DEVELOPMENTS IN USSR WORK ON ABSORPTION

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000700240063-4
• Release Decision: RIPPUB
• Original Classification: S
• Document Page Count: 8
• Document Creation Date: December 22, 2016
• Document Release Date: July 11, 2011
• Sequence Number: 63
• Publication Date: October 4, 1955
• Content Type: REPORT

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CLASSIFICATION S-E-C-R-E-T
CENTRAL INTELLIGENCE AGENCY REPORT
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS CD NO.
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BLISHED Bimonthly periodical, 8 times yearly periodical
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.BLISHED Moscow
DATE
PUBLISHED 1953-1955
LANGUAGE Russian
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DEVEIAPMENTS IN USSR WORK ON ADSORPTION
[Comment: Although a considerable amount of research dealing with phys-
ical adsorption is being conducted in the USSR, and new results in this field
have been obtained (cf. the account of M. M. Dubinin's work below), in^reasing
emphasis is being placed on the type of chemical adsorption which involves ion
exchange and the use of ion-exchange agents (sy:thetic resins). There is s
tendency to emphasize the specific, chemical aspects of adsorption processes
on agents which hithertc have been regarded as purely physical and unspecific
in their action (e.g., silica gel).
The reasons for the changed approach to the study of adsorption processes
arise partly from the expansion of research and of practical work on industrial
catalysts (i.e., agents on which highly specific processes of adsorption and
desorption take place) and partly from current efforts to isolate on an indus-
trial, semi-industrial, or analytical scnle, substances which are present in
very high dilutions. This applies to alkaloids, amino acids, antibiotics, and
toxic agents present in the air. As far as toxic agents are concerned thew
can be analyzed after being concentrated by adsorption and must be adsorbe3 in
any case to protect persons exposed to,them. Research on adsorbents is very
essential from rk on gas masks leading to developments of
the typ
As far as work cn atomic energy is concerned, the isolation and separation
by adsorption of rare earth elements (with which thorium is frequently associ.-
ated), transuranium elements, and radioactive isotopes is of importance. Gome
USSR work in this field is mentioned below. Iu addition to the old method of
adsorptive coprecipitation, ion-exchange chromatographic separation of radio-
active isotopes (A. K. I,avrukina), and of rare earths (D. I. Ryabchikov) is
discussed by USSR investigators on the basis of work done in that country. 1n
view of the fact that some rare earth elements are used as carriers in the iso-
lation of radioactive isotopes by coprecipitation methods, USSR work on rare
earth elements is also of significance from this standpoint.
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In the field of chromatography, the chromathermographic method described
by Zhukltovitekiy et sl., is of outstanding importance as an analytical pro-
cedure xhich appears to have nearly the same capabilities as mass spectrography
(ef. R. H. Munch, "Vapor Phase Chromatography," Abstracts of Payers Presented
at the 127th Meeting of the American Chemical Society, Cincinnati, 1955, P 8-B).
Attempts to apply this method on an industrial scale as a means of separating
and isolating substances present in a state of high dilution wiles bear watching.
As indicated is an article by N. A. Izmaylov (see below), industrial installs-
tiona for ion-exchange chromatographic separation and ton-exchange adsorption
are definitely under consideration in the USSR and may alregdy be in operation
as far ea the production of alkaloids is concerned. The designing of continu-
ously working installations of this type and experimental work in that connec-
tion are significant, because ion-exchange resins can be used for the isolation
and concentration of transuranium elements and radioactive iso'~pes.
Numbers in parentheses refer to appei.ded sources,)
In reviewing the work done in 1954 by institutes of the Department of
Chemical Sciences USSR, M. M. Dubinin, Academician-Secretary of the department,
mentioned work on activated carbon adsorption and research on chromatography
xith the use of synthetic ion-exchange resins as ctu?omatographic adsorbents.
He also referred to the use of tracer atoms in work on adsorption phenomena.
(See oo-w-31423.) Some of the work mentioned by Dubinin is discussed in greater
detail belox.
Activated Carbon
In an article dealing with the pore structure of activated carbon:;, M. Id.
