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LIX. Safety Manuals and Handbooks e. Loborotory Sofefy Handbook, Mollinckrodt Chemical Works, P.O. Box 5439, St. Louis, Mo. 6 3 7 6 0 This safety hxndhm,k has hccn pvcp,zrcd by the Mxllinek~.odt L a b o r ~ t r r ~Safety y Commit,lec. The Commitfcc's objective was to prepape a getwal safely guide which wmld be usefit1 to pe~.so~mel i t ) all Mallinckn,dt Labotztorie.; and also be helpful in the safety i~~doctrination of new Ishwatory employees. In this revisiolt, tho sirrc of lhc hoaklct was reduced and the "Useftd Lz~horntoryInformation" section was i~leluded 10 i~twrnsethe day-to-day ut.ility of thc booklet. Tho safety rnnterial pl.escnled is genevnl in nat.ut.e, except for the tahle of data on hasardans chemicals. The booklet also cont,ains an exteusive list of refel.elms
references for specific information concerning specific lnhorstoty problems. Spsee is provided for you l o write dowr, the location of emergency equipmeut, emergency phone nomhew, elc. This is your hook. Use i t and wo1.k safely.
TABLE OF CONTENTS
USEFUL LABORATORY INFORMATION REFERENCES
SAFETY RESPONSIBILITY AND POLICY Our Philosophy The individual 11enl.i primary wsponsibilily for snfcly nl llrtllinck~~adt.This means YML! Ilon'l lnkc rhsnaes! Ohcy the safety rules! If not sore-ASIC! 1)on't h ~ m y ! USE COilIMON SENSE!
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The Mallinckrodt Policy Safety ranks oqud in importance t o all other ohjeclivcs of the Company. Safety is achieved thlm~tghpropel. engineering, educn!ioir, training, providiug pl.nteative equipment, and cnfot~cement, of safety rides. Maw.grment is respowil,lr for pmviding safe apw,zting conditions. L i w Supct.vision is directly respo~~sil,le f w tho snfcty of the individual. Each irdividnnl is ~wponsihlefol.snirty on thc job for himself alld his fellow workers. Ilc zhndd he alert for and I P P O I ~unsafe c o ~ ~ l i t i om wd arts. The Safely I)epnrtmrl~t is responsible for administerittg ( h e Company's safety policy arid progmm. The Laboratoty Snfct,y Committ,ee was organized to develop, review, ~.eeommeild and pmvide e o ~ ~ s u l l n t ion o ~ ~lahoratory safety programs, and pt.ohlems. ~
SAFETY GUIDELINES RESPONSIBILITY and POLICY . . . . . . . . . . GENEltALERIERGENCY INSTRUCTIONS. . . . . FightingSmdl Fires . . . . . ~ i k l ~ .i a. . . . . SAFETY E Q U I P M E N T Emergency Equipment . . . . Pelaonal Prolortive Eqnipment. SAFE PI?ACTICE SUG(;ESTIONS . . . . . . . . . Geueral Safety Rules . . . . . Housekeeping . . . . . . . . General Handling and Storage of Chemicals . . . . . . . Waste l ) i s ~ ~ o a.l . . . . .
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IladiaartiveChemienls . . . . ITANIILINO IABOI?ATORY EQUIPMENT . . . . . . Glassware Ilistillation Appara1,na (Vaeuum) . . . . . . . . . . Distillat,ion Apparatus (Atmospheric). . . . . . . . . . VacuumEquipmcnt . . . . . PressureEqr~ipmcnt, . . . . . ElectricalEq,lipmcnt . . . . PLANNING LABORATORY EXPERIMENTS . . . . . . INCOMPATIBLES . . . . . .
Note
To help those who may have responsihilit,y for developing written safety guidelines for a laboratory, we continue a sories of excerpts from some Ishoratory safely manuals and handhooks. The series will include examples of detailed safety practice, basic saiety policies, reasonable safet,y regulations, and flexible administrative procedures. Tahle of contents is listed only to show ertenl of coverage and variations hotween organiaations. Sperific questions or comments nhaot any mnnnal or handbook excerpt should he directed t.o the contact person noted st bhe end of the article. Whether or not they car, provide copies of their manual will depend on the policy of their organization. In a Intel. issue, we plan to have a leport of progress on the development of s comprehensive leharatory safety manual hy the Research and 1)evelopmen1 Section of the National Safety Council, one of three gronps active in lahorntory safcty. The American Chemical Soricty and the National Fi1.e 1'1mloction Assoriation both have rommittces working on guidelines and s t a n d a d s that will he appropriate in 8. Inlm~.atory safety manual. Purposes and activities of the three gmups will he deserihed here in the near future.
