Standard Operating Procedure
Settlement Class: Water Reactive Chemicals
Common groups: Grignard reagents (RMgX); Alkali metals (Li, Na, K); Alkali metal amides;
Alkali metal hydrides (Lithium aluminum hydride); Metal alkyls (Lithium and aluminum alkyls);
Chlorosilanes; Halides of nonmetals (BCl3, BF3, PCl3, PCl5, SiCl4, S2CL2); Inorganic acid
halides (POCl3, SOCl2, SO2Cl2); Anhydrous metal halides (AlCl3, AlBrx, TiCl4, ZrCl4, SnCl4);
Organic acid halides; and anhydrides of low molecular weight. See Appendix A for the actual
settlement list pertaining to this hazard family/class.
NOTE: Water reactive material may also present additional hazards such as corrosivity or
toxicity. These materials may also have pyrophoric properties.
Print a copy and insert into your
Laboratory Safety Manual and Chemical Hygiene Plan.
Department:
Chemistry
Date SOP was written:
Date SOP was approved by PI/lab
supervisor:
Principal Investigator:
Internal Lab Safety Coordinator/Lab
Manager:
Lab Phone:
12/5/2012
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
1/13/2013
Richmond Sarpong
Rebecca Murphy
510-643-2485
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
A.
Water Reactive Chemicals
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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
Water reactive materials can react violently with water or atmospheric moisture to produce gas
and heat. The risks associated with a specific chemical depend on its reactivity and the nature
of the gaseous product (flammable, toxic, or both). The mutual production of flammable gas and
heat can lead to spontaneous ignition or explosion. Typical gases produced are: H2, CH4, H2S,
NH3, PH3, HCN, HF, HCl, HF, HI, SO2, and SO3. Prior to working with any water reactive
chemicals you must identify which gas may be formed in case of exposure to water and learn
the risks associated with this gas.
The reaction rate of solid material (and therefore heat and gas generation) depends on the
material's surface area. Therefore smaller particle size increases the hazards associated with
these materials.
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 water reactive materials:
1. Work under an inert atmosphere (e.g., argon, nitrogen) in a glove box.
If work in a glove box is impractical or otherwise not indicated; be certain the material in not
pyrophoric.
1. Work in a properly functioning certified chemical fume hood when handling water reactive
materials. Work with the sash as low as possible.
2. Work away from any water sources or where there is the potential of water splash.
3. Use fresh, dry solvents.
4. Keep the material under inert atmosphere (e.g., nitrogen, argon) when not in use.
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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: 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”. http://www.ehs.berkeley.edu/hs/126-standard-operating-procedures-sop.html
Eye Protection
Tightly fitting safety goggles. Use face shield (8-inch minimum) when appropriate (not protected by fume
hood sash for example). 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-based clothing/attire, and flame resistant lab
coat must be worn for protecting against chemical hazards.
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.
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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
 Unless it is known otherwise, assume the material is pyrophoric.
 To be handled always in a glove box or under inert atmosphere.
 Design a quenching scheme for residual materials prior to using water reactive materials.
 Never use water to quench the material itself or a reaction where a water-reactive 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
 Provide appropriate exhaust ventilation at places where dust is formed.
 Take measures to prevent the build-up of electrostatic charge.
 Keep away from sources of ignition – Open flames (e.g., Bunsen Burner)
 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
"Water Reactives Use Area".
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

