Direct dynamics study on hydrogen abstraction reaction of morpholine with hydroxyl radical

Gao, Hong; Wang, Miaomiao; Jin, Tao; Shi, Jianwu; Yao, Xiaojun; Jin, Neng-Zhi

doi:10.1007/s00214-015-1699-2

Cited by 4 publications

(9 citation statements)

References 33 publications

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“…When released into the atmosphere, Pz is expected to react predominantly with the • OH radical, , via abstraction from C–H sites to form an alkyl radical (PzC) or from N–H sites to form an aminyl radical (PzN). The extent of branching to the PzN radical is of particular interest, as aminyl radicals can react with NO and NO 2 to generate toxic nitrosamines and nitramines, respectively. − However, α-aminoalkyl radicals such as PzC have been shown to predominantly react with O 2 to produce imines. , Experimentally, Pz has been shown to react with • OH mainly via C–H abstraction, although there is limited information on further reaction products under atmospheric conditions. ,, This motivated us to carry out a theoretical kinetics investigation into the Pz + • OH reaction through multiple reaction stages, to help validate existing experimental results as well as to provide new insight into the ultimate products of atmospheric oxidation.…”

Section: Introductionmentioning

confidence: 54%

“…The extent of branching to the PzN radical is of particular interest, as aminyl radicals can react with NO and NO2 to generate toxic nitrosamines and nitramines, respectively. [22][23][24][25][26][27][28][29] On the other hand, α-aminoalkyl radicals such as PzC have been shown to predominantly react with O2 to produce imines. 30,31 Experimentally, Pz has been shown to react with • OH mainly via C-H abstraction, although there is limited information on the further reaction products under atmospheric conditions.…”

Section: Introductionmentioning

confidence: 99%

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Atmospheric Oxidation of Piperazine Initiated by OH: A Theoretical Kinetics Investigation

Silva

2019

ACS Earth Space Chem.

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Piperazine (Pz) mixed with other amines is a proposed carbon capture solvent, but there is concern about the impact of Pz on air quality, including the potential to produce toxic products. Here, the • OH initiated oxidation of Pz has been studied by ab initio modelling and RRKM / master equation kinetic simulations. The Pz + • OH reaction is found to proceed at around the capture rate, consistent with experiment, with abstraction predominantly from C-H sites, forming an alkyl radical (PzC). The subsequent reaction kinetics of carbon centred Pz radicals with O2 are also studied, so as to determine the first-generation oxidation products. We find that the PzC radical predominantly reacts with O2 to produce a cyclic imine product + HO2 • under tropospheric conditions, with the stabilized peroxyl radical formed as a minor product. Subsequent reaction of the peroxyl radical with NO produces an alkoxyl radical that can react with O2 to yield a cyclic amide or undergo unimolecular ring opening followed by a second O2 addition / HO2 • elimination step to produce CH2=NCH2CH2NHCHO.

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Section: Introductionmentioning

confidence: 54%

Section: Introductionmentioning

confidence: 99%

Atmospheric Oxidation of Piperazine Initiated by OH: A Theoretical Kinetics Investigation

Silva

2019

ACS Earth Space Chem.

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“…•OH and •Cl are found to be two main daytime initiators for the formation of N-center radicals, the precursor of carcinogenic nitrosamine, in the atmospheric oxidation of reported amines. 8,21,[30][31][32]38,39 Generally, reactions of amines with •OH mainly form C-center radicals with N-center radicals as minor products. 8,30,32,38,39 However, the reactions with •Cl mainly form N-center radicals.…”

Section: ■ Introductionmentioning

confidence: 99%

Atmospheric Oxidation of Piperazine Initiated by ·Cl: Unexpected High Nitrosamine Yield

Ding

Elm

et al. 2018

Environ. Sci. Technol.

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Chlorine radicals (·Cl) initiated amine oxidation plays an important role for the formation of carcinogenic nitrosamine in the atmosphere. Piperazine (PZ) is considered as a potential atmospheric pollutant since it is an alternative solvent to monoethanolamine (MEA), a benchmark solvent in a leading CO capture technology. Here, we employed quantum chemical methods and kinetics modeling to investigate ·Cl-initiated atmospheric oxidation of PZ, particularly concerning the potential of PZ to form nitrosamine compared to MEA. Results showed that the ·Cl-initiated PZ reaction exclusively leads to N-center radicals (PZ-N) that mainly react with NO to produce nitrosamine in their further reaction with O/NO. Together with the PZ + ·OH reaction, the PZ-N yield from PZ oxidation is still lower than that of the corresponding MEA reactions. However, the nitrosamine yield of PZ is higher than the reported value for MEA when [NO] is <5 ppb, a concentration commonly encountered in a polluted urban atmosphere. The unexpected high nitrosamine yield from PZ compared to MEA results from a more favorable reaction of N-center radicals with NO compared to O. These findings show that the yield of N-center radicals cannot directly be used as a metric for the yield of the corresponding carcinogenic nitrosamine.

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“…MC‐QCISD/3, BMC‐CCSD, and BMC‐QCISD have been widely employed in the direct dynamics for the calculations the potential energy surfaces on the fly . MC‐UT/3 and MC‐QCISD/3 have been applied to calculate the heats of formation for coumarin and chromone, and show very good agreements with experiments .…”

Section: N6 Methodsmentioning

confidence: 97%

Multi‐coefficients correlation methods

Zhang

Kong

Liu

et al. 2020

WIREs Comput Mol Sci

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A composite quantum chemical method is an approximated computational protocol designed to obtain highly accurate energies for different types of interactions. In this review, we summarize the recent advance in the evolution, assessments, and applications of the multi-coefficients correlation methods (MCCMs) and doubly hybrid MCCMs, especially the recent Wuhan-Minnesota-Scaling method, for accurate calculations of Born-Oppenheimer energies of molecular systems. The review gives an overview of the methods along with their performance on the W4-17 database.

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Direct dynamics study on hydrogen abstraction reaction of morpholine with hydroxyl radical

Cited by 4 publications

References 33 publications

Atmospheric Oxidation of Piperazine Initiated by OH: A Theoretical Kinetics Investigation

Atmospheric Oxidation of Piperazine Initiated by OH: A Theoretical Kinetics Investigation

Atmospheric Oxidation of Piperazine Initiated by ·Cl: Unexpected High Nitrosamine Yield

Multi‐coefficients correlation methods

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