J more m , I Chem. t97s. Vol. 37. pp 2171-2176. Pergamon Press.

Printed in Great Britain

SOLUBILITY AND THERMODYNAMIC FUNCTIONS FOR

A 3-2 SALT, SAMARIUM SULFATE, IN WATER AND
SULFURIC ACID SOLUTIONS AT TEMPERATURES
TO 350°C *

WILLIAM U MARSHALL and RUTH SLUSHER+

Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, TN 37830, U.S.A.

(Received 10 February 1975)

Abstract--To broaden the types of salts studied in high temperature aqueous systems, solubilities of 3-2 samarium
sulfate hydrates have been determined in water (25-350°C) and in aqueous sulfuric acid (150-250°C). The values in
water for the octahydrate decrease from 0.033 m at 25°C to 8 x 10 ~ m for a lower hydrate at 350°C. Assumptions of
several sets of ionic species saturating the sulfuric acid solutions have been tested by extended Debye-Hficket
theory, which suggests that the 3-2 samarium sulfate may behave predominantly as a 2-2 sulfate at high
temperatures, thus producing Sm2(SO4).,> and SO2" ions in solution. Similar treatment of Lietzke and Stoughton's
solubilities of lanthanum sulfate in sulfuric acid at 135-160°C is not inconsistent with this suggestion. Based on
behavior as a 2-2 salt, thermodynamic functions for the solubility of samarium sulfate hydrate at 150-250°C are
presented, together with some comparisons from the solubilities of lanthanum sulfate hydrate.

INTRODUCTION
IN MANY previous studies, solubilities of 1-2 and 2-2
metal sulfate salts have been obtained at temperatures
from 0 to 350°C in 1-1 aqueous salt and in separate
sulfuric and nitric acid solutions [1,2]. These studies have
shown that solubility products (Qsp) for the various
sulfate salts and ionization quotients (Q_,, Q,,) for HSO4
and HNO3 derived therefrom are described to high
concentrations by an extended Debye-Htickel equation,
which includes a single parameter (A~p) related to the "ion
size". However, the solubility of only one 3-2 metal
sulfate (Laz(SO4)~.n H_,O) has been studied in this fashion
in HzSO~-H~,O solutions at high temperatures (135-160°C),
by Lietzke and Stottghton[3]. In their study, solubility
product constants and A,~ parameters were obtained at
the several temperatures based on ionization of La,_(SO~)~
to produce 2La > and 3 S O l in solution.
To aid in attaining a broader description of general
solubility and activity coefficient behavior of metal sulfates
in electrolyte solutions, we decided to obtain solubilities at
high temperatures for another 3-2 metal sulfate
ISm:{SO4),.n H:O) in water (25-350°C) and in sulfuric acid
solutions 1150-250°C). A moderately wide range of
molality of H_,SO~ (0-0.9 m) would be covered for both
testing adherence to the extended Debye-Hfickel equation
and evaluating several models of 3-2 electrolyte ionization
at the high temperatures. A successful description would
allow additional confidence in applying the Debye-Htickel
theory, which is of fundamental interest. Of perhaps
greater importance, predictions of activity coefficients and
of precipitation limits for minerals would be broadened for
specific application to geothermal solutions used in power
production and for other applications to high temperature
aqueous technologies. The relative success in achieving
these goals is presented.
EXPERIMENTAL
All experimental procedures have been described in detail in
previous papers[l, 2]. Briefly, solution samples for analysis were
obtained by direct sampling from high pressure vessels at a given
temperature after attainment of equilibrium. The saturating solid.
Sm2(SO4), hydrate, was obtained from Lindsay Chemical Com-
pany. By spectrographic analysis no significant metallic impurity,
other than faint traces of magnesium, was present. This solid was
water washed several times at 25°C and also at 100°C in order to
remove any excess H2SO~ (as an impurity) that may have been
present. Reagent-grade concentrated H_,SO4 was used for prepar-
ing the diluted stock solutions.
The saturated solutions were titrated for samarium by the use of
ethylenediaminetetraacetate (EDTA) in the manner described
previously for calcium and magnesium in solution[4]. The
concentration of total sulfate was obtained by passing a known
volume of solution sample through a Dowex-50 cation exchanger
bed in the hydrogen form, and the H2SO4-H:O eluent titrated for
H + ion. Some small excess of H2SO4 in the studies of
Sm2(SO4h'n HzO initially in water alone was detected also by this
method. This excess H:SO, presumably was formed by hydrolytic
precipitation from the Smz(SO~)~-H20 solution of a small amount
of samarium oxysulfate or hydroxide solid. Units of molarity
obtained by volumetric analysis were converted to molafity by
using the densities of H,~SO~-H:O at 25°C given elsewhere [5]: the
low concentration of Sm2(SO~)~in the solutions was insignificant in
making this conversion. Equilibrium at each temperature ap-
peared to be attained within 2 hr based on some solution samplings
taken 16-27 br later with no significant change in concentration of
Sm~(SO~),.
From the fiterature[6-10], and with agreement of solubilities
from this study, the solid phase at temperatures below 125°C was
taken to be the octahydrate. At higher temperatures, we were
unable to confirm the extent of hydration of the saturating solid,
but believe thal this solid may be a pentahydrate [6-10], possibly a
monohydrate based on observances of some 2-2 sulfates at high
temperatures [2l, or the anhydrous salt. We therefore have chosen
to define the high temperature saturating solid as one containing
nH~O both for Sm2(SO~), and La,,(SO~)~.

