Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air

Autores
Gibilisco, Rodrigo Gastón; Uranga, Jorge Gustavo; Santiago, Ana Noemi; Teruel, Mariano Andres
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The product distribution of the gas-phase reaction of OH radicals with methyl methacrylate (CH2═C(CH3)C(O)OCH3, MMA) in the absence of NOx was studied at 298 K and atmospheric pressure of air. The experiments were performed in a Teflon chamber using solid-phase microextraction (SPME) with GC–MS and GC–FID for product identification and quantification, respectively. In the absence of NOx, methyl pyruvate (CH3C(O)C(O)OCH3) was identified with a yield of 76 ± 13% in accordance with the decomposition of the 1,2-hydroxyalkoxy radicals formed. In addition, a detailed quantum chemical study of the degradation of MMA was performed by density functional theory (DFT) methods using the MPWB1K functional. This calculation suggests that formation of methyl pyruvate, from C1–C2 scission of 1,2-hydroxyalkoxy radical, is kinetically and thermodynamically the most favorable reaction path taking into account the electronic properties of reaction intermediates and transition states. The difference observed on the degradation mechanism of MMA in the presence and absence of NOx was explained in terms of the associated thermochemistry. Furthermore, this study propose that reaction between peroxy radical (RO2•) and hydroxyl radical (OH) became relevant at NOx-free environments. This statement is in agreement with recent studies concerning small peroxy radicals such as CH3OO•.
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: Uranga, Jorge Gustavo. 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: Santiago, Ana Noemi. 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
Spme Gas-Phase Reaction
Methyl Methacrylate
Density Functional Theory
Peroxy Radical
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:11336/47376
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/47376
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free airGibilisco, Rodrigo GastónUranga, Jorge GustavoSantiago, Ana NoemiTeruel, Mariano AndresSpme Gas-Phase ReactionMethyl MethacrylateDensity Functional TheoryPeroxy Radicalhttps://purl.org/becyt/ford/1.5https://purl.org/becyt/ford/1The product distribution of the gas-phase reaction of OH radicals with methyl methacrylate (CH2═C(CH3)C(O)OCH3, MMA) in the absence of NOx was studied at 298 K and atmospheric pressure of air. The experiments were performed in a Teflon chamber using solid-phase microextraction (SPME) with GC–MS and GC–FID for product identification and quantification, respectively. In the absence of NOx, methyl pyruvate (CH3C(O)C(O)OCH3) was identified with a yield of 76 ± 13% in accordance with the decomposition of the 1,2-hydroxyalkoxy radicals formed. In addition, a detailed quantum chemical study of the degradation of MMA was performed by density functional theory (DFT) methods using the MPWB1K functional. This calculation suggests that formation of methyl pyruvate, from C1–C2 scission of 1,2-hydroxyalkoxy radical, is kinetically and thermodynamically the most favorable reaction path taking into account the electronic properties of reaction intermediates and transition states. The difference observed on the degradation mechanism of MMA in the presence and absence of NOx was explained in terms of the associated thermochemistry. Furthermore, this study propose that reaction between peroxy radical (RO2•) and hydroxyl radical (OH) became relevant at NOx-free environments. This statement is in agreement with recent studies concerning small peroxy radicals such as CH3OO•.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: Uranga, Jorge Gustavo. 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: Santiago, Ana Noemi. 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; ArgentinaAmerican Chemical Society2015-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/47376Gibilisco, Rodrigo Gastón; Uranga, Jorge Gustavo; Santiago, Ana Noemi; Teruel, Mariano Andres; Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air; American Chemical Society; Journal of Physical Chemistry A; 119; 33; 7-2015; 8775-87831089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpca.5b04273info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.5b04273info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:07:10Zoai:ri.conicet.gov.ar:11336/47376instacron: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 10:07:10.293CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air
title Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air
spellingShingle Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air
Gibilisco, Rodrigo Gastón
Spme Gas-Phase Reaction
Methyl Methacrylate
Density Functional Theory
Peroxy Radical
title_short Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air
