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6.1 Theory of Bipolar Electrochemistry

DOI: 10.1055/sos-SD-236-00125

Villani, E.; Inagi, S.Science of Synthesis: Electrochemistry in Organic Synthesis, (20211156.

To explain the theory of bipolar electrochemistry, one should consider the following example where a conducting object (any material composed of metal, carbon, conductive metal oxides, etc.) is placed in an electrolytic solution in between two feeder electrodes (collectors). In a solution containing a low concentration of supporting electrolyte, electrical double layers at the electrode/solution interface are poorly formed; instead, the generation of an electric field extending into the bulk solution is expected when a potential difference is applied between the feeder electrodes. As a consequence, and due to the fact that the conducting object can be considered as equipotential, individual anodic and cathodic overpotentials can be established at every point of the object, with opposite polarization respective to the polarization of the feeder electrode; for example, the side of the object facing the feeder anode will become cathodic and vice versa. When electroactive species, red1 and ox2, are present in the electrolytic solution, electrochemical reactions can occur at the opposite sides of the object as shown in the equations in Figure 3, where n1 and n2 are the number of electrons involved in each electrochemical process, red1/ox1 and ox2/red2 are the two redox couples, and E1° and E2° the standard potentials of each reaction.

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