Nitrogen dioxide formation from

Metal- and proton-exchanged zeolites have been recently attracted much attention because of their selective catalytic activity to efficiently reduce nitrogen monoxide (NO) by hydrocarbon in an 02-rich atmosphere [1]. The formation of nitrogen dioxide (NO2) from NO and O2 has been suggested as an important step in the selective reduction [2, 3] NO2 is one of rare stable paramagnetic gaseous molecules and has been subjected to electron spin resonance (ESR) studies [4-7]. The ESR parameters and their relation/to the electronic structure have been well established [4] and NO2 can be used as a "spin probe" for the study of molecular dynamics at the gas-solid interface by ESR. 

The formation of the nitrogen oxides, nitric oxide (NO) and nitrogen dioxide (NO2) from N2 and O2, provides an example of the interplay between thermodynamics and kinetics. The calculation of the equilibrium concentrations of NO and NO2 is straightforward if we assume that these are the only compounds formed and that the initial pressures of N2 and O2 are known. 

III) Formation of nitrogen dioxide gas from dinitrogen tetroxide N204(g) 2N02(g)... 

Consider the formation of nitrogen dioxide (NO2) from nitric oxide (NO) and oxygen ... 

It must be achieved under very precise experimental conditions in order to avoid the formation of nitrogen dioxide NO2 from nitric oxide NO by reaction with the air dioxygen. Nitric acid itself is formed by the oxidation reaction of iodide ions. Nitrogen oxides, present in the medium, catalyze the oxidization of iodide ions by dioxygen and result in too great a release of iodine. 

The carbon dioxide removed in synthesis gas preparation can be reacted with ammonia, to lonn urea CO(NH2)2- This is an excellent fertilizer, highly concentrated in nitrogen (46.6%) and also useful as an additive in animal feed to provide the nitrogen for formation of meat protein. Urea is also an important source of resins and plastics by reacting it with formaldehyde from methanol. 

In contrast to carbon monoxide, small hydrocarbon molecules and soot that result from incomplete conversion of the hydrocarbon fuels, nitric oxide and nitrogen dioxide, are noxious emissions that result from the oxidizer—air. However, fuel components that contain nitrogen may also contribute, in a lesser way, to the formation of the oxides of nitrogen. 

Investigation into the effect has been mainly devoted to reactions with red fuming nitric acid . It seems that in red fuming nitric acid a preliminary reaction results in the formation of a surface deposit of finely divided metallic titanium ignition or pyrophoricity can then be initiated by any slight impact or friction. The tendency to pyrophoricity increases as the nitrogen dioxide content of the nitric acid rises from zero to maximum solubility at about 20%, but decreases as the water content rises, the effect being nearly completely stifled at about 2% water. 

N,4-DinitrO N-methylaniline, bright yellow needles from benz, mp 142.5° (Ref 2) CA Registry No 16698-03-6. It is prepu by the alkylation of N,p-dinitroaniline with methyl iodide in alk soln (Refs 8 9). It is one compd isolated from aged NC propints stabilized with N-methyl-p-nitroaniline. Hollingsworth at ERDE examined the reaction of nitrogen dioxide with this stabilizer in order to elucidate the mechanism of the formation of the compds isolated. He found that after 7 days at 35°,. a good yield of N,4-dinitro-N-methylaniline was obtd and postulated that it arose from the oxidn of N-nitroso-4-nitroaniline (Ref 16)... 

Ponzio Reaction. The formation of phenyl-dinit romethane from benzaldoxime by oxidation with nitrogen dioxide in eth (Refs 1 2) CH=NOH CH(N02)2... 

The reaction with nitrite proceeds smoothly and with relatively high yields of the corresponding nitroarene (see Sec. 10.6). Obviously a major part of the driving force of this reaction is the formation of a stable, i. e., an energetically favorable, radical, nitrogen dioxide. With the hydroxide ion — a much stronger nucleophile than the nitrite ion — the reaction is expected to produce very unstable radicals, the hydroxy radical OH and the oxygen radical anion O, from the diazohydroxide (Ar - N2 — OH) and the diazoate (Ar-N20 ) respectively. Consequently, dediazoniation in alkaline aqueous solution does not follow the simple Scheme 8-41 with Yn = OH, but instead involves diazoanhydrides (Ar — N2 —O —N2 —Ar) as intermediates (see Sec. 8.8). 

