Environmental Health & Safety

Page 1 of 5

April 2009

Guidelines for Safe Handling and Disposal of Peroxide Forming Chemicals † ‡ There are several compounds/elements that can react with oxygen and become increasingly more dangerous upon prolonged storage because they tend to form explosive peroxides with age. These types of chemicals can be divided into two general chemical categories (TABLE 1). Peroxides may form in freshly distilled, undistilled, and unstabilized ethers in less than two weeks. Exposure of these types of chemicals to light, air, and heat may accelerate the formation of the peroxides. Many ethers tend to absorb and react with oxygen from the air to form unstable peroxides which may detonate with extreme violence when concentrated by evaporation or distillation. These ethers may also explode when combined with other compounds that produce a detonable mixture or when disturbed by heat, shock, or friction. Peroxides formed in compounds by auto-oxidation have caused many accidents, including the unexpected explosions of the residue of solvents after distillation. While ethers present one of the most commonly known peroxidizable compound risks, other common solvents such as isopropanol have exploded upon distillation due to peroxide concentration. Peroxide forming chemicals can be divided into four hazard classes based on the route of peroxide formation (TABLES 2-6). TABLE 1: ORGANIC COMPOUNDS FORMING PEROXIDES±

1. Ethers, acetals. 2. Olefins with allylic hydrogens, chloro- and fluoro-olefins, terpenes 3. Dienes, vinyl acetylenes. 4. Aldehydes. 5. Ureas, amides, lactams. 6. Vinyl monomers including vinyl halides, acrylates, methacrylates, vinyl esters. 7. Secondary alcohols

INORGANIC COMPOUNDS OR ELEMENTS

1. Alkali metals, particularly potassium. 2. Alkali metal alkoxides and amides. 3. Organometallics.

GUIDELINES FOR SAFE HANDLING AND DISPOSAL 1. PURCHASE Please DO NOT purchase large quantities of peroxide forming chemicals. Purchase the amount that you will use in a 3-6 month time period. When possible, purchase peroxide forming chemicals that have peroxide inhibitors added by the manufacturer. Label all peroxide forming chemicals with date received and date opened. 2. STORAGE Store peroxide forming chemicals in sealed, opaque, airtight containers with tight-fitting caps. DO NOT store these chemicals in open, partially empty, or transparent containers since these conditions promote peroxide formation. Store peroxide forming chemicals (especially those in TABLE 3) under nitrogen or other inert gas or in an inert atmosphere chamber. Note: Some inhibitors, such as BHT, actually need small amounts of oxygen to prevent peroxide formation and it is recommended that inhibited chemicals are not stored under an inert atmosphere. Always follow the manufacturer’s recommendations. With all peroxide forming chemicals, it is preferable to use small containers that can be completely emptied, rather than take small amounts from a large container over time. Materials should be stored in amber bottles or other opaque containers and under a blanket of inert gas, such as nitrogen or argon, or over a reducing agent to inhibit formation of peroxides. Containers of ether and other peroxide forming chemicals in Tables 3, 4, & 5 should be labeled with date received and date opened. (See sample label immediately below)

Environmental Health & Safety

Page 2 of 5

April 2009

3. HANDLING AND USE Test for the presence of peroxides before distilling peroxide forming chemicals. Most explosions of peroxide forming chemicals occur when a material is distilled to dryness (leave at least 10-20% in bottoms). Stir distillations with a mechanical stirrer or a bubbling inert gas. Never use air or an oxygen-containing mixture for bubbling or stirring a peroxide forming chemical. DO NOT OPEN the container of a peroxide forming chemical that has obvious crystal formation; the friction caused by opening a crystallized lid can cause an explosion. Do not handle the container or force open the lid. Treat as potentially explosive material. CALL EH&S IMMEDIATELY at 314-362-6816. 4. DISPOSAL With the exception of those provided in TABLE 3, discard all peroxide forming chemicals within 12 months of opening (or within 18 months if unopened). All peroxide forming chemicals must be properly disposed through the University’s chemical waste program. If the peroxide forming chemical has crystal formation, CALL EH&S IMMEDIATELY at 314-362-6816. Any additional charges for handling expired/unstable materials through our waste vendor will be charged back to the appropriate department or lab. Charges can range from $1800 to $3500.

