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化学学报
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化学学报 ›› 1990, Vol. 48 ›› Issue (11): 1064-1070. 上一篇    下一篇

研究论文

稀土与双偶氮变色酸反应系列的动力学和机理特征

林智信;安从俊;杨林;陈丹华;王丽莎;方贤安   

  1. 武汉大学化学系
  • 发布日期:1990-11-15

The kinetics and mechanism characteristic for a series of reactions between rare earth and bisazo chromotropic acid

LIN ZHIXIN;AN CUNGJUN;YANG LIN;CHEN DANUA;WANG LISHA;FANG XIAN AN   

  • Published:1990-11-15

PDF

435

被引次数

15 | 2

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, 实验获得速度方程的通式为:r=K-[RE(H2O)m3+m][H6R]β[H3O+]-1β=1或2。实验活化能分别处在40-70kj,mol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。

关键词: 反应机理, 反应动力学, 铁络合物, 动力学方程, 稀土金属络合物, 偶氮氯膦, 镧络合物, 钆络合物, 钆络合物, 铒络合物

The kinetics of a series of coordination reactions between rare earth metals and bisazochromotropic acid were studied. The common formula of rate law is r = k[RE(H2O)m3+] [H6R]b (H3O+)-1, where b = 1 or 2. Their Arrhenius activation energies are 40-70 kJ/mol. According to the composition of the transition state of the rate-detg. step from the rate law, 2 types of mechanism, i.e. the dehydration step of coordination complex and the proton transfer step, are proposed. The rate equation obtained from either mechanism is in conformity with the experimental rate law.

Key words: REACTION MECHANISM, REACTION KINETICS, IRON COMPLEX, KINETICS EQUATIONS, RARE EARTH METAL COMPLEX, CHLOROPHOSPHONAZO, LANTHANUM COMPLEX, GADOLINIUM COMPLEX, GADOLINIUM COMPLEX, ERBIUM COMPLEX

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