Shock wave and modelling study of the dissociation kinetics of C₂F₅I

Autores
Cobos, Carlos Jorge; Sölter, L.; Tellbach, E.; Troe, J.
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The thermal dissociation of C₂F₅I was studied in shock waves monitoring UV absorption signals from the reactant C₂F₅I and later formed reaction products such as CF, CF₂, and C₂F₄. Temperatures of 950–1500 K, bath gas concentrations of [Ar] = 3 × 10⁻⁵ –2 × 10⁻⁴ mol cm⁻³, and reactant concentrations of 100–500 ppm C₂F₅I in Ar were employed. Absorption-time profiles were recorded at selected wavelengths in the range 200–280 nm. It was found that the dissociation of C₂F₅I → C₂F₅ + I was followed by the dissociation C₂F₅ → CF₂ + CF₃, before the dimerization reactions 2CF₂ → C₂F₄ and 2CF₃ → C₂F₆ and a reaction CF₂ + CF₃ → CF + CF₄ set in. The combination of iodine atoms with C₂F₅ and CF₃ had also to be considered. The rate constant of the primary dissociation of C₂F₅I was analyzed in the framework of statistical unimolecular rate theory accompanied by a quantum-chemical characterization of molecular parameters. Rates of secondary reactions were modelled as well. Experimental rate constants for the dissociations of C₂F₅I and C₂F₅ agreed well with the modelling results. The comparably slow dimerization 2CF₂ → C₂F₄ could be followed both by monitoring reactant CF₂ and product C₂F₄ absorption signals, while CF₃ dimerization was too fast to be detected. A competition between the dimerization reactions of CF₂ and CF₃, the recombination of CF₂ and CF₃ forming C₂F₅, and CF-forming processes like CF₂ + CF₃ → CF + CF₄ finally was discussed.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Materia
Física
Química
thermal dissociation
dimerization
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc/3.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/139723

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network_name_str SEDICI (UNLP)
spelling Shock wave and modelling study of the dissociation kinetics of C₂F₅ICobos, Carlos JorgeSölter, L.Tellbach, E.Troe, J.FísicaQuímicathermal dissociationdimerizationThe thermal dissociation of C₂F₅I was studied in shock waves monitoring UV absorption signals from the reactant C₂F₅I and later formed reaction products such as CF, CF₂, and C₂F₄. Temperatures of 950–1500 K, bath gas concentrations of [Ar] = 3 × 10⁻⁵ –2 × 10⁻⁴ mol cm⁻³, and reactant concentrations of 100–500 ppm C₂F₅I in Ar were employed. Absorption-time profiles were recorded at selected wavelengths in the range 200–280 nm. It was found that the dissociation of C₂F₅I → C₂F₅ + I was followed by the dissociation C₂F₅ → CF₂ + CF₃, before the dimerization reactions 2CF₂ → C₂F₄ and 2CF₃ → C₂F₆ and a reaction CF₂ + CF₃ → CF + CF₄ set in. The combination of iodine atoms with C₂F₅ and CF₃ had also to be considered. The rate constant of the primary dissociation of C₂F₅I was analyzed in the framework of statistical unimolecular rate theory accompanied by a quantum-chemical characterization of molecular parameters. Rates of secondary reactions were modelled as well. Experimental rate constants for the dissociations of C₂F₅I and C₂F₅ agreed well with the modelling results. The comparably slow dimerization 2CF₂ → C₂F₄ could be followed both by monitoring reactant CF₂ and product C₂F₄ absorption signals, while CF₃ dimerization was too fast to be detected. A competition between the dimerization reactions of CF₂ and CF₃, the recombination of CF₂ and CF₃ forming C₂F₅, and CF-forming processes like CF₂ + CF₃ → CF + CF₄ finally was discussed.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas2021-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf4394-4403http://sedici.unlp.edu.ar/handle/10915/139723enginfo:eu-repo/semantics/altIdentifier/issn/1463-9084info:eu-repo/semantics/altIdentifier/issn/1463-9076info:eu-repo/semantics/altIdentifier/doi/10.1039/d0cp06414ainfo:eu-repo/semantics/altIdentifier/pmid/33594391info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc/3.0/Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:32:06Zoai:sedici.unlp.edu.ar:10915/139723Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:32:07.26SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Shock wave and modelling study of the dissociation kinetics of C₂F₅I
title Shock wave and modelling study of the dissociation kinetics of C₂F₅I
spellingShingle Shock wave and modelling study of the dissociation kinetics of C₂F₅I
Cobos, Carlos Jorge
Física
Química
thermal dissociation
dimerization
title_short Shock wave and modelling study of the dissociation kinetics of C₂F₅I
title_full Shock wave and modelling study of the dissociation kinetics of C₂F₅I
title_fullStr Shock wave and modelling study of the dissociation kinetics of C₂F₅I
title_full_unstemmed Shock wave and modelling study of the dissociation kinetics of C₂F₅I
title_sort Shock wave and modelling study of the dissociation kinetics of C₂F₅I
dc.creator.none.fl_str_mv Cobos, Carlos Jorge
Sölter, L.
