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A singular perturbation analysis has been developed for the dissolution of a copper rotating disk in 0.1N HCl that is based on an assumed E/sub r/C/sub i/ reaction mechanism. The underlying objective of the paper is to explore the effect that finite rates of a homogeneous chemical reaction can have on the preceding heterogeneous electrode reaction. Calculated complex-plane and Bode plots, for a wide range of values of the homogeneous-reaction rate constant {kappa}/sub b/, demonstrate the significant effect that the chloride complexing reaction can have on the frequency dependence of the faradaic impedance. An additional semicircle results in the complex plane due to the chemical reaction, and provides a basis for determining the homogeneous-reaction rate constant from frequency-response data. Other reaction mechanisms that possibly describe the copper dissolution process, as well as ways to distinguish experimentally between the different cases are discussed. Comparison of the available experimental copper dissolution data with the dimensionless faradaic impedance complex-plane plot yields a value of the order of a 10/sup 7/ s/sup -1/ for {kappa}/sub b/. Also, results from the perturbation formulation of the problem are compared to the numerically-calculated results of the Stefan-Maxwell impedance model.

Singular Perturbation Analysis of the Faradaic Impedance of Copper Dissolution Accounting for the Effects of Finite Rates of a Homogeneous Reaction