The Allotropy of the Elements
W. E. Addism, University of Nottingham, England. Daniel Davey and Co., Inc., New York, 1966. vii 132 pp. Figs. and tables. $5.
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Although there are some exceptions, introductory and intermediate level treae ment of the chemistry of the solid state has been somewhat neglected in books published in this country. Thus this monograph in the Oldbourne Chemistry Series is a partimlarly welwme and needed work. I t might seem a t first surprising that somewhat less than half the book is devoted speoificdly to a disoussion of the properties of the allotropic forms of the elements. However, the author has wisely seen fit to lay the foundations in thermodynamics, chemical bonding, and crystal structure and then to use these concepts widely in the descriptive part. Chapter one (26 pages) begins with an introduction which provides some useful definitions snd distinctions and a rather brief treatment of experimental methods. There follows a, thorough discussion of the phase n l e and its applications to systems of one component and s. development of the thermodynamio aspects of allotropy. The chapter concludes with a detailed consideration of the mechanism of allotropic transform* tions which includes a brief discussion of martensitic transformations. Chapter two (27 pages) deals with chemical bonding. A brief, but lucid, presentation of the electronic theory of the atom and of the periodic table is followed by a discussion of chemical bonding under the subheadings of diatomic molecules, polyatomic molecules with localized orbitals, polyatomic molecules with delocali~edorbitals, and some molecules of an intermediate nature (e.g., amne). The perspective is principally that of molecular orbital theory and band theory. The third chapter (16 pages) is concerned with orystal structure. Metal structures are discussed with particular emphasis on the close-packed (hexagonal and cubic) and body-centered cubic types and their inter-relrttionships. The structures of the nonmetals are first related to their electronic configurations; then follows a description of the zinc blende and sodium chloride structures and examples of nonmetal structures arising from each. The chapter concludes with a consideration of the interrelationship of the polymeric structures of the elements of Groups IV, V, and VI. Chapter four (50 pages) is a systematic presentation of the properties of the allotropic elements. The organization is socording to electronic configuration. Although the information given is quite spec5c and some workers' names are given, the only references are the twelve given in the appendix as Suggested Further Reading. Any reader of such a book will wish that the author h d treated some particular points in greater depth or may koow of some more recent work on a ~peciGcitem that had not come to the author's attention. For example, this reader might have wished
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Journal of Chemiml Edumtion
for 8. brief discussion of anisotropy in the electrical conductivity of graphite (pp. 51, 91). In another instrtnce, the author states (p. 75) that iron "has never been obtained in the stable form of its cogeners ruthenium and osmium, i.e., hexaguud close-peeked," hut this farm of iron has been reported recently as being obtained a t very high pressures (T. Takahashi and W. A. Basset, Sciace, 145,483-6 [1964]). Chapter five (five pages) gives a brief account of variant forms of gaseous elements, particular attention being given ortho and para hydrogen and active nitrogen. On the whole, the book is quite carefully and lucidly written, the figures me easily understood, and the index is very good. This work would be quite well suited for supplementary reading in an upper division c o m e in inorganic chemistry and could possibly be used in the same manner in some high-level general chemistry courses. Thns any minor defeote noted above should not unduly detract from what is an excellent monograph, one well worth adding to a personal or institutional library. CLIFFORD E. MYERS Harpur College Binghamtm, New York
Photochemistry Jack G. Calvert, Ohio State University, Columbus, and James N . Pitts, Jr., University of California, Riverside. John Wiley and Sons, Inc., New York, 899 pp. Figs. and 1966. xvii tables. 16 X 23.5 cm. $19.50.
