A new insight into the nanostructure of alkylammonium alkanoates based ionic liquids in water

Abstract

In this paper, small angle X-ray scattering has been used to study a series of ionic liquids, alkylammonium alkanoates ([N_{0 0 0 n}][C_mCO₂]), with varying alkyl chain lengths in the cation and the anion. We investigate the behaviour and the structure of such ionic liquids in their neat state, and in binary mixtures with water. To the best of our knowledge, this is the first structural study dealing with the behaviour of propylammonium propanoate [N_{0 0 0 3}][C₂CO₂], butylammonium propanoate [N_{0 0 0 4}][C₂CO₂], propylammonium butanoate [N_{0 0 0 3}][C₃CO₂] and butylammonium butanoate [N_{0 0 0 4}][C₃CO₂] when mixed in water. Generally, in the ionic liquids containing alkyl chains on both the cation and the anion, the correlation distance and the resulting scattering peak, which signal intermediate range order, are affected equally by both of the chains. The interesting result obtained regarding these systems is that the shift of the pre- and principal peaks with the addition of water depends on the overall molar concentration of the chains and is generally cumulative. Although, for a given sum of cation and anion chain lengths, the shift is reliant on the cation–anion combination in the neat state, it is not the case in their mixtures with water. In some recent papers, it has been reported that with addition of water, the pre-peak position remains constant, but our results show a shift in both pre- and principal Q peaks.