Chemical Class Standard Operating Procedures

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1 Chemical Class Standard Operating Procedures Strong Reducing Agents (SRA) Print a copy and insert into your laboratory SOP binder. Department: Chemistry Date SOP was written: 11/06/2013 Date SOP was approved by PI/lab supervisor: 11/06/2013 Principal Investigator: Name: Felix R. Fischer Signature: Name: Justin Bours Internal Lab Safety Coordinator or Lab Manager: Lab Phone: Office Phone: Emergency Contact: Name: Felix R. Fischer Phone Number: Location(s) covered by this SOP: Tan Hall 674, 675, 676, 680, 683, Purpose This SOP covers the precautions and safe handling procedures for the use of Strong Reducing Agents in the Fischer group, which include the following chemicals and their uses: Chemical(s) Sodium Lithium Potassium Calcium Magnesium Barium Lithium aluminumhydride Sodium borohydride Use(s) 2. Strong Reducing Agents Information Rev. Date: May 30, Strong Reducing Agents Class SOP

2 Strong reducing agents are defined as compounds that have a high reducing potential (low electro- negativity). Generally the most hazardous (inadvertent) reactions occur when a strong reducing agent comes in contact with an oxidizing agent. The most violent examples are combinations of hydrazine with oxidizers such as liquid oxygen or dinitrogen tetroxide. The compounds shown in the table below are examples of a large group of strong reducing agents. Reducing agents include Group 1A alkali metals and Group 2A alkaline earths metals; all metals that form hydrides or borohydrides; including Group 1A and 2A; complex hydrides having the general formula M1 m+ (M2H n ) m- where M1 can be, for example, Al, Be, Cs, Ca, Cu(I), Li, Na, K, Mg, Hf, U(III); M2 can be, for example, B, Al, Cu(I), Ga, Zn, Mg. Metal phosphides are strong reducing agents that evolve phosphine (PH 3 ) in contact with water or dilute solutions of mineral acids. Phosphine is a highly toxic gas and is combustible. Phosphine is spontaneously flammable if contaminated by low levels of di- phosphine, P 2 H 4. Many organo- phosphines are strong reducing agents. Sulfite salts are strong reducing agents, liberating SO 2 in contact with dilute mineral acid. The following materials are the identified as Strong Reducing Agents in the Settlement Agreement: Chemical Name/Formula CAS# Chemical Name/Formula CAS# Sodium, Na Calcium, Ca Lithium, Li Magnesium, Mg Potassium, K Barium, Ba Lithium aluminum hydride, LiAlH Sodium borohydride, NaBH These chemicals are discussed in the group SOP for water reactive chemicals (WRC). 3 - Potential Hazards/Toxicity The Strong Reducing Agents identified in the Settlement Agreement include low- valent metals and related hydrides. Because of their high reactivity with moisture in air or water, Group 1A alkali metals (sodium, lithium, potassium) must be stored in oil to insure no moisture contact whereas Group 2A alkaline earth metals (calcium, magnesium, barium) are stored in a manner to prevent direct contact with water. The hydrides are also extremely moisture sensitive and reactive. These materials should be protected from contact with oxidizing agents. The phosphides must also be stored so as to eliminate inadvertent contact with water which would lead to the formation of phosphine (IDLH = 50ppm; OSHA PEL: TWA 0.3 ppm). Avoid contact of sulfites with mineral acids which would lead to the formation of sulfur dioxide (IDLH = 100ppm; OSHA PEL: TWA 5 ppm). These materials, unreacted have a low to moderate toxicity and can cause skin irritation or corrosive damage. However, these materials are highly reactive with water and air and tissue damage will result from the energy of chemical reactions of these products. Most strong reducing agents listed under the Settlement Agreement do not have an established Cal OSHA permissible exposure limit except for Barium, PEL 8- hr TWA: 0.5 mg/m Engineering Controls Use the engineering controls listed below unless other lab- specific information is included in the Protocol/Procedure section: A laboratory type fume hood with the sash position closed as much as possible; Rev. Date: May 30, Strong Reducing Agents Class SOP

3 A glove box for pyrophorics and any water reactive chemicals. Glove boxes may also be required for other chemicals; Supplemental protective equipment such as a blast shield, where appropriate, to protect from explosions when using peroxide formers, pyrophorics, water reactives, and potentially explosive chemicals. Laboratories and rooms where strong reducing agents are used shall have general room ventilation that is at negative pressure with respect to the corridors and external environment. The laboratory/room door must be kept closed at all times. 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: laboratory- safety/94- glove- selection- and- usage.html 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 materials 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. Rev. Date: May 30, Strong Reducing Agents Class SOP

4 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. 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. Rev. Date: May 30, Strong Reducing Agents Class SOP

5 Precautions for safe handling Depending on the level of reactivity of the reducing agent, care must be taken to insure that the proper storage requirements are in place as the agent is being used. Group 1A elements must not be exposed to moisture in the air. Group 2A elements must not be exposed directly to water. Hydrides must be handled that prevents contact with air or water. Phosphides must be handled and stored to avoid incidental contact with water. Conditions for safe storage Do not store near combustible materials or other chemicals that are easily reduced, i.e., strong oxidizers. Keep container closed when not in use. Store in a cool, dry, well- ventilated area away from incompatible substances. Store protected from moisture. Sulfides should be stored to avoid contact with acids. 8 - Spill and Accident Procedure 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.). Minor Spill (<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. Major Spill (>1 L) Dial 911 and 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 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 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 to report the incident. Non- Life Threatening Emergency Rev. Date: May 30, Strong Reducing Agents Class SOP

6 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 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 to report the incident. 9 - Cleaning and Decontamination Lab- specific information on cleaning/decontamination may be included in the Protocol/Procedure section. Wearing proper PPE, laboratory work surfaces should be cleaned at the end of each work day. Dispose of contaminated materials in accordance with hazardous waste disposal guidelines referenced below. Decontaminate all equipment before removing from a designated area. 10 Hazardous Waste Disposal Procedure Label Waste Label all containers with the label provided at new- hazardous- waste- program- hwp.html. 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: May 30, Strong Reducing Agents Class SOP

7 12. Protocol/Procedure Strong Reducing Agents Preparation Lab- specific Information The strong reducing agents (SRA) covered by the Settlement Agreement (Na, Li, K, Ca, Mg, Ba, LiAlH 4, NaBH 4 ) are also classified as water reactive chemicals (WRC). Please refer to the WRC class SOP for protocols and procedures applicable to handling SRA s See WRC s for specific information on Na, Li, K, Ca, Mg, Ba, LiAlH 4, NaBH 4 Decontamination & Waste Disposal See WRC s for specific information on Na, Li, K, Ca, Mg, Ba, LiAlH 4, NaBH 4 Rev. Date: May 30, Strong Reducing Agents Class SOP

8 13. Documentation of Training (signature of all users is required) Prior to conducting any work with strong reducing agents, 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: Name Signature Initials Identification Date Rev. Date: May 30, Strong Reducing Agents Class SOP