Nitrous effect

The influence of added species upon the rates and kinetic forms of nitration in organic solvents were of the greatest importance in elucidating details of the processes involved, particularly of the steps leading to the nitronium ion. These influences will first be described, and then in the following section explained. The species to be considered are sulphuric acid, nitrate ions, urea and water. The effect of nitrous acid is considered later ( 4.3). 

In experiments on the nitration of benzene in acetic acid, to which urea was added to remove nitrous acid (which anticatalyses nitration 4.3.1), the rate was found to be further depressed. The effect was ascribed to nitrate ions arising from the formation of urea nitrate. In the same way, urea depressed the rate of the zeroth-order nitration of mesitylene in sulpholan. ... 

Solutions of dinitrogen tetroxide (the mixed anhydride of nitric and nitrous acids) in sulphuric acid are nitrating agents ( 4.3.2), and there is no doubt that the effective reagent is the nitronium ion. Its formation has been demonstrated by Raman spectroscopy and by cryoscopy ... 

We are not concerned here with the mechanism of nitrosation, but with the anticatalytic effect of nitrous acid upon nitration, and with the way in which this is superseded with very reactive compounds by an indirect mechanism for nitration. The term nitrous acid indicates all the species in a solution which, after dilution with water, can be estimated as nitrous acid. 

The anticatalytic effect of nitrous acid in nitration The effect of nitrous acid was first observed for zeroth-order nitrations in nitromethane ( 3.2). The effect was a true negative catalysis the kinetic order was not affected, and nitrous acid was neither consumed nor produced by the nitration. The same was true for nitration in acetic acid. In the zeroth-order nitrations the rate depended on the reciprocal of the square root of the concentration of nitrous acid =... 

For nitrations carried out in nitric acid, the anticatalytic influence of nitrous acid was also demonstrated. The effect was smaller, and consequently its kinetic form was not established with certainty. Further, the more powerful type of anticatalysis did not appear at higher concentrations (up to 0-23 mol 1 ) of nitrous acid. The addition of water (up to 5 % by volume) greatly reduced the range of concentration of nitrous acid which anticatalysed nitration in a manner resembling that required by the inverse square-root law, and more quickly introduced the more powerful type of anticatalytic effect. 

If we consider the effect of nitrous acid upon zeroth-order nitration in organic solvents we must bear in mind that in these circumstances dinitrogen tetroxide is not much ionised, so the measured concentration of nitrous acid gives to a close approximation the concentration of dinitrogen tetroxide. Further, the negligible self-ionisation of nitric acid ensures that the total concentration of nitrate ions is effectively that formed from dinitrogen tetroxide. Consequently as we can see from the equation for the ionisation of dinitrogen tetroxide ( 4.3.1),... 

The weak effect of nitrous acid upon nitration in nitric acid is a consequence of the already considerable concentration of nitrate ions supplied in this case by the medium. 

In contrast to its effect upon the general mechanism of nitration by the nitronium ion, nitrous acid catalyses the nitration of phenol, aniline, and related compounds. Some of these compounds are oxidised under the conditions of reaction and the consequent formation of more nitrous acids leads to autocatalysis. 

The effect of nitrous acid on the nitration of mesitylene in acetic acid was also investigated. In solutions containing 5-7 mol 1 of nitric acid and < c. 0-014 mol of nitrous acid, the rate was independent of the concentration of the aromatic. As the concentration of nitrous acid was increased, the catalysed reaction intervened, and superimposed a first-order reaction on the zeroth-order one. The catalysed reaction could not be made sufficiently dominant to impose a truly first-order rate. Because the kinetic order was intermediate the importance of the catalysed reaction was gauged by following initial rates, and it was shown that in a solution containing 5-7 mol 1 of nitric acid and 0-5 mol 1 of nitrous acid, the catalysed reaction was initially twice as important as the general nitronium ion mechanism. 

