Physical methods in organic Chemistry. Edited by Arnold Weissberger. Interscience Publishers, vol. I, N. Y., 1945, vol. II, N. Y., 1946.

Physical Methods in Organic Chemistry. Edited by Arnold Weissberger, vol. I, 1945; vol. II, 1946. In both volumes, 1367 pp.

A fundamental publication of at least 100 author’s sheets in extent, whose content is broader than its title. It is, in essence, an exposition of all physical methods of investigation and analysis used in chemistry in general. The specificity of organic chemistry, if it is reflected at all, is only in the selection of examples by which particular methods are illustrated. The book consists of 26 chapters, each of which is devoted to a separate method. Individual chapters were written by different persons; thus, in all, 27 authors took part in preparing the book. Most of the authors are leading specialists in their fields. Thus, for example, the section on determination of dipole moments was written by Smyth, that on electron diffraction by Brockway, that on crystal-chemical analysis by Donohue, etc. We give the titles of the chapters: 1. Determination of melting points, 2. Determination of boiling points, 3. Determination of density, 4. Determination of solubility, 5. Determination of viscosity, 6. Determination of vapor pressure, 7. Determination of the properties of monolayers and films, 8. Determination of osmotic pressure, 9. Determination of the diffusion coefficient, 10. Calorimetry, 11. Microscopy, 12. Determination of crystal form, 13. Crystal-chemical analysis, 14. X-ray structural analysis, 15. Electronography, 16. Refractometry, 17. Spectroscopy and spectrophotometry, 18. Colorimetry, photometric analysis and fluorometry, 19. Polarimetry, 20. Determination of dipole moments, 21. Conductometry, 22. Potentiometry, 23. Polarography, 24. Determination of magnetic susceptibility, 25. Determination of radioactivity, 26. Mass spectrography.

The task which the publisher set before himself was to gather into one book everything that a chemist might need in his ...

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everyday work. Each chapter gives a description of the technique of the method and of the corresponding apparatus, the theoretical foundations of the method necessary for understanding and applying it, as well as the information needed for a critical approach to the numerical data obtained as a result of measurement. The main emphasis is placed on the methodological part. In almost all chapters the description of the various apparatuses and the technique of measurement is given in excessive detail. Very little is said about the place of the method among others, about the relative value of one method as compared with another. The application of one method or another is discussed not in connection with general chemical problems, but only as an illustration of the technical possibilities of the method. In most chapters only the most general statements are made about the application of the method. Thus the whole publication appears as a collection describing chiefly the technique of laboratory physical measurements. Moreover, the manner of presentation is extremely uneven. The degree of detail of the exposition and the main emphasis of each article differ sharply from one another. In this respect, as also in the absence of a general approach to the application of physical methods in chemistry, the lack of an editor’s hand is felt. The individual chapters are united to a greater extent by a common binding than by a common orientation. This circumstance is also reflected in the large number of repetitions. A few examples will suffice: two adjacent articles on crystalline form and on crystallochemical analysis contain a detailed account of the description of the seven crystal systems. A more detailed discussion of the passage of light through a crystal and a description of the construction of polarizing prisms are read twice, in the chapters “Microscopy” and “Polarimetry.” In three places the reader is given data on the transparency of various materials with respect to light of different wavelengths. The book would have gained considerably if it had been subjected to thoughtful and thorough editing, as a result of which the proportionality and relation of the parts would have assumed the proper form.

Despite the substantial shortcomings indicated, the usefulness of the book is obvious. The importance of physical methods in chemistry is exceptionally great, and their application has become very widespread over the last 20 years. A great specialization has arisen in individual methods; specialists have appeared who master the method and are indifferent to its applications. However, many of the physical methods have reached such a perfected state that, after becoming acquainted with them, the chemist can use them in his work without being, in essence, a specialist in the method. There has already arisen a number of specialist chemists who have mastered many methods of investigation which they apply to the chemical problems that interest them. These are no longer specialists in the method, but chemists who have mastered the technique of measurement and calculation in the field of chemical methods of analysis. The importance for chemistry of specialists of this type is difficult to overestimate. The education of specialists of this type should be facilitated by the book under review. It will prove of great use, since it will make it possible to become acquainted with the present state of the technique of the method and with the exhaustive literature of the method (as regards bibliography, all the articles are excellently compiled) without tedious, and sometimes very complicated, searches in the journal literature. These searches have recently become especially difficult because of the enormous number of very diverse journals printing articles on one and the same subject. This applies in particular to the question of the application of physical methods in chemistry; articles on this subject are printed in physical, chemical, physicochemical, and, finally, technical journals.

