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

dc.contributor.authorCobos, C. J.
dc.contributor.authorHintzer, K.
dc.contributor.authorSölter, L.
dc.contributor.authorTellbach, E.
dc.contributor.authorThaler, A.
dc.contributor.authorTroe, J.
dc.date.accessioned2019-09-30T14:13:17Z
dc.date.available2019-09-30T14:13:17Z
dc.date.issued2019de
dc.relation.ISSN1463-9084de
dc.identifier.urihttp://resolver.sub.uni-goettingen.de/purl?gs-1/16446
dc.description.abstractThe 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 literaturede
dc.language.isoengde
dc.rightsopenAccess
dc.rights.urihttps://creativecommons.org/licenses/by-nc/3.0/
dc.subjectShock wavede
dc.subject.ddc540
dc.titleShock wave and modelling study of the dissociation pathways of (C2F5)3Nde
dc.typejournalArticlede
dc.identifier.doi10.1039/C9CP01142K
dc.type.versionpublishedVersionde
dc.relation.pISSN1463-9076
dc.relation.eISSN1463-9084
dc.bibliographicCitation.volume21de
dc.bibliographicCitation.issue19de
dc.bibliographicCitation.firstPage9785de
dc.bibliographicCitation.lastPage9792de
dc.type.subtypejournalArticle
dc.identifier.pmid31025686
dc.description.statuspeerReviewedde
dc.bibliographicCitation.journalPhysical Chemistry Chemical Physicsde


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