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Solubility of Calcium Sulfate Hemihydrate in CaMgK Chloride Salt Solution at (353.0 to 371.0) K
Xiaoqin Wu,*,, Kemiao Wang, Zhiyang Xiong, and Xiaoli Ye

College of Chemical Engineering and Technology and Hubei Province Key Laboratory of Coal Conversion and New Carbon Materials, Wuhan University of Science and Technology, Wuhan 430081, China ABSTRACT: The solubility of -calcium sulfate hemihydrate in CaCl2MgCl2KCl solution at temperatures from (353.0 to 371.0) K was measured by the dissolution equilibrium method. The investigated concentration ranges of CaCl2, MgCl2, and KCl were up to (6.01, 4.50, and 0.27) m, respectively. The calcium ion demonstrates the common ion eect, which results in the decreased solubility of -calcium sulfate hemihydrate in CaCl2 solution. The solubility of -calcium sulfate hemihydrate is augmented due to the association eect caused by the formation of stable MgSO40 in MgCl2 solution. Also it is shown that potassium chloride can increase the solubility of -calcium sulfate hemihydrate slightly, which may be attributed to the salt eect. In the mixed salt solution, the solubility of -calcium sulfate hemihydrate decreases because of the dominating action of the common ion eect. Compared with the solubility of calcium sulfate dihydrate in the mixed solution, the solubility of -calcium sulfate hemihydrate is lower than that of calcium sulfate dihydrate above 363.0 K, which is benecial to the conversion of uegas-desulfurized gypsum into -calcium sulfate hemihydrate.

1. INTRODUCTION There are three main forms of calcium sulfate: calcium sulfate dihydrate (DH), calcium sulfate hemihydrate (HH), and calcium sulfate anhydrite (AH). In recent years, -HH has gained more application in the elds of precision instrument molds, ceramics, industrial arts, and architecture because of its superior workability and high strength.1 The knowledge of solubility and phase equilibrium of solid calcium sulfate in aqueous electrolyte solution is considered important in the gypsum product development. Much work had been carried out about the solubility of calcium sulfate hydrate in dierent aqueous solution systems.28 However, there has been no report of the systemic solubility data of -HH in alkali/alkaline earth metal chloride solutions in literature. -HH is becoming important in the gypsum industry because of its outstanding properties. Therefore, it is necessary to understand the basic properties of -HH for its preparation and further utilization. -HH is usually produced from DH by the methods of solid autoclaving or slurry autoclaving in industry.9 Another suitable method for the conversion of ue-gasdesulfurized gypsum (FGD gypsum) into -HH is the salt solution method at atmospheric pressure, which seems to be more attractive due to the employment of atmospheric pressure and mild transformation temperature.10,11 Hence, the acquirement of solubility data of -HH is of great signicance for the conversion of FGD gypsum into -HH in the salt solution at atmospheric pressure. We previously achieved the modication of FGD gypsum and successfully prepared -HH from DH in the hydrothermal mixed salt solution at atmospheric pressure.12,13 We also investigated the solubilities of DH in alkali/alkaline earth metal chloride solutions, that is, CaMgK chloride salt solution in temperature range of (348.0 to 371.0) K.14 The goal in our
2012 American Chemical Society

current study was to determine the solubilities of -HH in Ca MgK chloride solution at the temperature from (353.0 to 371.0) K. Moreover, by comparison of the solubilities of DH and -HH, we can have a better understanding of the conversion of FGD gypsum into -HH in the CaMgK chloride salt solution at atmospheric pressure and better control over the conversion.

