Book Review Rntgenbeugung an Kristallen (X-Ray Diffraction by Crystals). By K. H. Jostкод для вставкиСкачать
BOOK REVIEWS Reaktionstypen in der anorganischen Chemie (Reaction types in inorganic chemistry). By I. Fitz. Akademie-Verlag, Berlin 1975. 1st Edit., 465 pp., 98 figures, 105 tables, bound, DM 58.This book, which is concerned with the laws governing inorganic reactions in aqueous solution, is divided into nine sections. A general chapter about bonding and chemical reactivity is directly followed by an account of the principles of chemical reaction-then follow the most important types of reaction: complex reactions, redox reactions, and acid-base reactions. The work concludes with polymerization and depolymerization reactions, coupled reactions, and a survey of the common and distinguishing features of inorganic reaction types. The first chapter mainly compares and contrasts the various kinds of chemical bonds, not always as clearly as desired. Terms such as bond lengths, ionic and atomic radii, force constants, bond energies, polarizability, electronegativity, and electron affinity have not been forgotten. It ends with a brief introduction to ligand field theory. Before describing the three reaction types, the author attempts to clarify the principles of a chemical reaction by demonstrating the significant role of thermodynamics and kinetics in inorganic reactions in aqueous solution. Free energy and free enthalpy are just as important as, say, entropy in complex chemistry. Terms connected with kinetics such as activation energy, transition state, kinetic isotope effects, steric influence, and electronic effects are considered in detail. Predictions of the course and mechanism of a chemical reaction on the basis of thermodynamics and kinetics conclude this section. In connection with complex reactions particular emphasis is placed upon thermodynamic aspects and ligand field theory. A separate section is devoted to stereochemistry and the stereochemical consequences of substitution reactions whose mechanisms are discussed with the aid of numerous examples. Among the most important reaction types in organic chemistry are redox and acid-base systems. In both cases we are concerned with “particle-transfer reactions”. An historical development of the concepts is given, and all relevant modem theories are mentioned. In such cases the present book replaces an analytical textbook for the treatment of redox equilibria and all kinds of p H calculations are discussed in the same great detail as thedouble logarithmic Hagg diagrams of corresponding acid-base pairs. The work supplements available inorganic and analytical textbooks for undergraduates, even though the subject matter is sometimes of a more advanced nature. Clear tabulations of data are abundant. It is only regrettable that a number of factual and printing errors have crept into the book. Thus not all alkali halides have the NaCl structure, as claimed in Table 9. Table 16 contains misleading printing errors in the hybridizations and bond angles; the examples of Table 17 would have been better in Table 16. A better choice of examples would also have been desirable. For this reason the book can only be recommended with reservation. Ekkehard Lindner [NB 328 IE] Lehrbuch der Elektrochernie (Textbook of Electrochemistry). By J . Koryta, J . DvoFa’k, and VI Bohdtkova’. Translated by Helga Baiantova’. Springer-Verlag, Vienna-New York 1975. 1st Edit., xv, 348 pp., 108 figures, bound, 145.--. The decision to market a translation of the Czech work “Textbook of electrochemistry” probably represents something of a gamble, particularly since the opportunities for Angew. Chem. I n t . Ed. Engl. J Vol. 15 ( 1 9 7 6 ) N o . 9 developing a completely new concept deviating from the usual presentation and didactic approach are rather limited. Although the treatment ofindividual topicsin this book resembles that in other textbooks, a certain degree of originality is to be seen in the subdivision of the material. Our attention is first directed to equilibria in electrolytes, a brief introduction containing definitions of equilibrium constants and activities and activity coeficients being followed immediately by the Debye-Huckel law and its extension, as well as methods for determining the activity coefficients of electrolytes. There follow the theory of weak electrolytes and a consideration of the pH value, paying attention to varying definitions and acidity functions. The chapter closes with an account of ampholytes and polyelectrolytes. The second chapter is concerned with the transport processes so important for practical electrolysis and electrochemical methods of analysis. Not only diffusion and migration, but also convective diffusion, which is frequently neglected in other books, are all considered. The third chapter discusses