J. Phys. Chem. B 124 (9) 1767-1777 [2020-03-05; online 2020-02-20]
We investigate the effect of adding different molecular cosolvents, water or imidazole, to the protic ionic liquid 1-ethylimidazolium bis(trifluoromethanesulfonyl)imide, i.e., [C2HIm][TFSI]. We explore how the added cosolvent distributes within the ionic liquid by means of molecular dynamics simulations and X-ray scattering. We also analyze the degree of short-range heterogeneity in the resulting mixtures, finding that while imidazole easily mixes with the protic ionic liquid, water tends to form small clusters in its own water-rich domains. These differences are rationalized by invoking the nature of intermolecular interactions. In aqueous mixtures water-water hydrogen bonds are more likely to form than water-ion hydrogen bonds (water-TFSI bonds being particularly weak), while imidazole can interact with both cations and anions. Hence, the cation-anion association is negligibly influenced by the presence of water, whereas the addition of imidazole creates solvent-separated ion pairs and is thus able to also increase the ionicity. As a consequence of these structural and interactional features, transport properties like self-diffusion and ionic conductivity also show different composition dependencies. While the mobility of both ions and solvent is increased considerably by the addition of water, upon adding imidazole this property changes significantly only for molar fractions of imidazole above 0.6. At these molar fractions, which correspond to a base-excess composition, the imidazole/[C2HIm][TFSI] mixture behaves as a glass-forming liquid with suppressed phase transitions, while homomixtures such as imidazole/[HIm][TFSI] can display a eutectic point.