DIRECT DIGITAL-SIMULATION OF THE STEADY-STATE LIMITING CURRENT AT A ROTATING-DISK ELECTRODE FOR A COMPLEX MECHANISM

The steady-state limiting current at a rotating disk electrode was simulated for a complex mechanism involving homogeneous electron transfer from a mediator to an alkyl halide leading to a short-lived radical that either couples with the anion radical of the mediator or is reduced by it. The simulations consisted of the iterative solutions of the linearised form of the nonlinear system of equations resulting from the formulation. The working curves derived from the simulation were compared with experimental curves, and the competition parameter and the rate constant for homogeneous electron transfer were measured. The results were compared with results obtained by other electrochemical techniques, and generally good agreement was found.