Marcus theory of outer-sphere heterogeneous electron transfer reactions: High precision steady-state measurements of the standard electrochemical rate constant for ferrocene derivatives in alkyl cyanide solvents

Electrochemistry in media of exceptionally low polarity: Voltammetry with a fluorous solvent

“…It has been reported previously that for ferrocene as the redox-active analyte and a variety of solvents ranging from chloroform to acetonitrile [32,41] (see also Figure 7) a plot of log k ° versus log τ L shows the expected linear relationship. This shows that for ferrocene the term K p κ EL ( ΔG OS *) 1/2 (4 πRT ) −1/2 exp(− ΔG */ RT ) has only a small dependence on the solvent.…”

“…Log-log plot of k ° versus τ L along with a linear fit for the literature data (open circles, [32,40,41]) only. The fit is extrapolated to the τ L for perfluoro(methylcyclohexane) (filled circle).…”

Thin-layer cyclic voltammetric studies electron transfer across liquid/liquid interface

“…The results show that it is essentially insensitive for rate constants of ET at ITIES to depend on the potential applied across the interface. However, improving driving force further, liquid/liquid interface may be entered into the inverted region of Marcus theory [62], which is also observed by Bard and others. Results indicate the values of ket decrease with the values of Δw o Φ increasing high enough, which is not in agreement with previous conventional Bulter-Volmer treatment.…”

Electrochemical Behavior of Cobaltocene in Ionic Liquids

“…For comparison, the D (Fc)/ D (Cc + ) ratio is also higher than unity in solutions with molecular solvents. For example D (Fc)/ D (Cc + ) = 1.77 in acetonitrile { D (Fc) = 2.3 × 10 −5 cm 2 ·s −1 [49] and D (Cc + ) = 1.30 × 10 −5 cm 2 ·s −1 [39]}. All of this information suggests that the Fc molecule and Cc + cation, although of similar shape and radius, are probably solvated differently, as suggested in Ref.…”