The initial formation of alcohols during the slow combustion of methane and ethane at atmospheric pressure

Abstract

It has been shown in recent papers that during the slow combustion of the paraffin hydrocarbons at high pressures hydroxylation of the hydrocarbon molecule takes place with the formation of the corresponding alcohols in considerable quantities. Thus, for example, when a 9 : 1 methane-air mixture at 50 atms undergoes reaction at 430° C as much as 51% of the methane burnt appears in the products as methyl alcohol. At atmospheric pressure, however, although strong indirect evidence points to a similar initial formation of alcohols the absence of a sufficiently sensitive test has hitherto prevented their detection by chemical means; and this circumstance has led to the suggestion that a secondary mechanism, operative chiefly at high pressures, may be responsible for their formation. Thus in a recent paper Norrish has stated, in reference to the oxidation of methane (p. 41), that “methyl alcohol arising of necessity according to a tertiary process—O + CH 4 + X = CH 3 OH + X' + 88 k. cals—will only appear in quantity at high pressures or in the presence of a high concentration of inert gas as is actually found to occur in the work of Newitt and Haffner” and again (p. 42) that “the formation of methyl alcohol as a stable product of the oxidation of methane is thus, according to the atomic chain hypothesis, only a limiting condition at high pressures”.