Lab Safety Policy
Safety should always be the first priority when working in the laboratory. This primer outlines many of the important chemical, electrical, and radiation safety considerations germane to research in the School of Materials Science and Engineering at Georgia Tech.
Beyond protective clothing, sensors, and hardware, the most important safety protection is knowledge. A fundamental understanding of potential occurrences in a chemical reaction may be deduced from thermodynamic calculation, and purview of MSDS1 (material safety data sheets), or phone consultation with the Georgia Tech Department of Environmental Science, Health and Safety (DESHS). Electrical safety stems from knowledgeable use of multimeters and reading of circuit diagrams. In all cases, precautions must be made so that the laboratory environment is not booby trapped for future users-sloppy wiring or mis-labeled chemicals are disasters awaiting unknowing downstream researchers.
Accidents and Emergencies
POLICE, FIRE, AMBULANCE: 4-2500
For medical emergency and/or police, dial 4-2500. For fire, pull nearest alarm and call the campus police at 4-2500. Dialing 911 will circumvent the university police, but ambulance response will be slower. In the case of clear emergency, instruct the campus police to call the ambulance immediately, rather than waiting for an officer to arrive and assess the situation. Provide adequate information on the phone: name, telephone number, building, floor, room number, condition of any injured individuals (e.g., unconscious, burned, trapped), type of fire, if any. Do not move seriously injured people unless they are in danger of further injury.
If there is a fire, use proper extinguishers-cut off electrical circuits, gas lines. Close doors. If clothing is on fire, help the individual to the floor and roll him or her around to smother the flames, or if a safety shower is immediately available, douse the person with water. Running to a not immediately accessible safety shower or other source of water will only serve to fan the flames and intensify the clothing fire. Fire blankets are intended primarily as a first-aid measure for prevention of shock rather than against smoldering or burning clothes. By wrapping a person who is on fire, heat is retained and the clothing may continue to smolder, resulting in serious burns. In addition, if the person who is wrapped in the safety blanket is standing, a chimney effect may occur-smoke from the smoldering clothing would continue to rise past the person's face.
If chemicals have been spilled over large area of the body, quickly remove all contaminated clothing while using the safety shower. Immediately flood the exposed areas with cold water for a least 15 minutes; resume if pain returns. Wash off chemicals by using a mild detergent or soap (preferred) and water; do not use neutralizing chemicals or salves.
If chemicals have been spilled on a confined area of the skin immediately flush with cold water and wash by using mild detergent or soap (preferred) a water. Remove any jewelry in the affected area. If a delayed action the chemical is possible (e.g., methyl and ethyl bromides), obtain medical attention promptly.
If a chemical has been splashed into the eyes, immediately wash the eye and inner surface of the eyelid with copious amounts of water for 15 minutes. The eye must be held open. Check for and remove any contact lenses at once (contact lenses should not be used in the laboratory). An eyewash fountain should be used if available.
In case of ingestion of a toxin, dilute the poison by having the victim drink large amounts of water (do not give liquids to an unconscious or convulsing victim). Attempt to learn what the ingested substances were. Save the label or container for transportation with the victim to the medical facility.
Water fire extinguishers are effective against burning paper and trash. They should not be used on electrical, liquid or metal fires. Carbon dioxide extinguishers are effective against burning liquids such as hydrocarbons, and electrical fires. They are recommended for fires involving delicate instruments and optical systems because they do not damage such equipment. They are less effective against paper, trash or metal fires and should not be used against lithium aluminum hydride fires. Dry powder extinguishers are also effective against liquid and electrical fires. They are less effective against paper/trash and metal fires. Met-L-X extinguishers and others that have special granular formulations are effective against burning metal. Included in this category are fires involving magnesium, lithium, sodium, and potassium; alloys of reactive metals; and metal hydrides, metal alkyls, and other organo-metallics. These extinguishers are less effective for the other types of fires.
Any student with working status is protected under the Workers' Compensation plan. Benefits are paid to cover injuries resulting from work, whether the injury occurred on or away from the employee's normal work site. Regardless of the nature or severity, all injuries incurred must be reported immediately to your supervisor and to MSE's Facilities Manager, John Holthaus in room 181, Love Building. Procedures and information on this policy is posted in all labs.
Compressed Gas Cylinders
One great concern with compressed gas cylinders is that they fall over and the valve stem is sheared off. These cylinders are typically charged to 1500-2500 psi (that is the pressure on a square inch of your hand would feel like 2500 lbs.) In such a case the cylinder functions like a rocket, blasting through wall after wall, or could behave as a grenade. For that reason, cylinders must be chained or strapped in place to prevent them from falling over. Metal cylinder caps for valve protection should be kept on at all times when the cylinders are not in use. Do not use cylinders without a pressure regulator. Inspect regulator inlets and cylinder valve outlets for foreign matter; it is essential that the threads aren't damaged so that a tight seal can be maintained. These regulators are intended for use with specific gases, and to ensure compatibility, the threads on regulators vary. Make sure the connections are compatible; if the inlet of the regulator does not fit the cylinder valve outlet, do not force it! Contact the supplier or producer of the gas or regulator if advice is needed on the selection of a regulator.
Transport cylinders only via hand truck; attempting to rock-walk the cylinder runs the danger of the cylinder slipping and falling. All gas cylinders should be labeled to identify their contents. Do not rely on color codes. Close cylinder valves when not in use. Do not rely on a regulator to stop the gas flow overnight. Close valves on empty cylinders and mark the cylinder ``empty". Store and use in well-ventilated areas, away from heat or ignition sources. Store oxygen away from flammable gases. A regulator, valve or other equipment that has been used with another gas should never be used with oxygen.
Note that H2 is extremely flammable, beware of any reaction in which this is given off as a product. O2readily supports combustion and is thus also considered flammable. Serious explosions have resulted from contact between oil and high-pressure oxygen. Oil should not-be used on connections to an O2 cylinder. Cylinders of combustible gases, e.g. CH4, H2, O2 should be stored in continuously exhausted areas. Inert gases can act as suffocants, so make sure that adequate ventilation exists when large quantities of N2, Ar, He and other inert gases are used.
