Appendix I - Hazards

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Hazards Of Functional Groups

  

The following information gives a basic overview of the hazards of functional groups. This information is not meant to replace material safety data sheets for the specific chemical(s) used in your experiments. While these functional groups are listed alphabetically for convenience, chemicals should be segregated and stored by hazard classes – see the EH&S Segregation Scheme for more information.

ALCOHOLS  

  • The lower aliphatic alcohols are low to moderately toxic and usually have low vapor pressures, therefore inhalation toxicity is low.
  • Vapors may be an irritant to the eyes and mucous membranes.
  • Ingestion and absorption of the liquids through the skin can be a major health hazard.
  • Lower alcohols containing double or triple bonds exhibit a greater degree of toxicity and irritation.
  • Fatty alcohols (derived from oils, fats, and waxes) are almost nontoxic.
  • Lower alcohols are flammable or combustible liquids.
  • Flammability decreases with an increase in the carbon number.
  • Solubility of alcohols decrease with increase in carbon chain length.
  • Toxicity tends to decrease with an increase in carbon number.
    • Examples:
      • Allyl alcohol
      • 1-Butanol 
      • Cyclohexanol
      • 1,2-Ethanediol 
      • Ethanol
      • Methanol
      • 1-Propanol
      • 2-Propyn 1-ol
 ALDEHYDES  
  • Aldehydes are intermediate products in the conversion of primary alcohols to carboxylic acids or vice versa.
  • The low molecular weight aldehydes are more toxic than the higher ones.
  • Toxicity decreases with increase in the carbon chain length.
  • Aromatic aldehydes are less toxic than low molecular weight aliphatic aldehydes.
  • Low molecular weight aldehydes are highly flammable, with flammability decreasing with increasing carbon chain length.
  • Low aromatic aldehydes are combustible or nonflammable liquids.
    • Examples:
      • Acetaldehyde
      • Acrolein
      • Benzaldehyde 
      • Formaldehyde
      • Glutaraldehyde 
      • 1-Hexanal
      • Isobutyraldehyde
      • Propenal
 ALIPHATIC AMINES  
  • The toxicity of most aliphatic amines may fall in the low to moderate category.
  • The health hazard from amines arises primarily from their caustic nature.
  • All lower aliphatic amines are severe irritants to the skin, eyes, and mucous membranes.
  • All of these compounds have a strong to mild odor of ammonia and their vapors produce irritation of the nose and throat.
  • Aliphatic amines, especially the lower ones, are highly flammable liquids, many which have flashpoints below 0 degrees Celsius.
  • The vapors are heavier than air.
  • They react vigorously with concentrated mineral acids.
  • The flammability decreases with an increase in the carbon number.
  • The reactivity of amines in general, is low.
    • Examples:
      • Aminocyclohexane 
      • Ethyleneimine
      • Methylamine
      • 2-Propylamine
 ALIPHATIC and ALICYCLIC HYDROCARBONS  
  • Organic compounds composed solely of carbon and hydrogen.
  • Hydrocarbons may be classified into 3 broad categories:
    • Open-chain aliphatic compounds
    • Cyclic or alicyclic compounds of naphthalene type
    • Aromatic ring compounds
  • Open chain aliphatic hydrocarbons constitute alkanes, alkenes, alkynes, and their isomers. Alkenes or olefins are unsaturated compounds, characterized by one or more double bonds between the carbon atoms. Alkynes or acetylenic hydrocarbons contain a triple bond in the molecule and are highly unsaturated. An alicyclic hydrocarbon is a cyclic ring compound of 3 or more carbon atoms. Aromatics are ring compounds too, but are characterized by a 6 carbon atom unsaturated benzenoid rings.
  • The toxicities of aliphatic and alicyclic hydrocarbons in humans and animals are very low.
  • The gaseous compounds are all nontoxic and are simple asphyxiants.
  • Lower hydrocarbons are highly flammable substances, an increase in the carbon number causes a decrease in flammability.
  • It is the flammable properties that make hydrocarbons hazardous.
