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

被引:9
作者
Xing, Li-li [1 ]
Zhang, Xiao-yuan [1 ]
Wang, Zhan-dong [1 ]
Li, Shuang [1 ]
Zhang, Li-dong [1 ]
机构
[1] Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Peoples R China
基金
中国国家自然科学基金;
关键词
Hydroperoxymethyl formate; RRKM/master equation calculations; Low temperature oxidation; Dimethyl ether; Chain branching; DIMETHYL ETHER OXIDATION; THERMAL-DECOMPOSITION; REACTION-KINETICS; AB-INITIO; HO2; OH; RADICALS; IGNITION;
D O I
10.1063/1674-0068/28/cjcp1503053
中图分类号
O64 [物理化学(理论化学)、化学物理学]; O56 [分子物理学、原子物理学];
学科分类号
070203 ; 070304 ; 081704 ; 1406 ;
摘要
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.
引用
收藏
页码:563 / 572
页数:10
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