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VOL.4, NO.

S
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
HZSO No so.
15
50

so
Z
fl NO So..
2
-
KzSO,MgSO,6H
Z
O
14
"ZSO,'H
2
O
lJTNnzSO,1Ollz0
0
I
r;;zSO"NaZSO,

Il
ZlCCL

VI lDl \

Fig. 4. Potassium sulphate
crystallisation zone in the
K, Na, Mg 11 Cl, SOCH20
system at 0.
Fig. 3. Glaserite crystal-
lisation zone in the K, Na,
Mg 11 Cl, SO,-H
2
0 system
at 0.
,'--____ .:.-___ ...JJMgCl,
Fig. 5. Sodium sulphate
crystallisation zone in the
K; Na, Mg 11 Cl, SO,-H
2
0
system at 0.
Glaserite first appears at between 8 and 10% of chloride
(solutions corresponding to pOints xn and xvm, Tables 2
and 3); as the amount of chloride is increased the glaserite
zone expands considerably.
SUMMARY
1. Investigation of the solubility isotherm at 0 of the
-H
2
0 ternary system has shown that the solid
pnases are potassium sulphate monohydrate . HaO)
and sodium sulphate deCahydrate .1OH
a
O).
Glaserite is formed only in the presence of the chlorides
864
of potassium, sodium or magnesium and does not
lise froin the sulphate solutions. A glaserite crystal_
lisation zone oreurs in the K, Na 11 Cl, 80
4
-H
2
0 and
K, Na, Mg 11 Cl, 804 - systems when about 8 -10%
chloride is present and becomes more extensive with
increasing chloride concentration.
2. The three-dimensional crystallisation zones of gJ<l.SE!rit ....
potassium sulphate monohydrate, and Glauber's
been determined in the K, Na, Mg 11 Cl, 804 - H
2
0 qU:i.narill
system at 0; there is a small glaserite ZOne
the two sulphate zones which occupy the greater part
the diagram.
1. "Spravochnik po Rastvorimosti Solevykh Sistem" (Handbook
Solubility of Salt Systems), Part 1, Moscow-Leningrad,
1953.
2. W.Meyerhoffer and A.P.Saunders, Z.phys.Chem., 28, 453
453 (1899).
3. M. P. Shul'gina, 0. S. Kharchuk and 0. K. Yanat'eva, Dok!.
Nauk SSSR, '73, No. 3, 507 (1950).
4. M. P. Shul'gina, 0. S. Kharchuk and 0. K. Yanat'eva, Izv.
Fiz. Khim .Anal.lnst. Obshch. Neorg. Khim. Akad. Nauk SSSR,
198 (1955).
5. W. C. Blasdale, J.lnd. Eng. Chem., 10, 344 (1918).
6. A. I. Zaslavskii, S. S. Sinani and L. A. Sokolova, Izv. Akad.
SSSR, Ser. Khim., No. 1, 47 (1938).
7. "Spravochnik po Rastvorimosti Solevykh Si stem " (Handbook
Solubility of Salt Systems), Part I, Leningrad, GONTI,
Kurnakov Institute of General
and Inorganic Chemistry, the
USSR Academy of Sciences
SOLUBILITY POLYTHERM IN THE Li
2
S0
4
-
-NaaS04-H20 SYSTEM
Khu Ke-Yuan'
We have begun to study solubility relations in the .
reciprocal system (Li2Cla + -=LiaS04 +
at 25 and 50, and here report results for the Li
2
S04 - J
-NaaS04-H20 ternary system from _23.4 to 100. Of
binary systems LiaS04-H20, NaaS04-H20, and LizS
0
4-
c
-NaaS04 which make up the ternary one, the Li
2
S0
4
-H20 J
system has been described by John and Friend.
