Thermodynamics Research Center / ThermoML | Thermochimica Acta

ABSTRACT

In this work the thermodynamics of intermolecular interactions for imidazolium based ionic liquids in solutions of proton donor solvent chloroform and proton acceptor solvent tetrahydrofuran was studied using solution calorimetry technique. Enthalpies of solution of 1-ethyl- and 1-butyl-3-methylimidazolium based ionic liquids with tetrafluoroborate, methylsulfate, ethylsulfate, butylsulfate, dicyanoamide, trifluoromethanesulfonate, thiocyanate anions were measured in two solvents over concentration range 0.18-3.60 mmol kg-1at 298.15 K. Enthalpies of transfer from tetrahydrofuran to chloroform derived from experimental data were exothermic for all studied ionic liquids. Proton acceptor scale of ionic liquids as solutes was proposed on the basis of thermochemical data. Enthalpy of hydrogen bonding of ionic liquids with proton donor solvent chloroform increases in the range of anions [BF4]-less than [SCN]-less than [TfO]-less than [N(CN)2]-less than [AlkSO4]-. At the same time these values remain constant for ILs with different length of alkyl group in cations and anions. Thermochemical proton acceptor scale of ILsin solution correlates well with COSMO-RS hydrogen-bonding energies in equimolar cation anion pairs of ILs.