scholarly journals Comment on “Isotopic evidence for dominant secondary production of HONO in near-ground wildfire plumes” by Chai et al. (2021)

2021 ◽  
Vol 21 (22) ◽  
pp. 16793-16795
Author(s):  
James M. Roberts
Keyword(s):  
Nitric Oxide ◽  
Nitric Acid ◽  
Secondary Production ◽  
Nitrous Acid ◽  
Nitrogen Compound ◽  
Decomposition Reaction ◽  
Organic Radicals ◽  
Organic Nitrates ◽  
Oxides Of Nitrogen ◽  
Model Reactions

Abstract. Chai et al. (2021) recently published measurements of wildfire-derived (WF) oxides of nitrogen (NOx) and nitrous acid (HONO) and their isotopic composition. The method used to sample NOx, collection in alkaline solution, has a known 1:1 interference from another reactive nitrogen compound, acetyl peroxynitrate (PAN). Although PAN is thermally unstable, subsequent reactions with nitrogen dioxide (NO2) in effect extend the lifetime of PAN many times longer than the initial decomposition reaction would indicate. This, coupled with the rapid and efficient formation of PAN in WF plumes, means the NOx measurements reported by Chai et al.​​​​​​​ were severely impacted by PAN. In addition, the model reactions in the original paper included neither the reactions of NO2 with hydroxyl radical (OH) to form nitric acid nor the efficient reaction of larger organic radicals with nitric oxide to form organic nitrates (RONO2).

scholarly journals Comment on “Isotopic evidence for dominant secondary production of HONO in near-ground wildfire plumes.”

2021 ◽  
Author(s):  
James Roberts
Keyword(s):  
Nitric Oxide ◽  
Secondary Production ◽  
Nitrous Acid ◽  
Nitrogen Compound ◽  
Decomposition Reaction ◽  
Organic Radicals ◽  
Organic Nitrates ◽  
Oxides Of Nitrogen ◽  
Wild Fire ◽  
Model Reactions

Abstract. Chai et al. recently published measurements of wild fire (WF) derived oxides of nitrogen (NOx) and nitrous acid (HONO) and their isotopic composition. The method used to sample NOx, collection in alkaline solution, has a known 1:1 interference from another reactive nitrogen compound, acetyl peroxynitrate (PAN). Although PAN is thermally unstable, subsequent reactions with nitrogen dioxide (NO2) in effect extend the lifetime of PAN many times longer than the initial decomposition reaction would indicate. This, coupled with the rapid and efficient formation of PAN in WF plumes, means the NOx measurements reported by Chai et al. were severely impacted by PAN. In addition, the model reactions in the original paper did not include the reactions of NO2 with hydroxyl radical (OH) to form nitric acid, nor the efficient reaction of larger organic radicals with nitric oxide to form organic nitrates (RONO2).

Initial Reaction Intermediates in the Oxidation of Ascorbic Acid by Nitrous Acid

1981 ◽  
Vol 44 (1) ◽  
pp. 28-32 ◽  
Author(s):  
JAY B. FOX ◽  
ROSEMARY N. FIDDLER ◽  
AARON E. WASSERMAN
Keyword(s):  
Nitric Oxide ◽  
Ascorbic Acid ◽  
Nitrous Acid ◽  
Organic Radicals ◽  
Initial Reaction ◽  
Reaction Intermediates ◽  
Absorption Bands ◽  
Visible Absorption ◽  
Decomposition Products

Nitrite and ascorbate react to form nitric oxide at pH 5.5. In the initial stages of the reaction, seven intermediates can be identified spectrally and chromatographically; these include two colorless nitroso derivatives which contain 30–60% of the initial nitrite, two nitroso reductant derivatives absorbing at 345 and 412 nm, diketogulonic acid and two further decomposition products. None of the intermediates was paramagnetic; except for diketogulonic acid, all decomposed rapidly during or after isolation. Based on the order of appearance of the ultraviolet and visible absorption bands in the reaction mixtures, the observed characteristics of the intermediates, and the lack of organic radicals, a sequence is proposed for the initial steps in the oxidation of ascorbic acid by nitrous acid.

