化学学报 ›› 1983, Vol. 41 ›› Issue (5): 441-447. 上一篇    下一篇

研究论文

脂族酰基过氧化物分解动力学的分研究 III: 过氧化3,5,5-三甲基己酰在萃中的解动力学和机理

雷学工;刘有成   

  1. 兰州大学化学系
  • 发布日期:1983-05-15

Studies on the kinetics of decomposition of acyl peroxide. III: Kinetics and mechanism of decomposition of 3,5,5 -tri-methylhexanoyl peroxide in benzene.

LEI XUEGONG;LIU YOUCHENG   

  • Published:1983-05-15

关键词: 反应动力学, 苯, 分解反应, 过氧化物, 三甲基, 酰基

The kinetics of decomposition of 3, 5, 5-trimethylhexanoyl peroxide (1) in benzene has been studied at 30, 40 and 50`C and the cage effect of decomposition has been determined by scavenging method. The relative amounts of the main products of decomposition of 1 at 50`C with change of initial concentration have been determined. The results showed that the decomposition of 1 followed first plus three halves order kinetics as reported for lauroyl peroxide (2), but had a larger cage effect of 0.6. The mechanism of decomposition of 1 is practically the same as what we have proposed for 2. The faster rate and larger cage effect but less induced decomposition of 1 than that of 2 are attributed to the branching of the molecule of 1, especially to the presence of β-methyl group, which causes a larger entropy increase in the transition state.

Key words: REACTION KINETICS, BENZENE, DECOMPOSITION REACTION, PEROXIDE, TRIMETHYL GROUP, ACYL GROUP

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