Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol
Autor(a) principal: | |
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Data de Publicação: | 2005 |
Outros Autores: | , , |
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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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 |
format |
article |
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 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
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) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799133906924994560 |