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The chemical effects of alpha particles and electrons
July, I928.]
BOOK REWEWS.
II 7
LIBRARY NOTES. Recent Additions ABEGG'S Handbuch der anorganischen Chemie. Vierter Band, dritte Abteilung, erster Teil. I928. American Electrochemical Society. Transactions 1927 . Volume 51 . 1928. CKAMBERLAIN, JOSEPH SCUDDER. A Textbook of Organic Chemistry. 1928. CREW, HENRY. The Rise of Modern Physics. I928. DAVIS, A. H., AND G. W. C. KALE. The Acoustics of Buildings. 1927. GOLDSCHMIDT, VICTOR, AND SAMUEL G. GORDON. Crystallographic Tables for the Determinations of Minerals. I928. History of Science Society. Sir Isaac Newton, I727-I927: a Bicentenary Evalua tion of his Work. I928. KEEN, R. Wireless Direction Finding and Directional Reception. Second enlarged edition. I927 . MACINTIRE, H . J . Handbook of Mechanical Refrigeration. I928. MARSHALL, C. F. DENDY. Two Essays in Early Locomotive History. I928. MOTTELAY, P. FLEURY. Life and Work of Sir Hiram Maxim. 192o. O'LLIVER, C . W . The A.C. Commutator Motor. I927 . PALMER, L . S . Wireless Principles and Practice. 1928. POME¥, J . B . Cours d'l~lectricit6 ThGorique. Tome I. I9I 4. QUAERIS, Q. M., AND OTHERS. Notre Mis~re Scientifique: ses Causes--ses RemSdes. L'Appel du Roi. 1928. Society of Chemical Industry. Reports of the Progress of Applied Chemistry. Volume 12, 1927 . TURNBULL, ARCHIBALD DOUGLAS. John Stevens: an Americal Record. 1928. WALTON, ROBERT P., Editor. A Comprehensive Survey of Starch Chemistry. I928. WEISER, HARRY BOYER. The Hydrous Oxides. 1926. WIEN, W., AND F. HARMS, Editors. Handbuch der Experimentalphysik. Band 19. 1928. WILCOX, EDGAR A. Electric Heating. 1928. WILSON, WILLIAM. Electric Control Gear and Industrial Electrification. I927.
BOOK REVIEWS. THE CHEMICAL EFFECTS OF ALPHA PARTICLES AND ELECTRONS. By Samuel C. Lind, Ph.D., Director of the School of Chemistry, University of Minnesota. Second (revised and enlarged) edition. American Chemical Society Monograph Series, Number 2. 252 pages, 42 tables, 13 illustrations, cloth, 8vo. New York, The Chemical Catalog Company, Inc., 1928. Price, $5T h a t the subject of this volume represents a live and rapidly growing division of experimental and theoretical science, may be realized fully from a comparison of the first and second editions. In the six years which have elapsed between the issuance of the first and second editions sufficient additional information has become available to make this monograph one-half as large again.
II8
BOOK
REVIEWS.
[J. F. I.
Doubtless, there are but few who can realize and appreciate the full significance of these recent discoveries and fewer still who would dare to predict the status of this subject six years from now. As in all branches of scientific investigation many difficulties have been encountered and are being overcome, one by one, by dint of brilliant thought and plenty of hard work. T h a t the chemical effects of alpha particles and electrons may be investigated with any degree of success a satisfactory source of radiation is imperative. As a source of alpha-particle radiation radium-C and radium-F (polonium) have been utilized to advantage. Yet, their relatively short periods of existence have made impossible any sustained investigation of their chemical effects. Until recently no constant source of electron (beta particle) radiation has been available. However, this problem has been solved ingeniously by Dr. Coolidge of the General Electric Co., who, has developed a tube which will produce electronic radiations of controlled intensity and make them available for experimental purposes. So far the effects produced by this beta ray (particle) radiation have been studied only in a qualitative way. Such phenomena as already observed, indicate t h a t in the near future these rays will play an important part not only chemically but also physiologically and therapeutically. In studying the chemical effects of these radiations both qualitatively and quantitatively the chemist must adopt a specialized technique already acquired by the physicist who has been studying intensively the physical properties of these radiations for three or four decades. There seems to be no doubt but what continued investigation in this field will disclose many fascinating problems. Already anomalies in the predicted behavior of the various reactants have been observed and organic compounds of unsuspected constitution evolved. A very comprehensive perspective of the widespread advances in the field of radiochemistry during the past six years may be obtained from the author's preface to the second edition. The progress accomplished in this sphere has necessitated the addition of seven new chapters and an extensive revision of the others. New discoveries have added support to the theory of reaction mechanism in ionized gases and emphasized the idea of ion clustering. The work of Mund on the development of a general equation for calculating gas ionization by radon in spheres is outstanding. Results obtained in the investigation of the catalytic influence of foreign gases make necessary a broader view on the probability of electron exchange, while the determination of the size of effective ion clusters in different gaseous systems looms up as perhaps the most outstanding problem at the present time. The first chapter, "Radiochemistry," has been enlarged by a paragraph on the utility of the Einstein law of photochemical equivalence. In addition the author has defined the term radiochemistry, outlined the field embraced by it and shown its relation to t h a t branch of the study known as photochemistry. Chapter two contains a brief outline of radioactivity and some properties of the radiations. Such knowledge concerning the radioactive series of elements is necessary if the reader would have a clear understanding of the controlling factors in the various experiments to be described later. Chapter three deals with the electrical effects produced by the various radiations, alpha, beta, gamma and X-rays and the general characteristics of gaseous ionization, A paragraph
July, I928.]
