The mechanistic details of this reaction are of great interest due to the notable reactivity difference observed between DC and rAP. A truly authoritative and complete understanding of this phenomenon would likely entail the use of various electroanalytical methods involving microelectrodes as well as rotating disc electrodes to dissect fast electron transfer kinetics under stationary and non-stationary electrolysis conditions. Such detailed studies are beyond the scope of this Communication, and will form the basis of a separate endeavor. For the time being, several pieces of empirical evidence are presented in Figure that help to rationalize the differences in bulk reactivity. For instance, a large reactivity difference was observed in the reduction of compound 43 between DC and rAP. Remarkably, the reduction potential of this compound (<-3V) resides far outside the reduction potential of the reaction solvent (Figure , solvent CV), yet rAP delivered the product in 45% NMR yield. In contrast, under otherwise identical conditions employing a standard DC waveform resulted in mostly recovered starting material. The most notable visual difference between these two reactions was gas evolution. With DC, gas evolution was clearly visible from the cathode, whereas this phenomenon was not apparent in the rAP experiment. Consistent with this observation, gas evolution from the working electrode was also confirmed after measuring CV of the solvent. We hypothesized that hydrogen gas was being formed on the cathode (reductive) in the protic medium. To prove the existence of H2 qualitatively, simple hydrogenation experiments were performed; namely, either DC or rAP was applied to the reaction solvent including cyclooctene in the presence of Pd/C catalyst (Figure ). To be sure, cyclooctene is unreactive under the arene reduction conditions, and redox perturbation of Pd/C catalyst by electrodes is unlikely since Pd/C does not dissolve in the solvent. A considerable quantity of hydrogenated product 45 was observed in the DC electrolysis, while 45 was below the GC/MS detection limit in the rAP experiment, suggesting that H2 gas was not generated to an appreciable extent.