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Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone
Bo Long1,2, Ming-qiang Huang1, Zhen-ya Wang1, Wei-jun Zhang*1
1.Laboratory of Environment Spectroscopy, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China;2.School of Physics and Information Science, Guizhou University for Nationalities, Guiyang 550025, China
Abstract:
The interconversion between the two distinct isomers of methyl vinyl ether (MVE), the formation of the primary ozonides from O3-initated reactions of MVE, the transformation between the primary ozonides, and the subsequent fragmentation were studied using quantum chemical methods at the BHandHLYP/6-311++G(d,p) level of theory for optimized geometries and frequency calculations and at the QCISD/6-31G(d,p) level for the single point energy calculations. The rate coe±cients were calculated for the temper-ature range 280-440 K by using the canonical transition state theory (TST). For ozone addition to MVE, there are two different possibilities discussed on the basis of two different possible orientations for ozone attack. The results of the theoretical study indicate that although the synperiplanar-MVE is 7.11 kJ/mol more stable than the antiperiplanar-MVE, the antiperiplanar-MVE plays a more important role in formation of the primary ozonides because the primary ozonides formed from the ozone addition antiperiplanar-MVE are more stable and the energy barriers corresponding to transition states are lower. The interconversion between the primary ozonides formed from the ozone addition to antiperiplanar-MVE is the most accessible compared with the transformations between other primary ozonides. The cleavage of the primary ozonides mainly leads to the formation of the CH2OO, which is in agreement with the experimental estimates. The calculated overall rate constant for the ozone-initiated reactions is 4.8×10-17cm3/(moleculec∙s) at 298.15 K, which agrees with the experimental value for ethyl vinyl ether
Key words:  Methyl vinyl ether, Ozone, Reaction pathway, Primary ozonide, Interconversion, Rate constant, Transition state theory
FundProject:
Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone
龙波1,2, 黄明强1, 王振亚1, 张为俊*1
1.中国科学院安徽光学精密机械研究所环境光谱学研究室,合肥230031;2.贵州民族学院物理与电子信息科学学院,贵阳550025
摘要:
利用量子化学从头计算的方法对甲基乙烯醚的两个异构体之间的转化、臭氧与甲基乙烯醚的环加成反应、臭氧化物的裂解以及主要臭氧化物异构体的之间的转化的反应通道进行了研究,并用经典过渡态理论在280~440 K计算了反应的速率常数.对于臭氧和甲基乙烯醚的反应,考虑了臭氧从两个可能的不同方向进攻甲基乙烯醚.计算结果表明,顺式-甲基乙烯醚是比较稳定的,但是反式-甲基乙烯醚与臭氧反应所要跨越比较低的能垒, 分别为1.7和7.5 kJ/mol,而其产物更稳定,在形成的臭氧化物中占绝对比例,臭氧化物的裂解主要导致CH2-OO的生成,在298 K时的反应速率常数为4.8×10^-17 cm3/(molecule?s).
关键词:  甲基乙烯醚,臭氧,反应通道,主要臭氧化物,异构化,过渡态理论,速率常数
DOI:10.1088/1674-0068/21/04/324-332
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