硝酸介质中锝与肼的反应研究
STUDY OF THE REACTION BETWEEN TECHNETIUM AND HYDRAZINE IN NITRIC ACID MEDIUM
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摘要: 利用溴代丁二酰亚胺滴定肼和跟踪Tc(Ⅶ)浓度随时间变化的方法,研究了硝酸介质中锝与肼的反应。实验证实了锝与肼的反应存在诱导期,该诱导期的长短与Tc(Ⅶ)的初始浓度有关,与肼的初始浓度无关;诱导期之后进入快速反应阶段,此时反应速率与锝的浓度无关,动力学方程可表示为:-dc(N2H4)/dt=kc(N2H4)·c-1(H+),反应的活化能为91.8kJ/mol。快速反应完成后体系中残留一定浓度的肼,Tc(Ⅶ)浓度又逐渐上升。Abstract: The reaction between technetium and hydrazine in nit ric acid medium is studied by the titration of the concentration of hydrazine and pursuing the concentration of heptavalent technetium along with time. It is approved that the reaction between technetium and hydrazine includes a inducing period, a fast reaction stage and the termination of the reaction. The inducing period is relevant to the initial concentration of heptavalent technetium, temperature and acidity and no relationship between its length and the initial concentration of hydrazine. It is tetravalent technetium existing as TcO 2 and TcO 2+ who catalyzes the oxidation of hydrazine. In fast reaction stage, the kinetics equation can be written as follows: -d c (N 2H 4)/d t = kc (N 2H 4)· c -1 (H +), which is no relation with the concentration of heptavalent technetium. The activation energy of the stage is 91.8 kJ/mol. In the termination period some hydrazine remains in the system and the concentration of heptavalent technetium begins to rise.