TYPES OF CHEMICAL HAZARDS- UNDERSTANDING M.S.D.S. OF CHEMICALS

TYPES OF CHEMICAL HAZARDS- UNDERSTANDING M.S.D.S. OF CHEMICALS
(By Dr. K U Mistry)

People working in chemical factories and dwelling nearby are exposed to various types of chemical hazards. Inflammable, explosive, toxic, corrosive, reactive, radio active, oxidising, reducing, decomposing, compatible and hidden hazardous nature of chemicals pose material or property hazards. In process, chemical and physical change, chemical reaction, pressure, temperature, level, flow, quantity and other parameters create process hazards. The vessels and equipment in which the chemicals are stored, handled or processed, pose vessel hazards. The inadequate, defective, under designed or wrongly modified control devices or failure thereof cause control hazards. Fire or explosion cause fire hazards. Effluent disposal and gaseous emissions bring pollution and toxic hazards. Leaks, spills and splashes cause handling hazards. Absence, non-use or failure of fire fighting equipment, personal protective equipment, emergency control devices reveal accident and emergency hazards. All other unsafe working conditions and unsafe actions pose a variety of hazards that all need to be prevented and controlled. Many safety measures are available to deal with above hazards. Identification of contents, properties, hazards and quantity of chemicals, their content minimisation, proper storing, handling and packing; auto control, recording and warning devices for level, pressure, vacuum, temperature, flow, feed, speed, cooling, heating, stirring, discharge, contamination; remote control devices, proper ventilating, exhaust, scrubbing, neutralising, inactivating and incinerating devices; monitoring, measuring, recording, tripping, correcting and controlling system, fire fighting and personal protective equipment, emergency and disaster planning, controls and all engineering well designed process and plant layout and fully safe actions of work-people are utmost necessary to fight these hazards and to control over them. The basic steps in short are as follows : 1 Identification of Health (Toxic) Hazards : (a) Types of effects are - Allergy, Irritation, Oxygen deficiency (asphyxiation), Systemic poisoning (eg damage to liver, kidney, CNS, reproductive system etc.), Cancer, Damage to unborne foetus(teratogenesis), Genetic effects on future generations (mutagenesis), Dust effect (pneumoniosis). Some effects are acute (local or short term) and some are chronic (long term, delayed or after repeated exposures). (b) Factors creating effects are - Type of concentration of chemical, Combined effects of mixtures, Properties of the material including its toxicity, Work methods, Nature of exposure (short term, long term) Routes of entry (through nose, mouth or skin) and Individual susceptibility. 2 Identification of other hazards : (a) Fire and Explosion Hazards : Heat generation due to chemical reaction, Open flame, Radiant heat, Fricton, Spontaneous combustion, Electric current, Static electricity etc. (b) Fuel or Solvents - Low flashpoint and Low boiling point liquids, Gases and Solids (dusts, powders, lumps, crystals) (c) Atomic Radiation - Radioactive substances and Radiation processes (X-ray, NDT, Nuclear power plant etc.) 3. Preventive & Control Measures : (a) Six Basic Principles - · Elimination of substance or process. · Substitution of safer alternative. · Distance, Guard, Enclosure, Isolation, Shielding or Segregation of hazardous process. · Ventilation, general & local exhaust. · Personal Protective Equipment. · Personal hygiene. (b) Management Control - Identification, MSDS, Labelling, Safe storage, Safe Transfer procedure, Safe handling & use, Safe processes & operations, Safe disposal methods, Good housekeeping, Measurement & assessment (Monitoring), Medical examination, record and treatment (medical surveillance), Record-keeping of work exposure monitoring, environmental or air quality monitoring, medical and biological monitoring, Training & education to workers and Supervision including safety work permits and safe work methods. 