Structure of the Electrical Double Layer Revisited: Electrode Capacitance in Aqueous Solutions

The structure of the electrical double layer at the interface of planar electrodes and aqueous solutions is investigated. Electrical impedance spectroscopy is used to measure the impedance of aqueous solutions of sodium chloride and two different surfactants over a wide range of concentrations. The electrode capacitance is directly inferred from the admittance spectra as well as by regression of the impedance spectra to an equivalent circuit. It is found that the electrode capacitance remains on the same order of magnitude over the entire range of investigated concentrations. This is contradictive to the predictions of the Gouy-Chapman-Stern theory which predicts that, at low concentrations, the electrode capacitance should be determined by the diffuse layer. It is concluded that the Stern layer capacitance always dominates the electrode capacitance, even at very low concentrations, and the establishment of a diffuse layer capacitance requires an ionic strength of around 1 mM.