THE REACTION OF t-BUTYL ALCOHOL VAPOR WITH Hg 6(3P1) ATOMS

Abstract

The nature of the decomposition of t-butyl alcohol vapor, photosensitized by Hg 6(3P1) atoms in a static system at room temperature, has been examined under a variety of conditions of continuous and intermittent illumination. The inhibiting effect of nitric oxide has also been studied, as well as the influence of added inert gas.In the decomposition of pure substrate, the reaction products, with the initial quantum yields, Φ°, under continuous illumination in parenthesis, were: H2 (0.045), Me2CO (0.090), CO (0), CH4 (0.015), C2H6 (0.030) together with lesser amounts of C3H8, Me3CH, Me3CMe, and Me3COMe. On addition of nitric oxide, Me3CONO, Me2CO, N2O, N2, H2O, and trace quantities of H2 and CO were the only products observed.The reaction[Formula: see text]is proposed as the primary process in the decomposition and kinetic evidence is presented that the initially formed t-butoxy radicals possess excess energy and that their principal subsequent reaction is unimolecular cleavage into acetone and methyl. The results furthermore indicate that the substrate itself is quite inert to abstractive attack by the primary radicals.