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GENERAL EMERGENCY INSTRUCTIONS Sperific emwgcnry and evacuation i l l s t r u e l i o r ~are given ntt the inside hnck cover of this h n d x m k .
Fighting Small Firer In ease of fire, ho surc that it ha.; been reported and that cvcryom is out of the area. Re sure that you have a n oscago mute. Then, if the fire is still small, fight. it. Usc water lo p ~ oilt t tra.11 rail fires. For other 1nho1.nto1.yfircs, use a t 1 appropvinte fi1.e exli~,gnisher. C s r b o ~dioxide ~ extingnishe~.~arc tho mast commol~. Fire entineoishus in v o w area arc lo-
I n case of burning clothing, use an emergency shower or wrap the individual in a fire blanket. The emergency shower in your area is located The fire blanket is located
First Aid Never move or lift an accident victim unless he is in danger of further injury. If he must he moved from a hazardous area, grasp his feet and drag him away while protecting his head from injury. Calm and comfort the victim and do not alarm him. If the victim's injuries will permit, summon and wait for a trained person t o arrive t,o give first aid. If immediate action is needed, one or more of t,he following may he done while waiting for first aid assistance. Acid and alkali bums: Flush the affected area with water and remove or cut away clothing. Cyanide inhalation: Remove victim t o fresh air. Break an amyl nitrite capsole in a handkerchief or gauze pad and hold below victim's nose, a t chin level, for 1:~30 see, every 2 min. Do not ezeeed 6 applications of a m ~ lnitrite. Avoid excitement or exercise. (Cmtinued on page A814)
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Electrical shock: Remove the source of shock a? soon as possible. Use a dry towel when moving "live" wires or e q u i p ment. If the victim is not breathing, give rtrtificid respiration. Swallowed poisons : Dilute strong acids and alkalies by quickly administering large amounts of water. For other poC sons, follow instructions on label. Never give liquids to an unconscious person. Bleeding: Hold a clean cloth psd directly on the wound, snd apply hand pressure. Do not apply a. tourniquet. Not breathing : St,art artificial respiration as soon as possible. Fractures: Do not move victim unless absolutely necessary. Thermal bums: Do not attempt to remove clothing.
SAFETY EQUIPMENT Safety equipment may be divided into two general classes: First, that used far protection of life or property in case of emergency or unusual happening; and second, that used daily as protection against known and anticipated hasards. Each person must know the function of how to use all articles of safety equipment except for the articles whieh aredesignated as "To be used by trained personnel only."
Emergency Equipment When emergency equipment is required, speed is essential. Each person must know the exact location m d use of all emergency equipment in his areit. Instruction in the proper use of this equipment is given periodically. If you are not sure how to use any of the equipment, ask your supervisor to arrenee a demonstration. Emergency equipment generally available includes: Fire alarms Building emergency alarms Fire extinguishers Safety showers Eye wash fountains Emergency exits Fire blankets Amyl nitrit,e capsules Stretchers' Gas masks1 Rope and belt'
Personal Protective Equipment Mallinckrodt believes that eye protection in the laboratory is so important that the following rule has been established. AU personnel working in or passing through lsboratory areas, including secretaries and visitors, must have eye protection. Exceptions: 1. At the discretion of the department head, personnel working a t their desks in lab areas or adjacent to lab benches need not wear eye protection a t the desk, but eye protection must he worn
' To be used by trained personnel only. A814 / Journal of Chemical Education
when leaving the desk and entering work areas (lab benches, lab hoods, equipment areas, etc.). 2. Offices and locker rooms. 3. Specialized laboratory areas as designated by the department head. Equipment available for the protection of eyes and face from spills, fllmes, gases, breakage and explosion, etc: Safety glasses Safety goggles Face shields Exhaust hoods Protective shatterproof shields Equipment availahle for the protection of the body from flying glass, spills, splashes, burns, etc.: Protective shstterproof shields -. Gloves: Asbestos for handling hot objects. ..Ifor halldliw corrosive &miRubber uars.
