| 乙酰乙酸乙酯-BrO3--Mn2+-H2SO4振荡体系的非线性动力学研究 |
| Study of Non-Linear Kinetics on the Oscillating Reactions in the System of AA -BrO3--Mn2+-H2SO4 |
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| 摘要: 研究了乙酰乙酸乙酯(AA)-BrO3--Mn2+-H2SO4体系不经过诱导期而直接进入振荡状态的非线性化学反应新特征。测定了各物种的起振浓度范围及最佳反应条件。升高温度T，振荡周期tp、寿命tl均显著缩短，且ln(1/tp)与(1/T)具有良好线性关系，周期表观活化参数为41.94 kJ·mol-1。Ag+、维生素C(Vc)、葡萄糖(G)、H2O2、C2H5OH等共存时，或使振荡周期增长，或具有显著的抑制作用。另外，AA的酸性水溶液放置120～720 min后重新参与振荡反应时，可产生诱导期，甚至抑制振荡反应, 表明AA的水解性对振荡反应有一定的影响。最后结合FKN机理，对本振荡反应机理进行了初步探讨。 |
| 关键词: 振荡反应 乙酰乙酸乙酯 机理 |
| 基金项目: |
| Abstract: The new character of non-linear chemical reaction of the AA(acetacetic ether)-BrO3-Mn2+-H2SO4 system was studied. The best reaction condition and the concentration ranges for starting oscillation of each reactant were determined. The oscillatory phase and life period shortened remarkably with rising temperature, ln(1/tp) had a good linear relationship with (1/T), viz. ln(1/tp)=-Ep/ RT+Ap. The apparent activation parameter of oscillatory period was obtained to be 41.94 kJ·mol-1. The effects of many factors on oscillation reaction were investigated, such as reactant initial concentration, Ag+, scorbutanin, Glucose, H2O2, C2H5OH, free radical inhibitor and temperature. In addition, there would be an induction period, even inhibition of the oscillation reaction when the acidic aqueous solution was taken to participate in the oscillation reaction after standing for 120～720 min, and this shows that the hydrolyzation of AA may have some effect on the oscillation reaction. Together with the FKN mechanism, the oscillating mechanism of the oscillating reaction in the present system was discussed briefly. |
| Keywords: oscillating reaction acetacetic ether mechanism |
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| 张业中,安从俊,丁宗洲,郑 丹,张竹青.乙酰乙酸乙酯-BrO3--Mn2+-H2SO4振荡体系的非线性动力学研究[J].无机化学学报,2004,20(5):519-523. |
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