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本文研究了硫酸溶液中铀酰离子的激光光化还原,选用CW He-Cd激光器的波长为4416(?),测得25℃时生成U(Ⅳ)的量子产额为0.69±0.03;研究了乙醇,硫酸和铀酰离子浓度对量子产额的影响。在[C_2H_5OH]>0.5M、[H_2SO_4]>2.0M和[UO_2~(2+)]>7.0×10~(-3)M时,它们的浓度变化对量子产额影响不大。在25℃和1.7M乙醇浓度下,测定了硫酸中氢离子和铀酰离子浓度与反应速率的关系,得到在一定条件下光化还原生成U(Ⅳ)的速率ν与[H~+]和[U(Ⅵ)]的关系式为: v=k[H~+]°[UO_2~(2+)]~6 由实验求得上式中常数a和b分别为0.16和1.3,计算出表观反应速率常数为4.1×10~(-5)(M,sec,mW)。
In this paper, the laser photolysis of uranyl ion in sulfuric acid solution was studied. The wavelength of CW He-Cd laser was 4416 (?), And the quantum yield of U (IV) was 0.69 ± 0.03 at 25 ℃. Effect of Ethanol, Sulfuric Acid and Uranyl Ion Concentration on Quantum Yield. When [C_2H_5OH]> 0.5M, [H_2SO_4]> 2.0M and [UO_2 ~ (2 +)]> 7.0 × 10 ~ (-3) M, their concentration changes have little effect on the quantum yield. Under the conditions of 25 ℃ and 1.7 M ethanol concentration, the relationship between the concentration of hydrogen ion and uranyl ion in sulfuric acid and the reaction rate was determined. Under the certain conditions, the rate ν and [H ~ +] of U (Ⅳ) The relationship between [U (VI)] is: v = k [H ~ +] ° [UO_2 ~ (2 +)] ~ 6 From the experiment, the constants a and b are 0.16 and 1.3 respectively, The reaction rate constant is 4.1 × 10 -5 (M, sec, mW).