Fluid Phase Equilibria 290 (2010) 88–94

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Thermodynamic modeling and experimental measurement of

calcium sulfate in complex aqueous solutions
G. Azimi, V.G. Papangelakis ∗
Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College St., Toronto, ON, M5S 3E5 Canada

a r t i c l e i n f o a b s t r a c t

Article history: A newly developed database for the Mixed Solvent Electrolyte (MSE) model of the OLI Systems software
Received 6 July 2009 was employed to model the solid and aqueous phase equilibria of calcium sulfate hydrates in electrolyte
Received in revised form solutions containing NiSO4 , H2 SO4 , MgSO4 , Fe2 (SO4 )3 , LiCl and HCl from 25 to 90 ◦ C. The MSE model is
24 September 2009
a variant of an excess Gibbs free energy model for Mixed Solvent Electrolyte systems which takes into
Accepted 28 September 2009
account long-range electrostatic interactions from a Pitzer–Debye–Hückel equation, middle-range inter-
Available online 7 October 2009
actions from a second virial coefficient-type equation and short-range interactions from the UNIQUAC
model. The effect of cations with similar anions on the solubility was investigated and it was found that
Keywords:
Calcium sulfate
the solubility depends mainly on the anion type while the cation has a minor effect. The effect of acid
Dihydrate (DH) addition and the acid type was also studied. The addition of both HCl and H2 SO4 increases the solubility;
Hemihydrate (HH) however H2 SO4 has a less pronounced effect due to the common ion effect. Furthermore, the effect of
Anhydrite (AH) phase transitions between different calcium sulfate hydrates was studied. The transformation of CaSO4
Phase transformation dihydrate to anhydrite results in a significant decrease in the solubility, which complicates the chem-
Solubility istry of the system. Since it is not practical to measure solubility data under all conditions of interest,
Chemical modeling the model developed and the experimental results obtained serves the purpose of assessing the calcium
sulfate scaling potential for a wide variety of complex aqueous industrial streams.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction are dealing with the formation of CaSO4 hydrates as undesirable

The knowledge of the phase equilibria and solubility of inorganic
salts in electrolyte solutions is essential in the development, design,
optimization and operation of many chemical processes including
environmental applications (gas treatment, wastewater treat-
ment, or chemical disposal), separation processes (crystallization,
extractive distillation and seawater desalination), electrochemical
processes (corrosion or electrolysis), energy production sources
(scaling in production wells) and hydrometallurgical processes
[1].
Several inorganic salts exist in more than one crystalline form,
the stability of which depends on the solution conditions in
terms of temperature or composition. Calcium sulfate is one of
the most common salts in this category, occurring as three dif-
ferent hydrates: dihydrate (DH: CaSO4 ·2H2 O), hemihydrate (HH:
CaSO4 ·0.5H2 O) and anhydrite (AH: CaSO4 ).
Many industrial processes including wastewater treatment,
desalination, sulfur dioxide removal from the exhaust gas of coal-
driven power plants [2,3] and hydrometallurgical processes [4–6]
∗ Corresponding author.
E-mail address: vladimiros.papangelakis@utoronto.ca (V.G. Papangelakis).
byproducts, mostly as scale. As the scale layer becomes increasingly
thicker, it reduces the production capacity and process efficiency
because of increased heat transfer resistance, reduction of material
flow and operating volumes, corrosion and wearing out of construc-
tion materials.
The stability regions of the CaSO4 hydrates depend on the solu-
tion conditions. Each crystalline phase can be stable, metastable or
unstable at certain temperatures and compositions. The transfor-
mation of calcium sulfate dihydrate (DH) to anhydrite (AH) results
in a significant decrease in the solubility level that makes the
prediction and control of calcium sulfate formation complicated.
Therefore, understanding the chemistry of CaSO4 phase equilibria
and being able to estimate its scaling potential in industrial pro-
cesses involving electrolytes is of great theoretical significance and
practical importance [5,7].
The purpose of this work is to use a recently developed database
for the Mixed Solvent Electrolyte (MSE) model of the OLI Systems
software [8,9] and map the effect of temperature and acidity as
well as sulfate and chloride concentrations on the phase equilibria
of CaSO4 hydrates and provide practical guidelines for solubility
prediction of the thermodynamically stable phase under a partic-
ular solution composition and temperature. To this end, a number
of experiments were conducted in electrolyte solutions containing

