Nitric acid and mixtures

The powdered metal reacts violently with nitric acid, and mixtures with potassium chlorate or nitrate explode on heating. Heated germanium bums with incandescence in oxygen. 

Nickel-silicon alloys with the chemical composition given in Table 4.36 are used in handling hot sulfuric acid, 50% nitric acid and mixtures of sulfuric and nitric... 

The action of concentrated sulphuric acid and the formation of mixed sulphuric-nitric esters, as well as the action of nitric acid and mixtures of nitric-sulphuric acid and water and of hydrochloric add have been discussed above. Concentrated hydriodic add of 1.5 density decomposes nitroglycerine to glycerol and nitric oxides. 

Longstaff and Singer studied the oxidation of formic acid in both nitric acid and mixtures of nitric and other mineral acids at 25°, and found that no oxidation took place in the absence of N(III) (HNO2 or NO ). (4) They observed autocatalysis and acid catalysis and proposed that NO was the effective oxidizer in the system. Their scheme (simplified here) was... 

Prepare a mixture of 25 ml. of concentrated nitric acid and 80 ml. of water in a 750 ml. flat-bottomed flask for which a steam-distillation fitting is available for subsequent use. Warm a mixture of 20 g. of phenol and 15 ml. of water gently in a small conical flask until the phenol is molten on shaking the... 

Fit a 3-litre rovmd-bottomed flask with a long reflux condenser and a dropping funnel (1). Place a mixture of 400 ml. of concentrated nitric acid and 600 ml. of water in the flask and heat nearly to boiling. Allow 100 g. (116 ml.) of cycZopentanone (Section 111,73) to enter the hot acid dropwise, taking care that the first few drops are acted upon by the acid, otherwise an explosion may occur the addition is complete in 1 hour. Much heat is evolved in the reaction so that the flame beneath the flask must be considerably lowered. Omng to the evolution of nitrons fumes, the reaction should be carried out in the fume cupboard or the fumes... 

Nitrations are usually carried out at comparatively low temperatures at higher temperatures there may be loss of material because of the oxidising action of the nitric acid. For substances which do not nitrate readily with a mixture of concentrated nitric and sulphuric acids ( mixed acid ), the intensity of the reaction may be increased inler alia by the use of fuming sulphuric acid (containing up to 60 per cent, of sulphur trioxide) or by fuming nitric acid. Thus nitrobenzene is converted by a mixture of fuming nitric acid and concentrated sulphuric acid into about 90 per cent, of wi-dinitrobenzene and small amounts of the o- and p-isomers the latter are eliminated in the process of recrystallisation ... 

A brief account of aromatic substitution may be usefully given here as it will assist the student in predicting the orientation of disubstituted benzene derivatives produced in the different substitution reactions. For the nitration of nitrobenzene the substance must be heated with a mixture of fuming nitric acid and concentrated sulphuric acid the product is largely ni-dinitrobenzene (about 90 per cent.), accompanied by a little o-dinitrobenzene (about 5 per cent.) which is eliminated in the recrystallisation process. On the other hand phenol can be easily nitrated with dilute nitric acid to yield a mixture of ortho and para nitrophenols. It may be said, therefore, that orientation is meta with the... 

Add 25 g. of finely-powdered, dry acetanilide to 25 ml. of glacial acetic acid contained in a 500 ml. beaker introduce into the well-stirred mixture 92 g. (50 ml.) of concentrated sulphuric acid. The mixture becomes warm and a clear solution results. Surround the beaker with a freezing mixture of ice and salt, and stir the solution mechanically. Support a separatory funnel, containing a cold mixture of 15 -5 g. (11 ml.) of concentrated nitric acid and 12 -5 g. (7 ml.) of concentrated sulphuric acid, over the beaker. When the temperature of the solution falls to 0-2°, run in the acid mixture gradually while the temperature is maintained below 10°. After all the mixed acid has been added, remove the beaker from the freezing mixture, and allow it to stand at room temperature for 1 hour. Pour the reaction mixture on to 250 g. of crushed ice (or into 500 ml. of cold water), whereby the crude nitroacetanilide is at once precipitated. Allow to stand for 15 minutes, filter with suction on a Buchner funnel, wash it thoroughly with cold water until free from acids (test the wash water), and drain well. Recrystallise the pale yellow product from alcohol or methylated spirit (see Section IV,12 for experimental details), filter at the pump, wash with a httle cold alcohol, and dry in the air upon filter paper. [The yellow o-nitroacetanihde remains in the filtrate.] The yield of p-nitroacetanihde, a colourless crystalline sohd of m.p. 214°, is 20 g. 

