SOURCES OF ENERGY 169 



of the crust of the Earth (mainly methane, ethane, acetylene, 

 etc.) were, in part, given off directly into the atmosphere 

 while, in part, they under^vent various chemical changes 

 Avithin the lithosphere itself. We will only discuss a few of 

 the many reactions which may have taken place there. 



The simple thermal polymerisation of methane to ethane, 

 propane and other higher hydrocarbons would seem to be 

 out of the question, since ethane cannot be formed at tem- 

 peratures above 227° C or propane above 180° C and, within 

 the limits of these temperatures, methane is quite stable and 

 has no tendency to dehydrogenation or polymerisation. It 

 has, however, been shown by V. Sokolov that, under the 

 action of a-radiation from the radioactive elements of the 

 crust of the Earth, the molecules of methane may become 

 more complicated with the evolution of hydrogen and the 

 formation of ethane and also of the simplest olefines. Further 

 polymerisation takes place, with the formation of gaseous 

 and liquid hydrocarbons of high molecular weight. 



Without receiving energy from external sources molecules 

 of methane can undergo conversion according to the equa- 

 tion": 



CH4 -t- H20->C0 -f 3H2 



The change in free energy, Az cal/mole, in this equation 

 has been calculated by A. Pasynskii from the table of V. 

 Korobov and A. Frost : ®* 



Az= - 49270 + 5i-3T-f ii-i/ (t/ 298- 16)* 



It only enters a region of positive values (w^hen the process 

 comes to a standstill spontaneously for thermodynamic 

 reasons) above 650° C. 



At far lower temperatures (of the order of 100-200° C), 

 though under increased pressure, methanol is formed from 

 carbon monoxide and hydrogen according to the equation: 



CO -t- 2Ho->CH30H 



* In this calculation, as in those which follow, values for AZ have been 

 calculated for standard conditions and for the ,a;aseous state. T is tempera- 

 ture in degrees Absolute. The function / (T/298-i6) = Ln (T/298-i6)-f 

 (298-16/T) — 1. All have been made by A. Pasynskii from the table of 

 Korobov and Frost. — Author. 



