New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum.
The influence of the potential pulse height of square-wave voltammetry (SWV) (i.e., the SW amplitude) is studied for a variety of quasireversible electrode mechanisms, including a simple solution-phase electrode reaction at a planar or spherical electrode, a solution phase electrode reaction coupled...
| Main Authors: | , , , |
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| Format: | Journal article |
| Language: | English |
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2013
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| _version_ | 1797052130506309632 |
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| author | Mirceski, V Laborda, E Guziejewski, D Compton, R |
| author_facet | Mirceski, V Laborda, E Guziejewski, D Compton, R |
| author_sort | Mirceski, V |
| collection | OXFORD |
| description | The influence of the potential pulse height of square-wave voltammetry (SWV) (i.e., the SW amplitude) is studied for a variety of quasireversible electrode mechanisms, including a simple solution-phase electrode reaction at a planar or spherical electrode, a solution phase electrode reaction coupled with a reversible follow-up chemical reaction, and a diffusionless surface confined electrode reaction. The electrode kinetics of all the electrode mechanisms depends critically on the SW amplitude, and the quasireversible kinetic region is a function of both frequency-related electrode kinetic parameters and the SW amplitude. Thus, a novel methodology for electrode kinetics measurements is proposed by altering the SW amplitude only, at a fixed frequency of the SW potential modulation, that is, at a constant scan rate of the voltammetric experiment. Electrode kinetic measurements at a constant SW frequency are of exceptional importance especially when complex electrode mechanisms are studied, which depend on several frequency-related kinetic parameters. The electrode kinetic measurements are based on a novel feature termed the "amplitude-based quasireversible maximum", manifested as a parabolic dependence of the amplitude-normalized net SW peak current versus the SW amplitude. The position of the amplitude-based quasireversible maximum depends on the standard rate constant of the electrode reaction, enabling estimation of this important kinetic parameter in a simple and fast procedure. The novel quasireversible maximum is attributed to all studied electrode mechanisms, implying that it is a general feature of most electrode mechanisms under conditions of SWV. |
| first_indexed | 2024-03-06T18:28:24Z |
| format | Journal article |
| id | oxford-uuid:08c5c4d6-1d37-4037-9b2a-2812f4750afa |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T18:28:24Z |
| publishDate | 2013 |
| record_format | dspace |
| spelling | oxford-uuid:08c5c4d6-1d37-4037-9b2a-2812f4750afa2022-03-26T09:14:45ZNew approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:08c5c4d6-1d37-4037-9b2a-2812f4750afaEnglishSymplectic Elements at Oxford2013Mirceski, VLaborda, EGuziejewski, DCompton, RThe influence of the potential pulse height of square-wave voltammetry (SWV) (i.e., the SW amplitude) is studied for a variety of quasireversible electrode mechanisms, including a simple solution-phase electrode reaction at a planar or spherical electrode, a solution phase electrode reaction coupled with a reversible follow-up chemical reaction, and a diffusionless surface confined electrode reaction. The electrode kinetics of all the electrode mechanisms depends critically on the SW amplitude, and the quasireversible kinetic region is a function of both frequency-related electrode kinetic parameters and the SW amplitude. Thus, a novel methodology for electrode kinetics measurements is proposed by altering the SW amplitude only, at a fixed frequency of the SW potential modulation, that is, at a constant scan rate of the voltammetric experiment. Electrode kinetic measurements at a constant SW frequency are of exceptional importance especially when complex electrode mechanisms are studied, which depend on several frequency-related kinetic parameters. The electrode kinetic measurements are based on a novel feature termed the "amplitude-based quasireversible maximum", manifested as a parabolic dependence of the amplitude-normalized net SW peak current versus the SW amplitude. The position of the amplitude-based quasireversible maximum depends on the standard rate constant of the electrode reaction, enabling estimation of this important kinetic parameter in a simple and fast procedure. The novel quasireversible maximum is attributed to all studied electrode mechanisms, implying that it is a general feature of most electrode mechanisms under conditions of SWV. |
| spellingShingle | Mirceski, V Laborda, E Guziejewski, D Compton, R New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum. |
| title | New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum. |
| title_full | New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum. |
| title_fullStr | New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum. |
| title_full_unstemmed | New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum. |
| title_short | New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum. |
| title_sort | new approach to electrode kinetic measurements in square wave voltammetry amplitude based quasireversible maximum |
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