4742. Dinitrogen tetraoxide (Nitrogen dioxide)
HCS 1980, 675 (cylinder)
The equilibrium mixture of nitrogen dioxide and dinitrogen tetraoxide is completely associated at —9°C to the latter form which is marginally endothermic (ΔH°f (g) +9.7 kJ/mol, 0.10 kJ/g). Above 140°C it is completely dissociated to nitrogen dioxide, which is moderately endothermic (ΔH°f (g) +33.8 kJ/mol, 0.74 kJ/g).
MRH Acetonitrile 7.87/25
Addison, C. C. et al., Chem. & Ind., 1958, 1004
Shaking a slow-reacting mixture caused detonation, attributed to indium-catalysed oxidation of acetonitrile.
Daniels, F., Chem. Eng. News, 1955, 33, 2372
A violent explosion occurred during the ready interaction to produce alkyl nitrates.
Mellor, 1940, Vol. 8, 541
Liquid ammonia reacts explosively with the solid tetraoxide at —80°C, while aqueous ammonia reacts vigorously with the gas at ambient temperature.
Mellor, 1940, Vol. 8, 545
In contact with the gas at 200°C the oxide suddenly reacts, reaches red heat and melts.
Mellor, 1946, Vol. 5, 132
Interaction is energetic.
Mellor, 1940, Vol. 8, 543
Sorbe, 1968, 132
Liquid mixtures proposed for use as explosives are stable up to 200°C , but can be detonated by mercury fulminate, and the vapours by sparking .
Cloyd, 1965, 74
Combination is hypergolic.
Cellulose, Magnesium perchlorate
See Magnesium perchlorate: Cellulose, etc.
Lachowicz, D. R. et al., US Pat. 3 621 050, 1971
Contact of cycloalkenes with a mixture of dinitrogen tetraoxide and excess oxygen at temperatures of 0°C or below produces nitroperoxonitrates of the general formula — CHNO2—CH(OONO2)—which appear to be unstable at temperatures above 0°C, owing to the presence of the peroxonitrate group.
See Hydrocarbons, below
Mahler, W., Inorg. Chem., 1979, 18, 352
A reaction, to produce the phosphine oxide on 12 mmol scale, ignited.
See Dimethyl sulfoxide: Dinitrogen tetraoxide
Pollard, F. H. et al., Trans. Faraday Soc., 1949, 45, 767—770
Rastogi, R. P. et al., Chem. Abs., 1975, 83, 12936
The slow (redox) reaction becomes explosive around 180°C , or even lower .
See other REDOX REACTIONS
MRH Chloroform 2.38/67, 1,2-dichloroethane 5.06/42, 1,1-dichloroethylene 5.06/46, trichloroethylene 3.97/56
Turley, R. E., Chem. Eng. News, 1964, 42(47), 53
Benson, S. W., Chem. Eng. News, 1964, 42(51), 4
Shanley, E. S., Chem. Eng. News, 1964, 42(52), 5
Kuchta, J. M. et al., J. Chem. Eng. Data, 1968, 13, 421—428
Mixtures of the tetraoxide with dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethylene and tetrachloroethylene are explosive when subjected to shock of 25 g TNT equivalent or less . Mixtures with trichloroethylene react violently on heating to 150°C . Partially fluorinated chloroalkanes were more stable to shock. Theoretical aspects are discussed in the later reference [2,3]. The effect of pressure on flammability limits has been studied .
See Uranium: Nitric acid
See Vinyl chloride: Oxides of nitrogen
MRH Pyridine 7.82/22, quinoline 7.87/22
Mellor, 1940, Vol. 8, 543
Pyridine and quinoline are attacked violently by the liquid oxide.
Cloyd, 1965, 74
Miyajima, H. et al., Combust. Sci. Technol., 1973, 8, 199—200
Combinations with hydrazine, methylhydrazine, 1,1-dimethylhydrazine or mixtures thereof are hypergolic and used in rocketry . The hypergolic gas-phase ignition of hydrazine at 70—160°C/53—120 mbar has been studied .
