Type of SOP: Process Hazardous Chemical Hazardous Class s3

Standard Operating Procedure Phosgene Gas

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Laboratory Safety Manual and Chemical Hygiene Plan.

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Department: Chemistry Date SOP was written: 11/21/2012 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: 510-643-2407

Emergency Contact: Richmond Sarpong, 626-644-2407

Latimer Hall, 836, 837, 838, 839, 842, 844, 847, Location(s) covered by this SOP: 849, 907

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

Purpose

This standard operating procedure provides general guidance to the lab researcher and worker for phosgene, Phosgene is a highly toxic and dangerously reactive compressed gas. May cause respiratory tract burns, skin burns, eye burns, mucous membrane burns. Containers may rupture or explode if exposed to heat. Releases toxic, corrosive, flammable or explosive gas. Can be fatal if swallowed.

Physical & Chemical Properties/Definition of Chemical Group

CAS#: 75-44-5

Class: Highly toxic, corrosive

Molecular Formula: COCl2

Form (physical state): gas

Phosgene Gas 1 Date: 1/10/2013 Color: colorless

Boiling point: 8°C

Potential Hazards/Toxicity

Before working with any Acutely Toxic Gases, review the UC-Berkeley EH&S publication Toxic Gas Program (2011). http://www.ehs.berkeley.edu/images/ehs/healthsafety/toxicgasprogram.pdf

Phosgene is highly toxic, poisonous and corrosive gas. Can cause acute toxicity by inhalation, skin corrosion and serious eye damage. Can be fatal if inhaled. Phosgene is very destructive to mucous membranes and respiratory tract and can be harmful if absorbed through the skin. Acute inhalation exposure causes severe respiratory effects, including pulmonary edema, pulmonary emphysema, and possibly death. Can cause burning of the eyes and harmful if swallowed. Phosgene has a threshold limit value of 0.1 ppm. Death results from anoxemia causing respiratory paralysis, asphyxiation, or heart failure.

Reacts vigorously with water or moisture and with amines, ammonia, and alcohols.

LC50 toxicity: (inhalation): 0.084 mg/L (rat)

Cal-OSHA Permissible Exposure Limit (PEL): 0.1 ppm (0.4 mg/m3)

Engineering Controls

NOTE: Lab-specific information on engineering controls may be included in the Protocol/Procedure section.

Work with acutely toxic gases should be conducted in a fume hood unless other controls are designated in the lab-specific Protocol/Procedure section. Sash height should be kept low to avoid escaping fumes and provide a physical barrier. Fume hood must have electrically grounded lines , plug outlets and equipment.

The publication Toxic Gas Program (2011) describes the many requirements applicable to the safe handling and use of acutely toxic gases. Topics included in the publication are definitions, roles/responsibilities, purchase approval process, receiving, storage, fundamental handling requirements and disposal. http://www.ehs.berkeley.edu/images/ehs/healthsafety/toxicgasprogram.pdf

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.

Phosgene 2 Date: 1/10/2013 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-and-usage.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 lab coat must be worn for protecting against chemical hazards.

Hygiene Measures Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of 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

Phosgene Gas 3 Date: 1/10/2013 Move person into fresh air. If not breathing, give artificial respiration. Immediately 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 using an eyewash station for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid immediately.

If swallowed Do not induce vomiting unless specified otherwise in the SDS. 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.

Storage The publication Toxic Gas Program (2011) describes the many requirements applicable to the safe handling and use of acutely toxic gases. Topics included in the publication are definitions, roles/responsibilities, purchase approval process, receiving, storage, fundamental handling requirements and disposal. http://www.ehs.berkeley.edu/images/ehs/healthsafety/toxicgasprogram.pdf

 It is essential that phosgene be stored separately from all chemicals with which it may react.  Store at 2 – 8 C.  Keep tightly closed.  Ensure segregation of incompatible chemicals per guidance within EH&S guidelines.  Store cylinders in well-ventilated areas.  Store full cylinders away from sparks, flames, direct sunlight, or hot surfaces.  Store cylinders away from corridors, paths of egress, and stairways.  Keep away from flammables, and incompatible materials (moisture, protic solvents, strong bases, ammonia, copper).  Keep away from oil, grease and other combustibles.  When cylinder is not in use, it MUST BE stored with valve-caps in place.  When cylinder is in use, the cylinder MUST BE turned off by the cylinder valves and NOT the regulator.  Store cylinder in upright position. To prevent from falling, use two non-combustible restraints (1/3 of the way from top and bottom). Attach the restraints securely to a wall, rack, or other solid, non- combustible structure.  Each regulator valve should be inspected by user annually for damage.

Phosgene 4 Date: 1/10/2013  Also, follow any substance-specific storage guidance provided in Safety Data Sheet (SDS) documentation.

Spill and Accident Procedure

Chemical Release Dial 911

Accidental Release – Help contaminated or injured persons. Evacuate the release area. Avoid breathing vapors. Eliminate sources of ignition. Keep others from entering this area (e.g., use caution tape, barriers, etc.). Notify supervisor and EH&S immediately. Follow up with a call to 510-642-9090

Contact with 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

Contact with Eyes – Immediately rinse eyeball and inner surface of eyelid with water for 15 minutes using an eyewash station by forcibly holding the eye open. Seek medical attention. Notify supervisor and EH&S immediately. Follow up with a call to 510-642- 9090

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.

Phosgene Gas 5 Date: 1/10/2013 All lines or ducts carrying purged or exhausted emissions of gases must be connected to a mechanical exhaust system that discharges to a safe location (i.e., presents no potential for re-entrainment into any building supply air intake or occupied area). Construction of the exhaust ducts shall be chemically resistant to degradation by the gas in use. Significant emissions of corrosive or toxic gases require an emission control device (e.g., scrubber, flare device, adsorbent) before the purged gas can be vented into the exhaust duct system (refer to UCB publication Toxic Gas Program (2011)).