THE EQUILIBRIUM BETWEEN NITRIC ACID, NITROUS ACID AND NITRIC OXIDE.

1911 ◽  
Vol 33 (3) ◽  
pp. 292-299 ◽  
Author(s):  
Gilbert N. Lewis ◽  
Arthur Edgar
Keyword(s):  
Nitric Oxide ◽  
Nitric Acid ◽  
Nitrous Acid

scholarly journals IV. The conditions of chemical change between nitric acid and certain metals

1891 ◽  
Vol 48 (292-295) ◽  
pp. 458-459 ◽  
Keyword(s):  
Nitric Oxide ◽  
Hydrogen Peroxide ◽  
Nitric Acid ◽  
Potassium Permanganate ◽  
Nitrous Acid ◽  
Chemical Change ◽  
Potassium Chlorate ◽  
Cent Concentration ◽  
Preliminary Communication ◽  
A Current

This paper is in continuation of a preliminary communication on the same subject; the main points contained in it are as follows: I. The metals copper, mercury, and bismuth do not dissolve in nitric acid of about 30 per cent, concentration (the acid commonly employed for the preparation of nitric oxide gas) and heated to a temperature of 30ºC., provided that nitrous acid is neither present initially nor formed subsequently. To prevent this, it is nocessary in the cases of copper and bismuth to add a small quantity of some oxidising substance, such as hydrogen peroxide or potassium chlorate, or, as less efficacious, potassium permanganate, or to pass a current of air or, lastly, such a substance as urea, which destroys the nitrous acid by its interaction.

Organic nitrates, thionitrates, peroxynitrites, and nitric oxide: a molecular orbital study of the (X = O, S) rearrangement, a reaction of potential biological significance

1995 ◽  
Vol 73 (10) ◽  
pp. 1627-1638 ◽  
Author(s):  
Dale R. Cameron ◽  
Alison M.P. Borrajo ◽  
Gregory R.J. Thatcher ◽  
Brian M. Bennett
Keyword(s):  
Nitric Oxide ◽  
Nitric Acid ◽  
Molecular Orbital ◽  
Biological Significance ◽  
Intrinsic Reaction Coordinate ◽  
Organic Nitrates ◽  
Molecular Orbital Calculations ◽  
Peroxynitrous Acid ◽  
Structural Reorganization

The rearrangement of organic thionitrate to sulfenyl nitrite potentially mediates the release of nitric oxide from organic nitrates, such as nitroglycerin, in the presence of thiol. The biological activity of these nitrovasodilators is proposed to result from release of nitric oxide in vivo. The thionitrate rearrangement bears analogy to the rearrangement of peroxynitrous acid to nitric acid, which has been proposed to mediate the biological toxicity of nitric oxide and superoxide. In this paper, the two concerted rearrangement processes and competing homolytic reactions are explored using molecular orbital calculations at levels up to MP4SDQ/6-31G*//MP2/6-31G*. Examination of structure and energy for all conformers and isomers of RSONO2 (R = H, Me), models for organic thionitrates and their isomers, demonstrates that structures corresponding to thionitrates and sulfenyl nitrates are of similar energy. Free energies of reaction for homolysis of these compounds are low (ΔG0 < 19 kcal/mol), whereas the barrier for concerted rearrangement is large (ΔG≠(aq.) = 56 kcal/mol). The larger barrier for concerted rearrangement of peroxynitrous acid to nitric acid (ΔG≠(aq.) = 60 kcal/mol) again compares unfavourably with homolysis (ΔG0 < 11 kcal/mol for homolysis to NO2 or •NO). The transition state structures, confirmed by normal mode and intrinsic reaction coordinate analysis, indicate that considerable structural reorganization is required for concerted rearrangement of the ground state species. These results suggest that concerted rearrangement is not likely to be a viable step in either biological process. However, rearrangement via homolysis and radical recombination may provide an energetically accessible pathway for peroxynitrous acid rearrangement to nitric acid and rearrangement of thionitrate to sulfenyl nitrite. In this case, NO2 will be a primary product of both reactions. Keywords: thionitrate, nitric oxide, peroxynitrite, nitrovasodilator, nitrate.

