Chemical Reactivity and Storage

Chemical Reactivity and Storage
Presented by QBE Loss Control Services This presentation addresses issues related improperly stored chemicals. Many chemicals are incompatible and precautions need to be taken to ensure they cannot come into contact.

Objectives To understand basic terminology relating to chemical hazard classes and reactivity To be able to identify chemicals that pose a high potential risk for property loss or injury To be able to identify common incompatible chemicals that might be stored together As QBE’s appetite for manufacturing business increases, there will be more potential exposure to losses relating to chemical hazards. We need to evaluate how these chemicals are stored and used during our risk evaluation.

Pretest What are the 4 principles for good chemical storage?
Match the following chemicals to the appropriate reactivity hazard: ___Peroxides A- Air Sensitive ___Acrylic Resins B- Spontaneous Peroxide Formation ___Metal Dusts C- Strong Oxidizers ___Ethers D- Polymerization Hazard ___Hydrogen E- Reducer Explain why intentional chemistry processes are a major concern from a potential loss standpoint. List 10 things that should be reviewed when evaluating chemical storage areas.

Former Ammonium Nitrate Plant
Improper chemical use and storage can lead to catastrophic consequences.

Potential Losses Relating to Chemicals
Property Fire Explosions Environmental Release Workers Compensation Respiratory Disease Dermatitis Chemical Burns Physical Injuries General Liability Losses related to chemical use and storage can affect property, work comp and general liability coverages. Chemicals need to be evaluated as they relate to all of these coverages in the loss control survey.

Use of Chemicals Manufacturing Processes Distributors Warehouses
Chemical Product Manufacture Paint Manufacture Plating Metal Heat Treating Metal Cleaning Metal Degreasing Printing Plastics Concrete Additives Food Additives Adhesives Circuit Boards Distributors Warehouses Stores Ancillary Activities Painting Waste Treatment Water Treatment Sanitation/Janitorial Laboratories Pest Control Swimming Pools Fertilizers Lawn/garden Chemicals Ammonia Refrigeration These are some of the types of operations insured by GC where chemicals are used or stored. Chemicals are used in a wide variety of manufacturing processes. Chemical products can be made from other chemical raw materials by chemical reaction. An example is a hydrated lime plant where limestone (calcium carbonate) is heated and reacted with water to form hydrated lime (calcium hydroxide). The chemical reaction is as follows: CaCO3 + Heat CaO + CO2 CaO + H2O Ca(OH)2 Chemical are also used in certain processes within an operation and are unchanged by the process (metal degreasing). Chemical such as paints, fertilizers, pesticides and herbicides may be stored and distributed by store chains. Chemical are also used in special circumstances such as sanitation at a food processor or to treat the waste stream leaving a facility.

Terminology Oxidizer Polymerization Reducer Pyrophoric Alkali Acid
Explosives Reactive There are a number of specialized chemical terms that loss control staff need to be familiar with. Oxidizer- Chemicals that supply oxygen or chlorine that accelerates combustion of other materials. The reaction can be spontaneous or may occur under slight heating. Oxidizers are severe fire and explosion hazards. Polymerization- Chemicals that have a tendency to self-react to form larger molecules. They may generate heat during this self reaction causing containers to burst and materials to ignite. Reducer- Chemicals that are the opposite of oxidizers. These chemicals want to gain oxygen in a chemical reaction. Pyrophoric- Chemicals that ignite spontaneously when exposed to air. Alkali- Bases. Corrosive chemicals with a pH greater than 7. Acid- Corrosive materials with a pH less than 7. Explosives- Materials that under conditions of shock, temperature or chemical reaction decompose violently releasing large amounts of gas and heat. Reactive- Chemicals that are unstable, explosive, water reactive, air sensitive, oxidizing or reducing. These chemicals have a tendency to readily combine chemically with other materials releasing heat, toxic vapors and gases.

Basic Chemistry Oxidizers want to gain electrons to be more stable
Reducers want to lose electrons to be more stable The stronger the oxidizer, the more it wants to gain electrons The stronger the reducer, the more it wants to lose electrons Most chemical reactions we are concerned with involve oxidation of one chemical in conjunction with reduction of the other chemical at the same time. Chemical reactions involve the transfer of electrons from one atom to another. A strong oxidizer has a very high affinity for these electrons to make them more stable. Reducers on the other hand want to readily give up electrons to make them more stable. When these two types of compounds are mixed, this transfer of electrons is very rapid releasing large amounts of heat and energy. This heat and energy can cause fires and explosions.