2. EXPERIMENTAL SYSTEM AND METHODS

2.1. Materials and Experimental Equipment. Generally, two ways were used to determine the solubility of substances. One was the precipitation method, and the other was the isothermal dissolution equilibrium method. However, the latter was regarded more reliably because it avoided complications during precipitation. Therefore, the isothermal dissolution equilibrium method was employed to determine the solubility of -HH in the present work. Reagent-grade CaCl2, MgCl26H2O, and KCl were used to prepare the salt solutions, and ultrapure water (conductivity <0.1 scm1, prepared by UPT-I-520T) was used in all experiments. Self-made -HH12 with 96.5 % (by weight) purity has a volume mean particle size of 43 m was used in solubility measurement, which was determined by the dierential scanning calorimetry/thermo gravimetric analysis (TG-DSC analysis) shown in Figure 1. The graph in Figure 1 shows a characteristic exothermic peak at around 182.5 C of -HH with combined water content of 6.10 % (by weight).
Received: July 9, 2012 Accepted: November 30, 2012 Published: December 10, 2012
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Figure 1. TG-DSC curves for -calcium sulfate hemihydrate.

The experimental device included a 500 mL four-necked round-bottom ask for solubility determination which was equipped with a spiral condenser for vapor reux in the system to keep constant boiling point. Heat was provided by an oilbath thermostat keeping constant temperature regulated at 0.1 K adjusted according to a precise mercury thermometer. Uniform agitation of (100 to 150) rpm for the suspension was supplied by an electromagnetic stirrer. 2.2. Procedure. First, the prepared salt solution was added into the ask and then preheated to (353.0, 358.0, 363.0, 368.0, and 371.0) K according to experimental scheme that was kept constantly for half an hour. Then, 6.00 g of excess solid -HH was quickly introduced into the salt solution. After that, the mixture was kept at a constant temperature until the dissolution equilibrium process completed. During experiment, a 10 mL slurry sample was taken at dierent intervals and immediately ltered with a 0.45 m cellulose lter. A 2.00 mL clear ltrate was quantied by pipet (Gilson, P5000) and diluted with ultrapure water in a 100.00 mL volumetric ask. The solubility of -HH was expressed as CaSO4 g/100 mL solvent, based on the measured S abundance from ICP analysis (IRIS Advantage Radial, ThemoElemental). A calibrating solution was used as a standard for every set of analyses, to ensure that the analyses were accurate to within 1 %. The densities of the saturated ltrate were determined using a portable density meter (DMA 35N) from Anton Paar. The measured densities were uncertain to 0.001 gcm3. The residual solid phases were quickly washed with boiling ultrapure water three times and then with 10 mL acetone once and dried at 333.0 K in an oven for (2 to 4) h. Then, the dried solid samples were stored in a glasswaredesiccator and analyzed by DSC/TG (Netzsch STA 449 Luxx, Germany) analysis. 2.3. Determination of Equilibration Time. The equilibration time between -HH and salt solutions should be predetermined. Much work has been done to determine the equilibration time of -HH. Ling and Demopoulos7 indicated that the -HH could reach solubility equilibrium in sulfuric acid solution at 371.0 K within 5 min. Yang8 reported that 10 min was adopted as equilibration time of -HH at (353.0 to 358.0) K and 40 min for temperatures higher than 358.0 K in pure water. Li and Demopoulos5 indicated that the solubility equilibrium between solid -HH and HCl + CaCl2 solutions at the temperature range of (283.0 to 353.0) K was established within 1 h. We also studied the equilibration time in our research. It has been indicated in our previous study14 that the dissolution equilibration time of DH was 4 h. In addition, the solubility data of -HH vs time in pure water and the salt solution are shown in Figure 2, in which the error bars represent the
49

Figure 2. Equilibration time tests of -calcium sulfate hemihydrate (HH) in pure water and in salt solution: (a) in pure water at 368.0 K. (b) , in pure water at 353.0 K; , in mixed salt solution (Ca, Mg, and K chloride, total concentration = 30 %) at 353.0 K.

