Estimation of infinite dilution activity coefficients in aqueous mixtures via molecular simulation

Abstract

Molecular dynamics simulations are employed to calculate infinite dilution activity coefficients of water and methanol-like species in binary mixtures using a variant of the Kirkwood coupling parameter method. Differences in residual Gibbs free energies are obtained as integrals over ensemble averages of the derivatives of total potential energy with respect to simple functions of the intramolecular potential energy parameters. The calculated limiting activity coefficients are compared with the experimental values at the same temperature obtained by direct measurement of the water/methanol binary and via extrapolation from vapor–liquid equilibria data.