title_full Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air
title_fullStr Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air
title_full_unstemmed Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air
title_sort Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air
dc.creator.none.fl_str_mv Gibilisco, Rodrigo Gastón
Uranga, Jorge Gustavo
Santiago, Ana Noemi
Teruel, Mariano Andres
author Gibilisco, Rodrigo Gastón
author_facet Gibilisco, Rodrigo Gastón
Uranga, Jorge Gustavo
Santiago, Ana Noemi
Teruel, Mariano Andres
author_role author
author2 Uranga, Jorge Gustavo
Santiago, Ana Noemi
Teruel, Mariano Andres
author2_role author
author
author
dc.subject.none.fl_str_mv Spme Gas-Phase Reaction
Methyl Methacrylate
Density Functional Theory
Peroxy Radical
topic Spme Gas-Phase Reaction
Methyl Methacrylate
Density Functional Theory
Peroxy Radical
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The product distribution of the gas-phase reaction of OH radicals with methyl methacrylate (CH2═C(CH3)C(O)OCH3, MMA) in the absence of NOx was studied at 298 K and atmospheric pressure of air. The experiments were performed in a Teflon chamber using solid-phase microextraction (SPME) with GC–MS and GC–FID for product identification and quantification, respectively. In the absence of NOx, methyl pyruvate (CH3C(O)C(O)OCH3) was identified with a yield of 76 ± 13% in accordance with the decomposition of the 1,2-hydroxyalkoxy radicals formed. In addition, a detailed quantum chemical study of the degradation of MMA was performed by density functional theory (DFT) methods using the MPWB1K functional. This calculation suggests that formation of methyl pyruvate, from C1–C2 scission of 1,2-hydroxyalkoxy radical, is kinetically and thermodynamically the most favorable reaction path taking into account the electronic properties of reaction intermediates and transition states. The difference observed on the degradation mechanism of MMA in the presence and absence of NOx was explained in terms of the associated thermochemistry. Furthermore, this study propose that reaction between peroxy radical (RO2•) and hydroxyl radical (OH) became relevant at NOx-free environments. This statement is in agreement with recent studies concerning small peroxy radicals such as CH3OO•.
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: Uranga, Jorge Gustavo. 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: Santiago, Ana Noemi. 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 product distribution of the gas-phase reaction of OH radicals with methyl methacrylate (CH2═C(CH3)C(O)OCH3, MMA) in the absence of NOx was studied at 298 K and atmospheric pressure of air. The experiments were performed in a Teflon chamber using solid-phase microextraction (SPME) with GC–MS and GC–FID for product identification and quantification, respectively. In the absence of NOx, methyl pyruvate (CH3C(O)C(O)OCH3) was identified with a yield of 76 ± 13% in accordance with the decomposition of the 1,2-hydroxyalkoxy radicals formed. In addition, a detailed quantum chemical study of the degradation of MMA was performed by density functional theory (DFT) methods using the MPWB1K functional. This calculation suggests that formation of methyl pyruvate, from C1–C2 scission of 1,2-hydroxyalkoxy radical, is kinetically and thermodynamically the most favorable reaction path taking into account the electronic properties of reaction intermediates and transition states. The difference observed on the degradation mechanism of MMA in the presence and absence of NOx was explained in terms of the associated thermochemistry. Furthermore, this study propose that reaction between peroxy radical (RO2•) and hydroxyl radical (OH) became relevant at NOx-free environments. This statement is in agreement with recent studies concerning small peroxy radicals such as CH3OO•.
publishDate 2015
dc.date.none.fl_str_mv 2015-07
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/11336/47376
Gibilisco, Rodrigo Gastón; Uranga, Jorge Gustavo; Santiago, Ana Noemi; Teruel, Mariano Andres; Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air; American Chemical Society; Journal of Physical Chemistry A; 119; 33; 7-2015; 8775-8783
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/47376
identifier_str_mv Gibilisco, Rodrigo Gastón; Uranga, Jorge Gustavo; Santiago, Ana Noemi; Teruel, Mariano Andres; Atmospheric degradation of CH2C(CH3)C(O)OCH3 initiated by OH radicals: Mechanistic study and quantification of CH3C(O)C(O)OCH3 in NOx free air; American Chemical Society; Journal of Physical Chemistry A; 119; 33; 7-2015; 8775-8783
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/acs.jpca.5b04273
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.5b04273
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
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 13.13397

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