三元体系K~+,Cs~+∥SO_4~(2-)-H_2O 298.2 K稳定相平衡研究
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摘要
采用等温溶解法开展了三元体系K~+,Cs~+∥SO_4~(2-)-H_2O 298.2 K稳定相平衡研究,测定了该体系溶解度、密度及折光率。结果表明,该三元体系在298.2 K下属于复杂体系,有固溶体(K,Cs)_2SO_4产生,且固溶体相区最大;其稳定相图包含3条单变量曲线、3个析出相区和2个共饱点;共饱点处对应的液相组成分别为w(K_2SO_4)=11.69%、w(Cs_2SO_4)=4.02%和w(K_2SO_4)=3.39%、w(Cs_2SO_4)=60.84%。平衡液相的密度和折光率随Cs_2SO_4含量的增大呈现递增的趋势。采用经验公式对平衡液相的折光率进行理论计算,计算值和实验值具有良好的一致性。
The stable phase equilibrium of the ternary system K~+,Cs~+∥SO_4~(2-)-H_2O has been studied using the isothermal dissolution method at 298.2 K.The solubilities,densities and refractive indices of the equilibrated solution were determined experimentally.The results showed that the ternary system was of complex type with solid solution [(K,Cs)_2SO_4] formed at 298.2 K,and with the largest crystalline region for the solid solution [(K,Cs)_2SO_4].The stable phase diagram of this ternary system contained three univariant curves,three crystalline zones and two invariant points.The mass fraction composition of the two invariant points were w(K_2SO_4) 11.69% 、w(Cs_2SO_4) 4.02% and w(K_2SO_4) 3.39% 、w(Cs_2SO_4) 60.84%,respectively.The density and refractive index of the solution increased along with the increase of the Cs_2SO_4 contents.Furthermore,the empirical equation developed in the previous study was used to calculate refractive index of the equilibrated solutions,the calculated values results indicated good consistency with the experimental values.
The stable phase equilibrium of the ternary system K~+,Cs~+∥SO_4~(2-)-H_2O has been studied using the isothermal dissolution method at 298.2 K.The solubilities,densities and refractive indices of the equilibrated solution were determined experimentally.The results showed that the ternary system was of complex type with solid solution [(K,Cs)_2SO_4] formed at 298.2 K,and with the largest crystalline region for the solid solution [(K,Cs)_2SO_4].The stable phase diagram of this ternary system contained three univariant curves,three crystalline zones and two invariant points.The mass fraction composition of the two invariant points were w(K_2SO_4) 11.69% 、w(Cs_2SO_4) 4.02% and w(K_2SO_4) 3.39% 、w(Cs_2SO_4) 60.84%,respectively.The density and refractive index of the solution increased along with the increase of the Cs_2SO_4 contents.Furthermore,the empirical equation developed in the previous study was used to calculate refractive index of the equilibrated solutions,the calculated values results indicated good consistency with the experimental values.
引文
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[2]黄万抚,李新冬.铯的用途与提取分离技术研究现状[J].稀有金属与硬质合金,2003,31(3):18-20.
[3]董普,肖荣阁.铯盐应用及铯(碱金属)矿产资源评价[J].中国矿业,2005,14(2):30-34.
[4]Merbach A,Gonella J.Contributionàl′étude du système quaternaire KCl-RbCl-H2O:Ⅰ.Les isothermes de 25°des systèmes ternaires limites[J].Helvetica Chimica Acta,1969,52(1):69-76.
[5]Merbach A,Gonella J.Contributionàl′étude du système quaternaire KCl-RbCl-CsCl-H2O:Ⅱ.L′isotherme de 25℃[J].Helvetica Chimica Acta,1971,54(5):1380-1389.
[6]Yu X,Zeng Y,Yao H,et al.Metastable phase equilibria in the aqueous ternary systems KCl+MgCl2+H2O and KCl+RbCl+H2O at298.15 K[J].Journal of Chemical&Engineering Data,2011,56(8):3384-3391.
[7]宝阿敏,钱志强,郑红,等.铷、铯的分离提取方法及其研究进展[J].应用化工,2017,46(7):1377-1382.
[8]汪傲,赵元艺,许虹,等.青藏高原盐湖资源特点概述[J].盐湖研究,2016,24(3):24-29.
[9]郑绵平,侯献华.青海盐湖资源综合利用与可持续发展战略[J].科技导报,2017,35(12):11-13.
[10]冯凯,孙亚猛,袁梦,等.以盐湖高含泥提钾尾矿制备微孔分子筛的研究[J].无机盐工业,2018,50(5):76-80.
[11]宋彭生,李武,孙柏,等.盐湖资源开发利用进展[J].无机化学学报,2011,27(5):801-815.
[12]牛自得,程芳琴.水盐体系相图及其应用[M].天津:天津大学出版社,2002.
[13]伍倩,乜贞,卜令忠,等.三元体系Li+,K+//CO32--H2O 298.15 K稳定相平衡研究[J].无机盐工业,2018,50(6):28-31.
[14]Hu M C,Zhang W J,Li S N,et al.Thermodynamic investigation of a ternary mixed electrolyte(CsCl/MgCl2/H2O)system using electromotive force measurement at 298.15 K[J].Journal of Chemical&Engineering Data 2009,54(7):2023-2027.
[15]Balarew Chr,Christov Chr,Valyashko Vl,et al.Thermodynamics of formation of carnallite type double salts[J].Journal of Solution Chemistry,1993,22(2):173-181.
[16]Li Y,Song P,Xia S,et al.Effects of Pitzer mixing parameters on the solubility prediction of HCl-CsCl-H2O system at 25℃[J].Russian Journal of Inorganic Chemistry,2006,51(10):1659-1663.
[17]Hu B,Song P,Li Y,et al.Solubility prediction in the ternary systems NaCl-RbCl-H2O,KCl-CsCl-H2O and KBr-CsBr-H2O at 25℃using the ion-interaction model[J].Calphad-Computer Coupling of Phase Diagrams and Thermochemistry,2007,31(4):541-544.
[18]Guo L,Wang Y,Tu L,et al.Thermodynamics and phase equilibrium of the system CsCl-MgCl2-H2O at 298.15 K[J].Journal of Chemical&Engineering Data,2017,62(4):1397-1402.
[19]Zhang Y M,Ma L C,Liu C L,et al.Phase diagram and research for the ternary system of NaCl-CsCl-H2O at 50℃[J].Advanced Materials Research,2013,706-708:193-196.
[20]保英莲,孙海霞,曹红翠,等.Pitzer混合参数对CsCl-Cs2SO4-H2O体系25℃时溶解度预测的影响[J].盐业与化工,2012,41(10):17-19.
[21]Hu B,Song P,Li Y.Solubility prediction of CsCl-Cs2SO4-H2O system at 298.15 K using the ion-interaction model[J].The Open Thermodynamics Journal,2007,1:1-3.
[22]中国科学院青海盐湖研究所分析室.卤水和盐的分析方法[M].北京:科学出版社,1988.
[23]姚允斌,解涛.物理化学手册[M].上海:上海科学技术出版社,1985.
[24]金利华.稀碱金属铯盐在脂肪醇水体系的等温相行为及热力学研究[D].西安:陕西师范大学,2006.
[25]秦善.晶体学基础[M].北京:北京大学出版社,2004.
[26]Gao Y,Li S,Zhai Q,et al.Phase diagrams and physicochemical properties for the ternary system(CsCl+NaCl+H2O)at T=(298.15,308.15,and 318.15)K[J].Journal of Chemical&Engineering Data,2017,62(9):2533-2540.