Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)

Autores
Vila, Jesús Alberto; Iriarte, Ana Graciela; Chiappero, Malisa Susana; Malanca, Fabio Ernesto
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The atmospheric degradation of molecules containing the CxF2x+1C(O) moiety, such as perfluoroaldehydes CxF2x+1C(O)H (x = 2–4) formed in the degradation of telomeric alcohols, could lead to the formation of perfluoroacyl peroxynitrates CxF2x+1C(O)OONO2. The thermal decomposition of the CxF2x+1C(O)OONO2 family (x = 2, 3, 4) was investigated by infrared spectroscopy and computational models. Each peroxynitrate synthesis was performed through the photolysis of gas mixtures of the corresponding perfluoroaldehyde, chlorine, nitrogen dioxide, and oxygen. Kinetic analysis for the thermal decomposition of peroxynitrates were performed in the range from 297.0 to 313.7 K at a total pressure of 1000 mbar and the activation energy was experimentally determined. Experimental data were complemented with theoretical data using the Gaussian09 Program Suite. The structures of peroxynitrates were optimized using DFT methods. The activation energies were calculated and investigated taking into account the stereoelectronic effects and using theoretical calculations as well as NBO analysis. The influence of anomeric interaction over the O–N bond was evaluated for all the molecules. Analysis of the results shows that CxF2x+1C(O)OONO2 stability is independent of CxF2x+1 chain length, in contrast to the behavior for perfluoroalkyl peroxynitrates (CxF2x+1OONO2).
Fil: Vila, Jesús Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina
Fil: Iriarte, Ana Graciela. 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: Chiappero, Malisa Susana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina
Fil: Malanca, Fabio Ernesto. 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
PERFLUOROALKYL PEROXYNITRATES,
THERMAL DECOMPOSITION
STABILITY
STEREOELECTRONIC EFFECTS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/141991
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/141991
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)Vila, Jesús AlbertoIriarte, Ana GracielaChiappero, Malisa SusanaMalanca, Fabio ErnestoPERFLUOROALKYL PEROXYNITRATES,THERMAL DECOMPOSITIONSTABILITYSTEREOELECTRONIC EFFECTShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The atmospheric degradation of molecules containing the CxF2x+1C(O) moiety, such as perfluoroaldehydes CxF2x+1C(O)H (x = 2–4) formed in the degradation of telomeric alcohols, could lead to the formation of perfluoroacyl peroxynitrates CxF2x+1C(O)OONO2. The thermal decomposition of the CxF2x+1C(O)OONO2 family (x = 2, 3, 4) was investigated by infrared spectroscopy and computational models. Each peroxynitrate synthesis was performed through the photolysis of gas mixtures of the corresponding perfluoroaldehyde, chlorine, nitrogen dioxide, and oxygen. Kinetic analysis for the thermal decomposition of peroxynitrates were performed in the range from 297.0 to 313.7 K at a total pressure of 1000 mbar and the activation energy was experimentally determined. Experimental data were complemented with theoretical data using the Gaussian09 Program Suite. The structures of peroxynitrates were optimized using DFT methods. The activation energies were calculated and investigated taking into account the stereoelectronic effects and using theoretical calculations as well as NBO analysis. The influence of anomeric interaction over the O–N bond was evaluated for all the molecules. Analysis of the results shows that CxF2x+1C(O)OONO2 stability is independent of CxF2x+1 chain length, in contrast to the behavior for perfluoroalkyl peroxynitrates (CxF2x+1OONO2).Fil: Vila, Jesús Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: Iriarte, Ana Graciela. 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: Chiappero, Malisa Susana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; ArgentinaFil: Malanca, Fabio Ernesto. 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 Society2020-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/141991Vila, Jesús Alberto; Iriarte, Ana Graciela; Chiappero, Malisa Susana; Malanca, Fabio Ernesto; Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4); American Chemical Society; Journal of Physical Chemistry A; 124; 31; 8-2020; 6363-63691089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/reference/url/http://hdl.handle.net/11336/31480info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.0c04833info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.0c04833info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:30:52Zoai:ri.conicet.gov.ar:11336/141991instacron: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:34982025-09-29 10:30:52.292CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)
title Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)
spellingShingle Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)
Vila, Jesús Alberto
PERFLUOROALKYL PEROXYNITRATES,
THERMAL DECOMPOSITION
STABILITY
STEREOELECTRONIC EFFECTS
