Abstract
Two classes of kinetics are exhibited in the γ-radiation-induced radical-chain reduction of toluene-p-diazonium ions with the above reducing agents in aqueous oxygen-free solution, the overall reaction being ArN2++ RH2→ ArH + N2+ R + H+. In class A, G(–ArN2+) is proportional to [RH2]/[ArN2+] and independent of dose rate; and in class B, proportional to [ArN2+]/(dose rate)1/2 and independent of [RH2]. A reaction sequence to account for these observations is proposed, the relative rates of the reactions involved determining the class of kinetics exhibited. By altering the concentration of ArN2+ it is possible to change the behaviour of the system from one class to the other. The rate of hydrogen abstraction by the p-tolyl radical from RH2 is in the order hypophosphite and phosphite > formate > methanol > formic acid. Addition of acid decreased G(–ArN2+) in the case of the oxyanions, but not for methanol.
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