Modification of PSRK mixing rules and results for vapor-liquid equilibria, enthalpy of mixing and activity coefficients at infinite dilution

The predictive Soave-Redlich-Kwong (PSRK) equation of state (EOS) is a well-established method for the prediction of thermodynamic properties required in process simulation. But there are still some problems to be solved, e.g. the reliability for strong asymmetric mixtures of components which are very different in size. The following modifications are introduced in the PSRK mixing rules: the Flory-Huggins term in the mixing rule for the EOS parameter a, and the combinatorial part in the UNIFAC model are skipped simultaneously; a nonlinear mixing rule for the EOS parameter b, instead of the linear mixing rule, is proposed. With these two modifications better results are obtained for vapor-liquid equilibria and activity coefficients at infinite dilution for alkane-alkane systems, specially for asymmetric systems. In order to obtain better results for enthalpy of mixing, temperature-dependent parameters are used. Group interaction parameters have been fitted for several groups, and the results are compared with the Modified UNIFAC (Dortmund), and the PSRK methods. (C) 2002 Elsevier Science B.V All rights reserved.