Vaporization of the prototypical ionic liquid BMImNTf2 under equilibrium conditions: a multitechnique study

The vaporization behaviour and thermodynamics of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf2) were studied by combining the Knudsen Effusion Mass Loss (KEML) and Knudsen Effusion Mass Spectrometry (KEMS) techniques. KEML studies were carried out in a large temperature range (398–567) K by using effusion orifices with 0.3, 1, and 3 mm diameters. The vapor pressures so measured revealed no kinetically hindered vaporization effects and provided second-law vaporization enthalpies at the mean experimental temperatures in close agreement with literature. By exploiting the large temperature range covered, the heat capacity change associated with vaporization was estimated, resulting in a value of −66.8 J K−1 mol−1, much lower than that predicted from calorimetric measurements on the liquid phase and theoretical calculations on the gas phase. The conversion of the high temperature vaporization enthalpy to 298 K was discussed and the value ΔglHm(298 K) = (128.6 ± 1.3) kJ mol−1 assessed on the basis of data from literature and present work. Vapor pressure data were also processed by the third-law procedure using different estimations for the auxiliary thermal functions, and a ΔglHm(298 K) consistent with the assessed value was obtained, although the overall agreement is sensitive to the accuracy of heat capacity data. KEMS measurements were carried out in the lower temperature range (393–467) K and showed that the largely prevailing ion species is BMIm+, supporting the common view of BMImNTf2 vaporizing as individual, neutral ion pairs also under equilibrium conditions. By monitoring the mass spectrometric signal of this ion as a function of temperature, a second-law ΔglHm(298 K) of 129.4 ± 7.3 kJ mol−1 was obtained, well consistent with KEML and literature results. Finally, by combining KEML and KEMS measurements, the electron impact ionization cross section of BMIm+ was estimated.