Practical physical chemistry (James, Arthur M.)

alkali metals; the position of substitution in heterocyclic ringsbased on transition state structures rather on ground state structures; and conformat...
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Chapter 5, Chemical Bonding, intmduces electrostatic theory, the variation method, and molecular orbitals. Valence bond calculations for the hydrogen molecule are described, and finally the hybridization of s and p orbitals is considered. Unfortunately this is not extended to include a similar treatment for d orbitals. Chapter 6, Inorganic Stereochemistry, presents a very interesting examination of electron correlation and a discussion of the stereochemistry of molecules in terms of electron repulsions. Chapters 7 and 8, Electromotive Force and Acids and Bases, treat these subjects in an adequate manner. Chapter 9, CoArdination Chemistry, constitutes an excellent introduction to recent developments in transition metal chemistry and includes a comparison of the crystal field, ligand field, and valence bond Llleories. Magnetoehemistry, stability, and spectra are treated in more detail than is usual. Chapter 10, Nonaqueous Solvents, is closely related to chapter 8, and the topics such as solubility and acid strength are treated quantitatively. The find chapter, Theory of the Nucleus, is an introduction to nuclear structure and radioactive decay. Many excellent illustrations and tzbles are to be found throughout, and each chapter is followed by a set of references to the recent literature. Although free use is made of mathematics, derivations me carried out in detail; and only a knowledge of basic calculus is required. I t does seem regrettable that no problems or exercises are provided. For a year's course, most teachers will want to supplement this text with a good book covering the descriptive chemistry of the elements. This book nil1 not replace any of the standard works in quantum chemistry. I t can be recommended as providing a very interesting and timely introduction to bonding and structure. It should serve to stimnlat,e the mathematieallv inclined stu-

R. STUARTTOBIAS

University of Minnesota, Alinneapolis

Orgmnic Chemistry

Ray Q. Brewster and William B. IllcEwen, both oi the University of Kansas, Lawrence. 3rd ed. Prentice-Hall. 1 Englewood Cliffs, New ~ e r s e y ; 1961. x 854 pp. Figs. and tables. 10 X 23.5 cm. $10. ~

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This undergraduate textbook has not been written along t h e conventional lines of organization but rather is a combin* tion in which the aliphatic and aromatic compounds are kept separate and in which react,ion mechanism considerations are

in the text. Thus, conformations appear in Chapter 2, which considers alkanes. The same chapter presents the chlorination of methane as n free radical reaction, including initiation stage, propagation

steps and possible termination resctions. Ionic reaction mechanisms are introduced in Chapter 3 in connection with the synthesis of olefins and the mechanics of ozonolysis and the addition of halogens t o double bonds. Thus, as the material is presented, i t is possible for the lecturer to speak in a more sophisticated manner shout mechanism as well as about syntheses. It becomee unnecessary to save the discussion of reaction mechanisms and conformational asnalysis as a surprise in a later part of the year. After a short introductory chapter, Part 1 considers aliphatic compounds in chapters 2 through 22. Chapter 18 is a special chapter on eiptrans isomerism and unsaturated acids. Chapter 19 emphasiaes optical isomerism along with halogenated, hydroxy, aldehydic and ketonic acids. Tautomerism and base-catalyzed condensations are considered specifically in Chapter 20. I n Chapters 21 and 22, amino acids, proteins, and carbohydrates are taken up. Part 2 concerns aromatic compounds. Among ttromatic hydrocarbons, which are first discussed, are nonclassical aromatic compounds, such as tropolone, aaulene, the tropylium cation, the cyclopentsdienide anion, and ferrocene-all explained on the basis of Hiickel's rnle. The usual types of aromatic oompounds are each treated in a chapter. A numher of miscellaneous topics are dealt with in chapters on alicylic compounds and terpenes, heterocyclic compounds and alkaloids, organametallic compounds, and polymers. The chapters on organometallic compounds and polymers draw on both aliphatic and aromatic compounds. Problems are provided in two general categories for each chapter. The first is made up of drill questions for which answers will be found in the text: the second

text. Among the second class are many problems which require quantitative reasoning from numerical data, which this reviewer considers quite appropriate and necessary t o the general treatment of orgmic chemistry. Among the special topics which are considered in the later chapters in the text are the atactic, isotactic, polymers based on t h e Newman stereoehcmical formulations of trans and skew conformations; treatment of orgmometallic compounds of zinc, cadmium, mercury, germanium, tin and lead, silicon and iron and msngnnese, as well as the more commonly discussed derivatives of magnesium and the alkali metals; the position of substitution in heterocyclic rings based on transition state structures rather on ground state structures; and conformational effects on t h e reactions of cyclic compaunds. This book is designed to suit t h e instructor who wants a modern first-year text which is of sufficient scope so as to allow some selection of topics, and for those who feel they would prefer to treat aliphatic and aromatic chemistry as two separate lines of development.

