Pyrophoric Chemicals

Pyrophoric and air/water sensitive chemical hazards

Neal LangermanAdvanced Chemical Safety

San Diego, CA

NATURE OF PROBLEM◦ Safely handling highly reactive chemicals in a

dynamic, competitive research environment◦ (Apparent) increased use of pyrophoric and

reactive chemicals in synthetic chemistry research

◦ Increased awareness of chemical safety at the institutional level

◦ Increased information sharing about incidents No method to determine if incidents (number or

severity) has changed over time

Advanced Chemical [email protected]

Reactive Safety

Air/Water/Pyrophoric Chemicals

http://www.chemical-safety.com/

Chemical Reactivity Hazards


Silane release Cylinder in a gas cabinet Apparatus in open lab area Student adjusting apparatus initiated release Minor injuries Loss of lab

Air/Water/Pyrophoric Chemicals Thermal

reflux/distillation◦ Sodium metal◦ THF ◦ Student adjusted jammed

overhead stirrer while system was hot

◦ Round-bottom cracked, releasing contents into hood

◦ Student burned◦ Lab destroyed◦ Building closed to 7 days◦ 4 EH&S “terminated” over

next months

Air/Water/Pyrophoric ChemicalsC&EN 22 Jan 2009 Researcher Dies After Lab Fire

◦ UCLA research assistant burned in incident with tert-butyl lithium

◦ Pyrophoric liquid◦ Working alone during shutdown


Air/Water/Pyrophoric Chemicalstert-Butyl Lithium

A 23 year old female research associate/laboratory technician intended to add an (unknown) aliquot of 1.6 M t-Bu-Li (in pentane) to a round bottom flask, placed in a dry ice/acetone bath. ◦ She had been employed in the lab for about 3 months. ◦ Limited experience with pyrophors◦ Attempted to transfer 160 mL with successive aliqouts in a

50 mL plastic syringe Somehow, the syringe plunger popped out or was pulled out

of the syringe barrel, splashing the employee with t-Bu-Li and pentane. ◦ Ignited 4 L bottle of hexane in hood

The mixture caught fire, upon contact with air. She was wearing Nitrile gloves, safety glasses and synthetic

sweater. She was not wearing a lab coat. ◦ The fire ignited the gloves and the sweater.


Air/Water/Pyrophoric ChemicalsMost authoritative report Jyllian Kemsley, Ph.D., C&EN Reporter

◦ http://pubs.acs.org/cen/science/87/8731sci1.html


UCLA Update◦ 12 March 2010

CAL/OSHA cites campus for failure to report 2007 injury to TA (employee)/Grad Student in Chemistry & Biochemistry

CAL/OSHA cites campus for ongoing violations following the 2009 fatality

Campus announces its intention to contest the citations



Reactive Safety


UCLA Update 17 March 2010 2007 Lab Fire

◦ Biochem grad student seriously burned when alcohol spill ignited by Bunsen burner

◦ 7 days in hospital◦ Student was paid UCLA employee


Page

9

UCLA Update 17 March 2010 Citations

◦ Failure to report injury◦ Failure to correct unsafe working conditions

Flammable liquid and open flame◦ Inadequate PPE

No lab coat, insufficient clothing Proposed fine: $29,300


UCLA Update 17 March 2010 Follow-up inspection of Chemistry &

Biochemistry◦ Prompted by complaints from (unionized)

university employees UCLA plans to contest both sets of citations


UCLA Update 17 March 2010


10 REGULATORY 1 Improper classification of injury/illness 1 Injury & Illness Program Violation 3 Non-compliance with PPE or Monitoring requirements 3 Improper storage or labeling 1 Inadequate Chemical Hygiene Plan compliance 1 MSDSs not available; do not have 5 SERIOUS 2 Injury & Illness Program implementation violations 1 Improper storage of flammable gas, pyrophoric liquid, flammable liquid 2 Inadequate implementation of CHP; unqualified CHO 1 REPEAT VIOLATION 1 No training of supervisors on requirements for handling particularly hazardous

substances PROPOSED FINE $67,720

During the past ten days:◦ UCSD terminated the campus CHO

Allegedly due to budget constraints◦ The UCSD Director of EHS resigned on very short

notice Reportedly is taking a position at Ann Arbor

◦ Money is “found” to re-hire the CHO No relationship to UCLA has been

established

UCSD Update

Advanced Chemical [email protected] (from title page)

Common sense is not common



The incident◦ Sodium was used in an organic synthesis reaction◦ Knife used to cut Sodium was rinsed in a regular sink

with Methanol◦ Piece of Sodium hit water in sink, igniting the

Methanol◦ Fire spread to 20 liter poly bottle of Acetone on shelf

above sink Bottle burst

Common sense is not common



The incident, continued◦ A burning pool of acetone spread over lab◦ Excess quantities of solvents ignited

Two labs totaled Major flooding & smoke damage $750,000 property loss No injuries Same incident occurred 10 years later at

another major research center

MANY CAUSES:SOME COMMON THEMES◦ Insufficient training/Insufficient supervision◦ Intense time/productivity pressure◦ Safety institutionalized/Safety not functional at

the lab level◦ Academic culture rewards productivity with no

attention to safety Safety must be given the same priority in academic

culture given to publications and funding



Reactive Safety


What must be done?◦ EHS –

Shift responsibility for safety to PI’s Make it very clear that EH&S are consultants, not the

“Safety Cops” Change the culture by shifting responsibility Get Provost-level support

◦ CAMPUS Include “safety performance” in PI evaluation

Teaching Grants & Funding Lab Space Tenure



Reactive Safety


What must be done?◦ National

Give CSB Funding/Authority to investigate laboratory-scale incidents

Place “Safety Performance” at an equal level of importance as research performance



Reactive Safety


What must be done?◦ The Chemical Safety Community

Define “Safety Performance” Lead rather than push

And before ending …



Reactive Safety


Questions - Comments



Reactive Safety


Pyrophoric Chemicals

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