Interactions of ionic liquids and water.

Experimental excess enthalpies of ionic liquid and water mixtures in combination with calculated CHELPG atomic charges were used to investigate the interactions between the species in solution. The excess enthalpies of ionic liquids in water were obtained by calorimetry, using a Setaram C80 calorimeter, including temperatures from (313.15 to 348.15) K and the entire range of composition. The ionic liquids investigated all contain the 1-ethyl-3-methylimidazolium cation except one, which has an added hydroxyl group on the cation (1-(2-hydroxyethyl)-3-methylimidazolium cation). The anions investigated are ethylsulfate, methylsulfate, hydrogensulfate, trifluoromethanesulfonate, methanesulfonate, and trifluoroacetate, and these will demonstrate the effect of systematically varying the substituents on the anion. The CHELPG atomic charges on the cations and anions were calculated using the Gaussian 03 program. The CHELPG atomic charges are consistent with the observed trends in excess enthalpy and provide insight into cation/water, anion/water, and cation/anion interactions.

Equimolar CO(2) absorption by anion-functionalized ionic liquids.

Amino acid ionic liquid trihexyl(tetradecyl)phosphonium methioninate [P(66614)][Met] and prolinate [P(66614)][Pro] absorb CO(2) in nearly 1:1 stoichiometry, surpassing by up to a factor of 2 the CO(2) capture efficiency of previously reported ionic liquid and aqueous amine absorbants for CO(2). Room temperature isotherms are obtained by barometric measurements in an accurately calibrated stirred cell, and the product identity is confirmed using in situ IR. Density functional theory (DFT) calculations support the 1:1 reaction stoichiometry and predict reaction enthalpies in good agreement with calorimetric measurements and isotherms.