Publication Type Journal Article
Title Revisiting the Reactions of t-BuX (X = Br, I) with Monoalcohols: A Mechanistic Analysis through Numerical Integration and Nonlinear Regression Methods
Authors R. Elvas-Leitão F. Martins
Groups MET
Journal INTERNATIONAL JOURNAL OF CHEMICAL KINETICS
Year 2017
Month February
Volume 49
Number 2
Pages 100-111
Abstract 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 Goncalves, Martins, and Simoes 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. (C) 2016 Wiley Periodicals, Inc.
DOI http://dx.doi.org/10.1002/kin.21059
ISBN
Publisher
Book Title
ISSN 0538-8066
EISSN 1097-4601
Conference Name
Bibtex ID ISI:000393876500003
Observations
Back to Publications List