Study Pvojacts in Physical Chemistry
P. E. C a d a , The City College, New York. Academic Press, Inc., New 203 pp. Figs. and York, 1963. xii tahles. 21 X 26.5 cm. Paperbound $4.75.
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It appears to the reviewer that this campil~tionof 24 work projects is a very successful effort to fill the gap between class theory and laboratory practice. The author has selected classical materid from the research literature in four important areas: Properties of Matter, Thermodynamics and Chemical Equilihrium, Electrochemistry and Electrolytic Solutions, and Chemical Kinetics. In each of the projects within these aEa8, the objective of the study is clearly stated and a very brief review of the theory is given. The data presented are discussed and specific directions are given for graphing and for the graphical evaluation or the mathematical handling of the material. In many cases there are suggestions far further study. Adequate tables of data, combined with "tally sheets" having columns properly headed for recording the derived values follow. The irrdivid~lillprojects have bern well e of methchos~ntu illustratea ~ i d variety ode for data evaluation. In some cases, blanks are purposely left in the tables to he filled by interpolation or other means. There is excellent emphasis on the meaning and validity of the results of calculations. once thev are accomnlisbed. 8nd upon the wtrnt of s l g n l h n t figures. I ~ r f ~ r e n eto~ stlw onginnl r o u r w a we given in footnows, and follonins, the table of contents there is a two page chart giving cross references to twelve recent physical chemistry texts for each of the projects. This should be especially valuable to the student who needs a thorough review of theory before undertaking actual work on a project. Sketches of the apparatus used to obtain the data are shown in only a few cases. We believe it would increase interest and give a feeling of immediacy to include more of these since the principal use of these projects will probably be as "dry" or non-experimental laboratory exercises. Criticism might also he directed toward t,be selection of material only from the older and more trmditional a r e a of physical chemistry. However, the emphasis is on the methods of handling the data rather than on its intrinsic importance. Yet it would seem that equally good examples could have been chosen from research articles of more nearly current interest. The reviewer feels that he can highly recommend this book to his colleagues. He recently had the opportunity to observe a class, not his own, working on several of these projects, and there was no question but that interet was high and that a high degree of learning was taking place. The author is to be congratulated on lilling a serions gap in the resources available for teaching physical chemistry.
W. C. OELKE Ginnell College Ginnd,Ima
Physics and Chemistry of the Organic Solid State. Volume 1 Edited by David Foz, State University of New York at Stony Brook, Mortimw M. Labes, Franklin Institute Laboratories, Philadelphia, and Arnold Weissbwger, Eastman Kodak Co., Rochester, New York. Interscience Publishers (a division of John Wiley and Sons), New 823 pp. Figs. and York, 1963. xvi tables. 16 X 23.5 cm. Anyone familiar with the many ouG standing publioationa of each of the three editors would expect their joint effort in the area covered by this volume to be superlative. The reader will not be disappointed. The editors have selected a group of authors widely recognized as leading contributors in their fields. A feeling of objectivity and immediacy permeates each chapter. There have been few attemots to develo~solid-state oreanio
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dicate, a large number of disciplines are involved in both study and applications. Biologists, physicists, and chemiets of all kinds, electrical engineers and many others should find intense interest in the subject matter covered. The huge bibliography (nearly 2500 cited references), alone, is worth the cost of the volume to the individual interested in entering or already working in the field. Together with the summaries of thermodynamic, electrical, and other physical and chemical data for organic crystals (often by formula) and a fine index, the lists of citations makes this volume especially valuable as a reference work. The Thermodynamics of Crystals is well-chosen ss the leading section. This is the largest contribution with a monumental list of 798 references. It embraces a beautiful treatment of introductory thermodynamics, experimental techniques, diagrams and data from the literature, a historical summary and implications of this type of study. A similar organizs, tion of topic and the same careful ariting (with a. few minor exceptions) are met in the other sections of the book. These include: The Definition and Attainment of High Purity of Organic Compounds; Crystal Growth, including the theory of perfect and imperfect crystals, dislocations and slippages and crystalline impurities, together with an excellent compendium of practical techniques; Thermal Reactions of Organic Solids, for example, radiation effects, organic explosives, and solid-phase polymerization; The Photochemistry of the Organic Solid State; Crystal Form and Crystal Structure, includiug a study of organic "whiskers"; Structure of Surfaces including epitaxial overgrowth; The Crystallization of LongChain Polymem; Plastic Crystab; Visible and Ultraviolet Absorption by Molecular Crystals, (a well-handled discussion of electronic energy states and energy transport mechanism is included); Infrared Spectra of Moleculrtr Crystals; Dielectric Phenomena; and Electron Transfer Across the Boundaries of Organic Solids, including organic semiconductors, contact electrification phenomena, and photovoltaic effects.
