General chemistry. - ACS Publications

---

684

JOURNAL O F CHEMICAL EDUCATION

supplement the two classics; Frohlich's monograph fills thr need

about the oossible value of weiehine on s. mioro scale. Aooar-

as far as modernization of theory goes, because the author handles

the theoretical derivations with complete competence. In this reviewer's opinion, however, the book could have been considerably strengthened and made much more valuable by a more liberal use of experimental examples. If the author insisted on holding so rigorously to his title, he might s t least have included aome references for supplementmy reading. Several i t e m of nomenolsture call for comment. 1)escribing the real and imaginary components of r as "two different dielectric constants" is objectionable, because the accepted name "loss factor" is so aptly descriptive for the imaginary component,. Introduction of the symbols q and re for the familiar r' and 6'' seems a.needless conflict with convention. Loss angle and phnse angle have also been confused, by implication at. least, if we compare Eqs. 2.2, 2.5, and 10.17. The opening chapter presents the fundamental electrostatic relationships in essentially axiomatic form and introduces almost at the outset the timedependent field. This procedure seems much better than the traditional one of starting with static fields and then, after many pages, letting the reader in on the secret that the fields of practical interest are variable. Another excellent ieature of the initial chapter is the treatment there of electrical energy and dissipation from the point of view of thermodynamics; this introduction anticipates the order-disorder problem. Next, the static dielectric constant is discussed; here we find again a seleome hreak with the tsadition of presenting Lorente theor,", building up an elaborate structureon this limiting case, then backtracking to consider real systems a t finite dipole concentrations. Instead, the ideas of reaction field and dipolar interaction are introduced early, and the treatment follows the Onsager-Kirkwood theory with the ClausiusNIosotti formula. included as a special ease. This chapter also contains some useful original derivation-. The third chapter includes the familiar Debye theory of relaxation in dipolsr system. In view of the practical importance of polymeric dielectrics more space might have been found far mention of Cole's and Kirkwood's work on the distribution of relaxation times. Also Kauzmann's application of Eyring's rate theory seem to be dismissed too hastily. The fourth (and final) chitp t,er contains a series of well-chosen examples illustrating the application of the theory to experimentally studied systems. It is in this chapter that expansion in an eventual revised edition would be desirable. The monogrrtph closes with an appendix in whieh mathematical details of a number of derivations are given. The book is recommended as a reference work far advanced aomses in physical chemistry. RAYMOND M. FUOSS YALEUNIVERSITY NEW HAVEN,CONNECTICUT

QUANTITATIVE PHARMACEUTICAL CHEMISTRY Glenn L. Jenkins, Dean, School of Pharmacy. Purdue Universit)r, Lafayette. Indiana; Andrew G. DuMez, Dean, School of Pharmacy, University of Maryland, Baltimore, Maryland; John E. Christian, Associate Professor of Pharmaceutical Chemistry, Purdue University; and George P. Hoger, Associate Professor of Pharmaceutical Chemistry, University of Maryland. Third edi531 pp. tion, McGraw-Hill Book Ca., New York, 1949. xii 68 figs. 7 5 tables. 14.5 X 21.5 cm. $4.75.

+

THISis the third edition of the only practical modern textbook on quantitative analysis of drugs, and it exhibits some improvement over previous editions, both in format and freedom from gross errors. I t will of necessity constitute a part of the training of every student of pharmacy and should be avdeble to any chemist who is concerned with analytical work on medicinal suhstances. Nevertheless, there are several shortcomings of the earliw editions that unfortunately have not been corrected. While n good description is given of the analyticd bdance nothing whatever is said a b u t the ever more popular chainomatic variety and

sampling is itlmast neglected, except for copying the pharmacopaeial directions, and no explanation is offered for the process of quartering. The statistical treatment of results is considered somewhat superfioially in the light of modem trends, dthough perhaps this might be excused in an elementary text. I t must also be pointed out that there are quite a number of inaccuracies in the statements about ionization. esoeoiallv in reeard to ore-

chloride. In the reviewer's mind this is a seriously poor custom and inexcusable in any textbook, lecture, or discussion, and certainly the student should not be allowed to acquire the habit. To hear a teacher say "Add two grams of En-A-2-Ce-Ar-2Oh-7" when the words sodium dichromate contain three fewer syllables seems almost ridiculous. It is recognized that many modern texts are equally a t fault but that does not excuse any of them. The end results become serious when a formula. such tL8 HC1 is used to mean 10 per cent hydrochloric acid and when HIOl is employed for tho common 3 per cent solution of hydrogen peroxide. While in general official titles hilvc been changed to conform with the new system, unfortunately there have been some oversights. For example, one will find Extract of Beef and Pills of Ferrous Carbonate. Furthermore. substances that are not now official are still described, e. g., we'find on page 137 Diluted Hydrooyanio Acid N. F. and on page 142, Strong Silver Prot,ein u. S. P. E. Y. LYNN x1*r9.,cauarTTs C"LLEO& OF PR*RM*CI

