RADIOCHEMICAL RESEARCH IN THE USSR/THE USE OF TRACER ATOMS IN THE PHYSICO-CHEMICAL STUDY OF SOME INORGANIC POLYCOMPOUNDS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP81-01043R002000070006-2
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 114
• Document Creation Date: December 23, 2016
• Document Release Date: June 25, 2013
• Sequence Number: 6
• Publication Date: April 2, 1958
• Content Type: REPORT

Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
--: - --I-42z�Z-M-1.4t-L- - SEE BOTTOM OF PAGE FOR SPECIAL CONTROLS, IF ANY
1 N FORMAT' ON REPORT
This material contains information affecting the
National Defense of the United State- �" -
50X1-HUI
meaning of the Espionage Lam,- Till_
Secs. 793 and 794, the trcmsraltsion or revelation
of which in any manner to an unauthorized per.
son is prohibited by law.
PREPARED AND DISSEMINATED BY
CENTRAL INTELLIGENCE AGENCY
50X1-HUM
COUNTRY
USSR
SUBJECT
Radiochemical Resesrch in the USSR/The Use of
Tracer Atom in tb.e Play131.co�Chemical Sturly of
Some Inorganic PoityconTomat4
DATE DISTRIBUTFn
NO. OF PArgbxi -HUM
1
1 .-
SUPPLEMENT TO REPORT #
50X1-HUM
THIS IS l INFVAI I !ATP') tnirnPrina-rintu ,^
50X1-HUM
cDpiss of two scientific moaners
h
Victo_ aft_itfi.,Nmentist
50X1
-HUM
Prof opa.Lsyn is a member of the faculty of
Moscow" ihia.versity and a Concseptanding bitteber of the USSR Academy of Sciences.
The titles of the two pveral arras
50X1-HUM
"T.1%dlochaaite,1 Reemrch in the ussR".�
ntrile.f use of Tgacez� Atom in the Physico-Chemical
Stztiky of Stow Inorannic Polycompounds"
50X1-HUM
- end -
,
DISTRIBUTION
STATE
-'11ssliZs&ss-
ARMY NAVY I AIR I I
NOFORN
NO DISSEM ABROAD
LIMITED
LimiTED: Dissemination litnitsd to full-time employees of CIA, AEC and FBI; and, within State and Defense, to the intelligence components, other offices
producing NIS elements, and higher echlons with their immediate supporting stalls. Not to be disseminated to consultants, external projects or reserve
personnel on short term active duty (excepting individuals who are normally full-time employees of CIA, AEC, FBI, State Or Defense) unless the written
permission of the priginatina office has been obtained through the Assistant Director for Central Reference, CIA.
-
�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
a
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�����11.e.,
FORFirli �Ty tpc5 tri
L. 41; y
� 4. /
RADIOCHEMICAL RESEARCH IN THE USSR
By Victor Spitsyn,
Professor of Moscow university, Corresponding Member of
the.USSR Academy of Sciences.
Studies of radioactive elenents began in Russia soon after
radioactivity had been discovered. They were conducted in close
cooneration between scientists of various specialities: minera-
logists, physicists, chemists, technologists and physicians.
The physicists A.P.Sokolov (1903) and I.I. Borgaan (1904)
studIed the radioactivity of various natural objects - mineral
water, medicinal mud, rook and soil, and considerably improved
the methods of radiometry. A.P.Sokolov notably developed a
compensation method for determining radium by radon, which sub-
sequently found wide application.
N.A.Orlov (1904) discovered radiation-ch3mical transfama-
tions of paraffin and other organic substances during the action
of radium eaanatlen. Y.N.Antonov (1913) discovered a new
k%
radiotelement, uraniumr:,among the products of decay of uranium.
L.S.Kolovrat.Chervinsky (1914), conducted major research on the
isolation of radium emanation by solid and molten salts. V1. I.
Spitsyn (1917) used radiactive tracer atoms (RdTh, U14) to
measure the solubility of slightly soluble compounds of thorium.
I.A.Antipov (1900) discovered a uranium deposit in the
Ferghana Region, the first in Russia. V.I.Vernadsky (1910)
expe itions aimed at a wide-scale research of
vo
Cz,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
*
`W.
rif 'nr t111,.gity
� � '
- 2
uranium-radium and thorium Ores and undertook an extensive
study of the geochemistry of radio.:elaments. Kha. Ant4novich
(1908) carried out experimental refining of Russian uranium-
4 vanadium ores,but the attempts to isolate radium from it en-
countered great difficulties.
Even at that time Russian' scientists took full account of
the importance of research in the field of radioactive elements.
In 1910, V.I.Vernadsky (1) wrote: �Today sources of atomic
power are revealed before us in the phenomena of radioactivity,
exceeding millions of times those which man's imagination
could picture/ sources which by their Dower and importance dwarf
the power of 'steam, electricity and xp osion processes ....
Mankind has entered the new age of radiant, i.e. atom10, power,"
The level of imlustrial production was; however; very low in
pierevolutionary Russia. As a result, the material and engineeri
ing opportunities for the advancement of research, notably, on
radiochemistry, were greatly limited..
The situation has abruptly changed after the Great October
Socialist Revolution. One of the first tasks set by the Soviet
government in 1918 before the Acadmny of Sciences was to
elaborate a method for extracting radium out of Soviet uranium-.
vanadium ores,: The task, difficult at the times, was success-
fully resolved under the guidance of V.G.Iblopin, an outstand-
ing Russian chemist, and in 1921 the staff of the Experimental
iecotfite,_
Radium Plant produced the first preperetrien of radium bromide.
r\11 gal
�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
1
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�j�������������������
4
�
1-
V.
��������
.;k101,1, fi
- 3 -
The production of pure compounds of uranium was started in the
USSR a few ater on the basis of these raw materials.
The further development of radioohemistry in the USSR was
closely connected with the activities of the Radium Institute
founded in 1922 and attached to the Academy of. Sciences. Under
".441.440t -
the guidance of V.G.Khlopin, the seepawark4Lioo-were-imPooid-
8.41A of the process ocourri in fractional crystallization of
e.44�44
barium-radium salts he ow e ge of whioh proved indispens-
able in ensuring the progress of the Soviet radium industry.
According to the rule evolved long ago by K.FIranv-F.PanstIL
(1913), a radioelement in solution in a state 9f.micr000noent-
1=44:elliorevie
ration is supposed to be absorbed by the;
e if the
element forms with an ion of the reverse sgn of th0-solid
5
phase. a compound which is difficul+e-ti-eselle in the given
medium. In 1924, Kblopin (2) proved that isownibism of the
V
and the radium salt so formed is an indispensable
condition of such coprecipitation, while the degree of solubil-
ity is of no considerable importance. For example,. during the
crystallization of gypsum out Of a solution, the radium.pre-
Aff#4
sent there does not pass into the -as gypaum and radium
sulphate are not isomorphous. Anhydrous strontium nitrate -
isolated from aqueous solutions at a temperature above 349 is
isoslorphous.with radium nitrate and captures it iirtbe course
of crystallization.. On the other hand, with a temperature
below 34dc, when ate Sr(NO3)2.4H204 is formed, which is
r
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
1
&
_LA.4
- 4 -
6.1�����������,,,
not isomorphous with radium nitrate, the latter is not
included at all in the solid phase. If, however, crystalliza-
tion of strontium nitrate is carried out at 0�0, the isolated
crystals of Sr(No3)2.4H20 again begin to capture radium as a
result of formin& tetrahydrate of radium nitrate, similar to
barium,. which does not exist in a free state but which is
capable of producing isomorphous -mixtureswith Sr(NO3)2.41120.
V.G.Khlopin was the first tO employ quantitative physico-
chemical methods to. study two-phase systems, of the type salt-
water, containing a micr000mponent. It was demonstrated that
Miring crystallization equilibrium is attained much slower by
the microcomponent than by the mr000nyonent. This pointed
to the great role played by the process qlresidue recrystal-
lizat ion, occurs for a long period of time, after the
apparent equilibrium between the maorocomponent and the sc4u-
r:
tiOn has already set in, and which replaces the phenomenon
of diffusion, practically absent in the solid phase,
V.G.Ehlopin'(3) and. his associates made a stuO:of over 30
systems containing compodnds of strontium, barium4 lead, cerium,
uranium, etc. as a macrocomponent', and radium, polonium, and
*lead4 bismuth and thorium isotopes (RaD0 Rai and Uk) as a
microcomponent. It appeared in every case under investigation
that the miorocomponent producing a compound isomorphous with
the solid �hage is distributed between the or stals and the
iolution like a diluted substnace betwean two non-mixin sol;-
Cr
ILI.1 L..
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
s sou iss,ai. .1flt Ute. rfltW-'1��������: �"'" "� � """
11/ ���� � �����, ,te4 �� � -�
� � �
ea 440 4.4 444-44 4./44..� � 40 1144,....� 4�414�1444, It�444444.41.6444 � V* 4.4 c.a....ow.... ���� �
� $ , �I "
FOR OFEC-iitt USE ONLY
- 5-.
vents (V.G.IChlopin, 1024) �
The following formula was suggested for quantitatively
--appim*eiag the distribution of radium between the crystals of
barium salt and the solution:
x Kl'x
(x)
where x is the amount of radium which passed into the crystal
in is the weight of the so lid phase, 1 - x is the amount Of
radium remaining in the solution, v is the 'volume of the aolu-
tion?., and K is some constant typical or every pair of mita,
Subsequently V.G.Xhlopin and B.AXikitin (4) modified the
tt
equation in the following way.:
xSi (1-x)So
(2)
�
where 'x, lx and in have the former -guinea, q is the w�
of
the -liquid Phase, and S1 and So are the specific *eights of
the solid and liquid phase.
If one deSignates by x and 1-x �reepecitively the amount at
the miorocoMponent which passed into the �crystals or rmaidasid �
�cent;
in the solution, and by y and 1-y the, amount of thi,magroOorsitioni
wht�hpu5ed into the crystals or rime:laid in thi, 161
, �
the
praCess of 'fractional crystallization may -bialpfinad,by-
,
the f011owing equattims
a
where D is the ooeffioimeq,
�
�
,
e.oning, repreilent.ing the
. �
_
� Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�����������"....."'"
P.
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
-4
Frnrh".."1" "cr ONLY
a k�iir Avg
-
��
' meat in tbs crystals and the coefficient of microcomponent
impoverielment in the solution.
In c ase ,fraotionel crystallization proceeds in a normal
lwayethe''ooefficient of crystallization remains constant and,
at :the 0=4' time,,, corresponds to equation (3) throughout the
t.,
,prohess. This regularity was repeatedly checked in practice
And served as a sOientific basis in controLling and adjusting
be indetri�'methods ibr isolating radium and some other
'WOO,
'7.71
si
radioelements.
04,4^7
Proceeding from the -deetrritte of the thermodynamic potentia
..,t.
an the theory of �activities, A.P. Ratner (5)Ps'theoa;'-
retiosa4y.C._eneral equation demors trating the regularity of
distribution of the rai.orocomponent between the solid,.,.:OrYstal.:!,
-and ltqaid phases and established a connection between. _the
coi4!ficitent of fractioning and the concentrations,af the
llomp.onents in the two phases, and the proper tie a of pure
components., The eiiiition he obtained proved to fully 'A.COOied.:
, with the experimental data.
, � ,, �
The research outlined above has made it alsci%POsing* 4
, ..,
,
draw the following important theoretic al conclusion:
�
ppliiabili.tyof the lavie'of distribution to thejbehavio
;N� "
fit:Olre niroicidOmpor,tent .between the crystals Of some salt an' d
� �v �
solution is proof of the preseAoe of isomorphism betwStir.l.tbe
� Kc �
available Compound of the mioroctimponent and the,saitiOr
. , ,
-
a solid Phe.sel2 and of the similarit�rof3 ir:otomposit
$1.; � .
npciassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�
ators-1
0 004 in
oixne media. � �
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
phendmexitia:- The ratio' of radon and sul hurOus exiby440
�the *le:w$
of Ldistribittionf? It has thus been_ established. tha�tciadon
forms a hydrate isomorphous with rate of So2 and? ..eieeedtta,
by its cOmpositi formula Rn..6H20.. Radon is absorbed in
a Oipilar way by �lid hydrate of hydrogen sulphide 1123,41120*
.,-.Nikitin calculated that the PeosliPrezietryf dissopia:5.,0' dr, radon*
, . e
hydrate%amounts to 760. mra at about 0000 Hence,, pure ran
�
ohonld, ;interact in suah conditions directly with ic,e*.fong
, . .
, ,.� . � '1 .4
-p.milar. phenomena were discovered by Niki.44,,tor o:t4ei.
,
inqiitgasesin.amelyq argon �and neon.,. TaeYooerfibient:'pr dig:- i
I !�, ' - '� :,,e.-,.ts, .1 -
triblvtion *depends on the nature of inert gases i The. great
� ... . , _ � ., !,��: , .... , � , i
ilieli.� gi.9'thiii : radii and tke higher the ifif!isfe;, - . ..,pM. �".19 T: -1.i.,:".:4.14, ,
� ���,5_,..,-,_t:.:4,,,,-..:4,:, ... ,
� eqitronger the hydrates s.o form.ed. �-.� �LIAJLT.b.. ,...,,,e,.�-�:,.case,,
, . .. - A . � 1 I. - - � , � - '
, 1
t
;,._
. . *11*
it gap.e8 investigated ' by..N13.:itili the ,coie#ciiimia.
...�,,, : f ..i*- - , ..,. : .. 4 ..,.. '. �� . 4 ..ti t.1�..11i.;:;'
is.
4#' 1- .�,-
dis tribution ,betwe ea the gaseous phase and th4,..i:Foliid,v.
. '
4.7,44(vil, E,02:11291 had 44 flp,31.ow,in_g ,y,i4..meei..'.
lin AX ...,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
was reoorded. Henoe, anomalous mixed crystals,p0seati a micro-
.
--. � . , .,, - .:tit.- ,'.; .. - cn
. . ,..
,;....-.,, ,..,
rdiepersed mosaic struottx a; lo,ut. in . the co ursei , o f, thgzakr � ,- isolatra
..� . , .-,.1..,%...-.4-,,�.
�.,- - ...:.,��- 1,.:,�-, , -
- there remains a constant value of the erystelliz4tionradoef-
,
. , .
fioient. ,
. _
V.G.Khlopin and 11.13./Ifirktirova (14) disooverod'-'a' lower
4
"' $1
r,
� -
�
* t
04~ "..46.**141.iito;440t,.../oup 01*$4,44,t54:1...*! t4.434,411*.****4-�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
A
1717441! P1111
F6ht r y
-11-
MO' ������.,,,
boundary of mixing also during copreoipitation of radium and
thorium (in the case of tai) with lanthanum fluoride. Hence,
anomalous mixed crystals are formed in the systems LaF3 -
RaF2 and La1r3 - ThF4.
Interesting data were obtained by M.S.Merkulova (15) in
studying a more.00mplex oases hamely the coprecipitation of
bivalent metal ions with salts of the type of NaCl. NO lower
boundary of mixing was found in this case. In the systems
NH4]. - 2b12 - H20, NaCl. Pb012- H20 ahd Na 01 - sr012
diatribation of the mioroamounts of lead and strontium.
isotopes (ar89) 000urs in suoh a way that the orystallization
,
coefficients, Dt is a constant, irrespective of the amount of
tek-401:1444
the solid phase i4t1ataLL..4.ai.e.44a0--aoia-this,, and of the presenoe
of foreigaTiallsh alent ions in the solution. Analysis of the
epeed at which equilibrium was established by the mioroaompon-
, .
ent. in the system Waal - P41412 - H20 demonstrated that equill=,
brim was attained diiiIng a lo (for over 30 hoars):!,-
Th.1:41 WInaccorahoe with the measnism of formation of solid� : r -
solutions. IA the Case under examination, the miamoompOwenV
*enters lihe.orystal laAtioe of the maorocoMmeni Salk only tip
�
to a certain limit-(the upper boundary of mixing). The results
,�
f=1 t
:J... �
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
tj
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
0.,�����r����.�
�
4
�
..04.40;1(04 4:001�WA
FOR OFFP-71
alb
EA
rrir lAU.W/
Lz!".1.
110.0��������114i�
mixing. This is a new type of coprecipitation, which cannot
,
be classified as any of the types already known.. �
In the course of the .given analysis it was established ,
the crystallization coefficient for lead possesses a very high
Ttalue (Dpik! 220 at' 25oC). It v�possible to upe this pheno-
merlon to separate small amounts of isotopes of lead (T4IROM)
and bismuth (Ram). The latter are distributed between the
crystals and, the saturated solution of eodium chloride in-
dependent of one another and with their own coefficients of
'distribution, which quito-diffe eir absolute value
0141.. When 5% of NaC1 is isolated from an oversaturated,
solution; 964% of Rap and 2:9% of Re E pass into the
,A,fter repeatOd precipitation, 93.7% of PaD and 0,464 of Ra2
are4oncentrated in the residue. Complete separation of the
isotopes of lead and bismuth may be attained byapplying the
method of isothbrmal evaporation of the saturatell'Polution
of eodiuo chloride, -containing microquaatities of.PbOlA and.
. 4
4013.
N45,JAAr1culova (16) and her assopiates have,alsoana'lysed
recently the processes of copreoipitation4.attendsd,with.the
formation of inner adsorption systems. A study M$ besi;'
VI
made of the systems K2804 Pb804 X:2804Ra.104
and 1C2CrOitP13Q/z04 - ff20. It appeared thett. thereidp*eid
. � ". �
a iSgular capture of tbeAiorocomponent by the'stalid'itiis,
,..
%
< Z.'
-, .
� -,.... .... 4 A ,"2 r 74,4 t. ,
V. .4 440.40.46160f:.2*.I.A.. A'" ;;;10,"..t14 *NM 'Lb 2.1 f.:2'' � '
esilts'1/4�11
�
� ..�.4 410 (Ai 22A 12, ;' ; 111V A .2 � IA '
.0
AA.2. A AA �
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
whanArystals of sodium sulphate and potassiiiiii.,16,4**ati are
.1
� � isolated cluti. of the solutibn In the presence, OV,lead, and
1:��
�
.F:acittunkf In this case the behaviour of lead
:.rilictOPeg is likewise subordinated to the law of-diatilibu4on,
- ., �
��:. 4R, dj-til0. pr.y�stallizatiati doefficiellti Di has a 1316/1s:taut ivalue-_,
r
Piitibbnienon 4raivs a sharp diatinctioti;-Vetsimesii
�
minivis eel , points, however; to the ab'so rpti on natt, of:.' Vie.
phailomfinoiq The presence of easily adsorbed. iiitilvalentt, 4.0ns 1
in.-:tiliteSolUti1..on g.reattly. reduces the coefficient -,,o'i,Y�'-ilrY.Sta:ilt,iza-,:%
� ,���� ......1...... ' ! �
, ..,
.,'. ���.�,, � '41 . '
� t
oo#64pitation attended with the.. forration of. r4ii*:
�
���� �
8ypiti4C4-4ie�ohe � in the agape of isomorphous and ex4xi44iiiik,,.
- '
ih,t
tti348141.4'4 For example; � an increase � In .t440-0�!#:15#it'i..on
�
-
� *11:1 nofid,
,golten slta 'and -tI sold
1
IW 4 .4 4.$1;, **..ktl' 4.44U4 ,r..444# .0 ft s'&141A4 .0040.'0'04
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
FL7,7 L "c'T FI PPI
- 14-
covered in the case of solutions. D, the coefficient of
crystallization, remains a oonstant value, irrespective of the
amount of the precipitated solid phase and the method of its
precipitation. 7.GaChlopin and B.R.Klokman (17, 18) have
proved this when studying a number of systems containing
barium, lead, strontium and calcium salts as a maorocomponent,
and radium, ThX and ThB as a mior000mponent. Molten systems
also exhibited the formation of anomalous mixed crystals.
(1aF3 - RaF2) and inner adsorption compounds (K2SO4 - RaSO4).
At high temperatures the process of recrystallization 000urea
however, much faster than in solutions.
There are also some peculiarities in the behaviour of the
miorooOMponents in molten media. BaC12 proved to produce a
continuous series of mixed crystals both with Pb012 and 8r012,
while Ra012 oopreoipitates only with Pb012. Hence, there is
a shark,difference,in the behaviour of radium and barium in
this case (19).
A. number of investigations were also conducted in the
USSR,, devoted to the problems of adsorption of radiCelementp
and the formation of radiocolloids. It has long been known
that' some radioelements exhibits the properties Of collOida
�
*a4d can,., for example,
opinion was,. however,
be separated
woIee4ethat,
by means of d.ialYsia;,-The
while in ,infinitely
,solutions, radioelements do not form colloidal. particiliapf
their owns but are adsorbed on colloidal particles of.other
fr:F. ONLY
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
it
fier
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 CIA-RDP81-01043R002000070006-2
A
Frit 10-77.11R.1 11.nir /R.% lok
- 15 -
substances, namely compounds of ordinary elements.
