ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics and equilibria in the system Br + t-BuO2H ⇆ HBr + t-BuO2· have been measured in the range of 300-350 K using the very low pressure reactor (VLPR) technique. Using an estimated entropy change in reaction (1) ΔS1 = 3.0 ± 0.4 cal/mol·K together with the measured ΔG1, we find ΔH1 = 1.9 ± 0.2 kcal/mol and DHº (t-BuO2-H) = 89.4 ± 0.2 kcal/mol ΔHf·(tBuO2·) = 20.7 kcal/mol and DHº (t-Bu-O2) = 29.1 kcal/mol. The latter values make use of recent values of ΔHf·(t-Bu) = 8.4 ± 0.5 kcal/mol and the known thermochemistry of the other species. The activation energy E1 is found to be 3.3 ± 0.6 kcal/mol, about 1 kcal lower than the value found for Br attack on H2O2. It suggests a bond 1 kcal stronger in H2O2 than in tBuO2H.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550150810
