Standard Operating Procedure

Quenching and Disposal of Water Reactive Materials

Examples: lithium, sodium, cesium, lithium aluminum hydride, calcium
hydride, potassium hydride, Grignard reagents

This is an SOP template and is not complete until: 1) lab-specific information is entered into
the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and
3) SOP has been signed and dated by the PI and relevant lab personnel.
Print a copy and keep with your
Chemical Hygiene Plan and/or Lab Safety Resources Binder

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Type of SOP: Process ✘ Hazardous Chemical Equipment

1. Purpose
This SOP covers the precautions and safe handling procedures for the Quenching of Water
Reactive Materials.
Also, this SOP covers any material synthesized using water-reactive chemicals.
If you have questions concerning the applicability of any recommendation or requirement listed
in this procedure, contact the Principal Investigator/Laboratory Supervisor or EH&S.
2. Physical & Chemical Properties/Definition of Chemical Group
For physical and chemical properties on water-reactive materials, please refer to specific Safety
Data Sheets (SDS) of chemicals in use (See Section 11 – SDS Location).
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 3. Potential Hazards
When quenching water-reactive materials, the hazards of the mixture, the WR chemical and the
solvent, must be considered together and procedures for safe quenching must reflect the hazard
properties of both solvent and solute.
As defined by the Globally Harmonized System of Classification and Labeling of Chemicals
(GHS), water-reactive materials are defined as “substances and mixtures which, in contact with
water, emit flammable gases” and are designated by one or more of the following H codes:
H260 In contact with water releases flammable gases which may ignite spontaneously
H261 In contact with water releases flammable gases
It is the Principal Investigator’s responsibility to ensure activity-specific laboratory procedures
and/or processes are taken into account when using this Hazardous Operation Class SOP.
Please, review the SDS of any chemical before use (see Section 11 – SDS Location)
4. Safety Data Sheet (SDS) Location
Online SDS can be accessed at (http://oregonstate.edu/ehs/sds). A hard copy can be found at Oak
Creek Building with Environmental Health & Safety.
5. Engineering Controls
The following is the set of engineering controls required when quenching WR chemicals:

 Use a clean fume hood, preferably with the sliding sash windows.
 If procedure is done in the fume hood, use the sash as a safety shield. For hoods with a
horizontal sliding sash, position the sash all the way down, stand behind the sliding
windows and reach around to perform the manipulations required. For hoods with
vertical sliding sash, keep the sash as low as possible.
 Remove any flammables (squirt bottles, solvents, oil bath) and combustibles (KimWipes,
paper towel) from area that will be used for the quenching.

6. Personal Protective Equipment (PPE)

At a minimum, the following PPE must be worn at all times:
Eye Protection
A. ANSI Z87.1-compliant safety glasses with side shields, or chemical splash goggles.
 Ordinary prescription glasses will NOT provide adequate protection unless they also
meet ANSI standard and have compliant side shields.
B. If the potential for explosion/splashing exists, and adequate coverage is not provided by
the hood sash, a face shield should be worn.

Skin Protection
A. Flame-resistant lab coat (Nomex IIIA, NFPA 2112) should be worn when working with
pyrophoric and self-healing materials.

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 B. Gloves are required when handling hazardous materials. Refer to the specific chemical
SDS for information on glove selection.
C. Long pants, closed-toe/closed-heel shoes, covered legs, and ankles. Cotton-based, non-
synthetic clothing should be worn.

7. Administrative Controls:
 Anyone who uses Pyrophoirics is required to review this SOP and the attached Safety
Data Sheet (SDS) prior to work.
 Keep quantities to a minimum and only order what you will be using.
 An eyewash must be available in the room with a safety shower accessible nearby.

