Communication: Glass transition and melting lines of an ionic liquid

The phase diagram of the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesufonyl)imide, [Pyrr1,4][NTf2], was explored by synchroton X-ray diffraction and Raman scattering measurements as a function of temperature and pressure. Glass transition Tg(p) and melting Tm(p) temperatures were obtained from atmospheric pressure up to ca. 2.0 GPa. We found that both the Tg(p) and Tm(p) curves follow essentially the same pressure dependence. The similarity of pressure coefficients, dTg/dp ≈ dTm/dp, is explained within the non-equilibrium thermodynamics approach for the glass transition by assuming that one of the Ehrenfest equations is appropriated for Tg(p), whereas Tm(p) follows the Clausius-Clapeyron equation valid for the first-order transitions. The results highlight that ionic liquids are excellent model systems to address fundamental questions related to the glass transition.