8.1 Explosives

Under the OSHA Laboratory Standard and the Globally Harmonized System (GHS), explosive chemicals include substances or mixtures that can rapidly release gas, heat, and pressure due to shock, friction, impact, heat, or contamination. For transportation purposes, the Department of Transportation (DOT) classifies explosives as Hazard Class 1.

Although most laboratories do not routinely work with primary explosives, a number of laboratory chemicals can become shock-, friction-, or heat-sensitive over time due to aging, drying, contamination, or peroxide formation. These materials can pose serious risks even when stored in closed containers.

Explosive or potentially explosive materials can cause significant damage to equipment, ventilation systems, glassware, and building structures, and may generate toxic byproducts. Before performing any experiment with an explosion risk, determine whether a safer substitute is available. If the use of an explosive or potentially explosive material is necessary, you must obtain prior approval from your Principal Investigator and review all relevant safety information (e.g., SDS, technical literature, and EHS guidance).

For non-urgent questions regarding explosive or potentially explosive chemicals:
Contact EHS at askEHS@cornell.edu .

When preparing or conducting experiments involving potentially explosive materials:

• Use the smallest feasible quantity of material.
• Conduct work behind an appropriate blast shield and within an area that provides adequate protection. Some energetic reactions may require a designated workspace outside the fume hood; consult EHS for guidance.
• Remove unnecessary equipment and incompatible chemicals (especially flammables and toxics) from the immediate work area.
• Notify laboratory personnel of the planned work, hazards involved, and anticipated timing.
• Use spark-resistant, non-metallic tools when manipulating sensitive materials; avoid scraping or friction.
• Ensure temperature-control, pressure-relief, and quench systems are in place when required by the procedure.
• Dispose of waste promptly through EHS and clearly indicate if the waste contains any potentially explosive constituents.
• Wear appropriate PPE, including gloves compatible with the chemical hazard, a lab coat or apron, chemical splash goggles, and a face shield or blast shield when required.

Storage: Date all chemical containers when received and when opened. Certain compounds must remain wetted to remain stable (e.g., picric acid, 2,4-dinitrophenylhydrazine). Never attempt to open or move a container that appears to show signs of aging or instability, including:

• Deterioration or corrosion of the container
• Crystalline deposits in or around the cap or threads
• Discoloration of the solid or liquid contents

If any of these conditions are observed, stop immediately and call Cornell Public Safety Dispatch at 911 from a Cornell landline or 607-255-1111 from a mobile phone.

Examples of explosive or potentially explosive chemicals include:

• Chemicals containing azide, diazo, nitroso, acetylide, haloamine, peroxide, or ozonide functional groups
• Nitrocellulose (especially when dry or aged)
• Di- and tri-nitro aromatic compounds
• Peroxide-forming compounds
• Picric acid (dry)
• 2,4-Dinitrophenylhydrazine (dry)
• Benzoyl peroxide (dry or contaminated)

8.2 Flammable and Combustible Liquids

The OSHA Laboratory Standard defines a flammable liquid as any liquid having a flashpoint below 100 degrees F (37.8 degrees C), except any mixture having components with flashpoints of 100 degrees F (37.8 degrees C) or higher, the total of which make up 99% or more of the total volume of the mixture.

Flashpoint is defined as the minimum temperature at which a liquid gives off enough vapor to ignite in the presence of an ignition source. The risk of a fire requires that the temperature be above the flashpoint and the airborne concentration be in the flammable range above the Lower Explosive Limit (LEL) and below the Upper Explosive Limit (UEL).

The OSHA Laboratory Standard defines a combustible liquid as any liquid having a flashpoint at or above 100 degrees F (37.8 degrees C), but below 200 degrees F (93.3 degrees C), except any mixture having components with flashpoints of 200 degrees F (93.3 degrees C), or higher, the total volume of which make up 99% or more of the total volume of the mixture. OSHA further breaks down flammables into Class I liquids, and combustibles into Class II and Class III liquids.

Under the Department of Transportation (DOT) hazard class system, flammable liquids are listed as hazard class 3.

Flammable and combustible liquids are one of the most common types of chemicals used at Cornell and are an important component in a number of laboratory processes. However, in addition to the flammable hazard, some flammable liquids also may possess other hazards such as being toxic and/or corrosive.

When using flammable liquids, keep containers away from open flames; it is best to use heating sources such as steam baths, water baths, oil baths, and heating mantels. Never use a heat gun to heat a flammable liquid. Any areas using flammables should have a fire extinguisher present. If a fire extinguisher is not present, then contact EHS at 607-255-8200 for more assistance.

