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Chemicals in this group can form peroxides over time and can become sensitive to heat, shock, and/or friction. Accumulation of peroxide formers in the laboratory has resulted many documented lab accidents. Peroxide formation is an autoxidation reaction that can be initiated by light, heat, concentration, contamination, and/or loss of an inhibitor. Peroxide‐forming chemicals are divided into three categories (Class A, B, and C) outlined in the tables below.

The chemicals listed below should be tested for the formation of peroxides on a periodic basis and documented in a testing log. Information documented shall include the name, manufacturer, lot number, and chemical inventory # of the tested chemical, the method of

testing, and results. Lab Safety inspectors may request to see documentation of testing when observing any PFC container that is improperly dated and/or expired.

Class 1 PFC (Storage)

This group forms explosive levels of peroxides without concentration; these are the most hazardous and can form explosive peroxide levels even if not opened.

Several methods are available to check for peroxides; the two most common are the use of peroxide test strips or the potassium iodide test. These chemicals shall be tested for peroxide formation or discarded after 3 months of receiving the chemicals.

* Indicates a peroxide former when stored as a liquid monomer.

Peroxides From Storage
Butadiene *
Chloroprene *
Divinyl acetylene
Isopropyl ether
Potassium amide
Potassium metal
Sodium amide
Tetrafluoroethylene *
Vinyldiene chloride

Class 2 PFC (Concentrated)

This group of chemicals will readily form peroxides when they become concentrated (e.g., via evaporation or distillation). The concentration process defeats the action of most auto‐oxidation inhibitors. As a result, these chemicals shall be tested for peroxide formation or disposed of within 12 months of receiving.

Peroxides from Concentration
Acetal
Acetalaldehyde
Benzyl alcohol
Chlorofluoroethylene
Cumene (isopropylbenzene)
Cyclohexene
2-Cyclohexen-1-ol
Cyclopentene
Decahydronaphthalene (decalin)
Diacetylene (butadiyne)
Dicyclopentadiene
Diethylene glycol dimethyl ether (diglyme)
Dioxane
Ethyl ether
Furan
4-Heptanol
2-Hexanol
Methyl acetylene
3-Methyl-1-butanol
Methyl-isobutyl ketone
Methylcyclopentane
2-Pentanol
4-Penten-1-ol
Phenylethanol
Tetrahydrofuran
Tetrahydronaphthalene
Vinyl ethers
Other secondary alcohols

Class 3 PFC (Polymerization)

This group of chemicals forms peroxides due to initiation of polymerization. When stored in a liquid state, the peroxide forming potential dramatically increases. Liquids shall be tested for peroxide formation or discarded after 6 months, gases after 1 year.

** Can form explosive levels of peroxides if stored as a liquid. When stored as gas, peroxide accumulation may cause autopoly- merization.

Peroxides from Polymerization
Acrylic acid
Acrylonitrile
Butadiene **
Chlorobutadiene
Chloroprene **
Chlorotrifluoroethylene
Styrene
Tetrafluoroethylene **
Vinyl acetate
Vinyl acetylene
Vinyl chloride
Vinyl pyridine
Vinyldiene chloride

References

Clark, Donald E., Peroxides and Peroxide Forming Compounds, 2000. Texas A&M University. Boston University

Work Practices

  • Never work alone with peroxide forming chemicals.
  • Due to the strict limitations on prolonged storage of peroxide formers, do not order large containers, only order the amount of peroxide formers you need for planned or foreseeable experiments.
  • Always keep a testing record for peroxide forming chemicals including the date received, date opened, and date last tested. Each bottle should be labeled with this information.
  • Review the Safety Data Sheets (SDSs) for all chemicals used in the experiment.
  • All manipulations of peroxide formers should be conducted in containment devices (e.g. fume hoods, gloveboxes, or similar devices). When working in a fume hood keep the sash as low as possible.
  • If there is a high probability of fire or explosion a portable blast shield inside the fume hood is recommended.
  • Test for peroxides before any distillation or purification of peroxide forming chemicals. Use extreme caution when concentrating or purifying peroxide forming chemicals as explosions can occur (https://ehs.uci.edu/safety/pdfs/lesson‐learned_peroxide.pdf).
  • Never allow peroxide formers to evaporate to dryness, such as during distillation, always leave a minimum of 20% liquid.
  • Peroxide crystals formed in a chemical container are particularly likely to accumulate within the threads of the screw cap and may explode when subject to heat, light, friction, or mechanical shock (e.g. unscrewing the cap). Never open, move, or disturb a bottle that is suspected to have peroxides.
  • For liquids evidence of possible peroxide formation includes formation of solids or crystals, visible discoloration, and liquid stratification.
  • For solids evidence of possible peroxide formation includes formation of a surface crust, and discoloration of the solid.
  • Alkali metals and amides should be evaluated based on visual criteria only. There are no peroxide tests that can be used on these materials.
  • Never open, disturb, or move a container suspected of having peroxides, immediately notify UK EQMD (859) 323‐ for evaluation or disposal.

 

NOTE: The use of certain concentrations of perchloric acid must be performed in a fume hood equipped with washdown facilities.

Storage Guidance for PFC

  • Label every container of peroxide forming chemicals with the date received, date opened, and date last tested.
  • Segregateperoxide forming chemicals from incompatible materials.
  • Store away from ignition and initiation sources such as flames, static electricity, heat, and light.
  • Peroxide forming chemicals should be stored in their original manufacturer’s container.
  • Minimize the quantity of peroxide forming chemicals stored in the lab.
  • If possible, keep the material under an inert atmosphere (e.g. nitrogen, argon) when not in use, except for chemicals that contain an inhibitor that requires oxygen to function.