BOOK REVIEWS.
II
9
on the relation between beta and gamma rays has been added. Chapter four, "Qualitative radiochemical effects," has been largely rewritten and contains much new material. The author arbitrarily classifies radiochemical investigations under eight headings depending upon the amount of definite knowledge available. A timely paragraph on precautions in sealing radium salts has been inserted. Radium sealed in small tubes for a considerable length of time has caused the tubes to explode with a resultant loss of its valuable contents. A farreaching disintegration of quartz containers has been reported and pyrex containers also have been found to be unsuitable for radium solutions. Other topics dealt with in this chapter are the luminescence of radium salts, the coloration of glass and minerals, thermo- and photo-phosphorescence and the discharge of color, constant light sums of thermo-phosphorescence, etc. The paragraph on luminescence and phosphorescence produced by radiation is particularly interesting containing as it does an exposition on the preparation and properties of luminous paints. Chapter five deals with chemically quantitative investigations in liquid systems and includes a study of the decomposition of water by radium salts in solution, the formation of hydrogen peroxide in water and reactions produced by penetrating rays. The effects of the penetrating rays have been studied extensively by Kailan and included such things as the decomposition of the alkaline and rare earth iodides, the reduction of ferric sulphate, the inversion of cane sugar, the conversion of nitrobenzaldehyde into nitrobenzoic acid, the action on chloroform and carbon tetrachloride and the oxidation of toluene. In some of these experiments a comparison was made with ialtraviolet radiation which produced similar effects one hundred to one thousand times as rapidly. Chapter six contains a description of the first experiments upon the reactions produced by radon. These consisted of the decomposition of carbon monoxide, hydrogen chloride, ammonia, and the decomposition of water as well as the combination of hydrogen and oxygen both dry and moist. Considerable work also has been done on the equilibrium between hydrogen, nitrogen and ammonia. Considered in the light of experimental technique and the application of theoretical knowledge chapter seven is no doubt the most important in the book. It begins with an outline of the historical development of the ionization theory of the chemical effects of corpuscular radiation. This is followed by a paragraph on how to construct and use an alpha-ray bulb, the calculation of ionization from such a bulb and the purification of radon to be used in the bulb. The development of an equation for calculating the average path of alpha particles in a sphere is clearly described. This is followed by an equation for the calculation of ionization of radon in small spheres and a detailed description of Mund's equation for calculating ionization by radon in large spheres. This chapter also contains an exceedingly valuable and comprehensive table giving a comparison of the chemical action and ionization by alpha particles. Chapter eight occupies itself with a development of a general kinetic equation for the action of radon when mixed with gases in small volumes and the application of this equation to experimental results. Chapter nine, "Chemical effect of recoil a t o m s " corresponds to the latter part of chapter eleven in the first edition. A comparison of the absorption of alpha rays and recoil atoms is made; the latter's general properties, chemical reactions described and the results of later experiments outlined. Chapter ten on additional relationships of the radiochemical effects discusses
120
BOOK REVIEWS.
