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A method of parameters fitting to the experimental vapour - liquid - liquid equilibrium (VLLE) data is presented for the NRTL and the Uniquac equations for six quaternary mixtures. The same equations but with coefficients taken from the simulator Chemcad database were also used for calculation of the VLLE for the same mixtures. The calculated equilibrium temperatures and compositions for all the three phases were compared with the experimental data for these four cases. The investigated models were also applied for calculation of the compositions and temperatures of ternary azeotropes occurring in the considered quaternary mixtures. The computed values were compared with the experimental ones to appreciate the model's accuracy and to confirm whether the model correctly predicts the presence of homo- or heteroazeotrope. The NRTL equation with coefficients fitted to the VLLE data proved to be the most accurate model. For the mixtures containing water, ethanol and two different hydrocarbons this model shows particularly high accuracy. In three cases the mean deviations between the calculated and measured temperatures do not exceed 0.25 K, and for the fourth mixture the difference equals 0.33. Besides, the mean deviations between the calculated and the measured concentrations in the gas and liquid phases, with one exception do not exceed 1 mole %.
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