γ-Radiolysis of liquid t-butyl hydroperoxide

Abstract

The ⁶⁰Co γ-radiolysis of liquid t-butyl hydroperoxide gives O₂ as the principal gaseous product together with small amounts of H₂, CH₄, C₂H₆, C₂H₄(CH₃)₂CCH₂ and CO. The liquid products are t-butanol, water, di-t-butyl peroxide, acetone and traces of t-butyl methyl ether and t-butyl methyl peroxide. A satisfactory material balance was obtained between the disappearance of the hydroperoxide (G_–But_OOH= 33.7 at 20°C) and the yields of the products detected. G values have been measured over a range of radiation doses, dose rates and temperatures and the influence of radical scavengers has been examined. Nitrous oxide and benzene did not cause any changes in the product yields. The results indicate that radiolytic decomposition occurs predominantly in the hydroperoxy group, and they are discussed in terms of a mechanism which leads to a G value of 14.2 for direct radiolysis of the liquid hydroperoxide.