Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode

Autores
Gómez Avila, Jenny; Burgos Gómez, Jhan Carlos; Heredia, Angelica Constanza; Crivello, Mónica Elsie; Garay, Fernando Sebastian
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Despite arsenite can be reduced to As(0) and deposited at the surface of solid electrodes such as gold, platinum, or copper, it cannot form amalgams with mercury, and so the addition of other metal ions is required for its deposition. In this manuscript, mechanistic analysis of the cathodic stripping square-wave voltammetric response of the system copper‑arsenic is presented. For the analysis of experimental responses, a mathematical model is used to consider that a surface-active reagent undergoes a charge transfer step followed by a chemical reaction. The dependences of the differential peak current, and the respective peak potential and half-peak width on the square-wave frequency were used to estimate the apparent stability constant of arsenide formation and that the electrode reaction would involve the direct transfer of 2 electrons, while the simulation and fit of forward and backward voltammetric responses have been useful for inferring other parameters such as the formal charge transfer rate constant of the global electron transfer reaction, a pseudo-first order homogeneous rate constant associated with arsenide formation, and the charge transfer coefficient of the global electron transfer reaction. Besides the values estimated for each of those parameters, all simulations indicate that the reduction of copper instead of arsenic would be taking place during the cathodic stripping scan. Accordingly, the trace-analysis reaction of arsenic in the presence of copper would be based on the surface accumulation of a metal complex, where Cu2+ would be the metal cation and an arsenide species the ligand. The stability of that complex at the surface of a mercury electrode would depend not only on the applied potential, but also on the ratio between copper, arsenic, and protons.
Fil: Gómez Avila, Jenny. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Pontificia Universidad Católica Madre y Maestra; República Dominicana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Burgos Gómez, Jhan Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Heredia, Angelica Constanza. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Fil: Crivello, Mónica Elsie. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Fil: Garay, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
ARSENIC
CS-SWV
COPPER-ARSENIC
MERCURY ELECTRODE
Nivel de accesibilidad
acceso embargado
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/121087
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrodeGómez Avila, JennyBurgos Gómez, Jhan CarlosHeredia, Angelica ConstanzaCrivello, Mónica ElsieGaray, Fernando SebastianARSENICCS-SWVCOPPER-ARSENICMERCURY ELECTRODEhttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2Despite arsenite can be reduced to As(0) and deposited at the surface of solid electrodes such as gold, platinum, or copper, it cannot form amalgams with mercury, and so the addition of other metal ions is required for its deposition. In this manuscript, mechanistic analysis of the cathodic stripping square-wave voltammetric response of the system copper‑arsenic is presented. For the analysis of experimental responses, a mathematical model is used to consider that a surface-active reagent undergoes a charge transfer step followed by a chemical reaction. The dependences of the differential peak current, and the respective peak potential and half-peak width on the square-wave frequency were used to estimate the apparent stability constant of arsenide formation and that the electrode reaction would involve the direct transfer of 2 electrons, while the simulation and fit of forward and backward voltammetric responses have been useful for inferring other parameters such as the formal charge transfer rate constant of the global electron transfer reaction, a pseudo-first order homogeneous rate constant associated with arsenide formation, and the charge transfer coefficient of the global electron transfer reaction. Besides the values estimated for each of those parameters, all simulations indicate that the reduction of copper instead of arsenic would be taking place during the cathodic stripping scan. Accordingly, the trace-analysis reaction of arsenic in the presence of copper would be based on the surface accumulation of a metal complex, where Cu2+ would be the metal cation and an arsenide species the ligand. The stability of that complex at the surface of a mercury electrode would depend not only on the applied potential, but also on the ratio between copper, arsenic, and protons.Fil: Gómez Avila, Jenny. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Pontificia Universidad Católica Madre y Maestra; República Dominicana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Burgos Gómez, Jhan Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Heredia, Angelica Constanza. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; ArgentinaFil: Crivello, Mónica Elsie. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; ArgentinaFil: Garay, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaElsevier Science SA2020-11-11info:eu-repo/date/embargoEnd/2021-06-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/121087Gómez Avila, Jenny; Burgos Gómez, Jhan Carlos; Heredia, Angelica Constanza; Crivello, Mónica Elsie; Garay, Fernando Sebastian; Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode; Elsevier Science SA; Journal of Electroanalytical Chemistry; 11-11-20201572-6657CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://linkinghub.elsevier.com/retrieve/pii/S1572665720310626info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jelechem.2020.114833info:eu-repo/semantics/embargoedAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:22:00Zoai:ri.conicet.gov.ar:11336/121087instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:22:01.233CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode
title Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode
spellingShingle Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode
Gómez Avila, Jenny
ARSENIC
CS-SWV
COPPER-ARSENIC
MERCURY ELECTRODE
title_short Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode
title_full Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode
