An introduction to molecular kinetic theory (Hildebrand, Joel H

An introduction to molecular kinetic theory (Hildebrand, Joel H.) Lawrence P. Eblin. J. Chem. Educ. , 1964, 41 (3), p 171. DOI: 10.1021/ed041p171.2. P...
0 downloads 0 Views 2MB Size
BOOK

Steroid Reactions: Organic Chemists

An

Outline

REVIEWS

for

Edited by Carl Djerassi, Stanford University, Stanford, California. Holden-Day, Inc., San Francisco, 1963. vi 657 pp. 19 X 26 cm. $9.75.

+

Using the steroid nucleus as a vehicle, this book presents a summery of a number of the more important reactions in organic chemistry. Such general topics as carbonyl and hydroxyl blocking groups, selective oxidations, selective reductions, introduction of fluorine, introduction of double bonds and the formation and reactions of epoxides and episulfides are considered as well as more specific topics for the steroid chemists. The book is a collection of structural formulas and equations with very little text and was compiled by 16 graduate students under the general direction of the editor. It contains fourteen chapters and should he of interest to organic chemists of all persuasions. The stated purpose of this hook is to make available to the non-steroid chemist the wealth of information which has a+

-Reviewed

cumulated in the steroid field. The editor correctly states that "The appearance of the cyclopentanoperhydrophenanthrene skeleton in a journal article is often sufficientto make even the most experienced organic research chemist turn the pages rapidly without a further glance." At least a portion of this reflex action may be traced to the trivial nature of a goodly portion of the steroid work and to the extreme financial orientation of much of it. Be that as it may, the book fulfills its purpose beautifully. There is, of course, some question about the utility to a non-steroid chemist of such chapters as the Conversion of 2Bketosteroids to 17-ketosteroids or the Preps, ration of Steroidal m-Hydroxy and aAcetoxy Ketones, but the majority of the hook is devoted to topics of wider interest. On the other hand, the utility to steroid chemists is beyond question and, as the editor states, the steroids do present a goad background for such a discussion due to their varied and precise stereochemistry. This book is reminiscent of the classic "Synthetic Organic Chemistry" by Wagner and Zook or "A Texthook of Practical

in This Issue

Carl Djerassi, editor, Steroid Reactions: An Outline for Organic Chemiats Joel H. Hildebrand, An Introduction to Molecular Kinetic Theory Harry H. Sisler, Elertrooic Structure, Properties, and the Periodic Law Robert G. Paw, Quantum Theory of Molecular Electronic Structure Thomas S. Kuhn, The Structure of Scientific Revolutions Roland R'ard, symposium chairman, Nonstoichiometric Compounds Helrnl~tSchmidt and Mark won Stackelberg, Modem Polarographic Methods James M . Miller, Experimental Gas Chromatography

Alezander Haddoto, editor, Advances in Cancel Research, Volume 7 Paul Delahay, editor, Advances in Electrochemistry and Electrochemical Engineering, Volume 3, Electroehemistry G. N . Ramachandmn, editor, Crystallography and Crystal Perfection: Proceedings of a Symposium held in Madras, J a n u a ~14-18, 1963 and Organized by the University of Madras

Organic Chemistry" by Vogel in that it will help prescribe conditions for a number of simple conversions and reactions. A particularly outstanding section on the protection of carhonyl and hydroxyl groups details not only the various blocking groups and how to supply and remove them, but even describes a number of conditions and ~eaelions to which they are stable. The most exciting feature of this book is the basic concept itself. A book t h t is presented almost entirely as a collection of structures is quite unique. It is concise, elem knowledge a t its best and should he the forerunner of an extensive line of such hooks. The price of the hook is reasonable. The drawings, although photocopied, are clear and the abbreviation system, after a little study, is logical.

JAMES M. BOBBITT The University of Connedicut Stows, Connecticut

A n Introduction t o Molecular Kinetic Theory

Joel H. Hildeb~and, University of California, Berkeley. Selected Topics in Modem Chemistry. Reinhold Publishing Corp., New York, 1963. x 105 pp. Figs. and tables. 12.5 X 19 em. Paperbound. $1.95.