Only use if the area is properly equipped with a certified eye wash/safety shower within ten seconds
of travel.
Never use water to extinguish fires caused by water reactive materials.
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
 Never allow contact with water.
 Always handle inside a glove box.
 Over time, pressure may increase causing containers to burst. Keep container tightly closed in a cool,
dry, well-ventilated place and protected from sunlight.
 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) free of moisture/humidity.
 Store away from heat sources and in a flame proof area
 Do not leave the container near a lab sink, emergency eyewash or safety shower.
 Store in a location, separated from acids, oxidizing and other incompatible materials.
 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.
 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.
 Follow any substance-specific storage guidance provided in Safety Data Sheet documentation.
 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.
Spill and Accident Procedure
Fire-fighting & Extinguishing media
Suitable extinguishing media
Carbon dioxide (CO2), Dry powder, and Class D fire extinguisher
DO NOT use water
Special Protective Equipment for Fire-Fighters
Wear Self-Contained Breathing Apparatus (SCBA) for fire-fighting if necessary.
Personal precautions




Avoid dust formation.
Ensure adequate ventilation.
Remove all sources of ignition.
Evacuate personnel to safe areas.
Environmental precautions
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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.
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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.
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
NOTE: Lab-specific information on decontamination/waste disposal may be included in the
Protocol/Procedure section.
Wearing proper PPE, please decontaminate equipment and bench tops using procedures made in
cooperation with site EHS&S. Please dispose of the water reactive and disposables contaminated with
water reactives as hazardous waste.
General hazardous waste disposal guidelines:
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.
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Store Waste




Call EH&S for proper procedure to dispose of waste
Store hazardous waste in closed containers, in secondary containment and in a designated
location
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 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
Safety Data Sheet (SDS) Location
SDS can be accessed online at http://ucmsds.com
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Documentation of Training (signature of all users is required)

Prior to conducting any work with water reactive chemicals, 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.

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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Water Reactive Chemicals
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SOP Template developed by The UC Center for Laboratory Safety
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Date: 1/2/2013
Appendix A (from Case Settlement Appendix 2)
Water Reactive Chemicals
Aluminum alkyl halides
Aluminum alkyl hydrides
Aluminum alkyls
Aluminum borohydride or Aluminum borohydride in devices
Aluminum Carbide
Aluminum ferrosilicon powder
Aluminum hydride Aluminum phosphide
Aluminum powder, uncoated
Aluminum silicon powder, Uncoated
<
Barium
~.
I
Boron trifluoride dimethyl etherate
Calcium
Calcium carbide
Calcium cyanamide with more than 0.1percent of calcium carbide
Calcium hydride
Calcium manganese silicon
Calcium phosphide
Calcium silicide
Cells, containing sodium
Cerium, turnings or gritty powder
Cesium or Caesium
Diethylzinc
Dimethylzinc
Water Reactive Chemicals
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SOP Template developed by The UC Center for Laboratory Safety
Date: 1/2/2013
Ethyldichlorosilane
Ferrosilicon, with 30 percent or more but less than 90 percent silicon
Hexyllithium
Lithium
Lithium alkyls
Lithium aluminum hydride
Lithium aluminum hydride, ethereal
Lithium borohydride
Lithium ferrosilicon
Lithium hydride
Lithium hydride, fused solid
Lithium nitride
Lithium silicon
Magnesium alkyls
Magnesium aluminum phosphide
Magnesium granules, coated, particle size not less than 149 microns
Magnesium hydride
Magnesium phosphide
Magnesium silicide
Magnesium, powder or Magnesium alloys, powder
Maneb or Maneb preparations with not less than 60 percent maneb
Methyl magnesium bromide, in ethyl ether
Methyldichlorosilane
Phosphorus pentasulfide, free from yellow or white phosphorus
Potassium
Potassium borohydride
Potassium phosphide
Potassium sodium alloys
Water Reactive Chemicals
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SOP Template developed by The UC Center for Laboratory Safety
Date: 1/2/2013
Potassium, metal alloys
Rubidium
Sodium
Sodium aluminum hydride
Sodium borohydride
Sodium hydride
Sodium phosphide
Starmic phosphide
Strontium phosphide
Trichlorosilane
Zinc ashes
Zinc phosphide
Zinc powder or Zinc dust
[Water Reactive Chemicals]
12
SOP Template developed by The UC Center for Laboratory Safety
Date: 1/2/2013