Nitric acid, decomposition

Mercury fulminate is relatively resistant to the action of dilute acids, in particular to that of nitric acid, but concentrated acids cause decomposition. Thus, under the influence of nitric acid decomposition occurs with evolution of NO, CO, acetic acid and mercuric nitrate. Under the influence of concentrated hydrochloric acid free fulminic acid is evolved (with an odour resembling that of hydrogen cyanide) as well as the decomposition products hydroxylamine hydrochloride, formic acid, mercuric chloride (Carstanjen and Ehrenberg [32] Scholl [33]). Mercury fulminate explodes on direct contact with concentrated sulphuric acid. 

Dilute nitric acid decomposition upon warming, a red colouration is produced, and nitrogen oxide and hydrogen cyanide (POISONOUS) are evolved ... 

Wiirfels, M. Voltammetric determination of metal traces in marine samples after nitric acid decomposition. Marine Chem. 28, 259-264 (1989)... 

WiiEEELS M (1989) Voltammetric Determination of Meted Traces in Marine Samples after Nitric Acid Decomposition. Marine Chem 28 259 - 264. 

HAZARD RISK Combustible when exposed to heat or flame can react vigorously with oxidizers hypergolic reaction with concentrated nitric acid decomposition emits acrid smoke and irritating fumes NFPA Code H 3 F 1 R 0. 

HAZARD RISK Extreme fire hazard by spontaneous chemical reaction ignition or violent reaction with air, oxidants, silver nitrate and concentrated nitric acid decomposition emits highly toxic fumes of phosphorus oxides NFPA Code H 4 F 4 R 2. 

A similar decomposition occurs if nitric acid is subjected to a temperature above its boiling point. 

Procedure for Bromine and Iodine Estimations. Again cover the beaker as before, but before adding the nitric acid add i g. of hydrazine sulphate and heat the solution on the water-bath until evolution of gas ceases. To ensure complete decomposition of an iodate, however, the heating should be continued for i hour. 

Dissolve 10 g. of lactose (1) in 100 ml. of nitric acid, sp. gr. 115, in an evaporating dish and evaporate in a fume cupboard until the volume has been reduced to about 20 ml. The mixture becomes thick and pasty owing to the separation of mucic acid. When cold, dilute with 30 ml. of water, filter at the pump and set the filtrate A) aside. Wash the crude acid with cold water. Purify the mucic acid by dissolving it in the minimum volume of dilute sodium hydroxide solution and reprecipitating with dilute hydrochloric acid do not allow the temperature to rise above 25°. Dry the purified acid (about 5 g.) and determine the m.p. Mucic acid melts with decomposition at 212-213°. 

Oxidation of galactose (or a galactose-containing sugar) to mucic acid. Dissolve 1 g. of galactose or lactose in a mixture of 10 ml. of water and 5 ml. of concentrated nitric acid contained in a small evaporating dish, and evaporate the solution to dryness on a water bath. Stir the cold residue with 10 ml. of cold water, filter off the mucic acid, wash it with cold water, dry and determine the m.p. (212-213° with decomposition). 

Davies and Warren" found that when 1,4-dimethylnaphthalene was treated with nitric acid in acetic anhydride, and the mixture was quenched after 34 hr, a pale yellow solid with an ultraviolet spectrum similar to that of a-nitro-naphthalene was produced. However, if the mixture was allowed to stand for 5 days, the product was i-methyl-4 nitromethylnaphthalene, in agreement with earlier findings. Davies and Warren suggested that the intermediate was 1,4-dimethyl-5 nitronaphthalene, which underwent acid catalysed rearrangement to the final product. Robinson pointed out that this is improbable, and suggested an alternative structure (iv) for the intermediate, together with a scheme for its formation from an adduct (ill) (analogous to l above) and its subsequent decomposition to the observed product. 

Thompson points out that there is no evidence that adducts give other than acetates on thermolysis. The exocyclic methylene intermediate (iv) postulated by Robinson could arise by proton abstraction from a Wheland intermediate analogous to (vll) above, rather than from the adduct (in). Similarly its decomposition does not necessarily require the intermediacy of the adduct (v). The fact that i -methyl-4-nitromethylnaphthalene is the product even when the nitrating medium is nitric acid and nitromethane would then require no separate explanation. 

