【摘要】 用激光光解-激光诱导荧光方法研究了室温下(T=293K)HCF(X%A′)自由基与SO2分子的反应动力学.实验中1HCF(X%A′)自由基是由213nm激光光解HCFBr2产生的,用激光诱导荧光(LIF)检测HCF(X%A′)自由基的相对浓度随着11反应时间的变化,得到此反应的二级反应速率常数为:k=(1.81±0.15)×10-12cm3?molecule-1?s-1,体系总压为1862Pa.高精度理论计算表明,HCF(X%A′)和SO2分子反应的机理是典型的加成-消除反应.我们运用RRKM-TST理论计算了1此二级反应速率常数的温度效应和压力效应,计算结果和室温下测定的二级反应速率常数符合得较好.更多还原

【Abstract】 HCF(~1A’) radicals were produced by laser photolysis of HCFBr2 at 213 nm, and electronically 1excited from the ground state to A%1A′′(030) at 492.70 nm with a dye laser pumped by a Nd∶YAG laser.The reaction rate constant of HCF(~1A’) with SO2 at room temperature (T=293 K) was determined to be 1k=(1.81±0.15)×10-12 cm3?molecule-1?s-1, when the total pressure was 1862 Pa. Based on the high levelab initio calculations, the mechanism of this reaction was proved to be a typical addition-elimination reac-tion. The temperature and pressure dependences of the total reaction rate constant were calculated by apply-ing RRKM-TST model. The calculations could provide a well consistent description for our experimentalwork.更多还原