SOURCES OF ENERGY 177 



A large number of oxygen-containing derivatives ot hydro- 

 carbons are also easily formed under the influence of electric 

 discharges. The conversion of methane, CH4 + HoO^co + 3H2, 

 which could only take place in the lithosphere at compara- 

 tively high temperatures, occurred in the cold in the primi- 

 tive atmosphere by making use of the energy of electric 

 discharges. The carbon monoxide thus formed reacted, in its 

 turn, with methane, according to the equation: 



CH4 -f CO-^CH3.CHO 



Calculations for this reaction give Az = 4,800 -f 28-2T. This 

 means that, for thermodynamic reasons, the reaction by 

 which acetaldehyde is formed from methane and carbon 

 monoxide cannot occur spontaneously at any" temperature. 

 Nevertheless S. M. Losanitsch and M. Z. Jowitschitsch^"^ 

 submitted a mixture of carbon monoxide and methane to the 

 action of silent discharges and obtained an oily condensation 

 product containing acetaldehyde. On continued action of 

 the discharge this polymerised to aldol and more complicated 

 condensation products. 



QCHa.CHO-^CHj.CHOH.CHo.CHO^ (CHa.CHOH.CHo.CHO)^ 



The acetaldehyde itself forms a number of gaseous and 

 liquid products when its vapour is mixed with hydrogen and 

 submitted to the action of a silent discharge. The following 

 equations express some of the individual reactions"^: 



2CH3.CHo->H2 + CO + CH3.co.CH3 (acetone) 

 3CH3.CH0^2H2 + 2CO + C2H5.CO.CH3 (methyl ethyl ketone) 

 2CH3.CHO-^H2 + CH3.CO.CO.CH3 (diacetyl) 

 2CH3.CHO^C2H4 + CH3.C00H (acetic acid) 

 4CH3.CHO->C2H4 + 2C2H5.COOH (propionic acid) 



Reactions by which aldehydes are formed directly from 

 hydrocarbons and carbon monoxide appear to be very 

 general. For example, under action of electric discharges 

 a mixture of ethylene and carbon monoxide gives rise to 

 acrolein,"'^ 



CH2:CH2 + CO-^CHolCH.CHO 



12 



