Chemical Class Standard Operating Procedures

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1 Chemical Class Standard Operating Procedures Acutely Toxic Gases (ATG) Print a copy and insert into your laboratory SOP binder. Department: Chemistry Date SOP was written: June 10, 2013 Date SOP was approved by PI/lab supervisor: Principal Investigator: Internal Lab Safety Coordinator or Lab Manager: Emergency Contact: Location(s) covered by this SOP: Name: Richmond Sarpong Signature: Name: Paul Leger Lab Phone: Office Phone: Name: Richmond Sarpong Phone Number: Latimer Hall: 834, 836, 837, 838, 839, 842, 847, 849, Purpose This SOP covers the precautions and safe handling procedures for the use of Acutely Toxic Gases in the Sarpong group, which include the following chemicals and their uses: Chemical(s) ATGs Carbon monoxide Ammonia Use(s) 1. Use as a reagent. 2. Transferring carbon monoxide to a pressurized reaction vessel. 3. Synthesis with gaseous ammonia 4. Condensing ammonia 5. Quenching/Evaporating ammonia Sarpong inventory chemicals covered by this SOP Ammonia Boron trichloride Carbon Monoxide Rev. Date: June 10, Acutely Toxic Gases Class SOP

2 2 - Physical & Chemical Properties/Definition of Chemical Group Before working with any Acutely Toxic Gases, review the UC-Berkeley EH&S publication Toxic Gas Program (2011). This is a chemical class SOP. Some uses of the chemicals in this class require specific SOPs. Chemicalspecific SDSs and all relevant SOPs must be reviewed prior to use of any chemical in this class. It is the Principal Investigator s responsibility to ensure activity specific laboratory procedures and/or processes are taken into account when using this Chemical Class SOP. This Chemical Class SOP is intended to provide general guidance on how to work safely with acutely toxic gases. If you have questions concerning the applicability of any item listed in this procedure, contact the Principal Investigator/Laboratory Supervisor of your laboratory or EH&S. 3 - Potential Hazards/Toxicity There is a broad spectrum of toxic compressed gases. Increased recognition of the hazards associated with the transportation, operation, and storage of these gases is essential. Toxic gases are gases that may cause significant acute health effects at low concentrations. Health effects may include severe skin or eye irritation, pulmonary edema, neurotoxicity, or other potentially fatal conditions. The Acutely Toxic Gases in the Settlement Agreement are listed in the Appendix. Acutely toxic gases may also have other hazardous properties in addition to acute toxicity. Safe use requires assessing all potential hazards. 4 - Engineering Controls Use the engineering controls listed below unless other lab-specific information is 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. 5 - Personal Protective Equipment For additional information on PPE requirements, go to: Use the PPE listed below unless other lab-specific information is included in the Protocol/Procedure section. Eye and Face Protection ANSI-approved safety glasses with side shields or chemical splash goggles must be worn at all times when handling chemicals in the lab. Skin and Body Protection 1. Gloves are required when handling hazardous chemicals. a. Specific glove type recommendations are provided in the Protocol/Procedure section. b. Inspect gloves prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Wash and dry hands after handling chemicals, before breaks, and at the end of the workday. c. For additional information on glove selection, go to: Rev. Date: June 10, Acutely Toxic Gases Class SOP

3 2. Lab coats are required when handling hazardous chemicals in the lab. a. Nomex 3A flame-resistant lab coats are required when working with pyrophorics (H250) and explosives (H200, H201, H202, H203) b. Flame resistant lab coats (Nomex or other material) should be worn when working with hazardous chemicals such as Category 1 or 2 flammable liquids (H224 and H225). 3. Cotton-based, non-synthetic clothing (including long pants; no skin exposed below the waist) should be worn. 4. Closed-toe and closed-heel shoes are required in the lab. Respiratory Protection Respiratory protection is normally not required for UC Berkeley laboratory activities. Any lab personnel considering the use of a respirator must contact EH&S for a workplace assessment. Respirator users will be provided with specific instructions if a respirator is deemed necessary by EH&S. 6 - First Aid Procedures and Medical Emergencies Notify supervisor and EH&S immediately. Follow up with a call to to report the incident. Life Threatening Emergency, After Hours, Weekends and Holidays Call 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 to report the incident. Assess the extent of danger. If you cannot assess the conditions of the environment well enough to be sure of your own safety, do not enter the area. If possible, help contaminated or injured persons. Obtain medical attention for the individual as soon as possible by calling 911. Provide a copy of the appropriate SDS to the emergency responders or physician, as needed. If inhaled Move into fresh air. Go to the Occupational Health Facility (Tang Health Center) and after hours, go to the nearest emergency room. If person is not breathing, call 911 and give artificial respiration. If unconscious, call 911. In case of skin contact Immediately flush with flowing water for no less than 15 minutes; remove any jewelry or clothing as necessary to facilitate clearing of any residual materials. Wash off with soap and plenty of water for 15 minutes. If skin contact requires medical assistance, go to the Occupational Health Facility (Tang Health Center) and after hours, go to the nearest emergency room. If this is a large or serious injury, call 911. 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. Call 911. If swallowed Call 911. Do not induce vomiting unless directed otherwise by the SDS. Never give anything by mouth to an unconscious person. Rinse mouth with water. Go to the Occupational Health Facility (Tang Health Center) and after hours, go to the nearest emergency room. Rev. Date: June 10, Acutely Toxic Gases Class SOP

