The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation
Autor(a) principal: | |
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Data de Publicação: | 2022 |
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/10400.21/16105 |
Resumo: | Quantitative structure-property relationships were established using multiple linear regressions to cor-relate log k values for the heterolysis reaction of 3-bromo-3-ethylpentane using three well-known model equations, the Kamlet-Abraham-Taft (KAT), the Catalan (Cat) and the Laurence (Lau) equations. The a pri-ori exclusion of the hydrogen bond acceptor (HBA) basicity descriptor for all tested models led to similar responses, thus emptying the argument of an alleged use of a non-balanced set of solvents. Concurrently, a new method was devised to split the original Kamlet-Taft p* descriptor into two independent contri-butions which separately quantify the solvent's polarizability (DI) and dipolarity (Dip). A modified version of the KAT equation (mKAT) including both DI and Dip, together with the exclusion of the HBA basicity descriptor was applied to five selected solvent-dependent physicochemical processes. Results showed that the mKAT model provided significant improvements over the original KAT model. Additionally, it was shown that the introduction of DI in the truncated KAT equation could lead to misleading or, at best, inconclusive interpretations of solvent effects. Finally, the performance of mKAT model was compared with Catalan's and Laurence's model equations in terms of statistical results, relevance of descriptors and gas-phase predictions. In general, these three model equations show very similar outcomes although the mKAT model exhibits an overall better performance. |
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The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equationQuantitative structure property relationshipsKineticsSolvent effectsSolvent polarizabilitySolvent dipolarityModel equationsQuantitative structure-property relationships were established using multiple linear regressions to cor-relate log k values for the heterolysis reaction of 3-bromo-3-ethylpentane using three well-known model equations, the Kamlet-Abraham-Taft (KAT), the Catalan (Cat) and the Laurence (Lau) equations. The a pri-ori exclusion of the hydrogen bond acceptor (HBA) basicity descriptor for all tested models led to similar responses, thus emptying the argument of an alleged use of a non-balanced set of solvents. Concurrently, a new method was devised to split the original Kamlet-Taft p* descriptor into two independent contri-butions which separately quantify the solvent's polarizability (DI) and dipolarity (Dip). A modified version of the KAT equation (mKAT) including both DI and Dip, together with the exclusion of the HBA basicity descriptor was applied to five selected solvent-dependent physicochemical processes. Results showed that the mKAT model provided significant improvements over the original KAT model. Additionally, it was shown that the introduction of DI in the truncated KAT equation could lead to misleading or, at best, inconclusive interpretations of solvent effects. Finally, the performance of mKAT model was compared with Catalan's and Laurence's model equations in terms of statistical results, relevance of descriptors and gas-phase predictions. In general, these three model equations show very similar outcomes although the mKAT model exhibits an overall better performance.ElsevierRCIPLMoreira, L.Elvas Leitao, RubenMartins, Filomena2023-05-23T08:05:57Z2022-09-152022-09-15T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.21/16105engMOREIRA, Luís; ELVAS-LEITÃO, Rúben; MARTINS, Filomena – The separation between solvent polarizability and solvent dipolarity: Revisiting the Kamlet-Abraham-Taft model equation. Journal of Molecular Liquids. ISSN 0167-7322. Vol. 362 (2022), pp. 1-8.0167-732210.1016/j.molliq.2022.1196561873-3166metadata only accessinfo: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:RCAAP2023-08-03T10:14:25Zoai:repositorio.ipl.pt:10400.21/16105Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:23:42.123886Repositório 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 |
The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation |
title |
The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation |
spellingShingle |
The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation Moreira, L. Quantitative structure property relationships KineticsSolvent effects Solvent polarizability Solvent dipolarity Model equations |
title_short |
The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation |
title_full |
The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation |
title_fullStr |
The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation |
title_full_unstemmed |
The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation |
title_sort |
The separation between solvent polarizability and solvent dipolarity: revisiting the Kamlet-Abraham-Taft model equation |
author |
Moreira, L. |
author_facet |
Moreira, L. Elvas Leitao, Ruben Martins, Filomena |
author_role |
author |
author2 |
Elvas Leitao, Ruben Martins, Filomena |
author2_role |
author author |
dc.contributor.none.fl_str_mv |
RCIPL |
dc.contributor.author.fl_str_mv |
Moreira, L. Elvas Leitao, Ruben Martins, Filomena |
dc.subject.por.fl_str_mv |
Quantitative structure property relationships KineticsSolvent effects Solvent polarizability Solvent dipolarity Model equations |
topic |
Quantitative structure property relationships KineticsSolvent effects Solvent polarizability Solvent dipolarity Model equations |
description |
Quantitative structure-property relationships were established using multiple linear regressions to cor-relate log k values for the heterolysis reaction of 3-bromo-3-ethylpentane using three well-known model equations, the Kamlet-Abraham-Taft (KAT), the Catalan (Cat) and the Laurence (Lau) equations. The a pri-ori exclusion of the hydrogen bond acceptor (HBA) basicity descriptor for all tested models led to similar responses, thus emptying the argument of an alleged use of a non-balanced set of solvents. Concurrently, a new method was devised to split the original Kamlet-Taft p* descriptor into two independent contri-butions which separately quantify the solvent's polarizability (DI) and dipolarity (Dip). A modified version of the KAT equation (mKAT) including both DI and Dip, together with the exclusion of the HBA basicity descriptor was applied to five selected solvent-dependent physicochemical processes. Results showed that the mKAT model provided significant improvements over the original KAT model. Additionally, it was shown that the introduction of DI in the truncated KAT equation could lead to misleading or, at best, inconclusive interpretations of solvent effects. Finally, the performance of mKAT model was compared with Catalan's and Laurence's model equations in terms of statistical results, relevance of descriptors and gas-phase predictions. In general, these three model equations show very similar outcomes although the mKAT model exhibits an overall better performance. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-09-15 2022-09-15T00:00:00Z 2023-05-23T08:05:57Z |
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/10400.21/16105 |
url |
http://hdl.handle.net/10400.21/16105 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
MOREIRA, Luís; ELVAS-LEITÃO, Rúben; MARTINS, Filomena – The separation between solvent polarizability and solvent dipolarity: Revisiting the Kamlet-Abraham-Taft model equation. Journal of Molecular Liquids. ISSN 0167-7322. Vol. 362 (2022), pp. 1-8. 0167-7322 10.1016/j.molliq.2022.119656 1873-3166 |
dc.rights.driver.fl_str_mv |
metadata only access info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
metadata only access |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
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 |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799133509504204800 |