Date: Mon, 5 Jan 2009 15:34:39 -0500
Reply-To: ILPI <info**At_Symbol_Here**ILPI.COM>
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From: ILPI <info**At_Symbol_Here**ILPI.COM>
Subject: Re: UCLA Lab Fire
In-Reply-To: <ECF489F5-42A5-4D09-9CCE-6345464CAFEA**At_Symbol_Here**>

While I have no knowledge of the UCLA situation other than what we  
have all read, I have firsthand knowledge/involvement of several  
laboratory accidents that were reported in the press.  I can say that  

in none of these were the printed reports anywhere near correct.   
Which has led me to basically not take anything I hear in the media as  

a fact....


It is easy to imagine that the worker could have pulled the plunger  
all the way out.  For example, if he/she needed 10 mL and was using a  

10 mL syringe (or got a little creative and tried to draw 11 mL in one  

fill).   And if that happened, then you would have 10+ mL of hexanes  
burning on your hands, with a stream spewing from the syringe and  
inverted bottle.  =46rom there, you could easily spray it on yourself or 
panic and drop the bottle....

It is also possible that the worker did not appreciate the  
pyrophoricity, and so I will relate a similar story in both these  
veins.  This incident occurred a bit over 20 years ago.


A former lab mate of mine needed to do a routine deprotonation  
reaction.  He went to the fridge looking for a bottle of n-BuLi.  He  
couldn't find any, but he did find a bottle of t-BuLi.  Apparently, he  

thought "n-BuLi, t-BuLi, eh, it's all the same", and he decided to go  

with it.

Before we go further, I should note that's a bad inference.  I got  
some n-BuLi on my hand once.  It was a bit warm and slippery feeling,  

but it didn't spontaneously inflame.  t-BuLi is a whole other ball of  

wax.  It *will* spontaneously inflame, period.  There is no margin of  

error with it.

Both of these come in Aldrich Sure-Seal=99 bottles, which I have  
affectionately nicknamed the Aldrich "Suuuuure, it's sealed" bottle.    

For those of you unfamiliar with the closure, it has a flat circular  
rubber septum underneath what is essentially a standard beer bottle  
metal crown cap that has a 1/4" hole in it so you can stick your  
syringe through the septum and into the bottle:

There's an unfortunate tendency to buy alkyllithiums in large bottles,  

but use them in small amounts.  So if you have a 500 mL bottle of 2.0  

M t-BuLi in hexanes and it's been around a while, that septum starts  
to give out.  It becomes second nature to plug the hole with some  
Parafilm and strap that down with more Parafilm until you can't even  
see the seal or septum.  I'm not endorsing this kind of jury-rigging,  

just explaining what the practice in that lab was.

To dispense the reagent, the procedure is 1)  fill the syringe with a  

volume of nitrogen equal to the volume you wish to withdraw 2) inject  

that into the bottle, 3) invert the bottle, 4) draw the desired amount  

into the syringe, and 5) withdraw the syringe *after* tilting the  
bottle to the side.

The reason for the tilt is that if the bottle has been over- 
pressurized and you withdraw the syringe while the bottle is still  
inverted, and the liquid inside can either leak out or spurt out,  
depending on the condition of that septum.    So, back to our story....

Nameless Labmate proceeds with his reaction.  He withdraws the syringe  

from the bottle while it is still inverted, and the moment he does, a  

stream of burning t-BuLi sprays itself all over the benchtop.  This,  
in itself, was actually no big deal, as it would simply burn itself  
out.   But Nameless had a stream of consciousness that went along  
these lines: "Aiiiiggghhh, fire.  OK, OK, OK, I am working alone in  
the lab at the moment, I must go pull the fire alarm."   Which is not  

a bad thought, except that he put the bottle of t-BuLi down ***on the  

burning bench top***.   He runs out to pull the fire alarm, in the  
meantime, the bottle of tBuLi is spewing flames and igniting a pretty  

hairy mess.   About that time, someone else came in and put the whole  

mess out with some Class D powder.  We later found an intact container  

of toluene on that benchtop that had a big char mark on it, so,  
basically, Nameless missed having a Major Incident by about 30  
seconds.  NOTE: I missed seeing the event happen, but arrived on scene  

about 10 minutes later.

