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Technique of organic chemistry. Vol. VIII. Investigations of rates and mechanisms of reactions
244
BOOK
REVIEWS
What the controversy that ended with Pasteur’s experiments disposed of is only that living organisms are not spontaneously generated under present conditions. This much granted, the problem now is to understand how they may have so arisen formerly. It is this problem for which Oparin’s book attempts to provide a reasonable argument. Oparin reviews the evidence that the atmosphere of the early earth contained almost no oxygen or carbon dioxide. Under what were therefore anaerobic and sterile conditions, organic compounds of increasing complexity gradually accumulated in the seas, then came together in various types of colloidal aggregation. One of Oparin’s most interesting ideas is that natural selection began to operate at this colloidal level, favoring the growth of certain more efficiently constructed particles at the expense of the others. Eventually, living organisms evolved from such particles. In the absence of oxygen the primal organisms had no recourse but to ferment the organic matter which lay about them. This process introduced large amounts of carbon dioxide into the air and waters, with which eventually organisms began the process of photosynthesis. Photosynthesis in turn introduced oxygen into the earth’s atmosphere; and with this, at last organisms could begin to respire. Much of the biochemistry in this book is now badly out of date. The 17 years since its publication have brought many changes. It is significant that for the most part these advances have been kind to Oparin’s argument. It would go all the better, brought up to date. A new edition or a comparable work from another hand would be welcome. Until that becomes available, this is the best discussion of the subject that we have. GEORGE WALD, Cambridge, Massachusetts Technique of Organic Chemistry. Vol. VIII. Investigations of Rates and Mechanisms of Reactions. Edited by S. L. FRIESS and A. WEISSBERGER. Interscience Publishers, New York, London, 1953. xxiv + 760 pp. Price $12.50. This book, written by 15 contributors, necessarily exhibits diversities of style and viewpoint, but has the advantage of breadth of coverage. Modern reactionrate theory is very well presented in the first chapter by Robert Livingston. In the second chapter, Livingston discusses fundamental operations and measurements, and in the fourth chapter the evaluation of data. The contributors to the book are G. M. Burnett, B. Chance, E. Grunwald, S. L. Friess, F. M. Huennekens, T. H. James, T. S. Lee, J. E. Leffler, R. Livingston, H. W. Melville, B. K. Morse, Paul R. O’Connor, W. J. Priest, F. J. W. Roughton, and W. D. Walters. Chapter 3 is written by four authors. Connor gives a good discussion of what can be learned of the course of reactions by labeling reacting groups with isotopes and also by labeling them by chemically changing the group. The preparation of radioactive reactants, the study of the reaction itself, and the identification of radioactive products all figure in the discussion. Lee gives an extended and rather abstract discussion of the theory of the relative rates of competitive reactions with some examples. Grunwald gives a very short but interesting discussion of the advantages and methods of obtaining instantaneous reaction rates. Chapter 3 is concluded by Melville and Burnett’s discussion of the measurement of the lifetime of the transient atoms or radicals entering into reactions. The
1llfvwt ical 1re:tiri~e~~t of the results of intermittent illumitmt~ion of reacting sy st ems is followed by a discussion of the experimental methods which are employe~l. In Chap V Walters considers homogeneous gss-phase reactions in which he is especially conccrnecl wit,h techniques rnthcr than with the kinet its of liart icul:it react ious. (:lr~cf considrr:t.tion is given lo org:iuic dr~compositioris, isomrriz:t,t ions, and l)ol\mrriz:ltioIls. “React ious in 1he Liquid Staic” constitutes Clmp. VI. In the first part,, Leffler ;tntl Grunwald consider the general methods of studying reactions based upon t I.;l,lsitioll-stxte theory. This is followed by Kathleen Morse’s discussion of Edpcrimcnts involving substitut,ion, addition, and elimination rractions. Frirss then summarizes results on rcnrrangemcrit and isonierization r~f~:cctiofls in an itit ercst ing fashion. (‘txtpt er VII It!