THERMODYNAMICS OF HOMOGENEOUS OXIDATIONS .3. KINETICS AND THERMODYNAMICS OF CATALYTIC EPOXIDATION OF CYCLOHEXENE WITH RU(III)-EDTA-ASCORBATE-HYDROGEN PEROXIDE SYSTEM

被引:11
作者
KHAN, MMT
SHUKLA, RS
机构
[1] Discipline of Coordination Chemistry and Homogeneous Catalysis, Central Salt and Marine Chemicals Research Institute, Bhavnagar
来源
JOURNAL OF MOLECULAR CATALYSIS | 1990年 / 58卷 / 03期
关键词
D O I
10.1016/0304-5102(90)85030-L
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The Ru(III)-EDTA-ascorbate-hydrogen peroxide system was found to be an efficient catalytic system for epoxidation of cyclohexene in mixed aqueous acidic solvent 1:1 water:dioxan (v/v) under mild conditions. The kinetics and thermodynamics of the reaction have been studied over a wide temperature range 28812318 K at μ = 0.1 M KNO3. First-order dependence of the epoxidation reaction was observed with respect to the concentrations of Ru(III)-EDTA, ascorbic acid, hydrogen peroxide and cyclohexene. The rate of epoxidation is inverse first order with respect to hydrogen ion concentration. Thermodynamic and activation parameters corresponding to equilibrium and rate constants of the complicated reaction were computed. An oxygenase model mechanism is proposed for the epoxidation reaction, and kinetic and thermodynamic data were compared with those of saturated hydrocarbons. © 1990.
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页码:405 / 413
页数:9
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