Alkylperoxy radical isomerization and cool flames

Abstract
Studies of the combustion ofn-hexane with special reference to theO-heterocyclic products formed show that these compounds are present in the largest quantities under cool flame conditions and that their concentration decreases sharply at the ignition boundary.O-heterocyclic compounds appear to be the main products of the intramolecular rearrangement of hexylperoxy radicals and their structure shows that they are derived predominantly from the 2-hexylperoxy radical. The amounts of the differentO-heterocycles produced can, on the basis of reasonable assumptions, provide information regarding the relative susceptibility to intramolecular hydrogen abstraction of the 3-, 4- and 5-positions in the 2-hexylperoxy radical.