  • The reactivity of alkanes and cycloalkanes is very low.
  • Alkenes and alkynes containing double and triple bonds are reactive.
    • Examples:
      • Butane 
      • Cyclohexene
      • Cyclopentane
      • Methane
      • n-Pentane
  ALKALI and OTHER REACTIVE METALS  
  • Alkali metals constitute Group IA of the periodic table.
  • Alkaline-earth metals constitute Group IIA and are less active than the alkali metals.
  • These can be water and/or air reactive.
  • Several of these metals are flammable, too, but only in finely divided state.
  • Reactions with water produce strong bases.
    • Examples:
      • Aluminum 
      • Calcium 
      • Lithium
      • Magnesium 
      • Potassium
      • Sodium
 ALKALIES  
  • Water-soluble bases, mostly the hydroxides of alkali- and alkaline-earth metals.
  • Certain carbonates and bicarbonates also exhibit basic properties but are weak bases.
  • These compounds react with acids to form salts and water.
  • The health hazard from concentrated solutions of alkalies arises from their severe corrosive actions on tissues.
  • These compounds are bitter to taste, corrosive to skin and a severe irritant to the eyes.
  • The toxicity of alkalies is governed by the metal ions.
  • Hydroxides and carbonates of alkali-and alkaline-earth are noncombustible.
  • Strong caustic alkalies react exothermically with many substances, including water and concentrated acids, generating heat that can ignite flammable materials.
    • Examples:
      • Lithium hydroxide 
      • Potassium hydroxide
      • Potassium carbonate
      • Sodium hydroxide
 AROMATIC AMINES  
  • Compounds that contain one or more amino groups attached to an aromatic ring.
  • These amines are similar in many respects to aliphatic amines.
  • These amines are basic, but the basicity is lower to aliphatic amines.
  • The health hazard from aromatic amines may arise in two ways:
    • Moderate to sever poisoning, with symptoms ranging from headache, dizziness, and ataxia to anemia, cyanosis, and reticulocytosis.
    • Carcinogenic, especially cancer of the bladder.
  • Many amines are proven or suspected human carcinogens, among aromatic amines, ortho-isomers generally exhibit stronger carcinogenic properties than those of the para- and meta-isomers.
  • Unlike aliphatic amines, the aromatic amines do not cause severe skin burn or corneal injury.
  • The pure liquids (or solids) may produce mild to moderate irritation on the skin.
  • Lower aromatic amines are combustible liquids and form explosive mixtures with air.
  • Amines may react violently with strong oxidizing compounds.
    • Examples:
      • Aniline 
      • Benzidine
      • o-Toluidine
AROMATIC HYDROCARBONS  
  • Aromatics are a class of hydrocarbons having benzene-ring structures.
  • Many polyaromatics are carcinogens.
  • The acute toxicity of mononuclear aromatics is low.
  • Inhalation of vapors at high concentrations in air may cause narcosis with symptoms of hallucination, excitement, euphoria, distorted perception, and headache.
  • Benzene is the only mononuclear aromatic with possible human carcinogenicity and other severe chronic effects.
  • With a greater degree of substitutions in the benzene ring and/or increase in the carbon chain length of the alkyl substituents, the flammability decreases.
    • Examples:
      • Benzene
      • Benzolalpyrene 
      • Pyrene
      • Toluene
      • Xylene
 AZIDES, FULMINATES, ACETYLIDES, and RELATED COMPOUNDS  
  • These compounds form highly explosive shock- and heat-sensitive salts with many metals.
  • Structurally they differ from each other, but have similar detonating characteristics.
  • While alkali metal azides are inert to shock, the salts for copper, silver, lead, and mercury are dangerously shock sensitive.
  • Fulminates of heavy metals are powerful explosives.
  • These compounds are highly sensitive to impact and heat.
  • Acetylides of heavy metals are extremely shock sensitive when dry, whereas, the salts of alkali metals are fairly stable.
  • Most azides, fulminates, acetylides, nitrides and related compounds are highly unstable and constitute an explosion hazard.
