Standard Operating Procedure
Settlement Class: Pyrophorics
Print a copy and insert into your
Laboratory Safety Manual and Chemical Hygiene Plan.
Department:
Chemistry
Date SOP was written:
12/5/2012
Date SOP was approved by PI/lab supervisor:
1/13/2013
Principal Investigator:
Richmond Sarpong
Internal Lab Safety Coordinator/Lab Manager:
Rebecca Murphy
Lab Phone:
510-643-2485
Office Phone:
510-643-6312
Emergency Contact:
Richmond Sarpong, 626-644-2407
(Name and Phone Number)
Latimer Hall: 834, 836, 837, 838, 839, 842, 847, 849,
907
(Building/Room Number)
Location(s) covered by this SOP:
Type of SOP:
Process
Hazardous Chemical
Hazardous Class
Purpose
This is a chemical class SOP. Some uses of the chemicals in this class require specific SOPs.
Chemical-specific SDSs and all relevant SOPs must be reviewed prior to use of any chemical in this
class.
A complete list of the water reactive chemicals from the Settlement Agreement can be found in Appendix
Examples of Pyrophorics
 Metal alkyls and aryl compounds: diethyl zinc, dimethyl cadmium, trimethyl
aluminum
 Alkyl lithium or organolithium compounds: tert-butyllithium, sec-butyllithium, nbutyllithium,methyl lithium. T-butyllithium is most pyrophoric
 Grignard Reagents: RMgX (R=alkyl, X=halogen), methylmagnesium bromide
 Metal carbonyls: nickel tetracarbonyl
 Metal powders (finely divided): Cobalt, iron, zinc, zirconium, barium strontium,
calcium, hafnium
 Metal hydrides: Sodium hydride, lithium aluminum hydride; Nonmetal hydrides:
Diethylarsine, diethylphosphine
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SOP Template developed by The UC Center for Laboratory Safety
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Non-metal alkyls: R3B, R3P, R3As; tetramethyl silane, tributyl phosphine
White and red phosphorus
Group I (Alkali) metals: Lithium, potassium, sodium, sodium-potassium alloy
(NaK), rubidium, cesium
 Pyrophoric gases (e.g. silane, dichlorosilane, phosphine) are covered in the UCB
toxic gas program (http://www.ehs.berkeley.edu/images/ehs/pubs/32toxgas.pdf)
For a more complete listing of pyrophoric materials and examples, as described in
the Settlement Case, please go to Appendix A.
Physical & Chemical Properties/Definition of Chemical Group
CAS#: List here
Class: List here NOTE: this may vary from the Settlement Category
Molecular Formula: List here
Form (physical state): List here
Color: List here
Boiling point: List here °C (List here °F) - lit.
Potential Hazards/Toxicity
Pyrophorics react to air spontaneously. Also, most pyrophorics react violently with water.
Therefore, water should not be allowed to contact pyrophoric materials. The reaction rate of
pyrophorics (and therefore heat and gas generation) depends on the material's surface area.
Therefore smaller particle size or liquids increases the hazards associated with these materials.
Because of the potential reactivity, pyrophorics must be handled under an inert atmosphere and
in such a way that rigorously excludes air/moisture. Many come dissolved or immersed in a
flammable solvent that may pose additional hazards. Most of these materials are toxic and may
cause damage to the liver, kidneys, and central nervous system.
Additional hazards to specific pyrophoric chemicals must be identified by a review of the
appropriate Safety Data Sheets prior to commencing lab work.
Engineering Controls
NOTE: Lab-specific information on engineering controls may be included in the Protocol/Procedure
section.
The following is a general plan for all pyrophoric materials:
1. Work under an inert atmosphere (e.g., argon, nitrogen) in a glove box, vacuum manifold
or any enclosed inert environment inside a fume hood.
2. Keep the material under inert atmosphere (e.g., nitrogen, argon) when not in use.
3. Only when absolutely necessary to transfer larger quantities of pyrophorics, use an
appropriately-designed, engineered system that is tested and properly used.
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SOP Template developed by The UC Center for Laboratory Safety
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Personal Protective Equipment (PPE)
NOTE: Lab-specific information on PPE selection may be included in the Protocol/Procedure section.
Respiratory Protection
NOTE: Lab personnel intending to use/wear a respirator mask must be trained and fit-tested by EH&S.
This is a regulatory requirement.
Respirators should be used only under any of the following circumstances:
 As a last line of defense (i.e., after engineering and administrative controls have been
exhausted).
 When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will
be exceeded.
 Regulations require the use of a respirator.
 An employer requires the use of a respirator.
 There is potential for harmful exposure due to an atmospheric contaminant (in the absence of
PEL)
 As PPE in the event of a chemical spill clean-up process
Hand Protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique (without
touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves
after use in accordance with applicable laws and good laboratory practices. Wash and dry hands.