0378-3812/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2009.09.023
 G. Azimi, V.G. Papangelakis / Fluid Phase Equilibria 290 (2010) 88–94
Fig. 1. Scheme of the glass reactor used in this work.
NiSO4 , H2 SO4 , MgSO4 , Fe2 (SO4 )3 , LiCl and HCl. The specific objec-
tives are:
• To investigate whether the type of cation has a significant effect
on the solubility of calcium sulfate or all cations in the solution
can be substituted with an arbitrary pseudo cation.
• To study the effect of acid addition on the solubility of CaSO4
hydrates and to investigate the model performance in predict-
ing the chemistry of calcium sulfate phase equilibria in acidic
solutions.
• To study the effect of the phase transformation on the solubility
of calcium sulfate.
2. Experimental
2.1. Reagents
In this work, all solutions were prepared by dissolving reagent
grade chemicals directly without further purification. Both CaSO4
solids phases (DH and AH) used in this work were from J.T. Baker. X-
ray powder diffraction was carried out on both solids using a Philips
PW3719 diffractometer. Result showed 100% dihydrate (DH) and
anhydrite (AH), respectively. No traces of hemihydrate (HH) or
anhydrite (AH) were found in the dihydrate (DH) solid powder.
2.2. Apparatus
The experiments were performed inside 1 L double-layer glass
reactors where heating was provided through a circulating oil
jacket. Temperature was controlled within ±1 ◦ C of the set-point.
The reactor slurry was kept suspended by a shaft stirrer. Sam-
ples were withdrawn through a dip rubber tube using preheated
syringes, and filtrations were performed using 0.22 ␮m PTFE
syringe filters from Fisher. Fig. 1 represents a scheme of the
experimental set-up used in this work. To avoid solution evapo-
ration during the runs, the stirrer bushing was fully sealed using
Dow Corning® high vacuum grease, which basically contains poly-
dimethylsiloxane.
89
2.3. Procedure
Solutions of known composition were placed in the reaction ves-
sels with an excess of saturating solid phase. Experiments were
started by heating the charged reactors to temperature under vig-
orous agitation and allowing sufficient time to reach equilibrium.
Samples were withdrawn after equilibration, immediately filtered,
and diluted by 5% HNO3 and kept in test tubes at room temperature.
In the systems studied the solubility of calcium sulfate decreases
with decreasing temperature. Therefore, samples withdrawn at
higher temperatures, e.g., 90 ◦ C, will form dihydrate (DH) precip-
itate upon cooling to room temperature. In order to avoid this
phenomenon, samples were diluted by 5% nitric acid.
In each sampling step, 5 mL of the solution was withdrawn
which does not affect the molarity of different elements in the
system. The concentration of other elements than Ca was also mon-
itored through out all experiments to confirm that the solution
compositions remained unchanged. During solid samples with-
drawal, only ∼1 g of the solid was taken, and since dihydrate was
added in excess (∼50 g) initially, solid sampling would not have a
significant effect on the overall composition of the solid phase.
The Ca concentration was determined by Inductively Coupled
Plasma (ICP-OES) analysis. The density of all liquid samples was
measured at temperature using a portable density meter (DMA
35N ) from Anton Paar. Samples of the equilibrating solid phase were
withdrawn at various temperatures for X-ray diffraction, thermo
gravimetric (TGA) and scanning electron microscope (SEM) analy-
sis. They were filtered, and washed with alcohol and dried at below
40 ◦ C in an oven under vacuum.
2.4. Equilibration time
Equilibration time in solubility measurements varies from sev-
eral hours to several days depending on the dissolution rate of the
solid phase under applied conditions. In this work, several kinetic
tests were conducted at various temperatures and the results
showed that around 24 h was necessary to achieve saturation.
Reproducibility tests showed that the experimentally measured
data are accurate to within ±5%.
3. Theory
The following reactions govern the solubility of CaSO4 hydrates:
CaSO4 ·nH2 O(s) = Ca2+ + SO4 2− + nH2 O (1)
Ca2+ + SO4 2− = CaSO4(aq) o (2)
The solubility of calcium sulfate is:
[Ca]total = [Ca2+ ] + [CaSO4(aq) o ] (3)
To obtain the equilibrium constants of reactions (1) and (2) at tem-
perature T and pressure P, the standard state chemical potentials
of the products and reactants are required. These data are widely
available in standard thermodynamic compilations. To extrapolate
the standard state thermodynamic properties to high temperatures
and pressures, the HKF model, developed by Tanger and Helge-
son [10], embedded in the OLI software was employed. To account
for the non-ideality (excess properties) of the electrolyte solutions
studied, the MSE activity coefficient model [11,12], which is also
embedded in the OLI Systems software, was used. In the end, a self-
consistent and calibrated model was produced. More details on the
modeling methodology and the database developed are available
elsewhere [8,9,13].
90 G. Azimi, V.G. Papangelakis / Fluid Phase Equilibria 290 (2010) 88–94

