcntions a number of names of scientists specificrtlly,it must also be pointed out that he has overlooked the names of such people as Freundlich. Weiser. Holmes. v. Weimam. Duelertux. and Houwink, only 'to mention a few,'all of whom must be conkidered pioneers in this branch of natural science. With the reservations pointed out above, the reviewer nevertheless hopes that t,his hook will accomplish one purpose, namely to arouse the interest of the general public in this world of dimensions which has been overlooked so long. Then the colloid chemist will be in a better position than he is today to make his contributions of more general value. ERNST A. HAUSER MABBACAUS~TTB INSTITUTE OF TBO~NOLOL~Y C*uamoae. M * s s a c a o a ~ ~ ~ s
CHEMICAL PROCESS PRINCIPLES. modynamics
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Gessner G. Hawley. Wred A. Knopf, New York, 1947. 220 pp. 53.50. has attempted with this book to e x p l b to "those THEA-OR who have the curiosity but lack the time to study more erudite treatises" what the term 'colloid' actually implies. This is unquestionably a very worthy and very timely undertaking. From the point of view of the teacher in chemistry or physics, however, the book does not seem acceptable without some reservations, the most important one being that it should not be used as reading matter in science courses at either the high-school or the university level. The main reason for this criticism is that the reader who has not the background needed to realize that this book is written for the layman, might get an entirely wrong understanding of the fundamentals of colloid chemistry. This refers quite specifically to the way the author has defined colloids, how he has discussed the history of this branch of chemistry, ,how he has attempted to explain many of their specific properties, and his explanition of the way many of these have been successfully appliedinindustry. Afurtber objection must be voiced from the ooint of view of a colloid chemist to the elaborate discussion given on the electron microscope and its use and the lack of any wirthwhile discussion of the application of ultra microscopy and other tools specific for matter present in the colloidal range of dimensions. One other point: To the uninformed reader, it would appear that praoticdly every important contribution to colloid chemistry, including the development of the electron microscope, was made in the United States of America. I t might be well to point out here that science is still an international field of endeavor, and, with d l due respect to our own contributions, we must admit that the pioneer contributions to colloid chemistry, as well as the development of the electron microscope, were made on the European continent. This refers also to the statement that the first periodical devoted exclusively to colloid chemistry is the Journal qf Colldd Sciaee, which appeared for the f i s t time in Jan-, 1946. The Germans had two periodicals devoted in itheir entirety to colloid chemistry, since 1906; the French, one,
II: Ther-
Olaf A. Hougen and Kenneth M. Watson, professors of Chemical Engineering, University of Wisconsin. John Wiley and Sons, Inc., New Yak, 1947. xlviii f 3 6 8 pp. 64 figs. 14 22 om.,
5s. THIS VOLUME is the second part of a series under the title of Chemical Process Principles," in which Part I covers Material and Energy Balances, Part I1 covers Thermodynamics, and Part I11 covers Kinetics and Catalysis, reviewed in THISJOURNAL 25, 1 (1948). The pagination is continuous throughout the three parts so that Part I1 contains Chapters 11 to 17 and pages 437 t o 804. The index is for all three ~- oart,s. Part I1 as a tcvt for t h rmodynn~rucsfur chemical engineering students cart hc vicwcd assuch onlv by considering Parts I and I1 together. Part I contains most of the nhaterid dealing with the fir61 Isw, cncrgy balances, thcrmophvaics, t l ~ c r ~ ~ ~ ~ ~ u l ~ r m i s t r y , xnd thrir applirntion to industrinl processes at aum,sphrrie prer sure. The seven vhnoteri in Pnrt I1 den1 with tlwrmudvuumic principles, thermody&nic properties of fluids, expansibn and compression of fluids, thermodynamics of solution, physical equilibrium, chemical equilibrium, and thermodynamic properties from molecular structure. The chapter on thermodynamic principles opens with a discussion of reversibility and the second law, develops the concept of entrap,", and introduuw the rhcrmodynsmic cocrgy functillus, OiLbs' her cuprey (now dtsiwared by G in accordance with .I. 3. A. and A. I. Ch. E. ~tandurdn),and total work function. The relationships among the thermodynamic energy functions and reference functions are derived after a, short explanation of exact diiIercntial equations. Shaw's method using Jaeobisns is cupl3i~rvrl. Thc propertic3 01 nrulal ~ : t s warc explained briefly by 1l.c van dcr \\'ask equation bur thrir thermodynamic properties are developed in terms of the compressibility factor, Z . The law of corresponding states has been used to derive a series of equations which allow the values of heat ertpacity, enthalpy, and entropy a t high pressures to be calculated from the generalized Z chart and the reduced temperature and oressure. (Such charts are &en in 8Ilr ~-a . - X ll-inch size in SCpRrRtC publication. "Cheuical Process l'rinviplw Chnna.", Although 1 hc maximum errors (page 518) in sucL chwts may be up to 32 per cent, which would appall nun? a tl~ermoJynnmist, the i,hrm~cnlcnginccr apprcrintci having availablr il group of corrclntionr thsr will mnblc him to r:~lculatcthc magq.itude of the emwr on thcrmod\nnmir functions of the high rxcssures he must use in his equipment to force the chemical r&tions to give commercial results. Those familiar with the mechanical eneineer's aooroaeh 60 *he expansmn and compression of fluids will look in vain for the polytropic coefficient. Again the generalized charts have been used to evaluate the changes in the thermodynamic properties of the actual gas passing from one state to another. The Carnot cycle is not introduced until this chapter and plays only a minor role in the development of thermodynamic reasoning based ~~