corresponding standard deviation. The stabilization of solubility achieved in pure water was about 5 h at 368.0 K, as shown in Figure 2a. The equilibration time experiments at 353.0 K continued for 84 h in pure water and in the mixed salt solution, shown in Figure 2b, which indicates that the solubility of -HH was stabilized after 12 h at 353.0 K. Therefore, 6 h was selected as the equilibrium time of -HH in the temperature from (363.0 to 371.0) K, and 12 h was selected at (353.0 to 358.0) K to ensure the dissolution equilibrium. 2.4. Reproducibility. The solubility data of -HH in pure water were determined to verify the reproducibility and the accuracy of the adopted procedure in this paper. The result is shown in Table 1. The data collected in this work and literature values8,15 are demonstrated in Figure 3. Three replicate measurements of -HH solubility were carried out to get the nal averaged solubility. The uncertainty of the measured solubility values is within 0.0063 g/100 mL, and the average relative deviation is 3.81 %. The solubility of -HH decreases with temperature increasing, which is mostly consistent with the tendency reported in the literatures.8,15 However, the solubility determined in this work is higher than the data in the literature, especially in the lower temperature range. The dierence in properties of -HH could be responsible for this discrepancy. -HH mentioned in the literature8 is a commercial product with 95 wt % purity prepared from natural gypsum using the processes of solid autoclaving, while -HH in this work with 96.5 wt % purity is produced from a industrial byproduct gypsum (FGD gypsum) in the mixed salt solution under atmospheric pressure. The dierence in raw materials, preparation method, and crystal growth condition would result in dierent crystal habits and properties. Therefore, there may be deviations in solubility to some degree. Also the deviations
dx.doi.org/10.1021/je300751h | J. Chem. Eng. Data 2013, 58, 4854

Journal of Chemical & Engineering Data Table 1. Solubility of -Calcium Sulfate Hemihydrate in Water
T/K s/g100 mL1 353.0 0.2001 358.0 0.1946 363.0 0.1926 371.0 0.1755 373.0 0.1643 378.0 0.1456

Article

383.0 0.1273

Figure 3. Solubility of -calcium sulfate hemihydrate (-HH) in water at dierent temperatures: , data of Hulett and Allen15 and Yang et al.;8 , this work.

are in allowable range. In this work, the solubility of -HH in water can be correlated to the temperature as following equation with a standard deviation of 0.0648 g/100 mL.
1 sCaSO4 /g100 mL = 9.6784 + 0.05603T 0.005354T 2

(1)

3. RESULTS AND DISCUSSION The solubility data of -HH in dierent salt solutions were obtained in the temperature from (353.0 to 371.0) K under atmospheric pressure. Tables 2 through 5 show the solubility data in dierent chloride salt solutions. The relationship of the solubility of -HH vs overall ionic strength is displayed in Figures 4 to 7. Thermal analysis (DSC/TG) detected no phase change under all of the above tested conditions. 3.1. Solubility of -HH in CaCl2 Solutions. Figure 4 shows the solubility of -HH in CaCl2 solution as a function of concentration of CaCl2 in the temperature from (353.0 to 371.0) K. The solubility data of -HH are listed in Table 2. The uncertainties for the values measured are 0.0004 molkg1 for solubility and 0.001 gcm3 for the density of saturated ltrate. It is clear that the solubility of -HH decreases signicantly as the concentration of CaCl2 in solution increases. The correlation of the solubility of -HH with CaCl2 concentrations could be attributed to the common ion eect of the calcium ion. Similar results have been reported.5,14 The inuence of

temperature on the solubility of -HH depends on the concentration of CaCl2 in solution. For instance, below the concentration of 1.59 m, the solubility of -HH varies obviously with temperature. The inuence of temperature on the solubility above 1.59 m is slight. Compared with the solubility of DH, the solubility of -HH is higher than DH in CaCl2 solutions. According to the theory of crystallization, DH could not been transformed into -HH in CaCl2 solutions in the investigated temperature range, which is consistent with the results in our previous study.13 3.2. Solubility of -HH in MgCl2 Solutions. The solubility of -HH was measured in MgCl2 solution from (353.0 to 371.0) K. The solubility data of -HH are given in Table 3. The uncertainties for the values measured are 0.0003 molkg1 for solubility and 0.001 gcm3 for the density of saturated ltrate. As shown in Figure 5, the solubility of -HH increases by 1 to 5-fold in MgCl2 solution compared with the solubilities in pure water. The augmentation in solubility is because the magnesium cation associates the partial sulfate ion in the form of stable MgSO40 ion pairs. The association eect of magnesium has been reported in some other literature.1620 However, the solubility of -HH decreases when the concentration of chloride magnesium solution increases further. The explanation for the decrease of solubility in more concentrated MgCl2 solution is due to the change in activity coecient. The thermodynamic equilibrium constant (Ksp) of -HH can be expressed as below:15
K sp = aCa 2+aSO4 2(a H2O)0.5 aCaSO4 0.5H2O(s)
4

