Sodium nitrites

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 

Sodium nitrite is stable in alkaline solutions. Acidification liberates nitrous acid which is unstable. The decomposition of nitrous acid yields nitric acid [7697-37-2] HNO, according to the following reaction  

Sodium nitrite has been synthesized by a number of chemical reactions involving the reduction of sodium nitrate [7631-99-4] NaNO. These include exposure to heat, light, and ionizing radiation (2), addition of lead metal to fused sodium nitrate at 400—450°C (2), reaction of the nitrate in the presence of sodium ferrate and nitric oxide at - 400° C (2), contacting molten sodium nitrate with hydrogen (7), and electrolytic reduction of sodium nitrate in a cell having a cation-exchange membrane, rhodium-plated titanium anode, and lead cathode (8). 

Industrial production of sodium nitrite is by absorption of nitrogen oxides (NO ) into aqueous sodium carbonate or sodium hydroxide. NO gases originate from catalytic air oxidation of anhydrous ammonia, a practice common to nitric acid plants  

Gas contact is typically carried out in absorption towers over which the alkaline solutions are recirculated. Strict control over the conditions of absorption are required to efficiendy capture the NO and convert it predominantly to sodium nitrite according to the following reaction, thereby minimizing the formation of by-product sodium nitrate. Excessive amounts of nitrate can impede the separation of pure sodium nitrite from the process. 

White or slightly yellow granules, rods, or powder hygroscopic mp, 271°C.  

Mixtures of sodium nitrite and combustible materials are readily ignited mixtures with finely divided combustible materials can react explosively. Extinguish fire with water spray.2 

Soluble in water. Poisonous nitrous fumes produced by the action of acids. Avoid contact with combustible materials or acids.2 

Amidosulfates. Warming with metal amidosulfates (sulfamates) may become explosively violent.3 

Aminoguanidine Salts. Sensitive explosive formed in the absence of acid.4 Ammonium Salts. Violent explosion occurs on heating a mixture.4,5 Metal Cyanides. Mixtures explode on heating.6,7 Phenol. Mixture explodes violently on heating.8 

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They are prepared by the action of HNO2 on aromatic amines. The amine is dissolved in excess of mineral acid and sodium nitrite is added slowly until a slight excess of HNO2 is present. The reaction is usually carried out in ice-cold solution. The solution then contains the diazonium salt of the mineral acid used, anhydrous diazonium salts of unpredictable stability may be precipitated with complex anions like PF , SnCl6 BF4 . 

Steam is by far the most widely used medium, useful up to about 475 K. Up to about 700 K organic liquids such as the dowtherms and mineral oil may be used. Mercury and molten salts, such as the eutectic mixture of sodium nitrite, sodium nitrate and potassium nitrate may be used up to 875 K, while above this temperature air and flue gases must be used. 

H—N—N=N. It is prepared by the oxidation of hydrazine in strongly acid solution the oxidising agent used is usually nitrous acid (i.e. sodium nitrite is added to the acid solution of hydrazine) ... 

Too rapid heating produces explosive decomposition. The reaction between hydroxyammonium chloride, NHjOH. Cl , and sodium nitrite gives pure dinitrogen oxide ... 

Cobalt(II) is also easily oxidised in the presence of the nitrite ion NO2 as ligand. Thus, if excess sodium nitrite is added to a cobalt(II) salt in presence of ethanoic acid (a strong acid would decompose the nitrite, p. 244), the following reaction occurs ... 

C2H5ONO + NaOH C2H5OH + NaNOa sodium nitrite. The second compound is nitroethane, C,H NO, of b.p. 114° its identity is clearly shown by the action of reducing agents, which convert it into ethylamiiie, CjHjNHj, thus proving the presence of a nitrogen carbon... 

Nitromethane, CH3NO2, the first member of the homologous series, can, however, be readily prepared by a special reaction. When equimolecular amounts of sodium nitrite and sodium monochloroacetate are heated together in aqueous solution, the chlorine in the monochloroacetate is replaced by the nitro group, and the sodium nitroacetate thus formed undergoes hydrolysis follow ed by decarboxylation ... 

Required Monochloroacetic acid, 50 g. anhydrous sodium carbonate, 30 g. sodium nitrite, 36-5 g. 

Dissolve a few drops of nitromethane in 10% sodium hydroxide solution. Add a few crystals of sodium nitrite and shake. Now add dilute sulphuric acid drop by drop. A brownish-red coloration develops, but fades again when an excess of acid is added. The sulphuric acid has thus liberated nitrous acid, which has in turn reacted with the nitromethane to give a nitrolic acid, the sodium salt of which is CH3NO2 + ONOH = CH(N02) N0H + HgO reddish-brown in colour, probably owing to mesomeric ions of the type ... 

The solution of the aniline hydrochloride should be cooled to 5°C., and this temperature maintained throughout the addition of the sodium nitrite solution. External cooling has to be maintained, otherwise the heat of the reaction would cause the temperature to rise, with the consequent decomposition of the diazonium chloride and the production of phenol. If, on the other hand, the temperature is reduced to about o , diazotisation becomes extremely slow and unchanged nitrous acid may remain in the solution for an impracticably long time. 

Sufficient sodium nitrite must be added to diazotise all the aniline present, otherwise the unchanged aniline will react with the diazonium chloride to give diazoaminobenzene (p. 187) ... 

To ensure the presence of a slight excels of nitrous acid, potassium iodide-starch paper is sometimes used as an external indicator, a drop of the solution being removed from time to time during the addition of the sodium nitrite, and then dropped on to the paper. When an excess of nitrous acid is present, iodine is liberated, and gives the familiar... 

Required Aniline, 15 ml. hydrochloric acid, 40 ml. sodium nitrite, 12-5 g. potassium iodide, 35 g. 