Practical Physical Chemistry

A~lhurM. James, Chelsea College of Science and Technology, England. J. and A. Churchill, Ltd., London, 1961. xiv 339 pp. Figs. and tables. 16 X 24 cm. $6.30 net from publisher.

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This is a laboratory manual of physical chemistry compiled to meet the needs of elementary as well as more advanced courses in several types of degree-granting institutions in Great Britain. As a result i t includes many experiments which currently, in the United States, would be included in volumetric analysis or elementary instrumental mdysis rather than in physical chemistry. With the present trend toward offering physical chemistry earlier in the curriculum, teaehors of such coursos will find many of these more simple experiments highly desirable. The book contains introductory chapters on Errors and the Mathematical Treatment of Results, including a brief section on report writing with a model report; Instruments for Measurement of Mass, Volume, Length, Time, and Temperature, with empha~ison the use of the balance; Electrical Instruments; and Optical Instruments. This material takes but 87 pages and is limited to concise descriptions of typical instruments with brief theory and methods for their use. The chapter on optical instruments is somewhat more detailed than the others. While this material is excellent for laying a general foundation, the average student will find more specific directions, or personal instruction, necessary. The 162 experiments which follow are logically arranged in 11 chapters covering the entire range of physical chemistry with the exception of nuclear chemistry. The variety of experiments is greater than that in any single manual published in the United States. PITearly all of the rustomary determinations are represented. I n many cases, several experiments of increasing difficulty are offered under one heading. The directions for each experiment include a. statement of theory with equations, "requiremenb" in terms of apparatus often with a line drawing, a very brief outline of procedure without details of specific techniques, and a, statement of the calculations or graphs required. The writing is simple, direct, and rarely uses terms unfamiliar in this country. While most of the experiments might be described as routine, several are ingenious and deserve special mention. Experiment 5.6 is the determination of surface tension by an unusual double capillary method and involves a test oi the constancy of the Parachor. Experiment 5.9 determines the interfwial tension uf benzene and water and serves to test Antonoff's rule. Experiment 6.4 involves an interesting apparatus for studying the rate of effusion of COz,but the directions are so brief as to leave some questions as to the exact procedure. Experiment 11.17 on the thermal decomposition of ammonia. on s. tungsten filament is unique and most interesting, as are several on adsorption and colloidal properties. Some very goad

Volume 39, Number 8, August 7962

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experiments are included on column and

on the part of research-minded students. Nevertheless, questions raised in alert minds by many of these interesting experiments will lead to additional study. The general impression of the manual is that of careful, competent writing baaed upon wide experience in the field. WILLIAMC. OELKE Grinnell College Clinnell. Iowa

Dynamic Physical Chemistry: A Textbook of Thermodynamics, Equilibria, a n d Kinetics

J . Rose, Birkenhead Technical College, England. John Wiley 8- Sons, Inc., 1218 pp. New York, 1961. xii Figs. and tables. 14.5 X 22 cm. $11.50.

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The avowed purpose of this volume is to he a text and reference for persons with an elementary knowledge of the subject and some mathematical understanding. It is to be intermediate between single volume treatises and hooks "written by experts for experts." Although the production by one man of a hook of this length on such a range of topics is no small feat (and one which the author has performed moderately well), this reviewer cannot escape the conclusion that the possession of two or three separate volumes selected from ones already in print by different authors would better meet the need for an advanced text or referenee than this book. The first two laws of thermodynamics are presented in a standard manner using Cilrnot cycles. The approach through CarathQodory's principle is given in a bit less than three pages near the end of this section, hut it seems that considerably more thought and space could and should be devoted to this elegant approach if i t is to he discussed a t all, The CarathBodory treatment is cited by the author as a special feature of the hook. The like amount of time devoted to irreversible thermodynamics appears to be too short to be of significant help to a person not already familiar with the material. The sections an s t a t i s t i d thermadynamics are also 8. hit frustrating in terms of an incomplete or diffusediscussion of fundamental points. The Bolt~mann equation derivation is started (equation 8.2) midstream, and after deriving the mean kinetic energy of an ideal gas molecule to be 3/28, where 0 is the usual undetermined multiplier, thia energy was asserted to be 3/2 kT. This assertion is not obvious, and unless an explicit connection is made with experiment the argument would appear to be a bit circular. The term "phase space" is used on p. 259 without previous or future explanations. These and other such objections might seem unimportant in considering a condensed summary work if the author had not spent one hundred and forty pages in discussing many aspects and cases of phase rule studies. Value

