Structure and anomalous underscreening in ethylammonium nitrate solutions confined between two mica surfaces

The observation of long-range interactions across ionic liquids and highly concentrated electrolytes, extending far beyond the Debye-Huckel prediction and beyond the range predicted in liquid state theory, has been called 'anomalous underscreening'. A number of theoretical and experimental works have explored this phenomenon over recent years, although its origin is not yet fully understood. Most of the experimental studies of anomalous underscreening until now involved aprotic ionic liquids, and so it is of interest to explore interactions in protic ionic liquids where the distribution of charge in the fluid is different in nature. Here we present direct measurements of the interaction force as a function of separation distance, measured using a surface force balance, across solutions of a protic ionic liquid ethylammonium nitrate (EAN) and its mixtures with water over a range of volume fractions from 10 vol% to 100 vol% EAN. The results reveal intricate details about near-surface ordering and dynamics at the EAN-mica interface as well as anomalous underscreening consistent with that observed in the past with aprotic ionic liquids.