1
Etard;
first pointed out the inflection in the solubility curve of .
lithium sulphate at -9, below which the solubility decreaS(
rapidly. According to John and Friend, 1 the inflection ..
occurs' at -8, and below this the dihydrate LizS0
4
. 2H20, C
which the solubility increases as the temperature is reduce
probably exists. Campbell
3
examined the behaviOur of .
Li
2
S0
4
jn water between _13.8 and _2.2 1::y a dilatometrl
C
method but did not confirm the existence of the new hydrat
Neither has it been observed in the solubility isotherm oft!
LiCl- LizS04'-H20 system at -12.8, probably because Lie
is a strong dehydrating agent. Campbell showed that
is a transition point from Liz80
4
. H
2
0 to LiaS04 at 232.8 a
26.7 atm. ..
VOL. 4, NO.S
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY AUGUST 19511
--------------------------------------------------------------------------------------------------------
,_ Solubility relations in the -H
2
0 system have been
(jJlllmarised.
The melting-,Point diagram of the system
has been obtained. 5-8 Bergman and Luzbnaya found a con-
tinuous series of solid solutions and the
LimBO. which dissociates on melting. The existence of
NaJl
0
4. Li:zS0. and . has been claimed by
Akopov and Bergman.
Spielrein 9 refers to the existence, in!be Li:zS0
4
-
-H ternary system, of the double salts Li:zS
0
4 .
. 5.5H
2
0, Li
2
S0
4
. 12H
2
0, NIl:!S04' 4Li:zS0
4
. 5H
2
0
and NIl:!S04 . . 3H
2
0. From studies of the solubilities
of salts at 27, 45.6 and 0 it has been concluded 10,11 that
only 3NIl:!S04 . Li
2
S0
4
. 12H
2
0 . Li:zS04 exist between
0
0
and 45.6. Lepeshkov et al. 12 confirmed that only
3NamB04' . 12H
2
0 is formed at 25. According to
campbell and Kartzmark, 13 however, solid solutions of
Li S04 and are formed at 25 and 39.5 and not the
2NIl:!S04' Li
2
S0
4
. 12H
2
0.
Solubility Isotherms at 0, 50 and 100
C
ISOIUbilitieS were measured in a thermostat within 0.05
:0) 0.20. Sodium sulphate was recrystallised twice.
Lithium was determined by a volumetric method,14 sulphate
gravimetrically as barium sulphate, and sodium by difference.
The liquid and solid phases were analysed after four days
at 0, three days at 50, and two days at 100. The com-
positions of the solid phases. were determined by Schreine-
makers' residue method and by an optical (immersion)
method. The diagrams show the results in wt. %.
TABLE 1. Solubility isotherms.
Comp. of solution, wt. %
LI:SO.. I NaaSO.
24.76
d
4
.
13 1.97
j3.02 5.02
8:77 _1.75
21.27 10.82
21.21 10.85
19.56 12.35
17.76 14.18
15.29 17.41
13.85 19.65
10.57 24.47
10.56 24.61
9.01 25.98
4.68 28.65
1.97 30.41
31.78
23.49
22.68 3.39
21.92 7.24
21.26 9.67
21.27 9.72
20.33 10.46
16.98 13.SO
13.86 17.20
12.31 19.38
10.18 23.39
9.35 24.611
8.86 26.16
8.67 26.13
6.27 27.25
3.47 28.42
29.80