Peroxidizable Chemical

Classification Disposal Timeline

Unopened chemicals from the

manufacturer

18 months after receipt or

printed manufacturer’s

expiration date (earliest)

Opened containers

Table 3 Chemicals 3 months

Table 4 Chemicals 12 months

Table 5 Chemicals 12 months

Table 6 Chemicals Inspect periodically

Note: Never open or test containers of unknown origin or age, or

those that have visible evidence of peroxides!

TABLE 2:

Environmental Health & Safety

Page 3 of 5

April 2009

5. OPTIONAL TESTING OF MATERIALS FOR PEROXIDES Laboratories can petition EH&S to keep potential peroxide forming materials which are rare/expensive or critical to the function of the lab past the original expiration date. Chemicals which have lasted beyond the recommended shelf life but have been tested and show no detectable peroxides, or whose peroxide concentrations are less than 100 ppm, may be retained but should be tested according to TABLE 2 above. For a list of detection techniques see R. J. Kelly’s article, "Review of Safety Guidelines for Peroxidizable Organic Chemicals," published in Chemical Health & Safety. Always visually inspect the integrity of the material prior to testing. Old bottles may contain concentrated peroxides, or peroxides may have crystallized in the cap threads, which would present a serious hazard when opening the bottle for testing. Dispose of any chemicals found to have a peroxide concentration greater than or equal to 100 parts per million. Testing date and results for materials listed in Tables 3, 4, & 5 must be recorded on the container (see sample label immediately below) and method of testing/results must be kept in the “Blue Book”. Contact EH&S for removal of old containers. Remember to test all peroxide formers prior to distillation, regardless of age.

LIST OF PEROXIDE FORMING CHEMICALS (CAS #) TABLE 3: Severe Peroxide Hazard. These are chemicals that can spontaneously decompose, becoming explosive after exposure to air without concentration. These chemicals must be stabilized or decontaminated and discarded within 3 months of opening. This list is not all inclusive! Isopropyl ether (108-20-3) Potassium amide (17242-52-3) Divinylacetylene (31014-03-6) Potassium metal (7440-09-7) Sodium amide (7782-92-5) Vinylidene chloride (75-35-4) Butadiene (106-99-0) (liquid) Chloroprene (126-99-8) (liquid) Tetrafluoroethylene (116-14-3) (liquid) TABLE 4: Concentration Hazard. These chemicals typically require external energy for spontaneous decomposition, forming explosive peroxides when distilled, evaporated or otherwise concentrated. The formation of peroxides in these chemicals is also highly dependent on the amount of head space (air/oxygen) that exists in the container. These chemicals must be discarded within 12 months of opening. This list is not all inclusive! Acetal (105-57-7) Diethyl ether (60-29-7) 2-Pentanol* (6032-29-7)

