Thermal Decomposition of HO2NO2 (Peroxynitric Acid, PNA):  Rate Coefficient and Determination of the Enthalpy of Formation

Gierczak, Tomasz; Jiménez, Elena; Riffault, Véronique; Burkholder, James B.; Ravishankara, A. R.

doi:10.1021/jp046632f

Cited by 33 publications

(25 citation statements)

References 29 publications

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“…Ab initio CBS‐QB3 calculations carried out as part of the present work (Fig. 7) indicate that at subambient temperatures, NO 2 and HO 2 predominantly add to form stabilized HOONO 2 , as described by Gierczak et al 142. However, this pathway is suppressed at elevated temperatures, including those considered in the present work.…”

Section: Detailed Kinetic Modelsupporting

confidence: 71%

Experimental measurements and kinetic modeling of CO/H₂/O₂/NO_x conversion at high pressure

Rasmussen

Hansen

Marshall

et al. 2008

Int J of Chemical Kinetics

178

207

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This paper presents results from lean CO/H 2 /O 2 /NO x oxidation experiments conducted at 20-100 bar and 600-900 K. The experiments were carried out in a new high-pressure laminar flow reactor designed to conduct well-defined experimental investigations of homogeneous gas phase chemistry at pressures and temperatures up to 100 bar and 925 K. at 780-1100 K and 1-10 bar. Moreover, introduction of the reaction CO + H 2 O 2 → HOCO + OH into the model yields an improved prediction, but no final resolution, to the recently debated syngas ignition delay problem compared to previous kinetic models.

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Section: Detailed Kinetic Modelsupporting

confidence: 71%

Experimental measurements and kinetic modeling of CO/H₂/O₂/NO_x conversion at high pressure

Rasmussen

Hansen

Marshall

et al. 2008

Int J of Chemical Kinetics

178

207

View full text Add to dashboard Cite

show abstract

“…This method of HONO production is instantaneous and does not require the period of stabilization that is necessary for acid-salt reaction-based sources (Febo et al, 1995). HONO standard production via the reaction of HO 2 and NO provides a good alternative to previously used I − CIMS calibration methods .…”

Section: Honomentioning

confidence: 99%

Peroxynitric acid (HO2NO2) measurements during the UBWOS 2013 and 2014 studies using iodide ion chemical ionization mass spectrometry

et al. 2015

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Abstract. In this paper laboratory work is documented establishing iodide ion chemical ionization mass spectrometry (I − CIMS) as a sensitive method for the unambiguous detection of peroxynitric acid (HO 2 NO 2 ; PNA). A dynamic calibration source for HO 2 NO 2 , HO 2 , and HONO was developed and calibrated using a novel total NO y cavity ring-down spectroscopy (CaRDS) detector. Photochemical sources of these species were used for the calibration and validation of the I − CIMS instrument for detection of HO 2 NO 2 . Ambient observations of HO 2 NO 2 using I − CIMS during the 2013 and 2014 Uintah Basin Wintertime Ozone Study (UBWOS) are presented. Strong inversions leading to a build-up of many primary and secondary pollutants as well as low temperatures drove daytime HO 2 NO 2 as high as 1.5 ppbv during the 2013 study. A comparison of HO 2 NO 2 observations to mixing ratios predicted using a chemical box model describing an ozone formation event observed during the 2013 wintertime shows agreement in the daily maxima HO 2 NO 2 mixing ratio, but a differences of several hours in the timing of the observed maxima. Observations of vertical gradients suggest that the ground snow surface potentially serves as both a net sink and source of HO 2 NO 2 depending on the time of day. Sensitivity tests using a chemical box model indicate that the lifetime of HO 2 NO 2 with respect to deposition has a nonnegligible impact on ozone production rates on the order of 10 %.