\
Comp_ of reSidue, wt. %
LI,sO. I Na,sO.
so
79.70 0.51
76.63 v.58
75.43 1.21
48.35 34.46
44.98 35.66
41.28 51.04
40.22 50.82
40.00 49.90
40.73 51.73
25.89 . 40.09
14.12 66.31
4.SO 60.49
1.62 55.58
100
83.13 0.27
84.40 0.87
84:14 13.85
64.66 18.84
37.62 46.31
38.22 46.54
38.76 SO.75
38.51 47.68
35.27 48.48
20.38 SO.61
18.37 47.66
Solid phose
Li,sO,H,O
ditto


Li,SO, H,O + Na.SO Li,sO.
ditto
Na,sO,Li,sO,
ditto


NasSO, Li,sO. + Na,SO
Na,sO.
Na,sO.
Na,SO.
NasSO.
LisSO H.O
ditto
, .
LisSO, H.O + NasSO.L1sS0.
NasSO,LisSO.
ditto


Na,SO,Li,SO. + Na,SO.
NasSO.
ditto
Na,SO,
Na,SO.
--
i
loJ
i
2
5O
,
U,so,'H,O
80
60
40
ZO

wt. % N0
2
So.
Fig.1. Isotherm of the
ternary system at 50.
As the solubility at 0 has been determined by Skarulis
and Horan, 11 we verified only two double pOints for which
the solid phases were Li
2
S0
4
. H
2
0 + Li
2
S0
4
. 12H
2
0
and 3NIl:!S04' Li
2
S0
4
. 12H
2
0 + NIl:!S04' 10H
2
0. At the former
the solution contains 24.02 wt. % Li
2
S0
4
and 5.86 wt. %
NIl:!S04' and at the latter 23.22 wt. % Li
2
S0
4
and 6.21 wt. %
NIl:!S04' Our results agree with those of Skarulis and Horan.
The solubilities at 50 and 100 had not been previously
examined. The solubility isotherm at 50 (Fig. 1, Table 1)
consists of three crystallisation branches; Li
2
S0
4
. H
2
0,
NIl:!S04' Li:zS04 and at 100 it consists of the same
three branChes, but the Na
2
S0
4
. LizS0
4
branch is longer than
at 50.
Solubility Polytherm in the Li:zS04 - NIl:!S04 - H
2
0 Ternary
System from _23.4 to 25
Solubilities over a wide temperature range were exami-
ned by a visual polythermal method in a glass test-tube
with a platinum stirrer and a copper-constantan thermo-
couple, the junction 'of which was enclosed in a glass
capillary; the thermocouple was calibrated at the melting
points of ice, carbon tetrachloride and mercury, at the
eutectic temperature of KzS04 -H
2
0, and with a standard
thermometer above 0. As the zero of the galvanometer
drifted during the experiment, periOdiC checks of the cali-
bration were made and corrections applied. The accuracy
of temperature measurement was 0.4 . To accelerate
crystallisation the solutions were seeded with the appro-
priate salts.
The study of the Li
2
S0
4
-H
2
0 system, which yielded
results in agreement with published data, 1,3 was compli-
cated by the increase in solubility of lithium sulphate with
decreasing temperature. Saturated solutions were pre-
pared at lower temperatures and warmed until crystals
865
VOL. 4, NO. 8
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
AUGOST
30

