Abstract
Here we report the theory and experimental study of the steady-state voltammetric behavior of a microelectrode used as a limiting pole in a closed bipolar electrochemical cell. We show that the steady-state voltammetric response of a microelectrode used in a closed bipolar cell can be quantitatively understood by considering the responses of both poles in their respective conventional two-electrode setups. In comparison to a conventional electrochemical cell, the voltammetric response of the bipolar cell has a similar sigmoidal shape and limiting current; however, the response is often slower than that of the typical two-electrode setup. This leads to a broader voltammogram and a decreased wave slope, which can be somewhat misleading, causing the appearance that the process being studied is irreversible when it instead can be a result of the coupling of two reversible processes. We show that a large limiting current on the excess pole would facilitate the observation of a faster voltammetric response and that both redox concentration and electrode area of the excess pole affect the wave shape. Both factors should be maximized in electroanalytical experiments in order to obtain fast voltammetric responses on the main electrode of interest and to detect quick changes in analyte concentrations.