Double-Layer Correction for Electron-Transfer Kinetics at Glassy Carbon and Mercury Electrodes in N,N-Dimethylformamide

The double‐layer properties of the glassy carbon electrode in N,N‐dimethylformamide (DMF) containing tetrabutylammonium perchlorate (TBAP) at different concentrations have been studied by cyclic voltammetry and impedance. The results were compared with analogous results obtained for the mercury/DMF interface. For both electrodes, the double‐layer data were treated to obtain useful equations describing the dependence of the outer Helmholtz plane potential on the applied potential. The kinetics of the dissociative reduction of a sulfide in DMF/0.1 M TBAP was studied by convolution analysis on both glassy carbon and mercury and used as an example to test the double‐layer results and compare the behavior of the two electrodes.