  • Salts of Group IB and IIB metals are especially explosive.
  • Azides of nonmetals, such as those of halogens or organic azides such as that of cyanogen, are also extremely shock sensitive.
  • Some of these compounds may even explode on exposure to light.
    • Examples:
      • Cuprous acetylide
      • Hydrazoic acid 
      • Lead azide 
      • Mercury fulminate
      • Silver fulminate
      • Silver nitride
      • Sodium azide
CARBOXYLIC ACIDS  
  • Weak organic acids, their strength is much weaker than mineral acids.
  • Toxicity of monocarboxylic acids is moderate to low and decreases with carbon chain length.
  • Some of lower dicarboxylic acids are moderate to high toxicity, becoming less toxic with increasing carbon chain length.
  • Low molecular weight carboxylic acids are combustible liquids.
  • Aromatic acids are of low toxicity.
    • Examples:
    • Acetic acid
    • Butyric acid 
    • Formic acid 
    • Methacrylic acid 
    • Oxalic acid
    • Propionic acid
    • Succinic acid
    • Valeric acid
 EPOXY COMPOUNDS  
  • Epoxides, also called oxiranes and 1,2-epoxides.
  • Exposure to epoxides can cause irritation of the skin, eyes, and respiratory tract.
  • Low molecular weight epoxides are strong irritants and more toxic than higher ones.
  • Inhalation can produce pulmonary edema and affect the lungs, central nervous system and liver.
  • Many epoxy compounds have been found to cause cancer in animals.
  • Lower epoxides are highly flammable.
  • They also polymerize readily in the presence of strong acids and active catalysts, this reaction generates heat and pressure that may rupture closed containers.
  • Therefore contact with anhydrous metal halides, strong bases, and readily oxidizable substances should be avoided.
    • Examples:
      • Butylene oxide 
      • Epichlorohydrin 
      • Ethylene oxide
      • Glycidaldehyde 
      • Glycidol
      • Isopropyl glycidyl ether
ESTERS  
  • Lower aliphatic esters have a pleasant fruity odor.
  • The acute toxicity of esters is generally of low order, they are narcotic at high concentrations.
  • Vapors are an irritant to the eyes and mucous membranes.
  • Toxicity increases with an increase in the alkyl chain length.
  • Lower aliphatic esters are flammable liquids, some have low flash points and may cause flashback to an open container.
  • The vapors form explosive mixtures with air.
  • The flash point increases with increase in the alkyl chain length.
  • The reactivity of esters is low.
  • Aromatic esters are similar in effects as aliphatic esters.
    • Examples:
      • Ethyl acetate 
      • Ethyl formate 
      • Methyl acrylate
      • Methyl formate
      • n-Propyl acetate
      • (Aromatics) Methyl benzoate 
      • Methyl salicyate
 ETHERS 
  • Widely used as solvents.
  • They have a high degree of flammability.
  • They tend to form unstable peroxides, which can explode spontaneously or upon heating.
  • The flash point decreases with increase in carbon chain.
  • Lower aliphatic ethers are some of the most flammable organic compounds and can be ignited by static electricity or lightning.
  • The vapor densities are heavier than air.
  • They form explosive mixtures with air.
  • Aromatic ethers are noncombustible liquids or solids and do not exhibit the flammable characteristics common to aliphatic ethers.
  • Ethers react with oxygen to form unstable peroxides, this reaction is catalyzed by sunlight, when evaporated to dryness, the concentrations of such peroxides increase, resulting in violent explosions.
  • The toxicity of ethers is low to very low, at high concentrations these compounds exhibit anesthetic effects.
    • Examples:
      • Butyl vinyl ether
      • Ethyl ether
      • Isopropyl ether
      • Methyl propyl ether 
      • Vinyl ether
GLYCOL ETHERS  
  • Also known by the name Cellosolve.
  • The toxic effects are mild, however, moderate to severe poisoning can occur from excessive dosage.
  • The routes of exposure are inhalation, ingestion, and absorption through the skin.
