One more useful document in addition to Mikhail’s JCHAS article, about Butyl lithium safety and handling. Rob made excellent points, which is regular practice in syntheses lab.

 

http://131.104.156.23/lectures/7113/7113_Literature/FMC%20Lithium%20pdf/FMC_ButylCat_web.pdf

 

Tilak

 

 

 

Jenny,

The point was made to not put them solutions in a freezer.  The inevitable ice buildup adds danger and doesn’t improve safety like the other aspects.  I hope your chemists agree.

All in my opinion.  Good luck with the lab workers,

Lee



On 11/19/15, 6:46 AM, "Fu, Zhen" <zfu3**At_Symbol_Here**CENTRAL.UH.EDU> wrote:

Hi Tilak, Debbie, Kimi, David, Lee and Alnajjar,
 
Thank you for the suggestions on storage of pyrophorics in freezer!! Debbie is right, instead of an explosion-proof refrigerator which is designed to prevent ignition of flammable vapors or gases that may be present outside the refrigerator, Flammable material refrigerator/freezers is more appropriate in my case. Secondary containment, room-temp opening advice, and also managing supply which is the key are all great points. Thanks again.
 
Jenny

Best Regards,
 
Zhen (Jenny) Fu, Ph.D., Sr. Safety Specialist, Environmental Health & Life Safety
Administration & Finance / Dept. of Public Safety
University of Houston


From: DCHAS-L Discussion List [mailto:dchas-l**At_Symbol_Here**med.cornell.edu] On Behalf Of Alnajjar, Mikhail S
Sent: Wednesday, November 18, 2015 11:58 AM
To: DCHAS-L**At_Symbol_Here**MED.CORNELL.EDU
Subject: Re: [DCHAS-L] Storing Pyrophoric/Water-Reactive Reagents at low temperature

Jenny:
 
Lee and Rob Toreki covered the storing of lithium reagents very well.  The only other suggestion I can propose is to “purchase” what is needed so that it can be used in a timely manner.  The old idea of trying to buy the biggest container possible to save $$$ is no longer (or was never really) valid.  Proper planning can remove such complexity as it is not easy to store in the refrigerator and keep dry.  
 
About 5 years ago, an article in the Journal of Chemical Health And Safety (JCHAS) dealing with handling and storing of pyrophorics might also be of help.  It may be 100% elated, but it may help.  Good luck
 
Methods for the safe storage; handling; and disposal of pyrophoric liquids and solids in the laboratory <https://urldefense.proofpoint.com/v2/url?u=http-3A__www.sciencedirect.com_science-3F-5Fob-3DGatewayURL-26-5Fmethod-3DcitationSearch-26-5Feidkey-3D1-2Ds2.0-2DS1871553210000289-26-5Forigin-3DSDEMFRHTML-26-5Fversion-3D1-26md5-3D14bc5bd9eb5365f579cf9f4723b60bfc&d=BQMFAg&c=lb62iw4YL4RFalcE2hQUQealT9-RXrryqt9KZX2qu2s&r=meWM1Buqv4IQ27AlK1OJRjcQl09S1Zta6YXKalY_Io0&m=1oc5HCoIGf_flY8HQduI2E2Dt4EohJxeQ3I3XADNqDc&s=HTMjsOCMo0m4r94jbdzorK7duVYtu54kAu05hKXBZ-Y&e=>  Original Research Article
Journal of Chemical Health and Safety, Volume 18, Issue 1, January-February 2011, Pages 5-10
Mikhail Alnajjar, David Quigley, Murty Kuntamukkula, Fred Simmons, David Freshwater, Samuel Bigger


 

From: DCHAS-L Discussion List [mailto:dchas-l**At_Symbol_Here**med.cornell.edu] On Behalf Of Lee Latimer
Sent: Wednesday, November 18, 2015 8:59 AM
To: DCHAS-L**At_Symbol_Here**MED.CORNELL.EDU
Subject: Re: [DCHAS-L] Storing Pyrophoric/Water-Reactive Reagents at low temperature

Jenny, et al.,

As a former frequent user of alkyllithium reagents, this is a key issue.  The primary issue for users with storing t-BuLi and related compounds is the drop in titer with time.  This is best managed by using good technique with parafilm around the septum sealing the bottle.  

Catastrophic situations only happen when an outside agency like another bottle is “crashed” into the BuLi bottle (very rare exceptions could occur according to Prof. Murphy).  Thus, secondary containers are best at protecting from damage from other containers.  We used the metal cans the solutions arrived in frequently (after removal of the tops).  An individual secondary container for these solutions is always good practice rather than them sharing.  I would also recommend a wide enough base to increase stability when other items are being placed in the space.  Good practice would also take the secondary with the bottle to the location where it is clamped, in a perfect world.

Of course, good practice is managing the supply so bottles with low quantities are properly disposed of before problems arise (don’t let them collect).  I have not seen date labeling included in stock management, but it could be if you can get the users to cooperate.