Always keep flammable liquids stored away from oxidizers and away from heat or ignition sources such as radiators, electric power panels, etc.

When pouring flammable liquids, it is possible to generate enough static electricity to cause the flammable liquid to ignite. If possible, make sure both containers are electrically interconnected to each other by bonding the containers, and connecting to a ground.

Always clean up any spills of flammable liquids promptly. Be aware that flammable vapors are usually heavier than air (vapor density > 1). For those chemicals with vapor densities heavier than air (applies to most chemicals), it is possible for the vapors to travel along floors and, if an ignition source is present, result in a flashback fire.

8.3 Flammable Solids

The OSHA Laboratory Standard defines a flammable solid as a “solid, other than a blasting agent or explosive, that is liable to cause fire through friction, absorption of moisture, spontaneous chemical change, or retained heat from manufacturing or processing, or which can be ignited readily and when ignited, burn so vigorously and persistently to create a serious hazard.” An example of a flammable solid is gun powder.

Under the DOT hazard class system, flammable solids are listed as hazard class 4. Flammable solids are further broken down into three subcategories:

• Flammable Solids – Class 4.1
• Spontaneously Combustible – Class 4.2
• Dangerous When Wet – Class 4.3
• Many of the same principles for handling and storage of flammable liquids apply to flammable solids. Always keep flammable solids stored away from oxidizers, and away from heat or ignition sources such as radiators, electric power panels, etc.

8.4 Spontaneously Combustible

Spontaneously combustible materials are also known as pyrophorics; these chemicals can spontaneously ignite in the presence of air, some are reactive with water vapor, and most are reactive with oxygen. Two common examples are tert-Butyllithium under Hexanes and White Phosphorus. In addition to the hazard of the spontaneously combustible chemical itself, many of these chemicals are also stored under flammable liquids. In the event of an accident, such as a bottle being knocked off a shelf, the chemical can spontaneously ignite and a fire can occur. Extra care must be taken when handling spontaneously combustible chemicals. When transporting these chemicals, it is best to use a bottle carrier and carts.

8.5 Dangerous When Wet

Dangerous when wet compounds react violently with water to form toxic vapors and/or flammable gases that can ignite and cause a fire.

It is important to note that any paper toweling, gloves, etc., that have come into contact with these materials need to be quenched with water before disposing of in metal trash cans in order to prevent potential fires.

If you are using dangerous when wet compounds and do not have a Class D fire extinguisher present, then please contact EHS at 607-255-8200 for more assistance.

8.6 Oxidizers and Organic Peroxides

The OSHA Laboratory Standard defines an oxidizer as “a chemical other than a blasting agent or explosive that initiates or promotes combustion in other materials, thereby causing fire either of itself or through the release of oxygen or other gases.” Under the DOT hazard class system, oxidizers are listed as hazard class 5.1 and organic peroxides are listed as hazard class 5.2.

The OSHA Laboratory Standard defines an organic peroxide as “an organic compound that contains the bivalent –O-O- structure and which may be considered to be a structural derivative of hydrogen peroxide where one or both of the hydrogen atoms have been replaced by an organic radical.”

Oxidizers and organic peroxides are a concern for laboratory safety due to their ability to promote and enhance the potential for fires in labs.

As a reminder of the fire triangle (now referred to as the fire tetrahedron), in order to have a fire, you need:

• A fuel source.
• An oxygen source.
• An ignition source.
• A chemical reaction.

Oxidizers can supply the oxygen needed for the fire, whereas organic peroxides supply both the oxygen and the fuel source. Both oxidizers and organic peroxides may become shock sensitive when they dry out, are stored in sunlight, or due to contamination with other materials, particularly when contaminated with heavy metals. Most organic peroxides are also temperature sensitive.

As with any chemicals, but particularly with oxidizers and organic peroxides, quantities stored on hand should be kept to a minimum. Whenever planning an experiment, be sure to read the SDS and other reference documents to understand the hazards and special handling precautions that may be required, including use of a safety shield. Also be aware of the melting and autoignition temperatures for these compounds and ensure any device used to heat oxidizers has an overtemperature safety switch to prevent the compounds from overheating.

Laboratory staff should be particularly careful when handling oxidizers (especially high surface area oxidizers such as finely divided powders) around organic materials.

Avoid using metal objects when stirring or removing oxidizers or organic peroxides from chemical containers. Plastic or ceramic implements should be used instead. Laboratory personnel should avoid friction, grinding, and impact with solid oxidizers and organic peroxides. Glass stoppers and screw cap lids should always be avoided and plastic/polyethylene lined bottles and caps should be used instead.

