NaBr-CaBr2-H2O和KBr-CaBr2-H2O三元体系273.15 K相平衡实验及计算

doi:10.11949/0438-1157.20210189

化工学报 ›› 2021, Vol. 72 ›› Issue (9): 4479-4486.DOI: 10.11949/0438-1157.20210189

NaBr-CaBr₂-H₂O和KBr-CaBr₂-H₂O三元体系273.15 K相平衡实验及计算

张学平^1,²(),崔瑞芝³,桑世华¹()

^1.成都理工大学材料与化学化工学院，四川成都 610059
^2.四川文理学院化学化工学院，四川达州 635000
^3.中国科学院青海盐湖研究所，中国科学院盐湖资源综合高效利用重点实验室，青海西宁 810008

收稿日期:2021-01-31 修回日期:2021-07-16 出版日期:2021-09-05 发布日期:2021-09-05
通讯作者: 桑世华
作者简介:张学平(1992—)，男，博士研究生，1519188046@qq.com
基金资助:
国家自然科学基金项目(41873071);青海省自然科学基金项目(2020-ZJ-970Q)

Experiment and calculation of phase equilibrium in ternary systems NaBr-CaBr₂-H₂O and KBr-CaBr₂-H₂O at 273.15 K

Xueping ZHANG^1,²(),Ruizhi CUI³,Shihua SANG¹()

^1.College of Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, Sichuan, China
^2.College of Chemical & Chemical Engineering, Sichuan University of Arts and Science, Dazhou 635000, Sichuan, China
^3.Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, Qinghai, China

Received:2021-01-31 Revised:2021-07-16 Online:2021-09-05 Published:2021-09-05
Contact: Shihua SANG

摘要/Abstract

摘要：

采用等温溶解平衡法对两个三元体系NaBr-CaBr₂-H₂O和KBr-CaBr₂-H₂O在273.15 K下的固液相平衡关系进行了研究，测定了相关盐在水溶液中的溶解度，绘制其等温相图。结果表明，两个三元体系均为水合物型，即平衡固相中未发现任何复盐及固溶体。两个三元体系在273.15 K下的等温相图均由一个共饱点、两条等温溶解度曲线、两个平衡固相结晶区组成。三元体系NaBr-CaBr₂-H₂O在273.15 K的两个结晶区的平衡固相分别为NaBr·2H₂O和CaBr₂·6H₂O，NaBr·2H₂O的结晶区远大于CaBr₂·6H₂O。三元体系KBr-CaBr₂-H₂O在273.15 K的两个结晶区的平衡固相分别为KBr和CaBr₂·6H₂O，KBr的结晶区远大于CaBr₂·6H₂O。基于Pitzer模型，运用已报道的Pitzer参数对所研究的两个三元体系在273.15 K下的等温溶解度进行模拟计算，其计算结果与实验结果基本吻合。

关键词: 相平衡, 溶解度, 溴化钙, Pitzer模型

Abstract:

The relationship of solid-liquid phase equilibrium in the two ternary systems NaBr-CaBr₂-H₂O and KBr-CaBr₂-H₂O were conducted at 273.15 K by using the isothermal dissolution equilibrium method. The results show that the two ternary systems are of hydrate type. That is, there is absence for double salt and solid solution identified in the equilibrium solid phase. The isothermal phase diagrams of the two ternary systems NaBr-CaBr₂-H₂O and KBr-CaBr₂-H₂O at 273.15 K are composed of an invariant point, two isothermal dissolution curves, and two equilibrium solid phase crystallization regions. The equilibrium solid phases of the ternary system NaBr-CaBr₂-H₂O in the two crystallization regions at 273.15 K are NaBr·2H₂O and CaBr₂·6H₂O, respectively, and the crystallization region of NaBr·2H₂O is much larger than that of CaBr₂·6H₂O. The equilibrium solid phases of the ternary system KBr-CaBr₂-H₂O in the two crystalline regions at 273.15 K are KBr and CaBr₂·6H₂O, respectively, and the crystalline region of KBr is much larger than CaBr₂·6H₂O. Based on the Pitzer model, the reported Pitzer parameters are used to calculate the isothermal solubility of the two ternary systems studied at 273.15 K, and the calculated results are basically consistent with the experimental results.

Key words: phase equilibrium, solubility, calcium bromide, Pitzer model

中图分类号:

O 642

张学平, 崔瑞芝, 桑世华. NaBr-CaBr₂-H₂O和KBr-CaBr₂-H₂O三元体系273.15 K相平衡实验及计算[J]. 化工学报, 2021, 72(9): 4479-4486.