Fig. 2. CaSO4 solubility as a function of MSO4 (M = Ni, Mg, Mn) concentration; MgSO4
experimental data are from [14–17]; NiSO4 experimental data are from [17,18];
MnSO4 experimental data are from [17,19]; curves are model predictions. Fig. 3. CaSO4 solubility in CaSO4 –MgSO4 –HCl (0.5 M)–H2 O solution; experimental
data are from this work, and curves are the model predictions.

4. Results and discussion

4.1. Effect of divalent cations on the solubility of CaSO4 hydrates
Fig. 2 presents a comparison between the solubility of
CaSO4 dihydrate (DH) in ternary solutions of CaSO4 –NiSO4 –H2 O,
CaSO4 –MgSO4 –H2 O and CaSO4 –MnSO4 –H2 O along with the model
“predictions” at two different temperatures: 25 and 75 ◦ C. It is
clear that the difference between CaSO4 solubilities in these sys-
tems at both temperatures is always less than ∼15% indicating
that the cation type does not have a dramatic effect on the CaSO4
solubility. For all three cations, as the metal sulfate concentra-
tion increases from pure water, the solubility initially drops and
then increases gradually. After passing a maximum, the solubility
decreases smoothly with further increasing the MSO4 (M = Mg, Mn,
Ni) concentration. The initial drop is due to the common ion effect
which shifts the dissolution reaction (Eq. (1)) to the left; the subse-
quent increase is attributable to the association of Ca2+ and SO4 2−
ions and formation of calcium sulfate neutral species (Eq. (2)). The
solubility decrease in concentrated solutions is due to the salting-
out effect due to the decreased number of free water molecules in
the solution to dissolve calcium sulfate.
In industrial applications, particularly in hydrometallurgy, solu-
tions sometimes contain several cations for which there are no
experimental data available. By knowing that cation type does not
have a significant effect on the solubility level, all divalent cations
can be substituted with a certain cation for which experimental
data are available during the simulation of the process.
4.2. Effect of different acids on the solubility of CaSO4 hydrates
To compare the effect of H2 SO4 and HCl on the solubility of
calcium sulfate dihydrate (DH), two different sets of experiment
were performed: first, the solubility was measured as a function of
MgSO4 concentration in 0.5 M HCl solutions. Second, the solubility
was measured as a function of NiSO4 concentration in 0.5 M H2 SO4
solutions. The measured data are presented in Tables 1 and 2.
Figs. 3 and 4 show the measured solubility data in comparison
with the model prediction results from 25 to 90 ◦ C. In both sys-
tems, the solubility first decreases with increasing MSO4 (M = Ni,
Mg) concentration due to the common ion effect of the added
SO4 2− ions. This effect is nullified by further increasing MSO4 con-
centration because of the association of Ca2+ and SO4 2− ions and

Table 1
Solubility of CaSO4 dihydrate in 0.5 M HCl solutions at various MgSO4 concentrations.

