Books
The Teaching of Analytical Chemistry Chemical Separations and Measure ments: Theory and Practice of Analyti cal Chemistry. Dennis G. Peters, John M. Hayes, and Gary M. Hieftje. xxii + 749 pages. W. B. Saunders Co., West Washington Square, Philadelphia, Pa. 19105. 1974. $15.95
Reviewed by Robert L. Pecsok, De partment of Chemistry, University of Hawaii, Honolulu, Hawaii 96822 Here is another book that can be judged by its cover—a reproduction of a 200-peak chromatogram of marijua na. It is modern, relevant, detailed— beautiful but overpowering. In an swering the question posed on page 1, "What is analytical chemistry?" the authors have taken a broad view and included an in-depth coverage of more than enough topics to fill a four-unit course (excluding laboratory) for a full year. Its rigor and completeness will impress analytical professors and will probably appeal to the serious chemis try major who will find it a valuable reference work or mini-treatise. By using over-size pages, narrow margins, and thin paper, the publisher has in cluded about twice the usual amount of material for a book of ordinary size. The material falls into five units: statistics, chemical equilibria, electro chemistry, separations, and spectrochemical analysis. A very brief intro ductory chapter is followed by 30 pages of statistical definitions and equations. After the next 35-page chapter on solute-solvent interactions (activity coefficients) and a kinetic and thermodynamic treatment of equilibrium, the student may wonder if he is in the wrong course. And we have just arrived at the usually dull subject of acid-base equilibria. By this time the 80% of the students in typical elementary analytical courses who are med techs, pre-dents, biology majors (or even preorganic chemists) will sim ply be overwhelmed. Actually, this text has much to rec ommend it. The writing style is clear, concise, informal, and occasionally spiced with bits of humor. Taken topic at a time, it is easy to conclude that this is the best treatment to be found in any text. Extensive sets of very challenging problems are a welcome improvement over the stereotyped
problems of a generation ago. Numeri cal answers are included in an appen dix. I like everything about this book ex cept that I cannot use it. My students would object to a required text that contained 4-5 times as much material as can be covered in a one-semester course. And I would object to having to spell out which 20% of the book they were responsible for. A compan ion text by Harris and Kratochvil (see following review) is needed for labora tory experiments. In my view this is the kind of mate rial that we should be teaching in our analytical courses. If our colleagues in other branches of chemistry would take the time to look at it, perhaps we could reestablish a proper role for ana lytical chemistry courses. Chemical Separations and Measure ments: Background and Procedures for Modern Analysis. Walter E. Harris and Byron Kratochvil. χ + 284 pages. W. B. Saunders Co., West Washington Square, Philadelphia, Pa. 19105. 1974. Paperbound. $6.50
Reviewed by Gary D. Christian, De partment of Chemistry, University of Washington, Seattle, Wash. 98105 This is a laboratory manual for in troductory analytical chemistry. There are some 30 experiments in 12 chapters, beginning with basic analyti cal operations and building progres sively from classical methods of analy sis to some optical, electrochemical, and basic separation techniques. The emphasis in the latter chapters is on the measurement and separation step rather than instrumentation. The manual is clearly written and easy to follow. Each experiment is preceded by a qualitative discussion of the principles involved. They tend to tie together principles nicely without going into detailed equilibria. Taken alone, though, some may leave the student with an incomplete understanding. For example, on page 95 the student is instructed to adjust the p H of an arse nic (III) solution to 7.9 to stabilize the arsenic (III), but he is not told why it is otherwise unstable. On page 134 the method of standard additions is used
in an atomic absorption experiment, but no discussion is given of its advan tages. There are problems at the end of the experiments, along with selected references. Several of the problems re quire information not given in the text and so would serve primarily as sup plementary problems for a textbook. A useful feature of the manual is that the authors have listed the medi an time required for each experiment, as experienced in their laboratory over the years. The manual is written on the as sumption that experiments will be performed in the approximate order presented. Detailed calculations are given in the earlier experiments, with gradually fewer details as the experi ments progress, in order to build the student's confidence. The concept of normality is not used, only molarity, in keeping with a number of modern texts. Chapter 1 starts out with an excel lent description of the use of the single pan balance and the reading of a buret. Chapter 2 offers suggestions for grading, based on confidence limits using the t-test for each step of the ex periment. A short treatment of volu metric calculations is given in this chapter, and one wonders why a treat ment of gravimetric calculations is not also included here. In Chapter 3, sodi um cyanide is employed as a masking agent for iron for the EDTA determi nation of calcium in limestone. This could be eliminated for safety pur poses in the EDTA standardization when the EDTA is used in the water hardness experiment. An interesting historical account of atomic weight de terminations is given in Chapter 5, as an illustration of the capabilities of gravimetric analysis. Chapter 7, on nonaqueous titrimetry, has only one experiment, which employs a photometric end point and a gravimetric titration. This is not very representative, and an alternate experiment would have been desir able. The experiments in Chapter 10 offer a good blend of techniques (sol vent extraction coupled with, e.g., EDTA titration or gravimetry) as an example of a real world solution to an interference problem.
