Rate coefficients for fuel + NO2: Predictive kinetics for HONO and HNO2 formation

Chai, Jiajue; Goldsmith, C. Franklin

doi:10.1016/j.proci.2016.06.133

Cited by 74 publications

(57 citation statements)

References 45 publications

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“…As said by Zhang et al [37], the total rate of the 3 isomers formation calculated by Chai and Goldsmith [30] is in excellent agreement with that reported in both the Park et al [36] experimental measurement and Rasmussen et al [9] calculation. In this work, we use the recent kinetic parameters for the three different isomers from Chai and Goldsmith [30]. Although modeling studies rarely distinguish the HON O isomers as the products of R9, a slight improvement in the onset temperature of H 2 conversion at all conditions was found in this work including the different isomers.…”

Section: Kinetic Modelsupporting

confidence: 87%

“…Chai and Goldsmith [30] studied rate coefficients for fuel+N O 2 , predicting the formation of HONO, and they distinguished 3 different isomers (cis-HON O, trans-HON O and HN O 2 ). As said by Zhang et al [37], the total rate of the 3 isomers formation calculated by Chai and Goldsmith [30] is in excellent agreement with that reported in both the Park et al [36] experimental measurement and Rasmussen et al [9] calculation. In this work, we use the recent kinetic parameters for the three different isomers from Chai and Goldsmith [30].…”

Section: Kinetic Modelmentioning

confidence: 99%

“…At high pressures, the N O/N O 2 interconversion becomes important, specially at low temperatures and high O 2 concentrations, where N O 2 presence is favored. The presence of N O x under engine-relevant conditions might infuence notably the reactivity of the fuel, through a sequence of reactions in which N O and N O 2 convert less reactive peroxy radicals into more reactive OH and alkyloxy radicals [30]. Knowing accurately the amount of N O/N O 2 that interacts with the fuel seems to be an important task to approach.…”

Section: Introductionmentioning

confidence: 99%

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High pressure study of H oxidation and its interaction with NO

Colom-Díaz

Millera

Bilbao

et al. 2019

International Journal of Hydrogen Energy

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The present study deals with the oxidation of H 2 at high pressure and its interaction with N O. The high pressure behavior of the H 2 /N O x /O 2 system has been tested over a wide range of temperatures (500-1100 K) and different air excess ratios (λ= 0.5 -6.4). The experiments have been carried out in a tubular flow reactor at 10, 20 and 40 bar. N O has been found to promote H 2 oxidation under oxidizing conditions, reacting with HO 2 radicals to form the more active OH radical, which enhances the conversion of hydrogen. The onset temperature for hydrogen oxidation, when doped with N O, was approximately the same at all stoichiometries at high pressures (40 bar), and shifted to higher temperatures as the pressure decreases. The experimental results have been analyzed with an updated kinetic model. The reaction N O+N O+O 2 N O 2 +N O 2 has been found to be important at all conditions studied and its kinetic parameters have been modified, according to its activation energy uncertainty. Furthermore, the kinetic parameters of reaction HN O+H 2 N H+H 2 O have been estimated, in order to obtain a good prediction of the oxidation behavior of H 2 and N O conversion under reducing conditions. The kinetic model shows a good agreement between experimental results and model predictions over a wide range of conditions.

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Section: Kinetic Modelsupporting

confidence: 87%

Section: Kinetic Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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High pressure study of H oxidation and its interaction with NO

Colom-Díaz

Millera

Bilbao

et al. 2019

International Journal of Hydrogen Energy

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“…However, two recent directions for engine improvement, such as exhaust gas recirculation [12] and the addition of alkyl-nitrates as additives to increase reactivity [13], introduce larger concentrations of NO x in the fuel-air mixture prior to ignition. As reported by Chai and Goldsmith [14], the reaction between fuel (RH) and NO 2 : RH+NO 2 R+HONO is one reaction channel for HONO formation (Figure 1). Moreover, previous studies on the effects of NO addition during alkanes oxidation [15] reported another HONO reaction channel via NO+OH+MHONO+M at low temperatures is a key chain-terminating reaction to inhibit reactivity.…”

Section: Introductionsupporting

confidence: 53%

First detection of a key intermediate in the oxidation of fuel + NO systems: HONO

Marrodán

Song

Herbinet

et al. 2019

Chemical Physics Letters

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This paper reports the first online gas phase detection of absolute concentrations of HONO under engine relevant conditions, during the oxidation of an alkane in the presence of NO x. The detection was achieved at laboratory scale thanks to the coupling of a jet-stirred reactor to a continuous-wave Cavity Ring-Down Spectroscopy cell. The evidence of the formation of HONO was obtained by comparing measured cw-CRDS spectra with a literature one. The formation of HONO was simultaneously observed with the appearance of another nitrogen compound: NO 2. This confirms that HONO could also be formed from NO 2 under engine conditions.

