Preparation and thermal decomposition of pernitric acid (HOONO2) in aqueous media

Kenley, Richard A.; Trevor, P. L.; Lan, B.

doi:10.1021/ja00399a012

Cited by 61 publications

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“…HOONO is prepared by reacting H 2 O 2 vapor with solid NOBF 4 in situ, analogous to the production of HO 2 NO 2 from NO 2 BF 4 described in Ref. 24. Using this preparation method, we observe no temperature dependence of the relative peak intensities in the cis-cis HOONO spectrum in the range 193-273 K ͑Fig.…”

mentioning

confidence: 79%

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

Fry

Nizkorodov

Okumura

et al. 2004

The Journal of Chemical Physics

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The weakly bound HOONO product of the OHϩNO 2 ϩM reaction is studied using the vibrational predissociation that follows excitation of the first OH overtone (2 1 ). We observe formation of both cis-cis and trans-perp conformers of HOONO. The trans-perp HOONO 2 1 band is observed under thermal ͑223-238 K͒ conditions at 6971 cm Ϫ1 . We assign the previously published ͑warmer temperature͒ HOONO spectrum to the 2 1 band at 6365 cm Ϫ1 and 2 1 -containing combination bands of the cis-cis conformer of HOONO. The band shape of the trans-perp HOONO spectrum is in excellent agreement with the predicted rotational contour based on previous experimental and theoretical results, but the apparent origin of the cis-cis HOONO spectrum at 6365 cm Ϫ1 is featureless and significantly broader, suggesting more rapid intramolecular vibrational redistribution or predissociation in the latter isomer. The thermally less stable trans-perp HOONO isomerizes rapidly to cis-cis HOONO with an experimentally determined lifetime of 39 ms at 233 K at 13 hPa ͑in a buffer gas of predominantly Ar͒. The temperature dependence of the trans-perp HOONO lifetime in the range 223-238 K yields an isomerization barrier of 33Ϯ12 kJ/mol. New ab initio calculations of the structure and vibrational mode frequencies of the transition state perp-perp HOONO are performed using the coupled cluster singles and doubles with perturbative triples ͓CCSD͑T͔͒ model, using a correlation consistent polarized triple basis set ͑cc-pVTZ͒. The energetics of cis-cis, trans-perp, and perp-perp HOONO are also calculated at this level ͓CCSD͑T͒/ cc-pVTZ͔ and with a quadruple basis set using the structure determined at the triple basis set ͓CCSD͑T͒/cc-pVQZ//CCSD͑T͒/cc-pVTZ͔. These calculations predict that the anti form of perp-perp HOONO has an energy of ⌬E 0 ϭ42.4 kJ/mol above trans-perp HOONO, corresponding to an activation enthalpy of ⌬H 298 ‡0 ϭ41.1 kJ/mol. These results are in good agreement with statistical simulations based on a model developed by Golden, Barker, and Lohr. The simulated isomerization rates match the observed decay rates when modeled with a trans-perp to cis-cis HOONO isomerization barrier of 40.8 kJ/mol and a strong collision model. The quantum yield of cis-cis HOONO dissociation to OH and NO 2 is also calculated as a function of photon excitation energy in the range 3500-7500 cm Ϫ1 , assuming D 0 ϭ83 kJ/mol. The quantum yield is predicted to vary from 0.15 to 1 over the observed spectrum at 298 K, leading to band intensities in the action spectrum that are highly temperature dependent; however, the observed relative band strengths in the cis-cis HOONO spectrum do not change substantially with temperature over the range 193-273 K. Semiempirical calculations of the oscillator strengths for 2 1 (cis-cis HOONO) and 2 1 (trans-perp HOONO) are performed using ͑1͒ a one-dimensional anharmonic model and ͑2͒ a Morse oscillator model for the OH stretch, and ab initio dipole moment functions calculated using Becke, Lee, Yang, and Parr density functional theory ͑B3LYP͒,...

