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Abstract: Local electrochemical impedance spectroscopy provides a powerful tool for the investigation of surface heterogeneities on electrode surfaces. However, measurements are greatly influenced by geometry-induced frequency dispersion. In order to account for this frequency dispersion, both simulations and experiments were performed to explore the influence of a recessed electrode on the local and global impedance response. The calculations presented here demonstrated that the depth of the recessed electrode required to achieve a uniform primary current distribution was twice the electrode radius. The calculations provide guidelines for design of LEIS measurements, and were in good agreement with results obtained for a stainless steel disk electrode in a Na2SO4 electrolyte. [Copyright &y& Elsevier]

A detailed analysis from both numerical calculations and experimental results is presented for the local electrochemical impedance spectroscopy (LETS) measurements of a disk electrode, which accounted for the placement of the LEIS probe above the electrode surface. The calculations for an electrode with a local constant phase element behavior were in excellent agreement with experimental observations for a stainless steel electrode in a Na2SO4/NaCl (pH 4) electrolyte. Measurement of the local impedance at two positions above the electrode surface allowed estimations of the local interfacial impedance and the local ohmic impedance, which were in excellent agreement with the simulations. The results demonstrate that the local impedance measurement itself cannot be used to estimate the surface area sampled by the LETS probe. The area sampled must be determined instead by the probe geometry. [ABSTRACT FROM AUTHOR]

Abstract: Two different mathematical formulas for estimating effective capacitance from Constant-Phase-Element (CPE) parameters, taken from the literature, are associated unambiguously with either surface or normal time-constant distributions. Application to different systems are used to illustrate the importance of using the correct formula that corresponds to a given type of distribution. Experiments and simulations are used to show that the effective capacitance obtained for a normal distribution yields correct values for the film thickness under conditions where the local resistivity does not vary significantly. When the local resistivity varies considerably over the thickness of a film, the experimental frequency range may preclude observation of the capacitance contribution of a portion of the film, resulting in under prediction of the film thickness. [Copyright &y& Elsevier]