2.xx LITHIUM DIISOPROPYLAMIDE IN HEPTANE/THF CAS: 4111-54-0 Lithium Diisopropylamide (108-18-9) Heptane (142-82-5) Tetrahydrofuran (THF) (109-99-9) Ethyl Benzene (100-41-4) 3 3 2 W A. PURPOSE & SCOPE Lithium diisopropylamide in heptane/THF is a pyrophoric material that is highly flammable, water reactive, toxic, corrosive and known to be carcinogenic and teratogenic. If not stored and handled properly, this can pose a serious threat to the health and safety of laboratory personnel, emergency responders and chemical waste handlers. B. INTRODUCTION Lithium diisoproplyamide, 2.0M solution (abbreviated LDA) is a solution containing Heptane, Tetrahydrofuran, Ethyl benzene and Diisopropylamine. It is a pyrophoric chemical that catches fire spontaneously when exposed to air. Contact with water releases flammable gases. It is toxic if inhaled and harmful if ingested or absorbed through the skin. It causes burns by all exposure routes. It is a suspected carcinogen and teratogen. Lithium diisopropylamide is a commonly used reagent in organic synthesis. It is used as a strong base for deprotonation of weakly acidic compounds. Danger! Flammable Pyrophoric Corrosive Water Reactive Toxic Carcinogenic Teratogenic Incompatibility Heat Fire Air Water Acids Oxidizing chemicals Hazardous Decomposition Products: Lithium oxide, hydroxide and hydride. Potential Hazards/Toxicity LITHIUM DIISOPROPYLAMIDE is a highly flammable liquid or vapor. It is pyrophoric and will catch fire spontaneously if exposed to air. It reacts violently with water. Contact with water releases flammable gases. May form explosive peroxides. Handle and store under inert gas and protect from moisture. It is toxic if inhaled and harmful if ingested or absorbed through the skin. It causes burns by all exposure routes. Material is extremely destructive to the tissue of the mucous membranes and upper respiratory tract. Causes severe skin burns and eye damage. It is an aspiration hazard and may enter lungs to cause damage. Symptoms of exposure include burning sensation, coughing, wheezing, laryngitis, shortness of breath, headache, nausea, vomiting, inflammation and edema of the larynx and bronchi, spasms,pneumonitis, pulmonary edema, blurred vision, and central nervous system effects. Prolonged exposure may casue adverse liver and kidney effects. May cause cancer. May damage fertility and the unborn child. C. RESPONSIBILITIES Principal Investigators (PI) Shall ensure that this guideline is read and implemented in their work areas and labs. All work areas using LITHIUM DIISOPROPYLAMIDE will be marked to alert all persons of the presence of LITHIUM DIISOPROPYLAMIDE or Pyrophoric. They shall ensure that all workers using LITHIUM DIISOPROPYLAMIDE receive the appropriate training before using LITHIUM DIISOPROPYLAMIDE. PIs will provide all workers with the MSDS, protective equipment and warning signs for LITHIUM DIISOPROPYLAMIDE. PIs will notify Environmental Health & Safety of LITHIUM DIISOPROPYLAMIDE use in the laboratory. Ensure that quick-drench eyewash and safety showers are immediately nearby. LITHIUM DIISOPROPYLAMIDE (LDA) Users Shall ensure this guideline is read and implemented in all work areas and labs that are using, storing, and disposing of LITHIUM DIISOPROPYLAMIDE. All users will attend a documented training session on the proper handling, storage and first aid procedures for LITHIUM DIISOPROPYLAMIDE and Pyrophorics. All users will read the MSDS for LITHIUM DIISOPROPYLAMIDE, know the first aid/medical treatment procedures and spill response for LITHIUM DIISOPROPYLAMIDE. The Environmental Health & Safety (EHS) Office Shall ensure that PIs and users notify the Environmental Health & Safety of LITHIUM DIISOPROPYLAMIDE use in the laboratory. D. HEALTH HAZARD DATA Potential Health Effects Target Organs: Lungs, liver, kidney and central nervous system. Inhalation: Inhalation of vapors may cause central nervous system effects including