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This is the most comprehensive book on photochemistry yet to appear. All areas of photochemistry excepting photobiology are covered in this book. The authors have produced afull account of our present knowledge of the photochemistry of organic and inorganic compounds in the gaseons phase and in the solution phase. The work reviews thousands of references and therefore also serves as a valuable source of bibliography on the subject. The book is self-contained in that it oontaina a detailed review in the first four chapters of the physical problems asso-' ciated with photochemistry, notsbly the quantum mechanics of electronically excited states of molecules. This is followed by a treatment of the photochemistry of polyrttomic molecules, and then follows two chapters on rate mechanisms in photochemical reactions. The final c h a p ter is a modern account of experimental methods in photochemistry including the newer light sources and acthometry. There are also useful appendixes including tsbles of dissociation energies and pertinent thermocbemical data. Professors Calvert and Pitts are to be congratulated for their excellent book. It represents a great service to the field of photochemistry. This book will, no
d o ~ ~ b: te,w e A, the fund~imenrnlrcfcrence mlrrc 11. all laboratories purwing m e or nnorhcr a.jpevl of photorhmGrry. GERALDOSTER PolytedLnie Institute of B~wIclyn Brooklyn, New York
Mmcrornoleculer in Solution Herbert Morawetz, Polytechnic Institute of Brooklyn, New York. Interscience Publishers (a division of John Wiley and Sons, Inc.), New York, 1965. 495 pp. $16.50. mi
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This is a most stimulating and informative book, much more so than the stark simplicity of the title indioates. Its aim is to draw together the two related fields of solution studies of synthetic and natural mmacromolecules and to show how they complement and reinforce each other. At the end, it suggests, through a survey of association phenomena, and reactivity of polymers in solution, that it should be possible to make synthetic systems designed to imitate eneymes in their reactivity toward specific molecules or chemical processes. Professor Mar* wetz succeeds in his objective very well and shows many fruitful opportunities for cross fertilhation between the two fields. Although the relation between natural and synthetic polymers has heen a.subject of speculation for a long time, Morawetz points out that two developments of the last decade, now make it reasonable to resurvey the two areas as they relate to each other. First, Ziegler and Natta demonstrated that regularity of structure is not solely a property of natural polymers. Instead great wntrol can be exercised over the details of the structure of synthetic polymers. Thus, for example, synthetic "natural rubber," which closely duplicates natural rubber, can now be made after many fruitless earlier attempts. Second, the evistence of both natural and synthetic polymers in regular helical wnfigurations in solution demonstrates transfer of observed behavior between the two divisions. The original studies of helical structures in natural systems have been more and mare helpful in e x p l s i ~ n gaspects of the behavior of iynthetic materials. I t seems most reasonable that further similar interactions will be utilized. The book is designed for the reader who has some familiarity with polymer science as applied to synthetic macromolecules, but not necessarily an advanced understanding of the theories describing the behavior of polymers in solution. I t will be useful to graduate students, teachers of polymer ohernistry, and researchers in the area who want to have an authoritative sunrey of one of theimportantpt~rts of polymer science. The subjects include: thermodynamics of solutions, configurations of long chain molecules, dilute solution properties, interactions of polymeric solutions with radiation, polyelectrolytes, associations with macromolecules, and chemical reactions as affectedb y the presence of polymer (Cmtinued on page A.912)
molecules. I n all cases the treatment of the material is fresh and stimulating. This hook should he a pleasure to those who are interested in this advancing front of polymer science.
Methods of Thermodynamics
Howard Reiss, North American Aviation Science Center, Thousand Oaks, California. Blaisdell Publishing Co. (' TEOMAB E. F E R I N Q ~ N division of Ginn and Co.), New York, 1965. xvii 217 pp. Figs. and W. R. Grace and Co. tables. 15.5 X 23.5 cm. $8.50. Clorksville, Md.
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Statislicol Theory of Liquids
I. Z. Firher, Moscow. Translated by Theodore W. Switz, with a supplement by Stuart A. Rice and Peter Gray. University of Chicago Press, 1964. xii 335 pp. Figs. and tables. 14.5 X 22 em. $12.50.
