in the text, footnotes, addenda, and even interspersed in the answers to the problems, cover a widevariety of topicsfromBr0nsted acid-base theory of dimensional analysis to the thermodyanrtmics of rubber ela.ticity. In summary, this is a mast interesting text which should find its widest use a s a supplement or problem book, or as the perfect text in a liberal arts honors course.
Introduction to Mars Spectrometry and Its Applications
The submioromethods dmrribed represent a scaling-dawn operation of one-hundredth of the microscale. The advantages of Rob& W . Kiser, Kansas State Unisuch ultramicro methods are obvious to versity, Manhattan. Prentice-Hall, those who have only an extremely limited Inc., Englewood Cliffs, New Jersey, sample size for characteriastion. 1965. xii 356 pp. Figs. and tables. The author describes the Oertling Q 01 16 X 23.5 em. $10.50. balance which was especially developed for submicro assay. This is the cornerAccording to its preface the purpose of stone of all of the techniques described in this book is to teach mass spectrometry to the text. From all appearances the balRUBINBATTINO those who know very little or nothing ance should sewe its purpose admirably. about it. The background expected of Illinois Institute of Technology Since gravimetric methods are generally the reader is a basic course in physics, Chicago unsuitable, the balance is used exchrsively rudimentary preparation in mstheto weigh the original sample. mstics, and freshman chemistry. This Because most of the methods are titriis an exceedingly difficult assignment and metric (for greater precision), a goodly the author has not succeeded. remainder of the foundation of the techThe hook is organized into three a p Mechanisms of Inorganic Reactions nique is dependent upon the burette proximately equal sections dealing with employed. Professor Belcher recommends instrumentation, chemical physics of ionJacob Kleinbwg, qmposium director. the use of a modified Agla micrometer ization phenomena, and analytical and R. K a t M u m n n , University of syringe burette with a total capacity of application. Although each miacellaneous Missouri, Columbiq R. T . M. Fraser, 0.6 ml. with graduations of 0.2 "1. section contains many items of interestand John Bauman, editorial committee. Usually, visual indicators are used ing information, welkeferenced, there is Advances in Chemistry Series, No. 40. wherever possible as opposed to potentiovery little systematic exposition of parACS, Washington, D. C., 1965. vii metric measurements. Where no suitable ticular topics. Many equations are pre266 pp. Figs. and tables. 16 X 23.5 titrimetric method was available, ss in the sented without any derivation which might em. $8. arsenic and fluoride determinations, speomake them meaningful to readers having trophotometric procedures were employed. This volume contains the proceedings the expected background. Further, the The oxygen-flask combustion was utilized of the 1964 Summer Symposium of the hook is filled to an irritating extent with for 8ulfur and halogen determinations, Division of Inorganic Chemistry (ACS) on numerical examples consisting of nuleaving only nitrogen to he determined via. merical substitutions into the preceding the topic of the same name. The ten sealed tube decomposition. papers a r e research-oriented with some equations and carried out in great detail. Only carbon-hydrogen ltnalysis requires background in the nature of specific deI n the section on instrumentation there highly specialized equipment in this new is no mention or introductory develop taik from the literature. Each paper technique. The hydrogen analysis a p wvers a single %re&; e.g., Chapter 4 ment of ion optics. The section on chemparently was the real stumbling block in by F. Basolo coven Substitution Reactions ical physics of ionization phenomena conestablishment of the whole scheme of tains both very elementary (and inof Square Planar Complexes. For those submicro organic analysis. The carhonreaders who are seriously interested in complete) verbal definitions of molecule hydrogen method which har been d e mechanisms, the book will he of some ions, and a section starting with an (undeveloped involves catalytic decomposition interest. A revier* which dismssee the rived) secular determinant based on an in an oxygen stream, trapping of the water bwk in aresearch context may be found in approximate farm of molec~ilar orbital and carbon dioxide at -80" and -196", Inmgunic Chemistry (5, 702 [1966]). theory. removal of excess oxygen and manometric The usefulness of this hook in a teachIn summary, this book can serve as a measurement of the water and carbon ing context seems quite limited, and it meful guide to the literature on the many dioxide. appears worthwhile to review for Tars aspects of mass spectrometry to which it The excellent method descriptions, the JOURNAL the applicability of this book alludes. However, it cannot be recommeans of overcoming interferencer, and as a text. Admittedly, however, this book mended as a text. the techniques for difficultly analyzahle wasnot designed as a text. HENRY ROSENSTOCE moieties would make this book of conThere is no general introduction to ~VationalBureau of Standards siderable v a h ~ eto any andytiesl chemist inorganic reaction mechanisms therein, whether engaged in submicro, micro or Washington, D.C. and the individual papers assume a macro organic analysis. familiarity with