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Quantum chemistry
284
BOOK
REVIEWS
profit by graduate student and mentor alike. The chapters on “Centrifuging, Filtration, and Solvent Removal,” etc., impressed this reviewer as having been written primarily from the standpoint of the chemical engineer and of the chemist handling large-scale work. It is surprising that Broughton’s discussion of drying agents makes no mention of the excellent properties of calcium hydride and similar substances. This volume is remarkably free of grammatical or typographical errors. The few found on a careful inspection include: “A refutation of Frondel’s objections are given. . .” (p. 435) ; “electroendomosis” (p. 72) ; “reversable” (p. 140). In conclusion, an up-to-date library of organic chemistry cannot be without this volume. I. MOYER HUNSBEROER, New York, New York
Quantum Chemistry. By WALTER KAUZMANN, Chemistry Department, Princeton University, Princeton, New Jersey. Academic Press Inc., New York, New York, 1957. xii f 744 pp. Price $12.00. Professor Kauzmann’s work is the third to bear the title of Quantum Chemistry, and, in addition, the subject matter it covers may be said to be among the main topics of several others. The growing number of books available in this area reflects the ever-increasing demand among chemists for more fundamental understanding of the methods and particularly the language of quantum mechanics. Kauzmann’s Quantum Chemistry is some 50-6Oyc longer than the usual texts in this area, but it does not cover more extensive material. The difference is largely in a more detailed exposition and a more conversational approach to the subject without, however, lowering its mathematical level. The author devotes about the first 20% of the book to developing the necessary mathematical tools. This is done largely in the framework of classical vibration theory. It is unfortunate that no introductory material on group theory is included, for this subject is becoming increasingly important to the chemist, both for its own sake and for the profound influence it has on the nomenclature of modern chemistry. The next 15% of the text covers the introduction to the Schrodinger equation and its application to systems for which exact solutions can be obtained. Then comes the main body of the material, consisting of about 35yc of the volume, covering the application of the principles developed to atomic and molecular systems. The final 30% considers nonstationary states with particular emphasis on interaction of molecular systems with radiation. Undoubtedly as a result of Prof. Kauemann’s own interest in the subject, an unusually high proportion of the material in this section is devoted to the nature and foundation of the theories of optical rotatory power, dispersion, and related material. As a whole, the text is well done. It maintains throughout a properly critical attitude concerning the validity and limitations of the approximations and approaches necessary in applying quantum mechanics to chemically interesting systems. Perhaps occasionally this critical attitude is overdone, but errors in this direction are probably better for the developing chemist than in the direction of being not critical enough.
BOOK
285
REVIEWS
The chief shortcomings of the text are most apparent in those areas in which the author has not been actively involved in research. This is especially obvious in the interpretation of the results of calculations on simple atoms and molecules. It is unfortunate that the author defines the term “correlation energy” in a manner contrary to general current usage, that such very large importance is attached to the virial theorem in discussing approximate wave functions, and that insufficient and inaccurate attention is given to the valence states of atoms in molecules (the valence state of the carbon atom in sp3 bonding, for example, is not the same as the spectroscopically observed 6s state). Despite these criticisms, Kausmann’s &~~ntum Chemistry is a welcome addition to the selection available. It has many stimulating and refreshing viewpoints. Finally the up-to-date coverage of the literature will be much appreciated, especially the extensive references to the original literature, occurring at the end of each chapter. By and large, one can say that the author has accomplished well his goal to “help chemists understand the more important concepts that quantum mechanics has introduced into chemistry.” HARRISON SHULL, Bloomington,
Indiana
A Guide to Qualitative Organic Analysis. By R. P. LINSTEAD and B. C. L WEEDON, Imperial College of Science and Technology. Academic Press Inc., New York, and Butterworths Scientific Publications, London, 1956. xi + 169 pp. Price $4.50. This book is an outgrowth of a manual used since 1930 for instruction in qualitative organic analysis at the Imperial College of Science and Technology. The authors emphasize that no routine system of qualitative analysis is possible for organic compounds. They “strongly deprecate” systems of analysis depending on determination of melting points and of solubility in various solvents and declare that such systems “may in practice lead to grotesque errors.” Nevertheless, information obtainable from solubility tests quite naturally appears with regularity throughout the book. Description of manipulative techniques is omitted purposely. The text of this book is presented in nine chapters comprising only 104 pages. The first two chapters are devoted, respectively, to an introduction and to the preliminary examination of unknowns. Elemental tests for fluorine, arsenic, and mercury are presented along with those for the more usual elements. The next six chapters are devoted to procedures for examination of single unknowns. The “system” used depends primarily upon the elemental composition. Thus, organic compounds are divided into 23 groups depending on whether or not nitrogen, sulfur, halogen, and metals are present. For example, compounds containing only carbon, hydrogen, and (possibly) oxygen are divided into nine groups. This approach naturally causes some compounds containing a given functional group to appear in one and some in another group. Most groups are discussed under the following headings: general properties, group tests, more specific tests, identifica-