High voltage is dangerous, not high current, unless of course the current is running though the human body. For example, if one grabs the two live ends of a SiC heating element which is drawing 20 A at an applied 40V, what determines the current though the grabber's body is the 40 volts and the resistance of the current path through the body. The 20A in the parallel circuit is immaterial. High voltages are especially accessible in our furnace room. Technically, touching a live connection (that is a connection which has a potential relative to ground), will not cause electrocution unless a portion of the body also touches ground. This is easy to do since all metal casings for electrical devices must be, by law, connected to ground. For this reason, when working/debugging malfunctioning equipment, it is good idea to avoid working with two hands; if one hand touches a live location while the other hand touches grounded metal, the current path goes through the human heart. Shoes are essential in this environment since naturally moist feet in contact with the floor make an excellent ground connection. The fluid in the body acts as an excellent electrical conductor, and the dominant resistance to current flow is the skin. Therefore, avoid working with wet hands, and take precautions against electrical components piercing the skin. Voltages on the order of flashlight batteries may be fatal if the skin is pierced.
When trouble-shooting equipment, make sure that all power has been removed from the equipment. It is good practice to always know where the upstream breaker box for an given power source is. Also, be aware that removal of power from equipment does not mean that high voltages will not persist, particularly if the equipment contains sizable capacitances which are charged by high voltage. An ``off'' switch does not guarantee that all power to an instrument box is off. To work on instrument electronics, it is better to unplug it and/or flip the upstream breaker. Before touching a malfunctioning instrument, it is a good idea to test separately for ac and then dc voltages using a multimeter: touch one end to the location of interest, and the other to ground. All metal enclosures are, by law, grounded, so touching one probe to a screw (avoid painted surfaces) on the box will be a ground connection.
One of the most important safety precautions when building or repairing equipment is to make sure that it is adequately grounded. Electrical work has strict color conventions, the most important of which is that the green wire is ground. This wire should connect at one end to the ground connection from the power supply (e.g. the ground plug on a 110V wall receptacle) and at the other end, intimately to the metal housing. The purpose of this is so that if a live wire makes contact to the chassis, extreme current will pass though the metal which will immediately blow a fuse. Fuses and breakers thus serve a very important function and should never be bypassed. Note that if a high frequency (e.g., rf) ground is required, the shape of the conductor may differ from that used for a D.C. ground. When designing high power apparati for a moist environment, ground fault circuit interruption should be added to the design.
Radiation Safety for X-ray Diffraction and Spectroscopy
Analytical x-ray machines produce intense beams of ionizing radiation that are used for diffraction and fluorescence studies. The most intense part of a beam is that corresponding to the K emission of the target material and is called characteristic radiation. In addition to the characteristic radiation, a continuous radiation spectrum of low intensity is produced ranging from a very low energy to the maximum kV-peak setting. This is referred to as ``bremsstrahlung" or white radiation.
X-rays in the range of 15 to 40 keV produced by diffraction machines are readily absorbed in the first 5-10 millimeters of the skin, and do not contribute to a deep dose to the internal organs of the body. However, the eyes, because of the aqueous nature of the tissue, do receive deep dose. Overexposure of lens tissue can lead to the development of lens opacities and cataracts; therefore, safety glasses should be worn when operating x-ray producing equipment (for this application, glass lenses are preferred).
Absorbed doses on the order of 100 rads may produce a reddening of the skin (erythema) which is transitory in nature. Higher doses - 10,000 rads and greater - may produce significant cellular damage resulting in pigment changes and chronic radiation dermatitis. It should be remembered that exposure to erythema doses may not result in immediate skin reddening. The latent (waiting) period may be from several hours to several days. (Note: X-rays used for medical diagnosis are about one order of magnitude shorter in wavelength for tissue penetration and are carefully filtered to avoid x-ray damage to the skin caused by the longer wavelengths).
Avoiding the primary beam does not necessarily mean that one is not being exposed to ionizing radiation. Faulty high-voltage vacuum-tube rectifiers may emit x-rays of twice the kilovoltage applied to the x-ray tube. Other sources of potentially hazardous radiation are: 1. Secondary emission (scattering) from the sample, shielding material, and fluorescent screens. 2. Scattering from a faulty beam trap. 3. Leakage of primary x-rays through gaps and cracks in shielding. 4. Penetration of the primary beam through faulty shutters, or through insufficient thickness of shielding material.
The equipment operator is responsible for his own safety and the safety of others when using an analytical x-ray machine. The written procedures developed for individual instruments should be sequentially followed. Never put any part of the body in the primary beam. Exposure of any part of the body to the collimated beam for even a few seconds may result in damage to the exposed tissue. A person not knowledgeable about x-ray equipment should not attempt to make repairs or remedy malfunctions. Always consult the designated representative first. Remember, safety devices and warning systems are not fool-proof or fail-safe. A safety device should be used as a back-up to minimize the risk of radiation exposure. Never as a substitute for proper procedures and good judgment. The operator may use a radiation survey meter to detect the presence of unwanted radiation and to trace the origin of leaks. The recommended instrument is a Geiger-Mueller meter with a thin window "pancake" detector. It should be remembered that most meters do not respond accurately all the energies used for analytical x-rays. Correction factors of 3x to 10x may be required. Each user of APD x-ray equipment is recommended to wear a film badge. It must be recognized that the badge indicates only the level of whole body radiation dose intercepted by the badge, or the level of scattered radiation in the room. The office of radiation safety offers a quarterly course on radiation safety.
In the event of an accident or unusual incident involving an analytical x-ray machine, proceed as follows: 1.Turn off the machine. 2. Call the Office of Radiation Safety at 894-3600. 3. Call the principal investigator responsible for the machine. 4. Record all important parameters (e.g. kV-peak, mA, nature and duration of the possible exposure, and distance from the x-ray source).
Lasers present an eye hazard if a person stares into the beam and resists the natural reaction to blink or turn away. Lasers with powers in excess of 500 mW may produce eye or skin damage from diffuse scattered light. Laser warning signs need to be posted for lasers with power in excess of 5 mW. A warning light should be activated when the laser is on.
Eye protection is required not only from direct impact of the direct beam, but also reflection (diffuse or concentrated) from surfaces. Goggles or safety glasses specifically designed for laser work are needed. They need to be fitted so that stray light cannot come in from oblique angles. The type of glasses needed depends on the laser type, wavelength, and optical density. Undesirable reflecting surfaces can be rough-finished and painted with flat charcoal black paint.
