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Book Review Grundzge der anorganischen Kristallchemie. Mit einer Einfhrung in die Theorie der chemischen Bindung (Fundamentals of Inorganic Crystal Chemistry. With an Introduction to the Theory of the Chemical Bond). By H. Krebs

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BQOK REVIEWS
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
welcome.
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
746
(isopolar) transition states are then given 50 and 60 pages
respectively.
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
reactions.
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
material has been subjected to highly judicious pruning so as
to preserve clarity and facilitate understanding of the seemingly boundless data. The form and arrangement of the
individual sections (atomic structure; bond systems and their
utilization; description and explanation of the structures of
elements, binary and ternary compounds, alloys and glasses)
are novel and are completely subordinated to the chemical
problems involved in structural geometry, stoichiometry,
and bonding.
A drawback of the book is the scant treatment given to metals
and intermetallic phases. One also notes the total absence of
complex compounds in the narrower sense. This despite the
fact that, in view of the selected framework, the structures of
thesesubstances would have been of considerable importance.
Furthermore, t o the quantum chemist the facts may appear
t o be clear and understandable - but is this in fact the case?
H.-G. v. Schnering [NB 891 IE]
Enamines. Synthesis, Structure, and Reactions. Edited by
A . G. Cook. Marcel Dekker Inc., New York-London 1969.
1st ed., xi, 515 pp., numerous formulas and tables, $ 35.75.
The first review of enamines (113 pp.) was written in 1963 in
“Advances in Organic Chemistry” by a single author, J.
Szmuszkovicz. The present second review, which is also the
first book o n enamines, has eight authors, each of whom
contributed a self-contained chapter.
In the first chapter, “Structure and physical properties of
enamines” (54 pp.), S. K. MaIhotra discusses the influence of
steric and electronic factors, taking the cyclanone enamines
as examples. Only a little information is found o n the other
enamines in the short sections o n IR-, UV-, mass-, and
particularly NMR-spectroscopy. N o coupling constants or
chemical shifts of RzN-CH=,
vinylogous amides, dienamines, enediamines, ketene aminals, and immonium salts or
comparisons with the values for other nucleophilic olefins
are given here.
The second chapter (46 pp.). “Methods and mechanisms of
enamine formation” by L . W. Haynes, is mainly confined to
tertiary enamines with no functional groups. An excellent
survey is presented, though the fundamental work by S u e r
and Prahl o n the cis,trans isomerism of the enamines deserves a more detailed (and more positive) discussion.
The third chapter (13 pp.), “Hydrolysis of enamines” by
E. J. Stamhuis, presents a thorough discussion of the kinetics
and mechanism of the hydrolysis as a function of the p H
value and the structure of the enamine. It shows how the
C-protonation, as the rate-determining step, is replaced with
decreasing p H by the hydration of the immonium ion and
then by the decomposition of the amino alcohol.
In the fourth chapter (54 pp.), “Electrophilic substitutions
and additions to enamines”, G . H. Alt discusses protonation,
alkylation, acylation, and reactions with other electrophiles,
all reactions that reappear in other chapters. This is only
observed later; too late, many readers will think, as they
bemoan the lack of coordination. Following the demonstration, by many examples, of the close relationship of electrophilic substitutions and additions with cycloadditions, it
would perhaps have been better t o consider these reactions
together in one large chapter. Mention should be made of
the improbable formulation of the reaction with acrolein
Cpp. 128,429) and to exceptions (ref. 22) t o 0-protonation
and 0-alkylation of the acetylacetone enamines.
J. V. Paukstelis gives a very good, concise review of “Nucleophilic addition to iminium salts” in the fifth chapter (41 pp.).
I n the sixth chapter (42 pp.), “Cycloaddition reactions of
enamines”, A. G. Cook surprises the reader with his liberal
interpretation of the term “cycloaddition” and by his failure
to include orbital symmetry considerations. H e assumes a
two-step mechanism for all cycloadditions, and this is
probably why he is rather sparing with formulated mechanisms and with formulas in general. The range of addends
Angew. Chem. internat. Edit. / Vol. 9 (1970) J No. 9
includes not only alkenes, alkynes, cumulenes, 0 2 , isobenzofuroxane, carbenes, carbenoids, and 1,3-dipoles, but also
cyclopropanes, cyclopropenes, aziridines, quinones, c u m u enes + S , and cumulenes + isocyanide.
In the lengthy seventh chapter (60 pp.), “Heterocyclic enamines” by 0. C’ervinka, the preparation, structure, properties, and reactions are followed by a section on aldol reactions
of heterocyclic enamines and their importance to the biosynthesis of alkaloids.
The eighth chapter (156 pp.), “Enamines in organic synthesis”
by M. E. Kuehtze, is a n excellently written survey. It is
characterized by equations in the short form without numbering, more formulas than text, and everything presented in a n
extremely concentrated manner, though even the most outof-the-way literature is covered. This chapter is recommended
to anyone who wishes a quick survey on enamines.
Rigorous dividing lines between the various chapters have
been deliberately avoided, with the result that a n unusual
amount of overlap occurs. Repetitions, which are quite
useful here and there in different contexts, become a problem
when e.g. alkylation and acylation are discussed in four
chapters, and cycloaddition in two chapters besides the
chapter devoted to this topic. The number of authors and
the number of pages reflect not only the rapid development
of enamine chemistry, but also the individual plan of the
book: “The objective of this book is to review and correlate
in depth the synthetic, mechanistic, and physical properties
of enamines. This has been done by surveying the field from
eight different perspectives. Since these prespectives have
certain common areas between them, and since i t seemed
desirable to allow each contributor to tell his story in its
fullest scope and in his own style, there is some overlapping
of material between the chapters. However, it is hoped that
the difference of viewpoints and context in which this
material appears in these chapters will provide the reader
with fresh insights and stimulate further research”.
This has led to a very comprehensive but readily readable
book.Variety is provided by the different styles of the authors.
However, what is a n advantage for reading is a disadvantage
for reference. Though searches are facilitated by detailed
author and subject indexes, it is usually necessary to refer t o
several chapters (in some cases with the same examples,
different nomenclature, and relatively many printing errors
and inaccuracies). Apart from the unnecessary overlapping,
however, the shortcomings are unimportant against the
abundance of information that is provided without verbosity.
The monograph is the most comprehensive review so far of
the preparation, structure, physical properties, and reactions of the enamines, mainly the simple enamines with n o
functional groups o n the double bond. The book is generously provided with formulas. Reaction mechanisms are
given in varying depths of detail. The literature is covered up
to 1968. There is no comparable book on the market, and
it is hoped that the price will not prove a n excessively severe
obstacle to its wide use.
Giinfer Opitz
[NB 883 IE]
Fuel Cells and Fuel Batteries. By H. A . Liebhafsky and E. J .
Cairns. J. Wiley and Sons, Inc., New York-LondonSydney-Toronto 1968. 1st ed., x, 692 pp., 190 figures,
3 tables, bound 258 s.
The book is subtitled “A Guide to Their Research and
Development”. This points out the main purpose of the
authors. They are not concerned predominantly with describing the present position of research and technology in the
field o n fuel cells, but with showing the reader how, i.e. by
what paths (and detours) this position has been reached,
where the main problems lie, and in what direction further
investigation seems necessary and worthwhile. This has led
t o a sort of textbook on battery research, and in fact a
textbook of electrochemistry. The first nine chapters (about
half of the book) deal with fwdamental electrochemical
747
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