Protic ionic liquids and ionicity

Protic ionic liquids (PILs) are a subset of ionic liquids formed by the equimolar mixing of a Bronsted acid and a Bronsted base. PILs have been categorized as poor ionic liquids. However, the issue of assessing the ionicity of PILs is still a matter of debate. In this work we studied some physicochemical properties of three chosen PILs, namely, ethanolammonium acetate (EOAA), 2-methylbutylammonium formate (2MBAF), and pentylammonium formate (PeAF), at the initial equimolar (stoichiometric) acid/base ratio and in the presence of excess acid and base. DSC phase-transition studies along with NMR, IR, and Raman spectroscopy were performed on the chosen PILs. The results are discussed in terms of the degree of ionization (extent of proton transfer from the Bronsted acid to Bronsted base), and the possibility of the formation of polar 1:1 complexes and larger aggregates in the neat stoichiometric PILs.