Reactions of Hot Hydrogen Atoms with Halocarbons

Recoil Reactions of Tritium with Organic Compounds

“…Similar selectivity of tritium incorporation has been observed for other compounds: substitution of tritium for fluorine occurs more easily in CH3F than in CH2F2 (the yield of CH3T from the former is larger than the yield of CH2TF from the latter) [25]. To account for these results, Odum and Wolfsang [26] proposed a reaction model that involves the inertia of the fragments produced in the reaction. This can be briefly explained for the molecules CH3C1 and CH2C12 (see Figure 3, a and d): after fission of a C-C1 bond by collision with the hot tritium atom (Figure 3, b and e), the CH3 formed from CH3CI can rotate quickly into a position favorable for bond formation with the tritium (Figure 3, c), whereas the CH2C1 formed from CH2C12 rotates more slowly because of its higher moment of inertia and allows sufficient time for the tritium atom to escape before CHZTC1 can be formed.…”

Reactions of Recoil Τ Atoms with Liquid Chloroethylenes

“…The somewhat higher T-for-H substitution yield for 1,1-C 2 H 2 C1 2 may be due to addition of a Τ atom at the CH 2 site, followed by the loss of a Η atom. Comparison with the T-for-H substitution yields in gaseous CH 3 C1 (8.3%) and CH 2 C1 2 (2.9%) [13] suggests that Η substitution in chloroethylenes is not much hampered by the presence of an unsaturated bond and that the reaction proceeds by energetic Τ atoms. The retention of the original configuration in cis and trans 1,2-C 2 H 2 C1 2 (86%) is somewhat lower than found by WAI and KING (93%) [2], but is still consistent with the proposition of a hot substitution reaction.…”

Computer Simulation Evaluating Kinetic Theory Parameters in Hot Atom Chemistry

“…The physical impact [17,18] and inertial [19] models of the system, although largely successful, were found to require modifications based on other physical parameters such as steric effects [11] and kinetic energy moderation [15] as well as chemical parameters such as bond energies [12][13][14][15] and radical scavengers [16].…”