PROBLEM OF THE CONNECTION BETWEEN VISCOSITY AND ELECTRICAL CONDUCTIVITY IN SOLUTIONS OF SALTS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600320971-8
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 10
• Document Creation Date: December 22, 2016
• Document Release Date: August 18, 2011
• Sequence Number: 971
• Publication Date: July 20, 1950
• Content Type: REPORT

Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
CLASSIFICATION CoNFIDENTIAI
CENTRAL INTELLIGENCE AGENCY
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS
SUBJECT
HOW
PUBLISHED
WHERE
PUBLISHED
DATE
PUBLISHED
LANGUAGE
Scientific - Chemistry
Monthly periodical
Moscow
Jan 1948
REPORT
CD NO.
DATE OF
DATE DIST. ay Jul 1950
SUPPLEMENT TO
REPORT NO.
THIS DOCUNINT CONTAINS INFORMATION Ar-ICTINN TMR NATIONAL OEfIES
Or THE UNITNO STATES WITHIN THIN %RAMINO OF ISFIONAO[ ACT 10
S. S. C.. SI AND SE. AN AMR ROAD. ITS TRANSMISSION ON TMN NOVILAT10N
0( ITS CONTENTS IN ANT BANNER TO AN UNAUTHORIINO PINNED 12 PRO-
NISITNO ST LAW. N[FROOUCTIOM OF THIS FORM 15 PNONINIT[O.
SOURCE
PROBLEM OF THE CONNECTION BETWEEN VISCOSITY AND
ELECTRICAL CONDUCTIVITY IN SOLUTIONS OF SALTS
D. A. Pospekl}ov
Kiev Tech Inst of Light Industry
Submitted 12 Apr 1947
K. S. Yevstrop'yev f1, 2, 3-7, in treating the experimental data of
a number of authors regarding the viscosity and electrical conductivity
of aqueous solutions of salts, fused salts, and their binary mixtures, n
noted the presence of several relationships. (1) Johnston's equation,/1
equals coast, where.A is the molecular electrical conductivity and is
the viscosity [4), is correct for aqueous solutions of salts; (2) the
relation between ig K or ig A ( where % is the specific electrical Conducti-'
vity), and the composition of a binary mixture expressed in molecular
percentages is represented in a majority of cases by a straight line,
if the components form a simple eutectic; if the components form a cI}Pmical
compound, this relation is represented by sections of straight lines in-
tersecting at a point approximately coinciding with the composition of the
compound; if the components form solid solutions, the dependence is re-
presented by a smooth curve.
The present ,work deals mainly with solutions in organic substano s,
which Yevstrop'yev did not especially examine; he merely noted that the
data on a solution of AgN03 in pyridine confirm the general picture.
Yevstrop'yev demonstrated the applicability of Johnston's equation
to aqueous solutions of salts, finding a rectilinear dependence between
lgA and lg I for a number of temperatures in solutions'of NaCl, LiCl,
BaC12, ZnS04, and others.
Treating the experimental data of Ye, Ya, Gorenbeyn [5, 6, 77
on non.aqueous solutions, we found that Johnston's equation is also appli-
cable in.this case, but at relatively high concentrations. As may be
seen from Figures 1 - 4, which refer respectively to solutions of
~ 7ta gti,:M s
1!'a.
Zhurnal Fizicheskoy Khimii, Vol XXII, No 1, 1948
CONFIDENTIAL
Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
 Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
Sbbr- . AlBr3 in benzene, toluene, and nitrobenzene, and to a solution of
CuBr A12Br6 in Toluene, a deviation from rectilinear dependence is ob-
served at various concentrations. For solutions of SbBr3 . A1Br3 these
concentrations are rather large, but for the second salt, apparently, they
are below 3.7 percent (molecular percentage). On the diagrams, the con-
centration is designated beside each curve in molecular percentages, and the
corresponding temperatures are indicated at the points on the curves.
it is possible to assume that the establishment of the lower limit of
concentration at which Johnston's equation is observed for solutions may
contribute to the understanding of their structure by establishing the con-
nection between this limit and the other properties of the solutions. At
present, nothing can be?said concerning the existence of any such lower
limits for aqueous solutions; Yevstrop'yev's calculations dealt with only one
concentration of each salt with the exception of NaCl, for which is observed
a parallelism of straight lines expressing the dependence of lg x on lg.
in 0.1 N and 4 N solutions Z-1-7.
Solutions of AlBrq in ethyl bromide (Figure 5) give a picture similar
to the preceding (Figures 1 - 4). It must be. noted that in the given.
case. electrical conductivity develops as a result of the interaction of
the salt and the solvent, because A1Br3, unlike SbBr3 . AlBr3, does not conduct
in a fused condition. According to the data of Wohl and Wertyporoch 8],
based on the inv-tigation of the migration of ions, the solvate AlL AlBr4J3
is the electrolyte,
For solutions of SbBr3 A1Br3 in ethyl bromide (Figure 6) recti-
linear dependence between lgA and lgj is absent at almost all concentrations.
