Bo Long, Ming-qiang Huang, Zhen-ya Wang, Wei-jun Zhang. Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone[J]. Chinese Journal of Chemical Physics , 2008, 21(4): 324-332. doi: 10.1088/1674-0068/21/04/324-332
Citation: Bo Long, Ming-qiang Huang, Zhen-ya Wang, Wei-jun Zhang. Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone[J]. Chinese Journal of Chemical Physics , 2008, 21(4): 324-332. doi: 10.1088/1674-0068/21/04/324-332

Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone

doi: 10.1088/1674-0068/21/04/324-332
Funds:  This work was supported by the Chinese Academy of Sciences (No. KJCX2-YW-N24).
  • Received Date: 2007-11-11
  • Rev Recd Date: 2007-12-04
  • 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
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Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone

doi: 10.1088/1674-0068/21/04/324-332
Funds:  This work was supported by the Chinese Academy of Sciences (No. KJCX2-YW-N24).

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

Bo Long, Ming-qiang Huang, Zhen-ya Wang, Wei-jun Zhang. Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone[J]. Chinese Journal of Chemical Physics , 2008, 21(4): 324-332. doi: 10.1088/1674-0068/21/04/324-332
Citation: Bo Long, Ming-qiang Huang, Zhen-ya Wang, Wei-jun Zhang. Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone[J]. Chinese Journal of Chemical Physics , 2008, 21(4): 324-332. doi: 10.1088/1674-0068/21/04/324-332

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