A global investigation of phase equilibria using the Perturbed-Chain Statistical-Associating-Fluid-Theory (PC-SAFT) approach

TL;DR

This paper investigates the PC-SAFT model's ability to predict phase equilibria in one-component systems, revealing complex phase behavior including multiple critical points and demixing phenomena, supported by analytical and simulation studies.

Contribution

It provides a comprehensive analysis of PC-SAFT's predictions for phase behavior, uncovering phenomena like liquid-liquid and gas-gas equilibria not typically associated with single-component systems.

Findings

Identification of multiple phase separation regions in PC-SAFT models

Discovery of liquid-liquid and gas-gas demixing in one-component systems

Correlation of polymer melt density data using PC-SAFT

Abstract

The recently developed Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) is investigated for a wide range of model parameters including the parameter m representing the chain length and the thermodynamic temperature T and pressure p. This approach is based upon the first-order thermodynamic perturbation theory for chain molecules developed by Wertheim and Chapman et al. and includes dispersion interactions via the second-order perturbation theory of Barker and Henderson. We systematically study a hierarchy of models which are based on the PC-SAFT approach using analytical model calculations and Monte Carlo simulations. For one-component systems we find that the analytical model in contrast to the simulation results exhibits two phase-separation regions in addition to the common gas-liquid coexistence region: One phase separation occurs at high density and low temperature. The second demixing takes place at low density and high temperature where usually the ideal gas phase is expected in the phase diagram. These phenomena, which are referred to as "liquid-liquid" and "gas-gas" equilibria, give rise to multiple critical points in one-component systems, as well as to critical end points (CEP) and equilibria of three fluid phases, which can usually be found in multicomponent mixtures only. Furthermore, it is shown that the "liquid-liquid" demixing in this model is not a consequence of a "softened" repulsive interaction as assumed in the theoretical derivation of the model. Experimental data for the melt density of polybutadiene with molecular mass Mw=45000g/mol are correlated here using the PC-SAFT equation. It is shown that the discrepancies in modeling the polymer density at ambient temperature and high pressure can be traced back to ...