Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol

Detalhes bibliográficos
Autor(a) principal: Jesus, A. J. Lopes
Data de Publicação: 2005
Outros Autores: Tomé, Luciana I. N., Eusébio, M. Ermelinda, Redinha, J. S.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10316/10661
https://doi.org/10.1021/jp051621n
Resumo: The enthalpies of sublimation of erythritol and l-threitol have been determined at 298.15 K by calorimetry. The values obtained for the two diastereomers differ from one another by 17 kJ mol-1. An interpretation of these results is based on the decomposition of this thermodynamic property in a term coming from the intermolecular interactions of the molecules in the crystal (ΔintH°) and another one related with the conformational change of the molecules on going from the crystal lattice to the most stable forms in the gas phase (ΔconfH°). This last term was calculated from the values of the enthalpy of the molecules in the gas state and of the enthalpy of the isolated molecules with the crystal conformation. Both quantities were obtained by density functional theory (DFT) calculations at the B3LYP/6-311G++(d,p) level of theory. The results obtained in this study show that the most important contribution to the differences observed in the enthalpy of sublimation are the differences in the enthalpy of conformational change (13 kJ mol-1) rather than different intermolecular forces exhibited in the solid phase. This is explained by the lower enthalpy of threitol in the gas phase relative to erythritol, which is attributed to the higher strength of the intramolecular hydrogen bonds in the former. The comparison of the calculated infrared spectra obtained for the two compounds in the gas phase supports this interpretation.
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spelling Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and ThreitolThe enthalpies of sublimation of erythritol and l-threitol have been determined at 298.15 K by calorimetry. The values obtained for the two diastereomers differ from one another by 17 kJ mol-1. An interpretation of these results is based on the decomposition of this thermodynamic property in a term coming from the intermolecular interactions of the molecules in the crystal (ΔintH°) and another one related with the conformational change of the molecules on going from the crystal lattice to the most stable forms in the gas phase (ΔconfH°). This last term was calculated from the values of the enthalpy of the molecules in the gas state and of the enthalpy of the isolated molecules with the crystal conformation. Both quantities were obtained by density functional theory (DFT) calculations at the B3LYP/6-311G++(d,p) level of theory. The results obtained in this study show that the most important contribution to the differences observed in the enthalpy of sublimation are the differences in the enthalpy of conformational change (13 kJ mol-1) rather than different intermolecular forces exhibited in the solid phase. This is explained by the lower enthalpy of threitol in the gas phase relative to erythritol, which is attributed to the higher strength of the intramolecular hydrogen bonds in the former. The comparison of the calculated infrared spectra obtained for the two compounds in the gas phase supports this interpretation.American Chemical Society2005-09-29info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/10661http://hdl.handle.net/10316/10661https://doi.org/10.1021/jp051621nengThe Journal of Physical Chemistry B. 109:38 (2005) 18055-180601520-6106Jesus, A. J. LopesTomé, Luciana I. N.Eusébio, M. ErmelindaRedinha, J. S.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2020-03-05T09:25:39Zoai:estudogeral.uc.pt:10316/10661Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:35.667626Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
title Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
spellingShingle Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
Jesus, A. J. Lopes
title_short Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
title_full Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
title_fullStr Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
title_full_unstemmed Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
title_sort Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
author Jesus, A. J. Lopes
author_facet Jesus, A. J. Lopes
Tomé, Luciana I. N.
Eusébio, M. Ermelinda
Redinha, J. S.
author_role author
author2 Tomé, Luciana I. N.
Eusébio, M. Ermelinda
Redinha, J. S.
author2_role author
author
author
dc.contributor.author.fl_str_mv Jesus, A. J. Lopes
Tomé, Luciana I. N.
Eusébio, M. Ermelinda
Redinha, J. S.
description The enthalpies of sublimation of erythritol and l-threitol have been determined at 298.15 K by calorimetry. The values obtained for the two diastereomers differ from one another by 17 kJ mol-1. An interpretation of these results is based on the decomposition of this thermodynamic property in a term coming from the intermolecular interactions of the molecules in the crystal (ΔintH°) and another one related with the conformational change of the molecules on going from the crystal lattice to the most stable forms in the gas phase (ΔconfH°). This last term was calculated from the values of the enthalpy of the molecules in the gas state and of the enthalpy of the isolated molecules with the crystal conformation. Both quantities were obtained by density functional theory (DFT) calculations at the B3LYP/6-311G++(d,p) level of theory. The results obtained in this study show that the most important contribution to the differences observed in the enthalpy of sublimation are the differences in the enthalpy of conformational change (13 kJ mol-1) rather than different intermolecular forces exhibited in the solid phase. This is explained by the lower enthalpy of threitol in the gas phase relative to erythritol, which is attributed to the higher strength of the intramolecular hydrogen bonds in the former. The comparison of the calculated infrared spectra obtained for the two compounds in the gas phase supports this interpretation.
publishDate 2005
dc.date.none.fl_str_mv 2005-09-29
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
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status_str publishedVersion
dc.identifier.uri.fl_str_mv http://hdl.handle.net/10316/10661
http://hdl.handle.net/10316/10661
https://doi.org/10.1021/jp051621n
url http://hdl.handle.net/10316/10661
https://doi.org/10.1021/jp051621n
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv The Journal of Physical Chemistry B. 109:38 (2005) 18055-18060
1520-6106
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dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
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