Xueping ZHANG, Ruizhi CUI, Shihua SANG. Experiment and calculation of phase equilibrium in ternary systems NaBr-CaBr₂-H₂O and KBr-CaBr₂-H₂O at 273.15 K[J]. CIESC Journal, 2021, 72(9): 4479-4486.

参考文献 28

1	林耀庭, 陈绍兰. 四川盆地地下卤水勘探开发前景展望[J]. 盐湖研究, 2008, 16(1): 1-7, 21.
	Lin Y T, Chen S L. Exploration and development prospect of underground brine in Sichuan basin[J]. Journal of Salt Lake Research, 2008, 16(1): 1-7, 21.
2	林耀庭. 我国卤水溴资源及其开发前景展望[J]. 盐湖研究, 2000, 8(2): 59-67.
	Lin Y T. Bromine resource in brines and its exploitation prospect[J]. Journal of Salt Lake Research, 2000, 8(2): 59-67.
3	张杰, 史学伟, 赵双良, 等. 水盐体系相平衡研究进展[J]. 化工学报, 2016, 67(2): 379-389.
	Zhang J, Shi X W, Zhao S L, et al. Progress in study on phase equilibria of salt-water systems[J]. CIESC Journal, 2016, 67(2): 379-389.
4	Christov C. Temperature variable chemical model of bromide-sulfate solution interaction parameters and solid-liquid equilibria in the Na-K-Ca-Br-SO₄-H₂O system[J]. Calphad, 2012, 36: 71-81.
5	Christov C. Study of bromide salts solubility in the (m₁KBr + m₂CaBr₂)(aq) system at T = 323.15 K. Thermodynamic model of solution behaviour and (solid + liquid) equilibria in the ternaries (m₁KBr + m₂CaBr₂)(aq), and (m₁MgBr₂ + m₂CaBr₂)(aq), and in the quinary (Na + K + Mg + Ca + Br + H₂O) systems to high concentration and temperature[J]. The Journal of Chemical Thermodynamics, 2012, 55: 7-22.
6	Meng L Z, Li D, Deng T L, et al. Measurement and thermodynamic modeling study on the solid and liquid equilibrium of ternary system NaBr-CaBr₂-H₂O at 288.15 K[J]. Journal of Chemical & Engineering Data, 2014, 59(12): 4193-4199.
7	Hu J X, Sang S H, Liu Q Z. Solid-liquid equilibria in the ternary systems KBr-CaBr₂-H₂O and NaBr-CaBr₂-H₂O at 348 K[J]. Journal of Chemical & Engineering Data, 2015, 60(4): 993-998.
8	Cui R Z, Wang W, Yang L, et al. Phase diagram of quaternary system NaBr-KBr-CaBr₂-H₂O at 323 K[J]. Russian Journal of Physical Chemistry A, 2018, 92(3): 475-481.
9	Kartzmark E M. Solubilities in the system indium tribromide - sodium bromide-water at 25 ℃[J]. Canadian Journal of Chemistry, 1976, 54(12): 1884-1885.
10	Donchev S, Ismailov I, Parushev I, et al. Solubility in the NH₄Br-CaBr₂-H₂O system at T = (298.15 and 323.15) K[J]. Research Journal of Pharmaceutical, Biological and Chemical Sciences, 2019, 10(5): 83-88.
11	Chernykh L V, Eysseltova J, Skripkin M Y. Solubility and ionic processes in the CuX₂-MX-H₂O (X^-=Cl^-, Br^-; M⁺=Li⁺, Na⁺, K⁺, NH₄⁺, Cs⁺) systems[J]. Monatshefte Für Chemie / Chemical Monthly, 2003, 134(5): 751-761.
12	Gusev I M, Skripkin M Y. Comparative analysis of the solubility in the systems CuBr₂-NR₄Br-H₂O at 25 ℃[J]. Russian Journal of Applied Chemistry, 2009, 82(2): 222-227.
13	Zhang X P, Wang W, Zhang H Z, et al. Solid-liquid phase equilibria in the ternary system CaBr₂-SrBr₂-H₂O at 273, 298, and 323 K[J]. Journal of Chemical & Engineering Data, 2021, 66(1): 138-145.
14	林耀庭, 姚有成, 康正华, 等. 四川宣达盐盆富钾富矿卤水地球化学特征及资源意义研究[J]. 盐湖研究, 2004, 12(1): 8-18.
	Lin Y T, Yao Y C, Kang Z H, et al. Study on the geochemical characteristics and resource significance of the highly mineralized potassium-rich brine in the Sichuan Xuanda salt basin[J]. Journal of Salt Lake Research, 2004, 12(1): 8-18.
