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化学学报
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化学学报 ›› 2000, Vol. 58 ›› Issue (3): 267-272. 上一篇    下一篇

研究论文

F~2+2HCl→2HF+Cl~2反应机理的密度泛函理论研究

王遵尧;陈兆旭;肖鹤鸣;贡雪东;杨春生   

  1. 南京理工大学化工学院.江苏;盐城工学院化工系
  • 发布日期:2000-03-15

A study on the mechanism of the reaction F~2+2HCl→2HF+Cl~2 using density functional theory

Wang Zunyao;Chen Zhaoxu;Xiao Heming;Gong Xuedong;Yang Chunsheng   

  1. School of Chemical Engineering,Nanjing University of Science and. Nanjing
  • Published:2000-03-15

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用密度泛函理论(DFT)B3LYP方法,在6-311G^*^*基组下,计算研究了反应F~2+2HCl→2HF+Cl~2的机理。求得各可能反应途径的系列过渡态,并通过振动分析和内禀反应坐标(IRC)分析加以证实。比较反应能垒(理论计算活化能)发现,标题反应若以分子与分子作用机理进行,则需克服的最大能垒为150.63kJ.mol^-^1;若以F~2分子先裂解为F原子再反应的机理进行,则需越过能垒154.82kJ.mol^-^1,求得反应F+HCl→HF+Cl的线形和三角形两种过渡态,以三角形较稳定;求得反应HCl+Cl→H+Cl~2的两种过渡态,以线形较稳定。

关键词: 氯化氢, 氟, 反应机理, 密度泛函理论, 过渡态理论

The mechanism of the reaction F~2+2HCl→2HF+Cl~2 has been investigated using density functional theory (DFT) at the B3LYP/6- 311G^*^* level. The transition states for all the possible reaction paths are obtained and verified by vibrational analyses and IRC calculations. By comparing the calculated barriers, it is found that the largest barrier for the mechanism of molecule-molecule interaction is 150.63kJ.mol^-^1. The corresponding barrier for the mechanism in which F~2 is cleavaged first before the resulting F atoms react with the other reactants is 154.82kJ. For the reaction F+HCl→HF+Cl, two types of transition states are located. One is linear, the another is triangle and it is more stable. Between two transition states for the reaction HCl+Cl→H+Cl~2, the linear one is more stable.

Key words: HYDROGEN CHLORIDE, FLUORINE, REACTION MECHANISM, TRANSITION STATE THEORY

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