Canvas for general use. Plastic far handling solvents. Rubber aprons Rubber suik Bottle carriers Substantial shoes (canvas or open shoes are not acceptable).
Exhaust hoods Filter respirators Chemical cartridge respirators The above protective equipment is usually available in the area needed or in the storeroom. If the proper safety equipment is not available, or if you are in doubt aa t o what eqnipment is required for a given job, consult your supervisor.
SAFE PRACTICE SUGGESTIONS General Safety Rules Fallow safet,vinstructions carefullv. Perform only authorized experiknt,s. Research people who are responsible far their own experimental programs should inform othem workiug in t,he a *a of the chemicals being used and the possible hazards involved. Report all accidents and unusual accnrrences a t once. s I , : I ' I!'.. d.,,,gmw . \ w i d u d > ~ ~ r t l t I.Ut I, h~-l:d>~r:t~arv. r l h ~~x wxr i r ~I W l x b ~ ~ r . t ~ towr vv p t I!. designated areas. Smoking is permitted in most lilhoratory areas, but strictly prohibited in a few posted areas. Smokers should never place cigarettes directly on lab henches (they may become contaminated). Never leave lighted cigarettes unatt,ended. Appropriate warming signs should he posted near any dangerous equipment, reaction or condition.
Housekeeping Each worker is responsible for keeping his or her work area neat and orderly. All workers using community areas such as hoods, ovens, and balances, should share responsibility for keeping those are as
neat and orderly. Laboratory benches and aisles should not be used as storage areas, but should be cleared upon completion of each experiment or job. Laboratory apparatus ~hould be assembled in a. stable, orderly fashion. Safety equipment such as fire extinguishers and safety blankets are to be kept clear and readily accessible. All spills and leakages should he cleaned up immediately. Neutralize acid spills with sodium carbonate and alkali spills with boric acid. Mercury spills should be vacuumed up by means of a suction flask or dusted with sulfnr.
General Handling and Storage of Chemicals All containers most be labeled plainly and permanently. After llsing a. reagent, be that any residual material is wiped or rinsed from the external surface of the container. Any material in unlabeled containers should he disposed of carefully. Oxidizing materials, such as nitrates and chlorates, should be stored in a dry area apart from organic material. Care must he taken to be certain that all chcmieals are compatible with the material of construction of the containers in whieh they are handled. For example, hydrofluaric acid is not to be handled in glass equipment. Flammable solvent,^ should be stored in an approved solvent storage cabinet or a well ventilated area. Avoid storing salvents above eye level in work area. When opening hot,tles which may he under pressure (e.g., hydrochloric acid or ammonium hydroxide) cover the bottle with a towel to divert any chemical spray. Use bottle carriers when t,ransporting glass battles oantaining hazardous chemicals (acids, corrosives or flammable liquids).
Waste Disposal Small quantities of acids or alkalies may he disposed of by slowly pouring into a stream of water and flushing down the drain with a large quantity of water. Large quantities of any chemical should be returned to the plant for recovery or disposal. See your supervisor for specific instructions. Cyanide wastes must he placed in a n appropriate waste bottle and the solution kept alkaline a t all times. Dry ehemicah, in an appropriate container, should be placed in a drum labeled "Waste Chemicals for Disposal.'' St,rong oxidizing and reducing agents (chlarates, bramatea, peroxides, nitrates, iodides, metal dusts, hypochlorites, ete.) should not he placed in this drum. See your supervisor for inst,ructions on tho disposal of these reactive dry chemicals. Small quantities of waste solvents should he placed in an approved container for disposal. Special arrangements should be made fgr disposing of large quantities of waste solvent. Under no circumstances should amines, phosphorus compounds, acetic anhydride, acetyl chloride or any other highly reactive (Continued on page A8161
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compound be placed in a common waste solvent container. See your supervisor for instructions on the disposal of these reactive compounds.
