Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study

Autores
Murillo, Juliana; Henao Arboleda, Diana Patricia; Vélez, Ederley; Castaño Espinal, Diana Carolina; Quijano, Jairo; Gaviria, Jair; Zapata, Edilma
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The mechanism of thermal decomposition of 4-hydroxy-2-butanone in m-xylene solution was studied experimentally and theoretically at the M05-2X/6-31G(d, p) level of theory. It follows first-order kinetics and appears to be homogeneous and unimolecular. The proposed mechanism is via a six-membered cyclic transition state to give a mixture of formaldehyde and acetone. Rate constant values were experimentally determined at three temperatures: 483.15, 493.15, and 503.15 K. Calculated rate constants are of the same order of magnitude than the experimental ones. Calculated Gibbs energies of activation agree very well with the experimental values. Computationally, the progress of the reactions was followed by means of the Wiberg bond index. The results indicate that the transition state has an intermediate character between reactants and products, and the calculated synchronicity shows that the reaction is slightly asynchronous. The bond-breaking processes are more advanced than the bond-forming ones, indicating a bond deficiency in the transition state.
Fil: Murillo, Juliana. Universidad Nacional de Colombia; Colombia. Universidad Andrés Bello; Chile
Fil: Henao Arboleda, Diana Patricia. Universidad Nacional de Colombia; Colombia. 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: Vélez, Ederley. Universidad Nacional de Colombia; Colombia
Fil: Castaño Espinal, Diana Carolina. Universidad Nacional de Colombia; Colombia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Quijano, Jairo. Universidad Nacional de Colombia; Colombia
Fil: Gaviria, Jair. Universidad Nacional de Colombia; Colombia
Fil: Zapata, Edilma. Universidad Nacional de Colombia; Colombia
Materia
decomposition
4-hydroxy-2-butanone
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:11336/271277
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/271277
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational studyMurillo, JulianaHenao Arboleda, Diana PatriciaVélez, EderleyCastaño Espinal, Diana CarolinaQuijano, JairoGaviria, JairZapata, Edilmadecomposition4-hydroxy-2-butanonehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The mechanism of thermal decomposition of 4-hydroxy-2-butanone in m-xylene solution was studied experimentally and theoretically at the M05-2X/6-31G(d, p) level of theory. It follows first-order kinetics and appears to be homogeneous and unimolecular. The proposed mechanism is via a six-membered cyclic transition state to give a mixture of formaldehyde and acetone. Rate constant values were experimentally determined at three temperatures: 483.15, 493.15, and 503.15 K. Calculated rate constants are of the same order of magnitude than the experimental ones. Calculated Gibbs energies of activation agree very well with the experimental values. Computationally, the progress of the reactions was followed by means of the Wiberg bond index. The results indicate that the transition state has an intermediate character between reactants and products, and the calculated synchronicity shows that the reaction is slightly asynchronous. The bond-breaking processes are more advanced than the bond-forming ones, indicating a bond deficiency in the transition state.Fil: Murillo, Juliana. Universidad Nacional de Colombia; Colombia. Universidad Andrés Bello; ChileFil: Henao Arboleda, Diana Patricia. Universidad Nacional de Colombia; Colombia. 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: Vélez, Ederley. Universidad Nacional de Colombia; ColombiaFil: Castaño Espinal, Diana Carolina. Universidad Nacional de Colombia; Colombia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Quijano, Jairo. Universidad Nacional de Colombia; ColombiaFil: Gaviria, Jair. Universidad Nacional de Colombia; ColombiaFil: Zapata, Edilma. Universidad Nacional de Colombia; ColombiaJohn Wiley & Sons2012-04info: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/11336/271277Murillo, Juliana; Henao Arboleda, Diana Patricia; Vélez, Ederley; Castaño Espinal, Diana Carolina; Quijano, Jairo; et al.; Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study; John Wiley & Sons; International Journal of Chemical Kinetics; 44; 6; 4-2012; 407-4130538-8066CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/kin.20591/abstractinfo:eu-repo/semantics/altIdentifier/doi/10.1002/kin.20591info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:43:29Zoai:ri.conicet.gov.ar:11336/271277instacron: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:34982025-10-15 15:43:29.913CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study
title Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study
spellingShingle Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study
Murillo, Juliana
decomposition