This circumstance may be explained by the insufficient stability of the solu-
tions; for example, due to the decomposition of a binary salt under the in-
fluence of ethyl bromide.
We should further note that in nitrobenzene, the dielectric constant
of which is rather large ( a equals 36.4), a normal dependence of conducti-
vity on concentration is observed. In the other nonaqueous solutions in
question, the dependence is anomalous. This may be seen if one compares
the sequence of distribution of the curves in dependence on the concentra-
tion in nitrobenzene (Figure 3) and other solutions (Figures 1, 2, 4, 5, 6).
The presence of an exponential relationship between lgZ or lg A
and lg I , on the one hand, and the composition of the binary mixture, on
the other, was demonstrated by Yevstrop'yew in binary fusions of inorganic
salts. If one regards a solution of salt in a liquid solvent, for example,
in water or some organic substance, as a binary system, the following picture
is revealed; the relation between lg ~ and the composition is expressed by
two intersecting straight lines. This may be seen from the diagrams which
were constructed by us on the basis of the rbspective conversion of the
experimental data of Gorenbeyn [5, 6] (Figures 7 - 11) and A. I. Rabinowitsch
L9_7 (Figure 12),
Ar exception occurs in the case of solutions of CuBr . Al2Br6 in toluene,
where the dependence of lg Y on the composition is completely rectilinear-
(Figure 14). The data for the calculation of the latter solutions were
taken by us from Gorenbeyn [7], who does not indicate whether or not
saturation was reached. Therefore, nothing definite can be said about the
possibility of a break on the curve representing the dependence of lg Yf
on the composition with further increase of concentration. The figures
standing by the indices of -] and also by the indices of A on the diagrams
beside the corresponding curves designate the temperature. The content of
salt is the solution (molecular percentage) is indicated in all cases on the
axis of the abscissas.
Sanitized
Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
 Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
C019FIDENTIAL
t,t us examine the diagrams in Figures 7 - 12 and 14, The intersection of
straight lines, turned at an angle from the axis of the composition (Fig-
ures 10, 12), was not observed in Yevstrop?yev's work. Such an intersection
may be i.r.terpreted within the framework of the established conceptions of
physicochemical analysis as an indication of the presence of a chemical com-
pourd. The position of the point of intersection, which we will call the angle
point:, corresponds to the ratio 1-.8 for solutions of AgNO in water (Figure
12, but it does not correspond to any definite stoichiome ric ratio for
solutions of SbBr3 . A.IBr3 in ethyl bromide (Figure 10).
The intersection turned at an angle to the axis of the composition
corresponds to the ration 1.,8 for solutions of SbBr3 . A1Br3 in toluene
(Figure 3); and l;3 for AlBr3 in ethyl bromide (Figure 11). It does
not seem possible, however, without an appropriate investigation to inter-
pret, this circumstance as an indication of the presence of definite chemical
compounds by means of a transference to the given solutions of the conclu-
sions made 'by Yevstrop'yev for binary fusions of salts.
It must be noted that the abscissa of the angle point does not depend
-0 on the temperature (Figures 7 - 10). In the case of solutions of A1Br3
in ethyl bromide (Figure 11) a slight displacement is noted; this dis-
placement is possibly caused by a chemical interaction between the dissolved
subttance and the solvent In Yevstroplyev?s work [3] there is a similar
displacement on the diagram of lg X and the composition for the system of
CdC1,2 - MCI, Yevstrop'yev, however, does not interpret this displacement
in the sense given by usy for according to his judgment the presence in
general of an angle point In. the fusions studied by him indicates the
formation of a chemical compound.
If one. turns to the consideration in our objectives of the connection
between the logarithm of conductivity and composition, in general a more
complicated picture is observed than in the cases of the connection of the
logarithm of viscosity and composition. The concurrence of the abscissas
of the angle points at. curves lg A and lg I is observed in the case of solu-
tions of AgN03 in water (Figure 12) and solutions of SbBr3 . A3Br3 in nitro-
b enzeue (Figure 9). Also, the angles are turned to the opposite sides in ac-
cordance with the fact that an increase of electrical conductivity cor-
responds to a drop in viscosity.. This observation is not correct for specific
electrical conductivity (Figure 12), the values of which give an obscure pic-
ture in other cases as well.
