Explosion from peroxidation reactions

Propellant. The catalytic decomposition of 70% hydrogen peroxide or greater proceeds rapidly and with sufficient heat release that the products are oxygen and steam (see eq. 5). The thmst developed from this reaction can be used to propel torpedoes and other small missiles (see Explosives and propellants). An even greater amount of energy is developed if the hydrogen peroxide or its decomposition products are used as an oxidant with a variety of fuels. 

The cure reaction of structural acrylic adhesives can be started by any of a great number of redox reactions. One commonly used redox couple is the reaction of benzoyl peroxide (BPO) with tertiary aromatic amines. Pure BPO is hazardous when dry [39]. It is susceptible to explosion from shock, friction or heat, and has an autoignition temperature of 79°C. Water is a very effective stabilizer for BPO, and so the initiator is often available as a paste or a moist solid [40], The... 

During preparation of peracetic acid solutions for textile bleaching operations, the reaction mixture must be kept acid. Under alkaline conditions, highly explosive diacetyl peroxide separates from solution [1], An excess of the anhydride has the same effect [2],... 

A large volume (11.25 m3) of mixed fatty acids was to be bleached by treatment with successive portions of 50 wt% hydrogen peroxide. 2-Propanol (450 1) was added to the acids (to improve the mutual solubility of the reactants). The first 20 1 portion of peroxide (at 51°C) was added, followed after 1 min by a second portion. Shortly afterwards an explosion occurred, which was attributed to spontaneous ignition of a 2-propanol vapour-oxygen mixture formed above the surface of the liquid. Oxygen is almost invariably evolved from hydrogen peroxide reactions, and volatile flammable solvents are therefore incompatible components in peroxide systems. 

Peroxyacetic acid (CH3CO3H) is a weak oxidant. Strong solutions are potentially explosive and hazardous to store, although a 40 % solution in acetic acid is available commercially. Emmons prepared anhydrous solutions of peroxyacetic acid from the reaction of 90 %+ hydrogen peroxide with acetic anhydride in chloroform containing a trace of sulfuric acid. 

The presence of HMX as an impurity in RDX is not a problem when the product is used as an explosive. However, the need for an analytical sample of RDX makes other more indirect methods feasible. One such method involves the oxidation of 1,3,5-trinitroso-1,3,5-triazacyclohexane (109) ( R-salt ) with a mixture of hydrogen peroxide in nitric acid at subambient temperature and yields analytical pure RDX (74%) free from HMX." The same conversion has been reported in 32 % yield with three equivalents of a 25 % solution of dinitrogen pentoxide in absolute nitric acid. l,3,5-Trinitroso-l,3,5-triazacyclohexane (109) is conveniently prepared from the reaction of hexamine with nitrous acid at high acidity. ... 

No peroxide has found practical use as an explosive, a consequence of the weak oxygen-oxygen bond leading to poor thermal and chemical stability and a high sensitivity to impact. Hexamethylenetriperoxidediamine (HMTD) (46) is synthesized from the reaction of hexamine with 30 % hydrogen peroxide in the presence of citric acid. HMTD is a more powerful initiating explosive than mercury fulminate but its poor thermal and chemical stability prevents its use in detonators. 

Anhydrous diethyl ether, freshly obtained from a commercial supplier, is preferred for the reactions involving lithium hydro-aluminaie. The ether must be peroxide-free. Carbon dioxide must be rigorously excluded from these reaction systems. Explosions have been observed during evaporation of solutions of aluminum hydride and related compounds when carbon dioxide is present as an impurity.If it is necessary to concentrate ether solutions of lithium hydroaluminate by distillation, the following precautions must be observed. A large fluid volume must be maintained in the distillation flask such solutions should never be concentrated so far that very little ether remains in the reaction flask. Distillations must be effected in a protective atmosphere. Cyclic ethers, and especially tetrahydropyran solutions of lithium hydroaluminate, present a far greater explosion risk than diethyl ether solutions. 

TATP and DADP neither detonate nor deflagrate they are rare entropy explosions. The effect is from rapid dissociation of weak atomic bonds within the acetone peroxide molecules, not from a chemical reaction as seen in all common explosives. Acetone peroxides require neither heat to form nor do they release heat when they dissociate the effect is similar to the solid-to-gas reaction that deploys automobile air bags. 

AMYL-METHYL-CETONE (French) (110-43-0) Forms explosive mixture with air (flash point 102°F/38°C). Violent reaction with strong oxidizers, aldehydes, nitric acid, perchloric acid. A variety of unstable peroxides may be formed from the reaction with hydrogen peroxide. Incompatible with aliphatic amines, aldehydes, strong bases, hydrogen peroxide, nitric acid, perchloric acid. Attacks some plastics and rubber. 

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