Strong Oxidizers Fluorine Nitrates Chlorine Nitrites Ozone
Persulfates Peroxides Perchlorates Dichromates Chromates Permanganates Hypochlorites Nitrates Nitrites Liquid oxygen Chlorates This is a list of some of the more common strong oxidizers. There are others. If there are questions about a particular chemical consult the MSDS.

Reducers Finely divided metals Hydrazine Hydrides Hydrogen Aniline
Sodium Lithium Potassium These are some common reducers. There are others. Check the MSDS is there is uncertainty in regards to a particular chemical that may be a reducer.

Chemical State Solid Liquid Gas
Chemical state is important in regards to the hazard of a particular chemical. Gases are usually the greatest concern because if they leak they quickly move over large areas. Gases are also readily absorbed into the bloodstream through the thin membranes in the lung. Liquids are usually the next most hazardous form of chemicals. They flow easily over a surface and make contact an ignition source causing a fire if they are flammable. Solids are usually the least hazardous form of a chemical. They remain in a set location and are more easily contained and cleaned up.

Scale of Chemical Use When evaluating chemical risks the amount of chemicals is one of the most critical pieces of information. In this case small quantities- gallons, few ounces are used in a research lab.

Scale of Chemical Use In this case hundreds of gallons of chemicals are used and stored at a printing operation.

Chemical Reaction Equipment
The scale of chemical reaction equipment is important. This picture shows a small chemical reactor in a laboratory.

Scale of Chemical Use This picture shows large tanks of chemicals used in a plating process.

Other Storage Issues When evaluating chemical storage don’t forget about containment, ignition sources, bonding, grounding, fire protection, etc.

Other Safety Equipment
Eyewash stations, showers and fire extinguishers should be in place where chemicals are used and stored.

Flammables Not addressed in this presentation
Store according to NFPA and QBE property guidelines This presentation will focus on chemical reactivity hazards. Loss control staff should be familiar with storage and use of flammable materials. These topics have been covered in previous property training. Consult the flammable solvents and property training PowerPoints for additional information.

Water Reactive Chemicals
Alkali metals (lithium, sodium, magnesium) Hydrides (diborane, sodium hydride) Peroxides (sodium peroxide) Carbides (calcium carbide) Oxides (sodium oxide) Phosphides (aluminum phosphide) Anhydrides (acetic anhydride) These are some of the more common water reactive chemicals. Some react slowly when wet. Others may react violently. Humidity in the air may also cause reaction. Water reactive chemicals typically decompose water molecules (H2O) creating free hydrogen. Hydrogen gas is highly explosive.

Polymerizable Chemicals
Chemical chain reaction of monomers to form polymers May self react May react vigorously with water May give off hazardous gases May cause high pressure in storage container Inhibitors are used to prevent reaction Polymerizable chemicals have a tendency to self react. When they self react energy is released. If this energy is not dissipated as fast it is generated, it can preheat the unreacted material increasing the acceleration of the chemical reaction until it is out of control causing fires and explosions.

Polymerizable Chemicals
Acrylic acid Acrylonitrile Ethyl acrylate Methyl acrylate Methacrylic acid Vinyl acetate These are some common materials susceptible to polymerization.

Unstable/Shock Sensitive Chemicals
Very unstable React vigorously Mechanical shock, elevated temperature or pressures can cause reaction Unstable compounds have a tendency to break down (decompose) over time or when subject to heat, sunlight, shock, friction or a catalyst with resulting decomposition products being toxic or flammable. Decomposition can be rapid enough to cause explosive energy release causing fires and explosion.

Unstable/Shock Sensitive Chemicals
Ammonium perchlorate Azo, diazo or azide chemicals Fulminates Hydrogen peroxide Organic peroxides Nitro or nitroso compounds Picric acid Perchloric acid Triazines These are some common unstable chemicals.

Air-Sensitive Compounds
Reactive with oxygen in air Usually pyrophoric Usually stored under inert gas or liquid Air-sensitive compounds readily reactive with oxygen in the atmosphere, igniting and burning without an ignition source. Pyrophoric materials ignite spontaneously on short exposure to air.