[J. F. I.
the influence of varying the proportions of reactants, the action of alpha rays on pure oxygen, activity of gaseous hydrogen ions, energy utilization of alpha rays in chemical reactions and includes a general discussion of ionic-chemical equivalence. Chapter eleven deals exclusively with what is known as the M/N ratio or the relation of chemical reaction to ionization. Chapters twelve to fifteen inclusive deal with the effects of radiation upon saturated one-component systems, unsaturated one-component systems, oxidation in two-component systems and hydrogenation in two-component systems respectively. An excellent summary of the material is given by the table in chapter seven as mentioned above. Chapter sixteen on the catalytic effect of ions of inert gases deals with some of the more recent investigations in this field. In general, the presence of an inert gas has caused an acceleration in the reaction produced by the radiations. The mechanism of these catalytic ion reactions has been a source of speculation and at present is believed to involve an exchange of electrons between the molecules of inert gas and those of the reactants. A chapter (seventeen) on the chemical effects of electrical discharge in gases is certainly not amiss in a book like this. Investigations in this sphere seem to have been more or less incidental and have resulted in a great variety of phenomena being recorded. The ionization theory has been applied to these electrochemical effects in gases more or less successfully. Chapter eighteen contains an elucidation of the law of photochemical equivalence and a comparison with ionic-chemical equivalence. The relation between the two is striking. So far this book has dealt with the effects produced by the alpha rays colliding with the electrons of the atoms or molecules. However, an occasional alpha particle will collide with the nucleus of the atom and cause a disruption of the latter. The book would not be complete without the last chapter which outlines the research done on the atomic disruption by alpha particles. The author critically examines the results of these investigations which are of comparatively recent origin. The appendix consists of tables giving the decay of radon, conversion factors, ordinary isotopes of the elements, list of radioactive isotopes by groups, Mund's factor for the efficiency of ionization by radon in spheres and a list of papers by the author and his collaborators respectively. The book contains both an index of authors and of subjects. Dr. Lind has done a splendid piece of work in the rewriting and revision of the first edition of his book. When the abundance of widely scattered and seemly unrelated data concerning this subject is taken into consideration, then it will be realized just how difficult it must have been to evolve a system of classification such as this book embodies. THEODORE K. CLEVELAND. THE METHODS OF ORGANIC CHEMISTRY. A LABORATORY MANUAL. By C. W. Porter, T. D. Stewart and G. E. K. Branch, Members of the Faculty of the College of Chemistry in the University of California. i v - 3 I I pages, 8vo., illustrated. Boston, Ginn and Company, i92 7. Price, $2. The authors make very modest claims in regard to the r61e this book is supposed to fill in the study of organic chemistry. They have started out with the expressed intention to prepare an outline providing material for a laboratory course in organic chemistry. When they finished they had a manual which not only students but those doing research will find to be of inestimable value as a
BOOK REWEWS.
II 7
LIBRARY NOTES. Recent Additions ABEGG'S Handbuch der anorganischen Chemie. Vierter Band, dritte Abteilung, erster Teil. I928. American Electrochemical Society. Transactions 1927 . Volume 51 . 1928. CKAMBERLAIN, JOSEPH SCUDDER. A Textbook of Organic Chemistry. 1928. CREW, HENRY. The Rise of Modern Physics. I928. DAVIS, A. H., AND G. W. C. KALE. The Acoustics of Buildings. 1927. GOLDSCHMIDT, VICTOR, AND SAMUEL G. GORDON. Crystallographic Tables for the Determinations of Minerals. I928. History of Science Society. Sir Isaac Newton, I727-I927: a Bicentenary Evalua tion of his Work. I928. KEEN, R. Wireless Direction Finding and Directional Reception. Second enlarged edition. I927 . MACINTIRE, H . J . Handbook of Mechanical Refrigeration. I928. MARSHALL, C. F. DENDY. Two Essays in Early Locomotive History. I928. MOTTELAY, P. FLEURY. Life and Work of Sir Hiram Maxim. 192o. O'LLIVER, C . W . The A.C. Commutator Motor. I927 . PALMER, L . S . Wireless Principles and Practice. 1928. POME¥, J . B . Cours d'l~lectricit6 ThGorique. Tome I. I9I 4. QUAERIS, Q. M., AND OTHERS. Notre Mis~re Scientifique: ses Causes--ses RemSdes. L'Appel du Roi. 1928. Society of Chemical Industry. Reports of the Progress of Applied Chemistry. Volume 12, 1927 . TURNBULL, ARCHIBALD DOUGLAS. John Stevens: an Americal Record. 1928. WALTON, ROBERT P., Editor. A Comprehensive Survey of Starch Chemistry. I928. WEISER, HARRY BOYER. The Hydrous Oxides. 1926. WIEN, W., AND F. HARMS, Editors. Handbuch der Experimentalphysik. Band 19. 1928. WILCOX, EDGAR A. Electric Heating. 1928. WILSON, WILLIAM. Electric Control Gear and Industrial Electrification. I927.
