Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids

Autores
Blanco, Maria Belen; Bejan, I.; Barnes, I.; Wiesen, P.; Teruel, Mariano Andres
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A 1080 L environmental chamber with in situ FTIR spectroscopy detection was used to study the product distribution and the mechanism of the Cl-initiated photooxidation of a series of fluoroacetates. The gas-phase reactions of Cl atoms with ethyl trifluoroacetate (CF3C(O)OCH2CH3), methyl trifluoroacetate (CF3C(O)OCH3), and methyl difluoroacetate (CF2HC(O)OCH3) were investigated at 296(2 K and atmospheric pressure (¡­760 Torr) of synthetic air. The fate of the fluoroalkoxy radicals formed in the reaction with Cl atoms mainly occurs through (i) an H-atom abstraction by reaction with O2, to produce the corresponding fluoroanhydride and (ii) anR-ester rearrangement via a five-membered ring intermediate to give the corresponding fluoroacetic acid. The yields of fluoroacids (CF2XC(O)OH, with X ) H, F) obtained were as follows: 78 ( 5, 23 ( 2, and 30(5%for CF3C(O)OCH2CH3,CF3C(O)OCH3, and CF2HC(O)OCH3,, respectively. Yields ofe20,e80, ande55% have been estimated for the anhydride formation from CF3C(O)OCH2CH3,CF3C(O)OCH3, and CF2HC(O)OCH3, respectively. Formation of CF2O, with yield of 13 ( 2% has been observed for the reaction of Cl with CF2HC(O)OCH3. The measured yields are rationalized in terms of mechanisms consisting of competitive reaction channels for the radicals formed in the oxidation, that is, reaction with O2, R-ester rearrangement and a decomposition pathway. The stability of the five-membered transition state of the R-ester rearrangement is correlated with the acid yields observed for the different fluoroacetates. Atmospheric implications, especially with regard to the fluorocarboxylic acid formation, 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; Argentina
Fil: Bejan, I.. University of Iasi; Rumania
Fil: Barnes, I.. Bergische Universitaet Wuppertal; Alemania
Fil: Wiesen, P.. 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
FLUOROESTERS
ATMOSPHERIC CHEMICAL MECHANISMS
GAS PHASE
PRODUCT YIELDS
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:11336/277618
Acceder
id CONICETDig_91e7c4ab151114534acecd9550eaf1da
oai_identifier_str oai:ri.conicet.gov.ar:11336/277618
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic AcidsBlanco, Maria BelenBejan, I.Barnes, I.Wiesen, P.Teruel, Mariano AndresFLUOROESTERSATMOSPHERIC CHEMICAL MECHANISMSGAS PHASEPRODUCT YIELDShttps://purl.org/becyt/ford/1.5https://purl.org/becyt/ford/1A 1080 L environmental chamber with in situ FTIR spectroscopy detection was used to study the product distribution and the mechanism of the Cl-initiated photooxidation of a series of fluoroacetates. The gas-phase reactions of Cl atoms with ethyl trifluoroacetate (CF3C(O)OCH2CH3), methyl trifluoroacetate (CF3C(O)OCH3), and methyl difluoroacetate (CF2HC(O)OCH3) were investigated at 296(2 K and atmospheric pressure (¡­760 Torr) of synthetic air. The fate of the fluoroalkoxy radicals formed in the reaction with Cl atoms mainly occurs through (i) an H-atom abstraction by reaction with O2, to produce the corresponding fluoroanhydride and (ii) anR-ester rearrangement via a five-membered ring intermediate to give the corresponding fluoroacetic acid. The yields of fluoroacids (CF2XC(O)OH, with X ) H, F) obtained were as follows: 78 ( 5, 23 ( 2, and 30(5%for CF3C(O)OCH2CH3,CF3C(O)OCH3, and CF2HC(O)OCH3,, respectively. Yields ofe20,e80, ande55% have been estimated for the anhydride formation from CF3C(O)OCH2CH3,CF3C(O)OCH3, and CF2HC(O)OCH3, respectively. Formation of CF2O, with yield of 13 ( 2% has been observed for the reaction of Cl with CF2HC(O)OCH3. The measured yields are rationalized in terms of mechanisms consisting of competitive reaction channels for the radicals formed in the oxidation, that is, reaction with O2, R-ester rearrangement and a decomposition pathway. The stability of the five-membered transition state of the R-ester rearrangement is correlated with the acid yields observed for the different fluoroacetates. Atmospheric implications, especially with regard to the fluorocarboxylic acid formation, 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, I.. University of Iasi; RumaniaFil: Barnes, I.. Bergische Universitaet Wuppertal; AlemaniaFil: Wiesen, P.. 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; ArgentinaAmerican Chemical Society2010-03info: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/11336/277618Blanco, Maria Belen; Bejan, I.; Barnes, I.; Wiesen, P.; Teruel, Mariano Andres; Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids; American Chemical Society; Environmental Science & Technology; 44; 7; 3-2010; 2354-23590013-936XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/es903357jinfo:eu-repo/semantics/altIdentifier/doi/10.1021/es903357jinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-01-08T12:54:35Zoai:ri.conicet.gov.ar:11336/277618instacron: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:34982026-01-08 12:54:35.696CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids
title Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids
spellingShingle Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids
Blanco, Maria Belen
FLUOROESTERS
ATMOSPHERIC CHEMICAL MECHANISMS
GAS PHASE
PRODUCT YIELDS
title_short Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids
title_full Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids
title_fullStr Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids
title_full_unstemmed Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids
title_sort Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids
dc.creator.none.fl_str_mv Blanco, Maria Belen
Bejan, I.
