Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications

Autores
Straccia Cepeda, Vianni Giovanna; Rivela Fretes, Cynthia Beatriz; Blanco, Maria Belen; Teruel, Mariano Andres
Año de publicación
2023
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The relative rate coefficient of the gas-phase reaction of methyl dichloroacetate (CHCl2C(O)OCH3) with Cl atoms (kCl) was obtained at 298 K and atmospheric pressure. All the experiments were performed in a 480 L Pyrex glass atmospheric simulation reactor coupled to an “in situ” Fourier transform infrared (FTIR) spectrometer. The rate coefficient obtained from the average of different experiments was: kCl = (3.31 ± 0.88) × 10−13 cm3 per molecule per s. In addition, the product studies were performed in under similar conditions to those of the kinetic experiments in two different photoreactors by in situ FTIR spectroscopy and GC-MS/SPME. Dichloroacetic acid, phosgene, methyl trichloroacetate, and carbon monoxide were the main products identified and quantified. The obtained product yields for the reaction with Cl atoms were as follows: (24 ± 2), (19 ± 3), (16 ± 1), and (44 ± 2)% for Cl2CHCOOH, COCl2, CO, and CCl3C(O)OCH3, respectively. The initial pathway for the degradation of methyl dichloroacetate in the reaction with Cl atoms occurs via H-atom abstraction at the alkyl groups. The atmospheric implications of the reactions were assessed by the estimation of the tropospheric lifetime of τCl = 3 years. In addition, an acidification potential of 0.45 was estimated, suggesting a possible impact of the emission of methyl dichloroacetate on the rainfall acidification. On the other hand, significant global warming potentials of 8.2, 2.2, and 0.6 were calculated for the studied chloroester for the time horizons of 20, 100, and 500 years, respectively. Chlorinated persistent products, such as dichloroacetic acid, could have an impact on the atmosphere and other environmental matrixes as well as on human health and the biota.
Fil: Straccia Cepeda, Vianni Giovanna. 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
Fil: Rivela Fretes, Cynthia 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. Universität Wuppertal. Wuppertal Institut Für Klima; Alemania. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
Materia
KINETICS
PRODUCTS
METHYL
DICHLOROACETATE
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/226818
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/226818
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network_name_str CONICET Digital (CONICET)
spelling Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implicationsStraccia Cepeda, Vianni GiovannaRivela Fretes, Cynthia BeatrizBlanco, Maria BelenTeruel, Mariano AndresKINETICSPRODUCTSMETHYLDICHLOROACETATEhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The relative rate coefficient of the gas-phase reaction of methyl dichloroacetate (CHCl2C(O)OCH3) with Cl atoms (kCl) was obtained at 298 K and atmospheric pressure. All the experiments were performed in a 480 L Pyrex glass atmospheric simulation reactor coupled to an “in situ” Fourier transform infrared (FTIR) spectrometer. The rate coefficient obtained from the average of different experiments was: kCl = (3.31 ± 0.88) × 10−13 cm3 per molecule per s. In addition, the product studies were performed in under similar conditions to those of the kinetic experiments in two different photoreactors by in situ FTIR spectroscopy and GC-MS/SPME. Dichloroacetic acid, phosgene, methyl trichloroacetate, and carbon monoxide were the main products identified and quantified. The obtained product yields for the reaction with Cl atoms were as follows: (24 ± 2), (19 ± 3), (16 ± 1), and (44 ± 2)% for Cl2CHCOOH, COCl2, CO, and CCl3C(O)OCH3, respectively. The initial pathway for the degradation of methyl dichloroacetate in the reaction with Cl atoms occurs via H-atom abstraction at the alkyl groups. The atmospheric implications of the reactions were assessed by the estimation of the tropospheric lifetime of τCl = 3 years. In addition, an acidification potential of 0.45 was estimated, suggesting a possible impact of the emission of methyl dichloroacetate on the rainfall acidification. On the other hand, significant global warming potentials of 8.2, 2.2, and 0.6 were calculated for the studied chloroester for the time horizons of 20, 100, and 500 years, respectively. Chlorinated persistent products, such as dichloroacetic acid, could have an impact on the atmosphere and other environmental matrixes as well as on human health and the biota.Fil: Straccia Cepeda, Vianni Giovanna. 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: Rivela Fretes, Cynthia 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. Universität Wuppertal. Wuppertal Institut Für Klima; Alemania. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaRoyal Society of Chemistry2023-01info: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/11336/226818Straccia Cepeda, Vianni Giovanna; Rivela Fretes, Cynthia Beatriz; Blanco, Maria Belen; Teruel, Mariano Andres; Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 1-2023; 872-8812634-3606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2023/EA/D3EA00004Dinfo:eu-repo/semantics/altIdentifier/doi/10.1039/D3EA00004Dinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:27:44Zoai:ri.conicet.gov.ar:11336/226818instacron: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:34982025-10-15 14:27:44.458CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications
title Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications
spellingShingle Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications
Straccia Cepeda, Vianni Giovanna
KINETICS
PRODUCTS
METHYL
DICHLOROACETATE
