The main products formed in the oxidation of methane at 300-450° C are methyl alcohol, formaldehyde, formic acid, carbon monoxide, carbon dioxide and water (Bone and Wheeler 1903; Bone and Allum 1932). It was suggested by Bone that these substances were produced in a series of successive steps by hydroxylation of the methane molecules, thus: It was concluded that the initial step in this reaction was termolecular since the rate of the reaction for the mixture 2CH
4
: O
2
was Considerably faster than those for CH
4
: O
2
and 3CH
4
: O
2
. In the above hydroxylation scheme, methyl alcohol is an intermediate product and the precursor of formaldehyde. This has been disputed by Norrish (1935), who taking into account the difficulty of detecting methyl alcohol in oxidations at atmospheric pressure, and the chain characteristics of the reaction, came to the conclusion that methyl alcohol is a side product of the reaction. The first result of the oxidation was regarded as being an unstable molecule, CH
4
O*, which breaks down within a short time interval to the methylene radical and water. Methyl alcohol arises only if this molecule collides with an inert gas molecule or with the walls of the containing vessel. The results of Newitt and Haffner (1936), who obtained high yields of methyl alcohol in the combustion of methane at 100-500 atm. pressure, can be taken as confirming this view of the mode of origin of the methyl alcohol. The following reaction scheme was proposed for the decomposition of CH
4
O*:
Does Water Relay Play an Important Role in Phosphoryl Transfer Reactions? Insights from Theoretical Study of a Model Reaction in Water andtert-Butanol
