Dissecting the Vaporization Enthalpies of Ionic Liquids by Exclusively Experimental Methods: Coulomb Interaction,Hydrogen Bonding,and Dispersion Forces

The quantification of hydrogen bonding and dispersion energies from vaporization enthalpies is a great challenge. Dissecting interaction energies is particularly difficult for ionic liquids (ILs), for which the composition of the different types of interactions is known neither for the liquid nor for the gas phase. In this study, we demonstrate the existence of ion pairs in the gas phase and dissect the interaction energies exclusively from measured vaporization enthalpies of different alkylated protic ILs (PILs) and aprotic ILs (AILs) and the molecular analogues of their cations. We demonstrate that the evaporated ion pairs are characterized by H‐bond‐enhanced Coulomb interaction. The overall interaction energy for the ILs in the bulk phase is composed of Coulomb interaction (76 kJ mol^?1), hydrogen bonding (38 kJ mol^?1), and minor dispersion interaction (10 kJ mol^?1). Thus, hydrogen bonding prominently contributes to the overall interaction energy of PILs, which is reflected in the properties of this class of liquids.