Books
Outline of the Basic Principles and Modern Methodology of Electrochemistry
Experimental Electrochemistry for Chemists. Donald T. Sawyer and Julian L. Roberts, Jr. χ + 435 pages. John Wiley & Sons, Inc., 605 Third Ave., New York, NY 10016. 1974. $18.50
Reviewed by Larry R. Faulkner, Department of Chemistry, University of Illinois, Urbana, IL 61801 In their preface, the authors state their intention, ". . . to outline the basic principles and modern method ology of electrochemistry, in such a way that the uninitiated may gain suf ficient background to use electro chemical methods for the study of chemical systems." Recent years have seen an important rise in the usage of electrochemical tools by workers who are not formally trained in the area, and this book is intended largely for them. Especially with regard to exper imental aspects, it meets their needs for a source book, and it has much to offer the experienced electrochemist. The first third of the volume treats the design of electrochemical appara tus in valuable detail. Topics such as the choice of electrode materials, the fabrication of working electrodes, pretreatment procedures, and cell design are covered thoroughly. References are made to the special design prob lems encountered in thin-layer work, spectroelectrochemistry, and largescale electrolysis. Extraordinarily well done is the section on reference elec trodes and liquid junctions. The un usual value of these early chapters is that they record many trade secrets that have been handed down like oral legends through the generations. This tradition contributes to the mystical atmosphere surrounding electrochem ical practice, and both the atmosphere and the lack of practical information sources have inhibited wider use of electrochemical approaches. The ma terial in these sections will go a long way toward reducing the barriers. Moreover, there is much in them that even the specialist would like to have readily available. The subsequent chapter on solvents and supporting electrolytes is a conve
nient companion to Mann's wellknown works in the area. It is not as thorough in treating working ranges, purification methods, and electro chemical properties of solvents; but it introduces some useful ideas about miscibilities and donor/acceptor prop erties that are not extensively treated in other electrochemical review litera ture. Several tables in this chapter are especially helpful. In their approach to instrumenta tion, the authors depart from their more common practice by beginning on a level which requires the reader to have a fair foreknowledge of electrical circuit analysis. In the absence of pre vious experience, I would have found it very difficult to learn about opera tional amplifier applications from their presentation. They begin with the limitations of these devices and discuss first such concepts as drift sta bilization and common mode rejec tion. Certainly, these are important items, but they probably should be de ferred until ideal amplifier circuits are understood. Moreover, it strikes me as inappropriate that the first discussion of a real potentiostat involves simulta neous control of two working electrode potentials. Later treatments of IR compensation and high-frequency ef fects are superficial, but (in keeping with the rest of the book) the litera ture is well referenced. The last third of the text treats var ious kinds of electrochemical experi ments and the information that can be had from them. The descriptions are succinct, and fundamental mathemat ical relations are usually presented without derivation. Basic phenomena pertaining to mass transfer, the elec trical double layer, or electrode kinet ics are not elaborated. Even so, refer ences are sufficiently plentiful that one could use these sections conve niently as a guide to more detailed lit erature. Neither this book nor any other will tell an interested reader all he needs to know about electrochemistry, but Professors Sawyer and Roberts can give him some real help with experi
mental aspects. That alone is a valu able contribution, so I am sure that many practitioners of electrochemis try, whether specialists or not, will find this book well worth its reason able purchase price.
