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Solubility and Thermodynamic Analysis of Lithium Hydroxide in Lye System

  • PHYSICOCHEMISTRY OF SOLUTIONS
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Abstract

Selectively crystallization and separation of LiOH·H2O from the bipolar membrane preparation lye is the key to the direct preparation of lithium hydroxide from bipolar membranes, and the thermodynamic equilibrium data of LiOH·H2O in the lithium-sodium mixed lye system is crucial for the control of the crystallization process. The solubility of LiOH·H2O has been determined at different temperatures and sodium hydroxide solution concentrations in the temperature range from 278.15 to 328.15 K. It has been found that none of the effects of temperature on the solubility of LiOH·H2O in the alkaline system are obvious, and the solubility only decreased firstly and then increased with the increase of temperature in a small magnitude; the concentration of aqueous NaOH solution was the main factor affecting the solubility. The experimental data of LiOH·H2O solubility have been corrected using E-DH and Apelblat equations, and the relative deviations have been calculated within ±0.06. The enthalpy change of dissolution ΔHd, entropy change ΔSd, and Gibbs free energy change ΔGd of LiOH·H2O in NaOH have been obtained by the thermodynamic calculations of dissolution, which indicates that the dissolution process is an exothermic, entropy-decreasing, and non-spontaneous process, and that the enthalpy change of dissolution and entropy change increases with the concentration of NaOH, and decreases slightly in the high concentration region, and the Gibbs free energy change ΔGd increases with the concentration of NaOH, and the Gibbs free energy change ΔGd increases with the concentration of NaOH. The Gibbs free energy change ΔGd increases with NaOH concentration, and the dissolution process is entropy-controlled at low NaOH concentration, and gradually changes to enthalpy-controlled process with increasing NaOH concentration. The results of the study provide fundamental data for the design of the distillation crystallization process of LiOH·H2O, a LiOH base prepared from bipolar membrane.

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Funding

The authors gratefully thank the National Natural Science Foundation of China (grant no. U20A20138) for financial support of this work.

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Authors and Affiliations

  1. Qinghai Provincial Engineering Technology Research Center of Green Mining and Efficient Utilization Technology for Low Permeability Salt Lake Brine, 816000, Minmetals Salt Lake Co.Ltd., Xinning, China

    Z. F. Hou

  2. Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province, Chinese Academy of Sciences, 810008, Xining, China

    H. W. Ge, Y. J. Zhao, D. M. Zhao & M. Wang

Authors
  1. Z. F. Hou
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  2. H. W. Ge
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  3. Y. J. Zhao
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  4. D. M. Zhao
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  5. M. Wang
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Correspondence to H. W. Ge or M. Wang.

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Hou, Z.F., Ge, H.W., Zhao, Y.J. et al. Solubility and Thermodynamic Analysis of Lithium Hydroxide in Lye System. Russ. J. Inorg. Chem. 68, 1972–1979 (2023). https://doi.org/10.1134/S0036023623602714

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