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

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

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 mech...

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Detalles Bibliográficos
Autores:	Berasategui, Matias, Argüello, Gustavo Alejandro, Burgos Paci, Maximiliano Alberto
Tipo de recurso:	artículo
Estado:	Versión publicada
Fecha de publicación:	2019
País:	Argentina
Institución:	Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:	CONICET Digital (CONICET)
Idioma:	inglés
OAI Identifier:	oai:ri.conicet.gov.ar:11336/125648
Acceso en línea:	http://hdl.handle.net/11336/125648
Access Level:	acceso abierto
Palabra clave:	FTIR Cinética Halogenados Medioambiente https://purl.org/becyt/ford/1.5 https://purl.org/becyt/ford/1

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repository_id_str
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"Hâ§§ = 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 Técnicas2024-05-08T13:41:58Zoai: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:34982024-05-08 13:41:59.022CONICET 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 https://purl.org/becyt/ford/1.5 https://purl.org/becyt/ford/1
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 https://purl.org/becyt/ford/1.5 https://purl.org/becyt/ford/1
topic	FTIR Cinética Halogenados Medioambiente https://purl.org/becyt/ford/1.5 https://purl.org/becyt/ford/1
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"Hâ§§ = 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
instname_str	Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str	CONICET Digital (CONICET)
collection	CONICET Digital (CONICET)
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	15,811543

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

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