Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure

Autores
Cardona, Alejandro L.; Gibilisco, Rodrigo Gastón; Blanco, Maria Belen; Wiesen, Peter; Teruel, Mariano Andres
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Relative rate coefficients and product distribution of the reaction of 2-butanethiol (2butSH) with OH radicals and Cl atoms were obtained at atmospheric pressure and 298 K. The experiments were performed in a 480 L borosilicate glass photoreactor in synthetic air coupled to a long path "in situ" FTIR spectrometer. The rate coefficients obtained by averaging the values from different experiments were: kOH = (2.58 ± 0.21) × 10-11 cm3 per molecule per s and kCl = (2.49 ± 0.19) × 10-10 cm3 per molecule per s. The kinetic values were compared with related alkyl thiols and homologous alkyl alcohols, where it was found that thiols react faster with both oxidants, OH radicals and Cl atoms. SO2 and 2-butanone were the major products identified for the reactions of 2-butanethiol with OH radicals and Cl atoms. The product yield of the reaction of 2-butanethiol and OH radicals were (81 ± 2)%, and (42 ± 1)% for SO2 and 2-butanone, respectively. For the reactions of 2-butanethiol with Cl atom, yields of SO2 and 2-butanone were (59 ± 2)% and (39 ± 2)%, respectively. A degradation mechanism was proposed for the pathways that leads to formation of identified products. The product distribution observed indicated that the H-atom of the S-H group abstraction channel is the main pathway for the reaction of OH radicals and Cl atoms with 2-butanethiol.
Fil: Cardona, Alejandro L.. 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: Gibilisco, Rodrigo Gastón. Bergische Universitat Wuppertal; Alemania. 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: Blanco, Maria Belen. 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: Wiesen, Peter. Bergische Universitat Wuppertal; Alemania
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
Materia
THIOLS
FTIR IN SITU
KINETICS
PRODUCTS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
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Consejo Nacional de Investigaciones Científicas y Técnicas
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oai:ri.conicet.gov.ar:11336/120844
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oai_identifier_str oai:ri.conicet.gov.ar:11336/120844
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressureCardona, Alejandro L.Gibilisco, Rodrigo GastónBlanco, Maria BelenWiesen, PeterTeruel, Mariano AndresTHIOLSFTIR IN SITUKINETICSPRODUCTShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Relative rate coefficients and product distribution of the reaction of 2-butanethiol (2butSH) with OH radicals and Cl atoms were obtained at atmospheric pressure and 298 K. The experiments were performed in a 480 L borosilicate glass photoreactor in synthetic air coupled to a long path "in situ" FTIR spectrometer. The rate coefficients obtained by averaging the values from different experiments were: kOH = (2.58 ± 0.21) × 10-11 cm3 per molecule per s and kCl = (2.49 ± 0.19) × 10-10 cm3 per molecule per s. The kinetic values were compared with related alkyl thiols and homologous alkyl alcohols, where it was found that thiols react faster with both oxidants, OH radicals and Cl atoms. SO2 and 2-butanone were the major products identified for the reactions of 2-butanethiol with OH radicals and Cl atoms. The product yield of the reaction of 2-butanethiol and OH radicals were (81 ± 2)%, and (42 ± 1)% for SO2 and 2-butanone, respectively. For the reactions of 2-butanethiol with Cl atom, yields of SO2 and 2-butanone were (59 ± 2)% and (39 ± 2)%, respectively. A degradation mechanism was proposed for the pathways that leads to formation of identified products. The product distribution observed indicated that the H-atom of the S-H group abstraction channel is the main pathway for the reaction of OH radicals and Cl atoms with 2-butanethiol.Fil: Cardona, Alejandro L.. 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: Gibilisco, Rodrigo Gastón. Bergische Universitat Wuppertal; Alemania. 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: Blanco, Maria Belen. 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: Wiesen, Peter. Bergische Universitat Wuppertal; AlemaniaFil: 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; ArgentinaRoyal Society of Chemistry2019-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/120844Cardona, Alejandro L.; Gibilisco, Rodrigo Gastón; Blanco, Maria Belen; Wiesen, Peter; Teruel, Mariano Andres; Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure; Royal Society of Chemistry; RSC Advances; 9; 39; 7-2019; 22618-226262046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c9ra04051jinfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2019/ra/c9ra04051j#!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 Técnicas2025-09-03T09:51:58Zoai:ri.conicet.gov.ar:11336/120844instacron: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:34982025-09-03 09:51:58.912CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
title Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
spellingShingle Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
Cardona, Alejandro L.
