Li-li Xing, Xiao-yuan Zhang, Zhan-dong Wang, Shuang Li, Li-dong Zhang. New Insight into Competition between Decomposition Pathways of Hydroperoxymethyl Formate in Low Temperature DME Oxidation[J]. Chinese Journal of Chemical Physics , 2015, 28(5): 563-572. doi: 10.1063/1674-0068/28/cjcp1503053
Citation: Li-li Xing, Xiao-yuan Zhang, Zhan-dong Wang, Shuang Li, Li-dong Zhang. New Insight into Competition between Decomposition Pathways of Hydroperoxymethyl Formate in Low Temperature DME Oxidation[J]. Chinese Journal of Chemical Physics , 2015, 28(5): 563-572. doi: 10.1063/1674-0068/28/cjcp1503053

New Insight into Competition between Decomposition Pathways of Hydroperoxymethyl Formate in Low Temperature DME Oxidation

doi: 10.1063/1674-0068/28/cjcp1503053
  • Received Date: 2015-03-30
  • Hydroperoxymethyl formate is a crucial intermediate formed during the low-temperature oxidation of dimethyl ether. The decomposition pathways of HOOCH2OCHO were calculated at QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants are computed using microcanonical variational transition state theory coupled with the RRKM/master equation calculations. The calculations show that a pathway leads to the formation of formic acid and a Criegee intermediate does exist, besides the direct dissociation channel to OH and OCH2OCHO radicals. However, formation of the Criegee intermediate has never been considered as an intermediate in dimethyl ether combustion before. The computed rate constants indicate that the newly confirmed pathway is competitive to the direct dissociation route and it is promising to reduce the low-temperature oxidation reactivity. Also electronic effect of groups, e.g. -CHO and O atom, is taken into account. Moreover, Hirshfeld atomic charge and natural bond order analysis are performed to explain this phenomenon from a perspective of chemical nature.
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    沈阳化工大学材料科学与工程学院 沈阳 110142

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New Insight into Competition between Decomposition Pathways of Hydroperoxymethyl Formate in Low Temperature DME Oxidation

doi: 10.1063/1674-0068/28/cjcp1503053

Abstract: Hydroperoxymethyl formate is a crucial intermediate formed during the low-temperature oxidation of dimethyl ether. The decomposition pathways of HOOCH2OCHO were calculated at QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants are computed using microcanonical variational transition state theory coupled with the RRKM/master equation calculations. The calculations show that a pathway leads to the formation of formic acid and a Criegee intermediate does exist, besides the direct dissociation channel to OH and OCH2OCHO radicals. However, formation of the Criegee intermediate has never been considered as an intermediate in dimethyl ether combustion before. The computed rate constants indicate that the newly confirmed pathway is competitive to the direct dissociation route and it is promising to reduce the low-temperature oxidation reactivity. Also electronic effect of groups, e.g. -CHO and O atom, is taken into account. Moreover, Hirshfeld atomic charge and natural bond order analysis are performed to explain this phenomenon from a perspective of chemical nature.

Li-li Xing, Xiao-yuan Zhang, Zhan-dong Wang, Shuang Li, Li-dong Zhang. New Insight into Competition between Decomposition Pathways of Hydroperoxymethyl Formate in Low Temperature DME Oxidation[J]. Chinese Journal of Chemical Physics , 2015, 28(5): 563-572. doi: 10.1063/1674-0068/28/cjcp1503053
Citation: Li-li Xing, Xiao-yuan Zhang, Zhan-dong Wang, Shuang Li, Li-dong Zhang. New Insight into Competition between Decomposition Pathways of Hydroperoxymethyl Formate in Low Temperature DME Oxidation[J]. Chinese Journal of Chemical Physics , 2015, 28(5): 563-572. doi: 10.1063/1674-0068/28/cjcp1503053

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