MgSO4 (mol/L) 25 ◦ C 45 ◦ C 70 ◦ C 90 ◦ C

CaSO4 (mol/L) Density (g/mL) CaSO4 (mol/L) Density (g/mL) CaSO4 (mol/L) Density (g/mL) CaSO4 (mol/L) Density (g/mL)

0.0 0.0810 1.007 0.0940 1.005 0.1300 1.004 0.1560 0.997

0.1 0.0456 1.021 0.0594 1.013 0.0785 1.008 0.0987 0.999
0.5 0.0168 1.057 0.0205 1.047 0.0231 1.038 0.0292 1.030
1.0 0.0110 1.112 0.0139 1.100 0.0153 1.105 0.0188 1.080
1.5 0.0087 1.162 0.0105 1.158 0.0113 1.102 0.0135 1.128

Table 2
Solubility of CaSO4 dihydrate in 0.5 M H2 SO4 solutions at various NiSO4 concentrations.

NiSO4 (mol/L) 25 ◦ C 45 ◦ C 70 ◦ C 90 ◦ C

CaSO4 (mol/L) Density (g/mL) CaSO4 (mol/L) Density (g/mL) CaSO4 (mol/L) Density (g/mL) CaSO4 (mol/L) Density (g/mL)

0.00 0.0190 1.030 0.0258 1.022 0.0403 1.010 0.0545 1.002

0.10 0.0180 1.044 0.0234 1.037 0.0351 1.026 0.0454 1.015
0.25 0.0166 1.060 0.0210 1.056 0.0298 1.044 0.0383 1.029
0.50 0.0166 1.106 0.0196 1.095 0.0266 1.085 0.0329 1.071
1.00 0.0148 1.180 0.0172 1.170 0.0234 1.157 0.0314 1.141
1.50 0.0131 1.238 0.0158 1.230 0.0194 1.218 0.0245 1.202
 G. Azimi, V.G. Papangelakis / Fluid Phase Equilibria 290 (2010) 88–94 91

Fig. 5. CaSO4 solubility in CaSO4 –NiSO4 (1.4 M)–H2 SO4 (1 M)–Fe2 (SO4 )3
Fig. 4. CaSO4 solubility in CaSO4 –NiSO4 –H2 SO4 (0.5 M)–H2 O solution; experimental (0.2 M)–LiCl (0.3 M)–H2 O solutions at various retention times and different
data are from this work, and curves are the model predictions. temperatures.

formation of calcium sulfate neutral species. Also, the solubility the equilibrating solid phase was estimated semi-quantitatively by
of dihydrate (DH) is significantly higher in the presence of HCl measuring the peak intensities of the different X-ray diffraction
(Fig. 3) compared to that in H2 SO4 (Fig. 4). This effect is most pro- patterns and was confirmed by thermo gravimetric analysis (TGA).
nounced near zero metal sulfate concentrations. The addition of Hemihydrate was not detected in any of the samples despite a care-
both H2 SO4 and HCl increases the solubility of CaSO4 dihydrate ful search for this phase. The experimentally measured solubility
(DH) due to the formation of bisulfate ions; however, in the case
of H2 SO4 , there is a common ion effect due to the produced SO4 2−
from the second dissociation of H2 SO4 hindering the dissolution
reaction.
In both systems, model “predictions” are in good agreement
with the experimental data. It should be emphasized that no
extra fitting were perfumed in these systems which proves the
predictability of the model in multicomponent systems using
the interaction parameters obtained in binary and ternary sys-
tems, i.e., CaSO4 –H2 O, CaSO4 –MgSO4 –H2 O, CaSO4 –NiSO4 –H2 O,
CaSO4 –HCl–H2 O and CaSO4 –H2 SO4 –H2 O which have been studied
previously [8,9].

