Phase equilibrium and calorimetric measurements provide complementary data that are vital for process models. The combined use of vapor–liquid equilibrium (VLE) data and excess enthalpies (HE) makes the thermodynamic model more reliable in extrapolation outside the conditions of the measurement. This is important during the tight time schedule of process development. In this work, phase equilibrium and excess enthalpies of binary mixtures were measured by using three apparatuses. Two types of VLE runs were conducted by using a circulation still of the Yerazunis-type and by using Agilent headspace sampler with a gas chromatograph (HS-GC). A SETARAM C80 calorimeter equipped with a flow mixing cells was taken into use for excess enthalpy measurements. New data of phase equilibrium, excess molar enthalpy, and excess molar volume were obtained for industrially relevant binary mixtures of methyl isobutyl ketone (MIBK) with alcohols (2-butanol, tert-pentanol, 2-ethyl-1-hexanol). Excess enthalpy data at 298.15 K are well in line with equilibrium data obtained in the range of (294 to 368) K. Azeotropic behavior was observed in the MIBK + tert-pentanol system. The experimental data were used for the optimization of Wilson and Redlich–Kister equation parameters.
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