R"sT"N. M*sa*cnosp.r~a

GENERAL CHEMISTRY A. W. Laubengoyer, Professor of Chemistry, Cornell University, Ithaca, New York. Rinehart and Co., Inc., New York, 1949. nvi 528 pp. 57 figs. 90 tables. 16 X 23.5 cm. $4.25.

+

PROFESSOR LAUBENGAYER has followed the order most commonly found in heginning chemistry hooks. A statement of the simplified atomic theory is followed by material on oxygen, hydrogen, states of matter, and elementary physical chemistry, leading up to the discussions of the elements according to the groups in whieh they are found in the long form of the periodic table, including simple organic chemistry. Discussions of radioactivlty and colloids complete the book. The appendixes include, in addition to the usual conversion tables, summaries of the use of enponentials and the concept of significant figures, and s. table of oxidatian-reduction hdf reaction potentials. The book accents, considerably more than most of its class, the geometrioal arrangements of the atoms in the substances discussed and contains more than one hundred line drawings of the "stick and hall" or "symk>oland bond" type to illustrate various structures. These should be very valuable for students who have concepts of spatial geometry. The general pedagogy in the majority of subjects discussed is to present ra chemical theory or define a chemical concept and then to show how these &reconsistent with the experimental data. Thus conclusions are first presented and the facts supporting those conclusions then fitted into place. The treatment of solvation. and oartieularlv hvddration is

only varying degrees of approach to reality. Equations for net reactions are used in the main as the closest feasible approach to the real situations. Relatively little space is devoted to industrial preparations, only three of t,he line drawings being at all related to industry.

DECEMBER. 1949

685

There are indeed no half tone cuts a t all in the book but only line drawings of such simplicity as to be readily comprehended by the student. The errors, both typographical and factual, are fewer than in manv books coverine the same subiects. The ~roblemsare well chosen, and varied, with an avers& of about i 0 for each of the ~

26 .. . rhnntem. .

Tllc majority of rmclrrrs of bryirrning chcmiirry will rwr.tinly find it worth their a.l.il~t o Iouk o w r thi; volumr fur it voraraiqe. mueh of the n.rm rwcnt contributioni of arrudural rlwmi-trv without breaking sharply with the most common order and content in elementary chemistry courses. J. A. CAMPBELL O ~ ~ n m Com,Eaa s O B E R ~ NOar0 ,

MATHEMATICAL FOUNDATIONS OF STATISTICAL MECHANICS

A. I. Khinchin. Translated from the Russian by G. Gamow, Proflesor at George Washington University. First American Edition. Dover Publications. Inc., 1780 Broadway. New York 19, 1949. viii 179 pp. 12.75 X 18.75 cm. $2.95.

+

ACCORDING t o the publisher's circular the author "has been prominently identified with the remarkable researoh devclopments in mathematied analysis a t the First Moscow University." The translator is a well-known physicist and author. It is difficult to sppraise what a book like the present one will contribute toward helping the efforts of physical chemists engaged in applying statistical mechanics to their many problc~m. Fundamental and laudable as they are, the preoccupations of this hook are more of the type of those of the mathematician and of the theoretical physicist. As explicitly stated in the Preface, "the hook is written, above all, for the msthematician, and its purpose is to introduce him t o the problems of statistical mechanics in an atmosphere of logical preoision, outside of which ho cannot assimilate and work, and which, unfortunately, is lacking in the existing physical expositions." The titles of the eight chapters will give B more ooncrete idea, of the author's purpose and scope: Introduction, Geometry and kinematics of the phase space (not "phas3 rule" as is hopefully stated on the jacket), Ergodic problem, Reduction to the problem of the theory of probability, Application of the central limit theorem, Ideal monatomic gas, The Foundation of thermodynamics, Dispersion and the distributions of sum functions. There is an Appendix entitled "The proof of the oentral limit theorem of the theory of probability," a. table of Notations and a short Index. The physical chemist may accept, no doubt with a mild shock, that the mathcmaticrtl level of the Maxwell-Boltammn invcstigations is "quite low" and that of Gibbs' Elementary Principles of Statistical Mechanics "not high" and he may go along with the author toward the summits of Birkhoff's theorem with its implications concerning the ergodic hypothesis. The esthetic and logicd reward may be great but the new outlook cannot be very different from that so aptly stated by Tolman ("The Principles . .it is of Statistical Mechanics, Oxford Press, 1938, p. 70): evident that such studies can neither contradict the mechanical possibility for some paths, which would exhibit time averages quite different from the ensemble averages, nor eliminate the ultimate necessity for recourse to a postulate as to a priori probabilities." To t,hose students of statistical mechanics who have made the effort of mastering the Fowler-Darwin method of steepest descents as well as to the more numerous ones who have remained eatisfied with the Stirling approximation type of derive

