Concentration Profiles at the Electrode Surface

In an unstirred solution, mass transport of the analyte to the electrode surface occurs by diffusion alone.¹ Fick’s Law for mass transfer diffusion relates the distance from the electrode (x), time (t), and the reactant concentration (CA) to the diffusion coefficient (DA).

During a reduction, current increases until it reaches a peak: when all M+ exposed to the surface of an electrode has been reduced to M. At this point additional M+ to be reduced can travel by diffusion alone to the surface of the electrode, and as the concentration of M increases, the distance M+ has to travel also increases. During this process the current which has peaked, begins to decline as smaller and smaller amounts of M+ approach the electrode. It is not practical to obtain limiting currents Ipa, and Ipc in a system in which the electrode has not been stirred because the currents continually decrease with time.¹

In a stirred solution, a Nernst diffusion layer ~10^-2 cm thick, lies adjacent to the electrode surface. Beyond this region is a laminar flow region, followed by a turbulent flow region which contains the bulk solution.¹ Because diffusion is limited to the narrow Nernst diffusion region, the reacting analytes cannot diffuse into the bulk solution, and therefore Nernstian equilibrium is maintained and diffusion-controlled currents can be obtained. In this case, Fick’s Law for mass transfer diffusion can be simplified to give the peak current