Self-Diffusion and Binary Maxwell–Stefan Diffusion Coefficients of Quadrupolar Real Fluids from Molecular Simulation

Abstract

Self- and binary Maxwell–Stefan (MS) diffusion coefficients were determined by equilibrium molecular dynamics simulations with the Green–Kubo method. This study covers self-diffusion coefficients at liquid states for eight pure fluids, i.e., F₂, N₂, CO₂, CS₂, C₂H₆, C₂H₄, C₂H₂, and SF₆ as well as MS diffusion coefficients for three binary mixtures N₂+CO₂, N₂+C₂H₆, and CO₂+C₂H₆. The fluids were modeled by the two-center Lennard–Jones plus point-quadrupole pair potential, with parameters taken from previous work of our group which were determined solely on the basis of vapor–liquid equilibrium data. Self-diffusion coefficients are predicted with a statistical uncertainty less than 1%, and they agree within 2–28% with the experimental data. The correction of the simulation data due to the finite size of the system increases the value of the self-diffusion coefficient typically by 10%. If this correction is considered, better agreement with the experimental data can be expected for most of the studied fluids. MS diffusion coefficients for three binary mixtures were also predicted; their statistical uncertainty is about 10%. These results were used to test three empirical equations to estimate MS diffusion coefficients in binary mixtures, i.e., the equations of Caldwell and Babb, of Darken, and of Vignes. The equations of Caldwell and Babb and of Vignes show qualitatively different behavior of the MS diffusion coefficient than that observed in the simulations. In agreement with previous work, the best results are obtained in all cases with the equation of Darken.