How Proton Transfer Equilibria Influence Ionic Liquid Properties: Molecular Simulations of Alkylammonium Acetates

AT Nasrabadi and LD Gelb, JOURNAL OF PHYSICAL CHEMISTRY B, 122, 5961-5971 (2018).

DOI: 10.1021/acs.jpcb.8b01631

Protic ionic liquids (PILs) form through proton transfer from a Bronsted acid to a Bronsted base. In this work we use molecular dynamics simulation to study how PIL properties vary with chi, the extent of the proton transfer reaction. Three PILs are considered: N-propylam-monium acetate, N3Ac, N-butylammonium acetate, N4Ac, and N,N-dimethylbutylammonium acetate, N114Ac. In all cases density and viscosity increase with increasing chi, while diffusivities of all species decrease with increasing chi. In each PIL the ionic conductivity exhibits a maximum at intermediate chi due to competition between increasing ion concentration and decreasing ion mobility. Ionicity analysis suggests that strongly correlated behavior is present at all chi. Finally, we determine the chi for which the properties of each simulated PM best agree with experimental data; these are chi = 0.86, 0.80, and 0.18 for N3Ac, N4Ac, and N114Ac, respectively. These results suggest that proton transfer is nearly complete in the primary ammonium Pits but not in the tertiary ammonium PIL, consistent with recent experimental observations. We propose that this difference is due to cooperative production of hydrogen bonds with increasing chi in the primary ammonium PILs, which does not occur in the tertiary ammonium PIL.

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