Title: Relevance of the Concentration Dependence of Methyl Radical Formation from Methyl Bromide Solutions to the Distribution of Ion-Pair Separation Distances in Irradiated Hydrocarbons
Abstract: A radiochromatographic technique for measuring the yields of methyl radicals formed on electron capture by methyl bromide in irradiated liquid hydrocarbons is described. G(CH3) has been measured in n-hexane, cyclohexane, and iso-octane from 3 × 10−6 to 0.3M CH3Br. Below 3 × 10−4M the yields are described by the equation G(CH3) = Gfi + K(CH3Br)1/2 in agreement with theory. The values of Gfi (free-ion yield) determined are 0.12, 0.13, and 0.36 for n-hexane, cyclohexane, and isooctane, respectively. Over the entire concentration range studied, G(CH3) can be described by the empirical expression G(CH3) = Gfi + (Ggi(αCH3Br[CH3Br])1 / 2 / {1 + (αCH3Br[CH3Br])1 / 2}). A value of approximately 4 is found for the yield of geminately recombining ion pairs for the three hydrocarbons. It is argued from the high-concentration data that the distribution of thermalization distances are closely similar for the different hydrocarbons, in contradiction to the predicted longer distances in iso-octane required to explain the high free-ion yield.
Publication Year: 1970
Publication Date: 1970-01-15
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 37
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