Dubinin outlines research on this subject xhich has been conducted :vainly b~?
him and by his collaborators. The data obtained indicate that as far es 'the
dimensions of the pores are concerned, activated carbons are neither monodi-
sperse nor polydisperse systems, but exhibit a so-called pol,ymcual distribution
of pare sizes. This means that the curve of pore size distribution has a few
relatively narrox and tall peaks. According to the data described, activated
carbons in general have a tridisperse structure, i.e., their curves of porgy
size distribution exhibit three peaks which correspond to macropores,to pores
of intermediate size, and to micropores. In view of the fact that in '-any
types of carbon the volume of the intermediate pores is very small (less than
0.05 cubic centimeters per gram), these carbons constitute for all practica.L
purposes bidisperse systems having only two varieties of pores, i.e.,
micropores and macropores. When such carbons are subjected to an activation
xhich approaches the limiting degree, the micropores are enlarged to the size
of intermediate pores. At the same time the micropores are also enlarged and
a bidisperse carbon having only intermediate pores and micropores results. in
a carbon of this type the specific surface of the adsorption film must for a.11
practical purposes coincide with the specific surface corresponding to the
pore contours.
According to Dubinin's treatment of the subject, carbons of the micropore
type (first structural type) have a heightened adsorption potential, because
the adsorption fields of the opposite xalls of the micropores overlap. Sueh
carbons have small micropores and their adsorption space is equal +,o the pore
volume. Carbons of this type are best suited for the adsorption of gases and
vapors.
In carbons of the second structural type, which have only large micropores
or are practically devoid of micropores, the dimensions of the pores are not
commensurate with the size of the molecules being adsorbed, as they are in
carbons of the first structural type. Here the curvature of the surface exerts
no influence on the adsorption, so that carL.ns of the second structural type
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carbon adsorbents such as heat-treated carbon yblackLLSeCarbonsiofmthensecond
structural type are beat suited for decolorization, because the open pore
structure of these carbons facilitates the entrance of large molecules and
colloidal particles into the pores.
Carbons with a mixed pore structure intermediate between the first and
second structural types are best suited for the recovery of products by ad-
sorption because oi' the relatively easy desorption from these carbons.
Dubinin points out that the relationships and formulas pertaining to acti-
vated carbon which have been developed in his article also apply to other
adsorbents such as silica gels, alumina gels, etc.(1)
Ion-Exchange Adsorbents
The subject of chromatography with the use of synthetic ion-exchange
udsorbenta is discussed in an article entitled "Cation-Exchange and Electron-
Exnhange Resins" by Ye. B. Trostyanskaya, I. P. Losev, and A. S. Tevlins. The
use by Ye. N. Gapon, T. B. Gapon, and F. M. Shea~yakin (Doklady Akademii Nauk
SSSR, Vol 58, 1947, p 597) of a Permutit in the chromatographic separation
of ions carried out for the first time is mentioned. According to tkie authors
of the article, this Permutit was developed by the Institute of Applied ~Sin-
eralogy. On the basis of articles that appeared in several collections of ;
USSR published papers nn chromatography which have been edited by ye. D. Trost-
yanakaya and I. B. Losev, the authors describe the properties of synthetic
cation-exchange resins of the carboxylic acid type, pointing out that these
resins show a high selectivity of adsorption depending on the pH and the valency
of the ions being adsorbed. They also discuss phosphorylated cation-exchange
resins and (on the basis of work by I. P. Losev and A. S. Tevlina) the prop-
erties of resins which in addition to adsorbing cations also reduce them.
According to Losev and Tevlina, some reducing properties are possessed by phenol-
formaldehyde resins, by all sorbents xhich have been modified by the introduction
of acidic groups, and by all sulfonated polymers of styrene-containing su~-
stituents which form cross-links between the straight-chain polystyrene mole-
cules. After describing the properties of resins which i'unction both as cation-
exchangers and reducing agents (i.e., electron e:changers), the authors dis-
cuss electron exchangers proper (i.e., resins which act as reducing agents but
do not adsorb cations) on the basis of foreign publicntions.(2)
Chromatography
By applying a method of paper chromatography which us':; :;mall quai~ti..:iea
of substance and is best suited for analyCical deterc;irr.1.~:~c, V. L. Zoloi.:.vin
of the Ural Polytechnic Institute imeri v. M. Kirov d~?c_rmined the order in
which metal cations are adsorbed on aluminum hydro:;ir'e with which the paper hru~
been impregnated. kte also car'ricJ out separations, '.r, this method, of ~et? ~,?a'
pairs of ions and of mixtures consisting of three io:7.;.(j)
The chromathermographic method which has bean developed by A. ;. Zl,ub;hr,??
