Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue

Autores
Gibilisco, Rodrigo Gastón; Kieninger, Martina; Teruel, Mariano Andres; Ventura, Oscar
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The rate coefficient for the reaction of propargyl alcohol (2-propyn-1-ol, 2P1OL) with OH radicals has been determined using gas chromatography with a flame ionization detector (GC/FID) at 298 K and atmospheric pressure. The experimental value obtained by the relative method using methyl methacrylate and butyl acrylate as references was (2.05 ± 0.30) × 10−11 cm3 per molecule per s. The present value was compared with previous determinations and a theoretical study of the reaction was performed in order to explain the differences in reactivity of the alcohol with that of the corresponding alkyne (propyne, P). A full discussion of the addition and abstraction mechanisms was developed for 2P1OL at the density functional and ab initio composite model levels. It was found that addition is much faster than abstraction for propyne but occurs at approximately the same rate for 2P1OL. In this last case, however, abstraction of hydrogen from the C1 carbon leads to a complex which can react further to yield addition products. Thermodynamic and kinetic data calculated for these reactions suggest that the products would be the 1,2- and 1,3-propanediol radicals. These products would react further with O2, in the case where it is present in the reaction mixture.
Fil: Gibilisco, Rodrigo Gastón. 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: Kieninger, Martina. Universidad de la República; Uruguay
Fil: Teruel, Mariano Andres. 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: Ventura, Oscar. Universidad de la República; Uruguay
Materia
Addition Mechanisms
Abstraction Mechanisms
Thermodynamic Data
Kinetic Data
Propargyl Alcohol
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/47442
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogueGibilisco, Rodrigo GastónKieninger, MartinaTeruel, Mariano AndresVentura, OscarAddition MechanismsAbstraction MechanismsThermodynamic DataKinetic DataPropargyl Alcoholhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The rate coefficient for the reaction of propargyl alcohol (2-propyn-1-ol, 2P1OL) with OH radicals has been determined using gas chromatography with a flame ionization detector (GC/FID) at 298 K and atmospheric pressure. The experimental value obtained by the relative method using methyl methacrylate and butyl acrylate as references was (2.05 ± 0.30) × 10−11 cm3 per molecule per s. The present value was compared with previous determinations and a theoretical study of the reaction was performed in order to explain the differences in reactivity of the alcohol with that of the corresponding alkyne (propyne, P). A full discussion of the addition and abstraction mechanisms was developed for 2P1OL at the density functional and ab initio composite model levels. It was found that addition is much faster than abstraction for propyne but occurs at approximately the same rate for 2P1OL. In this last case, however, abstraction of hydrogen from the C1 carbon leads to a complex which can react further to yield addition products. Thermodynamic and kinetic data calculated for these reactions suggest that the products would be the 1,2- and 1,3-propanediol radicals. These products would react further with O2, in the case where it is present in the reaction mixture.Fil: Gibilisco, Rodrigo Gastón. 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: Kieninger, Martina. Universidad de la República; UruguayFil: Teruel, Mariano Andres. 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: Ventura, Oscar. Universidad de la República; UruguayRoyal Society of Chemistry2015-12-07info: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/11336/47442Gibilisco, Rodrigo Gastón; Kieninger, Martina; Teruel, Mariano Andres; Ventura, Oscar; Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue; Royal Society of Chemistry; RSC Advances; 5; 129; 7-12-2015; 106668-1066792046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/C5RA19432Finfo:eu-repo/semantics/altIdentifier/doi/10.1039/c5ra19432finfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:13:50Zoai:ri.conicet.gov.ar:11336/47442instacron: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 10:13:50.372CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue
title Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue
spellingShingle Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue
Gibilisco, Rodrigo Gastón
Addition Mechanisms
Abstraction Mechanisms
Thermodynamic Data
Kinetic Data
Propargyl Alcohol
title_short Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue
title_full Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue
title_fullStr Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue
title_full_unstemmed Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue
title_sort Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue
dc.creator.none.fl_str_mv Gibilisco, Rodrigo Gastón
Kieninger, Martina
Teruel, Mariano Andres
Ventura, Oscar
author Gibilisco, Rodrigo Gastón
author_facet Gibilisco, Rodrigo Gastón
Kieninger, Martina
Teruel, Mariano Andres
Ventura, Oscar
author_role author
author2 Kieninger, Martina
Teruel, Mariano Andres
Ventura, Oscar
author2_role author
author
author
dc.subject.none.fl_str_mv Addition Mechanisms
Abstraction Mechanisms
Thermodynamic Data
Kinetic Data
Propargyl Alcohol
topic Addition Mechanisms
Abstraction Mechanisms
Thermodynamic Data
Kinetic Data
Propargyl Alcohol
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 reaction of propargyl alcohol (2-propyn-1-ol, 2P1OL) with OH radicals has been determined using gas chromatography with a flame ionization detector (GC/FID) at 298 K and atmospheric pressure. The experimental value obtained by the relative method using methyl methacrylate and butyl acrylate as references was (2.05 ± 0.30) × 10−11 cm3 per molecule per s. The present value was compared with previous determinations and a theoretical study of the reaction was performed in order to explain the differences in reactivity of the alcohol with that of the corresponding alkyne (propyne, P). A full discussion of the addition and abstraction mechanisms was developed for 2P1OL at the density functional and ab initio composite model levels. It was found that addition is much faster than abstraction for propyne but occurs at approximately the same rate for 2P1OL. In this last case, however, abstraction of hydrogen from the C1 carbon leads to a complex which can react further to yield addition products. Thermodynamic and kinetic data calculated for these reactions suggest that the products would be the 1,2- and 1,3-propanediol radicals. These products would react further with O2, in the case where it is present in the reaction mixture.
Fil: Gibilisco, Rodrigo Gastón. 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: Kieninger, Martina. Universidad de la República; Uruguay
Fil: Teruel, Mariano Andres. 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: Ventura, Oscar. Universidad de la República; Uruguay
description The rate coefficient for the reaction of propargyl alcohol (2-propyn-1-ol, 2P1OL) with OH radicals has been determined using gas chromatography with a flame ionization detector (GC/FID) at 298 K and atmospheric pressure. The experimental value obtained by the relative method using methyl methacrylate and butyl acrylate as references was (2.05 ± 0.30) × 10−11 cm3 per molecule per s. The present value was compared with previous determinations and a theoretical study of the reaction was performed in order to explain the differences in reactivity of the alcohol with that of the corresponding alkyne (propyne, P). A full discussion of the addition and abstraction mechanisms was developed for 2P1OL at the density functional and ab initio composite model levels. It was found that addition is much faster than abstraction for propyne but occurs at approximately the same rate for 2P1OL. In this last case, however, abstraction of hydrogen from the C1 carbon leads to a complex which can react further to yield addition products. Thermodynamic and kinetic data calculated for these reactions suggest that the products would be the 1,2- and 1,3-propanediol radicals. These products would react further with O2, in the case where it is present in the reaction mixture.
publishDate 2015
dc.date.none.fl_str_mv 2015-12-07
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/11336/47442
Gibilisco, Rodrigo Gastón; Kieninger, Martina; Teruel, Mariano Andres; Ventura, Oscar; Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue; Royal Society of Chemistry; RSC Advances; 5; 129; 7-12-2015; 106668-106679
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/47442
identifier_str_mv Gibilisco, Rodrigo Gastón; Kieninger, Martina; Teruel, Mariano Andres; Ventura, Oscar; Atmospheric reactivity of HC≡CCH2OH (2-propyn-1-ol) toward OH radical: Experimental determination and theoretical comparison with its alkyne analogue; Royal Society of Chemistry; RSC Advances; 5; 129; 7-12-2015; 106668-106679
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/url/http://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/C5RA19432F
info:eu-repo/semantics/altIdentifier/doi/10.1039/c5ra19432f
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/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 13.070432

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