electrode reaction rate constants

Also contains definitions of: conditional rate constant of an electrode reaction, standard rate constant of an electrode reaction
https://doi.org/10.1351/goldbook.E01961
The @[email protected] rate constants are related to the partial currents by \[k_{\mathrm{ox}}=\frac{l_{\text{a}}}{n\ F\ A\ \Pi\: c_{i}^{\nu _{i}}}\] \[k_{\mathrm{red}}=\frac{l_{\text{c}}}{n\ F\ A\ \Pi\:c_{i}^{\nu _{i}}}\] where \(k_{\mathrm{ox}}\) and \(k_{\mathrm{red}}\) are the rate constants for the oxidizing (anodic) and reducing (cathodic) reactions respectively, \(n\) is the @[email protected] of the cell reaction, \(F\) is the @[email protected] and \(A\) is the geometric area of the electrode, the product \(\Pi\:c_{i}^{\nu _{i}}\) includes all the species \(i\) which take part in the partial reaction, \(c_{i}\) is the volume concentration of species \(i\) and \(\nu _{i}\) is the order of the reaction with respect to species \(i\). The conditional rate constant of an electrode reaction is the value of the @[email protected] @[email protected] at the @[email protected] of the @[email protected] When \(\alpha \) the transfer @[email protected] is independent of potential, \[k_{\text{c}} = \frac{k_{\text{ox}}}{\text{e}^{\frac{\alpha _{\text{a}}\ (E- E_{\text{c}}^{0'})\ n\ F}{\nu \ R\ T}}} = \frac{k_{\text{red}}}{\text{e}^{\frac{-\alpha _{\text{c}}\ (E- E_{\text{c}}^{0'})\ n\ F}{\nu \ R\ T}}}\] where \(\alpha _{\text{a}}\) and \(\alpha _{\text{c}}\) are the anodic and cathodic transfer coefficients respectively, \(E\) is the @[email protected] difference, \(E_{\text{c}}\) is the @[email protected], \(\nu \) is the @[email protected], \(R\) is the @[email protected] and \(T\) is the @[email protected] Similar rate constants can be defined using activities in place of concentrations in the first two equations, and the @[email protected] in place of the conditional potential in the latter two equations. This type of @[email protected] is called the standard @[email protected] of the @[email protected] The observable electrode @[email protected] is the constant of proportionality expressing the dependence of the rate of the @[email protected] on the @[email protected] of the chemical species involved in the reaction.
Sources:
PAC, 1974, 37, 499. (Electrochemical nomenclature) on page 515 [Terms] [Paper]
PAC, 1980, 52, 233. (Electrode Reaction Orders, Transfer Coefficients and Rate Constants. Amplification of Definitions and Recommendations for Publication of Parameters) on page 236 [Terms] [Paper]