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What are dangerously reactive liquids and solids?

Workplace Hazardous Material Information System (WHMIS) criteria define dangerously reactive liquids and solids as those that can:

  • undergo vigorous polymerization, condensation or decomposition
  • become self-reactive under conditions of shock or increase in pressure or temperature
  • react vigorously with water to release a lethal gas

What is vigorous polymerization?

Polymerization is a chemical reaction in which many small molecules (monomers) join together to form a large molecule (polymer). Often the reaction produces heat and pressure. Industry carries out these processes under closely monitored conditions. Other chemicals (catalysts and initiators) and controlled amounts of heat, light and pressure are often involved.

Vigorous polymerization is potentially hazardous because the reaction may get out of control. Once started, the reaction is accelerated by the heat that it produces. The uncontrolled buildup of heat and pressure can cause a fire or an explosion, or can rupture closed containers. Depending on the material, temperature increases, sunlight, ultraviolet (UV) radiation, X-rays or contact with incompatible chemicals can trigger such reactions.

Many pure substances (i.e. uninhibited) can undergo vigorous polymerization quite easily by themselves when they are heated slightly or exposed to light. These include:

  • acrylic acid
  • acrylonitrile
  • cyclopentadiene
  • diketene
  • ethyl acrylate
  • hydrocyanic acid
  • methacrylic acid
  • methyl acrylate
  • vinyl acetate

What is an inhibitor?

An inhibitor is a chemical that is added to a material to slow down or prevent an unwanted reaction such as polymerization. Inhibitors are added to many materials that can polymerize easily when they are pure.

Inhibitor levels in materials may gradually decrease during storage even at recommended temperatures. At storage temperatures higher than recommended, inhibitor levels can decrease at a much faster rate. At temperatures lower than recommended, the inhibitors may separate out. This action can result in some part of the material having little or no inhibitor.

Some inhibitors need oxygen to work effectively. Chemical suppliers may recommend checking oxygen and inhibitor levels regularly in stored materials and adding more if levels are too low.

Vapours from inhibited materials do not contain inhibitors. If these vapours condense and form polymers, they can block vents or flame arrestors in process equipment or containers.


What is vigorous condensation?

Condensation is a chemical reaction in which two or more molecules join together to form a new substance. Water or some other simple substance may be given off as a by-product. Some polymers, such as nylon, can be formed by condensation reactions.

Vigorous condensation can produce more energy than the surroundings can safely carry away. This could cause a fire or explosion, or rupture closed containers.

Few common pure chemicals undergo vigorous condensation by themselves. Some members of the aldehyde chemical family, including butyraldehyde and acetaldehyde, condense vigorously, but bases or sometimes strong acids must also be present. Some commercial products sold to be mixed for specialized applications may undergo vigorous condensation if they are not stored, handled and used as directed by the chemical supplier.


What is vigorous decomposition?

Decomposition is a chemical change in which a molecule breaks down into simpler molecules. Vigorous decomposition is potentially hazardous because large amounts of energy can be released very quickly. This could result in a fire or explosion, or rupture a closed container causing the release of dangerous decomposition products. Some pure materials are so chemically unstable that they vigorously decompose at room temperature by themselves. For example, some organics are relatively safe only when refrigerated or diluted.


What is meant by self-reactivity under conditions of shock or increase in temperature or pressure?

Materials in this group are chemically very unstable. Depending on the material, they can react vigorously and, in some cases, explosively under conditions of mechanical shock such as a hammer blow or even slightly elevated temperature or pressure. Materials in this category include:

  • ammonium perchlorate
  • azo and diazo compounds
  • acetylides
  • azides
  • fulminates
  • hydrogen peroxide solutions (91% by weight)
  • many organic peroxides
  • nitro and nitroso compounds
  • nitrate esters
  • perchloric acid solutions (over 72.5% by weight)
  • picric acid
  • picrate salts
  • triazines
  • some epoxy compounds

Can vigorous reactivity with water release deadly gas?

Some materials can react vigorously with water to rapidly produce gases which are deadly at low airborne concentrations. For example, sodium or potassium phosphide release phosphine gas when they contact water. Alkali metal cyanide salts, such as sodium or potassium cyanide, slowly release deadly hydrogen cyanide gas on contact with water. The cyanide salts of alkaline earth metals such as calcium or barium cyanide react at a faster rate with water to produce hydrogen cyanide gas. This can result in a life-threatening problem in confined spaces or poorly ventilated areas.

Large amounts of corrosive hydrogen chloride gas are rapidly released when water reacts with aluminum chloride, phosphorous trichloride, tin chloride and chlorosilane compounds. When water contacts thionyl chloride or sulphuryl chloride, they decompose rapidly giving off sulphur dioxide gas and hydrogen chloride gas.

Treat all unknown materials as very hazardous until they are positively identified.


How are dangerously reactive liquids and solids hazardous to my health?

Dangerously reactive liquids and solids can be extremely hazardous. Accidental or uncontrolled chemical reactions are important causes of severe personal injury and property damage. Rapid release of very toxic or corrosive gases occurs when water contacts some dangerously reactive materials. In addition, many dangerously reactive materials are themselves toxic or very toxic. Depending on the material, route of exposure (inhalation, eye or skin contact, or swallowing) and dose, they could harm the body. The Material Safety Data Sheet (MSDS) should describe what these hazards are for the particular product you are working with.


What are the fire and explosion hazards of dangerously reactive chemicals?

Highly reactive chemicals may undergo vigorous, uncontrolled reactions that can cause an explosion or a fire, or rupture sealed reaction vessels or storage containers.

Even slow reactions can be hazardous if they involve large amounts of material or if the heat and gases are confined, such as in a sealed storage drum. Drums that are swollen and distorted from over-pressurization are potentially very dangerous. They may rupture at any time without warning and release their contents.

Some dangerously reactive liquids such as methyl acrylate and acrylonitrile, are also flammable liquids. They give off enough vapour at normal workplace temperatures to form flammable mixtures with air. They can be serious fire hazards at temperatures lower than those at which they would begin to polymerize or decompose.

Fires involving dangerously reactive materials can be more hazardous than normal. The heat from the fire can lead to violent, uncontrolled chemical reactions and potentially explosive ruptures of sealed containers.


Are there other hazards associated with dangerously reactive chemicals?

Many dangerously reactive materials can also undergo dangerous reactions from direct contact with other, incompatible materials. Incompatibility hazards can be complicated. The chance of a dangerous reaction depends not just on the different combinations of chemicals involved. It also depends on the amounts of each, the surrounding conditions such as temperature, and whether the substances are enclosed in a sealed container.

The MSDSs and the container labels should explain all of the hazards of the dangerously reactive liquids and solids that you work with.

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Document last updated on August 13, 2004

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