title_short Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications
title_full Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications
title_fullStr Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications
title_full_unstemmed Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications
title_sort Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications
dc.creator.none.fl_str_mv Straccia Cepeda, Vianni Giovanna
Rivela Fretes, Cynthia Beatriz
Blanco, Maria Belen
Teruel, Mariano Andres
author Straccia Cepeda, Vianni Giovanna
author_facet Straccia Cepeda, Vianni Giovanna
Rivela Fretes, Cynthia Beatriz
Blanco, Maria Belen
Teruel, Mariano Andres
author_role author
author2 Rivela Fretes, Cynthia Beatriz
Blanco, Maria Belen
Teruel, Mariano Andres
author2_role author
author
author
dc.subject.none.fl_str_mv KINETICS
PRODUCTS
METHYL
DICHLOROACETATE
topic KINETICS
PRODUCTS
METHYL
DICHLOROACETATE
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 relative rate coefficient of the gas-phase reaction of methyl dichloroacetate (CHCl2C(O)OCH3) with Cl atoms (kCl) was obtained at 298 K and atmospheric pressure. All the experiments were performed in a 480 L Pyrex glass atmospheric simulation reactor coupled to an “in situ” Fourier transform infrared (FTIR) spectrometer. The rate coefficient obtained from the average of different experiments was: kCl = (3.31 ± 0.88) × 10−13 cm3 per molecule per s. In addition, the product studies were performed in under similar conditions to those of the kinetic experiments in two different photoreactors by in situ FTIR spectroscopy and GC-MS/SPME. Dichloroacetic acid, phosgene, methyl trichloroacetate, and carbon monoxide were the main products identified and quantified. The obtained product yields for the reaction with Cl atoms were as follows: (24 ± 2), (19 ± 3), (16 ± 1), and (44 ± 2)% for Cl2CHCOOH, COCl2, CO, and CCl3C(O)OCH3, respectively. The initial pathway for the degradation of methyl dichloroacetate in the reaction with Cl atoms occurs via H-atom abstraction at the alkyl groups. The atmospheric implications of the reactions were assessed by the estimation of the tropospheric lifetime of τCl = 3 years. In addition, an acidification potential of 0.45 was estimated, suggesting a possible impact of the emission of methyl dichloroacetate on the rainfall acidification. On the other hand, significant global warming potentials of 8.2, 2.2, and 0.6 were calculated for the studied chloroester for the time horizons of 20, 100, and 500 years, respectively. Chlorinated persistent products, such as dichloroacetic acid, could have an impact on the atmosphere and other environmental matrixes as well as on human health and the biota.
Fil: Straccia Cepeda, Vianni Giovanna. 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
Fil: Rivela Fretes, Cynthia 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. Universität Wuppertal. Wuppertal Institut Für Klima; Alemania. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
description The relative rate coefficient of the gas-phase reaction of methyl dichloroacetate (CHCl2C(O)OCH3) with Cl atoms (kCl) was obtained at 298 K and atmospheric pressure. All the experiments were performed in a 480 L Pyrex glass atmospheric simulation reactor coupled to an “in situ” Fourier transform infrared (FTIR) spectrometer. The rate coefficient obtained from the average of different experiments was: kCl = (3.31 ± 0.88) × 10−13 cm3 per molecule per s. In addition, the product studies were performed in under similar conditions to those of the kinetic experiments in two different photoreactors by in situ FTIR spectroscopy and GC-MS/SPME. Dichloroacetic acid, phosgene, methyl trichloroacetate, and carbon monoxide were the main products identified and quantified. The obtained product yields for the reaction with Cl atoms were as follows: (24 ± 2), (19 ± 3), (16 ± 1), and (44 ± 2)% for Cl2CHCOOH, COCl2, CO, and CCl3C(O)OCH3, respectively. The initial pathway for the degradation of methyl dichloroacetate in the reaction with Cl atoms occurs via H-atom abstraction at the alkyl groups. The atmospheric implications of the reactions were assessed by the estimation of the tropospheric lifetime of τCl = 3 years. In addition, an acidification potential of 0.45 was estimated, suggesting a possible impact of the emission of methyl dichloroacetate on the rainfall acidification. On the other hand, significant global warming potentials of 8.2, 2.2, and 0.6 were calculated for the studied chloroester for the time horizons of 20, 100, and 500 years, respectively. Chlorinated persistent products, such as dichloroacetic acid, could have an impact on the atmosphere and other environmental matrixes as well as on human health and the biota.
publishDate 2023
dc.date.none.fl_str_mv 2023-01
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/11336/226818
Straccia Cepeda, Vianni Giovanna; Rivela Fretes, Cynthia Beatriz; Blanco, Maria Belen; Teruel, Mariano Andres; Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 1-2023; 872-881
2634-3606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/226818
identifier_str_mv Straccia Cepeda, Vianni Giovanna; Rivela Fretes, Cynthia Beatriz; Blanco, Maria Belen; Teruel, Mariano Andres; Kinetics and products study of the reaction of Cl atoms with methyl dichloroacetate: Reactivity, mechanism, and environmental implications; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 1-2023; 872-881
2634-3606
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.rsc.org/en/Content/ArticleLanding/2023/EA/D3EA00004D
info:eu-repo/semantics/altIdentifier/doi/10.1039/D3EA00004D
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 13.22299

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