The ability of ionic liquids to form hydrogen bonds with organic solutes evaluated by different experimental techniques. Part I. Alkyl substituted imidazolium and sulfonium based ionic liquids

Abstract

© 2018 This work is devoted to the quantitative study of hydrogen bond formation of N-alkyl substituted ionic liquids with proton acceptor and proton donor organic solvents. 1-Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [BMIM][NTf2], 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4], 1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM][TfO], 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], triethylsulfonium bis(trifluoromethylsulfonyl)imide [Et3S][NTf2], 1-butyl-3-methylimidazolium tricyanomethanide [BMIM][TCM], 1-hexyl-3-methylimidazolium tetrafluoroborate [HMIM][BF4] were investigated by solution calorimetry and FTIR-spectroscopy techniques. The stretching vibration region of C[dbnd]O group of 2-pentanone in mixture with N-alkyl substituted ionic liquid in inert solvent carbon tetrachloride was analyzed at different concentrations of components for the estimation of proton donor ability of ionic liquids. Also, the stretching vibration region of the OH-group of methanol was studied in a ternary system carbon tetrachloride (inert solvent), methanol (proton donor) and N-alkyl substituted ionic liquid for the estimation of proton acceptor ability of ionic liquids. The hydrogen bond enthalpy of methanol in ionic liquids was calculated using data of measured solution enthalpies and data extracted from the literature. The frequency shifts of the OH-group of methanol induced by intermolecular interactions within ionic liquids in a carbon tetrachloride solution were compared with the hydrogen bonding enthalpies of methanol with ionic liquids. A linear relationship between the frequency shifts of the OH-groups and hydrogen binding enthalpies of methanol in ionic liquids were found. According to measured FTIR-spectroscopy data, the N-alkyl substituted ionic liquids analyzed in this work possess weak proton donor properties, and at the same time their proton acceptor ability (basicity) is much higher and shows dependency on anion structure.