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Oklahoma State University

Peroxide Forming Chemicals

Peroxide-Forming Chemicals

Peroxide-forming chemicals are compounds that have the capability to form explosive peroxides. Many of these peroxide-forming chemicals are commonly used organic solvents, but when they are allowed to form peroxides, they can become more shock-sensitive than TNT. Users of these chemicals should pay special attention to when the chemical was received, when the chemical was opened, and when the chemical should be tested for peroxide concentration. Some common peroxide forming chemicals are listed in the table below.

Classes of Peroxide-Forming Chemicals

Class A: Chemicals that form explosive peroxides without concentration

(Should be discarded or evaluated for peroxides within 3 months of the opening date. If unopened, should be stored for no more than 18 months.)

Isopropyl ether

Sodium amide (sodamide)

Butadiene

Tetrafluoroethylene

Chlorobutadiene (chloroprene)

Divinyl acetylene

Potassium amide

Vinylidene chloride

Potassium metal

 

Class B: Chemicals that form peroxides upon concentration (distillation/evaporation)  

(Should be discarded or evaluated for peroxides within 12 months of the opening date. If unopened, should be stored for no more than 18 months.)

Acetal

Dioxane (p-dioxane)

Cumene

Ethylene glycol dimethyl ether (glycol)

Cyclohexene

Furan

Cyclooctene

Methyl acetylene

Cyclopentene

Methyl cyclopentane

Diaacetylene

Methyl isobutyl ketone

Dicyclopentadiene

Tetrahydrofuran

Diethylene glycol dimethyl ether (diglyme)

Tetrahydronaphthalene

Diethyl ether

Vinyl ethers

Class C: Unsaturated monomers that may autopolymerize as a result of peroxide accumulation if inhibitors have been removed or are depleted

(Uninhibited materials should not be stored for longer than 24 hours. Opened, inhibited materials should be discarded or evaluated within 12 months. If unopened, should be stored for no more than 18 months.)

Acrylic acid

Styrene

Butadiene

Vinyl acetate

Chlorotrifluoroethylene

Vinylacetylene

Ethyl acrylate

Vinyl chloride

Methyl methacrylate

Vinyl pyridine

 *This table is not all inclusive, but includes common peroxide-forming chemicals found at OSU

Inventory and Purchasing

When purchasing a peroxide-forming chemical, consider chemicals inhibited with butylated hydroxytoluene (BHT). Also, only purchase the amount needed for the storage timeframe given for the class of peroxide-forming chemical. Not only is this the safer practice, but it is much more cost effective than disposing of a chemical that has a high peroxide concentration.

Labeling

It is very important when using peroxide-forming chemicals to list the date received, the date opened, and the date tested on the bottle. EHS has created some labels for this purpose.

Testing

Methods for testing for peroxides are listed in the OSU Laboratory Safety Manual. It is important to note that these methods should not be used on peroxide-forming chemicals that show signs of shock-sensitivity. If the concentration of peroxides is greater than 25 ppm, the chemical is not recommended for distillation or concentration. If the concentration of peroxides is greater than 100 ppm, contact EHS for disposal and avoid handling the chemical. Chemical Removal Request Form.

Storage and Use

Store peroxide-forming chemicals in airtight bottles, away from light and heat. Avoid using containers with loose-fitting lids and ground glass stoppers. If crystallization, discoloration, or stratification are present, the chemical may have become shock-sensitive. Do not use or move the container, and contact EHS.

 

Useful Links:

Sigma Aldrich: Peroxide-Forming Chemicals

Kelly, R.J, Review of Safety Guidelines for Peroxidizable Organic Compounds, Chemical Health and Safety, 1996, 3 (5), 28-36.

Prudent Practices in the Laboratory: Handling and Management of Chemical Hazards. Washington, D.C.: National Academies, 2011.