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Book Review Polyofins. Structure and Properties. By H. von Boenig

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Although the most recent knowledge is not considered in all
the chapters, a particular merit of this book is the consistently
brief presentation of the most important results in this field,
a presentation that is based on a n underlying knowledge of
the literature. The book provides a worthwhile foundation
for all who may be occupied with the special questions of the
functions of nerves or brain. Further, the text is everywhere
so richly provided with references that it eases the way to
further information for those interested in greater detail.
H . Wiegundt [NB 661 IE]
Die Entwicklung der Chemie in der neueren Zeit (The Development of Chemistry in Modern Times) by H . Kopp. Geschichte der Wissenschaften in Deutschland, Band X (History of Science in Germany, Vol. 10). Johnson Reprint
Corp., New York. Georg Olms Verlagsbuchhandlung, Hildesheim 1966. Reprographic reprint of the 1873 Munich
edition. xx, 854 pp., D M 118.-.
The Development of Chemistry constitutes Volume 10 of the
“Geschichte der Wissenschaften in Deutschland - Neuere
2eit” (History of Science in Germany - Modern Times),
issued by the Historical Commission of the Royal Academy
of Sciences in Munich under the patronage of Maximilian 11,
King of Bavaria. Other volumes included Kurmursch, “The
History of Technology” (Vol. 11, 1872) and Hirsch, “The
History of Medicine” (Vol. 22,1893). This series, to which the
reprint unfortunately makes no reference, was a continuation
of a similarly conceived encyclopedia entitled “A history of
arts and sciences from the Renaissance to the end of the
18th century”, including contributions by J. F. Gmelin on
chemistry (1797-1799), Poppe o n technology (1807-1811),
and Hueser on medicine (1846-1860). These form the subject of an earlier review [I].
The present work, entitled “Development” by the author in
order to “eliminate the possibility of confusion with my
earlier 11843-471 ‘History of Chemistry’ ” is interesting for
two reasons. Shortly after the proclamation of the Empire in
1871, which put a n end to the multiple-state system in Germany, i.e. in a strongly national, even emphatically nationalistic epoch, Kopp wrote in a preface “chemistry belongs . . .
to those branches of knowledge which neither in regard to
the subject matter, nor in the treatment, nor in the form in
which the results obtained are expressed, can be property of a
particular nation”. For this reason “the historian must consider himself as having no particular home, and as a citizen
of no particular country”. In complying with this premise,
Kopp did not write a history which put the development of
chemistry in Germany in the foreground, but one in which
the individual national contributions were given a status
according to their importance. On the other hand, Kopp’s
“Development”, which records the results up to around 1858,
is to a large extent a contemporary account of the origins of
the “knowledge now becoming important”. Although the
author did not himself set out to present this, he had to
report o n its origin. Thus, only about the first 200 pages of
the book lead the reader from the chemical knowledge of
antiquity to the general acceptance of the antiphlogiston
system of Lavoisier. The major part of the book is taken up
by discussion concerning the development of the theoretical
aspects of chemistry, above all progress in organic chemistry
up to about the time of Luurenf, Gerhurdr, and KGlbe; Kekuu ’ s treatise “On the constitution and the metamorphoses of
chemical compounds” 118581 forms the conclusion, because
“these reflections belong to the chemistry of the present . . .
and should not form the subject of a historical essay”.
Both Kopp’s “History” and “Development” are standard
works in the history of chemistry; a reprint of the latter is
therefore very welcome.
W. Ruske
[NB 654 IE]
111 W. Ruske, Angew. Chem. 79, 587 (1967); Angew. Chem.
internat. Edit. 6 , 578 (1967).
Angew. Chem. internut. Edit.
1 VoI. 7 (1968) / No. 3
Actions Chimiques et Biologiques des Radiations. (Chemical
and Biological Action of Radiation.) Edited by M . Huissinsky with contributions by E. J . Hurt, C . Ferrudini, T. J .
Hurdwick, and A . Chapiro. 10th series. Masson & Cie.
Editeurs, Paris 1966. 1st Edit., 324 pp., 78 figures, 49
tables, F 120.-.
This new volume in the series, which is intended as an exchange of information between radiochemists and radiobiologists, again contains four authoritative reviews of the
latest developments in certain fields of radiochemistry.
The first article is on the hydrated electrons formed on
radiolysis of water (E. J. Hurt, English, 88 pp., 150 references). A short introduction o n their discovery is followed by a
description of the experimental methods that are used for
their production and detection. The physical properties and
the structure of the hydrated electrons are then described, as
are their reactions with free radicals and with stable inorganic
and organic substances. The rate constants of the reactions
discussed are tabulated in a 12-page appendix. I t would have
done no harm to mention in connection with the discovery
of hydrated electrons that they were first observed and
identified in irradiated frozen aqueous systems in a German
radiochemical laboratory.
