物理化学学报 >> 2006, Vol. 22 >> Issue (10): 1260-1265.doi: 10.1016/S1872-1508(06)60060-0

研究论文 上一篇    下一篇

丙烯的臭氧化反应动力学研究

贾龙;徐永福;葛茂发;杜林;王庚辰;庄国顺   

  1. 北京师范大学大气环境研究中心, 北京 100875; 中国科学院大气物理研究所, 大气边界层物理和大气化学国家重点实验室, 北京 100029; 中国科学院化学研究所, 北京分子科学国家实验室, 北京 100080; 中国科学院大气物理研究所, 中层大气遥感与探测开放实验室, 北京 100029
  • 收稿日期:2006-04-19 修回日期:2006-06-13 发布日期:2006-10-11
  • 通讯作者: 葛茂发 E-mail:gemaofa@iccas.ac.cn

Kinetic Study of the Gas-phase Ozonolysis of Propylene

JIA Long;XU Yong-Fu;GE Mao-Fa;DU Lin;WANG Geng-Chen;ZHUANG Guo-Shun   

  1. Research Center for Atmospheric Environment, Beijing Normal University, Beijing 100875, P. R. China; State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, P. R. China; Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China; Division for Middle Atmosphere and Remote Sensing, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, P. R. China
  • Received:2006-04-19 Revised:2006-06-13 Published:2006-10-11
  • Contact: GE Mao-Fa E-mail:gemaofa@iccas.ac.cn

摘要: 使用自行研制的烟雾箱实验装置, 研究了模拟实际大气环境臭氧浓度下(最小浓度6.6×10−8)臭氧与丙烯的反应动力学. 结合Model 49C-O3 Analyzer与GC-FID对臭氧与丙烯在282~314 K温度范围内的速率常数进行了测定, 得到臭氧初始浓度为6.61×10−8、温度为282 K时臭氧与丙烯的反应速率常数为6.73×10−18 cm3•molecule−1•s−1. 并根据不同温度下测得的反应速率常数, 求得该反应的阿仑尼乌斯方程为k2=(5.8±1.2)×10−15e(−1907±53)/T. 对比前人结果, 我们测得的速率常数偏小, 活化能偏高, 但速率常数的最大误差仅为11%, 活化能的最大误差为5%. 说明我们的研究设备在实际大气条件下是可靠的, 可用于进一步深入研究臭氧有关的反应.

关键词: 臭氧, 丙烯, 反应动力学, 速率常数, 气相反应

Abstract: Kinetics of the reaction of ozone with propylene under real atmospheric environmental conditions with an ozone concentration of ca 6.6×10−8 has been investigated in a self-made Teflon Chamber. Using Model 49C-O3 Analyzer and GC-FID, reaction rate constants at temperature range of 282~314 K are determined by an absolute rate technique in terms of measurement of ozone concentrations. Results show that the reaction rate constant is 6.73×10−18 cm3•molecule−1•s−1 for the initial ozone concentration of 6.61×10−8 and the temperature of 282 K. According to the reaction rate constants under different temperatures, the Arrhenius equation of k2=(5.8±1.2)×10−15e(−1907±53)/T is obtained. Compared with the results reported by other researchers, although the rate constants obtained in this study are systematically underestimated and the activation energy of the reaction overestimated, the results are satisfactory. For example, the largest relative error is only 11% and 5% for the rate constant and activation energy, respectively. These demonstrate that the research equipment used in this study is reliable under real atmospheric conditions and can be used to do further studies related to ozone reactions.

Key words: Ozone, Propylene, Kinetics, Rate constant, Gas-phase reaction