Books
Ion-Exchange Resins and Chromatography Chromatography: An Adventure in Graduate School. Guy Alexander. 163 pages. American Chemical Society, 1155 Sixteenth St., N.W., Washington, D.C. 20036. 1977. $7.50 ($4.50, paperbound)
Reviewed by James M. Bobbit, Dept. of Chemistry, University of Connecti cut, Storrs, Conn. 06268 In this book, Professor Alexander has presented a reminiscence of his graduate school experience and, as a part of this experience, has attempted to present an overview or an introduc tion to ion-exchange resins and chro matography. T h e reminiscence is quite successful, although I felt t h a t there was a little too much chemistry a t times. However, as a technical book, it is less successful, and the main title "Chromatography" implying such is most unfortunate. Actually, the book is more devoted to ion-exchange resins than it is to chromatography.
CHROMATOGRAPHY An! Adventure in Graduate School Guy Alexander
is beautifully presented. T h e author has managed to describe accurately t h e fascination and enthusiasm t h a t many of us, this reviewer included, felt when we first encountered chromatog raphy and ion-exchange resins and re alized what fabulous things one could do with these concepts and materials. T h e overview and introduction of chromatography are presented through the medium of a seminar, a t least partially mythical, given by an other graduate student named Jim. Such a seminar would have some his torical interest, but is not an effective method for presenting technical mate rial. Besides, the bell rang, and the "seminar" was over just when it start ed to become interesting. T h e intro duction to ion-exchange resins and their use in chromatography is excep tionally well presented and was in fact the subject of the author's thesis (spe cifically, t h e separation of rhenium and molybdenum salts by ion-ex change chromatography). In the Ap pendix, discussions of some gas chro matography theory and distillation column theory including the ubiqui tous "theoretical p l a t e " concept are given. T h e actual description of gas chromatography in the text is given in such a cursory fashion t h a t the the oretical discussion seems almost pointless. T h e description of distilla tion column theory as a key to chro matography is not often found and is most useful. Thin-layer chromatogra phy is mentioned only as thin-film chromatography and is discussed as it existed about 20 years ago. In summary, the book is interesting as a reminiscence but would not be a very useful technical book.
Introduction to Semimicro Qualitative Analysis, 5th Ed. C. H. Sorum and J. J. Lagowski. χ + 309 pages. PrenticeHall, Inc., Englewood Cliffs, N.J. 07632. 1977. $8.95
As a reminiscence of Professor Alex ander's experience as a graduate stu dent at the University of Wisconsin just before and just after World War II, the book was a delight to read. Rarely does one find a scientist, at least a chemist, writing dialog and writing it so successfully. T h e t r a u m a of being married and in graduate school at a great university with all of the tensions and pleasures a t t e n d a n t
Reviewed by Stanley T. Marcus, Dept. of Chemistry, Cornell Universi ty, Ithaca, N.Y. 14853 As in previous editions, this wellknown book is divided into two parts, the first of which is concerned with the theory, i.e., the underlying facts and principles and the logic behind qualitative analysis. T h e second part consists of the systematic procedures
using the traditional H2S-based ana lytical scheme. Except for a few very minor changes, such as verifying zinc using diphenylthiocarbazone paper in stead of using K 4 Fe(CN) 6 , P a r t II has been left as it was, a thoroughly tested set of procedures. P a r t I, on the other hand, has been almost completely re written, and it has been expanded considerably (from 86 to 137 pages). Surprisingly, in the revision of P a r t I, a number of important topics, such as the relationship between ionic strength and activity to molar solubili ty and solubility product, were elimi nated. T h e new edition states without qualification, " T h e entire sample of an ionic substance exists as ions in so lution." T h e section on chemical kinetics has been expanded and updated con siderably. Except for the fact t h a t t h e topic of inhibitors is introduced with out adequate explanation, the presen tation is straightforward. The treat m e n t of free energy and equilibrium, on the other hand, is very weak, and at times, misleading. It