wt. %
Fig. 2. Sections of the
ternary system:
1) 4.0% Li
2
SO, Na2SO,; 2) 8.0% ..
3) 12.0% Li
2
SO, Na2SO,; 4) 16.0% Li
2
SO, Na2S0,;
5) 20.1% Na2S0,; 6) 21.4% Li
2
SO, Na
2
S
O
,;
7) 25.1% Li
2
SO, Na2SO,; 8) 25.6%
9) The Na2SO,-H20 system.
appeared. The high viscosity of the solutions at low tem-
peratures made it difficult to observe the appearance and
disappearance of crystals. 'Apart from the eutectic point
we could not obtain experimental data on the lithium sul-
phate crystallisation branch at temperatures below -8.
The lowest temperature attained was -22.9, at which the
solution contained 27.2 wt. % lithium sulphate. The eutectic
obtained by extrapolationS lies at _23 with 27.9 wt. %
lithium sulphate in solution.
The results for the NaJ304 -H
2
0 system (Fig. 2, curve 9}
up to +18 agree with those in the literature. 4
Eight sections of the ternary system -N3.:zS04-
- H
2
0 were examined (Fig. 2), and data for the -15, -10,
0, 15 and 25 isotherms were obtained from the poly-
thermal sections (Table 2); they agree with published iso-
thermal data for 0 and 25. 11,12 The eutectic for ice,
mirabilite and lithium sulphate monohydrate was found to
be at _23.4 with the solution containing:
866
wt. %
26.66
26 .. 78
NaaS04 wt. %
1.87
1.79
Boundaries have been delineated for the zones: ice,
.10H20, N3.:z
S0
4' 3N3.:zS04 . 12H
2
0, N3.:zS04 LizSO
and . H
2
0 (Table 3).
Non-variant Transition Points in the
Ternary System from -23.4 to 100
Solubilities in the - - H
2
0 system were
studied between -23.4 and 100 and six crystallisation zon .
were found. The temperatures of the two non-variant tr
sition points
o
H
2
0 + 10H
2
0 + 3N3.:zS04 Li:aS
12H
2
0 (-1.7 ) and 3Na
2
S0
4
LizS04 12Hz0 + N3.:zS0
4
. LizS
+ H
2
0 (29.3) were determined by projection of .
polytherm of the ternary system on the si
From the isothermal data the non-variant points 3N3.:zS0 J'
. 12Hz0 + N3.:zS04 . + N3.:zS04 and 3N3.:zS04. 4
. 12H
2
0 + N3.:zS04 . 10H
2
0 + N3.:zS04 should occur re
pectively at between 46 and 50 and a little below 32.38
0
,
the NaJ304 . 10H
2
0 --+ N3.:zS04 transition point. The tempera-
tures and compositions at the non-variant point were
mined by making solutions corresponding to the double I"
point and allowing them to stand in the thermostat at tem-
peratures close to the transition temperature until equilh
brium was reached. For the non-variant + 3N3.:zS0.
Li
2
S0
4
. 12H
2
0 + N3.:zS04. 10H
2
0 point, a solution correspar
ding to the double point N3.:zS04 + 3N3.:zS04. Li
2
S0
4
. 12H
2
0 ;it
32 was prepared, the temperature was lowered gradually,
and the composition of the solid phases was followed by an
optical method. At 31.0 it was unchanged, at 30.6 the-X
nardite replaced mirabilite and at 30.8 thenardite and i
f
TABLE 2.
Solubilities in the ternary system
at - 15, - 10, 0 , 10 and 25.
t 0C soln., wt.%
I C=p.ol I
LI,soINa,so.
Solid phose
soln.,wt.% I I Comp.ol I
'. C L1:S0.IN
a
zSO.
Solid phose
-15 27.0 Li,SO.H,O 10 26.1 Li,SO.H,O
25.11 3.0 Li,SO.H,O + 24.8 2.8
+ Na,s0.10H,0
24.8 2,8 Na,s0.10H,O 23.3 7.2 Li,SO.H.O +
+3Na,s0. Li,s0,j2ll
24.5 2.6 22.2 7.8 3Na,SO. Li,sO, .128,(
20.4 2.5
Na,SO. 1OH.O + ice 18.7 9.7 3Na,SO, . Li,SO, . 121l,(
+ N.,SO, .10H,0
21.3 .1.5 ice 18.2 9.6 Na,SO, .1OH,O
22.2

14.5 9.3
-10 26.8 Li,SO.H.O 10.9 9.0
25.3 3.8 Li,sO,H,O + 7.3 8.9
+ Na,SO,.10H,O
24.6 3.7 N .,SO, !OH,O 3.6 8.8
23.3 3.5 8.7

19.5 3.1

25.6 Li,SO,10H.0
15.5 2.9 N.,sO, 10H.0 + Ice 25 23.9 4.8
16.5 1.6
ice 21.1 10.3
Li,SO. H,O 3N.,sc 21.5 10.9
17.4 . Li,SO, . 12H.0
0 26.5 Li,sO,H.O 17.5 13.1 3Na,SO,.Li.SO, .12",
24.02 5.86 Li,SO,H,O + 13.5 15.7
+ 3Na,s0,Li,s0,.
.1211.0
23.22 6.21 3Na,SO, Li,sO, 9.7 19.3
12H,0 + Na.SO,
.10H,O
3N.,SO,. Li,SO . 128, 27.7 5 9 1'\.,s0, 1OH.O 7.2 21.8
+ Na.SO, .10H,0
19.1 5.3
6.3 21.7 Na,SO, .10H,0
15.2 5.0
3.1 21.4

