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Environmental Management > Information & List of Peroxide-Formers

Peroxides are very unstable and some chemicals that can form them are commonly used in laboratories. This makes peroxide-forming materials some of the most hazardous substances found in a lab. Peroxide-forming materials are chemicals that react with air, moisture, or impurities to form peroxides. The tendency to form peroxides by most of these materials is greatly increased by evaporation or distillation. Organic peroxides are extremely sensitive to shock, sparks, heat, friction, impact, and light. Many peroxides formed from materials used in laboratories are more shock sensitive than TNT. Just the friction from unscrewing the cap of a container of an ether that has peroxides in it can provide enough energy to cause a severe explosion.


Use and Storage of Peroxide-Formers

1. Do not open the chemical container if peroxide formation is suspected.
    The act of opening the container could be sufficient to cause a severe
    explosion. Visually inspect liquid peroxide-forming materials for crystals or
    unusual viscosity before opening. Pay special attention to the area around
    the cap. Peroxides usually form upon evaporation, so they will most likely be
    formed on the threads under the cap.

2. Date all peroxide forming materials with the date received, and the expected
    shelf life. Chemicals such as diisopropyl ether, divinyl acetylene, sodium amide,
    and vinylidene chloride should be discarded after three months.

3. Store all peroxide-forming materials away from heat, sunlight, and sources of
    ignition. Sunlight accelerates the formation of peroxides.

4. Secure the lids and caps on these containers to discourage the evaporation
    and concentration of these chemicals.

5. Never store peroxide-forming materials in glass containers with screw cap lids
    or glass stoppers. Friction and grinding must be avoided. Also, never store
    these chemicals in a clear glass bottle where they would be exposed to light.

6. Contamination of an ether by peroxides or hydroperoxides can be detected
    simply by mixing the ether with 10% (wt/wt) aqueous potassium iodide
    solution - a yellow color change due to the oxidation of iodide to iodine
    confirms the presence of peroxides. Small amounts of peroxides can be
    removed from contaminated ethers via distillation from lithium aluminum
    hydride (LiAlH-4-), which both reduces the peroxide and removes
    contaminating water and alcohols. If you notice crystal formation in the
    container or around the cap, do not attempt to open or move the container.
    Call the Department of Environmental Health and Safety at 274-4351
    for proper disposal.

7. Never distill an ether unless it is known to be free of peroxides.

COMMON PEROXIDE-FORMING CHEMICALS

SEVERE PEROXIDE HAZARD ON STORAGE WITH EXPOSURE TO AIR

DISCARD WITHIN 3 MONTHS OF OPENING

Diisopropyl ether (isopropyl ether)   Potassium amide
Divinylacetylene (DVA)   Sodium amide (sodamide)
Potassium metal   Vinylidene chloride (1, 1-dichloroehtylene)


PEROXIDE HAZARD ON CONCENTRATION: DO NOT DISTILL OR EVAPORATE
WITHOUT FIRST TESTING FOR THE PRESENCE OF PEROXIDES

DISCARD OR TEST FOR PEROXIDES AFTER 6 MONTHS

HAZARD OF RAPID POLYMERIZATION INITIATED BY INTERNALLY FORM

Acetaldehyde diethyl acetal (acetal)   Ethylene glycol ether acetates
Cumene (isopropylbenzene)   Ethylene glycol monoethers (cello-solve)
Cyclohexane   Furan
Decalin (decahydronaphthalene)   Methylacetylene
Diacetylene (butadiene)   Methylecyclopentane
Dicyclopentadiene   Methyl isobutyl ketone
Diethyle ether (ether)   Tetrahydrofuran (THF)
Diethylene glycol dimethyl ether (diglyme)   Tetralin (tetrahydronaphthalene)
Dioxane   Vinyl ethers
Ethylene glycol dimethyl ether (glyme)
   

HAZARD OF RAPID POLYMERIZATION INITIATED BY
INTERNALLY FORMED PEROXIDES

Liquids:

DISCARD OR TEST FOR PEROIDES AFTER 6 MONTHS
 
Chloroprene (2-chloro-1,3-butadiene)   Vinyl acetate
Styrene   Vinylpyridine

Gases:

DISCARD AFTER 12 MONTHS
 
Butadiene   Vinylacetylene (MVA)
Tetraflouroethylene (TFE)   Vinyl chloride


 
Reference: Prudent Practices for Disposal of Chemicals from Laboratories, 1983 edition.


 
 
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This document was last modified December 2007
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