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Book Review Encyclopedia of Chemical Technology by R. K. Kirk and D. F

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968, 922, 850, and 799 cm-1. The possibility of the presence
of ZnCO3, basic ZnC03 or Zn(0H)z can be excluded. In
approximately 2 2 alkaline sodium zincate solutions, no
absorptions were observed in these regions.
Cleavage Reactions with the Chlorosilanes
SizC16, Si~Cls,and SiSC112
E. Wiberg and A . Neumaier, Munich (Germany)
Under the catalytic influence of trimethylamine, hexachlorodisilane should disproportionate into SIC4 and Sic12 [25].
A re-examination showed that only 0.75 mole Sic14 is formed
per mole SizCls and that the silicon subchloride has the
empirical formula “SiC12.40”. Its mulecular formula is Si5C112
[26]. The disproportionation equation is therefore
4 SiZCk
-+
3 Sic4
+ Si&llz
Si5C112, which is formed by allowing Si2Cl6 to stand for three
hours at room temperature in the presence of catalytic
amounts of trimethylamine, forms colorless moisture sen:
sitive crystals, m.p. 306°C (decomp.). They are readily
soluble in ether and benzene, difficultly soluble in carbon
[25] C. J. Wilkins, J. chem. SOC.(London) 1953, 3409.
[26] Cf.G . Urry and A . Knczmarczyk, J. Amer. chem. SOC. 82,
751 (1960); J. inorg. nucl. Chem. 17, 186 (1961).
tetrachloride. In a high vacuum above 5OoC they can be
sublimed without decomposition. Si3Cls also f o r m Si5C112:
2 SilCls
+
Sic14
+ SisCllz
With HC1 at 50-70 “ C , Si5C112 forms SIC4 -t 4 HSiC13. In
an ether solution at -100 “C, excess lithium aluminum hydride
hydrogenates SisCIIz in one hour to give a mixture of 1 mole
of SiH4 and 4 moles of SiHz. Chlorine converts Si5C112 into
5 moles SiC14 at 200°C but the reaction is slow and takes
several days. The reaction of SisCl12 indicate the structure
.
ClzSi C1,
/c1.sic12
Si
clzsi.c1/
‘cl.sicIz
\
They do not agree with a “n-pentane”, “isopentane” or
“neopentane” structure.
Treatment with trimethylarnine for several days at room
temperature or higher leads to disproportionation of SiSCllZ
(“SiC12.40”) into Sic14 and subchlorides containing less
chlorine, “Sic1 < 2.40”. Similarly, in an analogous reaction
between trimethylamine and Si2C16 over several days, products poorer in chlorine, “Sic1 <2.40”, are obtained besides
the disproportionation compound “SiC12.40”. The chlorine
content of the “Sic1 (2.40’’ product can fall even below the
value SiC12, especially on heating.
[VB 588/38 IE]
SELECTED ABSTRACTS
The continuous purificatiun of air contaminated with tetraethyl-lead by means of activated carbon was studied by I. F.
Zemskov, using a countercurrent, multi-stage fluid bed adsorber. The adsorber column contains four perforated plates.
Air is fed in below the bottom plate and flows upward at
a rate of 1.2 to 1.5 m/sec. Fresh carbon is continuously fed
onto the top plate. The activated charcoal passes from plate
to plate through overflows, a fluid bed 80 mm high being
maintained on each tray. A countercurrent flow of activated
carbon and contaminated air is thus established. The fourstage adsorption process achieves more than 85 % removal
of TEL from the air. Ninety nine percent of the activated
carbon entrained by the air is removed in a cyclone separator.
The carbon leaving the bottom of the adsorber is continously
treated with an air chlorine mixture, thus converting the
TEL into PbClz. The latter is extracted from the carbon with
hot water and the water extract treated with NazS04 to
precipitate PbS04. The carbon is continuously dried in a
fluid bed and recycled to the adsorber. / Zh. Prikl. Khimii
[Rd 218/74 IE]
35, 536 (1 962).
Metallo-organic syntheses involving aryl compounds have been
reported by D. Wittenberg. When aluminum is ground
together with small quantities of aluminum chloride, a metal
preparation is obtained which reacts with bromobenzene at
100°C or with chlorobenzene at its boiling point to produce
phenylaluminum sesquihalides in good yields.
3 GHsX
+ 2 Al + C~H~AIXZ.(C,~H&AIX X = C1, Br
Non-activated aluminum fails to react with aryl halides or
affords merely undefined products. Phenylaluminum sesquichloride, in contrast to phenylsodium and phenylmagnesium chloride, is readily soluble in aromatic compounds. It may be employed, like its Grignard analogues, as
an arylating agent. With phosphorus trichloride, it yields
93 % triphenylphosphine; with stannic chloride, depending
on the proportions employed, it produces, phenyltin trichloride, diphenyltin dichloride, triphenyltin chloride, or
tetraphenyltin. / Liebigs Ann. Chem. 654, 24 (1962) / -Sk.
