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Book Review Ionenustauscher (Ion Exchangers) Volume I Fundamentals. Structure Ц Manufacture Ц Theory by F

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Bis(trimethylsily1)carbodiimide. the first representative of a
new class of compounds, was synthetized by J . Pump and U.
Wannogut. Metalation of N,N'-bis(trimethylsily1)urea (obtained by silylation of urea with hexamethyldisilazane) with
LiCoH5 or NaNH2, and reaction with (CH3)3SiCl gave the
unusually stable bis(trimethylsilyl)carbodiimide, C,H18NzSiZ,
a colorless, highly mobile liquid, b.p. 164"C, n%= 1.4351,
d: - 0.821 I g/ml, Trouton's constant: 24.3 cal/molexdegree
(yield = 80 and 12 %), The infrared spectrum is in agreement with the structure. The remarkable stability can be explained on the basis of resonance stabilization due to several
limiting mesomeric structures, of which I probably exerts a
dominating influence.
'>
r,
RlSi -N
(ii
0
C N =SIR,
~
(1)
(R= CH,)
The chemical reactions of E differ from those of organic carbodiimidcs. The stability of the compound towards water is
greater than that of its organic analogue; the compound has
unlimited storage stability at room temperature and does not
react with H2S, NH3, anilinp, or catalytically activated Hz.
H2O and HCI split off the silyl group:
I i H2O
I -1- 4 HCI
t
~
~~
(R3Si)rO
+ H2N-CN.
-> 2 R3SiCI
a
@
+ CI0[H2N-C=NH@C1
Compound I can also be prepared in 60 % yield from bis(trimethylsily1)sodamide and phosgene or in 20 % yield from Si
tetraisocyanate, or in 90 % crude yield from di-Ag-cyanamide
and trirnethylchlorosilane. / Liebigs Ann. Chem. 652, 21
(1962) / Ma.
[Rd 210/67 IE]
Lead tetraalkyls and other metal alkyls resistant to hydrolysis can be prepared according to K. Ziegler and 0 . - W .
Steirdcl by electrolysis of aqueous solutions of sodium tetraalkylboranates using an anode of the desired metal (Pb, Sb,
Bi, Hg) and a mercury cathode. Compared to the electrochemical synthesis of tetraethyllead in molten sodium aluminium tctraethylene, the preparation of the compound by
this procedure has the disadvantage that a maximum current
density of only 3.5 amp. per square decimetre can be used for
prolonged periods, since at higher current densities the oily
reaction product, Pb(C2H5) . 4 B(CzH5)3, forms a n electrically insulating coating on the anode. / Liebigs Ann. Chem.
652, 1 (1962) / L.
[Rd 214/71 IE]
An opticallyactive borospiran was obtained by K. Torsell. The
diamine (I) was converted into the di-iodide by a Sandmeyer
reaction and then into the dilithium compound by reaction
with butyl-lithium. The dilithium compound yields the anion
(11) with BF3. Compound (11) in methanol and in the presence
of the optically active benzylmethylpropylphenylammonium
salt of bromo-(+)camphor-Ti.-sulphonic acid, gave the difficultly soluble salt(III).Crystallisation from nitromethane leads
to optically pure (111) with constant rotation [MID= -596".
/\/\
I/
\/'
I . HNOi
2. KJ
J
Since the rotation of the benzylmethylpropylphenylammonium ion ([MID approx. -259') is largely independent of the
nature of the anion, it is calculated that the optically pure
boron-containing anion has the large rotation [MID approx.
-338 '. /Acta chem. scand. 16,87 (1962). /- Sk. [Rd 194/61 IE]
Indenyl derivatives of titanium, in combination with metal
alkyls, catalyse the polymerisation of mono- and di-olefins.
Investigations have been reported by W. Marconi, M. L. Santostasi, and M. de Maldi. Highmolecular weight linear poly(ethylene), poly(butadiene) with predominantly 1,4-cis- and
1,4-trons-structures, and poly(isoprene) in the l,.l-trans form
are obtained by the reaction of bis(indeny1)titanium dihalides
with aluminium trialkyls, dialkylaluminium halides or Grignard compounds. Catalysis occurs under homogeneous conditions and possesses in itself a certain stereospecificity, e.g.
a poly(butadiene) with a high 1,4-cis content is obtained with
dialkylaluminium halide and bis(indeny1)titanium diiodide
while the corresponding bromo compound leads mainly to
1,4-trans-poly(butadiene)and -poly(isoprene). In the polymerisation of ethylene, the activity of the catalyst system diminishes in the order AIR21 > AIR2Br >- AlRzCl
AIR,
corresponding to the changed Al/Ti ratio; in the case of
poly(butadiene) and -(isoprene) the structure of the polymer is
influenced in addition to the catalytic activity and yields. /
Chim. e Ind. 44, 235 (1962). / -Pf.
[Rd 198/65 IE]
- I
BOOK REVIEWS
lonenaustauscher (Ion Exchangers), Volume I : Fundamentals.