vitskiy and members of his Troup involves passing of the mixture to be separated
through a column of chromatographic adsorbent with simultaneous application of
a temperature gradient. This method is used in prospecting for petroleum and
natural gas. It also has general applicability for the concentration, deter-
mination, and isolation (potentially on an industrial scale of substances
which occur in a state of high dilution
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earthlelementntbynmeanslof loniciexchangeeresinsefeThis subJectaistdiscussedre
in greater detail in a review article by D. I. Ryabchikov and Ye. A. Terent'-
yeva.(4) Elsewhere Ryabchikov in a communication from the Inatit~tte of Geo-
chemistry and Analytical Chemistry imeni V. I. Vernadskiy describes data demon-
strating the applicability of the method of ion-exchange chromatography to the
investigation of complex compounds (those of rhenium in this particular in-
stance.(5)
A. K. Lavrukhina states that during 1953-54 research on elements occurring
in ultrasmall quantities, i.e., radioactive isotopes, has been carried out at
the Institute of Geochemistry and Analytical Chemistry imeni V. I. Vernadskiy,
Academ;,? of Sciences USSR, with the view of determining the behavior of these
elements during precipitation, extraction, electrolysis, distillation, and ion-
exchange chromatographic separation. She adds that data of this type are of
importance for the isolation in a pure state (i.e., free of an admixture of
carrier substances of radioactive elements obtained in nuclear reactions. The
part of the investigation described in this instance deals with the precip-
itation together with hydroxides, sulfides, or some other compounds of the
radioactive isotopes of Bi, I, Zr, Y, Ce, Fe, P, As, Co, Sb, Zn, and Nd, with
particular attention to Bi 210 Ways of reducing the amount of the
radioisotope by reprecipitation, increasing the acidity, or adding a complex8ted
forming compound are also diacussed.(6) The method of eliminating coprecip-
itation is illustrated in an article by N. A. Rudnev (also a contribution from
the Institute of Geochemistry and Analytical Chemistry imeni V. I. Vernadakiy)
dealing with the prevention by means of basic dyestuffs of the coprecipitation
oi' the radioactive thalliua. isotope TI 204 with arsenic trisulfide.(7)
Coprecipitation procedures are discussed by Lavrukhina on the oasis oi'
V. Khlopin's work. She says that it has been established at present t}iat th_
following types of coprecipitation occur: isomorphic coprecipitation, colreci~_
station by adsorption, formation of irregular mixed crystals, and internal ad?
sorption in micro-fissures and microcaoillaries. According to Lavrukhina, tlit
adsorptive coprecipitation of radioisctopes with various precipitates is deter-
mined by the following factors:
1. I'he charge of the surface of the precipitate. Radioisotopes are affc~-
tively adsorbed by precipitates only when the charge of the surface of the prE-
cipitate is opposed to the charge of t}:e ions of the radioisotope.
2? i'he solubility of the compounds being adsorbed. Results of experi^t~,;.'s
by I.avrukhina et al. on I 131 and by A? Ratner on Pb 212 show that as the sc:,'u-
bility of the compound being adsorbed decreases, its adsorption by the nr_c+p?-
state increases. The solubility of the precipitate has no influence on tha ac-
sorption.
3? The surface of the precipitate. Precipitates consisting of smal?.cr~~s-
tals are better adsorbents..
Khlopin's work on isomorphic precipitation is b.?iefly reviewed by
Lavrukhina.(6)
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Industrial Adsorption Processes and Chromatograph
In an extensive article dealing with the application of adsorption proc-
esses in the isolation on an industrial scale of dissolved substances from
solutions, N. A. Izmaylov, Yu. V. Shostensko, and S. Kh. Mushinskaya (Khar'kov)
review this field mainly on the basis of their own work and of USSR publica-
tions on the aub~ect (the bibliography consisting of 71 titles, lists 9 for-
eign references and 62 USSR references . In the introduction to the article
the authors give a brief survey of industrial processes of adsorp~_on from solu-
tions, pointing out`ttiat ion-exchange resins are being used _~r the separation
of rare earth and transuranium elements and also for the isolation of copper,
gold, and silver from dilute solutions of the salts of these metals. They also
mention processes for the extraction of quinine, atropine, and scopolamine by
means of cationites and procedures for the adsorption of salsoline, cytisine,
and anabasine on bentonite.
The authors further point out that the technology of the adsorption of one
substance from a solution is only a special case of the technology of chromato-
graphic separation resulting in the isolation of several substances. They also
state that N. A. Shilov, M. M. Dubinin, and their collaborators have developed
a theory of the dynamic adsorption of gases, vapor,, and their mixtures which
forms the basis of the practical application of adsorption processes for captur-
ing substances present in the form of vapors and gases in the air; that the
basic postulates of this theory are applicable to adsorption from solutions as
well; that further work on the dynamics of adsorption has beer .:ne by A. A,
Zhukhovltskiy; that M. M. Dubinin et al. have recently achieved a considerable
amount of success in work on the criteria of adsorbability of various substances
on adsorbents of different structure; and that Ye. N. Capon and B. N. t71ko1'-
skiy have developed the theoretical fundamentals of the statics and dynamics
of ionic chromatography.
