Hydroxy! Radical-Induced Oxidation of Diisopropyl Ether in Oxygenated Aqueous Solution. A Product and Pulse Radiolysis Study

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Abstract
In the radiolysis of N2O/O2(4:1)-saturated aqueous solutions of diisopropylether(10-3 mol dm-3), OH radicals abstract H-atoms, thereby producing radicals at C(2) (1 .apprxeq. 78%) and to a lesser extent at C(1) (2 .apprxeq. 22%) which are converted by oxygen into the corresponding peroxyl radicals 3 and 4. Some O2-. radicals are formed by the reaction of radiolytically produced H atoms with oxygen. Methyl radicals formed in the course of the bimolecular decay of 3 and 4 give rise to methylperoxyl radicals. 5. At high dose rate as delivered by 2.8 MeV electron pulses the products (G values in parentheses) are: isopropyl acetate (2.6), acetone (1.1), isopropanol (1.1), 2-isopropoxypropanal (1.4, estimated), formaldehyde (2.0), organic hydroperoxides (0.4), organic acids (0.5) and hydrogen peroxide (1.9). At low dose rates (.ltoreq. 0.39 Gy s-1) G(acetone) is considerably increased and is no longer balanced by an equivalent yield of isopropanol. This is thought to be due to an intramolecular H-abstraction of radical 3. Pulse radiolysis studies revealed that 3, 4 and 5 decay by second order kinetics. At the early stages the bimolecular decay is faster (2 k .apprxeq. 6 .times. 107 dm3 mol-1 s-1) than toward the end (2k .apprxeq. 2 .times. 107 dm3 mol-1 s-1). It is suggested that the faster decay at the beginning is due to a preponderance of termination by the primary peroxyl radical 4 with the tertiary peroxyl radical 3 while at later stages termination is mainly governed by the reaction of 3 + 3 which produces 5. The rate constants k(5 + 3) and k(5 + 5) are very likely much higher than 2k(3 + 3), hence 2k(3 + 3) < 2 .times. 107 dm3 mol-1 s-1. On O2-saturated solutions O2-. plays a considerable role in the termination reactions, and organic hydroperoxides which are unimportant in N2O/O2-saturated solutions at high dose rates are now the major products.