sure may build up and adequate venting is required. If the liquid is flammable (e.g., hydrogen and methane), explosive concentrations may develop without warning unless an odorant has been added. Flammability, toxicity, and pressure buildup become more serious on exposure of gases to heat.
4.D.2 Reactive Hazards
4.D.2.1 Water Reactives
Water-reactive materials are those that react violently with water. Alkali metals (e.g., lithium, sodium, and potassium), many organometallic compounds, and some hydrides react with water to produce heat and flammable hydrogen gas, which ignites or combines explosively with atmospheric oxygen. Some anhydrous metal halides (e.g., aluminum bromide), oxides (e.g., calcium oxide), and nonmetal oxides (e.g., sulfur trioxide), and halides (e.g., phosphorus pentachloride) react exothermically with water, resulting in a violent reaction if there is insufficient coolant water to dissipate the heat produced.
For pyrophoric materials, oxidation of the compound by oxygen or moisture in air proceeds so rapidly that ignition occurs. Many finely divided metals are pyrophoric, and their degree of reactivity depends on particle size, as well as factors such as the presence of moisture and the thermodynamics of metal oxide or metal nitride formation. Other reducing agents, such as metal hydrides, alloys of reactive metals, low-valent metal salts, and iron sulfides, are also pyrophoric.
4.D.2.3 Incompatible Chemicals
Accidental contact of incompatible substances results in a serious explosion or the formation of substances that are highly toxic or flammable or both. Although trained laboratory personnel question the necessity of following storage compatibility guidelines, the reasons for such guidelines are obvious after reading descriptions of laboratories following California earthquakes in recent decades [see Pine (1994)]. Those who do not live in seismically active zones should take these accounts to heart, as well. Other natural disasters and chemical explosions themselves can set off shock waves that empty chemical shelves and result in inadvertent mixing of chemicals.
Some compounds pose either a reactive or a toxic hazard, depending on the conditions. Thus, hydro-cyanic acid (HCN), when used as a pure liquid or gas in industrial applications, is incompatible with bases because it is stabilized against (violent) polymerization by the addition of acid inhibitor. HCN can also be formed when cyanide salt is mixed with an acid. In this case, the toxicity of HCN gas, rather than the instability of the liquid, is the characteristic of concern.
Some general guidelines lessen the risks involved with these substances. Concentrated oxidizing agents are incompatible with concentrated reducing agents. Indeed, either may pose a reactive hazard even with chemicals that are not strongly oxidizing or reducing. For example, sodium or potassium, strong reducing agents frequently used to dry organic solvents, are extremely reactive toward halocarbon solvents (which are not strong oxidizing agents). Strong oxidizing agents are frequently used to clean glassware, but they should be used only on the last traces of contaminating material. Because the magnitude of risk depends on quantities, chemical incompatibilities will not usually pose much, if any, risk if the quantity of the substance is small (a solution in an NMR tube or a microscale synthesis). However, storage of commercially obtained chemicals (e.g., in 500-g jars or 1-L bottles) should be carefully managed from the standpoint of chemical compatibility.
4.D.3 Explosive Hazards
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 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 4.7 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 decom-