Most phenoxyl radicals rapidly oxidize ascorbate anion (rate constants from 4 to$20\times 10^{8}\ M^{-1}\ {\rm sec}^{-1}$) by a simple electron transfer process. The product radical anion is relatively unreactive and has a well-characterized absorption at 360 nm where it has an extinction coefficient of$3300\ M^{-1}\ {\rm cm}^{-1}$. In the case of a phenoxyl radical produced by OH attack on phenol, oxidation appears to be quantitative. Ascorbate is oxidized only slowly or not at all by less reactive radicals such as the alcohol radicals, para-semiquinones, or the phenyl radical. Ascorbate can, therefore, be used to selectively remove phenoxyl radicals from many mixed radical systems. Because ascorbate radical anion absorbs only weakly above 390 nm, where phenoxyl and para-semiquinone radicals absorb more strongly, ascorbate can be used to examine the oxidation of substrates in cases where phenoxyl and semiquinone radicals are produced simultaneously. This application is illustrated by a study of the attack of OH at the fluorine position of para-fluorophenol. A second illustrative example is provided by a study of the tertiary oxidation of ascorbate following reduction of the bromophenols by$e{}_{{\rm aq}}{}^{-}$. It is shown, in agreement with previous optical and ESR studies, that phenoxyl radicals are produced by rapid protonation of the hydroxyphenyl radical anion in the case of the ortho- and para-isomers but not in the case of the meta-isomer.

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