Barnes, I.
Wiesen, P.
Teruel, Mariano Andres
author Blanco, Maria Belen
author_facet Blanco, Maria Belen
Bejan, I.
Barnes, I.
Wiesen, P.
Teruel, Mariano Andres
author_role author
author2 Bejan, I.
Barnes, I.
Wiesen, P.
Teruel, Mariano Andres
author2_role author
author
author
author
dc.subject.none.fl_str_mv FLUOROESTERS
ATMOSPHERIC CHEMICAL MECHANISMS
GAS PHASE
PRODUCT YIELDS
topic FLUOROESTERS
ATMOSPHERIC CHEMICAL MECHANISMS
GAS PHASE
PRODUCT YIELDS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A 1080 L environmental chamber with in situ FTIR spectroscopy detection was used to study the product distribution and the mechanism of the Cl-initiated photooxidation of a series of fluoroacetates. The gas-phase reactions of Cl atoms with ethyl trifluoroacetate (CF3C(O)OCH2CH3), methyl trifluoroacetate (CF3C(O)OCH3), and methyl difluoroacetate (CF2HC(O)OCH3) were investigated at 296(2 K and atmospheric pressure (¡­760 Torr) of synthetic air. The fate of the fluoroalkoxy radicals formed in the reaction with Cl atoms mainly occurs through (i) an H-atom abstraction by reaction with O2, to produce the corresponding fluoroanhydride and (ii) anR-ester rearrangement via a five-membered ring intermediate to give the corresponding fluoroacetic acid. The yields of fluoroacids (CF2XC(O)OH, with X ) H, F) obtained were as follows: 78 ( 5, 23 ( 2, and 30(5%for CF3C(O)OCH2CH3,CF3C(O)OCH3, and CF2HC(O)OCH3,, respectively. Yields ofe20,e80, ande55% have been estimated for the anhydride formation from CF3C(O)OCH2CH3,CF3C(O)OCH3, and CF2HC(O)OCH3, respectively. Formation of CF2O, with yield of 13 ( 2% has been observed for the reaction of Cl with CF2HC(O)OCH3. The measured yields are rationalized in terms of mechanisms consisting of competitive reaction channels for the radicals formed in the oxidation, that is, reaction with O2, R-ester rearrangement and a decomposition pathway. The stability of the five-membered transition state of the R-ester rearrangement is correlated with the acid yields observed for the different fluoroacetates. Atmospheric implications, especially with regard to the fluorocarboxylic acid formation, 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; Argentina
Fil: Bejan, I.. University of Iasi; Rumania
Fil: Barnes, I.. Bergische Universitaet Wuppertal; Alemania
Fil: Wiesen, P.. 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 A 1080 L environmental chamber with in situ FTIR spectroscopy detection was used to study the product distribution and the mechanism of the Cl-initiated photooxidation of a series of fluoroacetates. The gas-phase reactions of Cl atoms with ethyl trifluoroacetate (CF3C(O)OCH2CH3), methyl trifluoroacetate (CF3C(O)OCH3), and methyl difluoroacetate (CF2HC(O)OCH3) were investigated at 296(2 K and atmospheric pressure (¡­760 Torr) of synthetic air. The fate of the fluoroalkoxy radicals formed in the reaction with Cl atoms mainly occurs through (i) an H-atom abstraction by reaction with O2, to produce the corresponding fluoroanhydride and (ii) anR-ester rearrangement via a five-membered ring intermediate to give the corresponding fluoroacetic acid. The yields of fluoroacids (CF2XC(O)OH, with X ) H, F) obtained were as follows: 78 ( 5, 23 ( 2, and 30(5%for CF3C(O)OCH2CH3,CF3C(O)OCH3, and CF2HC(O)OCH3,, respectively. Yields ofe20,e80, ande55% have been estimated for the anhydride formation from CF3C(O)OCH2CH3,CF3C(O)OCH3, and CF2HC(O)OCH3, respectively. Formation of CF2O, with yield of 13 ( 2% has been observed for the reaction of Cl with CF2HC(O)OCH3. The measured yields are rationalized in terms of mechanisms consisting of competitive reaction channels for the radicals formed in the oxidation, that is, reaction with O2, R-ester rearrangement and a decomposition pathway. The stability of the five-membered transition state of the R-ester rearrangement is correlated with the acid yields observed for the different fluoroacetates. Atmospheric implications, especially with regard to the fluorocarboxylic acid formation, are discussed.
publishDate 2010
dc.date.none.fl_str_mv 2010-03
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/11336/277618
Blanco, Maria Belen; Bejan, I.; Barnes, I.; Wiesen, P.; Teruel, Mariano Andres; Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids; American Chemical Society; Environmental Science & Technology; 44; 7; 3-2010; 2354-2359
0013-936X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/277618
identifier_str_mv Blanco, Maria Belen; Bejan, I.; Barnes, I.; Wiesen, P.; Teruel, Mariano Andres; Atmospheric Photooxidation of Fluoroacetates as a Source of Fluorocarboxylic Acids; American Chemical Society; Environmental Science & Technology; 44; 7; 3-2010; 2354-2359
0013-936X
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.acs.org/doi/10.1021/es903357j
info:eu-repo/semantics/altIdentifier/doi/10.1021/es903357j
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
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 13.25844

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