Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure

Autores
Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH2double bond, long C(CH3)C(O)OCH3 (MMA), CH2 double bond, long CHC(O)OCH3 (MAC) and CH2 double bond, long C(CH3)C(O)O(CH2)3CH3 (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10-10 cm3 molecule-1 s -1) as follows: k(Cl+MMA) = 2.82 ± 0.93, k(Cl+MAC) = 2.04 ± 0.54 and k(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287-313 K were used to derive the following Arrhenius expressions (in units of cm3 molecule-1 s-1) k(Cl+MMA) = (13.9 ± 7.8)  × 10-15 exp (2904 ± 420)/T, k(Cl+MAC) = (0.4 ± 0.2)  × 10-15 exp(3884 ± 879)/T], k(Cl+BMA) = (0.98 ± 0.42)  × 10-15 exp(3779 ± 850)/T. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above. An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log kOH = 1.09 log kCl -  0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also 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; Argentina
Fil: Bejan, Iustinian. Bergische Universitaet Wuppertal; Alemania
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
ACRYLATE-ESTERS
ARRHENIUS PARAMETERS
CHLORINE ATOMS
MARINE ENVIRONMENT
TROPOSPHERE
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:11336/114038
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/114038
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressureBlanco, Maria BelenBejan, IustinianBarnes, IanWiesen, PeterTeruel, Mariano AndresACRYLATE-ESTERSARRHENIUS PARAMETERSCHLORINE ATOMSMARINE ENVIRONMENTTROPOSPHEREhttps://purl.org/becyt/ford/1.5https://purl.org/becyt/ford/1Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH2double bond, long C(CH3)C(O)OCH3 (MMA), CH2 double bond, long CHC(O)OCH3 (MAC) and CH2 double bond, long C(CH3)C(O)O(CH2)3CH3 (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10-10 cm3 molecule-1 s -1) as follows: k(Cl+MMA) = 2.82 ± 0.93, k(Cl+MAC) = 2.04 ± 0.54 and k(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287-313 K were used to derive the following Arrhenius expressions (in units of cm3 molecule-1 s-1) k(Cl+MMA) = (13.9 ± 7.8)  × 10-15 exp (2904 ± 420)/T, k(Cl+MAC) = (0.4 ± 0.2)  × 10-15 exp(3884 ± 879)/T], k(Cl+BMA) = (0.98 ± 0.42)  × 10-15 exp(3779 ± 850)/T. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above. An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log kOH = 1.09 log kCl -  0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also 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. Bergische Universitaet Wuppertal; AlemaniaFil: 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; ArgentinaPergamon-Elsevier Science Ltd2009-08info: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/11336/114038Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure; Pergamon-Elsevier Science Ltd; Atmospheric Environment; 43; 38; 8-2009; 5996-60021352-2310CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.atmosenv.2009.08.032info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S1352231009007456info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:18:15Zoai:ri.conicet.gov.ar:11336/114038instacron: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:34982025-09-29 10:18:15.703CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure
title Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure
spellingShingle Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure
Blanco, Maria Belen
ACRYLATE-ESTERS
ARRHENIUS PARAMETERS
CHLORINE ATOMS
MARINE ENVIRONMENT
TROPOSPHERE
title_short Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure
title_full Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure
title_fullStr Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure
title_full_unstemmed Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure
title_sort Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure
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 ACRYLATE-ESTERS
ARRHENIUS PARAMETERS
CHLORINE ATOMS
MARINE ENVIRONMENT
TROPOSPHERE
topic ACRYLATE-ESTERS
ARRHENIUS PARAMETERS
CHLORINE ATOMS
MARINE ENVIRONMENT
TROPOSPHERE
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH2double bond, long C(CH3)C(O)OCH3 (MMA), CH2 double bond, long CHC(O)OCH3 (MAC) and CH2 double bond, long C(CH3)C(O)O(CH2)3CH3 (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10-10 cm3 molecule-1 s -1) as follows: k(Cl+MMA) = 2.82 ± 0.93, k(Cl+MAC) = 2.04 ± 0.54 and k(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287-313 K were used to derive the following Arrhenius expressions (in units of cm3 molecule-1 s-1) k(Cl+MMA) = (13.9 ± 7.8)  × 10-15 exp (2904 ± 420)/T, k(Cl+MAC) = (0.4 ± 0.2)  × 10-15 exp(3884 ± 879)/T], k(Cl+BMA) = (0.98 ± 0.42)  × 10-15 exp(3779 ± 850)/T. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above. An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log kOH = 1.09 log kCl -  0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also 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; Argentina
Fil: Bejan, Iustinian. Bergische Universitaet Wuppertal; Alemania
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 Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH2double bond, long C(CH3)C(O)OCH3 (MMA), CH2 double bond, long CHC(O)OCH3 (MAC) and CH2 double bond, long C(CH3)C(O)O(CH2)3CH3 (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10-10 cm3 molecule-1 s -1) as follows: k(Cl+MMA) = 2.82 ± 0.93, k(Cl+MAC) = 2.04 ± 0.54 and k(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287-313 K were used to derive the following Arrhenius expressions (in units of cm3 molecule-1 s-1) k(Cl+MMA) = (13.9 ± 7.8)  × 10-15 exp (2904 ± 420)/T, k(Cl+MAC) = (0.4 ± 0.2)  × 10-15 exp(3884 ± 879)/T], k(Cl+BMA) = (0.98 ± 0.42)  × 10-15 exp(3779 ± 850)/T. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above. An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log kOH = 1.09 log kCl -  0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.
publishDate 2009
dc.date.none.fl_str_mv 2009-08
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/11336/114038
Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure; Pergamon-Elsevier Science Ltd; Atmospheric Environment; 43; 38; 8-2009; 5996-6002
1352-2310
CONICET Digital
CONICET
url http://hdl.handle.net/11336/114038
identifier_str_mv Blanco, Maria Belen; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres; Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate, methyl acrylate and butyl methacrylate at atmospheric pressure; Pergamon-Elsevier Science Ltd; Atmospheric Environment; 43; 38; 8-2009; 5996-6002
1352-2310
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.atmosenv.2009.08.032
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S1352231009007456
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 Pergamon-Elsevier Science Ltd
publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
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 13.070432

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