the topic. Much of the No utilization has been made in this book is taken up with the presentation of text of the promising vapor chromstoindividual points of view on unsettled graphic techniqnes for mioroandysis. issues. The ten main papers are uneven Submicro Methods of Organic Analysis Undoubtedly, this is under consideration in style, quality and clarity; by and large, for future extensions of this excellent work. they seem to be hastily written. The Ronald Belcher, University of Birmingopen-floor discussion sections are rambling ham, Great Britain. AmericanElsevier ROBERTH. CUNDIFF and inconclusive as would be expected ... Co., Inc., New York, 1966. Publishing R. J . Reynolds Tobacco Co. fmm a meeting of this type. A number of vnl 173 pp. Figs. and tabler. W i n s h S a l e m , North Carolina errors, both scientific and typographical, 15.5 X 23 em. $10. were noted. Also, there are many stateThis is a superb contribution by one of ments which lack the firm,factual foundathe most eminent and distinguished tion appropriate for a text. Some improfessors and practitioners in the field of portant subjects such as outer-sphere analytical chemistry. electron-transfer reaetionn, ligand field Professor Belcher in this monograph has stabilization effects, and free radical redelineated a field of analysis that offers actions are not included. Introduction to Quantitative comparable ramifications to that opened I believe that the chemistry teacher Ultramicroanalysis by Pregl in his pioneering work in organic who wishes to give his students something microanalysis. He and his ca-workers outside of the ~resentlv-limitednumber of I . M . Koraman, Gorkiy State Univerover a period of the past 15 years have textbooks on &organic mechanisms would sity, U.S.S.R. Translated by Scripta developed techniques for accurate analysis find it more profit,able to pick sound reTeehnica, Inc. Academic Press, Inc., using sample weights in a 3W50 pg range. search papers and reviews from the liters, 234 pp. Figs. New York, 1965. ix are even more remarkThe achievements ture rather than to use this book as a text. 23.5 em. $9.50. and tables. 16 able when one considers that the average JOHN0. EDWARDS weight of a grain of sugar is 200 pg, and B r w n University they are dealing with samples nizes o n e Prm'denee, Rhocle Island eighth to onefourth of t h i ~ amount.
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Journal of Chemical Education
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when sample avdabilit,y is not a limiting factor. Although these techniques require some skill and close attention to detail, they are rarely so difficult that only a speeidist can use them. That this thesis is not new is well known to readers of the late Professor A. A. Benedetti-Pichler's book, "Introduction to the Microtechnique of Inorganic Analysis," (reviewed in J. CHEM.EDUC.20, 51 [1943]). Professor Korenman's book leaves the reader with the same impression. In discussing scales of working, the author defines ultramicrotechniques as thoae applied to quantities of a few micrograms or less, as well as t o solution volumes not exceeding 0.05 ml. A microscope and a micromanipulator are often required to work with such small quantities. The high surface-to-volume ratio of microliter qnantities of solutions greatly enhances problems such aq adsorption, atmospheric contamination, or loss by evaporat,ion. The minimization of these effects is admirably discussed. Chapter 2, which describes general apparatus and techniqueq, is strongly reminiscent of Benedetti-Pichler's t r e s e u#r!.t. .\I lloir pmn1 i l IW~IIIII.. dwiou. 111x1I'nic:or K l m ~ l t n n ' rImuk ~ntt!,.dwJ \lodrrn mifor I crogram ha.lanc,es, ultramioropipets, sophisticated miwomanipdators, and other commercially-available small-scale instrw ments are not described and are rarely mentioned. On the other hand, eonstructiond details are given for mast of the equipment,. This extends even to various forms of quarts-fiber microbalances, the constmct,ion of which is described in Chapter 3. Much of the simpler a p paratus is easily fabricated from meltingpoint tubes and thin glass rod. A leas obvious feature of ultramicroanalysis is that much can be done with a small budget, same manual skill, and a considerable amount of patience,
I.
Apparatus and techniques for chemicalindirator volumetric analysis are described in Chapter 4. The small depth of solution in drop-scde titrations makes the colorchange difficult to detect, so that a high concentration of indicator is used. Indicator corrections, which are highly important in t,his type of work, are extensively discussed and a small but useful selection of a c t d determinations is given. Although the treatment of physiachemical methodq of analysis in Chapt,er 5 is rather thin, t,he reviewer was glad to note reference to the modern and elegant bipotentiometric dropscale technique of Bishop. The book e o n d u d s with short chapters on miseellrtneous techniques and on gss analysis, then a bibliography with 395 entries. Occa~ionslmis~rintsexist. hut there are
out by use.
JOHN T. STOCK Uniuersity of Connectieul Storm
Quantum Organic Chemistry
Keniti Higasi and Hboaki Baba, bobh of Hokkaido University, Sapporo, Japan, and Alan Rembaum, California Institute of Technology, Pasadena. Interscience Publishers (a division of John Wiley and Sons, Inc.), New York, 1965. vii 358 pp. Figs. and tables. 15 X 23.5 em. $13.
