Demixing in binary mixtures of apolar and dipolar hard spheres

Abstract

We study the demixing transition of mixtures of equal size hard spheres and dipolar hard spheres using computer simulation and integral equation theories. Calculations are carried out at constant pressure, and it is found that there is a strong correlation between the total density and the composition. The critical temperature and the critical total density are found to increase with pressure. The critical mole fraction of the dipolar component on the contrary decreases as pressure is augmented. These qualitative trends are reproduced by the theoretical approaches that on the other hand overestimate by far the value of the critical temperature. Interestingly, the critical parameters for the liquid-vapor equilibrium extrapolated from the mixture results in the limit of vanishing neutral hard sphere concentration agree rather well with recent estimates based on the extrapolation of charged hard dumbbell phase equilibria when dumbbell elongation shrinks to zero [G. Ganzenmuller and P. J. Camp, J. Chem. Phys. 126, 191104 (2007)].