Abstract
The mechanism of photosensitized oxidation of methanol in acetonitrile was investigated in the presence of anthraquinone. Among the main stable products formaldehyde, formic acid, hydrogenperoxide and hydroxymethylhydroperoxide has been found. Their accumulation was measured in the range of 30–60°C. Specific experiments were carried out to prove the existence or negligibility of reactions proposed in the literature. The computer simulation based on literature data and on our results combined with estimation of certain rate coefficients as parameters resulted in good agreement with experimental product accumulation curves. The estimated value of monomolecular decomposition of hydroxymethylperoxyl radical (k325°C ≈ 3 s−1) is in favour of the lowest values that can be found in the literature. In the overall termination process the Russell-type termination step generally accepted in reactions between peroxyl radicals has decreasing importance with increasing temperature.
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