Convective mass transport in ionic liquids studied by electrochemical and electrohydrodynamic impedance spectroscopy

In this work, the role of convective mass transport in two ionic liquids (ILs) that differ by the anions 1-butyl-2,3-dimethyl-imidazolium bis(trifluoromethanesulfonyl)imide ([BMMI][Tf2N]) and 1-butyl-2,3-dimethyl-imidazolium tetrafluorborate ([BMMI][BF4]) were studied in the presence of ferrocene (Fe) as a redox tracer. A rotating disk electrode (RDE) system was used, and the use of electrochemical (EIS) and electrohydrodynamic (EHD) impedance spectroscopies allowed for a deeper analysis of mass transport and charge transfer at the surface of the electrode. The two ILs showed a viscoelastic character that was observed using a parallel plate geometry viscometer with a high storage-to-loss modulus ratio in a frequency domain where the RDE response was characterized by significant elongational flow kinematics. As a general conclusion, the observed effects were interpreted as unbalanced contributions of the elongational flow close to the electrode surface, which induced an anisotropic diffusivity that increased along the flow lines, and the effect of Fc and Fc(+) as structure breakers or strengtheners in the diffusion layer. Finally, from EIS analysis, it was established that increasing the overpotential in the anodic direction yielded an increased Schmidt number, which indicated a detrimental effect on the mass transport of Fc(+), whose production rate was also increased under the same conditions. EIS showed that the anion had an effect on the reaction rate of Fc oxidation and on the double-layer capacitance value. (C) 2013 Elsevier Ltd. All rights reserved.