= (mCa 2+Ca 2+)(mSO4 2SO 2)a H2O0.5 = mCa mSO4 Ca 2+SO 2a H2O0.5
2+ 2 4

(2)

where Ca2+ and SO42 are the activity coecients of Ca2+ and SO42, mCa2+ and mSO42 are the concentrations of Ca2+ and SO42, and aH2O is the activity of water. The activity of solid HH is set equal to 1 because the solid salt is at its standard state. According to Martynowics et al.,21 the solubility of -HH can be written as the following equation:

Table 2. Solubility of -Calcium Sulfate Hemihydrate (1) in CaCl2 (2) + H2O (3)
353.0 K m2 molkg
1

358.0 K sa m1 molkg
1

363.0 K sa gcm
3

368.0 K sa m1 molkg
1

371.0 K sa gcm
3

m1 molkg
1

m1 molkg
1

m1 molkg
1

sa gcm3 1.024 1.052 1.113 1.142 1.253 1.283 1.310

gcm

gcm

0.4742 1.0010 1.5898 2.2523 3.8610 4.8510 6.0060

a

0.0097 0.0080 0.0073 0.0057 0.0020 0.0010 0.0007

1.032 1.061 1.121 1.152 1.260 1.291 1.318

0.0098 0.0085 0.0074 0.0055 0.0016 0.0011 0.0006

1.030 1.059 1.119 1.150 1.259 1.289 1.316

0.0115 0.0110 0.0078 0.0058 0.0020 0.0009 0.0006

1.028 1.057 1.117 1.147 1.257 1.287 1.314

0.0105 0.0100 0.0078 0.0055 0.0019 0.0007 0.0005

1.025 1.054 1.114 1.144 1.254 1.285 1.312

0.0100 0.0093 0.0077 0.0054 0.0024 0.0010 0.0007

Experimental density of saturated ltrate.

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Journal of Chemical & Engineering Data Table 3. Solubility of -Calcium Sulfate Hemihydrate (1) in MgCl2 (2) + H2O (3)
353.0 K m2 molkg1 0.1061 0.2144 0.3249 0.4376 0.5528 0.6704 0.9134 1.1671 1.8536 2.6259 3.5012 4.5015
a

Article

358.0 K sa gcm3 0.997 1.006 1.015 1.023 1.031 1.037 1.069 1.086 1.108 1.154 1.202 1.258 m1 molkg1 0.0385 0.0549 0.0609 0.0676 0.0680 0.0704 0.0706 0.0702 0.0643 0.0433 0.0358 0.0187 sa gcm3 0.995 1.004 1.013 1.021 1.029 1.035 1.067 1.085 1.106 1.152 1.200 1.256 m1

363.0 K sa gcm3 0.993 1.002 1.011 1.019 1.026 1.033 1.065 1.083 1.104 1.150 1.198 1.254 m1 molkg1 0.0388 0.0625 0.0665 0.0759 0.0760 0.0772 0.0789 0.0752 0.0794 0.0537 0.0349 0.0193

368.0 K sa gcm3 0.991 1.000 1.009 1.017 1.024 1.031 1.063 1.081 1.102 1.148 1.196 1.252 m1 molkg1 0.0371 0.0584 0.0566 0.0740 0.0715 0.0703 0.0754 0.0750 0.0777 0.0536 0.0362 0.0188

371.0 K sa gcm3 0.989 0.998 1.007 1.015 1.023 1.029 1.062 1.080 1.100 1.146 1.194 1.250 molkg1 0.0364 0.0597 0.0621 0.0685 0.0661 0.0731 0.0795 0.0781 0.0825 0.0520 0.0349 0.0184

m1 molkg1 0.0383 0.0494 0.0576 0.0652 0.0672 0.0703 0.0704 0.0695 0.0629 0.0444 0.0380 0.0181

Experimental density of saturated ltrate.

