University of the Sciences
Environmental Health & Radiation Safety Department
Standard Operating Procedure
Pyrophoric Chemicals
Standard operating procedures (SOP) are intended to provide you with general guidance on
how to safely work with a specific class of chemical or hazard. This SOP is generic in nature.
It addresses the use and handling of substances by hazard class only. In some instances
multiple SOP’s may be applicable for a specific chemical (i.e., both the SOP’s for flammable
liquids and carcinogens would apply to benzene). If you have questions concerning the
applicability of any item listed in this procedure, contact the Environmental Health & Radiation
Safety Department (215-596-8925) or the Principal Investigator of your laboratory. Specific
written procedures are the responsibility of the principal investigator.
If compliance with all the requirements of this standard operating procedure is not possible, the
principal investigator must develop a written procedure that will be used in its place. This
alternate procedure must provide the same level of protection as the SOP it replaces. The
Environmental Health & Radiation Safety Department is available to provide guidance during
the development of alternate procedures.
Pyrophoric chemicals are liquids, solids, and gases that will ignite spontaneously in air at or
below 130°F.
Examples of Pyrophoric Reagents Commonly Found in Laboratories
Liquids/Solutions
Organolithiums
Alkyl and Aryl Lithiums
n-butylithium,
t-butylithium
Lithium Amides
Lithium Alkoxides
Organomagnesiums “Grignard Reagents”
Alkyl and Aryl Magnesium Halides
Methylmagnesium Chloride,
Allylmagnesium Bromide
Organozincs
Diethyl Zinc
Aluminum Alkyls
Trimethylaluminum
Diisobutylaluminum hydride
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Environmental Health & Radiation Safety Department
Metal Carbonyls
Nickel Carbonyl
Iron Pentacarbonyl
Silicon Halides
Dichloromethylsilane
Solids (may also come as solutions)
Metal Hydrides
Sodium Hydride
Potassium Hydride
Lithium Aluminum Hydride
Finely Divided Metals
Aluminum
Lithium
Magnesium
Titanium
Zinc
Zirconium
Sodium
Potassium
Used Hydrogenation Catalysts
Raney Nickel
Palladium on Carbon
Gases
Silane
Diborane
Phosphine
Pre-Requisites for Pyrophoric Use
Supervision and Training
All users of pyrophoric reagents in the laboratory must receive hands-on instruction
from a senior member of the laboratory (Principal Investigator or experienced user) and
must be closely supervised until safe work practices become proficient and are
consistently demonstrated. This training must be documented so that proof of training
is available upon request.
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Environmental Health & Radiation Safety Department
Consider performing a “dry run” to identify and resolve possible hazards before
conducting the actual procedure with the pyrophoric chemical.
The Sigma-Aldrich Technical Bulletins “Handling of Air-Sensitive Reagents (AL-134)”
and “The Aldrich Sure/PacTM System (AL-136)” provide further guidance.
Use the buddy system. Never work alone or work off-hours where there are few people
around to help.
Hazard Assessment
Hazard Assessment for work involving pyrophoric chemicals should thoroughly address
the issue of fire safety (including if there is the need for a Class D fire extinguisher),
proper use and handling techniques, chemical toxicity, storage, and spill response. The
SDS (formerly called MSDS’s) and other resources must be reviewed before using an
unfamiliar chemical and periodically as a reminder.
Contact EHRS if you would like assistance in performing a thorough hazard assessment
prior to starting your work.
EHRS Notification
Provide EHRS advance notice if planning an experiment requiring large quantities
(greater than 100 ml of liquid or 10 g of solid) of pyrophoric materials. EHRS should
also be notified if a particular laboratory group is planning to use pyrophoric reagents for
the first time.
Gas Cylinders
Cylinders of compressed pyrophoric gases must be handled as high energy sources.
When storing or moving a cylinder, have the cap securely in place to protect the stem.
Use suitable racks, straps, chains or stands to support cylinders.
The use of pyrophoric gases requires EHRS approval. If you anticipate the need to use
pyrophoric gases in your work contact the EHRS Department at 215-596-8925.
Work Practice Controls
 Never work alone.
 Keep combustible materials, including paper towels and kim-wipes, away from
pyrophoric reagents.
 It is better to do multiple transfers of small volumes than attempt to handle larger
quantities. It is recommended that the cannula method be used when transferring
more than 10 ml.
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Environmental Health & Radiation Safety Department
 Remove all excess and non-essential chemicals and equipment from the fume hood
or glove box where pyrophoric chemicals will be used to minimize the risk of fire.
 Designate a fume hood or glove box for hazardous work.
 Be prepared for the unexpected. For example, at least one extra set of clean, dry
syringes and needles or double-tipped needles should always be available in case
the first set becomes plugged. Remember, pyrophoric solutions must never be
allowed to come in contact with the atmosphere.
Engineering Controls
Ventilation
Always handle liquid pyrophoric chemicals in a fume hood or glove box.