Environmental Health & Safety

Page 4 of 5

April 2009

Acetaldehyde (75-07-0) Diethylene glycol dimethyl ether 111-96-6) 4-Penten-1-ol (821-09-0) Benzyl alcohol (100-51-6) Dioxanes (123-91-1) or (505-22-6) 1-Phenylethanol (98-85-1) 2-Butanol* (78-92-2) Ethylene glycol dimethyl ether (110-71-4) 2-Phenylethanol (60-12-8) Cumene (98-82-8) 4-Heptanol* (589-55-9) 2-Propanol* (67-63-0) Cyclohexanol* (108-93-0) 2-Hexanol* (626-93-7) Tetrahydrofuran (109-99-9) 2-Cyclohexen-1-ol (822-67-3) Methylacetylene (74-99-7) Tetrahydronaphthalene (119-64-2) Cyclohexene (110-83-8) 3-Methyl-1-butanol* (123-51-3) Vinyl ethers Decahydronaphthalene (91-17-8) Methylcyclopentane (96-37-7) Other secondary alcohols* Diacetylene (460-12-8) Methyl isobutyl ketone (108-10-1) Dicyclopentadiene (77-73-6) 4-Methyl-2-pentanol* (108-11-2) * note = typically form very slowly unless concentrated by processes such as distillation. Should be monitored periodically for peroxide concentration. TABLE 5: Shock and Heat Sensitive. These chemicals are highly reactive and can autopolymerize as a result of internal peroxide accumulation. The peroxides formed in these reactions are extremely shock and heat sensitive. The liquid chemicals in this group should be discarded within 12 months of opening. This list is not all inclusive! Acrylic acid (79-10-7) Methyl methacrylate (80-62-6) Vinyl chloride (75-01-4) (gas) Acrylonitrile (107-13-1) Styrene (100-42-5) Vinylpyridine (100-69-6) Butadiene (106-99-0) (gas) Tetrafluoroethylene (116-14-3) (gas) Vinylidiene chloride (75-35-4) Chloroprene (126-99-8) Vinyl acetate (108-05-4) Chlorotrifluoroethylene (79-38-9) (gas) Vinylacetylene (689-97-4) (gas) TABLE 6: Potential Peroxide Forming Chemicals. There are over 200 organic and inorganic compounds capable of forming peroxides under the right conditions. This list is not all inclusive! Lab personnel should always refer to the MSDS, contact the chemical manufacturer, or contact EH&S to determine if chemicals are potential peroxide formers. Acrolein Allyl ether Allyl ethyl ether Allyl phenyl ether p-(n-Amyloxy) benzoyl chloride n-Amyl ether p-Anisaldehyde m-Anisaldehyde m-Anisyl alcohol Azoxydianisole Benzoin methyl ether Benzyl n-butyl ether Benzyl ether Benzyl ethyl ether Benzyl methyl ether Benzyl 1-napthyl ether 1,2-Bis(2-chloroethoxy)ethane Bis(2 ethoxyethyl)ether Bis(2-(methoxyethoxy)ethyl) ether Bis(2-chloroethyl) ether Bis(2-ethoxyethyl) adipate Bis(2-ethoxyethyl) phthalate Bis(2ethoxyethyl)sebacate Bis(2methoxyethoxy)ethane Bis(2-methoxyethyl) carbonate Bis(2-methoxyethyl) ether Bis(2-methoxyethyl) phthalate Bis(2-methoxymethyl) adipate Bis(2-n-butoxyethyl) phthalate Bis(pentyloxy)azoxybenzene Bis(2-phenoxyethyl) ether Bis(4-chlorobutyl) ether Bis(chloromethyl) ether pBromoanisole 2-Bromomethyl ethyl ether 2-Bromoethyl methyl ether B-Bromophenetole o-Bromophenetole p-Bromophenetole 3-Bromopropyl phenyl ether 1,3-Butadiyne Buten-3-yne 2-Butoxyethanol 2-(butoxyethoxy)ethyl acetate tert-Butyl ethyl ether tert-Butyl methyl ether n-Butyl phenyl ether n-Butyl vinyl ether Chloroacetaldehyde diethylacetal 2-Chlorobutadiene 1-(2-Chloroethoxy)-2-phen-oxyethane Chloroethylene Chloromethyl methyl ether B-Chlorophenetole o-Chlorophenetole p-Chlorophenetole Cyclooctene Cyclopropyl methyl ether Decahydronaphthalene Diallyl ether p-Di-n-butoxybenzene 1,2-Dibenzyloxyethane p-Dibenzyloxybenzene 1,2-Dichloroethyl ethyl ether 2,4-Dichlorophenetole 2,4-Dichlorophenoxyacetic acid Diethoxymethane 2,2-Diethoxypropane Diethyl ethoxymethylenemalonate Diethyl fumarate Diethyl acetal Diethyketene m,o,p-diethoxybenzene 2,3-Dihydro2,5dimethoxyfuran 1,2-Diethoxyethane Diisobutylene(pract) Dimethoxymethane 1,1-Dimethoxyethane Dimethylketene 2,5-Dimethoxyaniline 3,4-Dimethoxybenzaldehyde

