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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Study on the Reaction Mechanism and Kinetics of Criegee Intermediate CH2OO with Acrolein
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Theoretical Study on the Reaction Mechanism and Kinetics of Criegee Intermediate CH2OO with Acrolein

机译：丙烯醛Criegee中间体CH2OO反应机制和动力学的理论研究

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摘要

The detailed reaction mechanism and kinetics of Criegee intermediate CH2OO with acrolein were investigated. CH2OO may add to the C=O or C=C double bond of acrolein to form a five-membered ring adducts, and it may also insert the terminal oxygen atom or insert itself into the C-H bond of acrolein. The addition reactions are more favorable in energy than the insertion reactions. The master equation calculation show that the most competitive reaction channel is the 1,3-cycloaddition of CH2OO across the C=O double bond forming the secondary ozonide (SOZ). The lowest energy pathway for SOZ decomposition involves the formation of the singlet biradical intermediate by ring fission, the H-shift isomerization and the dissociation to products. The calculated overall rate constant decreases as the temperature increases from 200 to 500 K, and at 298 K, it is 4.31 X 10(-12) cm(3) molecule(-1) s(-1). The branching ratio of collisionally stabilized SOZ increases with the increase of pressure. At low pressure, some of SOZ decompose to HCOOH + acrolein or HCHO + acrylic acid. The pressure dependence of this reaction is in agreement with the previous theoretical and experimental observations for the reaction of CH2OO with acetaldehyde.
机译：研究了Criegee中间体CH2OO与丙烯醛的详细反应机制和动力学。 CH2OO可以添加到C = O或C =丙烯醛以形成五元环加合物的C双键，并且它也可以插入终端氧原子或插入件本身转化为丙烯醛的C-H键。添加反应比插入反应更有利。主级等式计算表明，最具竞争力的反应通道是CH2OO的1,3-环加入，形成二次臭氧（SOZ）。用于SOZ分解的最低能量途径涉及通过环裂变，H型移位异构化和对产物的解离形成单次血管型中间体。计算出的总速率恒定随着温度从200至500k增加而降低，并且在298k时，它为4.31×10（-12）cm（3）分子（-1）s（-1）。牢固稳定的SOZ的分支比随着压力的增加而增加。在低压下，一些SOZ分解为HCOOH +丙烯醛或HCHO +丙烯酸。该反应的压力依赖性与先前与乙醛反应的真实性和实验观察结果一致。

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