Peroxide-forming Chemicals

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Overview

Peroxide-forming chemicals are a class of compounds that have the ability to form shock-sensitive explosive peroxide crystals. Many of the organic solvents commonly used in Weill Cornell Medical College’s laboratories have the potential to form explosive peroxide crystals, diethyl ether and tetrahydrofuran are two of the more common peroxide-forming chemicals used at WCMC. Therefore, it is extremely important that this procedure be followed regarding the identification, handling, storage, and disposal of peroxide-forming chemicals.

Under normal storage conditions the materials listed in this document have the potential to generate and accumulate peroxide crystal formations, which may violently detonate when subjected to thermal or mechanical shock. Peroxide-forming chemicals react with oxygen – even at low concentrations – to form peroxy compounds. The risk associated with peroxide formation increases if the peroxide crystallizes or becomes concentrated by evaporation or distillation. Factors that affect rate of peroxide formation include exposure to air, light and heat, moisture, and contamination from metals.
 

Peroxide crystals may form on the container plug or the threads of the lid and detonate when the lid is twisted.  Do not open a liquid organic peroxide or peroxide-forming chemical if crystals or a precipitate are present.

 

Applicability

This Update applies to all College Faculty, Staff, and Students and any other college employee who is involved with the ordering, storage, or use of laboratory chemicals/reagents.

 

 

Definitions

A peroxide is a chemical that contains a peroxo (O-O) unit, one that has the chemical formula of O2²―.

 

 

Responsibilities

Environmental Health and Safety (EHS) provides technical assistance lab personnel about the safe handling, storage and disposal of peroxide-forming chemicals and training as needed.

Lab personnel ensure that peroxide-forming chemicals are properly managed and disposed in accordance with this Update.

 

Procedure

Purchasing Considerations

  • When possible, purchase only peroxide-forming chemicals which contain a peroxide formation inhibitor (e.g., tetrahydrofuran or diethyl ether inhibited with butylated hydroxytoluene (BHT)).

  • Only purchase quantities of peroxide-forming chemicals that you expect to use within expiration and disposal timeframes.

Labeling Requirements

  • All bottles of peroxide-forming chemicals must have the date received marked on the container.

  • When the bottle is first opened, the container must be marked with the date opened.

Example Label

Peroxide-Forming Chemical

     Date Received:___________________

       Date Opened:___________________

 

Storage and Use Requirements

  • Do not store peroxide-forming chemicals in direct sunlight as light can accelerate the chemical reactions that form peroxides.

  • If the peroxide-forming chemical is flammable and requires refrigeration, then an explosion-proof refrigerator must be used.

  • Do not distill, evaporate or concentrate a peroxide-forming chemical until you have first tested it for the presence of peroxides. (Peroxides are usually less volatile than their parent material and will tend to concentrate in the hot distillation pot).

  • NEVER UNDER ANY CIRCUMSTANCES touch or attempt to open container of a peroxide-forming liquid if there are whitish crystals around the cap and/or in the bottle. The friction of screwing the cap may detonate the bottle. If you encounter such a bottle, contact the Environmental Health and Safety office immediately for removal. DO NOT TOUCH OR MOVE THE SUSPECT BOTTLE YOURSELF FOR ANY REASON.

Disposal Requirements

  • There are four classes of peroxide-forming chemicals based upon the peroxide formation hazard:

    • Class A – Severe Peroxide Hazard

    • Class B – Concentration Hazard

    • Class C – Shock and Heat Sensitive

    • Class D – Potential Peroxide-Forming Chemicals

  • Peroxide-forming chemicals must be disposed within the timeframes specified in the table below regardless if the container has unopened. Disposal with EHS must occur within the timeframe allowed once the container is received or opened, which ever the earlier of the two dates.

 

Class A

Class B

Class C

Class D

Date Opened

3 months

6 months

6 months

Only if peroxide crystals are present.

Date Received

1 year

1 year

1 year

  • Submit an online chemical collection request form to EHS to request the disposal of a peroxide-forming chemical. The online form is available on EHS’ website at: http://www.med.cornell.edu/ehs. NOTE: If the peroxide-forming chemical has a visible peroxide formation or is greater than a year old, bypass the online form and contact EHS immediately. Do not move or handle these containers.

  • EHS has contractors available to test and, if necessary, stabilize peroxide-forming chemicals.

    

Peroxide Forming Chemical Lists

Class A – Severe Peroxide Hazard

Spontaneously decompose and become explosive with exposure to air without concentration.

Butadiene (liquid monomer)

Isopropyl ether

Sodium amide (sodamide)

Chloroprene (liquid monomer)

Potassium amide

Tetrafluoroethylene (liquid monomer)

Divinyl acetylene

Potassium metal

Vinylidene chloride

 

Class B – Concentration Hazard

Require external energy for spontaneous decomposition.  Form explosive peroxides when distilled, evaporated or otherwise concentrated.

Acetal

Diethylene glycol dimethyl ether (diglyme)

4-Methyl-2-pentanol

Acetaldehyde

Diethyl ether

2-Pentanol

Benzyl alcohol

Dioxanes

4-Penten-1-ol

2-Butanol

Ethylene glycol dimethyl ether (glyme)

1-Phenylethanol

Cumene

Furan

2-Phenylethanol

Cyclohexanol

4-Heptanol

2-Propanol

Cyclohexene

2-Hexanol

Tetrahydrofuran

2-Cyclohexen-1-ol

Methylacetylene

Tetrahydronaphthalene

Decahydronaphthalene

3-Methyl-1-butanol

Vinyl ethers

Diacetylene

Methylcyclopentane

Other secondary alcohols

Dicyclopentadiene

Methyl isobutyl ketone

 

 

 

 

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.

