Shock wave and modelling study of the dissociation pathways of (C2F5)3N

Autores
Cobos, Carlos Jorge; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; Troe, J.
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The thermal decomposition of perfluorotriethylamine, (C2F5)3N, was investigated in shock waves by monitoring the formation of CF2. Experiments were performed over the temperature range of 1120–1450 K with reactant concentrations between 100 and 1000 ppm of (C2F5)3N in the bath gas Ar and with [Ar] in the range of (0.7–5.5) × 10−5 mol cm−3. The experiments were accompanied by quantum-chemical calculations of the energies of various dissociation paths and by rate calculations, in particular for the dissociation of C2F5via C2F5 → CF3 + CF2. The overall reaction can proceed in different ways, either by a sequence of successive C–N bond ruptures followed by fast C2F5 decompositions, or by a sequence of alternating C–C and C–N bond ruptures. A cross-over between the two pathways can also take place. At temperatures below about 1300 K, yields of less than one CF2 per (C2F5)3N decomposed were observed. On the other hand, at temperatures around 2000 K, when besides the parent molecule, CF3 also dissociates, yields of six CF2 per (C2F5)3N decomposed were measured. The rate-delaying steps of the dissociation mechanism at intermediate temperatures were suggested to be the processes (C2F5)NCF2 → (C2F5)N + CF2 and (CF2)N → N + CF2. The reduction of the CF2 yields at low temperatures was tentatively attributed to a branching of the mechanism at the level of (C2F5)2NCF2, from where the cyclic final product perfluoro-N-methylpyrrolidine, (C4F8)NCF3, is formed which was identified in earlier work from the literature.
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. Institut Max Planck fuer Bioanorganische Chemie; Alemania
Materia
Shock wave
modelling study
dissociation pathways of (C2F5)3N
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/118914

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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Shock wave and modelling study of the dissociation pathways of (C2F5)3NCobos, Carlos JorgeHintzer, K.Sölter, L.Tellbach, E.Thaler, A.Troe, J.Shock wavemodelling studydissociation pathways of (C2F5)3Nhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The thermal decomposition of perfluorotriethylamine, (C2F5)3N, was investigated in shock waves by monitoring the formation of CF2. Experiments were performed over the temperature range of 1120–1450 K with reactant concentrations between 100 and 1000 ppm of (C2F5)3N in the bath gas Ar and with [Ar] in the range of (0.7–5.5) × 10−5 mol cm−3. The experiments were accompanied by quantum-chemical calculations of the energies of various dissociation paths and by rate calculations, in particular for the dissociation of C2F5via C2F5 → CF3 + CF2. The overall reaction can proceed in different ways, either by a sequence of successive C–N bond ruptures followed by fast C2F5 decompositions, or by a sequence of alternating C–C and C–N bond ruptures. A cross-over between the two pathways can also take place. At temperatures below about 1300 K, yields of less than one CF2 per (C2F5)3N decomposed were observed. On the other hand, at temperatures around 2000 K, when besides the parent molecule, CF3 also dissociates, yields of six CF2 per (C2F5)3N decomposed were measured. The rate-delaying steps of the dissociation mechanism at intermediate temperatures were suggested to be the processes (C2F5)NCF2 → (C2F5)N + CF2 and (CF2)N → N + CF2. The reduction of the CF2 yields at low temperatures was tentatively attributed to a branching of the mechanism at the level of (C2F5)2NCF2, from where the cyclic final product perfluoro-N-methylpyrrolidine, (C4F8)NCF3, is formed which was identified in earlier work from the literature.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. Institut Max Planck fuer Bioanorganische Chemie; AlemaniaRoyal Society of Chemistry2019-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/118914Cobos, Carlos Jorge; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; et al.; Shock wave and modelling study of the dissociation pathways of (C2F5)3N; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 19; 5-2019; 9785-97921463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C9CP01142Kinfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2019/cp/c9cp01142k#!divAbstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:19:07Zoai:ri.conicet.gov.ar:11336/118914instacron: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 10:19:07.416CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Shock wave and modelling study of the dissociation pathways of (C2F5)3N
title Shock wave and modelling study of the dissociation pathways of (C2F5)3N
spellingShingle Shock wave and modelling study of the dissociation pathways of (C2F5)3N
