Experimental determination of solvation free energy of protons in non-protic ionic liquids using Raman spectroscopy

Abstract

Room temperature imidazolium-based ionic liquids (ILs) often present super-acidity, which can be characterized by the free energy of solvation of protons in ILs, Δ_solvG°(H⁺)_IL. It can be derived from the consensus value of the free energy of solvation of protons in water if the free energy of transfer of protons from water to the ILs, Δ_tG°(H⁺), is determined. However, the experimental determination of the free energy of transfer of protons relies on extra-thermodynamic hypotheses, as protons cannot be transferred from one solvent to another without a counterion. Here we propose to measure the Hammett acidity functions, which relies on the protonation equilibrium of specific pH-reporters, for the first time by Raman spectroscopy directly in acidic solution of 2,6-dichloro-4-nitroaniline in three 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ILs. We demonstrated that the Δ_tG°(H⁺) obtained by Raman spectroscopy and UV-visible spectroscopy were identical in the same 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Also, when the butyl substituent is replaced by a longer alkyl chain such as an octyl chain, the acidity in the IL is lowered. The free energies of solvation are calculated in four ILs from Raman spectroscopy data recorded directly in the acidic solutions. These values confirmed that the protons are less solvated in ILs than in water, hence their acidity. Raman spectroscopy also enables determination of the solvation number of the proton in imidazolium-based bis(trifluoromethylsulfonyl)imide ILs. The benefits of implementing Raman spectroscopy to determine the Hammett acidity function in ILs using a non-colored pH-reporter and in colored media are also discussed.