Heterophase fluctuations at the gas-liquid phase transition

TL;DR

This paper investigates the role of mesoscopic heterophase fluctuations in the gas-liquid phase transition, introducing a mesoscopic equation of state and analyzing their impact on thermodynamic and structural properties near criticality.

Contribution

It develops a mesoscopic model linking bubble and droplet sizes with a two-component order parameter, revealing mesoscopic effects on phase coexistence and critical non-analyticity.

Findings

Mesoscopic heterophase fluctuations induce non-analyticity in the phase coexistence diameter.

The mesoscopic equation of state describes the structure and thermodynamics of the heterophase fluid.

Percolation thresholds of droplets and bubbles define the applicability of the droplet model.

Abstract

The problem of the gas-liquid heterophase fluctuations of a fluid within the critical and supercritical regions is revisited. To describe the thermodynamics and structure of the heterophase fluid, the mesoscopic equation of state is deduced. The mesoscopic scale is connected with the sizes of the mixed bubbles and droplets (g-fluctuons and l-fluctuons). The two-component order parameter of the heterophase fluid describes the gas-like and liquid-like fractions. Its interconnection with the van der Waals order parameter is ascertained. The non-symmetric Ising-type equation of state of the heterophase fluid is analyzed using the standard methods. The manifestations of the mesoscopic effects in the structural and thermodynamic properties of the fluid are investigated. The domain of applicability of a classical model is found using the mesoscopic Ornstein-Zernike equation. The asymmetry and non-analyticity of the diameter of the phase coexistence curve is researched. It is shown that that the critical non-analyticity of the diameter is induced by the mesoscopic heterophase fluctuations. The percolation thresholds of the droplets and bubbles in the critical and supercritical fluid are determined. On the phase diagrams they bound the domains of applicability of the droplet model.