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Effect of ohmic, mass-transfer, and kinetic resistances on linear-sweep voltammetry in a cylindrical-pore electrodeA means is presented to account for the effect of ohmic, mass-transfer, and kinetic resistances on linear-sweep voltammograms 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(-) yield 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 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.
Document ID
19910067150
Acquisition Source
Legacy CDMS
Document Type
Reprint (Version printed in journal)
Authors
Weidner, John W.
(North Carolina State Univ. Raleigh, NC, United States)
Fedkiw, Peter S.
(North Carolina State University Raleigh, United States)
Date Acquired
August 14, 2013
Publication Date
September 1, 1991
Publication Information
Publication: Electrochemical Society, Journal
Volume: 138
ISSN: 0013-4651
Subject Category
Inorganic And Physical Chemistry
Accession Number
91A51773
Funding Number(s)
CONTRACT_GRANT: NAG3-649
Distribution Limits
Public
Copyright
Other

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