Wave mechanics for chemists (Cumper, C. W. N.) - Journal of

Wave mechanics for chemists (Cumper, C. W. N.). J. de Heer. J. Chem. Educ. , 1967, 44 (5), p A468. DOI: 10.1021/ed044pA468.2. Publication Date: May 19...
0 downloads 0 Views 3MB Size
B O O K REVIEWS and a separate supplement on the compounds of sodium and lithium and systems with two or more anions is anticipated. These volumes will bring the main volume on sodium, origindy published in 1928, completely np to date.

JANETB. VANDOREN College of Wooste~ Wooster, Ohio

Techniques of Oscillographic Polarography

Robert Kalooda, Prague. Translated by Ziarel Micka. 2nd ed. American Elsevier Publishing Co., Inc., New York, 1966. 214 pp. Figs. and tables. 15.5 X 23 em. 512.50. Dr. Robert Kalvoda's monograph on techniques of oscillographic polarography was designed to serve as a. training manual for aspiring practitioners of this wellknown electroandytical technique. Dr. Kalvods is probably the world's most qualified individual in the field of oseillographic polarography, having worked with this technique for many years in an environment where its applications are truly ubiquitous and demanding. The excellence of this monograph clearly demonstrates Dr. Kalvoda's qualifications. The level of presentation is aimed at the beginner in the field. The aim is true! Dr. Kalvods succeeds in explaining the basic principles of the technique in quditative terms which demand a minimal background of knowledge in modern electroanalytical methods. The cumbersome mathematical description of the technique is omitted, except for a few illustrative equations. The clarity of presentation for the most part is excellent. For this we apparently owe much to the translator, Dr. Karel Micke. The monograph consists of four c h a p ters. The first chapter provides a summary of principles of the method, its scope, techniques employed in analytical applications and typical instrumentation. Nearly one-half of the text is devoted to Chapter 2 which describes eramples of applications of the oscillopolarographic method. Tbis review of applications probably represents the most extensive and complete one of its kind. Applics, tions in analysis represent by far the most frequent use of oscillographic polarogrsphy. The content of Chapter 2 is distributed wxordingly. I n this chapter the author confronts the reader with an analytical methodology of truly amazing scope which includes analysis schemes for over 53 elements, for numerous organic compounds ranging through aliphatics, aromatics, heterocyclics, alkaloids, amino acids, hormones, vitamins, proteins, etc., as well as applications in characterization of emulsions, insoluble subst,ances and the like. Applications in kinetic and mech% nistic studies of electrode reactions receive a mere 511% page treatment which is prohahly justifisd due to the lass frequent

A468

/

Journal of Chemical Education

applieabions of this nature. Chapter 3 presents ts well-chosen group of exercises in the use of the oscillopolarographic method, while Chapter 4 deals with circuitry end maintenance of apparatus. Clearly this text fulfills its intended purpose. Students learning to apply oscillographic palarography with the aid of the Czechoslovak P576 and LP600 Polaroscopes are particularly fortunate that this monograph exists. However, many readers of this review rue not in a position to h w e developed a highly specialized interest in oscillographic polarography. To them, this monograph which deals with a specific technique applied in a rather specified manner (50 c.p.s. alternating current polarization, readoct consisting of dE/dt vs E curves) with the aid of a. particuh~ type of instrument (the Czech Palaroscapes) may represent a text of rather narrow content. Such a view would not be surprising, nor would it reflect in a negative way on the abilities of the author who had a rather specific objective in mind. However, this reviewer believes that the careful, percep tive reader will find something in this book which is of much broader significance than oscillographic polarography itself. Through thoughtful perusal one finds an implicit development of a hasio philosophy of application of electroanalyticd techniques to chemical problems which transcends the bounds of oscillographic polsrogrrtphy to include all related methods. The philosophy is one which includes, among other things, an apprecis, tion of the rewards that care and attention to detail bring to electroanalytical methods, and a confidence that the technique a t hand is a powerful one which can be applied successfully even in relatively unfavorable circumstances by a proper blend of basic knowledge and empiricism. In addition to this, readers living in the many countries where applications of electroandytical methods are rare will find the scope of application described in Chapter 2 an education in itself. The content of this chapter should lead one to question whether the electroanalyticd methods do not have more to offer than many of us think. There are a few items in this monograph which appear objectionable, although they scarcely dampen this r e viewer's enthusiasm. With one excep tion, most are minor points unworthy of mention. However, in pages 12 and 13 the author makes statements which imply that, while oscillogrrtphic polarography with controlled alternating current is a unique method which truly supplements chssio~lpolmography (which is true), the controlled potential analogs of os,cillographic polarographic (e.g., rapid h e a r scan or cyclic voltammetry) do not share these properties and provide nothing new. The reader should be aware that there are many, including this reviewer, who do not share this rather disparaging opinion of the controlled potential analogs. The literature abounds in theoretical and experimental evidence from which the reader can draw his own conclusions.

