Measurement and thermodynamic analysis of the solubility and supersolubility of lithium carbonate in water

doi:10.16085/j.issn.1000-6613.2016.08.07

Abstract

Abstract: The solubility and supersolubility determines the width of the metastable state and the crystallization process is operated in the metastable zone. Therefore,the solubility and supersolubility are an important basic data in industrial crystallization process. In this study,lithium carbonate was used as solute and the solubility of lithium carbonate in water was measured at (283.15 to 318.15) K and atmospheric pressure by using a gravimetric method. The supersolubility was measured by using a laser dynamic method. It was obviously showed that the solubility and supersolubility of lithium carbonate in water and the width of the metastable zone decreased with increasing temperature. The solubility data was correlated by Van't Hoff equation and modified Apelblat equation. The results indicated that the solubility of calculated values was in good agreement with the experimental values. The average relative deviation of the Van't Hoff equation and the modified Apelblat equation were 0.54% and 0.20%,respectively. The changes of enthalpy(ΔH_d),entropy(ΔS_d)and Gibbs free energy (ΔG_d)of the dissolving process were obtained by the thermodynamic calculation. The dissolving process was a non-spontaneous process of exothermic and Entropy. The entropy change was the main influencing factor in the dissolution process.

Key words: lithium carbonate, water, solubility, supersolubility, metastable zone, thermodynamic calculation

摘要： 固体溶质在溶剂中的溶解度和超溶解度数值决定了结晶介稳区的宽度，而溶质结晶分离过程又是在介稳区中进行操作，因此固体溶质的溶解度和超溶解度在工业结晶中是很重要的基础数据。本文以碳酸锂为溶质，在标准压力条件和283.15~318.15K温度条件下，用重量分析法测定其在水中的溶解度；用激光动态法测定其在一定温度条件下在水中的超溶解度，从而得到碳酸锂在水溶液中的介稳区；结果显示，碳酸锂在水中的溶解度和超溶解度均随温度的升高而减小，介稳区宽度随温度的升高而变窄；其溶解度数据用Van't Hoff方程和修正的Apelblat方程进行了热力学关联计算，结果表明，两种热力学模型对碳酸锂在水中溶解度的关联效果都很好，其中Van't Hoff方程和修正的Apelblat方程的计算值与实验值的平均相对偏差分别为0.54%和0.20%。通过溶解热力学计算，得到碳酸锂在水中的溶解焓ΔH_d、熔解熵ΔS_d和溶液标准吉布斯自由能变ΔG_d，结果表明该溶解过程为放热熵减小的非自发过程，并且溶解熵变对溶解过程的影响较大。

关键词: 碳酸锂, 水, 溶解度, 超溶解度, 介稳区, 热力学计算

CLC Number:

TQ013.1

SONG Changbin, LI Runchao. Measurement and thermodynamic analysis of the solubility and supersolubility of lithium carbonate in water[J]. Chemical Industry and Engineering Progree, 2016, 35(08): 2350-2354.

宋昌斌, 李润超. 碳酸锂在水中的溶解度和超溶解度的测定及热力学分析[J]. 化工进展, 2016, 35(08): 2350-2354.

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