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Book Review Kinetics and Mechanism. A Study of Homogeneous Chmical Reactions. By J. W. Moore and R. G. Pearson. 3rd edition

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121 Cf. a) A. Muller, E. Diemann, R. Jostes, H. Bogge, Angew. Chem. 93
(1981) 957: Angew. Chem. Inr. Ed. Engl. 20 (1981) 934; b) W. Clegg, N.
Mohan, A. Muller, A. Neumann, W. Rittner, G . M. Sheldrick, Inorg.
Chem. 19 (1980) 2066; A. Miiller, W. Jaegermann, Coord. Chem. Rev.. in
press.
[3] Procedure: (PPh4),MoS4(0.6 g) was added to dimethylformamide (p.a.:
25 mL) in a 100 m L Erlenmeyer flask. The mixture was stirred at 20 “C
under N 2 until dissolution was complete. After addition of 25 mL of anhydrous ethanol (p.a.) the mixture was heated at 60 “C for 15 min, whereupon reprecipitated (PPh,),MoS, was essentially dissolved. The flask was
stoppered and allowed to stand at 20°C for 16 h (all operations were car-
ried out under N?). The solution was filtered in presence of air. and the
filtrate stored in a closed vessel at 20 “C for 14 d. The reaction mixture
was then treated with 75 mL of ethanol and once again allowed to stand
for 16 h at 20 “C in a stoppered 250 mL Erlenmeyer flask. The precipitated reddish-brown crystals were filtered off, washed with anhydrous
EtOH, CS,, and Et,O and dried in a vacuum (yield 0.15 g). 1 cannot be
obtained in the pure state using reaction (a).-In a modified method
(b),
either
the
novel
black
“mixed
valence”
complex
(PPh~)2[(S2)0Mo”SzMoVO(Mov~S4)]
(characterized by crystal structure
determination), or the monothiosulfate complex corresponding to 1 can
be obtained.
BOOK R E V I E W S
Kinetics and Mechanism. A Study of Homogeneous Chemical Reactions. By J. W. Moore and R . G. Pearson. 3rd
edition, Wiley-Interscience, Chichester 1981. xv, 455 pp.,
bound, L 23.70.
For the generation of chemists who first came into contact with chemical kinetics in the ‘fifties and ‘sixties
“Frost-Pearson” was a standard introductory textbook and
review of the field of homogeneous reaction kinetics“]. A
new edition of “Kinetics and Mechanism” by J. W. Moore
and R . G . Pearson has now appeared after 20 years, and
the expectations are naturally running high, in view both
of the renown of the older work and the competition that
has meanwhile arisen from other monographs in this field.
It is a pleasure to say that these expectations can be regarded as having been satisfied. Through a far-reaching revision of the book (about four-fifths of it has been newly
written) it has been possible to include the developments
of the last 20 years so successfully that the new work constitutes an excellent review of the present state of kinetics
and of its concepts, methods, and applications in the clarification of reaction pathways.
The classification of the material has remained substantially unchanged from the second edition. The number of
detailed examples of elucidated reaction mechanisms has
been drastically cut down to make room for the treatment
of more recent theoretical and experimental developments,
and the previous two concluding chapters have been eliminated. The book opens with a discussion of the empirical
foundations for the treatment of rate constants, and goes
on with a chapter o n experimental methods and the analysis of kinetic measurements in which-as in a later chapter
on complex systems-the appropriate use of computers in
data analysis, numerical integration, and simulation with
models is also briefly considered. The chapters “Collisions
between Molecules” and “Potential Surfaces and the Theory
of the Transition State” treat current theoretical concepts
and principles for the analysis and calculation of homogeneous reactions under the common term of “elementary
processes”. Some important and topical aspects such as
the pressure dependence of unimolecular processes or
problems o n energy transfer between and within molecules
are discussed in the following chapter which, however, is
mainly devoted to experimental examples from the stand[*] Cf. Angew. Chem. 73 (1961) 719.
Angew. Chem. Int. Ed. Engl. 21 (1982) No. 10
point of interaction between theory and experiment. This
is followed by the treatment of neutral and ionic reactions
in solutions. Formal and experimental aspects of composite reaction pathways are the subject of the next chapter,
o n “Complex Reactions”. A longer chapter deals with homogeneous catalysis, and finally with chain reactions
and-only very briefly-with photochemistry.
The text is unfailingly very clear and comprehensible
and, with about 800 references (up to 1980!), it is prepared
carefully with an eye to further study. The idea of communicating basic principles and central results so plainly that
the reader acquires a sound basis for direct independent
applications is everywhere in evidence. Thus, there are
sound discussions on the prerequisites (e.g. the theory of
the transition state or the concept of the steady state) and a
detailed notation of equations and their derivations are
given. All this is most helpful to the user. The high degree
of balance between theoretical explanations and application-oriented preparation makes the book particularly suitable for the experimental scientist, even if only a potential
one. Of course, one could always criticize this or that detail, but such objections pale into insignificance in comparison with the sheer solid worth of the book.
Summarizing, this new edition of “Kinetics and Mechanism” can be recommended without any reservations to
the advanced student and to the practising scientist who
from inclination or necessity wants a new general account
and concrete access to kinetics. Those already experienced
in kinetics will find it useful as a handy and rapidly accessible work of reference.
Klaus Luther [NB 567 IE]
Structure and Bonding in Crystals. Volume 1. Edited by M .
O’Keefe and A . Navrotsky. Academic Press, New York
1981. xviii, 327 pp., bound, $ 48.00.
This is the first of two volumes containing the material
of a conference on solid-state problems. It comprises 13
chapters-writen by 17 authors-each giving a unified account of one aspect of the solid state. The book must be
praised for its sturdy appearance and many references, the
latter enabling the interested reader to learn more about
the background and the problems associated with the 13
797
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