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arXiv · 2610.39159

A Geometry-Induced Finite Warburg element for Reversible Diffusion Impedance at Microdisk Electrodes

Kazuhiko Seki·Yuko Yokoyama·Masahiro Yamamoto
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Abstract

A compact analytical representation is developed for the diffusion impedance of a disk electrode under reversible conditions, obtained by transforming the chronoamperometric relaxation function into the frequency domain. A Padé approximant is constructed for the uniform-concentration boundary condition, preserving the finite low-frequency diffusion resistance of the steady-state disk current and the high-frequency Cottrell regime. It is extended to reactions in which both oxidized and reduced species contribute, with unequal diffusion coefficients and surface concentrations. Its accuracy is quantified against converged numerical solutions, including an exact solution of the coupled problem with finite-rate kinetics. The approximant reproduces the Saito resistance and the $45^{\circ}$ Warburg phase exactly; its modulus is within 0.6\% of the converged solution for $ωa^2/D\le12$ and 7\% below the Cottrell amplitude at high frequency. The uniform-concentration and uniform-flux boundary conditions both give a diffusion impedance of geometric origin, but differ by up to 11\% in modulus because each couples differently to the spreading diffusion field; a criterion based on the rate constant and the disk radius delineates where each applies. The exact solution shows that this crossover is broad and that the decomposition into a charge-transfer resistance and a diffusion impedance is accurate to about 5\% for $1\le2k^0a/D\le100$. Fitted to a published spectrum of a platinum microdisk, it reproduces the reported diffusion coefficient within 1\%, while the two limiting elements lie 4.8\% below and 4.1\% above it. The element is a practical tool for microdisk impedance analysis.

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Kazuhiko Seki, Yuko Yokoyama, Masahiro Yamamoto. 2026-10-29. A Geometry-Induced Finite Warburg element for Reversible Diffusion Impedance at Microdisk Electrodes. https://arxiv.org/abs/2610.39159

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