Fume 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 fume hood (or
glove box) is required to prevent the release of flammable vapors in the
laboratory.
Glove (dry and inert) Box
Glove boxes are an excellent device to control pyrophoric chemicals when dry or
inert atmospheres are required.
Gas Cabinet
Ventilated compressed gas cylinder storage cabinets may be required for high
hazard gases such as pyrophorics. Consult EHRS before purchasing any
pyrophoric gases.
Vacuum Protection
Evacuated glassware can implode and eject flying glass and splattered
chemicals. Vacuum work involving pyrophoric chemicals must be conducted in a
fume 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
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Environmental Health & Radiation Safety Department
must be vented into an exhaust hood. Vacuum pumps should be rated for use
with pyrophoric chemicals.
Personal Protective Equipment
Protective Apparel
A flame resistant lab coat (e.g., cotton or nomex), closed toed shoes and longsleeved clothing should be worn when handling pyrophoric chemicals. Additional
protective clothing should be worn if the possibility of skin contact is likely. A
chemical resistant apron worn over the lab coat is required for working with large
quantities.
Gloves
Gloves should be worn when handling pyrophoric chemicals. Disposable nitrile
gloves provide adequate protection against accidental hand contact with small
quantities of most laboratory chemicals, but are highly combustible. Consider the
use of Nomex/Leather pilot’s gloves, which provide fire resistance without
compromising manual dexterity. The pilots gloves should be worn over nitrile
gloves and are required during syringe/cannula transfers of pyrophoric liquids.
Lab workers should contact the manufacturer or EHRS for advice on chemical
resistant glove selection when direct or prolonged contact with a hazardous
chemical is anticipated.
Eye Protection
Chemical splash goggles or safety glasses that meet the current ANSI Z.87.1
Standard must be worn whenever handling pyrophoric chemicals. Ordinary
prescription glasses will NOT provide adequate protection. When there is a
potential for splashes, goggles must be worn, and when appropriate, a face
shield added.
A face shield, worn over safety eyewear, is required anytime there is a risk of
explosion, large splash hazard or a highly exothermic reaction. All manipulations
of pyrophoric chemicals which pose this risk should also occur in a fume hood,
with a working sash, in the lowest feasible position.
Portable shields, that provide protection to all laboratory occupants, are
advisable.
Emergencies
Emergency Procedure
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Environmental Health & Radiation Safety Department
Emergency procedures which address response actions to fires, explosions,
spills, injury to staff, or the development of sign and symptom of overexposure
must be developed and included in the information and training provided. The
procedures should address as a minimum the following:
 Who to contact: (University Public Safety, the Environmental Health
& Radiation Safety Department, Principal Investigator of the laboratory
including evening phone number)
 The location and proper use of all safety equipment (showers, eye
wash, spill clean-up materials, and fire extinguishers, etc.)
 The method used to alert personnel in nearby areas of potential
hazards.
 Special spill control materials based on the specific pyrophoric
chemical handled.
Eyewash
Where the eyes or body of any person may be exposed to pyrophoric chemicals,
suitable facilities for quick drenching or flushing of the eyes and body shall be
provided within the work area for immediate emergency use. Bottle type
eyewash stations are not acceptable. Eyewashes should be activated/flushed by
laboratory personnel weekly.
Safety Shower
A safety or drench shower should be available in a nearby location where the
pyrophoric chemicals are used. Researchers should familiarize themselves with
the location of the two nearest safety showers and eyewash stations both in and
outside the laboratory prior to beginning work with pyrophoric materials.
Spill Response
Anticipate spills by having the appropriate clean-up equipment on hand. The
appropriate clean-up supplies can be determined by consulting the safety data
sheet (MSDS). This should occur prior to the use of any pyrophoric chemicals.
Spill control materials for pyrophoric chemicals are designed to be inert and will
not react with the reagent.
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Environmental Health & Radiation Safety Department
Do not use combustible materials (paper towels) to clean up a spill, as these may
increase the risk of igniting the pyrophoric material.
A standard dry powder (ABC) type fire extinguisher is recommended for most
pyrophoric chemicals. However, Class D extinguishers are recommended for
combustible solid metal fires (e.g., sodium, LiAH). Also, please note that CO2
extinguishers can react with many pyrophoric chemicals which can greatly
exacerbate the problem.
Sand or soda ash (powdered lime) should be readily available where work is
performed. Also, a small beaker of sand can be used to safely extinguish any
small spills (completely smother and cover) or used for small fires occurring at
the tips of needles used to transfer liquid pyrophorics. (Keep the beaker of sand
available at arms length.)
In the event of a spill, alert personnel in the area. Evacuate the spill area. Do not
attempt to clean-up a large spill of pyrophoric chemicals. Turn off all ignition
sources and vacate the laboratory immediately. Call for assistance.
 Environmental Health & Radiation Safety Department – 215-596-8925 or
215-596-8843
 Public Safety & Security – 215-596-7000. This is a 24 hour service.
