Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue

Autores
Da Silva Barbosa, Thais; Nieto, Jorge Daniel; Cometto, Pablo Marcelo; Lane, Silvia Irene; Bauerfeldt, Glauco Favilla
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, the first and rate determining steps on the mechanism of the OH addition to 2-methyl-2-propen-1-ol (MPO221) and methylpropene (M2) have been studied at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets. The thermochemical properties of equilibrium (enthalpy, entropy and Gibbs free energies) have been determined within the conventional statistical thermodynamics relations and the rate coefficients have been determined on the basis of the variational transition state theory. The adoption of the microcanonical variational transition state theory was proved to be crucial for the description of the kinetics of OH addition to these unsaturated compounds. The rate coefficients obtained for the OH reactions with MPO221 and M2 at 298.15K deviate, respectively, 27% and 13% from the experimental rate coefficient available in the literature. A non-Arrhenius profile is observed for the rate coefficients. Moreover, the values of the rate coefficients for the MPO221 + OH reaction are greater than those for the M2 + OH reaction, suggesting that the substitution of the hydrogen atom in an alkene by the ?OH functional group, increases the reactivity in respect to the hydroxyl radical.
Fil: Da Silva Barbosa, Thais. Departamento de Físico-química, Instituto de Química; Brasil
Fil: Nieto, Jorge Daniel. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
Fil: Cometto, Pablo Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
Fil: Bauerfeldt, Glauco Favilla. Universidade Federal Rural Do Rio de Janeiro; Brasil. Departamento de Química, Instituto de Ciencias Exatas; Brasil
Materia
TRANSITION STATE THEORY
DFT
OH RADICAL
VOLATILE ORGANIC 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:11336/103866
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/103866
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogueDa Silva Barbosa, ThaisNieto, Jorge DanielCometto, Pablo MarceloLane, Silvia IreneBauerfeldt, Glauco FavillaTRANSITION STATE THEORYDFTOH RADICALVOLATILE ORGANIC COMPOUNDShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In this work, the first and rate determining steps on the mechanism of the OH addition to 2-methyl-2-propen-1-ol (MPO221) and methylpropene (M2) have been studied at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets. The thermochemical properties of equilibrium (enthalpy, entropy and Gibbs free energies) have been determined within the conventional statistical thermodynamics relations and the rate coefficients have been determined on the basis of the variational transition state theory. The adoption of the microcanonical variational transition state theory was proved to be crucial for the description of the kinetics of OH addition to these unsaturated compounds. The rate coefficients obtained for the OH reactions with MPO221 and M2 at 298.15K deviate, respectively, 27% and 13% from the experimental rate coefficient available in the literature. A non-Arrhenius profile is observed for the rate coefficients. Moreover, the values of the rate coefficients for the MPO221 + OH reaction are greater than those for the M2 + OH reaction, suggesting that the substitution of the hydrogen atom in an alkene by the ?OH functional group, increases the reactivity in respect to the hydroxyl radical.Fil: Da Silva Barbosa, Thais. Departamento de Físico-química, Instituto de Química; BrasilFil: Nieto, Jorge Daniel. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: Cometto, Pablo Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: 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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; ArgentinaFil: Bauerfeldt, Glauco Favilla. Universidade Federal Rural Do Rio de Janeiro; Brasil. Departamento de Química, Instituto de Ciencias Exatas; BrasilRoyal Society of Chemistry2014-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/103866Da Silva Barbosa, Thais; Nieto, Jorge Daniel; Cometto, Pablo Marcelo; Lane, Silvia Irene; Bauerfeldt, Glauco Favilla; Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue; Royal Society of Chemistry; Royal Society of Chemistry Advances; 4; 4-2014; 20830-208402046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c4ra00695jinfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2014/RA/C4RA00695J#!divAbstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:27:08Zoai:ri.conicet.gov.ar:11336/103866instacron: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 11:27:09.188CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue
title Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue
spellingShingle Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue
Da Silva Barbosa, Thais
TRANSITION STATE THEORY
DFT
OH RADICAL
VOLATILE ORGANIC COMPOUNDS