states, for ex ample, " T h e relationship between the equilibrium constant for a reaction and the free energy of the system is given by . . . G = - R T l n K . " Topics given more thorough treat m e n t in this edition include acid and bases, stepwise ionization, hydrolysis, buffers, solubility, and colloids. Un fortunately, neither the BronstedLowry nor the Lewis acid-base sys tems are utilized. It was somewhat distressing to see the unqualified use of the symbol " N H 4 O H " for aqueous ammonia. T h e expanded discussion of colloids represents a distinct im provement, in t h a t colloid formation is a frequent source of frustration to students in qualitative analysis. Another topic given more thorough coverage is bonding in complex com pounds. T h e discussion of crystal field theory is generally straightforward, b u t it contains several careless errors. An energy diagram (page 97) is misla beled, for example, and it is suggested t h a t crystal field stabilization energy results from a gain, rather than a low ering, energy of the t2 g orbitals in an octahedral field compared with their energy in a spherical field. In general, I think the revision rep resents an improvement over the pre vious editions, but I feel it could have been written with more care. In any
ANALYTICAL CHEMISTRY, VOL. 50, NO. 4, APRIL 1978 · 479 A
ANALYSIS OF FOOD AND BEVERAGES Headspace Techniques Edited by GEORGE CHARALAMBOUS Proceedings of a symposium organized by the Flavor Subdivision of the Agricultural and Food Chemistry Division of the American Chemical Society at the 174th national meeting, Chicago, Aug. 27-Sept. 2, 1977. CONTENTS: S. G. Wyllie et al., Headspace Sampling: Use and Abuse. H. Maarse and J. Schaefer, Quantitative Headspace Analysis: Total and Specific Group Analysis. F. Z. Saleeb and T. W. Schenz, A Technique for the Determination of Volatile Organic Compounds under Equilibrium and Non-Equilibrium Conditions. A. L. Boyko et a/., Porous Polymer Trapping for GC/MS Analysis of Vegetable Flavors. D. A. Withycombe et al., Isolation of Trace Volatile Constituents of Hydrolyzed Vegetable Protein via Porous Polymer Headspace Entrainment. /. Klimes and D. Lamparsky, Headspace Techniques Utilized for the Detection of Volatile Flavor Compounds of the Vanilla Bean. 0. G. Vitzthum and P. Werkhoff,.Aroma Analysis of Coffee, Tea, and Cocoa by Headspace Techniques. E. D. Lund and H. L. Dinsmore, Determination of Citrus Volatiles by Headspace Analysis. J. T. Hoft et al., Flavor Profiling of Beer Using Statistical Treatments of GLC Headspace Data. A. C. Noble, Sensory and Instrumental Evaluation of Wine Aroma. H. Akiyama et al., Sake Flavor and Its Improvement Using Metabolic Mutants of Yeast. R. ter Heide et al., Concentration and Identification of Trace Constituents in Alcoholic Beverages. D. A. M. Mackay and M. M. Hussein, Headspace Techniques in Mouth Odor Analysis. J. A. Singleton and H. E. Pattee, Headspace Techniques Used in the Analysis of Volatile Components from Lipoxygenase Catalyzed Reactions. 7978, 416 pp., $21.001'£13.65 ISBN: 0-12-169050-4
GAS CHROMATOGRAPHY WITH GLASS CAPILLARY COLUMNS By WALTER JENNINGS CONTENTS: Introduction. The Glass Capillary Column. Column Coating. Inlet Systems. Column Installation. Measuring Column Efficiency. Treatment of Retention Data. Temperature Programming and Carrier Flow Considerations. Column Stability. Column Selection. Sample Preparation. Analysis of Materials of Restricted Volatility. Applications of Glass Capillary Gas Chromatography. Appendix 1. Nomenclature. Appendix II. Liquid Phases. Appendix III. Porous Polymer Data. Appendix IV. Silylation and Derivazation Reactions. 1978, 200 pp., $16.501£.11.70 ISBN: 0-12-384350-2
ph MEASUREMENTS By C. CLARK WESTCOTT pH Measurements provides a basic, practical source of information about the principles, equipment and technique of this operation. Based on the author's experience with pH measurement for over a decade, this simplified guide is geared to laboratory applications for problem solving, training personnel, and obtaining accurate results. Chapters cover the theory of pH, characteristics, care, and performance of pH equipment and standard solutions, the use of proper technique in difficult applications, and troubleshooting, with examples drawn from everyday laboratory and field experience. 1978, 192 pp., $16.00/£10.40 ISBN: 0-12-745150-1 Send payment with order and save postage plus 50C handling charge. Prices are subject to change without notice.
