Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications

Autores
Jara Toro, Rafael Alejandro; Barrera, Javier Alejandro; Aranguren Abrate, Juan Pablo; Taccone, Raúl A.; Pino, Gustavo Ariel
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, we investigate the degradation process of 1-chlorobutane, initiated by OH radicals, under atmospheric conditions (air pressure of 750 Torr and 296 K) from both experimental and theoretical approaches. In the first one, a relative kinetic method was used to obtain the rate coefficient for this reaction, while the products were identified for the first time (1-chloro-2-butanone, 1-chloro-2-butanol, 4-chloro-2-butanone, 3-hydroxy-butanaldehyde, and 3-chloro-2-butanol) using mass spectrometry, allowing suggesting a reaction mechanism. The theoretical calculations, for the reactive process, were computed using the BHandHLYP/6-311++G(d,p) level of theory, and the energies for all of the stationary points were refined at the CCSD(T) level. Five conformers for 1-chlorobutane and 33 reactive channels with OH radicals were found, which were considered to calculate the thermal rate coefficient (as the sum of the site-specific rate coefficients using canonical transition state theory). The theoretical rate coefficient (1.8 × 10-12 cm3 molecule-1 s-1) is in good agreement with the experimental value (2.22 ± 0.50) × 10-12 cm3 molecule-1 s-1 determined in this work. Finally, environmental impact indexes were calculated and a discussion on the atmospheric implications due to the emissions of this compound into the troposphere was given.
Fil: Jara Toro, Rafael 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: Barrera, Javier 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: Aranguren Abrate, Juan Pablo. 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: Taccone, Raúl A.. 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: Pino, Gustavo Ariel. 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
Haloalkane
Hydroxyl radicals
Environmental impact indexes
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:11336/125445
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/125445
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implicationsJara Toro, Rafael AlejandroBarrera, Javier AlejandroAranguren Abrate, Juan PabloTaccone, Raúl A.Pino, Gustavo ArielHaloalkaneHydroxyl radicalsEnvironmental impact indexeshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In this work, we investigate the degradation process of 1-chlorobutane, initiated by OH radicals, under atmospheric conditions (air pressure of 750 Torr and 296 K) from both experimental and theoretical approaches. In the first one, a relative kinetic method was used to obtain the rate coefficient for this reaction, while the products were identified for the first time (1-chloro-2-butanone, 1-chloro-2-butanol, 4-chloro-2-butanone, 3-hydroxy-butanaldehyde, and 3-chloro-2-butanol) using mass spectrometry, allowing suggesting a reaction mechanism. The theoretical calculations, for the reactive process, were computed using the BHandHLYP/6-311++G(d,p) level of theory, and the energies for all of the stationary points were refined at the CCSD(T) level. Five conformers for 1-chlorobutane and 33 reactive channels with OH radicals were found, which were considered to calculate the thermal rate coefficient (as the sum of the site-specific rate coefficients using canonical transition state theory). The theoretical rate coefficient (1.8 × 10-12 cm3 molecule-1 s-1) is in good agreement with the experimental value (2.22 ± 0.50) × 10-12 cm3 molecule-1 s-1 determined in this work. Finally, environmental impact indexes were calculated and a discussion on the atmospheric implications due to the emissions of this compound into the troposphere was given.Fil: Jara Toro, Rafael 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: Barrera, Javier 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: Aranguren Abrate, Juan Pablo. 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: Taccone, Raúl A.. 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: Pino, Gustavo Ariel. 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 Society2019-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/125445Jara Toro, Rafael Alejandro; Barrera, Javier Alejandro; Aranguren Abrate, Juan Pablo; Taccone, Raúl A.; Pino, Gustavo Ariel; Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications; American Chemical Society; Journal of Physical Chemistry A; 124; 1; 12-2019; 229-2391089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.jpca.9b10426info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.9b10426info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:47:09Zoai:ri.conicet.gov.ar:11336/125445instacron: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 09:47:09.979CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications
title Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications
spellingShingle Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications
Jara Toro, Rafael Alejandro
Haloalkane
Hydroxyl radicals
Environmental impact indexes
title_short Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications
title_full Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications
title_fullStr Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications
title_full_unstemmed Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications
title_sort Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications
dc.creator.none.fl_str_mv Jara Toro, Rafael Alejandro
Barrera, Javier Alejandro
Aranguren Abrate, Juan Pablo
Taccone, Raúl A.