The indicated concurrence of the abscissas of the angle points, how-
ever, is not compulsory for all aqueous solutions. This may be seen
from Figure 13, which refers to aqueous solutions of AgTl(N03)2i for which
complicated relationships may be seen. Apparently, this binary salt undergoes
decomposition into its component salts to a certain extent. The diagram
is constructed on the basis of the conversion of the data of A. I. Rabino-
vitsch L 9).
In solvents with low dielectric constants benzene, toluene, ethyl
bromide), a direct comparison of the relations between lg A and the com-
position. and lg and the composition is not feasible (Figures 7, 8, 10,
11, 14). In certain cases there is a sharp drop in conductivity corres-
ponding to the angle point on curve lg I (Figures 7, 8,).. It is interesting
that for these same cases, the concentration corresponding to the angle
point on curve lg ~ coincides approximately with the lower limit of concen-
trations at which Johnston's equation is observed (Figures 1, 2). The pic-
ture is complicated in the case of solutions of SbBr3 . AlBr3 in ethyl
bromide, where no noticeable points on the curve of viscosity correspond
to the maximum on the curve of conductivity (Figure 10); and in the case of
solutions of CuBr . A12Br6 in toluene (Figure 14), where the relation be-
tween lg q and the composition is completely rectilinear, but the course of
the dependence of lg A on the composition has a complicated character.
-3-
CONFIDENTIAL
Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
 Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
It should be noted, additionally, that we have avoided encumbering the
reproduced diagrams with all the isotherms characterizing the dependence
of lgA on the composition, for in every nonaqueous solution examined by
us they have a very similar character.
The material expounded above makes it possible to conclude that the de-
pendence of lg y) on the composition frequently finds no parallel with the
dependence of lg A on the composition. This circumstance has an essential
importance for the consideration of the problem of the applicability of a simple
correction for viscosity in the case of electrical conductivity. As is
known, this correction has the following form:
where I is the viscosity of the solution in poises; 7 oo is the viscosity
of the solvent; and A is the measured molecular electrical conductivity.
The correction assumes an inverse ratio between viscosity and electrical
cductivity. The problem of the presence of an inverse ratio may be solved
oW
by p ,ting the dependence of lg A q on the composition. This may also
be accomplished graphically by the addition of the ordinates lg~ and lg A for
each composition,
it is fully evident that with the presence of an inverse ratio the curve
must be parallel to the axis of composition. This parallelism in the
systew,i studied by us takes place only in solutions'of A1Br3 . SbBr3 in nitro-
benzene in concentrations from 0.6 (P equals 17,200) to 8-I0 molecular percent
( equals 1,200 milliliters) (Figure 9); and in solutions of AgN03 in water
in concentrations from 3..8 (26.5 percent by weight) to 15.5 molecular percent
(63.l percent by weight). In the case of the other solutions, I;here can be no
question of parallelism, because of the obvious disparity between the course of
the curves of lgA and the composition and lg .9 and the composition (Figures
7, 8; 10, 11, lk). The same must be said of the curves of lg k and the composi-
tion (Figures 8, 10, 14). In the case of the absence of parallelism of a recti-
linear section of the curve lg Ii 7 to the axis of the composition, this sec-
tion has an ascending character towards higher concentrations (Figures 9, 12, 13).
The parallelism of the values of lg A Ito the axis of the composition in
a definite interval of concentrations is-evidence of the fact that here,
(1) the composition of the electrolyte remains unchanged; (2) the structure
of the solution noes not undergo changes; (3) the degree of dissociation
of the electrolyte does not depend on the dilution.
There is a rather extensive literature on the problem of a simple
correction for viscosity in the values for electrical conductivity (see Gatchek
[11 7). From this, one may obtain the general indication that this correction
is definitely applicable in the zone of concentrations in which the viscosity of
the solution does not greatly deviate from the viscosity of the pure solvent.
In the solutions analyzed by us, one may see that a rigid inverse ratio be-
tween viscosity and molecular electrical conductivity is also observed in in-
dividual cases in concentrated solutions greatly differing from the pure solvent
in viscosity.
Ye. Ya., Gorenbeyn 5, 6, 7, 127 applies a simple correction for vis-
cosity electrical conductivity in the case of all solutions analyzed in the
present work. As could be seen from what has been said, the application
of such a correction is, in almost all cases, unfounded. The correlations
between viscosity and electrical conductivity have proved to be complicated
and diverse. Therefore., the generalizing conclusions made by Gorenbeyn, on
the basis of a uniform and unconditioinal application of the correction, do
not correspond to fact [107.
Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971
 Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
Conclusions
The relation between viscosity, electrical conductivity, and compo-
sition for the following solutions has been considered: for aqueous solutions
of AgNO3 and AgT1 (N0 )2 investigated by A. I. Rabinowitsch; for solutions
of A1Br3 . SbBr in ethyl bromide; benzene, toluene, and nitrobenzene; and for
solutions of CuflrA12Br6 in toluene and of A1Br3 in ethyl bromide, investigated
by Ye. Ya. Gorenbeyn.