+

The editors of the series, Selected Topiw in modern Chemistry, chose Professor Joel Hildehrand, who is well known for his vital interest in teaching and for his rich understanding of physical chemistry, to write the volume on moleculsr kinetic theory, a most important item in the theoretical structure of science. Any firsbyear text deds with the gas laws and kinetic theory to some extent.. The purpose of this little book is to develop the subject moreextensively than any of the standard texts. Presentation in the early pages of introductory material which is duplicated in many texts protects the student against the possibility that his particular text might not lead up to the point where Hildebrand begins. Some textbook authors shy away from historical matter and thus deprive their readers of insight into how scientific knowledge develops. In most of the volumes in the Selected Topics series the subjects are developed historically. Chapter 1 of the present volume deals with the two lines of approach which led to the development of the kinetic theory: attempts to develop a theory of heat (starting with Count Rumford and his cannon) and efforts to account for the properties of gases (starting with Torricelli and his barometer). The kinetic theory of gases was successfully launched by August Kronig in 1856 and independently a year later by Rudolf Clausius. I n Chapter 2, Hidebrand develops the bas3 equation of this theory, P V = 1/3Nmua. He develops the explanation for Dalton's partial pressure law, Avogadro's principle, and the law of combining volumes. He calculates mean

:

(Continued on page 172) Volume dl, Number 3, March 1964

/

171 '

cluding the four quantum numbers, Pauli's Exclusion Principle, shells and subshells, orbitals, and Hund's Rule. The author displays his talent for good writing in discussing spin and orbital contributions to the magnetic moments of atoms. The discussion of probability distributions for electrons in different states is aided artistically by spatial contour diagrams for s, p, and d orbitals that have been constructed with care. The chapter includes a table showing the electronic configurations of the first 98 elementa. Configurations of elements beyond californium have not yet been established. The theme of the second chapter is the ability of the chemist to predict the types of chemical bonds which two specific kinds of atoms will form. The difference between ionic and covalent bonding is reviewed, as well as the need for hyhridization to account for the many instances in which molecular geometry does not correspond to the orientation of atomic orbitals in space. A useful table of types of hybrid bond orbitals and their geometrical configurations is included. Ionization energies, electron affinities, and electronegativities are set forth ss measures of attraction for electrons essential for p r e dicting the type of bond which two atoms will form. Factors affecting each of these measures are correlated with location in the Periodic Chart. The third chapter considers the question, What reliable predictions can be LAWRENWP. EBLIN made concerning the properties of a Ohio University substance which contains a given type of Athens bond? Crystdine solids are here classified as ionic substances, nonpolar covalent substances, polar covalent substances, network solids, and metallic substances. The properties of substances of each type are interpreted in terms of the bonding forces and structures which are characteristic of them. A two-page chart summarizes the characteristics of the five types. In Electronic Structure, Properties. and the addition to van der Waals forces and elecPeriodic Low trostatic dipole interactions, hydrogen bonding is considered in the discussion Harry H. Seler, University of Florida, of polar molecular substances. This Gainesville. Selected Topics in Modern chapter is excellent in every respect. Chemistry. Reinhold Publishing Corp., The first three chapters a v e r a s 34 120 pp. New York, 1963. vii pages each. The fourth chapter is a Figs. and tables. 12.5 X 19 em. briefer one in which the correlation of Paperbound. $1.95. properties with structure and position in the Periodic Chart is illustrated with a One of the editors of the paperback discussion of the binary compounds of series, Selected Topics in Modern Chemishydrogen, oxygen, and the halogens with try, is the author of this little book, which the other chemical elements. The chapter is the second volume in the series to he concloses with a. summary of facts that have cerned with the correlation of structure recently come to light in the currently with properties. There is, however, a aotive area of research that is concerned substantial difference in emphasis between with the chemistry of the elements of this book and Rysehkewitaeh's "Chemical the helium family. These are theelements Bonding and the Geometry of Molecules," which was reviewed in THIS JOURNAL which were known as the inert gases until Bartlett discovered in 1962 that they were (40, 441 [1963]). not really as inert as was generally supIn the first chapter of this book, Sisler posed. develops the theme that the periodic reThis is the ninth volume in the Selected currence of similar properties among the Topics series. The value of the book is elements results directly from the periodic enhanced by a good index, useful diagrams recurrence of similar electronic configuraand tables, and s. list of suggested readings tions in their atoms. Although the disa t the end of each of the first three chapcussion of atomic structures is briefer than ters. that found in the Ryschkewitsch hook it is A student whose text does not adeadequate for the development of the quately discuss the relation between themes of this chapter and the ones that structure and properties would find this follow. The basic concepts of the theory book valuable for supplementary reading. of the nuclear atom and the wave mechaniFew teachers would wish to recommend cal theory of the atom are reviewed, in-

