Structure-reactivity studies on the nature of transients formed on reaction of OH radicals with chloroiodoalkanes in aqueous solution

Mohan, Hari ; Mittal, Jai P. (1992) Structure-reactivity studies on the nature of transients formed on reaction of OH radicals with chloroiodoalkanes in aqueous solution Journal of the Chemical Society, Perkin Transactions 2 (10). pp. 1731-1736. ISSN 0300-9580

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Official URL: http://pubs.rsc.org/en/Content/ArticleLanding/1992...

Related URL: http://dx.doi.org/10.1039/P29920001731

Abstract

The transient optical absorption bands (λ max= 315 and 345 nm) formed on reaction of OH radicals with 1-chloro-3-iodopropane in N2O-saturated neutral aqueous solutions have been assigned to an OH-adduct formed between iodine atom and OH radicals (t½= 1.5 µ s, Î μ 350= 2.46 × 103 dm3 mol-1 cm-1). In acidic solutions, iodine-centred radical cations (λ max= 345 nm, t½= 4.0 µ s, Î μ 345= 2.41 × 103 dm3 mol-1 cm-1) are formed at low solute concentrations and dimer radical cations (λ max= 430 nm, t½= 16.0 µ s, Î μ 430= 6.7 × 103 dm3 mol-1 cm-1) at high solute concentrations. In chloroiodomethane, the OH radicals do not seem to form OH-adducts in neutral aqueous solutions. In acidic solutions, intramolecular radical cation (λ max= 430 nm, t½= 8.0 µ s, Î μ 430= 2.63 × 103 dm3 mol-1 cm-1) with oxidized iodine and chlorine is observed. The intermolecular dimer radical cations are formed at high solute concentration (λ max= 500 nm).

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