The chemical behavior of Np is influenced by many factors, such as U(IV), hydrazine, Pu and Tc, which coexist in U/Pu separation stage of PUREX process. Firstly, the reduction of Np(V) to Np(IV) by Tc(IV) was studied in nitric acid media, and the rate equation could be expressed as −d[Np(V)]/d = [Np(V)][Tc(IV)] 0.8 [HNO 3 ] 1.2 ,= 28.5 ± 0.9 (L/mol) 2 /min at 25 ∘ C, the activation energy was a = 70.0 kJ/mol. Thereafter, the chemical behavior

In order to understand the equilibrium state, conversion process and mechanism of Np(V)/Np(VI) in nitric acid solution, the redox kinetics of neptunium with nitrous and nitric acids was studied spectrophotometrically by an nonlinear fitting method. The rate equation of the redox reaction was acquired. Apparent activation energy of forward reaction and reverse reaction are approximately the same of 80 kJ/mol. Varying the concentrations of nitric and nitrous acids will change the reaction rate of forward and reverse reaction in different degrees. As a result, the equilibrium state of Np(V)/Np(VI) is altered, but it is not influenced by temperature.

In order to understand the complex and dynamic neptunium process chemistry in the TBP-HNO 3 system, the kinetics involved reversible redox reaction and extraction mass transfer was investigated. The results indicates that the mass transfer rate of Np(VI) is much faster than the redox reaction in aqueous solution. The concentrations of nitric acid and nitrous acid not only can change the Np(V) oxidation reaction and Np(VI) reduction reaction rate, but also can ultimately determine the distribution of neptunium extraction equilibrium. The variety of temperature can only influence the extraction equilibrium time, but cannot alter the equilibrium state of neptunium.

The kinetics of U(IV) produced by hydrazine reduction of U(VI) with platinum as a catalyst in nitric acid media was studied to reveal the reaction mechanism and optimize the reaction process. Electron spin resonance (ESR) was used to determine the influence of nitric acid oxidation. The effects of nitric acid, hydrazine, U(VI) concentration, catalyst dosage and temperature on the reaction rate were also studied. In addition, the simulation of the reaction process was performed using density functional theory. The results show that the influence of oxidation on the main reaction is limited when the concentration of nitric acid is below 0.5 mol/L. The reaction kinetics equation below the concentration of 0.5 mol/L is found as: −d c(UO22+)/d t= kc0.5323(UO22+) c0.2074(N2H5+) c−0.2009(H+). When the temperature is 50 ◦C, and the solid/liquid ratio r is 0.0667 g/mL, the reaction kinetics constant is k=0.00199 (mol/L)0.4712/min. Between 20 ◦C and 80 ◦C, the reaction rate gradually increases with the increase of temperature, and changes from chemically controlled to diffusion-controlled. The simulations of density functional theory give further insight into the influence of various factors on the reaction process, with which the reaction mechanisms are determined according to the reaction kinetics and the simulation results.