Study of the BHT Oxidation Mechanism Coupling Theory and Experiment

Autores
Gavilán Arriazu, Edgardo Maximiliano; Alaniz, Rubén Darío; Charoen Amornkitt, Patcharawat; Fernández, Juan Manuel; Pierini, Gastón Dario; Rodríguez, Sergio Antonio
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In the present work, the oxidation mechanism of di-t-butyl-hydroxytoluene (BHT) was studied in an aqueous medium through different approaches to have a thorough vision of the physical chemistry: experiments with cyclic voltammetry (CV), quantum chemical calculations, and simulations of CV. Calculations of thermodynamic parameters, such as pKa and standard oxidation potential (Eox°), were used to analyze and rationalize the CV experiments. Subsequently, different pathways of the mechanism were constructed, and the most thermodynamically favorable one was selected. Numerical simulations were then used to model this mechanism and compare it with the experimental data. The results show that the oxidation process is due to the coupled loss of an electron and a proton in the first instance, followed by an irreversible second electron-transfer process without loss of protons, mainly due to the adsorption of the products of the first oxidation on the electrode surface. The effect of different pH values on this oxidative mechanism was also analyzed, with alkaline pH of 12 as a medium where changes in reactivity were observed as the appearance of a new peak in the second voltammetric sweep, the interpretation of this peak is also provided.
Fil: Gavilán Arriazu, Edgardo Maximiliano. Universidad Nacional de Santiago del Estero. Instituto de Bionanotecnología del Noa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Bionanotecnología del Noa; Argentina
Fil: Alaniz, Rubén Darío. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; Argentina
Fil: Charoen Amornkitt, Patcharawat. Mongkut’s University of Technology Thonburi; Tailandia
Fil: Fernández, Juan Manuel. Universidad Nacional de Santiago del Estero. Instituto de Bionanotecnología del Noa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Bionanotecnología del Noa; Argentina
Fil: Pierini, Gastón Dario. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; Argentina
Fil: Rodríguez, Sergio Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Santiago del Estero. Facultad de Agronomía y Agroindustrias. Instituto de Ciencias Químicas; Argentina
Materia
DI-T-BUTYL-HYDROTOLUENE
CYCLIC VOLTAMMETRY
OXIDATION MECHANISM
SYNTHETIC ANTIOXIDANT
DFT
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/247420
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/247420
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Study of the BHT Oxidation Mechanism Coupling Theory and ExperimentGavilán Arriazu, Edgardo MaximilianoAlaniz, Rubén DaríoCharoen Amornkitt, PatcharawatFernández, Juan ManuelPierini, Gastón DarioRodríguez, Sergio AntonioDI-T-BUTYL-HYDROTOLUENECYCLIC VOLTAMMETRYOXIDATION MECHANISMSYNTHETIC ANTIOXIDANTDFThttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In the present work, the oxidation mechanism of di-t-butyl-hydroxytoluene (BHT) was studied in an aqueous medium through different approaches to have a thorough vision of the physical chemistry: experiments with cyclic voltammetry (CV), quantum chemical calculations, and simulations of CV. Calculations of thermodynamic parameters, such as pKa and standard oxidation potential (Eox°), were used to analyze and rationalize the CV experiments. Subsequently, different pathways of the mechanism were constructed, and the most thermodynamically favorable one was selected. Numerical simulations were then used to model this mechanism and compare it with the experimental data. The results show that the oxidation process is due to the coupled loss of an electron and a proton in the first instance, followed by an irreversible second electron-transfer process without loss of protons, mainly due to the adsorption of the products of the first oxidation on the electrode surface. The effect of different pH values on this oxidative mechanism was also analyzed, with alkaline pH of 12 as a medium where changes in reactivity were observed as the appearance of a new peak in the second voltammetric sweep, the interpretation of this peak is also provided.Fil: Gavilán Arriazu, Edgardo Maximiliano. Universidad Nacional de Santiago del Estero. Instituto de Bionanotecnología del Noa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Bionanotecnología del Noa; ArgentinaFil: Alaniz, Rubén Darío. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; ArgentinaFil: Charoen Amornkitt, Patcharawat. Mongkut’s University of Technology Thonburi; TailandiaFil: Fernández, Juan Manuel. Universidad Nacional de Santiago del Estero. Instituto de Bionanotecnología del Noa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Bionanotecnología del Noa; ArgentinaFil: Pierini, Gastón Dario. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; ArgentinaFil: Rodríguez, Sergio Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Santiago del Estero. Facultad de Agronomía y Agroindustrias. Instituto de Ciencias Químicas; ArgentinaAmerican Chemical Society2024-09info: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/11336/247420Gavilán Arriazu, Edgardo Maximiliano; Alaniz, Rubén Darío; Charoen Amornkitt, Patcharawat; Fernández, Juan Manuel; Pierini, Gastón Dario; et al.; Study of the BHT Oxidation Mechanism Coupling Theory and Experiment; American Chemical Society; ACS Organic & Inorganic Au; 9-2024; 1-132694-247XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acsorginorgau.4c00067info:eu-repo/semantics/altIdentifier/doi/10.1021/acsorginorgau.4c00067info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:57:25Zoai:ri.conicet.gov.ar:11336/247420instacron: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:34982025-11-12 09:57:26.224CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Study of the BHT Oxidation Mechanism Coupling Theory and Experiment
title Study of the BHT Oxidation Mechanism Coupling Theory and Experiment