I.E.Starik (20) has shown that in polonium compounds
the colloidal properties are most pronounced precisely in
those media where a minimum of adsorption is observed on pre-
liminarily prepared colloidal particles. This was convincing
proof of the fact that polonium forms genuine colloidal solu-
tions. The conditions of their existence have been specified
by subsequent research, use being made of centrifuging, ultra-
filtration and other research methods (21.). It appeared that
at concentrations of 10-'9 - 1012 mol/1 with pH ranging from
8 to 10, polonium, which is apparently in a quadrivalent state,
mostly forms insoluble compounds and under such conditions is
detained by ultrafilters to the utmost.
. A..P.Ratner (22) and his associates applied the method
of centrifuging and dialysis to 10-5 M solutions of zircoraum.,
niobium and tantalum compounds tagged with corresponding radio-,
active isotopes. The hydroxides bf the elements under investi-
gation proved to exist in a colloidal state in the range of pil*
from 1-2 to 12-13. During centrifuging, the colloidal parti-
cles of iirconium are separated allilost to the full, while' .
niobium and tantalum are practically not isolated. Analyile
of centrifuging and Ultrafiltration of polonium solUtioni and
of SOMB isotopes of thorium Mil and RdTh) at various values
Of pH permitted to discover the presence in these Solution8.
nrs.1,p1A1 rsz nt�14,V
- ,
r
� t � :4.� . &-.
Os.' twlcfr.,�0"wp4 UI'!"4-10100q1.40% '044;.".'"464 ��'."" ,.1{1.6�45.24-4, iVikt,ota;!*- � idagita'swa. �
nprlacsifiPci in Part - Sanitized Copy Approved for Release 2014/11/04 CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
-
- 16 -
A
"
A
of two groups of particles some scores of mierons and about
� 64) 47. 4
3i la in size. The radioelem s
ent in the -hape of roughly
dis-
persed particles passes through the dialyser, though rather
slowly, while the one in the shape- of finely dispersed partic-
les does not pass at all. An assumption has beeh made that th(
roughly dispersed /5articles represent a radioelement adsorbed
J-1
4
.,Lef..
4
on impurities, while the finely dispersed particles are formed
by the radioelement itself. Partial ionization of the colloid-
diluted solid phase of the radioelement appears to play some
t .
part in the latter case. After equilibrium has. been establish-
ed between the ionic part of the inner solution and the outer
solution, the process of dialysis comes to a stop.
Recently I.E. Stank (23) and his associates have been
systematically studying the condition:of small amounts of
various radioelements in solutions,. The formation;�of' aolloids
c -
has been established by the method Of ultra-filtration with
the aid of ri4pactive isotope Ru103: ln the o4;t ofty.i7and
quadrivalent ruthenium within a narrow range, of tyy,, a
4,
reohargitys of colloidal particles being *record:44:: Th. absence
of a pOS-litLy?isly charged 'oolloid was proved in'rh.oi,'�io.ikater:.�O.tri-
, _
Valent thallium hydroxide T127.4 was used its'a tracer.
Irtit# *pit aOtouitt,ing to 3; coagulation is record'edirs0C40 ,131r
04- -�-
exceeding 7.1, a stable negatively charged colloid .is , '.c;rplked.
,,� ')
, . :
At a concentration of .1011 - mo1/14.,,fission'zirconi*95
is to 13 *f9und in acid nitrate 'splittiond. aRT
. t.Ty' '
elmA9 .Lfl j;
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
41.444444�4
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
vaa
rrIn frrv.ftlrl rsT cpu
ivaa
1.7
, , i..,�=1..
'�)tieh.pttpranging from 1.6 to 4.24 Zr95 is markedly adsorbed on
. ,�4 :. , ...,:p..egatiliely charged partioles of impurities "and� behaves like
i , � .: - ..
, . , -, � . ..
a, iiquililyt 1 i sp era ea colloid. With pH amoUnting to ,4:24 86113.-
4,
41.
S.
.� ,. c
,
, ...,., � � .;.
In the case of uranylohlor.ide in a hydroohlOrids.�Medium,
,.. I � " ' 1,./. -i:, :,' ,:. . k .
74 ;
. � ' 1 s - ..I.,..; i i' ;' .t.' .:,,,14, ..
-. ge:ja...qoncentration of 5-1074 mo1/1., a collo-140r formaPii3On
(if.hydrolysis produots was found., with plf ranging. frcpi 2,i5
i
.,.....5.t.
.... s ,.,
e . ti).'16t54 in the case. of concentrations of the qider .of
i. ....1,,
..
� ����,�-,,
m91/1, uranium forms a pseudocolloid, ,with :pH ranging 'frOm ,-
� ...,,,A.,-..,,' �
-� .,:- .;.! t, z : .. � , t
. . - . . - .... ,...,,
� ''���,-i.oi 21,:t.�0 6 4 ,i.ti.i� dug- to the adsorption of themioroimp#ritietf� on
. . . Y
r
r� ,t,A4�,,i,1. , .....,� ..,I ,__
. It
: :-- '': j', � 4.�:::'i.: '''' ...,ehe.
particles existliag' in the solution (25):6. t"
. ,.., 1...� , , ..', .. , i
' .. 3. � l� , .'S 40 - 4, �
� ,...,..4� `..P. .....�tty?..4,�41 �..- � . a : t
:The above &research has grse.tly clarified the. conditions e
r'. ...1 t
id:� .. 1 . ----` ,, tt . ri, ' I , �
,,, . ., � , undtir,which real collOids of radidelements and their.. pseudo-.
� .,--- - �,, - ..*- " .,
.�,--r ,,,,t1v1.7kn>r ....*. , - - f'';, ' , f - "*��.....7.- .: if:::
t.
;.:14. .+.f.. rt,4..':...":4.;,!...:i� t� ��:oolloidg so1R.ti Oile are to ritiedt, ' .
,..- . . 44 ..t,,,,s., ... ,...:,, . .:.ci�tly...7 ..
i � ,. .
' .4 A A .1..t.. -4.'14 ...wea.016-1,..*AAJA.........a...fe .4 . . . Z-..'
�
�"-",.;ILAi 'l . t,w;",,� �'Investigation into the phenomena of sorptiOn-,,011.2-radi:0-1-. 7
�4."'117 i ."�.1 4 .. ' .TP.. '
. k � - t '' , 1...4: t- '����7: � i,. .
1 ' . . ' � .. r t ++.W'� '...�',. 4 '. ... 4.
4%, �1.-.N.' 4 ',' g "�'.. '1 � � t .t tV't , �.: '
:�,' j 1 ,..A.f. ,:" 4 ':'`..4:11", .,.1% pl,..fpn.sares -likewise attragied muoh thp- attpntion..tifft,)..,.' et'-",1--
t.-!, I.,. ,-� ., , �� � � -,,
t a e ,� .., -"-k::
roiseakoberikt., 17:41,,Kbloplia f 31 suggested getneiraliinek :.,,,ii
-,�,,,�t, , -�!. ,)q-- '7, S. -,..- ,.,.47:.,,i .,,,-.: ,-- .:47.,..,...
kl.s.:. � �� ,. , , , . �.
- ,e,...t* 9 �b7,4 distinguish istimorphous toerystallizatitin', ant�, ,
..y,.'1.i.' oi..:', f '.., I i , ...�.'t;'.. - , . , " 1. ) ;,' :Lt �-, �. i-1,. ,t,..--,::- - z.-',..-1-..;.,-'. ,
. eir ., .;., ' ... ' k.,,,- � . a � . 4 � . Q474 kfl
Z ' , , � , i 4 'V.i UkCli ' ' capture'; i*e is � ,t1g3oe.esary to teste kp.....- Sped of
ti-of,--
..,,,-...:,,,,,,. � ti6 � 4 e, I 12 -
. I . .. :'..",t, 7' ...", I r� �
/ ... ....
1...k., ., , ..4.. .sc. I, ",e. ,,.� � -
eetablfihirigt,eialibrium. between the a cliition- and ,the, residue
a � . ,,,t
,
I- � � � ,'� I.
.
,. . -71-
0 Pr :a .-� .4. c.� . ;,-,... .
,,i }, ). , -. -) �:: ,':, 4.4.1,
1, : � ..4 , ...41;;;;;', t � " �''.1)3r,i' :0)747rp,dioelomeintri; onotriP bi,-precipftating the.-`,eolitt php.sei4
, . , .
...,, .....,..;,�:,-,-,.., �.
1. . ...,,,--..,,, c.-4..�.,��.�,..,-._.. $4.4..,1 A.--, ..,..,4,
)� ' ' ' 4 I � , ..- . , .r, -1- .
.:. ,. .,, '''':(f 't,*,Ct,,: ...,' from the; fioluefon.-., Containing � the � radio elementi,'-. and..(`..-,,t4e '"�..13,6 and
"-."----' ill, p...; ' ....,.: � . 4
7. t :.,i- - . - , t tf;-4 . ' � , 4 ' '-!1� t
i. '�� ., "i
' � ..� t" '. 'kik: "I . t. , ; V. ' ..-1 ' l'.. ...I. ', i �
I'l'elF ' �'.� ''..V.-
� `.1.'' � .1 l'` 4'i :` �1
c..., I � A. 1. - O. � ' s ,' ,T) V !Vs, A
� 4. , �-.. ...,.. �,e,w,, * ,- 4 .,., .... 4 � � -... t
i .1 �t- .. �44 .4, ,4 - -,414r. f ....6",, � ..:pi.:2 4
g. a preliminarily �preggpLeaV ,reeidtle�.:-...ew-
..... 7.,,,..t=01.n. 1.1 i f. � t
' 7 . .: ,
.. 4 ���� - 4 ..,S. 1
4 i4.: . . 47 . a R f. . � - '...� 1 ).- .. ire U1,1 '''�'' ' �� � t , :�4` 1, �// 1"
4 � � jr, �� � ' e
� ., : , , e ,v1 3 - '��
'i: .
.,Y ,. It ,- - ,'� --4. . . 44, .. ' .�
-0 e�
- "'" -*moot* 1�41of ortesgeffi.auturatkrtimmosireemooie Alt*,A;r1 i I% Pr^ litak�ir IR w 41, to 4,,,, 41,... ir VS 0�0114 "4,04 444 A' ow" '1: i.h,i' %�-�4',-1-4--- 1.I.%Ai'�' I/01,- .4 Zo.,ve%!%40.11,0,4114:-
tivg4ArliNi)*Ii-4.4140;:kiecWii-19)oit�-�-swires4.k. t 4,-4) Ait4,-...�r ;4 o 46i$ w � , it c- 1 -.A� -
bility product Zr(OH)4 us attained, and a prop* negatively
rrbe r �
� i�O v �
Charged zirconium hydroxide colloid is. forinedF
-itifth--'th& part-
ioiea. approxlinately lm in size (24.,
A. � v
4 � .���.
� �A'Y'
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy A proved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�11...��������
rrimi "r.errvi r7f,tr v
- E..)11,.5
,
solution. In the ease of isomorphous doorystallization, the
magnitudes so found sharply'differ from one another, while
during adsorption capture they approximate one another. Apart!
from this, the process of recrystallization influences in a
different way the relative amount of the radioelement which
has passed into the solid phase: if isomorphous 000rystailiza-
tion*takes place., the degree of capture of the radioelenent
does not practically change in the case of adsorption, the
degree of capture .of the radioelement diminishes as well-
formed crystals are obtained.
Numerous experiments were carried out to study the
adsorption of polonium from solutions (20, 21,2). Minimum
adsorption by negatively charged surfaces, such as glass,
was recorded in a neutral and a weekly alkaline media; when
polonium exists in a colloidal form. Polonium is adsorbed
to a considerable extent in an acid medium as ions Pok+ or
20024. Desorption by means. of INHNO3 occurs the easiest when
the absorption of polonium by glass has taken plaop from:
niitril or weakly alkaline solutions, as colloidal -particles
are dambined with the sorbing surface less firaili
tban high-
valent cations. Quartz glass and pyrex glass rien in eilioa'
1 4
4
possess the greatest capacity for sorption in relation ,to
4
polonium. Preliminary treatment of glass with an alkali.
increase's the adsorption of polon4.um, while acid:trecae:nt
produces no tangible effect.
frrira?.11 rn.a. v
.... �
. ,
" ,
�sfrft t
. _ ,
rt if_ 0.'4 .""*..."4" .".40411110r$V110}-41.0 Obi ks.,147.1Aiiiiri/74 'A4 ailefTte, I �,�� Woe; ,�! loor� fee vow, �
# ,
Declassified in Part - Sanitized Copy A �proved for Release 2014/11/04 CIA-RDP81-01043R007onnn7nnnA
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
MID frrIPIA1 0�,117
19....
The adsorption of radium by glass was studied by many
investigators (26)i. Reduced data on the solubility of radium
sulphate were obtained because this phenomenon was not duly
taken into account. Correot results were obtained by y
0:3rbakher and B.A.Nikitin (27). VOLVdovenko and .A.,.(1.Samailo-L-
vioh (28) have shown that adaorptiOn of radium on glass at
concentrations of 10-7 - 10-11 mol/mi, with pH ranging from
2 to T, is subordinated to Guils theory, as applied to high-
valent ions. �
T.G!Kblopin (29) and his associates studied the adsorption
Of radium on a ototdue of lead sulphate. Particular attention IT
was gp:en to investigating the conditions for obtaining an �
adsorbent with a constant surface and potential. The
above-paid researchers noted that adsorption of isomorphous
ions was reduced to nothing but primbry exchange adsorption,
i.e. kinetic exchange with- the ions of the surface. The
t.
iirepettoo of surface active substances in the solutions impedes
the 'proposal
.A...-study was also made of adsorption of uranium by glass
and .paper filters, which is important in analytical woltic
Adsorption on glass proved insignificant. and diminished in
, propOrtion to. an increase in the concentration of acids or
.,
� . , , .
".,alkaline carbonate: Adsorption on filters wows as gi rises
. .
� andreaches 7% id a nconditionally-neutral solution with a
, . , . .
.. ,. ..�. ,. -. .
.` 1�;" ^
Pa* tprop.4,"^ remaisit faisir � * *Ivo n.f 041 'i��
Declassified in Part - Sanitized Copy Approved for Release 2014/11
�
*4I fP-.44010.4. � � ",w.".-
etS...1�"!
Wilr4,4%.**.aaft
. -R
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
J
e
�
ron ririmmiq pr,fil I
L,
- 20 -
concentration of uranium amounting to 5.10-5g/ml.
By comparing the adsorption and colloidal properties of ia
number of radioactive isotope6 under investigation, it is
possible to distinguish several typical cases (31):
1) The maximum of adsorption properties corr#spOnds to a
minium of colloidal properties, and vice versa (PolBi).
2) The maxima of-adsorption and colloidal propertieb are
Coincidental 011U,T13Pm, Las etc.).
� In the above two oases the elements form real 'colloids.
3) In the range of small plis when there is no adsorption
on glass or paper, a maximum of x colloidal properties (zr,u)
is recorded, Pseudocolloids are evidently formed, in this case.
4) Adsorption of the radioelement grows in proportion to
the inorease in pH, and no maximum is formsd on the 'adsorption
cur.vi
There appears t9 be no colloidal' phase in
this case.
By comparing the adsorption and colloidal properties ,of
radioelements, it has been possible to.clarify their state in
diluted solutiohs in many cases at different value0.of
The adsorption and colloid-ohedical proi,artieis orrtdio-
.
active isotopes were studied by AIK:Lavrukhina,(32),1n, ponnection:
A . � r
� �
with the processes of their coprecipitation with:slitn't1y '
, .
_
lAble.hydroxides*iF619H)), Cd(OE)2, Th(OH) eo0;and i;Ulpadesl.
4s � , ,
(Fe0iBi2531,PbBopuS', etc.): As is well known, theie'ph.enoena,
, �
rITI1 r17 7V1
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-7
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Oi
A
rtnr f1 , r ,
- 21-
important for radiochenical analysis, are supposed to result
eighter from mechanical capture by the precipitated residue
of radiocolloids for-led by radioisotopes, or from surface
adsorption. It has been proved that coprecipitation of rad.:-
isotopes does not depend on the molar solubility of compounds
used as carriers or the cOnditions of their precipitation,
Of considerable inportance is only the 'rianitude or molar
solubility of the corresponding radioisotope compound. The
degree of precipitation of the rudiisotopes under investitLa-
tion (IA2101 ce1442 pb212, zr952 61
Cu 43 etc) with the above
hydroxides corresponds to the amount of procipitated hydro-
xide. The followinL: mechanism of the process has been stle..--
ed: when pH is below the beginning of precipitation of hydro-
xides colloidal particles are formed of a non-isotopic carrier
and of a radioisotope :.ith similar adsorbed cations, the nuclei
of the colloidal particles of the hydroxodes are merged during
coagulation. The logarithm of the ratio between the molar
solubility cf tr3 hydrooxide of some metal and the molar
solubility of the radioisotope hydroxide points to the magni-
tude of coprecipitation of the radioisotope with the given
hydroxide in tho course of its precipitation.
Various phenomena related to new forws of radioactive
transformations wee the subject of intensive study in the
USSR. B,V.Kurchatov, I.V.Kurchatov, L.V.Ilysovsky and
L.I.Rusinov (3)) discovered in 1935 the pheAomenon of nuclear
eNg� fOktil
- .
r1.11 r
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 � CIA
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
;�7� � ' rt,5
fop-ox-ftek.t...ttelbuizeiri.
A
r,Pn
- 22-
isomerism for artificia3,1y radioactive isotopes. These
researchers obtained 36-hour bromine-82 by irradiating ethyl
bromide with neutrons and ascertained that the formerly des-
.
oribed 18-minute and 40-hour idotoPes both correspond to
. .
brimine-80 whose nucleus, in addition to the basio state., ma
also be in a state of excitation.
Soon after geltb.em and F.Shtrasgman (1939) discovered ,tiolp
Ilssionof uranium when the latter is acted upon by neutrons,
the Soviet physicists K.A.Zetrzhak and GX.Flerov (34)" proved
that-fisSion of the atomic nuclei of uranium may also take .
place spontaneously, at a speed, however, fax below th'at.Of
ordinary alpha-decay.
A cyclotron, the first in the Soviet Union and in Europe,
was set .up at the Radium Institute., by means of .which a number
of important investigations were carrted out, and, notablyV�
Study was made of the chemical nature of fission of heavi
atomic nuclei; V.G.Ihlopins 111.Avidaik.i1tillopina and ,)T-i-g:Volko
(3'5) found in 1939 that on irradiating urahium:oompoundg with
. �
neutrons, the fission products, collected, by the m'etho4 of- ,
recoil,',evolve.in the course of time radfoactive.gad4Up:piO-
duots whiCh proiiid to be krypton and xenon isotopee,f It was:
proved, in contradistinction to the papers by other ,:aMitaiarg,
$0that viiioaotive krypton and xenon .are forpsci.
maryjroduots of the fission of uranium,-. but also appear in
�
the:-.SubOquent stages of transfoz.ini at-ions- of, some ,
P477.74:1,1
ft Z A
tkli'44:44W! -
4
narlaccifipri in Part - Sanitized CoPv Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
s
-411*"4,0;60(.04�A-VIWOW
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
ducts, such as _radioactive isotopes of broaine, amtimonr,:etc. t
Numerous investigations were carried out in the USSR,
devoted to the chemistry of individual nature' radioactive
and synthesized elements as veil as radioisotopes.
BUOgikitin (36) developed the analytical chemistry of
radium. A new method for radiochemical reining of Piotactin
ium has been suggested (37). Precipitation with the aid 'Of'
amygdalic acid permits to isolate quite completelY protactinium-.
, .
from a solution, purifying it at the same time of pacentam,!
actinium., radium and thorium. The potentials of its40.!**447en
a �
num and gold were measured during.'investigatiob.6,0n
the'electrocheastry of polonium (344 and a study sad
of the valent states in solutions, the phenomenon.of-Aspropq,
tioning of quadrivalent polonium NISS found and the,`' Oleo tro`d-
potentials of hexavalent polonium were determined. Using:
tellurium as a carrier, V,D Nefedov and 11.4,TAr,p
synthesized dimethyldiiodopolonide (67.3Te(E0)%!,and proved,
� ;" -X ,� ' � ���!.
by the method of isotopic exchange of Iodine 'Ial:.th.011.T.-that.' n"
this compound the bond Te(Po) = I is of."anIcatigdito'sma *.S4
Data tae ben obtained to the 'Offect-that (C43,2!):Ein'd-
(CE )2PoIg are less stable than the tellurium
compounds.
Considerable research was .conducted on the,
t,
uraniud and ',thorium compounds..�' is4lij4.r.4*Pr
� ". � -�����1
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 CIA
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
;
'
00
FR
- 214. -
P "
p:Ipt y
JA,14
11'
associates studied the properties of the oxalates of these. ,
elements. It has been shown that the oxalate of quadrivaleit
uranium, U(C204)266E20 represents an aoid with pE of t.he., 4
�
saturated salution equalling 403. The oxalate of thor&ux"
Th(C204)e6E20, to all int4nts and purposes possess:es no
..,
properties. Uranium oxalate is dissociated acoordipsto' 4c
. ; �.� j'' '"
' .
