Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation

Autores
Peirone, Silvina Anahí; Nieto, Jorge Daniel; Cometto, Pablo Marcelo; Barbosa, Thaís da Silva; Bauerfeldt, Glauco Favilla; Arbilla, Graciela; Lane, Silvia Irene
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The compared kinetics of the reactions of unsaturated alcohols and alkenes with OH radicals is a topic of great interest from both the theoretical chemistry and the atmospheric chemistry points of view. The enhanced reactivity of an unsaturated alcohol, with respect to its alkene analogue, toward OH radicals has been previously demonstrated, at 298 K, by experimental and theoretical research. In this work, a new comparative investigation of such reactions is performed for 3-buten-1-ol and 1-butene. The model assumes that the overall kinetics is governed by the first OH addition steps of the mechanism. Calculations have been performed at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets, and the rate coefficients have been determined on the basis of the microcanonical variational transition state theory. The rate coefficients obtained for the OH reactions with 3-buten-1-ol (kOH31BO) and 1-butene (kOH1B) at 298.15 K are lower than the experimental rate coefficient available in the literature, showing deviations of 18% and 25%, respectively. Negative temperature dependence is verified for these rate coefficients. The kOH31BO/kOH1B ratios have also been investigated as a function of the temperature, suggesting that at room temperature the unsaturated alcohol reacts with the OH radicals faster than 1-butene, by a factor of 1.2, but at higher temperatures (400–500 K), the alkene should react faster, and that the stabilization of prebarrier complexes and saddle points due to hydrogen bonds is no longer an important factor to govern the reactivity of the unsaturated alcohol toward OH radicals, with respect to the alkene analogue.
Fil: Peirone, Silvina Anahí. 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. Universidad Nacional de Córdoba. Rectorado. Centro Laser de Ciencias Moleculares; Argentina
Fil: Nieto, Jorge Daniel. Universidad Nacional de Córdoba. Rectorado. Centro Laser de Ciencias Moleculares; Argentina
Fil: Cometto, Pablo Marcelo. 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. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones y Transferencia de Villa María. Universidad Nacional de Villa María. Centro de Investigaciones y Transferencia de Villa María; Argentina
Fil: Barbosa, Thaís da Silva. Universidade Federal Rural do Rio de Janeiro; Brasil
Fil: Bauerfeldt, Glauco Favilla. Universidade Federal Rural do Rio de Janeiro; Brasil
Fil: Arbilla, Graciela. Universidade Federal do Rio de Janeiro; Brasil
Fil: Lane, Silvia Irene. 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
Kinetics Comparative
Rrkm
3-Buten-1-Ol
1-Butene
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:11336/44419
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/44419
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigationPeirone, Silvina AnahíNieto, Jorge DanielCometto, Pablo MarceloBarbosa, Thaís da SilvaBauerfeldt, Glauco FavillaArbilla, GracielaLane, Silvia IreneKinetics ComparativeRrkm3-Buten-1-Ol1-Butenehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The compared kinetics of the reactions of unsaturated alcohols and alkenes with OH radicals is a topic of great interest from both the theoretical chemistry and the atmospheric chemistry points of view. The enhanced reactivity of an unsaturated alcohol, with respect to its alkene analogue, toward OH radicals has been previously demonstrated, at 298 K, by experimental and theoretical research. In this work, a new comparative investigation of such reactions is performed for 3-buten-1-ol and 1-butene. The model assumes that the overall kinetics is governed by the first OH addition steps of the mechanism. Calculations have been performed at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets, and the rate coefficients have been determined on the basis of the microcanonical variational transition state theory. The rate coefficients obtained for the OH reactions with 3-buten-1-ol (kOH31BO) and 1-butene (kOH1B) at 298.15 K are lower than the experimental rate coefficient available in the literature, showing deviations of 18% and 25%, respectively. Negative temperature dependence is verified for these rate coefficients. The kOH31BO/kOH1B ratios have also been investigated as a function of the temperature, suggesting that at room temperature the unsaturated alcohol reacts with the OH radicals faster than 1-butene, by a factor of 1.2, but at higher temperatures (400–500 K), the alkene should react faster, and that the stabilization of prebarrier complexes and saddle points due to hydrogen bonds is no longer an important factor to govern the reactivity of the unsaturated alcohol toward OH radicals, with respect to the alkene analogue.Fil: Peirone, Silvina Anahí. 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. Universidad Nacional de Córdoba. Rectorado. Centro Laser de Ciencias Moleculares; ArgentinaFil: Nieto, Jorge Daniel. Universidad Nacional de Córdoba. Rectorado. Centro Laser de Ciencias Moleculares; ArgentinaFil: Cometto, Pablo Marcelo. 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. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones y Transferencia de Villa María. Universidad Nacional de Villa María. Centro de Investigaciones y Transferencia de Villa María; ArgentinaFil: Barbosa, Thaís da Silva. Universidade Federal Rural do Rio de Janeiro; BrasilFil: Bauerfeldt, Glauco Favilla. Universidade Federal Rural do Rio de Janeiro; BrasilFil: Arbilla, Graciela. Universidade Federal do Rio de Janeiro; BrasilFil: Lane, Silvia Irene. 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 Society2015-03-18info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/44419Peirone, Silvina Anahí; Nieto, Jorge Daniel; Cometto, Pablo Marcelo; Barbosa, Thaís da Silva; Bauerfeldt, Glauco Favilla; et al.; Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation; American Chemical Society; Journal of Physical Chemistry A; 119; 13; 18-3-2015; 3171-31801089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp512544xinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp512544xinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:30:04Zoai:ri.conicet.gov.ar:11336/44419instacron: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 10:30:04.317CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation
title Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation
spellingShingle Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation
Peirone, Silvina Anahí
Kinetics Comparative
Rrkm
3-Buten-1-Ol
1-Butene
title_short Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation
title_full Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation
title_fullStr Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation
title_full_unstemmed Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation
title_sort Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation
dc.creator.none.fl_str_mv Peirone, Silvina Anahí
Nieto, Jorge Daniel
Cometto, Pablo Marcelo
Barbosa, Thaís da Silva
Bauerfeldt, Glauco Favilla
Arbilla, Graciela
Lane, Silvia Irene
author Peirone, Silvina Anahí
author_facet Peirone, Silvina Anahí
Nieto, Jorge Daniel
Cometto, Pablo Marcelo
Barbosa, Thaís da Silva
Bauerfeldt, Glauco Favilla
Arbilla, Graciela
Lane, Silvia Irene
author_role author
author2 Nieto, Jorge Daniel
Cometto, Pablo Marcelo
Barbosa, Thaís da Silva
Bauerfeldt, Glauco Favilla
Arbilla, Graciela
Lane, Silvia Irene
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Kinetics Comparative
Rrkm
3-Buten-1-Ol
1-Butene
topic Kinetics Comparative
Rrkm
3-Buten-1-Ol
1-Butene
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 compared kinetics of the reactions of unsaturated alcohols and alkenes with OH radicals is a topic of great interest from both the theoretical chemistry and the atmospheric chemistry points of view. The enhanced reactivity of an unsaturated alcohol, with respect to its alkene analogue, toward OH radicals has been previously demonstrated, at 298 K, by experimental and theoretical research. In this work, a new comparative investigation of such reactions is performed for 3-buten-1-ol and 1-butene. The model assumes that the overall kinetics is governed by the first OH addition steps of the mechanism. Calculations have been performed at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets, and the rate coefficients have been determined on the basis of the microcanonical variational transition state theory. The rate coefficients obtained for the OH reactions with 3-buten-1-ol (kOH31BO) and 1-butene (kOH1B) at 298.15 K are lower than the experimental rate coefficient available in the literature, showing deviations of 18% and 25%, respectively. Negative temperature dependence is verified for these rate coefficients. The kOH31BO/kOH1B ratios have also been investigated as a function of the temperature, suggesting that at room temperature the unsaturated alcohol reacts with the OH radicals faster than 1-butene, by a factor of 1.2, but at higher temperatures (400–500 K), the alkene should react faster, and that the stabilization of prebarrier complexes and saddle points due to hydrogen bonds is no longer an important factor to govern the reactivity of the unsaturated alcohol toward OH radicals, with respect to the alkene analogue.
Fil: Peirone, Silvina Anahí. 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. Universidad Nacional de Córdoba. Rectorado. Centro Laser de Ciencias Moleculares; Argentina
Fil: Nieto, Jorge Daniel. Universidad Nacional de Córdoba. Rectorado. Centro Laser de Ciencias Moleculares; Argentina
Fil: Cometto, Pablo Marcelo. 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. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones y Transferencia de Villa María. Universidad Nacional de Villa María. Centro de Investigaciones y Transferencia de Villa María; Argentina
Fil: Barbosa, Thaís da Silva. Universidade Federal Rural do Rio de Janeiro; Brasil
Fil: Bauerfeldt, Glauco Favilla. Universidade Federal Rural do Rio de Janeiro; Brasil
Fil: Arbilla, Graciela. Universidade Federal do Rio de Janeiro; Brasil
Fil: Lane, Silvia Irene. 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 compared kinetics of the reactions of unsaturated alcohols and alkenes with OH radicals is a topic of great interest from both the theoretical chemistry and the atmospheric chemistry points of view. The enhanced reactivity of an unsaturated alcohol, with respect to its alkene analogue, toward OH radicals has been previously demonstrated, at 298 K, by experimental and theoretical research. In this work, a new comparative investigation of such reactions is performed for 3-buten-1-ol and 1-butene. The model assumes that the overall kinetics is governed by the first OH addition steps of the mechanism. Calculations have been performed at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets, and the rate coefficients have been determined on the basis of the microcanonical variational transition state theory. The rate coefficients obtained for the OH reactions with 3-buten-1-ol (kOH31BO) and 1-butene (kOH1B) at 298.15 K are lower than the experimental rate coefficient available in the literature, showing deviations of 18% and 25%, respectively. Negative temperature dependence is verified for these rate coefficients. The kOH31BO/kOH1B ratios have also been investigated as a function of the temperature, suggesting that at room temperature the unsaturated alcohol reacts with the OH radicals faster than 1-butene, by a factor of 1.2, but at higher temperatures (400–500 K), the alkene should react faster, and that the stabilization of prebarrier complexes and saddle points due to hydrogen bonds is no longer an important factor to govern the reactivity of the unsaturated alcohol toward OH radicals, with respect to the alkene analogue.
publishDate 2015
dc.date.none.fl_str_mv 2015-03-18
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/11336/44419
Peirone, Silvina Anahí; Nieto, Jorge Daniel; Cometto, Pablo Marcelo; Barbosa, Thaís da Silva; Bauerfeldt, Glauco Favilla; et al.; Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation; American Chemical Society; Journal of Physical Chemistry A; 119; 13; 18-3-2015; 3171-3180
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/44419
identifier_str_mv Peirone, Silvina Anahí; Nieto, Jorge Daniel; Cometto, Pablo Marcelo; Barbosa, Thaís da Silva; Bauerfeldt, Glauco Favilla; et al.; Comparative kinetics of the 3-Buten-1-ol and 1-Butene reactions with OH radicals: a density functional theory/RRKM investigation; American Chemical Society; Journal of Physical Chemistry A; 119; 13; 18-3-2015; 3171-3180
1089-5639
1520-5215
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/jp512544x
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp512544x
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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