NOTE: Lab-specific and chemical-specific information on glove selection may be included in the
Protocol/Procedure section. Refer to glove selection from the link below:
For glove selection, go to: http://ehs.berkeley.edu/hs/63-laboratory-safety/94-glove-selection-andusage.html
NOTE: Lab-specific and chemical-specific information on glove selection may be included in the
Protocol/Procedure section. Nomex-and-leather flight gloves over chemically resistant gloves are
recommended in the UC Berkeley Office of Environmental Health and Safety document “Safe Use of
Pyrophoric and Water Reactive Reagents”. See also, EHS&S document entitled “Glove Selection and
Usage.”
http://www.ehs.berkeley.edu/hs/63-laboratory-safety/94-glove-selection-and-usage.html
http://www.ehs.berkeley.edu/hs/126-standard-operating-procedures-sop.html
Eye Protection
At minimum, use chemical safety goggles or safety eyewear when working with pyrophorics in a glove
box or fume hood. Use face shield (8-inch minimum) with chemical safety goggles or protective eyewear
when not protected by a fume hood sash or glove box. Use equipment for eye protection tested and
approved under appropriate government standards such as NIOSH (US) or EN 166(EU) or ANSI Z87.1.
Skin and Body Protection
Long pants, closed-toed and closed-heeled shoes, cotton or wool-based clothing/attire, and flame
resistant lab coat must be worn for protecting against chemical hazards. Synthetic clothing is strongly
discouraged.
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SOP Template developed by The UC Center for Laboratory Safety
Date: 01/02/2013
NOTE: A Nomex lab coat is recommended in the UC Berkeley Office of Environmental Health and Safety
document “Safe Use of Pyrophoric and Water Reactive Reagents”.
http://www.ehs.berkeley.edu/hs/126-standard-operating-procedures-sop.html
Hygiene Measures
Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at
the end of workday.
First Aid Procedures
Notify supervisor and EH&S immediately. Follow up with a call to 510-642-9090 to report the incident.
If Inhaled
Move person into fresh air. If not breathing, give artificial respiration. Consult a physician.
In Case of Skin Contact
Take off contaminated clothing immediately. Wash off with soap and plenty of water for 15 minutes. Take
victim immediately to hospital. Consult a physician.
In Case of Eye Contact
Rinse thoroughly with plenty of water for at least 15 minutes, occasionally lifting the upper and lower
eyelids. Get medical aid immediately.
If Swallowed
Do not induce vomiting. Never give anything by mouth to an unconscious person. Rinse mouth with
water. Consult a physician.
Special Handling and Storage Requirements
NOTE: Lab-specific information on handling and storage may be included in the Protocol/Procedure
section.
Working Alone
Certain extremely hazardous operations should not be performed if the PI or Lab Safety Contact(s) are
not present. Never work alone with extremely hazardous materials/operations. See the
Protocol/Procedure section below for specific prohibitions (if any) on working alone.
NOTE: The UC Berkeley Office of Environmental Health and Safety document “Safe Use of Pyrophoric
and Water Reactive Reagents” specifies not to work alone or during off hours, when there are few people
around to help. http://www.ehs.berkeley.edu/hs/126-standard-operating-procedures-sop.html
Precautions For Safe Handling
 Design a quenching scheme for residual materials prior to using pyrophoric materials.
 Never use water to quench the material itself or a reaction where a pyrophoric reagent is used.
 Begin quenching with a low reactivity quenching agent and slowly add more reactive quenching
agents. For example, first quench residual sodium metal with isopropanol and then add ethanol to the
mixture.
 Design your experiment to use the least amount of material possible to achieve the desired result.
 It is better to do multiple transfers of small volumes than attempt to handle larger quantities. Before
transferring, make sure that the material is at room temperature.
 Avoid formation of dusts and aerosols
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SOP Template developed by The UC Center for Laboratory Safety
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Provide appropriate exhaust ventilation at places where airborne hazardous materials may be
generated.
Keep away from sources of ignition and combustible materials such as open flames, non-explosionproof hot plates, paper towels and KimiwipesTM.
Take measures to prevent the build-up of electrostatic charge.
Eliminate or substitute a less hazardous material when possible.
Verify your experimental set-up and procedure prior to use.
Inform colleagues that this material will be used and where. Label the work area with a sign saying
"Pyrophorics In-Use Area".
Ensure that the area is properly equipped with a properly functioning eye wash/safety shower within
ten seconds of travel.
Never use water to extinguish fires caused by water reactive materials. Be sure to use a an
appropriate fire extinguisher for the materials being used.