. YU( 0204 ) 2(I320 ))11 /TT( 0204) 2(H20)n.-1(0E)/11!: Eq, -
-.�
and thoritii oxalate according to
Th(0200 242 ThC204 �
Varidus salts ot uranium-oxalic acid were synthesized and theirr
e �
I
coordination structure established.,
� Physico-chemical analysis ofuranyl oxalate has shown
�
that this compound, t04,--; is di.ssoolated according t4O.�.--
��� � 1.4
� 2;
. '11192929 (112a)/ ' '/19.6292�4(q)e:0"
Uranil oxalate may be., considered as an acid %ital.
strength to carbonic acid. . . ..- .
�,.
- ' .�. -1:,., .
� -
_ . �, . .. , '�,,:f,',--�---�
Oxalate complexes of uranyl alsow,pokiess acid p;opertit!-.
;40
f .. t�
in aqueous solutions, whiph th6 series ,
x2/417o2o2o4) 2/. 31.V: :4c6((p�o2)'2(c2o0
� Su
��
A
,
The-,Ondtants were measured of the no*ustabilitk otthetl.b4*
,
complex aniOnsi
� �
�.����
; . .!�-�
�
� �
'OP �I
0 � he properties of some other o:taiitit
� �
0
'�were'd�ascribed such
�
la
:01E02/tIPAC2P0i(H2�)2/�
IiI.Chernyaev (43) an
�
.,
as anmionitim.1144,44.tedi
� � .
� , .
d his assqiiites *elaboraflia.f.a,:ia *
e; *ire � 4. � trrIfti"
� ;,:etiAtrilrVittiV 'Mkt:
tv L11
r
� t.
"
,T,4��� 2 ?./ f r41,1; ;14'4.1%.
NUIVIZSOV 4414.0***Atiaisi44tga.: � Itse.,ph1 wrI.1*.,A4s,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
PIP?
tr7.-1,1 re,r7 n51
for synthesizing aqueous uranyl monocarbonate, WiCO3*HiOs
from aqueous solutions of uranyl nitrate under the prefigure
of 002.4Anhydrous uranylcarbonate was obtained from suspen-
sions of Up) when 002 is passed through under nozmal Condi-
tions.
0.11�Avyagintsev and B.N,Sudarikov (44) established the
.1
composition of uranyl and thoritim salicylates, NE4/1702(Sal-43/r
44820. and Th0(Sal-)2, and defined some of their properties.
Thorium salioylate is stable only in weakly aid medium (pH
amounting to Its solubility is rather slight.. The
compOund rapidly hydrolyzes in a neutral or alkaline Medium
witUout a surplus of salioylate ions, fang thorium oxisali-i
oylates. When there is a surplus of a soluble ,
complex salicylatq of the compatfttion of /ThO(5a12-12/2- is
�
formed:, which easily hydrolyzes while being heAted?Uraziyi
salioylate-is by far more solUble and stable; which underlies
the suggested salicylate and oxigalicylate methods,of'separat-i
_jing uraniun and thorium.
E.A,Ippolitova and their asdociates (157)
comprehensively studied.the properties oturanateg of alkali
elements. % The Chermal stabilfty Of such elementgli.norAdOd
during the transition from .1.1.0)4 to Cs2U04, the greate'st
;�.sucatet=2;(' heat of formation beingi however foul* in,the:,case
of potassium, and rubidium uran.ates. ThermograDa7ce...and'roent-
.
0.� -
Frl
r-7 rt) 9V
� 1
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
1
S.
ID
Frin
- 26 -
Frt3 r.nr
�r:;/ y
.L LiLj
genophasic analysis of the processes of interaction between
the alkaline carbonates and uranium oxides has shown that
diuranates are, as a rule, formed in the first stage of the
reaction, at a temperature of about '0000; subsequently, depend
ing on the excess of one of the reagents, these turn into
normal uranates or into more acid polyllranates. Basic urana-
tes have been obtained of the composition of 11041up5.
roentgeno-structural examination of normal uranates.hai3howh
that they contain tetragonal or pseudotetragbnal layers of
(302)02 between which the atoms of the alkali elements are dis-
posed. Endless chains of octahedrons of U06, linked by common
ribs, were found in the structure Na2U04. When polyura-
nates were reduced by hydrogen, identified potassium and
sodium uranates (V) of the composition MelII03'were also
obtained as well as uranate (IV) for rubidium, Rb2UO3i..
Analysis of the precipitated uranates of varioui,alkaline'
� -.
elements has shown that analogous compounds are formed,0
approximating ;values of pH, irrespective of the natare.ofthe
hydroxide. As a result of washing off excessive of aikall
with water, their composition regularly changes during the
transition from ithium salt to �Si= salt, tendiAg to:fOrm
.,
more acid uranates. 4 similar regularity was disO.obed in.
analysing the composition of norMal uranate
duota.,
..�
Reactions of interaction between uranyl nitrate and
t" 1 .�t",77'., 1
4
I
1,4
;4' �T)14..A.tPSP*14".441142,41,..-Tad, t110144.t..,.0,14�5-*'""TVF k"--7.=-"Nr3g$tre:161`43i93%.3-1 4,0 ..1.1.;
V'.
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-7
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
7r7". r.e-'t ONLY
- 27 -
hydrogen peroxide were analysed in solutions (45)e It has
been shown that a peracid or tt c composition of H2G209 is
forfted, which produces salts of the NaHU209 and Na0T209 types.
In other conditions a formerly known salt' wa08,9112o is
obtained, , for which solubility in water and in solutions of
Na0H%and HNO3 was measured. The said salt enerEf into react-
ions of neutralization witiVtiO And Na11003:
.Na41108x 21NO3 lia21106 it� 2NaNQ3 11202
NONA give.Egp- Na2uo6 2Na003:4 F202
Compounds Na2U2b9.61120 and Na8U4022.3H20 are the products of
decomposition of salt Ne.41108.91120 during hes.ting'�. �
'Many investigators measured. the solubility of S.iiiitti4y
soluble compounds of uranium and thorium, A:tamely Oxalate (46),
. arsenates ' (47), uranyl, uranyl and thorium, phosphates '(40)4% andt
others4:
.1"
A study as made of uranium and thorium halide's. of 4-the
lowest valence. Cbnditions were elaborated to obtain qUinque-
.
valent 'uranium an aectrozhemical mv/(149) 1 It 'she' fii;en
Sr.
. � ,
proved that; with pH amounting to 3,..02 it is. in thk,
of an ion of tr02-4-: SaA.Sohalcarev. (5O and
do-
fined the pressure of saturated vapour of ITC1 at vamloG-,61 4**
, � ,
temperatures and the prbssuke of disproportlioning,u0.0, ,1
. A
17013e .Oxichforide of trivalent -uranium, MCI; WgEl ottaihed
and some of its properties were described,, The ,precesa..*10-
frogi
� t.. rrt...A.1\ � c
e ako,%.* ..xe 4, . 44!"-047.04.4.4 444,414.44 -044e4,44.4441,3r4.4.414.41*NVI,Vti...r-V,41g,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-7
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
0
0 0 ..omrG
rrn trrirRrr rv,ss
I L.:e.
- 28-
studied (51) of reducing thorium halides by means of hydrogen.
Some properties of Th011 and ThBr3 were cbfined..
Various ts&eal.eltea.s Obtained new complex dert7aties of ura-
nium with organic substances. JI.A.Grinberg (52) and his
associates studied compounds of uranyl .with 1.3 diketones
Uranyl benzoyl-acletonate, UO2(C6115.CO-CffeCO.CH3)2.41520 ysgas
synthesized, and the conditions for obtaining uranyl attetylace-
tonate, UO2(CH3000.CH.CO.CH3)41120, were specified, Expeilments
aimed at obtaining volatile uranium hexacarbonyl produced no
poslive results. Many intra-complex compounds of uranyl with
Sehiff bases were synthesized (53). Some of them may find
application in analytical chamistry.
0
The development of the atomic industry and of, the tech.,
niques of accelerating elementary particles in the USSR has made
1 available transuranium and fission products, a field in which
_
extensive research has been carried out.
0 ��
A.D.Gelman (54) and her associates studied the compoiition
of oxalate complexes of trivalent plutonium and determined .tie
0
constants of, their non-stability by the method of ion exChange.
Chemical Method has been suggested to obtain trivalent nePtut
using rongalite as a reducing agent.. ,
V.V.Fomin (55) has shown that .oxalates of triquad.A.,:and
hexavalent plutonium, when kept under various conditions the
air Or in a vaalm� at 25�C and -8000� bcth in light andjidark-;
ness) decompose under the effect of alpha- radiatton'ot,i5i4t9.-
ndat
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Or,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
6-11
e
- 29 -
/n this case Pu61 passes into Pu, and Pull4 into
Th.13- under the influence of the evolving 'carbon rnonoxide The
oxalates, turn 'into carbonates and; patly into oxides ; ,iThe 7
polarographic method was applied to study the complex oxalates t,
of plutonium (56).
M.N.Popov and M.I.Ivanov (57) .measured the heat
)0,
s"
tro
plutonium ditthde is formed. V.I.Grebenschikova and .V.N.,Bobrovak
(5d) studied.the coprecipitation of trivalent
19.1
-1434,2(SO4)3, with K2SO4and found t.hat anomalous
iire�'for;;id in this system. The crystals:have
americium,
cr,ystaIs'.
no idwer bit4fidiaif
of "mixing2 down to a concentration of the microcombontnt or,
nfOi/3.. go inner adsorption compounds are disclosed in
this case.
SOvietts4k2.71:,-,;ittirtis*t described the sulphate method of inlet
ing plutoniuti- and neptunium (59), based on the properties a
Np441. Pu3.4 afid;.Pulf4' to coprecipitate with binary plotassium
e � ,
sulphate and. lanthanum, 1c314,a(804...)3! It 'las shom the.p.ase
..� .
,of plutonium that anomalous mixed crystals are then ,:for.Med,
�
since Pu enters enters the crystal lattice of binarykotassiumfd
lanthanum ,ksit despite. the dif f er en t valence of ,lantitim
Tp separate nepturrium and plutonium In a Preliiiiner
a method was suggested (60) of
4
chlorides ,:formed in the course
fractioned sublimation,: of,
. � . -
of .Chlorinating dipxid
bepa.i.ation was based on the difference between the clAi dat
s , ss. s '� �
s- rfterst:�.^4.4s,,,M. � s 4.�ei t�t,,t � IN---,:.,�,���42,4-00,14%.;,,
I .
'""
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
'
rt.
, MRLG1 ,
.
,................
. ......�_._ ",..-- e --1 '4-- -
AU
' pp
ma 30 1011.
L..L
reduction properties of neptunium and plutonium when acidified
by potassium bromate.
A method was elaborated 01) for isolating americium from
fission waste solutions containing a fraction of rare earth .
elements. Coprecipitation of americium with potassium utanyl-
tricarbonate4%p2(col) / iss used for the purpose. Ame MA.
3 04
is first 1:e4-41. to a cnimintrevalent state by hypoohloritel
ammonium persulphate or ozone. The trioarbonates are repeatedly ;
coprdcipitated in an oxidizing medium.
Spectrophotometric analysis (62) of the behaviour of ameri-
cium ions in solutions has helped in discovering self-reduqtion
of Am5'1' to Am3:1" ..by the products of docomi0.sition of water. under
the influence of radiation of americium. A study was made, of the
[
process of disproportioning Am541 which occurs accoiding'tb
4
3AM02- 1 4H 2Am0224 Am34 2H20.
The hexavalen t americium s& formed is reduced under eftot
of its , own radiation up to .Am54.
Electrochemical methods . wqre 'elabo rated (3) � :t'ci. isolitte -�
, ,
fine oxide layers ,of plutonium and ip4ioaar 'amounts. ot - iljii
_
. A
rand amerioiumck
soviet reagilKOW...p 4(04 ) condo. et 61% eve riments
,obtaining einstenium and fermium isaopeta by ardmento
tuNuidiam target with nitrogen atfil oxygen nuclei - in a ,cYplqii*
, �
-
with, poles 150 cm in diameter. The maximum energy' of;.filoe
-
tia Uv6"--
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
.�����
ff4',
E,s
th.
�
t
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�
00
FonErrt--,rtrr r 1 17'7., e-1-111
ed six-charged oxygen ions amounted to 120 Mev., and of 'live-
charged nitrogen ions to some 100 Mev. Separation, of the
transplutonitua elements so obtained was made by the chroma-
tographic method. Irradiation of uranium with nitrogen ions
resulted in obtaining the einstdinium isotope with .a mass -
number of 247, and. irradiation with oxygen ions produced the'
fermium isotope, identified by the period of half-life and, the
_
energy of the alpha-particles. The chromatographic meth:)d,
was helpful in isolating californium, berkelium and curium,
isotopes to the amount of several hundred atoms....
Among the radioelements of fission produ eta, castles-4.37:
attracted great attention of Soviet researchers. B.A-Ztai*Eiv
A; I..drivkova, d oth.ers (195V) dev,e14ed
method for preparing its highly active sources. CeSium-137
is extracted out of the elpmarts of fission products on ti
-37-e-aidue of nickel-potassium feripdyanide; The product is
,
treated with diluted 13NO3, as a result sof which the*L.bulk. '
of re:dioactive and chemical 'substafic'es passes into ,the. Ei;93.utlo n.)
while cesium cesium remains'in the residue which is oxidrzed:14'�Stich
3 � " I: .
a treatment ,eirid is transformed into nicke1-potassium4eirb..4
., cyanide.; Subsequent alkaline .treatm6tit permits to.reicaie
-,. again. a part _of the substances, while ceiiium iti.13.' is*.itiSc,. c
fhthe insoluble remnant. Acid-alkaline traatment.',I'iv repeat-
ed seyeral times.: The final insoluble;� reninant.17ir.,.: subjected .:..
.... � Y e. '
to, .thermal decomposition, foll9w.l:f1/4-maqtr-.70, siti-Ais.': ciiit:'.- . - s.- '�
,
.. ,, , rh i . ,i -7 : X t� '...''.4 ,,,t,4". .,::�:-,-- ' orA . - '1- ..' -.� �
V
, , k ,. �
. .. "... Et
f .P1.1.' e ..-.1;
La I": "
-,
., ,.
, .-�,,,,. 2.,-_ ,,,, ,4,..,A,,,,, . ,, ..�,-,,,I. 4, A ,-, , ...�,, ,N 1,,f,, e,,Z,Eli..,.-- �:, � f�':0, 4-.I.-, . qd,,,---; -''.! , i.,,. 4-11.'1.-4,Pac,it:41-v5iitg-tt-xl.: .,;i"Ai..-k5.t--44'n:::44.;Af'.4.44::.Nid. -
.,_ .
t-.isti.A4t. truoit�-47 T4,34r4tulizPa.',&4�4er-444,140Wrirali=s7 t,,0,.14,7444,cog4. - _ tigtf(Stf.ktr:
f
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
ID
- 32 -
!Ay
completely leached out by water. Most foreign radioisotopes
remain then on the waste residue. The .solution of cesium
compounds is neutralized by diluted B01 end 'evaliorated. If
required, additional purification of chemical Subbtgance is
effected, based on the difference in the solubility or oosium
chloride and chlorides of other alkaline elements The above
Method has made it possible to obtain preparationq Of ati.sium-
137 With a specific activity of 26 curieig at a radloChemioal
purity of 99,9%.
Among synthesized elements', technetium presents now a
. considerable interest. The great progress achieved ii1-.the
building of iKctors permits to produce ever more'powerfUl
flaws of neutrons. In this connection it may beoome practical
ly profitable to obtain long-lived isotopes of teebnea-99
_
* out of irradiated. mo lybd �num.>
In the Soviet Union, Y.B..Gerlit (65) investigated ,,some
,
;
:Cheinloal properties of teohnetrumi, using the. -ihort'll'ved
- � 99
;.
isomer,. T099 m, isolated out at Mo The researcher studied
the condi tione, of extracting teohnetiuni by -:,vari.ou,q-.. alcohols,
-tr!`
ketones and amines. Many valent transitions .!of.ite,-'01iiiO4.uM
were established and data obtained on its exiatea0:e s'A: bi-
44:lent form. Other investigators (66) aucoqe'sf4
methylethylket one to extract technetium in thOriie'.6.6.06�o
'salting out agent, namely 1C2030:
�
T.I.Spitsyn and A.F.Kuzina j19,57)-tivvelo ecT.a:3 method'' for
rf�'t
- Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Co .y Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
pn r�rri rnr.
LLt vJLA
- 33 -
obtaining ponderable amounts of technetium out of molybdenum
irradiated with neutrons, making use of magnetium-ammonium
phosDhate as a carrier. The method permits at once to separat
technetium in an ammoniacal medium from the basic mass of
molybdenum present there. Further separation of technetium
nrd of the phosphate ion is based on the fact that when in a
reduced state, teohnetium is not absrobed by phosphate reeidues
For this reason magnesium-ammonium phosphate is dissolved
in hydrochloric acid and hydrogen sulphide is added An the solw
tion, as a result of which molybdenum is separated additional-
ly and technetium is reduced. SubseVeht pr.ecipitatioxi;of
magnesium phosphate under these conditions no longer reaUlts
in a capture of technetium by the residue. The solution is
the evaporated and the volatile chlorides areradoved from
the dry remnant by heating. The substances remaining in the
preparation are separated by the chromatographic metpod,in a
hydrochloric or nitric acid medium. After treatingsthe fi16ate
with ammonia and hydrogen perdxides.anmonium partechnate4s
iSolated. The above-mentioned researchers obtained new data on
the conditions of volatility of technetium at various oxida-
ticin treatment of its concentrates. A study was made of the
reactions of coprecipitation of technetium with various
hydroxides, sulphides and other compounds.
Research related to t!-.e. -"
--����-.1` -
;es D,ri� _ niti7Pr1 r.opv Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Co .y Ap roved for Release 2014/11/04 CIA-RDP81-01043R002000070006-2
�
.4
3
e.�
FrI
,,,---G
...6...L.m.............\.
,------
_
-34-
rr
7F1
t uct. Li 4 .. I
radioisotopes without carriers has acquired an ever inoreas-
ing importance in modern radiochemistity. N.P.Rudenkp-,(47)
and other Soviet scientists used for this purpose the methods
of coprecipitation chromatography extraction,,, formation of
complexes, electrical precipitation., to.
V.I.Kupetsov (68) widely used organic oopreoipitants
capable of precipitating microamounts of elements out of
extremely diluted solutions., which makes it possible to
isolate; for instance 10-;of the element out ,of a volume of
several litres. The burning of the residues so obtained per-
mits to produce a copreoipitated elemantAn the:State 'without
carrier." The above-mentioned researcher made a,det'alied
study of the mechanism of such processes.. In some ()apes the
oppreoipitation of the radioactive isotope and the precipitant
takes place as a result of some bhemical analogy in their
composition itor example, coprecipitation of non-ponderable
amounts of thallium with diphenyliodonium); sometimes the
intra-complex salt of cation in a mioroconcentration preoipi-
L
tates with an organic compound, dissolving in it (folinstance
,
radioactive Isotope ox..inate with phenolphthalein,: beta-Aniiiiol
and similar substances) ; flnal1, in other cases .the
radlo-
oolloid copr_ecip,Ittates with colloid-cherd. iirripOunc3:41, (for
,0484Ple1) coprecipitation of niobium, tantalum or tungsto;11 'With
. .
. ,
. .
basic dyesturfs and tannin). A number of methods have been
,
:.... �-�
,Tr,
..,...,,,,,,,,11, .e � ,. 0.-- ,
P'!" � '
..r...0',4.1.. X '4 .
".'1,. ''..r......r. '..:;.:.; 1
........1-----
r.onv Aooroved for Release 2014/11/04 CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy A roved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
ist4w.f.msriwYW
0Nrwr.. ,.�4 M
fon
-35-
t
'MO .11
elaborated to carry out each operations of coprecipitation,
and new organic precipitants were recommended.
A.11.2,10:rin and his associates (69) developed methods for
enriching radioetitive isotopes obtained by irradiating -
element-organic compounds with thermal neutrobs or gamma
-
quanta. The radioisotope atoms, whiahinere driven out of the
,preparation and which passed into an !,inorganic form" i WeFe
separated by the methods of extraction or adsorption. VII5sn
4tetraphenyl-germanitun was irradiated with neutrons, the YOU
, of Ge75 amounted to some 90%. To obtain Bi210, it pliolied:'
convenient to irradiate triphenyldichlorobismuth'; (0645))010
-
with neutrons i The factor of concentration was in this case
of the ordeir of 100. Still greater enrichment (103-104) was
achieved by irradiating the organic compounds of. germaatuN
arsenic and antimony with gamma-quanta with an energy of 26
M'ev (braking radiation of a synchrotron).
4-
V.D.Nefedov and 1.1.A.Torpoova (70) have shown-that,caron14Ar
1.
of metals are suitable for obtaining enriched radioistiibpbs'of
.chromiumi, molybdenum and tungsten. The factor of-enrip4ment'
was as high, as 104. Carbonyls 0(00)6 and 4(00)6 iirovet'64t-
',..:
able for isolating radioactive isotopes To99m and RR;1,-9ii4m15.4,
L,r7i
during the' Ustadecay of HC99 and 171118 respectively.i. '
The -electrochemical method of enrichment was apiaisd $y-
� �
ucing
::NRudsnko and Z.Vaastukhova (71) in p
4,ts,
'Oh
4\va-1
�
rnnv Anoroved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
01�11��
- 36 -
isotopes of indium. )Aetal tin irradiated with neutrons was
transferred into an intracomplex salt with 8-oxyquinoiine, -
and its saturated solution in chloroform was subjected to the
action of an electric field with a gradient of 3000v/am. The
greater part of the In113a so forned deposited on theEknode.
