Peroxide-Forming Chemicals
Some chemicals can form peroxides under normal storage conditions. Some of the peroxide chemicals are unstable, especially when dried or concentrated, and can explode violently when subjected to heat, light or mechanical shock. In addition, some of the inadvertently formed peroxides can initiate other unexpected violent reactions (e.g. polymerizations) with other chemicals.
When possible and practical for your work, purchase chemicals that have inhibitors added by the manufacturer. Label peroxide-forming chemicals with date received and date opened.
Store peroxide-formers in airtight opaque containers with screw caps. Consider oxygen exclusion methods such as purging with inert gas or sealing containers with parafilm.
Inspect containers for signs of peroxide formation. Do not open a container which has crystals or a visible cloudiness. Call EHS to come remove it. The friction caused by opening a lid can cause an explosion.
Liquids can be tested for presence of peroxide. This is especially important prior to distilation. Most explosions of peroxide forming chemicals occur when a material is distilled to dryness. Peroxide test kits are available from chemical vendors. Contact EHS for additional guidance.
Classification Table for Peroxide-Forming Chemicals
|
Class I: Unsaturated materials, especially those of low molecular weight, may polymerize violently and hazardously due to peroxide initiation. These chemicals can spontaneously decompose, becoming explosive after exposure to air with concentration. Discard unopened containers within 3 months. Opened containers should be tested for peroxides every 2 months. |
||
|
Acrylic acid |
Tetrafluoroethylene |
|
Acrylonitrile |
Vinyl acetate |
|
1,3-Butadiene |
Vinyl acetylene |
|
Chlorobutadiene (chloroprene) |
Vinyl chloride |
|
Chlorotrifluoroethylene |
Vinyl pyridine |
|
Methyl methacrylate |
Vinylidiene chloride |
|
Styrene |
|
|
Class II: The following chemicals are a peroxide hazard upon concentration (distillation/evaporation). A test for peroxide should be performed if concentration is intended or suspected. Discard unopened containers within 6 months. Opened containers should be tested for peroxides every 2 months. |
||
|
|
||
|
Acetal |
Diethylene glycol dimethyl ether (diglyme) |
Isopropyl alcohol |
|
Acetaldehyde |
Diethyl ether |
Isopropyl propyl ether |
|
Acrylamide |
Diethyl fumatate |
Isopropyl vinyl ether |
|
Allyl ethyl ether |
Diethylketene | 2-Isopropylacryladehyde oxime |
|
Allyl phenyl ether |
2,3-Dihydrofuran |
Isovaleraldehyde |
|
Allyl vinyl ether |
2,3-Dihydropyran |
Limonene |
|
1-Allyloxy-2,3-epoxypropane |
1,1-Dimethoxyethane | 1,5-p-Mentadiene |
|
Benzyl-1-naphthyl ether | 1,2-Dimethoxyethane | Methoxy-1,3,5,7-cyclooctatetraene |
|
Benzyl butyl ether | 2,2-Dimethoxypropane | 1-Methoxyethanol |
| Benzyl ethyl ether | 3,3-Dimethoxypropane | 2-Methoxyethyl vinyl ether | |
| Bis(2-ethoxyethyl ether | 2,2-Dimethyl-1,3-dioxolane |
Methyl acetylene |
|
| Bis(2-ethoxymethyl)ether | 2,6-Dimethyl-1,4-dioxane |
Methyl cyclopentane |
|
| 2-Butanol | 1,3-Dioxane | 4-Methyl-1,3-dioxane | |
| Buten-3-yne | 1,4-Dioxane | 2-(1-Methylheptyl)-4,6-dinitrophenyl ether | |
| Butyl ethyl ether | 1,2-Dioxep-5-ene |
Methylisobutyl ketone |
|
| Butyl formate | 1,3-Dioxol-4-3n-2-one | 2,3-Methyl-2-methylene butanal | |
| Butyl vinyl ether | Dipropoxymethane | 4-Methyl-2-pentanone | |
| 1-Chloro-2,2-diethoxyethane | Dipropylether | 2-Methyltetrahydrofuran | |
| 2-Chloroacrynitrile | Di(2-propynyl)ether | Methyl vinyl ether | |
| 2-Chloroethyl vinyl ether | 1,2-Epoxy-3-isopropoxy propane | 2-Penten-4-yn-3-ol | |
| Cinnamaldehyde | 1-Ethoxy-2-propyne | α-Pentylcinnamaldehyde | |
| Crotonaldehyde | 2-Ethoxyethanol | 2-Propanol | |
| Cumene | 2-Ethyl butanal | Propionaldehyde | |
| Cyclohexene | Ethyl isopropyl ether | 2-Propyne-1-thiol | |
| Cyclooctene | Ethyl propenyl ether | Sodium 5,8,11,14-eicosatetraenoate | |
| Cyclopentene | Ethyl vinyl ether | Sodium ethoxyacetylide | |
| Cyclopropyl methyl ether | 2-Ethylacryladehyde oxime | 1,1,2,3-Tetrachloro-1,3-butadiene | |
| Diacetylene |
Ethylene glycol dimethyl ether (glyme) |
Tetrahydrofuran | |
| Decahydronaphthalene | 2-Ethylhexanal | Tetrahydronaphthalene | |
| Decalin | 2-Ethylhexyl vinyl ether | Tetrahydropyran | |
| Diallyl ether | 2-Furaldehyde | Tetralin | |
| Dibenzyl ether | Furan | Tridecanal | |
| p-Dibenzyloxybenzene | 4,5-Hexadien-2-yl-1-ol | 1,3,3-Trimethoxypropene | |
| 1,2-DiBenzyoxyethane | 2,4-Hexadienal | 3,3,5-Trimethyl-2-cyclohexen-1-one | |
| Dibutyl ether | 2,5-Hexadiyn-1-ol | 4-Vinylcyclohexene | |
| Dicyclopentadiene | 2-Hexanal |
Vinyl ethers |
|
| 1,1-Diethoxyethane | Indole-2-carboxyaldehyde | ||
| 1,2-Diethoxyethane | Isobutyl vinyl ether | ||
| Diethoxymethane | Isobutyraldehyde | ||
| 3,3-Diethoxypropene | Isopropoxypropionitrile | ||
|
Class III: Peroxides derived from the following compounds may explode without concentration. |
|||
|
|
|||
| Organic |
Inorganic |
||
|
Divinyl ether |
Potassium metal |
||
|
Divinyl acetylene |
Potassium amide |
||
|
Isopropyl ether |
Sodium amide (sodamide) |
||
|
Vinylidene chloride |
|||
NOTE: Lists are illustrative but not exhaustive.
From Prudent Practices in the Laboratory, National Academy Press, 1995 and other sources.