Table 4. Solubility of -Calcium Sulfate Hemihydrate (1) in KCl (2) + H2O (3)
353.0 K m2 molkg
1

358.0 K sa m1 molkg
1

363.0 K sa gcm
3

368.0 K sa m1 molkg
1

371.0 K sa gcm
3

m1 molkg
1

m1 molkg
1

m1 molkg
1

sa gcm3 0.981 0.983 0.984 0.986 0.988 0.992 0.997

gcm

gcm

0.0269 0.0539 0.0810 0.1082 0.1355 0.2043 0.2737

a

0.0172 0.0179 0.0202 0.0229 0.0237 0.0282 0.0293

0.989 0.991 0.993 0.994 0.996 1.000 1.005

0.0172 0.0180 0.0197 0.0224 0.0236 0.0266 0.0289

0.987 0.989 0.990 0.992 0.994 0.998 1.003

0.0178 0.0237 0.0266 0.0289 0.0312 0.0319 0.0355

0.985 0.986 0.988 0.990 0.992 0.996 1.000

0.0173 0.0182 0.0203 0.0210 0.0256 0.0273 0.0301

0.983 0.984 0.986 0.988 0.990 0.994 0.998

0.0168 0.0179 0.0205 0.0229 0.0245 0.0252 0.0312

Experimental density of saturated ltrate.

Table 5. Solubility of -Calcium Sulfate Hemihydrate (1) in CaCl2 + MgCl2 + KCl (2) + H2O (3)
353.0 K m2 molkg1 0.4819 0.9860 1.5215 2.0843 2.6185 3.3088 4.0256 5.0578
a

358.0 K sa gcm3 1.031 1.083 1.121 1.146 1.179 1.220 1.257 1.305 m1 molkg1 0.0117 0.0099 0.0094 0.0064 0.0041 0.0025 0.0013 0.0005 sa gcm3 1.029 1.081 1.119 1.144 1.178 1.218 1.255 1.303 m1

363.0 K sa gcm3 1.027 1.079 1.117 1.142 1.176 1.216 1.253 1.302 m1 molkg1 0.0117 0.0119 0.0089 0.0063 0.0040 0.0016 0.0005 0.0004

368.0 K sa gcm3 1.025 1.077 1.115 1.140 1.174 1.214 1.251 1.300 m1 molkg1 0.0117 0.0112 0.0083 0.0054 0.0039 0.0010 0.0006 0.0005

371.0 K sa gcm3 1.023 1.076 1.114 1.139 1.172 1.213 1.250 1.299 molkg1 0.0114 0.0101 0.0080 0.0045 0.0034 0.0019 0.0003 0.0002

m1 molkg1 0.0119 0.0103 0.0095 0.0088 0.0047 0.0023 0.0015 0.0006

Experimental density of saturated ltrate.

solubility =

mCa 2+mSO4 2 =

K sp Ca 2+SO 2a H2O0.5
4

(3)

By dening B = Ca2+SO42aH2O0.5, the value of B can be estimated on the base of eq 3 combined with the solubility data of -HH in MgCl2 solution at a specic temperature. Corresponding to the maximum value of solubility of -HH, the value of B has a minimum. Therefore, the dened variable B decreases rst with solution ion strength and then increases with further addition of MgCl2. A similar relationship between the Ca2+SO42 and the solubility of calcium sulfate has been reported in KCl
51

solutions,8 HCl solutions,22 and H3PO4 solution.23 The solubility of -HH is lower than that of DH in the concentration range of (0.67 to 1.17) molkg1 (namely, (6 to 10) % by mass) when the temperature higher than 363.0 K, which indicates DH could be transformed into -HH.13 3.3. Solubility of -HH in KCl Solutions. The solubility data of -HH determined in potassium chloride solution from (353.0 to 371.0) K are listed in Table 4. The uncertainties for the values are 0.0003 molkg1 for solubility and 0.001 gcm3 for density of saturated ltrate. The curves of the solubility of -HH and DH vs KCl concentrations at dierent temperatures are plotted in Figure 6. The solubility of -HH increases with KCl concentration increasing in the whole investigated concentration range due to the salt eect. After KCl was
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Figure 4. Solubility of -calcium sulfate hemihydrate (-HH) and calcium sulfate dihydrate (DH) in calcium chloride solution: -HH: , 353.0 K; , 358.0 K; , 363.0 K; , 371.0 K; DH:14 , 358.0 K; , 363.0 K; , 371.0 K.