Direct laser impingement on the skin may cause considerable damage, especially where it is pigmented. A temporary injury to the skin may be painful and treated symptomatically. Injury to larger areas of the skin are far more serious as they may lead to serious loss of body fluids, toxemia, and systematic infections. Injuries to the skin can result either from thermal injury (temperature elevation in skin tissue) or from a photochemical effect (e.g. ``sunburn''). The warmth sensation resulting from absorption of radiation energy normally provides adequate warning for an avoidance reaction to prevent thermal injury of the skin from almost all sources except some high-powered, far infrared lasers.
Potentially toxic vapors which may result from laser-heating of materials need to be accounted for. Ozone is produced at times from flash lamps and high repetition rate lasers as the beam propagates through air. Ozone is extremely toxic. Proper ventilation is needed when vapors from liquid nitrogen coolants might otherwise starve the room of oxygen.
Typical machine shops have available (in working condition) drill presses, band saws, milling machines, lathes and others. In the use of all of these devices, eye protection is essential. Beware of any loose personal articles (lab coat, ties, long hair) which may be caught on moving parts of equipment. On a lathe, the rotating positioning wheel can easily catch a pocket. Machine shop equipment is completely unforgiving and will draw the body into it, tearing off fingers and limbs. Parts to be drilled or tapped should preferably be clamped down prior to use, or held down firmly. Otherwise the part may be lifted by the drill bit and turned into a propeller blade. A block of sacrificial wood should be used to push parts through the band saw, not the fingers. In all cases, one needs to pay full attention to the equipment and not be distracted during use. John Holthaus should be consulted for training before use of the equipment residing in the furnace room in MSE. Similarly for the use of the rolling mill, Dr. Sanders must be consulted.
The undergraduate mechanical testing area as well as the Mechanical Properties Research Laboratory (MPRL) are potentially hazardous areas where training and approval by R.C. Brown is required prior to use. Hazards are related to the very high loads applied by the testing machines and the high power motors used to generate them. The Satec machine in the undergraduate area will generate 50,000 pounds of force on anything in its path. For this reason, only one operator should have their hands between the pinch points (the cross head and the table) and this person should be the onlyone to start the machine. The machine should not be started until the safety shields are in place and the area for testing is clear. The shields are essential since under certain conditions of fracture under load, parts could be sent flying at great velocities into the room. With the Charpie machine, the hammer and anvil area are of greatest concern-the machine is capable of generating 250 ft-lbs of force (more force than a car's motor can generate, and on a small area.) The hammer must be lifted and held in place by a small pin, which is then lever released. So that the lever is not released with another individual in the flight path of the hammer, only the operator should be behind the safety barrier. The rolling mill will take anything fed into it and reduce its cross sectional area, including parts of the human body. For this reason, materials should be fed into the device with a push block, not directly with the hands.
The MPRL is a particularly hazardous area and admittance to the facility is available only to those who have completed the MPRL training requirements. This area has 3000 psi hydraulic fluid driving the servo controlled test frames. This fluid, if released in a fine jet, can cut through a steel plate. These machines are capable of generating 20,000 pounds of force at a rate of 10 m/s. A complete knowledge of the operator controls and operating software is necessary for the machine to be operated safely.
Protective Clothing and Equipment
Eye protection must be worn at all times in all laboratories where other than purely instrumental studies are being conducted. Ordinary prescription glasses will not provide adequate protection from injury to the eyes. The minimum acceptable protection are hardened glass or plastic safety glasses. Safety goggles or face shields should be utilized where there is a possibility of splashing chemicals, violent reactions or flying particles. This is also the case in the MPRL where brittle materials may fracture. Specific goggles need to be worn for protection against laser hazards, and ultraviolet or other intense light sources. Contact lenses should never be worn in the laboratory!
Skin contact is a potential route of exposure to toxic materials. Dermatitis, erythema, burns and absorption of toxic and/or carcinogenic chemicals are some of the consequences of exposing skin to hazardous liquids. Therefore, proper protective gloves need to be worn when working with toxic or corrosive materials or with materials of unknown toxicity. No one glove is suitable for handling all chemicals. Gloves should be selected on the basis of the material being handled and their suitability for the particular laboratory operation. Glove manufacturer's data (e.g. Fisher catalog) and the MSDS sheets for the chemicals provide useful information in this regard. Chemical resistance is the most common type of glove evaluation. It is a qualitative and subjective rating and refers to the ability of the material to resist decomposition or disintegration. It does not indicate the chemical protection afforded by the glove. Chemical permeation, on the other hand, does. Permeation is the process by which a hazardous liquid may pass through the glove material to the inside. Because the glove material is not physically destroyed, the individual may not be aware that breakthrough has occurred and that he/she is being exposed. The period of adequate protection, i.e., the breakthrough time plus some interval of time during chemical permeation, can only be determined by testing the glove with the chemical to be handled. When selecting gloves, determine which glove materials have the longest breakthrough times and lowest penetration rates.
Solid toed shoes should be worn at all times. Open toed shoes or sandals offer little or no protection against chemical spills or broken glass. Avoid wearing loose (e.g., saris, dangling neckties, and over-large or ragged laboratory coats), skimpy (e.g., shorts and/or halter tops), or torn clothing. If there is a possibility of contamination, personal clothing that will be worn home should be covered by protective apparel.
It is either learned up front, or with experience, neatness is required for all quality research. It is also a necessary safety precaution. Contamination of food, drink, and smoking materials are potential routes of exposure to hazardous materials. For this reason, food or beverage should not be taken into any laboratory where there is a toxicity hazard. Glassware or utensils that have been used for laboratory operations should never be utilized to prepare or consume food. Laboratory refrigerators and cold rooms should not be used for the storage of foods; separate, clearly labeled equipment should be employed. Smoking is prohibited in our building. It is good practice to wash hands often, even when gloves are being utilized. Avoid the use of solvents for washing; they remove the natural protective oils from the skin and can cause irritation and inflammation. In some cases, the solvents might even aid skin absorption of a toxic chemical.
Work areas need to be kept clean and free from obstructions. Cleanups should follow the completion of any operation or be done at the end of the day. Do not leave a disaster waiting for the next user. Aisles, hallways and stairways must not be used for storage areas. Avoid storing heavy objects on high places from which they could fall. Do not store bottles or equipment on shelves on laboratory benches unless there are restraining lips the shelves. Storage of bottles on benches is undesirable because of their propensity to be knocked over. Extended storage in hoods is also inadvisable because this practice interferes with the airflow in the hood, clutters up the working space, and increases the amount of material that could become involved in a fire.