4.3. Effect of phase transition on the solubility of CaSO4 hydrates

4.3.1. CaSO4 –NiSO4 –H2 SO4 –Fe2 (SO4 )3 –LiCl–H2 O System

Nickel processing solutions typically contain NiSO4 , H2 SO4 ,
Fe2 (SO4 )3 and small amounts of a chloride salt. In this work, the
solubility of calcium sulfate dihydrate (DH) was measured in a
solution of 1.4 M NiSO4 , 1 M H2 SO4 , 0.2 M Fe2 (SO4 )3 and 0.3 M LiCl.
Solubility measurements were carried out based on heating from
Fig. 6. CaSO4 solubility in CaSO4 –NiSO4 (1.4 M)–H2 SO4 (1 M)–Fe2 (SO4 )3
25 to 90 ◦ C followed by subsequent cooling. At a given tempera- (0.2 M)–LiCl (0.3 M)–H2 O solutions; solid curves are the model predictions,
ture, the relative amount of dihydrate (DH) and anhydrite (AH) in and the dashed line shows the phase transition region.

Table 3
Calcium sulfate concentration, saturated solution density and solid phase composition in 1.4 M NiSO4 , 1 M H2 SO4 , 0.2 M Fe2 (SO4 )3 , 0.3 M LiCl solutions at various temperatures
and retention times.

Time (h) T (◦ C) Density (g/mL) CaSO4 (mol/L) Method Solid phase composition

24 25 1.333 0.0079 Heating 100% DH

48 45 1.318 0.0106 Heating 100% DH
72 60 1.315 0.0136 Heating 100% DH
96 70 1.305 0.0155 Heating 100% DH
120 70 1.305 0.0127 Heating 80% DH + 20% AH
144 70 1.305 0.0089 Heating 100% AH
168 90 1.298 0.0085 Heating 100% AH
192 80 1.300 0.0084 Cooling 100% AH
216 60 1.315 0.0082 Cooling 100% AH
240 35 1.326 0.0082 Cooling 100% AH
264 25 1.333 0.0080 Cooling 25% DH + 75% AH
92 G. Azimi, V.G. Papangelakis / Fluid Phase Equilibria 290 (2010) 88–94
Fig. 7. SEM images of the solid phases at 70 ◦ C showing the different crystal mor-
phologies of (a) 100% dihydrate (DH) withdrawn after 24 h retention time (b)
transitional of 80% dihydrate (DH)–20% anhydrite (AH) mixture withdrawn after
48 h and (c) 100% anhydrite withdrawn after 72 h.
data, saturated solution densities and solid phase compositions at
various temperatures are summarized in Table 3.
Fig. 5 presents the solubility data as a function of the retention
time along with solid sample compositions at different tempera-
tures. As is shown, the solubility increases with temperature up to
70 ◦ C. The system was kept at 70 ◦ C for 3 days and slurries were
periodically sampled. The results showed a gradual decrease in the
solubility in the second and the third samples at 70 ◦ C withdrawn
on the day 2 and day 3, respectively. The solubility values measured
at 90 ◦ C had the same order of magnitude as the third sample with-
drawn at 70 ◦ C after 3 days. On cooling, a relatively flat solubility
curve is noted up to 25 ◦ C.
Fig. 8. CaSO4 solubility vs. temperature in CaSO4 –MnSO4 –H2 SO4 –H2 O solutions;
the experimental data are from [20]; the solid curves are the predicted values and
the dashed lines show the phase transition region.
Powder X-ray diffraction analysis of the equilibrating solid
phase showed only dihydrate (DH) during heating up to 70 ◦ C;
however, the solid sample withdrawn at 70 ◦ C after 3 days reten-
tion time and the one withdrawn at 90 ◦ C showed 100% anhydrite
(AH) in the composition. The solid sample withdrawn at 70 ◦ C
after 2 days retention time contained a mixture of dihydrate
(DH) and anhydrite (AH). On cooling, anhydrite remained the
dominant equilibrating solid phase above 25 ◦ C, but at 25 ◦ C
the conversion of anhydrite (AH) to dihydrate (DH) occurred.
Thus, the major drop in the solubility of calcium sulfate is due
to the transformation of dihydrate (DH) into anhydrite (AH), a
phase which has a significantly different solubility–temperature
relationship.
Fig. 6 shows CaSO4 solubility data as a function of temperature
along with the model predictions. As can be seen, the model pre-
dicts the solubility of dihydrate and anhydrite precisely. However,
the phase transition area, which is not thermodynamically stable,
cannot be predicted by the model and is marked by a dashed line
in the figure.
The SEM images of the solid samples withdrawn at 70 ◦ C after 24,
48 and 72 h retention times are presented in Fig. 7(a)–(c), respec-
tively. As mentioned above, the first solid sample presented in
Fig. 7(a) shows 100% dihydrate in composition, whereas, the sam-
ple shown in Fig. 7(b) reveals a mixture of 80% DH and 20% AH,
as estimated from XRD and TGA. Fig. 7(c) presents a solid sample
with 100% AH after complete transformation of dihydrate in the
system. As is clear, the morphologies of calcium sulfate dihydrate
and anhydrite are very different: DH crystals are in a monoclinic
form, whereas AH crystals have an orthorhombic structure and are
needle shaped.
4.3.2. CaSO4 –H2 SO4 –MnSO4 –H2 O system
There are some difficulties involved in the electrolytic process
for the winning of manganese dioxide from H2 SO4 /Mn2+ elec-
trolytes where CaSO4 scale develops in heat exchangers, pipes
and other equipment. These processes require regular cleaning to
maintain efficient process operation. Farrah et al. [20] studied the
effect of H2 SO4 , MnSO4 and temperature on the solubility of CaSO4
hydrates over the temperature range of 30–105 ◦ C.
Fig. 8 shows their experimental solubility data along with the
predicted results obtained from the new model, which are in very
good agreement. It is obvious from the figure that dihydrate (DH)
 G. Azimi, V.G. Papangelakis / Fluid Phase Equilibria 290 (2010) 88–94 93

