Recoil chlorine ¡Chlorotoluenes /Hot atom chemistry /Ipso attack AbstractThe chemical reactions of recoil 38 C1 atoms have been studied in liquid ortho, meta and para chlorotoluenes and in a 1 :1:1 mixture. In the pure liquids, the total organic yield is less in meta isomer compared to ortho and para isomers and is mainly due to a lower 3 * Cl-for-Cl substitution yield. In systems scavenged with 2 mol % I,, these substitution yields are about same for each of the three isomers. In a 1 :1 :1 mixture of the o : m : ρ isomers, containing 2 mol % I 2 , the ratios of the (hot) 38 Cl-for-Cl substitution yields are close to statistical. The distribution for thermal exchange reactions is however, selective. The 3, Cl-for-H substitution yield is less than 1 % per Η atom-aromatic and methylic-and is scavenger independent. The 3, Cl-for-CH 3 substitution yield is also about 1 %, whereas in a 1 :1 :1 mixture the o : m ; ρ ratio is not far from statistical.

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Using pulse radiolysis techniques, rates of recombination of electrons with Het ions in the presence of helium over a wide pressure range (40-900 Torr) and at temperatures of 200, 235, 275, and 295 K were measured. Two-and three-body recombination processes were resolved, and a temperature dependence for the three-body recombination rate constant of T(;;;.2.9± 1.2) observed. This result agrees well with theoretical predictions of a temperature expo~ent of -2.5 by Bates and Khare and Pitaevskii, and remarkably well with recent work by Cao and Johnsen which gave a temperature exponent of -2.9 for the rate constant for three-body recombination of electrons with simple molecular ions in the presence of helium.

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