Air-Sensitive Compounds
Metalic dusts (zinc, nickel, titanium) Alkali metals (potassium, sodium, magnesium) Hydrides (diborane, barium hydride) This is a list of common chemicals and materials that are sensitive to air.

Organic Peroxides Compounds having two oxygen atoms joined together (peroxy) Severe fire and explosion hazard Burn rapidly and intensely May be strong oxidizers Plastics and rubber industries Used as accelerators, activators, catalysts, curing agents, hardeners, initiators or promoters Solids liquids and pastes Can be formed spontaneously Peroxides are unstable materials because they contain excess oxygen. The oxygen to oxygen bond in peroxides is unstable and very energetic. When exposed to heat, fire, shock, friction or contamination the oxygen bond cleaves to form reactive oxygen free radicals that are available to recombine with other chemicals causing violent reactions.

Organic Peroxides Methyl ethyl ketone peroxide Benzol peroxide
Hydrogen peroxide Peracetic acid There are many other peroxides This is a list of some common peroxides. Methyl ethyl ketone peroxide is one of the more common peroxides. It is used for in place polymerization of reinforced plastics and fiberglass. Other peroxides are used as bactericides, fungicides, and bleaching agents.

Spontaneous Peroxide Formation
Some chemicals can form peroxides during storage Light and heat can cause peroxide formation Prolonged storage of susceptible chemicals Spontaneous formation of peroxides can occur due to reaction of some substances with atmospheric oxygen. Peroxide formation occurs slowly over time when a peroxide forming liquid is stored with limited access to air. Inhibitors and stabilizers are often added to these liquids to prevent peroxide formation. The friction of opening the chemical container or sudden shock or agitation of the container can cause explosive decomposition of the peroxide.

Spontaneous Peroxide Formation
Ethers Tetrahydrofuran p-Dioxane 2-Propanol 2-Butanol Methyl isobutyl ketone Styrene Vinyl acetate These are some common solvents that have the potential for peroxide formation during prolonged storage. There are many others. Check the MSDS if there is a question about peroxide formation.

NFPA Standards NFPA 430- Code for Storage of Liquid and Solid Oxidizers NFPA 432- Code for Storage of Organic Peroxide Formulations NFPA 484- Code for Combustible Metals, Metal Powders and Metal Dusts NFPA 490- Code for Storage of Ammonium Nitrate NFPA 495- Explosive Materials Code There are a number of NFPA codes that address storage requirements for some classes of chemicals. These should be consulted for specific storage requirements.

Swimming Pool Chemicals
Strong oxidizers 3.8 million swimming pools in U.S. Kill bacteria, fungi, viruses by releasing chlorine There are a couple of special chemical storage and handling issues we need to pay close attention to. The first are chemicals associated with maintenance and sanitation of swimming pools. Motels and apartment complexes that we insure may have swimming pools. Swimming pool water treatment chemicals can become hazards when they become wet or if they are mixed improperly. These chemicals can also be self reactive over time. Each year there are numerous incidents relating to exposure to toxic chemicals and fire caused by pool chemicals

Inorganic Calcium hypochlorite (Cal hypo) Lithium hypochlorite Sodium hypochlorite (bleach) Chlorine gas (large pools) Organic Trichloroisocyanuric acid (Trichlor) Potassium dichloroisocyanurate (Dichlor) Sodium dichloroisocyanurate (Dichlor) Sodium dichloroisocyanurate dihydrate (Dichlor) Brominated Hydantoin The most common pool disinfectant is calcium hydroxide or Cal Hypo. These chemicals are oxidizers which release chlorine that kills algae, bacteria and fungi. Sodium hypochlorite in diluted form is household bleach. Isocyanurates form cyanuric an hypochlorous acid in water solutions. Trichloroisocyanuric acid is the most common isocyanurate disinfectant. These chemicals are unstable and react with water if accidentally wetted during storage. These chemicals also are incompatible with many other chemicals such as ammonia, gasoline, paints, solvents and pesticides.

Cal hypo + Chlorinated Isocyanurate + Water = Chlorine Gas Cal hypo is a strong oxidizer. When mixed with an isocyanurate like Trichlor and water they react explosively and highly toxic chlorine gas is produced.

