Defining "Unsafe"

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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