STORYOF COLLODS
Part
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JOURNAL OF CHEMICAL EDUCATION
180 on the second law. Gas compressors, vapor-recompression evaporators and refrigeration (hut not the more general idea of the heat pump) are also discussed here. In the chapter on thermodynamics of solutions, the oompressihility of gaseous mixtures is f i s t discussed, followed by their critical phenomena. Liquid solutions are discussed briefly. The thermodynamic functions chemical: potential, fugacity, and activity are defined m d their application to nonideal systems is illustrated. The chapter on physical equilibrium deals largely with vaporliquid equilibrium, hoth at normal and high pressure, and solubility. Chemical equilibrium illustrates the application of thermodynamic dsta to the calcul;ltions of equilibrium oompositions for a given reaction. The newer methods of presenting the fundamental data are discussed. Equilibria in liquid solutions are considered briefly. The final chapter on thermodynamic properties from molecular structure is a brief treatment of the use of empirical coorrelations and statistical methcds to obtain thermodynamic data. Although the empirical correlations may he useful if no data are available it is doubtful if a, graduate student or professional chemical engineer can use the statistical methods to find what he needs. However, it may stimulate the graduate student to further study in this important field. For a text to be used at the senior level, the reviewer believes that the st.udent should he shown the classical (nonspectroscopic) experimental methods by which the values of thermodynzmnie functions have been determined and the agreement found among these methods. Then the tables of data. mean something in terms of what has been done to obtain them. Thus, the third law of thermodynamics is discussed in half a page and does not leave the student with the feeling that he knows how entropy could be determined. A t the senior level the instructor must use cam in selecting the material in each chapter that can he assimilated by his students in the time available. A repetition of d l the material at the firsbyear graduate level would fix many of the concepts which the student previously did not fully comprehend hoth as to their broad significance and their application. The chemical engineer and physical chemist in industrial work will weloome the practical viewpoint this hook has and the C. P. P. charts which will enahle him to calculate (or a t least approximate) the thermodynamic data he needs for his chemical or physical process. The reviewer will reiterate from his review of Part 111: "Every physical chemist should have the three parts of 'Chemical Process Principles' to learn whet the chemical engineer does with his physical chemistry." In this is implied that the chemical engineer already has the three parts and is using them.
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THE THEORY OF VALENCY AND THE STRUCTURE OF CHEMICAL COMPOUNDS
Pandit RGy, Professor and Head of the Department of Pure Chemistry, University College of Science, Calcutta, India. Published by the Indian Association for the Cultivation of Science, 81 pp. 22 figs. 98 refs., no index. 17 Calcutta, 1946. i v X 24.5 cm., paper bound.
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THESE CHAPTERS (Coach-Behar Professorship Leotures) about hoe and q h y atoms combine, "pass in 8. brief review the various stages of the theory of valency from t,he days of classical mechanics to the present time, with special reference to its later developments!' The first three chapters explain the historical origin and meaning of the term valenoy, snd elaborate on Werner's ooordination tbeory. The subsequent quantum mechanical concepts are given with a minimum of mathematics, with same helpful wave pattern illustrations, and with mind-opening vigor. Complex (coordination) compounds predominate among the types of structures discussed in this hook, since Professor RBy himself made numerous original mntributions in this field (in 1928) he challenged the simplicity of the Bose-Wela-Baudisch E. A. N. rule). The bond type transition hetween double salts and "stable" complexes is well emphasized, hut the preferred new nomenclature for these compounds is not mentioned. Molecular orbital theory is exphined and compared with spin theory and looalised atomic orbital theory. RBy mentions how it alone succeeds in correlating isosteres (molecules with similar physical propertie~,spectra, and electron configurations), such as Na with CO and HCN; or 0 2 with HaCO, C2H4,and B1H6; or F2 with C2Ha,etc. While magnetic properties of coordination complexes can he explained by the molecular orbitals as well as by Pauling's localized honds, RBy prefers the latter because of other evidences such as tracer chemistry-an excellent tool for this field-and for the direction-indicating value of localized honds in general. Multiple and metallic and ionic-crystal bonds are hriefly reviewed, as are resonance (benzene, etc.) and color. Certain other equally intriguing vdency problems could not be covered in this short survey, such as classifying "isoteric groups" of molecules like Periodic Groups of atoms. No mention is made of a recent preference for the old double hond structures instead of coordinate links in the familiar ooy-acids (Annual Reports, 1945, p. 66); nor of the relations between hond length, charge, and refractivity; nor of the electron "sextet" as the fundamental ohar~rscteristicin aromatic structures (Remick, 1943, pp. 154160). Nevertheless this little hook should serve well ss the author intended, "to stimulate the interest of advanced students and teachers of chemistry in the subject." WILLIAM WISWESSER WILLSONPRODOCTB, INC. Rsaonro, PENNSTLTANIA