There are lessons learned here, and that's the point of the story:

1. I have found that most accidents are due to complacency, either  
during routine operations or "just cleaning up".  Accidents with t- 
BuLi are incredibly rare because the laboratory worker is made  
painfully aware of the incredible power/reactivity and the precautions  

that must be taken.   However, if the first step - Hazard  
Communication, is skipped or the worker doesn't appreciate the  
dangers, then you have incidents like the one I just described.

2. Part of that Hazard Communication means explaining how to set up  
for a t-BuLi reaction and the possible problems.  Which means proper  
use of the reagent bottle, clearing all flammables and clutter out of  

the work zone, having a bucket or something to put the bottle in if  
there's a problem, having a Class D extinguisher immediately  
available, performing the reaction with an experienced co-worker  
available, thinking through what to do if you encounter a flaming  
stream of liquid, PPE, doing this in a hood rather than on an open  
bench, knowing the location of the shower etc.

3. Purchasing reagents in amounts far larger than you need because  
"it's 5 times as much for $3 more" is a false economy as far as  
disposal costs go, but this incident highlights the danger involved  
with purchasing large volumes of pyrophoric reagents that are used  
infrequently.  Peroxide-formers get  similar shout-out on this point.

4. People vary widely in their reactions to an emergency situation, no  

matter how good the training, and no matter their level of learning.    

About half will respond and automatically do what needs to be done,  
and the other half will simply panic, freeze, or focus on one single  
aspect of the situation.    This is an extremely difficult issue to  
overcome, and experience is, alas, the best teacher.  As part of all  
training, we must instill on laboratory workers to think "what would I  

do it..." whenever they plan and execute an experiment.  The research  

director should be sure to ask questions like this of his/her  
laboratory workers while they're working.  It not only demonstrates  
the culture of safety mindset, it instills on workers/students that  
when we plan an experiment, we address *all* considerations whether it  

they be yield, %ee or safety.

Additional reading here:  

and links therein.


Rob Toreki

On Jan 5, 2009, at 1:59 PM, Laurence Stock wrote:

> What does "the stopper on the syringe came undone" mean????
> There are no stoppers on a syringe??? Do they mean plunger not  
> stopper??   Was the plunger completely pulled out??
> On Jan 5, 2009, at 12:21 PM, List Moderator wrote:
>> Research assistant burned in chemical fire
>> written by Anna Andersen
>> Published: Thursday, January 1, 2009
>> A 22-year-old research assistant at UCLA remains in stable  
>> condition after a chemical fire left her with second- and third- 
>> degree burns on 40 percent of her body on Monday.
>> The victim, whose identity has not been revealed, was working with  

>> T-Butyl lithium, a pyrophoric compound which caught on fire when it  

>> was exposed to air, said James Gibson, director of UCLA  
>> Environment, Health and Safety.
>> While she was extracting the compound, the stopper on the syringe  
>> came undone and exposed the chemical to air.
>> Gibson said he did not know how the stopper came undone but said  
>> the syringe was found melted.
>> "This kind of accident is very rare," he added.
>> The fire, which occurred in the Molecular Science Building, was  
>> reported at 2:57 p.m., according to a report by Melissa Kelley, a  
>> spokeswoman for the Los Angeles Fire Department. A fellow research  

>> assistant was able to put the fire out with water before the fire  
>> department arrived, and there was no structural damage to the  
>> building.
>> The victim has since been transferred to the Grossman Burn Center  
>> in Sherman Oaks and remains in stable condition, Gibson said.

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