The kinetics of the addition reaction of carbon tetrachloride with styrene was investigated in the presence of immobilized cuprous chloride catalyst. As the CuCl / carbon nanotuble catalyst with the particle size of 10-8-10-7m was used and the stirring rates of the reaction were kept over 210 r·min-1, both the effects of internal and external diffusion could be ignored, and the reaction was controlled only by the kinetics of the addition reaction. The kinetic model, -rA=K[CA] [CB]+ kt[CB], was established based on free radical addition reaction mechanism and the assumption of single active site adsorption, which agrees well with the kinetic data measured in the temperature range of 65℃ to 75 ℃. The kinetic parameters were obtained by non-linear fitting, and the activation energy of the dissociative adsorption, which is the control step of the addition reaction, is 1.11×105 kJ·mol-1. The results obtained in this study are useful for the explanation of the addition reaction and the development of its industrial process.%以负载氯化亚铜为催化剂,研究了苯乙烯和四氯化碳加成反应的动力学,为工业反应过程的开发和操作提供了理论依据.在本实验条件下,催化剂的粒径为10-8～10-7m,内扩散影响可以忽略.当搅拌速度大于210 r·min-1时,外扩散影响基本消除,反应进入动力学控制区.系统地测定了65～75℃下的反应动力学数据.依据自由基加成反应机理和单活性位吸附的假设,建立了动力学模型,-rA=K[CA] [CB]+k1[CB].对实验数据进行非线性拟合,得到反应动力学模型参数.计算得到其控制步骤—解离吸附的反应活化能为1.11×103kJ·mol-1.动力学模型与实验数据吻合较好,在实验范围内可信度较高.
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