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
Résumé
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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