Shifts in Redox Formal Potentials Accompanying the Incorporation of Cationic Complexes in Perfluoro Polycarboxylate and Polysulfonate Coatings on Graphite Electrodes

The formal potentials of several redox couples incorporated in coatings of a perfluoropolycarboxylate on graphite electrodes were measured and compared with the formal potentials of the same couples in homogeneous solution. The differences observed agreed with those calculated from the Nernst equation with the independently measured incorporationcoefficients for both halves of the redox couples. The dependences of the shifts in formal potentials on the nature of theincorporating complex ion, the ionic strength, and the temperature were determined and indicated that the incorporationequilibrium is governed by electrostatic and hydrophobic interactions that act in opposite directions. The incorporation ofmost cations examined was driven by large increases in entropy which overcame the usually unfavorable enthalpy changes