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Book Review Physical Organic Chemistry. By K. B. Wiberg

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Colloidal Surfactants. Some Physicochemical Properties. By
K . Shinoda, T. Nakagawa, B. Tamamushi, and T. lsemura.
Physical Chemistry. A Series of Monographs, Vol. 12.
€dited by E. Hutclzinson and P . van Rysselberghe. Academic Press, New York-London 1963. 1st Edit., 310 pp.,
numerous figures and tables, linen, $11.50.
This book is divided into four sections dealing with I . the formation of micelles, 2. physicochemical studies in aqueous solutions of nonionic surfactants, 3. adsorption phenomena, and
4. monomolecular layers.
In parts 1 and 2, an extensive discussion is given of micelle
formation, the critical micelle concentration (CMC), and
the various factors effecting this concentration (e.g. the
structure of the surfactant, additives, or mixtures of surfactants). This text is based on a particularly broad review of the
literature. In part 3, the fundamentals for calcuiating adsorption and the influences on adsorption at air/solution, solution/
oil, and solution/solid interfaces are dealt with. Also some
special aspects of adsorption are described, viz. the adsorption at a solution/mercury interface and the interaction between surfactants and hydrophobic or hydrophilic colloids. In
part 4, the behavior of films of surface-active compounds and
polymers, particularly synthetic polymers, is discussed.
K . Shinoda and his colleagues have successfully evaluated recent literature in order to give a review mainly of micelle formation and adsorption phenomena from the standpoint of the
physicochemical properties of surfactants, paying particuIar
attention to Japanese publications. Many important research
communications in this field were written in Japanese and
were thus difficultly accessible to scientists in other countries.
P . Kurzendorfer
[NB 340/198 IE]
is given. There are several hundred - occasionally very
difficult - questions and exercises interspersed in the text,
which can only be answered by proper application and combination of these principles, not by unconnected knowledge of
facts. These “Problems” often go beyond the material dealt
with in the hook. This raises a problem only when the answers to such questions are essential for a n understanding of
the subsequent text or when important reactions appear only
in the exercises (e.g. sugar extensron or sugar degradation reactions or peptide syntheses with carhodiimides).
There is very little fault to be found with the excellently illustrated text: the bridged bromonium radicals rejected on p.
189 have been positively detected in the meantime by Skell;
the preference of a two-step mechanism for the Diels-Alder
reaction is not necessarily correct (p. 268) ; the intermediates
ofthe Bucherer reaction (p. 909) are tetralonesulfonic acids
and not bisulfite adducts of the keto form of naphtholes ( A .
Rieche 1960); Goldschmidt’s 9-chlorophenanthroxyl (p. 916)
does not give an electron spin resonance signal and is probably a dimeric quinol ether (E. Mufler 1959).
This didactically outstanding textbook can be heartily recommended to every student of chemistry and to chemists who
wish to refresh or renew their knowledge. It should be especially worthwhile for beginners to work through the not altogether easy text alongside their organic chemistry courses.
0. Riichardt
[NB 379J237 IE]
Basic Principles of Organic Chemistry. By J. D . Roberts and
M. C. Caserio. W. A. Benjamin, Inc., New York-Amsterdam 1964. Ist, edit., XXV + 1315 pp., numerous figs.
and tables, clothbound S 15.30.
This book is a successor to the 1935 edition of “Organic
Chemistry” by H . J. Lucas, and is no less original than its predecessor. Despite the conventional subdivision according to
substance classes, the authors manage to place the fundamental
principles of synthesis, structure and stereochemistry, honding
phenomena, and reaction mechanisms in the forefront of their
discussion. They also succeed in cleverly applying the latest developments in the subject in a didactic fashion without either
becoming unintelligible for the beginner or giving only superficial treatments. In all discourses on reaction mechanisms, they
carefully stress the pertinent experimental background.
The introduction t o spectroscopic methods in Chapter 2 is
particularly striking. Structure and bonding relationships
are given a solid theoretical foundation on the basis of
spectroscopic, thermochemical, and thermodynamic results.
Atomic and molecular orbitals are introduced critically
alongside the theory of resonance. The modern character
of the book is emphasized by its chapters o n the biogenesis
of terpenes and steroids, color photography, organic photochemistry, polymers, and organosiIicon, organophosphorus,
and organoboron chemistry, efc. No important facet of
organic chemistry has been overlooked.
The authors have successfully introduced a subdivision
according to reaction types subordinate to their main
division according to compound classes. For the compound classes, the modes of preparation are given only
in tables, and a detailed discussion of their scope, the
reaction conditions, and synthetic importance Is then to
be found under the reaction type. Thus, for example, “Aliphatic Substitution and Elimination” are to be found in the
chapter on alkyI halides, and “Addition Reactions” under
alkenes. Reaction mechanisms are always given if they are
required t o contribute to a n understanding of the reaction.
