Documente Academic
Documente Profesional
Documente Cultură
INTRODUCTION EXPERIMENTAL
IN MANY previous studies, solubilities of 1-2 and 2-2 All experimental procedures have been described in detail in
metal sulfate salts have been obtained at temperatures previous papers[l, 2]. Briefly, solution samples for analysis were
obtained by direct sampling from high pressure vessels at a given
from 0 to 350°C in 1-1 aqueous salt and in separate
temperature after attainment of equilibrium. The saturating solid.
sulfuric and nitric acid solutions [1,2]. These studies have Sm2(SO4), hydrate, was obtained from Lindsay Chemical Com-
shown that solubility products (Qsp) for the various pany. By spectrographic analysis no significant metallic impurity,
sulfate salts and ionization quotients (Q_,, Q,,) for HSO4 other than faint traces of magnesium, was present. This solid was
and HNO3 derived therefrom are described to high water washed several times at 25°C and also at 100°C in order to
concentrations by an extended Debye-Htickel equation, remove any excess H2SO~ (as an impurity) that may have been
which includes a single parameter (A~p) related to the "ion present. Reagent-grade concentrated H_,SO4 was used for prepar-
size". However, the solubility of only one 3-2 metal ing the diluted stock solutions.
sulfate (Laz(SO4)~.n H_,O) has been studied in this fashion The saturated solutions were titrated for samarium by the use of
ethylenediaminetetraacetate (EDTA) in the manner described
in HzSO~-H~,O solutions at high temperatures (135-160°C),
previously for calcium and magnesium in solution[4]. The
by Lietzke and Stottghton[3]. In their study, solubility concentration of total sulfate was obtained by passing a known
product constants and A,~ parameters were obtained at volume of solution sample through a Dowex-50 cation exchanger
the several temperatures based on ionization of La,_(SO~)~ bed in the hydrogen form, and the H2SO4-H:O eluent titrated for
to produce 2La > and 3 S O l in solution. H + ion. Some small excess of H2SO4 in the studies of
To aid in attaining a broader description of general Sm2(SO4h'n HzO initially in water alone was detected also by this
solubility and activity coefficient behavior of metal sulfates method. This excess H:SO, presumably was formed by hydrolytic
in electrolyte solutions, we decided to obtain solubilities at precipitation from the Smz(SO~)~-H20 solution of a small amount
high temperatures for another 3-2 metal sulfate of samarium oxysulfate or hydroxide solid. Units of molarity
ISm:{SO4),.n H:O) in water (25-350°C) and in sulfuric acid obtained by volumetric analysis were converted to molafity by
using the densities of H,~SO~-H:O at 25°C given elsewhere [5]: the
solutions 1150-250°C). A moderately wide range of
low concentration of Sm2(SO~)~in the solutions was insignificant in
molality of H_,SO~ (0-0.9 m) would be covered for both making this conversion. Equilibrium at each temperature ap-
testing adherence to the extended Debye-Hfickel equation peared to be attained within 2 hr based on some solution samplings
and evaluating several models of 3-2 electrolyte ionization taken 16-27 br later with no significant change in concentration of
at the high temperatures. A successful description would Sm~(SO~),.
allow additional confidence in applying the Debye-Htickel From the fiterature[6-10], and with agreement of solubilities
theory, which is of fundamental interest. Of perhaps from this study, the solid phase at temperatures below 125°C was
greater importance, predictions of activity coefficients and taken to be the octahydrate. At higher temperatures, we were
of precipitation limits for minerals would be broadened for unable to confirm the extent of hydration of the saturating solid,
but believe thal this solid may be a pentahydrate [6-10], possibly a
specific application to geothermal solutions used in power
monohydrate based on observances of some 2-2 sulfates at high
production and for other applications to high temperature temperatures [2l, or the anhydrous salt. We therefore have chosen
aqueous technologies. The relative success in achieving to define the high temperature saturating solid as one containing
these goals is presented. nH~O both for Sm2(SO~), and La,,(SO~)~.
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
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($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)
TEMPERATURE (°C)
Equation (7) was treated by a method of non-linear least
squares (NLLS)[15] to obtain simultaneously values of Fig. 3. The A,p parameter for describingthe variationof log Qcp vs
the two parameters log K,p and A,p at 150, 200 and 250°C x/(I)/[1 + A,pX/(I)] for Sm:(SO4)3hydrate, cases 1-4,150-250°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 The average of these values is 1.60, which is the same
deviations [A(log Qs,)] for the four assumed cases. value of A,p that has been used to fit variations in log Q,p
Figures 2 and 3 show plots of the standard deviations or log ~2 ((mean activity coefficient)2) for 2-2 metal
and values of A,,, respectively, vs temperature for the sulfates at temperatures of 100-350°C [2, 13]. It is close to
four cases for Sm2(SO4)3. We may now critically a value of 1.5 for A,p ordinarily applied at 25°C to the fit
compare these two calculated values in an attempt to of many 2-2 and also 1-2 and 1-1 salt systems[16]. (In the
select the assumed equilibrium that best describes the Guggenheim equation for activity coefficients, this A,p
experimental values. Figure 2 shows that the standard parameter is arbitrarily set equal to unity for all
deviations for Cases I and 2 are much lower than for electrolytes, but then an additional term or terms
Cases 3 and 4 over the entire range of temperature. containing interaction parameters must be added to an
Although Case 2 shows a somewhat closer fit than Case 1, extended Debye-Hiickel equation for a quantitative
it is difficult to choose between these two cases on the description[17]).