4 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. Go to the Occupational Health Facility (Tang Health Center) and after hours, go to the nearest emergency room. All needle stick/puncture exposures must be reported to EH&S within 8 hours. Follow up with a call to to report the incident. 7 - Special Handling and Storage Requirements 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. Precautions for safe handling 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. Conditions for safe storage It is essential that all acutely toxic gases be stored separately from all chemicals with which they may react. Ensure segregation of incompatible chemicals per guidance within EH&S guidelines. Also, follow any substance-specific storage guidance provided in Safety Data Sheet (SDS) documentation. All compressed gas cylinders must be stored with valve cover caps in place. Damage to a valve can cause the cylinder to become a dangerous projectile. Cylinders must be securely restrained to prevent them from falling at all times. 8 - Chemical Release 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 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 Contact with Eyes Immediately rinse eyeballs 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 Rev. Date: June 10, Acutely Toxic Gases Class SOP

5 9 - Cleaning and Decontamination Lab-specific information on decontamination may be included in the Protocol/Procedure section. 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 must 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 Toxic Gas Program (2011): Hazardous Waste Disposal Label Waste Label all containers with the label provided at: See the EH&S Fact Sheet, Hazardous Waste 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 with questions Safety Data Sheet (SDS) Location SDS can be accessed online at Rev. Date: June 10, Acutely Toxic Gases Class SOP

6 12 - Protocol/Procedure Acutely Toxic Gas (ATG) Before using any ATG be sure you are in compliance with the University of Berkeley Toixc Gas Program requirements. Acutely Toxic Gases can have a very broad range of additional hazards including but not limited to strong oxidizers, corrosives, water reactives, strong reducing agents, and flammables. Be sure you understand and take appropriate action to protect yourself and others from all hazards. Preparation All regulators, valves, and lines must be chemically compatible with the gases being used. Regulators shall be compatible with the size and type of gas cylinder being used and rated for full cylinder pressure. Know the location of the nearest fire extinguisher, eyewash, and safety shower before beginning work. Chemical Storage and Disposal Indoor storage of all ATG cylinders shall be in a mechanically ventilated, lockable area. All empty gas cylinders shall be labeled as empty; however, empty cylinders may still contain some toxic gas, so must remain in exhausted enclosures or fire code compliant gas storage rooms. Depleted gas cylinders should be returnable to the vendor according to their guidelines Reaction vessels and chambers should be inside exhausted enclosures like fume hoods. Where possible all operations must be conducted in a designated fume hood area with an appropriated warning sign, e.g. Warning! Acutely Toxic Gas in Use: Carbon Monoxide. Lab-specific Information Some ATG have poor warning properties. If a particular ATG falls into this category and work with this gas will be done routinely or larger quantities will be employed, consider installing a continuous electronic warning sensor with alarm if available. Insure that the fume hood is operating properly and keep the sash as low as possible at all times. A ventilation monitor is required on the hood 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. It may be appropriate to use some form of scrubber to remove any ATG that is vented from the reactor. This will depend upon the specific ATG that is in use. Rev. Date: June 10, Acutely Toxic Gases Class SOP