Cobos, Carlos Jorge
Shock wave
modelling study
dissociation pathways of (C2F5)3N
title_short Shock wave and modelling study of the dissociation pathways of (C2F5)3N
title_full Shock wave and modelling study of the dissociation pathways of (C2F5)3N
title_fullStr Shock wave and modelling study of the dissociation pathways of (C2F5)3N
title_full_unstemmed Shock wave and modelling study of the dissociation pathways of (C2F5)3N
title_sort Shock wave and modelling study of the dissociation pathways of (C2F5)3N
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
dc.subject.none.fl_str_mv Shock wave
modelling study
dissociation pathways of (C2F5)3N
topic Shock wave
modelling study
dissociation pathways of (C2F5)3N
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 perfluorotriethylamine, (C2F5)3N, was investigated in shock waves by monitoring the formation of CF2. Experiments were performed over the temperature range of 1120–1450 K with reactant concentrations between 100 and 1000 ppm of (C2F5)3N in the bath gas Ar and with [Ar] in the range of (0.7–5.5) × 10−5 mol cm−3. The experiments were accompanied by quantum-chemical calculations of the energies of various dissociation paths and by rate calculations, in particular for the dissociation of C2F5via C2F5 → CF3 + CF2. The overall reaction can proceed in different ways, either by a sequence of successive C–N bond ruptures followed by fast C2F5 decompositions, or by a sequence of alternating C–C and C–N bond ruptures. A cross-over between the two pathways can also take place. At temperatures below about 1300 K, yields of less than one CF2 per (C2F5)3N decomposed were observed. On the other hand, at temperatures around 2000 K, when besides the parent molecule, CF3 also dissociates, yields of six CF2 per (C2F5)3N decomposed were measured. The rate-delaying steps of the dissociation mechanism at intermediate temperatures were suggested to be the processes (C2F5)NCF2 → (C2F5)N + CF2 and (CF2)N → N + CF2. The reduction of the CF2 yields at low temperatures was tentatively attributed to a branching of the mechanism at the level of (C2F5)2NCF2, from where the cyclic final product perfluoro-N-methylpyrrolidine, (C4F8)NCF3, is formed which was identified in earlier work from the literature.
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. Institut Max Planck fuer Bioanorganische Chemie; Alemania
description The thermal decomposition of perfluorotriethylamine, (C2F5)3N, was investigated in shock waves by monitoring the formation of CF2. Experiments were performed over the temperature range of 1120–1450 K with reactant concentrations between 100 and 1000 ppm of (C2F5)3N in the bath gas Ar and with [Ar] in the range of (0.7–5.5) × 10−5 mol cm−3. The experiments were accompanied by quantum-chemical calculations of the energies of various dissociation paths and by rate calculations, in particular for the dissociation of C2F5via C2F5 → CF3 + CF2. The overall reaction can proceed in different ways, either by a sequence of successive C–N bond ruptures followed by fast C2F5 decompositions, or by a sequence of alternating C–C and C–N bond ruptures. A cross-over between the two pathways can also take place. At temperatures below about 1300 K, yields of less than one CF2 per (C2F5)3N decomposed were observed. On the other hand, at temperatures around 2000 K, when besides the parent molecule, CF3 also dissociates, yields of six CF2 per (C2F5)3N decomposed were measured. The rate-delaying steps of the dissociation mechanism at intermediate temperatures were suggested to be the processes (C2F5)NCF2 → (C2F5)N + CF2 and (CF2)N → N + CF2. The reduction of the CF2 yields at low temperatures was tentatively attributed to a branching of the mechanism at the level of (C2F5)2NCF2, from where the cyclic final product perfluoro-N-methylpyrrolidine, (C4F8)NCF3, is formed which was identified in earlier work from the literature.
publishDate 2019
dc.date.none.fl_str_mv 2019-05
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/11336/118914
Cobos, Carlos Jorge; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; et al.; Shock wave and modelling study of the dissociation pathways of (C2F5)3N; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 19; 5-2019; 9785-9792
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/118914
identifier_str_mv Cobos, Carlos Jorge; Hintzer, K.; Sölter, L.; Tellbach, E.; Thaler, A.; et al.; Shock wave and modelling study of the dissociation pathways of (C2F5)3N; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 19; 5-2019; 9785-9792
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/C9CP01142K
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2019/cp/c9cp01142k#!divAbstract
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/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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