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Publication details

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-Ciências - Centro de Química Estrutural-Ciências
Filomena Martins (Author)
Dep. Química e Bioquímica
CQB - Centro de Química e Bioquímica 

Scope
International

Refereeing
Yes

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

Volume
49
Number
2

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


Export

APA
Ruben Elvas-Leitão, Filomena Martins, (2016). Revisiting the Reactions oft-BuX (X = Br, I) with Monoalcohols: A Mechanistic Analysis through Numerical Integration and Nonlinear Regression Methods. International Journal of Chemical Kinetics, 49, 100-111. ISSN 0538-8066. eISSN . http://dx.doi.org/10.1002/kin.21059

IEEE
Ruben Elvas-Leitão, Filomena Martins, "Revisiting the Reactions oft-BuX (X = Br, I) with Monoalcohols: A Mechanistic Analysis through Numerical Integration and Nonlinear Regression Methods" in International Journal of Chemical Kinetics, vol. 49, pp. 100-111, 2016. 10.1002/kin.21059

BIBTEX
@article{36918, author = {Ruben Elvas-Leitão and Filomena Martins}, title = {Revisiting the Reactions oft-BuX (X = Br, I) with Monoalcohols: A Mechanistic Analysis through Numerical Integration and Nonlinear Regression Methods}, journal = {International Journal of Chemical Kinetics}, year = 2016, pages = {100-111}, volume = 49 }