Standard Operating Procedure Template
for work with Pyrophoric and other highly reactive materials
(Customized SOP required, see italicized text that indicates where chemical and project
specific information needs to be developed)
Chemical
Name/Class: _____________________________
CAS #:
_________________
PI:
_____________________________
Date:
_________________
Building:
_____________________________
Room #:
_________________
1. General Statement of hazards:
Pyrophoric chemicals are those compounds that will ignite spontaneously in air at
temperatures of 130° F or below in the absence of added heat, shock or friction.
Some classes and examples of pyrophoric materials are listed in the table below
Grignard Reagents
Metal alkyls and aryls
Metal Carbonyls
Alkali Metals
Metal Powders
Metal Halides
Nonmetal Halides
Nonmetal alkyls
Phosphorus (white)
RMgX
RLi (tert-butyl Lithium is very pyrophoric) RNa, R3Al, R2Zn
Ni(CO)4, Fe(CO)5, CO2(CO)8
Na, K
Al, Ca, Co, Fe, Mg, Mn, Pd, Pt, Ti, Sn, ZN, Zr
NaH, LiAlH4
B2H6 and other Boranes, PH3, AsH3, SiH4
R3B, R3P, R3As
2. Proposed Use(s):
This SOP must be customized, and a separate SOP should be developed for each
pyrophoric/highly reactive material in the lab. Use this section to describe the use(s) for
the chemical listed above.
3. Hazard Assessment:
A job hazard assessment must be performed for work involving the use of pyrophoric
materials. The hazard assessment should thoroughly address the issue of fire safety
(including the need for Class D fire extinguishers), proper use and handling techniques,
chemical toxicity, storage and spill response. Include hazards associated with the
experimental design (use of lasers, cryogens, high pressure, etc.). Once all the hazards
have been identified and noted in this space, you need to address how to eliminate or
reduce/mitigate the hazards by providing detailed information on proper use and
handling, storage, disposal, spill and other emergency response, including
SOP template (must be customized), rev. 1, Mar. 2014
page 1 of 8
Standard Operating Procedure Template
for work with Pyrophoric and other highly reactive materials
(Customized SOP required, see italicized text that indicates where chemical and project
specific information needs to be developed)
administrative, work practice and engineering controls and PPE requirements. Generic
information for your customization is provided below.
4. General Guidelines (for customization)
A. Engineering Controls
List the specific engineering controls that will be used with the listed chemical in
this section. See examples and generic information below.

Ventilation
Always handle liquid pyrophoric chemicals in a laboratory hood or glove
box/bag. If your research does not permit the handing of pyrophoric chemicals
in a fume hood or glove box, you must contact EH&S to review the adequacy
of all special ventilation.

Laboratory Hood
Many pyrophoric chemicals release noxious or flammable gases and should be
handled in a hood. In addition, some solid pyrophoric materials are stored
under kerosene (or other flammable solvents); therefore, the use of a hood is
required to prevent the release of flammable vapors in the laboratory. Glove
boxes may also be used.

Glove (dry and inert) Box/Bag
Glove boxes/bags must be used to handle pyrophoric chemicals if sufficient
inert or dry atmospheres cannot be achieved using a vacuum gas manifold
system.

Gas Cabinet
Ventilated compressed gas cylinder storage cabinets may be required for high
hazard gases such as pyrophorics. Consult EH&S before purchasing any
pyrophoric gases.

Safety Shielding
Safety shielding is required any time there is a risk of explosion, splash hazard
or a highly exothermic reaction. All manipulations of pyrophoric chemicals
which pose this risk should occur in a laboratory hood with the sash in the
lowest feasible position. Portable shields, which provide protection to all
laboratory occupants, are also acceptable in some situations.
SOP template (must be customized), rev. 1, Mar. 2014
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Standard Operating Procedure Template
for work with Pyrophoric and other highly reactive materials
(Customized SOP required, see italicized text that indicates where chemical and project
specific information needs to be developed)

Vacuum Protection
Evacuated glassware can implode and eject flying glass and splattered
chemicals. Vacuum work involving pyrophoric chemicals must be conducted
in a laboratory hood or isolated in an acceptable manner.
Mechanical vacuum pumps must be protected using cold traps and, where
appropriate, filtered to prevent particulate release. The exhaust for the pumps
must be vented into an exhaust hood. Vacuum pumps should be rated for use
with pyrophoric chemicals.

Pressurized Systems
Mineral oil bubbler must be used to release pressure from reagent or reaction
vessels. (NEVER use mercury bubblers. DRI has a metallic mercury use
prohibition in place.)