After this introduction, the authors discuss in detail the advantages of
adsorption from solutions as compared with extraction, the basic requirements
which must be fulfilled by effi_ient technological adsorption processes, the
adsorption on molecular adsorbents, the adsorption on ionic exchange agents,
complete adsorption and desorption in stepwise processes and continuous proc-
esses,?adsorption and desorption under dyi,:.:^i.r conditions, and the regeneration
of adsorbents. They point out that it is much easier +-~~?estore the activity
of ionic exchange agents than that of molecular adsorbents :.:~d illustrate
regeneration procedures with the example oi' adsorbents ,.;ed in the production
oi' alkaloids.
In conclusion the authors describe a technological scheme of a continu-
ous counter-current adsorption-desorption procedure in which every adsorbent
unit is replaced periodically by the folloxing adsorbent unit in such a manr:er
that the adsorbent moves in a closed cycle consisting of an adsorption stage,
a desorption stage, and a regeneration stage. According to the authors, the
process of dynamic adsorption xhich has been developed and described repre-
sents a continuously moving primary adsorption-column chromatogram in which the
adsorption zone of one substance is continuously widened. while the adsorptior.
zones of all other substances are continuously displaceu .rpm the adsorbent
as the current of the initial solution moves along. A characteristic trait o:i
the procedure is that desorption is not carried out from a column consisting
of a number of zones, but only from that part of the column in which the sing'_e~
substance that is being isolated is predominantly adsorbed. This form of chro-
matographic separation represents one oi' the possible solution of the problem
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in regard to the designing a continuoudl.y operating industrial chromatographic
installation. The authors conclude this discussion by saying that the solution
proposed by them in the terms outlined above can be extended to the case of the
isolation of n substances. In that case the numbe* of the required adeorption-
deaorption installations must be multiplied by n.(8)
Adsorption and Catal sis
The role of adsorption phenomena in heterogeneous catalysis is reviewed in
the subdivision "Kinetics and Mechanism of Catalytic Reactions," a collection
of papers dealing with problems to be discussed at the 1955 A11-Union Confer-
ence on Chemical Kinetics and Reactivity. A paper by V. V. Voyevodskiy, F. F.
Vol'kenshteyn, and N. N. Semenov discusses the adsorption of free atoms and radi-
cals on the surface of catalysts and the adsorption of saturated molecules on
catalyst surfaces with the formation of radicals. The crystalline catalyst is
regarded as a gigantic radical which has free valencies on the surface. The
authors point out that when the catalyst is treated as a radical, the difference
between heterogeneous and homogeneous catalysis dinappears.(9)
M. I. Temkin also emphasizes that the basic principle of catalytic activity
is the same in homogeneous as in heterogeneous catalysis. $e discusses the
phenomena of heterogeneous catalysis from the standpoint of the interaction be-
tween activates atoms on the surface of the catalyst and treats the properties
of gases adsorbed on metals in the light of results obtained in electrochemical
investigations carried out by A. N. Frumkin and members of his group.(10)
In an article dealing with the activated state in catalysis. A. A. Dalandin
discusses activated adsorption from the standpoint of his multiplet theory.(11)
V. B. Aleskovskiy, in a paper dealing with the chemical structure of sub-
stances which act as adsorbents and are effective as heterogeneous catalysts,
points out that catalysts remain unchanged during processes of catalysis and
for that re_:son must be stable, i.e., high-molecular compounds. Conglomerates
of small crystals would be too unstable to function effectively as catalysts
notwithstanding their relatively large surface. Aleskovskiy postulates that
adsorbents and catalysts consist of high-molecular, unsaturated, macroscopic
radicals forming a skeleton and of a great number of functional groups covering
this skeleton. These functional groups, although representing an insignificant
fraction of the weight of the high-molecular substance, determine its behavior
as a sorbent or catalyst, because they are attached nt the active centers.
According to Aleskovskiy, the fact that silica gel powder acts as a radi-
cal can be demonstrated by heating potassium iodide or carbon tetrachloride
with it. When this is done, libex?ation of iodine or chlorine, respectivel;/?
takes place at temperatures which are much lower than those necessary for the
decomposition of the substances in question in the absence of silica gel poud~~-.