8. Best Practices for Safe Handling:

Water-reactive chemicals can be handled and stored safely as long as all exposure to moisture or
other incompatible chemicals is minimized.
Lab-specific information on handling and storage may be included in Section 12 -
Protocol/Procedure section.
Any unused or unwanted water-reactive materials must be destroyed by following the Quenching
of Water Reactive Chemicals SOP. If you have large quantities of unreacted water-reactive
reagent material contact EH&S for guidance on disposal options.
• Waste materials generated must be treated as a hazardous waste.
• The empty container must be rinsed three times with a COMPATIBLE solvent; leave it open in
the back of the hood overnight.
• The empty container, solvent rinses and water rinse must be disposed of as hazardous waste.
• Do not mix with incompatible waste streams.
• Decontamination of containers in order to use them for other purposes is not permitted.
Working alone
OSU Environmental Health and Safety specifies not to work with pyrophorics alone or during
off-hours when there are few people around to help.
9. First Aid Procedures
If an accident happens the following documents must be completed:
- Online OSU HR Advocate Public Incident Reporting Form within 24 hours of the
incident
- If the employee’s incident resulted in the need for medical treatment, have the employee
complete the worker section of the SAIF 801 Form and fax to risk management at 541-
737-4855 within 24 hours.

In case of skin contact

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If skin contact occurs, and/or skin or clothing are on fire, immediately drench in the safety
shower with copious amounts of water for no less than 15 minutes to remove any remaining
contaminants. If possible to do so without further injury, remove any remaining jewelry or
clothing.
In case of eye contact
Rinse thoroughly with plenty of water using an eyewash station for at least 15 minutes,
occasionally lifting the upper and lower eyelids. Remove contact lenses if possible.
http://ehs.oregonstate.edu/sites/ehs.oregonstate.edu/files/pdf/si/
eyewash_and_safety_shower_si.pdf
If swallowed
Do NOT induce vomiting unless directed otherwise by the SDS. Never give anything by mouth
to an unconscious person. Rinse mouth with water.
Needle stick/puncture exposure
Wash the affected area with antiseptic soap and warm water for 15 minutes. For mucous
membrane exposure such as eyes, mouth and/or nose, flush the affected area for 15 minutes
using an eyewash station.
If inhaled
Move into fresh air.
10. Chemical Spill
OSU Chemical Spill Safety Instruction:
http://ehs.oregonstate.edu/sites/ehs.oregonstate.edu/files/pdf/si/spill_response-
chemicals_si.019.pdf
General Guidelines Water Reactive Spill Response
• In the case of a spill, announce the situation loudly in the immediate area and have any
nearby persons move to a safe location.
• Immediately eliminate/remove all nearby ignition sources.
• If spill occurs in a fume hood, cover with Met-L-X, dry sand, or other non-combustible
material, close the hood sash and if present, press the red purge button.
• If a spill occurs outside a fume hood, cover with Met-L-X, dry sand, or other non-
combustible material, and stand away from the spill.
• Locate and have a proper fire extinguisher (dry chemical-based) ready in case of
ignition/fire.
• Use clean, non-sparking tools to collect absorbed material and place into loosely-
covered metal or plastic containers ready for disposal.
• Do not use combustible materials (paper or cloth towels) to clean up a spill, as these
may increase the risk of igniting the reactive compound.
• If you cannot assess the situation well enough to be sure of your own safety, do not
approach the spill.
• Keep others from entering contaminated area (e.g., use caution tape, barriers, etc.).
• Report the spill to 541-714-SAFE.
Water Reactive Fire Response
• Call 911 for emergency assistance and for assistance with all fires, even if extinguished.

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 • If the spill ignites, and if you are trained and you feel comfortable to do so, consider
extinguishing the fire with an appropriate fire extinguisher. Use only dry chemical fire
extinguishers (classes ABC or D).
• A can of Met-L-X or dry sand in the work area, within arm’s reach, might be helpful to
extinguish any small fire as it can smother the flames.
• Do not use water to extinguish a WR chemical fire as it may enhance the intensity of
the fire. An exception to this would be in the case of skin contact or ignited clothing/skin.
In these cases rinsing any unreacted chemical off is of primary importance.

11. Decontamination/Waste Disposal Procedure

Lab-specific information on decontamination may be included in the Protocol/Procedure section.
 Wearing proper PPE, laboratory work surfaces should be cleaned at the end of each
workday.
 Store liquid wastes in designated waste containers. Dispose of according the OSU EH&S
hazardous waste guidelines.