Let us now try to characterize the individual chapters of the book. Ten pages are devoted to the description of what is most important for the chemist in measurement—the determination of melting and boiling points. These articles are written with a clear orientation toward the chemist-reader, for whom the indicated

measurements are the principal method for the identification of substances. The technique of measurements here is relatively uncomplicated and is familiar to every chemist; therefore a fairly detailed exposition of the thermodynamic foundations of these measurements is quite appropriate. In the chapter devoted to density, the first section discusses the dependence of density on temperature, pressure, impurities, etc.; the second section gives the technique of measuring the densities of liquids, and the third—the same for solids. The chapter concludes with guidance on choosing suitable methods of measurement. A very short (10-page) article by Hermann Mark on viscosity measurements can be regarded only as a bibliographical guide. Of all the instruments for measuring viscosity, only the Ostwald and Ubbelohde viscometers are briefly described. Measurements of surface tension have acquired importance in chemistry in connection with the widely practiced calculations of parachor. In Chapter 6, the methods for determining the surface-tension coefficient are set forth in sufficient detail: by the capillary-rise method, the drop method, the ring-detachment method, and the bubble-pressure method. Guidance is given on the choice of method. Only a few pages are devoted to the theory of surface tension and the theory of parachor. The chapter devoted to calorimetry treats the subject in great detail: it occupies 120 pages. Modern methods of the precise measurement of temperature and energy, and the construction of various calorimeters, are considered. In special sections, the measurement of heat capacities, heats of combustion, heats of fusion and vaporization, heats of solution, dilution and mixing, and, finally, heats of chemical reactions is discussed. Thermodynamic concepts and relations are explained in more or less detail, so that the article may also be read by a chemist who has only a weak recollection of thermodynamics. Also fundamental is the article on microscopy. A description of the construction of the ordinary polarizing microscope is followed by a brief but substantial account of the microscopy of thermal properties. Then, over twenty pages, crystalloptics is expounded. In the next section the operations performed in the examination of a crystal under the microscope are considered in sequence; namely, the technique of growing suitable crystals, orthoscopic and conoscopic observations, determination of refractive indices, determination of birefringence and its dispersion, and determination of the angle between the optical axes and its dispersion are discussed. The last section—microscopy of colored crystals—has a fresh character. In this field much work was done by the author of the article, E. Jelly. Picot’s article on the determination of crystalline forms does not give a clear idea of the subject. Apart from the concept of the crystal system, hardly anything can be extracted from what is written. In the chapter on crystal analysis, Barker’s method is expounded in detail, and the methods of Fedorov and Boldyrev less fully. The chapter on X-ray structural analysis is, perhaps, disproportionately small—it is presented in 35 pages. The article acquaints the reader with the general problems of X-ray structural analysis, but cannot teach one how to use it. There is no description of the apparatus, and only two or three phrases give an idea of how X-ray patterns should be calculated. In the chapter on electronography, only the application of this method to the study of gases is described—the specialty of the author of the article, Brockway. The chapter on refractometry, written by Bauer and Fajans, is a good introduction to the subject and can undoubtedly serve the chemist as a direct practical guide in his work. The second volume begins with a large article by Veitz, “Spectroscopy and Spectrophotometry,” which is methodical in character and very clearly presented. The question of the nature of spectra is set forth on one page. In separate sections, the apparatus and technique of measurements in the visible and ultraviolet regions, measurement of absorption spectra, spectroscopy in the infrared region, and Raman spectroscopy are considered. The article contains a very large number of practical instructions concerning

at all stages of the work (light sources, photographic technique, etc.). The book is quite satisfactory and consistently sets forth the question of the importance of spectroscopic investigations for chemistry and of the choice of one or another method for a particular purpose. The same author wrote the chapter “Colorimetry, Photometric Analysis, and Fluorimetry” in the same experimental-technical style. A disproportionately large amount of space is devoted to polarimetry. The material of this chapter is presented over 120 pages. In many respects it repeats the article on microscopy. As noted above, the article gives an exhaustive treatment of the subject, being one of its most complete expositions. By contrast, the chapter on dipole moments is written too concisely. It contains no material other than a cursory and rather sketchy description of five methods for measuring the dielectric constant. As far as I can judge, the chapters on conductometry, potentiometry, and especially polarography—this new branch of physicochemical investigation—present the subject with sufficient completeness. The chapter on the measurement of magnetic susceptibility is essentially an approximate synopsis of Klemm’s Magnetochemistry, a book known to the Russian reader. The last two chapters, devoted to radioactivity and mass spectrography, can provide only a general notion of the subject, but, of course, cannot serve as a practical aid in work, if only because investigations of this type cannot be pursued incidentally.

In general, it is a useful book. On the other hand, there is no doubt that translating the book into Russian would be desirable only on condition that it be thoroughly revised and edited in the spirit indicated at the beginning of this review.

A. I. Kitaigorodskii