Electrblysis was carried out of a saturated chloroform solu-
tion of a pyridine-!rhodanine complex of cadmium, /cd(a5H5y)4/
(sow)2. 4
In recent years the methods of chromatography and extrac-
tion have found wide application in radiochemloal reseq*.
This necessitated the elabarat.on of scientific principles.
of such methods, with the account for the peculiarities of the '
radiochemical systems, the microconcentrations of radio-
isotopes.
R.P.Nikblsky (72) evolved 4 theory' of ion exdhange wiiici
takes into aboount the basic factors influencing the 4x0hange
absorption of ions by. ionites, namely the pH, the napar,4q-.,
:
Val-shop and concentrationbf the iiiterchangeable ions, the nature:
!
of the ionite and the compogition of the sdlutiont Accordiwg
, �
to the theory-2,, the coefficient of distribution of the. micro-.
,
"
component ion ( i between the ibnite and the solution dbbs' .
not _depend on the concentration of the microcomponent.whan'the
,s.al-,pickground is constaat:
. � � � ::44i?'
4.4 littA
�57)z17z2 f (8)
Kz1(
p-A;
� e � v m ; r :)..1 Ly.
Lua
�,ifix-dt,',',44,414,nrasgif4ratty1=1,"t".11,..Mer4WSrla14...
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
f � -
t5trt..,
t
t
1 S
'
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
FP(17'1 17.7" A F �
- 37 -
Where and. are t!Le amounts of the absorbed ions of the
micro- and macrocomponent, C1 and C2 are the concentrations
of the respective ions z1 and z2 their valence, and rt )
is the multiplier containing the coefficients of ion activity
in the sorbent and in the solution: The numerical value of
changes when the r ture of the macro component ion, and
its concentration change, as well as during the introdUction
new ions of great concentration in the solution and (hiring
chEtngee in temperature and pressure.
V.I.Paramonova and her associates (73) conducted a number !
of experiments, on the application of the method of ion exchana
by means of absorption curves to the afudy,.of the state or
radioelements in a solution: the regions of existence of the
complex compounds so formed, and the determination: of their
constants of non-stability.. This method helped in clarify'ing
the behaviour of Nb95 and 731495 in sulphuric acid, nitric acid
and other solutions: the existence of ions of a new-type Of
'1.
.. A2 was established for 90when it formed a cOmp,lex. with
laCtic acid, and of 1123 molecules when there was an:,ezo""ei3
of addenda; 14..o ions of the composition of ;.� 24 vere
covered:
A.K.Lavrifichina and her associates (74) .Ptu..acl.ed the regula-�'
rities of ion exchange chromatoaphic separation of raise
:
earth element isotopes. A 3.6% solution of ammonium lactate
g--
,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
a
00
- 38 -
was used as an eluaqq. "yith an ultra-low concentration of
the elemsnts, their elution is peculiar of narrow peaks.
The addition of an isotopic carrier results in a shift of the
peaks with a tendency of slower elution, and deteriorates
their shape. There may also occur a superimposition of the
peaks of adjacent elements. The theory of separation of rare
earth elements by the chromatographic method was developed
by N.N. Tunitsky and his associates (75).
S.Y.Yelovich and V.N. Prusakov (76) proved that when stu-
dying radiometrically the chromatography of radioisotopes
Ce144 and Sr91�on resin KY-2, with ultra-low concentrations
(down to 16-9N) and even mith small volume speeds at which
the current of the liquid moves, account should be taken of
the phenomenon of ion diffusion. The speed of the diffusion
processes Proves to be of importance for the prooess as a
whole.
The mechanism of the radioelement extraction prooessfis
and the connection of the extraction properties with the .
structure of the solvent was studied by many researchers.�
V.M.Vdovenko and his associates analysed the distribUtion
of uranyl nitrate between an aqueous solution and diethyl-
ether in the presence of various salting out agents (sodium;
potassium, magnesium
tion cOefficient
aluminium nitrates, ,eto) The "iifstil:bu-t.
yl nitrate graws,in proportion to an ,
� rirl P:77-7
increase in the. concektraisionths:IsagaIddg out agent. At
k7,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
,.... -.01
RIP.
-'...-
�
- 39 -
I
equivalent concentrations of the ions, the salting out effect
of the additions under investigation grew in proportion to
the increase in the charge and the decrease in the radiva
of the cation. It has been established that uranyl nitrate
passes into diethyl ether with 4 molecules of water and is
to be found there in a molecular state. Solid phases of va-
rious composition, ranging froh1102(ND3)2.3H20(02H5)20 to
1102(NO3)2'03(C2H5)0) are isolated out of the ether solution)
depending on the given conditions. Tensimetric egaminations
have permitted to compute the heat at which otherwleul6s
combine with uranyl nitrate. The conditions of extracting
uranyl nitrate out of dibutyl ether were also analysed.
S.M. Karpachova and her associates (78) compared 'the
effect of various salting out agents during the extraction
of uranyl nitrate with diethyl and dibutyl ethers as well
V..
as with N butyl acetate. The quantitative definition of' the
effectiveness of the salting out agents has allowed to
introduce the term "equivalent of salting outt!' (amount of
salt-; equivalent to one mol of uranyl nitrate in an equili-
brium aqueous solution). A.M.ROzen (7,9) stated the' thermo-
dynamics of eitraction equilibriums of uranyl nitrate. -The-
, q' -
�sao6 1,g.s...e....arChers (80) produced quantitative data the4rp-1'
gess of extre:ntion -of uranyl nitrate with tributyl phbt*hate
togetheith vakious solvents
Radiochemical investigations Rived-40# p#ant'pe.#
� . .
a ;;.
- 4`...
Nkootit.:6' 4%.414014frealrer440
,
.4,43.. � '
������� --�������11
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
- 40 -
r -
in studying the processes of atomic nuclei fission under the -
actionof elementary particles with high energy. Special
methods of radiochemical analysis were elaborated, aimed at
separating and identifying the radioactive isotopes so formed.
A.P.VinCgradov and his associates (81) carried out a
great 4.e.a f work devoted to studying the nature of the pro-
ducts of fission of copper, silver, WismOh and. same other
elements by fast particles, protons and deutrons with ah
energy of 100-700 Mev. The application of the preeision
method of radiochemical analysis helped to discover some
scores of new radioactive isotopes and to calculate the yield
of individual isotopes during various nuclear transformations
(fission, splitting, knook-out of light nuclei, ete.) By way,
of illustration, the yields of 240 isotopes (aminly from
53,89 to Bu154) were defined when uranium was irradiated with
protons possessing an energy of 480 Mev. In the case of
thorium, 244 isotopes yore discovered (from Se83 to Eu132),
and 252 in the case of bismuth (from Ga72 to Ba129). The
4ra-rvq-er-oil yields of various isobars distributed according to
their consecutive numbers have a dome-like shape. Their '
width amounts to 2-3 units of the consecutive number: Tee
fission of nuclei by particles of high energy is ohdiAoVeazed-
by a constant distribution of the Charge, irrespective of
mass number of the fission products and the conseeutive number:
� ,�
-
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 � CIA-RDP81-01043R00200007000A-9
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
'!t
cT...r....." �j
-41-
�
of the fissionable nuclei. The above research helped to
clarify the mechanism of fissionof uranium and thorium. nuolei,
under the effect of high-energy particles. It appears to be f
A
mixed: the excited nucleus evaporates a certain number of
neutrons, following which the process of fisSion sets in. The
excited fission products so formed in their turn evaporate
neutraons,
B.V.Kurchatov and others (82) made a similar study of tungs-
ten fission products, with deutr one possessing an energy-of
280 iev. In this case, 28 radioactive isotopes were foun&0
chiefly in the region of z 33-52.
G.M.Gorodinsky, A.N.Mutin and others (83) applied the
ohromatogra.phic method to study long-lived isotopes of rare
earths, obtained by irradiating tantalum on a syndhrooyclotron
with protons possessing an energy of 680 LIB:V. A definition was.
made of the half-life periods, the type and energy Ofradiationv
of the isotopes so disoovered, including the new isotopes
;
b
. of gadollniuM.
* * *
This paper, brief as it necessarily is, could shed light,
only on the major trends along which radiochemistry developed
in the Soviet Union.
Twenty years.agos radiochemical science in the USSR was
represented but by a small staff-of-thw-RadithFIartipute.
"W
ft :4.r- ix= r$,I",4,-J.:et:-�"?.:'
'
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
TER 07712,1 USE Mill
-42-
Today radiochemical research is being conducted at many
institutes of the IrJSR Academy of Sciences and at industrial
research institutes, at thp chairs of higher educational
�
ntS
and .at factory laboratories. Numerous staffs
of research radioohemists and engineers have been trained.
The scope of scientific �ork on radioaheaistry is enlarged
year in: year out, and the range of subjects is being extended
in this country. Soviet radiochemists are proud of the pact
that they actively participate, jointly with scientists of
furthering the peaceful
other countries, in Isicx rtnYwAxTxxXX 154t_mxmtkeic application
of atomic energy for the good of mankind.
*YIN,
tOi
C`41"M
1ft f0,�
-
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 � CIA-RDP81 01041Pnn9nnnn7nrmg
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
a
RIR frrtillrr.n.1
Bi'oliography
u L
rir7,4
I. V.I.Vernadsky, Journal of the Russian oadeny of
Sciences, 5, 61 (1911),
2. V.G.Ichlopin, Reports of the Russian Academy of
Sciences (A), 101 (1924).
3. V.G.Khlopin Proceedings of theRadium Institute, 4, 34 (1938)
4. V.G.Khlopin, Z.anorg, allg.Ch., 166, 311 (1927).,
5. A.P.Ratner, Proceedings of the Radium Institute, 2, 67 (1933)
6. V.G.Khlopin, u.C.Samartseva, Reports of the UBSR
Academy of Sciences, IV, 433 (1934).
7. A.G.Samartseva, Reports of the USSR Academy of
Sciences, 33, 506 (1941).
8. B.A.Nikitin, Z.anorg.allg.Ch., 2273 81 (1936);
Jourme of General Chemistry 9, 1167, 1176 (1939).
9. B.A.Nikitin, Reports of the USSR Academy
of Sciences, 24, 564, 567 (1939). Sciences, 39(1940)
Journal of the USSR Academy of Sciences, Section of Chemical
10. B.A.Nikitin, E.M.Ioffe, 'Reports of the USSR Academy
of Sciences, 85, 809 (1952);
Reports of the USSR Academy of Sciences6.2, 595 (1948).
11. V.G.Khlopin, B.A.Nikitin, Z.phys.Ch.(A), 145, 137 (1929).
12. V.G.Ehlopin, n.A.Tolstaya, journal of Physical
Chemistry, 941 (1940).
13. .B.A.Nikitin, B.11.Ioffe,
.Acadeny of Sciences,
383 (1942); 157
Journal of theUSSR
Section of Chemical Sciences,
191 (1943).
14. V.G.Khlopin, M.S.MerkulovaL Relpb,rts of the
USSR Academy of Sciences, 65, 6 (1949);
7_14. 4. (1950).
15. N4S.Merkuloval Journal of Physical Chemistry 29, 10 (1955);
Journal of Inorganic Chemistry ,a, 25 (153).
16. Ii.S.Merkulova, V.I.Chastukhina4 L.N.Burtsevas
Reports of the USSR Academy of Sciences, 12, 1167 (1955);
Fa9
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part- Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
00
iirLy 4, 0-, (.:
� 1.4.
TA.S.Merkuloval S.A.Potapova, ibid, Ilas 643 (1955);
li.S.Merkulova, T.S.Shevelkina, ibid., 11D1, 457 (1955);
S.A.Potapova, T.S.Shevalana,
V.I.ChastUkhina, journal of Physical Chemistry,
21, 1056 (1957).
17.1b.dela1opin, V.R.Klokman, Ruports of the USSR
Academy of Sciences, .6.1, 1, 33 (1949);
journal of the USSR Academy of Sciences
(Section of Chemical Sciences), mip (1949).
18. V.GALhlopin, V.R.Klokman, A.N.Murin, V.D.Nefedov,
JOurnal of the USSR Academy of Sciences
(Section of Chemical Sciences) 127 (1950).
19. V.R.Klokman, Journal of Inorganic chemistry,l, 33 (1958).
20. I.E.Starik, Proceedings of the Radium Institute,
1, 29 (1930);
2, 91 (1933).
.E,Starik, N.G.Rozovskaya, Reports of the
'USSR Academy of Sciences i 107, 850 (1956)
.E.Starik, N.I.Alekseienko, N.G.RozovAkaya,
Journal of the USSR Academy of Sciences
(Section of Chemical Sciences), 755 (1956), I.E.Starik,
N.I.Alekseienko, journal of inorganic chemiOstry,
1, 1676 (1956)..
22. A.P.Ratner, Z.N.Simonyak, Collected Works on.
radiochemistry, published by Leningrad UniversitY.
17, (1955); A.P.Ratner, N.G.Rozovskayal
V.Gokhman, Proceedines of the Radium Institute
of the USSR Academy of Sciences, 1, 148, inst.2 (195)..
23. I.E.Starik, A.V.Kositsyn, Journal of Inorganic
Chemistry, 2, 444, 1171 (1947), I.E.Starik
L.B.Kolyudin, ibid. 21 1432 (1957).
24. I.E.St.irik;
journal of
25. I.E.Starik�
A.P.Ratne_r,
Inorganic Chemistry, 2, 1175 (1957).
N.G.Rozovskaya, Journal of inorganic
chmmistry, 1, 598 (1956).
26. I.E.Starik, A.M.Gurevich, Proceedings of the
Institute) 3, 241 (1937);
V.V7Vdovenko, ibid. 256.
�-
0;
Raditim.
'
,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 � CIA-RDP81-01043R00200007000s_9
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
-45-
27. OsErbakher, 2.phys.Chem.(A), 158, 216 (1932).
28 V,T.I.Vdovenko, A.C.Samoilovich, Acta Physicochim. URSS,
4, 613 (1936).
29. V.G.Khlopin, V.I.Kaznetsova (Brebenschikova), Journal
Of Physical Chemistry 13, 1145 (1939), V.GiChlopin
Z-oarnal of the USSR ..lcademy of
Sciences (ection of Chemical Sciences), 5 (1949),
30. I.E.Starik, G.G.Karsradze,
I.A.Etros, Collected works on radiochemistry,
published by Leningrad University, 7 (1955).
31. I.E.btarik, Journal of Inorganic Chemistry, 2, 7 (1958).
32. A.K.Lavrukhina, Journal of .-tnalytical Chemistry 10, 205
1(1955); 12, 41 (1957).
33. B.V.Kurchatov, I.V.Kurchatov, L.V.Mysovsky, L.I.Rusinov,
Cpmpt, rend.; 200, 1201 (1935).
34. K.A.Petrzhak, G.W.Flerov, Reports of the USSR
Academy of Sciences, 28, 500 (1940).
35. V.G.Khlopin, M.A.Pasvik-Khlopina, N.F.Volkov, Reports
Of the USSR Academy of Sciences, 4, 1171'665, 84/, 851,z.
(1939); N.F. lakov, a, 528 (1939).
36. B.A/likitin, Proceedings of the Radium Institute,
3, 228 (1937)
37. I.E.Starik, L.D.Sheidinal Journal of Inorganic Chemistry,
3, 139 (1958).
38. B',P.Nikolsky, G.S.Sinitsyna, V.I.Shestakov,
' Collected Works 1135 years of the Khlopin Radium -
Institute of the USSR Academy of Sciences" 39
(1957).
39. V.D.Nefedov, M..iu.Toropova, Collected Works on Radiochemi-
stry, published by Leningrad University, 139 (1955).
40. A.A.Grinberg, G.I.Petrzhak, Proceedings of the Radium
Institute of the USSR Academy of Sciences, 7$
17,50 (1956);
A..A.Brinbbrg, G.I.Pettzhak L.I.Evteiev, Journal of
" � � e. � 4034-% t,
.1
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
4Pr
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
-e
t�
0
vm��
-46-
Inorganic Chemistry, 3; 204 (1958).
41. A.A.Grinberg, B.V.Ptitsyn, E.N.Texter, Proceedings of
the Radium Institute of the U38R Acadany of
Sciences, 7, 74 (1956).
42. I.I.Chernyaev, V.A.Golovnya, G.V;Ellert, Journal
Of Inorganic Chemistry, 1, 2726 (1956).
43. I.I.Chernyaev, V.41..Go1ovnya, R.N.Schelokov, journal
of Inorganic Chemistry, 2, 1763 (1957).
44. 0.E.Zvyagintsev, B.N.Sudarikov, Journal of Inorganic
Chemistry, 1; 69 (1956); 2, 128 (1957).
45. A.M.Gursvitch; L.D.Preobrazhenskaya, E.V.Komarov,
'Journal of Inorganic Chemistry, 2; 2307 (1957);
L.P.Ratner, A.E.Gurevitch, 1:7P.Po1otenskayal ibid,
2316; L.P.Polotenskaya, ibid., ,2323
46. K.A.Bolshakov, S.S.Korovin, V.E.Plyuschev, T..4.17ermakova,
Journal of Inorganic Chemistry, 2, 222 (1957).
47. V.0.Chukhlantsev, A.K.Sharova, Journal of Inorganic
Chemistry; 1, 36 (1956).
48. V.G.ChUkhlantsev, S.I.Stepanov, Journal of Inorganic
Chemistry, 10 478 (1956).
49. st.P.Ratner, P.I.Chaikin, Collected Works on Radiochemistry
published by LeningFad University, 75 (1955).
50. SpA.Schukarev, I.V.Vasilkova, A.I.YSfimov, V.P.Kudryashov,
Journal of Inorganic Chemistry; 14 2272 (1956);
S.A.Schukarev, I.V.Vasilkova, A.I.Yefimov, ibid., 2652;
S.A.Schukarev, A.I.Yefimov. ibid., 2, 2304 (1957).
S.A.$11hukarev, G.I.Novikov, N.V.Andreieva, A.N.Ryabov,
Collected Works on Radiochemistry, published by Lenin-
grad University, 65, 1955; S.A.Schukarev, G.I.Novi-
, kovl A.V.Suvorov, Journal of Inorganic Chemistry,
1, 1948 (1956).
52. A.A.Grinberg, A.D.Troitskaya, Proceedings of th+adium
Trqtttute nf the USSR Academy of Sciences, 7, 5
(1956).c
t
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDp81-01043R002000070006-2
-
Eft
53. I.J.1avich,
Journal of Inorarie3 r:le:.istry3 1, 2736 (1956).
54. ;...D.Gelalan, 11.P.N.efodieva, RP2orts of the 7bSR
.!_cademy of 3cience,2, 117, 225 (1957).
55. V.V.F0min, R.E.Kertushova, (1.I.Rudenko, Atomic
'Energy, No.31 117 (1956).
56. V.V.Fomin, S.P.Vorobieva, M.A.I.Indreieva, Atomic Energy,
No.1, 63 (1958).
57. TI.U.Pgpov, n.I,Ivanov, . to:aic Energy, No.4, 360 (1957).
58. V.I.Grebenschikavey.N.Bobrova, Journal of Inorganic
Chemistry, 3, 40 (1958).
59. B.V.Kurchatov, V.I.Grebenschikova, Y.B.Ohernyavskayas
G.N.Yakovlev, Research jr the field of geology,
chemistry and metallurgy (Reports of the Soviet
Delegation to the Internal Conference on the peaceful
use of atomic energy) USSR Icademy of Sciences Publishing
House, 219 (1955).;.
60. I.K.StIvetsov, A.V.VOrobyov, ibid., 225.
61, G.N.Yakovlev, D.S.Gorbenko-Germanov, ibid., 230.
62. G.N.Yakovlev, V.NoKosyakar, ibid, 237.
63. V.B.Dedov, VX.Kosyakov, ibid, 250.
64. L.I.Gusevas r.V.Filippova, Y.B.Gerlit,
ILF.Myasoiedov, N.I.Tarantins Atomic Energy, No.2,
50 (1956).
65. Y.B.Gerlit. Research in the field of geology, chemistry,
and metallurgy (Reports of the Soil et Delegation.
to the International Confe-2ence on the peaceful use of
atomic energy). =SR Academy of Sciences Publishing
House, 202 (1955).
66. M.S.Faddeieva, 0.N.Pavlov, V.V.Bakunina, journal of
Inorganic Chemistry, 3, 165 (1958).
67. N.P.Rudenko, Collected Works "The use of tracer atoms in
.analytical chemistry,,, 1955, USSR Academy of Sciences
(1955); journal ARI orzanip phemis:try, 1, 109 (1956);
ibid., 3, 1 1;41 54)i.;LJLL t..,14 La.