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“…The net pernitric acid reaction consumes two HO x radicals (Wennberg et al, 1998) and, in this study, this net reaction accounts for 29% of the radicals terminated in the first 6 h. We recommend using the latest k OH + HO 2 NO 2 (Jimenez et al, 2004) which improves HO 2 NO 2 agreement with observations and increases competition of pernitric acid with NO 2 for OH · radicals. Even with this recommendation, the pernitric acid reaction rates have large uncertainties at low temperatures and laboratory studies are restricted to temperatures above those typical in the upper troposphere Gierczak et al, 2005;Sander et al, 2006).…”

Section: Chemical Mechanism Biases and Recommendationsmentioning

confidence: 99%

Evaluation of simulated photochemical partitioning of oxidized nitrogen in the upper troposphere

et al. 2011

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Abstract. Regional and global chemical transport models underpredict NO x (NO + NO 2 ) in the upper troposphere where it is a precursor to the greenhouse gas ozone. The NO x bias has been shown in model evaluations using aircraft data and total column NO 2 (molecules cm −2 ) from satellite observations (Napelenok et al., 2008). The causes of NO x underpredictions have yet to be fully understood due to the interconnected nature of simulated emission, transport, and chemistry processes. Recent observationbased studies, in the upper troposphere, identify chemical rate coefficients as a potential source of error (Olson et al., 2006;Ren et al., 2008). Since typical chemistry evaluation techniques are not available for upper tropospheric conditions, this study develops an evaluation platform from in situ observations, stochastic convection, and deterministic chemistry. We derive a stochastic convection model and optimize it using two simulated datasets of time since convection, one based on meteorology, and the other on chemistry. The chemistry surrogate for time since convection is calculated using seven different chemical mechanisms, all of which predict shorter time since convection than our meteorological analysis. We evaluate chemical simulations by inter-comparison and by pairing results with observations based on NO x :HNO 3 , a photochemical aging indicator. Inter-comparison reveals individual chemical mechanism biases and recommended updates. Evaluation against observations shows that all chemical mechanisms overpredict NO x Correspondence to: B. H. Henderson (barronh@gmail.com) removal relative to long-lived methanol and carbon monoxide. All chemical mechanisms underpredict observed NO x by at least 30%, and further evaluation is necessary to refine simulation sensitivities to initial conditions and chemical rate uncertainties.

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Thermal Decomposition of HO₂NO₂ (Peroxynitric Acid, PNA): Rate Coefficient and Determination of the Enthalpy of Formation

Cited by 33 publications

References 29 publications

Experimental measurements and kinetic modeling of CO/H₂/O₂/NO_x conversion at high pressure

Experimental measurements and kinetic modeling of CO/H₂/O₂/NO_x conversion at high pressure

Peroxynitric acid (HO<sub>2</sub>NO<sub>2</sub>) measurements during the UBWOS 2013 and 2014 studies using iodide ion chemical ionization mass spectrometry

Evaluation of simulated photochemical partitioning of oxidized nitrogen in the upper troposphere

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Thermal Decomposition of HO2NO2 (Peroxynitric Acid, PNA): Rate Coefficient and Determination of the Enthalpy of Formation

Cited by 33 publications

References 29 publications

Experimental measurements and kinetic modeling of CO/H2/O2/NOx conversion at high pressure

Experimental measurements and kinetic modeling of CO/H2/O2/NOx conversion at high pressure

Peroxynitric acid (HO&lt;sub&gt;2&lt;/sub&gt;NO&lt;sub&gt;2&lt;/sub&gt;) measurements during the UBWOS 2013 and 2014 studies using iodide ion chemical ionization mass spectrometry

Evaluation of simulated photochemical partitioning of oxidized nitrogen in the upper troposphere

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Product

Resources

About

Thermal Decomposition of HO₂NO₂ (Peroxynitric Acid, PNA): Rate Coefficient and Determination of the Enthalpy of Formation

Experimental measurements and kinetic modeling of CO/H₂/O₂/NO_x conversion at high pressure

Experimental measurements and kinetic modeling of CO/H₂/O₂/NO_x conversion at high pressure

Peroxynitric acid (HO<sub>2</sub>NO<sub>2</sub>) measurements during the UBWOS 2013 and 2014 studies using iodide ion chemical ionization mass spectrometry