BOOK
REVIEWS
profit by graduate student and mentor alike. The chapters on “Centrifuging, Filtration, and Solvent Removal,” etc., impressed this reviewer as having been written primarily from the standpoint of the chemical engineer and of the chemist handling large-scale work. It is surprising that Broughton’s discussion of drying agents makes no mention of the excellent properties of calcium hydride and similar substances. This volume is remarkably free of grammatical or typographical errors. The few found on a careful inspection include: “A refutation of Frondel’s objections are given. . .” (p. 435) ; “electroendomosis” (p. 72) ; “reversable” (p. 140). In conclusion, an up-to-date library of organic chemistry cannot be without this volume. I. MOYER HUNSBEROER, New York, New York
Quantum Chemistry. By WALTER KAUZMANN, Chemistry Department, Princeton University, Princeton, New Jersey. Academic Press Inc., New York, New York, 1957. xii f 744 pp. Price $12.00. Professor Kauzmann’s work is the third to bear the title of Quantum Chemistry, and, in addition, the subject matter it covers may be said to be among the main topics of several others. The growing number of books available in this area reflects the ever-increasing demand among chemists for more fundamental understanding of the methods and particularly the language of quantum mechanics. Kauzmann’s Quantum Chemistry is some 50-6Oyc longer than the usual texts in this area, but it does not cover more extensive material. The difference is largely in a more detailed exposition and a more conversational approach to the subject without, however, lowering its mathematical level. The author devotes about the first 20% of the book to developing the necessary mathematical tools. This is done largely in the framework of classical vibration theory. It is unfortunate that no introductory material on group theory is included, for this subject is becoming increasingly important to the chemist, both for its own sake and for the profound influence it has on the nomenclature of modern chemistry. The next 15% of the text covers the introduction to the Schrodinger equation and its application to systems for which exact solutions can be obtained. Then comes the main body of the material, consisting of about 35yc of the volume, covering the application of the principles developed to atomic and molecular systems. The final 30% considers nonstationary states with particular emphasis on interaction of molecular systems with radiation. Undoubtedly as a result of Prof. Kauemann’s own interest in the subject, an unusually high proportion of the material in this section is devoted to the nature and foundation of the theories of optical rotatory power, dispersion, and related material. As a whole, the text is well done. It maintains throughout a properly critical attitude concerning the validity and limitations of the approximations and approaches necessary in applying quantum mechanics to chemically interesting systems. Perhaps occasionally this critical attitude is overdone, but errors in this direction are probably better for the developing chemist than in the direction of being not critical enough.
BOOK
285
REVIEWS
The chief shortcomings of the text are most apparent in those areas in which the author has not been actively involved in research. This is especially obvious in the interpretation of the results of calculations on simple atoms and molecules. It is unfortunate that the author defines the term “correlation energy” in a manner contrary to general current usage, that such very large importance is attached to the virial theorem in discussing approximate wave functions, and that insufficient and inaccurate attention is given to the valence states of atoms in molecules (the valence state of the carbon atom in sp3 bonding, for example, is not the same as the spectroscopically observed 6s state). Despite these criticisms, Kausmann’s &~~ntum Chemistry is a welcome addition to the selection available. It has many stimulating and refreshing viewpoints. Finally the up-to-date coverage of the literature will be much appreciated, especially the extensive references to the original literature, occurring at the end of each chapter. By and large, one can say that the author has accomplished well his goal to “help chemists understand the more important concepts that quantum mechanics has introduced into chemistry.” HARRISON SHULL, Bloomington,
Indiana
A Guide to Qualitative Organic Analysis. By R. P. LINSTEAD and B. C. L WEEDON, Imperial College of Science and Technology. Academic Press Inc., New York, and Butterworths Scientific Publications, London, 1956. xi + 169 pp. Price $4.50. This book is an outgrowth of a manual used since 1930 for instruction in qualitative organic analysis at the Imperial College of Science and Technology. The authors emphasize that no routine system of qualitative analysis is possible for organic compounds. They “strongly deprecate” systems of analysis depending on determination of melting points and of solubility in various solvents and declare that such systems “may in practice lead to grotesque errors.” Nevertheless, information obtainable from solubility tests quite naturally appears with regularity throughout the book. Description of manipulative techniques is omitted purposely. The text of this book is presented in nine chapters comprising only 104 pages. The first two chapters are devoted, respectively, to an introduction and to the preliminary examination of unknowns. Elemental tests for fluorine, arsenic, and mercury are presented along with those for the more usual elements. The next six chapters are devoted to procedures for examination of single unknowns. The “system” used depends primarily upon the elemental composition. Thus, organic compounds are divided into 23 groups depending on whether or not nitrogen, sulfur, halogen, and metals are present. For example, compounds containing only carbon, hydrogen, and (possibly) oxygen are divided into nine groups. This approach naturally causes some compounds containing a given functional group to appear in one and some in another group. Most groups are discussed under the following headings: general properties, group tests, more specific tests, identifica-