Label Waste
 Affix an EH&S hazardous waste label on all waste containers
(http://ehs.oregonstate.edu/sites/ehs.oregonstate.edu/files/pdf/hwlabelfull.pdf) as soon as
the first drop of waste is added to the container.
Store Waste
 Store hazardous waste in closed containers, in secondary containment and in a designated
location. (http://ehs.oregonstate.edu/sites/ehs.oregonstate.edu/files/pdf/si/
waste_hazardous_disposal_si.pdf).
 Double-bag dry waste using transparent bags
 Waste must be under the control of the person generating & disposing of it
Dispose of Waste
 Dispose of regularly generated chemical waste within 90 days
 Put in a waste request at: http://ehs.oregonstate.edu/waste

12. References
[Include any references useful to employees]
UCSD - Working with Reactive Metals Video
13. Protocol/Procedure for: Quenching of Water Reactive Materials

Quenching of inorganic hydrides such as LiAlH4, NaBH4, CaH2, NaH, LiH, and metal powders
(Li, Na) left after reactions.
Up to 10g of material or up to 100 mL of a commercially acquired solution (3 M or lower).
Larger quantities of WR chemicals can be disposed of as hazardous waste.
Engineering controls

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Conduct in a clean and properly operating fume hood with the sash as low as possible.
Personel Protection Equipment (PPE)
Eye Protection: Wear tight-fitting safety goggles or safety glasses with side shields.
Face Protection: Face shields are to be used when there is no protection from the hood sash or
when the hood sash is in open position.
Hand Protection: Confirm compatibility of glove material with chemical being used. Gloves
must be inspected prior to use. Wash and dry hands after use.
General guidance : For indirect contact (closed-system procedures such as transfers via syringe
or cannula) AND direct contact (open system procedures such as spill handling, wiping of
residual pyrophorics) with pyrophoric material - a combination of fire resistant (FR) liners,
covered with a pair of chemical-resistant disposable gloves (e.g. nitrile gloves or those specified
in the specific SDS), must be worn AT ALL TIMES. The following products are Approved FR
Liners: Ansell Kevlar® Goldknit® Lightweight 70-200 and Hanz Extremity Wear Nomex®
Utility Liners.
Clothing: Wear Nomex IIIA (NFPA 2112) lab coat; full-length pants or equivalent; and close-
toed and close-heeled shoes.
Procedure Steps and Special Precautions for this Procedure
1. Quenching of inorganic hydrides such as LiAlH4, NaBH4, CaH2, NaH, LiH, and metal
powders (Li, Na) left after reactions.
General Procedure:
Quenching procedures usually involve the reaction of the WR material with a reagent that has a
reactive hydroxyl group.
Any reaction or suspension containing these reagents MUST be quenched carefully!
Addition of materials must be done SLOWLY and ensure adequate stirring/mixing.
Whenever quenching be sure that it is not done in a sealed vessel as pressure will build up.
If you’re quenching in a RB flask or any floating vessel in a bath, clamp it.
Typically, a suspension of less than 20 wt% of WR in an inert solvent (such as hexane or
toluene) is created, followed by the slow addition of isopropanol, under adequate stirring until no
more bubbling is observed. To avoid vigorous bubbling and any signs of overheating during the
quenching process, keep the solution cool by controlling the feed rate of the alcohol. If the
solution begins to warm up, stop and allow it cool down before continuing the addition of the
quenching agent.
For NaH, LiH, CaH2, NaBH4, small amounts LiAlH4: Start with the SLOW addition of
isopropanol or ethanol, under adequate stirring until no more bubbling is observed.

