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Thermodynamic equilibrium of CaSO4-Ca(OH)2-H2O system

PENG Xiao-yu(彭小玉), WANG Yun-yan(王云燕), CHAI Li-yuan(柴立元), SHU Yu-de(舒余德)
School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China
Received 18 January 2008; accepted 13 May 2008

Abstract: The pc—pH diagrams of the CaSO4-Ca(OH)2-H2O system and its two subsystems at 298.15 K were constructed according
to the theory of thermodynamic equilibrium. The interaction characteristics between the solubility of CaSO4(s) and Ca(OH)2(s) can be
found out from the diagrams. CaSO4(s), Ca(OH)2(s) and solution coexist when the pH value of solution is about 13.2. CaSO4(s) with
the minimum solubility of 0.411 g/L is in equilibrium with solution when the pH value is lower than 13.2, and Ca(OH)2(s) with the
minimum solubility of 2.749 g/L is in equilibrium with solution at the pH value over 13.2, which provides a theoretical basis for the
treatment and reuse of industrial wastewater, especially for the wastewater containing sulfate which can be treated by lime-milk
neutralization.
Key words: CaSO4-Ca(OH)2-H2O system; solubility; pc—pH diagram

CaSO4(s) and Ca(OH)2(s) could be found out, was
1 Introduction constructed according to the thermodynamic equilibrium
principle.
Large amounts of acidic sulfate wastewater
containing heavy metals are discharged every year from 2 Drawing of thermodynamic equilibrium
the sulfate system in a number of industries such as diagram
electroplating, steel pickling, mining, nonferrous
smelting and alkali making[1−4]. Now the lime-milk 2.1 Thermodynamic relationship between Ca(OH)2(s)
neutralization process is a conventional technique solubility and pH value
contributing to its advantages such as low investment, There are two kinds of calcium hydroxyl complex
mature technique, simple and convenient operation[5−6]. ions in Ca(OH)2-H2O system such as CaOH+ and
However, the purified water treated by such method Ca(OH)2. Correspondingly, their equilibrium equations
results in a series of problems which would influence the and cumulative formation constants at 298.15 K are
purification and reutilization of industrial wastewater for expressed as follows[11−14]:
the high concentration of calcium ion and sulfate ion[7]. Ca2++OH− CaOH+
Some related research works have been done and it was
[CaOH + ]
pointed out that it is feasible to separate CaSO4 β1 = = 101.4 (1)
[Ca 2+ ][OH − ]
precipitates from Na2SO4-H2O system in addition of
CaO[8−10], but the theoretical analysis concerned has Ca2++2OH− Ca(OH)2
not been reported in the literature up to now.
[Ca(OH) 2 ]
In this study, aiming at promoting and realizing the β2 = = 10 3.83 (2)
reuse and recycling of acidic sulfate wastewater treated [Ca 2+ ][OH − ] 2
by the lime-milk neutralization, the pc—pH diagram of Knowing that:
the CaSO4-Ca(OH)2-H2O system at 298.15 K, as a Ca(OH)2(s) Ca2++2OH−
theoretical guidance for the practical process, where the
Ksp=[Ca2+][OH−]2=5.5×10−6 (3)
interaction characteristics between the solubility of

Foundation item: Project(2007BAC25B01) supported by the National Key Project of Scientific and Technical Supporting Programs Funded by Ministry of
Science and Technology of China during the 11th Five-year Plan
Corresponding author: WANG Yun-yan; Tel: +86-731-8830875; E-mail: wyy@mail.csu.edu.cn.
DOI: 10.1016/S1003-6326(08)60260-5

