Abstract Thermodynamic models are essential to facilitate the advancement of process design, optimization, and operation of electrolyte systems. In this work, a comprehensive thermodynamic framework based on the Electrolyte Nonrandom Two-Liquid model is developed to calculate phase equilibria behavior and salt solubility of aqueous LiCl, LiBr, LiI, and LiNO3 solutions. The model describes the non-ideality of the electrolyte solutions by using two binary interaction parameters for each electrolyte-molecule pair in the system. Each binary interaction parameter is further expressed with up to three temperature coefficients which are regressed from experimental data. To take into account the hydration of lithium ion, two separate chemistries for the dissociation of lithium salts are investigated. In the first case, the lithium ion is considered as a bare ion, Li+, while in the second case hydration of the lithium ion from Li+ to Li(H2O)+ is considered. The calculated thermodynamic properties compare adequately with the experimental data for both sets of chemistries for concentrations up to saturation and temperatures from 273.15 K up to 623.15 K. Moderate to significant improvements are observed with the incorporation of the hydration chemistry for aqueous LiCl, LiBr, and LiI solutions when compared to the non-hydrated lithium ion model results.

中文翻译：

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LiCl、LiBr、LiI 和 LiNO3 水溶液的热力学建模

摘要 热力学模型对于促进电解质系统的工艺设计、优化和操作的进步至关重要。在这项工作中，开发了一个基于电解质非随机双液体模型的综合热力学框架来计算 LiCl、LiBr、LiI 和 LiNO3 水溶液的相平衡行为和盐溶解度。该模型通过为系统中的每个电解质-分子对使用两个二元相互作用参数来描述电解质溶液的非理想性。每个二元相互作用参数进一步用多达三个温度系数表示，这些温度系数从实验数据中回归。为了考虑锂离子的水合，研究了锂盐解离的两种不同的化学物质。在第一种情况下，锂离子被视为裸离子 Li+，而在第二种情况下，锂离子从 Li+ 到 Li(H2O)+ 的水合被考虑。计算的热力学性质与两组化学物质的实验数据充分比较，浓度最高可达饱和，温度从 273.15 K 到 623.15 K。通过加入 LiCl、LiBr 和 LiBr 水​​溶液的水合化学，观察到中度到显着的改善。 LiI 溶液与非水合锂离子模型结果相比。