Swimming Pool Chemical Storage
Secure Area should be posted with signs Well ventilated Away from sunlight Dry Store in original labeled containers Store away from acids Spills should be cleaned up immediately according to manufacturer’s procedures Swimming pool chemicals need to be stored in a secure area with access limited to authorized employees who are trained to use the materials properly. The storage area should be cool and dry and well ventilated and preferably in a detached location. Areas should be posted with signs identifying the major hazards of the chemicals stored in the area. Smoking should be prohibited in the storage area and the area should be clean and good housekeeping practices should be in place. Other chemicals like paints, solvents soaps, oils, etc. should not be stored in the same area as pool chemicals. If chlorine gas is used, cylinders should be upright and secure to prevent tipping with valve caps on. Pool chemicals should not be stored in basements or near elevator shafts, ventilation systems or other openings that might spread gases through the building if a leak occurs. Spilled chemicals should never be returned to the original container. Employees who apply pool chemicals should be properly trained so that they know how to apply the chemicals safely, using proper mixing and application techniques, dosage, and personal protective equipment.

Laboratories Small quantities of chemicals Wide variety of chemicals
Usually highly trained and employees Many QBE accounts have laboratories. These may be QC laboratories in food processing plants or materials testing labs in manufacturing plants. Some accounts are laboratory type facilities where small amounts of special formulation products are manufactured. Chemicals are used in smaller quantities than in a manufacturing setting but there may be a wide variety of chemicals from various incompatibility classes stored at the facilities. This may pose a problem from an incompatibility storage standpoint.

Chemical Reactivity Risk Evaluation
This flow chart provides a simple way of determining whether there is a possibility of potential chemical reactivity hazards at an account. The flow chart is broken down in the next few slides.

Go to Question 5 Intentional chemistry is defined as a process where a chemical reaction is intended to take place. Intentional chemistry produces products that are chemically different than the starting materials. Operations that involve chemical reactions are at increased risk for negative consequences if there is a problem. These might include run away reactions, equipment under pressure as gases are produced by the reaction, venting of toxins, or heat generation. Loss control reports need to include specific information about chemical processes including raw materials used, equipment used to carry out the chemical reaction and controls used to prevent fires, explosions, and release of toxic materials. Many operations involve chemicals but there are no chemical reactions taking place. These include things like using solvents to clean parts, oils and machining fluids that are used to lubricate parts and equipment or pesticides used at a facility.

Indicators of Intentional Chemistry
Products have different chemical formulas than the starting materials Gases are given off Solid is formed from liquid or gaseous starting materials A catalyst or initiator is used Heat is generated or must be added to the process These items are indicators that a chemical reaction is taking place. If there is a question about a particular process, contact the plant engineer, chemist or other technical specialist at the facility. Human resource personal and other loss control contacts may not understand the process themselves.

Problems with Intentional Chemistry
Wrong materials added Improper amounts of materials added Inadequate cleaning of equipment Materials added in wrong sequence Materials added to fast or too slow Contaminated feed materials Improper temperature of feed materials Air leaks Insufficient agitation Heat transfer inadequate Off-gas vent blocked or not open Intentional chemistry poses a high risk for losses due to these types of things that can go wrong. As an example- If a pump fails that provides cooling water to a chemical reaction vessel that heats up during a manufacturing process, the vessel may explode if a runaway reaction occurs. There are many other things that can lead to negative consequences not listed here. The account should have evaluated potential problems by performing a job hazard analysis or another hazard evaluation procedure.

Chemical Reaction Vessel
This is a small chemical reaction vessel used in a laboratory.

Go to Question 6 Even if intentional chemistry is not performed, mixing of chemical materials could pose a risk for losses if the wrong materials are accidentally mixed together or if the wrong amounts of materials are mixed, etc. Mixing operations should be identified in the loss control report.

Go to Question 6 Even if there is no intentional chemistry or mixing of different substances, some physical processing could pose a risk for losses. Drying operations could pose a fire risk or grinding operations of a flammable material could pose a risk for dust explosions.

Go to Question 7 If there is no intentional chemistry, mixing or physical processing of materials at the facility, there is still a potential risk for losses if hazardous materials are stored at the facility. If fertilizer is sold at a garden center and it is stored next to paint thinner in the warehouse storage racks, is there a problem? What happens if a fork-truck ruptures a can of the paint thinner and it spills on the bag of fertilizer? If there are no hazardous materials used or stored at the facility, then there are no issues of concern.

