Nitrate, small quantities

Adding to ammonium nitrate small quantities of Acid Magenta, a tri-sulpho-triamine-methyl-triphenylmethane dyestuff. According to Butchart and Whetstone [7] 0.1% of this dyestuff admixed with a saturated ammonium nitrate solution or 0.03% of the dye added to the crystals forms an effective layer that prevents ammonium nitrate from caking within the temperature range —18 to 32°C. 

The process acid, i.e., nitrating acid and residual acid, will dissolve the product to a greater or lesser extent. During nitration, small quantities of nitrous acid (HNO2) are usually formed. 

Ammoniacal Silver Nitr. te. Add 1 drop of 10% aqueous NaOH solution to about 5 ml. of silver nitrate solution in a test-tube then add dilute NHg drop by drop with shaking until only a trace of undissolved Ag O remains. A number of reductions require the presence of Ag " ions. It is often advisable, therefore, after adding the ammonia to add silver nitrate solution until a faint but permanent precipitate is obtained. The solution should always be prepared in small quantities immediately before use, and any unexpended solution thrown away afterwards. If the solution is kept for some time, it may form explosive by-products. 

Mono-substitution products of primary amines cannot easUy be prepared by direct action of the appropriate reagent for example, bromination of aniline yields largely the 2 4 6-tribomo derivative and nitration results in much oxidation. If, however, the amino group is protected as in acetanilide, smooth substitution occurs. Thus with bromine, />-bromoacetanilide is the main product the small quantity of the ortlio isomeride simultaneously formed can be easily eliminated by crystallisation. Hydrolysis of p-bromoacetanilide gives/ -bromoaniline ... 

The preparation of a number of miscellaneous acids is described. m-Nitrobenzoic acid. Although m-nitrobenzoic acid is the main product of the direct nitration of benzoic acid with potassium nitrate and concentrated sulphuric acid, the complete separation of the small quantity of the attendant para isomer is a laborious process. It is preferable to nitrate methyl benzoate and hydrolyse the resulting methyl w-nitrobenzoate, which is easily obtained in a pure condition ... 

The effect of potassium nitrate on the rate arises in a similar way. The concentration of nitrate ions in concentrated nitric acid is appreciable, and addition of small quantities of nitrate will have relatively little effect. Only when the concentration of added nitrate exceeds that of the nitrate present in pure nitric acid will the anticatalysis become proportional to the concentration of added salt. 

The catalysed nitration of phenol gives chiefly 0- and />-nitrophenol, (< 0-1% of w-nitrophenol is formed), with small quantities of dinitrated compound and condensed products. The ortho para ratio is very dependent on the conditions of reaction and the concentration of nitrous acid. Thus, in aqueous solution containing sulphuric acid (i 75 mol 1 ) and nitric acid (0-5 mol 1 ), the proportion of oriha-substitution decreases from 73 % to 9 % as the concentration of nitrous acid is varied from o-i mol l i. However, when acetic acid is the solvent the proportion of ortAo-substitution changes from 44 % to 74 % on the introduction of dinitrogen tetroxide (4-5 mol 1 ). 

Expts. I, 3, 5, 7, 9, II. Descriptions of these experiments are not always explicit, but the reagent was prepared from fuming nitric acid (d 1-5, 0 009 mol) and acetic anhydride (o-oi mol) a small quantity of urea was added before nitration. 

Nitration. Naphthalene is easily nitrated with mixed acids, eg, nitric and sulfuric, at moderate temperatures to give mostly 1-nitronaphthalene and small quantities, 3—5%, of 2-nitronaphthalene. 2-Nitronaphthalene [581-89-5] is not made in substantial amounts by direct nitration and must be produced by indirect methods, eg, the Bucherer reaction starting with 2-naphthalenol (2-naphthol [135-19-3]). However, the 2-naphthylamine [91-59-8] made using this route is a carcinogen thus the Bucherer method is seldom used in the United States. 

