Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis

Autores
Cafferata, Lazaro; Manzione, Carlos Jose
Año de publicación
2001
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Headspace gas chromatography is employed in order to study the thermal decomposition reaction of gaseous di-tert-butyl peroxide (DTBP) in the 130°C to 160°C temperature range and in the presence of n-hexane as the internal standard and nitrogen as the carrier gas. The reaction exclusively yields acetone and ethane as products. First-order kinetics are observed, including when the surface-to-volume ratio (S/V) of the Pyrex 20-mL vial employed as the reactor is increased by packing it with silanized glass wool. However, a small increase in the rate constant values is observed at each temperature, which supports a heterogeneous surface process in DTBP decomposition. The rate constant's dependence on the homogeneous unimolecular decomposition reaction corresponds to the O-O bond rupture of the DTBP molecule in a stepwise three-stage mechanism. Thus, the relevant question of the participation of a surface catalytic effect in the DTBP gas-phase thermolysis can easily be assessed through the procedure described in this work. In general, this is advantageous for the rapid investigation of the reaction kinetics of volatile compounds at different temperatures.
Fil: Cafferata, Lazaro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; Argentina
Fil: Manzione, Carlos Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; Argentina
Materia
Kinetics
Thermolysis
Headspace
Analysis
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/42628
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic AnalysisCafferata, LazaroManzione, Carlos JoseKineticsThermolysisHeadspaceAnalysishttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Headspace gas chromatography is employed in order to study the thermal decomposition reaction of gaseous di-tert-butyl peroxide (DTBP) in the 130°C to 160°C temperature range and in the presence of n-hexane as the internal standard and nitrogen as the carrier gas. The reaction exclusively yields acetone and ethane as products. First-order kinetics are observed, including when the surface-to-volume ratio (S/V) of the Pyrex 20-mL vial employed as the reactor is increased by packing it with silanized glass wool. However, a small increase in the rate constant values is observed at each temperature, which supports a heterogeneous surface process in DTBP decomposition. The rate constant's dependence on the homogeneous unimolecular decomposition reaction corresponds to the O-O bond rupture of the DTBP molecule in a stepwise three-stage mechanism. Thus, the relevant question of the participation of a surface catalytic effect in the DTBP gas-phase thermolysis can easily be assessed through the procedure described in this work. In general, this is advantageous for the rapid investigation of the reaction kinetics of volatile compounds at different temperatures.Fil: Cafferata, Lazaro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; ArgentinaFil: Manzione, Carlos Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; ArgentinaOxford University Press2001-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/mswordapplication/pdfhttp://hdl.handle.net/11336/42628Cafferata, Lazaro; Manzione, Carlos Jose; Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis; Oxford University Press; Journal Of Chromatographic Science; 39; 2; 2-2001; 45-480021-96651945-239XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://academic.oup.com/chromsci/article/39/2/45/379400info:eu-repo/semantics/altIdentifier/doi/10.1093/chromsci/39.2.45info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:00:15Zoai:ri.conicet.gov.ar:11336/42628instacron: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:34982025-09-10 13:00:16.088CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis
title Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis
spellingShingle Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis
Cafferata, Lazaro
Kinetics
Thermolysis
Headspace
Analysis
title_short Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis
title_full Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis
title_fullStr Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis
title_full_unstemmed Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis
title_sort Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis
dc.creator.none.fl_str_mv Cafferata, Lazaro
Manzione, Carlos Jose
author Cafferata, Lazaro
author_facet Cafferata, Lazaro
Manzione, Carlos Jose
author_role author
author2 Manzione, Carlos Jose
author2_role author
dc.subject.none.fl_str_mv Kinetics
Thermolysis
Headspace
Analysis
topic Kinetics
Thermolysis
Headspace
Analysis
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Headspace gas chromatography is employed in order to study the thermal decomposition reaction of gaseous di-tert-butyl peroxide (DTBP) in the 130°C to 160°C temperature range and in the presence of n-hexane as the internal standard and nitrogen as the carrier gas. The reaction exclusively yields acetone and ethane as products. First-order kinetics are observed, including when the surface-to-volume ratio (S/V) of the Pyrex 20-mL vial employed as the reactor is increased by packing it with silanized glass wool. However, a small increase in the rate constant values is observed at each temperature, which supports a heterogeneous surface process in DTBP decomposition. The rate constant's dependence on the homogeneous unimolecular decomposition reaction corresponds to the O-O bond rupture of the DTBP molecule in a stepwise three-stage mechanism. Thus, the relevant question of the participation of a surface catalytic effect in the DTBP gas-phase thermolysis can easily be assessed through the procedure described in this work. In general, this is advantageous for the rapid investigation of the reaction kinetics of volatile compounds at different temperatures.
Fil: Cafferata, Lazaro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; Argentina
Fil: Manzione, Carlos Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas ; Argentina
description Headspace gas chromatography is employed in order to study the thermal decomposition reaction of gaseous di-tert-butyl peroxide (DTBP) in the 130°C to 160°C temperature range and in the presence of n-hexane as the internal standard and nitrogen as the carrier gas. The reaction exclusively yields acetone and ethane as products. First-order kinetics are observed, including when the surface-to-volume ratio (S/V) of the Pyrex 20-mL vial employed as the reactor is increased by packing it with silanized glass wool. However, a small increase in the rate constant values is observed at each temperature, which supports a heterogeneous surface process in DTBP decomposition. The rate constant's dependence on the homogeneous unimolecular decomposition reaction corresponds to the O-O bond rupture of the DTBP molecule in a stepwise three-stage mechanism. Thus, the relevant question of the participation of a surface catalytic effect in the DTBP gas-phase thermolysis can easily be assessed through the procedure described in this work. In general, this is advantageous for the rapid investigation of the reaction kinetics of volatile compounds at different temperatures.
publishDate 2001
dc.date.none.fl_str_mv 2001-02
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/11336/42628
Cafferata, Lazaro; Manzione, Carlos Jose; Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis; Oxford University Press; Journal Of Chromatographic Science; 39; 2; 2-2001; 45-48
0021-9665
1945-239X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/42628
identifier_str_mv Cafferata, Lazaro; Manzione, Carlos Jose; Kinetics and Mechanism of Gas-Phase Thermolysis Using Headspace-Gas Chromatographic Analysis; Oxford University Press; Journal Of Chromatographic Science; 39; 2; 2-2001; 45-48
0021-9665
1945-239X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://academic.oup.com/chromsci/article/39/2/45/379400
info:eu-repo/semantics/altIdentifier/doi/10.1093/chromsci/39.2.45
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/msword
application/pdf
dc.publisher.none.fl_str_mv Oxford University Press
publisher.none.fl_str_mv Oxford University Press
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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score 12.48226

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