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The existence of two ternary azeotropes in a ternary system was experimentally confirmed for the first time. The boiling point and the composition of azeotropes benzene + water, perfluorobenzene + water, and benzene + perfluorobenzene + water (with a minimum boiling temperature) as well as the boiling point of the ternary azeotrope of the saddle type were measured at 101 kPa using distillation analysis, ebulliometric titration, and gas chromatography. The parameters of the NRTL-RK model were selected from the AspenPlus V.10.0 database, allowing an adequate description of the phase equilibrium in the system studied. Possible evolution of the VLE diagram under pressure change was discussed.

A method for the determination of vapor–liquid phase diagram structure of five-component systems based on the analysis of types and Poincare indexes of singular points of the geometric scan and full structure of the concentration simplex is proposed. Validity of the proposed method was demonstrated by vapor–liquid equilibrium modeling in five-component mixtures: ethanol + water + toluene + butanol + chlorbenzene and acetone + chloroform + ethanol + cyclohexane + water.

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