Heavy metal azides are notoriously explosive and should be handled by trained personnel. Silver azide (and also fulminate) can be generated from Tollens reagent, which is often found in undergraduate laboratories. Sodium azide is explosive only when heated to near its decomposition temperature (300 °C), but heating it should be avoided. Sodium azide should never be flushed down the drain. This practice has caused serious accidents because the azide can react with lead or copper in the drain lines to produce an azide that may explode. It can be destroyed by reaction with nitrous acid:
Procedure for destruction of sodium azide:
The operation must be carried out in a hood because of the formation of toxic nitric oxide. An aqueous solution containing no more than 5% sodium azide is put into a three-necked flask equipped with a stirrer and a dropping funnel. Approximately 7 mL of 20% aqueous solution of sodium nitrite (40% excess) per gram of sodium azide is added with stirring. A 20% aqueous solution of sulfuric acid is then added gradually until the reaction mixture is acidic to litmus paper. (CAUTION: The order of addition is essential. Poisonous, volatile hydrazoic acid (HN3) will evolve if the acid is added before the nitrite.) When the evolution of nitrogen oxides ceases, the acidic solution is tested with starch iodide paper. If it turns blue, excess nitrite is present, and the decomposition is complete. The reaction mixture is washed down the drain.
Alkali metals react violently with water, with common hydroxylic solvents, and with halogenated hydrocarbons. They should always be handled in the absence of these materials. The metals are usually destroyed by controlled reaction with an alcohol. The final aqueous alcoholic material can usually be disposed of in the sanitary sewer.
Procedure for destruction of alkali metals:
Waste sodium is readily destroyed with 95% ethanol. The procedure is carried out in a three-necked, round-bottomed flask equipped with a stirrer, dropping funnel, condenser, and heating mantle. Solid sodium should be cut into small pieces with a sharp knife while wet with a hydrocarbon, preferably mineral oil, so that the unoxidized surface is exposed. A dispersion of sodium in mineral oil can be treated directly. The flask is flushed with nitrogen and the pieces of sodium placed in it. Then 13 mL of 95% ethanol per gram of sodium are added at a rate that causes rapid refluxing. (CAUTION: Hydrogen gas is evolved and can present an explosion hazard. The reaction should be carried out in a hood, behind a shield, and with proper safeguards (such as in Chapter 5, sections 5.G.4 and 5.G.5) to avoid exposing the effluent gas to spark or flame. Any stirring device must be spark-proof.) Stirring is commenced as soon as enough ethanol has been added to make this possible. The mixture is stirred and heated under reflux until the sodium is dissolved. The heat source is removed, and an equal volume of water added at a rate that causes no more than mild refluxing. The solution is then cooled, neutralized with 6 M sulfuric or hydrochloric acid, and washed down the drain.
To destroy metallic potassium, the same procedure and precautions as for sodium are used, except that the less reactive t-butyl alcohol is used in the proportion of 21 mL/g of metal. (CAUTION: Potassium metal can form explosive peroxides. Metal that has formed a yellow oxide coating from exposure to air should not be cut with a knife, even when wet with a hydrocarbon, because an explosion can be promoted.) If the potassium is dissolving too slowly, a few percent of methanol can be added gradually to the refluxing t-butyl alcohol. Oxide-coated potassium sticks should be put directly into the flask and decomposed with t-butyl alcohol. The decomposition will require considerable time because of the low surface/volume ratio of the metal sticks.
Lithium metal can be treated by the same procedure, but using 30 mL of 95% ethanol per gram of lithium. The rate of dissolution is slower than that of sodium.
Metal catalysts such as Raney nickel and other fine metal powders can be slurried into water; dilute hydrochloric acid is then added carefully until the solid dissolves. Depending on the metal and on local regulations, the solution can be discarded in the sanitary sewer or with other hazardous or nonhazardous solid waste. Precious metals should be recovered from this process.
Liquid halides, such as TiCl4 and SnCl4, can be added to well-stirred water in a round-bottomed flask cooled by an ice bath as necessary to keep the exothermic