THIOLS
FTIR IN SITU
KINETICS
PRODUCTS
title_short Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
title_full Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
title_fullStr Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
title_full_unstemmed Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
title_sort Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
dc.creator.none.fl_str_mv Cardona, Alejandro L.
Gibilisco, Rodrigo Gastón
Blanco, Maria Belen
Wiesen, Peter
Teruel, Mariano Andres
author Cardona, Alejandro L.
author_facet Cardona, Alejandro L.
Gibilisco, Rodrigo Gastón
Blanco, Maria Belen
Wiesen, Peter
Teruel, Mariano Andres
author_role author
author2 Gibilisco, Rodrigo Gastón
Blanco, Maria Belen
Wiesen, Peter
Teruel, Mariano Andres
author2_role author
author
author
author
dc.subject.none.fl_str_mv THIOLS
FTIR IN SITU
KINETICS
PRODUCTS
topic THIOLS
FTIR IN SITU
KINETICS
PRODUCTS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Relative rate coefficients and product distribution of the reaction of 2-butanethiol (2butSH) with OH radicals and Cl atoms were obtained at atmospheric pressure and 298 K. The experiments were performed in a 480 L borosilicate glass photoreactor in synthetic air coupled to a long path "in situ" FTIR spectrometer. The rate coefficients obtained by averaging the values from different experiments were: kOH = (2.58 ± 0.21) × 10-11 cm3 per molecule per s and kCl = (2.49 ± 0.19) × 10-10 cm3 per molecule per s. The kinetic values were compared with related alkyl thiols and homologous alkyl alcohols, where it was found that thiols react faster with both oxidants, OH radicals and Cl atoms. SO2 and 2-butanone were the major products identified for the reactions of 2-butanethiol with OH radicals and Cl atoms. The product yield of the reaction of 2-butanethiol and OH radicals were (81 ± 2)%, and (42 ± 1)% for SO2 and 2-butanone, respectively. For the reactions of 2-butanethiol with Cl atom, yields of SO2 and 2-butanone were (59 ± 2)% and (39 ± 2)%, respectively. A degradation mechanism was proposed for the pathways that leads to formation of identified products. The product distribution observed indicated that the H-atom of the S-H group abstraction channel is the main pathway for the reaction of OH radicals and Cl atoms with 2-butanethiol.
Fil: Cardona, Alejandro L.. 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: Gibilisco, Rodrigo Gastón. Bergische Universitat Wuppertal; Alemania. 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: Blanco, Maria Belen. 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: Wiesen, Peter. Bergische Universitat Wuppertal; Alemania
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
description Relative rate coefficients and product distribution of the reaction of 2-butanethiol (2butSH) with OH radicals and Cl atoms were obtained at atmospheric pressure and 298 K. The experiments were performed in a 480 L borosilicate glass photoreactor in synthetic air coupled to a long path "in situ" FTIR spectrometer. The rate coefficients obtained by averaging the values from different experiments were: kOH = (2.58 ± 0.21) × 10-11 cm3 per molecule per s and kCl = (2.49 ± 0.19) × 10-10 cm3 per molecule per s. The kinetic values were compared with related alkyl thiols and homologous alkyl alcohols, where it was found that thiols react faster with both oxidants, OH radicals and Cl atoms. SO2 and 2-butanone were the major products identified for the reactions of 2-butanethiol with OH radicals and Cl atoms. The product yield of the reaction of 2-butanethiol and OH radicals were (81 ± 2)%, and (42 ± 1)% for SO2 and 2-butanone, respectively. For the reactions of 2-butanethiol with Cl atom, yields of SO2 and 2-butanone were (59 ± 2)% and (39 ± 2)%, respectively. A degradation mechanism was proposed for the pathways that leads to formation of identified products. The product distribution observed indicated that the H-atom of the S-H group abstraction channel is the main pathway for the reaction of OH radicals and Cl atoms with 2-butanethiol.
publishDate 2019
dc.date.none.fl_str_mv 2019-07
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/11336/120844
Cardona, Alejandro L.; Gibilisco, Rodrigo Gastón; Blanco, Maria Belen; Wiesen, Peter; Teruel, Mariano Andres; Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure; Royal Society of Chemistry; RSC Advances; 9; 39; 7-2019; 22618-22626
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/120844
identifier_str_mv Cardona, Alejandro L.; Gibilisco, Rodrigo Gastón; Blanco, Maria Belen; Wiesen, Peter; Teruel, Mariano Andres; Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure; Royal Society of Chemistry; RSC Advances; 9; 39; 7-2019; 22618-22626
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/c9ra04051j
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2019/ra/c9ra04051j#!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
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 13.13397

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