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- W2184758086 abstract "Electrochemical impedance spectroscopy (EIS) is commonly used by electrochemists to analyze multi-step reaction paths occurring at electrode/electrolyte interfaces. Since the kinetics of individual reaction steps is usually a function of electrode potential, the impedance of the interface is measured for different but constant potential values. In most cases, impedance diagrams are obtained from harmonic analysis: a surimposed low amplitude (typically 5-10 mV) ac potential modulations or alternatively, a low amplitude (typically a few mA) ac galvanostatic modulation, is used as perturbation. However, according to the theory of linear and time invariant systems, harmonic analysis should be restricted to the analysis of linear and reversible processes. To a certain extend, the problem of linearity can be circumvented by reducing the amplitude of the modulation. But that does not help to solve the problem of irreversibility. For example, a significantly large hysteresis is observed during the electro-insertion of hydrogen into palladium or palladium alloy electrodes. This is a clear indication that non-linear phenomena are taking place and therefore, the use of harmonic analysis should be prohibited because the system does not fulfill the requirements of linearity and time invariance imposed by the theory of systems. There is therefore a need to use non-alternating perturbations. The purpose of this paper is to report on the measurement of impedance spectra from exponentially-rising voltage-step excitations. This is a methodology-oriented communication. In the first part of the paper, an electrical circuit containing only electrical resistances and capacitances is used as a model system to explain how impedance diagrams can be obtained from such non-harmonic perturbations. In the second part of the paper, the methodology is extended to the electro-insertion of hydrogen in palladium foils." @default.
- W2184758086 created "2016-06-24" @default.
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- W2184758086 date "2012-01-01" @default.
- W2184758086 modified "2023-09-27" @default.
- W2184758086 title "Electrochemical impedance spectroscopy using exponentially-rising voltage steps. (I) Analysis of a model electrical circuit" @default.
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