Dinitrogen tetroxide, nitric acid, and their mixtures as media for inorganic reactions

Addison, C. C.

doi:10.1021/cr60323a002

Cited by 134 publications

(101 citation statements)

References 33 publications

(38 reference statements)

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“…NO 2 or its dimer can be diluted with many solvents to give small amounts of NO + and NO 3 À in some cases (Scheme 3). [30] The resulting NO + seems to be the real catalytic species because the oxidation of iodine to I + is possibly carried out by NO + in an inner-sphere electron transfer step, [31] which was also confirmed by our experimental result: the iodination with NOBF 4 instead of NO 2 proceeded efficiently with a high yield (Scheme 4). It is known that NO + is effective in oxidizing a number of aromatics and heteroaromatics to the cation radicals, [32] hence the resulting aromatic radical cations should react with another aryl ring to generate the biaryl by-poducts.…”

Section: Resultssupporting

confidence: 76%

Nitrogen Dioxide‐Catalyzed Electrophilic Iodination of Arenes

et al. 2013

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Nitrogen dioxide is demonstrated to be an effective catalyst precursor for the iodination of alkoxy-substituted benzenes and naphthalenes. Different from the transition metal catalysts, nitrogen dioxide can be easily separated from the final products, and is free of heavy metal waste. Although the present catalyst precursor is toxic, it does not stain the final products due to its low-boiling character. No other reagents apart from 0.5 equiv. of iodine (I 2 ), 6.5 mol% nitrogen dioxide and acetonitrile solvent were used in the iodination, and basically all the iodine atoms in the iodine source were transferred to the iodination products, showing that the presented protocol is highly atom-economic and practical.

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Section: Resultssupporting

confidence: 76%

Nitrogen Dioxide‐Catalyzed Electrophilic Iodination of Arenes

et al. 2013

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“…The role of water must be to form very stable nitric acid-water complexes or hydrates. Nitric acid is well known to form hydrates with water both in aqueous solution [99][100][101] and on ice. [102][103][104][105] In aqueous solution, as the concentration of nitric acid increases, the composition changes from the dissociated ions to the trihydrate and then the monohydrate, and finally pure HNO 3 .…”

Section: à3mentioning

confidence: 99%

“…[102][103][104][105] In aqueous solution, as the concentration of nitric acid increases, the composition changes from the dissociated ions to the trihydrate and then the monohydrate, and finally pure HNO 3 . [99][100][101] On ice, the dihydrate is also observed. [102][103][104][105] There is also theoretical evidence for nitric acid-water complexes.…”

Section: à3mentioning

confidence: 99%

“…2 is uptake of gaseous N 2 O 4 on the surface and its isomerization to surface asymmetric ONONO 2 . This isomerization is known to occur in solid matrices at low temperatures or high pressures, on ice and in solution, 101,[135][136][137][138][139][140][141][142][143][144][145][146][147][148][149][150] (although one study 151 observed only the symmetric form of N 2 O 4 on ice films). Koel and coworkers [148][149][150]152 proposed that this isomerization occurs via the free O-H groups on amorphous ice, and it is possible that a similar process occurs in the thin films studied here.…”

Section: Mechanisms and Modelsmentioning

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.

621

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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“…Nitrogen dioxide is known [43][44][45][46] to be generated in the decomposition of pure nitric acid, and indeed, some NO 2 formation was observed over time after the cell was pumped following the HNO 3 conditioning procedure. At 0% RH, the increase was small and represented less than 10% of the NO 2 formed in experiments where HONO was added.…”

mentioning

confidence: 99%

HONO decomposition on borosilicate glass surfaces: implications for environmental chamber studies and field experiments

Syomin

Finlayson-Pitts

2003

Phys. Chem. Chem. Phys.

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Nitrous acid (HONO) is the major source of OH in polluted urban atmospheres, so an understanding of its formation and loss processes both in urban atmospheres and in laboratory systems is important. Earlier studies over a limited range of conditions showed that HONO is taken up and undergoes reaction on surfaces. We report here a comprehensive set of studies of the decay of HONO and the formation of gas phase products over a range of initial HONO concentrations (0.1-11 ppm) at 1 atm pressure in N 2 at 296 K and 0, 20 and 50% relative humidity (RH), respectively. The loss of HONO and increase in gas phase products were measured over time using long path FTIR spectroscopy. Studies were carried out in an unconditioned borosilicate glass cell and in the same cell after pretreatment with dry gaseous nitric acid. In the HNO 3 -conditioned cell, the loss of HONO was first order at all values of relative humidity (RH), and NO 2 was the only significant gas phase product. For the unconditioned cell, the reaction order increased from first order at 0% RH to second order at 50% RH. The gas phase products at 0% RH were equal amounts of NO and NO 2 . The yield of NO increased to > 90% at 50% RH while the yield of NO 2 decreased to 10%. For both the unconditioned and the HNO 3 -treated cell, the rate of loss of HONO decreased with increasing RH. These results suggest that there is a competition between water, HONO and HNO 3 for surface sites. Displacement of HONO from the cell walls by water was observed in separate experiments. Possible mechanisms, and the implications for HONO formation in environmental chambers and in air, are discussed.

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Dinitrogen tetroxide, nitric acid, and their mixtures as media for inorganic reactions

Cited by 134 publications

References 33 publications

Nitrogen Dioxide‐Catalyzed Electrophilic Iodination of Arenes

Nitrogen Dioxide‐Catalyzed Electrophilic Iodination of Arenes

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

HONO decomposition on borosilicate glass surfaces: implications for environmental chamber studies and field experiments

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