Safety in an Organic Lab 1 Revised August BVH THE CHEMISTRY LABORATORY INCLUDES HAZARDS AND RISKS. This presentation summarizes some of the safety rules for an organic laboratory. If some of the material is unfamiliar, or you did not take general chemistry at the College of Charleston, you should review the information under Laboratory Safety in the attached link: General Chemistry Lab SafetyGeneral Chemistry Lab Safety 2 Personal Protective Equipment: What must be worn when you work in the laboratory PPE Eye Protection Lab Coat Long Pants Closed Toed Shoes no exposed skin around feet Lab gloves when required Eye Protection Contact lenses are OK as long as glasses/goggles are worn Prescription glasses you must wear goggles over them Safety goggles are provided in organic labs in UV irradiating cabinets Eye wash stations are present in all labs 4 Clothing must cover all exposed skin including legs/ankles Stockings or leggings do not provide good coverage Sandals, flip-flops, Crocs, open-toe and open-top (i.e. ballet flat) shoes and canvas shoes (i.e. Toms) are not appropriate. These are not going to protect your feet if you drop a piece of glass with a liquid chemical reagent in it. Clothing and Foot Protection 5 Be Smart about the shoes you elect to wear to lab This person has on pants and closed toed-shoes but this would not be allowed in lab due to the exposed skin This person added socks, so this option covers your skin but only offers minimal protection This option looks better, but imagine chemicals being spilled into the top of these boots Your best options are sturdy leather footwear that covers the entire top of the foot or a sturdy running shoe. Result of Improper Footwear in a Laboratory Your instructor will send you home to change if you do not have appropriate shoes or other required PPE. Northwestern University, Evanston, IL July Wear gloves of a material known to be resistant to permeation by the substances in use nitrile is good for most of our laboratory classes. Inspect each glove for small holes or tears before use. When you spill on your glove or tear it, change it immediately. Throw gloves away any time you take them off. Hand Protection: Chemically resistant Lab Gloves 8 Karen Wetterhahn (October 16, 1948 June 8, 1997) The latex gloves she was wearing were not resistant to methyl mercury it passed through the glove, through her skin, entered her blood system and resulted in her death weeks after the exposure. Dartmouth College 9 Use of Gloves Remove gloves before handling objects such as doorknobs, telephones, pens, computer keyboards, pH meter or other electronic buttons, or phones while in lab. It might be convenient to have one gloved hand and one ungloved hand to do procedures where these kinds of things are used. Throw away gloves anytime you take them off. Expect to use several pairs of gloves in a lab. Glove video 10 The number one responsibility of your lab instructor is to monitor maintain a safe working environment for everyone in the lab Your lab instructor will be in attendance during your lab walking around to monitor PPE and experiments. Everyone must wear the required PPE at all times. There are no exceptions, so dont ask for one. Do not ask permission to attend lab without PPE. It is your responsibility to be properly attired and if you are not, you will be asked to leave. 11 Instructor Responsibility 2. Safety Equipment in the Lab Eyewash and Safety Shower: Know where these are in your lab. 12 Eyewash / Safety Shower The eyewash is on the left. Pull the handle and a fountain of water will appear that you can use to bathe your eyes. The safety shower is on the right. Pull the handle and water will start spraying from the shower head on the ceiling. Theres no drain in the floor we only do this in emergencies, because a flood of water will have to be cleaned up. 13 14 Eye Wash Safety Shower 15 3. Chemical Fume Hoods: You must do your experiment in the hood if any of your reagents are flammable, have harmful fumes or present a splash or explosion hazard. This means pretty much at all times for organic chemists. 16 Using the Fume Hoods properly If this is not saying NORMAL, then the hood is not protecting you. Keeping the sash and sliding panels in proper position keeps this NORMAL, otherwise the alarm goes off. If the alarm goes off, you need to reposition things to the correct positions, then press the mute button to reset the controller. The sash should never be raised above the green operation level when you are working in the hood. This window/bar is called the sash. 17 Closed, not in use In use, side-to-side panel used as shield In use, sash (window) raised to less than 18 inches Dont open side shields to make one big window. 