Remain on the scene, but at a safe distance, to receive and direct
emergency personnel when they arrive.
 When necessary, off-campus assistance from the University’s emergency
chemical spill responders will be obtained (a 24 hour service).
In the event of skin exposure, wash body with copious amounts of water. Quickly
remove all contaminated clothing while using the safety shower for at least 15
minutes. (Seek medical attention)
If anyone is on fire – stop, drop and roll (cover face with hands) and/or use safety
showers to suppress the flame or cool the burns, when close by.
Consider purchasing a fire blanket and keeping it near the working area to
quickly extinguish flames on a person.
Storage and Disposal
Signs and Labels
Containers: All pyrophoric chemicals must be clearly labeled with the correct
chemical name (no abbreviations) and hazard information. Pyrophoric chemicals
should always be stored in their original commercial container.
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University of the Sciences
Environmental Health & Radiation Safety Department
Special Storage
Pyrophoric chemicals should be stored under an atmosphere of inert gas or
under an appropriate liquid. Do not store pyrophoric chemicals with flammable
materials or in a flammable-liquids storage cabinet. Store these materials away
from sources of ignition. Minimize the quantities of pyrophoric chemicals stored
in the laboratory. Store bottles of liquid pyrophorics inside the original metal
shipping can, if available, to provide additional protection/secondary containment.
Never return excess chemicals to the original container. Small amounts of
impurities may be introduced into the container which may cause a fire or
explosion.
Date containers upon initial receipt and upon opening. Take note of any printed
expiration dates on the container label and dispose of them as required. Many
pyrophoric reagents become unstable or more dangerous with age.
Purchase pyrophoric reagents in the minimum quantity required for the work to
be performed. Initial cost per volume/weight may be lower when reagents are
purchased in bulk, but repeated opening of containers and puncturing of septa
leads to product degradation and loss. Wasted material and disposal cost will
often offset any initial savings.
Use refrigerators designed for flammable liquid storage.
Designated Area
Any area where pyrophoric reagents will be handled must be carefully prepared
prior to starting work. All equipment and materials needed for the experiment
should be readily available, including appropriate extinguishing media. The work
area should be clear of reagents and equipment not pertinent to the current
experiment, including flammable and combustible reagents and materials.
Other lab occupants should be made aware when and where work with
hazardous materials will be performed.
Waste Disposal
A container with any residue of pyrophoric materials should never be left open to
the atmosphere due to uncontrolled ignition.
All materials that are contaminated with pyrophoric chemicals should be
disposed as hazardous chemical waste.
Proper and complete
chemical/hazardous waste tagging and labeling is vital.
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University of the Sciences
Environmental Health & Radiation Safety Department
Alert EHRS/Central Stockroom staff to the hazards of any wastes containing
pyrophoric chemicals.
Waste containing pyrophoric chemicals must not be left overnight in the
laboratory due to the flammability risk.
Mixtures of chemicals such as reaction mixtures containing pyrophoric reagents
should be carefully and completely quenched before disposal, when it can be
done safely. Please review the below Sigma-Aldrich technical bulletins.
Additional recommendations in the Sigma- Aldrich Technical Bulletin AL-136 on
the disposal of empty Sure-PacTM cylinders should be followed and may be
viewed at:
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull_al136.
Par.0001.File.tmp/al_techbull_al136.pdf.
Also, recommendations in the Sigma-Aldrich Bulletin AL-134 Sure/Seal bottles
should be followed and may be viewed at:
http://www.sigmaaldrich.com/etc/medialib/docs/Aldrich/Bulletin/al_techbull_al134.
Par.0001.File/tmp/al_techbull_al134.pdf
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University of the Sciences
Environmental Health & Radiation Safety Department
Standard Operating Procedure: The Safe Use of Pyrophoric Chemicals
in the Laboratory
Signature Page
Principal Investigators/Laboratory Supervisors:
Use the following table to list all personnel/student workers under your responsibility
who may be potentially exposed to pyrophoric chemicals. The laboratory staff
member’s initials indicates that he/she has read this SOP and understands the hazards
and safe work practices contained therein, and he/she accepts the procedures as a
working document that he/she will support and follow in their daily work.
Newer users of pyrophoric reagents must receive hands-on training and work under the
close supervision of an experienced user until proficiency is obtained. Remember, even
experienced researchers must never work alone.
As the Principal Investigator (PI) signing this Standard Operating Procedure, I am
also documenting that training on the specific hazards and equipment used in the
laboratory was conducted and I will ensure compliance with all applicable
requirements and safety procedures in this document and in the Laboratory
Safety Manual. Also, that workers/students are/will be provided appropriate
supervision and oversight.
Name
Job Title
Initials
Principal Investigator/Laboratory Supervisor (Print): __________________________________
Principal Investigator/Laboratory Supervisor (Signature): ______________________________
Date: _____________________
Please complete this form and return to the
Department of Environmental Health & Radiation Safety, Box #85 or STC #223.
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