ON SLOW OXIDATION OF HYDROCARBON AND COOL FLAMES

A mathematical model is devised to consider the thermokinetic coupling of an active intermediate and temperature in the slow oxidation of hydrocarbon. With a single set of assumed rate constants it is shown that explosion limits, cool flame oscillation limits, oscillation period and amplitude, explosion peninsula (lobe), and negative temperature coefficient effect can all be calculated in agreement with experimental observations. Detail kinetics are discussed. The RCO radical is tentatively identified as the autocatalytic carrier. The proposed branching scheme conforms with a previous proposal made by Knox and Norrish in their work on the oxidation of propane.