A thermodynamic model of aqueous electrolyte solution behavior and solid-liquid equilibrium in the Li-H-Na-K-Cl-OH-H2O system to very high concentrations (40 molal) and from 0 to 250  C

Abstract : This paper describes a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the Li-H-Na-K-Cl-OH-H2O system from dilute to high solution concentration within the 0 to 250 °C temperature range. The model coherently extends to Li the temperature-variable H-Na-K-OH-Cl-H2Omodel of Christov and Møller (2004b, p. 1309). The solubility modeling approach based on Pitzer’s (1973, p. 268) specific interaction equations is used. All binary (LiCl-H2O and LiOH-H2O) and ternary (LiCl-HCl-H2O, LiCl-NaCl-H2O, LiCl-KCl-H2O, LiOH-NaOHH2O, LiOH-KOH-H2O, and LiOH-LiCl-H2O) lithium subsystems are included in the model parameterization. The model for the LiCl-H2O system is parameterized using two different approaches: (1) with 4 ion interaction binary parameters ((0), (1), (2), and C), and (2) with 3 ion interaction binary parameters ((0), (1), and C) and including neutral aqueous LiCl0(aq) species. Approach (2) provides a better fit of activity data in unsaturated binary solutions and accurately predicts solid solubilities up to 40 mol.kg1 and up to 250 °C. Therefore, this approach was used to parameterize lithium chloride mixed systems. Temperature functions for the thermodynamic solubility product (as log Ko sp) of 5 simple lithium salts (LiCl.2H2O(cr), LiCl. H2O(cr), LiCl(cr), LiOH. H2O(cr), and LiOH(cr)) are determined. The log Ko sp values of 3 double lithium basic salts precipitating in the LiOH-LiCl-H2O system at 50 °C (3LiOH. LiCl(cr), LiOH.LiCl(cr), and LiOH.3LiCl(cr)) are also estimated using solubility data.
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American journal of science, American Journal of Science, 2015, 815 (8), pp.204-256. 〈10.2475/03.2015.02〉
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Arnault Lassin, Christomir Christov, Laurent André, Mohamed Azaroual. A thermodynamic model of aqueous electrolyte solution behavior and solid-liquid equilibrium in the Li-H-Na-K-Cl-OH-H2O system to very high concentrations (40 molal) and from 0 to 250  C. American journal of science, American Journal of Science, 2015, 815 (8), pp.204-256. 〈10.2475/03.2015.02〉. 〈hal-01331967〉

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