Acetone, heterogeneous decomposition

Inhibition by Sulfur Poisoning of the Heterogeneous Decomposition of Acetone... 

The main products in acetic acid medium (Fig. 27) are OZ, DMPC and AcP. The curve of CHP consumption is found to decrease exponentially (it becomes a straight line in semilogarithmic coordinates), the curve of OZ formation passes through a maximum, DMPC is accumulated linearly with the time and that of AcP formation is strongly accelerated after 50 min. The ratio of the initial rates of DMPC AcP and DMPC OZ formation are 1 1 and 1 5, respectively. Phenol (PhOH), which have been identified in the oxidate eould be obtained fi om the well-known heterogeneous decomposition of CHP in acid medium giving rise to phenol and acetone. 

Baldwin and Walker [99] have pointed out that, from kinetic considerations, surface reactions of alkylperoxy radicals cannot play a significant role except at very low overall rates of reaction and conclude that it is more likely that surface destruction of relatively stable intermediates such as the alkyl hydroperoxides or hydrogen peroxide are the main cause of surface effects in hydrocarbon oxidation. Luckett and Pollard [68, 134] have provided evidence, which suggests that the surface destruction of tert-butylhydroperoxide is indeed important during the oxidation of isobutane below ca. 320 °C. Since isobutene and acetone are known products of the decomposition of tert-butylhydroperoxide, it is clear that many of the foregoing results can be explained in these terms, but if this is the predominant heterogeneous reaction the yield of acetone would be... 

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