Figure 7. Solubility of -HH and DH in mixed salt solution: -HH: , 353.0 K; , 358.0 K; , 363.0 K; , 371.0 K; DH:14 , 353.0 K; , 358.0 K; , 363.0 K; , 371.0 K.

Figure 5. Solubility of -HH and DH in magnesium chloride solution: -HH: , 358.0 K; , 363.0 K; , 371.0 K; DH:14 , 358.0 K; , 363.0 K; , 371.0 K.

Figure 6. Solubility of -HH and DH in potassium chloride solution: -HH: , 353.0 K; , 358.0 K; , 368.0 K; , 371.0 K; DH:14 , 348.0 K; , 353.0 K; , 371.0 K.

added, the total molar concentration of ions increases, and the strong mutual action of calcium ions and sulfate ions results in activities of SO42 and Ca2+ decreasing. Therefore, precipitation in the form of CaSO40.5H2O is restrained, and the dissolution of solid -HH is improved. Then the solubility of -HH increases, which is consistent with the change trend of -HH in KCl solution when concentration lower than 2 %.8 As shown in Figure 6, the solubility of DH is lower than that of -HH when the temperature is below 371.0 K, and DH is the stable phase. This is consistent with our previous result.13
52

Clearly, there were dierent solubilities between our previous work14 and the present work with the same residual -HH solid at 371.0 K in KCl solution. In fact, the residual -HH solid was formed by dissolution and recrystallization from DH in our previous work. This transformation was a chemical process. While in present work, the solubility determination of -HH was only a physical dissolution process. Moreover, the dissolution equilibrium time of DH needs about 4 h, and the dissolution equilibrium time of -HH needs 6 h at 371.0 K in KCl solution. Therefore, the transformation of -HH from DH in our previous research14 was almost under the condition of a saturated solution of DH. So the solubility of calcium sulfate obtained in our previous work can represent DH even with the residual -HH solid. The physical dissolution of -HH can only reach to its dissolving limitation to obtain the solubility of HH in the present work. 3.4. Solubility of -HH in Ca Mg KCl Mixed Solutions (Ratio by Weight, 25:5:1). The solubility data of -HH in the mixed chloride salt solution are exhibited in Table 5. The uncertainties for the values measured are 0.0005 molkg1 for solubility and 0.001 gcm3 for density. The variations of solubility of -HH with concentrations of the mixed salt solution at dierent temperatures are illustrated in Figure 7. Figure 7 shows that the solubility of -HH decreases with the mixed salt concentration over the whole investigated concentrations. In the mixed salt solution, the coexistence of the common ion eect by calcium ion, the association eect by magnesium ion, and the salt eect by potassium chloride inuences the solubility of -HH. The common ion eect is superior to the other two eects in the mixed salt solution because of the largest portion of calcium chloride. Then the solubility of -HH decreases with the mixed salt concentration increasing but is still higher than in single calcium chloride solution due to the promoting action of the other two eects. The solubility of -HH inclines to decrease when temperature increases. When the concentration of the mixed salt solution exceeds 2.619 molkg1 (about 21.8 % by weight), and the temperature exceeds 363.0 K, the solubility of -HH is always lower than that of DH. So -HH is the thermodynamical stable phase under these conditions13 according to the crystallization theory.24 This result may explain why DH could be converted into -HH when the temperature is higher than 363.0 K and total salt concentration exceeds 20 %.12,14 3.5. Density of Calcium Sulfate-Saturated Solution. Although the chloride salt concentration and temperature have a complex inuence on the solubility of calcium sulfate in
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Journal of Chemical & Engineering Data CaCl2MgCl2KClH2O system, their impact on the density of the calcium sulfate-saturated solution is systematic, as is shown in Figure 8. The density of the calcium sulfate-saturated
Notes

Article

The authors declare no competing nancial interest.