ACADEMIC PRESS, INC. A Subsidiary of Harcourt Brace Jovanovich, Publishers 111 FIFTH AVENUE, NEW YORK, N.Y. 10003 24-28 OVAL ROAD, LONDON NW1 7DX CIRCLE 4 ON READER SERVICE CARD
480 A · ANALYTICAL CHEMISTRY, VOL. 50, NO. 4, APRIL 1978
Books case, the portion of the book likely to be used to the greatest extent is P a r t II, which remains very clear and error free. Trace Analysis of Atmospheric Samples. Eikuo Oikawa. viii + 1 5 8 pages. Halsted Press, 605 Third Ave., New York, N.Y. 10016. 1977. $22.50 Reviewed by E. W. Bretthauer, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, P.O. Box 15027, Las Vegas, Nev. 89114 This book is intended to describe the most recent methods for sample collection and analysis of metals in atmospheric particulates. T h e book was reviewed for use (1) as a reference book for the professional environmental analyst and (2) the student who desires a primer for background information. T h e sampling and the sample pretreatment sections meet the latter requirement b u t are far too brief and incomplete for a reference book, i.e., sample siting criteria are contained in one short paragraph without references. In practice, the professional environmental analyst would need much more information to adequately conduct atmospheric particulate sampling of metals. T h e analytical section was found inadequate for either purpose. T h e major deficiencies in the analytical section are as follows. 1. Much of the information is outof-date. For example, the described NASN method for emission spectroscopy analyses of air filters is approximately 10 years out-of-date. Many improvements have been made to the described NASN method and have been available in the literature for some time. 2. T h e author's greater familiarity with atomic absorption analysis appears to unfairly bias him against the other analytical techniques. For example, he states t h a t optical emission is an expensive analytical technique for single sample analysis. In reality, single sample analysis by optical emission spectroscopy may be less expensive than comparable analyses by atomic absorption, depending on the n u m b e r of elements analyzed in a sample. T h e author also states t h a t atomic absorption analysis always provides lower detection limits t h a n emission spectrometry with the exception of vanadium. Actually, the detection levels of the modern inductively coupled argon plasma optical emission spectrometer in most cases are equal to detection levels obtained by conventional atomic absorption. 3. Some of t h e information on ana-
Books
lytical techniques is incorrect. For example, x-ray fluorescence, described as an absolute method, is certainly not. Appropriate standards are always necessary for calibration. T h e author's statement t h a t x-ray fluorescence has an accuracy of 2-3% obviously is not correct. Poor syntax may be responsible for some of the incorrect material. 4. Many references t h a t should be cited are not a n d many cited are outof-date. T h e editing of t h e book is very poor. There are numerous typographical errors. Many instances of poor syntax (e.g., standard adding in place of stand a r d addition) are noted throughout.
Solvent Extraction Chemistry: Fundamentals and Applications. Tatsuya Sekone and Yuko Hasegawa. xii + 919 pages. Marcel Dekker, Inc., 270 Madison Ave., New York, N.Y. 10016. 1977. $75
Reviewed by A. S. Kertes, Dept. of Inorganic and Analytical Chemistry, The Hebrew University, Jerusalem, Israel According to the Contents, t h e book is divided into two parts, Fundamentals and Applications. In reality, however, it consists of three almost equal parts, with the third constituting 292 pages of references. T h e Fundamentals part, of which I am rather critical, begins with an introductory chapter describing the development of the solvent extraction technique in the inorganic and analytical chemistry fields. I t gives a rather fragmentary listing of review articles and monographs t h a t have appeared up to 1972, the last year covered by the book. With the exception of one monograph, no mention is made of the extensive list of Russian books p u b lished in the field, several of which have been translated into English. I will mention just three I consider important: Fomin: "Chemistry of Extraction Processes" (English translation 1962), Shmidt: "Amine Extraction" (English translation 1971), and a very useful bibliography for the period 1945-1967, compiled by Bargeev et al.: "Extraction of Inorganic Comp o u n d s " (1971), containing some 10 000 entries. Also missing from t h e list is a 600-page monograph, "Recent Advances in Liquid-Liquid Extraction", edited by Hanson, published in 1971, and since translated into German and Russian. Numerous books, monographs, and conference proceedings have appeared since 1972, and it is unfortunate t h a t the list of refer-
