Principles of Analytical Chemistry


a chapter on evalua- tion of data, which is intended for pre- sentation when the first laboratory re- sults are submitted. This strikes me as a good i...
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Principles of Analytical Chemistry Analytical Chemistry, 3rd ed. Douglas A. Skoog and Donald M. West, xii + 685 pages. Holt, Rhinehart & Winston, Inc., 383 Madison Ave., New York, N.Y. 10017. 1979. $17.95 Reviewed by Herbert A. Laitinen, Department of Chemistry, University of Florida, Gainesville, Fla. 32611 This third edition of a well-established text, like the first edition (1965) and the second (1974), is intended for a one-semester course for nonchemistry majors. T h e aim is to cover selected gravimetric and titrimetric procedures with an introduction to some of the basic instrumental measurements used in biological and medical sciences and engineering. Emphasis is on principles rather than on procedures or details. T h e book is designed for flexibility, allowing variations in the order of presentation and the omission of certain portions at the discretion of the instructor. A brief introductory section is presented as a review of principles, mainly stoichiometry and simple equilibrium calculations from general chemistry. Next comes a chapter on evaluation of data, which is intended for presentation when the first laboratory results are submitted. This strikes me as a good idea, especially in these days of the ubiquitous hand calculator when students tend to forget the concept of significant figures. A neat example calculation illustrates the origin of the familiar Gaussian curve for distribution of random errors. At this point, the third edition covers solubility equilibria and gravimetric analysis, followed by titrimetric analysis. Earlier editions had introduced here a section on chemicals, techniques and apparatus; in the third edition this section comes near the end, just before a concluding chapter, "Selected Methods of Analysis." This order of presentation represents a distinct improvement, not only for its logic, but for the psychological impact of stressing principles over routine details. A logical transition from "classical"

to "instrumental" is made through potentiometry and potentiometric titrations, and through electrodeposition and coulometry to polarography and amperometric titrations. T h e discussion of ion-selective electrodes, including solid and liquid membranes and gas-sensing electrodes is especially appropriate for the intended readership. In future editions, it is suggested t h a t enzyme electrodes might be included. The classification of optical methods does not seem entirely logical. A chapter entitled "Absorptiometric Methods of Analysis" includes all regions of the spectrum and perforce includes a section on generation of electromagnetic radiation as well as radiation detectors, which are used both in emission and absorption measurements. T h e other chapter on optical methods is entitled "Atomic Spectroscopy" and includes both emission and absorption methods. Atomic absorption is covered in both chapters. Finally, a chapter on analytical separations includes multiple extraction and chromatographic methods. It is not an easy matter to present analytical principles in an elementary fashion without doing violence to deeper understanding. For the most part, the authors have succeeded admirably, but in a few cases, this reviewer would take exception. On page 276, in discussing the signs of half-cell potentials, the authors state that "the choice as to which potential will be positive and which will be negative is purely arbitrary; however, the sign convention chosen must be used consistently." I would have preferred to say that whether one chooses the sign of the electrical charge on the metal or on the solution side of the double layer is purely arbitrary, but that the IUPAC system chooses the former. It is not arbitrary that zinc metal is negative with respect to hydrogen, and indeed it is this feature that makes the IUPAC system intuitively attractive. Another example is in using the Nernst equation to calculate titration curves even for thermodynamically

unstable and irreversible systems, such as in the region beyond the equivalence point of the permanganate-iron(II) titration. I believe an elementary presentation would be better restricted to reversible systems, or else t h a t further explanation is in order. A relatively minor suggestion is that the use of the symbol e~ rather than e for the electron is an aid in the balancing of half-reactions. Such details aside, this is a book worthy of serious consideration for a one-semester treatment of quantitative analysis for nonchemistry majors. T h e treatment emphasizes fundamentals, presents lots of good chemistry, and offers a selection of important chemical methods as well as an introduction to instrumental measurements.

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*u Time Domain Electron Spin Resonance. Larry Kavan, Robert N. Schwartz, Eds. viii + 414 pages. John Wiley & Sons, Inc., 605 Third Ave., New York, N.Y. 10016. 1979. $23.50 Reviewed by David H. Volman, Department of Chemistry, University of California, Davis, Calif. 95616 Chemists generally know that ESR spectroscopy is used in the identification and structure determination of paramagnetic species. T h a t it is used to provide information on molecular motion of the paramagnetic probe and on the structure and properties of its surroundings by time domain studies is less well known.

