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在恒定的离子强度(μ=0.30mol·dm~(-3)),碱性介质中([OH~-]=7.00×10~(-3)—0.200mol·dm~(-3))研究了二过碘酸合银(Ⅲ)配离子(DPA)氧化硫氰酸钾的动力学。发现反应对DPA为一级。反应速率对于[OH~-]的依赖关系暗示反应可能通过两个过程进行。两个过程对NCS~-均为分数级,与Michaelis-Menten过程相符合。考察了配体对反应的影响,推测了反应的活性物种。认为反应在两个过程都按配合物的内界双电子转移方式进行。导出了反应的速率方程,求得了反应机理中所有的平衡常数和速率常数。测定了一个过程的活化参数。
Under the condition of constant ionic strength (μ = 0.30mol · dm -3) and alkaline solution ([OH ~ -] = 7.00 × 10 -3 -0.200mol · dm -3) Kinetics of oxidation of potassium thiocyanate by diperiodate silver (Ⅲ) complex ion (DPA). The reaction was found to be DPA-grade. The dependence of reaction rate on [OH ~ -] implies that the reaction may proceed through two processes. Both processes are fractional for NCS ~ -, consistent with the Michaelis-Menten process. The effect of the ligand on the reaction was investigated, and the active species of the reaction was speculated. It is considered that the reaction proceeds according to the double-electron transfer method of the interior of the complex in both processes. The rate equation of the reaction is derived and all the equilibrium constants and rate constants of the reaction mechanism are obtained. The activation parameters of a process were determined.