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.