Are Room-Temperature Ionic Liquids Dilute Electrolytes?
An important question in understanding the structure of ionic liquids is whether ions are truly "free" and mobile, which would correspond to a concentrated ionic melt, or are rather "bound" in ion pairs, that is, a liquid of ion pairs with a small concentration of free ions. Recent surface force balance experiments from different groups have given conflicting answers to this question. We propose a simple model for the thermodynamics and kinetics of ion pairing in ionic liquids. Our model takes into account screened ion-ion, dipole-dipole, and dipole-ion interactions in the mean-field limit. The results of this model suggest that almost two-thirds of the ions are free at any instant, and ion pairs have a short lifetime comparable to the characteristic time scale for diffusion. These results suggest that there is no particular thermodynamic or kinetic preference for ions to reside in pairs. We therefore conclude that ionic liquids are concentrated, rather than dilute, electrolytes.
†Mathematical Institute, University of Oxford, Oxford OX2 6GG, United Kingdom.
Alpha A
AA
Lee
†Mathematical Institute, University of Oxford, Oxford OX2 6GG, United Kingdom.
Dominic
D
Vella
‡Department of Chemistry, University of Oxford, Oxford OX1 3QZ, United Kingdom.
Susan
S
Perkin
†Mathematical Institute, University of Oxford, Oxford OX2 6GG, United Kingdom.
Alain
A
Goriely
McMilan−Mayer model; Poisson−Boltzmann theory; associating liquids; electrolyte solutions; ion pairs