Oxidation studies by peroxy disulphate. I. Secondary and tertiary alcohols

Abstract

Results on the oxidation of secondary and tertiary alcohols(secondary butanol; cyclohexanol; tertiary butanol) by peroxydisulfate under uncatalysed, Ag+ Catalysed, and deaerated conditions in the temperature range 50 to 70˚ C Are presented. The rate of peroxydisulfate disappearance, under uncatalysed Conditions was found to be dependent (i) on [S2 O8-] for all the alcohols; (i i) on [secondary butanol] ½; and (i i i) indepcndent of [cyclohexanol] and [t-butanol] In the Ag+ catalysed oxidations an additional dependence on [Ag+]½ was observed. Effects of [H+], ionic strength, temperature, added products oxidation on the rates were studied, ∆E, A, ∆S+ were evaluated. Mechanism for Oxidations of alcohols based on S2O8- for uncatalysed conditions and by S2O8- + Ag+ reaction under catalysed conditions are suggested. Formation of reactive Ag++ is also postulated.