".

will prove of intenst. According to the author"'thi only essentially new material in this book consists of the systematic use of limit theorems of the theory of probability for rigorous proofs

of asymptotic formulas'' (i. e., formulas "which approach the precise ones when the number of pa~ticlesconstituting the system increases beyond any limit"). The avoidance of quantum st* tistics greatly but purposely limits the scope of the book from bath the theoretical and applied standpoints. In times like the present, when statistical mechanics enthusiastically attacks one new problem after another (as evidenced, for instance, by the colloquium recently held in Florence by the International Union of Physics), it is usoful and even essential to have available the cautious stability of books acutely concerned with fundamentals like the one under review. Should this translation do no more than succeed in obtaining the active interest of a few mathematicians as well as the studious curiosity of a few physical chemists its publication will he well justified. To some readers i t will perhaps be a matter for slight d i e appointment that the translator's customary humor and artistic akill could not be called in to relieve somewhat the arduousness of the mathematical arguments. PIERRE VAN RYSSELBERGHE T~NIYEASITY

01.OREGON

E V G E NO ~ .S ~ G O N

0

CHEMISTRY OF SPECIFIC, SELECTIVE AND SENSI. TIVE REACTIONS

Fritz Feigl, Engineer, Laboratory of Mineral Products, Ministry of Agriculture, Rio d e Janeiro, Brazil; formerly Professor of Analytical and Inorganic Chemistry at the University of Vienna. Translated by Ralph E. Oesper. Professor of Chemistry, University of Cincinnati, Ohio. Academic Press, Inc., New York City, 1949. xiv i-740 pp. 29 tables. 15 X 23 cm. $13.50. THE author states in the first sentence in the preface that "during the past twenty-five yeam andytieal methods based on the properties and reactions of the substances to be detected or identified have been improved to a greater extent than in all the preceding years." Older methods have been improved, new methods developed and rtnalytical procedures placed on a scientific basis. During this same period rapid progress has been made in the development of analytical instruments that often simplify the making of quantitative measurements and gotttly extend the accuracy and sensitivity of the methods. Tho present book is "an attempt to summarize our knowledge of the soientifio background of the specificity, selectivity, and analytical procedures." No other person is better qualified to do a job of this magnitude and scope than Dr. Feigl who has contrihuted so mueh through his researches in the field of spot test analysis for mare than a quarter of a oentury. Throughout the hook the experimental side has been stressed and the author has drawn on all fields of chemistry-inorganic, organic, physical, colloid, photochemistry, etc.-in his study of specificity, selectivity, and sensitivity. There are hundreds of references to the original literature, as well as many citations to work done in Dr. Feigl'a laboratory and published here for the first time. The book is replete with critical remarks pertinent to the subject. These not only enhance the value of the book but also should stimulate research in the field of specific, selective, and sensitive reaotions. These "critical remarks" arc frequently to be found in footnotes in smell print. A hasty count by the reviewer gave no less than 190 pages having one footnote and more than 40 pages with two or three. I t would have made reading easier had these footnotes been placed in the main body of the text (in the samo small type, perhaps, to emnomiae with space). Most of these would have required little or no change in their wording. This is only a suggestion which the author may wish to consider in a future

treated are: General oomments on the analytical usefulness oi chemical reactions (Chapter I, 5 pages); characterization of chemical tests by sensitivity, selectivity, specificity, and limiting