Quantitative HNO detection behind shock waves

Quantitative HNO detection behind shock waves
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冲击波后的定量耳鼻喉科检测

DOI:
10.1016/j.proci.2016.05.035
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发表时间:
2016
期刊:
影响因子:
--
通讯作者:
G. Friedrichs
G. Friedrichs
中科院分区:
--
文献类型:
--
作者:
N. Faßheber;M.C. Schmidt;G. Friedrichs

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HNO是NOx火焰化学中的一个关键组分,其高温动力学研究还很缺乏。利用非常灵敏的基于吸收的频率调制(FM)光谱学,首次在冲击波后测量了HNO。乙二醛/NO混合物在λ= 193 nm处的紫外光分解作为HNO源,通过快速初始形成HCO自由基,随后反应HCO+ NO→ CO+ HNO,产生稳定的HNO浓度平台。记录了HNO分子A → 1A ′′(100)-X → 1A ′(000)带三个选定跃迁的FM谱线形状,并测定了它们的压力展宽系数。通过分析在非常相似的反应条件下测量的HNO和HCO浓度-时间曲线,可以确认HCO/HNO形成机制并确定HNO吸收截面。建议用log [σ c(HNO,p= 0 bar,295 K< T< 1800 K)/cm 2 mol− 1]= 5.86-1.62× 10− 3× T/K+ 2.74× 10− 7× T2/K2表示RR 3(4)转动线在ν ε = 16173.86cm − 1(618.2816nm)处的转动线,σ c的不确定度为±40%.在冲击波后进行定量HNO测量的能力使得在未来的实验中直接研究HNO双分子反应的速率常数成为可能。
Abstract Knowledge about the high temperature kinetics of HNO, which represents a key species in NO x flame chemistry, is scarce. Using the very sensitive absorption based frequency modulation (FM) spectroscopy, HNO has been measured behind shock waves for the first time. The UV photolysis of glyoxal/NO mixtures at λ= 193 nm served as an HNO source with stable HNO concentration plateaus generated via the fast initial formation of HCO radicals followed by the reaction HCO+ NO→ CO+ HNO. FM line shapes of three selected transitions of the A˜ 1 A′′(100)− X˜ 1 A′(000) band of HNO have been recorded and their pressure broadening coefficient has been determined. By analyzing HNO and HCO concentration-time profiles measured under very similar reaction conditions it was possible to confirm an HCO/HNO formation mechanism and to determine the HNO absorption cross section. The expression log [σ c (HNO, p= 0 bar, 295 K< T< 1800 K)/cm 2 mol− 1]= 5.86–1.62× 10− 3× T/K+ 2.74× 10− 7× T 2/K 2 with an uncertainty of±40% in σ c is recommended for the R R 3 (4) rotational line at ν˜= 16173.86 cm− 1 (618.2816 nm). The capability to perform quantitative HNO measurements behind shock wave make possible direct rate constant studies of bimolecular HNO reactions in future experiments.
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