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Books The laboratory manual is accompa nied by a teacher's manual ("Teaching Introductory Analytical Chemistry"). It offers additional comments on the experiments to assist the laboratory instructor on matters that may give difficulty or that need special atten tion. For those in need of a laboratory manual, this one is to be recommend ed for consideration. Particularly for the beginning teacher, it offers many helpful suggestions, from setting up the laboratory to determining the final grade of the student.
Particle Size Analysis Z.K. Jelinek
oughly (10 or so pages). These include electron microscopy, light scattering methods, X-ray methods, and sedi mentation. Others are described in a page or two. In all cases, the author summarizes the principles, describes the appara tus, and gives at least one "practical example" taken from the literature to illustrate the use of the method in a specific situation. Naturally, with the wide variety of methods discussed, the basic principles range from the ob vious to the fairly complex. In the lat ter cases, the author generally cites the necessary mathematical relations, usually without derivation or citation as to source. In some cases, it would be helpful to learn what the limitations of a method are. Thus, in the discus sion of scattering methods by use of Zimm plots or dissymmetry, it is not made clear that both methods apply only to systems of relative refractive index close to unity. This is a minor criticism, and altogether the book can be recommended as very useful for those who need to know what methods exist for various size ranges and how to use them in practice.
Interpretation of Raman Spectra Characteristic Raman Frequencies of Organic Compounds. Francis R. Dollish, William G. Fateley, and Freeman F. Bentley, xviii + 443 pages. John Wiley & Sons, Inc., 605 Third Ave., New York, N.Y. 10016. 1974. $22.50
Principles Summarized, Apparatus Described Particle Size Analysis. Zdenek K. Jeli nek. 178 pages. Halsted Press, 605 Third Ave., New York, N.Y. 10016. 1974. $16.50
Reviewed by E. J. Meehan, Depart ment of Chemistry, University of Minnesota, Minneapolis, Minn. 55455 This is a brief, clearly written, and practical book. The author is a mem ber of the Organic Synthesis Institute, Pardubice, Czechoslovakia, and the book has been translated from the (presumably) Czech edition of 1971. The author has published in the Czech literature on the use of electron mi croscopy, sedimentation, and centrifugation. The range of sizes considered extends from about 5 Χ ΙΟ - 4 μ (lower limit for electron microscopy) to about 100 μ (upper limit for microscopy, elutriation, and permeation. Some of the methods are discussed fairly thor
Reviewed by James R. Durig, College of Science and Mathematics, Univer sity of South Carolina, Columbia, S.C. 29208 This book is written in the tradition of treatise like K. W. F. Kohlrausch's "Der Smekal-Raman-Effect," 1931; J. Hibben's "The Raman Effect and Its Chemical Applications," 1939; and L. Bellamy's "The Infrared Spectra of Complex Molecules," 1958, with com prehensive references (over 1400 ref erences to the Raman spectra of spe cific organic compounds are cited). It compares favorably with the earlier works in depth. The book covers ali phatic compounds, compounds con taining double or triple bonds, aro matic compounds, and heterocyclic compounds. The dependence of Raman frequencies upon inductive ef fects, field effects, rotational isomer ism, resonant effects, and upon intraand intermolecular bonding is dis cussed in detail. In addition, symme try arguments and normal coordinate analysis are used to support the assign ments proposed by the authors. Eigh teen chapters are used to cover the
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topics. In addition, there are over 100 tables that summarize the charac teristic Raman frequencies of the above referenced classes of organic compounds. In addition, Appendix I contains a summary of characteristic Raman frequencies with a reference to the section where the vibrational as signment is presented. Appendix II has 108 representative Raman spectra recorded. The book contains a very ex cellent compound reference index, a subject index, and an author index. It is written in the spirit of Bellamy's book on infrared spectra and com pares quite favorably in presentation and style. The book is well written, and it is quite up-to-date. The discussions are quite complete and easy to follow. The opening discussions to most of the chapters give references to the earlier work on the subject. Where reviews have been written on particular classes of compounds, these are always cited. It is believed that this book will be a valuable source of information for the molecular spectroscopist as well as the analytical or organic chemist who is interested in interpreting spectra, making empirical assignments, or solving chemical or structural prob lems. In addition, there are some in teresting discussions that both bio chemists and polymer chemists would find useful. In general, the authors have done a remarkably good job with the collection of a large amount of di versified material over a very broad area. It is presented in a rather uni form manner, and anyone interested in Raman frequencies of organic com pounds should find the text of consid erable use. The book is reasonably priced and attractively printed.