Overview of Thermal Techniques Advances in Polymer Science, Vol. 13: Thermal Analysis of Polymers. W. Wrasidlo. 99 pages. Springer-Verlag Berlin, Heidelberger Platz 3, 1 Berlin 33, Germany. 1974. $18.90
Reviewed by F. E. Karasz, Depart ment of Polymer Science and Engi neering, Materials Research Labora tory, University of Massachusetts, Amherst, MA 01002 In the past decade, thermal tech niques have become a routine charac terization tool in most laboratories concerned with the physical properties of macromolecules. In this field, ther mal analysis is now more or less estab lished as the method of choice for the determination of such key parameters as melting and glass transition tem peratures and degrees of crystallinity. This state of affairs has come about, characteristically, through the advent of commercial instrumentation, versa tile, sensitive, and sufficiently rugged to be made available for use, in many cases, on a self-service basis by rela tively inexperienced operators. The present monograph, a further volume in a well-established review series, could form a useful addition to the growing literature on the subject. It reviews, with extensive referencing, a number of topics in the field of ther mal analysis of polymers and should appeal both to the experimentalist who seeks a deeper understanding of the meaning of his measurements and to researchers who wish a relatively current (to about 1972) overview of the area. The author has limited his coverage to a few selected areas, an obvious de cision in view of the relative brevity of the volume (99 pages). Almost one
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Books third of the text is devoted to the glass transition, with a fairly comprehensive description of the nominally competi tive theoretical treatments for this im portant process. Most of the current approaches are covered, though not in a particularly critical fashion. One no ticeable omission is the area of order parameter theory; the important con tributions of Goldstein and Staverman, for example, are not mentioned. A collection of thermodynamic data pertaining to the transition for a large number of polymers is included in this section, as is a table of calculated hole energies, hole volumes, etc., based on a specific free volume model. Although interesting enough, it is difficult to be lieve that the latter will be of much help to most potential readers. Most of the remainder of the text is concerned with either the melting or the crystallization process in poly mers, and a considerable amount of information is presented in a relative ly short space. In consideration of the enormous body of pertinent literature now available, the material chosen is representative, relevant and, on the whole, well organized. There is also a short chapter on ex perimental techniques, including a useful section on sample preparation, a subject barely covered elsewhere. One could perhaps argue again about the desirability or necessity of includ ing some of the material chosen, for example, a block diagram of a customdesigned DTA apparatus, but these are subjective decisions at best. It is unfortunate that the volume is marred by an unusually large, well nigh incredible number of typographi cal errors, misspellings, missing defini tions of symbols, and similar blem ishes. How annoying this will prove to be might depend on the individual reader, but it is certainly bound to de tract from an otherwise informative and useful volume.
Most Valuable to the Beginner Absorption Spectroscopy of Organic Molecules. V. M. Parikh. χ + 325 pages. Addison-Wesley Publishing Co., Inc., Reading, MA 01867. 1974. Paperbound. $7.95
Reviewed by Warren B. Crummett, Analytical Laboratories, Dow Chemi cal USA, Midland, MI 48640 This book, according to the author, is intended "to introduce spectroscopy to students in the basic organic chem
istry course." These students "have had a variety of goals, many interests, and a wide spectrum of backgrounds." To accomplish this, Chapter 1 pre sents a quick review of basic physics. This is followed by chapters on ultra violet spectroscopy, infrared spectros copy, nuclear magnetic resonance spectroscopy, and mass spectrometry. The integration of the various tech niques is discussed in Chapter 6, and the appendix contains useful charts of spectroscopic correlations. The chapter on fundamental phys ics is well done, presenting consider able information pertinent to spec troscopy in general. Chapters 2-5 deal with basic theory, the construction and handling of in struments, the presentation of data, the interpretation of spectra, and some applications. Chapter 6 presents methods of correlating information from various techniques to identify or ganic compounds. All essential topics for a basic un derstanding of spectroscopy are dis cussed and usually well presented. Unfortunately, the author elected to include many "specialized topics." This caused him to be sidetracked by details which he appears to be unable to explain clearly, thus leading to con siderable confusion and frustration for the student just being introduced to the subject. The "typical UV spectrum" shown in the chapter on ultraviolet spectros copy is not a spectrum at all because the solution used to record the spec trum was too concentrated for the ab sorption maximum to be shown on the chart. The spectrum of benzene in ethanol is incorrect for the same rea son. The spectra of benzene are shown to show the effect of polar and nonpolar solvents on the fine structure of the absorption bands. This is an un fortunate choice as only small subtle differences are noted when the spectra are prepared correctly. The chapter on infrared spectrosco py is adequate but badly dated. The inconsistent use of units (microns and cm - 1 ) is unnecessarily confusing. The spectral presentation (linear in wave length) is outdated and contrary to modern practice (linear in c m - 1 ) . The quality of spectra presented as exam ples is substandard (dead spots and band squaring are evident). Consider able space is devoted to explaining the Raman effect; yet, no mention is made of Raman in the section on interpreta tion and group frequencies. The chapter on nuclear magnetic resonance spectroscopy should serve the main purpose of teaching the stu dent to perform basic structural anal ysis. However, some erroneous and contradictory statements are made. As examples, Boltzman is given credit for
