Violent heating tests

Accdg to Ficheroulle Gay-Lussac (Ref 6), Trinitroethanol is unstable and even at R.T evolves nitrous fumes. When heated to 120° it rapidly decomposes with evolution of nitrous fumes and then violently explodes. Its sensitivity to shock is comparable to that of NG. Although it is a good gelatinizer for NC, it cannot be recommended for use in expls and pioplnts on account of its poor stability. In the 100°C Heat Test, it lost 68% 1st 48 hrs and 26% second 4 hrs, with no expln in 100 hrs Refs 1) Beil, not found 2) W. Hunter et al, BIOS Final Rept No 709, HMStationary Office, London (1946), p 9 (Description of prepn of Trini tro ethanol by Dr Sc him m el schmidt of IG Farbenindustrie, Hochst-am-Main)... 

Dr Martin proposed a theory -to explain the expln and conducted experiments which proved that rapid heating of butyl peroxyacetate to a critical temp will cause the compd to detonate violently. According to Martin, a report from the Bureau of Explosives, Dept of Commerce, indicated in their application of heat tests that butyl peroxyacetate failed to explode. This was explained on the basis of too low a rate of applying heat. The Bureau did detonate a rnixt of the coral liq and a... 

Precaution Thermally unstable dec. rapidly R.T., violently when healed detonates In flame-heated test tube dangerous fire hazard exposed to heaf flames, oxidizers incompat. with carbonyls, pyridine explosive and vigorous reaclions possible... 

Handling and Storage. Cyanamide solution dimerizes to dicyandiamide and urea with the evolution of heat and a gradual increase in alkalinity accelerating the reaction. Storage above 30°C without pH stabilizer leads to excessive dimerization and can result in violent exothermic polymerization. Cyanamide should be stored under refrigeration and the pH tested periodically. Stabilized cyanamide can be kept at ambient temperature for a few weeks. 

The dearrangement of phenylthiourea may be demonstrated very simply by heating a small quantity of the material in a test-tube. It undergoes a violent decomposition slightly above its melting-point, the odors of ammonia, of aniline, and of phenyl mustard oil may be detected, and the residue which consists largely of sym.-diphenylthiourea gives with ferric chloride the a ed color characteristic of thiocyanic acid. 

Top spray systems During top-spray cooling of an overheated core, the wall temperature is usually higher than the Leidenfrost temperature, which causes water to be sputtered away from the wall by violent vapor formation and then pushed upward by the chimney effect of the steam flow generated at lower elevations (as shown in Fig. 4.25). A spray-cooling heat transfer test with BWR bundles was reported by Riedle et al. (1976). They found the dryout heat flux to be a function of spray rate and system pressure. The collapsed level required to keep the bundle at saturation for various pressures compared reasonably well with that in the literature (Duncan and Leonard, 1971 Ogasawara et al., 1973). 

It is extremely shock-sensitive, a 4.0 kg cm shock causing detonation in 50% of test runs (cf. 3.5 kg cm for propargyl bromide 2.0 kg cm for glyceryl nitrate). The intermediate bis-chlorosulfite involved in the preparation needs low temperatures to avoid vigorous decomposition. The corresponding diiodo derivative was expected to be similarly hazardous [1], and this has been confirmed [2]. Improvements in preparative techniques (use of dichloromethane solvent at —30°C) to avoid violent reaction have also been described [3], An attempt to distill the compound (b.p. 55-58°C/0.6 mbar, equivalent to about 230°C/l bar) at atmospheric pressure from a heating mantle led to a violent explosion [4], The compound involved was erroneously given as l,6-dichloro-2,4-hexadiene [5],... 

The explosive decomposition of the solid has been studied in detail [6], The effect of moisture upon ignitibility and explosive behaviour under confinement was studied. A moisture content of 3% allowed slow burning only, and at 5% ignition did not occur [7], Thermal instability was studied using a pressure vessel test, ignition delay time, TGA and DSC, and decomposition products were identified [8], The presence of acyl chlorides renders dibenzoyl peroxide impact-sensitive [9], There is a further report of a violent explosion during purification of the peroxide by Soxhlet extraction with hot chloroform [10], Residual traces of the peroxide in a polythene feed pipe exploded when it was cut with a handsaw [11]. The heat of decomposition has been determined as 1.39 kJ/g. The recently calculated value of 69° C for critical ignition temperature coincides with that previously recorded. 

Hatton, J. P., private comm., 1976 A mixture exploded violently on heating in a test tube. 

The endothermic nitride is susceptible to explosive decomposition on friction, shock or heating above 100°C [1], Explosion is violent if initiated by a detonator [2], Sensitivity toward heat and shock increases with purity. Preparative precautions have been detailed [3], and further improvements in safety procedures and handling described [4], An improved plasma pyrolysis procedure to produce poly (sulfur nitride) films has been described [5], Light crushing of a small sample of impure material (m.p. below 160°C, supposedly of relatively low sensitivity) prior to purification by sublimation led to a violent explosion [6] and a restatement of the need [4] for adequate precautions. Explosive sensitivity tests have shown it to be more sensitive to impact and friction than is lead azide, used in detonators. Spark-sensitivity is, however, relatively low [7],... 

Caution should be observed in handling this compound, as with all perchlorate salts. The tris(bipyridine)chromium(I1) perchlorate explodes violently on slow heating to 250° and can be set off by static electricity. It does not appear to be shock-sensitive on dropping an 8.8-g. steel ball from 4 ft., although the compound was tested only once. The explosive properties of related complexes have been described.16... 

Heat flask 7 on a water bath. When the phosphorus trichloride boils, turn test tube 3 in its ground-glass joint and introduce the aluminium chloride in small portions into the reaction mixture. Stop the heating because the reaction is very violent. Have at hand a bath with cold water to be able to retard the reaction by cooling the reaction mixture if required. The reaction ends when the liquid in the flask stops boiling. 

When a violent reaction stops, heat the metal again. After evaporation of all the halogen from test tube 2, seal ofi constriction 3 very carefully. Repeatedly pass the halogen over the heated metal. When the halogen vapour disappears in the apparatus, distil the product into section 4 or 7 and seal it ofi. 

N 36.84%, OB to CO, -42.1%. Ndls(from ether), mp 38°, d 1.2433 at 48.6°, nD 1.46l62 at 48.6°(Ref 2) expl violently when heated in a capillary(Ref 5)- Easily sol in w, ale, chlf benz less sol in eth very si sol in petr eth. Was first prepd by Franchi-mont Be Kiobbie(Ref 2) by nitration and hydrolysis of me thy 1-N-me thy 1-car bam ate, CHjCO, NH CH,. Other methods are known (Refs 1 4). Johnson(Ref 5) prepd it in 66% yield by nitration and hydrolysis of ethyl-N-methy 1-carbamate. Detailed description of procedure is given. It is a powerful expl, with a Trauzl test value of 144%PA. Its toxicity is probably similar to that of amino-methane(qv)... 

A small sample of AN in an evacuated tube was heated gradually to desired temps, and samples of the gas produced by decompn were pumped out, measured and tested. Decompn proceeded very quietly at temps below 200°, and only a small amt of gas was formed even on heating for several hours. The reaction proceeded more vigorously at higher temps and became rather violent at ca 260°. Between 260 and 269° gray smoke was produced and, after a time, an explosion took olacr. This also Orftirred after hearing... 

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