title_fullStr Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode
title_full_unstemmed Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode
title_sort Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode
dc.creator.none.fl_str_mv Gómez Avila, Jenny
Burgos Gómez, Jhan Carlos
Heredia, Angelica Constanza
Crivello, Mónica Elsie
Garay, Fernando Sebastian
author Gómez Avila, Jenny
author_facet Gómez Avila, Jenny
Burgos Gómez, Jhan Carlos
Heredia, Angelica Constanza
Crivello, Mónica Elsie
Garay, Fernando Sebastian
author_role author
author2 Burgos Gómez, Jhan Carlos
Heredia, Angelica Constanza
Crivello, Mónica Elsie
Garay, Fernando Sebastian
author2_role author
author
author
author
dc.subject.none.fl_str_mv ARSENIC
CS-SWV
COPPER-ARSENIC
MERCURY ELECTRODE
topic ARSENIC
CS-SWV
COPPER-ARSENIC
MERCURY ELECTRODE
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Despite arsenite can be reduced to As(0) and deposited at the surface of solid electrodes such as gold, platinum, or copper, it cannot form amalgams with mercury, and so the addition of other metal ions is required for its deposition. In this manuscript, mechanistic analysis of the cathodic stripping square-wave voltammetric response of the system copper‑arsenic is presented. For the analysis of experimental responses, a mathematical model is used to consider that a surface-active reagent undergoes a charge transfer step followed by a chemical reaction. The dependences of the differential peak current, and the respective peak potential and half-peak width on the square-wave frequency were used to estimate the apparent stability constant of arsenide formation and that the electrode reaction would involve the direct transfer of 2 electrons, while the simulation and fit of forward and backward voltammetric responses have been useful for inferring other parameters such as the formal charge transfer rate constant of the global electron transfer reaction, a pseudo-first order homogeneous rate constant associated with arsenide formation, and the charge transfer coefficient of the global electron transfer reaction. Besides the values estimated for each of those parameters, all simulations indicate that the reduction of copper instead of arsenic would be taking place during the cathodic stripping scan. Accordingly, the trace-analysis reaction of arsenic in the presence of copper would be based on the surface accumulation of a metal complex, where Cu2+ would be the metal cation and an arsenide species the ligand. The stability of that complex at the surface of a mercury electrode would depend not only on the applied potential, but also on the ratio between copper, arsenic, and protons.
Fil: Gómez Avila, Jenny. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Pontificia Universidad Católica Madre y Maestra; República Dominicana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Burgos Gómez, Jhan Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Heredia, Angelica Constanza. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Fil: Crivello, Mónica Elsie. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina
Fil: Garay, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description Despite arsenite can be reduced to As(0) and deposited at the surface of solid electrodes such as gold, platinum, or copper, it cannot form amalgams with mercury, and so the addition of other metal ions is required for its deposition. In this manuscript, mechanistic analysis of the cathodic stripping square-wave voltammetric response of the system copper‑arsenic is presented. For the analysis of experimental responses, a mathematical model is used to consider that a surface-active reagent undergoes a charge transfer step followed by a chemical reaction. The dependences of the differential peak current, and the respective peak potential and half-peak width on the square-wave frequency were used to estimate the apparent stability constant of arsenide formation and that the electrode reaction would involve the direct transfer of 2 electrons, while the simulation and fit of forward and backward voltammetric responses have been useful for inferring other parameters such as the formal charge transfer rate constant of the global electron transfer reaction, a pseudo-first order homogeneous rate constant associated with arsenide formation, and the charge transfer coefficient of the global electron transfer reaction. Besides the values estimated for each of those parameters, all simulations indicate that the reduction of copper instead of arsenic would be taking place during the cathodic stripping scan. Accordingly, the trace-analysis reaction of arsenic in the presence of copper would be based on the surface accumulation of a metal complex, where Cu2+ would be the metal cation and an arsenide species the ligand. The stability of that complex at the surface of a mercury electrode would depend not only on the applied potential, but also on the ratio between copper, arsenic, and protons.
publishDate 2020
dc.date.none.fl_str_mv 2020-11-11
info:eu-repo/date/embargoEnd/2021-06-11
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/121087
Gómez Avila, Jenny; Burgos Gómez, Jhan Carlos; Heredia, Angelica Constanza; Crivello, Mónica Elsie; Garay, Fernando Sebastian; Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode; Elsevier Science SA; Journal of Electroanalytical Chemistry; 11-11-2020
1572-6657
CONICET Digital
CONICET
url http://hdl.handle.net/11336/121087
identifier_str_mv Gómez Avila, Jenny; Burgos Gómez, Jhan Carlos; Heredia, Angelica Constanza; Crivello, Mónica Elsie; Garay, Fernando Sebastian; Mechanistic analysis of the cathodic stripping square-wave voltammetric response of the copper‑arsenic system at a mercury electrode; Elsevier Science SA; Journal of Electroanalytical Chemistry; 11-11-2020
1572-6657
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://linkinghub.elsevier.com/retrieve/pii/S1572665720310626
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jelechem.2020.114833
dc.rights.none.fl_str_mv info:eu-repo/semantics/embargoedAccess
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eu_rights_str_mv embargoedAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science SA
publisher.none.fl_str_mv Elsevier Science SA
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
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instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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