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Einstein's contributions, 19 F is some times written F 1 9 , "spin-spin split ting" is used as a coupling constant and to describe the appearance of a spectrum, couplings other than vicinal are listed under the "vicinal" heading, and the description of spin tickling is wrong. The chapter on mass spectrometry starts out with a misleading descrip tion of principles by stating that sub stances are "subjected to high-voltage electric current" when in reality a lowenergy electron beam is used. Also, the deflection depends on charge, mass, and energy, not "charge, mass, and ve locity." Other somewhat misleading statements occur throughout this chapter. Nevertheless, the treatment is adequate for a beginning course on the subject. The major strengths of this book in clude: the excellent questions at the end of each chapter which along with Chapter 6 give the whole book excel lent meaning and relevance; the refer ences; and the correlation tables in the appendix. In general, the sections on applica tions are not well done from an indus trial chemist's viewpoint. Therefore, the book will be most valuable to the beginning student or to a chemist en tering any of the treated fields. Once the errors and contradictions are cor rected, this will be an outstanding text.
X-ray Spectrometry: Second in Series An Introduction to X-Ray Spectrome try. Ron Jenkins, xi + 163 pages. Heyden & Son Ltd., Spectrum House, Alderton Crescent, London NW4 3XX, En gland. 1974. $14
Reviewed by John V. Gilfrich, Naval Research Laboratory, Washington, DC 20375 A review of a book of this type is a difficult endeavor. For the parochial views of this reviewer, there are few enough good books on X-ray spectrochemical analysis so that a new one is greeted with anticipation. Unfortu nately, this new book by Ron Jenkins does not come up to expectations. The preface describes (with some ambigu ity) the intent to publish a series of four integrated texts with a plan to cover the important aspects first and to follow with more detailed informa tion. It is not easy to differentiate this effort from the initial one (R. Jenkins and J. L. DeVries, "Practical X-Ray Spectrometry," Springer-Verlag Inc., New York, NY, 1967). I found it nec essary to go back and reread the first book to try to find how this one fit into the sequence. Although the orga nization is somewhat different, much
Books of the information is simply repeated. But unfortunately, the duplication of effort is not the main criticism. To the mind of this reviewer, the major difficulty with this book is an overemphasis on the wrong aspects (at least with respect to the needs of the potential X-ray analyst). For a commendably short "introduction to X-ray spectrometry," the detailed description of the electron configuration of the elements and energy level diagrams seems singularly inappropriate. Significant (presumably typographical) errors further detract from the value which this effort might have displayed, e.g., in a discussion of radioisotopes, Cd 109 is erroneously listed as CI 109 , and its emission energy is given unbelievably as 19,87.8 keV (sic). It is always possible to miss certain errors during proofreading, but the most intense emission from Cd 109 has an energy of about 22.1 keV. The overall impression is one of carelessness in preparation. There are some other important criticisms which may reflect a certain amount of personal preference on the part of the reviewer. The description of the Auger process (given in two places) seems overly simplistic. It is more appropriate to consider this process as a radiationless transition leading to the direct ejection of an electron rather than the photoemission sequence described. There are many better references to mass absorption coefficients than the one quoted on page 51. Figure 4-3, describing transmission through Be windows, would be much better as a semilogarithmic plot since absorption is an exponential process. In the description of the manner of operation of a gas proportional counter, the energy to produce an ionpair is listed in a table which does not describe the source for the numerical values (important because there does not seem to be any simple relationship to the first ionization potential). In this same discussion the description of the Fano factor for proportional counters seems garbled, and there is no mention of the Fano factor for scintillation counters. All of the illustrations of instrumentation in the book are slanted toward Philips equipment which is not surprising in view of Jenkins' affiliation. But the statement that flat crystals are more suited for scanning spectrometers and curved crystals best for multichannel instruments is certainly not consistent (nor accurate); also, the illustration showing the detector colli-
mator finer than the primary collimator is not usually the case and certainly not for Philips instruments. The implication that the secondary fluorescer concept is a recent advance for energy dispersion is misleading at best. It has been employed for at least 10 years. The generalization made that 2nd order diffraction is about 35% of 1st order diffraction is, like all generalizations, unfortunate. It can be readily demonstrated that for the most often used crystal, abraded and etched LiF, 2nd order diffraction is closer to 10% of 1st order for most of the wavelengths measured using this crystal, and for KAP it is about 4%. This reviewer finds it very disturbing to feel it necessary to be so critical of a book by an eminent X-ray spectroscopist. The above listed specific criticisms represent only a fraction of the difficulties with Jenkins' book. In summary, it must be said that the initial effort (by Jenkins and DeVries) has not been improved upon by the more recent endeavor. This book cannot in good conscience be recommended, but rather the student of X-ray spectrometry is directed to any of the other books available (including the previous book by Jenkins and DeVries).
