The decomposition of n -hexane II. By reaction with atomic hydrogen

Abstract

The reaction of hexane with hydrogen atoms produced by mercury photosensitization, has been studied in a flow system at 300° C. About one-third of the products had molecular weights greater than that of hexane, and dodecane was the main component of this product fraction. Hydrogen: hexane ratios up to 55:1 were employed and in these conditions virtually all the quenching of excited mercury atoms was brought about by hydrogen. The activation energy and steric factor of the reaction C 6 H 14 + H = C 6 H 13 + H 2 are estimated at 6 kcal and 10 -4 , respectively. These values are in accord with those recently obtained for the corresponding reactions involving other n -paraffins. The initial product distribution was similar to that obtained in the mercury photosensitized decomposition of hexane and the findings suggest that products of lower molecular weight than hexane derive almost completely from thermal decomposition of hexyl radicals. ‘Atomic cracking’ appears to be of little importance at these high temperatures.