[Rd 295/86 IE]
F-Nor-steranthrene (I) has been obtained by E. Buchta and
D . Kiessling from 2a,3,4,4a-tetrahydropyracene by way of
1’- 0x0 -I ‘,2’,3‘,4‘-tetrahydro -7,8-benzo -2a,3,4,4a-tetrahydropyracene (colorless platelets from petroleum ether, m. p.
103-104°C) in an eight-stage synthesis. I forms yellow
platelets m. p. 209-210°C (from ligroin/benzene) and, like
its 3,6,6-trimethyl derivative 11, represents, a ring system
derived from cholesterol. The in vivo conversion of cholesterol in to I1 is theoretically possible. / Naturwissenschaften
[Rd 288/82 IE]
49, 280 (1962 / -De.
BOOK REVIEWS
Encyclopedia of Chemical Technology, by R. E. Kirk and
D. F. Ofhrner, Second Supplementary Volume, edited by
Anthony Standen. Interscience Publishers, Inc., New York,
1960. XV,970 pp. Numerous Illustrations. Bound in black
buckram: $ 25.00 [l].
The second supplement has now appeared three years afler
the publication of the first supplement. This volume has been
[I] See previous reviews in Angew. Chem. 66, 343 (1954); 72,
426 (1960); 72, 356 (1960).
Angew. Chem. internat. Edir.
Vol. I (1962) / No. 9
edited by Anthony Standen, who was an assistant editor of
the main work. The volume contains 60 individual articles
that average approximately 15 pages each. The articles
emphasize the technological progress of recent years. Technological developments in the USA are given the most thorough
treatment; this is to be expected since all of the 80 authors,
except one, are Americans. Because 65 authors are active in
American industry, the new volume’retains its conventional
emphasis on Practical applications. Basic problems, such as
the thermodynamics of irreversible processes, the solid
517
<;
slate; and the dislocation theory, constitute 13.7
of thc
text (compared to 12 7; in the main work and 21 ”4in the
first supplementary volume). A larger portion of the text,
32.5 ?<:, is devoted 10 industrial processing methods and
equipment, such as nitric acid concentration and tool materials
for machining (compared to 13.3 7$ in the main work and
24.8 2; in the first supplementary volume). The remaining
text deals with chemical substances from an engineering
point of view.
In this short review it is possible to consider only a few details,, selected from the numerous diverse articles.
Acetylene (35 pp.): The preparation of acetylene from
hydrocarbons is treated extensively for the first time in this
work. The article is a good presentation of this topic and
one can gradually acquire an overall view of the field. The
Philiips and Tennessee-tastnian methods should have been
mentioned in the section on the two-stage flame. process.
Also. a more critical coniparison o f the individual methods
with greater emphasis on their advantages and disadvantages
wouid have been desirable. ‘The excellent description of the
explosive properties and lhi: industrial methods of handlins
acetylene is of considerable value.
C c l l s , e l e c t r i c W p p . ) , F u e l cells (22pp.): ‘Tne new
deveiopments in galvanic cells (dry cells, wet cells, reserve
cells, and fuels cells) are extensively treated. The tendency to
rec‘;uce the size of portable electronic equipment has considerably influenced these recent developments. Reserve cells
are: units that can be stored in their inactive state for a very
long time and can he activated before use, e.g. by flooding
with ammonia gas. These cells are capable of delivering a
sir&. electric discharge which i s high in relationship to the
ccl,i’s weight and volume. They are of great importance in
ology. For military reasons, new interest has
fuel cziis, which pro\Aide a noiseless and portable
source of electric power.
C e r a m i c s (28 pp.), G l a s s (19 pp.): The material in these
two articles informs the reatier about new developments for
special applicaf.ions, e.g. ceramies for electronic instruments,
new enameiling processes, ceramic tools. radiation-barrier
glass for ObSerVatiOtJ parts weighing up to six tons, photosensitive glasses, froin which articles can be prepared by
irradiation and a chemical machining process that cannot be
manufactured by ordinary mechanical methods, rtc. The
articies give numerous ~ ~ ~ r details.
~ ~ w ~ i ~ e
Chemic.al c o d i n g (29 pp.): This concept is defined as “An
analysis of chcimical information for concise recording to
facilitate its transmission, utilization, and correlation.” It is
expected that. substantial savings in the cost of research will
be achieved as a result of these eRorts, since too inany experiments are duplicated owing to lack of knowledge of the
literature. The author of this article expresses a significant
cpinion that it is as unreasonable to expect the busy experimental scientist to attend to his own l i t e r a t u ~search as it
vuouid be to expect him to do his own glass blowing. The
article conveys B good impression of the current American
attitude regarding docurncntation.
