ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics and equilibria of the reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br} + {\rm CH}_{\rm 3} {\rm CH}_{\rm 2} {\rm OCH}_{\rm 2} {\rm CH}_{\rm 3} {\rm}\mathop {{\rm \rightleftharpoons}}\limits^{\rm 1} {\rm HBr} + {\rm CH}_{\rm 3} {\rm CHOCH}_{\rm 2} {\rm CH}_{\rm 3} $$\end{document} have been studied in the temperature range 298-333 K by using the very low pressure reactor (VLPR) technique. Combining the estimated entropy change of reaction (1), ΔS°1 = 8.1 ± 1.0 eu, with the measured ΔG°1, we find ΔH°1 = 4.2 ± 0.4 kcal/mol; ΔH°f(CH3CHOC2H5) = -20.2 kcal/mol, and DH° [Et OCH(Me)-H] = 91.7 ± 0.4 kcal/mol. We find: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (1/{\rm mol s)} = 10.8(\pm 0.7) - (3.9 \pm 4.0)/\theta $$\end{document} where θ = 2.3 RT in kcal/mol. It has been shown that the reaction proceeds via a loose transition state and the “contact TS” model calculation gives a very good agreement with the observed value.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550160802