4. Emergency Control Procedures : · Speedy Leak & Spill Control procedures. · Emergency shut-down procedure. · On site emergency plan. · Off site emergency plan. · Mutual aid arrangement with neighbouring industries. · Retainer ship for help at the time of emergency. · Regular rehearsal of emergency procedures (drill), updating and reviewing of the plan. MATERIAL (PROPERTY) HAZARDS AND CONTROL Make a list of all raw materials, products, by-products and intermediates. Identify them by their nature of hazard and risk potentials. Classify them as inflammable, explosive, toxic, corrosive, radioactive, reactive, oxidising, irritant, unstable, compressed gases, dust and others. Also note their hazardous properties viz. boiling point, flash point, LEL, UEL, LD, LC, TLV, MAC, IDLH, density, solubility etc., to understand the ill-effects of the chemical. Reference No. 1 to 4 given at the end of this chapter explain all such terms and give them for various chemicals. Reference No. 11 gives such hazardous properties of some selected chemicals. The chemicals may cause either physical hazards or health hazards. The physical hazards are caused due to dust, corrosive, explosive, flammable and reactive chemicals, compressed gases and oxidisers. The health hazards are caused due to toxic, irritant and carcinogenic chemicals. Carcinogenic causes cancer. Mutagenic causes inherited changes and teratogenic causes harm to unborn. Micro-organisms and radioactive chemicals also cause health hazards. The hazards are also classified as first and second degree hazards. The first degree hazards are caused by corrosive, flammable, explosive, toxic and oxidising chemicals, heat or ignition source, human error and failure of equipment etc. The second degree hazards injure life and property and include fire, explosion, toxic exposure, corrosive chemicals, collision, slipping, falling etc. Identification of Chemicals Identification of chemicals begins with the knowledge of basic chemistry. Refer Table No. 1 in Chapter 32 to identify first some commonly used elements and radicals. This will help to identify the chemicals. Chemicals are classified in different ways. For study (chemistry) point of view, they are broadly classified as inorganic and organic chemicals. Inorganic chemicals are subclassified as metals and non-metals. Out of 104 elements, 80 are metals and majority of them (except mercury) are solids, shining, reflecting, good conductor and forming reducing agents and basic hydroxides. In non-metals, more than half are gases and remaining are hard solid, non-shining, less reflective, bad conductor and forming oxidising agent and acidic hydroxides. Some examples are given below : Metals : Aluminium, Arsenic, Beryllium, Calcium, Chromium, Cobalt, Copper, Iron, Lead, Manganese, Mercury, Nickel, Radium, Sodium, Tin, Uranium, Zinc etc. Non-metals : Bromine, Chlorine, Fluorine, Iodine, Oxygen, Phosphorous, Sulphur etc. Organic chemicals include carbon compounds. They are subclassified as under - Aliphatic Compounds (without benzene-rings) : Hydrocarbons, Halogen derivatives of paraffin, Alcohol, Ethers, Aldehydes, Ketones, Carboxylic acids and their derivatives, organic compounds of Nitrogen and Sulphur, Carbohydrates, Alicyclic compounds etc. Aromatic Compounds (with benzene-rings) : Benzene and its derivatives, Aromatic amines, Diazo compounds, Dyes, Phenols, Aromatic alcohol, Aromatic aldehydes, Ketones and quinones and Aromatic carboxylic acids. Heterocyclic Compounds and Polymers (with other-rings) : Furan, Pyrrole, Thiophene, Pyridine, Quinoline, Isoquinoline, Alkaloids-coniine, nicotine, Drugs, Hormones, Vitamins, Enzymes and Polymers - Natural and Synthetic Rubber like neoprene, butadiene; synthetic fibres like nylon, orlon, vinyon, terylene, Synthetic