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Book Review Photodissociation of Simple Molecules in the Gas Phase. By H. Sato

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which does not overload the reader with irrelevant details, is
one of the highlights of the two volumes, as also is the account by Barthelat and Durand of the theory of the effective
Hamiltonian operator. Such operators provide the theoretical basis for calculations on heavy atoms, and consequently
their importance can hardly be overstated. Such a readable
and full account of this topic is unlikely to be found elsewhere.
Other topics treated in these two volumes include mathematical fundamentals, atomic scattering experiments, biochemistry. quantum electrodynamics, N M R spectroscopy,
statistical mechanics, models of liquids, superconductivity,
crystal physics, and metallurgy. However, these topics are so
far removed from the title of the work that it is not possible
to review them here. Paradoxically, in contrast to this one
searches in vain for contributions on modern semiempirical
methods of calculation. It is unfortunate that readers interested in computational chemistry will have to load their
bookshelves with so much ballast in order to have access to
the few articles that are relevant.
RudoCf‘Janoschek
Institut fur Theoretische Chemie
der Universitlt Graz (Austria)
Photodissociation of Simple Molecules in the Gas Phase. By
H . Sato. Bunshin, Tokyo, 1992. V, 158pp., paperback
Yen 1100. -ISBN 4-89390-092-7-C3543-P1100E
For some years now H. Sat0 of Mi’e University has been
monitoring the literature on photodissociation processes of
small molecules in the gas phase, and at annual intervals
people interested in this field have received from him a booklet listing publications during the past year. All these references covering the years from 1970 to 1991 have now been
collected together into a book. This is the period that has
seen the laser become firmly established as a tool for photolytic studies and analysis. The book consists of two tables,
together with an associated list of over 1000 references. Altogether the compilation covers about 280 simple molecules
and more than 70 van der Waals molecules. Recently the
survey has also included organometallic compounds that are
of importance in chemical vapor deposition studies. The
structure of the tables is very simple, with entries listing the
initial molecular species, the photolyzing wavelength (or
generating source), method used to identify the breakdown
fragments, and final products, as well as the literature citation and a few brief comments. The entries are arranged
according to the initial species.
This is not a textbook, nor is it a monograph along the
lines of H. Okabe’s book Photochemistry of Small Molecules.
As Okabe notes in the foreword, it has more in common with
the much costlier spectroscopic data collection Constants of
Diatomic Molecules, by Huber and Herzberg. It is a book to
refer to when one is setting out to photolyze a new molecule
and wishes to find out what relevant work has been published recently. Thus it is intended for the active researcher,
for whom it can be thoroughly recommended. In my own
laboratory the booklets that were its forerunners have
proved invaluable when planning experiments. I would like
to have these data available on a floppy disk, which should
also make it possible to search according to reaction products.
According to the publishers, the price, including postage,
is $17.50 in the USA and $19.50 in Europe. I have just
learnt from Dr. Sat0 that Supplement VI of his collection
“Photodissociation of Simple Molecules in the Gas Phase”
Ai?,qiw. C’hem.
In[. Ed. EngI. 1993, 32. No. 4
has been published in Research Reports of the Faculty of’
Engineering, Mi’e University, Vol. 17, December 1992.
Friedrich Stuhl
Fakultat fur Chemie
der Universitat Bochum (FRG)
Entropy Analysis. An Introduction to Chemical Thermodynamics. By N . C . Craig. VCH Publishers, New York/VCH
Verlagsgesellschaft, Weinheim, 1992. XI, 208 pp.. hardcover D M 72.00.-ISBN 1-56081-539-613-527-89539-6
This book aims to provide students in their first semester
with an introduction to thermodynamics along new lines.
The author sets out to develop the fundamental laws of
thermodynamics from a global perspective instead of the
usual system-orientated viewpoint. As the title of the book
indicates, the treatment focuses on entropy as the key variable, since the first law (the conservation of energy) can be
regarded as being automatically fulfilled from the global
standpoint. The book consists of ten chapters and an appendix. After an introduction the author deals with the fundamental principles of thermodynamics (the first law, the
concept of enthalpy, the second law), then with their application to heat engines, the molecular significance of entropy,
applications to chemical reactions (the definition of the
Gibbs energy, chemical equilibria, electrochemical reactions), and the interconversion between different forms of
energy. Each chapter ends with a detailed summary of its
contents. The appendix consists of four sections. The first
short one (three pages) discusses the relationship between the
global and system-orientated approaches to thermodynamics. Two further sections contain examples to illustrate the
interpretation of the proposed concepts from the molecular
(microscopic) point of view. The last section consists of
30 pages of tables listing standard enthalpies and entropies
of formation and Gibbs energies, and specific heats of the
elements and of more than a thousand compounds, mostly
inorganic.
The global approach chosen here undoubtedly has advantages in some parts of the subject. For example, it is found
that beginners often have great difficulty with problems
where, in order to apply the second law, one has to combine
the “system” and the “surroundings” to form a new “supersystem”. The global approach avoids the complications associated with systems that are not closed. Also the description of irreversible processes is simplified. The introduction
of the molecular significance of entropy at an early stage is
a welcome feature.
However, the author incurs a penalty for his approach,
since for each process he has to consider a number of systems, each with its own internal energy. The first law takes
the form:
AU,,,,,
=
AUv
+ AU8 + AU,,+
... = 0
in which the suffix o denotes the reacting system under consideration, e denotes a heat reservoir system, and wt a
mechanical system. These systems are illustrated by diagrams. The processes that are analyzed involve an exchange
of energy between the partial systems. However, in physical
terms this compartmentalization often breaks down; to take
the simple case of an exothermic reaction in solution, the
latter is also the heat reservoir. This is an abstract idea that
the beginner will not always find easy. The fundamental
difference between the internal energy as a state function on
the one hand, and on the other hand the concepts of work
VCH Verlagsfiesellschufi mhH. W-6940 Weinheim, 1993
0570-0833/93/0404-062f$ 10.00i ,2510
621
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