A separate index of methods of preparation of all classes of
compounds shows how much importance the authors justifiably attach to adequate training in methods of synthesis.
The length of the book is not caused by a n excess of material,
but by the thorough discussion of essential principles that
The valuable series on “Advances in Organic Chemistry”
continues with this third volume, which contains four
review articles. The first contribution by R . I. Reed o n
“Mass Spectrometry as a Structural Tool” discusses the most
important applications of mass spectrometry to structure
elucidations (74 pages). The literature is reviewed effectively
only until 1959; since then, good monographs o n this subject
have appeared, which also take the latest rapid developments
into account. However, the reviewer does not claim to be an
expert judge in this field.
The next essay by D . M. Brown on “Phosphorylation” gives
a surprisingly comprehensive survey in 83 pages. Such a
complete review of this subject was hitherto not available.
The report is critical and comprehensive, easy to read and
well organized. The fact that it will nonetheless not always
be easy for the newcomer to this field to find the most
suitable phosphorylation methods for his purposes by mere
perusal of this article, is probably due to the complicated
nature of the phenomenon of phosphorylation.
The following articles by R. A . Boissonnas on amine protecting groups for peptide syntheses (31 pp.) and by J. F. W.
McOmie on “Protective Groups” (103 pp.) fully discuss
these topics without any significant overlapping. The review
by McOmie is especially interesting and contains a wealth of
information: it was a n excellent idea of the editing committee
to include articles containing a review of all protective groups.
The series, particularly Vol. 3, belongs in every chemiF. Cramer
[NB 356/214 IE]
cal library.
614
Advances in Organic Chemistry: Methods and Results. Edited
by R . A . Raphael, E. C.Taylor, and H . Wynberg. Vol. 3.
Interscience Publishers, a Division of John Wiley & Sons,
New York-London 1963. 1st edit., 333 pp., several illustrs.
and tables, linen E5.5.0 (about S 14.50).
Physical Organic Chemistry. By K . B. Wiberg. John Wiley &
Sons, Inc., New York-London-Sydney 1964. 1st Edit.,
VIII f 591 pp., numerous illustrations and tables, linen,
E 4.0.0 (about S 11.00).
In the foreword to this book, K. B. Wiberg says that he has
made a n attempt to write a useful textbook which concentrates on the physical- chemical aspects of “Physical Organic
Chemistry”. By this he means the theoretical background of
physical measurements on organic compounds, the mathematical treatment of experimental data, and the physical interpretation of empirical relations. This also includes the quantum-mechanical theory of the chemical bond, which is disAngew. Ciicm. iriterimt. Edit. J Vol. 4(1965) / No. 7
cussed together with electronic spectra and the theory of vibrational and nuclear magnetic resonance spectra in the first
section on “Bonding and Spectra”. The second section, “Equilibria”, deals with chemical equilibria and includes chapters o n the partition function, heats of formation, solvent and
isotope effects, linear free energy relationships, and acidity
functions, etc. The third section, entitled “Kinetics”,
first describes methods of determining the rate constants and
rate laws from kinetic data and then discusses the absolute
rate theory, kinetic isotope effects, the influences of solvents,
linear free energy relationships, and acid catalysis. The book
closes with a long appendix containing tables, a discussion of
the mathematical treatment of N M R spectra and kinetic data,
and a n introduction to programming for electronic computers, together with a collection of Fortran programs for the
problems dealt with in the book. “Physical Organic Chemistry” is expressly written as a textbook and therefore does
not attempt an exhaustive compilation of the publications
that have appeared on individual fields; instead, the methodology is explained by means of carefully selected examples,
which are given a detailed treatment. Each chapter is rounded
off with problems and reading lists.
This brief description of the contents suffices to show that precisely those borderline fields are dealt with which are essential
for understanding many publications but which still receive
only little attention in textbooks and lecture courses. From this
point of view the attempt to write a useful textbook has been
highly successful. The value of the book is not impaired by the
relatively large number of misprints and by a n occasionally
subjective selection of material (e. g. the somewhat one-sided
presentation of the arguments of Dewar and Schmeising on
the delocalization of x-electrons). Unfortunately, however, the
book is rather unbalanced and at times didactically inadequate, as the following examples indicate, which could easily
be multiplied.
In the chapter on vibrational spectra, the terms normal modes,
degenerate vibrations, and parallel and perpendicular type
bands are applied without being explained. Methods are
given for calculating the spectrum of an A2X2 spin system,
but the definition of an A2X2 system is sought for in vain.