11.4 4.8
21.6
7.6 4.6

3.8 4.5
4.4
. . RUSSIAN JOURNAL OF INORGANIC CHEMISTRY AUGUST 1959
____ --------------------------------------------------------------------------------------
------BoundarieS of crystallisation zones in the LizSO,-NazSO,-
. ..B 3
L . -H2
0
ternary system from - 23.4 to 100.
The Na:aS04' 10lIzO crystallisation zone occupies a large
part of the diagram.
i:;;

.I
":. C-- of ... Iutl ...
Remark.
,"al."
I. 'C
Solid pho ..
.; ... - -
'.'1JIlIO. o.
54
-LO
leo + NaoSO,.10HtO Polytho .... 1 data
_ '.1 - O.
0.67
0.51
-2.6

ditto
,.111
3.80
1.40
0.49
-4.2
0 0
,.75
3.50
2.16
0.46
-6.6
0

It."
3.20
3.05
0.44
-9.9

0
ss-SO
2.90
3.95
0.40
-13.5
0

".IS
2.55
4.93
0.34
-18.3
Na.so,.Lilo,.12H.o +1

JS."
2.10
5.32
0.33
-20.0
11.
10
2.00
2.12
3.10
21.9

, . ., 18.50
+ Na.SO,.10H.O
2.95
2.21
16.0

p."
13.40
3.90
1.72
11.2


\1.05
10.35
4.89
1.16
3.2


ZZ4S
6.90
5.06
1.04
0.0

Isothermal data
:3.
22
6.21
5.26
0.99 0.0
3Na.SO,LioSO,12H.O+
ditto
:4.02
5.86
+ LioSO.H.O
7.90
5.12
1.36 13.7

Polythe, ... 1 data
:3.05
4.87 1.85
24.8
0
It
10.60
:1.110
10.84
4.78 1.88
SO.O Li.SO,H.O + NaISO,.
Isothermal data
21.24 Li,SO.
9.70
4.72 1.66
100.0
0
:1.27
24.38
2.01 4.33
37.0 3Na,SO, LhSO, 12H.O+
o
8. i7 + Na,SO.
16.66
3.85
2.95 37.0
3Na,SO, Li,SO . 12H,O+
16.BO + Na,SO,. Li.SO,
[",24.54
2.48 4.46 50.0
Na.SO,.Li.SO, + Na,SO,

