Small angle X-ray studies of short-range order in non-stoichiometric pseudoprotic ionic liquids: the influence of chemical structure

Abstract

Mixtures of organic acids and amines have been studied extensively owing to their unusual physicochemical properties and applications as solvents for extraction. In equimolar ratios they represent pseudoprotic ionic liquids, and in other, “nonstoichiometric” ratios they display a range of odd physicochemical behaviors. We report the results of small-angle X-ray scattering studies of a series of such systems with a range of chemical structures chosen to explore the link between molecular geometry and the character of the emergent nanoscale local liquid structure. We find that while the details vary, structure can emerge even when the hydrogen-bonding character of the components is changed significantly and the character of their hydrocarbon substituents is altered. The consistent emergence of local order in the face of varying chemical structures indicates that the process is robust. This implies that the emergence of such structure may in fact be far more common in liquid mixtures than is currently recognized, and a great many structures may be suitable for the synthesis of pseudoprotic ionic liquids.