物理化学学报 >> 1990, Vol. 6 >> Issue (01): 39-45.doi: 10.3866/PKU.WHXB19900107

研究论文 上一篇    下一篇

化学基波管中环氧丙烷异构反应动力学研究

覃志伟;杨惠星;韩德刚   

  1. 北京大学化学系
  • 收稿日期:1988-07-29 修回日期:1989-02-20 发布日期:1990-02-15
  • 通讯作者: 覃志伟

Kinetics of the Thermal Gas-Phase Isomerization of Epoxypropane in a Single-Pulse Shock Tube

Tan Zhi-Wei;Yang Hui-Xing;Han De-Gang   

  1. Department of Chemistry,Peking University
  • Received:1988-07-29 Revised:1989-02-20 Published:1990-02-15
  • Contact: Tan Zhi-Wei

摘要: 环氧丙烷低温热解过程的动力学研究, 已经进行了许多工作~[1,2,3], 但在较高温度条件下的热解过程尚不清楚. 因此我们利用化学激波管及相对速度常数法, 研究了在1045—1175K 温度范围内环氧丙烷(在NO中)的热解过程, 测定了热解过程的动力学参数。

Abstract: The kinetics of the gas-phase thermal isomerization of epoxypropane has been studied over the temperature range 1045-1175 K in a single-pulse shock tube. Uni-molecular isomerizations to propionaldehyde, acetone, methyl vinyl ether and allylol account for about 65% of the primary reactions which occur by first order, homoge-neous, non-radical processes. Secondary reactions, that make quantitative determina-tion of the individual rate constants difficult, were reduced by the addition of radi-cal scavenger nitric oxide.
k_(propionaldehyde)(s~(-1))=10~(14.3)exp(-262 kJmol~(-1)/RT)
k_(acetone)(s~(-1))=10~(14.0)exp(-268 kJmol~(-1)/RT)
k_(methylvinyl ether)(s~(-1))=10~(13.4)exp(-264 kJmol~(-1)/RT)
k_(allylol)(s~(-1))=10~(13.9)exp(-275 kJmol~(-1)/RT)
A biradical mechanism for the isomerization of epoxypropane has been preferred. It adequately exlained kinetic observations. The RRKM theory of unimolecular reactions was applied to explain the thermal isomerization of epoxypropane.