All reagents stored in other than their original containers must be labeled clearly as to the contents, date and name of the person storing the solutions. Do not label as ``Joe's solution'' since this is a significant impediment to waste disposal at a later date. Chemicals stored in the laboratory should be inventoried periodically, and unneeded items should be disposed of. Containers should also be examined for deteriorating labels. The quantity of chemicals stored in the laboratory should be kept as low as possible. Old or outdated solutions should be disposed of (see later section). Wastes needs to be placed in appropriate receptacles properly labeled. Broken glassware, pipettes, syringes need to be placed first into puncture proof containers. The laboratory supervisor should arrange for the removal or safe storage of all hazardous materials which personnel have on hand when they are about to terminate, graduate, or transfer.
Oil baths should always be monitored via a thermometer or other device to ensure that their temperature does not exceed the flash point of the oil being used. Smoking, caused by the decomposition of the oil or of organic materials in the oil, represents another hazard. A laboratory worker using an oil bath heated above 100°C should be careful to guard against the possibility that water (or some other volatile substance) could fall into the hot bath. Such an accident can splatter hot oil over a wide area. The oil bath should not be supported on an iron ring because of the possibility of accidental tipping.
The ordinary household refrigerator is not equipped with explosion-safe controls or door switches and should not be used to cool flammable liquids because sparks from controls or door switches may ignite the vapor-air mixture. Explosion-safe refrigerators are constructed with its controls mounted outside the storage compartment. This type refrigerator is suitable for storing flammable liquids. An explosion-proof refrigerator also has its controls mounted on the outside, but in addition, the controls are of an explosion-proof design. This type is needed only where both the internal and external environment present a fire or explosion hazard. Every refrigerator should be clearly labeled to indicate whether or not it is suitable for storage of flammable liquids. Flammable liquids stored in a refrigerator must be in closed containers. Laboratory refrigerators should not be used for storage of food or beverage unless used solely for that purpose and labeled as such.
Where (Bunsen) burners are used, distribute the heat with a wire gauze pad. Burners should not be left on when not in use. Workers should understand the hazards of burners before proceeding with an experiment.
Hand protection should be utilized when inserting glass tubing into stoppers or when placing rubber tubing on glass hose connections. To insert glass tubing, fire-polish the ends of the glass tubing; wet the glass and stopper hole with glycerin or water; wrap a cloth around the glass; hold hands close together and rotate the glass back and forth. Never attempt to push the glass into the stopper or tubing. To remove glass tubing and/or thermometers from stoppers: Lubricate the tubing with water or glycerin; wrap the tubing with a towel; gently twist the tubing, pulling lightly; if the tubing is stuck to the stopper, gently insert the end of a rat-tailed file between the tubing and stopper, and rotate gently, while lubricating with glycerin. If this method fails, cut the stopper away.
Eye protection should be worn whenever cryogenic liquids are handled. Where splashing is a possibility, face shields should be used. Appropriate gloves, shoes, and clothing should be worn. In case of a splash, immediately flood exposed areas and clothing with water. Avoid wearing watches, rings, bracelets, or other jewelry. Although many gases in the cryogenic range are not toxic (e.g. liquid nitrogen), they are all capable of causing asphyxiation by displacing the air necessary to support life. Therefore, they should be used only in well-ventilated areas. Venting should be provided to avoid quick and violent pressure changes when cryofluid vaporizes.
Handle combustible cryogens such as liquid hydrogen and liquid natural gas in the same way combustible gases are handled: provide ventilation, keep away from open flames and other ignition sources, prohibit smoking, and vent gases to a safe location. Exposed glass portions of the cryogenic container should be taped to minimize the flying glass hazard if the container should break or implode.
Predicting Outcomes of Experiments
The strong background given to MSE undergraduates in physical chemistry and thermodynamics should be exploited in predicting events which may occur in the laboratory. Using the fundamental laws developed in these courses, tabulated data can be used to predict potentially dangerous vapor pressures, whether or not reactions will occur, and whether the heats of reactions will approach explosive behavior. Useful tabulations may be found in the CRC Handbook of Chemistry and Physics, the JANAF thermochemical tables, and the North American Combustion Handbook. A few examples will be cited:
If we wish to melt copper in an evacuated and sealed fused silica ampoule, the vapor pressure of copper is negligible, and no dangerous pressures will build up. This is not true, however, for phosphorous, where as can be seen in Figure , the vapor pressure builds up appreciably with increasing temperature. From a standard glass science textbook, the tensile strength of silica glass is roughly 50 MPa, or 490 atm, thus the container will burst at 900°C, if not before. The figure was generated using the integrated form of the Clapeyron equation:
Where p is the equilibrium vapor pressure formed over the condensed phase in a closed system, R is the gas constant, DH is the heat of vaporization or sublimation of the condensed phase (assumed to vary insignficantly with temperature), T0 is the equilibrium boiling or sublimation temperature under atmospheric pressure, and T is temperature. For Figure , DH and T0 data were obtained from the CRC Handbook. In using equations such as this, it is important to understand the nuances of the terms and how they relate to a realistic experimental situation. These nuances can often only be elucidated by following the derivation of the expression and observing what simplifying or conditional assumptions were made.
The JANAF tables have very complete enthalpy and free energy tabulations. To predict whether a reaction will occur, the standard state Gibbs energy equation is useful:
DG° = -RT lnkp
where DG° is the standard state free energy change for a reaction, and kp is the equilibrium constant. For a equilibria
aA + bB = gC +
the value of DG° may be obtained from the standard state Gibbs energies of formation (products - reactants, each one multiplied by its stoichiometry constant) in the JANAF tables. The equilibrium constant for such a reaction is the ratio of product and reactant activities:
If gases are assumed ideal, the activities can be written as the pressure of the reaction constituent divided by its pressure in its standard state. For gases, the standard state is that it is pure and at one atmosphere. For condensed phases, the standard state requirement is simply that it is pure (thus the copper in brass is not in its standard state). Thus for all pure condensed phases, their activity is unity. As an example, consider what would happen if flowing CO2 atmosphere were used in a graphite furnace chamber. The equilibrium constant for CO2 + C = 2CO may be written:
Using tabulated data, this ratio is plotted as a function of temperature in Figure .
