Association Moléculaire et Paire Ionique dans le Verre et le Liquide du ‘Monohydrate de l'Acide Nitrique’

Herzog-Cance, M.H.; Potier, J.; Potier, A.; Dhamelincourt, P.; Sombret, B.; Wallart, F.

doi:10.1002/jrs.1250070603

Cited by 14 publications

(15 citation statements)

References 20 publications

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“…These indicate a change in the composition of the surface film, consistent with the preferential removal of water, and may reflect a change from the trihydrate through the dihydrate to the monohydrate and perhaps ultimately species such as 4HNO 3 ÁH 2 O as observed in solid and liquid mixtures of HNO 3 and water by Raman spectroscopy. 106 The combination of data suggests that there are significant amounts of undissociated nitric acid on the surface, perhaps in part in the form of hydrates. In concentrated HNO 3 solutions, NO 2 + is also generated via a self-reaction of HNO 3 :…”

Section: à3mentioning

confidence: 99%

“…[102][103][104][105] Different forms of the monohydrate such as H 2 OÁ Á ÁHONO 2 , (H 2 OH) + Á Á Á(ONO 2 ) À and 4HNO 3 ÁH 2 O have also been observed using Raman spectroscopy. 106,107 There is also theoretical evidence for nitric acid-water complexes. Ab initio calculations of the 1:1 nitric acid-water complex in the gas phase have been carried out, [108][109][110] showing that two hydrogen bonds form between HNO 3 and H 2 O with a binding energy for the complex of 9.5 kJ mol À1 .…”

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confidence: 99%

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The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism

Finlayson-Pitts

Wingen

Sumner

et al. 2002

Phys. Chem. Chem. Phys.

620

767

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The heterogeneous reaction of NO 2 with water on the surface of laboratory systems has been known for decades to generate HONO, a major source of OH that drives the formation of ozone and other air pollutants in urban areas and possibly in snowpacks. Previous studies have shown that the reaction is first order in NO 2 and in water vapor, and the formation of a complex between NO 2 and water at the air-water interface has been hypothesized as being the key step in the mechanism. We report data from long path FTIR studies in borosilicate glass reaction chambers of the loss of gaseous NO 2 and the formation of the products HONO, NO and N 2 O. Further FTIR studies were carried out to measure species generated on the surface during the reaction, including HNO 3 , N 2 O 4 and NO 2 + . We propose a new reaction mechanism in which we hypothesize that the symmetric form of the NO 2 dimer, N 2 O 4 , is taken up on the surface and isomerizes to the asymmetric form, ONONO 2 . The latter autoionizes to NO + NO 3 À , and it is this intermediate that reacts with water to generate HONO and surface-adsorbed HNO 3 . Nitric oxide is then generated by secondary reactions of HONO on the highly acidic surface. This new mechanism is discussed in the context of our experimental data and those of previous studies, as well as the chemistry of such intermediates as NO + and NO 2 + that is known to occur in solution. Implications for the formation of HONO both outdoors and indoors in real and simulated polluted atmospheres, as well as on airborne particles and in snowpacks, are discussed. A key aspect of this chemistry is that in the atmospheric boundary layer where human exposure occurs and many measurements of HONO and related atmospheric constituents such as ozone are made, a major substrate for this heterogeneous chemistry is the surface of buildings, roads, soils, vegetation and other materials. This area of reactions in thin films on surfaces (SURFACE ¼ Surfaces, Urban and Remote: Films As a Chemical Environment) has received relatively little attention compared to reactions in the gas and liquid phases, but in fact may be quite important in the chemistry of the boundary layer in urban areas.

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Section: à3mentioning

confidence: 99%

mentioning

confidence: 99%

The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism

Finlayson-Pitts

Wingen

Sumner

et al. 2002

Phys. Chem. Chem. Phys.

620

767

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“…Of these only the salt solubilities measured by Marshall and Slusher (28,29) have been studied at temperatures above 90°C, and we shall compare their results with those of the present study. We shall consider the overall dissociation though an intermediate step involving ion-pair formation and dissociation is thought to occur (7); evidence of bands due to the associated species H20---HN03 and H30t---NO, have been reported in a Raman study of the N = I liquid and glass (30), and at very high concentrations, (4HN03. HzO), evidence for [NO3.…”

Section: Dissociation Of H N 0 3 In Solutionmentioning

confidence: 99%

Vibrational spectral studies of solutions at elevated temperatures and pressures. VII. Raman spectra and dissociation of nitric acid

Ratcliffe¹,

Irish²

1985

Can. J. Chem.

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An exploratory study of the Raman spectra of nitric acid solutions up to 250 °C has been undertaken. The decrease in the frequencies of the νN—(OH) and δNO2 bands of HNO3 as temperature and concentration increase have been interpreted in terms of the reduced strength of hydrogen bonding. Approximate values of the degree of dissociation α have been determined and show that nitric acid is a very much weaker acid at high temperatures.

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“…2,3 Herzog-Cance et al published the first Raman spectra of these hydrates. 4,5 The interest in nitric acid hydrates had a renaissance with the discovery of the so-called ozone hole over the Antarctic polar region. Nitric acid and water had been identified as major constituents of Polar Stratospheric Clouds (PSC) which assist in transforming inactive reservoir compounds (e.g., HCl and ClONO 2 ) into active chlorine species (e.g., HOCl, Cl 2 , etc.)…”

Section: Introductionmentioning

confidence: 99%

Low-Frequency Raman Spectra of Nitric Acid Hydrates

2005

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Raman spectra of solid nitric acid hydrates (NAM, alpha- and beta-NAD, alpha- and beta-NAT, and NAP) are obtained in the low-frequency region 20-175 cm(-1) where phonon bands show characteristic patterns. This fingerprint information, intimately related to the structure and symmetry of the unit cell, is well suited for observation of phase changes in solid nitric acid hydrates and allows the distinction of mixtures of different hydrate phases. The low-frequency spectra are correlated with the spectra of the respective symmetric NO stretching vibration (1000-1080 cm(-1)), with literature data, and with X-ray diffraction patterns.

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Association Moléculaire et Paire Ionique dans le Verre et le Liquide du ‘Monohydrate de l'Acide Nitrique’

Cited by 14 publications

References 20 publications

The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism

The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism

Vibrational spectral studies of solutions at elevated temperatures and pressures. VII. Raman spectra and dissociation of nitric acid

Low-Frequency Raman Spectra of Nitric Acid Hydrates

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