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Book Review Mature Methods Chemistry of Non-Stoichiometric Compounds. By K. Kosuge

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Mature Methods
Chemistry of Non-Stoichiometric
Compounds. By K. Kosuge. Oxford
University Press, Oxford, 1994.
262 pp., hardcover E 55.00.-ISBN 019-855555-5
In this monograph Koji Kosuge, Professor of Solid-state Chemistry at Kyoto
University, reviews a subject that is of
fundamental importance to chemistry, It
is only through understanding theinternal
processes of solid materials, i.e. the nature
and behavior of the relevant particles or
chemical stimuli, that one can apply
chemistry to solids in analogy to the successes of the acid-base or redox concepts
of “wet chemistry”. The appearance of a
book on this subject is therefore to be welcomed. Regrettably, however, it does not
succeed very well in its aims.
The choice of topics seems promising at
first. The starting point is the thermodynamics of mixtures, which is then applied
to the equilibrium of defects, first in dilute
systems, then in more concentrated systems. and finally in those that deviate
greatly from the concentration of the ordered phase. However, there is no treatment of chemical diffusion. (In this book
the term “diffusion coefficient” is used
only in the sense of a tracer diffusion
coefficient.) The last chapter can be recommended. dealing with extended defects, shear structures, Vernier structures,
micro-twin structures, intergrowth structures, and adaptive structures, and containing a wealth of information that is
chiefly useful to the chemist interested in
crystallography. Unfortunately high-temperature superconductors. which would
have nicely completed this chapter, are
not covered.
The first of the three chapters, making
up at least half the book, cannot be recThis scction contains book reviews and a list of
new hooks received hy theeditor. Book reviews are
written by invit;ition from the editor. Suggestions
for books to be reviewed and for book reviewers
are welcome. Publishers should send brochures o r
(better) books to Dr. Ralf Baumann. Redaktion
Angewandte Chemie. Postfach 1011 61. D-69451
Weinhein]. Federal Republic ofGermany. The editor reserves the right of selecting which books will
be reviewed. Uninvited books not chosen for
revie% will not bc returned.
ommended. There are numerous inaccuracies and errors which will spoil the pleasure of reading the book. A few examples
The nomenclature is not in accordance
with conventions in the literature. Moreover, there is confusion between absolute
and relative charges. and worse still, the
symbols for these are confused. On page 45
the regular electronic state is denoted by
“eh”, whereas on page 85 it is correctly
identified by the symbol “0” in the building elements notation. In the case of ionic
equilibria a mixture of structure elements
and building elements is used. The introduction to chemical equilibria and the
configurational enthalpy (Ch. 1.2) is
clumsy and often inaccurate. One could
perhaps tolerate the frequent switching
between differences and differentials. but
not the identification of -(AGo-AG)/RT
as an equilibrium constant. In the discussion of the formation of defects (p. 18)
there is no mention of the vibrational entropy, which has an important influence
on the free enthalpy of formation, especially in high-temperature chemistry. The
fact that the temperature dependence of
the equilibrium constant for the bandband transition is determined by the band
gap is explained by the following curious
statement: “The rate of ionization is believed to be roughly equal to that of the
dissociation of water . . . and therefore we
put [eh] = 1 .” (?).This is just a small selection. The most annoying aspect of the
errors is that they destroy the reader’s
faith in those parts of the text that are
properly written.
Joachim Maier
fur Festkorperforschung
Stuttgart (FRG)
Principles of Electron Spin Resonance. (Physical Chemistry Series.)
By N . M . Arherton. Ellis H o r w o o d ,
Chichester, 1994. 585 pp., hardcover
$ 127.00.-ISBN
0-1 3-721762-5
This book is a revised and updated version of ESR--Theory and Applications
which appeared in 1973, and the change in
the title reflects the author’s aim of placing greater emphasis on the fundamentals
of ESR spectroscopy. Rapid changes are
currently occurring in the experimental
methods used in ESR spectroscopy,
summed up by the key phrase “pulsed
ESR spectroscopy”, opening up entirely
new possibilities in time-resolved and
multidimensional measurements. In turning back to basic principles at this time the
author is tapping a great potential but also running some risks.
As is to be expected for a method that
has reached maturity, the literature contains a wide variety of notations for the
treatment of special cases, making it difficult for students and users to relate the
techniques to their specific problems by
analogy with methods that are already familiar. Here we undoubtedly find one of
the strengths of the book. as the author
consistently treats spectral calculations
and relaxation processes at a level suitable
for the average reader. He also helpfully
“translates” even very recently published
papers, so that the reader who works consistently through the book gains a comprehensive insight into topical problems.
However, the discussion of the possibilities opened up by pulsed ESR spectroscopy is less successful. Only 80 pages
are devoted to recently developed methods such as pulsed ENDOR, 2 D ESR
spectroscopy, and optical spin polarization, and these are treated essentially at an
introductory level, in contrast to the first
ten chapters (440 pp.) which deal with
continuous-wave (CW) forms of ESR and
ENDOR spectroscopy, explaining their
capabilities and describing many examples of a nontrivial kind.
A work that has the word “principles”
in its title invites comparison with other
books that make similar claims. Examples
are: Principles of Magnetic Resonance in
One and Two Dimensions (Ernst. Bodenhausen and Wokaun), Principks of Magnetic Resonance (Slichter), Principles of
Nuclear Magnetism (Abragam). and EPR
of Transition Ions (Abragam and Bleaney),
all of which undoubtedly have the character of handbooks. In my view the
present book is instead more accurately
described as a “comprehensive introduction”, although this classification in no
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