book reviews The book is designed for the advanced student and the lower grades are advised t o read a more popular account prior t o tackling this volume. The probability of this restricted sale accounts perhaps for the relatively high price, hut the latter should not discourage libraries from acquiring this volume because it contains, among other things, the uncut text of the autobiographical Memoirs of Priestley. RALPHE. OESPER University of Cincinnati Cincinnati, Ohio
Laboratory Course in Organic Chemistry
David H. Rosenblatl and George T. Davis, The Johns Hopkins University. Allyn and Bacon, Inc., Boston, Mas320 pp. sachusetts, 1971. xiv Figs. and tables. 26 X 18 cm. 510.25.
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A new laboratory text in organic chemistry should be tested by criteria of orginality in approach t o laboratory work, inclusion of new experiments of instructional value, or a. superior organizarttion or presentation. This new text is conventional in approach, hut it does include some interesting new instructional examples, and its organization and presentation, while not differing greatly from those of the presently useful laboratory textsis an improvement on them. The most obvious innovative feature is the introduction of each laboratory experiment as a problem which a professional chemist or someone in a, related area. might face. For example, the preparation of 1,2,3,4tetrabromobutane (meso plus racemic isomers) from butadime is introduced as one synthesis which might be tried in order to obtain some materials of possible use as fire-retardants for party decorations. This is a kind of motivationsl device useful in itself, if the problem situations are not too contrived, but of more value if the inclusion of individual "experiments" is tested by the criterion of s. satisfaetorv ~ r o b l e msituathe second. New experiments are introduced primarily for their illustrative value in new experimental techniques or in new areas of interest in theory-the addition of bromine t o butadiene gives opportunity for handling of a reactant which is s. cylinder gas and for relation t o the sterochemistry of addition reactions. Some other "new" experiments are extensions of older ones, chosen t o fit the criteria of the motivational problem situation. For example, one of the FriedelLCrafts acylations chosen is the reaction of acetic anhydride with m-xylene and the product is then oxidized by hypohalite t o a substituted benzoie acid; a series of substituted benzoic acids is to be tested (the motivational introduction) for use a s food additives t o replece sodium benzoate.
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Journal o f Chemical Education
Of the forty experiments in the text, eight are, I believe, new to first year orsanic laboratorv texts (svntheses of deiane-l-d, resol"tion of a-phenylethylamine, meso and racemic 1,2,3,4-tetrahromobutadiene, 1,2-cyclohexanediol, npropylisopropylamine, and hromotrichloromethme by photobrominatian) and four seem to be useful extensions of commonly used experiments (dimethylaeetophenone and dimethylbenzoic acid, ethyl orange, triethylearbinol, and trihromobenzene from aniline). I n addition, there are four experiments, some new, in physical oarganio chemistry (potentiometric titration, kinetios of nucleophilic aromatic substitution, spectrophotometric determination of a pseudo firstorder rate constant for nucleophilic a m matic substitution, and nmr determination of keto-enol tautomerism). Two experiments in quditative organic (identification of elements and of carhonvl compounds) urr inrlud~das well as rhr prepctrion uf derivarivw f several i r f rhe rompuunds w n ~ l ~ + . r dend , qunlitative tests. TLC is introduced for identification of halides following Schbninper combustion or sodium fusion and used in two subsequent experiments: glc is introduced in the analysis of the product from horohydride reduction of 3-pentanone and used in two other experiments (but in one, with bromotrichloromethme, where thermal conductivity detectors may suffer). Spectroscopic experimental work includes electronic, infrared, and visible, with careful reference to its relevance in six or seven of theexperiments. The orgmizational features include, for each experiment, the introductory problem situation, a methodology (new techniques), a description of the nature of the reaction (including a rather thorough cross reference to Morrison and Boyd's text for related theory), experimental procedures, questions for consideration (well done), and footnotes. Mast techniques are introduced as part of a preparative experiment (fractional distillation, for example, in the separation of the products of the reaction of isopropylamine and n-propyl bromide). There are 17 experiments in the main sequence and 23 which can be used as alternate or additional experiments. An introduction discusses safety, equipment and supplies, notebooks, lahorrutory operations, and calculation of yields. The level of experimental difficulty is in part arranged to progress upward and the detail in directions for techniques used earlier t o he less in the later sections. A "library" experiment is really 8. list and description of selected reference sources (also well done) and questions requiring their use. Detailed directions are given for construction of some inexpensive equipment needed such as s. student polarimeter and a manometer. A short but useful Teacher's Manual ia provided. Minor reservations are: the danger of handling bromine is insufficiently emphasized; the background discussion, while usually good, could be improved in the sections on reduced pressure distillation and fractional distillation; the flexibility of use is a little inhibited by the style.
These reservations are small in consider* tion of this text's rather impressive new features. STANLEYC. BUNCE R,?nsselnerPolytechnic Institute Troy, New Yorlc 12181
Gillom and Stern's Introduction to Electronic Absorption Spectroreopy in Organic Chemistry
E. S. Stern, Imperial Chemical Industries Ltd., Runcorn Heath, Cheshire, and C. 3. Tirnmons, University of Nottingham. 3rd ed. St. Martin's 277 pp. Press, New York, 1971. vi Figs. and tables. 23.5 X 15.5 cm. $20.