plastics and resins like cellulose, formaldehyde, alkyd, vinyl, acrylate and polystyrene resins and silicones. Chemicals are also classified as under : 1. According to their Physical State i.e. solid, liquid or gases. Fine particles of solid like powder, dust, fumes and smoke are called particulate matter. Their suspension in air or gas also exists. Liquids are classified as acid, alkali, solvent, suspension, liquid mixture, aerosols etc. Gases are classified as inert (N2, CO2), reactive, toxic, irritant, corrosive etc. 2. Noxious Gases : · Irritant gases - Cl2, NH3, SO2, NO2, COCL2, Aldehydes etc. · Systemic poisons - C6H6, CS2, PH3, Stibine, Mn, Nickel carbonyl, Arsine, Halogenated hydrocarbons etc. · Simple asphyxiates - N2, CH4, CO2 etc. · Chemical asphyxiates - CO, H2S, HCN etc. 3. Dust (Particulate Matter) : · Causing plenumoconioses - Coal, Silica, Asbestos etc. · Causing Asthma - Cotton, Flour, TDI etc. · Causing allergy - fungal spores, bird fanciers, lung, bagassation etc. · Causing lung cancer - Chromium, Asbestos, Benzene etc. 4. Biological Agents and Diseases : · Virus Rickettisia - Psittacosis, rabbis etc. · Bacteria - Anthrax, Woolsorter's disease, Leptospirosis or Weal's disease, Brucellosis, Tetanus etc. · Fungi - Ringworm, Moniliasis etc. · Parasites - Hookworm · Plant products - Dermatitis due to mango tree and cashew seed processing. For details see the Schedule given under the Rules for manufacture, use, import, export and storage of hazardous micro-organism, genetically engineered organism or cells (Refer Part 2.34 of Chapter-28). Some physical, chemical or biological agents cause skin diseases (dermatitis) and alcoholism, sickness or accident may also cause health effects. The chemicals should be properly identified, classified and handled accordingly. Labelling on packages and containers is a basic requirement. For this purpose some major divisions are given below : Corrosive Chemicals : Amyl trichlorosilane, Anisoyl chloride, Antimony pentachloride, Antimony pentafluoride, Benzoyl chloride, Benzyl bromide, Benzyl chloride, Benzyl chloroformate, Boron trichloride, Bromine, Bromine pentafluoride, Bromine trifluoride, Caustic potash, Caustic soda, Chloroacetyl chloride, Chlorine trifluoride, Chlorosulphonic acid, Chromic acid solution, Diethyl dichlorosilane, Ethyl chloroformate, Formic acid, Fluorine, Hexafluorophosphoric acid, Hydrazine, Hydrobromic acid, Hydrochloric acid, Hydrofluoric acid, Methyl chloroformate, Nitric acid, Perchloric acid, Oxybromide, Oxychloride, Tribromide, Trichloride of phosphorous, Tetrachloride, Sodium aluminats, Spent sulphuric acid, Sulphur chloride (mono and di), Sulphuric chloride, Thionyl chloride, Titanium tetrachloride, Phenol etc. Oxidising Agent : Aluminium nitrate, Ammonium nitrate, Ammonium perchlorate, Ammonium permanganate, Barium chlorate, Barium nitrate, Barium perchlorate, Barium peroxide, Benzoyl peroxide, Nitrate peroxide, Permanganate of calcium, Chlorate and Magnesium chloride mixture, Chlorate of potash and soda, Chromic acid, Dimethyl hexane, Lead nitrate, Lithium peroxide, nitrate, perchlorate, Peroxide of magnesium, Potash permanganate, Permanganate of soda, Potassium bromate, nitrate, nitrite, perchlorate, permanganate and peroxide, Silver nitrate, chlorate, chlorite, permanganate, peroxide, and nitrite, Zinc ammonium nitrite, Zinc chlorate, Zinc permanganate, Zinc peroxide etc. Carcinogens : Asbestos, Acrolein, Aniline, Acrylonitrile, Alpha- Naphthylamine, Beta-Naphthylamine, Benzidine, Benzene, Benzyl chloride, Carbon tetrachloride, Chloroform, Chloropropane, Dioxin, Epichlorohydrin, Ethylene oxide, Formaldehyde, Perchloroethylene, Beta propiolacetone, Styrene, Tetrachloro ethane, Toluidine (ortho-meta), Toluenediamine, Trichloroethane, Trichloroethylene, Vinyl chloride, Pyridine, Phenol, 4-aminodiphenyl, N-nitrodiphenyl etc. Poisonous Chemicals : Aldrin mixture, Aniline, Arsenate of lead, Arsenic acid, Bromide, Chloride, Sulphide