Pino, Gustavo Ariel
author Jara Toro, Rafael Alejandro
author_facet Jara Toro, Rafael Alejandro
Barrera, Javier Alejandro
Aranguren Abrate, Juan Pablo
Taccone, Raúl A.
Pino, Gustavo Ariel
author_role author
author2 Barrera, Javier Alejandro
Aranguren Abrate, Juan Pablo
Taccone, Raúl A.
Pino, Gustavo Ariel
author2_role author
author
author
author
dc.subject.none.fl_str_mv Haloalkane
Hydroxyl radicals
Environmental impact indexes
topic Haloalkane
Hydroxyl radicals
Environmental impact indexes
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this work, we investigate the degradation process of 1-chlorobutane, initiated by OH radicals, under atmospheric conditions (air pressure of 750 Torr and 296 K) from both experimental and theoretical approaches. In the first one, a relative kinetic method was used to obtain the rate coefficient for this reaction, while the products were identified for the first time (1-chloro-2-butanone, 1-chloro-2-butanol, 4-chloro-2-butanone, 3-hydroxy-butanaldehyde, and 3-chloro-2-butanol) using mass spectrometry, allowing suggesting a reaction mechanism. The theoretical calculations, for the reactive process, were computed using the BHandHLYP/6-311++G(d,p) level of theory, and the energies for all of the stationary points were refined at the CCSD(T) level. Five conformers for 1-chlorobutane and 33 reactive channels with OH radicals were found, which were considered to calculate the thermal rate coefficient (as the sum of the site-specific rate coefficients using canonical transition state theory). The theoretical rate coefficient (1.8 × 10-12 cm3 molecule-1 s-1) is in good agreement with the experimental value (2.22 ± 0.50) × 10-12 cm3 molecule-1 s-1 determined in this work. Finally, environmental impact indexes were calculated and a discussion on the atmospheric implications due to the emissions of this compound into the troposphere was given.
Fil: Jara Toro, Rafael 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: Barrera, Javier 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: Aranguren Abrate, Juan Pablo. 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: Taccone, Raúl A.. 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: Pino, Gustavo Ariel. 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 In this work, we investigate the degradation process of 1-chlorobutane, initiated by OH radicals, under atmospheric conditions (air pressure of 750 Torr and 296 K) from both experimental and theoretical approaches. In the first one, a relative kinetic method was used to obtain the rate coefficient for this reaction, while the products were identified for the first time (1-chloro-2-butanone, 1-chloro-2-butanol, 4-chloro-2-butanone, 3-hydroxy-butanaldehyde, and 3-chloro-2-butanol) using mass spectrometry, allowing suggesting a reaction mechanism. The theoretical calculations, for the reactive process, were computed using the BHandHLYP/6-311++G(d,p) level of theory, and the energies for all of the stationary points were refined at the CCSD(T) level. Five conformers for 1-chlorobutane and 33 reactive channels with OH radicals were found, which were considered to calculate the thermal rate coefficient (as the sum of the site-specific rate coefficients using canonical transition state theory). The theoretical rate coefficient (1.8 × 10-12 cm3 molecule-1 s-1) is in good agreement with the experimental value (2.22 ± 0.50) × 10-12 cm3 molecule-1 s-1 determined in this work. Finally, environmental impact indexes were calculated and a discussion on the atmospheric implications due to the emissions of this compound into the troposphere was given.
publishDate 2019
dc.date.none.fl_str_mv 2019-12
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/11336/125445
Jara Toro, Rafael Alejandro; Barrera, Javier Alejandro; Aranguren Abrate, Juan Pablo; Taccone, Raúl A.; Pino, Gustavo Ariel; Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications; American Chemical Society; Journal of Physical Chemistry A; 124; 1; 12-2019; 229-239
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/125445
identifier_str_mv Jara Toro, Rafael Alejandro; Barrera, Javier Alejandro; Aranguren Abrate, Juan Pablo; Taccone, Raúl A.; Pino, Gustavo Ariel; Rate coefficient and mechanism of the OH-Initiateddegradation of 1-chlorobutane: atmospheric implications; American Chemical Society; Journal of Physical Chemistry A; 124; 1; 12-2019; 229-239
1089-5639
1520-5215
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/abs/10.1021/acs.jpca.9b10426
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.9b10426
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
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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