Figure 1: (left) Vapor pressures predicted by the integrated Clayperon equation.
Figure 2: (right) Equilibrium partial pressure ratio showing propensity of CO2 to react with graphite to form CO.
Clearly, around 800°C the carbon dioxide will react with the graphite chamber, making carbon monoxide. If the exit gas is vented into the room, the atmosphere in the room will be poisoned.
If a thermite reaction such as:
5Mg + TiO2 + B2O3 ® 5MgO + TiB
is to be investigated, the standard state enthalpies of formation in the JANAF tables can be used to determine a standard state enthalphy of reaction at 298 K of -1093.6 kJ/mol. The heat content tabulations on the same pages can be used to show that this reaction under adiabatic conditions will result in a product temperature of 2387°C. This certainly dictates the use of a highly refractory container for this reaction as well as other safety precautions.
Chemical spills can be handled effectively if some pre-planning has been conducted. Individuals should become familiar with proper clean-up procedures before a spill occurs. Commercial spill kits are available (chemistry stores) that have instructions, absorbents, reactants and protective equipment. Common examples: dolomite will neutralize HF. A sulfur-based mixture is used on mercury spills to form a compound with a much lower vapor pressure. A vacuum line, needle-nose pipette, and trap can be used to draw up the spill. The MSDS for a particular chemical will provide specific information about neutralizing agents.
For flammable liquids, spark-producing equipment should be turned off. The spilled liquid should absorbed and the absorbing material should placed in a plastic bag and kept away sources of ignition. This material should be disposed of in the same manner as hazardous chemical waste For toxic chemicals, all spark-producing equipment should be turned off, and all experiments shut down. The room should be evacuated until it is decontaminated. Call the DESHS on (894-6224 or 894-4635) how to deal with a particular toxic spill. With acids or alkalis, do not neutralize spilled liquid unless you are sure that the resulting reaction will not release hazardous fumes or cause explosion. Otherwise, neutralize the spilled liquid and absorb it. For a mercury spill, droplets and pools of mercury metal can be pushed together and then collected by suction using an aspirator bottle with a long capillary tube or a vacuum device made from a filtering flask, a rubber stopper, and several pieces of flexible and glass tubing. Cover droplets of mercury in non-accessible crevices with calcium polysulfide and excess sulfur. These will form compounds with the mercury with much lower vapor pressures. Dispose of this material in the same manner as hazardous chemical waste. For alkali metals, smother the spill with a special dry powder extinguisher, and keep any and all moisture away from the spill.
Chemical fume hoods are intended to remove vapors, gases, and dusts of toxic, flammable, corrosive or otherwise dangerous materials. With the sash lowered, laboratory fume hoods can also afford workers protection from such hazards as chemical splashes or sprays and fires. However, they are not designed to withstand explosions. Before performing hazardous operations, make simple checks to determine that the hood is working (e.g., a small piece of paper held at the face of the hood will be sucked inward). When work is being conducted within the hood, position the sash so that protection from splashes, flying debris, etc., is provided. Normally, this is a 12-16 inch work opening. Experimental procedures should be conducted well inside the hood. Moving an apparatus 5-10 cm back from the front edge into the hood can reduce the vapor concentration at the face by 90%. Hoods are not intended for the storage of chemicals. Materials stored in them should be kept to a minimum and in a manner that will not interfere with airflow. Hoods should be considered as backup safety devices that can contain and exhaust toxic, offensive, or flammable materials. They should not be regarded as a means of disposing of chemicals.
The use of perchloric acid requires specially designed Perchloric Acid Fume Hoods. For the specifications of a Perchloric Acid Fume Hood, as well as the requirements and procedures for installation, repair, removal and relocation, consult the Facilities Engineering Dept. or the DESHS.
Transporting chemicals may not only be dangerous to the individual undertaking the transport but to innocent bystanders unaware of the potential hazard. When chemicals are carried, they should be placed in a safety container, acid-carrying bucket, or other appropriate container to protect against breakage and spillage. When they are transported on a wheeled cart, the cart should have wheels large enough to negotiate uneven surfaces without tipping or stopping suddenly. Hazardous chemicals should be transported on freight elevators, wherever possible, so as to avoid exposure to persons on passenger elevators.
Flammable substances are the most common hazardous materials found in the laboratory. The propensity to vaporize, ignite, burn or explode varies with the specific type or class of substance. An indicator of the flammability of a solvent is its flash point, the lowest temperature at which a liquid gives off vapor in sufficient concentration to form an ignitable mixture with air. This information is usually available on the label affixed to the chemical container or in MSDS. Flammable liquids are defined as those liquids which have flash points below 100°F (37.7°C). Combustible liquids have flash points between 100°F and 210°F (93.3°C). The most hazardous liquids are those that have flash points at room temperature or lower, particularly if their range of flammability is broad. Flash points and flammability limits of some common chemicals appear in Table .
Table 1: Critical parameters for some common laboratory chemicals. Class IA - Flash point below 730°F, boiling point below 1000°F. Class 1B - Flash point below 730°F, boiling point at or above 1000°F. Class 1C - Flash point at or above 730°F, and below 1000°F.
|Flash Point||Boiling Point||Ignition Temperature||Flammable Limit
(percent by volume in air)
|Methyl ethyl ketone||1B||- 6.1||80.0||515.6||1.8||10.0|
For a fire to occur, three conditions must exist: a concentration of flammable vapor that is within the flammable limits of the substance; an oxidizing atmosphere, such as air; and a source of ignition. Elimination of one of these three will prevent the start of fire or extinguish an existing fire. Air cannot usually be excluded. Therefore, the problem usually involves preventing the coexistence of flammable vapors and an ignition source. Because spillage of a flammable liquid is always a possibility, strict control of ignition sources is important. The vapors of all flammable liquids are heavier than air, and capable of traveling considerable distances. This possibility should be recognized of ignition sources at a lower level than that at which the substance is used.
"NO SMOKING" signs should be posted and obeyed wherever flammable liquids are handled or stored. Never smoke or use an open flame near flammable liquids. Flammables should not be heated with an open flame. Some other type of heat source, such as a steam bath, water bath, or heating mantle should be used. Transfer flammable liquids with caution. The friction of flowing liquids may be sufficient to generate static electricity which in turn may cause a spark and ignition. Therefore, ground or bond all such large containers before pouring from them. (The DESHS can provide the details of this procedure.). Flammable liquids should be dispensed and used in a hood or well-ventilated area so that flammable vapors will not accumulate.
