вход по аккаунту


Book Review Radical Ions. Edited by E. T. Kaiser and L. Kevan

код для вставкиСкачать
E. Guibe-Jampel and M . Wakselman. ( I $ is a stable compound 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-BOCglutamic acid, 70% ; N“-BOC-Nu-Z-L-lysine,80% (Z = benzoxycarbonyl); 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 rearrangement’’ 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
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 investigated by F. P . Miknis and J . P . Biscar. Varying amounts o f
oxygen were added to a constant amount of liquid C,H,S
or C,H,S in a spherical Pyrex bulb and the gaseous mixture exposed to one pulse from a Q-switched ruby laser.
Each pulse had a peak power of over 100 MW and a duration of about 20 ns. With oxygen partial pressures between
100 and 1500 torr the pulses initiated a reaction accompanied 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 depending on the oxygen partial pressure. It is probable that the
reaction is started by multiphoton absorption : without Qswitching, 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 comprehensive 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-irradiation, 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.
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 developments. 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 opportunity 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
Karl Dimrofh [NB 942 JE]
Phase Equilibria, Basic Principles, Applications, Experimental 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 reactions, 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 important.
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 connection 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 mathematical treatment of these ideal systems provides an understanding 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 components. The calculated model systems, for which graphs are
constructed, are compared with examples from the literature. Even systems as unusual as those that exhibit continuous 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 reactions.
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.
Angew. Chem. internal. Edit.
Vol. 10 (1971) 1 N o . 6
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.
Hans Rau
[NB 947 IE]
The Theory of Adsorption and Catalysis. Physical Chemistry, 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 discussion of localized and non-localized adsorption on
homogeneous and heterogeneous surfaces for systems
without interaction between neighboring particles and
for systemswith 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 separately 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 heterogeneous 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
43 1
Без категории
Размер файла
234 Кб
kaiser, book, edited, kevan, radical, ions, review
Пожаловаться на содержимое документа