2351. ---------------. [MYDDLETON, W. W.] Application of Free-Energy Equations to the Study of the Synthesis of Hydrocarbons From Carbon Monoxide and Hydrogen. Jour. Inst. Petrol., vol. 30, 1944, pp. 211-224, 248.
Equations have been derived relating free energy of reaction to temperature in the synthesis of a series of gaseous hydrocarbons from CO and H2. In building up these equations, molecular heat-temperature curves were drawn for each reactant and product and molecular heat-temperature equations were fitted over the range 25°-250° C., existing equations being generally unsatisfactory for the temperature range covering synthesis. Some use has been made of molecular heat and entropy values calculated from statistical and spectroscopic data. The suppression of reactions in which CO2 is formed, in spite of free-energy changes favorable to them, is attributed to special conditions prevailing at the catalyst surface. The appearance of traces of ethylene among the products of synthesis instead of appreciable quantities predicated by the free-energy relationships is accounted for by the incorporation of ethylene actually formed into the building up of hydrocarbon chains. The possibility of increasing the yields of isobutane and isobutene is considered worthy of attention. The formation of aromatic hydrocarbons requires a special orientation of reactants on the surface of the catalyst, and the probability of the necessary conditions occurring is slight.
----------. See abs. 9.
MYDDLETON, W. W., AND WALKER, J. Production of Hydrocarbon Oils From Industrial Gases. II. See abs. 10.