Routes of oxidation reactions

Effect of Solvents on Rates and Routes of Oxidation Reactions... 

The effect of the medium on the rates and routes of liquid-phase oxidation reactions was investigated. The rate constants for chain propagation and termination upon dilution of methyl ethyl ketone with a nonpolar solvent—benzene— were shown to be consistent with the Kirkwood equation relating the constants for bimolecular reactions with the dielectric constant of the medium. The effect of solvents capable of forming hydrogen bonds with peroxy radicals appears to be more complicated. The rate constants for chain propagation and termination in aqueous methyl ethyl ketone solutions appear to be lower because of the lower reactivity of solvated R02. .. HOH radicals than of free RO radicals. The routes of oxidation reactions are a function of the competition between two R02 reaction routes. In the presence of water the reaction selectivity markedly increases, and acetic acid becomes the only oxidation product. 

TJecent research has established that the medium has an important effect on the rates and routes of oxidation reactions (4, 5, 10, 12). Chain oxidation reactions occur via peroxy radicals. The mechanism of liquid-phase oxidation at low extents of conversion is known to involve the following elementary reactions ... 

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