Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane

Autores
Inafuku, Maximiliano Nelson; Marceca, Ernesto José
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Infrared spectroscopy in the gas phase was used to study the formation reaction of the CH⋯O hydrogen bonding complex involving the CH group of trifluoromethane, as a hydrogen donor, and the carbonyl group of methyl acetate, as a hydrogen acceptor, under different (T, p) conditions. The hydrogen-bonded carbonyl stretch of the molecular pair was monitored in dilute mixtures of methyl acetate in trifluoromethane at near-critical temperatures, from gas- to liquid-like densities. In the gas region, it was possible to discriminate the carbonyl signal of the hydrogen-bonded complex from that of the free ester and have access to their relative concentration. The equilibrium constant of the hydrogen bonding reaction and the standard enthalpy and entropy changes in the process were determined using the spectroscopic data. CH⋯O bonding was favored by lowering temperature or pressurizing F3CH in the mixture, remaining essentially no free carbonyl groups about the critical density. The carbonyl band of the hydrogen-bonded pair appeared as a single symmetric peak up to liquid-like densities, suggesting that the 1:1 methyl acetate-trifluoromethane complex has the most abundant stoichiometry. Spectral features as frequency shift and bandwidth of the hydrogen-bonded carbonyl were studied as a function of temperature and solvent-density. A bathochromic (red) vibrational shift was registered for the bound carbonyl band against density, with a sudden change in behavior in the near-critical region, while the width of this band remains mostly unresponsive.
Fil: Inafuku, Maximiliano Nelson. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Materia
HYDROGEN BOND
INTERMOLECULAR INTERACTION
SUPERCRITICAL FLUIDS
CRITICAL PHENOMENA
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:11336/142364
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethaneInafuku, Maximiliano NelsonMarceca, Ernesto JoséHYDROGEN BONDINTERMOLECULAR INTERACTIONSUPERCRITICAL FLUIDSCRITICAL PHENOMENAhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Infrared spectroscopy in the gas phase was used to study the formation reaction of the CH⋯O hydrogen bonding complex involving the CH group of trifluoromethane, as a hydrogen donor, and the carbonyl group of methyl acetate, as a hydrogen acceptor, under different (T, p) conditions. The hydrogen-bonded carbonyl stretch of the molecular pair was monitored in dilute mixtures of methyl acetate in trifluoromethane at near-critical temperatures, from gas- to liquid-like densities. In the gas region, it was possible to discriminate the carbonyl signal of the hydrogen-bonded complex from that of the free ester and have access to their relative concentration. The equilibrium constant of the hydrogen bonding reaction and the standard enthalpy and entropy changes in the process were determined using the spectroscopic data. CH⋯O bonding was favored by lowering temperature or pressurizing F3CH in the mixture, remaining essentially no free carbonyl groups about the critical density. The carbonyl band of the hydrogen-bonded pair appeared as a single symmetric peak up to liquid-like densities, suggesting that the 1:1 methyl acetate-trifluoromethane complex has the most abundant stoichiometry. Spectral features as frequency shift and bandwidth of the hydrogen-bonded carbonyl were studied as a function of temperature and solvent-density. A bathochromic (red) vibrational shift was registered for the bound carbonyl band against density, with a sudden change in behavior in the near-critical region, while the width of this band remains mostly unresponsive.Fil: Inafuku, Maximiliano Nelson. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaAmerican Institute of Physics2020-08-24info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/142364Inafuku, Maximiliano Nelson; Marceca, Ernesto José; Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane; American Institute of Physics; Journal of Chemical Physics; 153; 8; 24-8-2020; 1-90021-9606CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1063/5.0019058info:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/5.0019058info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:22:13Zoai:ri.conicet.gov.ar:11336/142364instacron: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 15:22:13.333CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane
title Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane
spellingShingle Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane
Inafuku, Maximiliano Nelson
HYDROGEN BOND
INTERMOLECULAR INTERACTION
SUPERCRITICAL FLUIDS
CRITICAL PHENOMENA
title_short Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane
title_full Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane
title_fullStr Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane
