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In pure CC14 the reactions of 34m Cl recoil atoms result in the formation of 35% CCI 3 34 m Cl, 6% C2Cl5 34m Cland 3% C2Cl3 34m Cl.Product yields obtained with mixtures of CCI, and hydrocarbons lead to the conclusion that 3% CC13 34m Cl is formed via a hot direct reaction and 32% via cage reactions. Cage reactions are also supposed to be involved in the production of the main fraction of C2C1S 34m Cl by combination of CC12 34m Cl and CC13 radicals, but in the presence of hydrocarbons, these CC12 34m Cl radicals result in the formation of 5% CHC12 34m Cl. The rather high yields of R 34m Cl at low RH concentrations are explained by an abstraction-recombination reaction in a cage with excited molecules and radicals. The 12% yield of l,2-C6H12Cl 34m Clfound at low concentrations of 1-hexene sets an upper limit of 12% to a Cl-abstraction reaction by hot 34m Cl atoms. The 10% inorganic yield, formed in a mixture with 75% cycloheptatriene sets an upper limit of 10% to hot Η-abstraction. The high inorganic yield of 57% measured in pure CC14 is explained by cage reactions and by reactions of diffusive thermal 34m Cl-atoms. No clear explanation could be given for the formation of C2Cl3 34m Cl.

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The yield of 23% C 2 Cl 3 34m Cl measured in liquid C 2 Cl 4 is formed by direct hot replacement (5%) and via a 34m Cl addition/ CI elimination reaction sequence in an excited cage (18%). In the case of 1, 2-C 2 H 2 C1 2 2.6%ofthe 1, 2-C 2 H 2 tl 34m Cl yield is formed via a direct hot replacement reaction with retention of the original configuration and 13.3% by addition-elimination reactions with full racemisation. The addition of 34m Cl to 1,1-C 2 H 2 Cl 2 in a reaction cage proceeds mainly at the carbon atom of the CH 2 group. Replacement of H atoms can proceed via a direct hot reaction or via a cage reaction between a 34m Cl atom and a C 2 X 3 radical. The yield of high boiling compounds (about 44%) can be due to fragmentation/ addition reactions started by hot 34m Cl atoms, and partly by more thermal-like addition reactions of C 2 X s radicals. No satisfactory explanation could be given for the formation of inorganic yield of about 32%.

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