Flammable Chemicals When handling flammables, know the location of and proper use of fire extinguishers in your area. Do not smoke in the area. where flammables are being used. Post "No Smoking" signs. Never hest flammable liquids with an open flame, hot plate or uninsulated resistance heaters. Use a heating mantle, steam bath or hot water bath. If electrically driven st,irrers are used with flammable liquids, the motors should he explosion proof. Handle solvents in exhaust hoods ar a well ventilated area. Keep the solvent supply in the laboratory a t a minimum. Static sparks can start solvent fires. Ground containers when transferring solvent from one container to another.
Reactive Chemicals Understand possible dangers before using. See the Hazardous Chemicals Table. Keep the supply in the laboratory at a minimum. Segregate as much as possible chemicals that are canable of explosive reactions with each other, and take greater precautions as the quantities of such chemicals inereme.
Toxic and Corrosive Chemicals Understand possible dangers before using. See Hazardous Chemicals Table. Keep the supply in the laboratory a t a minimum. Store in proper containen; inspect regularly for damage and see that lids fit well. Follow all rules pertaining to good housekeeping, labeling, handling, and disposal. Avoid spillages. Use bottle carriers or other secondary containers when transporting toxic materials. Use only in hooded or well ventilated areas. Keep sealed when not in use. Use appropriate protective equipment. Good personal hygiene is extremely important in handling toxic and corrosive materials.
Compressed Gases Store and transport compressed gas cylinders with the shipping caps on. Transport large cylinders only by means of a wheeled cart to which the cylinder is secured. Store and use cylinders in an upright position. (Exception: Lecture bottles may be stored horiaontctlly.) Always securely clamp cylinder to a firm support. Know contents of cylinder before making any connections. Always use a, reducing valve or a pre-
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set pressure controller. Do not luhricrtte, modify or tamper with a wlinder valve. Do not heat cylinders or store near a heat source.
Radioactive Chemicals Apply all precautions that apply to toxic chemicals. Ilad~~ar~rivcrhernicalr~hould he handled by aurh~rircdperwanel wly. Radimcuvc rhen~ical- .ihould nor Ix used in unpasted or unauthorimd sreas. Do not use without an appropriate exposure control progrsm. "Dry run" procedures before actually using radioactive materisls. Waste disposal and effluents m u t he carefully controlled.
HANDLING LABORATORY EQUIPMENT Glassware Do not use broken, chipped, starred, or badly scratched glassware. Clem glassware before sending it to the glassblower for repair. Do not pick up broken glass with bare hands. Use gloves or sweep up. Fine glass particles may he picked up with wet paper toweling. Discard hmken glass in designtated cantainers. Fire polish all tubing and mds. Protect hands with gloves, towel, or tuhine holder when insertine tuhine into stoppers. Lubricate the tuhing with water or glycerine. Keep hand on tubing close to the stopper arid out of line with end of the tuhe. Remove frozen stoppers by cutting away or with the aid of a. cork borer. Protect glass vessels with asbestos centered wire gauze when heating them over a burner. Handle hot beakers with proper size and type of tongs. Use steam, heating tape, IR lamp, or heating mantle when heating a flammable solvent. Do not attempt to catch falling glassware.
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Distillation Apparatus (vacuum) Do not use cracked. starred. badlv scratched, or creased flasks. hey implode readily. Use only round bottom flasks. (Maximum size: 5 liters). Use protective shatterproof shield. Use stirrer, boiling chips or capillary tuhe with inert gas flowing through it,, to prevent bumping. Use steam or heating mantles @ heat flasks. Relieve vacuum slowly, avoid sudden pressure change which could cause hreakage or splattering of contents. Do not relieve vacuum until flask has cooled.