On the basis c: the experimental results obtained by him, Ales};ovski~: _c,n-
cludes that catalyst:; must be pseudomorphous substances of the type of cagr.eti:
ferric oxide (gamma - Fe203), which is pseudomorphous with respect +~ magnetite
(Fe~Olyl, having the same crystal structure a; the latter. When in the course
o" catalytic oxidations (e:g~, oxiflation of ]iydrogen with oxygen) carried cut
in the presence of gamma-ferric oxide this oxide undergoes a reversible trans-
formation into magnetite, it retains its original structure after reduction.
This makes the gamma-ferric oxide an effective catalyst.
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B Y sub,)ecting a ferric oxide catalyst to X-ray analysis during the process of
flsmeless ecmbustioa of hydrogen with oxygen, Aleakovskiy found that oxide re-
tains its crystal structure during the process of catalysis. When an excess of
hydrogen is used, an admixture of Fe 0 appears. Presence of an excess of
oxygen results in a change in the
t
~
c
s
S
u
ture of the catalyst: formation of a .
lattice of the corundum type takes place. When this happens, the catalyst loses
its activity. However, the activity can be restored by treatment with hydrogen.
Extraction with acid sharply reduces the structure) stability of the partly
reduced oxide: it immediately assumes the corundum structure during flameless
combustion of hydrogen and loses its activity. However,, when potassium ions
are introduced into the structure of the extracted catalyst, its structure and
stability during the process of catalysis are noticeably strengthened.(12)
1. bf. M. Dubinin, "Comprehensive Investigation of the Pore Structure of
Active Carbons," UspTkhi Khimii, Vol 24, No 1, Moscow, 1955, pp 1-13
2. Ye. B. Trostyanskays, I. P. Losev, A. S. Tevlina, "Cation-Exchange
and Electron-Exchange Resins,' Uspekhi Khimii, Vol 24, No 1, pp 69-92
3? V. L. Zolotavin, "Investigation of the Chromatographic Series of
Cations," pp 34-36, Sbornik State o Obshche IL'~imii (Collection of
Papers in General Chemistry ,Academy of Sciences USSR, Moscow-Lenin-
grad, 1953
D. I. Ryabchikov, Ye. p, Terent'yeva, "I1ew Developments in Methods of
the Separation"of Rare Earth Elements,' Usuekhi Khimii, Vol 24, No 3,
1955, PP 260-274 ~ ??,
D. Z. Ryabchikov, A. I. Lazaro+,?, "A Contribution to the Analytical
Chemistry of Rhenium," Zhurnal Analitichesko~v~Khimi~, Vol 10; No 4,
Moscow, Jul-Aug 1955, pp ~tf=23~j'"`"?'"'?""' `
A. K. Laorukhina, "Investigation of the Behavior of Ultrasmall Quan-
tities of Elements;' Communication 1, Zhurnal Analiticheskoy Khimii,
Vol 10, No 4, pp 203-209
N. A. Rudnev, "Application of Surface-Active Substances to Prevent
the Coprecipitation of Ions With Sulfide Precipitates," Zhurnal
Analiticheskoy Khimii, Vol 10, No 4, pp 217-221
N. A. Izniaylov, Yu. V. Shostenko, S. Kh. Mushinskaya, "The Principles
of the Application of Adsorption Technology to the Isolation of Sub-
stances From Solutions," Uspekhi Khimii, Vol 24, No 3, PP 346-376
V. N. Kondrat'yev and N. Id. Emanuel', editors, Vo rosy Khindcheskoy
Kinetiki Kataliza 1 Reaktsionno S osobnosti Problems of Chemical
Kinetics, Catalysis, and Reactivity , Acade~y of Sciences USSR,
Moscow, 1955, PP 423-440; article by V. V. Voyevodskiy, F. F. Vol'-
kenshteyn, and N. N. Semenov, "The Role of Free Valencies in Heterog-
eneous Catalysis."
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Kinetiki Kataliza i Reaktsionno-~S~osobnosti yProblemsnof Chemical
Kinetics, Catalysis, sad Reactivity ,Academy of Sciences USSR,
Moscow, 1955, pP 484-495 article by M. I. Temkin, "Concerning Reac-
tivity and the Influence of Adsorbed Atoms and Radicals on Each Other."
11. Ibid., pp 451_483; article by A. A. Balandin, "Concerning the Nature
of the Active State and Heterogeneous Catalysis."
12. Ibid., pp 569-587; article by v. g. pleskovskiy, "Concerning the Chemi-
cal Struc~ure of Substances Which Exhibit Adsorptive Capacity and
Catalytic Activity,"
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