Keep only small quantities of flammable materials available for immediate use. An approved safety can with a self-closing cover, vent, and flame arrester is the best container for storing flammable liquids or waste solvents in small quantities. An ordinary five-gallon container does not provide adequate protection in cases of fire. Refrigerators and cooling equipment used for storing flammable liquids should be explosion-safe (see Section 10).
Toxicity is the capability of a chemical to produce injury. Almost any substance is toxic when taken in doses exceeding "tolerable" limits. Hazard is the probability that an injury will occur or rather the prospect that an individual will receive a toxic dose. The effects of a toxic chemical may be qualified into several categories. Local toxicity is the effect a substance has on the body tissues at the point of contact. Acute toxicity is the effect a substance has after only one or a few short, relatively large exposures. Chronic toxicity is the effect a substance has as a result of many small exposures over a long period of time.
An individual may be exposed to a chemical substance via a number of different routes: inhalation ingestion, contact with skin or eyes. Inhalation of toxic vapors, mists, gases or dusts can result in poisoning by absorption through the mucous membrane of the mouth, throat, and lungs, and can cause serious local effects. Because of the large surface area of the lung (90 square meters total surface) along with its continuous blood flow, inhaled gases or vapor may be very rapidly absorbed and carried into the circulatory system. The rate of absorption will vary with the concentration of the toxic substance, its solubility and the individual inhalation rate. The degree of injury from exposure to a toxic substance depends on the toxicity of the material, its solubility in tissue fluids and the concentration and duration of exposure.
Ingestion of chemicals used in the laboratory may result in significant injury. The relative acute toxicity of a chemical can be determined by its oral LD50, that quantity of material which, when ingested, will cause the death of 50% of test animals. This LD50 is expressed usually in milligrams per kilogram of body weight. To prevent ingestion of chemicals, laboratory workers should wash their hands immediately after using a toxic substance and before leaving the laboratory. Food and drink should not be stored or consumed in areas where chemicals are being used. Chemicals should not be tasted, and pipetting and siphoning of liquids should never be done by mouth.
Skin contact is the most frequent route of exposure to chemical substances. A common result of skin contact is localized irritation, but some materials can be absorbed through the skin sufficiently to produce systemic poisoning. Contact of most chemicals with the eyes will result in pain and irritation. A considerable number of chemical substances are capable of causing burns or loss of vision. Alkaline materials, phenols and strong acids are particularly corrosive and may cause permanent loss of vision. Furthermore, the vascular network of the eyes may permit the rapid absorption of many chemicals.
Before initiating work with a chemical substance, the researcher or laboratory worker should be familiar with the types of toxicity, the toxic dose, and the hazards of the chemical. It is also important to realize that two or more substances may act synergistically to produce a toxic effect than that of either substance alone. Furthermore, chemical reactions involving two or more substances may form products significantly more toxic than the starting materials. Therefore, the entire experimental procedure should be evaluated.
Commonly Used Chemicals
The most common laboratory solvent sequence is trichloroethylene (TCE), acetone, methanol, and deionized water. Note that in particular trichloroethylene is a known carcinogen, and should be handled with extra caution. Some individuals are sensitive to darkroom chemicals (developer, fixer, stop bath), resulting in contact dermatitis. Tongs should be used to move photographic paper through these chemicals.
Corrosives consist of four major classes: Strong acids, strong bases, dehydrating agents and oxidizing agents. Inhalation of the vapors of these substances can cause severe bronchial irritation. These chemicals erode the skin and the respiratory epithelium, and are particularly damaging to the eyes. Acids and alkalis should be stored separately in a cool ventilated area, away from metals, flammables, and oxidizing materials. The storage area should be checked regularly for spills and leaks, and there should be suitable spill cleanup materials available. Protective clothing should be worn whenever acids or alkalis are handled.
Always pour acids into water, never the reverse. Cap bottles securely and store them securely, but do not store acids and alkalis together. Clean up spills promptly. Do not leave residues on a bottle or lab bench where another person may come in contact with them. Wear protective garb when handling acids or alkalis. This includes rubber gloves, apron, and eye protection.
Four acids deserve special attention because of the hazards they pose. These are: nitric acid, perchloric acid, picric acid, and hydrofluoric acid.
is corrosive and its oxides are highly toxic. Because nitric acid is also an oxidizing agent, it may form flammable and explosive compounds with many materials (e.g., ethers, acetone and combustible materials). Paper used to wipe up nitric acid may ignite spontaneously when dry. Nitric acid should be used only in a hood, and should be stored away from combustible materials.
(HClO4) forms highly explosive and unstable compounds with many organic compound and even with metals. Unstable perchlorate compounds may collect in the duct work of fume hoods and cause fire or violent explosions. Therefore, perchloric acid should be used with extreme caution and only in a fume hood designed for its use-a perchloric acid hood having corrosion-resistant duct work and washdown facilities. We have no such facilities in our school. Minimum quantities of perchloric acid should be kept on hand, and the container stored in a perchloric acid hood on a glass tray that is deep enough to hold the contents of the bottle. Perchloric acid should not be kept for more than one year since explosive crystals may form. A number of graduate students at universities have had their fingers blown off when unscrewing the cap from perchloric acid. Liquid residue forms a crust on the bottle and cap threads, which explode when the next user attempts to open the bottle. Similar explosions occurred when attempting to clean non-perchloric acid fume hoods, where vapors formed crystals in the crevices in the hood and duct work. Perchloric acid should be stored in an explosion proof refrigerator since it may become unstable at room temperature.
can form explosive compounds with many combustible materials. When the moisture content decreases, picric acid may become unstable and may explode from being shaken. Picric acid should be dated, stored away from combustible materials, and not kept for extend periods (i.e., longer than one year).
is extremely corrosive and will even attack glass. All forms-dilute, concentrated solutions or the vapor-can cause serious burns. HF does not produce overt tissue burns like most acids; instead, it diffuses through tissue and will dissolve bone. Burns from hydrofluoric acid heal slowly and with great difficulty. Therefore, hydrofluoric acid should be used in suitable fume hood while gloves, safety glass and lab coat are being worn. Inhalation of HF mists or vapor will cause serious respiratory tract irritation that may be fatal. Care should taken to avoid contacting hydrofluoric acid with metals or ammonia since toxic fumes may result.