RESULTS AND DISCUSSION

*This paper is based on work performed at the Oak Ridge
National Laboratory, which is operated for the U.S. Atomic
Energy Commission by Union Carbide Corporation.
+Computer Sciences Division of Union Carbide Corporation,
ORNI_
Solubility of Sm2(SO4)3 hydrate in water, 25-350°C. The
molal solubilities in water of Sm2(SO4)~.8H20 from 25 to
125°C and of the lower hydrate from 125 to 350°C are
given in Table 1, and are plotted in Fig. 1 to show the

2171
2172 W. L. MARSHALLand R. SLUSHER

Table l. The molal solubility (s) of Sm2(SO,)3'8H20 and both studies referred to the octahydrate, which we believe
Sm2(SO,)3.nH20 in water, 25-350°C. is an error in the compilation. Figure 1 shows the
discontinuity in the two solubility curves at approx. 130°C
t(Oc) Run Sm2 (SOa) 3 Rocking Time and also shows that the earlier values do not agree on the
No. (s) (hr) basis of the same saturating solid. (A solubility of
(Sm2(SO4)3"8H20)* 0'0602 m in HzO at 25°C by Wirth [7] was much higher
than the present values, and we did not include it in our
20 - 0.0364t - considerations.) However, upon extrapolating to low
25 1 0.03252 3
temperatures the present high temperature solubilities (at
25 1 0.03276 27
40 1 0.02451 2 135-350°C), the 25°C value of Spedding and Jaffe may be
40 - 0.0271t intersected. Whereas the two solubility values of Jackson
50 2 0.02126 2 and Rien~icker agree with our own values from 25 to 125°C
60 1 0.01966 2
(Curve A), that of Spedding and Jaffe at 25°C could be
75 2 0.01719 2
90 1 0.01939 2 consistent with our values at 135-350°C. The description
100 2 0.01547 1 in Fig. 1 is not unreasonable, and we therefore conclude
100 2 0.01571 17 that Sm2(SO4)3.8H20 reported earlier is a metastable
110 1 0.01477 2 saturating phase at 25-135°C, but that the stable saturating
110 1 0.01489 2
125 2 0.01416 2
phase is represented by Curve B and is a lower hydrate or
the anhydrous salt.
(Sm2(SO4)3"nH20)*
A problem of hydrolytic precipitation arises, however,
25 - 0.02029 # - in describing the solubility of Sm2(SO4)3 hydrate in water.
135 1 0.00604 2
150 2 0.00442 2
We know that some dissolved 2-2 metal sulfates, for
150 2 0.00409 2 example, MgSO~, NiSO, and CuSO4, hydrolytically
165 1 0.00283 2 precipitate small amounts of hydroxysulfates or the
175 2 0.00210 2 hydroxide to produce some excess acid in solution, which
190 1 0.00175 16
200 2 0.00138 2
prevents further hydrolytic precipitation of bases[2].
215 1 0.00104 2 Calcium sulfate is believed also to precipitate some
235 1 0.000699 2 Ca(OH)2, but not significantly until temperatures above
300 3 0.000093 24 300°C are reached[13, 14]. A similar, small amount of
350 3 0.000008 18
hydrolytic precipitation appears to occur for
*Saturating solid phase. Sm2(SO4)3'nH20 at temperatures above 125°C, and
%Jackson and Rienacker [81. therefore the saturating solid (Sm2(SO,)3.n H20) for curve
#Spedding and Jaffe [ 11 ]. B (125-350°C) contains some very small amounts of
bases, whereby the saturated solutions contain a very
small amount of excess H2SO4.
0.06 I I I I
Solubility products and assumed solution species in
t, Jockson, Rienocker ( t 9 5 0 )
sulfuric acid. The molal solubilities of Sm2(SO4)3 hydrate
Q Spudding, doffe ( 1 9 5 4 ) in aqueous sulfuric acid solutions at 150, 200 and 250°C
0.05 - • Present Study [Morsholl, Slusher (1975)] obtained in this study are given in table 2. By conductance
measurements at 25°C, it has been established that the 3-2
metal sulfates are highly associated [l l], which is a
E
0.04 -- o~ 0.001 B reasonable conclusion on the basis of the 3+ and 2 -
charges on separate ions Sm 3+ and SO42-. For the several
0.0005
2-2 sulfates, we believe that in strongly acidic H2SO4
>. 0.03 solutions the major species are M 2+ and HSO4- although a
~- 400
J )