  • Compounds with high molecular weights and low vapor pressures do not manifest an inhalation hazard.
  • Low molecular weight alkyl ethers are flammable or combustible liquids forming explosive mixtures with air.
  • The reactivity of glycol ethers is low.
  • There is no report of any violent explosive reactions.
  • The high molecular weight compounds are noncombustible.
    • Examples:
      • Ethylene glycol monobutyl ether
      • Ethylene glycol monomethyl ether
      • 2-Isopropoxyethanol
 HALOETHERS  
  • Haloethers are ethers containing hydrogen atoms.
  • Halogen substitutions make ether molecules less flammable or nonflammable.
  • The explosion hazards of low aliphatic ethers due to peroxide formation are not manifested by the haloethers. The halogens inhibit the ether oxidation to peroxides.
  • Inhalation of Fluoroethers can produce anesthesia similar to that of the lower aliphatic ethers. Lower aliphatic chloro-and bromoethers can be injurious to the lungs.
  • Many of these are cancer causing to lungs in animals or humans.
  • Aromatic chloroethers are toxic by inhalation, ingestion, and skin absorption only at high doses. These effects can be attributed to the chlorine content and to a lesser extent on the aromaticity of the molecule.
    • Examples:
      • Bis(chloromethyl)ether
      • 2-Chloroethyl vinyl ether
      • Pentachlorodiphenyloxide
HALOGENATED HYDROCARBONS 
  • The flammability of these compounds shows a wide variation.
  • Bromo compounds are less flammable than their Chloro- counterparts, the difference in flammability is not great though.
  • An increase in the halosubstitutions in the molecule increases the flash point.
  • The flammable hydrocarbons are stable compounds with low reactivity.
  • These compounds, however, may react violently with alkali metals and their alloys or with finely divided metals.
  • Violent reactions may occur with powerful oxidizers, especially upon heating.
  • Volatile halocarbons may rupture glass containers due to simple pressure build up or to exothermic polymerization in a closed vessel.
  • Halogenated hydrocarbons in general exhibit low acute toxicity.
  • Inhalation toxicity is greater for gaseous or volatile liquid compounds.
  • The health hazard from exposure to these compounds may be due to their anesthetic actions; damaging effects on liver and kidney; and in case of certain compounds, carcinogenicity.
  • The toxic symptoms are drowsiness, lack of coordination, anesthesia, hepatitis, and necrosis of the liver.
  • Vapors may cause irritation of the eyes and respiratory tract.
  • Death may result from cardiac arrest due to prolonged exposure to high concentrations.
  • Ingestion can produce nausea, vomiting, and liver injury.
  • Fluorocarbons are less toxic than the chloro-, bromo-, and iodo- compounds, the toxicity increases with increase in the mass number of the halogen atoms.
  • Some of the halogenated hydrocarbons cause cancer in humans.
    • Examples:
      • Benzyl chloride
      • Carbon tetrachloride
      • Chloroform
      • 1,2-Dichlorobenzene
      • Ethyl bromide
      • Fluorobenzene
      • Methylene chloride
HYDRIDES  
  • The single most hazardous property of hydrides is their high reactivity toward water.
  • The reaction with water is violent and can be explosive with liberation of hydrogen.
  • Many hydrides are flammable solids that may ignite spontaneously on exposure to moist air.
  • Many ionic hydrides are strongly basic; their reactions with acids are violent and exothermic, which can cause ignition.
  • Hydrides are also powerful reducing agents, they react violently with strong oxidizing substances, causing explosions.
  • Covalent volatile hydrides such as arsine, silane, or germane are highly toxic.
  • Ionic alkali metal hydrides are corrosive to skin, as they form caustic alkalies readily with moisture.
    • Examples:
      • Decarborane
      • Lithium aluminum hydride
      • Potassium hydride
      • Sodium borohydride
      • Sodium hydride
INDUSTRIAL SOLVENTS  
  • The toxic effects of most of the solvents are of low order, chronic exposures or large doses can produce moderate to severe poisoning.