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T h k baok contains a. well-organized, lucid description of the mechanics of the pi electron approximation at its lowest possible level of mathematical sophistication. The emphasis throughout is upon the Hiickel molecular orbital spproximation, although some space is devoted to the Slater-Pauling valence bond method. Any organic chemist willing to m e simple algebra should find this book an easy-tofollow guide to the use of the Hiickel method in those areas of organic chemistry where thk approximation is most sueeessful and useful. The authors are very careful in explaining virtually sjtep-hy-~tep how the calculations are done and bow they are applied to a variety of specific, well-chosen problems. The applications considered include the calculation of dipole moments, the interpretation of electronic absorption spectra, the electron fipin remnance speotroseopy of free radicals, chemical reactivity and polymerization reactions. I n their preface, the authors state: "The excellent texts in this field are still beyond the majority of scientists, and Quantum Organic Chemistry should t h e r e fore serve &S a stepping stone to a more If by a more adadvanced treatise." vsnced treatise the authors have in mind a book such a? Daudel, Lefebvre and Moser, "Quantnm Chemistry," then the statement seems fair. However, it is hard to see how "Quantum Organic Chemistly would be of more than minimal aid toward the understanding of treatises such a5 Eyring, Walter and Kimhall, "Quantum Chemistry" or Slater, "Quantum Thmry of Molecules and Solids.'' Although these latter texts are by no means advanced, both require mastery of a, great deal more mathematic2 than many organic ehemisL3 are likely to have or be willing to acquire. "Quantum Orgenic Chemistry" is written a t about the same level as Roberts, "Molecular Orbital Calculations,'' but has a more extensive coverage of applications. I n many respects "Quantum Organic Chemistry" is comparable to Streitwieser, "Moleculrtr Orbital Theory for Organic Chemisk," but is written in a clearer, more readable style and, therefore, is perhaps easier ta comprehend as to mechanical details of calculation. The former aka deals with fewer specific examples but these are treated with greater clarity bhan in Streitwieser. I n mmparisonwithKilragounis, "Introductory Quantum Organic Chemistry," one might say that whereas Kamgounis attempts to explain much theory and illustrate little faot, the opposite is attempted in "Qoanturn Organic Chemistry." For this reason "Quantum Organic Chemi~try"is a much more useful book for the chemirr who wishes to learn to apply some quantum chemistry to actual problem% On the debit side, there are no more than brief references to many of the important theoretical a3pects of the pi
electron approximation, i.e., virtually no attempt is made to place the Hiickel molecular orbital approximation or the Slater-Pauling valence bond method into any sort of proper perspective with r e spect to hasio Schradinger mechanics. The orbital approximation is nowhere defined in a general fashion, the variation theorem is given short shrift ($though the variational energy is stated ta be a minimum, it is not made clear that this energy is an upper bound to the exact energy) and little attempt is made to state precisely what the irr separation problem actually involves. However, it is only fair to say that references to the original literature dealing with such topics are copiously given and appear to he adequate. The book is also marred with numerous examples of rather careless language, e.g., the verb "to resonate" appears several times, and hybridization is referred to as "a basic a~snmptionof quantum organic chemistry." However, it is unlikely that such hlemishesnumerous as they a r e will serio~lslyhinder the reader in acquiring a goad mechanics1 facility in the methodq described. I n the final critique, this is an overall excellent baok which e m be enthusiastically recommended to any chemist who want3 to learn to use a9 much quantum chemistry ss possible without being exposed to the important but mathematically-structured fundaments of quantum theory. The book should be admirably suited for self-study or for use in comes in theoretical organio chemistry where use of simple mcleeulm orbital and valence bond methods i~appropriate. FaANK L. PILAR Uniuevsity of New Hampshire Durham
Supplemental Tables of Molecular Orbital Cdeulationr with a Dictionary of T-Elechon Calculations. Volumes 1 and 2
Andrm Sl~eitwieser,Jr.,University of California, Berkeley, J . I. B~auman, Stanford University, Stanford, California, and C . A. Coulson, Oxford University, England. Pergemon Press, Inc., New York, 1965. 1223 358 pp. Tables. 21.5 X 30 cm. $100 the set.
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These combined volumes present Hiickel molecular orbital calculations for over 600 compounds. The molecular orbital calculations section is limited to hydrocarbons; however. the r-electron section includes some important heteromolecul~% Overlap of data in the two parts is very small. Because the tables are printed directly from ha to graphs of the computer readout, typesetting errors me minimal. Use of the tables and the index scheme %reexplained in the peface along with a brief summary of the mathematical methods involved. Volume
43, Number 7, July 1966 / 395