Structure Manufacture ~ T h e o r yby
, F. Helfferich.Verlag
Chemie GmbH., Weinheim/Bergstr., 1959, VIII, 520 pages,
153 figures, 14 tables. D M 48.- (0 12.00).
Several books on ion exchangers have been written in recent
years. Most of these entailed summaries of studies and reviews of opinions published up to the corresponding periods.
A valuable contribution has been made by F. Helfferich in
perusing the numerous theoretical analyses scattered throughout the literature, and presenting these from a single point of
view. The various processes and physical relationships occurring in ion exchange are presented clearly in easily understandable fashion, by avoiding a detailed and complete description of all of the various published theories. The clarity
of the treatment is possibly also due to the fact that the author
has worked in the field of ion exchangers since the beginning
of his scientific career and was himself directly involved in
the development of the physicochemical concepts of ion exchange, in both Germany and the USA. Furthermore, in the
preparation of the manuscript, the author has leaned o n
the experience of the leading experts in the field of ion
exchange .
A n g e w . Chem. intermit. Edit.
Vol. I (1962) 1 No. 7
The book [ I ] deals first with the structure and properties of
various types of ion exchangers. The manufacture of ion exchange resins is also described in detail. Next, the fundamental theories required for the calculation of capacity, exchange
equilibria, and kinetics of ion exchange are individually explained. The electrochemical properties of ion exchange resins, ion exchange membranes, ion exchange beds, the behavior of ion exchangers in non-aqueous and in mixed solvents, the catalytic properties of ion exchangers, electron exchangers (redox resins), and redox ion exchangers are dealt
with in subsequent separate chapters.
In order to facilitate the understanding of the individual
chapters, in addition to a quantitative mathematical derivation, the author presents a qualitative, non-mathematical
picture of the ion exchange procssses involved.
In addition to the theoretical treatment, a description of the
experimental methods, as well as a clearly formulated summary are to be found at the end of each chapter. The summary
is particularly helpful because only essentials are emphasized.
The book may be recommended to persons interested in de[l] A revised English translation is being published by McGrawHill, New York.
413
tailed int‘ormation on the theory of ion exchange, as well as
to those who wsnuld like to acquire a practical knowledge of
the quantitative relationships involved in the application of
ion exchangers, i n order to optimize process conditions.
The book is thc lirst independent volume of a three-volume
work a n d can he purchased scparately, We can only express
our hope that the editor will be able to find authors, who will
he equally successful in preparing the next two volumes,
which are to describe applications o f ion exchangers in the
laboratory and in technology. G, ,j,faIleclte [NB 881/21 I E ]
Chemische lechnologie (Chemical Technology) in five volumes, edited by K . Winntrcker and L . Kuchler. Volume 3 :
Orgonische ’Technologic I (Organic Technology 1). Carl
Hanser Verlag, Munich 1959. Second Edition, XX, 912
pages, 347 figures, 226 tables, price cloth bound D M 98.(about 524.50).
In this new edition of Witr no & c r - Weingnrrtner, the editors
have tried to incorporate the continuous changes and the
mass of new accomplishment in this particular field, while
still maintaining as far as possible the original setup of the
book. The present volume deals with organic technology of
raw materials; the table below gives a comparison of the
iiumber of pagr:s included i n the individual chapters of the
ncw and old editions. Organic technology has undergone a
striking transformation, as a consequence of the removal on
J a n . 7 n d , 1953 ofimport duty on crude oilsimportedforchemiciil utiliration in new processes set in operation after that
date. This introduced a new source of raw materials and
made true petrochemistry possible in Germany for the first
time. I t has not only led to unusually rapid development of
new processes but has alm had a sustaining effect on the
I. I b k i
Pages
new
old
( ‘ I i e n i i i a l iiiilimtion OF coal . . .
C ’ l i ~ ; i u ~ ~utilization
al
of lignite. ctc
. . . . . . .
. . . . . .
.
(‘hsniical technology of petrolcum (including high
p i csIure hydrogenation and lubricating oil refining)
Mcilianol a n d isotutyl oil synthese\ . . . . . .
I i x h c r - rropsch synthesis . . . . . . . . . .
Wood ;ind i t \ c h e n i i c a l tcchnological proceasing
A l i p h a t i c chemicali and interincdintes . . . . .
Aromatic ~ n t e i n i i e d i i l t ~ \ . . . . . . . . . . .
Svnthelic f i b e r s . . . . . . . . . . . . . . .
