Photolysis of Benzyl Chloride Vapor in the Presence of Ethane or n-Butane

Benzyl chloride vapor has been photolyzed in the presence of ethane or n‐butane at 184.9, 206.2, and 253.7 nm. Pressure, wavelength, and temperature effects on the quantum yields of products were examined. Benzyl chloride was found to photodecompose predominantly to a benzyl radical and a chlorine atom. The chlorine atoms abstract the hydrogen atom from ethane or n‐butane to form ethyl or butyl radicals. The reaction of these radicals with benzyl radicals results in the formation of various products. The quantum yield of the initial photodecomposition of the $\mathrm{C}–\mathrm{Cl}$ bond in benzyl chloride at 184.9 nm (at zero n‐butane pressure) was obtained to be 0.9. The initial photodecomposition rate constant of benzyl chloride at 184.9 nm has been estimated. The ratio between disproportionation and recombination reaction rate constants of radicals has also been obtained.