Critical phase behavior in multi-component fluid mixtures: Complete scaling analysis

TY - JOUR

T1 - Critical phase behavior in multi-component fluid mixtures

T2 - Complete scaling analysis

AU - de Castro, Pablo

AU - Sollich, Peter Kurt

PY - 2018/11/30

Y1 - 2018/11/30

N2 - We analyze the critical gas-liquid phase behavior of arbitrary fluid mixtures in their coexistence region. We focus on the setting relevant for polydisperse colloids, where the overall density and composition of the system are being controlled, in addition to temperature. Our analysis uses the complete scaling formalism and thus includes pressure mixing effects in the mapping from thermodynamic fields to the effective fields of 3D Ising criticality. Because of fractionation, where mixture components are distributed unevenly across coexisting phases, the critical behavior is remarkably rich. We give scaling laws for a number of important loci in the phase diagram. These include the cloud and shadow curves, which characterise the onset of phase coexistence, a more general set of curves defined by fixing the fractional volumes of the coexisting phases to arbitrary values, and conventional coexistence curves of the densities of coexisting phases for fixed overall density. We identify suitable observables (distinct from the Yang-Yang anomalies discussed in the literature) for detecting pressure mixing effects. Our analytical predictions are checked against numerics using a set of mapping parameters fitted to simulation data for a polydisperse Lennard-Jones fluid, allowing us to highlight crossovers where pressure mixing becomes relevant close to the critical point.

AB - We analyze the critical gas-liquid phase behavior of arbitrary fluid mixtures in their coexistence region. We focus on the setting relevant for polydisperse colloids, where the overall density and composition of the system are being controlled, in addition to temperature. Our analysis uses the complete scaling formalism and thus includes pressure mixing effects in the mapping from thermodynamic fields to the effective fields of 3D Ising criticality. Because of fractionation, where mixture components are distributed unevenly across coexisting phases, the critical behavior is remarkably rich. We give scaling laws for a number of important loci in the phase diagram. These include the cloud and shadow curves, which characterise the onset of phase coexistence, a more general set of curves defined by fixing the fractional volumes of the coexisting phases to arbitrary values, and conventional coexistence curves of the densities of coexisting phases for fixed overall density. We identify suitable observables (distinct from the Yang-Yang anomalies discussed in the literature) for detecting pressure mixing effects. Our analytical predictions are checked against numerics using a set of mapping parameters fitted to simulation data for a polydisperse Lennard-Jones fluid, allowing us to highlight crossovers where pressure mixing becomes relevant close to the critical point.

KW - Criticality

KW - Polydispersity

KW - Phase behaviour

KW - Thermodynamics

KW - Scaling

U2 - 10.1063/1.5058719

DO - 10.1063/1.5058719

M3 - Article

SN - 0021-9606

VL - 149

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 20

ER -