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利用自制的烟雾箱系统研究了臭氧与二乙胺和三乙胺的气相反应动力学.实验过程中保证二乙胺和三乙胺浓度远远大于臭氧浓度,使得实验在准一级条件下进行.加入环己烷以消除实验过程中可能产生的OH自由基对反应的影响.在(298±1)K和1.01×105Pa条件下,测得臭氧与二乙胺和三乙胺反应的绝对速率常数值分别为(1.33±0.15)×10-17和(8.20±1.01)×10-17cm3·molecule-1·s-1.与文献中已有的其它胺类的臭氧反应数据比较后发现,臭氧与胺的反应可以用亲电反应机制来解释.另外,通过对比发现,臭氧与三取代的烷基胺类的反应速率要远远大于其与二取代的烷基胺类的反应速率.这在一定程度上可有助于解释外场观测到的气溶胶相中二烷基胺盐较多的事实.利用测得的速率常数和大气中臭氧浓度,还估算了二乙胺和三乙胺与臭氧反应的大气寿命.结果显示,与臭氧的反应是二乙胺和三乙胺在大气中的一种重要的消除途径,尤其是在污染严重地区.
The gas phase reaction kinetics of ozone with diethylamine and triethylamine was studied by a homemade smoke box system.The concentrations of diethylamine and triethylamine in the experiment were guaranteed to be much higher than that of ozone so that the experiments were carried out under quasi-first-order conditions Cyclohexane was added to eliminate the possible influence of OH radicals on the reaction.Under the conditions of (298 ± 1) K and 1.01 × 10 5 Pa, the absolute rate of ozone reaction with diethylamine and triethylamine was measured The constants were (1.33 ± 0.15) × 10-17 and (8.20 ± 1.01) × 10-17 cm3 · molecule-1 · s-1, respectively.Comparing with the ozone data of other amines in the literature, we found that ozone The reaction with amines can be explained by the electrophilic reaction mechanism. In addition, it is found by comparison that the reaction rate of ozone with trisubstituted alkylamines is far greater than that of the reaction with disubstituted alkylamines. To a certain extent, this can help to explain the fact that more aerosols are observed in the field with more dialkyl amine salts.Using the measured rate constants and ozone concentrations in the atmosphere, it is also estimated that diethylamine and triethylamine react with ozone Response to the life of the atmosphere The results show that the reaction with ozone is diethylamine and triethylene A atmospheric important route of elimination, especially in polluted areas.