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04:
31#4#,####1.4#444ftqm#10,,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
ID
�
rftr4 epr:-Ffnn,
r`�
- 48 -
2:11
68. 7.1.Kuznetsov, 7carn51 of '�nalytical C'emistry, 2, N954);
Session of the U_S? Academy of Sciences on the
peaceful use of atomic energy. Meetings of the
Section of Chemical Sciences, 301 (1955).
69. A.Pdlurin, 7.D.1,Tefedov, E.I.Yefimova, Collected -orks on
Radiochemistry, published by Leningrad University,
155, (1955); A..N.Murin, V.D.Nefedov, 159;
A.N.Hurin, V.D.Nefedov, V.P.Baranovsky, D.K.Popov,
Reports of the USSR 41cadamy of Sciences III, 806'
3:936).
70. V.D.Nefedov, M..,.Toropova, ,TouTnal of Inorganic Chemistry
1, 175 (1958).
71. N.P.Rudenko, :rournal of InorEanic Chemistry, 1, 1680 (1956)
N.P.Rudenko, Z.1T.2?astukhava, ibid., 1, 23:64 (1950..
72. B.P.Nikolsky, :rournal of Inorganic Chemistry, 2, 59 (1958).
73. V.I.Paramonova, ;Iournal of
ibid., 3, 212 (1958);
ibid., 11, 1896 (1956)
T 1905 (1956);
ibid;'," 3, 215 (1958),
ibid. -i , 74 (1958).
Inorganic Chemistry, 3_, 523
(1957);
V.I .Par amo nova , V.B .Kolychev
; V.I.Paramonova 2 A.S.Voievodsky,
V.I.Paramonov, A.14.Sergeiev,
'7.I.Paramonova) S.A.Bartenev,
74. A.K.Lavrukhina F.I.Pavlotskaya, A.A.Pozdnyakov, I.M.Gre-
ohischeva, Zrourns.1 of Inorganic Chemistry, 2, 8g.
(1958)
75. N.N.Tunitsky, V.V.Nekrasov, E.P.Chernyaleva, Xournal of
Inorganic Chemistry, 2, 66 (1958).
76. S.Y.Yelovich, ';,-.N.Prusakov, Reports of the USSR Academy
of Sciences, 112, 684 (1957).
77. V.M.Vdovenko, Xournal of Inorganic Chemistry, 3, 145 (1958
Collected Works n35 years of the Khlopin RaZium
Institute of the USSR ,Lcademy of Sciences", - 24 (1957
V.M.Vdovenko, m.V.Kovaleva, Collected Works on
Radiochemistry, 44, published by Leningrad University
(1955).
V.M.Vdovenko, N.I.P.Kovalskayeo, T.V.Kovaleva, Journal of
Inorganic Chemistry, 2, 1677 (1957); VALVdovenko,
T.V.Kovale va ibid.m 3, 1682 (1957 ) ; VM.Vdovenko,
� A.AeLipov, M.G.Kuzinai ibid., _a, 970, 975 (1957
LLi P-
� ri
to.bi,Y,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
RI
ff p
FOR CU ;
78. S,17.Karo t,.chc v, L.P,yharkhorina. G.D .ashkina J-ournal-
of Inorgani no-Aistry, 22 961 (1957).
79. .1.1:.nozen, ro.5, 445 (1957).
S.:%Kari ac! ova, L.P.Kharkhorina, flozen. Iournal
of Inorgan ic Chemi stry 2, 1441 (1957) .
81. A.P. Vinopradov, I.T.Alimarin, V.I. Baranov, A.K.Lavru-
khina, G.'T.Bar,Inova, F.I.Pavlotskeya, A.A.Bragina,
Y.V.Yukovlev, Sessiorlbf the 11SR Acaleny of Sciences
on the Peaceful Use of Atomic Energy, meetings of the
Session of CLemicril Scien ces 1 97 (1955); L.P.Vinogradov
I.P;Alimarin, V.I.eranov, 4...K.Luvrukhina2 G.V.Barano-
va2 w.I.Pavlotskaya, ibid., 132.
82. B.V...Uurchatov, V.Nalekhedov2 11.Y.Yuznetsov.a, L.N.Kurchato-
va, ibid., 120.
83. G.M.uorodinsky, V.N.Pokrovsky, B.K.PreobraLhen-
sky, N.E.Titov, Rel,orts of the ussa Academy of
56,1.ences, 112, 403 (1957).
Fic7r3
h
- Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
23
FCR
n
mi2c Lri;tr
��Lat
Ti7t7 Y"TP � - r
0 4 hISI00"*.
Aram
CHMICA.4. STUDY (dr
;- i;11.LC 70;',YCOLMOUNDS
Jy
Profsasoz. of -.06,:�* 'inisversity9
Corva*onLting ,emJsir 'the UbSR
Academy of aclenoas
Derivatives of aeuoDo17 ald heteropoly acids are the
most important representatives of the inorganic polycompoundS
class, It is already for over 130 years that heteropoly co
pounds have been the subject of numerous investigations,
Hundreds of their specimens have been synthesized, Many hete-
ropoly acids and their salts have found valuable practical
application, Yet soma important problems of the chemistry
of heternioly compounds have not been safficiently clarified
to this day. These include, for instance, such problems as
basicity of heteropoly acids, the mechanism and individual
stages of formation of heteropoly compounds, the role of water
in this process, and the structure of h teropoly compounds as
a whole and of the strqctural units of their inner sphere in
particular. The solution of these problems is also complicated
by the fact that the structure of crystalline lattices of hete-
ropoly compounds may differ from the structure of their mole-
cules in solutions.
The application of various physico-chemical methods plays
an important ri?.e in studying heterpTly,,comeTun-ds. MaT.Sobc-
lev (1) investigated the properties of phosphotungstic acid
r MrPi
in solution9 employing the mffdlatOr*aial.7sib raV050000ebul-
-i�
lioscopy and conductometry, He was the first to establish that
the a-cove heteropo vIcid is not a double compound or an
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
LI;
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
1,,A; �
. � � ,
FOR LJ il
I
- 2 -
A
isomorphous mixtures as avae r.a.ioeal,e11;erss but
renresente a complex utc u diseoclation in diluted
solutione.
In measuring the curves of neutralization of phosphomolyb-
clic and phvsnhotungstio aciass A.Milati (2) arived at the con�
clusion that these compounds passtssed high basicity exeseditg
that of phosphoric acia. Similar I:esults were obtained by
A.Rosenheim and his ssaoctatss (3) with regard to MY119 unsatur�
ated heteropoly acids.
A valuable contribution to the development of the chemistry
OX' heteropoly acids was mad* by the physico-chemical research
conducted by Gaander and his associates M. They achieved thei2
results by applying the methods of diffUsicas light absorptions
and notentiometrics sonductometric and thermometric titration.
While studyinc the conditions under which heteropoly compounds
are formeds they compared the behaviour of solutions of normal
malybdates and tunzotatee in an acid medium. According to
Zander's studies, when solutions containing salts of acids which
form a heteropoly coPipound are acidifieds asp for examples
tungstate and arsenates there first appears the anion of an
aquopoly compound namely hexatungstateo
is
6(wo0aq)2. A 711 (HW6021� aq) '2'a3O
and only then, already in a strongly acid rts?thara9 a heteropoly
compound is obtaineds
1- 7-
201W6021.0a0 4 H2A.SOL 4 4H (14-1156.0211e,liii_AS04). aq
e
. Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
���
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�G
,
ro"
FOR eiTrAlf
t�fizt-.L.
- 3 -
A
.1.
The transition of ion (W1160210ag)5- to ion:M.417602w cor.
responds to the transformation of paratungstats into metatung-
state.
P.no4shay () applied the mlarographia method to study thee),
rocese of hydrolysis oi a1li hospho- and horo-tungstates9
occurring under the effect of caustic alkali nnd resulting in
hetsropoly ooLspounds, He has proved that a number of mobile
equilibriums become established in this case. The revers�
reactions of formation of lansaturated compounds proceed in a
similar way when solutions of unsaturated heteropoly acid salts
are acidified.
The author and his asso&tes used tracer atoms and the
�
method of isotopic exchange in studying the propertiese structure
and reaction capacity of some aquopoly aud heteropoli compounds.
The isotope methods were combined with various physis3-ohamics1
ways of investigation (dialysis9 po1arography9 the Study of
spectra of light absorDtion in the ultra-violet end infra-red
regions, etc) As a result� it became possible to obtain new
data on the properties and structure of aquopoly and heteropoly
compounds end to gain 20M0 new ideas regarding their structimrs.
An opinion was voiced that the process of formation of aquopoly
and heteropoly compounris greatly depends on the propensity for
hydrogen bend of the anions of acids 9 participating in the said
reaction of formation of the complex. It may be assumed that
hydrogenions fix the anions participating in the building or the
Fe')
-ut L.
VOr r111,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
,
c7-1,
, , � � I
A.
4* _
�����,,,
oomplex i0D0 r_part from ev:lount should be taken of the
possible role of hydroxonttul icnz in the irmer structure of
aquopoly and heteropoly anions�
Of considerable interest is the problem dealing with this
mechanisa of the initial stages of the reaction which leads to
the formation of heterovoly compoundso
By uaing the el e ot:vo chemical method. to obtain heteropoly
Compoundsp VoIoSpitsyn and Kof;oKoneve (6) have shown that the
mixture of Na2HPO4 and Na2W04 passes through a series of stages
of formation of non -saturated heteropoly oompouads or of UN:4r
double salts with 1a2W04 in the anode space of tke electrolyser
with pH of the solutIons being gradually reduced9 before phospho-
tungstate of the saturated varies appears. Interaction between
NA2W04 and phosphate lone has already bean recorded with pH
amounting to 7.5 - 7. The composition of the crystalline pro-
ducts evolved from the solutions after electrolysis depends on
the magnitud s of pH so obtained as follows:
pH of solutions 7.2 6.3
5.0
4.0
3.0
208
2.3
Ratio 13:17 in
crystalline prodacts 13 1:6
1:7
1:8
1:8.5
1111
1:12
Taking these results into account9 it might be conceivable
that interaction between phoSphate and tungstate ions beings
already in the alkaline medium when ths acid tunggtates are not
yet formed. To cheek the correctness of this assumption,
V.I, Spitsyno F.M.Spiridonov and r.D.Xolly (1956) studied the
fal
.0+
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
t
process of interaetion between sodium phosphate, Na2HPO4� and
standard sodium tungstate� Ua2W040 by the method of self.diffu-
Edon using tracer atoms of phosphorus and tungsten, p32 and
W165. The teehniquee of investigation reoembled the one
developed by 3.Anderson and K.Saddington (7) for measuring
the coefficients of diffusion of tungstate ions at various
rates of pH, using a tracer atom W1135. In our experiments, the
,Na21704
solutions of NaiHFOOr their mixtures, tagged with radioactive
isotopes were poured into capillaries with a seldered bottom,
which were inserted in a solution of exaotly the same composi-
tion, but without radioaetive isotopes (Fig)0 As a result
of self-diffusion, the conoentration of tracer atoms docraasod
in the capillary. The coefficient of diffusion of the anions
under investigation was =muted by msane of Fickgs law. Normal
sodium tuagstate, Na2W04.2:5209 was selected as a compound with
a known molecular weight. The ionic weights of phosphotung-
states were eompared with the ionic weight of nermal tangstates
provisionally taken as a unit.
At a temperature of 200C and with pH about ay the ma-
floient of diffusion of phosphate ion exceeds almost three times
that of diffusion of the normal tangstate ions
Ion Coofficleat of diffusion, Do
BP042. $.3 23.001044
w042 Sot 8.7.104
r11114
rrin
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
-7
741
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�
* t I
FO
- 6 -
Y
��������..�.�
If such a quantity of phosphorus-tagged Na21tPO4 is added
to a 0.1 molar solution of Na2W04 that the ratio P:V/ amounts ix)
1:12 or 1:60 the coefficient of phosphate ion diffusion
abruptly diminishes and approximates the magnitude typical fbr
tungstate ions
PM rat t,H Coefficient of diiffUSiOn. of ion
4_0 2"'e_ps1 Jsea _
1:12 8.4 11.0 010-6
1:6
8.1
6.2 . 10-6
By tagging both solts0 Na2HPO4 and Na2W040 with radio-
active isotopes, we found that phoaphorus and tungsten posses-
sed in such conditions practically the same coefficients of
diffusion:
P:VI ratio Coefficient of cliffusione
D
hL2siht�....sn:
titcn
� -
1:6 7.8 6.3.1076 5.8.106
A radiometric definition of P32 and 11185 ulth both or theca
being present was made with the use of aluminium filters, as the.
illaXiM11171 energy of beta-ra.diation of P32 (E 3..701 MY) greatly ,
exceeds the energy of radiation of W185 (B 0.428 Mello The
method is outlined in the paper referred to above 16) e
The said results lead to the conclusion that the ions of
TIP042$1. and. W042' (or W04. 21120) interact already in the �
alkaline region, with RE amoun_tittg torming a complex ion _
0 i'ga UA, WIL1
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
FOR OFFAL ITF ONLY
� 7 �
��������������
with the mass approximating, that of a single tungetate ion�
It should be noted that covv3unds of this typo have been
mentioned in publications (8) ago for exezpioo 1W03.P2050
ZW0,02050 and Na2002WV3.P2050 although SO fa2 they have been
obtained only out of molttnieia ElorlidkTomeaus mediump the
zonation betwecn the ions of Ii7042-/appars to occar as a re-
sult of the anpearanos of a hydzogert bond accordiac 4ixo
(P0E4 .00 04T)4.L. or (RPOA4 �. 90H 0.0 OW020 600 HOH)44'.
On the other hand V.I.`,:pitsyn arid KoCT 0ozzova9 by uaing
the method of tracer atoms� hems proved. that sodium Lletatung-
of
stat s9 peculif,kro according to 179-1.d er I= the anion.
(E3176021) 3m aq does not 1.1-0,trast directly with phosphate ions.
The reaction occurs only during sub oequent a.cidification of the
mixture, Hence o 3-anderge capposition regarding the initial
formation of aquopoly compoustde and their subsequent reaction
with oomplex-forming acids does not conform to the recently
obtained experimental data The prooess413 of formation of
aquopoly and heteropoly compounea occur in the solution
sinvaltarteously and in parallel to: the lowering of. plito
The initial stages of the reactions to obtain heteropoly-
anions are to some degree accounted for by the above results. -
There still remaineD howeve�gi, much to be clezified a a to the
mechanism of the reaction of formation of paratungstates.
V.I.Spitsyn. end E0 Trche&cova ( 9 ) etudiesi this process with,
the OA of tracer atoms9 using the radioactive isotope of tunge-t:
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
C
WL V
ton W185 (period of half-life: 73.2 days).
The solutions of nal704 and of non-active sodium paratung-
state9 brought up to a certain value of pH by adding a small
quantity of HN039 were poured together and were kept for a fixed
time at a constant temperature. In terma of tungsten9 the
concentration of the solutions or normal tungstate amounted to
0.02-6 mg/m19 and of paratungstate to 4-20 mg/ml.
The transformation of normal tungstate into peratungstate
was detected by isolating into the residue of slightly soluble
sodlum-eesium
mixed poweekmagsleac of paratungstate whioh9 according to OUP
investigationso using the conventional formulae� has the come.
position Na2083lieli2(104)6/0 41320 and oaptures, as a result
of adsorption o not more than 0.5-0 of NaeD4 out of the solu-
tion.
It appeared that the exchange of tungsten between agdif-
led normal tungstate and paratungstate does not occur instantan-
eously, Thus, with pH amounting to 6.89 which oorresponds to
the region of existence of paratungstate9 the compound is not
formed at onoe (Table 1)4
FOR ELM
r+
- cnnifi7pri nnpv Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
3
�t�
-73
� ;
4!
!";�A�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
FOR
Aid
- 9 -
Table I
Speed of transformation of Na21104 into paratungstate
�ImImssimmISNEb
Duration of
reaction
5zin.
1 hour
24 hours
268 hours
Transition of tungsten-183 from Naer04
to saratu state or cent
4.4; 2.6 (average 3.5)
9.7; 10.8 (ditto 10,2)
20.6; 13.4 (ditto 18.0)
5506; 74.4 (ditto 65.0)
An stated below, the isotopic exchange of tungsten between_
paratungstate and the product formed durijg the acidification
of Na2IVO4 pro eds by far faster than the time taken to obtain
the product. Hence it may be assumod that 3-10% of the
exchangeable product is farmed from Na2W04 in a short period
ot tr' (5 min. - ). hr.) at e temperature of 25�C, and 65% in
268 hours. Suoh a behaviour leads to a critical appraisal of the
views expounded by Tender (10) and Souchey (U) on the mechenism
of formation of paratuntate in solution� according to which9
at pH amounting to 6-80 the normal tungstate ion, fixing the
ions of hydrogen9 instantaneously changes into a hexatungstate
5
anion (HT16021.aq)-
corresponding to�par atungstate 0
The transfornetion of Na21/04 into a product exchangeable
with paratungstate is accelerated at low values of pH and is
retaraed with transition to a neutral 'radium (Table 2), At the
same time the conclusion should be drawn that the normal tang-
state ion exchanges very slowly
44' re
mg ten atoms with the para-
:r 7Tt 4151141/
WO
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
00
tungetate ion0
OTT.IT"-:11 ONLY
-10-
Table 2
Influence of pH on the s ead of transfOrmation
of Nap04 into peratungstate
Temperature:25�C; duration of reaotion: 5 min,
PH
Transition of tungsten-165 from Na2W0 to paratungstatee _
608 3004 405 (average 307)
508 2205g 1601 (ditto 20.3)
5.1 2e04t 28.2 (ditto 28.3)
105 .6100; 4904 (ditto 5502)
An the temerature rises9 the speed of transition of
Na2W04, in Paratungstate increases (Table )),0
D.L312_13
in..1/2E+_�01..t�Lum_iratwe on tht_ggapd of transformation
of Nat70 into paratungstate
6 8 700
Duration of Transition of tungstsn-185
reaotioao haars from Na2WO to paratung-
Temperature9
state vent
305
2509
1800
5200
25
1
50
1
25
24
�50
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
ref?
Ns
41 Li
-11-
p.
- V
-
�������
Hence0 the conelusion may be drawn that the reaetion of
forming paratungstate when a solution of normal tungstate is
acidified is a complex process which oteurs slowly and which
possibly consists of several stages.
An important feature of paratungetates is that some of
their properties considerably change when the aqueous solutions
of these compounds are kept for a long time or heated. The
electric conductivity of heated and then cooled solutions of
seditut paratungstate is much higher than the initial one (12).
Fresh solutions of sodium paratungstate are precipitated in
cold by SOMB reagents (1,0 14)0 but they do not exhibit such
reactions after heating.
Proceeding from polarographic studies0 Souehay (11) expros-
sed the opinion that there exist two kinds of paratungstate0 one _
of which (A) is formed during acidification of normal sodiuz.
tungstate, and the other (B) during the dissolution of crystal-
line salt. It was assumed that the said modifications differed
by their hydrate composition.
V.I.Spitsyn and G.M.Pirogova (15) studied the properties
of sodium paratungstate solutions0 depending on the conditions
under which they are obtained0 the temperature of heating and the--
time of keeping. For this purpose the methods of dialysis0
polarography0 chromatography and light absorption were applied.
The colecular weights 'of the ions present in 0:01 molar
F 71 41
tungstate solutions were d nbd1i�jiSAhXo a cello'.
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
ft
Fog
rep, g
LL
, 117
� y
- 12 -
phane membrane at 25�00 The molecular weight of a hydrated ion
of normal tunr,stata (W0'. 2&20 g 284) was taken as a unit of
comparima. The fresh solution of crystalline paratungstata9
Wa1OW12041.0 28H20 possessed a moleGular weight of about 30009
which well corresponds to ion w1204119 28E10 (Mp3336S). After
the solution has been boiled9 the molecular weight of the anions
diminishes to 1500-16000 i.e. it is practically halved (Table 4)0
11111_k_
CocerriolaltUSALUOCALLITLIJE122212E-1411a12
of some tunrsstate ions in soluaga
Compound
Characteristics
og solution
Coefficient
pE of dialysis
Wa21104. 2R20
8,0
0.236
N101712�41�2
Fresh
6,1
00072
1111'101712�41�2
Heated f2r 8 hrs
at 1000
602
00098
Ea2T44013010/120
3.6
00033
Molecular
weight?
284
3000
1600
14000
The nhenomenon Go recorded may be expressed by the equation'
Ha1oW12041. 281320 2Na5/H300W6021/0 124E200
Evaporation results in the formation of crystalline para-
tungstate which, when in solution, again exhibits a doubled
molecular weight.
When solution/Cr
Frit
s,acidified with nitrio tusid; tha
ft. rTs;
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Ilh
MR (77711
-13-
composition of the anions so obtained depends on pH and the
duration of the reaction (Table 5)0 It is only in the region
of pH amounting to 7.0-6.6 that hexatungstate ions are formsd
at once, With pH amounting to 6.3-6.19 ions with a molecular
weight of 5000-10000 are the first to appear. Ten days latero
the weight drops to 1500. Ions of the (H300%021)5% nH2W04aq
type of high moleoular weight appear to be formedin this case.