Chemical Storage Storage of drums of chemicals on a rack system.

Even though there are some intentional chemical process such as combustion of fuel to heat the facility, we are not concerned with this in our evaluation of chemicals in this presentation. Refer to our regular property resources when evaluation heating and boiler systems.

If there is no intentional chemistry at the facility, but mixing or physical processing of a material causes heat to be generated there may be a potential fire hazard. How is the heat controlled during these processes?

If there is no intentional chemistry, mixing, or physical processing, or if there is mixing and physical processing but no heat is generated; then we only need to be concerned with stored materials that may be a concern if they are not handled properly. These are only a few examples of spontaneously combustible materials. There are many more. Check containers and MSDS if there is question concerning these materials.

Other storage hazards include materials that can form peroxides during storage. These are only a few examples. There are many more. Check containers and MSDS if there is question concerning these materials.

Water reactive chemicals are another storage concern
Water reactive chemicals are another storage concern. These are only a few examples. There are many more. Check containers and MSDS if there is question concerning these materials.

Oxidizers are another storage concern. These are only a few examples
Oxidizers are another storage concern. These are only a few examples. There are many more. Check containers and MSDS if there is question concerning these materials.

Materials that can polymerize or decompose are another storage concern
Materials that can polymerize or decompose are another storage concern. These are only a few examples. There are many more. Check containers and MSDS if there is question concerning these materials.

The last question in the flowchart has to do with mixing of incompatible materials. This is the main concern with storage of chemicals. If mixing could result in a negative consequence (fire, explosion, toxic release, etc.), then controls need to be in place to prevent accidental mixing.

Chemical Spills/Waste
Assume all chemicals are reactive Many fires start in dumpsters/waste containers due to mixing of incompatible chemicals Some reactions are immediate Many reactions may take hours or more Waste segregation by type Spill procedures and training HAZMAT procedures One of the most common ways incompatible materials get mixed together is during spill cleanup. If a strong oxidizer like a swimming pool chemical that is spilled on the floor is swept up and thrown into a waste basket with paper, the paper could combust due to oxidation. Some times a fire starts immediately but in most cases the fire starts many hours later. It is also important the waste handling procedures also incorporate analysis of chemical incompatibility. There should be containers for waste solvents, separate containers for waste acids, waste caustics, etc. so incompatible wastes are not mixed together.

Incompatible Materials Evaluation
Step one: Determine if there are Undesirable Consequences Toxic gas generation Corrosive gas or liquid generation Flammable gas generation Formation of shock-sensitive or explosive materials Explosion Fire Off-gas generation that can rupture containers Sufficient heating to cause runaway reaction An evaluation for chemical incompatibility involves 3 steps. The first is to determine if there are any negative consequences if specific materials are mixed. A review of MSDS, labels, and other technical resources can help with this determination. Use other reference materials (Bretherick’s Handbook of Reactive Chemical Hazards, Wiley’s Guide to Chemical Incompatibilities, NFPA 491- Hazardous Chemical Reactions. In some cases tactual testing is done in a laboratory to see if there are any chemical reactions when materials are mixed.

Step two: Identify Mixing Scenarios Leaking containers Pumping into wrong storage tank, vessel Cross connected line left open Material mislabeled or unlabeled Wrong material selected by operator Waste materials combined in tank or container Waste material combined in sewer Contaminated raw material Residue from previous batch in equipment Cleaning materials left in process equipment Fire or explosion Once the negative consequences of mixing are identified for specific materials then an evaluation needs to be conducted to determine the potential mixing scenarios where the materials could come into contact.

Step Three: Provide Controls to Prevent Mixing Training Segregation Engineering Controls The last step in the evaluation of incompatible chemical mixing is to implement controls.

Chemical Storage Principles
Segregation Protection from Physical Damage Hazard Identification Fire Control These are the 4 basic principles for storing chemicals. Incompatible materials should be segregated. Isolation in a separate building or by fire walls, or distance can be used. The extant of segregation depends on the quantities of materials stored. Containers of chemicals need to be protected from damage due to fork-trucks, weather, etc. All areas where chemicals are stored should have warning signs and specific containers should be labeled. The fire extinguishing system for the storage area should be compatible to the materials stored in the area.