equilibria in heterogeneous electrochemical systems, i. e. equilibrium electrode potentials or equilibrium cell potentials. The electrochemical double layer is also described. A brief treatment of membrane electrochemistry follows in the fourth chapter, which closes with a very short account of the electrochemistry of biological membranes. The final chapter is devoted to electrode kinetics. The book is supplemented by a mathematical appendix, in which the applications of Laplace transformation to the solution of the diffusion problems of Chapter 2 is presented. O n 320 pages the book deals with all the important fundamental aspects of electrochemistry in a correct, competent, and lively manner. Concerning the didactic concept, however, it should bementioned that in the chapter on electrode kinetics the reader often misses the right figure at the right place, and that some of the figures do more to disguise the situation than elucidate it (Fig. 3.11a, 3.19, 5.2, 5.3). Unfortunately the translator’s German leaves much to be desired, containing numerous Anglicisms, Gallicisms, and oldfashioned expressions. These weaknesses, however, could easily be remedied in a second edition. Hartmut Wendt [NB 329 IE] Rontgenbeugungan Kristallen (X-Ray Diffraction by Crystals). By K . H . Jost. Akademie-Verlag, Berlin 1975. 1st edit., xii, 404 pp., 332 figs., 18 tables, bound, ca. D M 98.--. Contrary to what might be assumed from the title, this book does not deal with the method of crystal structure determination. Instead, the origin of X-ray diffraction diagrams and their recording and evaluation are described. After two introductory chapters on the excitation of X-rays and the fundamental concepts of crystallography, the production of diffraction diagrams is discussed with particularly detailed treatment of the influence of disorders, thermal motion of atoms, and superstructures. The procedures now customary for recording the diffraction patterns and for measuring intensities are then presented, and the newer types of apparatus such as the Gandolfi camera and the Kappa four-circle diffractometer are also mentioned. A relatively large amount of space is taken up by a description of the methods of evaluation in comparison with that devoted to the determination of unit cell dimensions, symmetry and intensity. The last chapter deals with powder methods and their application. Noteworthy is that topics such as the investigation 565 of texture, indexing according to IT0 for any desired symmetry, and the investigations of pressure and temperature variations are also discussed. With its detailed and clear presentation of themes, which are seldom treated elsewhere, this book fills a gap and provides a valuable supplement to books previously available on crystal-structure determination. In spite of the rather high price it can thus be strongly recommended to all concerned with X-ray diffraction. Jouchim Struhle [NB 330 IE] Zum Ablauf ionischer Polymerisationsreaktionen(The course of Ionic Polymerizations). By G . Heublein. Akademie-Verlag, Berlin 1975. 1st edit., viii, 316 pp., numerous figs. and tables, bound, ca. DM 58.--. In comparison with the industrially much more important field of radical polyreactions there are considerably fewer proven results on ionic polymerizations. Thus, it is only in recent years that many of the “classical” concepts of cationic polyreactions have had to be revised. A critical presentation of the present state of our knowledge of ionic polyreactions is thus a difficult but undoubtedly highly valuable exercise. Following a brief comparison of ionic and radical polymerizations and a general outline of the course of ionic polymerizations, the book treats first cationically and then anionically initiated polyreactions; a subsequent chapter is devoted to ionic copolymerizations. In a section contributed by P . Hallpap the current possibilities for quantifying description of ionic polymerizations are collected together with their quantumchemical treatment. A field as wide as this cannot be described in all its parts in equal detail; one misses, e.g. the recent investigations by P . H . Plesch’s school on cocatalyst-free cationic initiation of polymerization with aluminum trichloride and the pseudocationic polymerizations by ester formation. Objections in principle must be noted concerning some of the concepts used; the phrase “Mischpolymerisation” (mixed polymerization) should be finally banned from scientific literature according to IUPAC rules. To describe the growth step of polymerizations as the “Polyadditionsschritt” (polyaddition step) (e.g . p. 16), is at least an error of judgement, since in German it can easily lead to confusion with other polyadditions occurring according to totally different mechanisms. These minor details d o not, however, detract from the book‘s value as an easily readable summary for a currently important area of macromolecular chemistry, particularly as the more than 600 literature references make it possible to delve deeper into the subject. A more serious deficiency-and one that must certainly be corrected in a new edition--is the absence of a subject index, particularly as the contents list is only crudely sectionalized. Dietrich Braun [NB 331 IE] IRSpektroskopie-Eine Einfuhrung. (Taschentext 43/44) (IR Spectroscopy-An Introduction. Pocket book 43/44). By H . Giinzler and H . Bock. Verlag Chemiephysik Verlag, Weinheim 1975. 