Korea Atomic Energy Research Institute, Yuseong, Daejeon, Republic of Korea.
J Hazard Mater. 2012 Sep 30;233-234:213-8. doi: 10.1016/j.jhazmat.2012.07.018. Epub 2012 Jul 13.
This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.
本工作采用吸收光谱和拉曼光谱研究了在过氧化氢存在下碳酸盐溶液中铀酰过氧碳酸根络合离子中过氧化物的稳定性，并评估了溶液中铀酰过氧碳酸根络合离子分解特性随温度的变化关系。在较高温度的碳酸盐溶液中，铀酰过氧碳酸根络合离子自身更快地分解为铀酰三碳酸根络合离子。溶液中无游离过氧化氢时过氧化物的浓度代表铀酰过氧碳酸根络合离子与铀酰三碳酸根络合离子混合物中铀酰过氧碳酸根络合离子的浓度。铀酰过氧碳酸根络合离子的自分解为一级反应，其活化能评估为 7.144×10(3) J mol(-1)。当溶液温度下铀酰三碳酸根络合离子的生成量超过溶液中铀酰三碳酸根离子的溶解度时，铀酰三碳酸根络合离子的分解会导致铀酸钠氧化氢的沉淀。
