期刊
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
卷 896, 期 -, 页码 -出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jelechem.2021.115206
关键词
Nonunity reaction orders; Analytical theory; Steady state voltammetry; Electrode kinetics; Electrocatalysis
资金
- Fundacion Seneca de la Region de Murcia [19887/GERM/15]
- Ministerio de Economia y Competitividad [PID2019-106097 GB-I00/AEI/10.13039/501100011033]
This study developed an analytical treatment for rate equations with non-unity reaction orders in electrochemical processes. By linearizing the current-potential response, reaction orders and half-wave potential values can be determined. Additional protocols of kinetic analysis are discussed based on Tafel and Koutecky-Levich-like plots.
Relevant electrochemical processes present rate equations with non-unity reaction orders. For such reactions, an analytical treatment is developed for the stationary voltammetric response and the surface concentrations at the rotating disc electrode and at microelectrodes of any shape, as frequently/preferably employed to reveal their electrode kinetics. The expressions deduced are applicable when one or both redox species are initially present and cover any degree of reversibility. From the general solution obtained, the limit cases of fully reversible and irreversible reactions are derived. By linearizing the current-potential response of the former, the reaction orders can be determined, as well as the value of the reversible half-wave potential that strikingly depends on whether one or both species are initially present in contrast with the case of unity orders. For irreversible processes, the linearization of the complete current-potential response is also possible and it enables us to extract the reaction order and the halfwave potential. An expression for the latter is given as a function of the heterogeneous rate constant and the mass transport coefficient. Additional protocols of kinetic analysis are discussed on the basis of Tafel and Koutecky-Levich-like plots.
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