Frequently (e. g . o n pp. 5 , 215, and 453), at the vital point
in a detailed mathematical derivation, the next step is introduced merely by “it can be shown that.. .”. On p. 16,
the same symbol is used within a single formula with two
different meanings. On p. 28, the text and the figure and on
p. 420 the text and the table d o not agree. The equations
are not numbered, and thus the text is sometimes hard to
understand and cross-references become difficult. Factual
errors occur, for example, on p. 116, where it is stated that
the integral (1 1/12) disappears when using orthonormal orbitals, but this is only true when applying the Mulliken approximation, which is not mentioned. On p. 453, it is stated:
“The properties of determinants deduced previously (e. g . by
multiplication of a row or a column with a factor, the determinant is multiplied by this factor) also apply to matrices”.
Most of the inaccuracies and broken trains of thought could
be remedied, and the missing definitions could be included
without increasing the size of the book if the figures o n pp.
29-35, etc. were reduced to reasonable dimensions and if the
appendix were shortened: Especially since it is assumed that
the reader makes use of electronic computers, 24 pages with
tables of the thermodynamic functions of a harmonic oscillator and 13 pages of overlapping integrals are superfluous,
when other sections are kept so brief (e. g . the treatment of
symmetry by the group theory is restricted to 3 pages!) that
they must necessarily remain incomprehensible without reverting to further literature.
One would like to see as many students as possible acquainted
with the material presented here. The book should therefore
be strongly recommended. UnfortunateIy, however, the reader
must be willing to take the trouble that the author should have
invested in order to develop this book into a r e a l l y u s e f u l
text. It can only be hoped that a completely revised edition
M. Klessirtgrr
[ N B 3411204 I € ]
will s3on appear.
Aitgew. Clzern. internat. Edit. 1 Vol. 4 (1965)
1 No. 7
Radiolysis of Hydrocarbons. Edited by A . V. Tupchiev. English
edition edited by R. A . Holroyd. Elsevier Publishing Co.,
Amsterdam-London-New York 1964. 1st Edit., XI1 + 232
pp., 69 figures, 35 tables, linen, D M 36.- (about $9.00).
In the radiation chemistry of hydrocarbons, there are some
reactions, e. g. cracking, that are of preparative and technological interest. Kinetic studies are of particular importance
since they furnish information on the reactions of radicals, on
energy-transfer mechanisms, and on the influence of catalysts
on radiolytic reactions. Topchiev’s book goes into all of these
matters insofar as they have been investigated in the Institute
for Petroleum Research in the U.S.S.R. between 1957 and
1961. The book contains a lot of experimentat results and
theories on the radiation chemistry of hydrocarbons, and thus
gives an excellent survey of advances in the radiolysis of hydrocarbons in the U.S.S.R. up till 1961.
Radiation chemistry flourishes and fades with the rapid
changes in theoretical concepts, which in turn depend upon
the advances in molecular and radiation physics and in experimental methods. Topchiev’s book conveys the impression
of being dedicated especially to energy transfer. The phenomenon of energy transfer is demonstrated convincingly by electron spin resonance measurements on irradiated solid hydrocarbons containing minute amounts of an inhibitor which,
although immobile, reduces the radical yield. The author
presents a theory according to which inhibition occurs by
radiationless transfer before the energy of electronic excitation is converted into vibrational energy. The assumption
that this theory - which is developed in clear and precise mathematical terms - is generally applicable to inhibition
effects, even in liquid systems, appears to be hardly justified,
because of the complexity of radiochemical reactions.
Energy transfer from oxide catalysts to adsorbed hydrocarbon
molecules is also described in detail and formulated mathematically. Attention is drawn to the difference between energy
dissipation by fast charged particles in gases and in condens&d materials. For example, the principle of “collective” excitation which is occupying the theoreticians in radiation chemistry so much a t present, is anticipated by the discussion on
p. 113.
In concluding it can be said that although some ofthe material
presented is probably already superseded by newer results because of the rapid development in this field of research, Tupchiev’s book contains many ideas on the theory of radiation
chemistry with which the expert in this discipline ought to be
familiar.
A . Henglein
[NB 343/200 IE]
Experimental Spectroscopy. By R . A . Sawyer. Dover Publications Inc., New York 1963. 3rd Edit., X + 358 pp., 110
figures, paperback, $2.00.
Sawyer restricts his discussion to spectroscopy in the range
from the ultraviolet to the infrared available with prism or
diffraction grating spectrographs: other ranges and interference methods are intentionally excluded. A simple, easily
understandable discourse o n the experimental aspects of
spectroscopy is developed in 13 chapters, starting from fundamentals and going on to instrumentation, then to photographic processes, the determination of wavelengths and intensities, and finally discussing ultraviolet and infrared spectroscopy and spectrochemical analysis. However, some essential points are overlooked; for example, the light intensity of
a spectrograph is characterized by its relative aperture, without making it clear to the inexperienced reader that the length
of the basis of the refracting element is the most important
factor for the energy density per wavelength region in the
plane of the image.
The chapter on photographic processes contains so many
elementary mistakes that it is hard to imagine how the
author’s attention has not been called to this by users of the
previous editions. The photographic process is described in
details that are unnecessary for practical spectroscopy and
615
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