title_full_unstemmed Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane
title_sort Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane
dc.creator.none.fl_str_mv Inafuku, Maximiliano Nelson
Marceca, Ernesto José
author Inafuku, Maximiliano Nelson
author_facet Inafuku, Maximiliano Nelson
Marceca, Ernesto José
author_role author
author2 Marceca, Ernesto José
author2_role author
dc.subject.none.fl_str_mv HYDROGEN BOND
INTERMOLECULAR INTERACTION
SUPERCRITICAL FLUIDS
CRITICAL PHENOMENA
topic HYDROGEN BOND
INTERMOLECULAR INTERACTION
SUPERCRITICAL FLUIDS
CRITICAL PHENOMENA
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Infrared spectroscopy in the gas phase was used to study the formation reaction of the CH⋯O hydrogen bonding complex involving the CH group of trifluoromethane, as a hydrogen donor, and the carbonyl group of methyl acetate, as a hydrogen acceptor, under different (T, p) conditions. The hydrogen-bonded carbonyl stretch of the molecular pair was monitored in dilute mixtures of methyl acetate in trifluoromethane at near-critical temperatures, from gas- to liquid-like densities. In the gas region, it was possible to discriminate the carbonyl signal of the hydrogen-bonded complex from that of the free ester and have access to their relative concentration. The equilibrium constant of the hydrogen bonding reaction and the standard enthalpy and entropy changes in the process were determined using the spectroscopic data. CH⋯O bonding was favored by lowering temperature or pressurizing F3CH in the mixture, remaining essentially no free carbonyl groups about the critical density. The carbonyl band of the hydrogen-bonded pair appeared as a single symmetric peak up to liquid-like densities, suggesting that the 1:1 methyl acetate-trifluoromethane complex has the most abundant stoichiometry. Spectral features as frequency shift and bandwidth of the hydrogen-bonded carbonyl were studied as a function of temperature and solvent-density. A bathochromic (red) vibrational shift was registered for the bound carbonyl band against density, with a sudden change in behavior in the near-critical region, while the width of this band remains mostly unresponsive.
Fil: Inafuku, Maximiliano Nelson. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Marceca, Ernesto José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
description Infrared spectroscopy in the gas phase was used to study the formation reaction of the CH⋯O hydrogen bonding complex involving the CH group of trifluoromethane, as a hydrogen donor, and the carbonyl group of methyl acetate, as a hydrogen acceptor, under different (T, p) conditions. The hydrogen-bonded carbonyl stretch of the molecular pair was monitored in dilute mixtures of methyl acetate in trifluoromethane at near-critical temperatures, from gas- to liquid-like densities. In the gas region, it was possible to discriminate the carbonyl signal of the hydrogen-bonded complex from that of the free ester and have access to their relative concentration. The equilibrium constant of the hydrogen bonding reaction and the standard enthalpy and entropy changes in the process were determined using the spectroscopic data. CH⋯O bonding was favored by lowering temperature or pressurizing F3CH in the mixture, remaining essentially no free carbonyl groups about the critical density. The carbonyl band of the hydrogen-bonded pair appeared as a single symmetric peak up to liquid-like densities, suggesting that the 1:1 methyl acetate-trifluoromethane complex has the most abundant stoichiometry. Spectral features as frequency shift and bandwidth of the hydrogen-bonded carbonyl were studied as a function of temperature and solvent-density. A bathochromic (red) vibrational shift was registered for the bound carbonyl band against density, with a sudden change in behavior in the near-critical region, while the width of this band remains mostly unresponsive.
publishDate 2020
dc.date.none.fl_str_mv 2020-08-24
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/11336/142364
Inafuku, Maximiliano Nelson; Marceca, Ernesto José; Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane; American Institute of Physics; Journal of Chemical Physics; 153; 8; 24-8-2020; 1-9
0021-9606
CONICET Digital
CONICET
url http://hdl.handle.net/11336/142364
identifier_str_mv Inafuku, Maximiliano Nelson; Marceca, Ernesto José; Carbonyl stretch of CH…O hydrogen-bonded methyl acetate in supercritical trifluoromethane; American Institute of Physics; Journal of Chemical Physics; 153; 8; 24-8-2020; 1-9
0021-9606
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1063/5.0019058
info:eu-repo/semantics/altIdentifier/url/https://aip.scitation.org/doi/10.1063/5.0019058
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 American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
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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