D
Table 2. The molal solubility (s) of Sm2(SO4)3.nH20 in aqueous
(/) 0.02 sulfuric acid solutions, 150-250°C.
t(Oc) Sm2(SO4)3"nH20* H2SO4 Rocking Time
-~ 0.01 -- Borg. Solids : "'-. (s) (m) (hr)
"- B
A. Sm2(SO4)3.SH20 ~'0~.
B. 8m2(804)3. # H20 ili~•.l, 150 0.00425 t 0.0000 26
0.00536 0.0135
0
o 5o Ioo t5o zoo z5o 0.00829 0.0776
0.01514 0.285
TEMPERATURE (°C)
0.03117 0.943
Fig. I. The molal solubility (s) of Smz(SO,)3 hydrates in water, 200 0.00138 t 0.0000 16
25-350°C. 0.00184 0.0135
0.00320 0.0786
0.00736 0.287
spatial relations of the two solubility curves. Included also
are the solubilities of Sm2(SO,)3.8H20 obtained by 250 0.00047 t 0.0000 6
Jackson and Rieniicker[8] at 20 and 40°C and of a 0.00064 0.0143
0.00143 0.0834
Sm2(SO4)3 hydrate at 25°C by Spedding and Jaffe[ll]. 0.00450 0.307
Although the first study[8] gives saturated solution
* Hydration number is unknown but believed to be
compositions based on Sm2(SOa)3"8H20 and the second less than 8.
study[ll] based on Sm2(SO4)3 (anhydrous), Seidell and
Linke[12] compile the same solution compositions for 1"Smoothed values in water from Fig. 1.
 Solubilitythermodynamicsof Sm_,(SO,)3in H20 and H~SO,-H_,Oto 350°C 2173

solubility product [Q,p (MSO4(solid) ~ M 2~+ SO42-)] can (H+)(SO42-) (5)