BOOK REVIEWS. THE CHEMICAL EFFECTS OF ALPHA PARTICLES AND ELECTRONS. By Samuel C. Lind, Ph.D., Director of the School of Chemistry, University of Minnesota. Second (revised and enlarged) edition. American Chemical Society Monograph Series, Number 2. 252 pages, 42 tables, 13 illustrations, cloth, 8vo. New York, The Chemical Catalog Company, Inc., 1928. Price, $5T h a t the subject of this volume represents a live and rapidly growing division of experimental and theoretical science, may be realized fully from a comparison of the first and second editions. In the six years which have elapsed between the issuance of the first and second editions sufficient additional information has become available to make this monograph one-half as large again.
II8
BOOK
REVIEWS.
[J. F. I.
Doubtless, there are but few who can realize and appreciate the full significance of these recent discoveries and fewer still who would dare to predict the status of this subject six years from now. As in all branches of scientific investigation many difficulties have been encountered and are being overcome, one by one, by dint of brilliant thought and plenty of hard work. T h a t the chemical effects of alpha particles and electrons may be investigated with any degree of success a satisfactory source of radiation is imperative. As a source of alpha-particle radiation radium-C and radium-F (polonium) have been utilized to advantage. Yet, their relatively short periods of existence have made impossible any sustained investigation of their chemical effects. Until recently no constant source of electron (beta particle) radiation has been available. However, this problem has been solved ingeniously by Dr. Coolidge of the General Electric Co., who, has developed a tube which will produce electronic radiations of controlled intensity and make them available for experimental purposes. So far the effects produced by this beta ray (particle) radiation have been studied only in a qualitative way. Such phenomena as already observed, indicate t h a t in the near future these rays will play an important part not only chemically but also physiologically and therapeutically. In studying the chemical effects of these radiations both qualitatively and quantitatively the chemist must adopt a specialized technique already acquired by the physicist who has been studying intensively the physical properties of these radiations for three or four decades. There seems to be no doubt but what continued investigation in this field will disclose many fascinating problems. Already anomalies in the predicted behavior of the various reactants have been observed and organic compounds of unsuspected constitution evolved. A very comprehensive perspective of the widespread advances in the field of radiochemistry during the past six years may be obtained from the author's preface to the second edition. The progress accomplished in this sphere has necessitated the addition of seven new chapters and an extensive revision of the others. New discoveries have added support to the theory of reaction mechanism in ionized gases and emphasized the idea of ion clustering. The work of Mund on the development of a general equation for calculating gas ionization by radon in spheres is outstanding. Results obtained in the investigation of the catalytic influence of foreign gases make necessary a broader view on the probability of electron exchange, while the determination of the size of effective ion clusters in different gaseous systems looms up as perhaps the most outstanding problem at the present time. The first chapter, "Radiochemistry," has been enlarged by a paragraph on the utility of the Einstein law of photochemical equivalence. In addition the author has defined the term radiochemistry, outlined the field embraced by it and shown its relation to t h a t branch of the study known as photochemistry. Chapter two contains a brief outline of radioactivity and some properties of the radiations. Such knowledge concerning the radioactive series of elements is necessary if the reader would have a clear understanding of the controlling factors in the various experiments to be described later. Chapter three deals with the electrical effects produced by the various radiations, alpha, beta, gamma and X-rays and the general characteristics of gaseous ionization, A paragraph
July, I928.]
BOOK REVIEWS.
