CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air

Autores
Oksdath Mansilla, Gabriela; Peñeñory, Alicia Beatriz; Albu, Mihaela; Barnes, Ian; Wiesen, Peter; Teruel, Mariano Andres
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Relative rate coefficients have been determined for the gas-phase reaction of hydroxyl (OH) radicals with ethyl methyl sulfide (EMS) using isobutene as a reference compound. The experiments were performed in a 1080 L quartz glass photoreactor in the temperature range of 286-313 K at a total pressure of 760W10 Torr synthetic air using in situ FTIR absorption spectroscopy to monitor the concentration-time behaviors of reactants and products. OH radicals were produced by the 254nm photolysis of hydrogen peroxide (H2O 2). The kinetic data obtained were used to derive the following Arrhenius expression valid in the temperature range of 286-313 K (in units of cm3 molecule-1 s-1): k = (3.0±0:6) × 10-15 exp [(2457 ± 65)/=T]The rate coefficient displays a negative temperature dependence and low pre-exponential factor which supports the existence of an addition mechanism for the reaction involving reversible OH-adduct formation. The results are compared with previous data of other sulfides from the literature and are rationalized in terms of structure-reactivity relationships. Additionally, product identification of the title reaction was performed for the first time by the FTIR technique under atmospheric conditions. Sulfur dioxide, formaldehyde, and formic acid were observed as degradation products in agreement with the two possible reaction channels (addition/abstraction). Copyright © 2010 John Wiley and Sons, Ltd.
Fil: Oksdath Mansilla, Gabriela. 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: Peñeñory, Alicia Beatriz. 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: Albu, Mihaela. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; Alemania
Fil: Barnes, Ian. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; Alemania
Fil: Wiesen, Peter. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; Alemania; 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
ARRHENIUS PARAMETERS
ETHYL METHYL SULFIDE
GAS PHASE
HYDROXYL RADICALS
TROPOSPHERIC CHEMISTRY
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:11336/186672
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/186672
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of airOksdath Mansilla, GabrielaPeñeñory, Alicia BeatrizAlbu, MihaelaBarnes, IanWiesen, PeterTeruel, Mariano AndresARRHENIUS PARAMETERSETHYL METHYL SULFIDEGAS PHASEHYDROXYL RADICALSTROPOSPHERIC CHEMISTRYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Relative rate coefficients have been determined for the gas-phase reaction of hydroxyl (OH) radicals with ethyl methyl sulfide (EMS) using isobutene as a reference compound. The experiments were performed in a 1080 L quartz glass photoreactor in the temperature range of 286-313 K at a total pressure of 760W10 Torr synthetic air using in situ FTIR absorption spectroscopy to monitor the concentration-time behaviors of reactants and products. OH radicals were produced by the 254nm photolysis of hydrogen peroxide (H2O 2). The kinetic data obtained were used to derive the following Arrhenius expression valid in the temperature range of 286-313 K (in units of cm3 molecule-1 s-1): k = (3.0±0:6) × 10-15 exp [(2457 ± 65)/=T]The rate coefficient displays a negative temperature dependence and low pre-exponential factor which supports the existence of an addition mechanism for the reaction involving reversible OH-adduct formation. The results are compared with previous data of other sulfides from the literature and are rationalized in terms of structure-reactivity relationships. Additionally, product identification of the title reaction was performed for the first time by the FTIR technique under atmospheric conditions. Sulfur dioxide, formaldehyde, and formic acid were observed as degradation products in agreement with the two possible reaction channels (addition/abstraction). Copyright © 2010 John Wiley and Sons, Ltd.Fil: Oksdath Mansilla, Gabriela. 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: Peñeñory, Alicia Beatriz. 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: Albu, Mihaela. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; AlemaniaFil: Barnes, Ian. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; AlemaniaFil: Wiesen, Peter. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; Alemania; 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; ArgentinaJohn Wiley & Sons Ltd2010-06-18info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/186672Oksdath Mansilla, Gabriela; Peñeñory, Alicia Beatriz; Albu, Mihaela; Barnes, Ian; Wiesen, Peter; et al.; CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 10; 18-6-2010; 925-9300894-32301099-1395CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/poc.1714info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/poc.1714info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:48:36Zoai:ri.conicet.gov.ar:11336/186672instacron: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 09:48:36.682CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air
title CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air
spellingShingle CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air
Oksdath Mansilla, Gabriela
ARRHENIUS PARAMETERS
ETHYL METHYL SULFIDE
GAS PHASE
HYDROXYL RADICALS
TROPOSPHERIC CHEMISTRY
title_short CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air
