Phase behaviour and particle-size cutoff effects in polydisperse fluids

TL;DR

This study combines simulations and theory to explore how polydispersity in particle size, coupled with size-dependent interaction strength, influences the liquid-vapor phase behavior of fluids, revealing significant effects on phase coexistence and critical points.

Contribution

It introduces a detailed analysis of size-dependent interactions in polydisperse fluids, highlighting the impact on phase diagrams and the importance of size cutoff effects, which were not addressed in earlier models.

Findings

Cloud and shadow curves are well separated in size-dependent interaction cases.

Critical point lies below the maximum of the cloud curve.

Phase behavior is highly sensitive to the particle size cutoff.

Abstract

We report a joint simulation and theoretical study of the liquid-vapor phase behaviour of a fluid in which polydispersity in the particle size couples to the strength of the interparticle interactions. Attention is focussed on the case in which the particles diameters are distributed according to a fixed Schulz form with degree of polydispersity $\delta=14%$. The coexistence properties of this model are studied using grand canonical ensemble Monte Carlo simulations and moment free energy calculations. We obtain the cloud and shadow curves as well as the daughter phase density distributions and fractional volumes along selected isothermal dilution lines. In contrast to the case of size-{\em independent} interaction strengths (N.B. Wilding, M. Fasolo and P. Sollich, J. Chem. Phys. {\bf 121}, 6887 (2004)), the cloud and shadow curves are found to be well separated, with the critical point lying significantly below the cloud curve maximum. For densities below the critical value, we observe that the phase behaviour is highly sensitive to the choice of upper cutoff on the particle size distribution. We elucidate the origins of this effect in terms of extremely pronounced fractionation effects and discuss the likely appearance of new phases in the limit of very large values of the cutoff.