E. Guibe-Jampel and M . Wakselman. ( I $ is a stable com- pound that reacts with the Na salts of amino acids in aqueous solution. The reaction is very fast at 25°C. The

C 1:)

BOC amino acids can be isolated in good yields by solvent extraction. Examples : N-BOC-glycine, 85% yield ; N-BOC- glutamic acid, 70% ; N“-BOC-Nu-Z-L-lysine, 80% (Z = ben- zoxycarbonyl) ; N-BOC-serine, 60% ; N-BOC-glycine ethyl ester, 90%. 1 Chem. Commun. 1971, 267 / -Ma.

[Rd 355 IE]

Ring expansion by two C atoms on “siloxy Cope rearrange- ment’’ to give good yields of unsaturated cyclic ketones is described by R. W Thies. For example, the trimethylsiloxy derivative of cis-I -vinylcyclonon-3-en-l-ol (1) undergoes thermal rearrangement via [1.3] and [3.3] sigmatropic

[ 1 . 3 \ /

J

n I

BOOK REVIEWS

I3.31 \ OSi (CII, )3 0

shifts to give six trimethylsiloxy enol ethers [four and two cis-trans isomers of (2) and of (3) respectively] whose hydrolyses lead to the ring-expanded ketones (4) and (5) and to the cyclononanone (6) in high yields. In contrast to the “oxy Cope rearrangement”, the reaction is accompanied by neither significant polymer formation nor cleavage to the P-hydroxy olefin. The trimethylsiloxy derivatives are readily obtainable in good yields. / Chem. Commun. 1971, 237 / -Ma.

[Rd 356 IE]

The vibrational spectra (IR and Raman) of oxalyl bromide in all physical states were recorded by J . R. Durig, S . E . Hannum, and F. G . Baglin. Whereas solid (COBr), occurs only in the trans form, the spectra of the liquid contain bands that can be ascribed to the cis form. The free enthalpy difference between cis and trans forms amounts to 2.9 0.1 kcal mold’, the trans form being the more stable of the two. At room temperature, 10f 5% of the liquid is in the cis form. Approximate values of the potential function parameters describing the rotation about the C-C bond are given. / J. Chem. Phys. 54,2367 (1971) / -Hz.

[Rd 357 IE]

Oxidation of thiacyclobutane and thiacyclopentane with oxygen initiated by Q-switched laser pulses was investigat- ed by F. P . Miknis and J . P . Biscar. Varying amounts of oxygen were added to a constant amount of liquid C,H,S or C,H,S in a spherical Pyrex bulb and the gaseous mix- ture exposed to one pulse from a Q-switched ruby laser. Each pulse had a peak power of over 100 MW and a dura- tion of about 20 ns. With oxygen partial pressures between 100 and 1500 torr the pulses initiated a reaction accom- panied by emission of radiation in the entire gas volume. The major products were CO,, SO,, and H,O, in addition H,S, COS, CS,, and C,H, were found in amounts depend- ing on the oxygen partial pressure. It is probable that the reaction is started by multiphoton absorption : without Q- switching, i.e. if the pulse energy is released over a time interval about lo3 times longer, no reaction occurred. / J. Phys. Chem. 75,725 (1971) 1 -Hz.

[Rd 358 IE]

Radical Ions. Edited by E.T. Kaiser and L. Kevan. Interscience Publishers, a Division of John Wiley and Sons, New York-London 1968. 1st Edit., ix, 800pp., numerous figures, bound, f. 14.00.

With its 13 selected topics from the realm of the chemistry and physical chemistry of radical ions, all of them written by eminent experts, this book offers a near com- prehensive survey of the most important modern aspects of the chemistry of cation- and anion-radicals. The single unifying theme-how could it be otherwise-is ESR spectroscopy and the relevant orbital theory. Thus, anyone interested in, for example, the radicals formed by y-irradia- tion, does not need to read the previous eight chapters. The

book begins with a survey of electron spin densities and their determination from the coupling constants observable in the ESR spectra. The following chapters, however, are all concerned with more specific topics from the chemistry of organic radicals : metal ketyls and related radical ions, semidione radical anions, radical cations, the effect of substituents on the electron spin densities in aryl radicals and its theoretical importance, aromatic anion radicals, radical anions in Group IV elements, and sulfur-containing aromatic radical anions. The book ends with the structure of inorganic radicals, fragments from the irradiation of solid ions, and the electron spin resonance of complex ions of transition metals of the first row.

430 Angew. Chem. internal. Edit. 1 Vol. I0 (1971) 1 No. 4

Each chapter is clearly written in the manner of an essay review and is provided with a good selection of references and graphic illustrations. There are no extensive historical introductions, but emphasis is placed on modern develop- ments. Since a great variety of topics are covered, the reader may treat the work selectively. It is, infact, more a collection of excellent individual articles, rather than a coherent entity. The thoroughness and conciseness with which the individual chapters are written provide an excellent oppor- tunity for readers, even those not directly concerned with this field, to gain an idea of the broad outlines of the rapidly developing radical chemistry. The book is indispensable for the library of any institute of chemistry or physical chemistry.