of arsenic, Calcium arsenate, Phenol, Dinitrochlorobenzol, Cyanide of potassium and sodium, Cyanogen gas, Cyclohexane, Dinitrophenol, Ethyldichloroarsine, Hexaethyl tetraphosphate, Hydrocyanic acid and its fumes, Mercuric acetate, Marcuric ammonium chloride and benzoate, Mercuric cyanide, bromide, oxide, Iodide, Methyl bromide, Methyl dichloroarsine, Mustard gas, Nickel cyanide, Nitrobenzol, Nitrogen peroxide, Phosgene, Thio phosgene, Zinc arsenate, MIC (methyl iso-cyanate), Carbon monoxide, Cadmium, DDT, Methanol, Phosphine and dangerous pesticides such as Parathion, Diazeomon, Tetraethyl pyrophosphate, Tetraethyl phosphate, Demeton, Scheadan, Methyl parathion, Cryolite, Pentachlorophenol. Dinitro-o-cresol, Endrin etc. Explosive Chemicals : Amyl acetate, Carbon dust, Aluminium dust, Wood saw dust, Hydrogen, Sodium metal, Sodium nitrate, Potassium nitrate, Ammonium nitrate, Benzoyl chloride, Nitro glycerine, Phosphorous trichloride, Titanium powder, Hexane, Trinitro toluene, Carbon disulphide, Ethylene oxide, Cellulose films etc. Solvents : Benzene, Acetone, Methanol, Ethanol, Toluene, Carbon tetrachloride, Methyl chloride, Methylene chloride, Ethyl acetate, Ethyl ether, Methyl bromide, Nitro propane, Propyl acetate, Spirit, Petrol, Carbon disulphide, Ethyl benzene, Methyl-propyl, Turpentine, Chloroform, Aniline, Benzyl chloride, Bromobenzene, Chlorobenzene, Ethyl benzene, Ethylamine, Formic acid, Heptane, Glycerol, Iso Propyl acetate, Methoxy benzene (anisole), Methyloleat, Naphthalene, Nitrobenzene, Oleic acid, Phenol, Styrene, Vinyl acetate, Xylene, Ether etc. Other Flammable Chemicals : Acetonitrile, Acrylonitrile, Aluminium triethyl, Amyl acetate, Amyl chloride, Amyl mercaptan, Amyl nitrate, Benzoyl peroxide, Butadiene, Calcium phosphide, Carbon disulphide, Carbon monoxide, Coal tar, Naphtha, Lacquer, Paint, Varnish, Diethyl aluminium chloride, Diethylamine, Dimethylamine, Ethyl aluminium dichloride, Ethyl chloride, Ethylene, Ethylene dichloride, Ethylene oxide, Ethyl nitrate, Ethyl nitrite, Heptane, Hexane, Iso octane, Liquefied Petroleum Gas (LPG), Lithium metal, Methane, Methyl acetone, Monoethylamine, Nickel carbonyl, Pentane, Petroleum naphtha, Phosphorous, Phosphorous anhydride, Photographic film, Sodium aluminium hydride, Sodium metal, Sodium methylate dry, Titanium metal powder, Vinyl chloride, Vinyl fluoride, X-ray film scrap etc. Reactive Chemicals : Acetic acid, Acetone, Acetylene, Sodium, Potassium, Lithium, Magnesium, Calcium, Aluminium powder, Anhydrous ammonia, Ammonium nitrate, Aniline, Bromine, Chlorates, Chromic acid, Chromium trioxide, Chlorine, Fluorine, Hydrocarbons (Benzene, Butane, Propane, Turpentine etc.), Hydrocyanic acid, Hydrofluoric acid (HF), Hydrogen peroxide, Hydrogen sulfide, Iodine, Mercury, Nitric acid (Conc.), Oxalic acid, Peroxides, Phosphorous (white), Potassium chlorate, Potassium permanganate, Silver, Sodium, Sodium nitrite, Sodium peroxide, Sulphuric acid etc. Pesticides - Insecticides : Pesticides : Aluminium phosphide, aldrin, acephate, antu, Butachlor, Chlordane, Chlorpyrifos, Cycocel, Cypermethrin, DDT, Dimethoate, Decamethrin, DDVP, Dieldrin, Endosulfan, EDB, Formothion, Fenitrothion, Fenvalerate, Hexachlorobenzene (BHC), Heptachlor, Glyphosphate, Glyphosine, Malathion, Monocrotophos, Mercuric acetate, MEMC, 2,4-D Phosphomidone, parathion, Permethrin, Phenthoate, Phenyl Mercuric acetate, Quinalphos, Zinc phosphide etc. Insecticides : Cupric sulfate, DDT, Leadarsenate, Liver of sulfur. Fungicides : Bordeaux mixture, Chlornil, Chloropicrin, Cyprus oxide, Mercurous chloride, Pentachlorophenol. Herbicides : Ammonium thiocynate NH4SCN Vermicides : Anisole. Alcohols : Allyl, ethyl, methyl, emyl, anisyl, benzyl, butyl, cetyl, citronellol, cyclohexanol, diols or glycols, lauryl, nerol etc. Refrigerant Gases : Carbon dioxide CO2, Ammonia NH3, Freon etc. Esters : Amyl