Alkali metals (e.g., sodium and potassium) react violently with water and decompose the water, giving off hydrogen, which may be ignited by the heat of reaction. This is similarly true for alkaline earth metals (calcium and magnesium). Alkali metals can also ignite spontaneously in air, especially when the metal is in powdered form, and/or the air is moist. Alkali metals should be stored under mineral oil or kerosene. Avoid using oils containing sulfur since a hazardous reaction may occur. Use only special, dry powder fire extinguishers on alkali metal fires. Any waste alkali metals should be placed in labeled, leak-proof container, covered with mineral oil and disposed of via the DESHS. Finely powdered metals (e.g. Al or Fe) that come in contact with acids may ignite and burn. Metal powders can also create a dust explosion hazard when the powders become airborne in an area where a spark or flame is present.
Mercury is a virulent poison and is readily absorbed through the respiratory tract, the gastrointestial tract, or through unbroken skin. It is therefore imperative that it not be touched, or its vapors inhaled. It acts as a cumulative poison (like arsenic) since only small amounts of the element can be eliminated at a time by the human organism. The vapor pressure of mercury is quite high; air saturated with mercury vapor at 20°C contains a concentration that exceeds the toxic limit more than 100 times. Therefore mercury should only be used in a well-ventilated hood. Mercury spills must be immediately covered with sulfur to bring down the vapor pressure (see section on chemical spills).
Highly Reactive Chemicals and Explosives
When chemical reactions are considered safe, it is generally because the reaction rate is relatively slow or can be easily controlled. Certain reactions proceed, however, at such a fast rate and generate so much heat, that they may result in explosion. Care should be taken to ensure there is sufficient cooling and surface area for heat exchange.
Many chemical reactions may involve hazards like those mentioned above, but can be handled safely if some preliminary planning has been done. Planning an experiment should include knowledge of the reactivity, flammability, and toxicity of the chemicals used in and produced by the experiment. This information may be obtained from the MSDS data base, using the Handbook of Reactive Chemical Hazards (L. Bretherck), or by calling the DESHS (4-4635). Such planning shall include selection of the proper safety procedures, clothing and equipment as well as consideration of the possibility of a power failure, equipment breakdown, or fire, and the precautions that can be taken to minimize the consequences.
Organic peroxides are a class of compounds that have unusual stability problems that make them among the most hazardous substances handled in laboratories. As a class, organic peroxides are considered to be powerful explosives. They are sensitive to heat, friction, impact, and light as well as to strong oxidizing and reducing agents. All organic peroxides are flammable. Types of compounds known to form peroxides are listed in Table
Table 2: Common compounds that form peroxides during storage.
|Ethyl ether||Isopropyl ether|
|Methy i-butyl ketone||Sodium amide|
|Ethelyene glycol dimethl ether (glyme)||Butadine|
|Methyl acetylene||Vinyl acetate|
All peroxidizable materials should be stored in a cool place, away from light. Metal cans are preferable; do not store ethers in ground stoppered bottles. Ethers and peroxidizable materials should be ordered only in small quantities, and should be dated upon receipt and when opened. They should be discarded within a year after receipt if unopened, or within months of opening. Ethers should always be handled in a hood to assure proper ventilation. This will protect individuals from inhaling the vapors and prevent accumulation of explosive concentrations of the vapor. For methods of peroxide detection and removal, consult the DESHS.
Certain combinations of chemicals are particularly dangerous and should be avoided. Table indicates the compatibility of various chemicals.
Table 3: Examples of incompatible chemicals
|Chemical||Is Incompatible With|
|Hydrofluoric acid (anhydrous)||Ammonia (aqueous or anhydrous)|
|Hydrogen peroxide||Copper, chromium, iron, most metals or their salts, alkochols, acetone, organic materials, aniline, nitromethane, combustible materials|
|Hydrogen sulfide||Fuming nitric acid, oxidizing gases|
|Hypochlorites||Acids, activated carbon|
|Iodine||Acetylene, ammonia (aqueous or anhydrous), hydrogen|
|Mercury||Acetylene, fulminic acid, ammonia|
|Nitroparaffins||Inorganic bases, amines|
|Oxalic acid||Silver, mercury|
|Oxygen||Oils, grease, hydrogen, flammable liquids, solids, or gases|
|Perchloric acid||Acetic anhydride, bismuth and its alloys, alcohol, paper, wood, grease, oils|
|Peroxides, organic||Acids (organic or mineral), avoid friction, store cold|
|Phosphorus (white)||Air, oxygen, alkalis, reducing agents|
|Potassium chlorate||Sulfuric and other acids|
|Potassium perchlorate (see also chlorates)||Sulfuric and other acids|
|Potassium permanganate||Glycerol, ethylene glycol, benzaldehyde, sulfuric acid|
|Silver||Acetylene, oxalic acid, tartartic acid, ammonium compounds, fulminic acid|
|Sodium||Carbon tetrachloride, carbon dioxide, water|
|Sodium nitrate||Ammonium nitrate and other ammonium salts|
|Sodium peroxide||Ethyl or methyl alcohol, glacial acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerin, ethylene glycol, ethyl acetate, methyl acetate, furfural|
|Sulfuric acid||Potassium chlorate, potassium perchlorate, potassium permaganate (similar compounds of light metals, such as sodium, lithium)|
Other chemical hazards that may result explosions or fires include:
are explosive in mixture 2.5-80% with air. At pressures of 2 or more atmospheres, acetylene (C2H2) subjected to electrical discharge or high temperature decomposes with explosive violence. Dry acetylides detonate on receiving the slightest shock.
(AlCl3) should be considered a potentially dangerous material. If moisture is present, there may be sufficient decomposition to build up a considerable pressure of HCl.
reacts with iodine to form nitrogen triiodide, which is explosive, and hypochlorites to form chlorine.
when dry, is easily ignited and sensitive to shock. It decomposes spontaneously at temperatures above 50°C
is both very toxic and very flammable; mixed with air, its vapors can be ignited by a steam bath or pipe, a hot plate, or a glowing light bulb.
may react violently with hydrogen or with hydrocarbons when exposed to sunlight.
complex (CrO3-C5H5N) may explode if the CrO3 concentration is too high. The complex should be prepared by addition of CrO3 to excess C5H5N.
(CH2N2) and related compounds should be treated with extreme caution. They are very toxic, and the pure gases and liquids explode readily. Solutions in ether are safer from this standpoint.
