Reactivities of peroxy radicals toward

VII. Reactivities of Peroxy Radicals Toward Hydrocarbons and Hydroperoxides... 

In recent years much emphasis has been placed on studies of co-oxidations, since they can provide quantitative data about fundamental processes (such as the relative reactivities of peroxy radicals toward various hydrocarbons48-50), which are difficult to obtain by other methods. Co-oxidations are also quite important from a practical viewpoint since it is possible to utilize the alkylperoxy intermediates for additional oxidation processes instead of wasting this active oxygen. That the addition of a second substrate to an autoxidation reaction can produce dramatic effects is illustrated by Russell s observation51 that the presence of 3 mole % of tetralin reduced the rate of cumene oxidation by two-thirds, despite the fact that tetralin itself is oxidized 10 times faster than cumene. The retardation is due to the higher rate of termination of the secondary tetralyl-peroxy radicals compared to the tertiary cumylperoxy radicals (see above). 

The reactivity of peroxy radicals towards other peroxy radicals varies over many orders of magnitude depending on the nature of the R group. Consequently, it is not possible to provide a simple accounting of the importance of peroxy self and cross reactions compared to the other possible loss mech-... 

Howard, J. A. Schwahn, W. J. Ingold, K. U. Absolute Rate Constants for Hydrocarbons autoxidation. VII. The Reactivities of Peroxy Radicals towards Hydrocarbons and Hydroperoxides, In Preprints of the International Oxidation Simposium. San Francisco, California. 1967 1, 3. 

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