RECENT SOVIET WORK IN THE FIELD OF CHEMICAL KINETICS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600380529-3
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 4
• Document Creation Date: December 22, 2016
• Document Release Date: September 12, 2011
• Sequence Number: 529
• Publication Date: March 21, 1951
• Content Type: REPORT

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INFORMATION FROM
FOREIGN DOCUMENTS OR R~:DIO BROADCASTS CD NO.
COUNTRY
SUBJECT
HOW
PUBLISHED
WHERE
PUBLISHED
DATE
PUBLISHED
LANGUAGE
CLASSIFICATION coNFInF,NTTAT? ~~r~~~~FR~~9~1
Scientific -Chemistry, kinetics of
oxidation and combustion
Monthly periodical
Moscow
oct 1950
DATE OF
INFORMATION 1956
GATE DIST. a ~ Mar 1951
NO.OF PAGES 4
SUPPLEMENT TO
REPORT N0.
THIS IS UNEVALUATED INFORMATION
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Vestnik Akademii Nauk SSSR, Vol XX, No 10, 1950, pp 108-110 .
RECENT SOVIET WORK IN THE FSELD OF CHEMICAL KINETICS
~Phe results and methods mentioned in this report are oY im-
portance not only in industrial work dealing with the synthesis
of chemicals from hydrocarbons, but also from the standpoint of
more efficient utilization of fuels and propellant.
After achieving a certain measure of success in solving problems con-
nected with the mechanism of fundamental types of reactions, particularly
chain reactions occurring in the gas phase, the institute could tackle the
prnblem of applying the developed concepts, methods, and techniques to the
investigation of reactions which are of practical interest.
In doing so, special attention was paid to the investigation of oxi-
dation reactions of hydrocarbons. It is well known that the USSR posesaes
huge resources as far~as natural and industrial hydrocarbons are concerned.
Utilization of these resources may in particular proceed along the line of
oxidizing hydrocarbon gases into valuable compounds Containing oxygen, i.e.,
aldehydes, alcohols, and carboxylic acids. '
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A. B. Nalbandyan, Doctor of Phyaico-Mathematical Sciences, carried out
a series of investigations devoted to the study of :,he mechanism of photo-
chemical oxidation of the simplest hydrocarbons (methane, ethane, end pro-
pane). Using the data obtained in this work, he then turned to the problem
of industrial conversion of methane by oxidation.
The development of this practical line of investigation induced a number
of new kinetic investigations which are of scientific interest and have had
the effect of advancing the whole field of chemical kinetics.
The work of the collaborators of Nalbandyan who were concerned with the
study of the photochemical oxidation of hydrocarbons way carried out in
close contact with the practical phase of the investigation.
One may mention in this connection that Nalbandyan established the chain
character of the photochemical oxidation of methane in the presence of mercury
acting as a "sensitizing" agent (catalystl together with the fact that a high
. yield of formaldehyde is obtained in this reaction. Eighty percent of the
methane is converted into formaldehyde in this reaction, while in the photo-
chemical~oxidation of propane at low temperatures there is formation of or-
ganic peroxides alone. The results obtained may be very well explained on
the basis of the existence of chain mechanisms and participation in them of
free radicals.
Interesting results were obtained by N. M. Emanuel', Doctor of Chemical
Sciences, and Z. K. Mayzus, who studied the oxidation of propane in the pres-
ence hydrogen bromide acting as a homogenous catalyst. Under the circumstances
very high yields of acetone (40-506 on the basis of the initial propane) are
obtained in the absence of practically any other oxidation products with the
exception of propionic acid. In the course of this investigation, new results
on catalysis by hydrogen bromide were obtained.
A notable result was obtained in the investigation of the reaction of
propene oxidation which was carried out by S. S. Polyak and V. Ye. Shtern,
Candidates of Chemical Sciences. These investigators demonstrated that the
oxidation of propene proceeds according to a branched chain mechanism with
degenerate branches. The intermediate product that is responsible for the
degenerate branching is acetaldehyde.
In connection with the general trend towards the study of the mechanism of
hydrocarbon oxidation; the question in regard to the elementary reactions
entering into the complex process of the oxidation of various hydrocarbons
became of particular importance.
L. I~ Avramenko, Candidate of Physico-Mathematical Sciences, who has
shown in a number of prior investigations that the free hydroxyl group (OH)
plays an essential role in oxidation reactions, extended his research to the
study of the interaction of a hydroxyl group with various hydrocarbon mole-
cules. In the course of this work, he investigated the interaction of free
hydroxyl with acetylene, ethylene, methane, et:~'~_, aldehydes, and other
substances. Obviously, the study of hydrocarbc ~xidatiott products which
often are formed in very small quantities required the application of new
analytical methods and the modification and further extension of old methods.
