500-g jars or 1-L bottles) should be carefully managed from the standpoint of chemical compatibility.

3.D.3 Explosive Hazards

3.D.3.1 Explosives

An explosive is any chemical compound or mechanical mixture that, when subjected to heat, impact, friction, detonation, or other suitable initiation, undergoes rapid chemical change, evolving large volumes of highly heated gases that exert pressure on the surrounding medium. The term applies to materials that either detonate or deflagrate. Heat, light, mechanical shock, and certain catalysts initiate explosive reactions. Hydrogen and chlorine react explosively in the presence of light. Acids, bases, and other substances catalyze the explosive polymerization of acrolein, and many metal ions can catalyze the violent decomposition of hydrogen peroxide. Shock-sensitive materials include acetylides, azides, nitrogen triiodide, organic nitrates, nitro compounds, perchlorate salts (especially those of heavy metals such as ruthenium and osmium), many organic peroxides, and compounds containing diazo, halamine, nitroso, and ozonide functional groups.

Table 3.11 lists a number of explosive compounds. Some are set off by the action of a metal spatula on the solid; some are so sensitive that they are set off by the action of their own crystal formation. Diazomethane (CH2N2) and organic azides, for example, may decompose explosively when exposed to a ground glass joint. The mechanisms of the explosions of nitro-aromatic compounds have been reviewed by Brill and James (1993).

3.D.3.2 Peroxides

Organic peroxides are among the most hazardous substances handled in the chemical laboratory. They are generally low-power explosives that are sensitive to shock, sparks, or other accidental ignition. They are far more shock-sensitive than most primary explosives such as TNT.

Also potentially hazardous are compounds that undergo autooxidation to form organic hydroperoxides and/or peroxides when exposed to the oxygen in air (see Table 3.12). Especially dangerous are ether bottles that have evaporated to dryness. A peroxide present as a contaminant in a reagent or solvent can be very hazardous and change the course of a planned reaction. Autoxidation of organic materials (solvents and other liquids are most frequently of primary concern) proceeds by a free-radical chain mechanism. For the substrate R—H, the chain is initiated by ultraviolet


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