Mechanism of the conversions of intermediate particles in liquid-phase radiolysis of acetic and propionic acids, investigated by ESR

The yields of radicals in the γ-radiolysis of liquid acetic and propionic acids were measured using spin traps MN and BNB. These conclusions are compared with the yields of the end products CH4, C2H6 and CO2, inhibited by addition of spin traps. The reduction of the yields of the trapped radicals is due to charge transfer from dimeric radical cations of the acids to the traps. A correlation was obtained between the yields of trapped radicals and the ability of the traps to capture a positive charge. The ionic-molecular reaction of proton transfer within the dimer, followed by decarboxylation of the acyloxy radical, is the predominant process; the yields of alkyl radicals formed are equal to the yields of R·CO radicals, within the limits of error. 10 refs., 4 figs., 1 tab