still be obtained and values of Q.,p can be well described 02 (HSO,-)
by an extended Debye-Hiickel equation [2]. In the present _ (m + x)(s + x) (6)
study, however, by assuming complete ionization we were (m - x )
unable to obtain satisfactory fits to the equation of
calculated values of Q~p for 3-2 Smz(SO4)'nH20. We where parentheses are used to designate molality in place
therefore assumed several types of ionization for of brackets customarily used for molarity.
comparisons of fit, as described by the following cases: Upon solving for x in each of the above relations for
Q~p, we may substitute these values of x into eqn (6) and
Qsp[I) rearrange to obtain an equation for Qs~ as a function of s,
2÷ 2
Case 1 Solid, ' Smz(SO4)2 + SO4 , aq (1)
m and Q2 for each of Cases 1--4. The molal ionic strength
Qsp(2)
(½E m~z~2 where z~ is the charge on ion i of molality ml) is
Case 2 Solid, ' 2SmSO~~++ SOn2-, aq (2) calculated from the expressions for the molalities of H +
SO42-, and HSO4 included in eqn (6) and the analytical
Q,v(3) molalities of the cationic species [eqns (1)-14)], which are
Case 3 Solid ( ~ Sm2S044. + 2SOl , aq (3) equivalent to the first term in each of the above
Qsp(41
expressions for Qsp (Cases 1-4). In obtaining separate
Case 4 Solid , , 2Sin~++3SO4z-, aq. (4) values of Q~ for each solubility point, successive
approximations of L Q2 (by an extended Debye-Hfickel
expression), and Q~ were calculated until repeated values
For each assumed case, the saturating solid is of Q~,, agreed within 0.1%[2]. Table 3 lists the calculated
Sm2(SO4)3'nH20, and all dissolved species are in aqueous values of Q~ and the corresponding values (in parenth-
(aq) solution. With each case, the second ionization eses) of I for the solubilities of Sm2(SO,);nH20 in the
quotient of H2SO4 (Q2) is used in the full description, and three highest molalities of H,_SO4at 150, 200 and 250°C for
the formation of neutral H:SO4 is assumed to be Cases 1-4. Similar calculations for La~(SO4)3-nH20 from
insignificant, the smoothed solubilities of Lietzke and Stoughton[3] are
The assumption of Case 1 is identical mathematically to also included.
the treatment of the 2-2 metal sulfates given previously Calculated values of Q~o for each case were fitted to an
[2-procedure 1 therein], whereby the only assumed extended Debye-H~ckel function as done previously for
species are Sm2(SO,)£'+, SO, 2-, H + and HSO4-. The the 1-2 and 2-2 sulfates[2],
assumptions of Cases 2-4 follow the same interpretation
but with development of different equations for Qsp and log Q~p = log K~,, + (Y(z~)%.S~/(I)/[I + A,p X/(I)] (7)
ionic strength (I).
Briefly, let s equal the molal solubility of the salt where K~ is the solubility product constant at l ~ 0 , z,
expressed formally as Sm.~(SO4)3and x equal the molality (the charge on ion i) is summed over the total number of
of SO, 2- originating from the ionization of HSO4 . Then ions in the solubility product expression, and S is the
values of Q,~ are (s).(s +x), (2s)2.(s +x), (s)(2s +x), theoretical Debye-Hfickel slope for a 1+ ion. Thus, the
and (2s)2.(3s + x) 3 for Cases 1-4, respectively. A value of Debye-Hfickel slope equals 8S, 6S, 24S and 30S for
Q2 is represented by Cases 1-4, respectively.
Table 3. Calculated values of log Q,p (Cases 1-4) and ionic strength for Smz(SO4h.nH20 and La2(SO4h'nH20 for
separate experimentalpoints.
H2SO4' Case: t l 2 3 4
Ira/
Sm2(SO4)3"nH20
(1500C)
0.0776 4.953(0.0969) :~ - 6A50(0.0885) :[: 7.477(0.148) :~ 11.34 (0.15721 ~
0.285 4.473(0.320) 5.702(0.305) 6.!)2110.412) 10.53 (0.428)
0.943 3.913(1.014) -- 4.824(0.982) 6.19011.201) - 9.33311.233)
(200°C)
0.0135 6.521 (0.0175) - 8.670(0.0157) 9.919(0.0287) 15.23 (0.0308)
0.0786 6.069(0.0856) 7.970(0.0824) 9.48510.1048) 14.75 10.108)
0.287 5.424(0.303) -- 6.96110.295) 8.604(0.347) 13.29 (0.354)
1250°C)
0.0143 7.724(0.0156) -10.32 (0.0150) 1210 (00195) -19.01 10.0201)
0.0834 7.040(0,0864) - 9.287(0.0850) 11.[6 (0.0950) 17.50 (0.0964)
0.307 6.19510.316) - 7.94410.312) 9.973(0.343) 15.48 (0.347)
La2(SO4)~'nH~O
(150°C) #
0.200 4.961(0.216) 6.56610.210) 7.597(0.254) --11.80 (0.26l)
0.300 -4.86810.317) -- 6.458(0.3ll) 7A6010.357) 11.61 (0.363)
0.400 4.750(0.420) . 6.28310.412) 7 29310.464) 1134 (0.472l
0.500 4.615(0.524) 6.062(0.515) 710810.578) 11.03 (0.587)
0.600 4.481(0.628) 5.83810.617) - 6.931(0.695) 10.71 (0.707)
0.700 4.357(0.734) 5.626(0.720) 6.'76710.816) 11).42 (0.8301