Nonferrous Met.0. Inserting Eq.92 (16) [HSO −4 ] exist stably.(10).749 g/L as the pH value is located at sulfate.(1) and Eq.(11) gives K 1′ K 2′ [Ca 2+ ] = [Ca ] t (1 + + ) −1 (14) [H + ] [H + ] 2 Sulphuric acid is a diprotic acid. their ionization equations and equilibrium constants are expressed as follows[11]: Fig. et al/Trans.43 (8) The mass balance for calcium in solution is[16] The concentrations of [Ca2+].1 Diagram of pc—pH of Ca(OH)2-H2O system at 298. pc—pH diagram of the Ca(OH)2-H2O system at 298. [S]t represents the total concentration of Ca(OH)2(s) is 2. [CaOH+] and [Ca]t=[Ca2+]+[CaOH+]+[Ca(OH)2] (11) [Ca(OH)2] can be calculated by Eqs.14 (7) [Ca 2+ ] p[Ca(OH)2]=1.2 Thermodynamic relationship between CaSO4(s) from Eq.74 (6) [Ca(OH) 2 ][H + ] 2 K 2′ = = 10 − 24.1 represent the concentrations of K a1 = = 103 (15) [H 2SO 4 ] different calcium-containing species related to the pH values when the corresponding ions are in equilibrium H SO −4 SO 24− + H + with Ca(OH)2(s). the following equations can be deduced: K1′ [CaOH + ] = + [Ca 2 + ] (12) [H ] K 2′ [Ca(OH) 2 ] = [Ca 2 + ] (13) [H + ]2 Inserting Eq.15 K. which may yield two protons. their equilibrium equations and cumulative formation constants at 298. China 19(2009) 249−252 The following equation and constant can be obtained 2.86 (4) Ca(OH)2. The area surrounded by all lines is the [SO 24− ][H + ] stable zone of Ca(OH)2(s).15 K H 2SO4 HSO 4− + H + [HSO −4 ][H + ] The lines in Fig. The others are the unsaturated zones of Ca(OH)2(s).(13) into Eq.(9) and Eq.6 (9) [Ca 2+ ] Taking logarithm of both sides of Eqs.(6)−(8) at given pH It should be noted that the [Ca]t. which is the as the solubility of calcium.1[16−18]. These values as functions of pH the total soluble concentration of calcium.(3) gives expressed as follows: the following equation and constant: Ca2++H2O CaOH++H+ Ca(OH)2(s) Ca(OH)2 [CaOH + ][H + ] K s2 = K sp ⋅ β 2 = [Ca(OH) 2 ] = 10 −1.1−14. which represents value. in which Ca(OH)2(s) could Ka2 = = 10 −1.250 PENG Xiao-yu. From Fig.(3)[15]: solubility and pH value There also exist two kinds of calcium hydroxyl Ca(OH)2(s) CaOH++OH− complex ions in CaSO4-H2O system such as CaOH+ and K s1 = K sp × β1 = [CaOH + ][OH − ] = 10 −3.(16) into Eq.(17) gives 12.1 it can also be seen that the minimum solubility of Similarly. respectively. From Eq. Soc.(15) and Eq. Correspondingly. combination of Eq. beyond this scope the solubility of Ca(OH)2(s) [H + ] [H + ] 2 −1 will increase gradually with the pH value declining.(12) and Eq. is also termed values are plotted as shown in Fig. Correspondingly.(3)−(5) gives Ca2++2H2O Ca(OH)2+2H+ p[Ca2+]=2pH−22.(2) and Eq. Boundaries constituting this stable zone can The mass balance for sulfate in solution is approximately illustrate the total solubility of Ca(OH)2(s) [S] t = [SO 24− ] + [ HSO −4 ] + [H 2 SO 4 ] (17) at the different pH values in the system.17 (10) + p[CaOH ]=pH−10.43 (5) K 1′ = = 10 −12.15 K are Similarly. [SO 24− ] = [S] t (1 + + ) (18) K a2 K a1 K a 2 .

