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Pulse Radiolysis Investigations On the Nature of Oh Radical Reactions With 1-Fluoro-2-Iodobenzene in Aqueous Solutions

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The transient optical absorption bands (λmax = 310 nm, 330-350 nm, k = 3.2×109 dm3 mol-1 s-1) formed on reaction of'OH radicals with 1-fluoro-2-iodobenzene in neutral aqueous solutions are assigned to OH-adduct, which decayed by second order kinetics with 2k = 2.9×109 dm3 mol-1 s-1. The absorption band (λmax = 630 nm) observed in acidic solutions (pH = 3) is assigned to solute radical cation formed on removal of an electron from iodine, which decayed by first order kinetics with k = 5.6×105 s-1. At pH = 1, the OH-adduct was found to react with H+ (k = 4.7×105 s-1) and formed a broad absorption band in 350 - 400 nm region. It is assigned to solute radical cation formed on removal of an electron from fluorine. Acid-catalyzed dehydration of OH-adduct is observed with ~85% at iodine and ~15% at fluorine. The iodine centered radical cation is a strong one-electron oxidant and is able to oxidize I- and Br- with rate constant in the diffusion controlled range. SO4*- radical anion is able to undergo electron transfer with the solute and absorption bands due to iodine centered radical cation (λ = 630 nm), and OH-adduct (λ = 310, 330-370 nm) are observed.

Affiliations: 1: Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India


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