Storage Guidelines Ensure containers are labeled
Segregate incompatibles by hazard class Do not store alphabetically Store flammables according to GC property guidelines Do not store chemicals above eye level Do not overcrowd shelves Avoid storing chemicals on floor Liquids should be stored in unbreakable packaging These are some basic general guidelines to be followed when storing chemicals.

Chemical Segregation Scheme
Compressed Gases- Flammable Compressed Gases- Oxidizing Acids Bases Flammable Liquids Flammable Solids Oxidizers Reducers Water-Reactive Peroxide Forming Chemicals Poisons/Toxins Carcinogens A storage scheme that segregates chemicals by their hazard class is a good way to separate incompatibles. These are the common classes of hazardous chemicals.

Chemical Incompatibility Chart
Acids Inorganic Oxidizing Organic Alkalis Bases Oxidizers Poisons Water Reactives Solvents X Charts such as this are another way of identifying chemical incompatibles. An “X” denotes that the two materials are incompatible.

Loss Control Evaluation of Chemicals
Improper storage of incompatibles Leaking or deteriorating containers Spilled chemicals Temperature extremes Lack of or low lighting levels Blocked exits or aisles Security of storage area Trash accumulation Evidence of smoking Adequate ventilation Hazard communication program Employee training Waste handling procedures HAZMAT procedures Intentional chemistry performed Fire extinguishers Sprinkler system Warning signs Labeling MSDSs For the most part loss control staff will not be involved with identification and analysis of some of the more technical areas of chemical storage and chemical processing. Experts are needed when determining the hazards of many chemical substances. We should be aware of some basic chemical storage principles and address these in the loss control surveys.

Housekeeping, labeling, and spill containment are typical things that should be evaluated.

Chemical Storage Cabinets
Are storage cabinets available and are they being used?

Storage Cabinets In this case the cabinets are not being used or the space for storage is inadequate.

Chemical Handling/Dispensing
How chemicals are handles by employees is important. Is PPE adequate?

Painting Area Poor housekeeping is typical of painting operations. The large number of solvents left on the bench poses a fire hazard.

DOT Labels Hazardous materials fall under the labeling requirements of U.S. DOT for placarding both for bulk transport and nonbulk transport DOT has assigned each hazardous material or group of materials a unique four digit ID number for cross reference by hazardous response personnel The labels are color coded and may also include a single digit Hazard Class Number and a universal symbol One of the best ways to evaluate chemicals quickly during a walk-through survey is to look at the labels and marking on the containers. There are a number of labeling systems. DOT labels and placards are one type of label that may be present.

DOT Labels DOT labels are the type we most often see on containers in the field Universal Symbol The Class number can be referenced to the DOT Emergency Response Guidebook to identify the specific chemical material and its hazards. U.N. Hazard Class Number

DOT Labels DOT labels classify materials according to the chemical hazard class.

DOT Labels Class 1 = Explosives Class 2 = Gases
Class 3 = Flammable Liquids Class 4 = Flammable Solids Class 5 = Oxidizers Class 6 = Poisons & Infectious Class 7 = Radioactive Class 8 = Corrosives Class 9 = Miscellaneous

DOT Labels Class 1- Explosives
Division 1.1- Explosives with a mass explosion hazard Division 1.2- Explosions with a projection hazard Division 1.3- Explosives that are a fire hazard Division 1.4- Explosives with no significant blast hazard Division 1.5- Very insensitive explosives Class 4- Flammable solids, Spontaneously combustible materials and materials dangerous when wet Division 4.1 Flammable solids Division 4.2 Spontaneously combustible materials Division 4.3 Materials that are dangerous when wet Class 5- Oxidizers and Organic Peroxides Oxidizers Organic Peroxides Hazard classes are also broken down further into divisions.

DOT Labels Pay particular attention to Explosive labels.

DOT Labels These are other labels that we should watch for.

NFPA Labels NFPA also has a labeling system that is commonly encountered. Labeling requirements are in NFPA 704- Identification of the Hazards of Materials for Emergency Response.

NFPA Labels Flammability Health Reactivity Special Hazard
The label is color coded with a rating from 0 to 4 for Health, Flammability and Reactivity. Special Hazards are also noted. Reactivity Special Hazard

NFPA Labels NFPA 704 Hazards rating based upon exposure hazards during fires Reactivity rating based on reactions with water It is important to remember that the hazard rating is based on the hazards in a fire situation. The scoring is designed to give fire fighters hazard information as they encounter chemicals while using water which is used to fight fires. Consequently, oxidizers and water reactive chemicals are rated high because they are water reactive.

