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. 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.