Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx

Autores
Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The products formed from the reactions of OH radicals with vinyl acetate and allyl acetate have been studied in a 1080 L quartz-glass chamber in the presence and absence of NOx using in situ FTIR spectroscopy to monitor the reactant decay and product formation. The yields of the primary products formed in the reaction of OH with vinyl acetate were: formic acetic anhydride (84 ± 11)%; acetic acid (18 ± 3)% and formaldehyde (99 ± 15)% in the presence of NOx and formic acetic anhydride (28 ± 5)%; acetic acid (87 ± 12)% and formaldehyde (52 ± 8)% in the absence of NOx. For the reaction of OH with allyl acetate the yields of the identified products were: acetoxyacetaldehyde (96 ± 15)% and formaldehyde (90 ± 12)% in the presence of NOx and acetoxyacetaldehyde (26 ± 4)% and formaldehyde (12 ± 3)% in the absence of NOx. The present results indicate that in the absence of NOx the main fate of the 1,2-hydroxyalkoxy radicals formed after addition of OH to the double bond in the compounds is, in the case of vinyl acetate, an α-ester rearrangement to produce acetic acid and CH 2(OH)CO• radicals and in the case of allyl acetate reaction of the radical with O2 to form acetic acid 3-hydroxy-2-oxo-propyl ester (CH3C(O)OCH2C(O)CH 2OH). In contrast, in the presence of NOx the main reaction pathway for the 1,2-hydroxyalkoxy radicals is decomposition. The results are compared with the available literature data and implications for the atmospheric chemistry of vinyl and allyl acetate are assessed. © 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 Universitaet Wuppertal; Alemania
Fil: Bejan, Iustinian. Bergische Universitaet Wuppertal; Alemania. University of Iasi; Rumania
Fil: Barnes, Ian. Bergische Universitaet Wuppertal; Alemania
Fil: Wiesen, Peter. Bergische Universitaet Wuppertal; Alemania
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
Materia
Acetates
Nox
Degradation Mechanism
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:11336/61799
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oai_identifier_str oai:ri.conicet.gov.ar:11336/61799
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOxBlanco, Maria BelenBejan, IustinianBarnes, IanWiesen, PeterTeruel, Mariano AndresAcetatesNoxDegradation Mechanismhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The products formed from the reactions of OH radicals with vinyl acetate and allyl acetate have been studied in a 1080 L quartz-glass chamber in the presence and absence of NOx using in situ FTIR spectroscopy to monitor the reactant decay and product formation. The yields of the primary products formed in the reaction of OH with vinyl acetate were: formic acetic anhydride (84 ± 11)%; acetic acid (18 ± 3)% and formaldehyde (99 ± 15)% in the presence of NOx and formic acetic anhydride (28 ± 5)%; acetic acid (87 ± 12)% and formaldehyde (52 ± 8)% in the absence of NOx. For the reaction of OH with allyl acetate the yields of the identified products were: acetoxyacetaldehyde (96 ± 15)% and formaldehyde (90 ± 12)% in the presence of NOx and acetoxyacetaldehyde (26 ± 4)% and formaldehyde (12 ± 3)% in the absence of NOx. The present results indicate that in the absence of NOx the main fate of the 1,2-hydroxyalkoxy radicals formed after addition of OH to the double bond in the compounds is, in the case of vinyl acetate, an α-ester rearrangement to produce acetic acid and CH 2(OH)CO• radicals and in the case of allyl acetate reaction of the radical with O2 to form acetic acid 3-hydroxy-2-oxo-propyl ester (CH3C(O)OCH2C(O)CH 2OH). In contrast, in the presence of NOx the main reaction pathway for the 1,2-hydroxyalkoxy radicals is decomposition. The results are compared with the available literature data and implications for the atmospheric chemistry of vinyl and allyl acetate are assessed. © 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 Universitaet Wuppertal; AlemaniaFil: Bejan, Iustinian. Bergische Universitaet Wuppertal; Alemania. University of Iasi; RumaniaFil: Barnes, Ian. Bergische Universitaet Wuppertal; AlemaniaFil: Wiesen, Peter. Bergische Universitaet Wuppertal; AlemaniaFil: 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; ArgentinaAmerican Chemical Society2012-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/61799Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx; American Chemical Society; Environmental Science & Technology; 46; 16; 8-2012; 8817-88250013-936XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/es3015869info:eu-repo/semantics/altIdentifier/doi/10.1021/es3015869info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:55:55Zoai:ri.conicet.gov.ar:11336/61799instacron: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:34982025-11-12 09:55:55.951CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx
title Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx
spellingShingle Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx
Blanco, Maria Belen
Acetates
Nox
Degradation Mechanism