4-hydroxy-2-butanone
title_short Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study
title_full Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study
title_fullStr Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study
title_full_unstemmed Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study
title_sort Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study
dc.creator.none.fl_str_mv Murillo, Juliana
Henao Arboleda, Diana Patricia
Vélez, Ederley
Castaño Espinal, Diana Carolina
Quijano, Jairo
Gaviria, Jair
Zapata, Edilma
author Murillo, Juliana
author_facet Murillo, Juliana
Henao Arboleda, Diana Patricia
Vélez, Ederley
Castaño Espinal, Diana Carolina
Quijano, Jairo
Gaviria, Jair
Zapata, Edilma
author_role author
author2 Henao Arboleda, Diana Patricia
Vélez, Ederley
Castaño Espinal, Diana Carolina
Quijano, Jairo
Gaviria, Jair
Zapata, Edilma
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv decomposition
4-hydroxy-2-butanone
topic decomposition
4-hydroxy-2-butanone
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 mechanism of thermal decomposition of 4-hydroxy-2-butanone in m-xylene solution was studied experimentally and theoretically at the M05-2X/6-31G(d, p) level of theory. It follows first-order kinetics and appears to be homogeneous and unimolecular. The proposed mechanism is via a six-membered cyclic transition state to give a mixture of formaldehyde and acetone. Rate constant values were experimentally determined at three temperatures: 483.15, 493.15, and 503.15 K. Calculated rate constants are of the same order of magnitude than the experimental ones. Calculated Gibbs energies of activation agree very well with the experimental values. Computationally, the progress of the reactions was followed by means of the Wiberg bond index. The results indicate that the transition state has an intermediate character between reactants and products, and the calculated synchronicity shows that the reaction is slightly asynchronous. The bond-breaking processes are more advanced than the bond-forming ones, indicating a bond deficiency in the transition state.
Fil: Murillo, Juliana. Universidad Nacional de Colombia; Colombia. Universidad Andrés Bello; Chile
Fil: Henao Arboleda, Diana Patricia. Universidad Nacional de Colombia; Colombia. 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: Vélez, Ederley. Universidad Nacional de Colombia; Colombia
Fil: Castaño Espinal, Diana Carolina. Universidad Nacional de Colombia; Colombia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Quijano, Jairo. Universidad Nacional de Colombia; Colombia
Fil: Gaviria, Jair. Universidad Nacional de Colombia; Colombia
Fil: Zapata, Edilma. Universidad Nacional de Colombia; Colombia
description The mechanism of thermal decomposition of 4-hydroxy-2-butanone in m-xylene solution was studied experimentally and theoretically at the M05-2X/6-31G(d, p) level of theory. It follows first-order kinetics and appears to be homogeneous and unimolecular. The proposed mechanism is via a six-membered cyclic transition state to give a mixture of formaldehyde and acetone. Rate constant values were experimentally determined at three temperatures: 483.15, 493.15, and 503.15 K. Calculated rate constants are of the same order of magnitude than the experimental ones. Calculated Gibbs energies of activation agree very well with the experimental values. Computationally, the progress of the reactions was followed by means of the Wiberg bond index. The results indicate that the transition state has an intermediate character between reactants and products, and the calculated synchronicity shows that the reaction is slightly asynchronous. The bond-breaking processes are more advanced than the bond-forming ones, indicating a bond deficiency in the transition state.
publishDate 2012
dc.date.none.fl_str_mv 2012-04
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/11336/271277
Murillo, Juliana; Henao Arboleda, Diana Patricia; Vélez, Ederley; Castaño Espinal, Diana Carolina; Quijano, Jairo; et al.; Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study; John Wiley & Sons; International Journal of Chemical Kinetics; 44; 6; 4-2012; 407-413
0538-8066
CONICET Digital
CONICET
url http://hdl.handle.net/11336/271277
identifier_str_mv Murillo, Juliana; Henao Arboleda, Diana Patricia; Vélez, Ederley; Castaño Espinal, Diana Carolina; Quijano, Jairo; et al.; Thermal decomposition of 4‐hydroxy‐2‐butanone in m ‐xylene solution: Experimental and computational study; John Wiley & Sons; International Journal of Chemical Kinetics; 44; 6; 4-2012; 407-413
0538-8066
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://onlinelibrary.wiley.com/doi/10.1002/kin.20591/abstract
info:eu-repo/semantics/altIdentifier/doi/10.1002/kin.20591
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 John Wiley & Sons
publisher.none.fl_str_mv John Wiley & Sons
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 13.22299

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