ences to this introductory chapter was not brought up-to-date when the camera-ready typed pages were proofread. Chapter 2 could easily have been omitted. Its 50 pages deal with t h e description of aqueous solutions, properties of liquids, aqueous and organic, and basic partition equilibria. Many general chemistry textbooks published in the last decade provide a more systematic, and if needed, a more detailed t r e a t m e n t of these topics. Rather disturbing are unsound statements such as t h a t on page 14 comparing the molecular weight of water a n d liquid hydrogen fluoride at room temperature, or t h a t on page 46 suggesting t h a t the synonym for inert solvent is aprotic solvent. Chapter 3, entitled "Statistical T r e a t m e n t of Liquid-Liquid Distribution Equilibria", is probably the weakest part of t h e book. T h e expression "statistical treatment", repeatedly used in the text, is completely misleading. On some 30 pages the authors elaborate the simplest possible sets of mass-action law equilibria for two-phase systems. This is what they term "statistical analysis". Any practicing analytical chemist, even if he has never used solvent extraction as a tool, should be familiar with such basic solution chemistry concepts as distribution ratio, association, dissociation, formation of metal chelates, and mixed ligand complexes. At t h e level presented, all these are textbook items. In Chapter 4, "Solvent Extraction Systems", t h e material is arranged in what I think is a reasonable classification of the major types of solvent extraction processes—but not more than that. There is no in-depth description of t h e fundamental chemistry involved, and there is an unnecessary amount of repetition. T h e same primitive set of equations (4.47, 4.57, 4.61, 4.67, etc.) is presented in a number of places, b u t in the very same context. P a r t II, Applications, has two chapters. Chapter 6 deals with t h e use of solvent extraction as a tool for the determination of thermodynamic activity of solvent, solute, t h e equilibrium constants of association and dissociation reactions, a n d complex formation. It is my considered opinion t h a t t h e recommendations concerning t h e usefulness of the method in deriving numerical equilibrium d a t a are overly optimistic and frequently thermodynamically unjustified, as for example, the assumptions needed for the determination of solute and solvent activities (pages 314-19). Chapter 7, "Application of Solvent Extraction t o Analytical a n d Inorganic
482 A · ANALYTICAL CHEMISTRY, VOL. 50, NO. 4, APRIL 1978
Chemistry", is a constructive p a r t of the volume. On some 280 pages of text, with 7300 references listed on 250 pages, this chapter is in effect an enormous bibliographic text, similar in style t o t h a t appearing annually in ANALYTICAL CHEMISTRY
Reviews.
T h e text is interspersed with many tabulations of numerical extraction data, unfortunately, representing an uncritical compilation. T h e coverage is exceedingly broad, including journals t h a t are not readily available, a n d the reader will welcome the extensive list of references. T h e chapter's weakness is the virtual absence of any critical evaluation of t h e analytical methods cited, and the reader is left alone in deciding t h e relative merits of t h e various extractants used for any particular compound. I can recommend this book as a reference source and believe t h e authors have succeeded in providing a wellordered bibliography. As such, it is valuable to practicing analytical chemists, provided they can afford t h e price. However, I do not think I can recommend it as a textbook. It is not a comprehensive text for a graduate course in analytical, solution, or separation chemistry, as the title might suggest.
New Books Toxic and Hazardous Industrial Chemicals Safety Manual. 580 pages. Lab Safety Supply Co., P.O. Box 1363, Janesville, Wis. 53545. $75
Toxicity and hazard d a t a are given for over 700 industrial chemicals t h a t pose danger t o workers. Toxicity data include answers to questions such as: W h a t are the acute and chronic symptoms of exposure? W h a t is the toxic dose? Will it cause cancer? T h e hazard data provide information on flammability and reactivity, as well as specific instructions for extinguishing fires and emergency first-aid procedures. T h e manual also provides handling and storage instructions.
Continuing Series Annual Reports on NMR Spectroscopy, Vol. 7. G. A. Webb, Ed. ix + 300 pages. Academic Press Inc., 111 Fifth Ave., New York, N.Y. 10003. 1977. $31.25
This is the first volume by G. A. Webb, who took over the editorship of this long-standing series on N M R
