Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF

Autores
Cobos, Carlos Jorge; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; Troe, J.
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The thermal decomposition of hexafluoropropylene oxide, C3F6O, to perfluoroacetyl fluoride, CF3COF, and CF2 has been studied in shock waves highly diluted in Ar between 630 and 1000 K. The measured rate constant k1 = 1.1 × 1014exp(-162(±4) kJ mol-1/RT) s-1 agrees well with literature data and modelling results. Using the reaction as a precursor, equimolar mixtures of CF3COF and CF2 were further heated. Combining experimental observations with theoretical modelling (on the CBS-QB3 and G4MP2 ab initio composite levels), CF3COF is shown to dissociate on two channels, either leading to CF2 + COF2 or to CF3 + FCO. By monitoring the CF2 signals, the branching ratio was determined between 1400 and 1900 K. The high pressure rate constants for the two channels were obtained from theoretical modelling as k5,∞(CF3COF → CF2 + COF2) = 7.1 × 1014exp(-320 kJ mol-1/RT) s-1 and k6,∞(CF3COF → CF3 + FCO) = 3.9 × 1015exp(-355 kJ mol-1/RT) s-1. The experimental results obtained at [Ar] ≈ 5 × 10-6 mol cm-3 were consistent with modelling results, showing that the reaction is in the falloff range of the unimolecular dissociation. The mechanism of secondary reactions following CF3COF dissociation has been analysed as well.
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Hintzer, K.. Dyneon GmbH; Alemania
Fil: Sölter, L.. Universität Göttingen; Alemania
Fil: Tellbach, E.. Universität Göttingen; Alemania
Fil: Thaler, A.. Dyneon GmbH; Alemania
Fil: Troe, J.. Universität Göttingen; Alemania. Max-Planck-Institut für Biophysikalische Chemie; Alemania
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acceso abierto
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https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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Consejo Nacional de Investigaciones Científicas y Técnicas
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Acceder
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network_name_str CONICET Digital (CONICET)
spelling Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COFCobos, Carlos JorgeHintzer, K.Sölter, L.Tellbach, E.Thaler, A.Troe, J.https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The thermal decomposition of hexafluoropropylene oxide, C3F6O, to perfluoroacetyl fluoride, CF3COF, and CF2 has been studied in shock waves highly diluted in Ar between 630 and 1000 K. The measured rate constant k1 = 1.1 × 1014exp(-162(±4) kJ mol-1/RT) s-1 agrees well with literature data and modelling results. Using the reaction as a precursor, equimolar mixtures of CF3COF and CF2 were further heated. Combining experimental observations with theoretical modelling (on the CBS-QB3 and G4MP2 ab initio composite levels), CF3COF is shown to dissociate on two channels, either leading to CF2 + COF2 or to CF3 + FCO. By monitoring the CF2 signals, the branching ratio was determined between 1400 and 1900 K. The high pressure rate constants for the two channels were obtained from theoretical modelling as k5,∞(CF3COF → CF2 + COF2) = 7.1 × 1014exp(-320 kJ mol-1/RT) s-1 and k6,∞(CF3COF → CF3 + FCO) = 3.9 × 1015exp(-355 kJ mol-1/RT) s-1. The experimental results obtained at [Ar] ≈ 5 × 10-6 mol cm-3 were consistent with modelling results, showing that the reaction is in the falloff range of the unimolecular dissociation. The mechanism of secondary reactions following CF3COF dissociation has been analysed as well.Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Hintzer, K.. Dyneon GmbH; AlemaniaFil: Sölter, L.. Universität Göttingen; AlemaniaFil: Tellbach, E.. Universität Göttingen; AlemaniaFil: Thaler, A.. Dyneon GmbH; AlemaniaFil: Troe, J.. Universität Göttingen; Alemania. Max-Planck-Institut für Biophysikalische Chemie; AlemaniaRoyal Society of Chemistry2017-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/64002Cobos, Carlos Jorge; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; et al.; Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 4; 3-2017; 3151-31581463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C6CP06816Binfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C6CP06816Binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:48:23Zoai:ri.conicet.gov.ar:11336/64002instacron: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 09:48:24.137CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF
title Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF
spellingShingle Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF
Cobos, Carlos Jorge
title_short Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF
title_full Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF
title_fullStr Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF
title_full_unstemmed Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF
title_sort Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF
dc.creator.none.fl_str_mv Cobos, Carlos Jorge
Hintzer, K.
