Unimolecular Decomposition of Vibrationally Excited Ethane and Ethyl Radicals

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Abstract
H or D atoms and ethyl radicals were concurrently produced by the mercury sensitized photolysis of mixtures of H2 (or D2) and diethyl ketone. Combination of an ethyl radical with a hydrogen atom produces vibrationally excited ethane molecules. Their rate of dissociation into methyl radicals relative to stabilization to ethane was studied as a function of pressure of ketone for both H and D. Similar studies were made of the mercury sensitized reactions of mixtures of D2 or H2 and ethylene, which permitted the measurement of the maximum rates of decomposition of excited ethyl radical and of excited ethane both as a function of pressure and of temperature. Our results show that vibrational energy is not used in overcoming the barrier for alkyl radical addition to an olefin bond.

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