In the course of time they become subject to disaggregationo
splitting off the lighter hexatungstate ions. This phenomenon
is manifested still more distinctly during further acidification.
If pH of the solution is brought down to 508-5060 the molecular
weight of the anions so formed at first reaches the enormous
magnitude of 53000-1200000 and egter being kept for 10 days
diminishes but to 14000. Such a molecular weight was exhibited
in our experiments by sodium motatungstateo Na2W40130 10H200
which corresponds to ions polymerized approximately 12 times
by 1130 (E7104),C112W04(H20)6/2'or /W40130 101120/2' 101/00
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 � CIA-RDP81-.01041Ron9nnnn7nnnR
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Chars in the
Fira NLY
- -
MALI
oasffizients of dial sis and molecular
wo.taktfLati.L.----11�"durinie. ko0ANS.121L9AULL11.
2!,32.11.2.152LNEk
01WIN.M!..6.00�����������Pa.
Ooeffi Dien tn.E.2.rAtiAlEglp
trirgEri--
after acid- the volution
ificatiam
pll
Time of kespiug
the solutions
(days)
Molecular weights
Directly After
after acid- keeping
ifying the the
soletion solutimn
6.6
6,3
6.1
5.6
5.6
19
19
14
6
11
00186
0.129
0,102
0.174
0.072
00180
0.029
o.o62
0O
o,o56
1500
130
5000
160
9900
150
55000
i20000
14000
1400
The transformations detected in the tungstate solutions
were likewise confirmed (16) by the poIarographio method with
the aid of Geyorovskrs micropolaregraph. The results of Us
polarographie examinations are given in Table 6 and in Figs. 2
and 3. It should bs noted that it is not the initial tungstate
ions that are present in a strongly acid midi= in which tuns-
states are9 as a rule supeoted to polarographyp but colloidal
tungstic acid or metatungstio acid. In this respect Na2,404 and
a fresh solution of paratungstato behave in a oim*lar may
(potentiala of half-wavess CralMUM garning one and. .the
r =4`1 L.�;E ELY
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
e
�.
t.t./
LA'
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
1111.."1.11milmmommanimmie
FCIP
-15-
-ALI
sane product in an acid r-Bditaac, A tungstate solution which
has been subjected to boiling produces already a different
polarogram with two waves CN11/2a 0026 and B111/2% 0044 v)9
which resembles to a great extent the polarogreas of nodiun
metatungstate and metatungstic acid� By its struetMre the
hexatungstate ion seems to be kindred to metatangstate and is
likely to be its structural unite Me above tronsforwattan of
paratunestate is polarographically recorded beginning vd.th a
temperatare of 35*c and torminates at 6000
FC 6p ttjLiI LE
-
jr.71.7i
V
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 � CIA-RDP81-01043R00200007000A-9
:Concent- :
:ration :
:of solut-:
;ion mol/1:
r
Character-; Potentials of half-waves (in volts) against
istics of : a ous bac ro nds
solution : CH3COOH-CH3COONa
: 12 N HC1 pH 4.6-5,6 1 N K2S0t
Na2.W04.2H20
Nalo w12041.2,31190
Ha10W12041.28H20
-0.26 -0.44 .00.40 -0.90 -0.44 -0.84 -1.04
-0.26 -0.44 -0.40-0.90 -0.44 -0.84 -1.04
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
...40����411.
t
r(:)-,
�Iummimmummumm.......mm
� , ,......
:7. ...iv.:G.
s.. ,.,.
r _ /
� jiliAe..4 ',:!:
1
-17-
The same variations in ths behaviour of fresh or boated
paratungstate solutions are observed with pli.amounting to
5005.4 (acetate buffer) and against the backgroluld of K2po4
(Fig03). It has long since been known that more acid (by the
W03 content) tungsten compounds ara reduced more readily to a
quinvalent state. This may acoount for the lower potential
of tho beginning of reduction (-0.26 vo) of metatungstio acid
(0=Foritawte 3 and 49 Table 6) as compared with ordinary tungstiO -
acid (experiments 1 and 29 Table 6). The latter is9 however,
also revealed during polarograpby as a product of partial
decomposition in solutions of metatungstic acid, produoing a
talf-wave with a potential of - 0044 or 0040 vo The prosenoe
of several waves on polarograms recorded in the medium of an
acetate buffer and against the bankground of It204 appears to
be related to the presence of several egailibxim tImns Of tun&
ston compounds which are reduced (W64 W54) at various
potentials of half-waves� In the case of a neutral or a weakly
acid medium it is unlikely that one and the save anion passes
through successive stages of deeper reduction,
The kinetics of transformation of paratangstate ions into
hexatungstato ions may also be traced by moans of absorption t2;
-L
spectra� The experiments wore conducted in the ultraviolet
region (220-290m )0 Fresh solutions of sodium paratungstate
,
produce a curve which drops down abruptly ao the length of the ,
-
malre increases (1?ig04)0 Daring the keepinuf the solution%
--."
re-n.
L tiNv
:
� t
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
17- "
A
Cf-�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
ill��11�11������=111�������11�MININD
-
FOR
A L.)
-18-
cti.x.1"
������������
ths drop of the curve in the region of 245-260 m is retarded,
and a platform appears there, followed by a maximum with the
length of the wave amounting to 256-257 m 0 This maximum
Increases slowly in the course of time and roaches a constant
magnitude a month after the solution has been prepared, Sub.
sequent observations during the year proved that there were no
changes in the optical properties of the solution-s0
Similar phenomena, th,oughat a more rapid rate, take place
when paratungstate solutions are heated to the boiling point
(Fig05)0 In three hours there appears a maximum in the region
of the length of waves amounting to 256-257 m 0 Its height
attains a constant magnitude after the solution has been boiled
for 10 to 16 hours. The coincidence of the values of maximum
of light absorption for solutions whioh have been kept tor a
long tine and for those which have been heated leads to the
assumption that the same prooess occurs in both cases: trans,.
formation of paratungstate 'ions into hozatungstate ions shiall'
are in correspondence with the above maximnmo It is worth
noting that in this case, too, similarity is revealed between
hexatungstato and metatungstate: their spectra of absorption
are quite approximate (F1g.3).
Directly after their preparation acidified solutions of
Ba2W04 produce absorption spectra an curves ',Mich abruptly drop
as the length of the waves increases. In the course of time
a platform is revealed on the curvege and then a maximum, This .
�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
� V .� 1.� � ,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
t.7111. USE ONLY
process occurs� howeve1r9 slower than in the ease of sodium
paratungstate solutions�
Final1y0 it should be noted that fresh or boiled solutions
of peratungstate behave in a somewhat different way in relation
.
to anionites (l6). The sorption of hexatungstate lone (mars
to a markedli lessor degree particularly in the as of small
concentratione (Fig. 6).
Of great interest Is the similarity of the studied propert,
les of hexatungstate and metatungstate. The transition of
paratungstate to hexatungstate during the boiling of the soln-
'blob. possibly represents an important intermediate stage Of
formation of motatungstates. On the other handl, hexatangstates
are likely- to be the most immediate products of metatungstate
hydrolysis�
The abovt-deneribed experimats demonstrate that esditated
aquopoly compound may have a different structure of the ion
as compared with the initial substance� Apart from thief,
in the first stages of formation of aquapoly compounds there
corm into being highly polymerited anions which but grSAuallY
beeome subject to disaggrec tion.
On the basis of the new experimental findings so obtaineds
it is possible to consider in greatex detail the poblem as to
the phenomena occurring during the acidification Of solutions
containing components likely to form haterOWAY 004oundeo
We shall express our opinion on tblo subjeoth proceeiling chiefft
Oat
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
FOR OFFE�
1
2c)
ly from the analysis of tungsten derivaties which, we have
studied in greater detail ands notablys of paratangstatess
metatun tate s and phoephatungetateso
It hags often been stated in publications (4) that the
formation of an aoid tang-states an aquopoly =pound of the
paratungstate typos is the primary stago of the reaotion
occurring during the acidification of solutions of normal
tungstateso And yet tt has been pointed out by may research.,
ors that the so-oalled *white hydrate* of tungstle acids
approrimating Be040fie by its compositions precipitates in
the initial stage of acidification of normal tungstate sobi
tion ss followed by its dissolution and the formation of acid
salt, namely aquopoly tungstateso VoI.Spitsyn and3C4Aoneva
(17) observed Isolation of the residue of white tungstic acid
in the range of pH amounting to 8-6 when phosphotungstates were
obtained OlObtro-ohealoallyo GeSoSavoheako (18) recorded the
formation of tungetio acid in the same range of awhen study-
ieg oxalate complexes of tungstaao Finallys the above results
of the experiments an the dialysis of acidified solutions of
2W04 have shown that anione of high molecular weights which
undoabtedly contain a great deal of tungstio acids are the firsti
ee
prodnets of the reaction in westiono
_
It may be thus assumed that the formation of tangstio
acids 1!0040%00 is apparently the first stage of the reaction.
which (Wars when aqueous solutions of norma/ tungstates are
1,� �
Ca
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy A proved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
rpr
nt
riug
ui
J.�""�������
aitfle Xt rxey be presumed that in a oertain range .ot pit
(84) the simultaneous rtcresenee is possible of b:itit the ions of
Mee' which did not partioipate in the reaction and a tba tungs-
tic acid which was being foritado There 049610 processes of for-
mation of aquopoly anions and of more complex heteropoly anions
with the partieipation of tungetio acid and WO4 ions() At the
same time one should take into account the rise of conoontrap
k
tion of ilydrozoniu.m ions.; 1130-0 in the solutions, ac w2.1 oe
the possible appoaranee of hydrozoniusi forms of tungstto wid9
EMp)w04 and. (1130)21/04.
accordance Wath the dbave oonsiderationse ValoBpitsyn
(11) saggeeted the following sohale of formation of paratapg-
state anions from normal tungstate with ph amouating to 0-61
� PO '17�4 /o (w04 (w04),fr
itp(V.T04) 3/5�26 3(1130)31704 AM) 0 0 0 IVIQ4)0 0 0 mo4m.p))01.23),...
non the viev7point of the nature cog stability of chemical
to all this hydrozord.wa ions should be coraidexed in this
cast) elS equivalent (Pigo7) 0
The. Salts of the composition 51&0012W034111200 ice� para.. -
tiniatateso correspond to talon /01130704),M104)(11,0)3(1120)3/5:
Me to the hydrogen bergo additional molecules of water may join
the hydrogen atoms of hydmenium ions; whew e the coordination_
number of hydrogen b.as not been used to the ful4 For ezamplep
e�odium. paratungstate has a compositica of Na10111200.02911/409 -
14*177
C14
L. .
�4'-'rs.,'?
- Cipv
-
Declassified in Part - Sanitized Copy A�proved for Release 2014/11/04 � CIA-RDP81 01n4Pnn9nnnn7rInna
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
a
�
VrYA:
TELV
With pH below 5 (optimum conditions: 405-34)0 aquopoly
compounds of tungsten, defined by the retie MA20:WD, equal
to 1:204 (paratungstates)0 are transformed, as is well known()
into mare acid compounds with ta3 ratio Me200103 equalling 1:4
(metatangstates)0 sodium metatungstate, No0401,010H20 or
Na012039030H2O9 is a most important representative of this
olass of substanoeso
The above reaction may be represented as a preeess of
aggregation of two hexatungstate ions (paratungstate) due to
hydrogen bonds3
24130(W04)(wRo4)(H30)(H20)3"%a gip 31120
/(IO) 307o4,1130 9(H2m4) 3(1120 9/6`"
A possible struoture of the matatungptate Jona in line with
sueh an approach, is given in Fig.8.
A0A0Babunkk1t0 GoV0Takhnevieha Y0F0Beryozkiss, and,
VoloSpitsyn (1957) studied the infra-red spectra of,abSorptton
of various sodium paratungstate hydrates. Sodilm paratungOatee
Containing a nozsaal quantity of.combined ater exhibited
in the region of high frequencies (000-3800 eel) a complex
band of absorption consisting of four components (Fisit)0
The band as a whole is related to tho manifestation of a
hpdrogen bond between the molecules Of water,! Individual
maxima of this band (3260033800400 And 3540 Gm) indicate
that there are several forms of bond of water between one
anotherlas well as a bond wiWthe-tungston Atom, These
L31 .
j " y
. �
� � ���������...".."
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy A proved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
j������.....411
"Y.
�
0,
7.
t.f.o
1
FEP
1:-
;'
Y
z
-23-
maxima correspond to the molecules of water.which an at dis-
tances Of 2.68 2,7; 209 and 5.1 A, Analysis of the spectra.
of absorption of sodium paratungstate solutions in 1:120 has led
to the conclusion that the hydrate of HalOW1204102,TO20 con-
tams water in the s different forms of coordination. The
result is in general agreement with the above sohems of form.
taco of the paratungatate ion.
In the transition to lover hydrate the coordination
of wator in paratungstate assumes another fccilac, Simultaneously
with this() the structure of the compound undergoes an abrupt
obanGo0 Analysis of sodium metatungetate by the game method
pointed to the presume in it of two %tome of coordination of
mater. One of th2tp as in paratungstates2 is effeOte4 in the
form of a breroxyL combint4 with the. Ungaten atom VX.aR4,
As to hateropay comptundsg their'OrnOtrstiti frcM t.
,
Vioupoplt Of brdrogen bonds and =atm goutsdvay be;voprosont
\ �
eath the ott5,0 rdwohotungotatee .as TOilOvip.'(9);
Oen no , t
tato Is avintled la t4e-p'reisen0o�of -
, � , � s ' , ,
0.091100 o,n,0\111) tO 04 0.,7 phqtsphotun 00 0.:the wisatarated
=Leo if forsd with the r4WPOffy?;, ; ille/i*etien ,
appears to pro0004 4wrianz to 'Oa 1104e4nit's0iT '
1,1
Declassified in Part - Sanitized Copy A 'proved for Release 2014/11/04 � CIA-RDP81 0104�1Pnn9nnnn7nrma
101,
s!:
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
?i.SE ONLY
- 24
(P0411000W04000H20)4'aIt (P04110�W04.0
Further
011200
INP(m4)(H3 / 2033w2W04 POO.
ott3o)''
'ft
40.4.0112
Down.%
vt'
Evoy000m2
The salta of the composition 3me20.P205061703.16H20
oorrespond to anion AVOW04)(EW04)2,0,0)3M20)2R" Thin
complex anion may additionally include in Its composition
molecules of 'water due to the hydrogen bond with hydroxoniwn
or ITI9422. ions. The salts of this serien are ganeral4 rePrasent
el by the formula We20017203.6170,01811200
When the acridity of the msdium I raissdp the ftghlte
hydrates? of tungstio aid o 11006.H.209 manifest80 as is well
Xnewno a propensity for trensitionto a yellow hydrateplUN.
A dearease in the amount or combined Witter per 3, atm of tum&
sten Am also recorded In the complex anions of agnopoly and
h4ter3po1y compounds a pBdecremSes.
In the case or phosphetungstates9 an ins:roans in the
relative content of tungsten in het4ropo1y anions results in
a greater role of the He04groups and a amaller number of
hydroxonium ions in the complex anions. The following
istructureS may be assum6d 'or phdsphOtungstate lons'of a
't1 7117 "
�� y
,. �
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Atr
,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
FOR
25
A
�����������
different degree of saturation with tungsten*
With pH amounting to 605-60 salts are formed with a ratio -
PIW l:49 which have a composition of the type 3Ue200P2050
121i0301$H200 The possible structure of their anion /P00004)- .
61(H20)3/3 is shown in Pig0100
With acidity of the solutions about pH %) luteophosAo-
tangatatas are formed of the composition 3Me200P205018r43�
lnig with a ratio PM ca 1490 The assumed structure of their
anions, /PO4(1121VO4)9k9 is shown in Fig� 11.0 The question
regarding the doubled strueture of the luteophosphotungstate
=imp raised on the basis of orystallo-ohemisal research
should be considered as being open to discussion� Experiments
on diffusion do not confirm the doubled molecular meight of
compounds oz' this type�
Fina13y0 with pH anounting to 2034050 phosphotungstates
of the saturated series are formed with a ratio :Nam 1:120 of
the compesitipn N*24.P205024W03,040 ( in the case of netrian
calt)0 The suggested structure of aniondt04(E004)X2CBOW
is given in Fig0120
�7
-
Proceeding from the above Considerattonsi hoterOpoly.sade
Of the saturated series may be conoelyed as prOduCts of 044itionj
of 12 molecules of a metal acid to an anion of a nonomotai achl,7
accorOUg to BWRQ4(Hg4)41H2X04)80e)n/9 where R is the non*
metal el_ emt.forming the compleze tv.is the baSicity or the
acid which eorrespondS to it and Ic is mo or WO 2tur mo4eales
r.41
41 gr.
erv.
"IP
�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
� C.
11
.0V^
FOR
Cla 26 426
A ,
Aid
t.F.r.r.,s1
1443
of 112X04join directly tetrahedron ao40 The other eight moleoule,
of %MI). are con/meted to one another� In this ease the hydrog-i
ea bomls must be of primary importance�
. The suggested schemes of the struotFe of aquoPo17 and
heteropoly compounds reflect the important role of water in
_ .
the.prOcess of foxmaticn of tb2se substanoes0 The behmtiou4 or
water in the said compemnds of several type svas studiedbr
menna of isotopic ezthange with DO and heavy oxygen water�
VaX08pitsyn. and iruPoBeryozidna (20). investigated the
lirgetyvio'.,exchango of deuterium and b.ydvogen between, vtatev
oontalang mpprozimately 20 molar per cent of DO and yarioue
hydrateo of sodium para. and matatungstate0 The heavy water
used for the purpose ha a surplUs density of 2400-2800 0 A
batch of en avopoly compound was introduced into a wighed
amount of heavy _water of a knor4 density�, The mizture wae- !tort
ft* a.aied time at a osnotent tomparaturop folleting*tok -
the =tor vao removed front the solution ana srlbSeOtea to�illtand**
11
ardlAwifiCation� Dua. to the slight solubility of vpitiPIP
peratangstutes there was always present it.sotp phase on the
bottom of the motion vessel, or this reason the 004404:
wao carefully deoanted before being distillati� .4:quantitatilre
appraisal of isotopic eNzhange was made by measmring the 4040
of the heavy water before ana after the experit; The 0444
r. �
of the wator was determineA vathin 3 by the, f3nlitioria0400
1011 00 ,1404 er-a hallow 104t 12pato Table 7 prpsonta datg:
LrYi
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
4
111
00
ID
FOP
r"777MAI
.14
OP 27
14'17
on the isotopic exohange between the heavy water and sodium
paratungstata.
able.1 �
OOiJ4X!hfl of en weal h.aa we.ter and
sodium paratungstatev Nai0.1MA..22L:.52NL
Temperatmres 20000
Toolof
ezperi-
ment
Composition of e
. um pare-
tun state
zehange Duration of
elsperiment
eavy hours
water
Participation
or E20 molecu-
les in the ex- Average
ehan
NO1/11012.11
1
2
).
40
4090522
.......A22a) 46
2093493
1,19260
00967
4028970
2
1107
�
7036239
2
1090
11.08 0.5
7031270
2
1184
6.73990
12
2609
. 2ito0 0.4
As can be seen from the above resultsi the =change of
1134rogen proceas at a high speed, Forty or 'eeni or the water
enterints into the composition of the whole of 'the batch 1/3 ex
-
*hanged in two hours, although by the magnitude Of selubility of
paratungstateo the 1ijidphase is supposed to contain bat
20020 of the salt used in the experiment. The, =bill* of hYd-
resort is so great that in 12 houria the exchange in the solid
;
At the temperature of 100- its, rate sg., z* 1e grows
phase attains 300%.
, � -
,
con.siderab1.70 In an henrys time as =oh as an (tviSrage of 175
I 4
r!----11
t
"
;
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�.1
C) 0
=
7-T7111
11 rrp,,
- E
A L)
EL Y
moletules of water is exchanged out of a 20ter hydrateg
. .
dehydrated sodium paratungstate exehanges with
heavy water at a much lower rate, The prodtet of the compositiOn
Na1042043.0904B00 prepared at a temperature.of 100POs does
not exhibit'eny propensity fOr exehanse at room tempasture.
Heating the solution to 100O makes 2.6 molecules of -the rater
exchangeable. Paratungstate hydrates containing water to Us
amount of 403 H20 and 211,20 do not exchange at all with heavy
=UV,
Sodium metatungstate was used as ordinari 1110water hYdrate
with a eompositiono according to enalysiap of 114100.309065H20.
Zits Capacity for exchange with heavy laster vas let pronounced
'than La paratungstate (Table 13). At room temp-oratml 74 mole- --
miles 'of water reotsGS3 Meat mobility and exchange elinest in.
stenteneously. Roue-vex,' the remaining 2-3 moleieuleS exChange by
Car
31awsk0 It is only in '36 hcztro.that the excg:ang0.4nvolves_z:
90 molecules of the initial hydratce At .1004).00. heating for an
heur suffices tor a complete exams of the watero
�
747117 'FP1,41y
,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
����������"".."."
