By computer simulation of the dependencies of the mole numbers of the ketones and alcohols derived from the starting paraffin, of the acids and esters, and in some cases also of the lower alkan‐2‐ones on the paraffin conversion relative rate constants were determined on the basis of a plausible kinetic model of the paraffin oxidation. The data obtained show that about 67% of the oxidation proceeds via bifunctional primary products. With the aid of the relative rate constants determined a good simulation of the experimental mole number‐conversion curves is possible.
The mole numbers of the starting paraffins, of the intermediate alcohols and ketones with the same chain lengths, of the lower alkan‐2‐ones, of the carboxylic acids, and of the esters were determined at different reaction times for the oxidations of n‐tridecane, n‐tetradecane, and n‐pentadecane with molecular oxygen at 140°C in the presence of 0.1% Mn‐stearate. In the stationary region of the oxidation about 1.2 moles of acids and 0.7 moles of esters are formed from 1 mole of paraffin consumed. The relative oxidation rates of alcohols and of ketones with reference to the starting paraffins were estimated from the mole numbers of the starting paraffins, the alcohols and the ketones at the maxima of the alcohols and the ketones. These values are higher than those determined by competitive oxidations, and this discrepancy is an indirect evidence of the formation of bifunctional intermediates from the starting paraffins. The relative rates of the formation of alcohols, ketones, and bifunctional products from normal paraffins were estimated.
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