Document Type

Article

Subject Area(s)

Chemical Engineering

Abstract

Extracting quantitative kinetic information from linear-sweep voltammograms (LSV) on porous electrodes is more difficult than on planar electrodes since the electrode surface is not uniformly accessible to the bulk supply of reactant or the counterelectrode. We present here a means to account for the effect of ohmic, mass-transfer, and kinetic resistances on LSV by modeling a pore in a porous matrix as a cylindrical-pore electrode, and solving the mass and charge conservation equations in the context of this geometry for the simply redox reaction O + ne <=> R where both O and R are soluble species. Both analytical and numerical techniques are used to solve the governing equations. The calculated peak currents and potentials are correlated by simple-to-apply empirical formulas to the measurable parameters: sweep rate, concentration of the redox species, diffusion coefficient, conductivity of the electrolyte, and pore dimensions. Using the correlations, a methodology is established for determining if the redox reaction kinetics are irreversible or reversible (Nernstian). If the reaction is irreversible, it is shown how the standard rate constant and the transfer coefficient may be extracted from linear-sweep voltammetry data, or if the reaction is reversible, how the number of electrons transferred may be deduced.

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