Total vapor pressures for liquid mixtures of xenon + ethane at 161.40 and 182.34 K and of xenon + propane at 161.40, 182.34, and 195.49 K have been measured. Both systems show negative deviations from Raoult's law at all temperatures. The corresponding excess molar Gibbs energies ( ) have been calculated from the vapor pressure results. Liquid molar volumes have also been measured for both mixtures at 161.40 K, leading to calculated excess molar volumes ( ) which are negative in all cases. Additionally, the excess molar enthalpies ( ) for the xenon + ethane system have been determined directly using a batch calorimeter and found to be negative. Xenon + ethane is thus the simplest system which exhibits negative values for all three major excess molar functions. The results were interpreted using the statistical associating fluid theory for potentials of variable attractive range (SAFT-VR). The theory is able to predict the phase behavior of both systems in close agreement with the experimental results. It was found that the xenon + n-alkane mixtures obey Lorentz−Berthelot combining rules, so that no unlike interaction parameters are fitted to experimental mixture data. The theory is therefore totally predictive. It was also found that the parameters calculated for xenon using this model lie within the average values of the parameters obtained for the n-alkanes. This implies that, in contrast with the anomalous behavior of methane, xenon can be treated as the first member of the n-alkane family. Furthermore, the xenon + n-alkane mixtures can be thought as a particular case of mixtures of n-alkanes.

The effect of mixing hydrogenated and fluorinated molecules that simultaneously interact through strong hydrogen bonding was investigated: (ethanol + 2,2,2-trifluoroethanol) binary mixtures were studied both experimentally and by computer simulation. This mixture displays a very complex behavior when compared with mixtures of hydrogenated alcohols and mixtures of alkanes and perfluoroalkanes. The excess volumes are large and positive (unlike those of mixtures of hydrogenated alchools), while the excess enthalpies are large and negative (contrasting with those of mixtures of alkanes and perfluoroalkanes). In this work, the liquid density of the mixtures was measured as a function of composition, at several temperatures from 278.15 to 353.15 K and from atmospheric pressure up to 70 MPa. The corresponding excess molar volumes, compressibilities, and expansivities were calculated over the whole (p, ρ, T, x) surface. In order to obtain molecular level insight, the behavior of the mixture was also studied by molecular dynamics simulation, using the OPLS-AA force field. The combined analysis of the experimental and simulation results indicates that the peculiar phase behavior of this system stems from a balance between the weak dispersion forces between the hydrogenated and fluorinated groups and a preferential hydrogen bond between ethanol and 2,2,2-trifluoroethanol. Additionally, it was observed that a 25% reduction of the F−H dispersive interaction in the simulations brings agreement between the experimental and simulated excess enthalpy but produces no effect in the excess volumes. This reveals that the main reason causing the volume increase in these systems is not entirely related to the weak dispersive interactions, as it is usually assumed, and should thus be connected to the repulsive part of the intermolecular potential.

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As part of a combined experimental and theoretical study of the thermodynamic properties of perfluoroalkylalkanes (PFAAs), the liquid density of perfluorobutylpentane (F4H5), perfluorobutylhexane (F4H6), and perfluorobutyloctane (F4H8) was measured as a function of temperature from 278.15 to 353.15 K and from atmospheric pressure to 70 MPa. The liquid densities of n-perfluoropentane, n-perfluorohexane, n-perfluorooctane, and n-perfluorononane were also measured at room pressure over the same temperature range. The PVT behavior of the PFAAs was also studied using the SAFT-VR equation of state. The PFAA molecules were modeled as heterosegmented diblock chains, using different parameters for the alkyl and perfluoroalkyl segments, that were developed in earlier work. Through this simple approach, we are able to predict the thermodynamic behavior of the perfluoroalkylalkanes, without fitting to any experimental data for the systems being studied. Molecular dynamics simulations have also been performed and used to calculate the densities of the perfluoroalkylalkanes studied.

A supramolecular hydrogel based on a metal-containing deep eutectic solvent (DES) is presented here for the first time. The phase diagram of the DES-based hydrogel was drawn and its rheological properties were determined.