18 When using a laboratory hood, Check that the airflow is in the normal range on the digital display Turn on the hood light Set the equipment and chemicals back at least 6 inches. Never lean in and/or put your head in the hood when you are working. This is worse than doing the experiment with no hood at all. Its a good idea to put liquid reagent containers in trays to catch all spills and drips 19 4. Know the risks of the chemical reagents you are working with 20 Labels are important Even if it seems obvious. In the chemistry lab, nothing is ever obvious. 21 Older NFPA labels with hazard levels identified on the diamond New GHS label system with pictogram hazards Students may want to bring a sharpie to lab for writing labels on solutions that they make. At a minimum, a student made solution should have the chemical name, the date, and the students initials. NFPA Diamond 22 New Standard: GHS (Globally Harmonized System) Under GHS regulations, each chemical product label must contain the following: Product Identifier, Signal Word, Pictogram, Hazard Statement, and Supplier Information. 23 GHS and NFPA Numbering Systems It is very important that you realize that the number codes for NFPA and GHS HazCom are not the same. For the NFPA diamond 4 is the most hazardous, for GHS HazCom 1 is most hazardous. Since many chemicals have a long shelf life, you may find many containers with the NFPA diamond in the years ahead. The GHS HazCom labeling began in SDS ( formerly known as MSDS ) Provides procedures for handling or working with that substance in a safe manner Includes physical data: melting point, boiling point, flash point, etc. Includes safety data: incompatibilities, toxicity, health effects, reactivity, storage, disposal: protective equipment & spill-handling procedures first aid 25 How to find an SDS There are on-line repositories of SDS that can be searched by the following methods: Common Name IUPAC (International Union of Pure and Applied Chemistry) Name C.A.S. NUMBER (Chemical Abstracts Service) a number assigned to all commercialized chemicals available in the US The easiest to use is the CAS number, as it is a unique identifier that isnt subject to spelling errors SDS for each experiment are posted on OAKS Many SDS are also in a MSDS folder in the laboratory 26 Incompatible materials Certain chemicals should not be stored and cannot be safely mixed with certain other chemicals due to severe reaction exotherm or uncontrolled production of a toxic product. 27 Every lab has a legible matrix that lists the general classes of materials that should not be mixed together: Texas City Disaster of 1947 Incompatible oxidizer and fuel source mixed Worst industrial accident in American history Freighter full of ammonium nitrate and fuel oil (ANFO) exploded, igniting other ships 581 dead, entire city devastated 28 Ship anchor thrown across city by explosion Introductory toxicology AN MSDS contains valuable information on the health dangers of the chemicals but often use concepts and acronyms that are new to students: 29 PEL TLV LD50 and LC50 CAS # STEL Right to Know acts TWA OSHA TOSCA NIOSH PROP 65 RCRA Mutagenicity vs. teratogenicity You need to know what is what to read an MSDS IDLH Regulatory agencies and standards Over the last 40 years the US and state governments and various international bodies have developed regulations and standards that try to improve safety and industrial hygiene standards including the following: EPA: Environmental Protection Agency, who have the primary responsibility to ensure chemicals are used and disposed of in an environmentally sensitive manner TOSCA: the Toxic Substances Control Act of 1976 regulates which chemicals may be produced or imported in the US OSHA: Occupational Safety and Health Administration is the US agency that assures safe and healthful working conditions by setting and enforcing standards NIOSH: National Institute for Occupational Safety and Health is responsible for researching the prevention of work-related injury and illness, and providing guidance to OSHA RCRA: the resource conservation and recovery act of 1976 that sets the standards for chemical waste disposal in this country and overseesthe superfund law CERCLA California Proposition 65: The state of California passed a very rigorous law to protect drinking and ground water from toxic chemicals. It is increasingly the standard for companies when evaluating chemical safety 30 All of these regulations have been developed to make the use and handling of chemical safer, so their impact on lab safety has been profound Acute and chronic toxicology Acute toxin: rapid absorption of the substance and the exposure is sudden and severe. Normally, a single large exposure is involved. Examples are carbon monoxide, hydrofluoric acid, hydrogen cyanide and nicotine Chronic toxin: prolonged or repeated exposures of a duration measured in days, months or years. Symptoms may