See ROCKET PROPELLANTS
MRH values below references
Mellor, 1967, Vol. 8, Suppl. 2.2, 264
Fierz, H. E., J. Soc. Chem. Ind., 1922, 41, 114R
Raschig, F., Z. Angew. Chem., 1922, 35, 117—119
Berl, E. Z. Angew. Chem., 1923, 36, 87—91
Schaarschmidt, A., Z. Angew. Chem., 1923, 36, 533—536
Berl, E., Z. Angew. Chem., 1924, 37, 164—165
Schaarschmidt, A., Z. Angew. Chem., 1925, 38, 537—541
MCA Case History No. 128
Folecki, J. et al., Chem. & Ind., 1967, 1424
Cloyd, 1965, 74
Urbanski, 1967, Vol. 3, 289
Biasutti, 1981, 50
Biasutti, 1981, 53—54
MRH Benzene 7.99/19, hexane 7.91/17, isoprene 8.28/18, methylcyclohexane 7.87/17
A mixture of the tetraoxide and toluene exploded, possibly initiated by unsaturated impurities . During attempted separation by low temperature distillation of an accidental mixture of light petroleum and the oxide, a large bulk of material awaiting distillation became heated by unusual climatic conditions to 50°C and exploded violently . Subsequently, discussion of possible alternative causes involving either unsaturated or aromatic compounds was published [3,4,5,6,7]. Erroneous addition of liquid in place of gaseous nitrogen tetraoxide to hot cyclohexane caused an explosion . During kinetic studies, one sample of a 1:1 molar solution of tetraoxide in hexane exploded during (normally slow) decomposition at 28°C . Cyclopentadiene is hypergolic with the oxide . These incidents are understandable because of their similarity to rocket propellant systems and liquid mixtures previously used as bomb fillings . The liquid oxide leaking from a ruptured 6 t storage tank ran into a gutter containing toluene and a violent explosion ensued . An alternative account describes the hydrocarbon as benzene .
See Cycloalkenes, above; Unsaturated hydrocarbons, below
Lewis, B., Chem. Rev., 1932, 10, 60
The presence of small amounts of the oxide in non-explosive mixtures of hydrogen and oxygen renders them explosive.
Isopropyl nitrite, Propyl nitrite
Safety in the Chemical Laboratory, Vol. 1, 121, Steere, N. V. (Ed.), Easton (Pa.) J. Ch. Ed., 1967
A pressurised mixture of the cold components exploded very violently during a combustion test run. The mixture was known to be autoexplosive at ambient temperature, and both of the organic components are capable of violent decomposition in absence of added oxidant.
Arapava, L. D. et al., Chem. Abs., 1985, 102, 169310
Contact of the lubricating grease Litol-24 with the oxidant at below 80°C led to explosion on subsequent impact. This involved nitration products of the antioxidant present, 4-hydroxydiphenylamine. Above 80°C decomposition superceded nitration, and no explosion occurred.
See other NITRATION INCIDENTS
Metal acetylides or carbides
MRH values show % of oxidant
Mellor, 1946, Vol. 5, 849
Caesium acetylide ignites at 100°C in the gas.
See Tungsten carbide: Nitrogen oxides
Ditungsten carbide: Oxidants
MRH Magnesium 12.97/50, potassium 3.72/46
Mellor, 1940, Vol. 8, 544—545; 1942, Vol. 13, 342
Pascal, 1956, Vol. 10, 382; 1958, Vol. 4, 291
Reduced iron, potassium and pyrophoric manganese all ignite in the gas at ambient temperature. Magnesium filings burn vigorously when heated in the gas . Slightly warm sodium ignites in contact with the gas, and interaction with calcium is explosive .
See Aluminium: Oxidants
Anon., CISHC Chem. Safety Summ., 1978, 49, 3—4
Process errors led to discharge of copious amounts of nitrous fumes into the glass reinforced plastic ventilation duct above a diazotisation vessel. On two occasions fires were caused in the duct by vigorous reaction of the dinitrogen tetraoxide with nitroaniline dusts in the duct. Laboratory tests confirmed this to be the cause of the fires, and precautions are detailed.