Useful Techniques for the Petroleum Industry Spectroscopic and Chromatographic Analysis of Mineral Oil. S. H. Kagler. xiii + 559 pages. Halsted Press, 605 Third Ave., New York, N.Y. 10016. 1974. $65
Reviewed by R. W. King, Applied Re search and Development Depart ment, Sun Oil Co., Marcus Hook, Pa. 19061 This book is intended to acquaint the reader with a number of modern spectroscopic and chromatographic techniques and to provide an account of their use in the petroleum industry. It is not offered as a textbook nor as a laboratory manual. The treatment of fundamental principles and working procedures is deliberately limited to that which is sufficient for an under-
Books
should be a part of every library's col lection on that subject.
Theory, Instrumentation, and Practice standing of the subject. The principal aim is to provide a useful and wellorganized source of information on the application of these methods by means of comprehensive bibliographi cal documentation. In this, the book succeeds fairly well. It will be helpful to the practicing analyst as a source of both background material and new ideas and should be recommended reading for the new chemist entering upon a career in petroleum analysis. The style and structure of the book have allowed a very large amount of valuable material to be included in this single 560-page volume. However, it would have been helpful if at least one example of a well-established ap plication of each technique could have been dealt with in detail. The author does provide an in-depth discussion of a number of specific procedures, but there is no consistent treatment throughout. This could have been ac complished without significantly lengthening the text by eliminating the material on microwave spectrosco py and lasers, masers, and fasers and curtailing the descriptions of commer cially available instrumentation. The former are little used in petroleum laboratories, and the latter only serve to date the book within a short period of time. The quality of the text reproduction is good. There are a small number of typographical errors, but none of them is serious. Some of the figures are less than satisfactory. Several would be much more easily understood if the coordinates were descriptively labeled. The legends and notations on others are much too indistinct to be easily read. One figure is upside down, an other backward. However, these criti cisms are relatively minor ones. The main problem with the book stems from the fact that this edition is a translation of the German text that was published in 1969. As a conse quence, the literature coverage which originally extended only through 1967 is seven years out of date, and recent developments have made the treat ments of several subjects such as sim ulated distillation, gel permeation chromatography, and selective detec tors for gas chromatography some what inadequate. This deficiency, along with its cost, will undoubtedly deter many potential buyers from pur chasing a copy for their personal use. Nonetheless, it is of substantial value in the field of petroleum analysis and
An Introduction to Liquid Scintillation Counting. A. Dyer, xiii + 1 1 1 pages. Sadtler Research Laboratories, Inc., Book Division, 3316 Spring Garden St., Philadelphia, Pa. 19104. 1974. $8.25
Reviewed by L. T. McClendon, Acti vation Analysis Section, Analytical Chemistry Division, National Bureau of Standards, Washington, D.C. 20234 Activity in the field of liquid scin tillation counting technology has in creased in the past several years, as evidenced in the literature and from the response given to several interna tional conferences held recently on liquid scintillation counting. In 92 pages the author successfully achieves his stated aim of presenting "an intro duction to liquid scintillation counting for scientists and technicians with some knowledge of radiochemical techniques". This book is a brief but straightforward presentation of the fundamental theory, instrumentation, and practice of liquid scintillation counting. The author makes adequate use of tables and figures to emphasize important parameters and present specific examples of the technique, as well as references to publications which describe the information in greater detail. The first two chapters present a brief history of liquid scintillation counting, its scopes, and terminology encountered in the use of the tech nique. The importance of solvents and solutes, their expected properties, and a survey of compounds used for these purposes are adequately discussed. Chapter 3 describes the instrumenta tion used in the early years of liquid scintillation counting and the new in novations that have occurred in this instrumentation from the early 1950's to the present-day sophisticated liq uid scintillation counters. The author concludes this chapter with an excel lent summary of features and func tions that are characteristic of instru ments in the liquid scintillation mar ket today. Chapter 4 presents an indepth discussion and well-referenced survey of methods used to prepare samples for counting, with special at tention focused on substances labeled with carbon-14 and tritium. Liquid scintillation counting has also been used very effectively to de termine the activity of isotopes other than the commonly studied 14C and 3 H isotopes. Chapter 5 describes vari