0. et al/Trans. Ca(OH)2 is system. triple point (13. And the solid line represents the total equilibrium concentration of calcium at different pH values.1[16−18].2 represents the total concentration concentration of the sulfate retains its original of calcium-containing species related to the pH value concentration as the solubility of Ca(OH)2(s) keeps a when the solution is in equilibrium with CaSO4(s).1 × 10 −6 (19) Inserting Eq.3 it The interaction characteristics between the solubility of can be concluded that the stable zones of Ca(OH)2(s) and CaSO4(s) and Ca(OH)2(s) can be found out from CaSO4(s) overlap partially.5−11.3 Fig.2 Diagram of pc—pH of CaSO4-H2O system at 298. combination of Fig.15 K are constructed CaSO4-Ca(OH)2-H2O system (Fig. Nonferrous Met. where CaSO4(s) could exist stably. and CaSO4(s) dissolves and Ca(OH)2 precipitation occurs. However. Fig. The area above the solid line is the stable zone where the corresponding precipitates exist at different pH values.3 also indicates that Ca(OH)2(s) dissolves into is the unsaturated zone.0.3 Diagram of pc—pH of CaSO4-Ca(OH)2-H2O system at sulfate in the system according to calcium sulfate 298. solubility of CaSO4(s) increases.2[16].(18) into Eq. are in equilibrium with the solution simultaneously. The equilibrium equation and the solubility-product constant are expressed as follows: CaSO4 Ca2++ SO 24 − K sp = [Ca 2+ ][SO 24− ] = 9.3) is constructed by according to the theory of thermodynamic equilibrium. beyond this scope the point. and below the curve Fig. Reversely.15 K also shows that the minimum solubility of CaSO4(s) is 0.411 g/L preponderance at the pH value over the triple equilibrium at the pH value of 3. and the dash line vertical to the pH axis from point a represents that both CaSO4(s) and Ca(OH)2(s) coexist at this pH value. . and the pc—pH diagram of the CaSO4-H2O system can be obtained according to Eq. The constant of 2.749 g/L at the pH value over that of the area above the curve is the stable zone of CaSO4(s).411 g/L at the pH values of 3. and Ca(OH)2(s) dissolves into the solution and CaSO4 precipitates. where the solubility of CaSO4(s) is less than that of Ca(OH)2(s). The area on the right of the dash line is the stable zone of Ca(OH)2(s).(19) gives K 1′ K1′ K sp = [Ca] t (1 + + ) −1 ⋅ [H + ] [H + ] 2 [H + ] [H + ] 2 −1 [S] t (1 + + ) (20) Ka2 K a1 K a 2 The total concentration of calcium is equal to that of Fig.(14) and Eq. it does dissolve slightly in water.2 and Fig. The point a represents the diagrams. Soc.2). China 19(2009) 249−252 251 Calcium sulfate is considered to be insoluble commonly.5−11. The area on the left of the dash line is the stable zone of CaSO4(s).(20) triple equilibrium point where CaSO4(s) and Ca(OH)2(s) as shown in Fig. 3 Conclusions 2. while the area below the solid line is the unsaturated zone where solution exists stably. From Fig.3 Thermodynamic equilibrium diagram of CaSO4- Ca(OH)2-H2O system 1) The pc—pH diagrams of CaSO4-Ca(OH)2-H2O The thermodynamic equilibrium diagram of the system and its subsystem at 298. PENG Xiao-yu. and the The curve in Fig. Boundary constituting this stable the solution and CaSO4 precipitates in the ternary system zone can approximately illustrate the total solubility of located on the equilibrium line at the pH value below the CaSO4(s) at different pH values in the CaSO4-H2O triple equilibrium point. The minimum solubility of CaSO4(s) is 0.15 K ionization equation.

