Abstract
Above 400 °C propane is oxidized by a two-stage degenerately branching chain reaction. The first 20% of reaction proceeds by an HO 2 /C 3 H 7 radical chain where the main immediate products are propylene and hydrogen peroxide. Pyrolysis of a small fraction of the propyl radicals gives rise to methyl radicals and finally formaldehyde. The further oxidation of formaldehyde by molecular oxygen probably accounts for the observed chain branching although at temperatures above 475 °C homogeneous decomposition of hydrogen peroxide may lead to the initiation of new chains. In the second stage of the reaction the secondary oxidation of propylene becomes important. While propane still in the main reacts to form propylene the subsequent oxidation of the propylene alters both the kinetics and the oxidation products so that the reaction appears overall to proceed by a mechanism similar to that operative at temperatures below 400 °C where the important branching agents are probably higher aldehydes.
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