Thermodynamics of small systems. Part 1 (Hill, Terrell L.) - Journal of

Part 1 (Hill, Terrell L.) Richard J. Bearman. J. Chem. Educ. , 1964, 41 (6), p A470. DOI: 10.1021/ed041pA470. Publication Date: June 1964. Cite this:J...
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BOOK REVIEWS ammonia. The last section consista of addends. to the preceding chapters and covers the more recent literature. With respect to coverage of the liters, tnre of the field in question, this monograph is comprehensive hut not exhaustive. The experienced research worker will easily detect omissions but on the whole they are not serious. The 1388 literature citations serve, directly and indirectly, to provide entree to the entire literature concerned with reactions of organic substances in m o n i a . The reader is impressed by the degree of detail tbet is included in the discussion of individual reactions and by the extent to which the author reinterprets some of the older work in the light of more modern ideas. On the whole, however, the treae ment is factual rather than critical. Although one is reluctant to be critical of so valuable a contribution, it is inescapable that the value of this volume could have been enhanced by greater emphasis upon experimental techniques. Use of liquid ammonia as a solvent and reaction medium under optimum conditions is both tedious and time-consuming. It is an unfortunate fact that many of the studies covered in thia monograph were carried out under conditions far short of optimum. This volume will be a standard reference book for m n y years. I t should be in every chemistry library and a pos-

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session of every research worker who may have occasion to wail himself of the unusual possibilities afforded by the use of smmonia as s. solvent and reaction medium. The author is to be commended for the thoroughness with which he has completed a task of magnitude likely to be appreciated fully only by those who have engaged in similar projects.

brought out separately at this time. First, the author hopes that this branch of thermodynamics will find application in experimental work. These applications should be expedited by the present edition. Second, readers with a borderline interest in the subject will probably find that Part I provides an adequate treatment for their needs. Third, small 8ystem thermodynamics might well serve a8 a special topic toW. W A ~ ward the end of a thermodynamioe course. GEORGE Un&e78itzl of Tezas T h e first six chapters would furnish more Austin than sufficient material for this purpose. Fourth, and mast important, comments made by readers of Psrt I should result in improvements in the combined volume." Hill proceeds hy considering a large Thermodynamics of Small Systems. number of independent small systems Palr I and assuming macroscopic thermodynamTmell L. Hill, University of Oregon, ics applies to the ensemble. The book is Cowallis. W. A. Benjamin, Inc., New concerned pmtly with the derivation of 171 pp. Figures. York, 1963. xii thermodynamic equations from his fun16 X 23.5 em. Cloth, $9. Paperdamental aassumption and partly with the bound, $5.95. application of the equstiona to 8. variety of examples selected mainly from statistical The recent rapid growth of experimental mechanical models. Without doubt, the techniques has created a need for a ideas contsined in this slim volume will phenomenologied theory of the equilibprove stimulsting to theoreticians as well rium behavior of nonmacroscopic systems as to colloid chemists and other experisuch as single colloidal particles and mentalists who are interested in smdl macromolecules. In response to this systems. need, Terrell L. Hill has been developing It is not entirely appropriate that the with vigor a, scheme of small nyatem same standards of criticism should he therrnodynmnics. applied to a preliminary edition as to a ''Thermodynamics of Small Syatems. f i s h e d work. In the present instance, Part I" comprises the first six chapters of a however, the author specifiedy invites projected fifteen chapter monograph which comments which will enable him to imis to present the results of his labors. In prove the find edition. The reviewer the words of the author, "there me several reasons why the first six chwters are being (Continued on w e A472)

