Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction

Autores
Niklas, Illmann; Gibilisco, Rodrigo Gastón; Bejan, Iustinian Gabriel; Patroescu Klotz Iulia; Wiesen, Peter
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The OH-radical-initiated oxidation of 3-methyl-3-penten-2-one and 4-methyl-3-penten-2-one was investigated in two atmospheric simulation chambers at 298±3 K and 990±15 mbar using long-path FTIR spectroscopy. The rate coefficients of the reactions of 3-methyl-3-penten-2-one and 4-methyl-3-penten-2-one with OH radicals were determined to be (6.5±1.2)×10-11 and (8.1±1.3)×10-11 cm3molecule-1s-1, respectively. To enlarge the kinetics data pool the rate coefficients of the target species with Cl atoms were determined to be (2.8±0.4)×10-10 and (3.1±0.4)×10-10 cm3molecule-1s-1, respectively. The mechanistic investigation of the OH-initiated oxidation focuses on the RO2+NO reaction. The quantified products were acetoin, acetaldehyde, biacetyl, CO2 and peroxyacetyl nitrate (PAN) for the reaction of 3-methyl-3-penten-2-one with OH radicals and acetone, methyl glyoxal, 2-hydroxy-2-methylpropanal, CO2 and peroxyacetyl nitrate (PAN) for the reaction of 4-methyl-3-penten-2-one with OH, respectively. Based on the calculated product yields an upper limit of 0.15 was determined for the yield of RONO2 derived from the OH reaction of 4-methyl-3-penten-2-one. By contrast, no RONO2 formation was observed for the OH reaction of 3-methyl-3-penten-2-one. Additionally, a simple model is presented to correct product yields for secondary processes.
Fil: Niklas, Illmann. Physikalische Chemie, Bergische Universität Wuppertal,; Alemania
Fil: Gibilisco, Rodrigo Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. 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: Bejan, Iustinian Gabriel. Faculty Of Chemistry And Environment Studies; Rumania
Fil: Patroescu Klotz Iulia. Physikalische Chemie, Bergische Universität Wuppertal,; Alemania
Fil: Wiesen, Peter. Physikalische Chemie, Bergische Universität Wuppertal,; Alemania
Materia
α,β-unsaturated ketones
Gas phase kinetics
Biomass burning
OH radicals
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/149180
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/149180
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reactionNiklas, IllmannGibilisco, Rodrigo GastónBejan, Iustinian GabrielPatroescu Klotz IuliaWiesen, Peterα,β-unsaturated ketonesGas phase kineticsBiomass burningOH radicalshttps://purl.org/becyt/ford/1.5https://purl.org/becyt/ford/1The OH-radical-initiated oxidation of 3-methyl-3-penten-2-one and 4-methyl-3-penten-2-one was investigated in two atmospheric simulation chambers at 298±3 K and 990±15 mbar using long-path FTIR spectroscopy. The rate coefficients of the reactions of 3-methyl-3-penten-2-one and 4-methyl-3-penten-2-one with OH radicals were determined to be (6.5±1.2)×10-11 and (8.1±1.3)×10-11 cm3molecule-1s-1, respectively. To enlarge the kinetics data pool the rate coefficients of the target species with Cl atoms were determined to be (2.8±0.4)×10-10 and (3.1±0.4)×10-10 cm3molecule-1s-1, respectively. The mechanistic investigation of the OH-initiated oxidation focuses on the RO2+NO reaction. The quantified products were acetoin, acetaldehyde, biacetyl, CO2 and peroxyacetyl nitrate (PAN) for the reaction of 3-methyl-3-penten-2-one with OH radicals and acetone, methyl glyoxal, 2-hydroxy-2-methylpropanal, CO2 and peroxyacetyl nitrate (PAN) for the reaction of 4-methyl-3-penten-2-one with OH, respectively. Based on the calculated product yields an upper limit of 0.15 was determined for the yield of RONO2 derived from the OH reaction of 4-methyl-3-penten-2-one. By contrast, no RONO2 formation was observed for the OH reaction of 3-methyl-3-penten-2-one. Additionally, a simple model is presented to correct product yields for secondary processes.Fil: Niklas, Illmann. Physikalische Chemie, Bergische Universität Wuppertal,; AlemaniaFil: Gibilisco, Rodrigo Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. 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: Bejan, Iustinian Gabriel. Faculty Of Chemistry And Environment Studies; RumaniaFil: Patroescu Klotz Iulia. Physikalische Chemie, Bergische Universität Wuppertal,; AlemaniaFil: Wiesen, Peter. Physikalische Chemie, Bergische Universität Wuppertal,; AlemaniaCopernicus Publications2021-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/149180Niklas, Illmann; Gibilisco, Rodrigo Gastón; Bejan, Iustinian Gabriel; Patroescu Klotz Iulia; Wiesen, Peter; Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction; Copernicus Publications; Atmospheric Chemistry and Physics; 21; 17; 9-2021; 13667-136861680-7324CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://acp.copernicus.org/articles/21/13667/2021/info:eu-repo/semantics/altIdentifier/doi/10.5194/acp-21-13667-2021info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:06:40Zoai:ri.conicet.gov.ar:11336/149180instacron: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 10:06:40.89CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction
title Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction
spellingShingle Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction
Niklas, Illmann
α,β-unsaturated ketones
Gas phase kinetics
Biomass burning
OH radicals
