A simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots
Abstract The practice of estimating the transfer coefficient ( $$\alpha$$ α ) and the exchange current ( $${i}_{0}$$ i 0 ) by arbitrarily placing a straight line on Tafel plots has led to high variance in these parameters between different research groups. Generating Tafel plots by finding kinetic c...
Guardado en:
| Autores principales: | , , , , , |
|---|---|
| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
Nature Portfolio
2021
|
| Materias: | |
| Acceso en línea: | https://doaj.org/article/f40f1428898d4e38b1ae79858d4aa297 |
| Etiquetas: |
Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
|
| id |
oai:doaj.org-article:f40f1428898d4e38b1ae79858d4aa297 |
|---|---|
| record_format |
dspace |
| spelling |
oai:doaj.org-article:f40f1428898d4e38b1ae79858d4aa2972021-12-02T16:55:45ZA simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots10.1038/s41598-021-87951-z2045-2322https://doaj.org/article/f40f1428898d4e38b1ae79858d4aa2972021-04-01T00:00:00Zhttps://doi.org/10.1038/s41598-021-87951-zhttps://doaj.org/toc/2045-2322Abstract The practice of estimating the transfer coefficient ( $$\alpha$$ α ) and the exchange current ( $${i}_{0}$$ i 0 ) by arbitrarily placing a straight line on Tafel plots has led to high variance in these parameters between different research groups. Generating Tafel plots by finding kinetic current, $${i}_{k}$$ i k from the conventional mass transfer correction method does not guarantee an accurate estimation of the $$\alpha$$ α and $${i}_{0}$$ i 0 . This is because a substantial difference in values of $$\alpha$$ α and $${i}_{0}$$ i 0 can arise from only minor deviations in the calculated values of $${i}_{k}$$ i k . These minor deviations are often not easy to recognise in polarisation curves and Tafel plots. Recalling the IUPAC definition of $$\alpha$$ α , the Tafel plots can be alternatively represented as differential Tafel plots (DTPs) by taking the first order differential of Tafel plots with respect to overpotential. Without further complex processing of the existing raw data, many crucial observations can be made from DTP which is otherwise very difficult to observe from Tafel plots. These for example include a) many perfectly looking experimental linear Tafel plots (R2 > 0.999) can give rise to incorrect kinetic parameters b) substantial differences in values of $$\alpha$$ α and $${i}_{0}$$ i 0 can arise when the limiting current ( $${i}_{L}$$ i L ) is just off by 5% while performing the mass transfer correction c) irrespective of the magnitude of the double layer charging current ( $${i}_{\mathrm{c}}$$ i c ), the Tafel plots can still get significantly skewed when the ratio of $${i}_{0}/{i}_{c}$$ i 0 / i c is small. Hence, in order to determine accurate values of $$\alpha$$ α and $${i}_{0}$$ i 0 , we show how the DTP approach can be applied to experimental polarisation curves having well defined $${i}_{L}$$ i L , poorly defined $${i}_{L}$$ i L and no $${i}_{L}$$ i L at all.Prashant KhadkeTim TichterTim BoettcherFalk MuenchWolfgang EnsingerChristina RothNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 11, Iss 1, Pp 1-15 (2021) |
| institution |
DOAJ |
| collection |
DOAJ |
| language |
EN |
| topic |
Medicine R Science Q |
| spellingShingle |
Medicine R Science Q Prashant Khadke Tim Tichter Tim Boettcher Falk Muench Wolfgang Ensinger Christina Roth A simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots |
| description |
Abstract The practice of estimating the transfer coefficient ( $$\alpha$$ α ) and the exchange current ( $${i}_{0}$$ i 0 ) by arbitrarily placing a straight line on Tafel plots has led to high variance in these parameters between different research groups. Generating Tafel plots by finding kinetic current, $${i}_{k}$$ i k from the conventional mass transfer correction method does not guarantee an accurate estimation of the $$\alpha$$ α and $${i}_{0}$$ i 0 . This is because a substantial difference in values of $$\alpha$$ α and $${i}_{0}$$ i 0 can arise from only minor deviations in the calculated values of $${i}_{k}$$ i k . These minor deviations are often not easy to recognise in polarisation curves and Tafel plots. Recalling the IUPAC definition of $$\alpha$$ α , the Tafel plots can be alternatively represented as differential Tafel plots (DTPs) by taking the first order differential of Tafel plots with respect to overpotential. Without further complex processing of the existing raw data, many crucial observations can be made from DTP which is otherwise very difficult to observe from Tafel plots. These for example include a) many perfectly looking experimental linear Tafel plots (R2 > 0.999) can give rise to incorrect kinetic parameters b) substantial differences in values of $$\alpha$$ α and $${i}_{0}$$ i 0 can arise when the limiting current ( $${i}_{L}$$ i L ) is just off by 5% while performing the mass transfer correction c) irrespective of the magnitude of the double layer charging current ( $${i}_{\mathrm{c}}$$ i c ), the Tafel plots can still get significantly skewed when the ratio of $${i}_{0}/{i}_{c}$$ i 0 / i c is small. Hence, in order to determine accurate values of $$\alpha$$ α and $${i}_{0}$$ i 0 , we show how the DTP approach can be applied to experimental polarisation curves having well defined $${i}_{L}$$ i L , poorly defined $${i}_{L}$$ i L and no $${i}_{L}$$ i L at all. |
| format |
article |
| author |
Prashant Khadke Tim Tichter Tim Boettcher Falk Muench Wolfgang Ensinger Christina Roth |
| author_facet |
Prashant Khadke Tim Tichter Tim Boettcher Falk Muench Wolfgang Ensinger Christina Roth |
| author_sort |
Prashant Khadke |
| title |
A simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots |
| title_short |
A simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots |
| title_full |
A simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots |
| title_fullStr |
A simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots |
| title_full_unstemmed |
A simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots |
| title_sort |
simple and effective method for the accurate extraction of kinetic parameters using differential tafel plots |
| publisher |
Nature Portfolio |
| publishDate |
2021 |
| url |
https://doaj.org/article/f40f1428898d4e38b1ae79858d4aa297 |
| work_keys_str_mv |
AT prashantkhadke asimpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT timtichter asimpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT timboettcher asimpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT falkmuench asimpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT wolfgangensinger asimpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT christinaroth asimpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT prashantkhadke simpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT timtichter simpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT timboettcher simpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT falkmuench simpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT wolfgangensinger simpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots AT christinaroth simpleandeffectivemethodfortheaccurateextractionofkineticparametersusingdifferentialtafelplots |
| _version_ |
1718382834947719168 |