Environmental Health & Safety

Page 5 of 5

April 2009

3,3'-Dimethoxy benzidine 2,4-Dimethoxybenzoic acid 4,4-Dimethoxy2butanone 1 ,2-Dimethoxyethane Dimethoxymethane 2,2-Dimethoxypropane 3,3-Dimethoxypropene 2,4-Dinitrophenetole 2,5-Dimethoxytoluene 1,3-Dioxepane p-Dioxane 1,3-Dioxolane Di(1-propynyl)ether Di(2-propynyl)ether Di-n-propoxymethane 1,2-Epoxy-3-isopropoxypropane 1,2-Epoxy-3-phenoxypropane p-Ethoxyacethophenone p-Ethoxybenzaldehyde o-Ethoxybenzoic acid 2-(2Ethoxyethoxy)ethanol 1-(2-Ethoxyethoxy)ethyl acetate 2-(2-Ethoxyethoxy)ethyl acetate 2-Ethoxyethyl acetate (2-Ethoxyethyl)-o-benzoyl benzoate 1-Ethoxynaphthalene p-Ethoxyphenol o,p-Ethoxyphenyl isocyanate 1-Ethoxy-2-propyne 3-Ethoxyopropionitrile 2-Ethylacrylaldehyde oxime 2-Ethylbutanol Ethyl B-ethoxypropionate Ethylenebis-(2-oxyethyl acetate) 2-Ethylhexanal Ethyl vinyl ether p-Formylphenoxyaceticacid) Furan 2,5-Hexadiyn-1-ol 4,5-Hexadien-2-yn-1-ol n-Hexyl ether p-Hexyloxybenzaldehyde (pHydroxyphenoxy)acetic acid o,p-Iodophenetole Isoamyl benzyl ether Isoamyl ether Isobutyl vinyl ether Isoeugenol Isopentyl ether Isophorane Isophorone Isoprene B-Isopropoxy propionitrile Isopropyl 2,4,5-trichlorophenoxy-acetate Ligroine Limonene 1,5-p-Methadiene Methofuran Methoxyaceticacid p-Methoxybenzylamine Methyl p-(n-amyloxy)benzoate 4-Methyl-2-pentanone n-Methylphenetole 2-Methyltetrahydrofuran 3-Methoxy-1-butyl acetate 2-Methoxyethanol 2-(2Methoxyethoxy)ethanol 2-Methoxyethyl acetate 3-Methoxyethyl acetate 2-Methoxyethylamine 2-Methoxyethyl vinyl ether 1-Methoxynaphthalene Methonxy-1,3,5,7-cycloocta-tetraene 4-Methoxy-2-nitroaniline m-Methoxyphenol Methoxyphenylacetic acid o-Methoxyphenyl isocyanate 3-Methoxypropionitrile B-Methoxypropionitrile o-Methoxypropionitrile m-Nitrophenetole o-Nitrophenyl phenylether 2,5-Norbornadiene 1-Octene Oxybis(2-ethyl acetate) Oxybis(2-ethyl benzoate) 4,4'-Oxydiphenol B,B-oxydipropionitrile 1-Pentene p-Pentyloxyaniline p-Pentyloxybenzaldehyde p-Pentyloxybenzoylchloride Phenoxyacetic acid Phenoxyacetyl chloride m-(mPhenoxyphenoxy)phenol a-Phenoxypropionyl chloride Phenyl o-propyl ether p-Phenylphenetone n-Propyl ether n-Propyl isopropyl ether Sodium 8,11,14-eicosa- tetraenoate Sodium ethoxyacetylide Tetrahydropyran Tetraethylene glycol Tetraethyleneglycolmonomethylether Triethylene glycol diacetate Triethylene glycol dipropionate Trimethoxybenzaldehyde 1,3,3-Trimethoxypropene 1,1,2,3-Tetrachloro-1,3 Butadiene 4-Vinyl cyclohexene Vinylene carbonate Vinylidene chloride † Modified from http://ccc.chem.pitt.edu/wipf/SOPs/Peroxide%20Forming%20Chemicals.pdf ‡ Modified from http://www.ehs.berkeley.edu/pubs/guidelines/pecguidelines.html#aboutperoxide. ± Modified from CRC Handbook of Chemistry and Physics 89th Ed., 2008-2009, Sec. 16-5.