Appendix I 2
Organic peroxides are some of the most hazardous substances handled in a laboratory. They are usually
sensitive to shock, sparks, or accidental ignition. These chemicals tend to be more shock-sensitive than
most primary explosives that we are familiar with such as TNT. An example of a particularly dangerous
situation that may be found in a lab is an ether bottle that has evaporated to dryness. In some chemicals,
inhibitors are added to extend the storage lifetime of the chemical. However, because distillation of such
a stabilized liquid will remove the inhibitor, the end product must be stored with care as a potential
peroxide-former. Please note: peroxide may form on the surface of alkali metals and their amides. Do
not perform standard peroxide tests to these materials (alkali metals & their amides) since they are water
reactive. All of these chemicals should be purchased in small quantities and used up as soon as
Georgia Fire Code (based on NFPA 45 (1991)) requires that all peroxide forming chemicals be dated
upon opening. It is also prudent to date these chemicals upon first arrival in the facility. Unopened
peroxide forming chemicals should not be used if greater than 1 year old.
Types of Compounds Known to Auto oxidize to Form Peroxides:
Ethers, especially cyclic ethers and those containing primary and secondary alkyl groups
(never distill an ether before it has been shown to be free of peroxides).
Compounds containing benzylic hydrogens
Compounds containing allelic hydrogens (C=C!CH), including most alkenes; vinyl and
Compounds containing a tertiary C!H group (e.g., decalin and 2,5!dimethylhexane)
Classes of Chemicals That Can Form Peroxides Upon Ageing:
Class I: Unsaturated materials, especially those of low molecular weight, may polymerize
violently and hazardously due to peroxide initiation.