Reactive Hazards

Oxidising Agents

Oxidizing agents are chemicals that bring about an oxidation reaction. The oxidizing agent may provide oxygen to the substance being oxidized (in which case the agent has to be oxygen or contain oxygen) or receive electrons being transferred from the substance undergoing oxidation (chlorine is a good oxidizing agent for electron-transfer purposes, even though it does not contain oxygen). The intensity of the oxidation reaction depends on the oxidizing-reducing potential of the material involved. Fire or explosion is possible when strong oxidizing agents come into contact with easily oxidizable compounds, such as metals, metal hydrides or organics. Because oxidizing agents possess varying degrees of instability, they can be explosively unpredictable.

 

Examples of Oxidizing Agents

Gases Fluorine, chlorine, ozone, nitrous oxide, oxygen
Liquids Hydrogen peroxide, nitric acid, perchloric acid, bromine, sulphuric acid
Solids Nitrites, nitrates, perchlorates, chromates, dichromates, picrates, permanganates, hypochlorites, bromates, iodates, chlorites, chlorates, persulphates.

 

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Explosives

Explosives cause sudden, almost instantaneous release of pressure, gas, and heat when subjected to sudden adverse conditions. Heat, light, mechanical shock, detonation, and certain catalysts can initiate explosive reactions. Compounds containing the functional groups azide, acetylide, diazo, nitroso, haloamine, peroxide, and ozonide are sensitive to shock and heat and can explode violently.

Peroxide Forming Compounds

Generally, organic peroxides are low-powered explosives that are sensitive to shock, sparks, and heat.

Some organic compounds such as ethers, tetrahydrofuran, and dioxan can react with oxygen from the air forming unstable peroxides. Peroxide formation can occur slowly under normal storage conditions -limited access to air and exposure to light. These accumulated peroxides can violently explode when exposed to shock, friction, or heat especially when concentrated and heated by distillation.

Bretherick (“Hazards in the Chemistry Laboratory”) points out the particular danger from peroxide formation by di-isopropyl ether.

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Water Reactive Compounds

These compounds react with water or moisture in the air releasing heat or flammable, toxic gas. Examples include alkali metals, alkaline earth metals, carbides, hydrides, inorganic chlorides, nitrides, peroxides, and phosphides.

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Toxic Hazards from Mixtures

Toxic gases may be evolved following the mixture of some chemicals e.g.

Chemical A Chemical B Product
Arsenical materials Any reducing agent Arsine
Azides Acids Hydrogen Azide
Cyanides Acids Hydrogen Cyanide
Hypochlorites Acids Chlorine or hypochlorous acid
Nitrates Sulphuric Acid Nitrogen Dioxide
Nitric Acid Copper, brass, any heavy metals Nitrogen Dioxide
Nitrites Acids Nitrous fumes
Phosphorus Caustic alkalis or reducing agents Phosphine
Selenides Reducing agents Hydrogen Selenide
Sulphides Acids Hydrogen Sulphide
Tellurides Reducing agents Hydrogen Telluride

 

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Reactive Hazards from Mixtures

Many chemicals may react violently on mixing accidentally or intentionally.

Chemical Incompatibles
Acetic acid Chromic acid, nitric acid, hydroxyl compounds, ethylene glycol, perchloric acid, peroxides, permanganates
Acetylene Chlorine, bromine, copper, fluorine, silver, mercury
Acetone Concentrated nitric and sulphuric acid mixtures
Alkali and alkaline earth metals (such as powdered aluminium or magnesium, calcium, lithium, sodium, potassium) Water, carbon tetrachloride or other chlorinated hydrocarbons, carbon dioxide, halogens
Ammonia (anhydrous) Mercury (in manometers, for example), chlorine, calcium hypochlorite, iodine, bromine, hydrofluoric acid (anhydrous)
Ammonium nitrate Acids, powdered metals, flammable liquids, chlorates, nitrites, sulphur, finely divided organic combustible materials
Aniline Nitric acid, hydrogen peroxide
Arsenical materials Any reducing agent
Azides Acids
Bromine See chlorine
Calcium oxide Water
Carbon (activated) Calcium hypochlorite, all oxidizing agents
Carbon tetrachloride Sodium
Chlorates Ammonium salts, acids, powdered metals, sulphur, finely divided organic or combustible materials
Chromic acid and chromium Acetic acid, naphthalene, camphor, glycerol, alcohol, flammable liquids in general
Chlorine Ammonia, acetylene, butadiene, butane, methane, propane (or other petroleum gases), hydrogen, sodium carbide, benzene, finely divided metals, turpentine
Chlorine dioxide Ammonia, methane, phosphine, hydrogen sulphide
Copper Acetylene, hydrogen peroxide
Cumene hydroperoxide Acids (organic or inorganic)
Cyanides Acids
Flammable liquids Ammonium nitrate, chromic acid, hydrogen peroxide, nitric acid, sodium peroxide, halogens
Fluorine All other chemicals
Hydrocarbons (such as butane, propane, benzene) Fluorine, chlorine, bromine, chromic acid, sodium peroxide
Hydrocyanic acid Nitric acid, alkali
Hydrofluoric acid (anhydrous) Ammonia (aqueous or anhydrous)
Hydrogen peroxide Copper, chromium, iron, most metals or their salts, alcohols, acetone, organic materials, aniline, nitromethane, combustible materials
Hydrogen sulphide Fuming nitric acid, oxidizing gases
Hypochlorites Acids, activated carbon
Iodine Acetylene, ammonia (aqueous or anhydrous), hydrogen
Mercury Acetylene, fulminic acid, ammonia
Nitrates Sulphuric acid
Nitric acid (concentrated) Acetic acid, aniline, chromic acid, hydrocyanic acid, hydrogen sulphide, flammable liquids, flammable gases, copper, brass, any heavy metals
Nitrites Acids
Nitroparaffins inorganic bases, amines
Oxalic acid Silver, mercury
Oxygen Oils, grease, hydrogen: flammable liquids, solids or gases
Perchloric acid Acetic anhydride, bismuth and its alloys, alcohol, paper, wood, grease, oils
Peroxides, organic Acids (organic or mineral), avoid friction, store cold
Phosphorus (white) Air, oxygen, alkalis, reducing agents
Potassium Carbon tetrachloride, carbon dioxide, water
Potassium chlorate Sulphuric and other acids
Potassium perchlorate (see also chlorates) Sulphuric and other acids
Potassium permanganate Glycerol, ethylene glycol, benzaldehyde, sulphuric acid
Selenides Reducing agents
Silver Acetylene, oxalic acid, tartaric acid, ammonium compounds, fulminic acid
Sodium Carbon tetrachloride, carbon dioxide, water
Sodium nitrite Ammonium nitrate and other ammonium salts
Sodium peroxide Ethyl or methyl alcohol, glacial acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerin, ethylene glycol, ethyl acetate, methyl acetate, furfural
Sulphides Acids
Sulphuric acid Potassium chlorate, potassium perchlorate, potassium permanganate (similar compounds of light metals, such as sodium, lithium)
Tellurides Reducing agents

 

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