Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes

A general relationship, arising from Danckwerts' expression (P.V. Danckwerts, Trans. Faraday Soc. 47 (1951) 1014), allows the computation of the transient limiting current in a system with a homogeneous first-order reaction regenerating the electroactive species (an EC′ mechanism), with diffusi...

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Autores: Galceran i Nogués, Josep, Taylor, S. L., Bartlett, P. N.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:1999
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10459.1/48896
Acceso en línea:https://doi.org/10.1016/S0022-0728(99)00103-5
http://hdl.handle.net/10459.1/48896
Access Level:acceso abierto
Palabra clave:Electroquímica
Anàlisi electroquímica
Electrochemistry
Electrochemical analysis
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spelling Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodesGalceran i Nogués, JosepTaylor, S. L.Bartlett, P. N.ElectroquímicaAnàlisi electroquímicaElectrochemistryElectrochemical analysisA general relationship, arising from Danckwerts' expression (P.V. Danckwerts, Trans. Faraday Soc. 47 (1951) 1014), allows the computation of the transient limiting current in a system with a homogeneous first-order reaction regenerating the electroactive species (an EC′ mechanism), with diffusion and convection, from the limiting currents at the same electrode when there is no homogeneous reaction. For the method to apply the boundary conditions and hydrodynamic regime must be time independent. A simple procedure (which could serve as an alternative to convolution or semi-integral methods) to determine the kinetic parameter from limiting currents obtained in an electrode of arbitrary geometry and size is suggested. An estimation of the time needed to approach steady-state is provided. Diffusion-limited transient currents at the inlaid and recessed microdisc electrode with first-order homogeneous kinetics are studied in detail, checking approximate analytical expressions and simulation data arising from the Finite Element Method. If diffusion is the only transport phenomenon, all currents tend to the planar (cottrellian) behaviour when t tends to 0, regardless of the kinetic constant or the shape of the electrode.Elsevier2015201519992015info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://doi.org/10.1016/S0022-0728(99)00103-5http://hdl.handle.net/10459.1/48896http://hdl.handle.net/10459.1/48896reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1016/S0022-0728(99)00103-5Journal of Electroanalytical Chemistry, 1999, vol. 466, num. 1, p. 15-25(c) Elsevier, 1999info:eu-repo/semantics/openAccessoai:recercat.cat:10459.1/488962026-05-29T05:05:01Z
dc.title.none.fl_str_mv Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes
title Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes
spellingShingle Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes
Galceran i Nogués, Josep
Electroquímica
Anàlisi electroquímica
Electrochemistry
Electrochemical analysis
title_short Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes
title_full Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes
title_fullStr Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes
title_full_unstemmed Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes
title_sort Application of Danckwerts' expression to first-order EC′reactions. Transient currents at inlaid and recessed microdisc electrodes
dc.creator.none.fl_str_mv Galceran i Nogués, Josep
Taylor, S. L.
Bartlett, P. N.
author Galceran i Nogués, Josep
author_facet Galceran i Nogués, Josep
Taylor, S. L.
Bartlett, P. N.
author_role author
author2 Taylor, S. L.
Bartlett, P. N.
author2_role author
author
dc.subject.none.fl_str_mv Electroquímica
Anàlisi electroquímica
Electrochemistry
Electrochemical analysis
topic Electroquímica
Anàlisi electroquímica
Electrochemistry
Electrochemical analysis
description A general relationship, arising from Danckwerts' expression (P.V. Danckwerts, Trans. Faraday Soc. 47 (1951) 1014), allows the computation of the transient limiting current in a system with a homogeneous first-order reaction regenerating the electroactive species (an EC′ mechanism), with diffusion and convection, from the limiting currents at the same electrode when there is no homogeneous reaction. For the method to apply the boundary conditions and hydrodynamic regime must be time independent. A simple procedure (which could serve as an alternative to convolution or semi-integral methods) to determine the kinetic parameter from limiting currents obtained in an electrode of arbitrary geometry and size is suggested. An estimation of the time needed to approach steady-state is provided. Diffusion-limited transient currents at the inlaid and recessed microdisc electrode with first-order homogeneous kinetics are studied in detail, checking approximate analytical expressions and simulation data arising from the Finite Element Method. If diffusion is the only transport phenomenon, all currents tend to the planar (cottrellian) behaviour when t tends to 0, regardless of the kinetic constant or the shape of the electrode.
publishDate 1999
dc.date.none.fl_str_mv 1999
2015
2015
2015
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://doi.org/10.1016/S0022-0728(99)00103-5
http://hdl.handle.net/10459.1/48896
http://hdl.handle.net/10459.1/48896
url https://doi.org/10.1016/S0022-0728(99)00103-5
http://hdl.handle.net/10459.1/48896
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1016/S0022-0728(99)00103-5
Journal of Electroanalytical Chemistry, 1999, vol. 466, num. 1, p. 15-25
dc.rights.none.fl_str_mv (c) Elsevier, 1999
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Elsevier, 1999
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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