7 Procedure/Use Scale Engineering Controls/Equipment 1. Use as a reagent Up to lecture bottle. Larger quantities require compound specific SOP Conduct all operations in a designated fume hood. Blast shields must be used if the reaction has the potential to generate large quantities of gases or is strongly exothermic. Open flames and possible sparking and static electricity must be avoided Open flames and possible sparking and static electricity must be avoided. PPE (eye, face, gloves, clothing) Eye protection: Wear ANSI Approved tightfitting safety goggles or safety glasses with side shields. Face protection: The need for face protection is based on the volume of solvents used or if the reaction will be externally heated or if needed. Wear a face shield when handling containers that are not behind a lab hood sash or blast shield. Gloves: Confirm the compatibility of the gloves you use with the specific ATG. At at a minimum wear 8 mil minimum Nitrile gloves must be used to prevent incidental contact. 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. Remove gloves immediately upon contamination. Wash and dry hands after use. Procedure Steps and Precautions Avoid inhalation of these materials. Be sure that the delivery pressure of the ATG is compatible with the reaction apparatus. Use a compatible gas regulator. Insure that the gas being passed through the reactor is properly vented into the fume hood and that any vented gases do not constitute a health threat to coworkers or nearby populations. Extreme care should be taken not to over pressurize glass reactors. Clothing: Wear fire/flame resistant lab coat (100% cotton based); cotton based clothing/attire; full length pants or equivalent; and close-toed, close-heeled shoes. Notes Any deviation from this SOP requires approval from PI. Rev. Date: June 10, Acutely Toxic Gases Class SOP

8 Procedure/Use Scale Engineering Controls/Equipment 2. Transferring The carbon All reactions must be carbon monoxide performed in a monoxide to a cylinder used properly operating pressurized must fit inside of fume hood. reaction vessel. the fume hood. A functioning carbon monoxide detector must be used. Notes Initials of individuals using this procedure Any deviation from this SOP requires approval from PI. PPE (eye, face, gloves, clothing) Eye Protection: Wear tight-fitting safety goggles or safety glasses with side shields. Face Protection: Use a face shield if not protected by the fume hood sash. Hand Protection: 8 mil minimum Nitrile gloves must be used to prevent incidental contact. Gloves must be inspected prior to use. Cotton or leather gloves may be used as well to prevent mechanical injury. Wash and dry hands after use. Clothing: Wear fire/flame resistant lab coat (100% cotton based); cotton based clothing/attire; full length pants or equivalent; and close-toed, close-heeled shoes. Procedure Steps and Special Precautions for this Procedure 1. Ensure carbon monoxide detector is on and in working order and hood inflow velocity is at least 100 fpm. 2. Ensure carbon monoxide tank is securely fastened with chain clamps or ring clamps inside the fume hood. The carbon monoxide tank must be stored and used in a fume hood at all times. 3. Unscrew cylinder cap. 4. Ensure main valve is completely closed. 5. Unscrew main valve cap. 6. Attach an appropriate pressure regulator and connect the hose to the reaction vessel. 7. Carefully pressurize reaction vessel to ca. 100 psi. 8. Carefully release pressure from reaction vessel into the fume hood. 9. Repeat steps 7-8 to purge the vessel of air. 10. Carefully pressurize reaction vessel to desired pressure. 11. Ensure reaction vessel is sealed. 12. Remove hose from reaction vessel. 13. Close main valve on tank. 14. Slowly release pressure from regulator into the fume hood. 15. Remove regulator from tank and allow to vent into the fume hood. 16. Secure main valve cap. 17. Secure cylinder cap. Rev. Date: June 10, Acutely Toxic Gases Class SOP

9 Procedure/Use Scale Engineering Controls/Equipment 3. Synthesis All reactions must be with Gaseous performed in a properly Ammonia operating fume hood. The ammonia cylinder used must fit inside of the fume hood. If the balloon apparatus involves a needle, make sure the needle is capped during any transport. PPE (eye, face, gloves, clothing) Eye Protection: Wear tight-fitting safety goggles or safety glasses with side shields. Face Protection: Use a face shield if not protected by the fume hood sash. Hand Protection: 8 mil minimum Nitrile gloves must be used to prevent incidental contact. Gloves must be inspected prior to use. Cotton or leather gloves may be used as well to prevent mechanical injury. Wash and dry hands after use. Clothing: Wear fire/flame resistant lab coat (100% cotton based); cotton based clothing/attire; full length pants or equivalent; and close-toed, closeheeled shoes. Procedure Steps and Special Precautions for this Procedure 1. Ensure hood inflow velocity is at least 100 fpm and that the ammonia tank is securely fastened with chain clamps or ring clamps inside the fume hood. The ammonia tank must be stored and used in a fume hood at all times. 2. Affix your balloon apparatus, which contains a valve, to end of the tubing from the ammonia tank regulator. Open the valve on the balloon apparatus, and then open the ammonia valve very slowly. Once the desired amount is obtained, close the valve on the ammonia tank, then close the valve on your balloon apparatus. Evacuate and backfill your reaction vessel using the ammonia gas balloon apparatus as desired. Notes Initials of individuals using this procedure Any deviation from this SOP requires approval from PI. Rev. Date: June 10, Acutely Toxic Gases Class SOP

