RESUMEN
In this paper, we investigated the effect of cation structure and water content on proton dissociation in alkylammonium [HSO4]- protic ionic liquids (ILs) doped with 20 wt % water and correlated this with experimental Hammett acidities. For pure systems, increased cation substitution resulted in a reduction in the number of direct anion-anion neighbors leading to larger numbers of small aggregates, which is further enhanced with addition of water. We also observed spontaneous proton dissociation from [HSO4]- to water only for primary amine-based protic ILs, preceded by the formation of an anion trimer motif. Investigation using DFT calculations revealed spontaneous proton dissociation from [HSO4]- to water can occur for each of the protic ILs investigated; however, this is dependent on the size of the anion aggregates. These findings are important in the fields of catalysis and lignocellulosic biomass, where solvent acidity is a crucial parameter in biomass fractionation and lignin chemistry.
