The vapor pressures of (ethanol + glycerol) and (water + glycerol) binary mixtures were measured by means of two static devices at temperatures between (273 and 353 (or 363)) K. The data were correlated with the Antoine equation. From these data, excess Gibbs free energy functions (GE) were calculated for several constant temperatures and fitted to a fourth-order Redlich-Kister equation using the Barker method. The (ethanol + glycerol) binary system exhibits positive deviations in GE where for the (water + glycerol) mixture, the GE is negative for all temperatures investigated over the whole composition. Additionally, the NRTL, UNIQUAC and Modified UNIFAC (Do) models have been used for the correlation or prediction of the total pressure. (C) 2013 Elsevier Ltd. All rights reserved.