acetate, arsenate, benzoate, borate, citrate, cynate, decanoate, glyceride, isocyanate, lipids, methacrylate, nitrite, oxalate, salicylate, stearate, succinate, sulfate, sulphonate, tertrate, thiocynate, thiosulphate, toluate, xanthates etc. Ethers : Anisole (methyl phenyl ether), benzyl cellulose, thio ethers, RSR, vinyl ether etc. Enzymes : Catalase, Deaminase, Dehydrogenase, Diastrate, Fermerit, hydrolases, lactose, oxidase, urease etc. Resins : Alkyd (glyptal), Allyl, Aminoplastic etc. Acids : Inorganic : Hydrochloric, hydrobromic, hydrofluoric, hydroiodic, nitric, sulphuric, nitrous, sulphurous, sulphonic, chlorosulphonic, boracic or boric, phosphoric, phosphorous, perchloric, arachidic, arsenic, ascorbic, aspartic, aspirin, hydrazoic, behenic or docosanoic, bromic, chloric, chloroplatinic, chlorous, chromic, iodic, manganic, metaphosphoric, perboric, permanganate, persulphuric etc. Organic : Acetic, acrylic, adipic, amino or carboxylic, alginic, uric, uncleic, succinic, barbituric, benzenesulphonic, benzoic, capric or decanoic, hexanoic, caprylic or octanoic, carbolic or phenol, carbonic, carboxylic, caro's or persulphuric, ricinoleic, chloroacetic, cinnamic, citric, crotonic or butenoic, cyanic, cyanuric or tricyanic, ethylene diamine tetraacetic acid (EDTA), fumaric, galic, gluconic, hexanoic, hydrodic, hydrobromic, hydrocyanic, hydrofluoric, hydrozy, hypoclorus, hypophosphorous, isophthalic, lactic, lauric, linolegic, meleic, malic, malonic, mandelic, methacrylic, molybdic, monobasic, necotinic, nucleic, octanoic, oleic, oleum, osmic, oxolic, oxydiacetic, oxydiethanoic, palmitic, pantothenic, pelargonic, phosphinic, phthalic, picric, pyrophosphoric, pyrosulphuric, pyruvic, racemic, ribonucleic, ricinoleic salicylic, sebacic, selenic, silicic, stannic, stearic, suberic, sulphanilic, fannic, tartaric, thiocyanic, thiosulphuric, tribasic, trihydroxybenzoic, uric, vanadic etc. Partial List of Incompatible Chemicals (Reactive Hazards) Substance in the left hand column should be stored and handled so that they cannot possibly accidentally contact corresponding substance in the right hand column under uncontrolled condition because violent reactions may occur. Acetic acid Chromic acid, nitric acid, hydroxyl-containing compound, ethylene, glycol, perchloric acid, peroxide and permanganates. Acetone Concentrated nitric & sulphuric acid mixtures Acetylene Chlorine, bromine, copper, silver, fluorine Alkali and alkaline earth metals such as sodium, potassium, lithium, magnesium, calcium, powdered aluminium Carbon dioxide, carbon tetrachloride and other chlorinated hydrocarbons (also prohibit water foam and dry chemical on fires involving these metals. Dry sand should be available). Ammonia (anhyd.) Mercury, chlorine, calcium hypochlorite, iodine, bromine and hydrogen fluoride Ammonium nitrate Acids, metal powders, flammable liquids, chlorites, nitrites, sulphur, finely divided organics or combustibles. Aniline Nitric acid, hydrogen peroxide Bromine Ammonia, acetylene, butadiene, butane and other petroleum gases, sodium carbide, turpentine, benzene and finely divided metals Calcium oxide Water Carbon, activated Calcium hypochlorite Chlorates Ammonium salts, acids, metal powder, sulphur, finely divided organic or combustibles Chromic acid and Chromium trioxide Acetic acid, naphthalene, champhor, glycerol, turpentine, alcohol and other flammable, Chlorine Ammonia, acetylene, butadiene, butane and other petroleum gases, hydrogen, Sodium carbide, turpentine, benzene and finely divided metals. Chlorine dioxide Ammonia, methane, phosphine and Hydrogen sulphide Copper Acetylene, Hydrogen peroxide Fluorine Isolates from everything Hydrazine Hydrogen peroxide, Nitric acid, any other oxidant Hydrocarbons (benzene, butane, propane, gasoline, turpentine) Fluorine, chlorine, bromine, Chromic acid, and peroxide Hydrocyanic acid Nitric acid, alkalis Hydrofluoric acid Ammonia Hydrogen peroxide Copper, chromium, iron, most metals or their salts, any inflammable liquid, combustible