Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene

Autores
Tucceri, Maria Eugenia; Badenes, Maria Paula; Cobos, Carlos Jorge
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A detailed theoretical study of the kinetics of the thermal decomposition of 2-chloropropene over the 600–1400 K temperature range has been done. The reaction takes place through the elimination of HCl with the concomitant formation of propyne or allene products. Relevant molecular properties of the reactant and transition states were calculated for each reaction channel at 14 levels of theory. From information provided by the BMK, MPWB1K, BB1K, M05-2X, and M06-2X functionals, specific for chemical kinetics studies, high-pressure limit rate coefficients of (5.8 ± 1.0) × 1014 exp[−(67.8 ± 0.4 kcal mol–1)/RT] s–1 and (1.1 ± 0.2) × 1014 exp[−(66.8 ± 0.5 kcal mol–1)/RT] s–1 were obtained for the propyne and allene channels, respectively. The pressure effect over the reaction was analyzed through the calculation of the low-pressure limit rate coefficients and falloff curves. An analysis of the branching ratio between the two channels as a function of pressure and temperature, based on these results and on computed specific rate coefficients, show that the propyne forming channel is predominant.
Fil: Tucceri, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Badenes, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Materia
2-Chloropropene
Thermal Decomposition
Kinetics
Quantum-Chemical Calculations
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:11336/5320
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/5320
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-ChloropropeneTucceri, Maria EugeniaBadenes, Maria PaulaCobos, Carlos Jorge2-ChloropropeneThermal DecompositionKineticsQuantum-Chemical Calculationshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A detailed theoretical study of the kinetics of the thermal decomposition of 2-chloropropene over the 600–1400 K temperature range has been done. The reaction takes place through the elimination of HCl with the concomitant formation of propyne or allene products. Relevant molecular properties of the reactant and transition states were calculated for each reaction channel at 14 levels of theory. From information provided by the BMK, MPWB1K, BB1K, M05-2X, and M06-2X functionals, specific for chemical kinetics studies, high-pressure limit rate coefficients of (5.8 ± 1.0) × 1014 exp[−(67.8 ± 0.4 kcal mol–1)/RT] s–1 and (1.1 ± 0.2) × 1014 exp[−(66.8 ± 0.5 kcal mol–1)/RT] s–1 were obtained for the propyne and allene channels, respectively. The pressure effect over the reaction was analyzed through the calculation of the low-pressure limit rate coefficients and falloff curves. An analysis of the branching ratio between the two channels as a function of pressure and temperature, based on these results and on computed specific rate coefficients, show that the propyne forming channel is predominant.Fil: Tucceri, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Badenes, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaAmerican Chemical Society2013-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/5320Tucceri, Maria Eugenia; Badenes, Maria Paula; Cobos, Carlos Jorge; Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene; American Chemical Society; Journal Of Physical Chemistry A; 117; 40; 9-2013; 10218-102271089-5639enginfo:eu-repo/semantics/altIdentifier/pmid/24032406info:eu-repo/semantics/altIdentifier/doi/10.1021/jp406931qinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp406931qinfo:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:47:22Zoai:ri.conicet.gov.ar:11336/5320instacron: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 09:47:23.046CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene
title Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene
spellingShingle Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene
Tucceri, Maria Eugenia
2-Chloropropene
Thermal Decomposition
Kinetics
Quantum-Chemical Calculations
title_short Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene
title_full Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene
title_fullStr Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene
title_full_unstemmed Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene
title_sort Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene
dc.creator.none.fl_str_mv Tucceri, Maria Eugenia
Badenes, Maria Paula
Cobos, Carlos Jorge
author Tucceri, Maria Eugenia
author_facet Tucceri, Maria Eugenia
Badenes, Maria Paula
Cobos, Carlos Jorge
author_role author
author2 Badenes, Maria Paula
Cobos, Carlos Jorge
author2_role author
author
dc.subject.none.fl_str_mv 2-Chloropropene
Thermal Decomposition
Kinetics
Quantum-Chemical Calculations
topic 2-Chloropropene
Thermal Decomposition
Kinetics
Quantum-Chemical Calculations
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A detailed theoretical study of the kinetics of the thermal decomposition of 2-chloropropene over the 600–1400 K temperature range has been done. The reaction takes place through the elimination of HCl with the concomitant formation of propyne or allene products. Relevant molecular properties of the reactant and transition states were calculated for each reaction channel at 14 levels of theory. From information provided by the BMK, MPWB1K, BB1K, M05-2X, and M06-2X functionals, specific for chemical kinetics studies, high-pressure limit rate coefficients of (5.8 ± 1.0) × 1014 exp[−(67.8 ± 0.4 kcal mol–1)/RT] s–1 and (1.1 ± 0.2) × 1014 exp[−(66.8 ± 0.5 kcal mol–1)/RT] s–1 were obtained for the propyne and allene channels, respectively. The pressure effect over the reaction was analyzed through the calculation of the low-pressure limit rate coefficients and falloff curves. An analysis of the branching ratio between the two channels as a function of pressure and temperature, based on these results and on computed specific rate coefficients, show that the propyne forming channel is predominant.
Fil: Tucceri, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Badenes, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Cobos, Carlos Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
description A detailed theoretical study of the kinetics of the thermal decomposition of 2-chloropropene over the 600–1400 K temperature range has been done. The reaction takes place through the elimination of HCl with the concomitant formation of propyne or allene products. Relevant molecular properties of the reactant and transition states were calculated for each reaction channel at 14 levels of theory. From information provided by the BMK, MPWB1K, BB1K, M05-2X, and M06-2X functionals, specific for chemical kinetics studies, high-pressure limit rate coefficients of (5.8 ± 1.0) × 1014 exp[−(67.8 ± 0.4 kcal mol–1)/RT] s–1 and (1.1 ± 0.2) × 1014 exp[−(66.8 ± 0.5 kcal mol–1)/RT] s–1 were obtained for the propyne and allene channels, respectively. The pressure effect over the reaction was analyzed through the calculation of the low-pressure limit rate coefficients and falloff curves. An analysis of the branching ratio between the two channels as a function of pressure and temperature, based on these results and on computed specific rate coefficients, show that the propyne forming channel is predominant.
publishDate 2013
dc.date.none.fl_str_mv 2013-09
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/11336/5320
Tucceri, Maria Eugenia; Badenes, Maria Paula; Cobos, Carlos Jorge; Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene; American Chemical Society; Journal Of Physical Chemistry A; 117; 40; 9-2013; 10218-10227
1089-5639
url http://hdl.handle.net/11336/5320
identifier_str_mv Tucceri, Maria Eugenia; Badenes, Maria Paula; Cobos, Carlos Jorge; Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2-Chloropropene; American Chemical Society; Journal Of Physical Chemistry A; 117; 40; 9-2013; 10218-10227
1089-5639
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/pmid/24032406
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp406931q
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp406931q
info:eu-repo/semantics/altIdentifier/doi/
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/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 13.070432

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