Reaction of Methyl Radicals with Ethylene

The gas phase reaction between methyl radicals and ethylene has been studied between 124° and 159° by the thermal decomposition of di‐t‐butyl peroxide in presence of ethylene. The value of k_4a/k₃^1/2 for the reactions, $${\mathrm{CH}}_3+{\mathrm{C}}_2{\mathrm{H}}_4\to {\displaystyle {lim}_{k_{\text{4a}}}}{\mathrm{C}}_3{\mathrm{H}}_7\text{\hspace{0.17em}\hspace{0.17em}2}{\mathrm{CH}}_3\to {\displaystyle {lim}_{k_3}}{\mathrm{C}}_2{\mathrm{H}}_6,$$ is ${\text{3.3×10}}^{\text{−7}}\mathrm{exp-8660}\mathrm{/RT\hspace{0.17em}}{\mathrm{molecule}}^{\text{−1/2}}{\mathrm{cm}}^{\text{3/2}}{\sec }^{\text{−1/2}}$ and the steric factor for the addition of methyl radicals to ethylene is about 7.6×10^—3. At low ethylene concentrations no evidence could be found for polymerization beyond the initial methyl radical addition.