Distillation Apparatus (atmospheric) Secure glass joints with wire or clamps to (Continued on page A818)
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prevent vapor leakage. Make sure system is vented and watch for plugging in the condenser. Use boiling chips or stirring to prevent bumping. Use heating mantle where possible. Avoid overheating still bottoms a t end of distillation. Do not distill ethers until peroxides have been removed. Vacuum Equipment
Apply vacuum only to glassware made for such services (e.g., desiccators and filter flasks). Be sure filter crucible can't slip through holders. Shield desiccators that are under vacuum in metal desiccator guards. Do not subject glassware under vacuum to mechanical shock. Use protective shatterproof shield. Always wrap glass Dewar flasks with tape before use. Do not stopper glass flasks containing hot, candensehle vapors. Check condition of mechanical vacuum pumps (oil level, e t a ) before using. Relieve vacuum in all parts of system before opening apparatus. Refer to the Vacuum Distillation Seetion for suggestions on the use of glass vacuum distillation apparatus. Pressure Equipment
Except for pressure transfer from carbays or other large containers, do not apply pressure to glassware. When transferring liquids by pressure, use a pressure reducing regulator valve. Never use direct line pressure. Do not use more than 4.6 psig pressure on glass carhoys. Before attempting to use equipment designed for high pressure (Pam bombs, autoclaves, etc.) see your supervisor for precise operating instructions. Be sure the r u ~ t u r ediscs or Dressure relief valves are ingood conditionbeforeusing. Provide adequate shielding to protect personnel. Set up equipment in a hood if reaction products are in any way toxic. Vent pressure in dl parts of the system before opening apparatus. Electrical Equipment
Do not use electrical equipment if power cords are frayed or control switches and thermostats are not in good working order. Keep all equipment and hands dry while handling. Do not try to repair equipment yourself. This should he done by qualified personnel. Use grounded outlets only. If equipment does not have a. three prong plug, ground the equipment separately to a cold water pipe. Outputs from variable transformers (powerstat, Variac, etc.) are usually not grounded even though the input line may be. Equipment regulated by a variable transformer should be grounded separately. Do not use electrical equipment such
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as mixers or hotplates around flammable solvents. Before adjusting or servicing large electrical equipment,, lock the main power switch in the "off" position. Special electrical equipment such as t,he X-ray and spectrographic power sources and r.f. generators should be operated only by trained personnel. Never try to hy-pass any safety device on a piece of electrical equipment. I n case of fire on or near any electrical equipment use only carbon dioxide or dry powder fire extinguishers.
PLANNING LABORATORY EXPERIMENTS I n order to foresee and avoid some of the booby-traps in a laboratory experiment: List all possible reactions including sidereactions before beginning. Think through all reactants, intermediates, and products in terms of flammability, toxicity, and reactivity hazards. Follow recognized szfe practice procednres concerning protective equipment,, housekeeping, the handling of hazardous as outlined chemicals and of eauiument . . above. I n an unknown reaction. alwavs start as temperature, color, viscosity, and physical state. If possible, obtain safety information about reactants and products from the Tahle on Hazardous Chemicals. the References List, or from laboratory analysi.; flash point, TGA, DTA, etc.). If the safety information is not available elsewhere, it may he obtained from some out,side laboratories that offer a test.ing service for the evaloation of exulosion hwards, e t a If possible, determine from thermodynamic and kinetic considerations, the tabal quantity of, and the rate of evolution of hest and gases to he released during the reaction. Provide adequate cooling, ventilation, pressure relief, and gaspurging. Isolat,e t,he react,ion vessel, if possible, snd make frequent inspections of eqnipment during reaction. no not leave n. hazardous system unattended. For each reactant, intermediate or product, ask: What is its flash point, flammability range, auto-ignition point, vapor pressure and vapor density? Does it decompose and if so, how rapidly and t,a what products? What is its stability on storage to heat, light, water, metals, etc.? I s i t impact sensit,ive? I s i t toxic? If so, what t,ype of hasard (inhalation, ingestion, skin contact)? What protective measures are required? What is the recommended first aid t,reatment in case of an accidental exposure? About the reaction it,seli, ask: Haw violent will i t he? What is the effect of c a t d y s t , ~or inhibitors? (Continued on page A8ZO)
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Will water or air affect the reaction? What would happen and what should he done if: Electric power fails? Cooling system fails? Pressure gets out of hand? Water leaks iuto system? Air leaks into system? Reaction container falls and breaks or spills contents? Remember that many explosions, fires, and asphyxiations aTe caused by the aocidental combinat,ion of potentially dangerous substsnces. The following is a partial list of such potentially dangerous combinations.
