Absolute rate constants for hydrocarbon autoxidation. XVI. Reactions of peroxy radicals at low temperatures
Open Access
- 15 October 1969
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 47 (20) , 3803-3808
- https://doi.org/10.1139/v69-634
Abstract
The equilibrium constants for the formation of some t-alkyl tetroxides and the rate constants for irreversible decay of the tetroxides have been measured by electron spin resonance spectroscopy at low temperatures. The equilibrium constant appears to be virtually independent of the nature of the alkyl groups. It is concluded that differences in the rate of constants for chain termination by t-peroxy radicals at ambient temperatures are due chiefly to the differences in rate constants for irreversible tetroxide decomposition. The activation parameters for this reaction indicate that it occurs by one bond rather than two bond scission.Keywords
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