materials, aniline, nitro methane Hydrogen sulphide Fuming Nitric acid, oxidising gases Iodine Acetylene, ammonia Mercury Acetylene, ammonia, fulminic acid Nitric acid (Conc.) Acetic acid, acetone, alcohol, aniline, Chromic acid, Hydrocyanic acid, Hydrogen sulphide, flammable gases and nitratable substance 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 Phosphorous (white) Air, oxygen Potassium chlorate Acids Potassium perchlorate Acids Potassium permanganate Glycerol, Ethylene glycol, benzaldehyde, Sulphuric acid Silver Acetylene, Oxalic acid, Tartaric acid, Ammonium compounds Sodium nitrite Ammonium nitrite and other Ammonium salts Sodium peroxide Any oxidisable substance such as ethanol, methanol, glacial acetic acid, Acetic anhydride, Benzaldehyde, Carbon disulphide, Glycerol, Ethylene glycol, Ethyl acetate, Methyl acetate Sulphuric acid Chlorate, perchlorates, permanganates Partial List of Incompatible Chemicals (Toxic Hazards) Substances in the left hand column should be stored and handled so that they cannot possibly accidentally contact corresponding substances in the centre column, because toxic materials (right hand column) would be produced. Arsenic material Any reducing agent Arsine Azides Acids Hydrogen azide Cyanides Acids Hydrogen cyanide Hypochlorites Acids Chlorine or hypochlorus acids Nitrates Sulphuric acids Nitrogen dioxide Nitric acids Copper, brass, any heavy metal Nitrogen dioxide Nitrites Acids Nitrous fumes Phosphorous Caustic alkalis Phosphine Selenides Reducing agents Hydrogen selenide Sulphides Acid Hydrogen sulphide Tellurides Reducing agents Hydrogen telluride Material Safety Data Sheet (MSDS) For proper identification of material hazards a material safety data sheet should be prepared and supplied with each chemical so that its safety precautions can be well understood. A specimen form is given below : 1. Chemical Identity : 1. Name of the Chemical 2. Formula 3. Synonyms 4. Trade name 5. Chemical Classification 6. Regulated identification 7. Shipping Name, Codes/Label 8. CAS No. 9. UN No. 10. ADR No. 11. Hazchem (EAC)No. 12. Hazardous Waste ID No. 13. Hazardous Ingredients and CAS No. 2. Physical & Chemical Data : 1. Appearance, State, Odour etc. 2. Specific gravity (Water = 1) 3. Vapour density (air = 1) 4. Boiling point 5. Melting/Freezing point 6. Vapour pressure 7. Solubility in water 8. Scrubbing/Neutralising/Inactivating media 9. pH 10. Others 3. Fire & Explosion Hazard Data : 1. Flash point 2. Autoignition Temperature 3. Flammable limits : LEL/UEL 4. TDG Flammability 5. Explosion Sensitivity to Impact 6. Explosion Sensitivity to static electricity 7. Explosive material 8. Flammable material 9. Combustible and flammable Liquid 10. Pyrophoric material 11. Hazardous Combustion products 12. Hazardous Polymerisation 13. Corrosive material 14. Organic Peroxide 15. Oxidiser 16. Others 4. Reactivity Data : 1. Chemical stability 2. Incompatibility (Materials to avoid) 3. Reactivity 4. Hazardous reaction products 5. Health Hazard Data : 1. TLV (ACGIH) 2. STEL/SET 3. LC50 or LD50 4. Odour threshold 5. Carcinogen ? Poison ? Liberates poisonous fume ? 6. Routes of entry 7. Body parts that may be affected 8. Effects of exposure and symptoms 9. Emergency and first aid treatment 10. Engineering controls necessary for safe handling. 11. NFPA Hazard signals 12. Special Health hazards. 6. Preventive Measures : 1. Ventilation required and type 2. Personal protective equipment required and type 3. Handling and storage precautions 7. Emergency and First-aid Measure : 1. Steps to be taken in case material is released or spilled. 2. Waste disposal method for solid, liquid and gaseous waste. 3. Fire, extinguishing media, special procedures and Unusual hazards. 4. Exposure - First-aid measures, Antidotes, Dosages. 