\; 26.15 2.03 4.74 100.0

. .-.1 33.24 -
5.94 32.38 Na.SO.l0H.O+Na.SO, Data of Bergmon and Luz.h
: . 2
-
5.77 -
22.2 Ice + Li,SO, .H.O Polythormol data
These two double points have been further investigated by
the authors.
mlrabilite coexisted. After four days of vigorous stirring
the composition of the mirabilite + thenardite + 3Na:aS04'
. Liil04 . 12HaO phase had not changed. The temperatures
and compositions corresponding to the other non-variant
poInts (Table 4) were determined in the same way.
The results are presented in Fig.3 as a diagram with
rectangular coordinates and in Fig. 4 as a projection on the
L1aS04-Na:aS04 side. The former shows the phase diagram
of the Li2S04-Na:aS04-H20 ternary system. The crystal-
lisation fields correspond to separation of the phases:
OAIB Ice
A ClVnI Naas04.10HaO
O
lVvmn 3Na:aS04' LizS04
12H
2
0
mnIB Li
2
S0
4
. H
2
0
E Na:aS04
E V mn Na:aS04' LiaS0 4
TABLE 4. Non-variant points in the LizSO,-NazSO,-HzO ternary
system from -23.4 to 100.
Comp. of solution
110. wt. ,.
I
mole%
t. C Solid pha
-
LI,sO,
I
NazBO. LI,sO,
I
Na,50.
I 26.66
1.83 5.74 0.31
-23.4
leo + NaoSO,.10H.O +
26.78
1.79 5.77 0.30 + LioSO,.H.O
11 24.14
5.69 5.29 0.96
-1.7
Na.SO, !OH,O + Li.SO. H.O +
24.17
5.53 5.28 0.94 + 3Na.SO,Li,SO,12H.O
III 21.15
12.08 4.24 1.87
29.3
3Na,SO, Li,SO . 12H,O +
21.09
12.05 4.22 1.87 + Na.SO Li.SO. + Li.SO H.O
Iv 2.95
31.32 0.69 5.66
30.8
3Na,SO.Li,SO.12H.O +
3.00
31.35 0;70 5.67 +Na,SO,10H,O + Na.SO,
V 10.53
24.68 2.48 4.49
48.5
NaoSO,Li,SO, + Na,SO, +
10.53
24.49 2.47 4.45 +3Na,SO. Li,SO, 12H,O
Li
2
SO H
2
0 and Naas04 have negative temperature co-
efficients of solubility, and hence the crystallisation zone
of the former appears superimposed on that of ice,
Na:aS04 . 10H
2
0 and 3Naas04 LizB0 . 12H
2
0, while that of
the latter partly covers those of 3NaJ304' LizSO . 12H
2
0
and NaaS04 . 10HzO. The NaaS04' LizB04 and 3Naas04'
LiaS04 . 12HaO zones are also superimposed. The zones
for 3Naas04' LiaS04 .12H
a
O and NaaS04' LiaS0. are super-
imposed because the solubility of the former increases
with temperature while that of the latter decreases.
The double salts 3Na:aS04' LiaS0 . 12HaO and Naas04.
LiaS04 were investigated by optical and thermographic
methods. The refractive indices are: 3Na:aSO . LizS04 .
12HaO, np 1.460, ng 1.464 (in agreement with Lepeshkov
et al. 12); Naaso . LiaS0., np 1.488, ng 1.497. Thermo-
graphic studies showed five endothermic effects in 3Na:aS04 .
LiaS0 . 12HaO at 50
0
, 106
0
, 240
0
, 480
0
and 670
0
(Fig. 5, I)
which were interpreted by progressive dehydration at 55
0
_
-60
0
(Fig. 5, n-IV). All were still present in the thermo-
gram obtained after the loss of 11. 7 wt. % of water (Fig. 5,
n), but the first two were less prominent. After the loss
of 87.6 wt. % of water (Fig. 5, m) the first had almost
naya disappeared and the second was greatly reduced. After
complete dehydration (Fig. 5, IV) both were absent; they
correspond to the loss of 12 molecules of water. Since
the first is still found after the loss of 87.6 wt. % of water,
it follows that complete dehydration occurs at 50
0
and that
Li,SO.
3D
ID
01 c2 "3 "'4
5
4

",0 A
fO
wt." 2D
Fig. 3. Solubility isotherm of the LizSO,-NazSO,-Hz{) ternary
system from - 23.4 to 100:
1) polythermal data; 2) isothermal data; 3) published data; 4)
non-variant points:
I) ice + NazSO,. 10Hz{) + LizSO,. HzO; n) NazSO,. 10H
2
0 +
i LizSO,. H
2
0.+ 3Na2S0,. LizSO,. 12H
2
0; nI) LizSO,. H
2
0 +
+ 3Na2S0t LizS0,. 12H
2
0 + NazSO,. LizS0,; IV) NazSO,.
. 10H
2
0 + 3NazSO,. LizS0,. 12H
2
0 + NazSO,; V) 3NazSO,.
. LizS0,. 12H
2
0 + NazSO,. LizSO, + NazSO,.
867
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
10
IIJ
o
Fig. 4. Projection of the
solubility polytherm of
the
ternary system from
- 23.4
0
to 100
0

at 106
0
only uncombined water is lost. The effects at 240
0
,
480
0
and 670
0
were reproducible onrepeated thermogram.s.
That at 240
0
corresponds to the polymorphic transformation
of according to K10chko 7 the other two represent
a solid-state transformation "at 480
0
and fusion at 670
0