If you suspect your oxidizer or organic peroxide has been contaminated (evident by discoloration of the chemical, or if there is crystalline growth in the container or around the cap), then dispose of the chemical as hazardous waste or contact EHS at 607-255-8200. Indicate on the hazardous waste tag that the chemical is an oxidizer or organic peroxide and that you suspect contamination.

8.7 Peroxide Forming Compounds

Many commonly used chemicals; organic solvents in particular, can form shock, heat, or friction sensitive peroxides upon exposure to oxygen. Once peroxides have formed, an explosion can result during routine handling, such as twisting the cap off a bottle – if peroxides are formed in the threads of the cap. Explosions are more likely when concentrating, evaporating, or distilling these compounds if they contain peroxides.

When these compounds are improperly handled and stored, a serious fire and explosion hazard exists. The following guidelines should be adhered to when using peroxide forming chemicals:

1. Each peroxide forming chemical container MUST be dated when received and opened. A list of common peroxide forming chemicals can be found in the appendix. Those compounds in the appendix listed in Table A should be disposed of within 3 months of opening and those compounds in the appendix listed in Tables B, C, and D should be disposed of within 12 months of opening.
2. Each peroxide forming chemical container must be tested for peroxides when opened and at least every 6 months thereafter. The results of the peroxide test and the test date must be marked on the outside of the container. There are sample peroxide labels on the Signs and Labels webpage.
3. Peroxide test strips can be purchased from the Chemistry Department stockroom or from a variety of safety supply vendors, such as VWR and Laboratory Safety Supply. An alternative to peroxide test strips is the KI (potassium iodide) test. References such as Prudent Practices in the Laboratory and the American Chemical Society booklet Safety in Academic Chemistry Laboratories outline ways to test for peroxides and ways to remove them if discovered. When using the test strips, if the strip turns blue, then peroxides are present. Light blue test results may be acceptable for use if your procedure does not call for concentrating, evaporating or distilling. Containers with darker blue test results must be deactivated or disposed of. You can test older test strips for efficacy with a dilute solution of hydrogen peroxide.
4. Due to sunlight’s ability to promote formation of peroxides, all peroxidizable compounds should be stored away from heat and sunlight.
5. Peroxide forming chemicals should not be refrigerated at or below the temperature at which the peroxide forming compound freezes or precipitates as these forms of peroxides are especially sensitive to shock and heat. Refrigeration does not prevent peroxide formation.
6. As with any hazardous chemical, but particularly with peroxide forming chemicals, the amount of chemical purchased and stored should be kept to an absolute minimum. Only order the amount of chemical needed for the immediate experiment.
7. Ensure containers of peroxide forming chemicals are tightly sealed after each use and consider adding a blanket of an inert gas, such as Nitrogen, to the container to help slow peroxide formation.
8. A number of peroxide forming chemicals can be purchased with inhibitors added. Unless absolutely necessary for the research, labs should never purchase uninhibited peroxide formers.
9. Before distilling any peroxide forming chemicals, always test the chemical first with peroxide test strips to ensure there are no peroxides present. Never distill peroxide forming chemicals to dryness. Leave at least 10-20% still bottoms to help prevent possible explosions.

While no definitive amount of peroxide concentration is given in the literature, a concentration of 50 ppm should be considered dangerous and a concentration of >100 ppm should be disposed of immediately. In both cases, procedures should be followed for removing peroxides or the containers should be disposed of as hazardous waste.

For those compounds that must be handled by an outside environmental “bomb squad” company, the cost for such an operation can result in charges of >$1000 per container. However, if laboratory staff follow the guidelines listed above, the chances for requiring special handling for these types of containers or for an explosion to occur is greatly diminished.

The appendix contains a listing of common peroxide forming chemicals. Please note this list is not all-inclusive, there are numerous other chemicals that can form peroxides. Be sure to read chemical container labels, SDSs, and other chemical references.

8.8 Poisons

For the purpose of this manual the word “Poison” will be used interchangeably with the word “Toxic”. OSHA defines “Toxic” as a chemical falling within any of the following categories:

• A chemical that has a median lethal dose (LD50) of more than 50 milligrams per kilogram, but not more than 500 milligrams per kilogram of body weight when administered orally to albino rats weighing between 200 and 300 grams each.
• A chemical that has a median lethal dose (LD50) of more than 200 milligrams per kilogram, but not more than 1000 milligrams per kilogram of body weight when administered by continuous contact for 24 hours (or less if death occurs within 24 hours) with the bare skin of albino rabbits weighing between two and three kilograms each.
• A chemical that has a median lethal concentration (LC50) in air of more than 200 parts per million, but not more than 2000 parts per million by volume of gas or vapor, or more than two milligrams per liter but not more than 20 milligrams per liter of mist, fume, dust, when administered by continuous inhalation for one hour (or less if death occurs with in one hour) to albino rats weighing between 200 and 300 grams each.