INCOMPATIBLES Do Not Contact Alkali metals, such as calcium, potassium and sodium with water, carbon dioxide, carbon tetrachloride, and other chlorinated hydrocarbons. Acetic Acid with chromic acid, nitric acid, hydmxyl-containing compounds, ethylene glycol, perohloric acid, peroxides and permanganates. Acetone with cmeentrated sulphuric and nitric acid mixtures. Acetylene with copper (tubing), fluorine, bromine, chlorine, iodine, silver, mercury and their compounds. Ammonia, Anhydrous with mercury, halogens, edcium hypochlorite, hydrogen fluoride. Ammonium Nitrate with acids, metal powders, flammable fluids, chlorates, nitrates, sulphur and finely divided organics or mmhustibles. Aniline with nitric acid, hydrogen peroxide. Bromine with ammonia, acetylene, hutadiene, butane, hydrogen, sodium carbide, turpentine, and finely divided metals. Chlorates with ammonium salts, acids, metal powders, sulfur, finely divided organics or combustibles, carbon. Chromic Acid wtth acetic acid, naphthalene, camphor, alcohol, glycerine, turpentine and other flammable liquids. Chlorine with ammonia, acetylene, butadime, benzene and other petroleum fractions, hydrogen, sodium carhids, turpentine and finely divided powdered metals. Cyanides with acids. Hydrogen Peroxide with copper, chromium, iron, mast metals or their respeotive salts, flammahle fluids and other combustihle materials, aniline and nitromethane. Hydrogen Sulfide with nitric acid, oxidizing gases. Hydrocarbons, general with fluorine, chlorine. bromine, chromic acid, sodium ~
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Iodine with acetylene, ammonia, etc. Mercury with acetylene, fulminic acid, hydrogen. Nitric Acid un'th acetic, chromic tsnd hydrocyanic acids, miline, carbon, hydroeen sulfide. flammahle media. fluids or gases and substances which are readily nitrated.
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Oxygen with oils, grease, hydrogen, flammable liquids, solids and gases. Oxalic Acid with silver, mercury. Perchloric Acid with acetic anhydride, bismuth and its alloys, alcohol, paper, wood and other organic materials. Phosphorous Pentoxide with water. Potassium Permanganate with glycerine, et,hylene glycol, bcnmldehyde, sulfuric acid. Sodium Peroxide with m y oxidizable suhstances, for instance: methanol, glacial acetic acid. acetic anhvdride, beosaldehyde, carbon disulfidk, glycerine, ethylene glycol, ethyl wetate, furfural, etc. Sulfuric Acid with chloratq perchlorates, permanganstes and water. Comighted b y Mallinckrodt Chemical W w k s 1969. Reprinted wilh permission. Inquiries should be directed to C . S . Kettler, Laboratory Chemicals and Plasticware, Mallinekrodl Chemical Works, Second and M a b linckrodt Streets, St. Louis, Mo. 63160.
AMA'S Occupational Exposure Registry-A Progress Report Many of the reports submitted to the American Medical ksociation's Registry on Adverse Reactions Due to Occupational Exposures are interesting and unusual. The Registry now has some single reports of adverse eReds which the Committee believes have never been reported to produce such reactions, hut not enough confirmatory reports to suhstantiate a causal relation. Several of the reports suggest that perhaps previously unrecognized syndromes may result from emosures to materials whose toxicitv is albut not well known hy inexperienced oecupat.ional physicians. The Committee ha3 been somewhat disappointed in the law volume of reports submitted to tho Registry. Some eampaniw are understandably relnctant to give such information. Many seem unaware that Registry procedwa are designed to guarantee confidential it,^. The Committee's purpose in initiating the Registry was t o create a central professional repository for information storage, retrieval, and dissemination of new information to professionals charged wiih protection of workers from ocenpat~ioual exposures to potentially hazardous subst,ances. A larger volume of reports must be collected before the present information will snpport reamnshly certain probability of causal relationships. . The Committee urges occupational health physicians to continue sending in new reports to the Registry. I t invites the support of t.he readers of Journal of Chemical Education. The information which ~the chemist m a k s available to the ~ reporting physician may cont,ribute immensely to the knowledge of control and prevention of occupational illness. For forbher information and report forms, contact: Mr. Jerome T. Siedlecki, Secretary, Committee on Occo~ationalToxieolnev. -. American Medical Assoriation, 53.5 North Dearhorn Street, Chicago, Illinois 60611.
