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Book Review An Introduction to Physical Organic Chemistry. By E. M. Kosower

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The Virial Coefficients of Gases. A Critical Compilation.
By J . H . Dymond and E. B. Smith (Oxford Science Research Papers No. 2) Clarendon Press: Oxford University
Press, London, 1969. 1st Edit., xv i 231 pp., bound, 45s.
Knowledge of the virial coefficients of a gas is very important
both from the point of view of industrial applications and for
theoretical investigations. This compilation of virial coefficients available up to the beginning of 1968 is therefore most
The authors begin with a clear and concise introduction to
the power expansion of the equation of state for gases, and
explain the relationship between the virial coefficients and
intermolecular potential. In addition, they give formulas for
the calculation of the thermodynamic properties of gases
from virial coefficients (fugacity, internal energy, enthalpy,
molar heat, entropy, and Joule-Thomson coefficients).
The tables of the virial coefficients of gases stem from earlier
work by McGlashan dating back to 1955. The substances are
arranged according to the Chemical Abstracts system. The
search for a given gas is also facilitated by a list of contents
arranged according to chemical formulas, as well as an alphabetical one arranged according to the common names.
The publications from which virial coefficients can be determined are given in chronological order for each substance.
In most cases there is a brief note stating the method of’
measurement, the number of coefficients in the power expansion of the equation of state, the maximum pressure and
temperature region, and remarks on the accuracy of the
measurements and on the agreement between the latter and
the data published by other authors. This is followed by
tables of values for the second and, where possible, third
virial coefficient as a function of temperature, taken from the
original literature. The temperatures are always quoted in K.
The virial coefficients were always converted to the usual
dimensions of cm3/mole and cm6/mole2 (for the second and
third virial coefficients). Whenever results showing satisfactory agreement were available from several authors, a
smooth curve was drawn through all the measurements. The
literature data are preceded by the resulting virial coefficients
or “best values”, for which the estimated error is also stated.
This inclusion of “best” values together with the limits of
error, the critical remarks on individual literature data, and,
not least, the conversion of the data cited to the same
dimensions, make Dymond and Smith’s book a valuable tool
for everyone engaged in the study of real gases and interKlaus Schafer WB 890 IE]
molecular forces.
An Introduction to Physical Organic Chemistry. By E. M .
Kosower. Wiley and Sons, Inc., New York-London-Sydney
1968. 1st Edit., xvi, 503 pp., numerous figures and tables,
115 s.
Once more an American author presents a book on a topic
that, since the appearance of Hammett’s “Physical Organic
Chemistry”, should be represented in the library of every
chemistry student. The successful textbooks o n this subject
so far concentrate either on a comprehensive discussion of
reaction mechanisms (Hine, Gould) or on the detailed description of methods ( Wiberg, Streitwieser).
E . M . Kosower includes his introduction in the first group
and divides it into three parts: 1. Substituent effects (250 pp.),
2. Solvent effects (120 pp.), and 3. Intermediates and unusual
moIecuIes (70 pp.).
In the first part, the acidity of organic compounds and the
substituent constants are dealt with first under the heading
“Polar Transition States” (1 30 pp.). Reaction mechanisms
follow in the sections on nucleophilic substitution and
carbonium ions. The reactions with free-radical and apolar
(isopolar) transition states are then given 50 and 60 pages
The treatment of the various fields is right up to date if one
considers the year of publication of the book (the references
extend up to 1967). Thus cycloadditions and rearrangements
are discussed in the light of the Woodward-Hoffmann rules.
Considerable space is also devoted to the discussion of
carbonium ion chemistry and of free-radical reactions.
However, the text is incomplete in other respects. Reactions
of the carbonyl group are practically ignored. Thus one will
search in vain for the aldol condensation and the Wittig
reaction to name only two examples. As for aromatic substitutions, only the nucleophilic variant is mentioned to
illustrate solvent effects. No mention is made of elimination
reactions, electrophilic substitutions, or a large number of
rearrangements that do not proceed concertedly.
The best rounded-off part of the book is undoubtedly the
chapter on solvent effects. The reader is familiarized here
with the significance and the problems of this field, which is
very important to our deeper understanding of chemical
Finally, the third part of the book is not satisfactory. Here
we again find more or less detailed discussions of carbonium
ions, carbanions, and free radicals, which should really have
been included in the first part. Thus the temperature-dependent NMR spectrum of the norbornyl cation appears on
p. 410, whereas it is discussed on p. 137. Carbene chemistry,
which is sought in vain in Part 1, is dealt with here in 15 pages.
A few “unusual” molecules are shown in a diagram, but are
not discussed further.
In the reviewer’s opinion, the book is unsuitable as an introduction, since it omits many important reactions. On the
other hand, it offers stimulating reading for the advanced
reader. The detailed discussion of solvent effects is very
welcome, and the introduction of a new nomenclature for
substitution reactions that takes into account the reaction
mechanism (with or without intermediate) deserves discussion. The use of the term “methylenoid” instead of
“carbenoid”, on the other hand, seems less successful.
Results of spectroscopic studies are mentioned in gratifying
numbers. In view of the large volume of material, it has not
always been possible to describe the methods mentioned in
detail, so that references to relevant monographs were
essential. A detailed grounding of the Woodward-Hoffmann
rules would however have been welcome (the non-crossing
rule is not mentioned). The book is excellently presented,
and 184 examples for practice provide an opportunity
reinforcing what has been read. The figures are also clear
throughout. In the graphical representation of qualitative
Hiickel-molecular orbitals (pp. 204, 206), however, the
electrons should not have been added as dots at discrete
points of the wave function.
Harald Gitnther
D B 879 IE]
Grundziige der anorganischen Kristallchemie. Mit einer Einfiihrung in die Theorie der chemischen Bindung (Fundamentals of Inorganic Crystal Chemistry. With an Introduction to the Theory of the Chemical Bond). By H . Krebs.
Ferdinand Enke Verlag, Stuttgart 1968. 1st Edit., xii
376 pp., 254 figures, 41 tables, bound DM 45.-.
A wide readership should derive benefit from this excellent
introduction to the problems of crystal chemistry. The subtitle gives an indication of the broad area which the author
sees as relevant to crystal chemistry (one third of the book).
Such a framework does, of course, mean that much appears
in unconventional presentation, but the logical application
of quantum-chemical theory to a few types of structure is
extremely valuable to those interested in this subject. The
Angew. Chem. internat. Edit. / Vol. 9 11970) / No. 9
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