Karl Dimrofh [NB 942 JE]

Phase Equilibria, Basic Principles, Applications, Experi- mental Techniques. By A . Reisman. Academic Press, New York-London 1970. xi, 541 pp., bound $27.50.

Until the mid-I950s, interest in phase equilibria was almost exclusive to metallurgists. Nowadays it calls to mind topics such as semiconductors, nuclear technology, space technology, zone melting, chemical transport reac- tions, and crystal growing. Whereas the metallurgist was mainly concerned with equilibria of condensed phases at normal pressure, both the gas phase and the influence of high pressures are nowadays becoming increasingly im- portant.

This was one reason why the author wrote the present book. Another reason was that the existing books dealing with this topic use a phenomenological approach and mainly graphical representation at the expense of a more detailed mathematical treatment. New paths in this connec- tion have been opened up by computers.

The thermodynamic basis is first elaborated and tested on the equilibria of one-component systems. In the subsequent binary and pseudobinary systems, the author considers only ideal model systems and deliberately omits such concepts as fugacity or activity. A systematic mathe- matical treatment of these ideal systems provides an under- standing of the laws to which the observed types of phase equilibria are subject. In particular, numerous examples are given to show quantitatively the influence of parameters such as the melting points and heats of fusion of the pure components, dissociation or association in melts or solids, external pressure, and the vapor pressures of the compo- nents. The calculated model systems, for which graphs are constructed, are compared with examples from the litera- ture. Even systems as unusual as those that exhibit continu- ous solid solution formation with a melting minimum are calculated on this basis. A few chapters dealing with ternary systems are then included. The picture is rounded off by examples of applications, such as purification by distillation or zone melting and chemical transport reac- tions.

The last, less successful, chapter deals with experimental methods. This discussion totally ignores some important methods, such as EMF or calorimetric measurements. Other aspects, such as the operation of a thermocouple, are discussed in too much detail.

In general, the book should facilitate the approach to the complex field of phase equilibria, and a great help here is the fact that it has been restricted to model systems.

It is thus suitable both for the advanced student and for the practical worker who wish to forge ahead to the fundamental rules of phase equilibria.

[NB 947 IE] ’ Hans Rau

The Theory of Adsorption and Catalysis. Physical Chemi- stry, A Series of Monographs. By A . Clark. Academic Press, New York - London 1970. 1st ed., x, 418 pp., bound DM 19.50.

The book presents a survey of the present position in the theoretical treatment of adsorption and catalysis. It is in the nature of things that theories based on models occupy the foreground in the first part, which is devoted to adsorption, whereas empirical relations receive more attention in the second part, which deals with catalysis.

A brief outline of the thermodynamics of adsorption serves as an introduction. This is followed by the dis- cussion of localized and non-localized adsorption on homogeneous and heterogeneous surfaces for systems without interaction between neighboring particles and for systems with such an interaction. Adsorption isotherms, heats of adsorption, entropies of adsorption, etc., are derived for these various adsorption systems with the aid of statistical thermodynamics.

One chapter each is devoted to the adsorption forces in physisorption, in chemisorption on metals, and in chemisorption on semiconductors. The dispersion and repulsion forces are discussed, as well as the analogy between chemisorption bonding and chemical bonding and the models for a quantum-mechanical treatment of chemisorption. The description of chemisorption on semiconductors is based mainly on the Hauffe and the Wolkenstein views. The first part of the book ends with a chapter on the kinetics of chemisorption.

The second part is introduced by an examination of the relation between adsorption and catalysis. The kinetics of heterogeneous catalytic reactions is considered se- parately for reactions in which diffusion plays no part and for diffusion-controlled reactions.

The “geometric factor” is discussed at length in connection with the effects of lattice structure, defects, and particle size on catalytic activity. The “electronic factor” is discussed for metals and semiconductors. A final chapter deals with the adsorbed species and their role in heteroge- neous catalysis.

The extensive bibliographies cite references up to 1969.

This well-written summary of present-day knowledge will be a welcome aid to anyone who is concerned with the fundamentals of adsorpticln and catalysis.

Gerd Wedler [NB 951 IE]

Computer Programs for Chemistry. By D. F. Detar. W. A. Benjamin Jnc., New York 1968. 1st ed., xx, 207 pp., bound $14.15.

The evaluation of experimental results or the calculation of molecular properties with the aid of computer programs is becoming increasingly important in chemistry. Whenever the considerations are based on a complicated calculation, it is advisable to use programs devised by personnel

Angew. Chem. internal. Edit. Vol. 10 (1971) 1 No. 6 43 1