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mentioning

confidence: 79%

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

Fry

Nizkorodov

Okumura

et al. 2004

The Journal of Chemical Physics

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“…Incomplete recovery would suggest (i) chemical decomposition, (ii) slow, continuous uptake, or (iii) irreversible adsorption of HO 2 NO 2 . (i) Decomposition of HO 2 NO 2 has been observed in water at moderate and acidic pH (Kenley et al, 1981;Lammel et al, 1990;Regimbal and Mozurkewich, 1997). HNO 3 , NO 2 , HONO, and H 2 O 2 have been identified as products.…”

Section: Adsorption Experimentsmentioning

confidence: 98%

“…Conventionally HO 2 NO 2 is synthesized in the aqueous phase by reaction of NO 2 BF 4 in 90 % H 2 O 2 or of NaNO 2 and HClO 4 in 30 % H 2 O 2 , which is then delivered to a gas-flow by bubbling carrier gas through the solution (Kenley et al, 1981;Appelman and Gosztola, 1995). One advantage of the gas-phase synthesis used here is that it can continuously provide HO 2 NO 2 levels over long time periods, as needed for our experiments.…”

Section: Synthesis Of Ho 2 Nomentioning

confidence: 99%

The adsorption of peroxynitric acid on ice between 230 K and 253 K

et al. 2012

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Abstract. Peroxynitric acid uptake to ice and snow has been proposed to be a major loss process from the atmosphere with impacts on the atmospheric oxidation capacity. Here we present results from a laboratory study on the interaction of peroxynitric acid with water ice at low concentration. Experiments were performed in a coated wall flow tube at atmospheric pressure and in the environmentally relevant temperature range of 230 K to 253 K. The interaction was found to be fully reversible and decomposition was not observed. Analysis based on the Langmuir adsorption model showed that the partitioning of peroxynitric acid to ice is orders of magnitude lower than of nitric acid and similar to nitrous acid partitioning behavior. The partition coefficient (K LinC ) and its temperature dependency can be described by 3.74 × 10 −12 × e (7098/T ) [cm]. Atmospheric implications are discussed and show that the uptake to cirrus clouds or to snow-packs in polar areas is an important sink for peroxynitric acid in the environment.

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“…This shifts the equilibrium of Eq. (16) to the left and depletes the peroxynitrate concentration (72,73). Therefore, if peroxynitrates are involved in the inactivation of alPI, they must be the short-lived, fastreacting oxidant; peroxynitrates are too short-lived to be a factor in the slow inactivation that occurs over several days.…”

Section: The Tar Radical(s) In Cigarette Smoke: Esr Studiesmentioning

confidence: 99%

Free-Radical Chemistry of Cigarette Smoke and Its Toxicological Implications

Church¹,

Pryor²

1985

Environmental Health Perspectives

330

297

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Cigarette smoke contains two very different populations of free radicals, one in the tar and one in the gas phase. The tar phase contains several relatively stable free radicals; we have identified the principal radical as a quinone/hydroquinone (Q/QH2) complex held in the tarry matrix. We suggest that this Q/QH2 polymer is an active redox system that is capable of reducing molecular oxygen to produce superoxide, eventually leading to hydrogen peroxide and hydroxyl radicals. In addition, we have shown that the principal radical in tar reacts with DNA in vitro, possibly by covalent binding.The gas phase of cigarette smoke contains small oxygen-and carbon-centered radicals that are much more reactive than are the tar-phase radicals. These gas-phase radicals do not arise in the flame, but rather are produced in a steady state by the oxidation of NO to NO2, which then reacts with reactive species in smoke such as isoprene. We suggest that these radicals and the metastable products derived from these radical reactions may be responsible for the inactivation of a,-proteinase inhibitor by fresh smoke.Cigarette smoke oxidizes thiols to disulfides; we suggest the active oxidants are NO and NO2. The effects of smoke on lipid peroxidation are complex, and this is discussed. We also discuss the toxicological implications for the radicals in smoke in terms of a number of radical-mediated disease processes, including emphysema and cancer.

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Preparation and thermal decomposition of pernitric acid (HOONO2) in aqueous media

Abstract: strong O1 2' and a weak OH" ligand in the axial direction and that the strong O2" ligand is preferable to the 5 = 1 spin state of the central metal ion.

Cited by 61 publications

References 0 publications

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

The adsorption of peroxynitric acid on ice between 230 K and 253 K

Free-Radical Chemistry of Cigarette Smoke and Its Toxicological Implications

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