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Chapter 8 - Chemical Hazards

 

8.0 Chemical Hazards

Chemicals can be broken down into hazard classes and exhibit both physical and health hazards. It is important to keep in mind, that chemicals can exhibit more than one hazard or combinations of several hazards. Several factors factors can influence how a chemical will behave and the hazards the chemical presents, including the severity of the response:
 
  • Concentration of the chemical.
  • Physical state of the chemical (solid, liquid, gas).
  • Physical processes involved in using the chemical (cutting, grinding, heating, cooling, etc.).
  • Chemical processes involved in using the chemical (mixing with other chemicals, purification, distillation, etc.).
  • Other processes (improper storage, addition of moisture, storage in sunlight, refrigeration, etc.).


The following sections describe general information and safety precautions about specific hazard classes. The chemical hazards listed are based on the Department of Transportation (DOT) hazard class system (which will be discussed in the Chemical Segregation section and where appropriate, will be noted as such). A listing of the DOT hazard classes can be found on the EH&S Signs and Labels webpage. A general description of the hazards of various chemical functional groups can be found in the appendix.

It is important to note that the following sections are general guidelines. Laboratory personnel should always review SDSs and other resources FIRST, before working with any chemical.

 

 

8.1 Explosives (Top)

The OSHA Laboratory Standard defines an explosive as a chemical that causes a sudden, almost instantaneous release of pressure, gas, and heat when subjected to sudden shock, pressure, or high temperature. Under the Department of Transportation (DOT) hazard class system, explosives are listed as hazard class 1.

Fortunately, most laboratories do not use many explosives; however, there are a number of chemicals that can become unstable and/or potentially explosive over time due to contamination with air, water, other materials such as metals, or when the chemical dries out.

If you ever come across any chemical that you suspect could be potentially shock sensitive and/or explosive, do not attempt to move the container as some of these compounds are shock, heat, and friction sensitive. In these instances, you should contact EH&S at 607-255-8200 immediately.

Explosives can result in damage to surrounding materials (hoods, glassware, windows, people, etc.), generation of toxic gases, and fires. If you plan to conduct an experiment where the potential for an explosion exists, first ask yourself the question; “Is there another chemical that could be substituted in the experiment that does not have an explosion potential?” If you must use a chemical that is potentially explosive, or for those compounds that you know are explosive, (even low powered explosives) you must first obtain prior approval from the Principal Investigator to use such chemicals. After obtaining prior approval from your Principal Investigator, thoroughly read the SDSs and any other chemical resources related to the potentially explosive compound(s) to ensure potential incidents are minimized.

 
Whenever setting up experiments using potentially explosive compounds:
  • Always use the smallest quantity of the chemical possible.
  • Always conduct the experiment within a fume hood and use in conjunction with a properly rated safety shield.
  • Be sure to remove any unnecessary equipment and other chemicals (particularly highly toxic and flammables) away from the immediate work area.
  • Be sure to notify other people in the laboratory what experiment is being conducted, what the potential hazards are, and when the experiment will be run.
  • Do not use metal or wooden devices when stirring, cutting, scraping, etc. with potentially explosive compounds. Non-sparking plastic devices should be used instead.
  • Ensure other safety devices such as high temperature controls, water overflow devices, etc., are used in combination to help minimize any potential incidents.
  • Properly dispose of any hazardous waste and note on the hazardous waste tag any special precautions that may need to be taken if the chemical is potentially explosive.
  • Always wear appropriate PPE, including the correct gloves, lab coat or apron, safety goggles used in conjunction with a face shield, and explosion-proof shields when working with potentially explosive chemicals.
  • For storage purposes, always date chemical containers when received and opened. Pay particular attention to those compounds that must remain moist or wet so they do not become explosive (ex. Picric acid, 2,4-Dinitrophenyl hydrazine, etc.). Pay particular attention to any potentially explosive compounds that appear to exhibit the following signs of contamination:
    • Deterioration of the outside of the container.
    • Crystalline growth in or outside the container.
    • Discoloration of the chemical.
 

