Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K
- Autores
- Blanco, Maria Belen; Barnes, Ian; Wiesen, Peter
- 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 4-hexen-3-one, 5-hexen-2-one, and 3-penten-2-one have been determined at 298 ± 2 K and atmospheric pressure of air. Rate coefficients for the compounds were determined using a relative kinetic technique with different reference compounds. The experiments were performed in a large photoreactor (480 L) using in situ FTIR spectroscopy to monitor the decay of reactants. From the different measurements the following rate coefficients (in units of cm 3 molecule -1 s -1) have been determined: k 1(OH + 4-hexen-3-one) = (9.04 ± 2.12) × 10 -11, k 2(OH + 5-hexen-2-one) = (5.18 ± 1.27) × 10 -11, k 3(OH + 3-penten-2-one) = (7.22 ± 1.74) × 10 -11, k 4(Cl + 4-hexen-3-one) = (3.00 ± 0.58) × 10 -10, k 5(Cl + 5-hexen-2-one) = (3.15 ± 0.50) × 10 -10 and k 6(Cl + 3-penten-2-one) = (2.53 ± 0.54) × 10 -10. The reactivity of the double bond in alkenes and unsaturated ketones at 298 K toward addition of OH radicals and Cl atoms are compared and discussed. In addition, a correlation between the reactivity of the unsaturated ketones toward OH radicals and the HOMO of the compounds is presented. On the basis of the kinetic measurements, the tropospheric lifetimes of 4-hexen-3-one, 5-hexen-2-one, and 3-penten-2-one with respect to their reaction with hydroxyl radicals are estimated to be between 2 and 3 h. © 2012 American Chemical Society.
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. Bergische Universität Wuppertal; Alemania
Fil: Barnes, Ian. Bergische Universität Wuppertal; Alemania
Fil: Wiesen, Peter. Bergische Universität Wuppertal; Alemania - Materia
-
Unsaturated Ketones
Oh Radicals
Cl Atoms - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/62410
Ver los metadatos del registro completo
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CONICET Digital (CONICET) |
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Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 KBlanco, Maria BelenBarnes, IanWiesen, PeterUnsaturated KetonesOh RadicalsCl Atomshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with 4-hexen-3-one, 5-hexen-2-one, and 3-penten-2-one have been determined at 298 ± 2 K and atmospheric pressure of air. Rate coefficients for the compounds were determined using a relative kinetic technique with different reference compounds. The experiments were performed in a large photoreactor (480 L) using in situ FTIR spectroscopy to monitor the decay of reactants. From the different measurements the following rate coefficients (in units of cm 3 molecule -1 s -1) have been determined: k 1(OH + 4-hexen-3-one) = (9.04 ± 2.12) × 10 -11, k 2(OH + 5-hexen-2-one) = (5.18 ± 1.27) × 10 -11, k 3(OH + 3-penten-2-one) = (7.22 ± 1.74) × 10 -11, k 4(Cl + 4-hexen-3-one) = (3.00 ± 0.58) × 10 -10, k 5(Cl + 5-hexen-2-one) = (3.15 ± 0.50) × 10 -10 and k 6(Cl + 3-penten-2-one) = (2.53 ± 0.54) × 10 -10. The reactivity of the double bond in alkenes and unsaturated ketones at 298 K toward addition of OH radicals and Cl atoms are compared and discussed. In addition, a correlation between the reactivity of the unsaturated ketones toward OH radicals and the HOMO of the compounds is presented. On the basis of the kinetic measurements, the tropospheric lifetimes of 4-hexen-3-one, 5-hexen-2-one, and 3-penten-2-one with respect to their reaction with hydroxyl radicals are estimated to be between 2 and 3 h. © 2012 American Chemical Society.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. Bergische Universität Wuppertal; AlemaniaFil: Barnes, Ian. Bergische Universität Wuppertal; AlemaniaFil: Wiesen, Peter. Bergische Universität Wuppertal; AlemaniaAmerican Chemical Society2012-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/62410Blanco, Maria Belen; Barnes, Ian; Wiesen, Peter; Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K; American Chemical Society; Journal of Physical Chemistry A; 116; 24; 6-2012; 6033-60401089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp2109972info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp2109972info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:44:12Zoai:ri.conicet.gov.ar:11336/62410instacron: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 09:44:12.955CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K |
title |
Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K |
spellingShingle |
Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K Blanco, Maria Belen Unsaturated Ketones Oh Radicals Cl Atoms |
title_short |
Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K |
title_full |
Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K |
title_fullStr |
Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K |
title_full_unstemmed |
Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K |
title_sort |
Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K |
dc.creator.none.fl_str_mv |
Blanco, Maria Belen Barnes, Ian Wiesen, Peter |
author |
Blanco, Maria Belen |
author_facet |
Blanco, Maria Belen Barnes, Ian Wiesen, Peter |
author_role |
author |
author2 |
Barnes, Ian Wiesen, Peter |
author2_role |
author author |
dc.subject.none.fl_str_mv |
Unsaturated Ketones Oh Radicals Cl Atoms |
topic |
Unsaturated Ketones Oh Radicals Cl Atoms |
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 4-hexen-3-one, 5-hexen-2-one, and 3-penten-2-one have been determined at 298 ± 2 K and atmospheric pressure of air. Rate coefficients for the compounds were determined using a relative kinetic technique with different reference compounds. The experiments were performed in a large photoreactor (480 L) using in situ FTIR spectroscopy to monitor the decay of reactants. From the different measurements the following rate coefficients (in units of cm 3 molecule -1 s -1) have been determined: k 1(OH + 4-hexen-3-one) = (9.04 ± 2.12) × 10 -11, k 2(OH + 5-hexen-2-one) = (5.18 ± 1.27) × 10 -11, k 3(OH + 3-penten-2-one) = (7.22 ± 1.74) × 10 -11, k 4(Cl + 4-hexen-3-one) = (3.00 ± 0.58) × 10 -10, k 5(Cl + 5-hexen-2-one) = (3.15 ± 0.50) × 10 -10 and k 6(Cl + 3-penten-2-one) = (2.53 ± 0.54) × 10 -10. The reactivity of the double bond in alkenes and unsaturated ketones at 298 K toward addition of OH radicals and Cl atoms are compared and discussed. In addition, a correlation between the reactivity of the unsaturated ketones toward OH radicals and the HOMO of the compounds is presented. On the basis of the kinetic measurements, the tropospheric lifetimes of 4-hexen-3-one, 5-hexen-2-one, and 3-penten-2-one with respect to their reaction with hydroxyl radicals are estimated to be between 2 and 3 h. © 2012 American Chemical Society. 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. Bergische Universität Wuppertal; Alemania Fil: Barnes, Ian. Bergische Universität Wuppertal; Alemania Fil: Wiesen, Peter. Bergische Universität Wuppertal; Alemania |
description |
Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with 4-hexen-3-one, 5-hexen-2-one, and 3-penten-2-one have been determined at 298 ± 2 K and atmospheric pressure of air. Rate coefficients for the compounds were determined using a relative kinetic technique with different reference compounds. The experiments were performed in a large photoreactor (480 L) using in situ FTIR spectroscopy to monitor the decay of reactants. From the different measurements the following rate coefficients (in units of cm 3 molecule -1 s -1) have been determined: k 1(OH + 4-hexen-3-one) = (9.04 ± 2.12) × 10 -11, k 2(OH + 5-hexen-2-one) = (5.18 ± 1.27) × 10 -11, k 3(OH + 3-penten-2-one) = (7.22 ± 1.74) × 10 -11, k 4(Cl + 4-hexen-3-one) = (3.00 ± 0.58) × 10 -10, k 5(Cl + 5-hexen-2-one) = (3.15 ± 0.50) × 10 -10 and k 6(Cl + 3-penten-2-one) = (2.53 ± 0.54) × 10 -10. The reactivity of the double bond in alkenes and unsaturated ketones at 298 K toward addition of OH radicals and Cl atoms are compared and discussed. In addition, a correlation between the reactivity of the unsaturated ketones toward OH radicals and the HOMO of the compounds is presented. On the basis of the kinetic measurements, the tropospheric lifetimes of 4-hexen-3-one, 5-hexen-2-one, and 3-penten-2-one with respect to their reaction with hydroxyl radicals are estimated to be between 2 and 3 h. © 2012 American Chemical Society. |
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/11336/62410 Blanco, Maria Belen; Barnes, Ian; Wiesen, Peter; Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K; American Chemical Society; Journal of Physical Chemistry A; 116; 24; 6-2012; 6033-6040 1089-5639 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/62410 |
identifier_str_mv |
Blanco, Maria Belen; Barnes, Ian; Wiesen, Peter; Kinetic investigation of the OH radical and Cl atom initiated degradation of unsaturated ketones at atmospheric pressure and 298 K; American Chemical Society; Journal of Physical Chemistry A; 116; 24; 6-2012; 6033-6040 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/jp2109972 info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp2109972 |
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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1842268649852764160 |
score |
13.13397 |