a b s t r a c tThe temperature and enthalpy of fusion of choline chloride -[Ch]Cl-are not directly measurable since this compound decomposes upon melting. Yet, given the wide use of this compound in the preparation of deep eutectic solvents (DES), its thermophysical fusion properties are very important for a better understanding of these mixtures and the thermodynamic description of their solid-liquid phase diagrams. In this work, the fusion properties of choline chloride were estimated using the solubility curves of choline chloride in ten different ionic compounds, forming simple binary eutectic mixtures with quasiideal liquid phases. Experimental solid-liquid equilibria data for these systems -[Ch]Cl þ ionic compounds-were measured, and the ideality of the systems assessed through the quantification of the activity coefficients and their comparison in each pair of binary solutions. The values estimated for the fusion properties of choline chloride are T fus, [Ch]Cl ¼ 597 ± 7 K and D fus H [Ch]Cl ¼ 4300 ± 600 J mol À1 . These were additionally checked by thermodynamic consistency tests and by the prediction of the solid-liquid curves with COSMO-RS model. The results obtained with both procedures allow us to guarantee the usefulness and robustness of the estimated data.

The solid−liquid equilibria phase diagrams of eight eutectic systems formed by choline chloride and fatty acids, or fatty alcohols, were measured to characterize the nonideality of the liquid phase of these systems, commonly reported in the literature as examples of type III deep eutectic solvents (DESs), and to evaluate the best modeling approaches to their description. Most of these systems are shown to present only slight deviations from ideal behavior, resulting from a fine balance of the hydrogen bonding between the hydroxyl/carboxylic groups with the chloride anion and the interactions present in the pure compounds. The phase diagrams measured were modeled with an associative equation of state (EoS) and a g E model. As an EoS, the perturbed-chain statistical associating fluid theory (PC-SAFT) was used, and this model was able to accurately describe the experimental data and to provide reliable estimates of the eutectic points using just a single binary temperature-dependent interaction parameter that often correlates with the acid/alcohol chain length. The performance of PC-SAFT was further compared with the g E model, a non-random two-liquid model (NRTL), and was found to provide a better description of the experimental data, especially for the more nonideal systems. Ultimately, the data gathered, and the molecular modeling, allowed the discussion of the behavior of fatty acids or fatty alcohols as hydrogen bond donors in choline chloride-based DESs.

In this work, a modified UNIFAC model that explicitly takes into account association effects is used to describe the thermodynamic properties of phase equilibria of mixtures containing common sugars, alcohols, and water. Three main groups were defined to represent the sugars family:  the sugar ring (pyranose and furanose), the osidic bond (−O−), and the hydroxyl ring group (OHring). For the association term, a general two-site OH associating group is used to represent association effects in these solutions, allowing a straightforward extension to multicomponent mixtures. Correlation of both solvent properties (osmotic coefficients, water activities, vapor pressures, and boiling and freezing points of binary aqueous sugar solutions) and sugar solubility in water and alcohols gives very accurate results. Good predictions are obtained for vapor−liquid equilibrium and solid−liquid equilibrium of ternary and quaternary mixtures of sugars in mixed solvents.