Settlement Class: Water Reactive Chemicals

Standard Operating Procedure

Trichlorosilane Settlement Class: Water Reactive Chemicals 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 insert into your Laboratory Safety Manual and Chemical Hygiene Plan.

Department: Chemistry Date SOP was written: 11/6/2012 Date SOP was approved by PI/lab supervisor: 1/13/2013 Principal Investigator: Richmond Sarpong Internal Lab Safety Coordinator/Lab Manager: Rebecca Murphy Lab Phone: 510-643-2485 Office Phone: 510-643-6312

Emergency Contact: Richmond Sarpong 626-644-2407 (Name and Phone Number) Latimer 834, 836, 837, 838, 839, 842, 844, 847, 849, Location(s) covered by this SOP: 907 (Building/Room Number)

Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class

Purpose

Trichlorosilane is highly flammable liquid and vapor, corrosive, and toxic by inhalation. May ignite or explode on contact with moist air. Reacts violently and/or explosively with water, steam or moisture.

Use extreme caution. Trichlorosilane is toxic if inhaled.

Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and skin, shortness of breath, headache, nausea.

Trichlorosilane is used in the production of purified polysilicons.

Trichlorosilane 1 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety Physical & Chemical Properties/Definition of Chemical Group

CAS#: 10025-78-2

Class: Highly Flammable, Corrosive, Toxic

Molecular Formula: HCl3Si

Form (physical state): liquid

Color: colorless

Boiling point: 31.8°C

Potential Hazards/Toxicity

Trichlorosilane is highly flammable liquid and vapor, corrosive, and toxic by inhalation.

Use extreme caution. May ignite or explode on contact with moist air. Reacts violently and/or explosively with water, steam or moisture.

Trichlorosilane is toxic if inhaled. Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and skin, shortness of breath, headache, nausea.

No permissible exposure limits are listed for Trichlorosilane

Has the following toxicity data:

Oral LD50 - rat - 1,030 mg/kg

Inhalation LC50- mouse - 2 h - 1,500 mg/m3

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.

Trichlorosilane 2 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety 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.

5. Handle using a chemical fume hood with good ventilation and electrically grounded lines and equipment.

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 Gloves must be worn. Use proper glove removal technique to avoid any skin contact. Nitrile gloves recommended.

NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with Trichlorosilane.

Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.allsafetyproducts.biz/page/74172 OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/

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.htmlEye Protection ANSI approved properly fitting safety glasses or chemical splash goggles. Face shield is also recommended.

Trichlorosilane 3 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety Skin and Body Protection Flame resistant lab coats must be worn and be appropriately sized for the individual and buttoned to their full length. Laboratory coat sleeves must be of sufficient length to prevent skin exposure while wearing gloves. As outlined in Policy 905 personnel should also wear full length pants, or equivalent, and close-toed shoes. Full length pants and close-toed shoes must be worn at all times by all individuals that are occupying the laboratory area. The area of skin between the shoe and ankle should not be exposed.

Hygiene Measures Wash thoroughly and immediately after handling. Remove any contaminated clothing and wash before reuse and at the end of the workday.

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  Avoid contact with skin and eyes and inhalation. Keep away from sources of ignition.  Avoid heat and shock or friction when handling.

Trichlorosilane 4 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety  Avoid strong acids or bases or strong oxidizing or reducing agents. 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. Trichlorosilane reacts violently with water, alcohols, amines, and alkalis to produce hydrochloric acid. It should be used under anhydrous conditions, with dry solvent, and in the absence of alcohols, amines, and alkalis. If the quenching of the reaction involves water, the reaction vessel should be cooled to avoid an exotherm.  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".

 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  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..  Store and handle under inert gas (Noble gases such as Nitrogen, Argon etc.)  Moisture sensitive.Keep in a dry place (such as a desiccator or a dry box or glove box).  Store in a location, separated from acids and protected from sunlight.

