Prediction of solid–gas equilibria with the Peng–Robinson equation of state

In many applications related to Supercritical-Fluid (SCF) technology, solids are dissolved in SC fluids. Experimental data are now available for many systems but cannot cover all cases of potential practical interest. The prediction of solid solubilities in SC fluids, often in the presence of co-solvents, is useful for rational design of SCF extraction and related processes. Recently, thermodynamics has made considerable steps towards describing complex systems (gases with polar compounds) at high pressures using the so-called Equation of State/Excess Gibbs Free Energy (EoS/GE) models. The success of these models is so far restricted to Vapor–Liquid Equilibria (VLE) for which they have been primarily developed and tested. In this work we evaluate such a predictive model, the LCVM EoS, for solid–gas equilibria (SGE) including systems with co-solvents. LCVM is chosen due to its success for VLE of asymmetric systems such as CO2 with heavy alkanes and alcohols. Successful predictions are obtained for several solids as well as for some systems with co-solvents, but the results are less satisfactory for complex, multifunctional solids. A discussion of several factors, which affect modeling of SGE with cubic EoS, is included.