Saturation Properties of 1‑Alkyl-3-methylimidazolium Based Ionic Liquids
datasetposted on 24.07.2014, 00:00 by Kaustubh S. Rane, Jeffrey R. Errington
We study the liquid–vapor saturation properties of room temperature ionic liquids (RTILs) belonging to the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][NTf2]) using Monte Carlo simulation. We examine the effect of temperature and cation alkyl chain length n on the saturated densities, vapor pressures, and enthalpies of vaporization. These properties are explicitly calculated for temperatures spanning from 280 to 1000 K for RTILs with n = 2, 4, 6, 8, 10, and 12. We also explore how the identity of the anion influences saturation properties. Specifically, we compare results for [C4mim][NTf2] with those for 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]). Simulations are completed with a recently developed realistic united-atom force field. A combination of direct grand canonical and isothermal–isobaric temperature expanded ensemble simulations are used to construct phase diagrams. Our results are compared with experimental data and Gibbs ensemble simulation data. Overall, we find good agreement between our results and those measured experimentally. We find that the vapor pressures and enthalpies of vaporization show a strong dependence on the size of the alkyl chain at low temperatures, whereas no particular trend is observed at high temperatures. Finally, we also discuss the effect of temperature on liquid phase nanodomains observed in RTILs with large hydrophobic groups. We do not observe a drastic change in liquid phase structure upon variation of the temperature, which suggests there is not a sharp phase transition between a nanostructured and homogeneous liquid, as has been suggested in earlier studies.