Prediction of Critical Properties of Binary Mixtures Using the PRSV-2 Equation of State

The aim of this work is to test the value of the Peng–Robinson–Stryjek–Vera (PRSV-2) equation of state for predicting the critical behavior of binary mixtures. A procedure adopted by Heidemann and Khalil, based on the Helmholtz free energy, has been followed. The resulting two complex nonlinear equations have been solved simultaneously for the critical temperature and volume, while the critical pressure is calculated from the PRSV-2 equation of state itself. Three forms of binary-interaction parameters have been tried: the zero-type, conventional one-parameter type, and Margules two-parameter type. The optimum values of the binary interaction parameters, based on minimizing the sum of the squares of the relative errors between predicted and experimental critical temperatures, have been calculated for 20 polar and nonpolar systems. The Margules two-parameter type gives the best results, but its mathematical derivation is cumbersome and it requires more computation time. The standard and the average of the absolute relative deviations in critical properties are included. The predicted critical temperatures and pressures agree well with the experimental results, and are always better than those predicted by the group-contribution method. The deviations in the predicted critical volumes using any of the tested binary-interaction parameter types are relatively large compared to those using the group-contribution method.