Abstract
Aqueous potassium peroxodisulphate (0.01 mol dm −3) together with tert-butanol (0.1 mol dm −3) was photolysed with 254 nm light at 20 °C. The peroxodisulphate ion is cleaved, giving rise to sulphate radicals SO 4 − . These attack the tert-butanol under hydrogen abstraction and hydrogen sulphate formation. In deoxygenated solutions, Φ(H +) = 1.4, Φ(SO 4 2−) = 1.4 and Φ((HOC(CH 3) 2CH 2) 2) is approximately 0.7; in the presence of oxygen, Φ(H +) = 1.8. The enhancement of Φ(H +) by oxygen comes about through the production of superoxide via one of the bimolecular decay channels of the tert-butanol-derived peroxyl radical. The superoxide radical reduces S 2O 8 2− under liberation of further SO 4 − . The oxygenated peroxodisulphate- tert-butanol system is shown to constitute a straightforward actinometer for 254 nm light. Some data and observations regarding the tert-butanol-free peroxodisulphate system are also presented.
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