If you discover a potentially explosive compound that exhibits any of these signs of contamination, contact EH&S at 255-8200 for more assistance.

 

Examples of explosive and potentially explosive chemicals include:

  • Compounds containing the functional groups azide, acetylide, diazo, nitroso, haloamine, peroxide, and ozonide
  • Nitrocellulose
  • Di- and Tri-nitro compounds
  • Peroxide forming compounds
  • Picric acid (dry)
  • 2,4-Dinitrophenylhydrazine (dry)
  • Benzoyl peroxide (dry)

 

8.2 Flammable and Combustible Liquids (Top)

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. Please note this classification is different than the criteria used for DOT classification. This distinction is important because allowable container sizes and storage amounts are based on the particular OSHA Class of the flammable liquid.

 
Classification
Flash Point
Boiling Point
Flammable Liquid
 
 
Class IA
<73 degrees F
<100 degrees F
Class IB
<73 degrees F
>=100 degrees F
Class IC
>=73 degrees F, <100 degrees F
>100 degrees F
 
 
 
Combustible Liquid
 
 
Class II
>=100 degrees F, <140 degrees F
--
Class IIIA
>=140 degrees F, < 200 degrees F
--
Class IIIB
>=200 degrees F
--
 

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 EH&S 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.
 
 
 
 

8.2.1 Flammable Storage in Refrigerators/Freezers (Top)

It is important to store flammable liquids only in specially designed flammable storage refrigerators/freezers or explosion-proof refrigerators/freezers. Do not store flammable liquids in standard (non-flammable rated) refrigerators/freezers. Standard refrigerators are not electrically designed to store flammable liquids. If flammable liquids are stored in a standard refrigerator, the build up of flammable vapors can be in sufficient quantities to ignite when the refrigerator’s compressor or light turns on, resulting in a fire or an explosion.

Properly rated flammable liquid storage refrigerators/freezers have protected internal electrical components and are designed for the storage of flammable liquids. Explosion-proof refrigerators/freezers have both the internal and external electrical components properly protected and are designed for the storage of flammable liquids. Refrigerators and freezers rated for the storage of flammable materials will be clearly identified as such by the manufacturer.

For most laboratory applications, a flammable storage refrigerator/freezer is acceptable. However, some operations may require an explosion-proof refrigerator/freezer. Flammable storage refrigerators currently cost approximately $1500 - $3000 each. In the case of limited funding where a laboratory cannot purchase a flammable storage refrigerator for the laboratory’s own use, EH&S strongly encourages departments and laboratory groups on each floor to consider purchasing a communal flammable storage refrigerator for the proper and safe storage of flammable liquids.

 

 

8.2.2 Flammable Storage Cabinets (Top)

The requirements for use of flammable storage cabinets are determined by the classification of the flammable liquids, the quantities kept on hand, the building construction (fire wall ratings), and the floor of the building the flammables are being stored on. As a general rule of thumb, if you have more than 10 gallons of flammable liquids, including materials in use, then you should store the flammable liquids in a properly rated flammable liquid storage cabinet. All flammable liquids not in use should be kept in the flammable liquid storage cabinet. For stand-alone flammable cabinets (as opposed to cabinets underneath fume hoods), there are vent holes on each side of the cabinet (called bung holes) that must have the metal bungs screwed into place for the cabinet to maintain its fire rating. Venting of flammable cabinets is NOT required, however, if a flammable cabinet is vented, it must be vented properly according to the manufacturer’s specifications and NFPA 30. Typically, proper flammable cabinet ventilation requires that air be supplied to the cabinet and the air be taken away via non-combustible pipes. If you are planning on venting your flammable storage cabinet, please contact EH&S at 607-255-8200 for more information.