II
9
on the relation between beta and gamma rays has been added. Chapter four, "Qualitative radiochemical effects," has been largely rewritten and contains much new material. The author arbitrarily classifies radiochemical investigations under eight headings depending upon the amount of definite knowledge available. A timely paragraph on precautions in sealing radium salts has been inserted. Radium sealed in small tubes for a considerable length of time has caused the tubes to explode with a resultant loss of its valuable contents. A farreaching disintegration of quartz containers has been reported and pyrex containers also have been found to be unsuitable for radium solutions. Other topics dealt with in this chapter are the luminescence of radium salts, the coloration of glass and minerals, thermo- and photo-phosphorescence and the discharge of color, constant light sums of thermo-phosphorescence, etc. The paragraph on luminescence and phosphorescence produced by radiation is particularly interesting containing as it does an exposition on the preparation and properties of luminous paints. Chapter five deals with chemically quantitative investigations in liquid systems and includes a study of the decomposition of water by radium salts in solution, the formation of hydrogen peroxide in water and reactions produced by penetrating rays. The effects of the penetrating rays have been studied extensively by Kailan and included such things as the decomposition of the alkaline and rare earth iodides, the reduction of ferric sulphate, the inversion of cane sugar, the conversion of nitrobenzaldehyde into nitrobenzoic acid, the action on chloroform and carbon tetrachloride and the oxidation of toluene. In some of these experiments a comparison was made with ialtraviolet radiation which produced similar effects one hundred to one thousand times as rapidly. Chapter six contains a description of the first experiments upon the reactions produced by radon. These consisted of the decomposition of carbon monoxide, hydrogen chloride, ammonia, and the decomposition of water as well as the combination of hydrogen and oxygen both dry and moist. Considerable work also has been done on the equilibrium between hydrogen, nitrogen and ammonia. Considered in the light of experimental technique and the application of theoretical knowledge chapter seven is no doubt the most important in the book. It begins with an outline of the historical development of the ionization theory of the chemical effects of corpuscular radiation. This is followed by a paragraph on how to construct and use an alpha-ray bulb, the calculation of ionization from such a bulb and the purification of radon to be used in the bulb. The development of an equation for calculating the average path of alpha particles in a sphere is clearly described. This is followed by an equation for the calculation of ionization of radon in small spheres and a detailed description of Mund's equation for calculating ionization by radon in large spheres. This chapter also contains an exceedingly valuable and comprehensive table giving a comparison of the chemical action and ionization by alpha particles. Chapter eight occupies itself with a development of a general kinetic equation for the action of radon when mixed with gases in small volumes and the application of this equation to experimental results. Chapter nine, "Chemical effect of recoil a t o m s " corresponds to the latter part of chapter eleven in the first edition. A comparison of the absorption of alpha rays and recoil atoms is made; the latter's general properties, chemical reactions described and the results of later experiments outlined. Chapter ten on additional relationships of the radiochemical effects discusses
120
BOOK REVIEWS.
[J. F. I.
the influence of varying the proportions of reactants, the action of alpha rays on pure oxygen, activity of gaseous hydrogen ions, energy utilization of alpha rays in chemical reactions and includes a general discussion of ionic-chemical equivalence. Chapter eleven deals exclusively with what is known as the M/N ratio or the relation of chemical reaction to ionization. Chapters twelve to fifteen inclusive deal with the effects of radiation upon saturated one-component systems, unsaturated one-component systems, oxidation in two-component systems and hydrogenation in two-component systems respectively. An excellent summary of the material is given by the table in chapter seven as mentioned above. Chapter sixteen on the catalytic effect of ions of inert gases deals with some of the more recent investigations in this field. In general, the presence of an inert gas has caused an acceleration in the reaction produced by the radiations. The mechanism of these catalytic ion reactions has been a source of speculation and at present is believed to involve an exchange of electrons between the molecules of inert gas and those of the reactants. A chapter (seventeen) on the chemical effects of electrical discharge in gases is certainly not amiss in a book like this. Investigations in this sphere seem to have been more or less incidental and have resulted in a great variety of phenomena being recorded. The ionization theory has been applied to these electrochemical effects in gases more or less successfully. Chapter eighteen contains an elucidation of the law of photochemical equivalence and a comparison with ionic-chemical equivalence. The relation between the two is striking. So far this book has dealt with the effects produced by the alpha rays colliding with the electrons of the atoms or molecules. However, an occasional alpha particle will collide with the nucleus of the atom and cause a disruption of the latter. The book would not be complete without the last chapter which outlines the research done on the atomic disruption by alpha particles. The author critically examines the results of these investigations which are of comparatively recent origin. The appendix consists of tables giving the decay of radon, conversion factors, ordinary isotopes of the elements, list of radioactive isotopes by groups, Mund's factor for the efficiency of ionization by radon in spheres and a list of papers by the author and his collaborators respectively. The book contains both an index of authors and of subjects. Dr. Lind has done a splendid piece of work in the rewriting and revision of the first edition of his book. When the abundance of widely scattered and seemly unrelated data concerning this subject is taken into consideration, then it will be realized just how difficult it must have been to evolve a system of classification such as this book embodies. THEODORE K. CLEVELAND. THE METHODS OF ORGANIC CHEMISTRY. A LABORATORY MANUAL. By C. W. Porter, T. D. Stewart and G. E. K. Branch, Members of the Faculty of the College of Chemistry in the University of California. i v - 3 I I pages, 8vo., illustrated. Boston, Ginn and Company, i92 7. Price, $2. The authors make very modest claims in regard to the r61e this book is supposed to fill in the study of organic chemistry. They have started out with the expressed intention to prepare an outline providing material for a laboratory course in organic chemistry. When they finished they had a manual which not only students but those doing research will find to be of inestimable value as a