To explore the kinetics somewhat more quantitatively, we specifically analyse the number of EC molecules in the reaction cell, defined by the distance of at most 1 nm from the electrode. Again the elementary electron transfer rate has been systematically varied. As seen in Figure (a), the reduction rate is effectively reduced to considerably smaller values at longer times due to the observed diffusion and migration effects. For a quantitative comparison of the effective rates, we have calculated the normalized rate ν ef f = ṅEC n EC by extracting the numerical time-derivative from the EC molecular number from Figure normalized by the EC number within the reaction cell shown in Figure (a). The result is shown in Figure . For short times the effective rates are proportional to the elementary rates (dashed lines). The difference expresses the necessity of the presence of a nearby lithium ion to perform a reaction. After the initial transient regime a transition to the "diffusioncontrolled regime" can be observed, where the elementary electron transfer rate has little influence and the effective reaction rate is limited by the available number of Li + ions.