title_short Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx
title_full Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx
title_fullStr Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx
title_full_unstemmed Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx
title_sort Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx
dc.creator.none.fl_str_mv Blanco, Maria Belen
Bejan, Iustinian
Barnes, Ian
Wiesen, Peter
Teruel, Mariano Andres
author Blanco, Maria Belen
author_facet Blanco, Maria Belen
Bejan, Iustinian
Barnes, Ian
Wiesen, Peter
Teruel, Mariano Andres
author_role author
author2 Bejan, Iustinian
Barnes, Ian
Wiesen, Peter
Teruel, Mariano Andres
author2_role author
author
author
author
dc.subject.none.fl_str_mv Acetates
Nox
Degradation Mechanism
topic Acetates
Nox
Degradation Mechanism
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 products formed from the reactions of OH radicals with vinyl acetate and allyl acetate have been studied in a 1080 L quartz-glass chamber in the presence and absence of NOx using in situ FTIR spectroscopy to monitor the reactant decay and product formation. The yields of the primary products formed in the reaction of OH with vinyl acetate were: formic acetic anhydride (84 ± 11)%; acetic acid (18 ± 3)% and formaldehyde (99 ± 15)% in the presence of NOx and formic acetic anhydride (28 ± 5)%; acetic acid (87 ± 12)% and formaldehyde (52 ± 8)% in the absence of NOx. For the reaction of OH with allyl acetate the yields of the identified products were: acetoxyacetaldehyde (96 ± 15)% and formaldehyde (90 ± 12)% in the presence of NOx and acetoxyacetaldehyde (26 ± 4)% and formaldehyde (12 ± 3)% in the absence of NOx. The present results indicate that in the absence of NOx the main fate of the 1,2-hydroxyalkoxy radicals formed after addition of OH to the double bond in the compounds is, in the case of vinyl acetate, an α-ester rearrangement to produce acetic acid and CH 2(OH)CO• radicals and in the case of allyl acetate reaction of the radical with O2 to form acetic acid 3-hydroxy-2-oxo-propyl ester (CH3C(O)OCH2C(O)CH 2OH). In contrast, in the presence of NOx the main reaction pathway for the 1,2-hydroxyalkoxy radicals is decomposition. The results are compared with the available literature data and implications for the atmospheric chemistry of vinyl and allyl acetate are assessed. © 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 Universitaet Wuppertal; Alemania
Fil: Bejan, Iustinian. Bergische Universitaet Wuppertal; Alemania. University of Iasi; Rumania
Fil: Barnes, Ian. Bergische Universitaet Wuppertal; Alemania
Fil: Wiesen, Peter. Bergische Universitaet Wuppertal; Alemania
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
description The products formed from the reactions of OH radicals with vinyl acetate and allyl acetate have been studied in a 1080 L quartz-glass chamber in the presence and absence of NOx using in situ FTIR spectroscopy to monitor the reactant decay and product formation. The yields of the primary products formed in the reaction of OH with vinyl acetate were: formic acetic anhydride (84 ± 11)%; acetic acid (18 ± 3)% and formaldehyde (99 ± 15)% in the presence of NOx and formic acetic anhydride (28 ± 5)%; acetic acid (87 ± 12)% and formaldehyde (52 ± 8)% in the absence of NOx. For the reaction of OH with allyl acetate the yields of the identified products were: acetoxyacetaldehyde (96 ± 15)% and formaldehyde (90 ± 12)% in the presence of NOx and acetoxyacetaldehyde (26 ± 4)% and formaldehyde (12 ± 3)% in the absence of NOx. The present results indicate that in the absence of NOx the main fate of the 1,2-hydroxyalkoxy radicals formed after addition of OH to the double bond in the compounds is, in the case of vinyl acetate, an α-ester rearrangement to produce acetic acid and CH 2(OH)CO• radicals and in the case of allyl acetate reaction of the radical with O2 to form acetic acid 3-hydroxy-2-oxo-propyl ester (CH3C(O)OCH2C(O)CH 2OH). In contrast, in the presence of NOx the main reaction pathway for the 1,2-hydroxyalkoxy radicals is decomposition. The results are compared with the available literature data and implications for the atmospheric chemistry of vinyl and allyl acetate are assessed. © 2012 American Chemical Society.
publishDate 2012
dc.date.none.fl_str_mv 2012-08
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/11336/61799
Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx; American Chemical Society; Environmental Science & Technology; 46; 16; 8-2012; 8817-8825
0013-936X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/61799
identifier_str_mv Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; Atmospheric oxidation of vinyl and allyl acetate: Product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NOx; American Chemical Society; Environmental Science & Technology; 46; 16; 8-2012; 8817-8825
0013-936X
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/es3015869
info:eu-repo/semantics/altIdentifier/doi/10.1021/es3015869
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 12.976206

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