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Repeat with methanol, and then repeat with water.
Be Very Careful with the addition of WATER! Even after methanol has been added, the water-
reactive agent can still react violently with water, especially is there hasn't been sufficient
mechanical stirring of the solution. So add in small aliquots.
Stir for an additional 2 hours before disposing of the aqueous organic waste.
If you are filtering out a solid residue containing a water-reactive chemical, be sure there is no
active residue on the filter paper before disposing of it in the solid waste. Wash the solid residue
with some methanol to quench any remaining WR material.
Alternative Procedure:
You can quench LiAlH4 reactions containing x g lithium aluminum hydride via the Fieser-Fieser
workup:
1. Either dilute with ether and cool to 0°C or cool to 0°C and slowly add EtOAc
2. Slowly add x mL water
3. Slowly add x mL 15 % aqueous sodium hydroxide
4. Add 3x mL water
5. Warm to RT and stir 15 min
6. Add some anhydrous magnesium sulfate
7. Stir 15 min and filter to remove salts
2. Quenching of Na or K.
Minimal quantities will be left after reactions carried out at scales listed in your laboratory “WR”
Class SOP.
Larger quantities of WR liquid chemicals can be disposed of as hazardous waste.
Engineering Controls
Conduct in a clean and properly operating fume hood with the sash as low as possible.
Personel Protection Equipment (PPE)
Eye Protection: Wear tight-fitting safety goggles or safety glasses with side shields.
Face Protection: Face shields are to be used when there is no protection from the hood sash or
when the hood sash is in open position.
Hand Protection: Confirm compatibility of glove material with chemical being used. Gloves
must be inspected prior to use. Wash and dry hands after use. General guidance : For indirect
contact (closed-system procedures such as transfers via syringe or cannula) AND direct contact

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(open system procedures such as spill handling, wiping of residual pyrophorics) with pyrophoric
material - a combination of fire-resistant (FR) liners, covered with a pair of chemical-resistant
disposable gloves (e.g. nitrile gloves or those specified in the specific SDS), must be worn AT
ALL TIMES. The following products are Approved FR Liners: Ansell Kevlar® Goldknit®
Lightweight 70-200 and Hanz Extremity Wear Nomex® Utility Liners.
Clothing: Wear Nomex IIIA (NFPA 2112) lab coat; full-length pants or equivalent; and close-
toed and close-heeled shoes.
Procedure Steps and Special Precautions for this Procedure
General Procedure:
Sodium/Potassium: Quenching procedures usually involve the reaction of the WR material with
a reagent that has a reactive hydroxyl group.
Any reaction or suspension containing these reagents MUST be quenched carefully!
Addition of materials must be done SLOWLY and ensure adequate stirring/mixing.
Whenever quenching be sure that it is not done in a sealed vessel as pressure will build up.
If you’re quenching in a RB flask or any floating vessel in a bath, clamp it.
A typical procedure involves suspending the Na/K alloy in DRY toluene to less than 20 wt%.
Slowly add the toluene to the stirring Na/K. To avoid vigorous bubbling and any signs of
overheating during the quenching process, keep the solution cool by controlling the feed rate of
the alcohol. If the solution begins to warm up, stop and let it cool down before continuing the
addition of the quenching agent.
Once all toluene has been added, allow to stir for 5-10 minutes then add DRY ethyl acetate
SLOWLY to the stirring solution. The ethyl acetate will quench the potassium.
Once addition is complete, let the solution stir for one hour.
At this point, only the sodium is remaining in the flask and can be quenched as described above
with isopropanol, methanol, and then water.
Be Very Careful with the addition of WATER! Even after methanol has been added, the alloy
can still react violently with water, especially is there hasn't been sufficient mechanical stirring
of the solution. So add in small aliquots.
Let stir for a couple of hours before disposing of the aqueous organic waste.
Documentation of Training

 Prior to conducting any work with pyrophorics, designated personnel must provide training
to their laboratory personnel specific to the hazards involved in working with this substance,
work area decontamination, and emergency procedures.

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 The Principal Investigator must provide this SOP and a copy of the SDS (can be available
online) available to all laboratory personnel.

 The Principal Investigator must ensure that his/her laboratory personnel have attended
appropriate laboratory safety training or refresher training.

Principal Investigator SOP Approval

By signing and dating here the designee certifies that the Standard Operating Procedure (SOP)
for Quenching of Water Reactove Materials is accurate and effectively provides standard
operating procedures for laboratory personnel.
______________________________________________________________________________
Signature Printed Name/Title Date

I have read and understood the content of this SOP:

Name Signature Date

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