Among the properties sought in the solvent are low cost, avadabihty, stabiUty, low volatiUty at ambient temperature, limited miscibility in aqueous systems present in the process, no solvent capacity for the salts, good solvent capacity for the acids, and sufficient difference in distribution coefficient of the two acids to permit their separation in the solvent-extraction operation. Practical solvents are C, C, and alcohols. For industrial process, alcohols are the best choice (see Amyl alcohols). Small quantities of potassium nitrate continue to be produced from natural sources, eg, the caUche deposits in Chile. 

Graining, flaking, and spraying have all been used to make soHd ammonium nitrate particles. Most plants have adopted various prilling or granulation processes. Crystallized ammonium nitrate has been produced occasionally in small quantities for use in specialty explosives. The Tennessee Valley Authority developed and operated a vacuum crystallization process (25), but the comparatively small crystals were not well received as a fertilizer. 

Nitration of 4-(2-thienyl)- (301) and 4-(3-thienyl)-pyrazoles (302) mainly occurs on the thiophene ring, but when acetyl nitrate is used as the nitration agent small quantities of products nitrated on the pyrazole ring are isolated (position of the nitro group uncertain) (80CS( 15)102). Pyrazol-l -ylpyridines (303) undergo electrophilic reactions (bromination, chlorination and nitration) preferentially in the pyrazole ring. Thus, the nitration of (303 R = R = = H) either with a mixture of nitric acid and sulfuric acid at 10-15 °C or with... 

Dissolved mineral salts The principal ions found in water are calcium, magnesium, sodium, bicarbonate, sulphate, chloride and nitrate. A few parts per million of iron or manganese may sometimes be present and there may be traces of potassium salts, whose behaviour is very similar to that of sodium salts. From the corrosion point of view the small quantities of other acid radicals present, e.g. nitrite, phosphate, iodide, bromide and fluoride, have little significance. Larger concentrations of some of these ions, notably nitrite and phosphate, may act as corrosion inhibitors, but the small quantities present in natural waters will have little effect. Some of the minor constituents have other beneficial or harmful effects, e.g. there is an optimum concentration of fluoride for control of dental caries and very low iodide or high nitrate concentrations are objectionable on medical grounds. 

The procedure may be illustrated by the following simple experiment, which is a modification of the Gay Lussac-Stas method. The sodium chloride solution is added to the silver solution in the presence of free nitric acid and a small quantity of pure barium nitrate (the latter to assist coagulation of the precipitate). 

Modified TNT. After WWI, a considerable quantity of Trojan grenade powd that had been spoiled by moisture, was available for use. It consisted of nitrostarch, Na nitrate, Amm nitrate, and a small quantity of oils. In order to utilize the powd, an equal amt of TNT was added, and the resulting mixt designated modified TNT was found to be an efficient expl. 

In the case of liq expls and propints, Myrol (methyl nitrate plus methanol) was used either by itself or in mixts with liqs such as benz, MNB, etc. For use as a plastic expl or propint, Myrol was treated with small quantities of NC to form a soft jelly. As a solid expl or propint, it was treated with 25-30% NC to form a hard jelly, or was mixed with the usual sol ingredients of dynamites, sUch as kieselguhr, sawdust, inorganic nitrates, lignin, etc... 

Nitrated Solvent Naphtha (N.S.N.). As nitration of crude solvent naphtha by the usual one-stage method results in yields that are too low, because of oxidation, E. Blecher et al (Ref 3) proposed nitrating only the refined material, and in two stages. The two-stage method is described in Colver, pp 255 686—87 (Ref 4). The product consists chiefly of 2,4,6-Trinitro-mesitylene (see under Mesitylene and Deriva- tives in this Vol), and 3,5,6-trinitropseudocumene, with small quantities of the nitrated products of xylene, ethylbenzene, etc... 

Mercurous Nitrate (Mercury Protonitrate). HgN03.H20, mw 280.64, OB to HgO N2 +17.1%, mp 70° dec, bp explds, d 4.78g/cc. Short prismatic crysts effloresces and becomes anhydrous in dry air sensitive to light. Sol in small quantities of warm w (hydrolyzes in larger quantities), w acidified with nitric acid. Prepd by action of cold dil nitric acid upon an excess of Hg with slight warming. Highly toxic may explode if shocked or heated. There is no US Specification for Mercurous Nitrate Refs 1) Merck (1968), 6,62-L 2) CondChem-... 