title_full CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air
title_fullStr CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air
title_full_unstemmed CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air
title_sort CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air
dc.creator.none.fl_str_mv Oksdath Mansilla, Gabriela
Peñeñory, Alicia Beatriz
Albu, Mihaela
Barnes, Ian
Wiesen, Peter
Teruel, Mariano Andres
author Oksdath Mansilla, Gabriela
author_facet Oksdath Mansilla, Gabriela
Peñeñory, Alicia Beatriz
Albu, Mihaela
Barnes, Ian
Wiesen, Peter
Teruel, Mariano Andres
author_role author
author2 Peñeñory, Alicia Beatriz
Albu, Mihaela
Barnes, Ian
Wiesen, Peter
Teruel, Mariano Andres
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv ARRHENIUS PARAMETERS
ETHYL METHYL SULFIDE
GAS PHASE
HYDROXYL RADICALS
TROPOSPHERIC CHEMISTRY
topic ARRHENIUS PARAMETERS
ETHYL METHYL SULFIDE
GAS PHASE
HYDROXYL RADICALS
TROPOSPHERIC CHEMISTRY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Relative rate coefficients have been determined for the gas-phase reaction of hydroxyl (OH) radicals with ethyl methyl sulfide (EMS) using isobutene as a reference compound. The experiments were performed in a 1080 L quartz glass photoreactor in the temperature range of 286-313 K at a total pressure of 760W10 Torr synthetic air using in situ FTIR absorption spectroscopy to monitor the concentration-time behaviors of reactants and products. OH radicals were produced by the 254nm photolysis of hydrogen peroxide (H2O 2). The kinetic data obtained were used to derive the following Arrhenius expression valid in the temperature range of 286-313 K (in units of cm3 molecule-1 s-1): k = (3.0±0:6) × 10-15 exp [(2457 ± 65)/=T]The rate coefficient displays a negative temperature dependence and low pre-exponential factor which supports the existence of an addition mechanism for the reaction involving reversible OH-adduct formation. The results are compared with previous data of other sulfides from the literature and are rationalized in terms of structure-reactivity relationships. Additionally, product identification of the title reaction was performed for the first time by the FTIR technique under atmospheric conditions. Sulfur dioxide, formaldehyde, and formic acid were observed as degradation products in agreement with the two possible reaction channels (addition/abstraction). Copyright © 2010 John Wiley and Sons, Ltd.
Fil: Oksdath Mansilla, Gabriela. 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: Peñeñory, Alicia Beatriz. 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: Albu, Mihaela. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; Alemania
Fil: Barnes, Ian. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; Alemania
Fil: Wiesen, Peter. Bergische Universitaet Wuppertal. Physikalische Chemie/FBC; Alemania; 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 Relative rate coefficients have been determined for the gas-phase reaction of hydroxyl (OH) radicals with ethyl methyl sulfide (EMS) using isobutene as a reference compound. The experiments were performed in a 1080 L quartz glass photoreactor in the temperature range of 286-313 K at a total pressure of 760W10 Torr synthetic air using in situ FTIR absorption spectroscopy to monitor the concentration-time behaviors of reactants and products. OH radicals were produced by the 254nm photolysis of hydrogen peroxide (H2O 2). The kinetic data obtained were used to derive the following Arrhenius expression valid in the temperature range of 286-313 K (in units of cm3 molecule-1 s-1): k = (3.0±0:6) × 10-15 exp [(2457 ± 65)/=T]The rate coefficient displays a negative temperature dependence and low pre-exponential factor which supports the existence of an addition mechanism for the reaction involving reversible OH-adduct formation. The results are compared with previous data of other sulfides from the literature and are rationalized in terms of structure-reactivity relationships. Additionally, product identification of the title reaction was performed for the first time by the FTIR technique under atmospheric conditions. Sulfur dioxide, formaldehyde, and formic acid were observed as degradation products in agreement with the two possible reaction channels (addition/abstraction). Copyright © 2010 John Wiley and Sons, Ltd.
publishDate 2010
dc.date.none.fl_str_mv 2010-06-18
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/11336/186672
Oksdath Mansilla, Gabriela; Peñeñory, Alicia Beatriz; Albu, Mihaela; Barnes, Ian; Wiesen, Peter; et al.; CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 10; 18-6-2010; 925-930
0894-3230
1099-1395
CONICET Digital
CONICET
url http://hdl.handle.net/11336/186672
identifier_str_mv Oksdath Mansilla, Gabriela; Peñeñory, Alicia Beatriz; Albu, Mihaela; Barnes, Ian; Wiesen, Peter; et al.; CH3CH2SCH3+OH radicals: Temperature-dependent rate coefficient and product identification under atmospheric pressure of air; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 23; 10; 18-6-2010; 925-930
0894-3230
1099-1395
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.1714
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/poc.1714
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
application/pdf
dc.publisher.none.fl_str_mv John Wiley & Sons Ltd
publisher.none.fl_str_mv John Wiley & Sons 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_ 1842268931724673024
score 13.13397

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