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By proposing a predictive method with no adjustable parameter and by using infinite dilution activity coefficients of components in binary mixtures obtained from UNIFAC model, the binary interaction parameters (k12) in van der Waals mixing rule (vdWMR) and Orbey-Sandler mixing rule (OSMR) have been evaluated. The predicted binary interaction parameters are used in Peng-Robinson-Stryjek-Vera equation of state (PRSV-EoS) to obtain the vapor-liquid equilibrium (VLE) for six strongly polar and asymmetric binary mixtures. The binary interaction parameters evaluated by correlation of VLE experimental data and by PRSV EoS are also used in VLE calculations of the same binary mixtures. The average absolute deviations (AADs%) of the calculated results by both predictive and correlative methods are reported. The results indicate that although the correlative method has a more flexibility to fit the VLE experimental data, the AAD% of the predictive method is comparable and in some cases even better than that of correlative method.