Abstract
The mercury-photosensitized decomposition of neopentane was investigated from 230 to 335 °C, and at pressures from 3 to 280 Torr. The following were identified as primary products and their initial rates of formation measured over a range of conditions: H2, CH4, C2H6, i-C4H8, neohexane and dineopentyl. The results are explained in terms of a mechanism in which the primary step involves the split of neopentane (Nptn) into the neopentyl radical (Nptl) and H; Nptl then undergoes further reactions including a split into i-C4H8 + CH3. Estimates are made of the free-radical concentrations at various temperatures and pressures. A simplified steady-state treatment is worked out and is shown to explain the pressure dependence of the rates of formation of the various primary products.

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