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

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] i...

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Autores principales: Cobos, Carlos Jorge, Hintzer, K., Sölter, L., Tellbach, E., Thaler, Arne, Troe, J.
Formato: Articulo
Lenguaje:Inglés
Publicado: 2019
Materias:
Química
Ciencias Exactas
perfluorotriethylamine
shock waves
thermal decomposition
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/138682
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-138682
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Química
Ciencias Exactas
perfluorotriethylamine
shock waves
thermal decomposition
spellingShingle Química
Ciencias Exactas
perfluorotriethylamine
shock waves
thermal decomposition
Cobos, Carlos Jorge
Hintzer, K.
Sölter, L.
Tellbach, E.
Thaler, Arne
Troe, J.
Shock wave and modelling study of the dissociation pathways of (C2F5)3N
topic_facet Química
Ciencias Exactas
perfluorotriethylamine
shock waves
thermal decomposition
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.
format Articulo
Articulo
author Cobos, Carlos Jorge
Hintzer, K.
Sölter, L.
Tellbach, E.
Thaler, Arne
Troe, J.
author_facet Cobos, Carlos Jorge
Hintzer, K.
Sölter, L.
Tellbach, E.
Thaler, Arne
Troe, J.
author_sort Cobos, Carlos Jorge
title Shock wave and modelling study of the 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
publishDate 2019
url http://sedici.unlp.edu.ar/handle/10915/138682
work_keys_str_mv AT coboscarlosjorge shockwaveandmodellingstudyofthedissociationpathwaysofc2f53n
AT hintzerk shockwaveandmodellingstudyofthedissociationpathwaysofc2f53n
AT solterl shockwaveandmodellingstudyofthedissociationpathwaysofc2f53n
AT tellbache shockwaveandmodellingstudyofthedissociationpathwaysofc2f53n
AT thalerarne shockwaveandmodellingstudyofthedissociationpathwaysofc2f53n
AT troej shockwaveandmodellingstudyofthedissociationpathwaysofc2f53n
bdutipo_str Repositorios
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