Laboratory Preparation of Absolute Nitric Acid, Strong nitric acid, 99%+, free from oxides (white) is used for many nitrations. Since nitric acid of this quality is not generally commercially available, it is usually prepd in small quantities in the laboratory as needed. The customary procedure is to mix one p of coned nitric acid ( d 1.42g/cc) with 2p of sulfuric acid (d 1.84g/cc) and to distill the nitric acid from this mixt under reduced press, using an all glass system... 

Theory D. The presence of small quantities of sulfate, either as combined or free acid which is readily removed, does not greatly affect the stability of the NC. The real cause of instability is the presence in more intimate association with the NC, of other compds which cannot be removed by exhaustive washings. These compds which are acidic in character and exist in small quantities, are formed during the nitration of the cellulose. They can be removed only by prolonged boiling in either w or ale. The presence of acid or salt solns does not increase the ease of stabilization during boiling... 

Urbanski and Sion (Ref 3) later prepd it in small quantities, together with 1-nitropropane, on treating n-propane vapor with gaseous nitrogen. More recently, Kisp ersky et al (Ref 5) prepd a product from 1,3-diiodopropane and Ag nitrate which was stable for at least 9 months Its Na compd, C3Hs(N02)2Na, was prepd by Keppler Meyer (Ref 2), and was reported to be a violent expl ( heftig explodierendes pulver in Ger)... 

Pyrogels used by the US armed forces include (1) PT1, which is a complex mixt based on a paste of Mg and an oxidizer, bound with petroleum distillate and asphalt. Isobutyl methacrylate is used as a thickener. (2) PT2, which contains 5% isobutyl methacrylate as a thickener, together with Ba nitrate and a small quantity of asphalt. (3) PTV, which is described as an improved oil and metal incendiary mixt composed of 5% poly butadiene, 6% Na nitrate, 28% Mg, and a trace of p-aminophenol in 60% gasoline (Ref 5)... 

Pyronome of DeTret. An inexpensive mining expl patented in Engl in 1859 contg Na nitrate 71.5, sulfur 13.5, and charcoal 15% (Refs 1 2). A subsequent Pyronome of Salle Sandoy was patented in Fr in 1881 and contd K nitrate 69 sulfur, charcoal, metallic Sb K chlorate 15% the balance being rye flour contg a small quantity of K dichromate (Ref 1)... 

A pyrotechnic mixture of sulphide/potassium chlorate/aluminium has led to regular detonations. This sulphide incandesces as soon as it is in contact with chloric acid. Mixtures of antimony trisuiphide with alkaline nitrates, which are probably used for pyrotechnic purposes, also lead to detonations. Bengal lights has been made with this mixture, which was used in small quantities in mixtures and no accidents were experienced. Finally, dichlorine oxide detonates in contact with this sulphide. 

Iodine reacts dangerously with numerous elements. Thus, with aluminium, magnesium or powdered zinc, the mixture with iodine in contact with a drop of water gives rise to a flash , which is extremely violent and blinding. In the very spectacular experiment involving ammonium nitrate and zinc described on p.208 and carried out with students, it is recommended to Incorporate a small quantity of iodine before throwing a few drops of water on the mixture. 

There is a synthesis, which is supposed to be safe and consists in using very small quantities of reagents and closely monitoring the temperature. However, the thermai control of the aromatic hydrocarbons/nitric acid reaction usually proves to be very difficult. Indeed, the temperature is either too high and the reaction is out of controi and can lead to detonation, or too low and the nitration or oxidation takes place too slowly causing the compounds to accumulate and the reaction to be delayed. The consequences are the same as before. 

Additional stabilizers for the emulsion can be multivalent inorganic salts, such as aluminum nitrate [1523], in small quantities of 30 ppm. 

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