judgments made by the reviewer favor a reapportionment of effort. A book such as the one by Aston and Fritz, "Statistical Mechanics and Thermodynamics" (Wiley, 19591, would be a preferred substitute to the first fourteen ohapters of this hook. It would he presumed that the methods of solving problems in chemical equilibria would have been thoroughly covered in the texts used to give the reader his "elementary knowledge of the subject." Books on reaotion kinetic6 such as the ones by Frost and Peamon and by Trotman-Dickenson provide coverages of chemioal kinetics whieh the reviewer thinks would be preferable to the nonspecialist interested in reaction rates from an experimental or theoretical point of view. It is true that there are topics not discussed in the three alternate hooks cited as preferenoes. Separate monographs or review articles would have to be consulted for the materid covered in this text on solid state and photochemical reactions, radiochemicd kinetics, and properties of high temperature reacting' systems; hence these parts are useful to have disoussed in one volume.

quantitative ealeulations and carrelations." The holding of such an opinion has not prevented the author from writing a fine book on molecular orbital theory (it may have helped). Still, the opinion itself represents to thia reviewer a state of affairs in organic chemistry in which it may be said that the pendulum has now swung the other way. WILLIAMT. SIMPSON University of Waskingla Seattle

Tutorial Questions in Organic Chemistry P. 8. Ongley, College of Technology, Birmingham, England. University of London Press, Ltd., London, 1959. xii f 276 pp. 14.5 X 22 em. $2.94.

Questions of three general types, and their answem, constitute the major portion of this hook, which is intended to serve as an aid to a student reviewing for an organic examination. Problems are given on preparations, organio reactions, and identification from behavior. Forty probJOHN P. CAESICK lems of the third type were selected tst random and solved by the reviewer. Yale University Four contained errors serious enough to Mew Hauen. Connecticut cause difficulty. In three, there was faulty reference to compounds in the succession of reactions, but the intent was clear from the answers. In another, an Molecular Orbital Theory for Organic incorrect moleoular formule. was given, Chemists with a corresponding pentavalent carhon Andrew St~eitwieser, Jr., University atom in the answer. The answer section of California, Berkeley. John Wiley would have been easier to use if the head& Sons, Ino., New York, 1961. xii ing of each page had given the page num489 pp. Figs. and tables. 15.5 X ber of the corresponding questions. 23.5 cm. $14.50. Two of the three appendices are of little value. The first, a list of trivial names As the author states in the Preface, with formulas, serves no purpose whieh in this book he tries to do three things: could not be met better hy the index of teach Hiickel theory, survey the literature, any good organio text. The second, on and present interpretations (some new) nomenclature, is poorly done. For exof various phenomena in organic ehemample, the prefix "n" is said to be needed istry. In the opinion of this reviewer the in IUPAC nomenclature for chains up to author has done an excellent joh with all six carbons in length. Thus the compound three. which ~ o u l dbe called 3-hexanone hy The teaching part is gentle without Chemical Abstracts and by American being undignified. Moreover, one does chemists is given as n-hexan-3-one. not get the feeling that rigor, or a. poThe position of the looant is British usage; tentiality far rigor, is being subverted either position is acceptable. Also, hyin the cause of simplicity. Topics covered bridization of trivial and IUPAC systems include s. matrix algebraic viewpoint, is frequently given in this book in ways factoring of the secular equation using which are generally avoided by Americans, group representation theory, and various hut which are sometimes used in England. accepted refinements of Hiickel theory are hotylene-1 instead of Examples on the one-electron level. a-butylene or l-hutene, isobutene inThe survey of the literature throughout stead of isohutylene or 2-methylpropene, is broad and balanced. One can see and isoprapanol instead of isopropyl that the author has put in a lot of hard alcohol or 2-propanol. work. 4 tmical example of a nrong and The applications to organic chemistry misleading statement is this quotation are likewise broad and balanced. A from the section on nomenclature of final major section of the book on wactions carboxylic acids. "The lover acids have is the same size as the preceding section trivial names; the higher, systematic; which deals with the better known and the intermediate, both trivial and properties of molecules. Among the less systematic." A s a matter of fact, the usual topics covered in the section on lower acids also have IUPAC names, and reactions are radical reactions and four many of the higher acids hrwe trivial center reactions. Two of the less usual names. On the next page the names topics in the section on properties of methanoic acid and ethanaic acid are used, molecules are electron spin resonances and elsewhere in the book one finds stearic and ionization potentials. acid, etc. The author states that "neither resoThe last appendix is a list of several nance theory nor its parent VB theory is suited for general quantitative or semi(Continued on page A604)

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