Diffusion of ions in supercritical water: Dependence on ion size and solvent density and roles of voids and necks

Abstract

We have performed molecular dynamics simulations of alkali metal (Li+, Na+, K+, Rb+, Cs+) and halide (F−, Cl−, Br−, I−) ions in supercritical water at 673 K. The calculations were done for water at three different densities of 1.0, 0.7 and 0.35 g cm−3 to investigate the effects of solute size on the diffusion of ions in supercritical water. On increase of ion size, we observe a maximum for diffusion of ions in supercritical water of higher densities (1.0 and 0.7 g cm−3). However, no such maximum is found for ion diffusion in the supercritical water of low density (0.35 g cm−3) or for diffusion of neutral solutes at all densities. These results are analyzed in terms of passage through voids and necks present in supercritical water. Correlations of the observed diffusion behavior with the sizes of ions and voids present in the systems are discussed.