1103. FROLICH, P. K., AND CRYDER, D. S. Catalysts for the Formation of Alcohols From Carbon Monoxide and Hydrogen. VI. Investigation of the Mechanism of Formation of Alcohols Higher Than Methanol. Ind. Eng. Chem., vol. 22, 1930, pp. 1051-1057; Chem. Abs., vol. 24, 1930, p. 5717. Frolich and Cryder continue their study of the high-pressure synthesis of alcohols from mixtures of CO and H2 (abs. 1100). The mechanism of formation of alcohols higher than MeOH has been determined by studying the behavior of the individual compounds that might form as intermediates. With MeOH as an intermediate product the higher alcohols are formed by successive condensation of lower ones. The initial condensation of MeOH to EtOH controls the overall rate of this stepwise process: 2MeOH→EtOH+H2O. The ease with which further condensation takes place accounts for the small amount of EtOH in the product. CO in excess aids in the formation of higher alcohols because it acts on the water vapor and removes it from the surface of the catalyst: H2O+CO→CO2+H2. This reaction explains the presence of large amounts of CO2 in the higher alcohol synthesis. Any acids formed are found as esters and these appear to be produced directly by polymerization of aldehydes rather than by the intermediate production of acids by addition of CO to MeOH. |