Evaluating the contributions to conductivity in room temperature ionic liquids.

The conductivity of room temperature ionic liquids is not described adequately by the Nernst-Einstein equation, which accounts only for Brownian motion of the ions. We report on the conductivity of the ionic liquid 1-butyl-3-methylimidazolum bis(trifluoromethylsulfonyl) imide (BMIM TFSI), comparing the known conductivity of this RTIL to the diffusion constants of the cationic and anionic species over a range of length scales, using time-resolved fluorescence depolarization and fluorescence recovery after photobleaching (FRAP) measurements of chromophores in the RTIL. Our data demonstrate that the diffusional contribution to molar conductivity is ca. 50%. Another mechanism for the transmission of charged species in RTILs is responsible for the "excess" molar conductivity, and we consider possible contributions.