THE OXIDATION OF DI-tertiary-BUTYL PEROXIDE

Abstract

The oxidation of di-t-butyl peroxide has been investigated in a static system at low conversion at 124 °C with sufficient oxygen present to suppress completely the formation of methane and ethane. The decomposition of the t-butoxy radical is unaffected by the presence of oxygen. A major product of the oxidation is formaldehyde whose yield rapidly approaches a stationary value. It is postulated that the major source of formaldehyde is the decomposition of methyl peroxy radicals, which may also abstract hydrogen from formaldehyde to form methyl hydroperoxide, and that this competition leads to the stationary concentration of formaldehyde actually observed. Methyl hydroperoxide was demonstrated to be unstable in the system and the predominant decomposition product was methanol, a compound also found in high yields in the oxidation. Experiments with added formaldehyde-C13 showed that formaldehyde can be converted to carbon monoxide in the system and indicated that formaldehyde was a likely precursor to the carbon monoxide found in the oxidation.