Tribromoacetic acid [75-96-7] (Br CCOOH), mol wt 296.74, C2HBr302, mp 135°C bp 245°C (decomposition), is soluble in water, ethyl alcohol, and diethyl ether. This acid is relatively unstable to hydrolytic conditions and can be decomposed to bromoform in boiling water. Tribromoacetic acid can be prepared by the oxidation of bromal [115-17-3] or perbromoethene [79-28-7] with fuming nitric acid and by treating an aqueous solution of malonic acid with bromine. 

F. J. Miner and P. G. Hagan, Pate oJHjdrogen Peroxide Decomposition in Nitric Acid Solutions, Dow Chemical USA, Golden, Colo. 

Red mercuric oxide generally is prepared in one of two ways by the heat-induced decomposition of mercuric nitrate or by hot precipitation. Both methods require careful control of reaction conditions. In the calcination method, mercury and an equivalent of hot, concentrated nitric acid react to form... 

Disulfides are susceptible to attack by strong oxidizing agents and this can result in decomposition of polysulftdes. For example, nitric acid causes violent decomposition of polysulftde polymers. 

Aluminum nitrate is available commercially as aluminum nitrate nonahydrate [7784-27-2], A1(N02)3 9H20. It is a white, crystalline material with a melting point of 73.5°C that is soluble in cold water, alcohols, and acetone. Decomposition to nitric acid [7699-37-2], HNO, and basic aluminum nitrates [13473-90-0], A1(0H) (N03) where x + = 3, begins at 130°C, and dissociation to aluminum oxide and oxides of nitrogen occurs above 500°C. 

Manufacture. Historically, ammonium nitrate was manufactured by a double decomposition method using sodium nitrate and either ammonium sulfate or ammonium chloride. Modem commercial processes, however, rely almost exclusively on the neutralization of nitric acid (qv), produced from ammonia through catalyzed oxidation, with ammonia. Manufacturers commonly use onsite ammonia although some ammonium nitrate is made from purchased ammonia. SoHd product used as fertilizer has been the predominant form produced. However, sale of ammonium nitrate as a component in urea—ammonium nitrate Hquid fertilizer has grown to where about half the ammonium nitrate produced is actually marketed as a solution. 

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 ... 

Several common acid treatments for sample decomposition include the use of concentrated nitric acid, aqua regia, nitric—sulfuric acids, and nitric perchloric acids. Perchloric acid is an effective oxidant, but its use is ha2ardous and requkes great care. Addition of potassium chlorate with nitric acid also assists in dissolving any carbonaceous matter. 

Barium nitrate is prepared by reaction of BaCO and nitric acid, filtration and evaporative crystallization, or by dissolving sodium nitrate in a saturated solution of barium chloride, with subsequent precipitation of barium nitrate. The precipitate is centrifuged, washed, and dried. Barium nitrate is used in pyrotechnic green flares, tracer buUets, primers, and in detonators. These make use of its property of easy decomposition as well as its characteristic green flame. A small amount is used as a source of barium oxide in enamels. 

Beryllium Nitrate. BeryUium nitrate tetrahydrate [13516-48-0], Be(N02)2 4H2O, is prepared by crystallization from a solution of beryUium hydroxide or beryllium oxide carbonate in a slight excess of dilute nitric acid. After dissolution is complete, the solution is poured into plastic bags and cooled to room temperature. The crystallization is started by seeding. Crystallization from more concentrated acids yields crystals with less water of hydration. On heating above 100°C, beryllium nitrate decomposes with simultaneous loss of water and oxides of nitrogen. Decomposition is complete above 250°C. 

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

When the alkaloid is heated with water at 150°, or boiled with dilute acids, it is hydrolysed into hydrocotarnine, and opianic acid. Similar decompositions are induced by acid oxidation or acid reduction, thus (1) dilute nitric acid furnishes opianic acid, CjoHioOj, and cotarnine, C12H15O4N (2) zinc and hydrochloric acid produce meconin, C10H10O4, and hydrocotarnine, C12H15O3N. 

---