294 PROF. W. A. BONE AND OTHERS ON 



From which it is evident that the passage from A to B involves an evolution of 

 30 heat units, of which 22 '8 would be absorbed if the transition B to B' supervened, 

 whereas the further passage from B to C involves an evolution of 59 heat units, of 

 which only 13 '4 would be absorbed during the transition C to C'. Hence, it might 

 be expected that, whenever circumstances are favourable or permit, the transition A to 

 B would be immediately followed by B to C, rather than by B to B'. Or, in other 

 words, there would usually be a strong tendency for a " non-stop " run from A to C 

 through B, that is, without any thermal decomposition in passing through B. The 

 last-named, although not precluded, would only occur exceptionally. Moreover, it 

 may be pointed out that the thermal decomposition of CH 3 OH(B to B') involves a 

 slightly greater heat absorbtion than the resolution of methane itself into its elements 

 (namely, 22'8 for methyl alcohol, as against 227 for methane) and that, therefore, 

 heat liberated by oxidation (A to B or B to C) would be just as likely to decompose 

 any residual methane as it would the methyl alcohol formed in passing through B. 

 This consideration is of importance in connection with the course of events when 

 methane is exploded with considerably less than its own volume of oxygen. 



Any theory must, however, be capable of accounting for the following outstanding 

 facts, namely (l) the ultimate formation of large quantities of both carbon and steam 

 in the explosion of the mixture 2CH 4 + 2 ; (2) the disappearance of carbon from the 

 products when the proportion of oxygen in the mixtures exploded exceeds 40 per cent.; 

 and (3) the occurrence of oxides of carbon and steam in the products of all the 

 mixtures fired. 



There is no difficulty in explaining, on the lines of the hydroxylation theory, the 

 facts comprised under (l) and (3), especially in view of the strong tendency there 

 would always be for a non-stop passage from CH 4 to CH 2 (OH) 2 , without any breaking 

 down at the intermediate CH 3 .OH stage. 



In the case of the equimolecular mixture, CH 4 + O 2 , the primary oxidation may thus 

 be represented as a single transaction, 



2 = [H 2 : C : (OH)J = H 2 : C : + H 3 



involving the formation of steam but no separation of carbon. The facts observed 

 with the mixture 2CH 4 + 3 , may also be explained on the supposition that in the 

 primary oxygen attack half of the methane molecules are directly transformed into 

 CH 2 (OH) 2 , and that the heat so liberated is sufficient to decompose part of the other 

 half of the methane into its elements, the remainder being found intact after the 

 explosion. 



To explain the non-separation of carbon when the mixture 3CH 4 + 2O 2 , was exploded, 

 it must be supposed that whilst one-third of the methane is direc.tly transformed into 

 CH 2 (OH) 3 , the other two-thirds cannot, for lack of oxygen, get beyond the CH 3 . OH 



