Journal of Physical Chemistry p. 5914 - 5919 (1984)
Update date:2022-08-04
Topics:
Manka, Michael J.
Stein, Stephen E.
Relative rates for radical disproportionation (R. + R'. <*> RH + R'd) and recombination (R. + R'. <*> RR') have been determined in the liquid phase at 150 deg C for a series of reactions involving resonance-stabilized hydroaromatic radicals.Self-reactions were studied for the 1-tetralyl, 1-indanyl, 9,10-dihydro-9-phenanthryl, and 9,10-dihydro-9-anthryl radicals.Four cross-radical reactions involving benzyl, diphenylmethyl, and 1-tetralyl radical as H-atom acceptors were also examined.Rate constant ratios (kd/kr) span the range of 1.34 for the self-reaction of 9,10- dihydro-9-phenanthryl radicals to 0.05 for the self-reaction of 9,10-dihydro-9-anthryl radicals.When disproportionation reaction exothermicity is sufficiently small, -ΔHd -1 (210 kJ mol-1), disproportionation rate constants decrease with decreasing exothermicity.A fit of liquid-phase data yields ln (kd/kr) per H atom = -10.1 - 0.163 ΔHd (kcal mol-1).
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