Lee



On 11/18/15, 8:20 AM, "Debbie M. Decker" <dmdecker**At_Symbol_Here**UCDAVIS.EDU <https://urldefense.proofpoint.com/v2/url?u=http-3A__dmdecker-40UCDAVIS.EDU&d=BQMFAw&c=lb62iw4YL4RFalcE2hQUQealT9-RXrryqt9KZX2qu2s&r=meWM1Buqv4IQ27AlK1OJRjcQl09S1Zta6YXKalY_Io0&m=iSjXvE5HgxzbiBU8BpblU_YaYgJ9EfV7xTjDFJzXJzo&s=dgXZjGzQx3t_toMJXOuv5KOTC8Hq5XsH2hLIm3bZWZo&e=> > wrote:
Okay – this is Debbie being nit-picky but I’m going to do it anyway because throwing around the wrong lingo drives me crazy.  And can cause you to spend a whole pile of money on the wrong type of refrigerator.
 
It’s not an “explosion-proof” refrigerator or freezer.  A true explosion-proof refrigerator is suitable for use when there’s a potentially explosive atmosphere both inside and OUTSIDE the refrigerator.  What you need is a flammable liquid storage refrigerator or “lab-safe” refrigerator.
 
Around here, pyrorphorics needing refrigeration are stored in flammable liquid storage refrigerators, in a dessicator or similar secondary containment..  It’s difficult to get pyrophorics completely segregated from flammables needing refrigeration which is why secondary containment becomes really important.
 
Hope this helps.
Debbie
 
Debbie M. Decker, CCHO, ACS Fellow
Chair, Division of Chemical Health and Safety
University of California, Davis
(530)754-7964
(530)304-6728
dmdecker**At_Symbol_Here**ucdavis.edu <https://urldefense.proofpoint.com/v2/url?u=http-3A__dmdecker-40ucdavis.edu&d=BQMFAw&c=lb62iw4YL4RFalcE2hQUQealT9-RXrryqt9KZX2qu2s&r=meWM1Buqv4IQ27AlK1OJRjcQl09S1Zta6YXKalY_Io0&m=iSjXvE5HgxzbiBU8BpblU_YaYgJ9EfV7xTjDFJzXJzo&s=aJP6_X2ITM886oI_dR1M2ZSgFDZfQZ_qNdSNRpoBUpo&e=> <mailto:dmdecker**At_Symbol_Here**ucdavis.edu>
 
Birkett's hypothesis: "Any chemical reaction
that proceeds smoothly under normal conditions,
can proceed violently in the presence of an idiot."

 

From: DCHAS-L Discussion List [mailto:dchas-l**At_Symbol_Here**MED.CORNELL.EDU] On Behalf Of TILAK CHANDRA
Sent: Wednesday, November 18, 2015 6:54 AM
To: DCHAS-L**At_Symbol_Here**MED.CORNELL.EDU
Subject: Re: [DCHAS-L] Storing Pyrophoric/Water-Reactive Reagents at low temperature
 
Hi Jenny:
 
It is ok to store water sensitive reagents (pyrophorics too) inside an explosion proof refrigerator. Make sure your reagent bottle is under nitrogen atmosphere and cap is closed properly. You may also apply a Teflon tape around the cap and use a secondary containment inside refrigerators main compartment to avoid the sliding of the reagent bottle.
 
Good luck.
 
Tilak
 

From: DCHAS-L Discussion List [mailto:dchas-l**At_Symbol_Here**med.cornell.edu <mailto:dchas-l**At_Symbol_Here**med.cornell.edu> ] On Behalf Of Fu, Zhen
Sent: Tuesday, November 17, 2015 4:01 PM
To: DCHAS-L**At_Symbol_Here**MED.CORNELL.EDU <mailto:DCHAS-L**At_Symbol_Here**MED.CORNELL.EDU>
Subject: [DCHAS-L] Storing Pyrophoric/Water-Reactive Reagents at low temperature

Hi All,
 
I read some Protocols for Safe Use of Pyrophoric/Water-Reactive Reagents mentioned “When refrigeration of materials is required, materials must be stored in an approved explosion-proof refrigerator/freezer.” As we all know, even the explosion-proof refrigerator/freezer cannot provide dry environment.
 
Can you share your experience on storing pyrophoric, flammable, and water-sensitive substances such as tBuLi solution in pentanes at low temperature? Great Thanks!

Jenny
 

Best Regards,
 
Zhen (Jenny) Fu, Ph.D., Sr. Safety Specialist, Environmental Health & Life Safety
Administration & Finance / Dept. of Public Safety
University of Houston
713-743-8723
zfu2**At_Symbol_Here**uh.edu <https://urldefense.proofpoint.com/v2/url?u=http-3A__zfu2-40uh.edu&d=BQMFAw&c=lb62iw4YL4RFalcE2hQUQealT9-RXrryqt9KZX2qu2s&r=meWM1Buqv4IQ27AlK1OJRjcQl09S1Zta6YXKalY_Io0&m=iSjXvE5HgxzbiBU8BpblU_YaYgJ9EfV7xTjDFJzXJzo&s=5jhsGjh1wql0j-akcOrxSroZkIikFaI9lg49tfrcxRI&e=> <mailto:zfu2**At_Symbol_Here**uh.edu>