Vapor–liquid equilibrium of binary mixtures containing isopropyl acetate and alkanols at 101.32 kPa

Isobaric vapor-liquid equilibria of binary mixtures of isopropyl acetate plus an alkanol (1-propanol, 2-propanol, 1-butanol, or 2-butanol) were measured at 101.32 kPa, using a dynamic recirculating still. An azeotropic behavior was observed only in the mixtures of isopropyl acetate + 2-propanol and isopropyl acetate + 1-propanol. The application of four thermodynamic consistency tests (the Herington test, the Van Ness test, the infinite dilution test, and the pure component test) showed the high quality of the experimental data. Finally, both NRTL and UNIQUAC activity coefficient models were successfully applied in the correlation of the measured data, with the average absolute deviations in vapor phase composition and temperature of 0.01 and 0.16 K, respectively.

Evaluation of the conductor-like screening model for real solvents for the prediction of the water activity coefficient at infinite dilution in ionic liquids

Ionic liquids (ILs) have attracted great attention, from both industry and academia, as alternative fluids for very different types of applications. The large number of cations and anions allow a wide range of physical and chemical characteristics to be designed. However, the exhaustive measurement of all these systems is impractical, thus requiring the use of a predictive model for their study. In this work, the predictive capability of the conductor-like screening model for real solvents (COSMO-RS), a model based on unimolecular quantum chemistry calculations, was evaluated for the prediction water activity coefficient at infinite dilution, gamma(infinity)(w), in several classes of ILs. A critical evaluation of the experimental and predicted data using COSMO-RS was carried out. The global average relative deviation was found to be 27.2%, indicating that the model presents a satisfactory prediction ability to estimate gamma(infinity)(w) in a broad range of ILs. The results also showed that the basicity of the ILs anions plays an important role in their interaction with water, and it considerably determines the enthalpic behavior of the binary mixtures composed by Its and water. Concerning the cation effect, it is possible to state that generally gamma(infinity)(w) increases with the cation size, but it is shown that the cation-anion interaction strength is also important and is strongly correlated to the anion ability to interact with water. The results here reported are relevant in the understanding of ILs-water interactions and the impact of the various structural features of its on the gamma(infinity)(w) as these allow the development of guidelines for the choice of the most suitable lLs with enhanced interaction with water.