Regimes of oxidation chemistry

For clarity, it is worth considering the regimes from the perspective of both products and rates. 

Secondary initiation (and sometimes spectacular acceleration of rate) may well occur through formation and subsequent homolysis of a molecular hydroperoxide such as CH3CO3H, particularly as the temperature is increased above 400 K. Marked autocatalysis and lengthy induction periods may result. Near quantitative yields of CH3CO3H have been observed [15] consistent with the following type of sequence  

CH3CO + 02 CH3CO3 CH3CO3 -h CH3CHO CH3CO3H -h CH3CO CH3CO3H CH3 + CO2 + OH 

A similar mechanism in which the peroxide ROOH formed from the alkane RH provides secondary initiation, occurs above 450 K for alkanes with tertiary C—H bonds and at increasingly higher temperatures where secondary and primary C—H bonds are involved. In the region 500-600 K, where the oxidation rate increases sharply with temperature, the equilibrium R -I- 02 R02 is well to the right and 

With further temperature increase, two features dominate. The ratio [R]/[R02] rises further as (6) becomes increasingly reversible, so that reactions of R radicals rather RO2 influence the oxidation. Of these the most important is the overall reaction (5A) which gives the 

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