Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms

Autores
Teruel, Mariano Andres; Benitez Villalba, Julio; Caballero, Norma Beatriz; Blanco, Maria Belen
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with methyl crotonate and ethyl crotonate have been determined at 298 K and atmospheric pressure. The decay of the organics was monitored using gas chromatography with flame ionization detection (GC-FID), and the rate constants were determined using the relative rate method with different reference compounds. Room temperature rate coeficcients were found to be (in cm 3 molecule -1 s -1): k 1(OH + CH 3CH=CHC(O)OCH 3) = (4.65 ± 0.65) × 10 -11, k 2(Cl + CH 3CH=CHC(O)OCH 3) = (2.20 ± 0.55) × 10 -10, k 3(OH + CH 3CH=CHC(O)OCH 2CH 3) = (4.96 ± 0.61) × 10 -11, and k 4(Cl + CH 3CH=CHC(O)OCH 2CH 3) = (2.52 ± 0.62) × 10 -10 with uncertainties representing ±2σ. This is the first determination of k 1, k 3, and k 4 under atmospheric pressure. The rate coefficients are compared with previous determinations for other unsaturated and oxygenated VOCs and reactivity trends are presented. In addition, a comparison between the experimentally determined k OH with k OH predicted from k vs E HOMO relationships is presented. On the other hand, product identification under atmospheric conditions has been performed for the first time for these unsaturated esters by the GC-MS technique in NO x-free conditions. 2-Hydroxypropanal, acetaldehyde, formaldehyde, and formic acid were positively observed as degradation products in agreement with the addition of OH to C2 and C3 of the double bond, followed by decomposition of the 2,3- or 3,2-hydroxyalkoxy radicals formed. Atmospheric lifetimes, based on of the homogeneous sinks of the unsaturated esters studied, are estimated from the kinetic data obtained in the present work.
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: Benitez Villalba, Julio. Universidad Nacional de Asunción; Paraguay
Fil: Caballero, Norma Beatriz. Universidad Nacional de Asunción; Paraguay
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
Materia
Cinética Química
Crotonatos
Fotólisis
Degradación
Nivel de accesibilidad
acceso abierto
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:11336/62146
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/62146
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atomsTeruel, Mariano AndresBenitez Villalba, JulioCaballero, Norma BeatrizBlanco, Maria BelenCinética QuímicaCrotonatosFotólisisDegradaciónhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with methyl crotonate and ethyl crotonate have been determined at 298 K and atmospheric pressure. The decay of the organics was monitored using gas chromatography with flame ionization detection (GC-FID), and the rate constants were determined using the relative rate method with different reference compounds. Room temperature rate coeficcients were found to be (in cm 3 molecule -1 s -1): k 1(OH + CH 3CH=CHC(O)OCH 3) = (4.65 ± 0.65) × 10 -11, k 2(Cl + CH 3CH=CHC(O)OCH 3) = (2.20 ± 0.55) × 10 -10, k 3(OH + CH 3CH=CHC(O)OCH 2CH 3) = (4.96 ± 0.61) × 10 -11, and k 4(Cl + CH 3CH=CHC(O)OCH 2CH 3) = (2.52 ± 0.62) × 10 -10 with uncertainties representing ±2σ. This is the first determination of k 1, k 3, and k 4 under atmospheric pressure. The rate coefficients are compared with previous determinations for other unsaturated and oxygenated VOCs and reactivity trends are presented. In addition, a comparison between the experimentally determined k OH with k OH predicted from k vs E HOMO relationships is presented. On the other hand, product identification under atmospheric conditions has been performed for the first time for these unsaturated esters by the GC-MS technique in NO x-free conditions. 2-Hydroxypropanal, acetaldehyde, formaldehyde, and formic acid were positively observed as degradation products in agreement with the addition of OH to C2 and C3 of the double bond, followed by decomposition of the 2,3- or 3,2-hydroxyalkoxy radicals formed. Atmospheric lifetimes, based on of the homogeneous sinks of the unsaturated esters studied, are estimated from the kinetic data obtained in the present work.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; ArgentinaFil: Benitez Villalba, Julio. Universidad Nacional de Asunción; ParaguayFil: Caballero, Norma Beatriz. Universidad Nacional de Asunción; ParaguayFil: 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; ArgentinaAmerican Chemical Society2012-06info: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/11336/62146Teruel, Mariano Andres; Benitez Villalba, Julio; Caballero, Norma Beatriz; Blanco, Maria Belen; Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms; American Chemical Society; Journal of Physical Chemistry A; 116; 24; 6-2012; 6127-61331089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp2113889info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp2113889info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:47:04Zoai:ri.conicet.gov.ar:11336/62146instacron: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:34982025-09-03 09:47:04.223CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms
title Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms
spellingShingle Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms
Teruel, Mariano Andres
Cinética Química
Crotonatos
Fotólisis
Degradación
title_short Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms
