Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions

Autores
Ladino Cardona, Miyer Alejandro; Blanco, Maria Belen; Teruel, Mariano Andres; Ventura, Oscar N.
Año de publicación
2023
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The addition mechanism of the OH-initiated oxidation of allyl methyl sulfide (AMS) under atmospheric conditions was studied theoretically using both density functional theory (DFT) and the SVECV-f12 composite method. We found that the addition does not occur directly but rather through a pre-reactive complex that serves as a previous stage for addition at both the C1 and C2 positions. However, based on thermodynamics the addition at C2 possibly occurs by branching of the C1 addition mechanism. Once the addition proceeds, the reaction with O2 under atmospheric conditions produces RO2 radicals that can decompose in multiple ways. Complex mechanisms of intramolecular rearrangement and decomposition both in the absence and presence of NOx have been examined. The thermodynamically most favourable decomposition paths produce 2-hydroxy-acetaldehyde, 2-methyl-thio-acetaldehyde, formaldehyde, and the methyl thiomethyl peroxy (MSP) intermediate. This latter species is proposed as the main source of sulfur dioxide (SO2), which is the product found in the highest yield during the experimental determinations.
Fil: Ladino Cardona, Miyer Alejandro. 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: Blanco, Maria Belen. 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: Teruel, Mariano Andres. 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: Ventura, Oscar N.. Universidad de la República; Uruguay
Materia
ALLYL METHYL SULFIDE
KINETICS
MECHANISM
ADDITION
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/226551
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/226551
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditionsLadino Cardona, Miyer AlejandroBlanco, Maria BelenTeruel, Mariano AndresVentura, Oscar N.ALLYL METHYL SULFIDEKINETICSMECHANISMADDITIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The addition mechanism of the OH-initiated oxidation of allyl methyl sulfide (AMS) under atmospheric conditions was studied theoretically using both density functional theory (DFT) and the SVECV-f12 composite method. We found that the addition does not occur directly but rather through a pre-reactive complex that serves as a previous stage for addition at both the C1 and C2 positions. However, based on thermodynamics the addition at C2 possibly occurs by branching of the C1 addition mechanism. Once the addition proceeds, the reaction with O2 under atmospheric conditions produces RO2 radicals that can decompose in multiple ways. Complex mechanisms of intramolecular rearrangement and decomposition both in the absence and presence of NOx have been examined. The thermodynamically most favourable decomposition paths produce 2-hydroxy-acetaldehyde, 2-methyl-thio-acetaldehyde, formaldehyde, and the methyl thiomethyl peroxy (MSP) intermediate. This latter species is proposed as the main source of sulfur dioxide (SO2), which is the product found in the highest yield during the experimental determinations.Fil: Ladino Cardona, Miyer Alejandro. 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: Blanco, Maria Belen. 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: Teruel, Mariano Andres. 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: Ventura, Oscar N.. Universidad de la República; UruguayRoyal Society of Chemistry2023-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/226551Ladino Cardona, Miyer Alejandro; Blanco, Maria Belen; Teruel, Mariano Andres; Ventura, Oscar N.; Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 7; 5-2023; 1075-10892634-3606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://xlink.rsc.org/?DOI=D3EA00010Ainfo:eu-repo/semantics/altIdentifier/doi/10.1039/D3EA00010Ainfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:05:46Zoai:ri.conicet.gov.ar:11336/226551instacron: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:34982025-09-10 13:05:46.356CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions
title Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions
spellingShingle Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions
Ladino Cardona, Miyer Alejandro
ALLYL METHYL SULFIDE
KINETICS
MECHANISM
ADDITION
title_short Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions
title_full Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions
title_fullStr Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions
title_full_unstemmed Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions
title_sort Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions
dc.creator.none.fl_str_mv Ladino Cardona, Miyer Alejandro
Blanco, Maria Belen
Teruel, Mariano Andres
Ventura, Oscar N.
author Ladino Cardona, Miyer Alejandro
author_facet Ladino Cardona, Miyer Alejandro
Blanco, Maria Belen
Teruel, Mariano Andres
Ventura, Oscar N.
author_role author
author2 Blanco, Maria Belen
Teruel, Mariano Andres
Ventura, Oscar N.
author2_role author
author
author
dc.subject.none.fl_str_mv ALLYL METHYL SULFIDE
KINETICS
MECHANISM
ADDITION
topic ALLYL METHYL SULFIDE
KINETICS
MECHANISM
ADDITION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The addition mechanism of the OH-initiated oxidation of allyl methyl sulfide (AMS) under atmospheric conditions was studied theoretically using both density functional theory (DFT) and the SVECV-f12 composite method. We found that the addition does not occur directly but rather through a pre-reactive complex that serves as a previous stage for addition at both the C1 and C2 positions. However, based on thermodynamics the addition at C2 possibly occurs by branching of the C1 addition mechanism. Once the addition proceeds, the reaction with O2 under atmospheric conditions produces RO2 radicals that can decompose in multiple ways. Complex mechanisms of intramolecular rearrangement and decomposition both in the absence and presence of NOx have been examined. The thermodynamically most favourable decomposition paths produce 2-hydroxy-acetaldehyde, 2-methyl-thio-acetaldehyde, formaldehyde, and the methyl thiomethyl peroxy (MSP) intermediate. This latter species is proposed as the main source of sulfur dioxide (SO2), which is the product found in the highest yield during the experimental determinations.
Fil: Ladino Cardona, Miyer Alejandro. 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: Blanco, Maria Belen. 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: Teruel, Mariano Andres. 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: Ventura, Oscar N.. Universidad de la República; Uruguay
description The addition mechanism of the OH-initiated oxidation of allyl methyl sulfide (AMS) under atmospheric conditions was studied theoretically using both density functional theory (DFT) and the SVECV-f12 composite method. We found that the addition does not occur directly but rather through a pre-reactive complex that serves as a previous stage for addition at both the C1 and C2 positions. However, based on thermodynamics the addition at C2 possibly occurs by branching of the C1 addition mechanism. Once the addition proceeds, the reaction with O2 under atmospheric conditions produces RO2 radicals that can decompose in multiple ways. Complex mechanisms of intramolecular rearrangement and decomposition both in the absence and presence of NOx have been examined. The thermodynamically most favourable decomposition paths produce 2-hydroxy-acetaldehyde, 2-methyl-thio-acetaldehyde, formaldehyde, and the methyl thiomethyl peroxy (MSP) intermediate. This latter species is proposed as the main source of sulfur dioxide (SO2), which is the product found in the highest yield during the experimental determinations.
publishDate 2023
dc.date.none.fl_str_mv 2023-05
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/11336/226551
Ladino Cardona, Miyer Alejandro; Blanco, Maria Belen; Teruel, Mariano Andres; Ventura, Oscar N.; Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 7; 5-2023; 1075-1089
2634-3606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/226551
identifier_str_mv Ladino Cardona, Miyer Alejandro; Blanco, Maria Belen; Teruel, Mariano Andres; Ventura, Oscar N.; Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 7; 5-2023; 1075-1089
2634-3606
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://xlink.rsc.org/?DOI=D3EA00010A
info:eu-repo/semantics/altIdentifier/doi/10.1039/D3EA00010A
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 12.993085

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