(in Chinese) trans. Application of acidic waste water after treatment (Edited by LI Xiang-qun) in non-ferrous hydrometallurgical enterprise [J]. 2003. Nonferrous Met. Thermodynamic principles and calculation of large smelters in china [J]. 2004(5): 18−20. J Wuhan Univ (Nat Sci Ed). trans.252 PENG Xiao-yu. 103−110. protactinium. Selected values of chemical [3] WANG Hua. Mining and Metallurgy. FU Bian-hong. actinium. (in Chinese) [14] WAGMAN. Rare Metals and Cemented Carbides. while the solution is in equilibrium [9] LONG Cheng-ming. HU Yao-hong. 9(2): 84−88. 20(4): 34−36. 838−901.749 g/L Chinese) at the pH value over 13. metallurgical solution [M]. CaSO4(s). 2007. 2003: 623−765.2. 2003. Theory and practice of heavy metal industrial wastewater [18] ZHENG Qing-kou. 2000(5): 10−11. 2004. 19(2): 46−48. XIE Tao. In the solution equilibrated with system (PartⅡ): Reaction thermodynamics [J]. [10] SUN Xiao-chun. Inorganic chemistry [M]. Washington: performance from trivalent chromium sulfate electrolyte [J]. China Chlor-Alkali. Beijing: Irrigation and 50(2): 187−191. Study on the process of thick chromium plating and coating thorium. Survey on treatment of acidic wastewater from [17] FU Chong-shuo. LIU Hao. Chemical equilibrium in silicate pH value of about 13. 1965: 121−165. Journal of Materials Protection. Department of Commerce. (in Chinese) [1] WANG Guang-xing. Aquatic chemistry [M]. (in Chinese) value below 13. Guo-dong. Nai-liang. DONALD D. SO42− content [J]. (in Chinese) References [11] YAO Yun-bin. SO42− disposal process by calcium method [J]. 1991: 9−1−9−25. ZHAO Guo-peng. China Chlor-Alkali. Soc. Study of electroplating with trivalent 34(2): 35−39. YU Zi-jian. 84−97. 2006(1): 44−48. the minimum solubility is 0. (in Chinese) [15] SUN Fang.2. Ca(OH)2(s) and solution coexist at the [8] MA Hong-wen. 26(6): 13−17. GAO Ying-min. HU Zhong-ming. [16] CHEN Shao-yan. Beijing: Metallurgical Industry Press. 1989: 58−72. Beijing: China Industry treatment recycle [J]. Beijing: Science Press. ZHAO Zhong-wei. Energy Saving of Non-ferrous Metallurgy. PENG Hui. 2006. CHENG of copper from sulfate bath [J]. Hunan Nonferrous Metals. 2000. Experiment of sulfate disposal by calcium chloride [J]. (in Chinese) [7] WANG Xiang-ping. Handbook of chemistry and physics [M]. Beijing: Science Press. (in Chinese) 1989: 215−243. ZUO Zheng-zhong. (in Chinese) . WANG Fang. KANG Jian-qiang.2. and the alkali metals [M]. (in with Ca(OH)2(s) and its minimum solubility is 2. YANG Ming-li. Lange’s chemistry handbook [M]. (in Chinese) chromium in sulfate system [J]. (in Chinese) Electrics Press. WANG Ying-bin. Geoscience. ZENG Zhen-ou. thermodynamic properties: Compounds of uranium. Shanghai: Shanghai Scientific and Technical Publishers. ZHAO Guo-peng. Thermodynamic analysis on calcium [4] WU Hui-min. Thermochemical data of pure substances [M]. Progress in electroplating [13] IHSAN B. 1985: 777−784. GUO Lian-cai. China Chlor-Alkali. SU Shuang-qing. et al/Trans. SHANG Jiu-fang. 1981: 152−156. (in Chinese) [5] WANG Xin-wen. China 19(2009) 249−252 2) CaSO4(s). Effective method of control [12] JOHN A D. 2006. 2006(1): 6−7. 812−817. (in Chinese) [6] LI Ying. Electroplating & Finishing. (in Chinese) [2] GU Min.411 g/L at the pH 20(3): 386−398. Press. LIANG phosphate system [J].