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 / RMgX
Metal alkyls and aryls / RLi (tert-butyl Lithium is very pyrophoric) RNa, R3Al, R2Zn
Metal Carbonyls / Ni(CO)4, Fe(CO)5, CO2(CO)8
Alkali Metals / Na, K
Metal Powders / Al, Ca, Co, Fe, Mg, Mn, Pd, Pt, Ti, Sn, ZN, Zr
Metal Halides / NaH, LiAlH4
Nonmetal Halides / B2H6 and other Boranes, PH3, AsH3, SiH4
Nonmetal alkyls / R3B, R3P, R3As
Phosphorus (white)

2. Proposed Use(s):

This SOP must be customized, anda 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.

  1. 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 administrative, work practice and engineering controls and PPE requirements. Generic information for your customization is provided below.

  1. General Guidelines (for customization)
  1. 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.

  • 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.

  1. 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

PNNL-18668 Handling Pyrophoric Materials

Aldrich Technical Bulletin AL-164—Handling Pyrophoric Reagents

Aldrich Technical Bulletin AL-134—Handling Air-Sensitive Reagents

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.
  • 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.
  1. 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 chemical-resistant 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.

  • 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 wherepyrophoric 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 whenworking with a pyrophoric material.

  1. 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. Removingpyrophoric reagents from needles and syringes)
  • Specific Spill and Accident Procedures

(Again customize the below as appropriate for the chemicals used.

All spills, no matter how small, must be reported to your supervisor and should be reported to EH&S.)

Spill - Small

  • Exert extreme caution due to potential spontaneous combustion.
  • Exert extreme caution due to potential ignition of flammable solvents or other materials.
  • If anyone is exposed, or on fire, wash with copious amounts of water, ideally in the lab shower.
  • Call for a coworker to provide backup.
  • Place a fire extinguisher nearby.
  • Carefully remove nearby flammable materials.
  • Powdered lime (calcium oxide, CaO) or dry sand should be used to completely smother and cover any spill that occurs.
  • Carefully quench by slow addition of isopropanol.
  • After complete quenching, double bag spill residues for hazardous waste pickup.
  • Call 911 then 4411 for emergency assistance if necessary.

Spill - Large

  • Exert extreme caution due to potential spontaneous combustion.
  • Exert extreme caution due to potential ignition of flammable solvents or other materials.
  • If anyone is exposed, or on fire, wash with copious amounts of water, ideally in the lab shower.
  • Call 911, then 4411 for emergency assistance.
  • Evacuate the spill area.
  • Post someone or mark-off the hazardous area with tape and warning signs to keep other peoplefrom entering.
  • 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. 2014page 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)

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 / Employee ID # / Signature / Date

SOP template (must be customized), rev. 1, Mar. 2014page 1 of 8