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
0 0
ilrOMMEINNImomommommulmimINM
_ � �
� �
lb
VW"
- 29 -
Table 8
motatungstateo Na2174013, 9065 H20
5',2mtratI..aL....es
170-0of Composition of exchange
experiment yrrAsixtra...�......
e awuns- eavy
state
water
oo86189
5.99456
2
10S5061
5.15554
3
/06912
5.94939
4
$o08151,
3.35999
5
1041M
8.5796/
6
405184)
0o29535
Duration
of experi-
mante hours
Participation
of Ei0 melecu- Average
Ie s rn the ex'.
ohan e
1
16,0
336
336
7,1
901
6,$
797
994
90,0
V+
92� O3:
703. � 0.3 ,.
In partly dehydrated sodium metal.:Ingstateo 11%04,91)0401.200
Onean1 a half molecales of water dO nat partioipaii'in the
.tgohango, .The mobility a hylrogen.in the product of turther
dehydratiork of soditua mstatungotateo of a Sa0401,0211,20 4er4
VoPitiono tEl very low, It is only durins boiling that a slight
charge is recorded* This suggesbe the existenceof water
bridges which cennoot the peripheral it of the Complex anion
with its structural units loaated deep in the mtaeaulo. The
broakmip of such a bridge during dehydration of the aldbOtance
09iMosAirilatada
normwsimm
latjaikm.irer
the progress of hyd.rogen exokansa,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�30-
Voloapitsyn and Yo.F0Beryozkina (21) stated isotopic
exchange between heavy rater containing deaterimm and an
aviecus sadisma salt of phosphotungstio acid of the saturated
seriesp, 3Nagq.0P205024=3*.3311,200 The rothed of performing the
ozporimsnta Imo similar to the one demi, bed for soawat pareee
tangotnteo At a temperature of 200O0 3309 M01001301.00 Of EP
Leo all the cazbined water of the initial heteropoly *mound
proved to possess a capacity for exchange within: ihc accuracy
Of.measursments (it 1,5 mole of g20)0 The remits sa Obtained
are not sufficient to confirm the assumption regarding the
presence of strongly conibiced water in the completzo simiXarp
far instmoveR to the one corresponang to the to or hydrogen
of s31t.14sU4/P(120.7)(J0nu200 socording to MlantiRosenheiWs.
tormalne ulltah are dittioalt to re1ses0 At a tamOerstvr6 of
99pc4 a considerable part of tho combinel water at modiu4
121100hotusgststo (2700* 107 mote) are obanged inituitSes
timep yet it is small= than at room temperature() The patiel
dehydration of salt which takes place at a 144terlteaperettre
appears to impede the penetration of the eit4b6004 olio
of heavy water deep into the complex aniqh0:'"
Tbs behaviour of the sombinedlmster of .12,104po
ve,O 61.17e0 Investigated by means or exttbasge with. hiStif,$
;
=too V0I0Spiikynp R0I0A1steva an4 V01101raeLUAW-(4)
rot
this woose voitvod*i
.1.400.mtiqof ":
,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�
00 .C7V�
� , 4.� I 4,
���� c�NY .�
cc. al: ab
r' � -� Ar !IX � -
r
r;�;.. 4:,43
doVes sx9hease IgaZ controlled mass-spootrometricelly, It
appeared that at a temperature of 20�0 sodium paratungatate
exchanged with H2018 not only the oxygen of its ocabined watery
but the whole of �mon contained in the salt under investimp.
tion as well, At a temperature of 95�00 the two phases of the
exahange tool: place in less than an hour. Apar,grgoln thief) ,
a considerable fractioning of hear' ozygen watl.reCordedttatatela
se:
�
eliTer1ments0 which Roc, 1 ted in the paratangatato anion to a
greater amoant then anticipated ty distr1batio40 Xt is worth
noting that normal ,diwa tungstate0 m2up4.2g09� do not
ozbibit such fractio4ne. The authors of the abbsFeteit4, .
paper suggested that the great masa of complez onion ot pant,
tungstate was t be_ cause of greater o.ocursao.tion g
wiles in this compOund. There are some pub1iched.tiat4
OUt-
'aci4onia of oxygen teat:vest ail..for instance eiTing hrtratian
of Elora ions in an asuetras solution. A gginDrea rttle;g0a.
poundOd .(23)
anointing to which heavier
,
atoms tend to es,vonplate--:
fr,
in heavier =loonies during the czaangeo �
Similar phenomena a isotopic exchange of Omen,
revealed by 170X0Spitsynes AoVe Ixertitskys 1L10/11'stovao
and VolioPoholkin (1957) in the case or Polini044043 fladj4!0!!_.,
talates. Heavy oxygan water was subjected to cx4h4mg0.04 Oatap
_
peraturs .of 95o with the follov,inft compty.tten
pentatEui4e4atl 40SOLV)0924,050290420.
talate 9092 200 O2641O 0 pentew#atViy, ,c.) "
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
-32-
9,92Na2003Ta205026,111206 potassium taxaniobata (1.
70041C20.61b20020111200 and potassium metaniobato
0096K200M20504036E200 The method for carrying out the ozperi-
mats and taking the measurerants vas similar to the one
deseribeld above for sodium paratungstateo
In the case of the nicbates under inveatigationp equili-
brium, was attained in 5 hoursa corresponding to equidistribwa
tion of 018 between the heavy oxygen water and all the niobate
anions combined by oxygen. In the cam) of tentalates, an addi-
tional phenomenon W88 discloseds namely the fraetioning of
oxygen-18p tending to enrieh the salts with the isotope of
%mono It is possible that the greater mass of tantalato
anions, as compared with niobates9 emervises the same influence t.
as has been noted in the case of paratungstateso
The resalts of the experinents devoted to a stud, of hydroc,--I
gen and oxygen exehange lead to the conelusion that in the
aquopoly and heteropoly oompounis all the hydrogen and oxygen
atoms are well eepable of 0:chan4ing with D20 and ham ozygefi
water� This does not preclude that in the said complex anionS
the seUr may be located along eeveral different tome of
coordination� though with approximate energies of bond* A
turthzr0 more detailed study of the kinetics� of hydrogen exchangki
10 bound to clarify this point� At any rate the sugstions
put forward by a number of inveetigators regarding the existon00
of particularly finally cso34in di atoms of hydrogon, in, the ariicns
,
-
;
neclassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
����
Ilb
- 33 -
ofegAc oly aa hoteropoly oompountis viers not confirmea by the
apyorimonts wa conducted on isotopic =amp�
&detailed -1411,1dy of the mocessca of dehydVating apopolr
and heteropoly oonTonnap of tAingstenp made by the auther atthis
paper end as associates (24025)D ba e shoran that a onsiderable
part of the water combined in them is removed in a reversible
lay� T his testlfies to tbs fact that wider eartd.n conlitions
the ,�yarczen bond ben the radicals of WDearaw to replaced
ty a bond of tetrahedrons of 104,2 duo to the commm atoms
of oxygen* The last 105.2 coleciules of water are tte most
difficult to remove from aquoray end beteropoly comvoundt), The
uater in the hetorepoly empounls appears to orleinata froi
hydrw,on atoms aombind with the central radical of anot.matal
uCid (for instancoo Y043280 Si04410 In aqmoyoly =pound� it
corresponds to the radicals of the in/me ophoro hydrozonium.
At tho sama tine it should be noted that th0 said
molecules of water eLw etplit ogr ix pearbso In FAZIO heteropoly
compounds the last amount of viator to be removed gorms 005Hep
which correspozds to one hydwgen atora0 It may Ike &apposed tLtat
this is the last ion of hydroeon cat of the eentual anion of the
add, fotang cevlex.
An important coaolusion suggests itself from the prop*sed
analysis of the structure of beteropoly acid animas) namely
that their baoleit7 ahould eqmel that of the nenial o4
LZ
OM-
ins the co1r,11=0 And yet tharo is quite an amount of publigu0a
--
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 CIA-RDP81 01041Rnn9nnnn7fInflP
, ,�
Declassified in Part - Sanitized Copy Ap�roved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
data on the possibility of obtaining heteropolv salts of high
substiloation in accordance with formulae whioh follow from
the conceptions of Miolati-Rosenheimo some researchers (26)
have notably� attempted to prove that din g the gradual action
of alkali noraal salts of heteropoly Rads are transformed Into
oats of htah substitVlon� as for example salt NajF qW207)6/
whioh Is transformed into salt Na4113/P(W207)6/ and so on up to
2a7/1(17207)6/0 There is no doubt that more light should be
thrown on those points � with new methods of investigation
employed for the purpose�
170I.Spitsyn and E.A.FabrIkova (27) used tracer atoms for
stadying the interaction betseen doublo-replaced sodkmm of
bhosphotungstate of the saturated series� 2aa200P205024ROpM20
and successively added amounts of Na0110 A sample of the above
salt was tagged by means of P320 The decomposition of sodium
phOsphotungstate during the aetion of NaUll� attended with the
tplitting off of phoophate and standard tungstate� vas establish&
ed by means of two methods (Table9)0 When the first method waS
applied� the product of the reaction was precipitated through
the effeot of quinoline aoetateu The free phosphate remained in_
the solution. The use of tagged phosphotungstata made it pos-
sible to observe the process of decomposition by the growth of
aetivIty it the filtrate or its deorease in the readue0 Tho -
s000td method was based on the fact established by the investi-
gators that there was no isotopic exchange of phosphorus between
^
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
NIP
,.._ �
k
� y�_
-35-
phosphotungstate and sodium phosphate. Tagget phosphate$
Wa010040 with a knoun specific activity vas added to
colutions of stable sodium phosphotungstate0 aixing of the
tagged phosphate ions with the ions of phosphate formed during
tbe decomposition of the hetaropoly compound results in the
folloiling: the reverse process of forming heteropoly nntens9
caused by adding hydrochloric acid and heattago ocoars already
with the ovituv) of tracer phosphorus. The deo of decomposi-
tion which bad taken place was calculated by the decrease in
the specific aativity of the phosphate added after the separam.
ties of the salts in ea acid solution by precipitating potasolown
pIlspilotungstate. The coinciding results of applying the two
methods point to the fact that the decomposition of Sodium
phosphotungstate into phosphate and sotUum tuagstate begins with
amuntinz to 68 aft's? the addition of 5 mols of MOH par 1
mol of double-substituted salt. Complete decomposition of the
beteropoly anion sets in after adding some 25 mole Of alkali Por
1 mol of phasphotungstateo
-
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Dommosition of sodimm .11aaohotungElialp. intzt
Maa11114.9.-124.11a.tung8tato ift s�104-�/15
oontaisinr various additions of caustic, soft.,
gOlo ot HaOS Ata ratio pH of Splitting ofr phosphoxua as phe pbato
&Idol per 1 ot Mar i olutiDn from ho hota etate cora
Li1,21.2g;.012,._ the oolutioa �"MR J. A STYarwi
0 2.)
X
2 4g1
4 4
5 7 a
7 9 a 1
12g
20 22 X
25 27
2.4 0 0
299 0 0
0 0
590 0 0
240
a
682
9501
0
20.0
3500
7005
In a ccoraance vith those datm0 the chemical analysis of the
products f trued during the effect of l ma of MOE oft 1 rzol ot
triple.,-sabstituted so0win phospkotungstate0 pa20.13205d240,,j
nks00 hes proved that a double salt of the composition
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
4plismigammommimmonommilli
�
tre3/n9o31io 3za2yro4.23.112o 1.B formed in this case, Hence�
oaustio Bode added even in smitil quantities produoes a partial
decomposition of the hetaropoly anion and brings about its trams�
ition to a compound of the unsaturated series0 but does not
produoe salts of high substitution,
Subsequently V.I.Spitsyn0 I.D.Kolly and I.S.Bashkirova
(1957) inv stigated in a similar way the isotopia exchange
of silicon between potassium si1ieotungstato0 2K200S102012W030
nH20 and the gel of silieio acid tagged by wens of the shortie.
.1tved isotope of silloon0 Si39(T1/2 m 2.8 hours), Finely ground
pouder of rook crystal uus irradiated with neutrons in an araniun
reactor for a day. Following this the preparation 'was fusee
with caustic soda. The silicate so obtained was decomposed by
hydwochlmrio acid. The gel of the silicic acid waS Numbed of
the imbarities by repeated decantations. The batOes of tagged
silicic acid were boiled far an hour with the initial solution
of potassium silicotungstate as well as with solutians of the
with
compounds) whioh had been pxelimizaray treateLukfth= small
amounts of eau io soda and brought up to an equilibrium value
of pH. The solutions were then centrifuged the oanttifugate
vas acidified and the al.lightly soluble oesima of siliootungstato
vas precipitated. In the case of tartial deomaposition of the ^,
hetsropoly anion with an increase in the pH of the mediums,
radicaotive silicon penotreited into it due to isotopic exchange
amA was fixed in the anion during the acidirleati.on of the
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy A
Release 2014/11/04: CIA-RDP81-01043R002000070006-2
^
- 38 -
so1ution0 The nature of interaction between the initial salt
and the added caustic soda could Was be judged by the activity
of the isolated residue of cesium silicotungstate0 The results
axe given in Table 100
Table 10
.X.Loluts�or.ohsne of silicon between thjel of silielo
acid andtb.e solutions of
Eak
Uols of KOE added pH of the Participating in the iso-
per 1 mel of silica- solution topic =Change of slalom
tungstato out of the niliootungatate
wiionj
2
6
3.2
503
702
801.
The conclusion nay be drain that patassium ;�cotantate
*'the saturated ieties does not el.S48sge �111000 stft0 with the
VOSidUe of the siIiolo acid� *The =baneiaL howervero�disoIosp
When two nols of alkali are added Par one mol of saioctuasstatc
which testifies to the beginningof the splitting 010 t00
silicotangstate anion0 It is just in this range*Of PH 451,4
that AMU:Wm t26) presumed the formatione higivsubSti5.7
Declassified in Part - Sanitized Copy A
�
4
proved for Release 2014/11/04 CIA_Rnoo4
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
tr."01.11imul
�.........., Aq
1
e. � � 41 I.--
-394
-.110,�����
tution salts to take places, it would be .124ka 'jug:iota in -
assuming that unsaturated hotoropoly cmounds or the sill'
cooitaustato type or th.f4r double sults with standard
tungstate are formed in this cas A orsOidorable doeoAposi-
tion of potassium silicatangstate is reowded with pH araoluxt-
igz to ea when it appears to turn into allittiokeptattnigstate4it
should be noted that the experiments with trauer: atoms point, to
a contdderably greater statIli4y o& iliootzingstatos as, tor
ao the effeot of -alkalis is contersod than of p.hosp)atungstatos,
The above results make highly Taostionable the possia,likr
of obtaining gaits of high substitution through .4he interaction
between emetic alkalis and hoteropoly pato, or a gtortal, coix-
korlitiono On the wholep however th,e problem, aolts et hi
mabatitutigag referred to in various publications recaires
/are thormsh systematic checking.
Valuable information on the properties of.hetekropoty Oem.
pti have been ol-eained as a result of studying the isot4pits
atwt ion exchange betwo various heterapoly atlio. Still more
important results woro provided by observing the isotopia
oxstange of the addenda Ot the inn e; sphere between $0001Y
and hateropoly compculids,
VaoSpitsni end B0A0Torchenkova (9) studieri thtt LO.
wittthange of tnimsten botvress siticotungstio aoid. trckged v=ith
Ii1"9 ale rhinPbottad0tie acid* The experiraisists soladucted
with various values or (10$1 44i 5.67)1 After :the OVA.*
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
II1
msatp the phosphotungstic acid was precipitated as a potassium
salt (potacHlum siliactungstate is soluble)p NO absorption vas
recorded of the radlocomponent on Oa potassium phosphotungstate;._
residnop With pH amounting to 105,408 and a temperature of
e0p the exChange proceeded to the degree e approximately
20%0 irrospecave of the time of interaction (ranging from 5
minutes to 240 hours) (Table 11)p It might be supposed that only
a part of the tungsten atoms of the hoteropoly anions is capable
O? participating in the exehange, Boiling mabps it possible
to raise tte degree of exchange to 30% in 3 hours and to 50%
in 16 hours, In this case a partial decomposition of the ooax.
pour_da. already appears to take place, With pH amounting to
4044970 the =ohmage proceeds at a faster /meet about sotA In
5 minutes, and 100% in an hour's tins (Table 12), Evidently
the pmiuots of partial decomposition Of the beteropay acids
exchange tangsten atoms vith less dIfflonitto
Table 11
to 0 exchan of t sten between
ELzhaulleampis acids In an acid medium
Wration of TemperatIrep gi Of Dee of tungOton axchamg00-
ex riment oo solution
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
.1
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
CD 41 t4D
TabXe 12 co
Xsotsak: exchaes e of tun- sten betwse nil/ 4t.lasag,..t.2
pat ..p.L.Los IttAtmatt.I9 acids iu a weakl acid mal7
Wiration of pH Or ' Devoe of Wnestan cticiaaaVsq,
eartratution oenli
. . .
3 rin.
1 houx
240 tonre
404 82,9; 7400 (averago 784)
404 11900; 8305 (average 1og02)
407 940); 10002 (average 9700
The deduction et wad be made from the above mperizmats
that the isotopic exchange of adde2da of the inner [There bo-
tween to hoteropoly anions rzay take place� The exchange
Inaeases durin.g the partial decomposition or hat.feropoly
cospourris 0
The ezbilago of aMenda between to hetaropoly aniong was
inviwagated. at greater detail by V0/0Spitnyn and Y010137107.,
skitya (g8) who used for thin plarpose
sodiutk phaOeptottliUgetate tagged with tang0.1,,. eziihazse
e.ppearS to resat iu the f ormation o 'nixed ketifiipoU
,
penttrlso such .as phosphamolybdenottuisstates0 The.-tiv0011043
were carried ant in an. amid medium at vatifte:*:tperep;reso
Illosipbottingstate Taws precipitated. as a pota tu ititts
simnar salt of silicamolybdic acid assolveo easi1y)0 Thp:
malts of the experinentS are shown in Taiale 33,0'
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 � CIA-RDP81-01043R002nnnn7nnnR 9
Declassified in Part - Sanitized Copy A proved for Release 2014/11/04 CIA-RDP81-01043R002000070006-2
Exchan of addonds sodium
phosphotpungstatoo Na21VPi712.040 181320 end allicomlybdi0
li.tungsten and ntolybdanna content in initial
solutionsn o0o2 dal teiversturo: 2000$ pli104
sent: Tim p Ds
13013 A OS S Hours so os
of =Dori- of (=port- Amaga or axperi.
moat tI4Arbe mats
903.96
11,3 113 12
11.O 144 33
7�S4 16 327
91 9O 192 4L9
2LQ 2I6
46 2L
9?0
254
2099
MX*
3.90
1296
484)
4600
5505 .
Vita avnulting tx) 1,6 and a t porattTo Of 2CPOs tha
exeharos proceas fca' the first 1340 minutes. to app370x.tatt
-_-
11:49 Tim degree of eXchange Glees not altar in the goilowing14.- t,--
bkiarso Then there ip an abrupt increase in Vie ti_ogree.of eza. �
oimiss tip to 20..2g0 Similar leaps to as high a of ozi.-
ammo as 33.1514 4046% me 53.'5,4 take place in 96on 160 '
im,,,Inecifiori in Part Sanitized Coov Approved for Release 2014/11/04 CIA-RDP81-01043R002000070006-2
..�
'
Declassified in Part - Sanitized Cop Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
a
216 hours respectively, Therefore the curve repressating the
bourse of exchange (Fig, 13) is of. a stage-like naimre, Thid
points to the non-equivalence of bond of indiviclu.al tungstate
ions inside tho heteropoly anions and leads to thp..assumption
that the inner sphere of heteropoly compounds has a matilayor
structlre, The abrupt i=crease in the degree of Isotopic
exchange at definite intervals of time seems to be related
to the beginning of exchange in a sou layer of addenda, Voatrn
ins mall'es for an itaressed degree of exchange,
The results of the egperiments on isotopic =ohm() are
aso in accordance with the assumptions stated above regarding
tbla Structure of hotaxsopoly anions, The noleoulta of a natal
add0 =woo. directly to the anion of a no .a1. must be
Combined more firmly than the otters,
Interesting results have been obtained by studying the
itotopio exchange between phosphotmngetates of lentaxated and
nen-saturated series, The experiments wore ma� With pH amount- 7,
in to about )0 at room temperature, The coups� of (=Change
Conteolled imcipitating phospho42'4ungstats as� 6 ptlit
Oium salt, The corresponding salt of luttephosphotuMgOtie aoid
is taubleo Tho results of the experiments are given in Table
140 In 192 hours the exchange proceeds by as little as 2.00
!
while betusen two saturated heteropoly comtpounts (sodium phospho,
tungSt o sploosolybdic acid) the degree 0#02Whenge LS O _ -
high as $0 during the same period of time, The rode d Mao--
Declassified in Part - Sanitized Cop Approved for Release 2014/11/04 � CIA-RDP81-01043Rnn7nnnn7nnnR
� �".`
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
r.
..."....
