Why Do Liquids Mix? The Mixing of Protic Ionic Liquids Sharing the Same Cation is Apparently Driven by Enthalpy, not Entropy

We study hydrogen bond (HB) redistribution in mixtures of two protic ionic liquids (PILs) sharing the same cation: triethylammonium-methanesulfonate ([TEA][OMs]) and triethylammonium-trifluoromethanesulfonate ([TEA][OTf]). The mixture is exhibiting large negative energies of mixing. Based on results obtained from atomic detail molecular dynamics (MD) simulations, we derive a lattice model, discriminating between HB and nonspecific intermolecular interactions. We demonstrate that due to the ordered structure of the PILs, mostly the HB interactions contribute to the mixing energy. This allows to us to connect the equilibrium of HBs to each of the two anion species with the corresponding excess energies and entropies. The entropy associated with HB redistribution is shown to be negative, and even overcompensating the positive entropy associated with a statistical distribution of the ions in the mixture. This is strongly suggesting that the mixing process is driven by enthalpy, not entropy.