not be immediately apparent. Examples of chemicals of high chronic toxicity include dimethylmercury, nickel carbonyl, benzo-a-pyrene, N- nitrosodiethylamine, and other human carcinogens or substances with high carcinogenic potency in animals 31 Carcinogens, mutagens and teratogens One of the most significant chronic risks associated with chemicals is their potential to cause cell mutation and proliferation. Carcinogen: chemicals that can increase the incidence of cancer in the body Mutagen: chemicals that cause mutations in DNA that lead to hereditary genetic defects in a fetus There are two other general classifications that you should be aware of: Teratogen: chemicals that induce non-hereditary malformations of a fetus Sensitizer: chemicals that no reaction in a person during initial exposures, but further exposures will cause an allergic response to the chemical 32 Routes of Entry and Allowable Exposure Limits There are four main routes by which hazardous chemicals enter the body: Inhalation: Absorption through the respiratory tract. Most important in terms of severity. Skin absorption. Ingestion: Absorption through the digestive tract. Can occur through eating or smoking with contaminated hands or in contaminated work areas. Injection. Can occur by accidental needle stick or puncture of skin with a sharp object. Most exposure standards, Threshold Limit Values (TLVs) and Permissible Exposure Limits(PELs), are based on the inhalation route of exposure. expressed in terms of either parts per million (ppm) or milligrams per cubic meter (mg/m3) concentration in air. Other measures of chemical exposure: Lethal dose or concentration for 50% of the exposed population (LD50 or LC50) expressed in mg contaminant per kg of body weight Short term exposure limit (STEL or TLV-STEL) is the amount of a substance you can be exposed to for 15 minutes four times a day 33 5. Fire Safety 34 Fire Alarms know the location of one close to your lab 35 Fire Extinguishers we have several in the labs and in the hallways. 36 37 Types of Fire Extinguishers Most of our fire extinguishers are ABC. It contains a dry powder to put out the kinds of fires we might encounter in the chemistry labs where we have class. This is a special fire extinguisher for combustible metal fires. It is a type D fire extinguisher. You wont need to use this unless you work in a research lab with combustible metals. 38 Student Reaction in a Fire Although we want you to be informed on the operation of a fire extinguisher, we do not expect you to use it. If a fire is ignited in your area, the proper STUDENT response is to: 1)Notify everyone in the room 2)If possible shutdown any reaction in progress by removing heat/energy source and/or pulling plug on power cord 3)Proceed to the nearest exit and pull the nearest fire alarm 4)Evacuate the building 5)Assemble in front of the library or in the former YWCA parking (currently CofC YW student) lot for a positive headcount 39 Flammables, combustibles, and potentially explosive materials There are different ways of designating that a chemical is a fire risk: Flashpoint - minimum temperature at which a liquid gives off a vapor in sufficient concentration to ignite in the presence of an ignition source Combustible liquid - Any liquid having a flashpoint at or above 37.8 o C (100 F) but below 93.3 o C (200 F) Flammable liquid - any liquid having a flashpoint below 37.8 o C Autoignition temperature - the lowest temperature at which it will spontaneously ignite in a normal atmosphere without an external source of ignition, such as a flame or spark Explosive - A chemical that causes a sudden, almost instantaneous release of pressure, gas, and heat temperature. 40 Synthesis of explosive material In organic lab we often do reactions to add functional groups to benzene rings. A simple reaction is shown below: If a student overcharged the amount nitric acid and overheats the reaction the following chemical is isolated: Another risk is the formation of Peroxides Explosives that can be generated in lab when organic ethers are heated for a prolonged period in the presence of air. 41 Trinitrotoluene If this is not handled carefully there are serious repercussions: Working with flames Never leave experiments unattended unless you take special precautions to avoid accidents and you notify the responsible individuals. Flames are never allowed when flammable gases or liquids are in use. Always alert others before lighting a flame. Never leave a flame unattended under any circumstances. Turn off the natural gas at the valve when you are finished with your work In the organic lab, Bunsen burners are rarely used to either (1) to pull TLC spotting tubes; or (2) to conduct flame or combustion tests. Closed valve is Perpendicular to hose 42 UCLA Lab Fire: December 29, 2008 Sheri Sangji was using this plastic syringe to transfer tert-butyllithium. This was not the correct procedure, because this compound is well-known to ignite if it is comes in contact with air. The syringe plunger dropped out of the syringe and the reagent ignited. Sheri died January 16, 2009 of severe burns. She was wearing nitrile gloves but no lab coat. The students assisting her did not remember to put her under the safety shower. 