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本文在前报基础上,对稀土与双偶氮变色酸配合物反应选用了一系列体系进行了较系统的动力学研究。实验获得速率方程的通式为:r=k·[RE(H_2O)_m~(3+)][H_6R]~β[H_3O~+]~(-1),β=1或2。实验活化能分别处在40—70kJ·mol~(-1)之间。根据速率方程所确定的速控步骤过渡态的组成,参照Eign-Tamm机理,它们可能遵循两种不同机理,一种是配合物失水作为速控步骤,一种是质子转移作为速控步骤。动力学处理导出的方程与经验速率方程获得满意的吻合。
Based on the previous reports, a series of systems were selected for the reaction of rare earth with disazoochromic acid. The general formula for the experimental rate equation is: r = k · [RE (H 2 O) _m ~ (3 +)] [H_6R] ~ β [H_3O ~ +] -1, β = 1 or 2. The activation energy of the experiment was between 40-70kJ · mol ~ (-1). According to the composition of the transition state of the speed-controlled step determined by the rate equation, referring to the Eign-Tamm mechanism, they may follow two different mechanisms, one is the water loss of the complex as the speed control step and the other is the proton transfer as the speed control step. The equations derived from the kinetic treatment agree well with the empirical rate equations.