化学激波管中环氧丙烷异构反应动力学研究

KINETICS OF THE THERMAL GAS-PHASE ISOMERIZATION OF EPOXYPROPANE IN A SINGLE-PULSE SHOCK TUBE

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,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。

The kinetics of the gas-phase thermal isomerization of epoxypropane has beenstudied over the temperature range 1045-1175K in a single-pulse shock tube. Uni-molecular isomerizations to propionaldehyde, acetone, methyl vinyl ether and allylolaccount 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(-262kJmol^(-1)/RT) k_(acetone)(S^(-1))=10^(14.0)exp (-268kJmol^(-1)/RT) k_(methyl vinyl ether)(S^(-1))=10^(13.4)exp(-264kJmol^(-1)/RT) k_(allylol(S^(-1))=10^(13.9)exp(-275kJmol^(-1)/RT) A biradical mechanism for the isomerization of epoxypropane has been preferred.It adequately explained kinetic observations. The RRKM theory of unimolecular reac-tions was applied to explain the thermal isomerization of epoxypropane.