Radiolytic yield of U(IV) oxidation into U(VI): a new mechanism for U(V) reactivity in acidic solution.

The yields of the radiolytic oxidation of U(IV) and of the U(VI) formation, measured by spectrophotometry, are found to be the same (G(-U(IV))(N2O) = G(U(VI))(N2O) = 8.4 x 10(-7) mol J(-1)) and almost double the H(2) formation yield (G(H(2)) = 4.4 x 10(-7) mol J(-1)) in the (60)Co gamma radiolysis of N(2)O-aqueous solutions in the presence of 2 mol L(-1) Cl(-) at pH = 0 (HCl). According to the mechanism of U(IV) radiolytic oxidation, we show that under the conditions of our experiments the U(V) ions do not disproportionate, but undergo a stoichiometric oxidation into U(VI) by H(+) with forming H(2).

Aqueous solution of UCl6(2-) in O2 saturated acidic medium: an efficient system to scavenge all primary radicals in spurs produced by irradiation.

Absorbance measurements find the yield of the oxidation of U(IV) to be (8.75 +/- 0.05) x 10(-7) mol J(-1) in the (60)Co gamma radiolysis of aqueous solutions containing 4.4 x 10(-3) mol L(-1) U(IV) in the presence of O(2) saturated 2 mol L(-1) Cl(-) at pH = 0. This high value of oxidation yield suggests that all primary radicals formed by water decomposition are scavenged in these solutions. Simulations using a nonhomogeneous stochastic kinetic track model agree with the experimental results and are used to explain the mechanism for scavenging radicals and oxidation of U(IV).