Lab Safety Officer Meeting - March 22nd, 2024 Agenda and Safety Minute on Pyrophoric Chemicals

Monthly Lab Safety Officer Meeting March 22nd, 2024

Agenda 1. Announcements a) Change of LSO Form https://forms.gle/BsQQuzsK5F7c3kqq6 b) Reporting Incidents to DRS Phone: 217-333-2755 Email: drs@illinois.edu Submit an Event Report: https://forms.illinois.edu/sec/1674176205?referrer=https://shibboleth.illinois.edu/ c) Anonymous Near Misses and Incidents Form for the JST https://forms.gle/88wVJ8gHXFoMqBtw5 d) New Slack Channel for LSOs https://join.slack.com/t/uiucchemistrylsos/shared_invite/zt-2d4ejfwcl- GK_WKPUM~HxEr05PS~TZvQ 2. Open Discussion Facilities Issues/Updates a) 3. Recent Near Miss/Incident Reports None submitted this month a) 4. Safety Minute Pyrophoric chemicals safety a) 2

Other Announcements For waste management questions to DRS: The cws@illinois.edu email address is no longer available. Please use DRS-waste@illinois.edu instead. 3

Open Discussion Any facilities issues or updates? Safety concerns or comments? Suggestions for future meeting topics? 4

Safety Minute: Pyrophoric Chemicals Pyrophoric chemicals are highly reactive to water and/or oxygen and are therefore among the most dangerous chemicals. They ignite spontaneously upon contact with air. They react violently with water, such as moisture in the air, and release toxic/flammable gases. This safety minute provides an overview of best practices involving these chemicals and does not take the place of official hands-on training provided by an experienced researcher. The hazards these materials pose should not be underestimated! 5 UIUC DRS webpage on Handling Pyrophoric and other Air/Water Reactive Materials https://drs.illinois.edu/Page/SafetyLibrary/PyrophoricMaterials

Safety Minute: Pyrophoric Chemicals 6 Kemsley, J. N. (2009). Learning from UCLA. Chem. Eng. News, 87(31), 29-34.

Safety Minute: Pyrophoric Chemicals Causes of the incident: Sangji, a post-graduate researcher, aimed to scale up a reaction she had run once before. Aimed to generate vinyllithium by reacting vinylbromide with pyrophoric tert-butyllithium (tBuLi) While working with tBuLi in the fume hood Sangji was drawing 50 mL of tBuLi into a 60 mL plastic syringe equipped with a 1.5- inch, 20-gauge needle The syringe plunger came out of the barrel, exposing the tBuLi An open flask of hexane in the hood (not part of the experiment) was knocked over The tBuLi ignited; the hexane and Sangji s clothes caught fire Sangji was wearing nitrile gloves, no lab coat, and possibly eye protection 7 Kemsley, J. N. (2009). Learning from UCLA. Chem. Eng. News, 87(31), 29-34.

Safety Minute: Pyrophoric Chemicals Response to the incident: The available safety shower was not used A labmate wrapped a labcoat around Sangji attempting to put out the fire, but it started burning The labmate next poured water on Sangji from the sink A researcher from a neighboring lab ran to the scene, called 911, and alerted Sangji s PI The fire was out upon arrival of emergency personnel. The upper half of Sangji s body was badly burned, but she was conscious Sangji was taken to the hospital where she died 18 days later 8 Kemsley, J. N. (2009). Learning from UCLA. Chem. Eng. News, 87(31), 29-34.

Safety Minute: Pyrophoric Chemicals What could have been done differently: A risk assessment outlining the procedure (specifically for a scaled- up version of the procedure) and emergency response should have been conducted before performing the experiment. This risk assessment should have been reviewed by a more experienced researcher and everyone in the lab should have been informed of the procedure to be undertaken. The researcher should have had more formal, documented training and should have been supervised during the first scaled-up experiment. Rather than using a syringe, using the cannulation technique (transferring the reagent from one dried, sealed, and clamped container to another by a 1-2 foot-long double-tipped needle) would have been safer, especially for large volumes. Flammable materials not involved in the experiment should have been moved to a flammable storage cabinet. Lab coats (particularly flame-resistant) should have been worn along with eye protection. 9 Kemsley, J. N. (2009). Learning from UCLA. Chem. Eng. News, 87(31), 29-34.

