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The polarographic method of analysis. Second Edition
242
BOOK
REVIEWS
The Editors of Advances in Calulysis set themselves the task “to present a picture of important new contributions by various workers to our scientific and technical knowledge of catalysts, catalytic reactions, and related fields.” This task has been admirably accomplished in the fourth volume of Advances which contains the following nine contributions: “Chemical Concepts of Catalytic Cracking,” by R. C. Hansford; “Decomposition of Hydrogen Peroxide by Catalysts in Homogeneous Aqueous Solution,” by V. H. Baxendale; “Structure and Sintering Properties of Cracking Catalysts and Related Materials,” by H. E. Ries, Jr.; “Acid-Base Catalysis and Molecular Structure,” by R. P. Bell; “Theory of Physical Adsorption,” by Terre11 L. Hill; “The Role of Surface Heterogeneity in Adsorption,” by George D. Halsey; “Twenty-Five Years of Synthesis of Gasoline by Catalytic Conversion of Carbon Monoxide and Hydrogen,” by Helmut Pichler; “The Free Radical Mechanism in the Reactions of Hydrogen Peroxide,” by Joseph Weiss; “The Specific Reactions of Iron in Some Hemoproteins,” by Philip George. The reviewer agrees wholeheartedly with the editors’ interpretation of the scope of the Advances in Catalysis in including articles pertaining to homogeneous catalysis and biochemical catalysis rather than treating exclusively the phenomenon par excellence-heterogeneous catalysis. However, it appears that one of the two very fine papers on hydrogen peroxide might have sufficed, especially since the last article also deals mostly with a similar subject. The reviewer was somewhat disappointed not to find a chapter on some aspect of the connection between electron transfer processes in solids and heterogeneous catalysis-a topic which featured prominently in the Discussions of the Faraday Society in 1956 and which is probably the most important idea introduced into catalysis since the conception of active centers. Each of the chapters is written by a recognized expert in the field, a guarantee that the articles are up-to-date, accurate, and authoritative. The typography is of the usual high quality, and there are very few misprints. An excellent subject index is included. This volume contains a wealth of information (there are over 866 references), and is recommended to all chemists concerned with catalysis. The reviewer has no doubt that it will receive just as warm a welcome as the preceding volumes. A. FARKAS, Jenkintown, Pennsylvania The Polarographic Method of Analysis. Second Edition. By OTTO H. MUELLER, Associate Professor of Physiology, State University of New York Medical Center at Syracuse, Syracuse, N. Y. The Chemical Education Publishing Co., 506 Fifth Avenue, New York, 1956.269 pp. Price $3.59. The present revised and enlarged edition has the same purpose as the first edition (1941) : “to present a simple account of polarography in a form which can be used by teachers and students of physical chemistry as well as in advanced courses of analytical chemistry.” The book should be particularly welcome to the laboratory worker who considers the use of polarography and who has had an elementary course in physical chemistry. The set of 26 experiments illustrating
BOOK
REVIEWS
243
various fundamentals are a good guide in a practical introduction to polarography. The material is divided over eight chapters which present the reader with an upto-date review of polarography and its applications. The first chapter is a review of electroanalytical methods in general. The omission of coulometric analysis (titrations) is rather serious. The discussion of a simple, flexible, and inexpensive polarograph from materials readily available (chap. II) with the contents of chaps. VII (called “Applications”) and VIII (Suggestions for Practical Polarography) serve as an excellent introduction into practical polarography. The brief statements on solid electrodes on p, 29 misrepresent the widely adopted use of the . rotated platinum electrodes (see also pp. 14’6147). Chapter III deals with quantitative polarography. Experiment 5 (p. 65) describes the electrolysis of a hexammine cobaltic solution in the absence of a maximum suppressor. The ratio of the second to the first wave is found to be 2.13 and would deviate considerably more from the theoretical value 2.90 if correction had been made for the rnzfa t116effect. A repetition of the experiment in the presence of a maximum eliminator with application of the correction would have given the theoretical ratio. In this chapter, Lingane’s definition of diffusion current constant should have been given. Chapter IV gives an adequate discussion of qualitative polarography. Chapter V discusses polarometry in general and polarometric titrations. If, in the “deadstop end point” of Foulk and Bawden the current were measured as the author states on p. 118 it would have been called an amperometric method. Figures 32 and 33 which illustrate two amperometric titrations are hard to interpret. The break in the precipitation line (curve h, Fig. 32) may be due to an iR effect. No correct8ion is made for the dilution effect which is very large in Expt. 20. The break in the precipitation line in Fig. 33 is hard to understand; no straight precipitation line can be obtained without correction for the dilution effect, while the slope of the line should change slightly after the end point. Chapter VI gives a brief review of differential, derivative, and oscillographic polarography and of the use of electrodes other than dropping mercury. For students’ use in courses it would be preferable to have a less personal and more objective evaluation of various topics. On the other hand, the book is recommended to those who wish to familiarize themselves with polarography and apply it in experimental work. I. M. KOLTHOFF, Minneapolis, Minnesota International Review of Cytology. Vol. 1. Edited by G. H. BOURNE, The London Hospital Medical College; and J. F. DANIELLI, Zoology Department, King’s College, London. Academic Press Inc. New York, N. Y., 1952. xvi + 368 pp. Price $7.80. A conspicuous recent trend in biology has led to re-emphasis of the problem of intracellular physiology. Investigators of biological activity at the level of its common denominator, the cell, are coming into possession of new techniques of inestimable potential, which are illuminating more brightly the picture of the basic biological unit, the cell. If this picture is to be sharply delineated there must be consistent effort to interrelate the individual elements which appear to con-
