Publication Type Journal Article
Title The separation between solvent polarizability and solvent dipolarity: Revisiting the Kamlet-Abraham-Taft model equation
Authors Luís Moreira Ruben Elvas-Leitao F. Martins
Groups MET
Journal JOURNAL OF MOLECULAR LIQUIDS
Year 2022
Month
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Volume 362
Number
Pages
Abstract 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. (c) 2022 Elsevier B.V. All rights reserved.
DOI http://dx.doi.org/10.1016/j.molliq.2022.119656
ISBN
Publisher ELSEVIER
Book Title
ISSN 0167-7322
EISSN 1873-3166
Conference Name
Bibtex ID WOS:000827266400012
Observations
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