Brethericks Handbook of Reactive Chemical Hazards

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Dougherty, V. Colclough, M. Ethyl [1], isopropyl, butyl, benzyl and triphenylmethyl nitrates [3] in contact with sulfuric acid [2], tin IV chloride [2,3] or boron trifluoride [3] interact violently after an induction period of up to several hours with gas evolution. An autocatalytic mechanism was proposed.

Although pure alkyl nitrates are stable in storage, traces of oxides of nitrogen sensitise them to decomposition, and may cause explosion on heating or storage at ambient temperature [4]. The most important applications of alkyl nitrates are based on their explosive properties.

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Methyl and ethyl nitrates are too volatile for widespread use; propyl nitrate has been used as a liquid monopropellant as also has isopropyl nitrate. Ethylene dinitrate, glyceryl trinitrate and pentaerythritol tetranitrate are widely used as explosives, the two former liquids adsorbed on or blended with other compounds [1]. Poly nitrate esters such as poly glycidyl nitrate are being studied as energetic binders for explosives and propellants [10].

The nitrate esters of many polyhydroxy compounds ethylene glycol, glycerol, 1-chloro-2,3-dihydroxypropane, erythritol, mannitol, sugars or cellulose are all more or less shock-sensitive and will ignite or 25 explode on heating [5]. Use of dichloromethane as diluent provides a low-hazard procedure for preparing such esters [7], and in a new method of preparation, the esters are not isolated from solution in acetonitrile [8]. Methods of assessing the relative thermal stabilities of formulated propellant materials containing nitrate esters are reviewed.

The decomposition rates of several glycol nitrates and glyceryl trinitrate are greatly enhanced by the presence of transition metal oxides or chelates.

Sorbe, , 2. Methyl nitrite explodes more violently than ethyl nitrite [2]. Lower alkyl nitrites have been known to decompose and burst the container, even in refrigerated storage [3].

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With other gaseous oxidants halogens, etc. Hofmann, K.

Meyer, J. Schumacher, , 4. Burton, H. Hoffman, D. Zefirov, N. Many of the explosions which have occurred on contact of hydroxylic compounds with conc. Safe procedures for preparation of solutions of 14 sec-alkyl perchlorates are described. Heated evaporation of solvent caused explosions in all cases [5].

Flame, , 2, — Measurements of the autoignition temperatures for several series of mono-, di-, triand tetra-alkylsilanes showed that the ease of oxidation decreases with increasing substitution. The reactions must be run in the dark to prevent precipitation of metallic silver, which will catalyse decomposition of the hydroperoxide or excess hydrogen peroxide.

In an experiment not run in the dark, the hydroperoxide from 3-chlorocyclohexene ignited spontaneously after isolation and concentration. A chilled sample of allyl triflate in a sealed ampoule exploded on being allowed to warm to ambient temperature. Time—temperature process data are fed as input to a kinetic simulation computer program which calculates conversions, heat release and pressure profiles. Results 34 are compared continuously on-line with measured batch data to detect any deviations from normal operating conditions.

Paradoxically, these tend to be the more stable members of the group, those which for conformational reasons cannot undergo the Cope rearrangement. As this class of compound is of growing importance, more incidents can be expected, possibly including violent decomposition of the alkylhydroxylamine products of the Cope reaction as well as the apparently radical branched chain, higher temperature decomposition which accounts for present reports.

Early workers developed spot tests for amine oxides which later study has shown they do not perform but hydrogen peroxide does; since amine oxides tenaciously hold water as hydrates it must be suspected that they can also form hydrogen peroxidates if made using excess hydrogen peroxide. These will be more dangerous than the amine oxide itself. Hazards Ind.

An industrial explosion consequent upon inadvertent isolation of such in part of a production plant, with subsequent overheating is reported [1]. This creates a high tendency towards explosive decomposition, which sometimes apparently occurs spontaneously. Joyner, T.

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Narang, K. Compounds were hexaamminecobalt triazide, pentaammineazidocobalt diazide, cis- and trans-tetraamminediazidocobalt azide, triamminecobalt triazide [1]. A variety of hydrazine complexed azides and chloroazides of divalent metals have been prepared. Those of iron, manganese and copper could not be isolated; cobalt, nickel, cadmium and zinc gave products stable at room temperature but more or less explosive on heating [2].

Although free from the formally oxidising anions present in the two groups below, a few of these compounds show instability. Compounds in this group show explosive instability tending towards that of the perchlorate analogues in the entry following. Mellor, , Vol. Tomlinson, W. Wendlandt, W. Ray, P. Hoppesch, C. Fuel Chem. Preprints, , 7 3 , — 8. Friederich, W. Anagnostopoulos, A. Patil, K. Acta, , 15, — Springborg, J.

Bretherick's Handbook of Reactive Chemical Hazards

Shidlovskii, A. Robinson, W. Hasenpusch, W. From tabulated data for 17 such compounds of Co and Cr, it is considered that oxygenated N-coordinated compounds, particularly those which are oxygen balanced cover 38 a wide range of explosive types; many may explode powerfully with little or no provocation, and should be considered extremely dangerous, as some are sensitive enough to propagate explosion under water.


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The same considerations may be expected to apply to ammines of silver, gold, cadmium, lead and zinc which contain oxidising radicals [2]. The topic has been reviewed [3] and possible hazards in published student preparations were emphasised [4]. Some of the derivatives of metal biguanide and guanylurea complexes [5] are of this group.

Unexpected uniformities observed in the impact-sensitivities of a group of 22 amminecobalt oxosalts are related to kinetic factors during the initiation process [6]. A series of ammine derivatives of cadmium, cobalt, copper, mercury, nickel, platinum and zinc with mainly iodate anions was prepared and evaluated as explosives [7]. Earlier, ammine and hydrazine derivatives of cadmium, cobalt, copper and nickel with chlorate or perchlorate anions had been evaluated as detonators. Dihydrazinecopper II chlorate had exploded when dried at ambient temperature [8].

The compounds are manganese sulfate complexed with 4 mol of pyrazole or 3-methylpyrazole, and cadmium or zinc sulfates complexed with 4 and 3 mol of 3-methylpyrazole, respectively [9]. The use of a soft polythene rod is recommended to reduce the possibility of explosions when handling perchlorate and similar salts on sintered filters [11].

A 3 g sample of the perchlorate salt of a polyaminerhodium complex exploded with great violence in a rotary evaporator flask heated in a water bath [13]. A series of tetrammine metal II nitrates Pt, Pd, Cu, Ni were all found to be practically and legally classifiable as sensitive explosives. Buckley, A. Banthorpe, D. A further potential hazard which should be considered is that some aprotic solvents, notably dimethyl sulfoxide [1] and dimethylformamide [2], as well as having dramatic effects upon reaction rates, may greatly promote the toxic properties of solutes because of their unique ability to penetrate synthetic rubber protective gloves and the skin.

Butyl rubber gloves are reputed to be more satisfactory than other types. The ether and cyclic ether solvents are also subject to peroxidation in storage. News, , 33, , , , Aqua regia nitric and hydrochloric acids, by vol. Internal pressure developed overnight, one bottle being shattered. Aqua regia decomposes with evolution of gas and should not be stored in tightly closed bottles and preferably not at all.

Biographical Memoirs, Royal Society, , Addition of a piece of sodium to aqua regia produces spectacular sparks.

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They are produced by interaction of alcohols with explosive bis arenediazo oxides, or of p-blocked phenols with diazonium salts. The thio analogues are similar. Other early names of the 1,2-diazonium oxides were based on the benzoxadiazole cyclised structure.