basis of fit. On the basis of the comparisons in Table 4 and Figs. 2
Figure 3 allows us to compare the relative values of the and 3, we suggest that Sm2(SO4)3 in solution at high
A,p parameter. For Cases 3 and 4 we observe values of temperatures behaves as a 2-2 metal sulfate salt (Case 1),
2.5-4.4, which are far greater than are observed for 1-2 that the predominant ionic species in the solubility
and 2-2 salts at 25°C or at high temperatures. Case 2 gives product expression are Sm2(SO4h2+ and SO42-, and that an
values of A.,p much smaller (0.5-0.12), with a sharp A,p parameter, constant at 1.6, describes well the
decrease with increasing temperature customarily not variation of Q,p (Case 1) for Sm2(SO4)3.nH20. Some
observed. Case l, however, yields values at 150-250°C comparative calculations of log Q,p, A,,, and the standard
that are relatively close together, i.e. 1.49, 1.77 and 1-55. 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
/, 14c°c_
Parameters'[" Standard 8 -4 i
Deviation >.
B C (A log Ksp)
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.
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 7.F. Wirth, Z. Anorg. Allg. Chem. 76, 174 (1912).
Sm2(SO4)2.n H20 in H2SO4-H20, produces an acceptable 8.K. S. Jackson and G. Rien/icker, J. Chem. Soc. 1687 (1930).
and constant value of As~, and equally well describes the 9.V. I. Ivanov, Kristallografiya 9, 655 (1964).
earlier high temperature studies of La2(SO4)3.nH20 in 10.W. W. Wendlandt and T. D. George, 3. Inorg. Nucl. Chem. 19,
245 (1961).
H2SO4-H20[3]. Therefore, it would appear reasonable to
11. F. H. Spedding and S. Jaffe, J. Am. Chem. Soc. 76,882 0954).
include these relationships for 3-2 salts into descriptions
12. A. Seidell and W. F. Linke, Solubilities of Inorganic andMetal
of high temperature complex solution behavior, of much Organic Compounds, 4th Edn, Vol. II, p. 1460. Van Nostrand,
present interest in application to geothermal power New York (1958).
evaluations [19, 20], to hydrothermal ore deposits [21], and 13. C. C. Templeton and J. C. Rodgers, Jr. Chem. EngngData, 12,
to high temperature sciences and technologies, for 536 (1967).
example, chemical processing of rare earths. 14. W. L. Marshall and Ruth Slusher, jr. Chem. Thermodyn. 5, 189
(1973).
15. M. H. Lietzke, Oak Ridge National Laboratory Report
REFERENCES ORNL-3259 (1962).
I. W. L. Marshall and Ruth Slusher, J. lnorg. Nucl. Chem.37, 1191 16. H. S. Harned and B. B. Owen, The Physical Chemistry of
(1975); 37, 2165 (1975) and references therein. Electrolytic Solutions, 3rd Edn, ACS Monograph, Rheinhold,
2. W. L. Marshall, J. Inorg. Nucl. Chem. 37, 2155 (1975) and New York 0958).
references therein. 17. E. A. Guggenheim, Phil. Mag. 19, 588 (1935).
3. M. H. Lietzke and R. W. Stoughton, J. Inorg. Nucl. Chem. 28, 18. L. G. Sill6n and A. E. Martell, Stability Constants of
1063 0966). Metal-Ion Complexes. The Chemical Society, London 0964);
4. H. A. Flaschka, EDTA-Titrations. Pergamon Press, London Supplement No. 1 0968).
0959). 19. P. Kruger and C. Otte (Editors), GeothermalEnergy. Stanford
5. E. W. Washburn (Editor), International Critical Tables, 1st University Press, Stanford, Calif. (1973).
Edn, Vol. III, p. 56. McGraw-Hill, New York (1928). 20. R. N. Lyon and G. A. Kolstad (Editors), U.S. Atomic Energy
6. J. W. Mellor, A Comprehensive Treatise on Inorganic and Commission Report WASH-1344 (1974).
Theoretical Chemistry, Vol. V, pp. 650-664. 21. H. L. Barnes (Editor), Geochemistry of Hydrothermal Ore
Longmans-Green, London (new impression, 1952). Deposits. Holt, Rinehart & Winston, New York (1967).