Sölter, L.
Tellbach, E.
Thaler, A.
Troe, J.
author Cobos, Carlos Jorge
author_facet Cobos, Carlos Jorge
Hintzer, K.
Sölter, L.
Tellbach, E.
Thaler, A.
Troe, J.
author_role author
author2 Hintzer, K.
Sölter, L.
Tellbach, E.
Thaler, A.
Troe, J.
author2_role author
author
author
author
author
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 of hexafluoropropylene oxide, C3F6O, to perfluoroacetyl fluoride, CF3COF, and CF2 has been studied in shock waves highly diluted in Ar between 630 and 1000 K. The measured rate constant k1 = 1.1 × 1014exp(-162(±4) kJ mol-1/RT) s-1 agrees well with literature data and modelling results. Using the reaction as a precursor, equimolar mixtures of CF3COF and CF2 were further heated. Combining experimental observations with theoretical modelling (on the CBS-QB3 and G4MP2 ab initio composite levels), CF3COF is shown to dissociate on two channels, either leading to CF2 + COF2 or to CF3 + FCO. By monitoring the CF2 signals, the branching ratio was determined between 1400 and 1900 K. The high pressure rate constants for the two channels were obtained from theoretical modelling as k5,∞(CF3COF → CF2 + COF2) = 7.1 × 1014exp(-320 kJ mol-1/RT) s-1 and k6,∞(CF3COF → CF3 + FCO) = 3.9 × 1015exp(-355 kJ mol-1/RT) s-1. The experimental results obtained at [Ar] ≈ 5 × 10-6 mol cm-3 were consistent with modelling results, showing that the reaction is in the falloff range of the unimolecular dissociation. The mechanism of secondary reactions following CF3COF dissociation has been analysed as well.
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Hintzer, K.. Dyneon GmbH; Alemania
Fil: Sölter, L.. Universität Göttingen; Alemania
Fil: Tellbach, E.. Universität Göttingen; Alemania
Fil: Thaler, A.. Dyneon GmbH; Alemania
Fil: Troe, J.. Universität Göttingen; Alemania. Max-Planck-Institut für Biophysikalische Chemie; Alemania
description The thermal decomposition of hexafluoropropylene oxide, C3F6O, to perfluoroacetyl fluoride, CF3COF, and CF2 has been studied in shock waves highly diluted in Ar between 630 and 1000 K. The measured rate constant k1 = 1.1 × 1014exp(-162(±4) kJ mol-1/RT) s-1 agrees well with literature data and modelling results. Using the reaction as a precursor, equimolar mixtures of CF3COF and CF2 were further heated. Combining experimental observations with theoretical modelling (on the CBS-QB3 and G4MP2 ab initio composite levels), CF3COF is shown to dissociate on two channels, either leading to CF2 + COF2 or to CF3 + FCO. By monitoring the CF2 signals, the branching ratio was determined between 1400 and 1900 K. The high pressure rate constants for the two channels were obtained from theoretical modelling as k5,∞(CF3COF → CF2 + COF2) = 7.1 × 1014exp(-320 kJ mol-1/RT) s-1 and k6,∞(CF3COF → CF3 + FCO) = 3.9 × 1015exp(-355 kJ mol-1/RT) s-1. The experimental results obtained at [Ar] ≈ 5 × 10-6 mol cm-3 were consistent with modelling results, showing that the reaction is in the falloff range of the unimolecular dissociation. The mechanism of secondary reactions following CF3COF dissociation has been analysed as well.
publishDate 2017
dc.date.none.fl_str_mv 2017-03
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/11336/64002
Cobos, Carlos Jorge; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; et al.; Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 4; 3-2017; 3151-3158
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/64002
identifier_str_mv Cobos, Carlos Jorge; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; et al.; Shock wave studies of the pyrolysis of fluorocarbon oxygenates. I. The thermal dissociation of C3F6O and CF3COF; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 4; 3-2017; 3151-3158
1463-9076
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/C6CP06816B
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C6CP06816B
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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