Corresponding solubilities are given in Table 2 for Sm2(SO4)3"nH20 and by Lietzke and Stoughton [31 for
La2 (SO4)3 "nH20.
+
AssumpHons for cases 1-4 given in text.
$ In order: log Qsp and ionic strength (in parentheses).
#Example calculations for La2(SO4)~'nH20 are given although calculations were made also for the published
values [31 at 135, 140, 145,155,and 160 C.
2174 W. L. MARSHALLand R. SLUSHER

Table 4. Simultaneouslydetermined values of log K,,, A,p, and standard deviation (A log Q,p) for assumed solubility
product equilibriaof Sm2(SO,)~.n H20 and La2(S04)~.n H:O in H2SO4-H20.

Sm2 (S04)3"nH20 150°C 200 °C 250°C

Case: 1" - 6.138(1.49 )0.017 t 7.254(1.77 )0.045 + - 8.581(1.35 )0.036 t

2 - 7.493(0.537)0.020 - 9.260(0.274)0.002 10.99 (0.138)0.038
3 -10.49 (2.97 )0.059 -11.91 (4.33 )0.13 -14.34 (3.80 )0.12
4 -15.58 (2.45 )0.11 -18.03 (3.63 )0.26 -22.15 (2.81 )0.18

La2 (SO4) a "nH20 140°C 150°C 160°C

Case: 1" - 6.365(1.23 )0.048 f - 6.596(1.36 )0.045 t - 6.818(1.45 )0.039 t

2 - 7.910(0.343)0.077 - 8.248(0.452)0.076 - 8.559(0.530)0.065
3 -10.92 (2.46 )0.059 -11.26 (2.64 )0.056 11.61 (2.76 )0.049
4 -16.52 (1.91 )0.11 -17.09 (2.06 )0.10 -17.67 (2.17 )0.091

*Assumptions of particular ionic species (casesl-4) are given in text.

tValues in order are log K~j,, A~p (in parentheses), and standard deviation of log Q~p.

0.4 , [ 5.0 I ' I

Sm2($04) 3 in H2SO4-HzO
Smz(S04) 5 in HzSO4 -H20

~0.3 4.0
<3 CASE : 4
z
0

0.2
3.0
#
z
#o~
O3 2.0

t.6
150 200 25O
t.0
TEMPERATURE (°C)

Fig. 2. The standard deviation (AlogQ,,) in describing the

variation of log Q~p vs x/(l)/[1 + A,p~/(I)] for Sm2(SO4)3hydrate,
cases 1-4, 150-250°C. 150 200 250

Equation (7) was treated by a method of non-linear least
squares (NLLS)[15] to obtain simultaneously values of
the two parameters log K,p and A,p at 150, 200 and 250°C
for Sm2(SO4)3"nH20 and at 135-160°C for
La2(SO4)3.nH20. These calculated values are given in
Table 4 for both salts. Also included are standard
deviations [A(log Qs,)] for the four assumed cases.
Figures 2 and 3 show plots of the standard deviations
and values of A,,, respectively, vs temperature for the
four cases for Sm2(SO4)3. We may now critically
compare these two calculated values in an attempt to
select the assumed equilibrium that best describes the
experimental values. Figure 2 shows that the standard
deviations for Cases I and 2 are much lower than for
Cases 3 and 4 over the entire range of temperature.
Although Case 2 shows a somewhat closer fit than Case 1,
it is difficult to choose between these two cases on the
basis of fit.
Figure 3 allows us to compare the relative values of the
A,p parameter. For Cases 3 and 4 we observe values of
2.5-4.4, which are far greater than are observed for 1-2
and 2-2 salts at 25°C or at high temperatures. Case 2 gives
values of A.,p much smaller (0.5-0.12), with a sharp
decrease with increasing temperature customarily not
observed. Case l, however, yields values at 150-250°C
that are relatively close together, i.e. 1.49, 1.77 and 1-55.
TEMPERATURE (°C)
Fig. 3. The A,p parameter for describingthe variationof log Qcp vs
x/(I)/[1 + A,pX/(I)] for Sm:(SO4)3hydrate, cases 1-4,150-250°C.
The average of these values is 1.60, which is the same
value of A,p that has been used to fit variations in log Q,p
or log ~2 ((mean activity coefficient)2) for 2-2 metal
sulfates at temperatures of 100-350°C [2, 13]. It is close to
a value of 1.5 for A,p ordinarily applied at 25°C to the fit
of many 2-2 and also 1-2 and 1-1 salt systems[16]. (In the
Guggenheim equation for activity coefficients, this A,p
parameter is arbitrarily set equal to unity for all
electrolytes, but then an additional term or terms
containing interaction parameters must be added to an
extended Debye-Hiickel equation for a quantitative
description[17]).
On the basis of the comparisons in Table 4 and Figs. 2
and 3, we suggest that Sm2(SO4)3 in solution at high
temperatures behaves as a 2-2 metal sulfate salt (Case 1),
that the predominant ionic species in the solubility
product expression are Sm2(SO4h2+ and SO42-, and that an
A,p parameter, constant at 1.6, describes well the
variation of Q,p (Case 1) for Sm2(SO4)3.nH20. Some
comparative calculations of log Q,p, A,,, and the standard
deviation for La2(SO, h.nH20, obtained from the sol-
 Solubilitythermodynamics of Sm:(SO,), in H.O and H.SQ-H.O 1o 350°C 2175