- JMWS is a short chapter dealin g wit II homoger~eous c:lt:tly-sis iti solution. Gcuf~ral considf?rations of principle are illustrated by :I fe~v c~sa~iiplcs. The methods and theory of polymerization and polymer reactions are becoming long and involved, as Priest’s Chap. VIII shows. He only finds room for a ver>few detailrcl examples in 94 pages. This is a useful discussion of a rapidly expanding fidd. In t.he first 92 pages of Chap. 1X, which deals with biological react ions, Hucrrnrkeus discusses measurements and general theory. He resolves the tourhy proI)lrm of what constitutes a biological reaction by including all processes where proteins assume the role of reactants or catalyst. Mostly he is concerned with re:ict ions with purified enzymes, but he does consider also some react ions in living systems. Chance concludes the chapter with a study- of the kinetics of catalasc aud peroxidase over-all activity, followed by the necessary direct studies of the kinetics of the enzyme-substrate complexes. The final Chap. X treats “Rapid Reactions.” Roughton considers the general principles of measurement of rapid reactions in solution. Chance reviews his own and related work on accelerat,ed and stopped flow methods using spectrophotomrt.ric measurement,s. Roughton then concludes the chapter with a consideratioit of t hernial measurements of rapid reactions followed by a discussion of quenching, elect remet ric, and other rapid reaction techniques. This is anot her good chapter. The contributions are informative and interesting account,s of developments in the resl)ectivr fields. The book should be useful to all types ot ct1emist.s intcrcst etl in react iou rates. Salt Lake City, T:t,ah HENRY EYRING,
Books
Received
for Review
A. I). ASI) BOOTH, I<. V. R., Automatic Digital Calculators. Academic Press, Sew York, 1953. viii, 231 pp. $6.09. R~LJRKE, G. H. A.L'D DAXIELLI, J. F. (eds.), International Review of Cyt,ology, Volume II. Academic Press, New York, 1953. xii, 545 pp. $11.00. HOURSE, G. H. AND KIDDER, G. W. (eds.), Biochemistry and Physiology of Nutrition, Volume II. Academic Press, New York, 1953. xii, 641 pp. $15.09. BRICSCIA. FRAXK, General College Chemistry. Hlakiston, Sew York and Toroutn, 1953. x, 581 pp. $6.00. I~OOTH,
BOOK
REVIEWS
What the controversy that ended with Pasteur’s experiments disposed of is only that living organisms are not spontaneously generated under present conditions. This much granted, the problem now is to understand how they may have so arisen formerly. It is this problem for which Oparin’s book attempts to provide a reasonable argument. Oparin reviews the evidence that the atmosphere of the early earth contained almost no oxygen or carbon dioxide. Under what were therefore anaerobic and sterile conditions, organic compounds of increasing complexity gradually accumulated in the seas, then came together in various types of colloidal aggregation. One of Oparin’s most interesting ideas is that natural selection began to operate at this colloidal level, favoring the growth of certain more efficiently constructed particles at the expense of the others. Eventually, living organisms evolved from such particles. In the absence of oxygen the primal organisms had no recourse but to ferment the organic matter which lay about them. This process introduced large amounts of carbon dioxide into the air and waters, with which eventually organisms began the process of photosynthesis. Photosynthesis in turn introduced oxygen into the earth’s atmosphere; and with this, at last organisms could begin to respire. Much of the biochemistry in this book is now badly out of date. The 17 years since its publication have brought many changes. It is significant that for the most part these advances have been kind to Oparin’s argument. It would go all the better, brought up to date. A new edition or a comparable work from another hand would be welcome. Until that becomes available, this is the best discussion of the subject that we have. GEORGE WALD, Cambridge, Massachusetts Technique of Organic Chemistry. Vol. VIII. Investigations of Rates and Mechanisms of Reactions. Edited by S. L. FRIESS and A. WEISSBERGER. Interscience Publishers, New York, London, 1953. xxiv + 760 pp. Price $12.50. This book, written by 15 contributors, necessarily exhibits diversities of style and viewpoint, but has the advantage of breadth of coverage. Modern