Liquid-liquid equilibrium data were measured and analyzed for two ternary systems (biodiesel + methanol + glycerol and methyl palmitate + methanol + glycerol). Biodiesel, produced by the conventional chemical route at 60 °C for 60 min, using methanol and soybean oil at a molar rate of 10:1 and potassium hydroxide concentration (KOH) of 1 wt% exhibited thermal decomposition at temperatures between 100 and 250 ºC, reaching mass loss of approximately 98.8%, confirming soybean oil conversion into biodiesel by gas chromatography and thermogravimetry. Tie line composition quality was verified using Othmer-Tobias and Hand correlation equations. The distribution and selectivity coefficients were calculated for the immiscibility regions. The experimental tie line data exhibited good correlation in the UNIQUAC and NRTL thermodynamic models. The biodiesel system displayed deviations of 0.66 and 0.53% for the UNIQUAC and NRTL models, respectively. In addition, the methyl palmitate system showed a 1.23 and 0.48% deviation for the UNIQUAC and NRTL model, respectively. The individual behavior of the main biodiesel esters , based on the UNIQUAC model parameters, demonstrated that the type of fatty acid does not interfere in model correlation, likely due to the similarity between their composition and properties.