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Atmospheric Oxidation of Piperazine Initiated by OH: A Theoretical Kinetics Investigation
ACS Earth and Space Chemistry ( IF 2.9 ) Pub Date : 2019-10-14 , DOI: 10.1021/acsearthspacechem.9b00227
Zhonghua Ren 1 , Gabriel da Silva 1
Affiliation  

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 modeling 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-centered 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.

中文翻译:

OH引发的哌嗪的大气氧化:理论动力学研究

与其他胺混合的哌嗪(Pz)是一种拟议的碳捕获溶剂,但人们担心Pz对空气质量的影响,包括产生有毒产品的潜力。在这里, OH发起的PZ氧化,研究了从头建模和RRKM /主方程动能模拟。发现Pz + OH反应以接近捕获的速率进行,与实验一致,主要是从C–H位抽象出来,形成一个烷基(PzC)。还研究了以碳为中心的Pz自由基与O 2的后续反应动力学,从而确定了第一代氧化产物。我们发现PzC自由基主要与O 2反应在对流层条件下生成环状亚胺产物+ HO 2 ,并形成稳定的过氧自由基,这是次要产物。该过氧自由基与NO的后续反应产生的自由基的烷氧基,可以被O反应2得到的环状酰胺或单分子经历开环,随后通过第二O 2加法/ HO 2 消除步骤,以产生CH 2 ═NCH 2 CH 2 NHCHO。
更新日期:2019-10-14
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