Publication Details (including relevant citation information):
Vorotyntsev Mikhail A., Zinovyeva Veronika A., Konev Dmitry V., Picquet Michel, Gaillon Laurent, Rizzi Cécile
J. Phys. Chem. B 2009, 113, 1085–1099
Several earlier studies of the electrochemical oxidation of ferrocene (Fc) in room-temperature ionic liquids revealed an essentially nonlinear dependence of the oxidation current on the Fc concentration in its relatively dilute solutions, with its formally calculated diffusion coefficient strongly increasing with the concentration. Since no plausible mechanism leading to this very unusual finding had been proposed, our study of Fc solutions in 1-butyl-3-methylimidazolium triflimide, [BMIM][NTf2], was performed to verify whether the above observation originated from an incorrect determination of the dissolved Fc concentration. Our observations have demonstrated that reliable control of the Fc concentration in solution is complicated by factors such as the low amount of Fc used to prepare small-volume solutions or the great difficulty to dissolve completely a solid powder in a solvent with an extremely high viscosity. An unexpected additional complication is related to a sufficiently high volatility of Fc which manifests itself even at room temperature and especially at elevated temperatures or/and in the course of vacuum treatment of its solutions or its solid powder. Parallel measurements of electrochemical responses and UV−visible spectra for several series of Fc solutions of various concentrations (prepared with the use of different procedures) have shown a perfect parallelism between the peak current and the intensity of the absorption band in the range of 360−550 nm, leading us to the conclusion of a linear relationship between the oxidation current and the molecularly dissolved Fc concentration. The relations of these measured characteristics with the estimated Fc concentration in these solutions have demonstrated a much greater dispersion (attributed to the difficulty of a precise measurement of the latter) but without a significant deviation from the linearity in general. This finding has allowed us to estimate the diffusion coefficient of this species: D = (1.7 ± 0.2) × 10−7 cm2/s. The extinction coefficients for the maximum of the absorption band (at 440 nm) of Fc have been compared for a series of solvents: [BMIM][NTf2], acetonitrile, THF, heptane, CH2Cl2, ethanol, and toluene. A simple method to estimate reliably the concentration of solute Fc in ionic liquids based on spectroscopic measurements has been proposed, owing to the proximity of Fc absorption properties for a great variety of solvents.
Address (URL): http://pubs.acs.org/doi/abs/10.1021/jp809095q