Quasi-equilibrium phase coexistence in single component supercritical fluids

A possible four-phase coexistence in a single-component system

For different phases to coexist in equilibrium at constant temperature T and pressure P, the condition of equal chemical potential μ must be satisfied. This condition dictates that, for a single-component system, the maximum number of phases that can coexist is three. Historically this is known as the Gibbs phase rule, and is one of the oldest and venerable rules of thermodynamics. Here we make...

Phase Coexistence Properties of Polarizable Stockmayer Fluids

We report the phase coexistence properties of polarizable Stockmayer fluids of reduced permanent dipoles |m0| = 1.0 and 2.0 and reduced polarizabilities α∗ = 0.00, 0.03, and 0.06, calculated by a series of grand canonical Monte Carlo simulations with the histogram reweighting method. In the histogram reweighting method, the distributions of density and energy calculated in Grand Canonical Monte...

Vapor–liquid coexistence of quasi-two- dimensional Stockmayer fluids

Electrochemistry in supercritical fluids

A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, ...

Density functional theory of phase coexistence in weakly polydisperse fluids

The recently proposed universal relations between the moments of the polydispersity distributions of a phase-separated weakly polydisperse system are analyzed in detail using the numerical results obtained by solving a simple density functional theory of a polydisperse fluid. It is shown that universal properties are the exception rather than the rule.