Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism

Autores
Rimondino, Guido Noé; Peláez, Walter José; Malanca, Fabio Ernesto
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The rate coefficient for the gas phase of diethyl carbonate with chlorine atoms has been determined at 298 K using a relative method, employing ethyl formate and ethyl acetate as reference compounds. The experimental value, (1.0 ± 0.2) × 10-11 cm3 molecule-1 s-1, is in good correlation with the one estimated by the SAR (Structure-Activity Relationship) method. The photo-oxidation mechanism of diethyl carbonate initiated by chlorine atoms was also studied at 298 K and atmospheric pressure as a function of the oxygen partial pressure. The main products identified by infrared spectroscopy were CH3CH2OC(O)OCHO, CH3CH2OC(O)OCH2CHO, CH3CH2OC(O)OC(O)CH3, CO2, CO, HCOOH, and CH3COOH. The results reveal that the oxidation process occurs by the abstraction of a hydrogen atom from the methyl (43%) and methylene (57%) groups. The relative importance of each reaction path from the primary radicals formed in photo-oxidation and the identity of CH3CH2OC(O)OCHO, CH3CH2OC(O)OC(O)CH3, and CH3CH2OC(O)OCH2CHO were determined using computational methods. The activation energy of reaction paths for the main oxygenated radicals formed during photo-oxidation was determined using Gaussian09 Program.
Fil: Rimondino, Guido Noé. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Peláez, Walter José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Malanca, Fabio Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
CHLORINE
CHEMICAL REACTIONS
ETHYL GROUPS
INORGANIC CARBON COMPOUNDS
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:11336/125139
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/125139
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction MechanismRimondino, Guido NoéPeláez, Walter JoséMalanca, Fabio ErnestoCHLORINECHEMICAL REACTIONSETHYL GROUPSINORGANIC CARBON COMPOUNDShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The rate coefficient for the gas phase of diethyl carbonate with chlorine atoms has been determined at 298 K using a relative method, employing ethyl formate and ethyl acetate as reference compounds. The experimental value, (1.0 ± 0.2) × 10-11 cm3 molecule-1 s-1, is in good correlation with the one estimated by the SAR (Structure-Activity Relationship) method. The photo-oxidation mechanism of diethyl carbonate initiated by chlorine atoms was also studied at 298 K and atmospheric pressure as a function of the oxygen partial pressure. The main products identified by infrared spectroscopy were CH3CH2OC(O)OCHO, CH3CH2OC(O)OCH2CHO, CH3CH2OC(O)OC(O)CH3, CO2, CO, HCOOH, and CH3COOH. The results reveal that the oxidation process occurs by the abstraction of a hydrogen atom from the methyl (43%) and methylene (57%) groups. The relative importance of each reaction path from the primary radicals formed in photo-oxidation and the identity of CH3CH2OC(O)OCHO, CH3CH2OC(O)OC(O)CH3, and CH3CH2OC(O)OCH2CHO were determined using computational methods. The activation energy of reaction paths for the main oxygenated radicals formed during photo-oxidation was determined using Gaussian09 Program.Fil: Rimondino, Guido Noé. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Peláez, Walter José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Malanca, Fabio Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2020-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/125139Rimondino, Guido Noé; Peláez, Walter José; Malanca, Fabio Ernesto; Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism; American Chemical Society; Journal of Physical Chemistry A; 124; 1; 1-2020; 56-621089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.9b09887info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.9b09887info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:34:18Zoai:ri.conicet.gov.ar:11336/125139instacron: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:34982025-10-22 11:34:18.336CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism
title Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism
spellingShingle Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism
Rimondino, Guido Noé
CHLORINE
CHEMICAL REACTIONS
ETHYL GROUPS
INORGANIC CARBON COMPOUNDS
title_short Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism
title_full Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism
title_fullStr Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism
title_full_unstemmed Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism
title_sort Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism
dc.creator.none.fl_str_mv Rimondino, Guido Noé
Peláez, Walter José
Malanca, Fabio Ernesto
author Rimondino, Guido Noé
author_facet Rimondino, Guido Noé
Peláez, Walter José
Malanca, Fabio Ernesto
author_role author
author2 Peláez, Walter José
Malanca, Fabio Ernesto
author2_role author
author
dc.subject.none.fl_str_mv CHLORINE
CHEMICAL REACTIONS
ETHYL GROUPS
INORGANIC CARBON COMPOUNDS
topic CHLORINE
CHEMICAL REACTIONS
ETHYL GROUPS
INORGANIC CARBON COMPOUNDS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The rate coefficient for the gas phase of diethyl carbonate with chlorine atoms has been determined at 298 K using a relative method, employing ethyl formate and ethyl acetate as reference compounds. The experimental value, (1.0 ± 0.2) × 10-11 cm3 molecule-1 s-1, is in good correlation with the one estimated by the SAR (Structure-Activity Relationship) method. The photo-oxidation mechanism of diethyl carbonate initiated by chlorine atoms was also studied at 298 K and atmospheric pressure as a function of the oxygen partial pressure. The main products identified by infrared spectroscopy were CH3CH2OC(O)OCHO, CH3CH2OC(O)OCH2CHO, CH3CH2OC(O)OC(O)CH3, CO2, CO, HCOOH, and CH3COOH. The results reveal that the oxidation process occurs by the abstraction of a hydrogen atom from the methyl (43%) and methylene (57%) groups. The relative importance of each reaction path from the primary radicals formed in photo-oxidation and the identity of CH3CH2OC(O)OCHO, CH3CH2OC(O)OC(O)CH3, and CH3CH2OC(O)OCH2CHO were determined using computational methods. The activation energy of reaction paths for the main oxygenated radicals formed during photo-oxidation was determined using Gaussian09 Program.
Fil: Rimondino, Guido Noé. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Peláez, Walter José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Malanca, Fabio Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The rate coefficient for the gas phase of diethyl carbonate with chlorine atoms has been determined at 298 K using a relative method, employing ethyl formate and ethyl acetate as reference compounds. The experimental value, (1.0 ± 0.2) × 10-11 cm3 molecule-1 s-1, is in good correlation with the one estimated by the SAR (Structure-Activity Relationship) method. The photo-oxidation mechanism of diethyl carbonate initiated by chlorine atoms was also studied at 298 K and atmospheric pressure as a function of the oxygen partial pressure. The main products identified by infrared spectroscopy were CH3CH2OC(O)OCHO, CH3CH2OC(O)OCH2CHO, CH3CH2OC(O)OC(O)CH3, CO2, CO, HCOOH, and CH3COOH. The results reveal that the oxidation process occurs by the abstraction of a hydrogen atom from the methyl (43%) and methylene (57%) groups. The relative importance of each reaction path from the primary radicals formed in photo-oxidation and the identity of CH3CH2OC(O)OCHO, CH3CH2OC(O)OC(O)CH3, and CH3CH2OC(O)OCH2CHO were determined using computational methods. The activation energy of reaction paths for the main oxygenated radicals formed during photo-oxidation was determined using Gaussian09 Program.
publishDate 2020
dc.date.none.fl_str_mv 2020-01
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/11336/125139
Rimondino, Guido Noé; Peláez, Walter José; Malanca, Fabio Ernesto; Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism; American Chemical Society; Journal of Physical Chemistry A; 124; 1; 1-2020; 56-62
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/125139
identifier_str_mv Rimondino, Guido Noé; Peláez, Walter José; Malanca, Fabio Ernesto; Atmospheric Photo-oxidation of Diethyl Carbonate: Kinetics, Products, and Reaction Mechanism; American Chemical Society; Journal of Physical Chemistry A; 124; 1; 1-2020; 56-62
1089-5639
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://pubs.acs.org/doi/10.1021/acs.jpca.9b09887
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.9b09887
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 12.982451

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