Dataset for Simulation of the cyclic voltammetric response of an outer-sphere redox species with inclusion of electrical double layer structure and ohmic potential drop

We also show that the concentrations of Oz and Rz 1 at the plane of electron transfer (PET) significantly depart from those predicted by the Nernst equation, even when the system is characterised by fast electron transfer/diffusion control. A mechanistic rationalisation is presented as to why the electric double layer has a negligible effect on the CV response of such reversible systems. In contrast, for quasi-reversible electron transfer the concentrations of redox species at the PET are shown to play an important role in determining CV wave shape, an effect also dependant on the charge of the redox species and the formal electrode potential of the redox couple.

Failure to consider electrostatic effects could lead to incorrect interpretation of electron-transfer kinetics from the CV response. Simulated CVs at scan rates between 0.1 and 1000 V/s are found to be in good agreement with experimental data for the reduction of 1.0 mM Ru(NH3)63+ at a 2-mm diameter gold disk electrode in 1.0 M potassium nitrate.