10 Procedure/Use Scale Engineering Controls/Equipment 4. Condensing Ammonia The ammonia cylinder used must fit inside of the fume hood. This procedure is for condensing up to 1 L of ammonia. Alternative procedure included for condensing <10 ml ammonia. All reactions must be performed in a properly operating fume hood. If the balloon apparatus involves a needle, make sure the needle is capped during any transport. If the balloon enlarges during condensation, lower the flow rate of ammonia to lower the internal pressure. Maintain both the cold finger / condenser and the main bath at -78 ºC for the duration of the condensation. PPE (eye, face, gloves, clothing) Eye Protection: Wear tightfitting safety goggles or safety glasses with side shields. Face Protection: Use a face shield if not protected by the fume hood sash. Hand Protection: 8 mil minimum Nitrile gloves must be used to prevent incidental contact. Gloves must be inspected prior to use. Cotton or leather gloves may be used as well to prevent mechanical injury. Wash and dry hands after use. Clothing: Wear fire/flame resistant lab coat (100% cotton based); cotton based clothing/attire; full length pants or equivalent; and close-toed, close-heeled shoes. Procedure Steps and Special Precautions for this Procedure 1. Ensure hood inflow velocity is at least 100 fpm and that the ammonia tank is securely fastened with chain clamps or ring clamps inside the fume hood. The ammonia tank must be stored and used in a fume hood at all times. 2. Flame dry a 2-necked flask. Fit one neck with a septum and the other neck with a -78 ºC (dry ice / acetone) cold finger or condenser, which is also connected to a balloon apparatus. The balloon apparatus will allow for a place for gaseous ammonia gas to escape to. Evacuate and backfill the system with N 2. Cool the flask down in a -78 ºC bath. Affix a long needle to the end of the tubing from the ammonia tank regulator. Pierce the needle into the septum and open the ammonia valve slowly. This will allow for the ammonia to condense into the reaction flask. Once a sufficient amount of ammonia has condensed into the flask, shut off the valve, and add your substrates/reagents to the reaction while maintaining a low temperature. 3. Procedure for condensing < 10 ml of ammonia: Same as above, except a balloon apparatus may be used in place of a cold finger or condenser that is attached to a balloon apparatus. Notes Initials of individuals using this procedure Any deviation from this SOP requires approval from PI. Rev. Date: June 10, Acutely Toxic Gases Class SOP

11 Procedure/Use Scale Engineering Controls/Equipment 5. Quenching/ Evaporating Ammonia The ammonia cylinder used must fit inside of the fume hood. This procedure is for quenching up to 1 L of ammonia. All reactions must be performed in a properly operating fume hood. Keep the reaction as far back in the hood as possible, keep the hood sash low, and avoid working in the hood while ammonia is evaporating. PPE (eye, face, gloves, clothing) Eye Protection: Wear tightfitting safety goggles or safety glasses with side shields. Face Protection: Use a face shield if not protected by the fume hood sash. Hand Protection: 8 mil minimum Nitrile gloves must be used to prevent incidental contact. Gloves must be inspected prior to use. Cotton or leather gloves may be used as well to prevent mechanical injury. Wash and dry hands after use. Clothing: Wear fire/flame resistant lab coat (100% cotton based); cotton based clothing/attire; full length pants or equivalent; and close-toed, close-heeled shoes. Procedure Steps and Special Precautions for this Procedure 1. Ensure hood inflow velocity is at least 100 fpm and that the ammonia tank is securely fastened with chain clamps or ring clamps inside the fume hood. The ammonia tank must be stored and used in a fume hood at all times. 2. When the reaction is complete, remove the cold finger or condenser from one neck, and replace the septum from the other neck with a gas inlet adapter with a positive flow of nitrogen. Remove the reaction vessel from the cold bath and let it stand at room temperature until all the ammonia is evaporated, and the vessel reaches room temperature. Optional: Before removing the reaction from the cold bath, slowly dilute the reaction mixture with an appropriate solvent, such as diethyl ether or methanol, with a volume equal to 20% of the reaction volume (e.g. 200 ml methanol for 1L of ammonia). Precaution: -Do not use a bath to warm the reaction unless the ammonia is diluted with a cosolvent. This is to prevent eruption of the reaction during warming. - Ammonia causes severe skin burns and eye damage. Avoid working in the hood while ammonia is evaporating. Notes Initials of individuals using this procedure Any deviation from this SOP requires approval from PI. Rev. Date: June 10, Acutely Toxic Gases Class SOP