headache, vertigo, drowsiness, anesthesia, unconsciousness, respiratory arrest. Skin: Contact with liquid is corrosive and pyrophoric. Will cause severe burns. Eyes: May cause irreversible eye injury. Exposure to the vapors or liquid may cause temporary blindness. Causes severe eye burns. Ingestion: Harmful if swallowed. Causes digestive tract burns. Acute: No data available for the product. This product reacts with water producing flammable gases and corrosive dusts. It is corrosive to the eyes (may cause blindness), skin, respiratory and gastrointestinal tracts. Inhalation of vapors may cause dizziness, drowsiness, unconsciousness, respiratory irritation and irritation to eyes, skin and mucous membranes. Ethlybenzene presents an aspiration hazard; vomiting after ingestion and/or ingestion of this product may result in chemical pneumonitis, asphyxia and/or fatal pulmonary edema. Chonic: No data available for the product. Repeated oral administration of ethylbenzene to laboratory animals caused slight liver and kidney effects. Prolonged worker exposure to ethylbenzene has been reported to cause upper respiratory tract irritation as well as possible gallbladder and liver effects. Repeated or prolonged skin contact with the solvents may cause dermatitis and skin sensitization. Chronic exposure to aromatic hydrocarbons may cause headaches, dizziness, loss of sensations or feelings (such as numbness), liver and kidney damage. Prolonged or repeated exposure to tetrahydrofuran has caused liver and kidney damage in laboratory animals. It has also been reported to be fetotoxic in mice. Preliminary results of studies conducted by the NTP on long-term inhalation effects of tetrahyrdofuran indicate clear evidence of carcinogenicity in female mice, and some evidence in male rats. Exposure Limits/Toxicity Chemical Name Tetrahydrofuran Diisopropylamine Ethylbenzene n-heptane TWA 200ppm 5ppm 100ppm 800ppm PEL 200ppm 5ppm 100ppm Engineering Controls Use in closed system under argon or nitrogen. If personal contact can occur, use local exhaust ventilation (explosion-proof), to keep airborne concentrations below exposure limits. E. FIRST AID NOTE: Individuals assisting victim should wear appropriate gloves to prevent secondary LITHIUM DIISOPROPYLAMIDE exposure. 1 Skin Exposure Immediately flush with plenty of water for at least 15 minutes while removing contaminated clothing. Seek immediate medical attention. 2 Eye Contact Immediately flush eyes with plenty of water lifting upper and lower eyelids. Seek immediate medical attention, while continuing to flush eyes during transport to hospital. 3 Inhalation of Vapors Move person into fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Seek immediate medical attention. 4 Ingestion of Acid DO NOT INDUCE VOMITING. Never give anything by mouth to an unconscious person. Seek immediate medical attention. F SAFETY CONTROLS: All personnel who work with LITHIUM DIISOPROPYLAMIDE should undergo safety training prior to working with this chemical, have access to and have read the Material Safety Data Sheet (MSDS), review and understand this guideline and understand emergency first aid treatment for LITHIUM DIISOPROPYLAMIDE exposure. Store & handle inside a glove box (under an inert atmosphere – preferably under Nitrogen). For additional information, please refer to the MSDS (i.e., sections on ‘Stability & Reactivity’ and ‘Handling & Storage’) from the same manufacturer. G. PERSONAL PROTECTIVE EQUIPMENT (PPE) Be sure that you are using personal protective equipment that has been shown to effectively protect against LITHIUM DIISOPROPYLAMIDE exposure. Always double check your equipment before each use of LITHIUM DIISOPROPYLAMIDE. 1 Respiratory Protection Use a full-face respirator with multi-purpose combinations (US) cartridges. 