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BOOK REVIEWS hopes, therefore, the following three criticisms will not seem unduly severe. The first criticism is that Hill does not always discuss adequately the physical significance of his assumptions and definitions. His explanations of basic equations tend to be superfieid and overly brief, especially in the Introduction where the philosophy of the theory is outlined. The second criticism is that HiU does not reveal clearly the value of his contributions. I t is not easy t o determine whether the pure thermodynamic theory of smdl systems is n fundamental advance in knowledge or whether it is merely convenient formalism. Nor is it easy to discover whether small system thermodynamics is applicable to experimental data without the use of molecular models. The final rriticism is that the book is not written with a polished style. The text frequently has a staccato quality which disrupts the flow of logical discourse. At times the ratio of the number of symbols to the number of wards is excessively high, which tends also to obscure the train of reasoning. I n short, Hill should have explained his unfamiliar subject matter with less haste and with greater fluency. Of the four reasons the author eivea for

who wish to apply small system thermodynamics and interested readers will communicate worthwhile suggestions to the author. However, readers with peripheral interest probably will not study the suhject unless it is presented more lucidly. It is equally unlikely that many thermodynamics instructors will teach the thermodynamics of smdl systems until further developments justify its inclusion in the already~crowdedcurriculum. RICH^

J. BEARMAN

plieatians in electronic devioes. The reduction in size of radios, television sets, and computers to the point where an entire circuit can be placed in the space the size of a thumb tack is a direct result of these new techniques, whieh, of course, go far beyond the chemistry of preparation of the simple compounds. The large numher of authors (over 60) who have contributed to this excellent volume, attest to the complexity and importance of the developments in this new art. In addition to the preparation of the compounds, there are detailed discussions of procedures t o purify the starting materials and to effect single crystal growth and to zone refine them. The methods of analysis, in the parts-per-billion range, involve colorimetry, ~pectroscopy, massspectrosoopy, and acbivation analysis. Measurement of residual electrical resistivity serves as an indicator of the progress in the removal of trace impurities. The discussion of crystal growth and crystal structure and of thin films, surfaces, diffusion phenomena, microsegregation, zone refining, and other important aspects of the art and science of transistors, are admirable. The discussion of the nature of the bonds in these compounds requires over thirty pages, hut the discussion of single crystal growth takes nearly one hundred. The last forty pages are concerned with phase diagrams and thermodynamic properties. The extensive hihliography (through 1960) includes 1172 references. This monograph promises to he a standard work on semiconductors for some time to come. It has much of interest to the solid-state physicist. as veil as the chemist. Teachers of inorganic chemistry will find i t t o he an excellent source of directions for the preparation of the restricted, hut extremely important, list of compounds that is represented by the title.

LAURENCE S. FOSTER U. S. Army Materials Research Agmey

University of Kansas Lawrence

Compound Semiconductors. Volume 1, Preparation of Ill-V Com~ounds

Edited by Robert K' WzZ1ardsan, and Howell Research Center, Pasadena, California, and Harvey L. Goering, Battelle Memorial Institute, Columbus, Ohio. Reinhold Publishing Carp., New 553 pp. Figs. York, 1962. xxii and tables. 18 X 25.5 cm. $25.

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Since the invention of the transistor, the inorganic chemistry of such elements as silicon, germanium, and the elements of Group 111 bas exploded way heyond the hounds of the "Inorganic Syntheses" series. This large volume is concerned only with the preparation and properties of semiconductor compounds of Group 111 elements with Group V elements, typified by aluminum, gallium or indium nitrides, phosphides, arsenides, and antimonides. More than chemistry, however, are r e ported the important developments in designing crystals with particular structures and purities that have specific a p

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Watertown Amma1 Watertown, Massachusetts

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Edited by C. A. MeDowell, University of British Columbia, Vsncouver. McGraw Hill Book Co., Iuc., New York, 1963. 639 pp. ~ i and~ tabl.bles ~ . 16.5 23.5 cm. $20. On page 4 of this book one h d a the followine statement: " . . thoueh the aim of tlhe editor was t o realize s. ;ohme whieh would he both eomprebensive and yet authoritative in treatment, covering the whole field of mass spectrometry, there was no attempt rat making the work encyclopedic.'' Professor MeDowell has succeeded quite well in fulfilling his stated objective. Althoueh a t first sinht it does amear that the subject matter of the boodis &proportionately instrumental, in reality the treatment has been quite well balanced. The chapters entitled Ion Sources (R. M. Elliot), Ion Optics (L. Kerwin), High-

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