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DOE-HDBK-1139/1-2000
defined as a part of the organization's chemical management program. NFPA 45 requires the
inspection of these types of chemicals in a laboratory every 6 months. However, some peroxide
formers, such as diisopropyl ether, may require more frequent inspections.
Do not assume that a new, recently purchased, unopened chemical is safe. Testing before initial
use is recommended.
Defining "Unsafe"
As chemicals are inspected, there needs to be a definition by the facility as to what constitutes an
unacceptable risk (or "unsafe). If "unsafe" is not defined, then one cannot determine when a
container fails inspection. If needed, review commercial industry practices for reported safe
storage times before chemical disposition occurs. DOE sites could also determine what other
DOE sites are doing.
It is important to note that some measurements such as peroxide determinations can be inherently
low. To prevent dangerous levels of peroxide, a routine monitoring program should be put in
place to watch the trend of peroxide concentrations. Once peroxide formation has started it will
tend to accelerate at a nonlinear rate and the container should be disposed as waste immediately
Managing "Unsafe" Chemicals
Once a chemical or waste stream has become unsafe due to dehydration, solvent evaporation, or
the formation of hazardous products, processes used to manage the material must be clearly
defined in the chemical management program. Employees need to know if they call the
professional expert designated by management, if they are to call the bomb squad or emergency
response, etc.
Reference Material:
1. Bailey, J., Blair, D., Boada-Clista, L., Marsick, D., Quigley, D., Simmons, F., Whyte, H.,
"Management of Time Sensitive Chemicals (I): Misconceptions Leading to Incidents",
Chemical Health & Safety, Vol. 11, No. 5, pgs. 14-17.
2. Bailey, J., Blair, D., Boada-Clista, L., Marsick, D., Quigley, D., Simmons, F., Whyte, H.,
"Management of Time Sensitive Chemicals (II): Their Identification, Chemistry, and
Management", Chemical Health & Safety, Vol. 11, No. 6 (to be published Nov/Dec 2004).
3. United States Department of Justice, Federal Bureau of Investigation, Bomb Data
Center, Technical Bulletin Dated November 10, 1982, "Warning: Picric Acid
San Mateo County, California", Washington, D.C.
4. Kelly, R. J., "Review of Safety Guidelines for Peroxidizable Organic Chemicals",
Chemical Health & Safety, Vol. 3, No. 5, Sept./Oct., 1996, pgs. 27-36.
5. Clark, Donald E., "Peroxide and Peroxide-forming Chemicals", American
Chemical Society, Chemical Health & Safety, Sept./Oct., 2001, Pgs.12-21.
6. Steere, Norman V., "Control of Hazards from Peroxides in Ethers", Journal of
Chem. Ed., Vol. 41, No. 8, August, 1964.
7. Davies, Alwyn G., "Explosion Hazards of Autoxidized Solvents", Journal of the
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