8. Additional Information / References : 9. Manufacturer / Supplier's Data : 1. Name of Firm 2. Mailing address 3. Telephone/Telex/Fax Nos. 4. Telegraphic address 5. Contact person in emergency 6. Local bodies involved 7. Standard packing 8. Tremcard Details / Ref. 9. Other 10. Disclaimer : 7.3 Interpretation and use of MSDS For the better understanding and use of the Material Safety Data Sheet, some terms are explained below : 1. Formula (Chemical) : It is a symbolic representation of a chemical entity or relationship between elements, molecule and atoms. e.g. H2 one molecule of hydrogen, 2H2SO4 two molecules of sulphuric acid, H2O one molecule of water wherein there are two atoms of hydrogen and one atom of oxygen. C6H6 benzene contains six atoms of carbons and six atoms of hydrogen in one molecule, group or ion. Thus by formula we can know the hazardous ingredient of a chemical. 2. Synonym : Indicates alternate name of a material. e.g. Dimethyl ketone or 2-Propanone for Acetone. 3. Trade Name : Commercial name of the product. 4. Chemical Classification : General classification is organic or inorganic. Hazardwise classification can be flammable, explosive, toxic or poisonous, corrosive, reactive, infectious, oxidising, radioactive etc. 5. CAS No. : It is Chemical Abstracts Service number to provide a single unique identifier with naming the chemical. e.g. CAS No. for acetic acid is 64-19-7. It does not indicate the hazards of a material. 6. UN No. : It is United Nations four digit number assigned to potentially hazardous material (e.g. Ammonia UN No. 1005) or Class of material (e.g. corrosive liquids UN No. 1760). These numbers are internationally recognised and used by emergency response personnel (including ire fighters) to identify material during transport emergencies. UN, Hazchem, NA and PIN numbers have the same uses. 7. Hazchem (EAC) No. : Hazchem (hazardous chemical) Code or EAC (Emergency Action Code) is an emergency code confirmed by the Health & Safety Executive, UK. It consists of a number (1 to 4) followed by one or two letters and signifies type of a fire extinguisher required, type of personal protective equipment required, whether the spillage should be contained or diluted with water, whether the material is reactive and whether evacuation of the surrounding area necessary. Hazchem No. of Sodium cyanide is 4X and that of Vinyl chloride is 2WE. 8. ADR No. : It is an Agreement concerning carriage of Dangerous goods by Road. This European agreement was arrived at Geneva by 19 European countries for the safety of international transport by road. It deals with the classification of hazardous substances, their packaging, loading and unloading, transportation and its equipment. It gives hazard identification numbers like UN hazard class number. Their comparison is given below. Classification of Dangerous Goods by UN Number ADR Number 1 Explosives. 2 Emission of gas 2 Gases- Compressed, due to pressure or liquefied, dissolved due to chemical under pressure or reaction. deeply refrigerated. 3 Flammability of 3 Flammable liquids. liquids (vapours) 4 Flammable solids. and gases. 5 Oxidising 4 Flammability of substances or gases. Organic Peroxides. 5 Oxidising (fire 6 Poisonous (Toxic) or intensifying) Infectious effect. substances. 6 Toxicity. 7 Radioactive 8 Corrosivity. substances. 9 Risk of sponta- 8 Corrosive neous violent substances. reaction. 9 Miscellaneous dangerous substances. Doubling (repeating) of an ADR digit indicates increase of that particular hazard. Prefix 'X' indicates that the substance can dangerously react with water. As an example ADR HIN (Hazard Identification No.) of Benzene is 33 (UN No. is 1114 and Hazchem No. is 3WE). 9. Appearance, State, Odour : Appearance includes colour. State means physical state - solid, liquid or gas. Odour indicates smell. Odour threshold is that minimum level (ppm) where the odour will start. If odour threshold is lower than the permissible safe limit (e.g. TLV, STEL, IDLH or LC), the odour indicates the presence of gas and some safety margin is available to run away or to take precautionary step. But if it is higher, the gas becomes toxic or hazardous before its odour starts and this condition is risky. In that event a reliable gas detector is useful. Sometimes odour is added to detect the gas leakage e.g. addition of mercaptan in domestic LPG. Ability to detect odour may vary from person to person and may mislead if the other odorous materials are simultaneously present. 