The Apparent Constant-Phase-Element Behavior of a Disk Electrode with Faradaic Reactions: A Global and Local Impedance Analysis

Abstract

Geometry-induced current and potential distributions modify the global impedance response of a disk electrode subject to faradaic reactions. The problem was treated for both linear and Tafel kinetic regimes. The apparent capacity of a disk electrode embedded in an insulating plane was shown to vary considerably with frequency. At frequencies above the characteristic frequency for the faradaic reaction, the global impedance response has a quasi-constant-phase element (CPE) character, but with a CPE coefficient α that is a function of both dimensionless frequency K and dimensionless current density J. For small values of J, α approached unity, whereas, for larger values of J, α reached values near 0.78. The calculated values of α are typical of those obtained in impedance measurements on disk electrodes. For determining the interfacial capacitance, the influence of current and potential distributions on the impedance response cannot be neglected, even if the apparent CPE exponent α has values close to unity. Several methods taken from the literature were tested to determine their suitability for extracting interfacial capacitance values from impedance data on disk electrodes. The best results were obtained using a formula which accounted for both ohmic and charge-transfer resistances.