Solubility and Thermodynamics of Lithium Carbonate in Its Precipitation Mother Liquors

This study systematically investigated the dissolution equilibrium of lithium carbonate (Li₂CO₃) in mixed Na₂CO₃-NaCl aqueous solutions through isothermal dissolution experiments spanning 283.15-353.15 K. Precise solubility determinations were conducted using a gravimetric analysis under controlled thermodynamic conditions. The obtained solubility data were successfully correlated with the Extended Debye-Hückel (E-DH) model, yielding residual standard deviations below 0.09, which validates the model's applicability in this ternary system. Both experimental observations and theoretical predictions confirmed that increasing the salt molality enhances the synergistic suppression of the Li₂CO₃ solubility through combined common-ion and salt effects. The thermodynamic analysis revealed the dissolution process to be exothermic (Δ<i>H_d</i> < 0), and entropy change dominates (<i>ξ_S</i> ≈ 78%), with negative entropy changes (Δ<i>S_d</i> < 0) indicating predominant hydration ordering effects. These mechanistic insights establish critical thermodynamic benchmarks for optimizing lithium carbonate precipitation processes in brine lithium extraction operations.