Storage Units
Liquid pyrophorics must be stored in sealed containers with (preferably)
PTFE-lined septa to prevent air exposure. Packaging, such as the Aldrich
Sure/Seal packaging system, must be used and must be maintained to ensure
container integrity. Pyrophorics will be stored by themselves in an
appropriately labeled flammable liquid storage cabinet or glove box under
inert atmosphere. If refrigeration is required, an explosion proof unit must be
used.
B. Work Practice Controls
Specific written procedures, approved in advance by the Principal Investigator,
are required. These must address all sections of this template. The use of
pyrophoric gases requires prior EH&S approval as a High Risk Procedure.
Before working with these types of compounds, read the SDSs and other reference
materials carefully. Some good web resources include:
 DOE Handbook Primer on Spontaneous Heating and Pryrophoricity
http://www.dri.edu/images/stories/editors/ehs/ehsdocs/Lab_Safety_pyro_DOE_Hand
book_Pyrophoricity.pdf
 PNNL-18668 Handling Pyrophoric Materials
 http://www.dri.edu/images/stories/editors/ehs/ehsdocs/Lab_Safety_pyro_DOE_PNN
L_Handling_Pyrophoric.pdf
 Aldrich Technical Bulletin AL-164—Handling Pyrophoric Reagents
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull_al164.Par.
0001.File.tmp/al_techbull_al164.pdf
 Aldrich Technical Bulletin AL-134—Handling Air-Sensitive Reagents
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull_al134.Par.
0001.File.tmp/al_techbull_al134.pdf
SOP template (must be customized), rev. 1, Mar. 2014
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Standard Operating Procedure Template
for work with Pyrophoric and other highly reactive materials
(Customized SOP required, see italicized text that indicates where chemical and project
specific information needs to be developed)
Standard practices that must be employed include

Before purchasing pyrophoric materials, consult with EH&S to select a
compatible fire extinguisher and to complete any PHS paperwork that may be
required due to the chemical’s health hazard(s).
(Note: the proper
extinguisher must be on hand before any work with pyrophoric materials
takes place and preferably before the material is ordered.)

Purchase minimal amounts, only what is needed and will be entirely
consumed in a 3-6 month time frame

Set up a designated area for working with pyrophoric chemicals. This area
must have a chemical lab hood and/or a (dry) glove box (with inert
atmosphere, if needed) that is located within 10 seconds of an eyewash and
safety shower and an appropriate fire extinguisher as determined in
consultation with EH&S. In addition:
 incompatible materials should be removed from the area,
 a container of powered lime (soda ash) or sand should be kept within
arm’s reach (for covering spills), and
 employees should be aware of the location of all emergency equipment
and should know how to use it if needed.
The designated area must be appropriately marked and labeled and any
changes to door or storage area signage required due to the hazardous nature
of the chemicals involved, must be in place. (Consult with EH&S for specific
details of signage requirements.)

Store and use pyrophoric chemicals under an inert atmosphere or under
kerosene or other solvent as appropriate. (Spell out here the specifics needed
for the pyrophoric chemicals to be used.)

Know the location of the nearest compatible fire extinguisher and other
emergency equipment and how to use it.

Discuss transfer and handling procedures for the chemicals involved in detail.
(See the above referenced Aldrich Technical Bulletins for recommendations
on the safe transfer of liquid pyrophorics. Use schematics and photos as
appropriate.)

Before conducting the actual procedure, always perform a dry run (without the
pryophoric material) to identify and resolve possible safety hazards.
SOP template (must be customized), rev. 1, Mar. 2014
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Standard Operating Procedure Template
for work with Pyrophoric and other highly reactive materials
(Customized SOP required, see italicized text that indicates where chemical and project
specific information needs to be developed)

Always use the buddy system, i.e., work within sight and/or hearing of at least
one other person who is familiar with the hazards and written procedures.

Manipulations using a syringe or cannula will be carried out in a laboratory
hood (over a spill tray if possible) with the sash position as low as possible.

Solid pyrophorics must be handled only in an inert atmosphere glove box or
glove bag.
C. Personal Protective and Emergency Equipment
Customize your SOP with the specific PPE required for the chemicals that will be
used. Ensure you have documented your selection and have documented training
for all employees involved in how to don, doff and maintain the required PPE and
how to obtain replacement PPE if required. The training records should be filed
in Section 6 of the lab’s Chemical Hygiene Plan (CHP) binder, and the
documentation of training should be recorded on a DRI Lab Specific Training
Form, Appendix D of the DRI CHP.




Eye and Face Protection
At a minimum, safety glasses with permanently attached top and side shields
must be worn in the laboratory. These glasses, however, do NOT protect
against splash hazards. When performing a hazardous activity, a face shield
must be worn in addition to the safety glasses OR switch to chemical splash
goggles (with shielded ventilation ports) and add a face shield over goggles if
splashing to the face is possible.
Gloves
Appropriate gloves should be worn when handling hazardous materials. For
handling pyrophoric chemicals, if no specific glove type is recommended, use
heavy latex (Playtex) gloves for very small manipulations and nitrile over
Nomex® aviator (or other fire resistant) gloves for larger manipulations.
Protective Clothing
Wear a fully-buttoned, flame-resistant lab coat (Nomex® or equivalent) with
sleeves extended to the wrists. If large quantities will be used, a chemicalresistant apron is also required. Note that personal clothing should not be of a
type that may easily ignite (such as polyester or nylon).
Respirators
The use of respirators requires medical certification, fit testing and training,
and should not be needed when using lab scale quantities and the proper
engineering controls. Consult with EH&S regarding questions about
respiratory protection requirements.
SOP template (must be customized), rev. 1, Mar. 2014
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Standard Operating Procedure Template
for work with Pyrophoric and other highly reactive materials
(Customized SOP required, see italicized text that indicates where chemical and project
specific information needs to be developed)



