Thermodynamics of ionic liquid evaporation under vacuum.

The low volatility of ionic liquids (ILs) is one of their most interesting physico-chemical properties; however, the general understanding of their evaporation dynamics under vacuum is still lagging. Here, we studied the thermodynamics of IL evaporation by employing thermogravimetry (TG) measurements under vacuum. The thermodynamic parameters of ILs, such as the evaporation onset temperatures, enthalpies, entropies, saturation vapor pressures, and boiling points were quantified by analyzing the TG data. The obtained evaporation enthalpies (110-140 kJ mol-1) were higher than those of typical molecular liquids, and the entropies (>88 J mol-1 K-1) suggested that they are exceptions of the Trouton's rule. The obtained Clausius-Clapeyron equations demonstrated that the saturation vapor pressures of ILs only depend on temperature. Further, we derived the empirical equation for estimating the upper limit temperature of the liquid phase of IL under given external pressures. Using the evaporation behaviors of referential normal alkanes and charge-transfer complex and the evaporation entropies of the ILs, the vaporized IL structure was thermodynamically modelled. The ILs were found to evaporate as ion pairs, instead of as individual ions or higher-ordered cluster structures. By comparing a series of ILs with various cations and a fixed anion, it was found that the IL evaporation dynamics under vacuum is strongly and systematically affected by their chemical structures, charge balances between the cations and the anions, molecular weights, and the higher-ordered structures including polar and non-polar regions. Our concept, measurement method, and equation can be extended to other ILs and low-volatile liquids under vacuum, and help with the design of ILs with higher thermal stabilities.