Does alkyl chain length really matter? Structure–property relationships in thermochemistry of ionic liquids

• Alkyl substituted imidazolium, pyridinium, and pyrrolidinium based ionic liquids with anions [Cl] and [Br] were studied using DSC and ab initio methods.
• The thermochemical properties of ILs generally obey the group additivity rules.
• A linear dependence on the chain length of the alkyl chain of cation was found.

DSC was used for determination of reaction enthalpies of synthesis of ionic liquids [Cnmim][Cl]. A combination of DSC with quantum chemical calculations presents an indirect way to study thermodynamics of ionic liquids. The indirect procedure for vaporization enthalpy was validated with the direct experimental measurements by using thermogravimetry. First-principles calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the CBS-QB3 and G3 (MP2) theory. Experimental DSC data for homologous series of alkyl substituted imidazolium, pyridinium, and pyrrolidinium based ionic liquids with anions [Cl] and [Br] were collected from the literature. We have shown that enthalpies of formation, enthalpies of vaporization, and lattice potential energies are linearly dependant on the alkyl chain length. The thermochemical properties of ILs generally obey the group additivity rules and the values of the additivity parameters for enthalpies of formation and vaporization seem to be very close to those for molecular compounds.

We have shown that enthalpies of formation, enthalpies of vaporization, and lattice potential energies of alkylsubstituted imidazolium, pyridinium, and pyrrolidinium based ionic liquids with Cl and Br anions are linearly dependant on the alkyl chain length. The thermochemical properties of ILs are generally obey the group additivity rules and the values of the additivity parameters for enthalpies of formation and vaporization are very close to those for molecular compounds.Figure optionsDownload as PowerPoint slide