Tellbach, E.
Troe, J.
author Cobos, Carlos Jorge
author_facet Cobos, Carlos Jorge
Sölter, L.
Tellbach, E.
Troe, J.
author_role author
author2 Sölter, L.
Tellbach, E.
Troe, J.
author2_role author
author
author
dc.subject.none.fl_str_mv Física
Química
thermal dissociation
dimerization
topic Física
Química
thermal dissociation
dimerization
dc.description.none.fl_txt_mv The thermal dissociation of C₂F₅I was studied in shock waves monitoring UV absorption signals from the reactant C₂F₅I and later formed reaction products such as CF, CF₂, and C₂F₄. Temperatures of 950–1500 K, bath gas concentrations of [Ar] = 3 × 10⁻⁵ –2 × 10⁻⁴ mol cm⁻³, and reactant concentrations of 100–500 ppm C₂F₅I in Ar were employed. Absorption-time profiles were recorded at selected wavelengths in the range 200–280 nm. It was found that the dissociation of C₂F₅I → C₂F₅ + I was followed by the dissociation C₂F₅ → CF₂ + CF₃, before the dimerization reactions 2CF₂ → C₂F₄ and 2CF₃ → C₂F₆ and a reaction CF₂ + CF₃ → CF + CF₄ set in. The combination of iodine atoms with C₂F₅ and CF₃ had also to be considered. The rate constant of the primary dissociation of C₂F₅I was analyzed in the framework of statistical unimolecular rate theory accompanied by a quantum-chemical characterization of molecular parameters. Rates of secondary reactions were modelled as well. Experimental rate constants for the dissociations of C₂F₅I and C₂F₅ agreed well with the modelling results. The comparably slow dimerization 2CF₂ → C₂F₄ could be followed both by monitoring reactant CF₂ and product C₂F₄ absorption signals, while CF₃ dimerization was too fast to be detected. A competition between the dimerization reactions of CF₂ and CF₃, the recombination of CF₂ and CF₃ forming C₂F₅, and CF-forming processes like CF₂ + CF₃ → CF + CF₄ finally was discussed.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
description The thermal dissociation of C₂F₅I was studied in shock waves monitoring UV absorption signals from the reactant C₂F₅I and later formed reaction products such as CF, CF₂, and C₂F₄. Temperatures of 950–1500 K, bath gas concentrations of [Ar] = 3 × 10⁻⁵ –2 × 10⁻⁴ mol cm⁻³, and reactant concentrations of 100–500 ppm C₂F₅I in Ar were employed. Absorption-time profiles were recorded at selected wavelengths in the range 200–280 nm. It was found that the dissociation of C₂F₅I → C₂F₅ + I was followed by the dissociation C₂F₅ → CF₂ + CF₃, before the dimerization reactions 2CF₂ → C₂F₄ and 2CF₃ → C₂F₆ and a reaction CF₂ + CF₃ → CF + CF₄ set in. The combination of iodine atoms with C₂F₅ and CF₃ had also to be considered. The rate constant of the primary dissociation of C₂F₅I was analyzed in the framework of statistical unimolecular rate theory accompanied by a quantum-chemical characterization of molecular parameters. Rates of secondary reactions were modelled as well. Experimental rate constants for the dissociations of C₂F₅I and C₂F₅ agreed well with the modelling results. The comparably slow dimerization 2CF₂ → C₂F₄ could be followed both by monitoring reactant CF₂ and product C₂F₄ absorption signals, while CF₃ dimerization was too fast to be detected. A competition between the dimerization reactions of CF₂ and CF₃, the recombination of CF₂ and CF₃ forming C₂F₅, and CF-forming processes like CF₂ + CF₃ → CF + CF₄ finally was discussed.
publishDate 2021
dc.date.none.fl_str_mv 2021-02
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/139723
url http://sedici.unlp.edu.ar/handle/10915/139723
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/1463-9084
info:eu-repo/semantics/altIdentifier/issn/1463-9076
info:eu-repo/semantics/altIdentifier/doi/10.1039/d0cp06414a
info:eu-repo/semantics/altIdentifier/pmid/33594391
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc/3.0/
Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc/3.0/
Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)
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4394-4403
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instname:Universidad Nacional de La Plata
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