Effect of Acetonitrile on the Solubility of Carbon Dioxide in 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)amide

Abstract

The effect of the addition of acetonitrile on the solubility of carbon dioxide in an ionic liquid, the 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide, [C2mim][NTf2], was studied experimentally at pressures close to atmospheric and as a function of temperature between 290 and 335 K. It was observed that the solubility of carbon dioxide decreases linearly with the mole fraction of acetonitrile from a value of 2.6 × 10-2 in the pure ionic liquid at 303 K to a mole fraction of 1.3 × 10-2 in the mixture [C2mim][NTf2] + CH3CN with xCH3CN = 0.77 at the same temperature. The gas solubility decreases with temperature, and the thermodynamic properties of solvation could be calculated. The vapor pressures of the [C2mim][NTf2] + CH3CN mixtures were measured in the same temperature range, and strong negative deviations from Raoult's law were obtained: up to 36% for a mixture with xCH3CN = 0.46 at 334 K. Negative excess molar volumes of approximately −1 cm3 mol-1 at equimolar composition could also be calculated from density measurements of the pure components and of the mixtures. These observations are confirmed by neutron diffraction studies and are compatible with the existence of strong ion−dipole interactions in the mixed liquid solvent.