title_short Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue
title_full Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue
title_fullStr Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue
title_full_unstemmed Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue
title_sort Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue
dc.creator.none.fl_str_mv Da Silva Barbosa, Thais
Nieto, Jorge Daniel
Cometto, Pablo Marcelo
Lane, Silvia Irene
Bauerfeldt, Glauco Favilla
author Da Silva Barbosa, Thais
author_facet Da Silva Barbosa, Thais
Nieto, Jorge Daniel
Cometto, Pablo Marcelo
Lane, Silvia Irene
Bauerfeldt, Glauco Favilla
author_role author
author2 Nieto, Jorge Daniel
Cometto, Pablo Marcelo
Lane, Silvia Irene
Bauerfeldt, Glauco Favilla
author2_role author
author
author
author
dc.subject.none.fl_str_mv TRANSITION STATE THEORY
DFT
OH RADICAL
VOLATILE ORGANIC COMPOUNDS
topic TRANSITION STATE THEORY
DFT
OH RADICAL
VOLATILE ORGANIC 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 In this work, the first and rate determining steps on the mechanism of the OH addition to 2-methyl-2-propen-1-ol (MPO221) and methylpropene (M2) have been studied at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets. The thermochemical properties of equilibrium (enthalpy, entropy and Gibbs free energies) have been determined within the conventional statistical thermodynamics relations and the rate coefficients have been determined on the basis of the variational transition state theory. The adoption of the microcanonical variational transition state theory was proved to be crucial for the description of the kinetics of OH addition to these unsaturated compounds. The rate coefficients obtained for the OH reactions with MPO221 and M2 at 298.15K deviate, respectively, 27% and 13% from the experimental rate coefficient available in the literature. A non-Arrhenius profile is observed for the rate coefficients. Moreover, the values of the rate coefficients for the MPO221 + OH reaction are greater than those for the M2 + OH reaction, suggesting that the substitution of the hydrogen atom in an alkene by the ?OH functional group, increases the reactivity in respect to the hydroxyl radical.
Fil: Da Silva Barbosa, Thais. Departamento de Físico-química, Instituto de Química; Brasil
Fil: Nieto, Jorge Daniel. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
Fil: Cometto, Pablo Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
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. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina
Fil: Bauerfeldt, Glauco Favilla. Universidade Federal Rural Do Rio de Janeiro; Brasil. Departamento de Química, Instituto de Ciencias Exatas; Brasil
description In this work, the first and rate determining steps on the mechanism of the OH addition to 2-methyl-2-propen-1-ol (MPO221) and methylpropene (M2) have been studied at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets. The thermochemical properties of equilibrium (enthalpy, entropy and Gibbs free energies) have been determined within the conventional statistical thermodynamics relations and the rate coefficients have been determined on the basis of the variational transition state theory. The adoption of the microcanonical variational transition state theory was proved to be crucial for the description of the kinetics of OH addition to these unsaturated compounds. The rate coefficients obtained for the OH reactions with MPO221 and M2 at 298.15K deviate, respectively, 27% and 13% from the experimental rate coefficient available in the literature. A non-Arrhenius profile is observed for the rate coefficients. Moreover, the values of the rate coefficients for the MPO221 + OH reaction are greater than those for the M2 + OH reaction, suggesting that the substitution of the hydrogen atom in an alkene by the ?OH functional group, increases the reactivity in respect to the hydroxyl radical.
publishDate 2014
dc.date.none.fl_str_mv 2014-04
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/11336/103866
Da Silva Barbosa, Thais; Nieto, Jorge Daniel; Cometto, Pablo Marcelo; Lane, Silvia Irene; Bauerfeldt, Glauco Favilla; Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue; Royal Society of Chemistry; Royal Society of Chemistry Advances; 4; 4-2014; 20830-20840
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/103866
identifier_str_mv Da Silva Barbosa, Thais; Nieto, Jorge Daniel; Cometto, Pablo Marcelo; Lane, Silvia Irene; Bauerfeldt, Glauco Favilla; Theoretical calculations of the kinetics of the oh reaction with 2-methyl-2-propen-1-ol and its alkene analogue; Royal Society of Chemistry; Royal Society of Chemistry Advances; 4; 4-2014; 20830-20840
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/c4ra00695j
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2014/RA/C4RA00695J#!divAbstract
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
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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