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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (19): 1951-1955. 上一篇    下一篇

研究论文

三氯化铝催化1,1,2,2-四甲基-1,2-二氯二硅烷的裂解机理研究

徐文媛*，龙威，杜瑞焕，郝伟   

  1. (华东交通大学化学化工系 南昌 330013)
  • 投稿日期:2009-11-19 修回日期:2010-03-28 发布日期:2010-06-23
  • 通讯作者: 龙威 E-mail:iamlongwei@139.com
  • 基金资助:

    国家自然科学基金资助项目(30760137)

Study on the Cracking Mechanism of 1,1,2,2-Tetramethyl-1,2- Dichlorodisilane Catalyzed by Aluminum Chloride

XU Wen-Yuan, LONG Wei, DU Rui-Huan, HAO Wei   

  1. (Department of Chemistry and Chemical Engineering, East China Jiaotong University, Nanchang 330013)
  • Received:2009-11-19 Revised:2010-03-28 Published:2010-06-23
  • Contact: Long Wei E-mail:iamlongwei@139.com

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1212

被引次数

22

采用DFT和MP2方法对1,1,2,2-四甲基-1,2-二氯二硅烷的催化裂解机理进行了研究. 结果表明, 催化剂三氯化铝先与二硅烷反应, 生成中间产物后再与裂解气三氯甲烷作用并生成产物. 反应分3步进行, 各步活化能分别为: 152.543, 79.322和128.889 kJ•mol－1. 速控步为第一步反应, 3步的焓变分别为: 83.785, －275.771和－120.712 kJ•mol－1, 总焓变为－312.698 kJ•mol－1, 即为放热的. 反应的标准摩尔吉布斯自由能为－306.462 kJ•mol－1, 裂解反应的平衡常数 ＝4.9295×1053, 在常温常压下反应的理论产率较高, 与实验结果一致.

关键词: 1,1,2,2-四甲基-1,2-二氯二硅烷, 催化裂解, 密度泛函(DFT), 二级微干扰(MP2)

Catalytic cracking mechanism of 1,1,2,2,-tetramethyl-1,2-dichlorodisilane has been studied using DFT and MP2 methods. The results showed that disilane cracked by CHCl3 would react with catalyst (AlCl3) first. The reaction included three steps and activation energy of each step was 152.543, 79.322 and 128.889 kJ•mol－1 respectively. The rate determining step was the first one. The reaction was exothermic, the enthalpy change of each step was 83.785, －275.771 and －120.712 kJ•mol－1. The standard gibbs free energy change was －306.462 kJ•mol－1. The standard equilibrium constant was 4.9295×1053, the theoretical productivity was high under normal temperature and pressure. The theoretical results agreed well with experimental data.

Key words: 1,1,2,2-tetramethyl-1,2-dichlorodisilane, catalytic cracking, density functional theory (DFT), second order Moller-Plesset (MP2)

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