140 of DA e* of =ban 1, 0 Wm
a7.4162rig-
lotus
MO0 0 �
,
/
� - _
���
-44-
natme of the increase in the degree of oxaange confirms
on more the assupption regarding the non-equivalence or the
Inner sphere in the hateropoly anion0
Table 14
istatatusa ho ot4itetun
70226Pten constant in initial solution!: 0002 8/m1;
tampe ature: 20�C; pH1 2090
0025
4
24 40
72 96 144 16$ 3.92
10,4
1002
12,4
10.3
1707
12,9
2002
2202
2609
2101
2
1102
1002
1108
1904
1705
1608
1604
2105
2000
210,1
Avtrailv
1008
1002
1201
1800
1706
3400
104
2108
2M,
.2101,
�
�
�
r-
The pxperbnents devoted to oladyipr, tkhe pesgplehntise
of the central atoms of hataropo1y cevontds yiel4p4 n'reiiatim
Vesultsio The toilowing aystamo.were investiKete4; tod1 pbo0
ophoturtgetate Opephorio adde.00dium intepphomkpttpadystiite
phoophoria add and :Jodi= phrisrlkalplybtiate 0140splitigtio
aelete AU the abovo-enuoreted pbaraphortia. eontapt,*.Ogrg0240
ttwe tagged by .mease et 020 AS tarey statelt,bDptOolttimr.
alliceturtgatato a the oatarated seriele c1oe0 ILO 41;01440,0
-������0
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
1
Ozs.,1 UN:k1
Con atama with the col of silicio aeldo The elven** of ex-
chance of the central atoms confirms the prevailing view that
they are firmly combined deep in the inner sphere of the hstero-
poly 04101$.Q
The method of isotopic exchange is of considerable import-
=co in ascertaining the genetic bond betfteen isopely Eind
aquopoly compounds on the one hand, and hoteropoly -compounds,
on the other, 1=Toceed1ng from: measurements taken by means of
the method of self -diffusion of the molecular weights of twag-
state ions termed in the solution with various valUos Of plto
470,Anderson and KoSaddintrton (7) have proved unambiguously that
lens of the composition of WoY4) or wpie" are formed in a
water medium, Thera is therefore no reason to sAPpOSe that
moil =nips exist in hoteronoly anions* It i0 more likety that
aquopoly anions containing constitutional water andfOrmad in a
water medium are present in them, It ie s homverp not clear in
thin case whether paratangstate ionsp,their kindred boxatane
state ions oro fiaallyp mdtatungstato ions are the structimal
untie of heteropoly anions.
V,I0Spitayn and E4A0TOrchonkova (9) studied the isotopio
=Ulnae of tungsten between an acidified vo3uit4on of Na0104
and se e heteropoly eompoundol sodixim. siliootu�tAteo na4/
01wW40/� Z43200 an4 seatam goliPhoi.laugetate#:
1/41120p wad tea= phoephottasetatel Vizt217Milez.
ittels*
adeggate keepirs of the ri4dt .s.olutionab phoephottmeetate tate
,
' :17
Declassified in in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
6
:00
Tif'
CP �.-
I Lni csiti
Iftit /4.6 Ob.
�;-17:
cA,
precipitated as a slightly solnblOotassium salty and ellicotun&
state as a cosi= ea1t0 The experiments have proved that
NnA04 easily exchanges tungsten with the two heteropoly comp.
pounds under investigation in a an acid medium0 with pH eslonut-
._�
lag to 4o5 and a temperature of 25�0c. sodiuM si,lieotungstatO
coletsly exchanges tungsten wilk.kt an adidified solution a
ria2W04 in a few hours (5-24)0 For this reason similar experi-
ments
ha a to bo conducted with pH of a higher value v, so as to
retard the formation of aquopoly compouude0 With pH amountin t .
601p the exchange or -banzten proceeds at a moderate rate
(Table 15) Q The rise of pH to 608 retards the exehange ta�e
*ttUcreater extent�
Ditto de ex* of tun,4$ on between en acidified
Volution 'of 'Usk and etdium siliapturtattate
Temperature; 2500; pHs 6010
Duration of experiment; Dope* of tungsten ozohang01:�-
or lent - � -
5 raillo
38h
lama
gri boat!
Ttli9n the co*.
,
107; 109 . .Coorage i0).
400; ;es_.44) .
154i 1104 (*to' 1)04).
ahead be drawn, that the StaUt104:1ti*V' 1
FRF? ri7r7nr�t1,1 ,
T.7.� -p 34._ -4
�
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2 .
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
lb
1112"""
Faq ( 77:11
q;.1113
L
state ion does not =bang� tungsten with haterspOly anions, :The
exchange proceeds with aquopoly compounds ro during the aol-
dification of solutions of standard tungstatco This leads to the
assuwption that the Woe� ion in not a structural unit or the
beteropol7 anions under investigatic
4xperiments with sodium phoephotnngstate end an aeidified
solution of Na2i104 have shown that with pE amounting to 1,0
(2X-)0 the isotopic exchange of tungsten proCeeds at a faster
speod. and amounts to 050.90% in an hour's timvo Paratungstate9
tagged with tung3ten185 and isolated from the solution as orystalsi
starts exgbanging with phosphotungstate at a much slpoer pace
than the acidified solution of Na217040 With at 20259.tha
exchange amounts only to 2071 in 24 hours*
Xt should be noted that the abovtodescribed Isotopit Ozf.
change ok tungsten between an acidified AolUtion otINe2WOkiala
heOrtV017 002pounis takes place even in a strongly add r10,4usa
$
. -
1009 when thie hstoropoly anion is still quite stable,
Eighly interesting results we obtained fraa_tho experiments ,-
on the isotopic exchange of tungsten betweea phostangeiio
aeid and tagged sodiummatatstate (9)0. With Pri to011atina to
10)g, when both =pounds are quito.stableo no exchange was record-
ed within, error even on the expiration Of 72 hoarOlTable 10.
IA a leaO acid medium (0 at 64)s the exchame 1/41310$ bolaterp
\
tO twoos40 19%...1.&42-..Vt1.7 due to the partial deompoOltUn ef the
,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
DTh
C.
r7.7,a
initial stbstanees0 The aboTe experivents demonstrate that the
nature of bond of the inner sphero addenda in the metatnngstato
anion and phosphotungstic aoid is quite different� Pessibly
there are differences also in the ehemical structure of mar-
dination anions�
Table 34
Zsoto io =hen or t s on betveon vedititt
raetatun-std 21.12.8.11Ltalstil
Temperaturel 23*C; Ma\J,
DavaitiOn or
Degree of tungsten
.746411MIt' 401.0.0.01.041PEMSe.......00ftrOMP e.117 � ant
5 min*
tour
774 Imure,
22 kzottzo.
Og 9 3 (Ocrago 409)
496: Q (Avogago 263)
5,8g 24 Worage 344
0 iilivaAell 0
,
Sy using the radioactive isotope or nolytodenumo 11609
VoloSpitsyn and Ta013ykovaka7a (23) studlod theVat(i.of =thane
OS' rioX00-041W1 between an acidified polution et NarA04,044
50.1tUmpb*sphemolyb1ate. The Oetwse or the lootelpic:Ormtanse
vas gottrolled by isolating into the residue it1iat4r-catib3S
r - :
i*taefiivaphtio lybdatoo Tho experimonts hevel.roved-that
palumoolybdate alraost instantanecAisly-exchangfg# maYbdanum
vith pheaphamolytdato in a cpup#1,7.aoid mo.41.ortio- nib 1400
�L,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
111
ID
rit
a, 49
vulnos at MI the rata or exchange is somewhat retarded* The
conclusion maybe dram that that the bond Of molyDdenum in
the pb*sPhemolytdats anion is loss firm as compared with the
gIrmness og the tungsten bond In thq�boaphotansotate anion;
The above renults of the experiments on Isotopic czehange
lead to the oenclueion that the paratungstate Ion and tho msta.
tungetate ion aro hardly structural'units of heteropoly anima
Xt is more likely that this role is directly igayed by tungstic
02 maybdia acido as shown in the schemes suggested atm� It
follows taros the paper by Ara� Spitsyn and 040Pirogova (15)
that a great amount or tungstic acid joins the hozatutentate
anion when ria44104 solutions ara asidi.tiedv
/
Thus!) proceeding from the reiilts of the previCus research
Carried out by other Larastigatomrst and using tracir ato4S and
nett data rrena physical and chemical studies ha A beOn Pe$w
Olble to advance the chemistry of heteropoly acids u413*.
rood ail! the it intricate repro sentativeS of the. 4,
complez compounA00
W9 do it deal in this paper with the prcab
stme:tiurc
of aquepoly and heteropoly compowadS in rlid MOOD
on which, there is much valuable mterial obtained as a rpsOttof
roenUedczraphie measurements� The task or our ilzrther research
ecnpists_in establishing bonil between the stra0t7uvils of 1104444�
DotY compounds in solutions and in a Crystal shapc.and brim
them to reciproCal Ocarormity0
LL
:�-� a
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
19 Traocv atoms were asod to ascertain the p311a17 stages
of formation, of aquopoly and hoteropoly oompeands9 as well as
for the purpose or Otudying their proparties and structurilt by
the methods of isotopic exchange* Alomg with this, other
various physical and ehemioal msthods of research were emplored* �
2,0 It has been established 'with the aid Ot tvacer atou
that in aolditiea solutions of VaiR4 the forOstio* patatun5,-
04te ions proceeds rather slowly And is aecslevatsd with szt
Wight.tise or tomparataro (up to 50�0 and the. /ipering of 04
30 Tho behaviour or codiam paratu4Otete ;solutions vas
etuaioa under Va4aus conditions lOy mnana of Several mothaa
(4441yoisp p4avograp40 /ight abgorption opoetlza0 ebromato.*
V401.7), a
40 Xt. 11.4#. Vlem sham that paraungstat
00 faxi0 in fresh oolowtIonapard that 8 J he
or heating or the solutions they ohmge to tomatunotatc L�
Becm,60 )f%12041 B209 with balf the inoleoular 1401.040 .
5, Eoxatungstate ions or anions or high molo014.e4t.ivOghtp
oonotining tungotte aotAp.are roma when It ifiks4iitioASeXia
tOidificarodepenafts OA p39 the anions being m7owl -Out4etea.),
,
� -
to the.prooes0 of dieaggreSatiOnp .
66 It kaS been prima that the tyit�t&on.hOmota the
.20 21p,
1104 lona haelon already iA.Oe t n ta
' Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 � CIA-RDP81-01043R002nnnn7nnnR 9
Declassified in Part - Sanitized Cop Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Lo�tii L.16Z
amounting to 04) ahd results in ttrattat.tinited phnObotetsstaten
Uleir 4aubXes Oempeunde with atore4 twist:tato�
7c. Sufficient nobility of inner 'sphere altentla hais 'bean
establishtd in the anions or heteropa7 (30000ands Thisot*P$0
and ion exaange to proOsed between th411.0
$0 A stage-like nature or isotopic cr ion exshange in tino
.
has been recorded between two hateropoly anions, which testifies
5
to the non-equivalonoe of the position of the inner Sphere
erade.nda atoms.
90 The isotopio =Lange of the addenda in tho latter sph3r0
of sore Iretszepoly onions withNe.21,704 and Na2.11a04 solationS has
been bye to a varim pa w�aluee.t, as well .a,e-rith part*
tuztgatato and. tat 'tats iQZi
100 Xt has been este.blished that the exesSe. Dziett4p,_
the; 19410 diffioulty in the ease of strongly 0.0.610,44.-0044.#.
Pr 17a004 and En2p040 On the busy; or those evei4p0:44
teen traggestell. that the addenda of the itteer Sp4ra... the1.40.
ropoly tinlione under investigation are the eleStis:Ooitrat rao'
leo of t,angetie or oIrbdie acids� � �
U0 A stutity has been made of the interaotion.listisisSn Salm
pillsphotungstato and Dota.ssinnt si1itotangstatigt�p24 oemstio.elo.
kale� It has been oborm that with pB amouAtih0togo00,440.6
lysis of the oomplex anion eomnenee90 WteSect4In or hjeh
substitution salts was revealed�
120 High motality bb,Ydrogga and egicsron atoms hi a Austber
r17-`7a7r.11 Egc
!.0 _
-
Declassified in Part - Sanitized Cop Approved for Release 2014/11/04 � CIA-RDP81-01043Rnn7nnnn7nnnR
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
a
11114"
LORI
_ �,�-
, � -
of evopoly and hotoropoly eoiTounds has boon daloastrated by -
using the rastb.ad or isotopio excivinge and applying Deo, which
mates it rather an likely that �cpacialn atovga of hydrogen or
firmly combined water molecules exist in them�
130 By the infra.red spectroscopy method a grout amoultk
Of hydro:Gen bonds has boon also/Deed in aquopOly tunositatooR
aS roll as tho prosonee of water in two or Mica fox.tis
natiou0
140 Xt tan bean suggested that the propose or torzation
aquopoly end hoteropoly tkmpounds is related to the appearenee
a hydrogen bonds botwaea tho etniona of aidso thieh ite
in the said interaotion� The exisf6enee of otOrtion mapo
the StrtiOtUro of atpoDely anions may also be assuned
_
�
150 The SUitaotaTo o heteadoray *wounds of 'the eaturatea
Davie:at Of the phosphonelybduto or ailicotuagatate typee may
be expre:SS4-4, 17.4t tin general formula 1:43/1104,(112X04)4012X04)30120)
_
nit uthergt R. in the nmetal elemat in the formation. Of_tist)
owsplezfr at is the basicity of the ontresponaing 0440 an& X is
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-7
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04 : CIA-RDP81-01043R002000070006-2
P00 Al
OA
r
sCAT.,"
-
,
� 53
LTRACR �
MM..% 0.AL STUDY OF SOME MOM= POTa.
COUPOUND3
vieteas spitsin
9.62.17,
rig. to Diegrin or deletes fox. studylAg the self-dittos/cm Of
phosphate md tatigstate ions*
1) Claw evi1le.14ese inner dierietor 008 nut
Plexiglass holdw
3) Plextgleco support
4) Stoppsr- holder
Fig* 2* Polarceo.haaphy again et the background Of 1111=
1) 20001.0433a01/1 rsagY0 4 � 2E20
23 I o 7�104.4rean. 11a101/3.20410 26i120
?pi 2.0679104:01/1 Nal0Ri2041028H0 (the tioIttio'n vas hoati,
fattoS iu's to bOiling rbint)
4) 401="1*rt3.il Naid4013010tre 0 Sen.oitivito
Polatograpky egainst the baelreirocte91 or
40629104r4f1ialovii2041021520
.21 40629101/1,Vtlowi2041.02880(tbelooluaon,�400,
for 6 hou .
rs.to (tlindmiat)0
.') '0089104 roV1 Nt2w01,010pip0 sonsittvtip. 1/00
1410 40 Light osaption cpootra0
1) 2 D * Ift2inigne. D142VO4 g Me 3
2)41400 caution 20,01r5=1/1 na1owi041028a0;
�.!
narlaccifipri in Part - Sanitized COPY Approved for Release 2014/11/04: CIA-R
DP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
11,
11
ND
3) In 4 &Will 4) In 11 .ay; $) In 13 &apt 6 In 10 dews;
7) Is 30 days; 8) In a your 9) 20501041m01/1
M2W4913,010E200
Fig050 Changes in the sodium paratangstate light, absorption
sPeOtrap depending on the ti ms of boiling the scaatUrpo
14 1 hour; 2) 2 Mural 3) 3 hoar; 44 4homval
5) 6 kaarog 4) hours; 7) 16 howls�
rAgo 60 Absorption of paratangstata by anionitp -100
1) Fresh solution of Nalowi204/026H20;
2) Oaation heated ftr 16 hours to bollim point0
Fig07. Schema of structure of hexatangstNte anion0
Fig.;80 sohomoo struottuv of Diettittlitegt041 417104o
ng09. spectra of infra-re4 absorption or variaae paraungstats
Odxates,
X) 26B20; 2) 19H20; 3) 9H20; 4) 4E0; 5) gzon
.0.002H29 per =01 or mill01041; 7) Dehydrated camounqt,
1ig0100 Schema of structure ot unsaturated phosphotwootealtiv
wi4h ratio Z)sw 1114 .
rtg0110 Scheme of strusturo of luteophosphOtnagqiat4"adiaft
Wio Pim 0 189)
1
). 2
Wig0120 Scheme of stiuottire of ph*sphoWngstate 1,*ion or tbs
. saturated saries (RstiO PM
040130 Exchange et addenda betwec4.s04t0a ph*-02.0tone4iiis
and sglicomiybdis acid,
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
'
ILA.b..11.52.LE-1.1.2.13.�Z
A
10 galosottoievo ;mama or Russian lity4.404
at Q.bertica.t SoeisU
fehtetical sootion); Zoanorgooherlo
20 11,041,o1ati0 (7.ourn0 prakt. 0 he
30 1100RO2e1heiM9 .44.Tra000 ZoanOrgoehaMoo
.4.0/1o661.thalist0 X02ttettlicate0 Z0anOrg0Ohozo0
G0and6r0 Doriajoast0 Th0000 Zioanots0
alga Ch00
GoXerider g E Tabr9 iceshemuo Z Mono
040000 151k!
G0;tlit.der.0 iloWit =tamp Z0amatagoa11s0Chozo9
la?
4.0
ip lefs (1096)
L2o16 (1096)
20 m 417 (.gOS)
920 6-79 491A$
2910249 (1917)6
le� 129 (1929)
, �
00;411409 110SpandatoZophyto.Obst6 COD
G�7614" 9 ZaPhrt3 o Oballo (.00
0,442446W0.YORZnarg 740,117(9.0.,010 (41)
So P0SOU4 Aifto hti0 (3,2)9
oSoikbArta :9rattAhOrrto atactS0060.11Pagro
(56,
60 voxospitsino z.o.arov.eyao ountai or.inekv.
garde Clipaiqry0
7o Zoitdormong KoSaa,ingt040 acriniftlos0400
$0 Z08olau1s0 Zoanorg0 all %0
1/07.091itarn0 It0A4Wehtiliww.4
Poa
383,4930)
450 a75 (1933)
(X940$.
49 0.91!9J,
(19'474
24$0 (1956)0
361
Melt 4956)
�
or tho vs= ACad011y.f4' 0e4010$610 Itt.) 261 fX9
).
100 Gatuulao tigKritarkep Z000.0reog11agehorlo# MN 244 (1051)!s
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
414
eh;
00
56
110 P0Souotay. Ann0 0140.0.
Cf.
120 Waist; Z0Avan.0 Wao SofooD
13? E SEA th har4 0 tiou
340 V0X08Rits:ps 0.i1.01roltsbz. ntoVaD
qourral of Inorganic obs,lotryp
1$0 irozospitoyo G0170Pirogova0 a:Ort.wsor of
12.0rezani3 Dhenistri 0
Lo 73 (1943);129102-:
(1944);20,0 73 (1945)0
4a20112 (1907)0
2,2L 220 (1928)0
�
140 V0X9Spitsyno Gadarogovap Reports
ot #44 VSSR Madmy of Extent:loop
/70 TotoSpitsyno 1C014t4tolleva0 Journal, of
Inorganic Mumasubyp
Gosoovellenko0 Selestea artioles on
nhe#13447 ot Rare TIAments .not02 0
. (195.5
19 1794 (1956)0
2 22.02 (1957)
lup (19$7)
I 941,4930�
190 T0X015 itOito Ottima 7arrganio cliOrlietq as g
200 17a0Eiii4vi Y0r0Xlarroskisa0 Reports a 142.0 � �
;
Azadeny of Soleno0301084013-
:
219 vapspitgrap I2roseryoodaa, otitne..1
of inbrottio cheati4nrp
22.0 Vox4001140.0.1/4.0A.1.0tovap TagovErpievo:._
. afiv'o0o, 9; tailo.xtoqi: .ficatioa7 of .0(,),X4.094;
23.0 11009.7000 P411310 , Po.; 0.
a,* 443100040740 r.D Upprtne*of tbsa
. pan AtialeraY SSieeto0s,'
4 �
1.9
'
424195G.
, � :
� .
741:(iM).47-
-
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
11
00
-57-
f's
250 IoDoEcollio GoiloPirogovao VoloSpitalyno
goimal of Inorganic Ohemistrro 1;4600470 (1956)0
260 Eato Nikitinao ;ournal of General Ohonli�
stry0 p)0 779 (1940)0
nokoNikittnap AoSoKokurinao aburna/ of
General Ohemistr79 120967 (1949)
27, Va03pitsyno BoApPabrikovao Report�
of the USSR Academy of Sciences 106864 (1956),
280 VoIoSpitcyno YoX0BykovsIsvao Reports of
tha USSR Amide-II of Sciences lav 256 (1956)
-
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81:01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
._ 4.. 1,1?##;-#- '
iv. c't�
';'��,".t7-,"?`,5:, � .57.. � - - -
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
"7-� � .�."' c'"V�5r4... -
- � �
_
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2
H Wq
H20. HL.4,1).)-1
Von.
ii
�
0
- 000A
0
�
II
'2H2
WvIr.14H OH.:
WO,H
Wac,H
I.
(')
Declassified in Part - Sanitized Copy Approved for Release 2014/11/04: CIA-RDP81-01043R002000070006-2