Table 5. Parameters for equation describing log K~. -5 I I ' I ' i

{Sm~(SO.h.n H~O and La2(SO.h.n H~O) for Cases 1-4, each K,,, /, From S o l u b i l i t i e s of L i e t z k e - Stoughton
obtained simultaneouslywith best fit A *.. ( d. I n o r g . Nucl. Chem. 288, 1 0 6 3 ( 1 9 6 6 ) )

/, 14c°c_
Parameters'[" Standard 8 -4 i
Deviation >.
B C (A log Ksp)

Sin2 (SOa)s "nH,~O (150-250°C)

Case: 1 :~
2
+23.09
+4.37
4420.
+691.
-0.04440
-0.03189
#
Sc,l / Delsye- Hucke Sh)pes

3 +95.72 -21033. -0.13353 2 L I

4 +162.36 35132. -0.22433
La2(SOa)3"nH20 (135 160°C) ~ -6 sose~on: -!
os/~)
c~ i L%(S04)5 " n H20 = , L % ( S 0 4 ) 22-. 9 0 4 2 , aq i
Case: 1:[c 16.537 +4204.8 -1"1" 0.009 k
2 23.187 +6319.8 0.026 ( Solid )
3 26.179 +6306.7 0.017 Ii
4 42.277 +10646.2 0.033 _71 i I t L ~ I ~____
020 0.25 0.30 035 0.40
*Simultaneously determined values of Ksp and Asp given in , / T / ( 1+ 1.6 ,/7- )
Table 4.
Fig. 5. Log so ubi ity products (Q,p ; case I) for La2(SO,), hydrate
]'For use in equation, log Ksp =A + BIT + CT, where T is in °K. vs a function of the ionic strength (I), 140-160°C.
:[CAssumptionsof cases 1 4 given in text.
#For Sm2(SOa)3"nH20 there were o n l y three points for three
Table 5 together with the standard deviations of fit.
parameters; therefore, equation is perfect fit. The logarithms of the solubility products based on Case
teFor La2(SOa)a-nH20 , the short range of t e m p e r a t u r e 1 [log Q,p(1)] for Sm2(SOa)3.n H20 are plotted against the
allowed an equivalent fit with only two parameters; thus C = O. extended Debye-Htickel function, X/(I)/[1 + l'6x/(l)], in
Figs. 4 and 5 for Sm2(SO4)cnH20 and La:(SOa)3.nH20,
-5
' I ' l ' I ' I respectively, where A.~pequals 1.6, the averaged value for
Case 1 shown in Fig. 3. The slopes as drawn are the

j. °c theoretical Debye-Hfickel slopes for Case 1 (8S). The

values at the intercept ( I = 0) are log K~,(l: A,~, = 1.6)
where Ks~,(1):is the solubility product constant, again
8 based on the assumed equilibrium of Case I. These
experimental values of log K,,,(1; A.,,, = 1.6) are listed in
%,-5 Table 6.
Thermodynamic functions. Values of log K,~,(I) given
in Table 6 for both Sm2(SO4)s and La2(804)3 were treated
L-6 by NLLS to yield the following equations describing their
variations with absolute temperature.
O3

