Protic Ionic Liquids:  Preparation, Characterization, and Proton Free Energy Level Representation

We give a perspective on the relations between inorganic and organic cation ionic liquids (ILs), including members with melting points that overlap around the borderline 100 °C. We then present data on the synthesis and properties (melting, boiling, glass temperatures, etc.) of a large number of an intermediate group of liquids that cover the ground between equimolar molecular mixtures and ILs, depending on the energetics of transfer of a proton from one member of the pair to the other. These proton-transfer ILs have interesting properties, including the ability to serve as electrolytes in solvent-free fuel cell systems. We provide a basis for assessing their relation to aprotic ILs by means of a Gurney-type proton-transfer free energy level diagram, with approximate values of the energy levels based on free energy of formation and pK a data. The energy level scheme allows us to verify the relation between solvent-free acidic and basic electrolytes, and the familiar aqueous variety, and to identify neutral protic electrolytes that are unavailable in the case of aqueous systems.