ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
An experimental study of the decomposition kinetics of chemically activated 2-methyl-l-butene and 3-methyl-l-butene produced from photolysis of diazomethane-isobutene-neopentane-oxygen mixtures is reported. The experimental rate constants for 3-methyl-l-butene decomposition were 1.74 ± 0.44 × 108 sec-1 and 1.01 ± 0.25 × 108 sec-1 at 3660 and 4358 Å, respectively. 2-Methyl-l-butene experimental decomposition rate constants were found to be 5.94 ± 0.59 × 107 sec-1 at 3660 Å and 3.42 ± 0.34 × 107 sec-1 at 4358 Å. Activated complex structures giving Arrhenius A-factors calculated from absolute rate theory of 1016.6 ± 0.5 sec-1 for 3-methyl-l-butene and 1016.2 ± 0.4 sec-1 for 2-methyl-l-butene, both calculated at 1000°K, were required to fit RRKM theory calculated rate constants to the experimental rate constants at reasonable E0 and E* values. Corrected calculations (adjusted E0 values) on previous results for 2-pentene decomposition gave an Arrhenius A-factor of 1016.45 ± 0.35 sec-1 at 1000°K. The predicted A-factors for these three alkene decompositions giving resonance-stabilized methylully radicals are in good internal agreement. The fact that these A-factors are only slightly less than those for related alkane decompositions indicates that methylallylic resonance in the decomposition products leads to only a small amount of tightening in the corresponding activated complexes. This tightening is a significantly smaller factor than the large reduction in the critical energy due to resonance stabilization.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550030507
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