43 Lessons from UCLA accident Lessons: Know the proper procedures for transferring dangerous reagents. Wear your lab coat at all times in the lab. Know where safety shower and other emergency equipment is you may need to be the one who needs to be ready to act when your lab mate is unable to help himself/herself. 44 7. Disposal Procedures 45 Broken Glassware Always check your glassware and discard any with chips, breaks, or obvious flaws. Throw away broken glassware into special glass waste containers, NOT the trash. 46 NO YES Waste Disposal Waste containers are provided for chemical waste generated in laboratories Some things can go down the sink, some cant. Always check with your instructor. Care must be used to avoid mixing incompatible chemicals such as Acids with Bases Oxidizers and Flammables Water reactive and aqueous solutions Cyanides and acids 47 University of Maryland September 26, 2011 Students were conducting an experiment with nitric acid and sulfuric acid was added into a chemical waste container, causing a violent chemical reaction sparked a small fire in and near the laboratory chemical ventilation hood. Two female students were injured as a result Sustained first- and second-degree chemical burns and superficial cuts. 48 Handling Waste in Organic Labs Organic liquids like CH 2 Cl 2 (aka methylene chloride, dichloromethane) & acetone, & TBME & liquid reagents PUT IN ORGANIC (HALOGENATED) LIQUID WASTE CONTAINER IN WASTE HOOD Aqueous neutral (not basic or acidic) containing organics PUT IN AQUEOUS WASTE CONTAINER IN WASTE HOOD Aqueous neutral (not basic or acidic) containing NONTOXIC salts with no organics CAN GO IN PUBLIC SEWAR, DOWN THE DRAIN Solid chemical old products, left over starting materials, includes organic and inorganic PUT IN SOLID WASTE CONTAINER IN WASTE HOOD Solid, non toxic waste (paper towels, notebook pages) PUT IN TRASH ONLY IF SAFE TO TOUCH WITH BARE HANDS 49 Think First, Dispose Second 50 XP APER, WITHOUT C HEMICAL R ESIDUE C LEAN B ROKEN G LASS XC HEMICAL W ASTE XP APER, WITHOUT C HEMICAL R ESIDUE XC LEAN B ROKEN G LASS C HEMICAL W ASTE P APER, WITHOUT C HEMICAL R ESIDUE XC LEAN B ROKEN G LASS XC HEMICAL W ASTE 8. How to be a good lab citizen 51 1. Be prepared before walking into the lab. 2. Think about the how and why before doing anything. 3. Begin with a clean, neat work area; make it so. 4. Minimize clutter; store book bags, equipment, etc. 5. Have instructions, pen and notebook available. 6. Return materials and equipment to proper places. 7. Make it clean and neat and orderly before leaving. SEVEN must-have habits for lab-work 52 Keep your lab area clean. Throw away used paper towels and used gloves, immediately. Dont block the floor in front of the eyewash/shower station. Dont leave things in the floor because someone will trip over it. Dont leave cords dangling because someone will trip over them. 53 Take care not to ingest anything in the laboratory! Food, gum, beverages, candy, and tobacco products are never allowed in the laboratory. Dont apply makeup, chap-stick, lotion, or anything to your face or hands during lab. Wash your hands with soap then leave the lab before touching your face or other exposed skin. Dont put anything on your face or in your mouth while youre in lab. 54 Dont use any distracting electronic devices while in laboratory. If you touch your phone during lab, youre contaminating it with whatever chemicals youve been working with. Do not wear earbuds in the lab. You need to be able to hear important announcements, especially in an emergency or when a safety concern is addressed. Stay aware of whats happening around you while youre working in the lab. 55 Chemical Spills Notify your instructor and your neighbors if you spill chemicals on the floor or bench. Dont try to clean it up yourself. Your instructor may need to use a specially designed chemical spill kit. 56 Texas Tech January 7, 2010 Conducting research funded by the U.S. Department of Homeland Security on energetic / explosive compounds Attempting to produce 100 times more of an explosive compound than the informal lab limit (100mg) Lesson: Follow instructions in the lab. 57 8. Procedures and Practices 58 Students must report any injuries, big or small. Report all injuries to the instructor. We will not call emergency services unless the instructor determines it is a serious injury. An incident report will be filled out whether it is small or serious. 