Free volume and density and temperature dependence of diffusion coefficients of liquid mixtures

A simple formula for the diffusion coefficient of liquid mixtures, expressed in terms of the work necessary to create a characteristic free volume in the liquid, is presented in the spirit of the Arrhenius activation theory and tested in comparison with available experimental data. If use is made of the generic van der Waals equation of state, the free volume appearing in the formula for the diffusion coefficient can be expressed in terms of the equilibrium pair correlation functions. The theoretical values for diffusion coefficients agree excellently with experimental values with regard to the density and temperature dependence of the diffusion coefficients of argon and krypton.