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Books Conventional ESR experiments may be carried out by chemists whose knowledge, of magnetic resonance spectroscopy is very limited; time domain studies require a good background in theory. In this volume of nine separately authored chapters, theory and experiment are firmly linked. Two chapters are devoted solely to the theory of the two principal methods of time domain studies, saturation recovery and spin-echo. Other chapters are devoted to the methodology, experimental and theoretical, of topics in the framework of time domain: spin-lattice relaxation; intersystem crossing dynamics; spin-spin interactions; and molecular triplet states in zero field. Although the parts of the book are separately authored, the volume reads almost as though it had a single author. T h e development is logical; each author shows, implicitly and sometimes explicitly, that he knows what the other parts are about and how his contribution fits in. T h e editors have gathered together a superb group of contributors. Each is well-qualified in his field and knows how to write. In the opening chapter James S. Hyde presents an excellent overview of saturation recovery methodology: instrumentation, theory, and applications. As he also compares saturation recovery with spin-echo methods, the chapter serves as an excellent orientation for the following chapters. T h e last chapter by J. Schmidt and J. H. van der Waals is a fitting climax as it demonstrates the power of time domain in an area, molecular triplet states, where important advances had already been made by conventional ESR. There is a considerable emphasis in the book on instrumentation, and there are many block diagrams. A recurring theme is t h a t commercial instrumentation is not available. Hence, it is interesting to note that as of now the first commercial spin-echo ESR instrument has been delivered. This does not detract from the value of the instrument discussion. On page 108 the authors state that the first ESR studies of transient radicals in liquids was by Fessenden and Shuler in 1963. (In fact this was preceded by work published by Fessenden and Shuler in 1960.) I need go no further than my own department to know that in 1959 Maki and Geske published an ESR study of transient radicals produced in liquid acetonitrile. (Perhaps this was the first but I make no such claim.) Wrong attributions can get locked-in and end up as "Guinness" records. One should be

particularly careful with ESR claims; after all, the Russians really did invent it. This book should be interesting and valuable to anyone who has a good background in any area of magnetic resonance spectroscopy. It should be particularly valuable to those who practice the science of identification and gross characterization of paramagnetic species, and who know there is much more t h a t can be done with ESR, but don't know how to do it. Treatise on Analytical Chemistry, Pt.

1, Vol. 2. 2nd ed. I. M. Kolthoff and Philip J. Elving, Eds. xxv + 815 pages. John Wiley & Sons, Inc., 605 Third Ave., New York, N.Y. 10016. 1980. $65 Reviewed by David N. Hume, Dept. of Chemistry, Massachusetts Institute of Technology, Cambridge, Mass. 01239 For two decades the Kolthoff and Elving "Treatise" has been the outstanding comprehensive work on analytical chemistry to which one could always turn, confident that the writer of a given section had gotten it all together and gotten it right. T h e longawaited second edition is now appearing and it is a pleasure to be able to report t h a t the high standards characteristic of the first edition are maintained in the second. T h e present section (Vol. 2 of Pt. 1), subtitled "Solution Equilibria and Chemistry, Chapters 15-23," covers the general area of six chapters (296 pages) by five authors in Volume 1, Part 1 in the first edition, but these have been expanded into nine chapters (792 pages) by 14 authors, only two of whom were represented in the first edition. T h e increase in pages represents growth, rather than inflation. Analytical chemistry continues to be a rapidly developing area. The volume begins with Erik Hôgfelt's chapter "Graphic Presentation of Equilibrium Data," a masterful revision of the original by the late Lars Gunnar Sillén, and is supplemented with a new chapter "Graphic and Computational Methods in the Evaluation of Stability Constants." Professor Kolthoff has himself revised his chapter "Concepts of Acids and Bases," which is followed by a very thorough treatment of "Acid-Base Equilibria, Buffers and Titrations in Water" authored by Donald Rosenthal and Petr Zuman. Chapter 19, "Acid-Base Equilibria in Nonaqueous Solutions," is actually five subchapters totaling 203 pages and consisting of a general introduction by I. M. Kolthoff and M. K. Chantooni followed

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by the sections "Amphiprotic Solvents" by A. I. Popov and H. Caruso, "Dipolar Aprotic Solvents" by Kolthoff and Chantooni, "Inert Solvents" by Joseph Steigman and "Inorganic Aprotic Solvents" by A. I. Popov. Another greatly expanded section is the chapter "Complexation Reactions," originally by the late Anders Ringbom, here revised by Professor Ringbom and Erkki Wànninen. One topic t h a t had been given a mere six pages in the previous version of t h a t chapter now stands on its own as the 44-page chapter "Masking and Demasking in Analytical Chemistry" by D. D. Perrin. Similarly, the original chapter by F. R. Duke on "Mechanisms of Oxidation-Reduction Reactions" now consists of a greatly expanded chapter with the same title by R. G. Linck and a new and even larger chapter "Induced Reactions in Chemical Analysis" by L. J. Csânyi. The editors have chosen their contributors wisely, as is evident from the authoritative, well-indexed and scholarly, yet eminently readable treatment the topics have been given. One is struck by the rapidity with which new developments in other areas of chemistry are being taken up and applied in analysis, and the "Treatise" is an excellent remedy for creeping obsolescence. T h e present state of the economy makes it unlikely t h a t many of us will own the new "Treatise," but we should undertake the responsibility of seeing to it that our librarians have no peace until they have made it available to us. Chemie Analytique des Solutions et Microinformatique (in French). Robert Rosset, Denise Bauer, and Jean Desbarres. vii + 1 5 9 pages. Masson Publishing USA, Inc., 14 E. 60 St., New York, N.Y. 10022. 1979. $22.50

