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Book Review Atlas d'quilibres lectrochimiques 25░C (Atlas of Electorchemical Equilibria at 25░C) by M.

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The possibility of the existence of dialkyl- and diacylnitronic
acids was in\-atigzted by F. K l r y e s , R . Heinle, H . Sitr, and
E. Speclit. All attempts to prepare dialkyl- and diacylnitronic
acids, RrSOOH. led to side reactions, but the reactlon products indicated intermediate formation of compounds of the
desired formula. Decomposition also occurs even under very
mild conditions, but the different courses of this reaction
could largel?- be elucidated. Nitronic acids with two organic
substituents on the nitrogen atom are not capable of existence.
x),
probably by
25 %) as well as N-benzylhydroxylamine (75
oxidation of ( I ) to dibenzylnitronic acid (2) followed by rearrangement. Oxidation of N-hydroxyphthalimide (3) with
H202 or PbO2 gave N20 and phthalic acid, possibly via the
primarily formed nitronic acid derivative ( 4 ) . N,N-Di-t-butylhydroxylamine and its 0-acetyl derivative always gave a
nearly quantitative yield of 2-nitroisobutane with peroxycarboxylic acids. An intermediate blue color seems to indicate transient formation of 2-nitrosoisobutane. / Chem.
Ber. 96, 2387 (1963) / -Ma.
[Rd 733/204 IE]
The synthesis of phenoxycyclopropanes ( I ) from phenoxycarbene (2) and olefins is reported by U . Schollkopf, A .
Lerch, and J. Pnirst. The carbene (2) is produced in the reaction mixture by elimination of hydrogen chloride from chloromethyl phenyl ether 13) with butyl-lithium, lithiochloromethy1 phenyl ether ( 4 ) probably occurring as an intermediate.
J
L
J
(41
Reaction of N,N-dibenzyl-0-ethylhydroxylamine ( I ) with
less than the theoretical amount of peroxyacetic acid yielded
equimolar amounts of benzaldehyde and acetaldehyde (20 to
The carbene (2) apparently acts as an electrophilic reagent,
for the yields of cyclopropane compounds are greater, the
higher the electron-density at the olefinic double bond. The
addition takes place stereospecifically as cis-addition. / Chem.
[Rd 7751199 IE]
Ber. 96, 2266 (1963) / -Sk.
B O O K REVIEWS
Atlas d'kquilibres electrochimiques a 25 "C (Atlas of Electrochemical Equilibria at 25 "C), by M . Pourbnix, in collaboration with a number of scientists. Gauthier-Villars and
Cie., Paris 1963. 1st edit. 644 pp., numerous illustrations;
linen, NF. 140.- (about S 28.-).
This atlas presents equilibrium data for a large number of
electrochemical reactions, which characterize the behavior of
metals and metaloids in aqueous solutions at 25 'C. The
equilibria are, i n general, represented graphically, the
reversible electrode tension being plotted against pH (tensionpH diagrams). For every element, a number of reactions,
particularly those involving hydroxide or oxide formation,
has been considered in most cases.
In the introduction, Von Rysselberghe develops concisely and
clearly the thermodynamic fundamentals of the book; he
uses the concepts of chemical, electrochemical, and electrical
tension, recommended by the CITCE nomenclature commission, which allow elegant derivation of the main basic
relationships. In a further section, Pourboix, Vcrletisi, Clitrrlor,
Hoar, and Carrels discuss the most important applications
of the tension-pH diagrams. These are primarily of interest
in connection with corrosion, but also with general inorganic
chemistry, analytical chemistry, the deposition and dissolution of metals by electrolysis, and even geology. Numerous
diagrams show the regions in which metals corrode and those
-_
in which they are immune or passive (immunity being
understood as the state in which corrosion by an adjacent
liquid is thermodynamically impossible, whereas in the case
of passivity, corrosion is prevented by a change in the surface
characteristics of the metal, owing, for instance, to the
formation of a compact surface layer). In general, the
equilibrium diagrams and analytical relationships given allow
one to state whether, for a given set of conditions, a n electrochemical reaction can take place or not. This does not mean,
of course, that a thermodynamically possible reaction will
in fact occur, because its rate may be impracticably slow.
However, this restriction in the use of the diagrams is also
encountered in the utilization of all the usual chemical free
energy tables in general. Compared to the latter, which even
to-day are often rather incomplete, the number of data
collected in the atlas under review is remarkable. Virtually
all the elements have been covered. This is the fruit of
years of relentless efforts on the part of M . Poirrbaix and
of the Cebelcor ["I of which he is director. This comprehensive, well arranged volume will be welcome, particularly to those interested in corrosion and passivity. The printing
and general appearance are good, the price can be regarded
N,Ib/ [NB 135/63 IE]
as modest for a book of this kind.
[*I Centre Belge d'Etude
de la Corrosion.
~-
Prgistered names, trademarks, etc. irsed in tliis jorrriial, eve11 withoirt specific indication thereof, are not to be ronsidercd unprotected by law.
0 1964 bqVerlag Cbemie, G m b H . - Printed in Germany by Druckerei Winter, Heidelberg.
All rights re;erved. No part of this journal may be reproduced i n any form whatsoever, e . g . by photoprint, microfilm, or any other means, without
written permasion from the publishers.
Editorial Office: Ziegelhauser Landstrasse 35, Heidelberg, Germany, Telephone 24975, Telex 04-61 855, Cable address: Chernieredaktion Heidelberg.
Chief Editor: W . Foersr . Editor: H. Griinervald.
Publishers: Verlag Chemie, GmbH. (President E d r r a ~ ~Kreiiiiiage),
l
Pappelallee 3, Weinheim/Bergstr., Germany, and Academic Press Inc. (President
Walter J. J o ~ ~ , s o n1) 1, I Fifth Avenue, New York 3, N.Y., U.S.A., and Berkeley Square House, Berkeley Square, London, W. 1, England.
Correspondence concerning advertisements should by addressed toVerlag Chemie, GnibH. (Advertising Manager W.Thiel),Pappelallee 3, WeinheimBergstr., Germ any, Telephone Weinheim 3635, Telex 04-65 516. Cable address Cheniieverlag Weinheimbergstr.
156
Angeiv. Cliem. iiitertiat. Edit./ Vol. 3 (1964)
I
No. 2
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