Kinetics of the Methane—Oxygen Reaction¹

Abstract

305In connection with studies on the utilization of waste natural gas, more information than vvas available in the literature was desired concerning the kinetics of the oxidation of methane. This reaction is so complicated that complete interpretation of the data previously available appeared impossible. Curtailment of funds has necessitated interruption of the present investigation, but publication of the results to date seemed desirable.Bone and Wheeler3 studied the rates of reaction of various methane-oxygen mixtures in a static system; they also employed circulatory experiments to isolate transient intermediate products.Bone and Allum'L have recently repeated some of this work in silica vessels, again having shown the high reactivity of 2 : 1 methane-oxygen mixtures, which they adduced in support of the hydroxylation theory of hydrocarbon combustion. Fort and Hinshelwood,j working at temperatures of 447 to 487' and a t pressures less than atmospheric, have shown by static experiments the relatively greater dependence of the reaction rate upon the concentration of methane than upon that of oxygen. Induction periods complicated their results so :as to preclude detailed analysis, but the order of the reaction appeared to lie between third and fourth, and the heat of activation was estimatled to be 61,500. Increase in the silica surface was shown to decrease the rate, indicating breakage of the reaction chains a t the walls. In the present work flow experiments were employed to study the yields of intermediate and final products as contact time, total pressure, and surface were systematically varied.