The Effect of NO, HNO2 and HNO3 On Corrosion of Stainless Steel by H2SO4★

CORROSION ◽  
1958 ◽  
Vol 14 (1) ◽  
pp. 27-30
Author(s):  
W. P. McKINNELL ◽  
L. F. LOCKWOOD ◽  
R. SPEISER ◽  
F. H. BECK ◽  
M. G. FONTANA
Keyword(s):  
Nitric Oxide ◽  
Stainless Steel ◽  
Nitric Acid ◽  
Nitrous Acid ◽  
Acid Solutions ◽  
Active Type ◽  
Nitrate Ions ◽  
Nitric Acid Solutions ◽  
Spot Tests

Abstract Earlier work by other investigators has shown that nitrous acid is involved in the passivation of iron in concentrated nitric acid solutions. This paper describes the effect of nitric oxide, HNO2 and HNO3 on the corrosion of active Type 302 stainless steel by 10 percent H2SO4. Specimens of Type 302 stainless steel, activated by abrading on 240 grit emery cloth and exposed to 10 percent H2SO4 solutions, were passivated by bubbling nitric oxide through the solution. Bubbling oxygen through the solution did not passivate these abraded specimens. Abraded specimens exposed to an atmosphere of nitric oxide before immersion in nitric oxide-free H2SO4 remained active. Spot tests of 10 percent H2SO4 treated with nitric oxide revealed the presence of nitrite and nitrate ions in the solution. The addition of one part of 10 percent HNO3 to 60 parts of 10 percent H2SO4 was found to produce passivity of abraded stainless steel specimens exposed to the solution. 4.3.2

scholarly journals Improvements in the profiles and distributions of nitric acid and nitrogen dioxide with the LIMS version 6 dataset

2010 ◽  
Vol 10 (10) ◽  
pp. 4741-4756 ◽  
Author(s):  
E. Remsberg ◽  
M. Natarajan ◽  
B. T. Marshall ◽  
L. L. Gordley ◽  
R. E. Thompson ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Nitrogen Dioxide ◽  
Theoretical Calculations ◽  
Spin Splitting ◽  
Oxides Of Nitrogen ◽  
Polar Night ◽  
Chemical Effects ◽  
Satellite Sensors ◽  
Precision And Accuracy

Abstract. The quality of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) nitric acid (HNO3) and nitrogen dioxide (NO2) profiles and distributions of 1978/1979 are described after their processing with an updated, Version 6 (V6) algorithm and subsequent archival in 2002. Estimates of the precision and accuracy of both of those species are developed and provided herein. The character of the V6 HNO3 profiles is relatively unchanged from that of the earlier LIMS Version 5 (V5) profiles, except in the upper stratosphere where the interfering effects of CO2 are accounted for better with V6. The accuracy of the retrieved V6 NO2 is also significantly better in the middle and upper stratosphere, due to improvements in its spectral line parameters and in the reduced biases for the accompanying V6 temperature and water vapor profiles. As a result of these important updates, there is better agreement with theoretical calculations for profiles of the HNO3/NO2 ratio, day-to-night NO2 ratio, and with estimates of the production of NO2 in the mesosphere and its descent to the upper stratosphere during polar night. In particular, the findings for middle and upper stratospheric NO2 should also be more compatible with those obtained from more recent satellite sensors because the effects of the spin-splitting of the NO2 lines are accounted for now with the LIMS V6 algorithm. The improved precisions and more frequent retrievals of the LIMS profiles along their orbit tracks provide for better continuity and detail in map analyses of these two species on pressure surfaces. It is judged that the chemical effects of the oxides of nitrogen on ozone can be studied quantitatively throughout the stratosphere with the LIMS V6 data.

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