wise addition of water to its solutions under nitrogen in a three-necked flask has frequently been used to decompose it, vigorous frothing often occurs. An alternative is to use 95% ethanol, which reacts less vigorously than water. A safer procedure is to decompose the hydride with ethyl acetate, because no hydrogen is formed.

To the hydride solution in a flask equipped with a stirrer, ethyl acetate is added slowly. The mixture sometimes becomes so viscous after the addition that stirring is difficult and additional solvent may be required. When the reaction with ethyl acetate has ceased, a saturated aqueous solution of ammonium chloride is added with stirring. The mixture separates into an organic layer and an aqueous layer containing inert inorganic solids. The upper, organic layer should be separated and disposed of as a flammable liquid. The lower, aqueous layer can often be disposed of in the sanitary sewer.

Decomposition of potassium or sodium hydride:

Potassium and sodium hydride (KH, NaH) in the dry state are pyrophoric, but they can be purchased as a relatively safe dispersion in mineral oil. Either form can be decomposed by adding enough dry hydrocarbon solvent (e.g., heptane) to reduce the hydride concentration below 5% and then adding excess t-butyl alcohol drop wise under nitrogen with stirring. Cold water is then added drop wise, and the resulting two layers are separated. The organic layer can be disposed of as a flammable liquid. The aqueous layer can often be neutralized and disposed of in the sanitary sewer.

Decomposition of sodium borohydride:

Sodium borohydride (NaBH4) is so stable in water that a 12% aqueous solution stabilized with sodium hydroxide is sold commercially. In order to effect decomposition, the solid or aqueous solution is added to enough water to make the borohydride concentration less than 3%, and then excess equivalents of dilute aqueous acetic acid are added drop wise with stirring under nitrogen.

Decomposition of calcium hydride:

Calcium hydride (CaH2), the least reactive of the materials discussed here, is purchased as a powder. It is decomposed by adding 25 mL of methyl alcohol per gram of hydride under nitrogen with stirring. When reaction has ceased, an equal volume of water is gradually added to the stirred slurry of calcium methoxide. The mixture is then neutralized with acid and disposed of in the sanitary sewer.

7.D.3.2 Inorganic Cyanides

Inorganic cyanides can be oxidized to cyanate using aqueous hypochlorite following a procedure similar to the oxidation of thiols. Hydrogen cyanide can be converted to sodium cyanide by neutralization with aqueous sodium hydroxide, and then oxidized.

Procedure for oxidation of cyanide:

An aqueous solution of the cyanide salt in an ice-cooled, three-necked flask equipped with a stirrer, thermometer, and dropping funnel is cooled to 4 to 10 °C. A 50% excess of commercial hypochlorite laundry bleach containing 5.25% (0.75 M) sodium hypochlorite is added slowly with stirring while maintaining the low temperature. When the addition is complete and heat is no longer being evolved, the solution is allowed to warm to room temperature and stand for several hours. The mixture can then be washed down the drain with excess water. The same procedure can be applied to insoluble cyanides such as cuprous cyanide (though copper salts should not be disposed of in the sanitary sewer). In calculating the quantity of hypochlorite required, the experimenter should remember that additional equivalents may be needed if the metal ion can be oxidized to a higher valence state, as in the reaction,

A similar procedure can be used to destroy hydrogen cyanide, but precautions must be taken to avoid exposure to this very toxic gas. Hydrogen cyanide is dissolved in several volumes of ice water. Approximately 1 molar equivalent of aqueous sodium hydroxide is added at 4 to 10 °C to convert the hydrogen cyanide into its sodium salt, and then the procedure described above for sodium cyanide is followed. (CAUTION: Sodium hydroxide or other bases, including sodium cyanide, must not be allowed to come into contact with liquid hydrogen cyanide because they may initiate a violent polymerization of the hydrogen cyanide.)

This procedure also destroys soluble ferrocyanides and ferricyanides. Alternatively, these can be precipitated as the ferric or ferrous salt, respectively, for possible landfill disposal.



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