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The first edition of this popular hook appeared in 19.54; the second edition in 1958; and with C. J. Timmons, a new collaborator, E. S. Stern has now furnished us with a. third edition. A statement on the dust jacket informs us that ,'To take account of the remarkable progress over the last fifteen gears this hook has been completely ~ezuettn" (italics in the original). I t seems that in common with many other old traditions, the British propensity far understatement has succumbed to advertising hyperbole. The authors are still deeply loyal to the orgilnisatian and focus originally set out by Dr. Gillam, who unfortunately, did not live to see even his first edition in print. As a matter of fact the present authors state that "In large part i t is to keep his memory fresh that this book has been rewritten in its present form." Indeed, it is fortunate that this hook has not been as much rewritten as updated. I n this edition, the authors expand the range and depth of examples, but because the focus is still on the empirical correlations between structure and spectra, this edition will continue to enjoy the popularity and utility of itspredecessors. This hook will do little to deepen the chemist's understanding of electronic spectra. The authors explicitly state that no attempt is made t o describe the basic quantum theory or calculations therefrom relating t o band assignments. This may be just as well since some elementary concepts, e.g., the difference between orbitals and state wavefunctions, are not accurately distinguished (p. 28). New and particularly attractive features of the third edition are: The indusion of many additional tables and the expansion of old ones; the commend~ble practice of giving all absorption data in em-' as well as nm; the liberal use of structural formulas; and the many reproductions of spectra. from the very fine colleetion of the "UV Atlas of Organic Compounds" (Messrs. Butterworth and Verlag Chemie). Each chapter is preceded by what is cdled a summary but which in fact is a table of contents of the chapter. The enormous effort that went into the production of this carefully prepared edi(Catinned on page A%0)
book reviews tion will be greatly appreciated by almost everyone wishing a small (albeit expensive) single source book of ultraviolet spectral data of organic compounds whose central theme is the empirical correhtion between molecular structure and low resolution electronic spectra. In this reviewer's opinion i t is one of the very best books available for this purpose. MILTONORCHIN University of Cincinnati Cincinnati, Ohio 45221
Atomic Absorption Specfrochemical Analysis
B. V. L'vov, Soviet Academy of Sciences, Leningrad. Translated by J. H. Dizon with a preface by A. Walsh, Commonwealth Scientific and Industrial &search Organization, Melbourne, Australia. American Elsevier Publishing Co., Inc., New York, 1971. 324 pp. Figs. and tables. 24.5 X 17 em. $43.
Dr. L'vov is, without a doubt, one of the three or four foremost thinkers in the field of atomic spectroscopy. Twelve years ago, when some of us were barely heginning to struggle with flames, he developed the far mare sensitive graphite curvette, and produced hardware which is still in significant ways better than anything that is now offered. He brings t o his work not only a lively imagination, but also a deep theoretical knowledge of gas phenomena, quantum mechanics, and other esoteric fields. His book, therefore, contains many revelations; he understands whet most of us only observe. Dr. L'vov's book is, thus, extremely valuable, probably indispensable, to workers in atomic spectroscopy who wish really t o comprehend their field. However, i t is by no means an introduction to the technique, nor does it contain anything like "Hints for the analyst." Mathematical derivations are presented t o explain the commonly observed fact that elements with resonsnee lines a t higher wavelengths are more sensitively determined by emission than by absorption, but that emission has more spectral interferences even when a. monochromator with high resolution is used. Some very interesting work is described with hollow cathode and electrodeless discharge lamps. Dr. L'vov has s. low opianion of multielement lamps heertuse they must sacrifice brightness for convenience. In the section on burners, convincing explanations are given for solvent enhancement and viscosity effects. An explanation is also tendered for the hitherto puzzling fact that the oxy-cyanogen flame, though far hotter than nitrous oxide, is nearly useless for spectroscopy. A cdculation is presented t o show that, with presently available or contem.plsted light sources, atomic fluorescence Eannot give detection limits as good as those far atomic absorotion (a view with which I aeree. , but others disp&e).
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Chapter V contains extended descriptions of flameless sampling devices. Calculations backed bv exoerimental data. eive the pros and cons bf p&k integration.- 1t is shown that the linearity of working curves improves when high gas pressures are used in the L'vov furnace, because Lorentz broadening of the absorption line compensates for the hyperfine structure of the emission wavelength. The need for background correction with a continuum source is indicated, and it is shown that a two-channel method involving a non-sbsorbable line is risky, because of abrupt changes of molecular absorption with wavelength. A final chapter on special applications describes the determination of sulfur, phosphorus, and iodine in the far ultraviolet range, the analysis of gases and isotopes, and the measurement of oscillator strengths. I have listed some of the nuggets in Dr. L'vov's book which are of special interest to me. Serious workers should study his work and seek their own. The task is not easy, but should be rewarding. HERBERT L. KAHN The Perkin-Elmer Corporation Norwalk, Connecticut
Analytical Methods for Atomic Absorption Spectrophotometry
Perkin-Elmer Corp., Narwalk, Cannecticut, 1971. 27.5 X 29.5cm. Looseleaf. $35. The Perkin-Elmer Corporation's Instrument Division has recently published an up-to-date version of their methods manual for atomic absorption entitled, "Analytical Methods for Atomic Absorption Spectrophotometry." This manual, published in looseleaf form, is designed to keep the practicing chemist up-to-date in the field of atomic absorption since supplements are sent t o the purchaser on an "indefinite" basis. I t contains information concerning the preparation of standard solutions, operating parameters for Perkin-Elmer instruments, short comments concerning sensitivity, linear working range, and flame emission conditions. The information is up-to-date and complete for the elements normally analyzed by atomio absorption technioue. Secricms of t h I~w A wpreseming 9 h m a l ~ s r n c ~of . wferenved pul~lished pro4 u r p - i w e dev