OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms

Autores
Straccia Cepeda, Vianni Giovanna; Blanco, Maria Belen; Teruel, Mariano Andres
Año de publicación
2023
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The relative rate coefficients of the gas-phase reaction of amyl acetate, (AA), CH3COO(CH2)4CH3 with OH radicals and Cl atoms were determined at (298 ± 2) K and 1000 mbar of pressure. The experiments were developed in two different atmospheric Pyrex chambers coupled with “in situ” Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography equipped with flame ionization detection (GC-FID). The rate coefficients obtained from the average of different experiments were (in units of cm3 molecule−1 s−1): kAA+OH-FTIR = (6.00 ± 0.96) × 10−12; kAA+OH-GC-FID = (6.37 ± 1.50) × 10−12 and kAA+Cl-GC-FID = (1.35 ± 0.14) × 10−10. Additionally, product studies were completed for the Cl-initiated oxidation of AA, in similar conditions of the kinetic experiments by Gas Chromatography coupled with a mass detector (GC-MS) with Solid Phase Micro Extraction (SPME). Acetic acid, formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde were the main products identified. Complementary Structure Activity Relationships (SAR) were developed to compare with the experimental kinetic results and to clarify the individual reactivity sites of the ester. The atmospheric oxidation pathways of the AA are postulated and discussed taking into account the observed products and the SAR estimations. The initial pathway for the degradation of AA initiated by Cl atoms and OH radicals occurs via H-atom abstraction at -C(O)OCH2- (C1); -CH2- (C2); -CH2- (C3); and -CH2CH3- (C4) moieties. The atmospheric implications of the reactions studied were evaluated by the estimation of their tropospheric lifetimes toward OH radicals and Cl atoms to be: τOH = 22 and τCl = 62 hours. Consequently, the estimated average ozone production ([O3] = 2.15) suggests a potential contribution of these compounds emission to the formation of photochemical smog. On the other hand, the Photochemical Ozone Creation Potential (POCP) for AA was calculated to be POCP = 70.2. A moderate risk of photochemical smog production suggests that this ester could be harmful to the health and the biota in urban environments.
Fil: Straccia Cepeda, Vianni Giovanna. 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: 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
Esteres insaturados
FTIR in situ
Mecanismos Químicos Atmosféricos
Reactividad en fase gaseosa
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:11336/226852
Acceder
id CONICETDig_45aed1c99e4cf7cb0b4a604c9c1b4c7e
oai_identifier_str oai:ri.conicet.gov.ar:11336/226852
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanismsStraccia Cepeda, Vianni GiovannaBlanco, Maria BelenTeruel, Mariano AndresEsteres insaturadosFTIR in situMecanismos Químicos AtmosféricosReactividad en fase gaseosahttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The relative rate coefficients of the gas-phase reaction of amyl acetate, (AA), CH3COO(CH2)4CH3 with OH radicals and Cl atoms were determined at (298 ± 2) K and 1000 mbar of pressure. The experiments were developed in two different atmospheric Pyrex chambers coupled with “in situ” Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography equipped with flame ionization detection (GC-FID). The rate coefficients obtained from the average of different experiments were (in units of cm3 molecule−1 s−1): kAA+OH-FTIR = (6.00 ± 0.96) × 10−12; kAA+OH-GC-FID = (6.37 ± 1.50) × 10−12 and kAA+Cl-GC-FID = (1.35 ± 0.14) × 10−10. Additionally, product studies were completed for the Cl-initiated oxidation of AA, in similar conditions of the kinetic experiments by Gas Chromatography coupled with a mass detector (GC-MS) with Solid Phase Micro Extraction (SPME). Acetic acid, formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde were the main products identified. Complementary Structure Activity Relationships (SAR) were developed to compare with the experimental kinetic results and to clarify the individual reactivity sites of the ester. The atmospheric oxidation pathways of the AA are postulated and discussed taking into account the observed products and the SAR estimations. The initial pathway for the degradation of AA initiated by Cl atoms and OH radicals occurs via H-atom abstraction at -C(O)OCH2- (C1); -CH2- (C2); -CH2- (C3); and -CH2CH3- (C4) moieties. The atmospheric implications of the reactions studied were evaluated by the estimation of their tropospheric lifetimes toward OH radicals and Cl atoms to be: τOH = 22 and τCl = 62 hours. Consequently, the estimated average ozone production ([O3] = 2.15) suggests a potential contribution of these compounds emission to the formation of photochemical smog. On the other hand, the Photochemical Ozone Creation Potential (POCP) for AA was calculated to be POCP = 70.2. A moderate risk of photochemical smog production suggests that this ester could be harmful to the health and the biota in urban environments.Fil: Straccia Cepeda, Vianni Giovanna. 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: 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 Chemistry2023-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/226852Straccia Cepeda, Vianni Giovanna; Blanco, Maria Belen; Teruel, Mariano Andres; OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 10; 8-2023; 1485-14962634-3606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2023/EA/D3EA00082Finfo:eu-repo/semantics/altIdentifier/doi/10.1039/D3EA00082Finfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:45:43Zoai:ri.conicet.gov.ar:11336/226852instacron: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 09:45:44.058CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms
title OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms
spellingShingle OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms
Straccia Cepeda, Vianni Giovanna
Esteres insaturados
FTIR in situ
Mecanismos Químicos Atmosféricos
Reactividad en fase gaseosa
title_short OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms
title_full OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms
title_fullStr OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms
title_full_unstemmed OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms
title_sort OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms
dc.creator.none.fl_str_mv Straccia Cepeda, Vianni Giovanna
Blanco, Maria Belen
Teruel, Mariano Andres
author Straccia Cepeda, Vianni Giovanna
author_facet Straccia Cepeda, Vianni Giovanna
Blanco, Maria Belen
Teruel, Mariano Andres
author_role author
author2 Blanco, Maria Belen
Teruel, Mariano Andres
author2_role author
author
dc.subject.none.fl_str_mv Esteres insaturados
FTIR in situ
Mecanismos Químicos Atmosféricos
Reactividad en fase gaseosa
topic Esteres insaturados
FTIR in situ
Mecanismos Químicos Atmosféricos
Reactividad en fase gaseosa
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 relative rate coefficients of the gas-phase reaction of amyl acetate, (AA), CH3COO(CH2)4CH3 with OH radicals and Cl atoms were determined at (298 ± 2) K and 1000 mbar of pressure. The experiments were developed in two different atmospheric Pyrex chambers coupled with “in situ” Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography equipped with flame ionization detection (GC-FID). The rate coefficients obtained from the average of different experiments were (in units of cm3 molecule−1 s−1): kAA+OH-FTIR = (6.00 ± 0.96) × 10−12; kAA+OH-GC-FID = (6.37 ± 1.50) × 10−12 and kAA+Cl-GC-FID = (1.35 ± 0.14) × 10−10. Additionally, product studies were completed for the Cl-initiated oxidation of AA, in similar conditions of the kinetic experiments by Gas Chromatography coupled with a mass detector (GC-MS) with Solid Phase Micro Extraction (SPME). Acetic acid, formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde were the main products identified. Complementary Structure Activity Relationships (SAR) were developed to compare with the experimental kinetic results and to clarify the individual reactivity sites of the ester. The atmospheric oxidation pathways of the AA are postulated and discussed taking into account the observed products and the SAR estimations. The initial pathway for the degradation of AA initiated by Cl atoms and OH radicals occurs via H-atom abstraction at -C(O)OCH2- (C1); -CH2- (C2); -CH2- (C3); and -CH2CH3- (C4) moieties. The atmospheric implications of the reactions studied were evaluated by the estimation of their tropospheric lifetimes toward OH radicals and Cl atoms to be: τOH = 22 and τCl = 62 hours. Consequently, the estimated average ozone production ([O3] = 2.15) suggests a potential contribution of these compounds emission to the formation of photochemical smog. On the other hand, the Photochemical Ozone Creation Potential (POCP) for AA was calculated to be POCP = 70.2. A moderate risk of photochemical smog production suggests that this ester could be harmful to the health and the biota in urban environments.
Fil: Straccia Cepeda, Vianni Giovanna. 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: 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 The relative rate coefficients of the gas-phase reaction of amyl acetate, (AA), CH3COO(CH2)4CH3 with OH radicals and Cl atoms were determined at (298 ± 2) K and 1000 mbar of pressure. The experiments were developed in two different atmospheric Pyrex chambers coupled with “in situ” Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography equipped with flame ionization detection (GC-FID). The rate coefficients obtained from the average of different experiments were (in units of cm3 molecule−1 s−1): kAA+OH-FTIR = (6.00 ± 0.96) × 10−12; kAA+OH-GC-FID = (6.37 ± 1.50) × 10−12 and kAA+Cl-GC-FID = (1.35 ± 0.14) × 10−10. Additionally, product studies were completed for the Cl-initiated oxidation of AA, in similar conditions of the kinetic experiments by Gas Chromatography coupled with a mass detector (GC-MS) with Solid Phase Micro Extraction (SPME). Acetic acid, formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde were the main products identified. Complementary Structure Activity Relationships (SAR) were developed to compare with the experimental kinetic results and to clarify the individual reactivity sites of the ester. The atmospheric oxidation pathways of the AA are postulated and discussed taking into account the observed products and the SAR estimations. The initial pathway for the degradation of AA initiated by Cl atoms and OH radicals occurs via H-atom abstraction at -C(O)OCH2- (C1); -CH2- (C2); -CH2- (C3); and -CH2CH3- (C4) moieties. The atmospheric implications of the reactions studied were evaluated by the estimation of their tropospheric lifetimes toward OH radicals and Cl atoms to be: τOH = 22 and τCl = 62 hours. Consequently, the estimated average ozone production ([O3] = 2.15) suggests a potential contribution of these compounds emission to the formation of photochemical smog. On the other hand, the Photochemical Ozone Creation Potential (POCP) for AA was calculated to be POCP = 70.2. A moderate risk of photochemical smog production suggests that this ester could be harmful to the health and the biota in urban environments.
publishDate 2023
dc.date.none.fl_str_mv 2023-08
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/11336/226852
Straccia Cepeda, Vianni Giovanna; Blanco, Maria Belen; Teruel, Mariano Andres; OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 10; 8-2023; 1485-1496
2634-3606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/226852
identifier_str_mv Straccia Cepeda, Vianni Giovanna; Blanco, Maria Belen; Teruel, Mariano Andres; OH and Cl radicals initiated oxidation of Amyl Acetate under atmospheric conditions: Kinetics, products and mechanisms; Royal Society of Chemistry; Environmental Science: Atmospheres; 3; 10; 8-2023; 1485-1496
2634-3606
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/2023/EA/D3EA00082F
info:eu-repo/semantics/altIdentifier/doi/10.1039/D3EA00082F
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
_version_ 1842268748439879680
score 13.13397

Publicaciones similares