Hydroperoxyalkylperoxy radicals

Hydroperoxyalkylperoxy radicals will also be potential abstracters of hydrogen from C H2n + 2, giving a dihydroperoxide and regenerating an alkyl radical in a Reaction 11 analogous to Reaction 3. 

Further oxidation of hydroperoxyalkyl radicals by addition of oxygen to give hydroperoxyalkylperoxy radicals, viz. 

A pseudo-steady-state treatment was developed for this scheme in which it was assumed that the chains are long, that the rates of formation of the products are controlled by the rates of propagation of the chains, that the formation of alkyl radicals occurs only via reaction (12) and that the sum of the rates of further reactions of hydroperoxyalkylperoxy radicals is Isirge compared with their rate of formation. In order to simplify the mathematical treatment, it was also necessary to assume that reactions (2) and (—4,1) Eire slow and that the more complex decomposition reactions of hydroperoxyalkyl radicals can be ignored. 

Finally, branching reactions involving free radicals as reactants may also play a part. Thus, for example, in the oxidation of n-heptane the hydroperoxyalkylperoxy radicals formed may decompose sufficiently rapidly, e.g. 

The framework of the mechanism involves alkyl R, alkylperoxy 00R, hydro" peroxyalkyl QOOH, hydroperoxyalkylperoxy OOQOOH and dihydroperoxyalkyl U(00H)2 radicals which are obtained from the R radical parent of the RH molecule... 

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See also in sourсe #XX -- [ ]

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