solubility decreases with an increase in MnSO4 concentration at
fixed H2 SO4 concentrations due to the common ion effect. Also,
there is a systematic increase in the solubility with temperature
in the presence of MnSO4 up to 80 ◦ C because of the tendency of
the sulfate ions to form bisulfate. Above 80 ◦ C, calcium sulfate sol-
ubility declines sharply as a result of dihydrate (DH) to anhydrite
(AH) transformation. It can be seen from the figure that the sol-
ubility of anhydrite is also depressed by subsequent addition of
MnSO4 .
5. Conclusions
Many industries are dealing with calcium sulfate scale for-
mation and need regular removal of precipitated calcium sulfate
hydrates. At elevated temperatures, the transformation between
the calcium sulfate phases has a complex effect on the solubility,
making the behaviour of calcium sulfate difficult to predict and
control.
In this work, a recently developed database for the MSE model
of the OLI Systems software was used to study the effect of dif-
ferent electrolytes on the CaSO4 solubility. It was found out that
it is mainly the anion which controls the solubility of calcium sul-
fate, while cations have a minor effect. The solubility behaviour
of CaSO4 is the same in all metal sulfate electrolytes with differ-
ent cations: as the metal sulfate concentration increases from pure
water, the solubility initially drops due to the common ion effect
and then increases gradually due to the formation of calcium sul-
fate neutral species. After passing a maximum, solubility decreases
smoothly with a further increase in the concentration due to the
salting-out effect and decreased number of free water molecules in
the solution.
The solubility of CaSO4 dihydrate was measured in solutions
containing NiSO4 , H2 SO4 , MgSO4 and HCl. It was found that the
solubility is significantly higher in the presence of HCl compared to
that in H2 SO4 because in the case of H2 SO4 , there is a common ion
effect due to the produced SO4 2− from the second dissociation of
H2 SO4 hindering the dissolution reaction.
Furthermore, the effect of the phase transformation of calcium
sulfate dihydrate (DH) into anhydrite (AH) on the solubility was
studied. The transformation takes place at higher temperatures
and acid concentrations and has a complex effect on the solubil-
ity. In this work, complete transformation was achieved at 70 ◦ C
after 3 days retention time in the presence of 1 M H2 SO4 . The solu-
bility of anhydrite is much lower than that of dihydrate (∼50–80%
lower); therefore process solutions which are saturated with dihy-
drate (DH) at ambient temperature and are recycled to autoclaves,
operating at temperatures above 100 ◦ C, need to be processed to
decrease their calcium content and make it less than anhydrite sat-
uration level inside an autoclave. Otherwise, scale formation will
be unavoidable.
Chemical modeling is a practical asset to map calcium sulfate
chemistry in electrolyte solutions over wide ranges of temperature
and concentration. This, in turn, results in gaining comprehensive
insight for process improvements and optimization in various pro-
cesses.
Acknowledgements
The authors would like to acknowledge the financial support
provided by Anglo American plc., Barrick Gold Corporation, OLI
Systems Inc., Sherritt International Corporation, Vale Inco Ltd., the
Ontario Graduate Scholarship (OGS) and the Natural Sciences and
Engineering Research Council of Canada (NSERC) for this project.
Appendix A. MSE middle-range interaction parameters
(OLI-version 8.1.3)