Extensive work in this connection was done by M. B. Neyman, Doctor of Chemical
Sciences, who developed and perfected polarographic methods for the deter-
mination of many organic substances including peroxides, unsaturated aldehydes
and ketones, acetone and other ketones, and organic halogen derivatives.
Neyman also obtained interesting data on the mechanism of hydrocarbon oxi-
dation by applying the method of tracer atoms.
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The question in regard to the proof of the existence oY the radical
II02 still remains a sub~act of current work. Thus, V. V. Voyevodakiy,
Candidate of Physico-Mathematical Sciences, who investigated in great 3eta11
the reaction of the oxidation of hydrogen, demonstrated that results ob-
tained in the study of the upper limit of spontaneous ignition of a hydrogen-
oxygen mixture under conditions corresponding to a slow reaction in the vi-
cinity of the thermal limit of ignition and in the latter's induction period,
are in quantitative agreement with the concept of the formation of R02
radicals in this reaction. Recently, N. M. Emanuel', Doctor of Chemical
Sciences, and K. Ye. Kruglyakova got new data on the mechanism of the de-
composition of. hydrogen perioxide in aqueous solutions. Their results can
be explained on the basis of the assumption that this reaction proceeds by
a chain mechanism which involves i'ormatioa of the H02 radical.
Voyevodskiy carried out a number of investigations to determine the re-
combination constants of hydrogen and oxyger. atoms on various surfaces. .The
results of this work have a bearing on questions of heterogenous catalysis
and for that reason may be of considerable interest from the point of view
of developments in various fields of chemical kinetics. These results, to-
gether with those of prior determinations of conatants~carried out by
AVTameIIkO, 1ValbtsA(lyaII, gild ~anitidat@ Gf ihemiCai $CiEuC2c ri. .c.. ~aiklopov,
have already been applied in the analysis of the kinetics of certain chain
reactions.
The extremely reliable and exact thermoelectric method for determining
the concentration of atomic hydrogen in dilute flames which has been devised
by V. N. Kondrat'yev, Corresponding Member of the Acader,; of Sciences USSR,?
deserves particular attention. By using this method, the active centers of
acetylene and carbon monoxide flames were investigated. It was shown that
active centers are formed in considerable concentrations during the reactions
in question.
Investigations by Emanuel' and his collaborators dealing with the pheno-
menon of chilling were completed. In the course of that work, mixtures of
aldehydes and oxygen which had been chilled were exploded after renewed heat-
ing at temperatures several scores of degrees lower than the usual explosion
temperature. The phenomenon of chilling is explained by the formation of
intramolecular hydrogen bonds in the hydroperoxides which appear as inter-
mediate products during reaction. In other words, chilling is an example of
the kinetic (chemical) manifestation of intramolecular hydrogen bonding.
Recently, new results on the formation of the hydrogen bond in propionic
acid hydroperoxide were obtained by Aspirant D. G. Knorre. The investi-
gation in question is of interest from the standpoint of the general aim
of chemistry to establish the connection between the constitution of sub-
stances and their reactive capacity.
Work done by S. S. Medvedyev, Corresponding Member of the Academy of
Sciences USSR, and P. S. Shaatarovich, Candidate of Chemical ScienceR, es-
tablished that all polymerization processes can be divided into two basic
groups as far as their kinetics are concerned: processes for which the
reaction mechanism of an unbranched chain is typical and processes which
are governed by laws applying to branched chain mechanism.
N. M. Chirkov, Candidate of Chemical Sciences, has made a further con-
tribution to the knowledge of ionic heterogenous processes. In processes of
this type the reaction takes place in a thin layer on the surface of the
catalyst,and proceeds according?to the mechanism of ionic catalysis. By
using this method, many important reactions can be carried out at high
velocities and with high ultimate yields of desired products.
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Significant results were obtained by A. A. Koval'skiy, Doctor of Chemical
Sc~.ences, and A. M. Markevich, Candidate of Chemical Sciences, in the study
of homogeno-heterogenous reactions, i.e., processes in which an important
role is played by the wall of the vessel or a solid catalyst while the re-
action also proceeds in the volume of the vessel. A number of valuable re-
sults obtained by these authors had already been published. Recently,
Koval'skiy, by using the method of separate calorimetry of the component ho-
mogenous and heterogenous reactions, succeeded in proving that high concen-
trations of intermediate substances appear in the course of branched chain
reactions, for instance, the reaction of ethane oxidation. This conclusion
of the chain theory was [..lso confirmed by other methods on other tegt ob-
~ects.
This is an incomplete enumeration of results in the Yield of chemical
kittetics that have been obtained recently at the institute off' Chemical
.Physics. The investigations in question have in many respects advanced further
than similar work which is being done abroad.
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