A generalized NRTL model was previously proposed for the modeling of non ideal systems and was extended to the prediction of phase equilibria under pressure according to the cubic NRTL-PR EoS. In this work, the model is reformulated with a predictive kij temperature and composition dependent mixing rule and new interaction parameters are proposed between permanent gases, ethane and nitrogen with hydrocarbons, ethane with water and ethylene glycol. Results obtained for excess enthalpies, liquid–vapor and liquid–liquid equilibria are compared with those provided by the literature models, such as VTPR, PPR78, CPA and SRKm. A wide variety of mixtures formed by very asymmetric compounds, such as hydrocarbons, water and ethylene glycols are considered and special attention is paid to the evolution of kij with respect to mole fractions and temperature.