Phosphorus. The presence of phosphorus may be indicated by a smell of phosphine during the sodium fusion. Treat 1 ml. of the fusion solution with 3 ml. of eoneentrated nitric acid and boil for one minute. Cool and add an equal volume of ammonium molybdate reagent. Warm the mixture to 40-50°, and allow to stand. If phosphorus is present, a yellow erystalline precipitate of ammonium phosphomolybdate wUl separate. 

Place 2 ml. of the periodic acid reagent in a small test tube, add one drop (no more—otherwise the silver iodate, if formed, will fail to precipitate) of concentrated nitric acid, and shake well. Add one drop or a small crystal of the compound to be tested, shake the mixture for 15-20 seconds, and then add 1-2 drops of 3 per cent, silver nitrate solution. The instantaneous formation of a white precipitate of silver iodate is a positive test. Failure to form a precipitate, or the appearance of a brown precipitate which redissolves on shaking, constitutes a negative test. 

During my Cleveland years, I also continued and extended my studies in nitration, which I started in the early 1950s in Hungary. Conventional nitration of aromatic compounds uses mixed acid (mixture of nitric acid and sulfuric acid). The water formed in the reaetion dilutes the acid, and spent aeid disposal is beeoming a serious environ-... 

In equimolar mixtures of nitric acid and water a monohydrate is formed whose Raman spectrum has been observed. There is no evidence for the existence of appreciable concentrations of the nitric acidium ion in aqueous nitric acid. 

Sulphuric acid catalysed nitration in concentrated nitric acid, but the effect was much weaker than that observed in nitration in organic solvents ( 3.2.3). The concentration of sulphuric acid required to double the rate of nitration of i-nitroanthraquinone was about 0-23 mol 1, whereas typically, a concentration of io mol 1 will effect the same change in nitration in mixtures of nitric acid and organic solvents. The acceleration in the rate was not linear in the concentration of catalyst, for the sensitivity to catalysis was small with low concentrations of sulphuric acid, but increased with the progressive addition of more catalyst and eventually approached a linear acceleration. 

In mixtures of nitric acid and organic solvents, nitrous acid exists mainly as un-ionised dinitrogen tetroxide. The heterolysis of dinitrogen tetroxide is thus complete in sulphuric acid ( 4 i), considerable in nitric acid, and very small in organic solvents. 

It has long been known that, amongst organic solvents, acetic anhydride is particularly potent in nitration, and that reaction can be brought about under relatively mild conditions. For these reasons, and because aromatic compounds are easily soluble in mixtures of nitric acid and the solvent, these media have achieved considerable importance in quantitative studies of nitration. 

When acetic anhydride was in excess over nitric acid, acetyl nitrate and acetic acid were the only products. When the concentration of nitric acid was greater than 90 moles %, dinitrogen pentoxide, present as (N02+)(N0a ), was the major product and there were only small traces of acetyl nitrate. With lower concentrations of nitric acid the products were acetic acid, acetyl nitrate and dinitrogen pentoxide, the latter species being present as covalent molecules in this organic medium. A mixture of z moles of nitric acid and i mole of acetic anhydride has the same Raman spectrum as a solution of i mole of dinitrogen pentoxide in 2 moles of acetic acid. 

An investigation of the infra-red spectra of mixtures of nitric acid and acetic anhydride supports these conclusions. The concentration of nitronium ions, measured by the absorption band at 2380 cm, was... 

Evidence from the viscosities, densities, refractive indices and measurements of the vapour pressure of these mixtures also supports the above conclusions. Acetyl nitrate has been prepared from a mixture of acetic anhydride and dinitrogen pentoxide, and characterised, showing that the equilibria discussed do lead to the formation of that compound. The initial reaction between nitric acid and acetic anhydride is rapid at room temperature nitric acid (0-05 mol 1 ) is reported to be converted into acetyl nitrate with a half-life of about i minute. This observation is consistent with the results of some preparative experiments, in which it was found that nitric acid could be precipitated quantitatively with urea from solutions of it in acetic anhydride at —10 °C, whereas similar solutions prepared at room temperature and cooled rapidly to — 10 °C yielded only a part of their nitric acid ( 5.3.2). The following equilibrium has been investigated in detail ... 

