2839.     ROBINET, P.  [Hydropolymerization of Carbon Monoxide.]  Chim. et ind., vol. 47, 1942, pp. 480-482; Chem. Zentralb., 1942, II, p. 1652; Chem. Abs., vol. 37, 1943, p. 6107.

        Following reaction types occur in hydropolymerization of CO:

        (1)    2CO+2H₂→CH₂(OH)CHOH₂ CH₂(OH) CH₂OH;

        (2)    2CO+4H₂→C₂H₄+2H₂O;

        (3)    4CO+2H₂→C₂H₄+2CO₂.  

The synthesis of higher hydrocarbons from water gas at normal pressures is regarded as a combination of (2) and (3).  At higher pressures (1) takes place predominantly, with the formation of O-containing compounds.  In the reaction mechanism proposed, H₂O is split off before condensation occurs.  A primary complex is formed upon the catalyst.  At normal pressure this complex decomposes into CH₄.  Under the influence of condensing catalysts, an increase in the complex occurs on certain active centers, and the reaction becomes strongly exothermic.  If the growth of the complex is not stopped by the cleavage of H₂O or CO₂, the evolution of heat become so great that sudden decomposition of the complex takes place, so that all of the active centers can form only CH₄, H₂O, and CO₂.  It is possible that the complex grows not only under the influence of CO and H₂, but under the influence of free radicals that originate simultaneously in other active centers.  Thus, not a polymerization of radicals, as contemplated by Fischer, but a kind of copolymerization takes place upon the active centers.

        ROBITSCHEK, F. O.  See abs. 587.