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This book is of interest primarily to graduate students and investigators in the field of fluids. Research in liquid structure theory has increased steadily since the pioneering work of Dehye and Menke, J. E. Mayer, and J. Frenkel about 35 years ago. About a dozen theories have been proposed to explain this state of matter. Only s. limited number of books on this subject have been published and Professor Fisher's hook is one of three or four printed in the 1960's (his original Russian edition was published in 1961). Professor Fisher surveys much of the current knowledge of liquid structure emphasizing the contributions of Russian scientists following the early developments of B o g o l ~ ~ h o vI. n this spproaeh the statistical theory of liquids is b a e d on the correlation functions of groups of malecoles. With the existing publications using the comparable molecular distribution function methods in the non-Russian English language. Since the time of Professor Fisher's writing considerable emphasis has been given to the cluster concept of J. E. Mayer. As an introduction to the newer approach an extensive Supplement, written by Stuart A. Rice and Peter Gray, has been added to Professor Fisher's book. I t is not easy to blend two diverse writings, but the results are acceptable and the publication timely. A discussion of clustering theory for simple liquids may also be found in H. L. Friedman's book, "Ionic Solution Theory" (Interscience, New York, 1962). Following the publication of the Supplement, Rice and Gray have written a more extensive work on "The Statistical Mechanics of Simple Liquids" (Interscience, New York, 1965). The two hooks cover the major developments in liquid structure theory. Professor Fisher's book is especially vsluahle as a somce of Russian developments and as a, bridge between the earlier investigations and the present statistical mechanical concepts. DALEDREISBACH Hiram College Hiram, Ohio
A912
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Journal of Chemical Education
This book contains an exposition of the general principles of chemical thermodynamics with a limited number of illustrative applications. It purports to do for the chemist what Pippard ("Elements of Classical Thermodynamics," Cambridge University Press, 1960) does for the physicist. Both strive for maximizrttion of the reader's intuitive appreciation of the foundations of thermodynamics by following a path intermediate between the postulationttl and empirical approaches. The former is represented, for example, by Callen's "Thermodynamics" (John Wiley & Sons, Inc., New York, 1960), in which the subject is compressed into a formalized msthemstical structure, logically consistent but not easily correlated with experience. The latter, more traditional a p prortch, based on idealized devices and processes, is usually easier for teaching and learning but sometimes leaves logic "limping about in eccentric and not quite completed cycles." Thermodynamics hooks can fairly well be described nowadays by the way they develop the second law. I n this book, the second law follows from consideration of what happens when constraints on macroscopic systems are successively relaxed. Such processes are quantitatively characterized by the "degree of constraint." the neeative of which is sub-
tuitively appealing connection between entropy and randomness is exploited. An outline of Carathhodory's principle is also given-in a section which the reader is invited to skip if he chooses. I declined the ootion., and found. somewhat to mv surprise, that the alternative treatment was hoth easier to grasp and more aestheti c d y appealing than the main route.
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A central theme of the book, as stated by theauthor, is to clarify thesignificance and applicability of the thermodynamic potentials. This is reasonably well fulfilled. A particularly lucid account of the themodynamics of surface phenomena is thereby made possible. Reiss' book, while not achieving the elegance or readability of Pippard, is the more accessible of the two for one trained in chemistry. I t is clearly not intended as a first introduction to thermodynamirs; it would probably not do even for the second time around. But, for an enterprising student or teacher, this hook offers several novel and perceptive insights into the fundamentals of thermodynamics. S. M. BLINDER University of Michigan Ann Arbor
Fundamentalsof Statistical Thermodynamics
Richard E. Sonntag and Gordon J. Van Wylen, both of the University of LMichigan,Ann Arbor. John Wiley and Sons, Inc., New York, 1966. xx 370 pp. Figs. and tables. 15.5 X 23.5 em. $8.95.
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Because engineering research and teehnology have expanded into a number of diverse areas, sltch as plasmas, thermoelectric power generation, etc., the need for thermodynamic information on a microscopic scale is more prevalent. Such information is also an educational aid: a student gains an increased understanding for the basis of macrosoopic thermodynamics. This introductory text on statistical thermodynamics presumes a student is familiar with the macroscopic laws; this background is generally necessary for one to gain an appreciation for the subject. Subsequent to a. brief introduction, the diseussinn in Chapter 2 is used to familiarize the reader with the mathematics which is used within the book. Chapters 3 and 4 are concerned with the development of the partition function, the counting procedures, and the connection between macroscopic and statistical thermodynamics. And finally, in Chapter 5 the qnantum mechanical foundations for the suhject are discussed. The selection of any engineering text depends upon the applications of the included subject matter. I n this regard, Chzpters 6 through 9 develop the theory for ideal gases and solids and for chemical equilibrium. The balance of the text is devoted to dependent degrees of freedom including the currently popular topic of irreveisible processes. The text is written withsufficient clarity that the hetter student should have no tmnhle with self-study. Furthermore, an ample number of problems of varying difficulty are included. These problems are designed to hoth complement and supplement the text material. The nomenelsture used is standard with the field, and. this will promote the book as an introductory reference. This text is the second of a series concerned with a unification of the teaching of thermodynamics, fluid mechanics, and heat and mass transfer. The area of thermodynamics for the undergraduate is containec! within this volume and another concerned with the macroscopic approach to the thermal sciences. One of t,he main advantages with this tent lies in the clarity with which the authors discuss the necessary assumptions nlch that mathematical complexity is reduced. This reduction in mathematics does, however, eliminate some of the more froitft~lmethods which have been applied in the field and somewhat restricts the number of applications. Of the many beginning texts that are currently being written in this field, this book is certainly one of the better ones.
J. P. STARK University of Tezas Austin (Continued on page A914)
