This work reports thermodynamic analysis of systems involved in the biodiesel production using ethanol at supercritical conditions. PC-SAFT equation of state was used from ASPEN Plus simulator for modeling all investigated systems. Binary and ternary phase equilibrium data at high pressure and temperature were used to assess the PC-SAFT capability of predicting the thermodynamic behavior of the complex mixture of interest in this work. The results showed that the PC-SAFT is a reliable tool to represent the phase behavior of mixtures involving ethanol, vegetable oil, fatty acid, ethyl esters of fatty acid and glycerol. Phase behavior of the reaction system was evaluated under specified experimental conditions and considering different reaction conversions. Pressure-temperature diagrams demonstrated that the two-phase region for the reaction mixture decreases as the extension of reaction is increased. The PC-SAFT equation of state was used to estimate the density of the reactant mixture and the effect of this parameter over the residence of the reaction was assessed, where it was clearly demonstrated that the density of the mixture greatly affects the residence time calculation for the reactions of biodiesel production at high pressure conditions. (C) 2018 Elsevier B.V. All rights reserved.