OSHA draws a distinction between toxic chemicals and acutely toxic chemicals. For more information on acutely toxic chemicals, see Particularly Hazardous Substances. OSHA also provides definitions for other health hazards on their website. Under the DOT hazard class system, poisons are listed as hazard class 6.

When working with known poisons, it is very important to have thought an experiment through, addressing health and safety issues before working with the poison. Safety Data Sheets (SDS) and other chemical references should be consulted before beginning the experiment. Some questions to ask before working with poisonous chemicals:

• Do I need to use the poisonous chemical or can a less toxic chemical be substituted?
• What are the routes of entry into the body for the poison (inhalation, ingestion, injection, or skin absorption)?
• What are the signs and symptoms of potential chemical exposure?
• What are the proper PPE required (type of glove, safety glasses vs. splash goggles, face shield, etc.)?
• Does the chemical require any special antidote?
• What are the emergency procedures to be followed?

When working with highly toxic chemicals, you should not work alone. Always wear proper PPE and always wash your hands with soap and water when finished, even if gloves were worn. Be aware that poisonous mixtures, vapors, and gases can be formed during an experiment. Be sure to research both the reactants and products of the chemicals you will be working with first. Additional information can be found in the Exposure Monitoring section and Routes of Chemical Entry section.

8.9 Corrosives

OSHA defines a corrosive as “a chemical that causes visible destruction of, or irreversible alterations in living tissue by chemical action at the site of contact.” Under the DOT hazard class system, corrosives are listed as hazard class 8.

Corrosive chemicals can be further subdivided as acids and bases. Corrosives can be in the liquid, solid, or gaseous state. Corrosive chemicals can have a severe effect on eyes, skin, respiratory tract, and gastrointestinal tract if an exposure occurs. Corrosive solids and their dusts can react with moisture on the skin or in the respiratory tract and result in an exposure.

Whenever working with concentrated corrosive solutions, splash goggles should be worn instead of safety glasses. Splash goggles used in conjunction with a face shield provides better protection.

Corrosive chemicals should be handled in a fume hood to avoid breathing corrosive vapors and gases.

When mixing concentrated acids with water, always add acid slowly to the water (specifically, add the more concentrated acid to the dilute acid). Never add water to acid, this can result in a boiling effect and cause acid to splatter. Do not pour the acid directly into the water; it should be poured in a manner that allows it to run down the sides of the container. Never store corrosive chemicals above eye level and always use a protective bottle carrier when transporting corrosive chemicals.

Some chemicals can react with acids and liberate toxic and/or flammable vapors. When working with corrosive materials, ensure spill cleanup material is available for neutralization, such as Calcium carbonate for acids and Citric acid for bases.

Wherever acids and bases are used, an eyewash and emergency shower must be available. If any corrosive chemical gets splashed in the eyes, immediately go to an eyewash station and flush your eyes for at least 15 minutes. The importance of flushing for at least 15 minutes cannot be overstated! Once the eyewash has been activated, use your fingers to hold your eyelids open and roll your eyeballs in the stream of water so the entire eye can be flushed. After flushing for at least 15 minutes, seek medical attention immediately and complete an Injury/Illness Report.

For small splashes of corrosives to the skin, remove any contaminated gloves, lab coats, etc., and wash the affected area with soap and water for at least 15 minutes. Seek medical attention afterward, especially if symptoms persist.For large splashes of corrosives to the body, it is important to get to an emergency shower and start flushing for at least 15 minutes. Once under the shower, and after the shower has been activated, it is equally important to remove any contaminated clothing. Failure to remove contaminated clothing can result in the chemical being held against the skin and causing further chemical exposure and damage. After flushing for a minimum of 15 minutes, seek medical attention immediately and complete an Injury/Illness Report.

• Hydrofluoric Acid Designated Area Sign (docx)
• Hydrofluoric Acid Prior Approval Form
• OSHA Definition of Health Hazard
• Prudent Practices in the Laboratory
• EHS Online Training Programs
• Hydrofluoric Acid Information from Honeywell
• Hydrofluoric Acid First Aid Sign (docx)