(CH3)2SO] decomposes violently on contact with a wide variety of active halogen compounds. Explosions from contact with active metal hydrides have been reported. Its toxicity is still unknown, but it does penetrate and carry dissolved substances through the skin membrane.
should not be kept in a container that is not designed to withstand pressure. Containers of other substances stored over dry ice for extended periods generally absorb carbon dioxide (CO2) unless they have been sealed with care. When such containers are removed from storage, and allowed to come rapidly to room temperature, the CO2 may develop sufficient pressure to burst the container with explosive violence. On removal such containers from storage, the stopper should be loosened, or the container itself should be wrapped in towels and kept behind a shield. Dry ice can produce serious burns.
“Ascarite'' should not be mixed with phosphorus pentoxide (P2O5) because the mixture may explode if it is warmed with a trace of water. Because the cobalt salts used as moisture indicators in some drying agents may be extracted by some organic solvents, the use of these drying agents should be restricted to gases.
Diethyl, diisopropyl, and other ethers
sometimes explode during heating or refluxing because of the presence of peroxides. Ferrous salts or sodium bisulfite can be used to decompose the peroxides, and passage over basic active alumina will remove most of the peroxidic material. In general, however, old samples of ethers should be discarded.
(C2H4O) has been known to explode when heated in a closed vessel. Experiments using ethylene oxide under pressure should be carried out behind suitable barricades.
Chloroform (CHCl3), carbon tetrachloride (CCl4), and other halogenated solvents should not be dried with sodium, potassium, or other active metal; violent explosions are usually the result of such attempts. Many halogenated compounds are toxic.
(H202) Stronger than three percent can be dangerous; in contact with the skin, it may cause severe burns. Thirty percent H2O2 may decompose violently if contaminated with iron, copper, chromium, or other metals or their salts.
open to the atmosphere rapidly condense liquid from the air. Then, when the coolant is removed, an explosive pressure buildup occurs, usually with enough force to shatter glass equipment. Hence, only sealed or evacuated equipment should be so cooled.
Lithium aluminum hydride
(LiAlH4) should not be used to dry inethyl ethers or tetrahydrofuran; fires from this are very common. The products of its reaction with CO2 have been reported to be explosive. Carbon dioxide or bicarbonate extinguishers should not be used against LiAlH4 fires, which should be smothered with sand or some other inert substance.
(O3) is a highly reactive and toxic gas. It is formed by the action of ultraviolet light on oxygen (air) and, therefore, certain ultraviolet sources may require venting to an exhaust hood.
Palladium or platinum on carbon, platinum oxide, Raney nickel, and other catalysts should be filtered from catalytic hydrogenation reaction mixtures carefully. The recovered catalyst is usually saturated with hydrogen and highly reactive and, thus, will inflame spontaneously to exposure to air. Particularly in large-scale reactions, the filter cake should not be allowed to become dry. The funnel containing the still moist catalyst filter cake should be put into water bath immediately after completion of the filtration. Another hazard in working with such catalysts is the danger of explosion if an additional catalyst is added to a flask in which hydrogen is present.
used for hydrogenations have been known to explode. They should be handled with care behind shields, and the operator should wear goggles.
The use of perchlorates should be avoided wherever possible. Perchlorates should not be used as drying agents if there is possibility of contact with organic compounds in proximity to a dehydrating acid strong enough to concentrate the perchloric acid (HClO4) more than 70% strength (e.g., in a drying train that has a bubble counter containing sulfuric acid). Safer drying agents should be used. Seventy percent HClO4 can be boiled safely approximately 200°C, but contact of the boiling undiluted acid or the hot vapor with organic matter, or even easily oxidized inorganic matter (such as compounds of trivalent antimony), will lead to serious explosions. Oxidizable substances must never be allowed to contact HClO4. Beaker tongs, rather than rubber gloves should be used when handling fuming HClO4. Perchloric acid evaporations should be carried out only in fume hoods designed specifically for this purpose.
are explosive when treated with sulfuric acid. When both compounds are used in an absorption train, an empty trap should be placed between them.
(inorganic)-when mixed combustible materials, barium, sodium, potassium peroxides form explosives that ignite easily.
(P) (red and white) forms explosive mixtures with oxidizing agents. White P should be stored under water because it is spontaneously flammable in air. The reaction of P with aqueous hydroxides gives phosphine, which may ignite spontaneously in air or explode.
(PCl3) reacts with water to form phosphoric acid, which decomposes on heating to form phosphine, which may ignite spontaneously or explode. Care should be taken in opening containers of PCl3, and samples that have been exposed to moisture should not be heated without adequate shielding to protect the operator.
(K) is in general more reactive than sodium. It ignites quickly on exposure to humid air and, therefore, should be handled under the surface of a hydrocarbon solvent such as mineral oil or toluene (see Sodium).
Residues from vacuum distillations
(for example, ethyl palmitate) have been known to explode when the still was vented to the air before the residue was cool. Such explosions can be avoided by venting the still pot with nitrogen, by cooling it before venting, or by restoring the pressure slowly.
(Na) should be stored in a closed container under kerosene, toluene, or mineral oil. Scraps of Na or K should be destroyed by reaction with n-butyl alcohol. Contact with water should be avoided because Na reacts violently with water to form H2 with evolution of sufficient heat to cause ignition. Neither carbon dioxide nor bicarbonate fire extinguishers should be used on alkali metal fires.
may react violently with benzoyl chloride plus potassium hydroxide, bromine, carbon disulfide, chromium oxychloride, copper, lead, nitric acid, dimethylsulfate and ibromomalonitrile. It is especially important that sodium azide not be allowed to come in contact with heavy metals (for example, by being poured into a lead or copper drain) or their salts; heavy metal azides detonate with notorious ease.
(H2SO4) should be avoided, if possible, as a drying agent in desiccators. If it must be used, glass beads should be placed in it to help prevent splashing when the desiccator is moved. The use of H2SO4 in melting point baths should be avoided (silicone oil should be used). To dilute H2SO4, add the acid slowly to cold water.
(Cl2CCHCl) reacts under a variety of conditions with potassium or sodium hydroxide to form dichloroacetylene, which ignites spontaneously in air and detonates readily even at dry-ice temperatures. The compound itself is highly carcinogenic, and precautions should be taken decreasing solvent.