Phase Diagram of Aqueous Solutions of LiCl: a Study of Concentration Effects on the Anomalies of Water

Abstract

We perform molecular dynamics simulations in order to study thermodynamics and the structure of supercooled aqueous solutions of lithium chloride (LiCl) at concentrations c = 0.678 and 2.034 mol/kg. We model the solvent using the TIP4P/2005 potential and the ions using the Madrid-2019 force field, a force field particularly suited for studying this solution. We find that, for c = 0.678 mol/kg, the behavior of the equation of state, studied in the P-T plane, indicates the presence of a liquid-liquid phase transition, similar to what was previously found for bulk water. We estimate the position of the liquid-liquid critical point to be at Tc ≈ 174 K, Pc ≈ 1775 bar, and ρc ≈ 1.065 g/cm3. When the concentration is tripled to c = 2.034 mol/kg, no critical point is observed, indicating its possible disappearance at this concentration. We also study the water-water and water-ions structure in the two solutions, and we find that at the concentrations examined the effect of ions on the water-water structure is not strong, and all the features found in bulk water are preserved. We also calculate the hydration number of the Li and Cl ions, and in line with experiments, we find the value of 4 for Li+ and between 5.5 and 6 for Cl-, confirming the good performances of the Madrid-2019 force field.