Species i Species j BMD0 BMD1 BMD2 CMD0 CMD1 CMD2 Temperature

range (◦ C)

MnSO4 –H2 O Mn2+ SO4 2− −716.157 0.9059 93031.7 255.511 – – 0–180

CaSO4 –H2 O Ca2+ SO4 2− 10887.73 −16.973 −1770400 −15416.42 24.215 2508590 0–400

Ca2+ Mn2+ 683.490 −2.0005 – −868.843 2.5173 –

CaSO4 –MnSO4 –H2 O 25–100
CaSO4(aq) Mn2+ 2134.468 −2.8306 −394938 – – –

Ca2+
Mg 2+
−2602.165 4.8761 333009 3630.73 −6.8234 −462726
CaSO4 –MgSO4 –H2 O 25–175
CaSO4(aq) Mg2+ 678.644 −1.529 −62232.5 −562.19 1.7298 –

CaSO4 –Na2 SO4 –H2 O Ca2+ Na+ 25.171 −0.0262 – −33.189 0.0210 – 25–300

Ca2+
HSO4 − 3715.460 −6.0144 −618224 −4472.033 7.3066 733093
CaSO4 –H2 SO4 –H2 O 25–300
CaSO4(aq) HSO4 − 393.149 −1.6809 11323.61 −671.232 2.5821 –

CaSO4 –CaCl2 –H2 O/CaSO4 – Cl− SO4 2− 465.363 −0.8069 −62105.4 −511.001 0.9236 64179.32
HCl–H2 O/CaSO4 –NaCl– Cl− HSO4 − −148.074 0.3573 – 176.162 −0.4188 – 22–300
H2 O/CaSO4 –MgCl2 –H2 O Cl− CaSO4(aq) 9.4550 0.0367 – −55.0627 0.02547 –

Ca2+ Ni2+ 269.924 −0.7478 97192 −1160.872 1.9865 –

CaSO4 –NiSO4 –H2 O 25–175
CaSO4(aq) Ni2+ −656.530 1.5199 – 863.322 −1.8770 –

CaSO4 –Fe2 (SO4 )3 – Ca2+ Fe3+ −172.067 −9.8085 955584 313.487 13.8038 −1362390
25–90
ZnSO4 –H2 SO4 –H2 O CaSO4(aq) Fe3+ 663.006 −1.1448 −104326 1099.014 −1.1435 −202962
94 G. Azimi, V.G. Papangelakis / Fluid Phase Equilibria 290 (2010) 88–94
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