NFPA Labels Health 4- Materials that can cause death or serious chronic injury with very short exposure 3- Materials that can cause serious temporary or chronic injury with short exposure 2- Materials that can cause temporary injury or possible chronic injury with intense exposure 1- Materials that can cause irritation but only minor chronic injury 0- Materials that cause no hazard beyond those of ordinary combustibles in a fire situation

NFPA Labels Flammability
4- Materials that rapidly or completely vaporize at atmospheric pressure and normal temperature and burn readily 3- Liquids and solids that can be ignited under almost all ambient temperature conditions 2- Materials that must be moderately heated before ignition occurs 1- Materials that must be preheated before ignition occurs 0- Materials that will not burn

NFPA Labels Reactivity
4- Materials that are readily capable of detonation or explosive decomposition at normal temperatures and pressures 3- Materials that are capable of detonation or explosive decomposition but require a strong initiating source or must be heated under confinement, or explosively react with water 2- Materials that readily undergo violent chemical change at elevated temperature or pressure, or react violently with water 1- Materials that are normally stable but can become unstable at elevated temperatures or pressures 0- Materials that are normally stable even under fire exposure and are not reactive with water

HMIG (Hazardous Material Information Guide)
HMIG labels are another common labeling system. Chemical manufactures may use this system for labeling health, flammability and reactivity hazards of chemicals. It is also used as a system for labeling containers of transferred chemicals in a facility for compliance to OSHA’s Hazard Communication Standard.

HMIG Labels Rating for each category is from 0 to 4 and is similar to the NFPA system except that the hazard is not based upon fire hazards of the chemical but on general toxicity, flash point and reactivity. A letter denotes the combination of PPE that should be worn when using the chemical.

Housekeeping Issues Housekeeping should be evaluated in conjunction with chemical storage area evaluations. Waste materials increase the fire hazard and likelihood that incompatibles may be mixed together.

Housekeeping & Storage

Labeling Unlabeled containers or containers without proper hazard information are an indicator of a problem. Incompatible materials or the wrong material may be mixed together as a consequence.

Chemical Storage/Reactivity Red Flags
Permanganates Hypochlorates Persulfate Water reactive Nitro Azides Curing agent Hardener Initiator Promoter Acids Bases Unstable Pyrophoric Peroxide Oxidizer Catalyst Accelerator Activator Polymerization Reducer Chromate Dichromates Nitrate Perchlorate Nitric acid Chlorates When evaluating chemical use and storage at a facility, these are some times of terms or chemicals that should raise your concerns about reactivity hazards and incompatible materials.

10 Loss Control Questions
Are hazardous substances stored or handled at the facility? Have materials been evaluated for potential reactivity hazards or incompatibility if they are accidentally mixed together? Is intentional chemistry performed? Is there mixing of different substances? Is heat generated during mixing or processing? Are any spontaneously combustible materials, peroxides, water reactive materials, oxidizers or self-reactive (polymerizable) materials used or stored? Are incompatible chemicals segregated? Are storage containers properly labeled and identified? Are storage containers in good condition? Are employees properly training in Hazard Communication and proper chemical handling and storage procedures? These are the 10 most important questions that need to be answered when evaluating chemical hazards. A good loss control survey report will discuss and analyze these issues.

Other Sources of Information
OSHA – Many resources are available under “chemical reactivity hazards” in the topics index Essential Practices for Managing Chemical Reactivity Hazards- Center for Chemical Process Safety- Download from OSHA’s website Organic Peroxides- E&S PC-30-11 Chlorinated Swimming Pool Sanitizers- E&S PC-30-02 Contact the HO EH Specialist

Post-test What are the 4 principles for good chemical storage?
Match the following chemicals to the appropriate reactivity hazard: ___Peroxides A- Air Sensitive ___Acrylic Resins B- Spontaneous Peroxide Formation ___Metal Dusts C- Strong Oxidizers ___Ethers D- Polymerization Hazard ___Hydrogen E- Reducer Explain why intentional chemistry processes are a major concern from a potential loss standpoint. List 10 things that should be reviewed when evaluating chemical storage areas.

Chemical Reactivity and Storage

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