title_short Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction
title_full Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction
title_fullStr Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction
title_full_unstemmed Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction
title_sort Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction
dc.creator.none.fl_str_mv Niklas, Illmann
Gibilisco, Rodrigo Gastón
Bejan, Iustinian Gabriel
Patroescu Klotz Iulia
Wiesen, Peter
author Niklas, Illmann
author_facet Niklas, Illmann
Gibilisco, Rodrigo Gastón
Bejan, Iustinian Gabriel
Patroescu Klotz Iulia
Wiesen, Peter
author_role author
author2 Gibilisco, Rodrigo Gastón
Bejan, Iustinian Gabriel
Patroescu Klotz Iulia
Wiesen, Peter
author2_role author
author
author
author
dc.subject.none.fl_str_mv α,β-unsaturated ketones
Gas phase kinetics
Biomass burning
OH radicals
topic α,β-unsaturated ketones
Gas phase kinetics
Biomass burning
OH radicals
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The OH-radical-initiated oxidation of 3-methyl-3-penten-2-one and 4-methyl-3-penten-2-one was investigated in two atmospheric simulation chambers at 298±3 K and 990±15 mbar using long-path FTIR spectroscopy. The rate coefficients of the reactions of 3-methyl-3-penten-2-one and 4-methyl-3-penten-2-one with OH radicals were determined to be (6.5±1.2)×10-11 and (8.1±1.3)×10-11 cm3molecule-1s-1, respectively. To enlarge the kinetics data pool the rate coefficients of the target species with Cl atoms were determined to be (2.8±0.4)×10-10 and (3.1±0.4)×10-10 cm3molecule-1s-1, respectively. The mechanistic investigation of the OH-initiated oxidation focuses on the RO2+NO reaction. The quantified products were acetoin, acetaldehyde, biacetyl, CO2 and peroxyacetyl nitrate (PAN) for the reaction of 3-methyl-3-penten-2-one with OH radicals and acetone, methyl glyoxal, 2-hydroxy-2-methylpropanal, CO2 and peroxyacetyl nitrate (PAN) for the reaction of 4-methyl-3-penten-2-one with OH, respectively. Based on the calculated product yields an upper limit of 0.15 was determined for the yield of RONO2 derived from the OH reaction of 4-methyl-3-penten-2-one. By contrast, no RONO2 formation was observed for the OH reaction of 3-methyl-3-penten-2-one. Additionally, a simple model is presented to correct product yields for secondary processes.
Fil: Niklas, Illmann. Physikalische Chemie, Bergische Universität Wuppertal,; Alemania
Fil: Gibilisco, Rodrigo Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. 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: Bejan, Iustinian Gabriel. Faculty Of Chemistry And Environment Studies; Rumania
Fil: Patroescu Klotz Iulia. Physikalische Chemie, Bergische Universität Wuppertal,; Alemania
Fil: Wiesen, Peter. Physikalische Chemie, Bergische Universität Wuppertal,; Alemania
description The OH-radical-initiated oxidation of 3-methyl-3-penten-2-one and 4-methyl-3-penten-2-one was investigated in two atmospheric simulation chambers at 298±3 K and 990±15 mbar using long-path FTIR spectroscopy. The rate coefficients of the reactions of 3-methyl-3-penten-2-one and 4-methyl-3-penten-2-one with OH radicals were determined to be (6.5±1.2)×10-11 and (8.1±1.3)×10-11 cm3molecule-1s-1, respectively. To enlarge the kinetics data pool the rate coefficients of the target species with Cl atoms were determined to be (2.8±0.4)×10-10 and (3.1±0.4)×10-10 cm3molecule-1s-1, respectively. The mechanistic investigation of the OH-initiated oxidation focuses on the RO2+NO reaction. The quantified products were acetoin, acetaldehyde, biacetyl, CO2 and peroxyacetyl nitrate (PAN) for the reaction of 3-methyl-3-penten-2-one with OH radicals and acetone, methyl glyoxal, 2-hydroxy-2-methylpropanal, CO2 and peroxyacetyl nitrate (PAN) for the reaction of 4-methyl-3-penten-2-one with OH, respectively. Based on the calculated product yields an upper limit of 0.15 was determined for the yield of RONO2 derived from the OH reaction of 4-methyl-3-penten-2-one. By contrast, no RONO2 formation was observed for the OH reaction of 3-methyl-3-penten-2-one. Additionally, a simple model is presented to correct product yields for secondary processes.
publishDate 2021
dc.date.none.fl_str_mv 2021-09
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/11336/149180
Niklas, Illmann; Gibilisco, Rodrigo Gastón; Bejan, Iustinian Gabriel; Patroescu Klotz Iulia; Wiesen, Peter; Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction; Copernicus Publications; Atmospheric Chemistry and Physics; 21; 17; 9-2021; 13667-13686
1680-7324
CONICET Digital
CONICET
url http://hdl.handle.net/11336/149180
identifier_str_mv Niklas, Illmann; Gibilisco, Rodrigo Gastón; Bejan, Iustinian Gabriel; Patroescu Klotz Iulia; Wiesen, Peter; Atmospheric oxidation of α,β-unsaturated ketones: Kinetics and mechanism of the OH radical reaction; Copernicus Publications; Atmospheric Chemistry and Physics; 21; 17; 9-2021; 13667-13686
1680-7324
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://acp.copernicus.org/articles/21/13667/2021/
info:eu-repo/semantics/altIdentifier/doi/10.5194/acp-21-13667-2021
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Copernicus Publications
publisher.none.fl_str_mv Copernicus Publications
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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