tions of chromatography. The papers are reprinted from the Journal of Chromatography. Atlas of Stereochemistry: Absolute Configurations of Organic Molecules. W. Klyne and J. Buckingham, xvi + 311 pages. Oxford University Press, 200 Madison Ave., New York, NY 10016. 1974. $39.95
The "Atlas" is the first extensive compilation of absolute configurations to appear in print. Over 3000 compounds are covered. All compounds are represented by their stereochemical formulas and are portrayed in a diagrammatic form. Official, Standardised and Recommended Methods of Analysis. Second edition. N. W. Hanson, Ed. xxiv + 897 pages. The Society for Analytical Chemistry, 9/10 Savile Row, London W1X 1AF, England. 1974. $17
This volume is a result of collaborative work contributed over a number of years by specialists and presents a body of practical methods that have been well tried as well as a collection of bibliographies that provides the means to a more extensive study of particular topics in analysis.
Continuing Series New Books Laser Spectroscopy. Richard G. Brewer and Aram Mooradian, Eds. xi + 671 pages. Plenum Publishing Corp., 227 West 17th St., New York, NY 10011. 1974. $34.50
The proceedings of the Laser Spectroscopy Conference held at Vail, CO, June 25-29, 1973, are presented in this volume. The development of tunable laser sources and their applications to very high-resolution optical spectroscopy are discussed. Topics include the technology of tunable lasers, fundamental physical constants, atomic and molecular hyperfine structure, coherent transient phenomena, and geophysical and astrophysical applications. The text is reproduced from typed copy. Advances in Chromatography 1974. A. Zlatkis and L. S. Ettre, Eds. xv + 772 pages. University of Houston, Department of Chemistry, Houston, TX 77004. 1974. $30
The proceedings of the ninth international symposium on advances in chromatography held in Houston, TX, November 4-7, 1974, are presented. The 61 papers are included under the broad topics new horizons, chromatographic columns and stationary phases, and theoretical and practical, biomedical, and environmental applica-
Encyclopedia of Electrochemistry of the Elements, Vol. 2. Allen J. Bard, Ed. xii + 515 pages. Marcel Dekker, Inc., 270 Madison Ave., New York, NY 10016. 1974. $60
The aim of the series is to provide a critical, systematic, and comprehensive review of the electrochemical behavior of the elements and their compounds. Volume 2 covers boron, arsenic, niobium, tantalum, rhenium, technetium, oxygen, and copper. The text is reproduced from typed copy. Spectroscopic Tricks, Vol. 3. Leopold May, Ed. xii + 400 pages. Plenum Publishing Corp., 227 West 17th St., New York, NY 10011. 1974. $22.50
The material contained in this volume originally appeared in Applied Spectroscopy from 1970 through 1973. Areas covered include Raman, infrared, emission, and atomic absorption spectroscopy, as well as nuclear magnetic resonance and X-ray spectrometric techniques. Annual Reports on Analytical Spectroscopy, Vol. 3. C. Woodward, Ed. x + 324 pages. The Society for Analytical Chemistry, 9/10 Savile Row, London W1X 1AF, England. 1974. Paperbound. $15
Volume three was prepared from information received during the year 1973. The review is intended to be
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