Urbanski, 1967, Vol. 3, 288
Kristoff, F. T. et al., J. Haz. Mat., 1983, 7, 199—210
Mixtures with nitrobenzene were formerly used as liquid high explosives, with addition of carbon disulfide to lower the freezing point, but high sensitivity to mechanical stimulus was disadvantageous . During the recovery of acids from nitration of toluene, mixtures of the oxide with nitrotoluene or dinitrotoluene may be isolated under certain process conditions. While such mixtures are not unduly sensitive to impact, friction or thermal initiation, when oxygen-balanced they are extremely sensitive to induced shock and are capable of explosive propagation at film thicknesses below 0.5 mm. It is suspected that many explosions in TNT acid recovery operations, previously attributed to tetranitromethane, may have been caused by such mixtures .
See Nitrogen trichloride: Initiators
Riebsomer, J. L., Chem. Rev., 1945, 36, 158
In a review of the interaction of the oxidant with organic compounds, attention is drawn to the possibility of formation of unstable or explosive products.
Yoshida, 1980, 269
MRH values calculated for 18 combinations with oxidisable materials are given.
See Ozone: Nitrogen oxide
See Phospham: Oxidants
See Phosphorus: Non-metal oxides
Beck, G., Z. Anorg. Chem., 1937, 233, 158
Interaction with the oxide in carbon tetrachloride is vigorous, producing sparks.
U.S. National Transportation Safety Board, Hazardous Materials Accident Brief,
A carbon steel tank for rail transportation of the tetroxide became contaminated with water, probably when a leaking valve, later replaced, was hosed down. After repair, the tank was charged with 50 tons of the oxide. This was later found to be wet, attempts were than made to empty the tanker. Acording to the single meter used to measure the transfer, this was accomplished (subsequent investigation suggested that only about 3 tons had been transferred because the dip pipes had corroded away). Water was charged to wash out the tank. The sequence of supposed emptying and washing was repeated and more water was added. It was noticed that pressure and fumes were excessive, atempts to deal with this continued some days. About a month after initial loading, and ten days after first washing, one of the heads blew off, throwing cladding about 100 m. Inspection of the remains showed several bands of corrosion, caused by nitric acid, produced from the oxide and water, reacting with steel to produce hydrogen and/or lower oxides of nitrogen which pressurised the weakened tank. Large tank cars are no longer used.
Bailar, 1973, Vol. 3, 1130
Interaction of the liquids is rather violent.
See Carbonylmetals, above
Bailar, 1973, Vol. 2, 355
Interaction is explosively violent even at —80°C, and dilution with with inert solvents is required for moderation.
Rastogi, R. P. et al., Indian J. Chem., Sect. A, 1980, 19A, 317—321
Reaction in this hybrid rocket propellant system is enhanced by presence of ammonium vanadate.
Davenport, D. A. et al., J. Amer. Chem. Soc., 1953, 75, 4175
The complex, containing excess oxide over amine, exploded at below 0°C when free of solvent.
Addison, C. C. et al., Chem. & Ind., 1953, 1315
The two component form an addition complex with diethyl ether, which exploded violently after partial desiccation: an ether-free complex is also unstable.
See Triethylamine, above
MRH Isoprene 8.28/18
Sergeev, G. P. et al., Chem. Abs., 1966, 65, 3659g
Biasutti, 1981, 123
Dinitrogen tetraoxide reacts explosively between —32° and —90°C with propene, 1-butene, isobutene, 1,3-butadiene, cyclopentadiene and 1-hexene, but 6 other unsaturates failed to react . Reaction of propene with the oxide at 2 bar/30°C to give lactic acid nitrate was proceeding in a pump-fed tubular reactor pilot plant. A violent explosion after several hours of steady operation was later ascribed to an overheated pump gland which recently had been tightened. A similar pump with a tight gland created a hot-spot at 200°C .
See Nitrogen dioxide: Alkenes
See Vinyl chloride: Oxides of nitrogen
Xenon tetrafluoride oxide
Christe, K. O., Inorg. Chem., 1988, 27, 3764
In the reaction of the pentaoxide with xenon tetrafluoride oxide to give xenon difluoride dioxide and nitryl fluoride, the xenon tetrafluoride oxide must be used in excess to avoid formation of xenon trioxide, which forms a sensitive explosive mixture with xenon difluoride dioxide.
See Xenon tetrafluoride oxide: Caesium nitrate
See other ENDOTHERMIC COMPOUNDS, NON-METAL OXIDES, OXIDANTS