(1) Guan, B.; Ma, X.; Wu, Z.; Yang, L.; Shen, Z. Crystallization routes and metastability of calcium sulfate hemihydrate in potassium chloride solutions under atmospheric pressure. J. Chem. Eng. Data 2009, 54, 719725. (2) Calmanovici, C.; Gabas, N.; Laguerie, C. Solubility measurements for calcium sulfate dihydrate in acid solutions at 20, 50, and 70 C. J. Chem. Eng. Data 1993, 38, 534536. (3) Yuan, T.; Wang, J.; Li, Z. Measurement and modelling of solubility for calcium sulfate dihydrate and calcium hydroxide in NaOH/KOH solutions. Fluid Phase Equilib. 2010, 297, 129137. (4) Raju, K. U. G.; Atkinson, G. The Thermodynamics of Scale Mineral Solubilities. 3. Calcium Sulfate in Aqueous NaCl. J. Chem. Eng. Data 1990, 35, 361367. (5) Li, Z.; Demopoulos, G. P. Solubility of CaSO4 phases in Aqueous HCl + CaCl2 solutions from 283 to 353 K. J. Chem. Eng. Data 2005, 50, 19711982. (6) Li, Z.; Demopoulos, G. P. Speciation-based chemical equilibrium model of CaSO4 solubility in the H + Na + Ca+ Mg + Al + Fe(II) + Cl + SO4 + H2O system. Ind. Eng. Chem. Res. 2007, 46, 63856392. (7) Ling, Y.; Demopoulos, G. P. Solubility of calcium sulfate hydrates in (0 to 3.5) molkg1 sulfuric acid solutions at 100 C. J. Chem. Eng. Data 2004, 49, 12631268. (8) Yang, L.; Guan, B.; Wu, Z.; Ma, X. Solubility and phase transitions of calcium sulfate in KCl solutions between 85 and 100C. Ind. Eng. Chem. Res. 2009, 48, 77737779. (9) Brosig, A. In Calcining Technologies for the Conversion of Fgd Gypsum into Alpha and Beta Hemihydrate Gypsum, Proceedings of the 6th International Conference on Natural and FGD Gypsum, Toronto, Ontario, Canada, May 2000; Process Research Ortech: Mississauga, Ontario, Canada, 2000; pp 26108. (10) Yang, L.; Guan, B.; Wu, Z. Characterization and precipitation mechanism of -calcium sulfate hemihydrate growing out of FGD gypsum in salt solution. Sci. China Ser. E: Technol. Sci. 2009, 52, 2688 2694. (11) Kirk, D. W.; Tong, S. Process for the production of Alpha Hemihydrate Calcium Sulfate from Flue Gas Sludge. U.S. Patent 5,562,892, Oct 8, 1996. (12) Wu, X.; Wu, Z. Modification of FGD gypsum in hydrothermal mixed salt solution. J. Environ. Sci. 2006, 18, 170175. (13) Wu, X.; Tong, S.; Guan, B.; Wu, Z. Transformation of Flue-GasDesulfurization Gypsum to -Hemihydrated Gypsum in salt solution at atmospheric pressure. Chin. J. Chem. Eng. 2011, 19, 349355. (14) Wu, X.; He, W.; Guan, B.; Wu, Z. Solubility of Calcium Sulfate Dihydrate in Ca-Mg-K Chloride Salt Solution in the Range of (348.15 to 371.15) K. J. Chem. Eng. Data 2010, 55, 21002107. (15) Hulett, G. A.; Allen, L. E. The solubility of gypsum. J. Am. Chem. Soc. 1902, 24, 667. (16) Elgquist, B.; Wedborg, M. Stability of Ion Pairs from Gypsum Solubility Degree of Ion Pair Formation between the Major Constituents of Seawater. Mar. Chem. 1975, 3, 215225. (17) Fisher, F. H.; Gieskes, J. M.; Hsu, C. C. MgSO4 Ion Association in Seawater. Mar. Chem. 1982, 11, 279283. (18) Johnson, K. S. A Comment on MgSO4 Ion Association in Seawater by Fisher, Gieskes and Hsu. Mar. Chem. 1982, 11, 285286. (19) Kester, D. R.; Pytkowicz, R. M. Theoretical Model for the Formation of Ion-pairs in Seawater. Mar. Chem. 1975, 3, 365374. (20) Glater, J.; Murdia, K. S.; Dooly, R. Calcium Sulfate Hemihydrate Scaling Threshold Enhancement by Magnesium Ion Augmentation. Desalination 1974, 14, 197207. (21) Martynowics, E. T. M. J.; Witkamp, G. J.; Van Rosmalen, G. M. The effect of aluminium fluoride on the formation of calcium sulfate hydrates. Hydrometallurgy 1996, 41, 171186. (22) Li, Z.; Demopoulos, G. P. Development of an improved chemical model for the estimation of CaSO4 solubilities in the HClCaCl2-H2O system up to 100 C. Ind. Eng. Chem. Res. 2006, 45, 2914.
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REFERENCES

