Thermodynamics Research Center / ThermoML | Journal of Chemical and Engineering Data

ABSTRACT

The solubility of O2 was measured gravimetrically in sixteen ionic liquids (ILs) containing piperidinium, methyltriazabicyclodecene, pyrrolidinium, or bis(trifluoromethanesulfonyl)imide, ammonium, guanidinium cations tetrahydrothiophenium, paired bis(perfluoroethylsulfonyl)imide with or perfluoropropanoyl(trifluoromethylsulfonyl)imide anions. The temperature dependence of the solubility was determined for eight of the ILs. Henry' law constants were determined from the solubility data, as well as standard enthalpies and entropies of absorption for systems with temperature dependent data. Knowledge of these thermodynamic properties is essential in guiding the structural design of ionic liquids for different applications involving O2. O2 solubility did not follow any obvious trend with regard to IL structure or molar volume; instead, the dipole-quadrupole interactions are the primary driving forces for O2 dissolution in ionic liquids, as demonstrated by negative standard enthalpies of absorption for all the ILs. In addition, diffusion coefficients of O2 in the ILs as a function of temperatures (293 K, 313 K, and 333 K) and applied O2 pressures (1 MPa, 3 MPa, and 5 MPa) were obtained by fitting the time-dependent absorption data to a widely used mass diffusion model. The diffusion coefficients of O2 in ionic liquids at 293 K and 1 MPa roughly correlate inversely with the pure IL viscosity, likely due to the relatively low and similar O2 solubilities at these conditions. As expected, O2 diffusivities increase with increasing temperature. However, they also increase with increase pressure, likely due to decreasing solution viscosity with increasing gas solubility.