reactionrate theory is very well presented in the first chapter by Robert Livingston. In the second chapter, Livingston discusses fundamental operations and measurements, and in the fourth chapter the evaluation of data. The contributors to the book are G. M. Burnett, B. Chance, E. Grunwald, S. L. Friess, F. M. Huennekens, T. H. James, T. S. Lee, J. E. Leffler, R. Livingston, H. W. Melville, B. K. Morse, Paul R. O’Connor, W. J. Priest, F. J. W. Roughton, and W. D. Walters. Chapter 3 is written by four authors. Connor gives a good discussion of what can be learned of the course of reactions by labeling reacting groups with isotopes and also by labeling them by chemically changing the group. The preparation of radioactive reactants, the study of the reaction itself, and the identification of radioactive products all figure in the discussion. Lee gives an extended and rather abstract discussion of the theory of the relative rates of competitive reactions with some examples. Grunwald gives a very short but interesting discussion of the advantages and methods of obtaining instantaneous reaction rates. Chapter 3 is concluded by Melville and Burnett’s discussion of the measurement of the lifetime of the transient atoms or radicals entering into reactions. The
1llfvwt ical 1re:tiri~e~~t of the results of intermittent illumitmt~ion of reacting sy st ems is followed by a discussion of the experimental methods which are employe~l. In Chap V Walters considers homogeneous gss-phase reactions in which he is especially conccrnecl wit,h techniques rnthcr than with the kinet its of liart icul:it react ious. (:lr~cf considrr:t.tion is given lo org:iuic dr~compositioris, isomrriz:t,t ions, and l)ol\mrriz:ltioIls. “React ious in 1he Liquid Staic” constitutes Clmp. VI. In the first part,, Leffler ;tntl Grunwald consider the general methods of studying reactions based upon t I.;l,lsitioll-stxte theory. This is followed by Kathleen Morse’s discussion of Edpcrimcnts involving substitut,ion, addition, and elimination rractions. Frirss then summarizes results on rcnrrangemcrit and isonierization r~f~:cctiofls in an itit ercst ing fashion. (‘txtpt er VII It!- JMWS is a short chapter dealin g wit II homoger~eous c:lt:tly-sis iti solution. Gcuf~ral considf?rations of principle are illustrated by :I fe~v c~sa~iiplcs. The methods and theory of polymerization and polymer reactions are becoming long and involved, as Priest’s Chap. VIII shows. He only finds room for a ver>few detailrcl examples in 94 pages. This is a useful discussion of a rapidly expanding fidd. In t.he first 92 pages of Chap. 1X, which deals with biological react ions, Hucrrnrkeus discusses measurements and general theory. He resolves the tourhy proI)lrm of what constitutes a biological reaction by including all processes where proteins assume the role of reactants or catalyst. Mostly he is concerned with re:ict ions with purified enzymes, but he does consider also some react ions in living systems. Chance concludes the chapter with a study- of the kinetics of catalasc aud peroxidase over-all activity, followed by the necessary direct studies of the kinetics of the enzyme-substrate complexes. The final Chap. X treats “Rapid Reactions.” Roughton considers the general principles of measurement of rapid reactions in solution. Chance reviews his own and related work on accelerat,ed and stopped flow methods using spectrophotomrt.ric measurement,s. Roughton then concludes the chapter with a consideratioit of t hernial measurements of rapid reactions followed by a discussion of quenching, elect remet ric, and other rapid reaction techniques. This is anot her good chapter. The contributions are informative and interesting account,s of developments in the resl)ectivr fields. The book should be useful to all types ot ct1emist.s intcrcst etl in react iou rates. Salt Lake City, T:t,ah HENRY EYRING,
Books
Received
for Review
A. I). ASI) BOOTH, I<. V. R., Automatic Digital Calculators. Academic Press, Sew York, 1953. viii, 231 pp. $6.09. R~LJRKE, G. H. A.L'D DAXIELLI, J. F. (eds.), International Review of Cyt,ology, Volume II. Academic Press, New York, 1953. xii, 545 pp. $11.00. HOURSE, G. H. AND KIDDER, G. W. (eds.), Biochemistry and Physiology of Nutrition, Volume II. Academic Press, New York, 1953. xii, 641 pp. $15.09. BRICSCIA. FRAXK, General College Chemistry. Hlakiston, Sew York and Toroutn, 1953. x, 581 pp. $6.00. I~OOTH,