Chloride Explosion

Repeat Problem 13-1 for the vinyl chloride explosion described in section 13-4. 

Some compounds (e.g. ammonium chloride) explosively sublime in the flame, thus enhancing atomization. By adding excess ammonium chloride to all samples and standards, this effect can be used to minimize interferences of types (a) and (c). 

Fig. 134. Relationship between charge limit and rate of detonation of explosives suspended in methane-air mixture, according to J. Taylor [41] /—explosive containing no cooling salt //—explosive containing 10% sodium chloride ///—explosive remaining 50% sodium chloride IV— explosive based on sodium nitrate.

Dimethyl sulfoxide (DMSO), (CH3)2SO, decomposes violently on contact with a wide variety of active halogen compounds, such as acyl chlorides. Explosions from contact with active metal hydrides have been reported. Dimethyl sulfoxide does penetrate and carry dissolved substances through the skin membrane. 

Ordinary commercial camphor is (-i-)-cam phor, from the wood of the camphor tree. Cinnamonum camphora. Camphor is of great technical importance, being used in the manufacture of celluloid and explosives, and for medical purposes, /t is manufactured from pinene through bornyl chloride to camphene, which is either directly oxidized to camphor or is hydrated to isoborneol, which is then oxidized to camphor. A large number of camphor derivatives have been prepared, including halogen, nitro and hydroxy derivatives and sulphonic acids. 

CH2=CHC = CCH = CH2. a colourless liquid which turns yellow on exposure to the air it has a distinct garlic-like odour b.p. 83-5°C. Manufactured by the controlled, low-temperature polymerization of acetylene in the presence of an aqueous solution of copper(I) and ammonium chlorides. It is very dangerous to handle, as it absorbs oxygen from the air to give an explosive peroxide. When heated in an inert atmosphere, it polymerizes to form first a drying oil and finally a hard, brittle insoluble resin. Reacts with chlorine to give a mixture of chlorinated products used as drying oils and plastics. 

Lead lV) chloride, PbCL, is a yellow liquid, m.p. — 15 C, decomposes explosively at lOC C (H2SO4 on (NH4)2PbCU). Yellow hexachloro-plumbales(IV), e.g. (NH4)2PbCl6, are precipitated from the yellow solution resulting from PbOj in cold HCl. 

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

The solid readily dissolves chemically in concentrated hydrochloric acid, forming a complex, and in ammonia as the colourless, linear, complex cation [H3N -> Cu <- NHj] (cf AgCl) if air is absent (in the presence of air, this is oxidis to a blue ammino-copper(II) complex). This solution of ammoniacal copper(I) chloride is a good solvent or carbon monoxide, forming an addition compound CuCl. CO. H2O, and as such is used in gas analysis. On passing ethyne through the ammoniacal solution, a red-brown precipitate of hydrated copper(I) dicarbide (explosive when dry) is obtained ... 

CAUTION. Ethers that have been stored for long periods, particularly in partly-filled bottles, frequently contain small quantities of highly explosive peroxides. The presence of peroxides may be detected either by the per-chromic acid test of qualitative inorganic analysis (addition of an acidified solution of potassium dichromate) or by the liberation of iodine from acidified potassium iodide solution (compare Section 11,47,7). The peroxides are nonvolatile and may accumulate in the flask during the distillation of the ether the residue is explosive and may detonate, when distilled, with sufficient violence to shatter the apparatus and cause serious personal injury. If peroxides are found, they must first be removed by treatment with acidified ferrous sulphate solution (Section 11,47,7) or with sodium sulphite solution or with stannous chloride solution (Section VI, 12). The common extraction solvents diethyl ether and di-tso-propyl ether are particularly prone to the formation of peroxides. 

CAUTION. The preparation of o-nitrobenzoyl chloride, o-nitrophenacetyl chloride and all o nitroacid chlorides should not be attempted by the above methods a violent explosion may occur upon distilling the product or when the last traces of thionyl chloride are removed in vacuo at 100°. Perhaps the safest method is to treat the pure acid in benzene solution with 1 1 mols of thionyl chloride and to reflux until evolution of sulphur dioxide and hydrogen chloride has ceased the solution of the acid chloride in benzene may then bo employed for most reactions. 

The incorporation of aluminum increases the blast effect of explosives but decreases the rates of detonation, fragmentation effectiveness, and shaped charge performance. Mixes with aluminum are made by first screening finely divided aluminum, adding it to a melted RDX—TNT slurry, and stirring until the mix is uniform. A desensitizer and calcium chloride may be incorporated, and the mixture cooled to ca 85°C then poured. Typical TNT-based aluminized explosives are the tritonals (TNT + Al), ammonals (TNT, AN, Al), minols (TNT, AN, Al) torpexes and HBXs (TNT, RDX, Al) (Table 14) (223-226). 

Aluminum bromide and chloride are equally active catalysts, whereas boron trifluoride is considerably less active probably because of its limited solubiUty in aromatic hydrocarbons. The perchloryl aromatics are interesting compounds but must be handled with care because of their explosive nature and sensitivity to mechanical shock and local overheating. 

Esters of nitro alcohols with primary alcohol groups can be prepared from the nitro alcohol and an organic acid, but nitro alcohols with secondary alcohol groups can be esterified only through the use of an acid chloride or anhydride. The nitrate esters of the nitro alcohols are obtained easily by treatment with nitric acid (qv). The resulting products have explosive properties but are not used commercially. 

The iodine compound is more stable and separates as so-called nitrogen trHodide monoammoniate [14014-86-9], NI NH, an insoluble brownish-black soHd, which decomposes when exposed to light in the presence of ammonia. In reactions of the halogens with the respective ammonium salts, however, the action is different. Chlorine replaces hydrogen and nitrogen chloride [10025-85-1], NCl, separates as oily, yeUow droplets capable of spontaneous explosive decomposition. 

Ammonium chloride has a number of iadustrial uses, most importantiy ia the manufacture of dry-ceU batteries, where it serves as an electrolyte. It is also used to make quarryiag explosives, as a hardener for formaldehyde-based adhesives, as a flame suppressant, and ia etching solutions ia the manufacture of ptinted circuit boards. Other appHcations iaclude use as a component of fluxes ia ziac and tin plating, and for electrolytic refining of ziac. 

Ammonium nitrate is normally classified as an oxidizing agent. The pure salt is not classed as an explosive because it is difficult to detonate. Spark, flame, or friction do not cause detonation, and ammonium nitrate is relatively insensitive to shock. However, a variety of substances, such as chloride and oil, are known to sensitize the material, so manufacturers strive to eliminate such substances from their processes. 

Quality of Product. Ammonium nitrate, commonly made from pure synthetic raw materials, is itself of high purity. If the product is intended for use in explosives, it should be at least 99% ammonium nitrate and contain no more than 0.15% water. It should contain only small amounts of water-insoluble and ether-soluble material, sulfates and chlorides, and should not contain nitrites. The soHd product ought to be free from alkalinity, but be only slightly acidic. 

The reactants are fed separately iato a stUl, from which the product is continuously removed by distillation (qv) (31). Isopropyl nitrate is a valuable engiae-starter fuel and can be used ia explosives (see Explosives and propellants) (32). The nitrite ester, isopropyl nitrite, can be prepared from the reaction of isopropyl alcohol and either nitrosyl chloride or nitrous acid at ambient temperature (33). The ester is used as a jet engine propellant (30). 

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