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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/114038
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oai:ri.conicet.gov.ar:11336/114038 |
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CONICET Digital (CONICET) |
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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 Técnicas2025-09-03T10:02:27Zoai: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:34982025-09-03 10:02:27.306CONICET 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 |
_version_ |
1842269756097298432 |
score |
13.13397 |