Figure 8. Density of calcium sulfate-saturated CaCl2MgCl2KCl solutions at dierent temperatures: , 0.4819 molkg1; , 0.9860 molkg1; , 1.5215 molkg1; , 2.0843 molkg1; , 2.6185 molkg1; , 3.3088 molkg1; , 4.0256 molkg1; , 5.0578 molkg1.

solutions increases systematically with the mixed salt concentration increasing. For a given mixed salt concentration, the density decreases in a nearly linear manner with temperature increasing in the whole range of the mixed salt concentrations. A very similar dependence of the density on chloride salt solution concentration and temperature is found in single CaCl2 solution, MgCl2 solution, and KCl solution, as shown in Tables 2 to 4. That is, the density of calcium sulfate-saturated is inuenced predominantly by the concentration of the chloride salt solution and temperature and is nearly not aected by the dissolved calcium sulfate. A similar relationship between the density of calcium sulfate-saturated and the salt solution concentration as well as temperature was reported by Dutrizac and Kuiper.25,26

4. CONCLUSIONS Solubilities of the -HH in CaCl2MgCl2KCl solution from (353.0 to 371.0) K were investigated. It has been found that the solubility of -HH is inuenced by three actions such as the common ion eect by calcium ion, the association eect by magnesium ion, and the salt eect by potassium chloride. Of the investigated system, the common ion eect inuences the solubility of -HH very much, the association eect less, and the salt eect the least. The solubility of -HH decreases with the mixed salt concentration increasing because of the strongest common ion eect of calcium ion. In the mixed salt solution, the solubility of -HH is lower when the concentration of the mixed salt solution exceeds 2.619 molkg1 and the temperature exceeds 363.0 K, which conrms the feasibility of conversion into -HH from DH.

AUTHOR INFORMATION

Corresponding Author

*Phone: +86-13657202189. Fax: +86-27-86556906. E-mail: leafwu205@yahoo.com.cn.

Funding

This work was supported by the Hi-Tech Research and Development Program (863 Program) of China (No. 2006AA06Z385).

Journal of Chemical & Engineering Data

(23) Messnaoui, B.; Bounahmidi, T. On the modeling of calcium sulfate solubility in aqueous solutions. Fluid Phase Equilib. 2006, 244, 117. (24) Mullin, J. W. Crystallization, 3rd revised ed.; Butterworth Heinemann: London, 1997. (25) Dutrizac, J. E.; Kuiper, A. The solubility of calcium sulphate in simulated nickel sulphatechloride processing solutions. Hydrometallurgy 2006, 82, 1331. (26) Dutrizac, J. E.; Kuiper, A. The solubility of calcium sulphate in simulated copper sulphate electrorefining solutions. Hydrometallurgy 2008, 92, 5468.

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dx.doi.org/10.1021/je300751h | J. Chem. Eng. Data 2013, 58, 4854