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. Lab personnel intending to use/wear a respirator mask must be trained and fit-tested by EH&S, x51823 2 Eye Protection ANSI approved, tight-fitting chemical splash glasses/goggles. Face shields are highly recommended in addition to. NOTE: Safety glasses with side protectors do not protect from splashes. 3 Body Protection Fire-resistant lab coat made of anti-static material. Full-length pants. Closed-toed impervious footwear, preferably leather and nylon will allow LITHIUM DIISOPROPYLAMIDE to pass straight through to skin. 4 Hand Protection Handle with gloves. Fluorinated rubber gloves are recommended. Because this compound contains THF, contact should be minimized. THF permeates standard nitrile gloves in less than 1 minute. 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/ 5 Hygiene Measures Avoid contact with skin, eyes, and clothing. Wash hands before breaks and immediately after handling LITHIUM DIISOPROPYLAMIDE. H. STORAGE & HANDLING REQUIREMENTS Engineering Controls LITHIUM DIISOPROPYLAMIDE should be used in a glove box or in a closed system in a certified chemical fume hood. Storage Keep container tightly closed in a cool, dry, and well-ventilated area. Opened containers must be carefully resealed and kept upright to prevent leakage. Never allow contact with water. Recommended storage temperature is 2-8C. Moisture and airsensitive. Handle and store under inert gas. Store in corrosives area. Containers should be dated when received and opened, and tested periodically for peroxides. Avoid strong oxidizing agents, alcohols, and acids Handling Avoid contact with skin, eyes, and clothing. Avoid inhalation and ingestion. Use sparkproof tools and explosion-proof equipment. Provide adequate ventilation. Keep away from heat and other sources if ignition- NO SMOKING. Prevent build-up of electrostatic charge. I. FIRE EXTINGUISHING and SPILL CLEANUP Fire Extinguishers and Extinguishing Media LITHIUM DIISOPROPYLAMIDE is a flammable liquid and vapor. Vapors are heavier than air. Vapors can form an explosive mixture with air. Flashback is possible. Containers may explode when heated. Unless you have a Self-Contained Breathing Apparatus (SCBA) mask and full protective gear, you WILL NOT engage in Fire Extinguishing activities. Evacuate area and call 9-1-1. Spills Outside Inert Gas Glove Box Remove all personal from lab and immediately call EH&S at (480) 965-1823, or 9-1-1 after hours. 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 ASU EH&S at (480) 965-1823. Chemical Splash into Eyes Immediately rinse eyeball and inner surface of eyelid with water for 15 minutes by forcibly holding the eye open. Seek medical attention. Notify supervisor and ASU EH&S at (480) 965-1823. Spills Inside Inert Gas Glove Box Inform all personnel of the spill. Restrict access to Glove Box until spill is cleaned up and neutralized. Spread absorbent (vermiculite or sand) onto spill. Allow LITHIUM DIISOPROPYLAMIDE to be absorbed. Transfer absorbent/LITHIUM DIISOPROPYLAMIDE to an air tight container. Do not flush with water. J. DECONTAMINATION/WASTE DISPOSAL No waste streams containing LITHIUM DIISOPROPYLAMIDE shall be disposed of in sinks. Wash hands and arms with soap and water after finished. Contaminated pipette tips, tubes and gloves should be collected as hazardous waste in an air tight container with inert atmosphere. 1 Label waste Attach a completed ASU Hazardous Waste tag to all waste containers as soon as the first drop of waste is added to the container. Containers of LITHIUM DIISOPROPYLAMIDE waste must be labeled with the following: “DANGER, PYROPHORIC HAZARD”. 2 Store waste Store hazardous waste in closed containers, in secondary containment and in a designated storage location. Double-bag dry waste using sealable transparent bags. Waste must be under the control of the person generating and disposing of it. 3 Dispose of waste Dispose of regularly generated chemical waste within 90 days. Use EHS Assistant online hazardous waste pick-up request system. Contact ASU EH&S at (480) 965-1823 with questions.