The content of the second article, “Reaction Rates of Free
Radicals in the Radiolysis of Water” (C. Ferrudini, French,
35 pp., 120 references), follows on from that of the first. It
deals with the rates of the reactions of the other radicals OH,
H, HOz, and 00,formed by the action of radiation on water,
with one another and with other inorganic and organic
substances (13 pages of tables giving rate constants).
In the next article, “Radiolysis of Liquid Hydrocarbons”
( T . J. Hurdwick, English, 61 pp., 120 references), a n attempt
is made in the introduction to explain the processes that
precede the actual chemical reactions when ionizing radiation
passes through a liquid system. This is followed by an
outline of the radiolysis of saturated and unsaturated aliphatic
compounds and of aromatic compounds, in which reaction
mechanisms and yields are given and discussed.
The last contribution is devoted to the interesting but as yet
unexplained “Radiation-Induced Polymerization in the Solid
Phase” ( A . Chupiro, French, 125 pp., 230 references). The
author confines his discussion to the polymerization of vinyl
derivatives, a few heterocyclic compounds, and aldehydes
and nitriles. Discussion of the kinetics of the reactions is
deIiberately avoided, but an attempt is made to apply the
general principles of radiochemistry to the reactions.
Since the coverage of the latest literature is very comprehensive, these very readable articles should provide valuable
information for all chemists and biologists working in
U. Schiitdewolf
[NB 684 IE]
related fields.
Polyolefins. Structure and Properties. By H . von Boenig.
Elsevier Publishing Company, Amsterdam-London-New
York 1966. 1st. Edit., ix, 319 pp.. 80 illustrations, 117
tables, Dfl. 47.50.
As can be seen from the subtitle, the author has set himself
the aim of accounting for the properties of the olefins on the
basis of their molecular structure, which immediately determines their crystalline, supermolecular structure (single
crystals, spherolithic aggregates) which in turn plays an
important role in the industrial applications of these compounds. The choice and subdivision of the material, which is
presented in a condensed form, corresponds to this aim.
A short consideration of the historical development in the
first chapter is followed by a treatment of the structure of the
polyolefins in the Chapter 2. The latter deals with the steric
regularity, the helix conforniation, and the connected problem
of crystallization from solution and from the melt.
In the third chapter the author considers in detail the dependence of some properties o n the density; a topic which permits
far-reaching conclusions to be drawn regarding the molec-
ular structure and also gives some indication of the tensile
strength, stiffness, hardness, and modulus of elasticity. Polyethylenes are therefore expediently classified as being of low,
medium, or high density.
In the remaining five chapters the connections are investigated which exist between the structure of polyolefins and
their physical, chemical, electrical, and thermal properties
and their behavior on being processed. The last chapter is
particularly important for people interested in the technology
of plastics. Great emphasis is placed upon the relation between structure and rheology, the melt flow index being
stressed as a suitable parameter. When the molecular weight
distribution, which determines inter alia the shrinkability and
distortion tendency, is taken into account, the melt flow
index proves a good numerical indication of the workability,
as well as of the shock and breaking behavior of formed
objects. The progress which has been made in the extrusion
of polymers is alluded to and phenonema such as melt fracture are discussed.
Boenig’s book should appeal to both researchers and technologists. The fruitfulness of the cooperation of these two
groups of workers is evidenced by the spectacular advances
made in the field of polyolefins during the last decade. The
book may well make an important contribution to this continuing development.
The book is comprehensibly written, comprehensively subdivided, richly furnished with illustrations and tables, and
contains a wealth of references to the original literature.
H. Weber
[NB 624 IE]
Electrophilic Additions to Unsaturated Systems. By P . B. D .
de la Mare and R . Bolton. Reaction Mechanisms in Organic Chemistry, Monograph 4. Edited by C. Eaborn and
E. D. Hughes. Elsevier Publishing Company, AmsterdamLondon-New York 1966. 1st Edit., x, 284 pp., numerous
schemes and tables, Dfl. 40.00.
The present monograph, which is the fourth in the series
“Reaction Mechanisms in Organic Chemistry”, deals with
electrophilic additions to unsaturated systems. One of the
authors, Professor de la Mare, has himself made numerous
experimental contributions in this field.
The book is divided into 13 chapters. A short introduction
and a chapter on the chemistry of carbonium ions are followed by a discussion of the principal electrophilic additions.