The thermogram of (Fig. 6) has three
well-marked effects at 480
0
, 508
0
and 600
0
The first
two represent solid-state transformations and the third
fusion at 600
0
7
C)
(c
868
Time, min
Fig. 5. Thermogram of
12H
2
0.
Fig. 6. Thermogram of
LizSO,.
SUMMARY
1. The solubility po1ytherm of the - - H 0
system has been studied from _23.4
0
to 100
0
by
and thermographic methods. The phase diagram shows
six crystallisation zones, for ice, 10H
2
0,
Li
2
S0
4
. and
Li
l
S0
4
HIO.
2. The temperatures and compositions corresponding to
the four non-variant transition points at 1. 7
0

.10H
2
0 + LiJ304 H
2
0 + 3NlizB04. 12H
2
0), 29.3
0
(3NaJ304 . LizS0
4
. 12H
2
0 + . LizS04 + LiaS04 .
. H
2
0), 30.9
0
Li
2
S0
4
. 12H
2
0 + 10H 0 +
+ 48.5
0
+ Li
2
S0
4
+ "
. LizB04 . 12H
2
0), and the eutectic point at _23.4
0
(ice\
+ . 10H
2
0 + LizB04. H
2
0) have been determined.
Dehydration of .10H
2
0 in this ternary system
occurs at 30.9
0
, 1.5
0
lower than in the binary system.
We thank 1. N. Lepeshkov and E.I. Luk'yanova for
directing this work.
1. John and A. N. Friend, J. Chem. Soc., 2330 (1929).
2. Etard, Ann. Chim. Phys., !, Series 7, 547 (1894).
3. A. N. CampbeU, J. Am er. Chem. Soc., 65, 2268 (1943).
4. A. G. Bergman and N. P. Luzbnaya, "Fizikokhimicheskie Osnovy
Izucheniya i Issledovaniya Solyanykh Mestorozhdenii Khlorid-
Sul'fatnogo Tipa" (Physicochemical Principles of Investigation
of Chloride-Sulphate Salt Deposits), Izd. Akad; Nauk SSSR,
p.46.
5. H. Le Chatelier, Compt. rend., 118, (1), 709 (1894).
6. R. Nacken, Neues Jahrb. Min., Geo!. und Palllontol.
Vol. 1 (1907).
7. M. A. Klochko, Zhur. Obshch. Khim., 1026 (1933).
8. E. K. Akopov and A. G. Bergman, Zhur. Obshch. Khim., 24, 1512'
(1954). .
9. C. Spielrein. Compt. rend., 155, 346 (1912); 157, 46 (1913).
10. L. Cavalca and M. Nardelli, Gazzetta, 82. 398 (1952).
11. I. A. Skarulis and H.A. Horan, J. Amer.Chem.Soc., 77, 3489
(1955).
12. 1. N. Lepeshkov, H. V. Bodaleva and L. T. Kotova, Zhur. Neorg.
Khim., .2, 2781 (1958).
13. A.N.Campbell and E.M. Kartzmark, Canad.J.Chem., 36, 171
(1958).
14. L. B. Rogers and E. R.Caley, J. Ind. Eng.Chem.Anal. Ed., 15,'
(1943).
Received 26th August 1958
POLAROGRAPHIC DETERMINATION OF THE
pH OF DISSOLUTION AND THE SOLUBILITY
PRODUCT OF TRN ALENT THALliUM
HYDROXIDE
"P. N. Kova1enko and T. V. Lindorf
By controlling the hydrogen ion concentration, it is
possible to separate salts of closely similar metals and
purify solutions from traces of metals which may interfere
in technical processes. The solubility product of
rl