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Book Review The Electronic Structure of Molecules. A New Approach. By J. W. Linnett

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edition had to be virtually a new book. It deals wholly with
new reagents and new applications in conventional analysis.
In the volumetric field, many new indicators are described,
in particular selective metal indicators. Gravimetric analysis,
partition methods, and spectrophotometry are also enriched
by new selective reagents, most of which are organic.
The new reagents and m thods are critically compared on
the basis of their analytical use and their advantages and disadvantages. Although a selection of this nature must necessa ily be subjective, so that the reader may not agree with the
author as to the best method., the book nevertheless fulfils the
function of bringinguseful new developments to the attention
o f t h e analys This book is even more welcome in that the
many progress reports on instrumental analysis often blind us
to the fact that there have been Just as many important new
developments in conventional analytical methods.
A systematic literature search for new methods appears to
have been carried out only for the period up to 1959, but a
number of publications in English, particularly in the authors’
own field, published up to 1963 have also been reviewed.
F. Umlnnd
[NB 414/286 IE]
The Electronic Structure of Molecules. A New Approach. By
J . W . Linnetr. Methuen & Co. Ltd., London and J. Wiley &
Sons IN., New York, 1964. 1st Edit., VII
167 pp.,
7 tables, 25 illustrations, E 1.5.0.
This book is evidently intended for undergraduate chemistry
students, and gives a very clear and easily understandable
introduction to the theory of the electronic structure of
molecules. Starting with sections on electrons and atoms,
and on the chemical bond, it deals with diatomic and other
small molecules, organic molecules and reactions, free
radicals, inorganic compounds containing elements of the
higher periods, and electronically excited states.
However, the reviewer would hesitate to recommend this
fine booklet to the beginner, simply because the approach
is very personal and one-sided. based on J. W. Linnert’s
suggestion that the Lewis octet should be regarded as a
double cpartet, i.e. the electrons with E spin should be
reg ded as practically independent of those with p spin.
This hypothesis is presented with striking consistency and
with surprisingly good results, but the connection with conventional methods of quantum chemistry (the MO and VB
methods) remains unclear. However, those who are familiar
with these methods will benefit greatly by perusal of this
book. The only regret is that the possibility of a mathematical
formulation of wave functions on the basis of the qualitative
ideas discussed is only touched upon in the closing paragraphs
of the last cliaptcr.
M. Klessinger [NB 4161288 IE]
Electrons and Chemical Bonding. By H . B . Gray. W. A. Benjamin Inc., New York-Amsterdam, 1964. 1st Edit.,
XIV + 223 pp., numerous illustrations and tables, paper
S 4.35, cloth S 8.80.
The quantum-mechanical treatment of atoms and molecules
has led to the development of ideas that are extremely
helpful to the chemist in the discussion of the structures and
reactivities of compounds, and which are indispensable for
the interpretation of the results obtained by the physical
methods that are becoming increasingly important in
chemistry. It is also becoming increasingly important,
therefore, that the chemist should familiarize himself with
these ideas right at the beginning of his training.
This is the purpose of H . B. Gray’s book, which is based on a
course of lectures for beginners. This book, with its 132 twocolor illustrations and 31 tables, gives an extremely lucid
introduction to the electronic theory of the chemical bond.
It contains nine chapters, and covers atoms, diatomic, linear
triatomic, planar trigonal, tetrahedral trigonal, pyramidal
and angular triatomic molecules, organic nelectron systems,
and bonds involving d-electrons. The purely qualitative discussion is based mainly on the MO theory, which is used
consistently, even for molecules such as CH4 and inorganic
complexes. For this reasan concepts such as “hybridization”
and “lone pairs pf electrons” are only touched upon, and it
is not clear \\thy the overlap can be used as a measure of the
strength of a bond, even though it is neglected in all of the
derivations. N o differentiation is made between VB structures
and localized molecular orbitals. A particularly good chapter,
on the other hand, is that dealing with bonds involving delectrons, which provides a good introduction to the theory
of inorganic coordination compounds. The book contains
very few printing errors or instances of vagueness in the text.
M . Klessinger
[NB 417/289 IE]
Acid-Base Equilibria. By E. J . King. The International
Encyclopedia of Physical Chemistry and Chemical Physics.
Edited by E. A. Guggenheim, J. E. Mnyer, and F. C. Tompkins. Volume 4/15. Pergamon Press. Oxford-LondonEdinburgh-New York-Paris-Frankfurt 1965. 1st Edit.,
X1 341 pp., € 6.0.0.
“Acid-Base Equilibria” is published as part of the “lnternational Encyclopedia of Physical Chemistry and Chemical
Physics”, which comprises about 100 volumes. However, the
present volume is complete in itself, and may be used independently of the other volumes. A more fitting title might
have been “The Physical Chemistry of Acid-Base Equilibria”.
The volume is intended for the reader who wishes to make an
extensive study of acid-base equilibria, and presupposes a
certain knowledge of thermodynamics and of the theory of
electrolytes. In five chapters the author gives a n excellent
introduction to the theoretical principles of the determination
of acidity constants (arranged according to the method of
determination). In the course of a comprehensive discussion
of the p H concept, he rightly points out that in spite of
notable advances in instrumentation, the p H value remains
an essentially empirical parameter. The relationships
between structure and acidity are dealt with rather briefly.
The author evidently recogniLes that the data available at
presem cannot be explained by a few neat thermodynamical
equations. Subsequent chapters are concerned with the effect
of pressure and temperature, the behavior of polyfunctional
compounds, and equilibria in non-aqueous solvent systems.
The author deliberately omits any discussion of analytical
aspects or of acid-base equilibria in melts.
The author has succeeded in giving a very readable account
of the physical chemistry of acid-base equilibria, taking into
account data from the literature up to 1963.
W. Simon [NB 419/291 IE]
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Q 1966 by Verlag Chemie, GmbH. - Printed in Germany by Druckerei Winter, Heidelberg.
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Angew. Chem. interrtat. Edit.
Vol. 5 (1966) 1 No. 2
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structure, book, approach, electronica, linnett, molecules, review, new
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