1. The dependence of viscosity on molecular electrical conductivity follows
Johnston's equation A", equals const above a definite concentration in the case
of all the nonaqueous solutions mentioned except for solutions of SbBr3 . A1Br3
in ethyl bromide.
2. The relationship of viscosity composition in a majority of cases
does not correspond to the relationship of molecular electrical conductivity-
composition An inverse ratio between molecular electrical conductivity and
viscosity is observed in solutions of AgN03, in water at 100 degrees centi-
grade at concentrations from 3.8 to 15.5 molecular percent; and in solutions
of SbBr3 . A1Br3 in nitrobenzene at concentrations from 0.6 to 8 - 10 mole-
cular percent.
3. The application of a simple correction for viscosity to values for
electrical conductivity, according to the expression A'-A. ~
70o
(where 1L is the measured molecular electrical conductivity; I is the viscosity
q.f the solution; and 7 00 is the viscosity of the solvent) is inadmissible with-
out a special study of the experimental data.
4. There is no basis for the universal application of the indicated cor-
rection to all of the solutions considered, as was done by Gorenbeyn.
1.
Yevstrop'yev, K. S., Zhurn. fiz. khim., 6, 454, 1935-
2.
Yevstrop'yev, K. S., Izv. AN SSSR, ser. .fiz., I, 359,
1937.
Yevstrop'yev, K. S., AN SSSR, ser, fiz., 4, 616,
1940.
4.
Johnston, J., J. Am. Chem. Soc., 31, 1010, 1909.
5.
Gorenbeyn, Ye. Ya; Zap. Inst. hbimii AN URSR, 7,
213,
1940.
6.
Gorenbeyn, Ye. Ya., Zap. Inst. khimii AN URSR, 7,
551,
1941.
7.
Gorenbeyn, Ye. Ya., Ridler, G. A., Zap. Inst. khimii AN URSR,
8, 39, 1941.
8.
Wohl, Wertyporoch, Ber., 64, 1357, 1931.
9.
Rabinowitsch, A. I., ZS. phys. Chem., 99, 338, 417,
1921.
10.
Pospekhov, D. A., Zhurn. fiz. Waimii, 21, 139, 1947-
11.
Gatchek, E., Vyazkost' zhidkostey, pp. 113, 155,
159,
160 - 163,
165, 166,'M. - L., 1932.
12.
Gorenbeyn, Ye. Ya., Zhurn. fiz. khim., 20, 881,
1946.
f-Appenued figures follow:]
-5-
CONFIDENTIAL
Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
 Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
Fib. System SbBr3 AlBr3 - C6H6.
ZfA
ZS zD, !0 Is
Figure 2. System SbBr3 . A1Br3 - c6H5CH3
Figure 3. System SbBr3 . A1Br3 - C6H5NO2.
- 6 - eAM1}ck`~,
CONFTDF,NTIAL ?ysaL~ u:~?:ti1
Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
 Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
Figure 5. System A1Br3 - C2H5Br.
Figure b. System CuBr . A12Br6 - C6H5CH3.
Figure 6. System SbBr3 . ALBr3 - C2H5Br.
e,. r- t F 15
a~ .
Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
 Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8 I
?rl~? 6 da~-~
-8-
CONFIDENTIAL
Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
 Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
/Z Hoc s 8~ zBq 26 ,m On the axis of the ordinates there is a
single scale for lg h , lgA , lg 7^
Figure 10. System SbBr3 . AlEr3 -
C2H55Br. The left scale is 1g I ,
lg /I ; the right-scale is lg x i
fS
/0 /6 20 2s' d0 ?R5
% Mot 71B5 At8
Figure 11. System A1Br3 - C2H5Br.
COYWIDENTIAL , 11 HE ,^ a
LSanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
 - Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8
10 2S _" 3S- 40 4S
7. NOG 4 MOy
Figure 13. System AgTl(N03)2 - H2O
at 100?. On the axis of the ordinates
thex'e is a single scale for lg , 19/1 lg/l .
-END-
- 10 -
CONFIDENTIAL
1.7.1? : r,1 , r`
LfrIUlWi.:3Bi
Figure 12. System of AgN03 -
1120 at.1000. On the axis of the
ordinates there is a single scale
for ig I , ig /1 , lg I A . The fig-
ures in parentheses are the val-
ues of lg x .
~P1 87 To 60 Sn yd JO 27 /0 0
% Ma 4g72 (Noy),
Figure 14. System CuBr . A12Br6 -
C6H5CH3
y7 7
Sanitized Copy Approved for Release 2011/08/18: CIA-RDP80-00809A000600320971-8