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在振动搅拌槽中,研究了UO_2(NO_3)_2-HNO_3-N_2H_5NO_3(H_2O)/30％TBP(煤油)体系的水相电解液组分浓度对U(Ⅵ)电解还原速率的影响。根据实验数据,经回归分析得反应动力学微分方程: -(d[U(Ⅵ)]/dt)=k[U(Ⅵ)]~(0.77)[N_2H_5~+]~(0.061)[HNO_3]~0.017式中速度常数k是温度的函数。25℃时,k=0.0019。在实验浓度范围内,U(Ⅵ)还原速率随U(Ⅵ)浓度升高而增大,表现反应级数为0.75级,而[N_2H_5~+]及[HNO_3]影响很小,反应级数近于0。初步探讨了硝酸的电解还原以及硝酸肼对其还原过程的抑制作用,给出了不同硝酸浓度下的极化曲线。对于硝酸电解还原过程中主要产物亚硝酸的生成量与硝酸浓度、电解时间及肼浓度等的关系进行了讨论。
The effect of aqueous electrolyte concentration of UO_2 (NO_3) _2-HNO_3-N_2H_5NO_3 (H_2O) / 30% TBP (kerosene) system on the electrolytic reduction rate of U (Ⅵ) was studied in a vibrating agitated tank. According to the experimental data, the differential equations of reaction kinetics were obtained by regression analysis: - (d [U (Ⅵ)] / dt) = k [U (Ⅵ)] ~ (0.77) [N_2H_5 ~] ~ (0.061) [HNO_3] ~ 0.017 where the velocity constant k is a function of temperature. At 25 ° C, k = 0.0019. Under the experimental concentration range, the reduction rate of U (Ⅵ) increases with the increase of U (Ⅵ) concentration, which indicates that the reaction order is 0.75 while the effect of [N_2H_5 ~ +] and [HNO_3] At 0. The electrolytic reduction of nitric acid and the inhibitory effect of hydrazine nitrate on the reduction process were discussed preliminarily, and the polarization curve under different concentrations of nitric acid was given. The relationship between the amount of nitrous acid produced during the electrolytic reduction of nitric acid and nitric acid concentration, electrolysis time and hydrazine concentration was discussed.