molecular velocities and discusses the change in velocity distribution with temperature. He describes the relation of heat capacity ratio to molecular complexity, dkcusses isothermal and adiabatic expansion, explains the variation of pressure with altitude, and outlines Perrin's historic work on sedimentation gradients in 1910. The chapter ends with 22 good exercises for bright students. The third chapter deals with real gases. Major topics include the van der Waals equation (1851), the relation of the van der Wads parameters to the coordinates of the critical point, the law of rectilinear diameter (1886), the reduced equation of state, virial equations of state, the Berthelot equation, Joule-Thomson expansion, the liquefaction of gases, transport phenomena, mean free path, and the determination of molecular diameters from viscosity. There are 11 good exercises a t the end of this chapter. In the last of the four chapters kinetic theory concepts are applied to liquids, solids, and solutions. Major topics include Raault's law and regular solutions. Exelusive of a good index, this little book contains only 98 pages of textual matter. This is 11 pages less than the average for the seven preceding volumes in the series. A few typographical errors were overlooked in proofreading but they are not the serious kind that preclude reader comprehension.

+

172

/

lournol of Chemical Edumfion

both the Sisler and the Ryschkewitach paperbacks for purchase by the same student. Both book6 should be carefully read before a choice is made, for both are well written and the choice would have to be made on the basis of preferred emphasis.

P. EBLIN LAWRENCE Ohio Uniuemity Athens

Quantum Theory of Molecular Electronic Structure

Robed G. Paw, Johns Hopkins University, Baltimore, Maryland. W. A. Benjamin, Inc., New York, 1963. xiv 510 pp. Figs. and tables. 18.5 X 23.5 em. Paperbound. $7.65. Cloth. $11.

+

"This book deals with the Quantum Theory of the electronic structure of molecules a t a level designated to take the reader to the borderlines of research in [A] knowledge this part of ohemistry. of elementmy quantum mechanics is presumed." In a text section of 125 pages which are photo-offset from a typewritten manuscript, the author very eloquently fulfills his purpose. Following an introduction which deals primarily with atoms, he discusses in detail small molecules and the a priori calculation of electronic wave functions for them, and planar unsaturated molecules and the variety of semiempirical methods used with them. In a final brief section he discusses the unsolved problems of the correlation of many electrons. Following this textual section and a bibliography of some 400 references, there are 340 pages of reprints of the more recent and more important papers in this area. While the selection of these papers naturally is a matter in which individual interests and individual tastes plays an important role this reviewer can find little to criticiee in the selections made. By making these important papers readily available on the theoretical chemists' hook-shelf the book will serve a very useful service. It is a little more difficultto assess what the overall utility of this book will be. For a lecture course in quantum chemistry, it is a little brief, m d in many areas incomplete. The appended original papers do not lend themselves readily to a classroom presentation of the course. For the expert in the field, the book does not present very much new, so that, to him, it will not be of great usefulness. Perhaps the most important function it might serve is to provide a means by which an interested and well-trained person can bring himself up to date by self study. Technically, the book is very well put together, although, of course, the typescript nature does detract from the pleasing appearance. The existence of a paperbound edition a t s reasonable cost is extremely welcome. The book can he highly recommended to anyone wishing to

. ..

(Coniinued on page AZ06)