  • Most organic solvents are flammable or combustible liquids, the vapors of which can form explosive mixtures with air.
  • Many of the common solvents can cause flashback of the vapors, and some form peroxide on prolonged storage, especially those compounds containing an ether functional group, some also can form shock-sensitive solvated complexes with metal perchlorates.
    • Examples:
      • Acetamide
      • Acetone
      • Benzene
      • Carbon tetrachloride
      • Chloroform
      • Methyl acetate
      • Pyridine
      • Tetrahydrofuran
 INORGANIC CYANIDES 
  • Inorganic cyanides are the metal salts of Hydrocyanic acid.
  • Cyanides of alkali metals are extremely toxic.
  • In addition to being extremely toxic by ingestion or skin absorption, most metal cyanides present a serious hazard of forming extremely toxic Hydrogen cyanide when they come into contact with acids.
    • Examples:
      • Barium cyanide
      • Cyanogen chloride
      • Cyanamide cyanogen
      • Hydrogen cyanate
      • Sodium cyanide
      • Potassium cyanide
 KETONES  
  • Similar to aldehydes.
  • In general, the toxicity is much lower than that of other functional groups, such as cyanides or amines.
  • Unlike aldehydes and alcohols, some of the simplest ketones are less toxic than the higher ones.
  • Beyond 7 carbons, the higher ones are almost nontoxic.
  • Substitution of other functional groups can alter toxicity significantly.
  • The simplest ketones are highly flammable.
  • The flammability decreases with increase in the carbon number.
  • Examples:
  • Acetophenone
  • Acetone
  • Ketene
  • Mesityl oxide
  • Methyl Ethyl Ketone
MINERAL ACIDS  
  • Acid strengths vary widely.
  • Sour in taste.
  • React with a base to form salt and water.
  • Produce hydrogen when reacting with most common metals.
  • Produce carbon dioxide when reacting with most carbonates.
  • All mineral acids are corrosive.
  • Noncombustible substances.
  • Some are highly reactive to certain substances, causing fire and/or explosions.
    • Examples:
      • Hydrochloric acid
      • Hydrofluoric acid
      • Hydroiodic acid
      • Phosphoric acid
      • Nitric acid
      • Sulfuric acid
ORGANIC CYANIDES (NITRILES)  
  • These are organic derivatives of Hydrocyanic acid or the cyano-substituted organic compounds.
  • Nitriles are highly reactive, the CN group reacts with a large number of reactants to form a wide variety of products, such as amides, amines, carboxylic acids, aldehydes, ketones, esters, thioamides, and other compounds.
  • Nitriles are highly toxic compounds, some of them are as toxic as alkali metal cyanides.
  • Lower aliphatic nitriles are flammable and form explosive mixtures with air. The explosive range narrows down with an increase in the carbon chain length.
    • Examples:
      • Acrylonitrile
      • Acetonitrile
      • Butyronitrile
      • Cyanohydrin
 ORGANIC ISOCYANATES  
  • Organic groups attached to the isocyanate group.
  • These compounds are highly reactive due to the high unsaturation in the isocyanate functional group.
  • Isocyanates in general are highly reactive toward compounds containing active hydrogen atoms.
  • Most isocyanates are hazardous to health.
  • They are lachrymators and irritants to the skin and mucous membranes.
  • Skin contact can cause itching, eczema, and mild tanning.
  • Inhalation if isocyanate vapors can produce asthma-like allergic reaction, with symptoms from difficulty in breathing to acute attacks and sudden loss of consciousness.
  • Toxicities of isocyanates vary widely, in addition, health hazards differ significantly on the route of exposure but occur primarily via inhalation exposure.
  • Most isocyanates have high flash points, therefore the fire hazard is low.
  • However, closed containers can rupture due to the pressure built up from carbon dioxide, which is formed from reaction with moisture.
    • Examples:
      • n-Butyl isocyanate
      • Hexamethylene diisocyanate
      • Methyl isocyanate
      • Phenyl isocyanate
 ORGANIC PEROXIDES
  • Compounds containing the peroxide group bound to organic groups.
