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Relative rates of formation of isotopic radicals in the photolysis of gaseous methyl and ethyl bromide have been measured. Photolyses (2537 A) were carried out in a large excess of cyclopentane. Methyl (or ethyl) radicals formed in the primary C☒Br bond scission abstract H from cyclopentane to form methane (or ethane). For methyl bromide, the C12/C13 enrichment factor for the first fraction of the methane was 1.039±0.003. The corresponding factor for the α‐carbon—Br rupture in ethyl bromide was 1.041±0.004. In the deuterium experiments, CH3Br—CD3Br mixtures in excess cyclopentane were photolyzed. The H/D fractionation factor (based on CH4/CD3H) was 1.41±0.01.The difference in rates of formation of isotopic radicals is due to the difference in ultraviolet absorption coefficients of the isotopic alkyl bromides. At 2537 A the observed ratio of the extinction coefficient of CH3Br relative to that of CD3Br is 1.38±0.05

C13 and Deuterium Isotope Effects in the Photolysis of Methyl and Ethyl Bromide