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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/118914
Ver los metadatos del registro completo
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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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1844614160343629824 |
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13.070432 |