Eye Wash
A plumbed eyewash must be readily accessible within 10 seconds of travel
time from the experimental set up. Bottle type eyewash stations are not
acceptable. Should flushing of the eyes or face be necessary, a minimum of
15 minutes in the eye wash is required. The victim should then seek medical
assistance and evaluation. The MSDSs for the chemicals believed to be
splashed to the eyes or face should be made available to the doctor.
Safety Showers
A plumbed safety shower must be readily accessible within 10 seconds of
travel time from the experimental set up. After turning on the water, while
standing in the shower, all potentially contaminated clothing (including shoes,
socks and under garments) must be removed. The victim must remain in the
running water for a minimum of 15 minutes. The victim should then seek
medical assistance and evaluation. The SDSs for the chemicals believed to be
involved should be made available to the doctor.
Fire Extinguishment
A Class ABC dry chemical fire extinguisher must be available within 10
seconds travel time from where pyrophoric chemicals are used. Know the
location of the nearest Class D fire extinguisher. If possible have one in the
lab where the work is being conducted. A container of powdered lime
(calcium oxide, CaO) or dry sand should be kept within arm’s length when
working with a pyrophoric material.
D. Protocols
Discuss here the specific handling, transferring, cleaning, storing and disposal
procedures to follow when working with the chemicals listed above using
information from the SDS, Aldrich Technical Bulletins, and the DRI Guidelines
for Safe Use of Pyrophoric/Water Reactive Reagents as applicable to this
particular use/situation. Sections to include are listed below.

Specific Handling of Pyrophoric Reagents and/or Solids Procedure
(Include detailed information on syringe or cannula transfer if your pyrophoric
chemical is a liquid.)

Specific Storage Procedure

Specific Cleaning Procedures (ex. Removing pyrophoric reagents from
needles and syringes)

Specific Spill and Accident Procedures
(Again customize the below as appropriate for the chemicals used.
SOP template (must be customized), rev. 1, Mar. 2014
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Standard Operating Procedure Template
for work with Pyrophoric and other highly reactive materials
(Customized SOP required, see italicized text that indicates where chemical and project
specific information needs to be developed)
All spills, no matter how small, must be reported to your supervisor and
should be reported to EH&S.)
Spill - Small
o Exert extreme caution due to potential spontaneous combustion.
o Exert extreme caution due to potential ignition of flammable solvents or
other materials.
o If anyone is exposed, or on fire, wash with copious amounts of water,
ideally in the lab shower.
o Call for a coworker to provide backup.
o Place a fire extinguisher nearby.
o Carefully remove nearby flammable materials.
o Powdered lime (calcium oxide, CaO) or dry sand should be used to
completely smother and cover any spill that occurs.
o Carefully quench by slow addition of isopropanol.
o After complete quenching, double bag spill residues for hazardous waste
pickup.
o Call 911 then 4411 for emergency assistance if necessary.
Spill - Large
o Exert extreme caution due to potential spontaneous combustion.
o Exert extreme caution due to potential ignition of flammable solvents or
other materials.
o If anyone is exposed, or on fire, wash with copious amounts of water,
ideally in the lab shower.
o Call 911, then 4411 for emergency assistance.
o Evacuate the spill area.
o Post someone or mark-off the hazardous area with tape and warning signs
to keep other people from entering.
o Provide emergency personnel with technical advice on the chemicals
involved.

Specific Deactivation/Disposal Procedures
5. Required Training
Outline here the required training for working in the lab and how the training will be
documented. In addition to specific training on using pyrophoric/water reactive
chemicals, some items to include are General Lab Safety Orientation/annual
refresher, Personal Protective Equipment training, Fire Extinguisher training, etc.
(See Section VII of the DRI Chemical Hygiene Plan for additional guidance).
SOP template (must be customized), rev. 1, Mar. 2014
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Standard Operating Procedure Template
for work with Pyrophoric and other highly reactive materials
(Customized SOP required, see italicized text that indicates where chemical and project specific information needs to be developed)
6. Acknowledgement of Receipt and Understanding of SOP Content
Maintain a copy of this page with signatures with the SOP in Section 5 of your CHP binder.
“I have read and understand this SOP. I agree to fully adhere to its requirements.”
Last
First
SOP template (must be customized), rev. 1, Mar. 2014
Employee
ID #
Signature
Date
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