Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F

Autores
Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The thermal decomposition of trifluoroacetic acid and carbonyl fluoride (CF2O) has been extensively studied because of their importance in the oxidation of hydrochlorofluorocarbons in the atmosphere. We hitherto present the study of the thermal reaction between these two molecules. The reaction mechanism was studied using Fourier transform infrared spectroscopy in the temperature range of 513-573 K. The reaction proceeds homogeneously in the gas phase through the formation of a reaction intermediate, here characterized as CF3C(O)OC(O)F (detected for the first time in this work), the major final products being CF3C(O)F, HF, and CO2. We demonstrate that the reaction is first-order with respect to each reagent, second-order global and the mechanism consists of two steps, the first being the rate-determining one. The Ea = 110.1 ± 6.1 kJ mol-1 and A = (1.2 ± 0.2) × 10-12 cm3 molec-1 s-1 values were obtained from the experimental data. The low activation energy is explained by the hydrogen-bond interactions between the -OH group of the acid and the F atom of the CF2O. First-principles calculations at the G4MP2 level of theory were carried out to understand the dynamics of the decomposition. Thermodynamic activation values found for this reaction are as follows: Î"H⧧ = 105.6 ± 6.4 kJ mol-1, δS- = -88.6 ± 9.7 J mol-1 K-1, and δG = 153.7 ± 13.5 kJ mol-1. The comparison between theory and experimental results showed excellent similarities, thus strengthening the proposed mechanism.
Fil: Berasategui, Matias. 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: Argüello, Gustavo Alejandro. 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: Burgos Paci, Maximiliano Alberto. 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
FTIR
Cinética
Halogenados
Medioambiente
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:11336/125648
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/125648
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)FBerasategui, MatiasArgüello, Gustavo AlejandroBurgos Paci, Maximiliano AlbertoFTIRCinéticaHalogenadosMedioambientehttps://purl.org/becyt/ford/1.5https://purl.org/becyt/ford/1The thermal decomposition of trifluoroacetic acid and carbonyl fluoride (CF2O) has been extensively studied because of their importance in the oxidation of hydrochlorofluorocarbons in the atmosphere. We hitherto present the study of the thermal reaction between these two molecules. The reaction mechanism was studied using Fourier transform infrared spectroscopy in the temperature range of 513-573 K. The reaction proceeds homogeneously in the gas phase through the formation of a reaction intermediate, here characterized as CF3C(O)OC(O)F (detected for the first time in this work), the major final products being CF3C(O)F, HF, and CO2. We demonstrate that the reaction is first-order with respect to each reagent, second-order global and the mechanism consists of two steps, the first being the rate-determining one. The Ea = 110.1 ± 6.1 kJ mol-1 and A = (1.2 ± 0.2) × 10-12 cm3 molec-1 s-1 values were obtained from the experimental data. The low activation energy is explained by the hydrogen-bond interactions between the -OH group of the acid and the F atom of the CF2O. First-principles calculations at the G4MP2 level of theory were carried out to understand the dynamics of the decomposition. Thermodynamic activation values found for this reaction are as follows: Î"H⧧ = 105.6 ± 6.4 kJ mol-1, δS- = -88.6 ± 9.7 J mol-1 K-1, and δG = 153.7 ± 13.5 kJ mol-1. The comparison between theory and experimental results showed excellent similarities, thus strengthening the proposed mechanism.Fil: Berasategui, Matias. 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: Argüello, Gustavo Alejandro. 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: Burgos Paci, Maximiliano Alberto. 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 Society2019-06info: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/11336/125648Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto; Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F; American Chemical Society; Journal of Physical Chemistry A; 123; 22; 6-2019; 4671-46781089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.9b00899info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.9b00899info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:37:48Zoai:ri.conicet.gov.ar:11336/125648instacron: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 14:37:49.25CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
title Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
spellingShingle Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
Berasategui, Matias
FTIR
Cinética
Halogenados
Medioambiente
title_short Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