There me a few minor errors and deficiencies in Volume 1. Chapter 2 did not sufficiently cover the attainment of ultrapurity, including reliability and analytical methods. The technique of Knypl and Zielenski, for example, was not mentioned. It is st,ated on page 303 that "It is very difficult, if at all possible, to prove conclusively whether. . . polymerizations proceed by aradicd or by an ionic mechanism, since the usually employed diagnostic tools are not applicable to solid state processes." I n fact, the natures of several solid-state reactions bave been reportedly determined by analytioalinstruments (and by rate studies under E M fields of varying energies). Where the substrate is non-scattering to electromagnetic radiation during the reaction, analysis of transmission, refraction, dispersion (iucluding rotatory dispersion), reradiation, and similar physicd data due to interactions will often produce strong evidence for a particular mechanisms. The discussion of electrets on p. 740 leaves one with the impression that this is a wellunderstood phenomenon. Such is not the case. There is a more adequate coverage of this interesting topic on p. 757. But these and others are minor defects in a very carefully written and edited work. Some fascinating topics are so briefly covered that they only serve to tantaliae the reader (examples include the photochemistry of elastomers, thermodynamics of clathrates, and "exoelectrons)." However, this may well result in the pursuit of further information in the cited references. Volume 1 contains a profusion of revealing phatograpbs (especially electron micrographs) and related diagrams of crystals in various states. The reader, like the original author, can often obtain direct data from them and confirm the accompanying interpretation. This monumental work is a landmark contribution and belongs on in the shelves of practicing chemists, teachers, and technical libraries as s mast vahmble reference source and as a stimulus to creative thinking. NORMANJ. JIISTER Pas& City College Pasadena, California
Advances in Photochemistry. Volume I Edited by W. Albert Noyes, Jr., University of Rochester, Rochester, New York, Gearge S. Hammond, California Institute of Technology, Pasadena, and J. N. Pi=, JI., University of California, Riverside. Interscience Publishers (a division of John Wiley and Sons, Inc.), 443 pp. Figs. New York, 1963. ix and tables. 16 X 23.5 cm. $16.50.
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The area of photochemistry has not been comprehensively surveyed, except for occasional review articles, since the publication of "Photochemistry of Gases" by Noyes and Leighton (1941) and "Fluorescence and Phhsphorescence" by Pringsheim (1949). Since that time, the advances made in quantitative spectroscopy, the development of new techVolume 41, Number 5, May 7 964
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niques, and the increased interest in the problem of energy transfer and exeited states have brought attention to photnchemistry and have given the chemist the means oE investigating "the detailed history of a molecule which absorbs radiat,ionU whieh the editors of this new serie~ consider to be the fundamental photochemical problem. The authors of the first article recognize one of the distinct difficulties of a field which has developed from diverse areas. The "vocnb~~lary" of photoehemist,r,y tends to be a mixture of d l the speeialiaed languages and Pitts, Wilkinson, and Hammond strive to bring unity to a potent,ial chemical Babel. The vvlume continues with eight artirles written by the foremost contribut,ors to the various aspects of photoehemistry. The Photoehemistry of Aromatic Hydrccarbon Solutions is discussed by E. J. Bowen. The problems current. in this field are analyzed bnt the lack of a table of contents preceding the article makes some of the material difficult to find in the body of the text. The gas phnee photochemistry of the hydrogen-oxygen system is the subject of a review by D. H. Volman. The author carefully reviews t,he status of the understanding of the reactions and unresolved mechanisms in this system. R. Srinivasan follows with the Photoehemistry of the Cyclic Ketones which mainly deals with the 4 to 7-nremher ring system in vapor and condensed phase. The status of the gas phase addition of atoms to olefins is next discussed in great detail by R. J. CvetanoviC. Alt,hough the reactions of oxygen atoms occupy ahout half of the author's attention, he does not neglect hydrogen, halogen, carbon, nitrogen, and sulfur atoms in his discussion. I n A Xew Approach t o Mechanistic Organic Photochemistry, H. E. Zimmerman considers the nature of the electronirally excited species which is formed as a consequenre of the absorption of the light quanta by the ground state. The presentation is lively and will undoubtedly arouse considerable interest. Gunning and Strausz are concerned with the mechanism of energy transfer in merrury photmensitiration and the use of isotope effects to aid in that understanding. Their treatment of kinetic isotope effects, although dealing only with hydmgen-deuterium, is quite comprehensive and t,he inclusion of references as recent as Spring 1963, gives the paper a "hot-offt,he-p-" quahty. Photochromism, the reversible color changes which certain aubstmces undergo upon exposure t o light, is the topic of the review by Dessauer and Paris. They catalogue a large number of chemical systems which exhibit this phenomenon and discuss the changes in physical properties whieh accompany the color change. The final paper, Photochemical Resrrangements of Organic Molecules by 0.L. Chapman, is a 90-page study whieh offers to its readers a survey of a great deal of organic chemistry from simple keto-end isomerisation to the photochemical trmsformations of the Vitamin D series. There is s sense of urgency about the article reflected in the fact
that the majority of the 225 references cited deal with papers published in 1960 or later. For the organic chemist there is a rirh source of interesting rearrangements which might otherwise have been lost in the onrush of the literature. An extensive author and subject index fnllows the articles. If this volume is represent,ative of those to come in this series, then a serious gap in t,he literature af photochemistry will have been closed with some exciting writing by pioneers in the field. I highly recommend this volume ss a valuable reference hook to all who are interested in energy transfer, the chemistry of excited statet, and the many aspects of photochemistry. This series is long overdue and its appearance in this form is most welcome.