Sm.,(SO~b.n H20 (Case 1,150-250°C)

e. log K~, = 8.257 - 900.9/T - 0.028859 T (9)

~9 La_-(SO~)cn H20 (Case 1,135-160°C)

°~_ 8 log K . = 19.230+5416.5/T. (10)

From these two equations, strictly applicable only over

-9
0 0.1 0.2 0.3
~ - / ( 1 + 1.6 v~- )
Fig. 4. Log solubility products (Q,,; case 1) for Sm2(S04)3
hydrate vs a function of ionic strength (I), 150-250°C.
ubilities of Lietzke and Stoughton[3], are included also in
Table 4. The standard deviations do not show a wide
spread between cases. However, the range of molality of
added H2SO4 (0.2-0.7m) is not as great as for the
corresponding Sm2(SO4)~ system (0.07-0.9 m and
0.013-0.3 m H2SO4).
The values of log K~ simultaneously obtained with A,~
for Cases 1--4for both salts were described as functions of
absolute temperature (T) by the equation,
log K,, = A + B I T + CT.
Parameters A, B and C were obtained by NLLS [which
gave an exact solution for Sm2(SO4)3 since there were only
3 temperatures for each case], and these are given in
the range of temperature of the data, some ther-
0.4 0.5 modynamic functions for the solubility product constant
behavior were calculated by the usual procedure [2] and
are included in Table 6. The quantitative similarities in the
functions for Smz(SO,)cn H,O and La2(SOa):n H~O at the
common temperature (150°C) are to be noted.
CONCLUSIONS
If solubility products of 3-2 metal sulfates in high-
temperature aqueous solutions behave as those for 2-2
sulfates, and produce essentially the same constant value
for the A,p parameter, the inclusion of these higher
valency salts into multicomponent solution descriptions
may become simpler. Although to our knowledge there
are no substantiations of the formation of a M2(SO~)f ~
complex, no olher aqueous studies of these 3-2 salts at
(8) temperatures over I00°C have been made. The formation
of this complex does not appear to be unreasonable:
somewhat similar types of complexes at low temperature
have been presented before[18]. In any event, from
considerations of Cases 1-4, its assumption provides the

JINC VoI. 17. Nil. IO~J

2176 W . L . MARSHALLand R. SLUSHER

Table 6. Thermodynamic functions for the solubility of Sm2(SO,,)3.nH20 and La2(SO,)3.nH~O in water solvent
based on M2(SO,)3.n H20(solid) ~ M2(SO,)22÷+ SO, 2-, aq; Case 1.

AGt AHt ASt

t(~C) Log Ksp (Exptl.)* Log Ksp (Calcd.)t (kcalmol-I ) (kcalmo1-1) (cal mol-l deg-1 )

Sm2(SO4)3"nH20~t
150 -6.084 -# +11.78 19.5 74.0
200 -7.302 - +15.81 -25.4 87.2
250 -8.563 - +20.50 -32.0 -100.4
La2(S04)a-nil20 ~:
140 -6.129 -6.120 +11.57 -24.85 -88.0 ¶
150 -6.445 -6.430 +12.45 -24.8 88.0
160 -6.726 -6.725 +13.33 24.8 -88.0

*Obtained by taking Ajp equal 1.6 in Eqn (7) and NLLS solvingfor the singleparameter,log Ksp.
rUse of Eqn (9) for Sm2(SO4)3"nl-I20and Eqn (10) for La2(SO4)3.nH20 (see text).
:~Saturating solid.
'~'Three parameter Eqn (9) obtained from only 3 points provides perfect fit.
~Constant with temperaturefrom use of two parameter Eqn (10).

best fit of the high temperature solubilities of
Sm2(SO4)2.n H20 in H2SO4-H20, produces an acceptable
and constant value of As~, and equally well describes the
earlier high temperature studies of La2(SO4)3.nH20 in
H2SO4-H20[3]. Therefore, it would appear reasonable to
include these relationships for 3-2 salts into descriptions
of high temperature complex solution behavior, of much
present interest in application to geothermal power
evaluations [19, 20], to hydrothermal ore deposits [21], and
to high temperature sciences and technologies, for
example, chemical processing of rare earths.
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