General hazardous waste disposal guidelines:

Label Waste Waste should be placed in a chemically compatible container with a sealed lid and clearly labeled. 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.

Dispose of Waste . 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

Phosgene 6 Date: 1/10/2013 Protocol/Procedure for Phosgene Gas CAS#: 75-44-5 Transport To move cylinder, remove regulator and secure protective valve cap. NEVER roll or drag a cylinder or allow cylinders to strike each other or other objects. Always use a suitable cylinder cart to move the cylinders, with the cylinder securely chained or strapped to cart. Do not lift or move cylinder by the cap. Cylinders should only be transported in freight/cargo elevators.

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 designated Information fume hood.)

Procedure/Use Scale Engineering PPE (eye, face, gloves, Procedure Steps and Special Controls/Equipment clothing) Precautions for this Procedure 1.Adding Phosgene Up to 100 mL Eye: Wear tightly fitting safety To add phosgene to a reaction flask, to a reaction flask goggles first flame dry the flask and fit it with a septum. Body: Wear flame-retardant lab Pierce the septum with a needle that coat with buttons. Wear long has been attached to a balloon pants and closed-toe shoes. apparatus. This will allow for a place for gaseous phosgene gas to escape to.

Cool the flask down to - 78 ºC, as it is easier to keep the phosgene condensed.

Affix a long needle to the end of the tubing from the phosgene canister.

Pierce the needle into the septum and open the phosgene valve slowly. This will allow for the phosgene to condense into the reaction flask.

Phosgene Gas 7 Date: 1/10/2013 Once a sufficient amount of phosgene has condensed into the flask, shut off the valve.

Continue maintaining a low temperature for the flask containing the phosgene.

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

Procedure/Use Scale Engineering PPE (eye, face, gloves, clothing) Procedure Steps and Precautions Controls/Equipment

2. Instrument 5-15 sccm Have appropriate Eye Protection: Wear safety Check that complete failure of cylinder Calibration (standard regulator for cylinder glasses or other shatter proof would not result in ambient cubic whenever the cap is glasses whenever the valve cap is concentrations that would exceed safety thresholds for phosgene gas This procedure is centimeters removed and the cylinder removed. (0.02-0.1ppm; 0.08mg/m3). about 10 minutes in per minute) is in use. < 500 ppb duration. Use appropriate mass flow Clothing: Wear closed-toe closed Check cylinder is secured with two controllers to control flow heel shoes when moving chains prior to removing cap. of gas from open cylinder. cylinders. Ensure cylinders are Room must be well ventilated before always chained at top and using cylinder. bottom of cylinder to a Cylinder must not be in contact with a secure location prior to heat source or in direct sunlight.

Phosgene 8 Date: 1/10/2013 use. Check regulator is correctly attached with no leaks.

Attach gas line to instrument NO2 in- port and check for leaks.

Open cylinder slowly for use.

Use valve on cylinder to stop gas flow when finished, as well as closing the regulator.

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

Phosgene Gas 9 Date: 1/10/2013 Procedure/Use Scale Engineering PPE (eye, face, gloves, clothing) Procedure Steps and Special Controls/Equipment Precautions for this Procedure 3. Fumigate 5-20 sccm Have appropriate Eye Protection: Wear safety Check that complete failure of cylinder chamber regulator for cylinder glasses or other shatter proof would not result in ambient < 500 ppb whenever the cap is glasses whenever the valve cap is concentrations that would exceed safety thresholds for phosgene gas This procedure is > removed and the cylinder removed. (0.02-0.1ppm; 0.08mg/m3). 30 minutes in is in use. duration. Use appropriate mass flow Clothing: Wear closed-toe closed Check cylinder is secured with two controllers to control flow heel shoes when moving chains prior to removing cap. of gas from open cylinder. cylinders. Ensure cylinders are Room must be well ventilated before always chained at top and using cylinder. bottom of cylinder to a Cylinder must not be in contact with a secure location prior to heat source or in direct sunlight. use. Check regulator is correctly attached with no leaks.

Attach gas line to chamber mixing board and check for leaks.

Open cylinder slowly.

4. Leak Detection Small Have appropriate Eye Protection: Wear safety Check that complete failure of cylinder bubbles regulator for cylinder glasses or other shatter proof would not result in ambient

Phosgene 10 Date: 1/10/2013 when placed whenever the cap is glasses whenever the valve cap is concentrations that would exceed in water removed and the cylinder removed. safety thresholds for phosgene gas 3 is in use. Clothing: Wear closed-toe closed (0.02-0.1ppm; 0.08mg/m ). Check cylinder is secured with two < 6 ppm Ensure cylinders are heel shoes when moving chains prior to removing cap, near always chained at top and cylinders. experimental area. bottom of cylinder to a secure location prior to Room must be well ventilated before use. using cylinder.

Cylinder must not be in contact with a heat source or in direct sunlight.

Check regulator is correctly attached with no leaks.

Attach micro gas line to cylinder with valve.

Open valve slowly. Direct micro line opening at connection points in gas line setup for a minimum of 10s in order to test for leaks into the system.

Replace cylinder in two-chained storage area when finished. Notes Any deviation from this SOP requires approval from PI. Initials of individuals using this procedure

Phosgene Gas 11 Date: 1/10/2013 Documentation of Training (signature and initials of all users is required)

 Prior to conducting any work with Phosgene, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with the specific chemical(s) used, 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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Phosgene Gas 13 Date: 1/10/2013