Application of Asymmetric Marcus–Hush Theory to Voltammetry in Room-Temperature Ionic Liquids

Asymmetric Marcus–Hush (AMH) theory is applied for the first time in ionic solvents to model the voltammetric reduction of oxygen in 1-butyl-1-methylpyrrolidinium bis-(trifluoromethylsulfonyl)-imide and of 2-nitrotoluene (2-NT), nitrocyclopentane (NCP), and 1-nitro-butane (BuN) in trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate on a gold microdisc electrode. An asymmetry parameter, γ, was estimated for all systems as −0.4 for the reduction of oxygen and −0.05, 0.25, and 0 ± 0.05 for the reductions of 2-NT, NCP, and BuN, respectively, which suggests equal force constants of reactants and products in the case of 2-NT and BuN and unequal force constants for oxygen and NCP where the force constants of the oxidized species are greater than the reduced species in the case of oxygen and less than the reduced species in the case of NCP. Previously measured values for α, the Butler–Volmer transfer coefficient, reflect this in each case. Where appreciable asymmetry occurs, AMH theory was seen...

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