Safety Minute: Pyrophoric Chemicals Examples of pyrophoric and air/water reactive materials: 10 UIUC DRS webpage on Handling Pyrophoric and other Air/Water Reactive Materials https://drs.illinois.edu/Page/SafetyLibrary/PyrophoricMaterials

Safety Minute: Pyrophoric Chemicals Best practices for handling pyrophoric chemicals: Use a less hazardous chemical instead (substitution) Use the chemical in a less hazardous form (attenuation) Use a hydrogen transfer agent instead of Raney nickel Use n-BuLi rather than t-BuLi Use NaH 60% dispersion in mineral oil instead of NaH, dry, 95% Use 10% Pd on carbon (wet) rather than 10% Pd on carbon (dry) Use 0.1% fluorine gas instead of 99% fluorine gas 11 UIUC DRS webpage on Handling Pyrophoric and other Air/Water Reactive Materials https://drs.illinois.edu/Page/SafetyLibrary/PyrophoricMaterials

Safety Minute: Pyrophoric Chemicals Best practices for handling pyrophoric chemicals: Before/during work with pyrophorics: Receive training before working with pyrophoric chemicals Inexperienced users should be supervised Do not work with pyrophorics alone Remove unnecessary flammable material from surroundings Perform all reactions involving pyrophorics while under an inert atmosphere (fume hood or glove box) Make sure to have Functional fire extinguisher nearby Dry powder (ABC) in most cases Class D for combustible solid metal fires An appropriate spill kit nearby (with sand, metal-x, or lime for smothering air/water reactive chemicals) Wear appropriate PPE (gloves, safety goggles, flame-resistant lab coat) 12 UIUC DRS webpage on Handling Pyrophoric and other Air/Water Reactive Materials https://drs.illinois.edu/Page/SafetyLibrary/PyrophoricMaterials

Safety Minute: Pyrophoric Chemicals Best practices for handling pyrophoric chemicals: Before beginning work, flame or oven dry all equipment (glassware, syringe body, needles, cannula, etc.) and cool to ambient temperature under inert atmosphere Manipulate air/water reactive chemicals using locking mechanisms (e.g., Luer-locks) and clamped apparatus connects (e.g., keck) Use gas/vacuum manifold systems under an inert gas and mineral oil bubblers to prevent over-pressurization Before adding air/water reactive chemicals to the apparatus, purge the apparatus with inert gas and keep it under low positive pressure Use septa to seal reaction vessels Never fill a syringe to its max volume. Max withdrawal should be to 2/3 of syringe capacity If 5 mL of chemical are needed, use a 10 mL syringe Keep the syringe barrel pointed away from you, so if pressure builds up and the plunger pops out, the contents will not spray directly on you Remember to quench the pyrophoric chemical left inside the needle 13 UIUC DRS webpage on Handling Pyrophoric and other Air/Water Reactive Materials https://drs.illinois.edu/Page/SafetyLibrary/PyrophoricMaterials

Safety Minute: Pyrophoric Chemicals Handling and Transfer Procedures Demonstration from Dartmouth (9:00 19:35) 14 Handling Pyrophoric Materials from Dartmouth YouTube channel https://www.youtube.com/watch?v=iLMl10X0Naw

Safety Minute: Pyrophoric Chemicals Storage of pyrophoric chemicals: Purchase at most a supply for 1-2 months Follow manufacturer instructions for storage Keep away from incompatible chemicals, heat, and flame Only keep in refrigerators that are appropriate for flammable liquids 15 Handling Pyrophoric Materials from Dartmouth YouTube channel https://www.youtube.com/watch?v=iLMl10X0Naw

Safety Minute: Pyrophoric Chemicals Emergency response: In the case of a spill or fire Flush the skin or clothing using the safety shower or eyewash station Close the fume hood sash and doors to the lab Extinguish the fire if safe to do so Pull the fire alarm Call 911 16 Handling Pyrophoric Materials from Dartmouth YouTube channel https://www.youtube.com/watch?v=iLMl10X0Naw

Thank you for coming! Please forward LSO meeting recap email/slides to your group! We can stay for a few minutes if there are further questions. 17