Reverse nonequilibrium molecular dynamics calculation of the Soret coefficient in liquid heptane/benzene mixtures.

We studied the thermal diffusion behavior of mixtures of benzene and heptane isomers by reverse nonequilibrium molecular dynamics. For n-heptane/benzene mixtures, we investigated the concentration dependence of the Soret coefficient. The Soret coefficient for equimolar mixtures of the three heptane isomers 3-methylhexane, 2,3-dimethylpentane, and 2,4-dimethylpentane in benzene has been calculated. Compared to the experimental data, the simulation results show the same trend in dependence of the mole fraction and degree of branching. The negative Soret coefficient indicates the enrichment of alkanes in the warm side. In the case of the heptane isomers in benzene, we could study the influence of the difference in shape and size on the thermal diffusion behavior at constant mass. In the simulation as well as in the experiment, we found that the Soret coefficients become higher with increasing degree of branching. Such behavior cannot be explained only by mass and size effects. The effect of the molecular shape needs to be considered additionally.