Gaseous Reaction of Methyl Radicals with Propylene

Abstract

A study of the gaseous pyrolysis of Di-t-butyl peroxide in presence of propylene indicates that methyl radicals add predominately (about 90%) to the terminal carbon atom of propylene. The value of k4a/k3½ for the reactions CH3+C3H6→ lim k4aCH3CH2CHCH3 2CH3→ lim k3C2H6is 2.07×10—7 exp (—8800/RT) molecule—½ cm32 sec—½. Disproportionation—combination ratios for methyl—secbutyl radicals and secbutyl—secbutyl radicals were 0.08 and ≈1.2, respectively, independent of temperature. Addition of secbutyl radicals also occurs to propylene under the experimental conditions with a rate about comparable to the initial CH3 addition.