Specific features of cumene oxidation in the presence of alkylammonium halides

The oxidation of cumene in the presence of a tetraethylammonium or tetrabut ylammonium halide in a benzonitrile solution or its mixture with chlorobenz ene at 358 K was investigated. The best linear correlation (R = 0.997-0.999 ) between the amount of absorbed oxygen ([O-2]) and the time (t) was observ ed on the [O-2] - t(1/2) coordinates. Based on this dependence, a method fo r assessing the severity of cumene oxidation was developed for varying both cumene and the catalyst concentrations within different periods of time. T he oxidation scheme involving the reversible reaction of equilibrium comple x formation between a hydroperoxide and a catalyst molecule [ROOH...Ct] fol lowed by decay of this complex to initiate the chain, the catalyst deactiva tion as a result of bimolecular reaction of these complexes, and reactions of cumylperoxy radicals with the catalyst itself or the products of its tra nsformation was suggested. Mathematical simulation of the scheme by the cor responding system of differential equations showed the scheme to ensure sat isfactory quantitative description of the main kinetic features of the proc ess.