The formation of aryl radicals from benzenediazonium ions, initiated by electron transfer from a nitrite ion, has already been discussed in Section 8.6. It is an excellent example of a dediazoniation assisted by a donor species that is capable of forming a relatively stable species on release of an electron, in this case a nitrogen dioxide radical NO2 (Opgenorth and Rtichardt, 1974). 

Our analysis of the reaction of nitrogen dioxide molecules is not unique. The same type of path can be visualized for any chemical reaction, as Figure 6-20 shows. The reaction enthalpy for any chemical reaction can be found from the standard enthalpies of formation for all the reactants and products. Multiply each standard enthalpy of formation by the appropriate stoichiometric coefficient, add the values for the products, add the values for the reactants, and subtract the sum for reactants from the sum for products. Equation summarizes this procedure ... 

Commercially produced amines contain Impurities from synthesis, thus rigid specifications are necessary to avoid unwanted Impurities In final products. Modern-day analytical capability permits detection of minute quantities of Impurities In almost any compound. Detection In parts per million Is routine, parts per billion Is commonplace, and parts per trillion Is attainable. The significance of Impurities In products demands careful and realistic Interpretation. Nltrosatlng species, as well as natural amines, are ubiquitous In the environment. For example, Bassow (1976) cites that about 50 ppb of nitrous oxide and nitrogen dioxide are present In the atmosphere of the cities. Microorganisms In soil and natural water convert ammonia to nitrite. With the potential for nitrosamine formation almost ever-present In the envlronmeit, other approaches to prevention should Include the use of appropriate scavengers as additives In raw materials and finished products. 

Figure 2.20. Transformation of silica supported dinitrosyl complexes of nickel(II) leading to formation of nitrogen dioxide and its final stabilization on the support. The picture shows the molecular structure and the spin density contours calculated with BP/DNP method of the involved species, and evolution of the X-band EPR spectra of the NiN02 Si02 complex due to spillover of the ligand (adopted from [71]).

It is believed that SCR by hydrocarbons is an important way for elimination of nitrogen oxide emissions from diesel and lean-burn engines. Gerlach etal. [115] studied by infrared in batch condition the mechanism of the reaction between nitrogen dioxide and propene over acidic mordenites. The aim of their work was to elucidate the relevance of adsorbed N-containing species for the F>cNOx reaction to propose a mechanism. Infrared experiments showed that nitrosonium ions (NO+) are formed upon reaction between NO, NOz and the Brpnsted acid sites of H—MOR and that this species is highly reactive towards propene, forming propenal oxime at 120°C. At temperatures above 170°C, the propenal oxime is dehydrated to acrylonitrile. A mechanism is proposed to explain the acrylonitrile formation. The nitrile can further be hydrolysed to yield... 

Electron-transfer activation. The observation of intense coloration upon mixing the solutions of hydroquinone ether MA and nitrogen dioxide at low temperature derives from the transient formation of MA+ cation radical, as confirmed by the spectral comparison with the authentic sample. The oxidation of MA to the corresponding cation radical is effected by the nitrosonium oxidant, which is spontaneously generated during the arene-induced disproportionation of nitrogen dioxide,239 i.e.,... 

Nitric oxide is the primary nitrogen oxide emitted from most combustion sources. The role of nitrogen dioxide in photochemical smog has already been discussed. Stringent emission regulations have made it necessary to examine all possible sources of NO. The presence of N20 under certain circumstances could, as mentioned, lead to the formation of NO. In the following subsections the reaction mechanisms of the three nitrogen oxides of concern are examined. 

Much evidence has been accumulated that the ozone-olefin reaction has a predominant role in aerosol formation from alkenes, cyclic olefins, diolefins, and other unsaturated compounds. Free radicals are formed in the reaction and can react further, along with nitric oxide and nitrogen dioxide, either with the various intermediates or with the olefin itself (see the recent review by Pitts and Finlayson ). 

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