title_full Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms
title_fullStr Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms
title_full_unstemmed Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms
title_sort Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms
dc.creator.none.fl_str_mv Teruel, Mariano Andres
Benitez Villalba, Julio
Caballero, Norma Beatriz
Blanco, Maria Belen
author Teruel, Mariano Andres
author_facet Teruel, Mariano Andres
Benitez Villalba, Julio
Caballero, Norma Beatriz
Blanco, Maria Belen
author_role author
author2 Benitez Villalba, Julio
Caballero, Norma Beatriz
Blanco, Maria Belen
author2_role author
author
author
dc.subject.none.fl_str_mv Cinética Química
Crotonatos
Fotólisis
Degradación
topic Cinética Química
Crotonatos
Fotólisis
Degradación
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with methyl crotonate and ethyl crotonate have been determined at 298 K and atmospheric pressure. The decay of the organics was monitored using gas chromatography with flame ionization detection (GC-FID), and the rate constants were determined using the relative rate method with different reference compounds. Room temperature rate coeficcients were found to be (in cm 3 molecule -1 s -1): k 1(OH + CH 3CH=CHC(O)OCH 3) = (4.65 ± 0.65) × 10 -11, k 2(Cl + CH 3CH=CHC(O)OCH 3) = (2.20 ± 0.55) × 10 -10, k 3(OH + CH 3CH=CHC(O)OCH 2CH 3) = (4.96 ± 0.61) × 10 -11, and k 4(Cl + CH 3CH=CHC(O)OCH 2CH 3) = (2.52 ± 0.62) × 10 -10 with uncertainties representing ±2σ. This is the first determination of k 1, k 3, and k 4 under atmospheric pressure. The rate coefficients are compared with previous determinations for other unsaturated and oxygenated VOCs and reactivity trends are presented. In addition, a comparison between the experimentally determined k OH with k OH predicted from k vs E HOMO relationships is presented. On the other hand, product identification under atmospheric conditions has been performed for the first time for these unsaturated esters by the GC-MS technique in NO x-free conditions. 2-Hydroxypropanal, acetaldehyde, formaldehyde, and formic acid were positively observed as degradation products in agreement with the addition of OH to C2 and C3 of the double bond, followed by decomposition of the 2,3- or 3,2-hydroxyalkoxy radicals formed. Atmospheric lifetimes, based on of the homogeneous sinks of the unsaturated esters studied, are estimated from the kinetic data obtained in the present work.
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: Benitez Villalba, Julio. Universidad Nacional de Asunción; Paraguay
Fil: Caballero, Norma Beatriz. Universidad Nacional de Asunción; Paraguay
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
description Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with methyl crotonate and ethyl crotonate have been determined at 298 K and atmospheric pressure. The decay of the organics was monitored using gas chromatography with flame ionization detection (GC-FID), and the rate constants were determined using the relative rate method with different reference compounds. Room temperature rate coeficcients were found to be (in cm 3 molecule -1 s -1): k 1(OH + CH 3CH=CHC(O)OCH 3) = (4.65 ± 0.65) × 10 -11, k 2(Cl + CH 3CH=CHC(O)OCH 3) = (2.20 ± 0.55) × 10 -10, k 3(OH + CH 3CH=CHC(O)OCH 2CH 3) = (4.96 ± 0.61) × 10 -11, and k 4(Cl + CH 3CH=CHC(O)OCH 2CH 3) = (2.52 ± 0.62) × 10 -10 with uncertainties representing ±2σ. This is the first determination of k 1, k 3, and k 4 under atmospheric pressure. The rate coefficients are compared with previous determinations for other unsaturated and oxygenated VOCs and reactivity trends are presented. In addition, a comparison between the experimentally determined k OH with k OH predicted from k vs E HOMO relationships is presented. On the other hand, product identification under atmospheric conditions has been performed for the first time for these unsaturated esters by the GC-MS technique in NO x-free conditions. 2-Hydroxypropanal, acetaldehyde, formaldehyde, and formic acid were positively observed as degradation products in agreement with the addition of OH to C2 and C3 of the double bond, followed by decomposition of the 2,3- or 3,2-hydroxyalkoxy radicals formed. Atmospheric lifetimes, based on of the homogeneous sinks of the unsaturated esters studied, are estimated from the kinetic data obtained in the present work.
publishDate 2012
dc.date.none.fl_str_mv 2012-06
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/11336/62146
Teruel, Mariano Andres; Benitez Villalba, Julio; Caballero, Norma Beatriz; Blanco, Maria Belen; Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms; American Chemical Society; Journal of Physical Chemistry A; 116; 24; 6-2012; 6127-6133
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/62146
identifier_str_mv Teruel, Mariano Andres; Benitez Villalba, Julio; Caballero, Norma Beatriz; Blanco, Maria Belen; Gas-phase oxidation of methyl crotonate and ethyl crotonate. Kinetic study of their reactions toward oh radicals and Cl atoms; American Chemical Society; Journal of Physical Chemistry A; 116; 24; 6-2012; 6127-6133
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jp2113889
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp2113889
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
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 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 13.13397

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