Cryogenics (10 pp.) : Methods of attaining low teniperalures
(below -100”Cj are covered briefly and ihe application of
products obtained in these processes, especially nitrogen, is
described. The article is Loo short to do even remotely justice
to the great importance of low-tcrnperature techniques,
particularly in the field o f hydrocarbon fractionation. i t is
written more from the point of view of the steel industry’s
need for oxygen. However, the article does not impart any
essentially new technical view points even i n the field of liquefaction of air.
G e o c h e m i c a l P r o s p e c t i n g (21 pp.): A good survey is
given of the chemical methods and the organization of lield
experinmitation for predicting geological deposits. A description is given of special techniques for analyzing rock
formations, soil, water. sediments, and plants, using the above
approach. These working methods have attained great importance. For example, the North Rhodesian copper companies process more than one million samples per year.
N o n i o n i c S u r f a c t a n t s ( 3 3 pp.): The field ofnonionic surface active agents i s covered extensively. A list giving approximately 600 trade names is, on account of its size, very
unsuitable for an encyclopedia, particularly if one considers
the fact that these trade names change very quickly.
Pokymethylbenzenes (45 pp.): This does not refer to
polymers but to dimethyl-, trimethyl-, and tetramethylbenzenes. The article is a careful, comprehensive, chemical
study of the yields of the various compounds and isomers
obtained in the petroleum industry, together with their properties, analytical determination, and the chemistry o f their
reactions.
P o l y p r o p y l e n e ( 1 1 pp.): ‘The article covers the essential
facts about the properties, preparation, and application of
this new synthetic material. A good detailed table gives a
comparison between the properties of polypropylene and
high density polyethylene; another table illustrates the chemical resistance of polypropylene. The stability to light and
oxygen might have been covered more extensively.
G a s C h r o m a t o g r a p h y (37 pp.): Since the entire subject
of chromatography was treated only very briefly in the main
work (a tota.1of 7 pages), this i s the first time that gas chromatography is presented herc in a complete unit. The various
types of detectors are compared according to their fields of
application. A separate section covers theoretical principles.
The applications of gas chromatography to process control
are mentioned.
Synt.hesis G a s (5 pp.): This short article provides data
primariiy on the Texaco Synthesis Gas Process. A more
thorough comparison of all the existing processes would
have been desirable, since this topic was only briefly touched
upon in lhe main work.
The above examples of the individual articles should be
sufficient to indicate the scope of the volume,
Summarily, it can be stated that the volume is a good supplement to the main work. Moreover, the volume is a stimulating
and interesting collection of industrial progress reports. The
work provides an insight into the current ideas and trends of
the American industry. Obviously, such a picture still only
indicates parts of the whole. The development of special
products, particularly for the communication and nuclear
industries, appears to be preponderant in many places of the
volume. The plastics industry and petrochemistry are less
well covered. Heavy inorganic industry (with the exception of
the articles on glass and ceramics) is not covered at all. One
must nevertheless agree with the point of view o f the editor
that in the supplementary volumes, it is important to describe
in full those subjects which have recently undergone changes
of a more fundamental character, rather than to make minor
additions to existing articles. Good indexes, with references to
the main work, facilitate the use of the supplementary volume.
We wish the book great success.
ti. Sncltsse [NB 872/19 IE]
~
~~
~
Rrgisfcred nrirnrs. rraden!ur.ks, ctc. I I S L ‘ ~in this joidrna/, even without specific indication tIwreq/; are not fo be considered by law.
Q 1962 by Verlag Cheniie, GnbEl. -- Printed in Germany by Druckerei Winter, Fleidclherg.
AII Fights reserved. No part of this journal ma);he reproduced in any form whatsoever, e.g. by photoprint, microfilm, or any other means. without
written permission from the publishers.
Editorial office: Ziegeihiiuser Landetrasse 35, Heidclherg, Germany, Telephone 24975, Telex 04-61 855, Cable address: Chernieredaktion Weidelberg.
Chief Editor: W . F C J W SEditors:
~
$7. Roschkc and H . Grunewald.
Publishers: Verlag Chemie GmbH. (President Cdurrrd Krauzhupe), Pappelallee 3, Weinheim/Bergstr., Germany, and Academic Press Inc. (President
Waller J. Johnson), 11 1 Fifth Avenue, New York 3, N.Y., U.S.A., and Berkeley Square House, Berkeley Squarc, London, W. 1, England.
Correspondence concerning advertisements should he addressed to VerlagChemie, GmbH. (Advertising Manager W.Thiel),Pappelallee 3. Weinheim/
Rergstr., Germany, To6ephoi1e Weinheim 3635, Telcx 04-65 516. Cable address: Chemieverlag Weinheimbergstr.
518
Angew. Chrm. internat. Edir.
Vol. I (1962) 1 No. 9
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