Tipo
Artigos em Revista
Tipo de Documento
Artigo Completo
Título
The separation between solvent polarizability and solvent dipolarity: Revisiting the Kamlet-Abraham-Taft model equation
Participantes na publicação
Luís Moreira (Author)
Ruben Elvas-Leitão (Author)
Filomena Martins (Author)
Dep. Química e Bioquímica
CQE
Resumo
Quantitative structure–property relationships were established using multiple linear regressions to correlate log k values for the heterolysis reaction of 3-bromo-3-ethylpentane using three well-known model equations, the Kamlet-Abraham-Taft (KAT), the Catalán (Cat) and the Laurence (Lau) equations. The a priori 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 π* descriptor into two independent contributions 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 Catalán’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.
Data de Submissão/Pedido
2022-04-12
Data de Aceitação
2022-06-16
Data de Publicação
2022-09
Instituição
FACULDADE DE CIÊNCIAS DA UNIVERSIDADE DE LISBOA
Suporte
Journal of Molecular Liquids
Identificadores da Publicação
ISSN - 0167-7322
Editora
Elsevier BV
Número de Páginas
8
Página Inicial
119656
Identificadores do Documento
DOI -
https://doi.org/10.1016/j.molliq.2022.119656
URL -
http://dx.doi.org/10.1016/j.molliq.2022.119656
Identificadores de Qualidade
Web Of Science Q1 (2022) - 6.0 - Physics, Atomic, Molecular & Chemical
Web Of Science Q2 (2022) - 6.0 - Chemistry, Physical
SCIMAGO Q1 (2022) - 0.914 - Physical and Theoretical Chemistry
Keywords
Quantitative structure property relationships Kinetics Solvent effects Solvent polarizability Solvent dipolarity Model equations