NOTE: See a more details on safe handling in the UC Berkeley Office of Environmental Health and
Safety documents “Safe Use of Pyrophoric and Water Reactive Reagents” and “Quenching of Pyrophoric
Substances”. http://www.ehs.berkeley.edu/hs/126-standard-operating-procedures-sop.html
Conditions For Safe Storage
 Whenever possible, store inside a glove box. Otherwise, store inside a container with an inert
atmosphere.
 Keep container tightly closed in a dry and well-ventilated place.
 Minimize dust generation and accumulation.
 Hazard communication label on the container must read ‘Water Reactive’. W
 Never allow product to get in contact with water or water based compounds during storage.
 Do not leave the container on the bench top - even momentarily.
 Do not leave the container near a lab sink, emergency eyewash or safety shower.
 Do not store in humid air/moisture.
 Store and handle under inert gas (Noble gases such as Nitrogen, Argon etc.)
 Keep in a dry place (such as a desiccator or a dry box or glove box).
 Use/purchase only amount that is needed in a reasonable amount of time. Use small quantities
whenever possible.
 Store in a separate secondary container and label the material clearly.
 Follow any substance-specific storage guidance provided in Safety Data Sheet documentation.
 Store in a cool, dry location, separated from acids.
 Monitor your inventory closely to assure that you have tight control over your material.
 Wash hands and arms with soap and water after handling.
 Minimize dust generation and accumulation.
 At the end of each project, thoroughly inspect the area for residual reactive material.
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NOTE: See a more details on safe handling in the UC Berkeley Office of Environmental Health and
Safety documents “Toxic Gas Program Document”
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http://www.ehs.berkeley.edu/hs/126-standard-operating-procedures-sop.html
Spill and Accident Procedure
Fire-Fighting & Extinguishing Media
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SOP Template developed by The UC Center for Laboratory Safety
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Prior to use, review the Safety Data Sheet for the proper fire extinguisher to use with the given material
Acceptable fire extinguishing media include Metal X, soda ash (lime) or dry sand to respond to small fires, and
an ABC extinguisher for large fires. The extinguishing media should be located near where the pyrophoric work
is occurring. DO NOT use water to attempt to extinguish a pyrophoric/reactive material fire as it can enhance
the combustion of some of these materials, e.g. metal compounds, and do not use water or CO2 extinguishers
on an organolithium fire. A small beaker of Metal X/LithX, dry sand or soda ash (lime) in the work area is useful
to extinguish any small fire that occurs at the syringe tip and to receive any last drops of reagent from the
syringe. . In general, an ABC dry powder extinguisher will put out the fire, but the pyrophoric reagent may
reignite.
Special Protective Equipment For Fire-Fighters
Wear Self-Contained Breathing Apparatus (SCBA) for fire-fighting if necessary.
Personal Precautions
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Avoid dust formation.
Ensure adequate ventilation.
Remove all sources of ignition and combustion.
Evacuate personnel to safe areas.
Environmental Precautions
Do not let product enter drains.
Methods and materials for containment and cleaning up
 Pick-up and dispose of as hazardous waste without creating dust.
 Do not flush with water or bring in contact with moisture.
 Keep in suitable, tightly closed containers for disposal.
Chemical Spill Dial 911
Spill – Assess the extent of danger. Help contaminated or injured persons. Evacuate the spill area.
Avoid breathing vapors. If possible, confine the spill to a small area using a spill kit or absorbent material.
Keep others from entering contaminated area (e.g., use caution tape, barriers, etc.).
Small (<1 L) – If you have training, you may assist in the clean-up effort. Use appropriate personal
protective equipment and clean-up material for chemical spilled. Double bag spill waste in clear plastic
bags, label and take to the next chemical waste pick-up.
Large (>1 L) – Dial 911 and 510-642-9090 for assistance.
Chemical Spill on Body or Clothes – Remove clothing and rinse body thoroughly in emergency shower
for at least 15 minutes. Seek medical attention. Notify supervisor and EH&S immediately. Follow up with
a call to 510-642-9090 to report the incident.
Chemical Splash Into Eyes – Immediately rinse eyeball and inner surface of eyelid with water from the
emergency eyewash station for 15 minutes by forcibly holding the eye open. Seek medical attention.
Notify supervisor and EH&S immediately. Follow up with a call to 510-642-9090 to report the incident.
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SOP Template developed by The UC Center for Laboratory Safety
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Medical Emergency Dial 911
Life Threatening Emergency, After Hours, Weekends And Holidays – Dial 911 or go to the nearest
emergency room. Note: All serious injuries must be reported to EH&S within 8 hours. Follow up with a
call to 510-642-9090 to report the incident.
Non-Life Threatening Emergency – Go to the Occupational Health Facility (Tang Health Center). After
hours go to the nearest emergency room. Note: All serious injuries must be reported to EH&S within 8
hours. Follow up with a call to 510-642-9090 to report the incident.
