Ion hydration and structural properties of water in aqueous solutions at normal and supercooled conditions: a test of the structure making and breaking concept

Abstract

We study with the method of molecular dynamics simulation the structural properties of aqueous solutions of NaCl, KCl and KF salts at ambient conditions and upon supercooling at constant pressure. The calculations are performed at increasing concentration of the salt starting from c = 0.67 mol kg⁻¹ up to 3.96 mol kg⁻¹. We investigate the modifications of the hydration shells and the changes in the water structure induced by the presence of the ions. The oxygen–oxygen structure is strongly dependent on the ionic concentration while it is almost independent from the cation. The hydrogen bonding is preserved at all concentrations and temperatures. The main effect of increasing the ionic concentration is the tendency of the water structure to assume the high density liquid form predicted for pure water upon supercooling. An important consequence of our analysis is that the concept of an ion as a structure maker or a structure breaker must be revisited to take into account the other ionic species, the ionic concentration and more generally the thermodynamic conditions of the solutions.