Dissolve 15 ml. (15-4 g.) of aniline in a mixture of 40 ml. of concentrated hydrochloric acid and 40 ml. of water contained in a 250 ml. conical flask. Place a thermometer in the solution, immerse the flask in a mixture of ice and water, and cool until the temperature of the stirred solution reaches 5°. Dissolve I2 5 g. of powdered sodium nitrite in 30 ml. of water, and add this solution in small quantities (about 2-3 ml. at a time) to the cold aniline hydrochloride solution, meanwhile keeping the latter well stirred by means of a thermometer. Heat is evolved by the reaction, and therefore a short interval should be allowed between consecutive additions of the sodium nitrite, partly to allow the temperature to fall again to 5°, and partly to ensure that the nitrous acid formed reacts as completely as possible with the aniline. The temperature must not be allowed to rise above 10°, otherwise appreciable decomposition of the diazonium compound to phenol will occur on the other hand, the temperature... 

When all the sodium nitrite has been added and diazotisation is complete, transfer the cold solution to a 600 ml. round-bottomed bolt-head flask. Dissolve 35 g. of potassium iodide in 50 ml. of water, and add this solution slowly with shaking to the cold... 

Hence all the following preparations involving diazotisation are based on the use of Sodium Nitrite Recryst." and not Sodium Nitrite Technical or "Commercial. ... 

Required Copper sulphate, 28 g. sodium chloride, 9-5 g. sodium bisulphite, 14 g. hydrochloric acid, 70 ml. aniline, 20 ml. sodium nitrite, 17 g. 

Meanwhile, during the cooling of the cuprous chloride solution, prepare a solution of benzenediazonium chloride by dissolving 20 ml. (20-5 g.) of aniline in a mixture of 50 ml. of concentrated hydrochloric acid and 50 ml. of water, and after cooling to 5°, adding slowly a solution of 17 g. of sodium nitrite in 40 ml. of water. Observe carefully the general conditions for diazotisation given in the preparation of iodobenzene (p. 184). 

Required />-Toluidine, 24 g. hydrochloric acid, 55 ml. sodium nitrite, 17 g. 

Required Sulphuric acid, 27-5 ml. aniline, 24 ml. sodium nitrite, 20 g. dry potassium carbonate, 3-4 g. (To ensure that the potassium carbonate is dry, it should be gently heated in an evaporating-basin over a small Bunsen flame for 4-5 minutes with stirring, and then allowed to cool in a desiccator.)... 

Required Anthranilic acid, 20 g. anhydrous sodium carbonate, 7 5 g, sodium nitrite, 12 g. concentrated hydrochloric acid, 190 ml. crystalline copper sulphate, 50 g. concentrated ammonia, 85 ml, hydroxylamine hydrochloride, 14-5 g. (or hydroxylamine sulphate, 17-4 g.) acetic acid, 10-20 ml,... 

A) Diazotisation of Anthranilic Acid, Dissolve 20 g. of anthranilic acid in a solution of 7 5 g. of anhydrous sodium carbonate in 200 ml. of water contained in a 400 ml. beaker, (The mixture may be warmed very gently with stirring to obtain a solution more rapidly, and then cooled.) Add slowly 12 g. of sodium nitrite and cool the stirred solution below 10 , Pour this cold solution slowly on to a vigorously stirred mixture of 40 ml, of concentrated hydrochloric acid and 120 g. of crushed ice in a 600 ml. beaker. 

Add 20 g. of /)-bromoaniline to 20 ml. of water in a 250 ml. beaker, and warm the mixture until the amine melts. Now add 23 ml. of concentrated hydrochloric acid and without delay stir the mixture mechanically in an ice-water bath, so that a paste of fine /> bromo-aniline hydrochloride crystals separates. Maintain the temperature of the stirred mixture at about 5° whilst slowly adding from a dropping-funnel a solution of 8 5 g. of sodium nitrite in 20 ml. of water con tinue the stirring for 20 minutes after the complete addition of the nitrite. 

The nitrosamines are insoluble in water, and the lower members are liquid at ordinary temperatures. The separation of an oily liquid when an aqueous solution of an amine salt is treated with sodium nitrite is therefore strong evidence that the amine is secondary. Diphenylnitrosoamine is selected as a preparation because it is a crystalline substance and is thus easier to manipulate on a small scale than one of the lower liquid members. For this preparation, a fairly pure (and therefore almost colourless) sample of diphenyl-amine should be used. Technical diphenylamine, which is almost black in colour, should not be employed. 

Prepare two solutions, one containing i g. of diphenylamine in 8 ml. of warm ethanol, and the other containing 0-5 g. of sodium nitrite in i ml. of water, and cool each solution in ice-water until the temperature falls to 5°. Now add o 8 ml. of concentrated hydrochloric acid steadily with stirring to the diphenylamine solution, and then without delay (otherwise diphenylamine hydrochloride may crystallise out) pour the sodium nitrite solution rapidly into the weil-stirred mixture. The temperature rises at once and the diphenylnitrosoamine rapidly crystallises out. Allow the mixture to stand in the ice-water tor 15 minutes, and then filter off the crystals at the pump, drain thoroughly, wash with water to remove sodium chloride, and then drain again. Recrystallise from methylated spirit. Diphenylnitrosoamine is thus obtained as very pale yellow crystals, m.p. 67 68° yield, 0 9-1 o g. 

Reaction of Diphenylnitrosoamine. Carry out Liebermann s Nitroso Reaction as described for phenol (p. 340), but use about 0 05 g. of the nitrosamine instead of the one crystal of sodium nitrite, and finally add only 3-4 drops of sulphuric acid. The deep greenish-blue colour is obtained, becoming red on dilution and reverting to blue on being made alkaline. 

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