Acrylic acid

Chlorotrifluoroethylene

Vinyl acetate

Acrylonitrile

Methyl methacrylate

Vinylacetylene (gas)

Butadiene (gas)

Styrene Vinylpyridine

Vinyladiene chloride

Chloroprene

Tetrafluoroethylene (gas)

Vinyl chloride (gas)

 

Class D – Potential Peroxide Forming Chemicals

May form peroxides but cannot be clearly categorized in Class A, B, or C.

Acrolein

p-Chlorophenetole

4,5-Hexadien-2-yn-1-ol

Allyl ether

Cyclooctene

n-Hexyl ether

Allyl ethyl ether

Cyclopropyl methyl ether

o.p-Iodophenetole

Allyl phenyl ether

Diallyl ether

Isoamyl benzyl ether

p-(n-Amyloxy)benzoyl chloride

p-Di-n-butoxybenzene

Isoamyl ether

n-Amyl ether

1,2-Dibenzyloxyethane

Isobutyl vinyl ether

Benzyl n-butyl ether

p-Dibenzyloxybenzene

Isophorone

Benzyl ether

1,2-Dichloroethyl ethyl ether

b-Isopropoxypropionitrile

Benzyl ethyl ether

2,4-Dichlorophenetole

Isopropyl-2,4,5-trichlorophenoxy acetate

Benzyl methyl ether

Diethoxymethane

n-Methylphenetole

Benzyl-1-napthyl ether

2,2-Diethoxypropane

2-Methyltetrahydrofuran

1,2-Bis(2-chloroethoxyl)ethane

Diethyl ethoxymethylenemalonate

3-Methoxy-1-butyl acetate

Bis(2-ethoxyethyl)ether

Diethyl fumarate

2-Methoxyethanol

Bis(2-(methoxyethoxy)ethyl) ether

Diethyl acetal

3-Methoxyethyl acetate

Bis(2-chloroethyl) ether

Diethylketene

2-Methoxyethyl vinyl ether

Bis(2-ethoxyethyl) adipate

Diethoxybenzene (m-,o-,p-)

Methoxy-1,3,5,7-cyclooctatetraene

Bis(2-methoxyethyl) carbonate

1,2-Diethoxyethane

b-Methoxypropionitrile

Bis(2-methoxyethyl) ether

Dimethoxymethane

m-Nitrophenetole

Bis(2-methoxyethyl) phthalate

1,1-Dimethoxyethane

1-Octene

Bis(2-methoxymethyl) adipate

Di(1-propynl) ether

Oxybis(2-ethyl acetate)

Bis(2-n-butoxyethyl) phthalate

Di(2-propynl) ether

Oxybis(2-ethyl benzoate)

Bis(2-phenoxyethyl) ether

Di-n-propoxymethane

b,b-Oxydipropionitrile

Bis(4-chlorobutyl) ether

1,2-Epoxy-3-isopropoxypropane

1-Pentene

Bis(chloromethyl) ether

1,2-Epoxy-3-phenoxypropane

Phenoxyacetyl chloride

2-Bromomethyl ethyl ether

p-Ethoxyacetophenone

a-Phenoxypropionyl chloride

beta-Bromophenetole

1-(2-Ethoxyethoxy)ethyl acetate

Phenyl-o-propyl ether

o-Bromophenetole

2-Ethoxyethyl acetate

p-Phenylphenetone

p-Bromophenetole

(2-Ethoxyethyl)-a-benzoyl benzoate

n-Propyl ether

3-Bromopropyl phenyl ether

1-Ethoxynaphthalene

n-Propyl isopropyl ether

tert-Butyl methyl ether

o,p-Ethoxyphenyl isocyanate

Sodium 8-11-14-eicosatetraenoate

n-Butyl phenyl ether

1-Ethoxy-2-propyne

Sodium ethoxyacetylide

n-Butyl vinyl ether

3-Ethoxypropionitrile

Tetrahydropyran

Chloroacetaldehyde diethylacetal

2-Ethylacrylaldehyde oxime

Triethylene glycol diacetate

2-Chlorobutadiene

2-Ethylbutanol

Triethylene glycol dipropionate

1-(2-Chloroethoxy)-2-phenoxyethane

Ethyl-b-ethoxypropionate

1,3,3-Trimethoxypropene

Chloroethylene

Ethylene glycol monomethyl ether

1,1,2,3-Tetrachloro-1,3-butadiene

Chloromethyl methyl ether

2-Ethylhexanal

4-Vinyl cyclohexene

beta-Chlorophenetole

Ethyl vinyl ether

Vinylene carbonate

o-Chorophenol

2,5-Hexadiyn-1-ol

 

 

References

National Safety Council: Data Sheet I-655 Rev. 87

NFPA: NFPA 432, Code for the Storage of Organic Peroxide Formulations

Reactive Hazards Reduction, Inc. http://www.rhr-inc.com/

FDNY: 3 RCNY Chapter §10-01 – Chemical Laboratories