Reviewed by Eric Schuttringer and George H. Nancollas, Department of Chemistry, State University of New York at Buffalo, Buffalo, N.Y. 14214 This book (in French) aims at presenting to the undergraduate student a systematic approach for the analysis of equilibrium data in solution. Simplified algebraic expressions are given for systems such as acid-base, oxidation-reduction and complex formation, and the limitations of these expressions are emphasized and profusely illustrated. T h e graphical presentation of the information is particularly useful for highlighting the differences introduced by changes in the base equilibrium data. In addition to the graphical representation, computer program information is given in some

Books detail. Although most workers will prepare their own algorithms, the computational details given in this book will be helpful to the uninitiated. Examples are given for the titration of particular acids in different solvents so t h a t the idea of solvent basicity and its influence on the experimental data is meaningfully presented. T h e titra­ tion information is well presented and a wide range of pk's of acids and bases is given with many examples. Practi­ cal problems in the determination of pk values of weak acids and bases through titration with either strong base or strong acid emphasize the lim­ itations due to properties of the sol­ vent medium and the relative magni­ tude of the pk values. An elementary introduction to oxi­ dation and reduction reactions is also presented. Even though this section is rather short, it emphasizes the similarity of the approach to t h a t for acid-base equilibrium. Again, the lim­ itation in titration data for the redox systems is emphasized by illustrations relating to nonaqueous titrations as well as water as solvent and the metastable state of some oxidant and reductant species. T h e treatment is also

extended to the formation of metal complexes in solution. T h e book is well written and the profuse illustrations will be a most useful feature for the undergraduate student. In presenting equilibria in so­ lution in a new and useful way, the book achieves a certain prominence and should be of considerable value to both students and teachers.

New Books Liquid Scintillation Counting: Recent Applications and Development. ChinTzu Peng, Donald L Horrocks, and Ed­ ward L. Alpen, Eds. Vol. 1, Physical As­ pects, xx + 414 pages, $27.50. Vol. 2, Sample Preparation and Applications, xx + 538 pages, $32. Academic Press, 111 Fifth Ave., New York, N.Y. 10003. 1980. These two volumes contain the pro­ ceedings of the International Confer­ ence on Liquid Scintillation, Recent Applications and Development, held August 21-24, 1979, at the University of California, San Francisco. T h e pro­ ceedings, consisting of 14 sections, in-

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1322 A • ANALYTICAL CHEMISTRY, VOL. 52, NO. 12, OCTOBER 1980

elude 76 invited and contributed pa­ pers. T h e first volume contains 37 pa­ pers dealing primarily with physical ' aspects of scintillation counting. These papers are grouped into sec­ tions devoted to general physics, scin­ tillation physics and scintillators, quenching, radioactivity standards, advances in instrumentation, alpha counting, and Cerenkov counting. T h e remaining papers in the second vol­ ume discuss sample preparation and applications such as emulsion count­ ing, chemiluminescence and biolumi­ nescence, environmental monitoring, and biomedical and radioimmunoas­ says. Amplitude Distribution Spectrometers. Waldemar Scharf and Waldemar Lisieski. χ + 568 pages. Elsevier Scientific Publishing Co., P. O. Box 211, 1000AE Amsterdam, Netherlands; 52 Vanderbilt Ave., New York, N.Y. 10017. 1979. $90.25 T h e original version of this book ap­ peared in Polish in 1973. T h e current volume has been updated and trans­ lated into English. In addition to cov­ ering the conventional analysis »f am­ plitude spectra and the relevant appa­ ratus, the book also deals with such measuring techniques as multiscaling, multispectral scaling, taking of histograms, and multichannel aver­ aging as well as correlation, Fourier and multiparameter analysis. Particu­ lar emphasis is placed on the interpre­ tation of the results, starting with the simplest manual methods and ending with highly sophisticated computer methods.

Continuing Series Advances in Chromatography, Vol. 18. J. Calvin Giddings, Eli Grushka, Jack Cazes, and Phyllis R. Brown, Eds. xiv + 292 pages. Marcel Dekker, Inc., 270 Madison Ave., New York, N.Y. 10016. 1980. $38.50 This latest volume in the long­ standing series on chromatography presents five review articles written by 10 international experts. T h e areas surveyed are: (1) characterization of long-chain fatty acids and their deriv­ atives by chromatography; (2) ion-pair chromatography on normal-and reversed-phase systems; (3) H P L C anal­ yses of free nucleotides, nucleosides, and bases in biological fluids, (4) reso­ lution of racemates by ligand-exchange chromatography; and (5) anal­ ysis of marijuana cannabinoids and their metabolites in biological media by GC and/or GC-MS.