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研究了几种配位体(环烷酸盐、硬脂酸盐、乙酰丙酮盐)对铈离子催化作用的影响。动力学结果表明,三种催化剂的反应级数几乎是相同的;表观活化能分别为15.2、17.0、10.2仟卡/克分子;对乙苯的反应级致为1。实验结果指出,反应的诱导期与催化剂、催化剂浓度、反应物浓度和反应温度有关。发现铈离子在诱导期结束后才发生价态变化,诱导期倒数与温度倒致成直线关系,由此求得的活化能与由阿累尼斯方程求得的相同。实验结果支持了络合-链锁机理。
The effects of several ligands (naphthenate, stearate, acetylacetonate) on the catalytic activity of cerium ions were investigated. The kinetic results show that the reaction orders of the three catalysts are almost the same; the apparent activation energies are respectively 15.2, 17.0 and 10.2 kcal / mol; the reaction order to ethylbenzene is 1. The experimental results indicate that the induction period of the reaction is related to the catalyst, catalyst concentration, reactant concentration and reaction temperature. It was found that the valence state of cerium ions did not change until the end of the induction period, and the reciprocal of the induction period was linearly related to the temperature. The activation energy obtained from this was the same as that obtained from the Arrhenius equation. The experimental results support the complexation-chain mechanism.