These include hydration, the addition of weak acids, of
mineral acids, and of halogens, epoxidation, and the addition
of sulfenyl halides and of compounds containing electrophilic nitrogen, phosphorus, or arsenic. The final chapter
deals with electrophilic additions to acetylenes, allenes, conjugated dienes, and to other systems such as C=O, C = N ,
S=O, and N = N double bonds.
The content of the book, which is built up on a purely theoretical basis, is extremely rich; the literature is covered up to
the end of 1964.
No procedures are given for the execution of electrophilic
additions, nor are any to be expected in view of the very
concise presentation.
The book is very well written, and as a valuable contribution
to theoretical organic chemistry it makes a n excellent companion to the volumes published earlier.
F. Asinger
[NB 583 IE]
Introduction to Practical High Resolution Nuclear Magnetic
Resonance Spectroscopy. By D. Chapman and P. D. Magnus. Academic Press Inc., -London-New York 1966. 1st
Edit., ix, 112 pp.. 30 illustrations, numerous tables,
25 s/%4.25.
This book is intended to provide a first introduction to
nuclear magnetic resonance spectroscopy and its potentialities
for students and for chemists engaged in structure determinations of organic molecules; its particular aim is to
introduce them to carrying out these studies in practice. For
this reason the authors intentionally desist from any form
of theoretical derivation.
The fundamental ideas such as chemical shift and spin-spin
coupling are introduced in a few words and are clearly
explained by means of examples. Reference is made to
detailed monographs for deeper study. The section on
experimental technique is somewhat more expansive. The
use of 19F, 3LP, 14N, and 13C nuclear resonance in organic
structural analysis, and five well chosen examples, close the
first part.
The second part consists of 37 very clearly arranged tables
of T values and coupling constants from recent literature.
This book can be recommended as a brief introduction into
the methods and experimental technique, and into the
analysis of spectra, for chemists who wish to use nuclear
resonance spectroscopy for determination of structure.
H . Friebclin
[NB 665 lE]
Advances in Alicyclic Chemistry. Edited by H. Hart and G. J.
Karabatsos. Academic Press Inc., London-New York 1966.
1st Edit., x, 395 pp.. numerous illustrations and tables,
bound $ 16.50.
This book is the first volume of a new series in which it is
intended regularly to report the most recent results in the
chemistry of alicyclic compounds. The reviewer agrees with
the editors that the explosive growth of the original literature
justifies a further new series.
The editors have been successful in obtaining for this volume
competent authors who in their own papers have contributed
important material to the fields which they treat here. Considered as a whole, the book provides a balanced and in
parts highly critical survey.
J. Meinwuld and Y. C. Meinwald report on bicyclo[n.l.l]alkanes and related tricyclic systems. It would be welcomed
by the reviewer if the nomenclature rules for bicyclic and tricyclic bridged compounds given by the authors in their
introduction were generally adopted. The main discussion of
the bicyclic compounds is devoted to the bicyclo[2.1 .l]hexane
and the bicyclo[l.l.l]pentane system, their syntheses and
reactions, and rearrangements of their derivatives. A special
section is devoted to consideration of highly strained tricyclic
compounds (tricyclopentane, -hexane, and -octane).
The chemistry of cyclopropenes is surveyed by G.L.Closs. H e
discusses in detail, not only the synthetic possibilities for
cyclopropene and its derivatives, but also their reactions, the
spectral properties, and the bonding. The peculiar “aromatic” properties of the cyclopropenyl cations and of the
cyclopropenones are treated in depth.
A detailed chapter (A. J. Waring) is devoted to cyclohexadienones. The author brings together the extensive and
widely scattered material with great care. Of the 121 pages
of this chapter, 53 pages are reserved for the varied ways of
forming cyclohexadienones; other parts describe their transformations and reactions. A special section is reserved for the
photochemistry of cyclohexadienones.
In the next chapter K . F. Koch surveys the photochemical
rearrangements of monocyclic tropolones and benzotropolones, and of colchicine and isocolchicine. The structures
of the “1umi”-products are discussed in detail with reference
to their UV, IR, and N M R spectra.
I n spite of two previous reviews of “reactions at a bridgehead” 111, the chapter by R. C. Fort and P. v. R . Schleyer on
the same theme contains much new experimental material
that has become available only during the last five years.
Besides containing a theoretical section, this chapter collects
[l] D. E. Applequist and J. D . Roberts, Chern. Reviews, 54, 1065
(1954); U.Schollkopf, Angzw. Chem. 72, 147 (1960).
Angew. Chem. internat. Edit. I VoI. 7 (1968) 1 No. 3
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