1st edit., xv, 363 pp., 152 figs., 50 tables, paperback, DM 38.-. The main emphasis of this book is laid on the description of group frequencies of organic compounds, which are discussed very expertly with the aid of many original spectra and tables. Inorganic compounds are mentioned in only one sentence. Details of the apparatus, its maintenance, and of the preparation of samples are discussed at length; this part is of real practical value even for the experienced user, and treatment of special techniques takes up much space. 566 Theoretical principles up to the rotational vibration spectra of an anharmonic oscillator are treated in only 30 pages. Without givingany derivation the authors cite the Schrodinger equation as a kind of magic formula from which everything else can follow; here there are formulations that run from the unfortunate through the inexact to the false, and other chapters too are not free from them. Because of the weaknesses in its treatment of the theoretical principles and its concentration on applications in organic chemistry, this book is certainly no general introduction to IR spectroscopy. The limitation to organic compounds should have been stated in the title. Gerhard Lehmann [NB 332 IE] Fortschritte der Massenspektrometrie.Progress in Mass Spectrometry. Edited by H . Budzikiewicz. Vol. 3. Alkaloide, ausser Indol-Triterpen-, und Steroidalkaloide. By M . Hesse and H . P . Bernhard. Verlag Chemie, GmbH, Weinheim 1975. 1st edit., xvii, 372 pp., 112 figs., 83 tables, bound, DM 148.-. In order to take into account the complexity and structural variety of this group of natural products the authors confine themselves in this book in the Progress series[*] to the nitrogen compounds that are not classifiable as indole, triterpene, steroid, or ergot alkaloids. The classification principle for the remahing compounds-structurally considered still imposing in number-is based on the practicable but not always relevant assumption that in alkaloids the decompositions induced by electron impact generally start from ionized nitrogen. In consequence, therefore, the “nitrogen” structural element is set up as the centerpoint, while the traditional classification based on skeletal or chromophore type and on biogenetic relationships serve as secondary classification characteristics. The presentation of the immense volume of material succeeds by skilful choice and combination of line spectra, principal routes of decomposition, conclusions by analogy (allowed and forbidden), critical commentaries on spectral interpretation, and a comprehensive literature search (1082 references distributed over seven main chapters that in turn are subdivided into 125 fields). The authors have succeeded very well indeed in directing the reader rapidly and clearly (often with use of structural formulas) to the data relevant to analytical use by means of precise formulation and designation of key fragments. Mechanistic aspects are, in general, considered and used for spectral interpretation only insofar as they have been proved by experiment. In spite of the extensive data material involved (an index, arranged by molecular weight and names of 1260 compounds, as well as a comprehensive subject index allow rapid orientation), this book will not only be valuable to the typical alkaloid chemist but will also prove to be a (provocative) source for mechanistic studies, as repeatedly indicated by the authors’ views and limits. How helpful and important is well-based knowledge of the decomposition principles for a correct interpretation of the mass spectra of alkaloids is shown impressively by Chapter 6 (putrescine, spermidine, and spermine alkaloids). On the basis of studies of model compounds, carried out by the Zurich group, it is demonstrated, inter alia, that the apparent complexity of the mass spectra of these alkaloids is due to the simple interaction of nonbonded centers ( e . g . specific, reciprocal H-transfers or electron-impact-induced SNi reactions). The book constitutes an important addition to the standard works already available for chemists concerned with the analytical side of alkaloid chemistry. Helmut Schwarz [NB 333 IE] [*] Cf. Angew. Chem. Int. Ed. Engl. 15, 58 (1976).