Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane

Autores
Cobos, Carlos Jorge; Sölter, L.; Tellbach, E.; Troe, J.
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Sölter, L.. Universitat of Gottingen; Alemania
Fil: Tellbach, E.. Universitat of Gottingen; Alemania
Fil: Troe, J.. Max-Planck-Institut für Biophysikalische Chemie; Alemania
Materia
Pentafluoroethane
2-H-Heptafluoropropane
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:11336/5221
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H HeptafluoropropaneCobos, Carlos JorgeSölter, L.Tellbach, E.Troe, J.Pentafluoroethane2-H-Heptafluoropropanehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Sölter, L.. Universitat of Gottingen; AlemaniaFil: Tellbach, E.. Universitat of Gottingen; AlemaniaFil: Troe, J.. Max-Planck-Institut für Biophysikalische Chemie; AlemaniaRoyal Society Of Chemistry2014-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/5221Cobos, Carlos Jorge; Sölter, L.; Tellbach, E.; Troe, J.; Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane; Royal Society Of Chemistry; Physical Chemistry Chemical Physics; 16; 21; 1-2014; 9797-98071463-9076enginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C3CP54274B#!divAbstractinfo:eu-repo/semantics/altIdentifier/doi/10.1039/c3cp54274binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:01:04Zoai:ri.conicet.gov.ar:11336/5221instacron: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 10:01:04.713CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
title Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
spellingShingle Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
Cobos, Carlos Jorge
Pentafluoroethane
2-H-Heptafluoropropane
title_short Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
title_full Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
title_fullStr Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
title_full_unstemmed Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
title_sort Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane
dc.creator.none.fl_str_mv Cobos, Carlos Jorge
Sölter, L.
Tellbach, E.
Troe, J.
author Cobos, Carlos Jorge
author_facet Cobos, Carlos Jorge
Sölter, L.
Tellbach, E.
Troe, J.
author_role author
author2 Sölter, L.
Tellbach, E.
Troe, J.
author2_role author
author
author
dc.subject.none.fl_str_mv Pentafluoroethane
2-H-Heptafluoropropane
topic Pentafluoroethane
2-H-Heptafluoropropane
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 thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Sölter, L.. Universitat of Gottingen; Alemania
Fil: Tellbach, E.. Universitat of Gottingen; Alemania
Fil: Troe, J.. Max-Planck-Institut für Biophysikalische Chemie; Alemania
description The thermal decomposition reactions of CF3CF2H and CF3CFHCF3 have been studied in shock waves by monitoring the appearance of CF2 radicals. Temperatures in the range 1400-2000 K and Ar bath gas concentrations in the range (2-10) × 10(-5) mol cm(-3) were employed. It is shown that the reactions are initiated by C-C bond fission and not by HF elimination. Differing conclusions in the literature about the primary decomposition products, such as deduced from experiments at very low pressures, are attributed to unimolecular falloff effects. By increasing the initial reactant concentrations in Ar from 60 to 1000 ppm, a retardation of CF2 formation was observed while the final CF2 yields remained close to two CF2 per C2F5H or three CF2 per C3F7H decomposed. This is explained by secondary bimolecular reactions which lead to comparably stable transient species like CF3H, releasing CF2 at a slower rate. Quantum-chemical calculations and kinetic modeling help to identify the reaction pathways and provide estimates of rate constants for a series of primary and secondary reactions in the decomposition mechanism.
publishDate 2014
dc.date.none.fl_str_mv 2014-01
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/11336/5221
Cobos, Carlos Jorge; Sölter, L.; Tellbach, E.; Troe, J.; Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane; Royal Society Of Chemistry; Physical Chemistry Chemical Physics; 16; 21; 1-2014; 9797-9807
1463-9076
url http://hdl.handle.net/11336/5221
identifier_str_mv Cobos, Carlos Jorge; Sölter, L.; Tellbach, E.; Troe, J.; Shock wave and modeling study of the thermal decomposition reactions of Pentafluoroethane and 2-H Heptafluoropropane; Royal Society Of Chemistry; Physical Chemistry Chemical Physics; 16; 21; 1-2014; 9797-9807
1463-9076
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C3CP54274B#!divAbstract
info:eu-repo/semantics/altIdentifier/doi/10.1039/c3cp54274b
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
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 13.070432

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