OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K

The kinetics of the gas-phase reactions of hydroxyl radicals (OH) with methyl methacrylate (k1), butyl methacrylate (k2), butyl acrylate (k3), and vinyl acetate (k4) have been investigated for the first time as a function of temperature using the relative technique. The experiments were performed in...

Descripción completa

Detalles Bibliográficos
Autores: Blanco, Maria Belen, Bejan, Iustinian, Barnes, Ian, Wiesen, Peter, Teruel, Mariano Andres
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2009
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/82858
Acceso en línea:http://hdl.handle.net/11336/82858
Access Level:acceso abierto
Palabra clave:Oh Reactions
Unsaturated Compounds
Temperature Dependencies
https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
id AR_e2a6efcafe5e649bfe2f2e46764f90ca
oai_identifier_str oai:ri.conicet.gov.ar:11336/82858
network_acronym_str AR
network_name_str Argentina
repository_id_str
dc.title.none.fl_str_mv OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K
title OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K
spellingShingle OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K
Blanco, Maria Belen
Oh Reactions
Unsaturated Compounds
Temperature Dependencies
https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
title_short OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K
title_full OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K
title_fullStr OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K
title_full_unstemmed OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K
title_sort OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K
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 Oh Reactions
Unsaturated Compounds
Temperature Dependencies
https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
topic Oh Reactions
Unsaturated Compounds
Temperature Dependencies
https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
description The kinetics of the gas-phase reactions of hydroxyl radicals (OH) with methyl methacrylate (k1), butyl methacrylate (k2), butyl acrylate (k3), and vinyl acetate (k4) have been investigated for the first time as a function of temperature using the relative technique. The experiments were performed in a 1080 L quartz glass photoreactor over the temperature range (T = 287-313 K) at a total pressure of 760 ± 10 Torr synthetic air using in situ FTIR absorption spectroscopy to monitor the concentration-time behaviors of reactants. OH radicals were produced by the 254 nm photolysis of hydrogen peroxide (H2O2). The following Arrhenius expressions (in units of cm3 molecule-1 s-1) adequately describe the measured rate coefficients as a function of temperature: k 1 = (1.97 ± 0.95) × 10-12 exp[(921 ± 52)/T], k2 = (1.65 ± 1.05) × 10-11 exp[(413 ± 34)/T], k3 = (4.4 ± 2.5) × 10-13 exp[(1117 ± 105)/T], and k4 = (4.06 ± 2.02) × 10-12 exp[(540 ± 49)/T]. All of the rate coefficients display a negative temperature dependence and low pre-exponential factor, which supports an addition mechanism for the reactions involving reversible OH-adduct formation. The rate coefficients (in units of cm3 molecule -1 s-1) determined at room temperature (298 K) were as follows: k1 = (4.30 ± 0.98) × 10-11, k 2 = (6.63 ± 1.42) × 10-11, k3 = (2.17 ± 0.48) × 10-11, and k4 = (2.48 ± 0.61) × 10-11. The results are compared with previous values of the rate coefficients reported in the literature, which were mainly measured at room temperature. The reactivity of the various unsaturated esters toward the OH radical is discussed in terms of structure activity relationships and parallels are drawn with the OH-radical activities of structurally similar compounds. Using the kinetic parameters determined in this work, residence times of the esters in the atmosphere with respect to their reaction with OH have been determined and are compared with other possible degradation pathways. Possible atmospheric implications of the various degradation pathways studied are discussed.
publishDate 2009
dc.date.none.fl_str_mv 2009-05
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/11336/82858
Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K; American Chemical Society; Journal of Physical Chemistry A; 113; 20; 5-2009; 5958-5965
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/82858
identifier_str_mv Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K; American Chemical Society; Journal of Physical Chemistry A; 113; 20; 5-2009; 5958-5965
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://www.ncbi.nlm.nih.gov/pubmed/19405497
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp901755x
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
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
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
_version_ 1799196010847666176
spelling OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 KBlanco, Maria BelenBejan, IustinianBarnes, IanWiesen, PeterTeruel, Mariano AndresOh ReactionsUnsaturated CompoundsTemperature Dependencieshttps://purl.org/becyt/ford/1.5https://purl.org/becyt/ford/1The kinetics of the gas-phase reactions of hydroxyl radicals (OH) with methyl methacrylate (k1), butyl methacrylate (k2), butyl acrylate (k3), and vinyl acetate (k4) have been investigated for the first time as a function of temperature using the relative technique. The experiments were performed in a 1080 L quartz glass photoreactor over the temperature range (T = 287-313 K) at a total pressure of 760 ± 10 Torr synthetic air using in situ FTIR absorption spectroscopy to monitor the concentration-time behaviors of reactants. OH radicals were produced by the 254 nm photolysis of hydrogen peroxide (H2O2). The following Arrhenius expressions (in units of cm3 molecule-1 s-1) adequately describe the measured rate coefficients as a function of temperature: k 1 = (1.97 ± 0.95) × 10-12 exp[(921 ± 52)/T], k2 = (1.65 ± 1.05) × 10-11 exp[(413 ± 34)/T], k3 = (4.4 ± 2.5) × 10-13 exp[(1117 ± 105)/T], and k4 = (4.06 ± 2.02) × 10-12 exp[(540 ± 49)/T]. All of the rate coefficients display a negative temperature dependence and low pre-exponential factor, which supports an addition mechanism for the reactions involving reversible OH-adduct formation. The rate coefficients (in units of cm3 molecule -1 s-1) determined at room temperature (298 K) were as follows: k1 = (4.30 ± 0.98) × 10-11, k 2 = (6.63 ± 1.42) × 10-11, k3 = (2.17 ± 0.48) × 10-11, and k4 = (2.48 ± 0.61) × 10-11. The results are compared with previous values of the rate coefficients reported in the literature, which were mainly measured at room temperature. The reactivity of the various unsaturated esters toward the OH radical is discussed in terms of structure activity relationships and parallels are drawn with the OH-radical activities of structurally similar compounds. Using the kinetic parameters determined in this work, residence times of the esters in the atmosphere with respect to their reaction with OH have been determined and are compared with other possible degradation pathways. Possible atmospheric implications of the various degradation pathways studied are discussed.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; ArgentinaFil: Bejan, Iustinian. University of Wuppertal; Alemania. University College Cork; IrlandaFil: Barnes, Ian. University of Wuppertal; AlemaniaFil: Wiesen, Peter. University of 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 Society2009-05info: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/11336/82858Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; OH-initiated degradation of unsaturated esters in the atmosphere: Kinetics in the temperature range of 287-313 K; American Chemical Society; Journal of Physical Chemistry A; 113; 20; 5-2009; 5958-59651089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pubmed/19405497info:eu-repo/semantics/altIdentifier/doi/10.1021/jp901755xinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2024-05-08T14:11:34Zoai:ri.conicet.gov.ar:11336/82858instacron: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:34982024-05-08 14:11:34.407CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
score 15,811543

Similares en LA Referencia