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ous methods used to determine the ac tivity of a number of other isotopes ( 35 S, 45 Ca, 5S Fe, 85 Kr, " T c , etc.) with liquid scintillation counting and the advantages thereof. Chapters 6 and 7 give an excellent discussion of the problems encountered in this tech nique—quenching, luminescence, noise, etc.—and most of all, discuss ways to minimize or eliminate these problems. The last chapter describes some of the novel methods that have resulted from the sensitive, modern instruments of today and the liquid scintillation phenomena. Quenching and luminescence are such serious problems in liquid scintillation count ing that manufacturers have designed contemporary instruments to be sensi tive to these effects. Scientists have taken advantage of this instrumental sensitivity and are using quenching and chemiluminescence as analytical tools. This chapter is concluded with a comprehensive discussion on Cerenkov counting. In summary, the book is well-con ceived and provides a good introduc tion to liquid scintillation counting for those persons intending to use the technique. The author includes an ex cellent bibliography which can be con sidered an up-to-date survey of the lit erature; thus, the reviewer would rec ommend this book as a current refer ence book for those involved in liquid scintillation counting. In contrast to the author's stated intent of having his book "serve as a text-book for courses at the undergraduate or post graduate level," the reviewer recom mends this as a source book for stu dents at these educational levels as well as workers in the radiochemistry discipline who want to evaluate the applicability of the method to prob lems that arise in their laboratories.
Introduction to Electrodics The Chemistry of Electrode Processes. liana Fried, χ + 225 pages. Academic Press, Inc. (London), Ltd., 24-28 Oval Rd., London, NW1 7DX, England. 1974. $13.75
Reviewed by Daniel S. Polcyn, De partment of Chemistry, University of Wisconsin, Madison, Wis. 53706 This book is concerned with the chemical aspects of electrode pro cesses and is designed "to introduce the field of electrodics to the advanced student or qualified chemist." The au thor presumes no previous electro chemical background and "develops the basic concepts of electrochemical cells, of potential, and of kinetics ac cording to the needs of the study of electrode processes." There are al-
Books ready in existence a number of text books professing to fulfill all the above goals, but many of them are neither readable nor simple. This book is readable and fulfills the author's pur pose of presenting "the subject matter simply, rather than rigorously." To introduce the subject of electrodies, the author has separated the study of electrode processes into three basic topic areas—fundamentals, ex perimentation, and applications. Fun damentals are covered in Chapters 14. Chapter 1 defines the field of electrodics, both in terms of basic science and technology, as well as its place in history. Basic definitions of the gal vanic cell and related concepts are presented in Chapter 2. Chapter 3, Electrode Kinetics, is introduced by comparing it with solution kinetics and evaluating similarities and differ ences. The remainder of the chapter then covers electrode kinetics in a re markably understandable manner. Chapter 4, The Electrode Solution In terphase, is the highlight of the book and provides a rather thorough de scription of the interphase region with emphasis on physical significance, and adequate but minimal mathematics. Techniques of Measurement is dis cussed in Chapter 5 and covers all the common classical techniques. Instru mentation for measurements is pre sented schematically and, therefore, is quite general. Operational amplifi ers are briefly mentioned in an appen dix. Spectroscopic electrochemical methods are briefly introduced, but no assessment is made as to their poten tial usefulness. Chapter 6 is concerned with the technological aspects of electrodics and discusses the principles of various applications. Electroanalysis, corro sion, electroplating, batteries, fuel cells, and electrochemical manufactur ing processes are briefly covered. This chapter should be of interest to the reader interested in applying electro dics to solve energy crisis problems. Since the book is brief, the author has left out many topics and, of course, has abbreviated those includ ed. Generally, this is no problem in that suitable references to the original literature or a comprehensive bibliog raphy can partially make up for this brevity. The author has provided a bibliography which is adequate but not complete. However, no references to the original literature are given which could be a handicap to the read er. There is confusion in the text about the signs of electrode potentials,
implying another convention, in addi tion to the "European" and "Ameri can." No uniform sign choice was used in presentation of current voltage curves which would cause confusion even for a beginning student. Care lessness in spelling is evident through out the text, occurring in both com monly used words, as well as in proper names. These defects are generally ob vious and, though trivial, are cause for concern about not so apparent errors. In conclusion, the text is quite suit able as a useful introduction to elec trodics but will not satisfy the more critical nonelectrochemical or electro chemical reader who prefers more than statements of fact and analogy.