 Store away from heat sources and in a flame proof area

 Recommended storage temperature: 2 - 8 °C.

 Keep away from incompatible materials and conditions.  Do not leave the container near a lab sink, emergency eyewash or safety shower.

Trichlorosilane 5 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety  Do not store in humid air/moisture.  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).  Store in a location, separated from acids and protected from sunlight.

 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.. 

Trichlorosilane 6 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety 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

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.

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.

Trichlorosilane 7 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety 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

Use proper personal protective equipment for chemical and properly dispose chemical and contaminated disposables as hazardous waste following the guidelines below.

General hazardous waste disposal guidelines:

Label Waste Label all containers with the label provided at http://ehs.berkeley.edu/hm/279-new-hazardous-waste- program-hwp.html. See the EH&S Fact Sheet, “ H azardous W a s t e Management ” for general instructions on procedures for disposing of hazardous waste.

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

Trichlorosilane 8 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety . 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

Trichlorosilane 9 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety Protocol/Procedure for Trichlorosilane

CAS#: 10025-78-2

Preparation List any other particular preparation requirements needs for this procedure (e.g., location of spill kit or keep water or ignition sources away from procedure area).

Know the location of the nearest fire extinguisher, eyewash, and safety shower before beginning work.

Lab-specific Add lab-specific information not included above if needed (e.g., all work for this procedure is to take place in the Information designated fume hood.)

Procedure/Use Scale Engineering Procedure Steps and Special Precautions for this Procedure Controls/Equipment Trichlorosilane can Suitable Trichlorosilane should be Trichlorosilane reacts violently with water, alcohols, amines, and alkalis to be used as a procedure for stored in chemical reagent produce hydrochloric acid. It should be used under anhydrous conditions, reagent in a wide volume up to bottles provided by with dry solvent, and in the absence of alcohols, amines, and alkalis. range of organic ~150 mL of chemical suppliers reactions. trichlorosilan If the quenching of the reaction involves water, the reaction vessel should be e Since trichlorosilane is cooled to avoid an exotherm. toxic, it should be used exclusively in a fume hood Since trichlorosilane is flammable (flash point -27 °C, boiling point 31.5-33 to avoid the inhalation of °C), it should not be measured out in the presence of a heat source (ex. vapors and exposure of the Bunsen burner, heat gun, non-sparking hot plate, etc.). It will ignite in the eyes to vapors. If inhaled or presence of a spark. exposed to the eyes, it has a corrosive effect. If it is used in a heated reaction, care should be taken not to superheat the reaction. A thick walled schlenk flask or a flask with a reflux condenser or Exposure to the air should other ventilation should be used. These precautions should be used to avoid be avoided, as it can the rupturing of the reaction vessel if there is a release of hydrogen chloride spontaneously catch fire gas as the reagent decomposes. due to moisture in the air.

Trichlorosilane 10 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety For small quantities (<10 mL) a syringe should be used to transfer trichlorosilane from its container to the reaction vessel. Large quantities (>60 mL) may be transferred using a cannula. For intermediate quantities (10-60 mL) either a syringe or a cannula may be used to transfer the reagent. Syringe and cannula transfer are used in all cases because trichlorosilane reacts with moisture in the air to form hydrochloric acid and a white residue

(silica gel, SiO2).

Trichlorosilane should be disposed of if it no longer appears as it should (based on the supplier description). To dispose of, it can be submitted to EH&S as is. It can also be added slowly to a solution of aqueous base at 0 °C to quench the reagent. The quenched reagent can then be added to standard liquid waste.

Notes Any deviation from this SOP requires approval from PI. Initials of individuals using this procedure

Trichlorosilane 11 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety Documentation of Training (signature of all users is required)

 Prior to conducting any work with Trichlorosilane, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, 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.

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

I have read and understand the content of this SOP:

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Trichlorosilane 12 Date: 12/18/2012 SOP Template developed by the UC Center for Laboratory Safety