15	巩学敏, 张嘉勇, 曹吉林. Na₂SO₄-MgSO₄-(NH₄)₂SO₄-H₂O四元体系相图研究及其应用[J]. 工业安全与环保, 2016, 42(7): 94-97.
	Gong X M, Zhang J Y, Cao J L. Study on the phase diagram of Na₂SO₄-MgSO₄-(NH₄)₂SO₄-H₂O system and their application[J]. Industrial Safety and Environmental Protection, 2016, 42(7): 94-97.
16	Haynes W M. CRC Handbook of Chemistry and Physics[M]. 97th ed. CRC Press, 2016.
17	Gao Y Y, Qi X Y, Sang S H, et al. Measurements and theoretical simulations of phase equilibria in the quaternary systems NaBr + KBr + SrBr₂ + H₂O, NaBr + MgBr₂ + SrBr₂ + H₂O and their subsystems at 273.15 K[J]. Fluid Phase Equilibria, 2020, 522: 112763.
18	Ye C, Wu Z Z, Sang S H, et al. Solid-liquid phase equilibria of ternary system KBr-LiBr-H₂O at 273 and 308 K[J]. Journal of Chemical & Engineering Data, 2019, 64(12): 5288-5294.
19	Cui R Z, Sang S H, Li D W, et al. Measurements and calculations of solid-liquid equilibria in the quaternary system NaBr-KBr-CaBr₂-H₂O at 298 K[J]. Calphad, 2015, 49: 120-126.
20	Christov C. Isopiestic investigation of the osmotic coefficients of aqueous CaBr₂ and study of bromide salt solubility in the NaBr-CaBr₂-H₂O system at 50 ℃: thermodynamic model of solution behavior and solid-liquid equilibria in the CaBr₂-H₂O, and NaBr-CaBr₂-H₂O systems to high concentration and temperature[J]. Calphad, 2011, 35(1): 42-53.
21	Krumgalz B S. Application of the Pitzer ion interaction model to natural hypersaline brines[J]. Journal of Molecular Liquids, 2001, 91(1/2/3): 3-19.
22	Keller A, Burger J, Hasse H, et al. Application of the Pitzer model for describing the evaporation of seawater[J]. Desalination, 2021, 503: 114866.
23	Cui R Z. Solubility measurement and prediction of phase equilibria in the quaternary system LiCl + NaCl + KCl + H₂O and ternary subsystem LiCl + NaCl + H₂O at 288.15 K[J]. Chinese Journal of Chemical Engineering, 2020, 28(8): 2137-2141.
24	Harvie C E, Møller N, Weare J H. The prediction of mineral solubilities in natural waters: the Na-K-Mg-Ca-H-Cl-SO₄-OH-HCO₃-CO₃-CO₂-H₂O system to high ionic strengths at 25℃[J]. Geochimica et Cosmochimica Acta, 1984, 48(4): 723-751.
25	Pitzer K S. Thermodynamics of electrolytes (I): Theoretical basis and general equations[J]. The Journal of Physical Chemistry, 1973, 77(2): 268-277.
26	Christov C. An isopiestic study of aqueous NaBr and KBr at 50 ℃: chemical equilibrium model of solution behavior and solubility in the NaBr-H₂O, KBr-H₂O and Na-K-Br-H₂O systems to high concentration and temperature[J]. Geochimica et Cosmochimica Acta, 2007, 71(14): 3557-3569.
27	Møller N. The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-Ca-Cl-SO₄-H₂O system, to high temperature and concentration[J]. Geochimica et Cosmochimica Acta, 1988, 52(4): 821-837.
28	Christov C, Møller N. A chemical equilibrium model of solution behavior and solubility in the H-Na-K-Ca-OH-Cl-HSO₄-SO₄-H₂O system to high concentration and temperature[J]. Geochimica et Cosmochimica Acta, 2004, 68(18): 3717-3739.

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NaBr-CaBr₂-H₂O和KBr-CaBr₂-H₂O三元体系273.15 K相平衡实验及计算

Experiment and calculation of phase equilibrium in ternary systems NaBr-CaBr₂-H₂O and KBr-CaBr₂-H₂O at 273.15 K

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