Needle stick/puncture exposure (as applicable to chemical handling procedure) – Wash the affected
area with antiseptic soap and warm water for 15 minutes. For mucous membrane exposure, flush the
affected area for 15 minutes using an eyewash station. Go to the Occupational Health Facility (Tang
Health Center). After hours go to the nearest emergency room. Note: All needle stick/puncture exposures
must be reported to EH&S within 8 hours. Follow up with a call to 510-642-9090 to report the incident.
Decontamination/Waste Disposal Procedure
Wearing proper PPE, decontaminate equipment and bench tops using procedures done in
cooperation with site EH&S. Dispose of any pyrophoric and water reactive waste materials and any
other disposables contaminated with these materials as hazardous waste.
NOTE: Lab-specific information on decontamination/waste disposal may be included in the
Protocol/Procedure section. See the EH&S Fact Sheet, “Hazardous Waste Management” for
general instructions on procedures for disposing of hazardous waste.
http://ehs.berkeley.edu/hm/279-new-hazardous-waste-program-hwp.html.
Label Waste
Label all containers with the label provided at http://ehs.berkeley.edu/hm/279-new-hazardous-wasteprogram-hwp.html. See the EH&S Fact Sheet, “Hazardous Waste Management” for general
instructions on procedures for disposing of hazardous waste.
Store Waste
 Store hazardous waste using procedures done in cooperation with site EHS&S.
Dispose of Waste
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Dispose of regularly generated chemical waste within 6 months
Call EH&S for questions
Empty Containers
o Dispose as hazardous waste if it once held extremely hazardous waste (irrespective of
the container size)
o Consult waste pick-up schedule
Prepare for transport to pick-up location
 Check on-line waste tag
 Write date of pick-up on the waste tag
 Use secondary containment
 Dispose of regularly generated chemical waste within 6 months
 Call EH&S for questions
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SOP Template developed by The UC Center for Laboratory Safety
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Safety Data Sheet (SDS) Location
SDS can be accessed online at http://ucmsds.com
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SOP Template developed by The UC Center for Laboratory Safety
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SOP Template developed by The UC Center for Laboratory Safety
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Documentation of Training (signature of all users is required)
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Prior to conducting any work with strong reducing agents, designated personnel must provide training to
his/her laboratory personnel specific to the hazards involved in working with the substance(s), work area
decontamination, and emergency procedures.
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The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of
the SDS provided by the manufacturer.
I have read and understand the content of this SOP:
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Initials
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Date: 12/12/2012
Appendix A (from Case Settlement Appendix 2)
Pyrophoric Chemicals
Chemical Family
1.1.
Aluminum alkyls:
R3Al, R2AlCl, RAlCl2
1.2. Grignard Reagents:
RMgX (R=alkyl, aryl, vinyl
X=halogen)
1.3. Lithium Reagents:
RLi (R = alkyls, aryls, vinyls)
1.4. Zinc Alkyl Reagents: RZnX,
R2Zn
1.5. Metal carbonyls
1.6. Metal powders (finely
divided)
1.7. Low Valent Metals
1.8. Metal hydrides
1.9. Nonmetal hydrides
1.10. Non-metal alkyls: R3B,
R3P, R3As
1.11. Used hydrogenation
catalysts
1.12. Activated Copper fuel cell
catalysts
1.13. Finely Divided Sulfides
1.14. Elements
Example
Et3Al, Et2AlCl, EtAlCl2, Me3Al, Diethylethoxyaluminium
Butyllithium, Isobutyllithium, sec-Butyllithium, tert-Butyllithium, Ethyllithium,
Isopropyllithium, Methyllithium, (Trimethylsilyl)methyllithium, Phenyllithium,
2-Thienyllithium, Vinyllithium, Lithium acetylide ethylenediamine complex,
Lithium (trimethylsilyl)acetylide, Lithium phenylacetylide
Et2Zn
Lithium carbonyl, Nickel tetracarbonyl, Dicobalt octacarbonyl
Bismuth, Calcium, Cobalt, Hafnium, Iron, Magnesium, Titanium, Uranium,
Zinc, Zirconium
Titanium dichloride
Potassium Hydride, Sodium hydride, Lithium Aluminum Hydride,
Diethylaluminium hydride, Diisobutylaluminum hydride
Arsine, Boranes, Diethylarsine, diethylphosphine, Germane, Phosphine,
phenylphosphine, Silane, Methanetellurol (CH3TeH)
Tributylphosphine, Dichloro(methyl)silane
Raney nickel, Palladium, Platinum
Cu/ZnO/Al2O3
Iron Sulfides (FeS, FeS2, Fe3S4), and Potassium Sulfide (K2S)
Phosphorus, Cesium, Lithium, Potassium, Sodium, Sodium Potassium Alloy
(NaK), Aluminum Phosphide (AlP)
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SOP Template developed by The UC Center for Laboratory Safety
Date: 12/12/2012