DCHAS-L Archives, Jun 6, 2025 - Re: [DCHAS-L] Controlled pyrophoric fire?

During the haydays of Chemical Safety Associates, Inc hands-on training (1983-1995) we (Eugene Ngai, Al Mossman, and I) developed a hands-on response training course for the semiconductor industry. This included a "controlled" silane release in a custom-built gas safety cabinet. Participants were able to see up close and respond to an actual silane fire. We did at least 50-70 of these courses all over the world. During the program, everyone was in high level fire protection gear including bunker suits and SCBAs. During the many evolutions, we experienced several "non-ignition events" which are exceedingly high risk. All were handled safely.

We also did a demonstration of an organic metal pyrophoric liquid (not R-Li) for a client, the local air quality regulators, and local FD. This was not hands-on for the participants. As the demonstrator, I was in high level PPE as above.

Finally, we demonstrated routinely the combination of a powerful oxidizer (isocyanuric acid) and brake fluid. We could do this in standard level C protection, as the reaction has an approximately 90 second delay before ignition which the reaction proceeds.

In all of these examples, the demonstrations and activities were closely supervised by highly experienced operators and extreme attention to every detail was practiced. We did a "lessons learned" debrief after every evolution.

Needless to say, these demonstrations were very expensive and required extensive prep work. While we had some unexpected events, we never had an injury or uncontrolled fire.

I totally concur with Craig, these activities are not to be undertaken casually.

Feel free to contact me directly if you want more details.

Neal

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On Fri, Jun 6, 2025 at 5:41 AM Craig Merlic <merlic**At_Symbol_Here**chem.ucla.edu> wrote:

Jessica,

Sounds like a bad idea.

Many fires from pyrophorics will be over in a few seconds, so action is limited to the secondary fires. For example, fires from solutions of tert-butyllithium, diisobutylaluminum hydride, and trimethylaluminum or even solid lithium aluminum hydride are instantaneous flashes. For some solid pyrophorics the fire takes time to burn through the quantity of material, so actions can be taken, but then you create a hazardous situation.

Real case: I took charge of a small fire involving a few grams of white phosphorous. The fire could be put out using a dry chemical fire extinguisher or a class D fire extinguisher, but as soon as the material was agitated, it burst back into flames. So the pile had to be left to burn out. The same could happen with a metal fire. In theory, one could attempt to wrap up a smothered pyrophoric solid without letting it burn out, but you would have to create an inert atmosphere so that it did not re-ignite while you were moving it. Not easy.

Thinking about solid sodium or potassium, they are stored under oil to keep them from igniting. So why not add oil back onto a burning chunk of metal to smother the fire? Because the standard oil is mineral oil – a hydrocarbon that will be ignited by the white hot burning metal. So the fire only gets worse.

Overall, a pyrophoric fire would not be a simple hands-on safety training exercise.

Craig

Craig A. Merlic
Professor of Chemistry, UCLA Department of Chemistry and Biochemistry
Executive Director , UC Center for Laboratory Safety
http://cls.ucla.edu
Los Angeles, CA 90095-1569

From: ACS Division of Chemical Health and Safety <DCHAS-L**At_Symbol_Here**Princeton.EDU> on behalf of "jmartin54321**At_Symbol_Here**gmail.com" <jmartin54321**At_Symbol_Here**GMAIL.COM>
Reply-To: ACS Division of Chemical Health and Safety <DCHAS-L**At_Symbol_Here**Princeton.EDU>
Date: Thursday, June 5, 2025 at 5:28 AM
To: <DCHAS-L**At_Symbol_Here**Princeton.EDU>
Subject: [DCHAS-L] Controlled pyrophoric fire?

Has anyone here ever attempted a controlled pyrophoric fire as a part of a hands-on safety training?

Jessica A. Martin, Ph.D.
323-327-3974
jmartin54321**At_Symbol_Here**gmail.com

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