Ill
65
120
113
209
53
82
129
I34
1 I3
183
51
124
141
96
-
69
896
897
.noniic impcrtancc of already existing processes. The
publishers have succeeded in taking this development into
account by making extensivc abridgements in the text (e.g.
i n the Fischcr-Tropsch process, high pressure hydrogenation,
isobutyl synthesis. and the saccharification of wood) as
well 21s by using a more concise style, while carefully maintaining the total coverage. Those who have observed these
technological developmcnts, e.g. in high pressure hydrogenation and the I-’ischer-Tropsch processes, can imagine how
difficult such deletions must be. since the technological information pertaining to the basic methods retains a certain
V ~ I I U C independent of the economic importance of the process
itsclf. Thus, it ‘was necessary to revise the entire text. The
number o f coilLiborators has increased from 26 for thc first
edition to 34, of whom 24 ware new to this task; of the eight
i i u t hors who signed and were responsible for the chapters,
o n l y two collaborated i n the first edition. Thus, the material
has been revised much more thoroughly than is apparent at a
first glance. The more concise style is evident also in the more
uniform subdivision of chapters, and the extensive bibliography at the end ofeach main chapter is a great improvement.
The two chapters on the c h e m i c a l u t i l i z a t i o n of c o a l
and l i g n i t e are condensed, have excellent review tables, and
are free of certain obsolete expressions, so that now more is
contained in less space. A welcome addition is the multilingual glossary of terms dealing with petrographic and other
properties of coal, which greatly facilitates orientation for
the nonspecialist. Gasification of coal and lignitc arc treated
separately, each within its own chapter. Here, combining the
two gasification processes would have meant a simplification.
In the lignite chapter, the production of montan wax by the
extraction method is given only rather cursory treatment. A
more detailed bibliography would also be desirable here.
The chapter on “Chemical Technology of Petroleum” by
Zorn, in which previous chapters on high pressure hydrogenation and lubricating oil refining have been incorporated,
is considerably enlarged. Special mention should be made of
the good presentation of the properties of petroleum, the
distribution of trace metals in crude oils of various origin,
the compositions, yields, and consumption requirements of
fuels (the question of octane number with instructive tables
and illustrations). Even a picture of a jet engine is included.
The section on lubricants is particularly well done. I t is
probably unavoidable that in such a presentation certain
areas must be slighted. The increasing importance of fuel oils
is only briefly mentioned; only two pages are devoted to fuel
oils themselves, barely one to petroleum bitumen. The section, “Petroleum and Natural Gas as Raw Materials for the
Chemical Industry” (8 pages), is also surprisingly short. In
such a small space, no more than a summary listing is possible, with no claim to completeness. In view of the key position of the olefins, especially ethylene, i n the chemical
industry, a more detailed description of their preparative processes would be very desirable.
In the chapter o n the Fischer-Tropsch processes by Kolhel,
the essential results of the recent extensive development are
deftly worked out. The developments during the last war and
our present competitive industrial economy system have had
the effect that a n extremely large volume of literature and
reference material on the Fischer-Tropsch processes is available, so that the author deserves praise for his condensed
survey. In the section o n w o o d , wood processing, wood coking, wood saccharification, and the preparation o f cellulose
and paper have been combined into a single chapter. Despite
the abridgements the informational content has increased.
The subsection on cellulose and paper is up-to-date in every
respect, and it is gratifying that the techniques involved,
which are of general interest, have finally found their way
into a modern textbook on chemical technology. In keeping
with its importance, the chapter o n a l i p h a t i c c h e m i c a l s
and intermediates by Horn and Besrian has also been expanded.
Winnacker-Kiichlcr bridges the gap in the literature between textbooks on the one hand, and technological encyclopedias on the other. We pay tribute to the publishers and
authors, most of whom are active in industry, for allocating
their time and effort not only to collecting the material, but
also to compiling, classifying, and condensing it. Especially
in vicw of thc rapid pacc of current developmcnta, their didactic approach becomes increasingly important.
We wish them continued success in their work.
H . Sachsse [NB S56/lS IE]
I<ryistcred N U I ~ C T rrailemarks,
,
e tc . irsrd i n this joirmal, even without specific indication thereof, a r e not to be considered unprotecred by law.
( ( 2 1962 by Verlag Chemie. G m b l I . - Printed in Germany by Druckerei Winter, Heidelberg.
A ll rights reserved. No part of this journal may be reproduced in any f o r m whatsoever, e . g . by photoprint, microfilm, o r any other means, without
wiiiten permisrion from the publishers.
Editorial office: Zicgelhauser Landstrasse 35, Heidelberg, Germany, Telephone 24975, Telex 04-61 855, Cable address: Chemieredaktion Heidelberg.
Chicf Editor: W. Foi,r.Tr. Editors: F. Rorchke and H . Griinrwald.
Publishers: Verlap Chemie G m b t l . (President Edrrard Kreuzhage), Pappelallee 3 , WeinheimlBergstr., Germany, and Academic Press Inc. (President
Wdrcr J. J d r n s o n ) , I I1 Fifth Avenue, New York 3, N . Y . , USA, a n d Berkeley Square House, Berkeley Square, London, W. I , England.
Correspondence concerning advertisements should by addressed t o Verlag Chemie, G m b H . (Advertising Manager W.Thiel), Pappelallee 3 , Weinheini/
tiergstr., Germany. Telephone Weinheim 3635, Telex 04-655 16. Cable address: Chemieverlag Weinheimbergstr.
414
Angew. Chem. internat. Edit. Vol.
I (1962) 1 No. 7
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