In addition to the initial reaction between nitric acid and acetic anhydride, subsequent changes lead to the quantitative formation of tetranitromethane in an equimolar mixture of nitric acid and acetic anhydride this reaction was half completed in 1-2 days. An investigation of the kinetics of this reaction showed it to have an induction period of 2-3 h for the solutions examined ([acetyl nitrate] = 0-7 mol 1 ), after which the rate adopted a form approximately of the first order with a half-life of about a day, close to that observed in the preparative experiment mentioned. In confirmation of this, recent workers have found the half-life of a solution at 25 °C of 0-05 mol 1 of nitric acid to be about 2 days. ... 

An observation which is relevant to the nitration of very reactive compounds in these media ( 5.3.3) is that mixtures of nitric acid and acetic anhydride develop nitrous acid on standing. In a solution ([HNO3] = 0-7 mol 1 ) at 25 °C the concentration of nitrous acid is... 

More information has appeared concerning the nature of the side reactions, such as acetoxylation, which occur when certain methylated aromatic hydrocarbons are treated with mixtures prepared from nitric acid and acetic anhydride. Blackstock, Fischer, Richards, Vaughan and Wright have provided excellent evidence in support of a suggested ( 5.3.5) addition-elimination route towards 3,4-dimethylphenyl acetate in the reaction of o-xylene. Two intermediates were isolated, both of which gave rise to 3,4-dimethylphenyl acetate in aqueous acidic media and when subjected to vapour phase chromatography. One was positively identified, by ultraviolet, infra-red, n.m.r., and mass spectrometric studies, as the compound (l). The other was less stable and less well identified, but could be (ll). 

The kinetics of the nitration of benzene, toluene and mesitylene in mixtures prepared from nitric acid and acetic anhydride have been studied by Hartshorn and Thompson. Under zeroth order conditions, the dependence of the rate of nitration of mesitylene on the stoichiometric concentrations of nitric acid, acetic acid and lithium nitrate were found to be as described in section 5.3.5. When the conditions were such that the rate depended upon the first power of the concentration of the aromatic substrate, the first order rate constant was found to vary with the stoichiometric concentration of nitric acid as shown on the graph below. An approximately third order dependence on this quantity was found with mesitylene and toluene, but with benzene, increasing the stoichiometric concentration of nitric acid caused a change to an approximately second order dependence. Relative reactivities, however, were found to be insensitive... 

Nitration Warming benzene with a mixture of nitric acid and sulfuric acid gives nitrobenzene A nitro group (—NO2) replaces one of the ring hydrogens... 

Acid mixtures containing nitric acid and a strong acid, eg, sulfuric acid, perchloric acid, selenic acid, hydrofluoric acid, boron trifluoride, or an ion-exchange resin containing sulfonic acid groups, can be used as the nitrating feedstock for ionic nitrations. These strong acids are catalysts that result in the formation of nitronium ions, NO" 2- Sulfuric acid is almost always used industrially since it is both effective and relatively inexpensive. 

Dinitration of toluene results in the formation of a number of isomeric products, and with a typical sulfuric—nitric acid nitrating mixture the following mixture ofisomers is obtained 75 wt % 2,4-dinitrotoluene [121-14-2] 19 wt % 2,6-dinitrotoluene [606-20-2], 2.5 wt % 3,4-dinitrotoluene [610-39-9], 1 wt %... 

The y -phenylenediamiaes are easily obtained by dinitrating, followed by catalyticaHy hydrogenating, an aromatic hydrocarbon. Thus, the toluenediamiaes are manufactured by nitrating toluene with a mixture of sulfuric acid, nitric acid, and 23% water at 330°C which first produces a mixture (60 40) of the ortho and para mononitrotoluenes. Further nitration produces the 80 20 mixture of 2,4- and 2,6-dinitrotoluene. Catalytic hydrogenation produces the commercial mixture of diamiaes which, when converted to diisocyanates, are widely used ia the production of polyurethanes (see Amines, aromatic, DIAMINOTOLUENES) (22). 

---