Explosive Peroxide

Forming Chemicals

2020

Prepared by Dr. Paul Rostron in

coordination with KH EHS
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Overview
• The hazard
• Identification and when to call the bomb squad
• Classes of chemicals and recommended shelf life
• Peroxide measurement
• Control measures
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The Hazard
• Several chemicals can age to form dangerous byproducts.
• Ethers can react to form peroxides.
• Light (UV) and the absence of water (dry ether) promotes peroxide
formation.
• These peroxides are shock and heat sensitive and can explode
• All bottles of ether should be tested for peroxide levels on a monthly basis.
• Ethers should never be evaporated to dryness, e.g. rotary evaporator.
• We can identify three classes or groups of peroxides- forming chemicals.
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Warning Call Bomb Squad

• Any ether bottles that show stratified layers
• White crystals in the bottle
• Or white crystals on the cap
• SHOULD NOT BE TOUCHED OR MOVED
• Call EHS for professional evaluation and
subsequent removal by the bomb squad
• Ethers in metal cans
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Class A Chemicals: Severe Peroxide Hazard

• Butadiene (liquid monomer) • These chemicals spontaneously
decompose to form peroxides without
• Isopropyl ether
exposure to air.
• Sodium amide (sodamide)
• After opening they should be disposed
• Chloroprene (liquid monomer) of after 3 months
• Potassium amide • Dispose of unopened bottles 1 year after
• Tetrafluoroethylene (liquid monomer) manufacture

• Divinyl acetylene
• Potassium metal
• Vinylidene chloride
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Class B: Moderate Hazard

• These chemicals form explosive peroxides upon concentration, i.e. distillation or rotary
evaporation.
• Disposal 6 months after opening and 1 year after manufacture

Acetal Diacetylene Methyl methacrylate 3-Methyl-1-butanol

Acetaldehyde Dicyclopentadiene Other secondary alcohols 4-Heptanol
Acrylonitrile Diethyl ether Tetrahydrofuran 4-Methyl-2-pentanol
Benzyl alcohol Diethylene glycol dimethyl Tetrahydronaphthalene 4-Penten-1-ol
ether (diglyme)
Cumene Vinyl ethers
Dioxanes
Cyclohexanol 1-Phenylethanol
Ethylene glycol dimethyl ether
Chlorotrifluoroethylene 2-Butanol
(glyme)
Chloroprene 2-Cyclohexen-1-ol
Furan
Cyclohexene 2-Hexanol
Methyl isobutyl ketone
Decahydronaphthalene 2-Pentanol
Methylacetylene
2-Phenylethanol
Methylcyclopentane
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Class C: Shock and Heat Sensitive

• Highly reactive and can auto-polymerize as a result of internal peroxide accumulation.
The peroxides formed in these reactions are extremely shock and heat sensitive.
• Disposal 6 months after opening and 1 year after manufacture

Acrylic acid Acrylonitrile

Chlorotrifluoroethylene Methyl methacrylate
Vinyl acetate Vinylacetylene (gas)
Butadiene (gas) Chloroprene
Styrene Vinylpyridine Tetrafluoroethylene
(gas)
Vinyladiene chloride
Vinyl chloride (gas)
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Ether Peroxide Explosions

Controlled Detonation Lab Explosion

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Testing for Peroxides

• Iodide Tests. The presence of most (but not all) peroxy compounds, including
hydroperoxides, can be detected by this method: Add 1 mL of the liquid to be
tested to an equal volume of glacial acetic acid in a test tube, add a few drops of
freshly prepared 5% aqueous potassium iodide solution and shake. A yellow color
indicates a low concentration of peroxide (40-100 ppm as hydrogen peroxide). A
brown color indicates higher concentration of peroxide. Run a blank to make sure
the test is really positive. (The test solution has a very short shelf life and will give
high blank values if stored for any length of time). Alternatively, addition of 1 mL of
a freshly prepared 10% aqueous solution of potassium iodide to10 mL of an
organic liquid in a 25 mL glass cylinder should produce a yellow color if peroxides
are present.
• Add 0.5mL 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.
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Control Measures
• Restrict purchases to 3 months supply
• No larger than 1 L bottle size
• Disposal through EHS unless no peroxides detected
• Receipt date and opened date written on the bottle
• Dark amber glass bottles, not opaque, no ground glass joints
• Monthly testing for peroxides and test result written on the bottle
• High peroxide concentration > 100 ppm must be disposed of immediately
• Any visible signs of crystals and the bottle must be treated as a potential bomb
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Recommended Work Practices

• Determine if the chemical in question poses a risk of forming peroxides.
• Inventory all chemical storage at least twice a year.
• Test all bottles containing ethers for peroxide levels on a monthly basis.
• Label containers with the date received, the date first opened and the date for disposal as recommended by
the supplier.
• Minimize peroxide formation in ethers by storing in tightly sealed containers placed in a cool place in the
absence of light. Do not store ethers at or below the temperature at which the peroxide freezes or the solution
precipitates.
• Choose the size container that will ensure use of the entire contents within a short period of time.
• Visually or chemically check for peroxides of any opened containers before use.
• Clean up spills immediately.
• More robust PPE and engineering controls may be required when working with peroxides and peroxide
forming compounds. Please contact EHS for a full risk assessment.
• Do not concentrate solutions that may contain peroxides. For example, rotary evaporation of an etheryl
solvent such as tetrahydrofuran or diethyl ether could pose a significant risk.
• Always purchase solvents that are inhibited against peroxide formation. Remove inhibitors using column
purification. If inhibitor free solvent must be purchased, follow all documented instructions for use and always
purge with nitrogen before storage.
• Do not use metal spatulas or magnetic stirring bars (which may leach out iron) with peroxide forming
compounds, since contamination with metals can lead to explosive decomposition. Ceramic, Teflon or wooden
spatulas and stirring blades are usually safe to use.
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Labelling
Label all Peroxide-Forming Chemicals (PFCs) with the following information:
 Date received
 Date opened
 Discard by date
 Peroxide test date (if open) and results
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