Document type
Journal articles
Document subtype
Full paper
Title
Revisiting the Reactions oft-BuX (X = Br, I) with Monoalcohols: A Mechanistic Analysis through Numerical Integration and Nonlinear Regression Methods
Participants in the publication
Ruben Elvas-Leitão (Author)
CQE
Filomena Martins (Author)
Dep. Química e Bioquímica
CQB
Summary
The reactions of two tertiary butyl halides, i.e., t?BuBr and t?BuI, with monoalcohols (methanol, i?propanol, and t?butanol) have been studied at several temperatures during extended periods of time to acquire kinetic data for both the solvolytic step and the subsequent reactions. Reaction progress was followed by conductimetry, and calibration curves were obtained for all systems under study to derive concentration versus time curves for the significant intermediate species, the formed acid, HX. The GMS comprehensive mechanism, previously proposed by Gonçalves, Martins, and Simões for these reactions, was successfully tested using numerical integration associated with nonlinear regression, confirming the predicted distinct behaviors for methanol (and for that matter also for primary alcohols), secondary, and tertiary alcohols. Results show that accurate rate constants could be obtained in all cases and that the step that follows solvolysis can affect significantly the solvolytic rate constant and therefore any consequent reliable mechanistic analysis.
Date of Submisson/Request
2016-09-28
Date of Acceptance
2016-11-02
Date of Publication
2016-12-13
Institution
FACULDADE DE CIÊNCIAS DA UNIVERSIDADE DE LISBOA
Where published
International Journal of Chemical Kinetics
Publication Identifiers
ISSN - 0538-8066
Publisher
Wiley
Number of pages
12
Starting page
100
Last page
111
Document Identifiers
URL -
http://dx.doi.org/10.1002/kin.21059
DOI -
https://doi.org/10.1002/kin.21059
Rankings
SCIMAGO Q3 (2016) - 0.392 - Physical and Theoretical Chemistry
SCOPUS Q3 (2011) - 0.827 - Physical and Theoretical Chemistry
Web Of Science Q3 (2016) - 2.919 - Chemistry, Physical