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Some current problems in oxidation kineticsExperimental data in low temperature and high temperature oxidations are examined from the point of view of reported quantitative inconsistencies. Activation energies for tBuO2 metathesis reactions with alkanes appear to be 7 kcal/mole higher than for comparable reactions of HO2. Related isomerization reactions are examined in the light of these differences without reaching any simple conclusions. The Russell mechanism for a 6-membered, cyclic, transition state for termination of primary and secondary alkyl peroxy radicals is shown to be either inconsistent with thermochemical data, or else unique to solution reactions. Addition reactions of O3 with olefins and acetylenes are shown thermochemically to have the possibility of following concerted and biradical pathways, respectively. Recent data showing strong inhibition by PbO coated surfaces of both oxidation and pyrolysis of i-C4H10 are examined in terms of mechanism.
Document ID
19730008415
Document Type
Conference Paper
Authors
Benson, S. W. (Stanford Research Inst. Menlo Park, CA, United States)
Date Acquired
August 7, 2013
Publication Date
June 1, 1972
Publication Information
Publication: NBS The Mech. of Pyrolysis, Oxidation, and Burning of Org. Mater.
Subject Category
CHEMISTRY
Funding Number(s)
CONTRACT_GRANT: NAS7-472
CONTRACT_GRANT: AP-00353-06
Distribution Limits
Public
Copyright
Work of the US Gov. Public Use Permitted.