  • In general the toxicity is low to moderate.
  • Peroxides are a hazardous class of compounds, some of which are extremely dangerous to handle.
  • The dangerous ones are highly reactive, powerful oxidizers, highly flammable and often form decomposition products, which are more flammable.
  • Many organic peroxides can explode violently due to one or a combination of the follow factors:
    • Mechanical shock, such as impact, jarring, or friction
    • Heat
    • Chemical contact
  • Short chain alkyl and acyl peroxides, hydroperoxides, peroxyesters, and peroxydicarbonates with low carbon numbers are of much greater hazard than the long chain peroxy compounds.
  • The active oxygen content of peroxides is measured as the amount of active oxygen (from peroxide functional group) per 100 gm of the substance. The greater the percentage of active oxygen in formulation, the higher is its reactivity. An active oxygen content exceeding 9% is too dangerous for handling and shipping.
    • Examples:
      • Benzoyl peroxide
      • Cumene hydroperoxide
      • Diacetyl peroxide
      • Diisopropyl peroxydicarbonate
      • Hydroperoxyenthanol
 OXIDIZERS  
  • Include certain classes of inorganic compounds that are strong oxidizing agents, evolving oxygen on decomposition.
  • These substances are rich in oxygen and decompose violently on heating.
  • The explosion hazard arises when these substances come into contact with easily oxidizable compounds such as organics, metals, or metal hydrides.
  • When the solid substances are finely divided and combined, the risk of explosion is enhanced.
  • The unstable intermediate products, so formed, are sensitive to heat, shock, and percussion.
  • The health hazard from the substances arises due to their strong corrosive action on the skin and eyes.
  • The toxicity depends on the metal ions in these molecules.
    • Examples:
      • Bromates 
      • Chlorites
      • Dichromates
      • Hypochlorites
      • Inorganic peroxides
      • Iodates
      • Nitrates
      • Periodates
      • Perchlorates
      • Permanganates
 PEROXY ACIDS  
  • There are 2 types: Peroxycarboxylic acids and Peroxysulfonic acids.
  • Peroxycarboxylic acids are weaker acids than the corresponding carboxylic acids.
  • Lower peroxy acids are volatile liquids, soluble in water.
  • Higher acids with greater than 7 carbons are solids and insoluble in water.
  • These compounds are highly unstable and can decompose violently on heating.
  • May react dangerously with organic matter and readily oxidizable compounds.
  • Among organic peroxides, peroxy acids are the most powerful oxidizing compounds.
  • The lower acids are also shock sensitive, but less than some organic peroxides.
  • Health hazard primarily due to their irritant actions.
    • Examples:
      • Peroxyacetic acid
      • Peroxybenzoic acid
      • Peroxyformic acid
 PHENOLS  
  • Phenols are a class of organic compounds containing hydroxyl groups attached to aromatic rings.
  • The hydroxyl group exhibits properties that are different from an alcoholic hydroxyl group.
  • Phenols are weakly acidic, forming metal salts on reactions with caustic alkalies.
  • In comparison, acid strengths of alcohols are negligibly small or several orders of magnitude lower than those of phenols.
  • In comparison with many other classes of organic compounds, phenols show relatively greater toxicity.
    • Examples:
      • Cresol
      • 2-Naphthol
      • Pentachlorophenol
      • Phenols
      • Resorcinol
 PHTHALATE ESTERS  
  • These are esters of Phthalic acid.
  • They are noncombustible liquids.
  • Some are EPA-listed priority pollutants.
  • The acute toxicity is very low.
  • High doses may produce somnolence, weight loss, dyspnea, and cyanosis.
  • The pure liquids are mild irritants to the skin.
  • These are relatively harmless and are among the least toxic organic industrial products.
    • Examples:
      • Dibutyl phthalate
      • Diethylhexyl Phthalate (DEHP)
Reference:
Patnaik, Pradyot, A Comprehensive Guide to the Hazardous Properties of Chemical Substances, Van Nostrand Reinhold, 1992.
   
 
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