title_short Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)
title_full Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)
title_fullStr Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)
title_full_unstemmed Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)
title_sort Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4)
dc.creator.none.fl_str_mv Vila, Jesús Alberto
Iriarte, Ana Graciela
Chiappero, Malisa Susana
Malanca, Fabio Ernesto
author Vila, Jesús Alberto
author_facet Vila, Jesús Alberto
Iriarte, Ana Graciela
Chiappero, Malisa Susana
Malanca, Fabio Ernesto
author_role author
author2 Iriarte, Ana Graciela
Chiappero, Malisa Susana
Malanca, Fabio Ernesto
author2_role author
author
author
dc.subject.none.fl_str_mv PERFLUOROALKYL PEROXYNITRATES,
THERMAL DECOMPOSITION
STABILITY
STEREOELECTRONIC EFFECTS
topic PERFLUOROALKYL PEROXYNITRATES,
THERMAL DECOMPOSITION
STABILITY
STEREOELECTRONIC EFFECTS
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 atmospheric degradation of molecules containing the CxF2x+1C(O) moiety, such as perfluoroaldehydes CxF2x+1C(O)H (x = 2–4) formed in the degradation of telomeric alcohols, could lead to the formation of perfluoroacyl peroxynitrates CxF2x+1C(O)OONO2. The thermal decomposition of the CxF2x+1C(O)OONO2 family (x = 2, 3, 4) was investigated by infrared spectroscopy and computational models. Each peroxynitrate synthesis was performed through the photolysis of gas mixtures of the corresponding perfluoroaldehyde, chlorine, nitrogen dioxide, and oxygen. Kinetic analysis for the thermal decomposition of peroxynitrates were performed in the range from 297.0 to 313.7 K at a total pressure of 1000 mbar and the activation energy was experimentally determined. Experimental data were complemented with theoretical data using the Gaussian09 Program Suite. The structures of peroxynitrates were optimized using DFT methods. The activation energies were calculated and investigated taking into account the stereoelectronic effects and using theoretical calculations as well as NBO analysis. The influence of anomeric interaction over the O–N bond was evaluated for all the molecules. Analysis of the results shows that CxF2x+1C(O)OONO2 stability is independent of CxF2x+1 chain length, in contrast to the behavior for perfluoroalkyl peroxynitrates (CxF2x+1OONO2).
Fil: Vila, Jesús Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina
Fil: Iriarte, Ana Graciela. 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: Chiappero, Malisa Susana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina
Fil: Malanca, Fabio Ernesto. 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 atmospheric degradation of molecules containing the CxF2x+1C(O) moiety, such as perfluoroaldehydes CxF2x+1C(O)H (x = 2–4) formed in the degradation of telomeric alcohols, could lead to the formation of perfluoroacyl peroxynitrates CxF2x+1C(O)OONO2. The thermal decomposition of the CxF2x+1C(O)OONO2 family (x = 2, 3, 4) was investigated by infrared spectroscopy and computational models. Each peroxynitrate synthesis was performed through the photolysis of gas mixtures of the corresponding perfluoroaldehyde, chlorine, nitrogen dioxide, and oxygen. Kinetic analysis for the thermal decomposition of peroxynitrates were performed in the range from 297.0 to 313.7 K at a total pressure of 1000 mbar and the activation energy was experimentally determined. Experimental data were complemented with theoretical data using the Gaussian09 Program Suite. The structures of peroxynitrates were optimized using DFT methods. The activation energies were calculated and investigated taking into account the stereoelectronic effects and using theoretical calculations as well as NBO analysis. The influence of anomeric interaction over the O–N bond was evaluated for all the molecules. Analysis of the results shows that CxF2x+1C(O)OONO2 stability is independent of CxF2x+1 chain length, in contrast to the behavior for perfluoroalkyl peroxynitrates (CxF2x+1OONO2).
publishDate 2020
dc.date.none.fl_str_mv 2020-08
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/11336/141991
Vila, Jesús Alberto; Iriarte, Ana Graciela; Chiappero, Malisa Susana; Malanca, Fabio Ernesto; Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4); American Chemical Society; Journal of Physical Chemistry A; 124; 31; 8-2020; 6363-6369
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/141991
identifier_str_mv Vila, Jesús Alberto; Iriarte, Ana Graciela; Chiappero, Malisa Susana; Malanca, Fabio Ernesto; Thermal Decomposition of CxF2x+1C(O)OONO2 (x = 2, 3, 4); American Chemical Society; Journal of Physical Chemistry A; 124; 31; 8-2020; 6363-6369
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/reference/url/http://hdl.handle.net/11336/31480
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.0c04833
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.0c04833
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv 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 13.070432

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