Wave Mechanics for Chemists

C . W. N . Cumper, Woolwich Polytechnic, London. Academic Press, Inc., 382 pp. Figs. New York, 1966. x and tables. 14.5 X 22.5 om. $11.50.

+

This book consists of three parts and a series of appendices. After a brief introduction to wave mechanics, the first part deals with exact solutions of the Sehrodinger equation for the harmonic oscillator, tbe rigid rotator and the hydrogen atom. The second part gives a. short description of the mathematical techniques involved in the most important approximation methods, and applies these to the elementary quantum mechanical treatment of atoms and molecules. The third part concerns itself with some rtpplicrttions to chemical problems. In the Preface the author states that "The intention of this hook is to cover the needs of students preparing for University (in Britain). Degree Examinations. I n the U. S. its contents should he accessible to the advanced chemistry undergraduate and may he of some use to the beginning graduate student. mathe em atical arguments have heen kept to a miniu , tlte n l d v , mum : t ~ dLIW p r e ~ w t n t i ~ ~1 i s dear. This revivucr itruwly ircL 1 h 1 ~ l l eworking our of scr j of problems iho\dd be an i n t e g d part of the &udy of many of the topics involved. He therefore regrets that no such exercises are included. Each chapter ends with list of Bibliographical References, which is helpful but frequently not up to date. It is amrteing how many features the author has managed to cover in anaverage sized book even when one realizes that such coverage does not always go very deep. 4 1 0 While there is heavy emphasis on 1 techniques, the valence bond method is not neglected altogether. I n several instances a more critical approach would have improved the presentation. For example, the discussion of Ionic-Covalent resonance is unsatisfilctory since it does not consider the problems created by the non-orthogomlity of the relevant wave functions. In the VB treatment of hutadiene, the arbitrary choice of basic structures is justified solely on the basis of "chemical preference." The reader is never told why some computed properties are independent of this choice but others are not. The Penney-Diarc-Moffitt scheme is only referred to in a footnote. Of course the question as to what to include and what not to include in a book of this type largely remains a, matter of personal preference. We can forgive the author for omitting van der Waals forces and for only briefly touching upon some aspects of optical spectroscopy, even for leaving out entirely EMR and NMR spectroscopy. But we cannot be reconciled with the omission of group theory; a t least some simplified discussion of the utilization of molecular symmetry in solving quantum chemical problems should have been given. In re-reading my comments up to this p i n t , I note that in no place have I been highly critical or very enthusiastic. This accurately summarizes my opinion of this book. It is commendable but it lacks E. SMITH originality, depth, critique, and challenge. DONALD Nodhweslen Uniuwsity (Continued on we A470) Euanston, Illinois

.."

BOOK REVIEWS It should be useful to prepare students for examinations, hut it would certainly not give them the ideal background to embark upon research activities in the general area of quantum chemistry. Several features of this monograph which have been mentioned make it less soitable as s. textbook for classroom use. J. DE HEER University of Colorado Boulder

Inlemclionr in Elsrtrolyle Solutions: Metal Complex and Ion-Pair Formation in Solution

George H. Nancollas, State University of New York a t Buffalo. American Elsevier Publishing Co., Inc., New York, 1966. Topics in Inorganic and General Chemistry, Monograph No. 8. x 214 pp. Figs. and tables. 14.5 X 22 em. $14.50.

