Phase separation of model adsorbates in random matrices

Abstract

The liquid–liquid phase behavior of binary mixtures in random pores is investigated with non-additive hard spheres using both ROZ (Replica Ornstein-Zernike) integral equations and cavity biased grand canonical Monte Carlo simulations. The critical densities of the coexistence phase envelopes are determined as function of the non-additivity parameter Δ, varying from Δ = 0.2, 0.4, 0.6, up to 0.8. The matrix is made of quenched hard spheres. Its porosity is varied to ascertain the effects of confinement, with packing densities ρ₀ ranging from 0.1, 0.3, to 0.5. To obtain fiduciary results from ROZ, we use the accurate ZSEP closure relation proposed earlier with and without thermodynamic consistency. The ZSEP closure is known to enforce the zero-separation theorems via special adjustable parameters in the bridge function. Two versions of this closure are used to assess their accuracies (vis-à-vis the Monte Carlo data): first ZSEP-T, namely, the ZSEP closure with added thermodynamic consistency (the Gibbs-Duhem relation); and second purely ZSEP without adding thermodynamic consistency. It is found that both closures give correct qualitative trend, with errors of ZSEP falling within 8–9%, while ZSEP-T, being more accurate, to within 1–2%. As non-additivity is increased, both versions become more accurate. The critical density ρ_c is found to decrease with decreasing porosity. In addition, ρ_c also decreases with increasing Δ, in a non-monotone fashion.