Thermodynamic modeling of vapor–liquid equilibrium of binary systems ionic liquid + supercritical {CO2 or CHF3} and ionic liquid + hydrocarbons using Peng–Robinson equation of state

Abstract

Vapor–liquid equilibrium (VLE) data from literature for binary systems involving several ionic liquids were correlated. The Peng–Robinson equation of state, coupled with the van der Waals and Wong–Sandler mixing rules, was used as the thermodynamic model to evaluate the fugacity coefficients. The UNIQUAC and NRTL models were used to calculate the excess Gibbs free energy in the Wong–Sandler mixing rule. A molecular modeling strategy using the software ChemOffice was used to calculate the volume and surface area parameters of ionic liquids for UNIQUAC, while the binary interaction energy parameters for UNIQUAC and NRTL models, as well as the binary interaction parameter of the van der Waals and Wong–Sandler mixing rules were estimated through a method based on the genetic algorithm. The results show that, as expected, the Wong–Sandler mixing rules represented better the data, with both activity coefficient models showing high accuracy. However, in one case, NRTL predicted an erroneous azeotropic condition, while UNIQUAC was able to correlate the data without this error.