Kinetics and mechanism of the plutonium catalysed nitric acid oxidation of U(IV) ions in 30% tributyl phosphate solution

The oxidation of U(IV) ions in the diluted solvent phase, 30% TBP/ n -dodecane, has been investigated in the presence of plutonium ions, which can act as catalysts for U(IV) oxidation. The reaction was shown to follow the cycle below, with the first and third stages being rate determining. U 4+ + 2Pu 4+ + 2H 2 O → UO 2 2+ + 2Pu 3+ +4H + 2Pu 3+ + HNO 3 + 2H + → 2Pu 4+ + HNO 2 + H 2 O Pu 3+ + HNO 2 + H + → Pu 4+ + NO + H 2 O 2NO + HNO 3 + H 2 O ⇔ 3HNO 2 The overall reaction stoichiometry is the same as for the oxidation of U(IV) by HNO 3 in TBP: U(NO 3 ) 4 ·2TBP + HNO 3 ·TBP + H 2 O·TBP + TBP ⇔ UO 2 (NO 3 ) 2 ·2TBP + HNO 2 ·TBP + 2HNO 3 ·TBP The rate equations of both these rate limiting steps have been determined, with that for the U(IV)-Pu(IV) reaction (5) being given by the equation below, where k 1 =74.4±6 M -1.2 min -1 at 25.2 °C and the activation energy is 72±11 kJ mol -1 (in 0.5 M HNO 3 ). The rate of the second slow stage, the Pu(III)-HNO 2 reaction, is given by the equation below, where the rate constant is k 2 =627±28 M -1 min -1 at 25.2 °C and the activation energy is 87.2±1.4 kJmol -1 (in 0.5 M HNO 3 ). Mechanistically, it was shown that the U(IV)-Pu(IV) reaction may proceed via the interaction of the hydrolysed actinide ions U(OH) 2 2+ and PuOH 3+ and the Pu(III)-HNO 2 reaction was found to most probably involve oxidation of Pu(III) ions by nitrinium nitrate (NONO 3 ) ions in its rate determining step.