cedure, rhoice of wavelength, methods of standardiaation and measurement, de, tection limits, and errors and interferences. The latter topics are particularly well treated. Detection limits are given s sound definition and s. tsble of limits for all elements determinable (up to mid1962) is presented whieh includes several wavelengths for each element in a variety of flames using both wrtter and nonqueous salverrts. Interference mechanisms and instrumental and procedural techniques for minimizing interferences m e very w d treated although only the most important, (alkali metal cation-cation and alkaline earth) are discussed sp~eifiedly. The chapter on applications is short and cursory except for the eection on medicine and biology where blood analysis is described in some detail. References to $1 Z.HOFFMAN specific analytical applications that are in MORTON Boston University the bibliography are included in the index, Boston, Massachusetts whieh is excellent,, and they are easily located. The appendix contains very extensive wavelength tabIe,les and intensity data for atomic and molecular flame emitters, both bv element and bv wavelenpth. Alao in-
Chemical Analysis by Flame Photometry
Roland Herrrnann, University of Giessen, Germany, and C. T. J . Alkemde, University of Utrecht, Holland. Translated by Paul T. Gilbert, Jr., Beekman Instruments, Inc., Fullerton, California. 2nd rev. ed. Interscience Publishers ( a division of John Wiley and Sons), New York, 1963. Chemical Analysis Series, 644 pp. Figs. and Volume 14. xiv tables. 16 X 23.5 em. $00.00.
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This monograph is the mast complete and up-to-date volume on flsme photametry readily accessible in this country and represents a fine addition to the Interscience series on Chemical Analysis. The authors are concerned with a critical evaluation of instn~mentationand analytical techniques and with the fundamental processes and reactions involved in flames and flame analysis. It. is not, and is clearly not intended to be a handbook of procedures and applications. The book begins with a discussion of the structure and properties of flames and reactions of analytical importance oceurring in them. I n this ehspter are also outlined in detail the various types of interferences occurring in flame photometry and their interdependence. This section is of particulas value because of the confusion surrounding the description and explanation of interferences that exist in t,he literature. One may disagree with details of their organization here but it is consistent, and it is helpful t,o have the terminology and definitions presented clearly and concisely at the start. A long chapter is devoted t o experimental variables and instrumentation. Components of flame photometers, spectrophotometers, and spectrographs and the variables involved in their onoration
amplifiration is given ts very brief treat. ment. Chapter 4, on analytical techniques is the heart of the text, containing detailed and critical discussions of andytical pro-
characteristics. A drawback to the book is the occasional awkward wording that occurs in the translation and makes rapid reading hard. Meaning is never obscured but this, eomb i n d with the detailed discussions and sonlo unfamiliar terminology may make i t difficult t o obtain information from the book quickly and efficiently. This is a minor flaw however, and the translator's contributions add significantly to the hook's usefulness. Research in fuel-rich flames, chemiluminescent excitation, and atomic absorption has progressed rapidly since the hook was written but, thanks t o the translator, much of i t is made available. As a. reference book this is superior t o Dean's "Flame Photometry," dthougb i t is not as concise or redable, and i t lacks the convenient summary of experimental conditions, interferences and applications given for each element by Dean. However, ita completeness and particularly the critical comparisons and evalnat,ions made by Herrmann and Alkemde throughout make their book a very valuable addition to any chemistry library. ALLENC. WEST Williams CoUege Williamtoum, Massachusetts
X-Ray Diffraction in Crystals, Imperfeef Cryrfalr, and Amorphous Bodies
Translated by Paul Lmrain, University of Montred, and Dnrothee Sainte-Marie Lorrain. W. H. Freeman and Company, San Franciso, 1963. x 378 pp. Figs. and tables. 16 X 24 cm. $11. A. Guinier, University of Paris.
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Perhaps the first point t o make about this book is that it is not, and is not intended t o be, an introductory text in X-ray crystallography; there is no discussion of
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