59 Injury procedure, continued First Aid kits are available in the lab with band aids and other items for treating small cuts and burns. If it is a serious injury, your instructor will call campus emergency services, Our campus officers will work with the instructor and/or injured student to determine whether or not 911 EMS should be called in. 60 Process safety When performing an experiment always consider the following: Is the material flammable, explosive, corrosive, or reactive? Is the material toxic, and if so, how exposure to the material occur What kind of personal protective equipment or ventilation is needed to protect myself? Will the process generate other toxic compounds, or could it result in a fire, explosion, etc.? Are storage facilities appropriate for the type of materials used? Can incompatible materials be properly segregated? What possible accidents can occur and what steps can be taken to minimize the likelihood and impact of an accident? What are the proper procedures for disposal of the chemical(s)? As an example of process safety consider distillation : 61 What I Dont Know Cant Hurt Me At a school far, far away; at a time long, long ago; there was an organic student performing a reaction that required heat. So the student, happily and cheerfully set about to heat the solution. The procedure stressed the need to prevent loss of material due to boiling off of solvent during the heating process. The student did not read over all the details carefully, but she did think to cap the top of the apparatus to prevent the solvent from boiling off. Pleased with herself for having remembered that little detail, she was shocked and mad when her instructor saw what she had done and asked her, in a rather loud and obnoxious voice: What the heck are you doing? Look at the picture when it pops up and see if you can identify what it was that had the instructor so upset. When the student was told by the instructor what the problem was, her response was (this is a true story): Well I do not think that matters, what I dont know cant hurt me. Trust us, you do not want to be that student. 62 The Apparatus 63 HINT: PV = n RT Distillation Dos Have apparatus inspected by instructor before using it Have apparatus elevated off bench top so heat can be removed quickly if needed Have a clamp around neck of flask so if heat source is removed, apparatus is still supported Make sure water flow goes uphill, and cooling water ends up going unimpeded down a drain. Perform inside hood, behind safety shield, with shield between your face and the apparatus. 64 Distillation Donts Heat a closed system Plug in heating mantel directly into outlet Use a Bunsen burner as the heat source Set up apparatus at awkward angles Leave glassware unsupported by clamps Let distillate come in contact with hot surfaces Have gaps or leaks between joints in glassware 65 Open System v. Closed System Always make sure there is pathway for gases to go in order to get out of a container BEFORE starting any chemical reaction unless using specialized equipment designed to withstand large pressure increases. 66 OSHA FACT SHEET Laboratory Safety Chemical Hygiene Plan (CHP) OSHAs Occupational Exposure to Hazardous Chemicals in Laboratories standard (29 CFR ), referred to as the Laboratory standard, specifies the mandatory requirements of a Chemical Hygiene Plan (CHP) to protect laboratory workers from harm due to hazardous chemicals. The CHP is a written program stating the policies, procedures and responsibilities that protect workers (at CofC workers includes faculty, students and staff) from the health hazards associated with the hazardous chemicals used in that particular workplace. 67 CofC - CHP Who wrote the CofC CHP? Director of Environmental Health & Safety (with input from faculty & staff) Where can you find the CofC CHP? In the lab On the lab web site or OAKS page On Departmental Web Site 68 GHS Now that youve had an overview of the various factors that will help you be safe in a lab, we need to introduce the next generation proposals: GHS: the Global Harmonization System GHS is being incorporated by OSHA into the Hazards Communication Standard (HAZCOM) that ensures people who handle chemicals are properly trained New symbols for labels with universal usage are being developed: 69 GHS Symbols Please take a moment now to program this number into your cell phone. Once again, the number to call in an emergency is : 71 Report any concerns If you have any safety concerns about the lab you are working in or the people working around you, you can contact: Your lab instructor Dr. Brooke Van Horn Head of the departmental safety committee Dr. Pamela Riggs-Gelasco Department Chair for Chemistry and Biochemistry Dr. Jim Deavor, Associate Dean of the School of Science and Mathematics. 72