BOOK
REVIEWS
The Editors of Advances in Calulysis set themselves the task “to present a picture of important new contributions by various workers to our scientific and technical knowledge of catalysts, catalytic reactions, and related fields.” This task has been admirably accomplished in the fourth volume of Advances which contains the following nine contributions: “Chemical Concepts of Catalytic Cracking,” by R. C. Hansford; “Decomposition of Hydrogen Peroxide by Catalysts in Homogeneous Aqueous Solution,” by V. H. Baxendale; “Structure and Sintering Properties of Cracking Catalysts and Related Materials,” by H. E. Ries, Jr.; “Acid-Base Catalysis and Molecular Structure,” by R. P. Bell; “Theory of Physical Adsorption,” by Terre11 L. Hill; “The Role of Surface Heterogeneity in Adsorption,” by George D. Halsey; “Twenty-Five Years of Synthesis of Gasoline by Catalytic Conversion of Carbon Monoxide and Hydrogen,” by Helmut Pichler; “The Free Radical Mechanism in the Reactions of Hydrogen Peroxide,” by Joseph Weiss; “The Specific Reactions of Iron in Some Hemoproteins,” by Philip George. The reviewer agrees wholeheartedly with the editors’ interpretation of the scope of the Advances in Catalysis in including articles pertaining to homogeneous catalysis and biochemical catalysis rather than treating exclusively the phenomenon par excellence-heterogeneous catalysis. However, it appears that one of the two very fine papers on hydrogen peroxide might have sufficed, especially since the last article also deals mostly with a similar subject. The reviewer was somewhat disappointed not to find a chapter on some aspect of the connection between electron transfer processes in solids and heterogeneous catalysis-a topic which featured prominently in the Discussions of the Faraday Society in 1956 and which is probably the most important idea introduced into catalysis since the conception of active centers. Each of the chapters is written by a recognized expert in the field, a guarantee that the articles are up-to-date, accurate, and authoritative. The typography is of the usual high quality, and there are very few misprints. An excellent subject index is included. This volume contains a wealth of information (there are over 866 references), and is recommended to all chemists concerned with catalysis. The reviewer has no doubt that it will receive just as warm a welcome as the preceding volumes. A. FARKAS, Jenkintown, Pennsylvania The Polarographic Method of Analysis. Second Edition. By OTTO H. MUELLER, Associate Professor of Physiology, State University of New York Medical Center at Syracuse, Syracuse, N. Y. The Chemical Education Publishing Co., 506 Fifth Avenue, New York, 1956.269 pp. Price $3.59. The present revised and enlarged edition has the same purpose as the first edition (1941) : “to present a simple account of polarography in a form which can be used by teachers and students of physical chemistry as well as in advanced courses of analytical chemistry.” The book should be particularly welcome to the laboratory worker who considers the use of polarography and who has had an elementary course in physical chemistry. The set of 26 experiments illustrating
BOOK
REVIEWS
243
various fundamentals are a good guide in a practical introduction to polarography. The material is divided over eight chapters which present the reader with an upto-date review of polarography and its applications. The first chapter is a review of electroanalytical methods in general. The omission of coulometric analysis (titrations) is rather serious. The discussion of a simple, flexible, and inexpensive polarograph from materials readily available (chap. II) with the contents of chaps. VII (called “Applications”) and VIII (Suggestions for Practical Polarography) serve as an excellent introduction into practical polarography. The brief statements on solid electrodes on p, 29 misrepresent the widely adopted use of the . rotated platinum electrodes (see also pp. 14’6147). Chapter III deals with quantitative polarography. Experiment 5 (p. 65) describes the electrolysis of a hexammine cobaltic solution in the absence of a maximum suppressor. The ratio of the second to the first wave is found to be 2.13 and would deviate considerably more from the theoretical value 2.90 if correction had been made for the rnzfa t116effect. A repetition of the experiment in the presence of a maximum eliminator with application of the correction would have given the theoretical ratio. In this chapter, Lingane’s definition of diffusion current constant should have been given. Chapter IV gives an adequate discussion of qualitative polarography. Chapter V discusses polarometry in general and polarometric titrations. If, in the “deadstop end point” of Foulk and Bawden the current were measured as the author states on p. 118 it would have been called an amperometric method. Figures 32 and 33 which illustrate two amperometric titrations are hard to interpret. The break in the precipitation line (curve h, Fig. 32) may be due to an iR effect. No correct8ion is made for the dilution effect which is very large in Expt. 20. The break in the precipitation line in Fig. 33 is hard to understand; no straight precipitation line can be obtained without correction for the dilution effect, while the slope of the line should change slightly after the end point. Chapter VI gives a brief review of differential, derivative, and oscillographic polarography and of the use of electrodes other than dropping mercury. For students’ use in courses it would be preferable to have a less personal and more objective evaluation of various topics. On the other hand, the book is recommended to those who wish to familiarize themselves with polarography and apply it in experimental work. I. M. KOLTHOFF, Minneapolis, Minnesota International Review of Cytology. Vol. 1. Edited by G. H. BOURNE, The London Hospital Medical College; and J. F. DANIELLI, Zoology Department, King’s College, London. Academic Press Inc. New York, N. Y., 1952. xvi + 368 pp. Price $7.80. A conspicuous recent trend in biology has led to re-emphasis of the problem of intracellular physiology. Investigators of biological activity at the level of its common denominator, the cell, are coming into possession of new techniques of inestimable potential, which are illuminating more brightly the picture of the basic biological unit, the cell. If this picture is to be sharply delineated there must be consistent effort to interrelate the individual elements which appear to con-