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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/271277
Ver los metadatos del registro completo
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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 Técnicas2025-09-29T10:45:02Zoai: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:34982025-09-29 10:45:03.084CONICET 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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1844614489174966272 |
score |
13.070432 |