spellingShingle Study of the BHT Oxidation Mechanism Coupling Theory and Experiment
Gavilán Arriazu, Edgardo Maximiliano
DI-T-BUTYL-HYDROTOLUENE
CYCLIC VOLTAMMETRY
OXIDATION MECHANISM
SYNTHETIC ANTIOXIDANT
DFT
title_short Study of the BHT Oxidation Mechanism Coupling Theory and Experiment
title_full Study of the BHT Oxidation Mechanism Coupling Theory and Experiment
title_fullStr Study of the BHT Oxidation Mechanism Coupling Theory and Experiment
title_full_unstemmed Study of the BHT Oxidation Mechanism Coupling Theory and Experiment
title_sort Study of the BHT Oxidation Mechanism Coupling Theory and Experiment
dc.creator.none.fl_str_mv Gavilán Arriazu, Edgardo Maximiliano
Alaniz, Rubén Darío
Charoen Amornkitt, Patcharawat
Fernández, Juan Manuel
Pierini, Gastón Dario
Rodríguez, Sergio Antonio
author Gavilán Arriazu, Edgardo Maximiliano
author_facet Gavilán Arriazu, Edgardo Maximiliano
Alaniz, Rubén Darío
Charoen Amornkitt, Patcharawat
Fernández, Juan Manuel
Pierini, Gastón Dario
Rodríguez, Sergio Antonio
author_role author
author2 Alaniz, Rubén Darío
Charoen Amornkitt, Patcharawat
Fernández, Juan Manuel
Pierini, Gastón Dario
Rodríguez, Sergio Antonio
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv DI-T-BUTYL-HYDROTOLUENE
CYCLIC VOLTAMMETRY
OXIDATION MECHANISM
SYNTHETIC ANTIOXIDANT
DFT
topic DI-T-BUTYL-HYDROTOLUENE
CYCLIC VOLTAMMETRY
OXIDATION MECHANISM
SYNTHETIC ANTIOXIDANT
DFT
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In the present work, the oxidation mechanism of di-t-butyl-hydroxytoluene (BHT) was studied in an aqueous medium through different approaches to have a thorough vision of the physical chemistry: experiments with cyclic voltammetry (CV), quantum chemical calculations, and simulations of CV. Calculations of thermodynamic parameters, such as pKa and standard oxidation potential (Eox°), were used to analyze and rationalize the CV experiments. Subsequently, different pathways of the mechanism were constructed, and the most thermodynamically favorable one was selected. Numerical simulations were then used to model this mechanism and compare it with the experimental data. The results show that the oxidation process is due to the coupled loss of an electron and a proton in the first instance, followed by an irreversible second electron-transfer process without loss of protons, mainly due to the adsorption of the products of the first oxidation on the electrode surface. The effect of different pH values on this oxidative mechanism was also analyzed, with alkaline pH of 12 as a medium where changes in reactivity were observed as the appearance of a new peak in the second voltammetric sweep, the interpretation of this peak is also provided.
Fil: Gavilán Arriazu, Edgardo Maximiliano. Universidad Nacional de Santiago del Estero. Instituto de Bionanotecnología del Noa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Bionanotecnología del Noa; Argentina
Fil: Alaniz, Rubén Darío. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; Argentina
Fil: Charoen Amornkitt, Patcharawat. Mongkut’s University of Technology Thonburi; Tailandia
Fil: Fernández, Juan Manuel. Universidad Nacional de Santiago del Estero. Instituto de Bionanotecnología del Noa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Bionanotecnología del Noa; Argentina
Fil: Pierini, Gastón Dario. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; Argentina
Fil: Rodríguez, Sergio Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Santiago del Estero. Facultad de Agronomía y Agroindustrias. Instituto de Ciencias Químicas; Argentina
description In the present work, the oxidation mechanism of di-t-butyl-hydroxytoluene (BHT) was studied in an aqueous medium through different approaches to have a thorough vision of the physical chemistry: experiments with cyclic voltammetry (CV), quantum chemical calculations, and simulations of CV. Calculations of thermodynamic parameters, such as pKa and standard oxidation potential (Eox°), were used to analyze and rationalize the CV experiments. Subsequently, different pathways of the mechanism were constructed, and the most thermodynamically favorable one was selected. Numerical simulations were then used to model this mechanism and compare it with the experimental data. The results show that the oxidation process is due to the coupled loss of an electron and a proton in the first instance, followed by an irreversible second electron-transfer process without loss of protons, mainly due to the adsorption of the products of the first oxidation on the electrode surface. The effect of different pH values on this oxidative mechanism was also analyzed, with alkaline pH of 12 as a medium where changes in reactivity were observed as the appearance of a new peak in the second voltammetric sweep, the interpretation of this peak is also provided.
publishDate 2024
dc.date.none.fl_str_mv 2024-09
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/11336/247420
Gavilán Arriazu, Edgardo Maximiliano; Alaniz, Rubén Darío; Charoen Amornkitt, Patcharawat; Fernández, Juan Manuel; Pierini, Gastón Dario; et al.; Study of the BHT Oxidation Mechanism Coupling Theory and Experiment; American Chemical Society; ACS Organic & Inorganic Au; 9-2024; 1-13
2694-247X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/247420
identifier_str_mv Gavilán Arriazu, Edgardo Maximiliano; Alaniz, Rubén Darío; Charoen Amornkitt, Patcharawat; Fernández, Juan Manuel; Pierini, Gastón Dario; et al.; Study of the BHT Oxidation Mechanism Coupling Theory and Experiment; American Chemical Society; ACS Organic & Inorganic Au; 9-2024; 1-13
2694-247X
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://pubs.acs.org/doi/10.1021/acsorginorgau.4c00067
info:eu-repo/semantics/altIdentifier/doi/10.1021/acsorginorgau.4c00067
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
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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score 12.976206

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