most hazardous substances commonly handled in laboratories, especially as initiators for free-radical reactions. Although they are low-power explosives, they are hazardous because of their extreme sensitivity to shock, sparks, and other forms of accidental detonation. Many peroxides that are handled routinely in laboratories are far more sensitive to shock than most primary explosives (e.g., TNT), although many have been stabilized by the addition of compounds that inhibit reaction. Nevertheless, even low rates of decomposition may automatically accelerate and cause a violent explosion, especially in bulk quantities of peroxides (e.g., benzoyl peroxide). These compounds are sensitive to heat, friction, impact, and light, as well as to strong oxidizing and reducing agents. All organic peroxides are highly flammable, and fires involving bulk quantities of peroxides should be approached with extreme caution.

Precautions for handling peroxides include the following:

  • Limit the quantity of peroxide to the minimum amount required. Do not return unused peroxides to the container.

  • Clean up all spills immediately. Solutions of peroxides can be absorbed on vermiculite or other absorbing material and disposed of harmlessly according to institutional procedures.

  • The sensitivity of most peroxides to shock and heat can be reduced by dilution with inert solvents, such as aliphatic hydrocarbons. However, do not use aromatics (such as toluene), which are known to induce the decomposition of diacyl peroxides.

  • Do not use solutions of peroxides in volatile solvents under conditions in which the solvent might be vaporized because this will increase the peroxide concentration in the solution.

  • Do not use metal spatulas to handle peroxides because contamination by metals can lead to explosive decomposition. Magnetic stirring bars can unintentionally introduce iron, which can initiate an explosive reaction of peroxides. Ceramic, Teflon, or wooden spatulas and stirring blades may be used if it is known that the material is not shock-sensitive.

  • Do not permit smoking, open flames, and other sources of heat near peroxides. It is important to label areas that contain peroxides so that this hazard is evident.

  • Avoid friction, grinding, and all forms of impact near peroxides, especially solid peroxides. Glass containers that have screw-cap lids or glass stoppers should not be used. Polyethylene bottles that have screw-cap lids may be used.

  • To minimize the rate of decomposition, store peroxides at the lowest possible temperature consistent with their solubility or freezing point. Do not store liquid peroxides or solutions at or lower than the temperature at which the peroxide freezes or precipitates because peroxides in these forms are extremely sensitive to shock and heat.

  • If a container of peroxide-forming material is past its expiration date, and there is a risk that peroxides may be present, open it with caution and dispose of it according to institutional procedures (see section 5.G.3.2).

  • Test for the presence of peroxides if there is a reasonable likelihood of their presence and the expiration date has not passed (see section 5.G.3.1).

(Also refer to Chapter 7, section 7.D.2.5.)

5.G.3.1 Peroxide Detection Tests

The following tests can detect most (but not all) peroxy compounds, including all hydroperoxides:

  • Add 1 to 3 milliliters (mL) of the liquid to be tested to an equal volume of acetic acid, add a few drops of 5% aqueous potassium iodide solution, and shake. The appearance of a yellow to brown color indicates the presence of peroxides. Alternatively, addition of 1 mL of a freshly prepared 10% solution of potassium iodide to 10 mL of an organic liquid in a 25-mL glass cylinder should produce a yellow color if peroxides are present.

  • Add 0.5 mL of the liquid to be tested to a mixture of 1 mL of 10% aqueous potassium iodide solution and 0.5 mL of dilute hydrochloric acid to which has been added a few drops of starch solution just prior to the test. The appearance of a blue or blue-black color within a minute indicates the presence of peroxides.

  • Peroxide test strips, which turn to an indicative color in the presence of peroxides, are available commercially. Note that these strips must be air dried until the solvent evaporates and then exposed to moisture for proper operation.

None of these tests should be applied to materials (such as metallic potassium) that may be contaminated with inorganic peroxides.

5.G.3.2 Disposal of Peroxides

Pure peroxides should never be disposed of directly but must be diluted before disposal. Small quantities (25 g or less) of peroxides are generally disposed of by dilution with water to a concentration of 2% or less, after which the solution is transferred to a polyethylene

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