Journal of Physical Chemistry B, Vol.119, No.25, 8146-8153, 2015
Stability of the Liquid State of Imidazolium-Based Ionic Liquids under High Pressure at Room Temperature
To understand the stability of the liquid phase of ionic liquids under high pressure, we investigated the phase behavior of a series of 1-alkyl-3-methylimidazolium tetrafluoroborate ([C(n)mim] [BPS4]) homologues with different alkyl chain lengths for 2 <= n <= 8 up to similar to 7 GPa at room temperature: The ionic liquids exhibited complicated phase behavior, which was likely due to the conformational flexibility in the alkyl chain. The present results reveal that [C(n)mim] [BF4] falls into superpressed state around 2-3 GPa range upon compression with an implication of multiple phase Or structural transitions to similar to 7 GPa. Remarkably, a characteristic nanostructural organization in ionic liquids largely diminishes at the superpressed state. The behaviors of imidazolium-based ionic liquids can be classified into, at least, three patterns: (1) pressure-induced crystallization, (2) superpressurization upon compression, and (3) decompression-induced crystallization from the superpressurized glass. Interestingly, the high-pressure phase behavior was relevant to the glass transition behavior at low temperatures and ambient pressure. As n increases, the glass transition pressure (p(g)) decreases (from 2.8 GPa to similar to 2 GPa), and the glass transition temperature increases. The results indicate that the p-T range of the liquid phase is regulated by the alkyl chain length of [C(n)mim][BF4] homologues.