Combined Experimental and Theoretical Studies on the Prediction of the Isobaric Vapor–Liquid Association Phenomena for Binary and Ternary Mixtures of Water, Ethanoic Acid, and Propanoic Acid

Abstract

It is a considerable challenge for the phase behavior of chemical separation industry to correlate and predict the vapor–liquid equilibria (VLE) data of the binary and ternary systems containing associating components because it is not known how these forms exist in the experimental condition, such as homogeneous or heterogeneous dimers or trimers, even polymers, and so on. Herein, VLE data for the associating ternary system, water + ethanoic acid + propanoic acid, and the three-constituent binary systems have been measured by different liquid-phase compositions using a Fischer ebulliometer at 101.33 kPa. The structures and distribution of various clusters in water, ethanoic acid, and propanoic acid systems were fully optimized at the B3LYP/6-31+G­(d) level of theory using Gaussian 09. Then, we developed a strategy that could calculate the liquid activity coefficients by considering the distribution of the associating components in the strong association systems. This method is called the discrete clusters (DC) model, and, for comparison, Wilson, NRTL, and UNIQUAC models were employed to correlate the VLE data for the three-constituent binary systems. Also, the VLE data of the ternary system were estimated from the DC, Wilson, NRTL, and UNIQUAC models without any additional adjustment. Our DC model, which considered the explicit number of various clusters, showed better agreement and a smaller deviation from the experimental data. These VLE data derived from the DC model can be used for the design and simulation of the distillation behavior of the binary and ternary association systems.

Mechanism of proton transport in water clusters and the effect of electric fields: A DFT study

“…We have tested the effect of basis set superposition error (BSSE) for the binding energy of dimer, trimer, pentamer and octamer and presented in the Table S2 in SI. Our results are in consistent with previous literatures [37,39,40]. The contribution of the BSSE to the total binding energy of water cluster is only around 1 kJ/mol per water-water interaction.…”

Measurement and Correlation of Isobaric VLE Data for 1-Propanol + Water + 1-Butyl/Decyl-3-methylimidazole Bromide/Nitrate ILs at 101.33 kPa

“…The VLE data were measured by using a VLE still ( i -Fischer Labodest VLE 602-D, Germany). The reliable validation of experimental measurements from the device is available in our previous references. , Before each experiment, the ILs were pretreated by including rotary evaporation and drying in a vacuum oven for 6 h. The samples were weighed by using a Sartorius electronic balance (model ER-182A) with an accuracy of 0.0001 g. The mass of the added components was predetermined and measured by a differential weighing method. Then, the demanded components were introduced into the still using a syringe.…”