12 Sarpong Group Notes on Acutely Toxic Gases Potential Hazards/Toxicity Before working with any Acutely Toxic Gases, review the UC-Berkeley EH&S publication Toxic Gas Program (2011). There is a broad spectrum of toxic compressed gases. Increased recognition of the hazards associated with the transportation, operation, and storage of these gases is essential. Toxic gases are gases that may cause significant acute health effects at low concentrations. Health effects may include severe skin or eye irritation, pulmonary edema, neurotoxicity, or other potentially fatal conditions. Required Training/Approvals Prior to conducting any work with an acutely toxic chemical, a designated person 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 Chemical Class SOP, any other relevant SOP, and a copy of relevant SDSs provided by the manufacturer. Administrative Controls Never work alone with extremely hazardous materials/operations. Ask the Principal Investigator for specific prohibitions (if any) on working alone with any acutely toxic chemical. Certain extremely hazardous operations should not be performed if the PI or Lab Safety Contact(s) are not present. Eliminate or substitute for a less hazardous material when possible. Design your experiment to use the least amount of material possible to achieve the desired result. Do not exceed the scale of procedures specified in Lab Specific Instructions without approval of the PI. Verify your experimental set-up and procedure prior to use. Know the location of the nearest eyewash, safety shower, and fire extinguisher before beginning work. Certain extremely hazardous operations should be performed in a designated area. A designated area is where select carcinogens, reproductive toxins, and highly toxic materials are used and stored. A designated area can be as large as the entire laboratory, or as small as a specific laboratory workbench, or a laboratory hood. Designated areas must be clearly marked with signs and may include an appropriate warning; for example: WARNING! ACUTELY TOXIC CHEMICAL WORK AREA! Upon leaving a designated area, remove any personal protective equipment worn and wash hands, forearms, face, and neck. Decontamination procedures vary depending on the material being handled. The toxicity of some materials can be neutralized with other reagents. Decontaminate vacuum pumps or other contaminated equipment (glassware) before removing them from the designated area. Rev. Date: June 10, Acutely Toxic Gases Class SOP

13 13 - Documentation of Training (signature of all users is required) Prior to conducting any work with acutely toxic gases, 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. I have read and understand the content of this SOP: Name Signature Identifier Date Rev. Date: June 10, Acutely Toxic Gases Class SOP

14 Appendix List of Acutely Toxic Gases in Settlement Agreement Chemical Name/Formula CAS# Chemical Name/Formula CAS# Ammonia NH Arsenic pentafluoride AsF Arsine AsH Boron trichloride BCl Boron trifluoride BF Carbon monoxide CO Cyanogen C 2 N Cyanogen chloride NCCl Chlorine Cl Diazomethane H 2 CN Diborane B 2 H Fluorine F Germane GeH Hexaethyltetraphosphate C 12 H 30 O 13 P 4 Hydrogen bromide HBr Hydrogen Chloride HCl Hydrogen fluoride HF Hydrogen sulfide H 2 S Hydrogen selenide H 2 Se Methyl mercaptan CH 3 SH Nitric oxide NO Nitrogen dioxide NO Nitrogen tetroxide N 2 O Oxygen difluoride OF Phosgene COCl Phosphine PH Phosphorous pentafluoride PF Selenium hexafluoride SeF Stibine SbH Sulfur tetrafluoride SF Trimethylsilyldiazomethane (CH 3 ) 3 SiCHN Rev. Date: June 10, Acutely Toxic Gases Class SOP

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