Digital simulation of chronoamperometry at an electrode within a hemispherical polymer drop containing an enzyme: Comparison of a hemispherical with a flat disk electrode

Current-time and steady state current behaviour was simulated for the cases of a hemispherical and flat inlaid disk electrodes located under a hemispherical polymer drop containing an enzyme which converts a substrate diffusing into the drop into a product that is electroactive at the electrode. As well, a cylindrical electrode with length much greater than its diameter and coated with a layer of polymer/enzyme was treated. The ratio of steady state currents at the hemispherical to the disk electrode is not, as has sometimes been assumed, always equal to π/2; indeed this is only approached for polymer drops with large spillover ratio, that is, having a radius much larger than that of the electrodes. Steady state currents for all electrode geometries (including the cylinder) go through a maximum for some spillover ratio and then approach a constant value for larger spillover ratios. This constant value is the same as that for the diffusion limited current in a semi-infinite medium. For a cylindrical electrode, the steady state current tends towards zero for large spillover ratios.