[elworthy] 



PARTIAL OXIDATION OF METHANE 



101 



found to contain polymerized aldehydes and resins, methyl alcohol, 

 formaldehyde and formic acid. The wash waters gave strong reactions 

 for formaldehyde but no quantitative examination was made. 



Several explosions occurred, however, in the course of the experi- 

 ments and the form of the apparatus was not quite satisfactory. 

 It seemed one of the most promising lines of attack and further 

 experiments S'.hould be made, using much greater space velocities, 

 different mixtures of gas and oxygen, and better cooling and safety 

 devices. 



Method III — TJie Reaction Between Methane and Carbon Dioxide 



It was thought that by passing natural gas and carbon dioxide 

 over heated metals the oxygen formed at least in small amounts by 

 the decomposition of the qarbon dioxide might react with the methane 

 or the fugitive rCHo and :CH groups, which are perhaps momentarily 

 existent with the formation of partial oxidation products. 



The work of Bone and Coward'^ on the decomposition of hydro- 

 carbons by heat showed that methane is the most stable of the simple 

 hydrocarbon gases and carbon and hydrogen are only formed when 

 this gas is heated to 900-1000°. With metallic oxides and substances 

 affording considerable surface decomposition is much greater, accord- 

 ing to Slater. 12 



The equilibrium between carbon dioxide, C3.rbon monoxide and 

 carbon has been studied by Rhead^^ and Wheeler and by Boudouard^'* 

 with the following results at atmospheric pressure. 



Temp. C. 

 Percentage CO2 

 PC02 

 PCO 



100 

 0.59 

 0.000593 



In mixtures of 40-60 per cent. CO2 with 60-40 per cent, the partial 

 pressure of the CO2 will be one-third to one-half of an atmosphere 

 tending to greater dissociation than given in the table. The presence 

 of this amount of CO2 will also check the tendency for the formation 

 of the complete oxidation products of methane. 



Experimental 



The arrangement of the apparatus used in the experiments is 

 shown in Fig. 4. 



I'Jour. Chem. Soc. Trans. 93, 1197-1225, 1908. 



i=Ibid, 109, 160-164, 1916. 



I'Jour. Chem. Soc. Trans. 2178, 1910, and 99, 1141, 1911. 



"Ann. Chim. Phys., Series 7, 24, 5, 1901. 



