Counting of Free Alkyl Radicals. Application to the Photolysis of Acetone

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Abstract
Long, heavy lead mirrors are deposited in a reaction tube, and metal is transported therefrom by free radicals according to the Paneth method. The lead alkyl is collected and the lead determined by a micro‐method. Assuming that all the alkyl radicals are mirror‐active and that all the lead is transported as PbR4, the number of radicals can be estimated. The method is applied to work on the photolysis of acetone at 2537A. It is shown that the difference in apparent half‐lives of radicals produced at 45°C (1.1×10−2 sec.) and at 100°C (8×10−3 sec.) may be explained on the basis of the instability of free acetyl. The actual concentration of methyl radicals in the flowing gas in the experiments reported is estimated to be ∼2×10−3 mole percent or 1.7×10−12 mole per cc, immediately past the irradiated zone.
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