+

This book presents a brief survey of metal-complex and ion-pair formation in aqueous solutions. The principal emphasis is an association constants for complexes and ion pairs containing one metal ion and one ligsnd (other than the solvent). These are examined with respect to the methods by which the association constants may be determined and the information which can he extracted from the values obtained. There is also a brief discussion of the rates of such association reactions which deals principally with very rapid reactions of this type. The presentation is a t the senior-first year graduate level, and the emphasis is on commentary rather than detailed derivations. A satisfactorily comprehensive eollection of literatore citations is given for the reader who desires more det,ailed information on the topics covered. Because of this, the hook should prove useful in the preparation of lectures on the topics it covers. thoueh it is desiened to be a mano-

water, with an emphasis on the important mle the structure of the solvent plays in detailed interpretations. The second chapter covers many of the experimental methods which have been used to determine association constants. It should prove useful to those who are beginning s. study of a particular system and need some assistance to seleot a suitable method from among the many available. Chapter 3 discusses methods for correcting association constants for the ionic strength of the medium and methods of computing such constants, from experimental data, for systems which contain one or two complexes. Chapter 4 covers the relstionships between association constants and other parameters such as radius of the ions involved, and the number of eleetrons in inner d and f orbitala. I t presents a very clear discussion of the problems involved in distinguishing ion pairs (outer sphere) from complexes of the more traditional sort (inner sphere).

Chapter 5 contains a very compact description of t,he thermodynamic properties for ionic hydrates and for complexes with simple and polydentate ligands. The data for chelsting agents and the treatment of the chelate effect are both reasonably detailed. The final chapter (Chap. 6) deals briefly with the rates and mechanisms involved in the farmstion of labile complexes. Here the emphasis is on the results obtained from the study of very fast reactions. At the end of the hook are to be found (1) s. 13-page summary of thermodynamic data on ion-pairs and metal complexes (2) an author index

which covers the same general area. Nancollas provides primarily an introduction to the ezperimental methods used in the study of ion pairs and complexes, while Hunt's emphasis is more on the theories nsed to explain the results obtained. Far this reason, Nancollas' boak should he valuable reading for the fledgling experimentalists in this area.

data. Absent from this hook are the extensive tables of economic data found in wme of the more "encyclopedia type" pnbhcations of the past. The style is pleasing and the author demonstrates repeatedly an ability to present rather difficult topics in an interesting and learnable fashion. Michigan Technological Uniumsity Hovghlon

The Encyclopedia of Physics

Edited by Robert M. Besangm, Wright Patterson Air Force Base, Ohio. Reinhold Publishing Corp., New York, 1966. 832 pp. Figs. and tables. 18 xii X 26 cm. 825.

+

This volume, one of a series of scientific and technical encyclopedias, contains 316 alphabetically arranged articles, written by as many subject specialists, which can introduce the reader to a great many different fields of physics. MARKM. JONES As stated in the preface, no attempt has Vanderbilt University been made to have all the articles a t the Nashville, Tennessee same technical level. On the whole, the broad, general articles are pitched a t a somewhat lower level than are the more specialized articles. Introduction to the Chemical Process This reviewer was impressed by the Industries amount of material which the individual authors managed to crowd into their Richard M . Stephenson, University of articles without loss of clarity. I n addiConnecticut, Storm. Reinhold Publishtion to the text, the authors have provided 474 ing Corp., New York, 1966. v both hib1iagrs;phicd and cross references pp. Figs. and tables. $14.75. to follow their articles. The aothor of this book has fulfilled a Although this boak was probably deneed for a reference book or an undersiened with ~hvsicistsin mind.. its ereatest vrdw m a y I,P 11, n.urken iu 1d91~ll field* graduate textbook of reasonable size (and nla, i.ped 119 l w w ~ ~ron\w.i~nr w tiirh mme price) filled with up-to-date infomation