Abstract
The reactions of OH radicals generated radiolytically in N2O-saturated aqueous solutions with phenol have been examined, focusing special attention on the addition of dioxygen and the competing dehydration reactions of the OH-adduct radicals. Using the pulse radiolysis technique, the overall rate constant of dioxygen addition to the dihydroxycyclohexadienyl radicals was determined to be k = 1.2 × 109 dm3 mol−1 s−1. This dioxygen addition reaction was found to be practically irreversible, in contrast to other hydroxycyclohexadienyl radicals. The so-formed dihydroxycyclohexadienylperoxyl radicals subsequently eliminate HO2˙/O2˙−. By using tetranitromethane (TNM) as a probe for O2˙− (formation of the nitroform anion), the overall rate constant of HO2˙-elimination (mainly of the para- and ortho-isomers, formation of hydroquinone and catechol, respectively) was determined to be 1.3 × 105 s−1. The rate constant of the dehydration of the p-OH-adduct in neutral to acidic solution was determined by monitoring the absorbance build-up of the phenoxyl radical to be k7 = 1.8 × 103 + 1.7 × 109 × [H+] s−1, and that of the o-OH-adduct to be k6 = 1.1 × 108 × [H+] s−1 (the uncatalysed reaction is too slow to be measurable by this technique). The HPO42−-catalysed dehydration rate constant of the p-OH-adduct was similarly determined to be 5.8 × 107 dm3 mol−1 s−1. Based on the above rate constant of dioxygen addition, the rate constant of the proton-catalysed dehydration of the p-OH-adduct was determined by the competition of these two reactions on the yield of hydroquinone to be 1.0 × 109 dm3 mol−1 s−1, and similarly that of the ortho-OH-adduct (on the yield of catechol) to be 2.1 × 108 dm3 mol−1 s−1.
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More From: Journal of the Chemical Society, Perkin Transactions 2
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