 

8.3 Flammable Solids (Top)

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 (Top)

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 (Top)

Dangerous when wet compounds react violently with water to form toxic vapors and/or flammable gases that can ignite and cause a fire. Please note, attempting to put out a fire involving dangerous when wet materials with water will only make the situation worse. Special “Class D” fire extinguishers are required for use with dangerous when wet compounds. Common examples include sodium metal and potassium metal.

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 EH&S at 255-8200 for more assistance.

 

  

8.6 Oxidizers and Organic Peroxides (Top)

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 EH&S 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 (Top)

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.
 
***However, compounds that are suspected of having very high peroxide levels because of age, unusual viscosity, discoloration, or crystal formation should be considered extremely dangerous. If you discover a container that meets this description, DO NOT attempt to open or move the container. Notify other people in the lab about the potential explosion hazard and notify EH&S at 607-255-8200 immediately.
 
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 (Top)

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.

As a general rule of thumb, all chemicals should be treated as poisons and proper procedures such as maintaining good housekeeping, use of proper PPE, good personal hygiene, etc., should be followed. 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. Material 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.

If you think you may have received an exposure to a poisonous substance, or may have accidentally ingested a chemical, seek medical attention immediately and/or call the Poison Control Center at 1-(800) 222-1222 or the University Police at 911 from a campus phone or 607-255-1111 from a cell phone or off campus phone. If possible, bring a copy of the SDS with you. Upon completion of seeking medical attention, complete an Injury/Illness Report.

 

 

8.9 Corrosives (Top)

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. Please note that a face shield alone does not provide adequate protection. Use of rubber gloves such as butyl rubber and a rubber apron may also be required.

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.

Please note some chemicals, such as Hydrofluoric acid, require the use of a special antidote (such as Calcium gluconate gel) and special emergency procedures. Read the SDSs for any chemical(s) you work with to determine if a special antidote is needed if a chemical exposure occurs.

 

 

8.9.1 Hydrofluoric Acid (Top)

Hydrofluoric Acid (HF) is one of the most hazardous chemicals at used Cornell. Small exposures to HF can be fatal if not treated properly. The critical minutes immediately after an exposure can have a great effect on the chances of a victim’s survival.

HF is a gas that is dissolved in water to form Hydrofluoric acid. The concentration can vary from very low such as in store bought products up to the most concentrated 70% form (anhydrous), with the most common lab use around 48%. The liquid is colorless, non-flammable and has a pungent odor. The OSHA permissible exposure limit is 3 ppm, but concentrations should be kept as low as possible. HF is actually a weak acid by definition and not as corrosive as strong acids such as Hydrochloric (HCl), however, corrosivity is the least hazardous aspect of HF. The toxicity of HF is the main concern.

HF is absorbed though the skin quickly and is a severe systemic toxin. The fluoride ion binds calcium in the blood, bones and other organs and causes damage to tissues that is very painful and can be lethal. At the emergency room, the victim is often given calcium injections, but pain medication is not generally given since the pain subsiding is the only indication that the calcium injections are working.

 
Due to the serious hazard of working with HF, the following requirements and guidelines are provided:

  • All users of HF must receive EH&S Hydrofluoric Acid Safety training as well as training by their supervisor. The EH&S Hydrofluoric Acid Safety training is available online.
  • A Standard Operating Procedure (SOP) must be written for the process in which HF is used. This SOP should be posted or readily available near the designated area where HF use will occur.
  • HF should only be used in a designated fume hood and the fume hood should be identified by posting a HF Designated Area sign.
  • First Aid - A HF first aid kit must be available that includes 2.5% calcium gluconate gel. The Calcium gluconate gel can be obtained at the Gannett Health Services dispensary with a department charge number and should be replaced with new stock annually. The Hydrofluoric Acid First Aid sign should be posted in a prominent place where the Calcium gluconate gel is located.
  • Spill Kits - An HF spill kit must be available with calcium compounds such as Calcium carbonate, Calcium sulfate or Calcium hydroxide. Sodium bicarbonate should never be used since it does not bind the fluoride ion and can generate toxic aerosols.
  • Prior approval - Before anyone uses HF they must have prior approval from the Principal investigator. The names of lab peresonnel should be added to an HF Prior Approval form showing that they have are familiar with the following:
    • Has read the SDS for HF
    • Has read the HF Use SOP developed by the lab
    • Has read the Hydrofluoric acid section in this Lab Safety Manual
    • Is aware of the designated area for HF use
    • Knows the first aid procedure in case of an HF exposure
    • Knows what to do incase of an HF spill
  • Personal Protective Equipment (PPE) – The following PPE is required for HF use:
    • Rubber or plastic apron
    • Plastic arm coverings
    • Gloves
      • Incidental use - double glove with heavy nitrile exam gloves and re-glove if any exposure to the gloves
      • Extended use – heavy neoprene or butyl over nitrile or silver shield gloves
    • Splash goggles in conjunction with a fume hood sash
    • Closed toed shoes
    • Long pants and a long sleeve shirt with a reasonably high neck (no low cut)
    • The following are safe practice guidelines when working with HF:
  • Never work alone with HF but have a buddy system.
  • Use a plastic tray while working with HF for containment in case of a spill.
  • Keep containers of HF closed. HF can etch the glass sash and make it hard to see through (if the hood sash becomes fogged and hard to see though due to etching, then please contact EH&S at 255-8200 about installing a polycarbonate sash)
  • Material Safety Data Sheet (SDS) – A SDS for HF must be available.
  • All containers of HF must be clearly labeled. EH&S recommends using Right-To-Know labels for all non-original containers.
  • The stock HF should be stored in plastic secondary containment and the cabinet should be labeled. HF should be stored in lower cabinets near the floor.
  • Wash gloves off with water before removing them. 
 

Additional information on the safe use and handling of Hydrofluoric acid (HF) can be found on the Honeywell website - the world's largest producer of Hydrofluoric Acid. This website contains useful information on HF such as:

  • Material Safety Data Sheets
  • Technical Data Sheets
  • Recommended Medical Treatment for HF exposure
  • HF Properties charts
  • Online Training

 

 

8.9.2 Perchloric Acid (Top)

Perchloric acid is a strong oxidizing acid that can react violently with organic materials. Perchloric acid can also explode if concentrated above 72%. For any work involving heated Perchloric acid (such as in Perchloric acid digestions), the work must be conducted in a special Perchloric acid fume hood with a wash down function. If heated Perchloric acid is used in a standard fume hood, the hot Perchloric acid vapors can react with the metal in the hood ductwork to form shock sensitive metallic perchlorates. When working with Perchloric acid, be sure to remove all organic materials, such as solvents, from the immediate work area. Due to the potential danger of Perchloric acid, if possible, try to use alternate techniques that do not involve the use of Perchloric acid. If you must use Perchloric acid in your experiments, only purchase the smallest size container necessary.

Because Perchloric acid is so reactive, it is important to keep it stored separate from other chemicals, particularly organic solvents, organic acids, and oxidizers. All containers of Perchloric acid should be inspected regularly for container integrity and the acid should be checked for discoloration. Discolored Perchloric acid should be discarded as hazardous waste. Perchloric acid should be used and stored away from combustible materials, and away from wooden furniture. Like all acids, but particularly with Perchloric acid, secondary containment should be used for storage.

 
 
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Other Resources​
OSHA Lab Standard OSHA Definition of Health Hazard
Department of Transportation (DOT) Hazard Class System EH&S Signs and Labels Webpage​
Safety in Academic Chemistry Laboratories Prudent Practices in the Laboratory
Material Safety Data Sheets Webpage ​EH&S Online Training Programs
​EH&S Right-To-Know Chemical Labels ​Hydrofluoric Acid Information From Honeywell
Hydrofluoric Acid Designated Area Sign Hydrofluoric Acid First Aid Sign
Hydrofluoric Acid Prior Approval Form ​SDS for Hydrofluoric Acid
Gannett Health Services​