Phase equilibria of quaternary system LiCl-LiBO2-Li2SO4-H2O at 298.15 K

doi:10.11949/j.issn.0438-1157.20151204

Abstract

Abstract:

The phase equilibria and phase diagram of the quaternary system (LiCl-LiBO₂-Li₂SO₄-H₂O) at 298.15 K, which was not reported in the literature, were studied with the isothermal dissolution equilibrium method. Solubilities and physicochemical properties including refractive index (n_D), density (ρ), pH and conductivity (κ) in the quaternary system were determined experimentally. According to the experimental data, the dry-salt diagram, water-phase diagram and the diagram of physicochemical properties versus lithium chloride concentration in the quaternary system were plotted, respectively. The experimental results showed that there were two invariant points named as invariant co-saturated point (Li₂SO₄·H₂O + LiCl·H₂O + LiBO₂·2H₂O) and incommensurate co-saturated point (Li₂SO₄·H₂O + LiBO₂·2H₂O + LiBO₂·8H₂O), five univariant curves and four crystalline regions corresponding to Li₂SO₄·H₂O, LiCl·H₂O, LiBO₂·8H₂O and LiBO₂·2H₂O in the quaternary system at 298.15 K. Neither double salt nor solid solution was formed, and the phase diagram of this system at 298.15 K belonged to hydrate-type Ⅱ. The two kinds of hydrate lithium-containing minerals (LiBO₂·2H₂O and LiBO₂·8H₂O) were found for the first time. The salting-out effect of LiCl in the solution was obvious for the composition of Li₂SO₄. The diagram of physicochemical properties including n_D, ρ, pH and κ versus composition shows that the physicochemical properties were changed regularly with increasing lithium chloride concentration in the solution and the singular values were achieved at the invariant points of the quaternary system at 298.15 K.

Key words: salt-water system, phase equilibria, aqueous solution, chemical analysis, borate, lithium sulfate, isothermal dissolution equilibrium method

摘要：

采用等温溶解平衡法开展了四元体系LiCl-LiBO₂-Li₂SO₄-H₂O在298.15 K时相平衡实验研究,测定体系溶解度和平衡溶液的折光率、密度、pH和电导率。根据实验数据,分别绘制该四元体系的干基图、水图以及相对应的物化性质-组成图。研究结果表明:在该四元体系298.15 K相图中,有2个无变度共饱点分别为相称共饱点(Li₂SO₄·H₂O + LiCl·H₂O + LiBO₂·2H₂O)和不相称共饱点(Li₂SO₄·H₂O + LiBO₂·2H₂O + LiBO₂·8H₂O)、5条溶解度曲线和4个单盐结晶相区(Li₂SO₄·H₂O、LiCl·H₂O、LiBO₂·8H₂O和LiBO₂·2H₂O),无复盐和固溶体产生,属于简单四元体系水合物Ⅱ型相图。实验研究中,发现2种偏硼酸锂水合矿物存在(LiBO₂·8H₂O和LiBO₂·2H₂O),LiCl对Li₂SO₄的盐析效应显著;四元体系平衡溶液物化性质随着溶液中氯化锂浓度的变化呈现规律性的变化。

关键词: 水盐体系, 相平衡, 水溶液, 化学分析, 硼酸盐, 硫酸锂, 等温溶解平衡法

CLC Number:

O642.4

CAO Lina, LI Long, ZHANG Nan, GUO Yafei, DENG Tianlong. Phase equilibria of quaternary system LiCl-LiBO₂-Li₂SO₄-H₂O at 298.15 K[J]. CIESC Journal, 2016, 67(4): 1117-1122.

曹丽娜, 李珑, 张楠, 郭亚飞, 邓天龙. 四元体系LiCl-LiBO₂-Li₂SO₄-H₂O在298.15K时的相平衡[J]. 化工学报, 2016, 67(4): 1117-1122.

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Phase equilibria of quaternary system LiCl-LiBO₂-Li₂SO₄-H₂O at 298.15 K

四元体系LiCl-LiBO₂-Li₂SO₄-H₂O在298.15K时的相平衡

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