Computational study on the mechanism and kinetics of Cl-initiated oxidation of ethyl acrylate
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The comprehensive and reasonable mechanisms of Cl-initiated oxidation of ethyl acrylate (EA) have been proposed by computing at the M06-2X/6-311++G(3df, 2p)//M06-2X/6-31+G(d, p) level of theory. The primary reaction includes eight channels: two Cl additions and six H abstractions. Comparing all calculated results, the reactions of Cl addition are easier to occur than those of H abstraction. However, the hydrogen abstraction from the -CH2 and -CH3 groups cannot be ignored. Based on the Rice–Ramsperger–Kassel–Marcus (RRKM) theory, the rate constants are determined employing the MESMER program. The calculated total rate constant (at 298 K and 760 Torr) is 1.80 × 10−10 cm3 molecule−1 s−1 and shows negative dependence on temperature in the range of 198–648 K. The rate constants for Cl atoms of methyl acrylate (MA), EA, methyl methacrylate (MMA), and allyl acetate (AAC) are k MMA(Cl) > k EA(Cl) > k MA(Cl) > k AAC(Cl). The atmospheric lifetime of EA is 154.3 h for Cl-initiated oxidation which is compared with that of the reaction of other oxidants (OH radicals, O3 molecules, and NO3 radicals) with EA.
KeywordsCl atoms Ethyl acrylate Mechanisms Rate constant
This work was financially supported by the National Nature Science Foundation of China (NSFC Nos. 21377001, 21477065, and 21077067) and Shandong Provincial Natural Science Foundation of China (Grant ZR2014BM037 and ZR2014EMM020).
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Conflict of interest
The authors declare that they have no conflict of interest.
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