Investigation of reactivity of ClΛ2- and BrΛ22 relative to vanadyl-ions in aqueous solutions by pulse radiolysis

Using the method of pulse radiolysis reaction kinetics of ion-radicals Cl2- and Br2- with vanadyl-ions in HCl, HBr and HClO4 solutions, has been studied. Electron energy is 5 MeV, pulse duration is 2.3 μs, dose per pulse is (0.5-2.0)x1017 eV/hr. Ion-radicals Cl2- and Br2- appearing during radiolysis disappear at the expense of disproportionation and reactions with other radiolysis products. Introduction of V(4) into solution increases the rate of Cl2- and Br2- disappearance and it causes changes of the order reaction from the first to the second one, at that, the rate constant is proportional to V(4) concentration. Rate constants of the reactions Cl21-+V(4) → V(5)+2Cl- and Br2-+V(4) → V(5)+2Br- increase with HCl and HBr concentration increase. It is explained by ''levelling'' of HVO3+ and VO3+ ion structure in strong acid medium