Radiation-induced oxidation of alcohols by TI(III) in acid aqueous solution

Abstract

In deaerated aqueous perchloric acid solution TI(III) is reduced and 2-propanol oxidized to acetone in essentially equivalent yields by a γ-ray induced chain reaction. The yields increase linearly with increasing alcohol concentration in the range (1–8) × 10−2 M, are independent of TI(III) concentration in the range (1–4) × 10−3 M and vary inversely with the square root of the dose rate over the range 1.6 × 1017 to 1.8 × 1019 eV l−1 s−1. A mechanism is proposed to account for the observed stoichiometry and kinetic parameters.The same mechanism is found to apply to the reduction of TI(III) by methanol and ethanol. t-Butyl alcohol gives a much lower yield of TI(III) reduction and alcohol fragmentation products: acetone, methane, and ethane.