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The Relative Reactivities of Ethane, Ethane-d6, n-Butane and Neopentane towards ‘Hot' Tritium Atoms

The reactions of recoil tritium with ethane—butane, and ethane—neopentane mixtures have been studied in the presence and absence of helium moderator. I t is shown that the larger molecules are labelled by recoil atoms of a higher mean energy than those which label ethane. I t is also shown that hydrogen atoms at CH2 sites are replaced by higher energy tritium atoms than those at CH3 sites. An analogy is drawn with the abstraction reaction and a simple unified model for high-energy recoil tritium reactions at a C—H site is proposed. The more complex the other groups attached to the carbon the greater the mean energy of the recoil atoms reacting with the C—H bond. Experiments with ethane-dj established that the primary isotope effect for abstraction is comparable to that for displacement with a value of 1.25 ~ 1.30.