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“…works (Chai and Goldsmith, 2017;Shrestha et al, 2018;Skreiberg et al, 2004). In 520 addition, Houshfar et al (2012) performed biomass combustion kinetic modeling with 521 reduced mechanism via sensitivity analysis.…”

mentioning

confidence: 99%

Isotopic characterization of nitrogen oxides (NOx), nitrous acid (HONO), and nitrate (NO3−(p)) from laboratory biomass burning during FIREX

Chai¹,

Miller²,

Scheuer³

et al. 2019

Preprint

Self Cite

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1 2 New techniques have recently been developed to capture reactive nitrogen species for 3 accurate measurement of their isotopic composition. Reactive nitrogen species play 4 important roles in atmospheric oxidation capacity (hydroxyl radical and ozone formation) 5 and may have impacts on air quality and climate. Tracking reactive nitrogen species and 6 their chemistry in the atmosphere based upon concentration alone is challenging. Isotopic 7 analysis provides a potential tool for tracking the sources and chemistry of species such 8 as nitrogen oxides (NO x = NO + NO 2 ), nitrous acid (HONO), nitric acid (HNO 3 ) and 9 particulate nitrate (NO 3 -(p)). Here we study direct biomass burning (BB) emissions 10 during the Fire Influence on Regional to Global Environments Experiment (FIREX, later 11 evolved into FIREX-AQ) laboratory experiments at the Missoula Fire Laboratory in the 12 fall of 2016. 13 14 An annular denuder system (ADS) developed to efficiently collect HONO for isotopic 15 composition analysis was deployed to the Fire Lab study. Concentrations of HONO 16 recovered from the ADS collection agree well with mean concentrations averaged over 17 each fire measured by 4 other high time resolution techniques, including mist 18 chamber/ion chromatography (MC/IC), open-path Fourier transform infrared 19 spectroscopy (OP-FTIR), cavity enhanced spectroscopy (CES), proton-transfer-reaction 20 time-of-flight mass spectrometer (PTR-ToF). The concentration validation ensures 21 complete collection of BB emitted HONO, of which the isotopic composition is 22preserved during the collection process. In addition, the isotopic composition of NO x and 23 NO 3 -(p) from direct BB emissions were also characterized. 24In 20 "stack" fires (direct emission within ~5 seconds of production by the fire) that 25 burned various biomass materials, δ 15 N-NO x ranges from -4.3 ‰ to +7.0 ‰, falling near 26 the middle of the range reported in previous work. The first measurements of δ 15 N-27HONO and δ 18 O-HONO in biomass burning smoke reveal a range of -5.3 -+5.8 ‰ and 28 +5.2 -+15.2 ‰ respectively. Both HONO and NO x are sourced from N in the biomass 29 fuel and δ 15 N-HONO and δ 15 N-NO x are strongly correlated (R 2 = 0.89, p<0.001), 30suggesting NO x and HONO are connected via formation pathways. 31 32Our δ 15 N of NO x , HONO and NO 3 -(p) ranges can serve as important biomass burning 33 source signatures, useful for constraining direct emissions of these species in 34 environmental applications. The δ 18 O of HONO and NO 3 obtained here verify our 35 method is capable of determining oxygen isotopic composition in BB plumes. The δ 18 O 36for both species in this study reflect the laboratory conditions (i.e. a lack of 37 photochemistry), and would be expected to track with the influence of ozone (O 3 ), 38 photochemistry and nighttime chemistry in real environments. The methods used in this 39 study will be further applied in future field studies to quantitatively track reactive 40 nitrogen cycling in fresh and aged Western US wild...

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Rate coefficients for fuel + NO2: Predictive kinetics for HONO and HNO2 formation

Cited by 74 publications

References 45 publications

High pressure study of H oxidation and its interaction with NO

High pressure study of H oxidation and its interaction with NO

First detection of a key intermediate in the oxidation of fuel + NO systems: HONO

Isotopic characterization of nitrogen oxides (NO<sub>x</sub>), nitrous acid (HONO), and nitrate (NO<sub>3</sub><sup>−</sup>(p)) from laboratory biomass burning during FIREX

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Rate coefficients for fuel + NO2: Predictive kinetics for HONO and HNO2 formation

Cited by 74 publications

References 45 publications

High pressure study of H oxidation and its interaction with NO

High pressure study of H oxidation and its interaction with NO

First detection of a key intermediate in the oxidation of fuel + NO systems: HONO

Isotopic characterization of nitrogen oxides (NO&lt;sub&gt;x&lt;/sub&gt;), nitrous acid (HONO), and nitrate (NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt;(p)) from laboratory biomass burning during FIREX

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Product

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First detection of a key intermediate in the oxidation of fuel + NO systems: HONO

Isotopic characterization of nitrogen oxides (NO<sub>x</sub>), nitrous acid (HONO), and nitrate (NO<sub>3</sub><sup>−</sup>(p)) from laboratory biomass burning during FIREX