Calculation of the stability and of the phase equilibrium in the system polystyrene plus cyclohexane plus carbon dioxide based on equations of state

In order to calculate spinodals for polymer systems with an equation of state (EOS), we developed a stability theory using continuous thermodynamics. Here, the mixture considered consists of a polydisperse polymer and two monodisperse components as for example a solvent and a gas. We derived the spinodal equation on the base of the segment-molar Helmholtz energy of the mixture. As a result, a determinant similar to that of the monodisperse case is obtained, but the polydisperse polymer is identified by its weight average of the molecular weight. Furthermore, our paper provides the equations for the cloud-point curve derived with the aid of continuous thermodynamics. The final equations are applied to the system polystyrene + cyclohexane + carbon dioxide using the EOS of Sake, Wu and Prausnitz (SWP-EOS). For parameter fit and to prove the accuracy of the treatment, experimental data of the high-pressure equilibrium of the binary subsystems and of the ternary system were taken from literature. (C) 1999 Elsevier Science B.V. All rights reserved.