Complementary to the Western Literature Vibrational Spectra of Polyatomic Mol ecules. L. M. Sverdlov, M. A. Kovner, and E. P. Krainov. xiii + 644 pages. Halsted Press, 605 Third Ave., New York, N.Y. 10016. 1974. $38
Reviewed by C. W. Kern, Department of Chemistry, Ohio State University, and Battelle Memorial Institute, Co lumbus, Ohio 43210 This 640-page volume is essentially divided into two independent parts. The first part presents the theory of vibrational spectra, and the second portion consists of a compendium of data on over 500 molecules. The first two of the 15 chapters deal with the general symmetry and kinematic fea tures of molecular vibrations. This part of the book, comprising only slightly more than 25% of the total pages, is rather sketchy. Although some new material is presented, for example, that related to the effect of aggregation on intensities, many fun damentals are treated superficially, and important formulas are given without proof. The remaining 13 chapters in the book are devoted to the analysis and classification of vibrational spectra of polyatomic molecules. The specific types of compounds discussed in Chapters III-IX include paraffins, naphthenes, and unsaturated and aro matic hydrocarbons, as well as their halogen derivatives. The last six chapters deal successively with oxy gen-, nitrogen-, sulfur-, silicon-, boron-, and phosphorus-containing molecules. In many cases, the book gives numeri cal values of force constants, characteristic frequencies, and various other parameters such as dipole moments. Citations are given to more than 2000 references in the bibliography. To review one concrete example, we consider the water molecule which is covered in about four pages of text.
1242 A · ANALYTICAL CHEMISTRY, VOL. 46, NO. 14, DECEMBER 1974
The symmetry, the equilibrium bond length and angle, quadratic force con stants, and the characteristic frequen cies for H 2 0 and its possible (D, T) and (O 17 , O18) isotopic derivatives are all given. Asymmetrical species such as HDO and DTO are also included. Table 208 presents anharmonicity constants for H 2 0 through cubic terms in the expansion of the vibra tional energy in powers of (u; + V2). The numerical values in this table, and in fact throughout much of the book, are taken from the Russian lit erature, in this case from the 1959 (partially unpublished) work of G. A. Khachkuruzov. This complementarity to the western literature forms one of the most useful and unique features of the volume. The small section on water contains one spelling error ("valence") and at least one serious obliteration in the value of χ 22 (Table 208) which is easi ly read as —47.04 cm"'. The first digit " 4 " is badly blurred and should be " 1 " according to the original source. Overall, this book is a worthwhile addition to the literature on the subject of its title but should be used in conjunction with other expositions of theory and compilations of data.
New Books The 'Practising Chemists:' A History of the Society for Analytical Chemistry 1874-1974. R. C. Chirnside and J. H. Hamence. xv + 225 pages. The Society for Analytical Chemistry, 9/10 Savile Row, London W1X 1AF, England. 1974. £3
"In recording the achievements of our Society over the past 100 years the authors have described its origins and its subsequent development up to present times when its scientiic stat ure and its international character have been fully recognised. But they have, in addition, taken the opportu nity to relate some of the events, espe cially those in the early life of the So ciety, to contemporary social history and social needs." (From the Foreword )
Evaluation of Ambient Air Quality by Personnel Monitoring. A. L. Lynch, xiv + 226 pages. CRC Press, Inc., 18901 Cranwood Pkwy., Cleveland, Ohio 44128. 1974. $23.50
This book presents an overall view of current air sampling techniques in cluding critical comment based on un published discussion with highly re garded specialists. It is divided into