Despite the fact that solutions of acetyl nitrate prepared from purified nitric acid contained no detectable nitrous acid, the sensitivity of the rates of nitration of very reactive compounds to nitrous acid demonstrated in this work is so great that concentrations of nitrous acid below the detectable level could produce considerable catalytic effects. However, because the concentration of nitrous acid in these solutions is unknown the possibility cannot absolutely be excluded that the special mechanism is nitration by a relatively unreactive electrophile. Whatever the nature of the supervenient reaction, it is clear that there is at least a dichotomy in the mechanism of nitration for very reactive compounds, and that, unless the contributions of the separate mechanisms can be distinguished, quantitative comparisons of reactivity are meaningless. 

Gate oxide dielectrics are a cmcial element in the down-scaling of n- and -channel metal-oxide semiconductor field-effect transistors (MOSEETs) in CMOS technology. Ultrathin dielectric films are required, and the 12.0-nm thick layers are expected to shrink to 6.0 nm by the year 2000 (2). Gate dielectrics have been made by growing thermal oxides, whereas development has turned to the use of oxide/nitride/oxide (ONO) sandwich stmctures, or to oxynitrides, SiO N. Oxynitrides are formed by growing thermal oxides in the presence of a nitrogen source such as ammonia or nitrous oxide, N2O. Oxidation and nitridation are also performed in rapid thermal processors (RTP), which reduce the temperature exposure of a substrate. 

Alkaline solutions of mononitroparaffins undergo many different reactions when stored for long periods, acidified, or heated. Acidification of solutions of mononitro salts is best effected slowly at 0°C or lower with weak acids or buffered acidic mixtures, such as acetic acid—urea, carbon dioxide, or hydroxyl ammonium chloride. If mineral acids are used under mild conditions, eg, dilute HCl at 0°C, decomposition yields a carbonyl compound and nitrous oxide (Nef reaction). 

Safety provisions have proven highly effective. The nuclear power industry in the Western world, ie, outside of the former Soviet Union, has made a significant contribution of electricity generation, while surpassing the safety record of any other principal industry. In addition, the environmental record has been outstanding. Nuclear power plants produce no combustion products such as sulfuric and nitrous oxides or carbon dioxide (qv), which are... 

Effect of Nitric Oxide on Ozone Depletion. Nitrous oxide is injected into the atmosphere from natural sources on earth about 10% is converted to nitric oxide (N20 + 0( D) — 2 NO), which in turn can catalyze the destmction of ozone (11,32,75). The two main cycles are 1 and 2. Rate constant data are given in Reference 11. 

Nitrous oxide produces respiratory depression (38,39). It has been shown to produce a direct myocardial depressant effect in dogs (40) and in humans breathing a 40% N2O/60% oxygen mixture (41) however, this may be offset by the activation of the sympathetic nervous system (42). The combination of nitrous oxide and opioids can produce decreases in myocardial contractiHty, heart rate, and blood pressure (43). 

There appear also to be toxic effects. In animals, nitrous oxide has been shown to inactivate methionine synthetase which prevents the conversion of deoxyuridine to thymidine and thus has the potential for inducing megaloblastic anemia, leukopenia, and teratogenicity (44—46). A variety of epidemiologic surveys suggest positive correlations between exposure to nitrous oxide and spontaneous abortion in dental assistants (47). 

Before coupling, excess nitrous acid must be destroyed. Nitrite can react with coupling components to form nitroso compounds causiag deHterious effects on the final dyestuff. The presence of nitrite can be detected by 4,4 -diamiQO-diphenyHnethane-2,2 -sulfone [10215-25-5] (Green reagent) or starch—iodide. Removal of nitrite is achieved by addition of sulfamic acid or urea [57-13-6], however, sulfamic acid [5329-14-6] has been more effective ia kinetic studies of nine nitrous acid scavangers (18). 

The unusual conditions needed to produce an a2o dye, namely, strong acid plus nitrous acid for dia2oti2ation, the low temperatures necessary for the unstable dia2onium salt to exist, and the presence of electron-rich amino or hydroxy compounds to effect coupling, means that a2o dyes have no natural counterparts. 

The behavior of aminopyrazole 88 (R = 4-NO2—C6H4) under these conditions was quite different diazotization using nitrous acid in concentrated hydrochloric acid afforded an alkynylpyrazole diazonium chloride, which did not participate in the Richter reaction, probably due to the electron-withdrawing effect of the nitro group. Instead, after neutralization of the hydrochloric acid with sodium hydrogen... 

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