Laser flash photolysis (at 248 or 308 nm) or aryl iodides in water or
water/methanol solutions produces iodine atoms and phenyl radicals. Io
dine atoms react rapidly with added I- to form I2- but do not react ra
pidly with O2 (k less-than-or-equal-to 10(7) L mol-1 s-1). Iodine atom
s oxidize phenols to phenoxyl radicals, with rate constants that vary
from 1.6 x 10(7) L mol-1 s-1 for phenol to about 6 x 10(9) L mol-1 s-1
for 4-methoxyphenol and hydroquinone. Ascorbate and a Vitamin E analo
gue are also oxidized very rapidly. N-Methylindole is oxidized by I at
oms to its radical cation with a diffusion-controlled rate constant, 1
.9 x 10(10) L mol-1 s-1. Iodine atoms also oxidize sulfite and ferrocy
anide ions rapidly but do not add to double bonds. The phenyl radicals
, produced along with the I atoms, react with O2 to give phenylperoxyl
radicals, which react with phenols much more slowly than I atoms. (C)
1995 John Wiley & Sons, Inc.