Nonadditivity of faradaic currents and modification of double layer capacitance in the voltammetry of mixtures of ferrocene and ferrocenium salts in ionic liquids

Electrochemical studies on the Fc + e(-) reversible arrow Fc(+) (Fc = ferrocene) process have been undertaken via the oxidation of Fc and reduction of Fc. as the hexafluorophosphate (Pr-6(-)) or tetrafluoroborate (BF4-) salts and their mixtures in three ionic liquids (ILs) (1-butyl-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium hexafluorophosphate). Data obtained at macro- and microdisk electrodes using conventional dc and Fourier-transformed large-amplitude ac (FT-ac) voltammetry reveal that diffusion coefficients for Fc and Fc(+) differ significantly and are a function of the Fc and Fc(+) concentration, in contrast to findings in molecular solvents with 0.1 M added supporting electrolyte media.