title_full Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
title_fullStr Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
title_full_unstemmed Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
title_sort Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F
dc.creator.none.fl_str_mv Berasategui, Matias
Argüello, Gustavo Alejandro
Burgos Paci, Maximiliano Alberto
author Berasategui, Matias
author_facet Berasategui, Matias
Argüello, Gustavo Alejandro
Burgos Paci, Maximiliano Alberto
author_role author
author2 Argüello, Gustavo Alejandro
Burgos Paci, Maximiliano Alberto
author2_role author
author
dc.subject.none.fl_str_mv FTIR
Cinética
Halogenados
Medioambiente
topic FTIR
Cinética
Halogenados
Medioambiente
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The thermal decomposition of trifluoroacetic acid and carbonyl fluoride (CF2O) has been extensively studied because of their importance in the oxidation of hydrochlorofluorocarbons in the atmosphere. We hitherto present the study of the thermal reaction between these two molecules. The reaction mechanism was studied using Fourier transform infrared spectroscopy in the temperature range of 513-573 K. The reaction proceeds homogeneously in the gas phase through the formation of a reaction intermediate, here characterized as CF3C(O)OC(O)F (detected for the first time in this work), the major final products being CF3C(O)F, HF, and CO2. We demonstrate that the reaction is first-order with respect to each reagent, second-order global and the mechanism consists of two steps, the first being the rate-determining one. The Ea = 110.1 ± 6.1 kJ mol-1 and A = (1.2 ± 0.2) × 10-12 cm3 molec-1 s-1 values were obtained from the experimental data. The low activation energy is explained by the hydrogen-bond interactions between the -OH group of the acid and the F atom of the CF2O. First-principles calculations at the G4MP2 level of theory were carried out to understand the dynamics of the decomposition. Thermodynamic activation values found for this reaction are as follows: Î"H⧧ = 105.6 ± 6.4 kJ mol-1, δS- = -88.6 ± 9.7 J mol-1 K-1, and δG = 153.7 ± 13.5 kJ mol-1. The comparison between theory and experimental results showed excellent similarities, thus strengthening the proposed mechanism.
Fil: Berasategui, Matias. 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: Argüello, Gustavo Alejandro. 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: Burgos Paci, Maximiliano Alberto. 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 The thermal decomposition of trifluoroacetic acid and carbonyl fluoride (CF2O) has been extensively studied because of their importance in the oxidation of hydrochlorofluorocarbons in the atmosphere. We hitherto present the study of the thermal reaction between these two molecules. The reaction mechanism was studied using Fourier transform infrared spectroscopy in the temperature range of 513-573 K. The reaction proceeds homogeneously in the gas phase through the formation of a reaction intermediate, here characterized as CF3C(O)OC(O)F (detected for the first time in this work), the major final products being CF3C(O)F, HF, and CO2. We demonstrate that the reaction is first-order with respect to each reagent, second-order global and the mechanism consists of two steps, the first being the rate-determining one. The Ea = 110.1 ± 6.1 kJ mol-1 and A = (1.2 ± 0.2) × 10-12 cm3 molec-1 s-1 values were obtained from the experimental data. The low activation energy is explained by the hydrogen-bond interactions between the -OH group of the acid and the F atom of the CF2O. First-principles calculations at the G4MP2 level of theory were carried out to understand the dynamics of the decomposition. Thermodynamic activation values found for this reaction are as follows: Î"H⧧ = 105.6 ± 6.4 kJ mol-1, δS- = -88.6 ± 9.7 J mol-1 K-1, and δG = 153.7 ± 13.5 kJ mol-1. The comparison between theory and experimental results showed excellent similarities, thus strengthening the proposed mechanism.
publishDate 2019
dc.date.none.fl_str_mv 2019-06
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/11336/125648
Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto; Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F; American Chemical Society; Journal of Physical Chemistry A; 123; 22; 6-2019; 4671-4678
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/125648
identifier_str_mv Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto; Gas-Phase reaction between CF2O and CF3C(O)OH: Characterization of CF3C(O)OC(O)F; American Chemical Society; Journal of Physical Chemistry A; 123; 22; 6-2019; 4671-4678
1089-5639
1520-5215
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.9b00899
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.9b00899
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 13.22299

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