10. Specific Gravity (water = 1) : It is the ratio of the density of a material to the density of water (which is 1 g/cc). Lighter material (Sp. gr. <1, e.g. benzene 0.88) will float and heavier material (Sp. gr. >1, e.g. sulphuric acid 1.84) will sink. This information is useful for spill or fire control. 11. Vapour Density (air = 1) : It is the vapour weight per unit volume. In MSDS it is given as the ratio of the density of a gas or vapour to the density of air. The air density is 1.293 gm/l, but here it is considered as 1 for easy comparison of gases. Lighter gases (Vd<1, e.g. ammonia 0.59) will go up (rise) in the air and heavier gases (Vd>1, e.g. chlorine 2.49) will come down on the bottom. This information is useful for ventilation design and evacuation (emergency) activity. 12. Boiling Point : It is that temperature at which the material changes from a liquid to a gas. Below this point the liquid can evaporate to form vapour but at the BP the change from liquid to vapour is faster. This increases the vapour concentration and its pressure. This condition poses higher risk of fire, explosion or toxicity. 13. Thermal Decomposition Products : If the material decomposes (breaks down) without boiling, the temperature at which it decomposes is given with the word 'dec'. Some of the decomposition products are hazardous. The thermal decomposition products may be quite different from the chemicals formed by burning the same material (hazardous combustion products). Information regarding thermal decomposition is useful to design ventilation system where a material may be heated. 14. Hazardous Decomposition Products : They are formed when a material decomposes (without heating) because it is unstable or reacts with common material like water or air (oxygen). This information is useful to design storage and handling procedures. For example, phosgene decomposes into corrosive and toxic fumes of HCl and CO because of heating or coming into contact of water or steam. Here HCl and CO are hazardous decomposition products. 15. Hazardous Combustion Products : These are the chemicals which are formed when a material burns. They may be toxic, flammable, smoke, carbon particles or other hazards. Their amount varies according to temperature and oxygen (air) available. They may be different from the thermal decomposition products. This information is useful to decide the fire fighting material and procedure. 16. Melting Point : It is that temperature at which a solid material melts and becomes a liquid. This information is useful for storage and handling purpose. A melted material may distort a container. 17. Freezing Point : It is that temperature at which a liquid material freezes and becomes solid. This information is useful for storage and handling purpose. A frozen material may burst a container. 18. Vapour Pressure : It is the pressure (mm of Hg) upon atmosphere of the vapour of a material at a fixed temperature (e.g. 20 0C). Higher vapour pressure indicates higher concentration and therefore higher hazard due to fire or inhalation. 19. Solubility : It is the ability of a material to dissolve in water or another liquid (solvent). It may be expressed as a ratio or described by words like insoluble, very soluble, sparingly soluble or miscible. This information is useful to decide a scrubbing media, spill control or fire fighting material and procedure. Such solvent should not be hazardous. 20. Scrubbing neutralising or inactivating media : These are those materials (liquids) which dissolve or react with the hazardous material (gas, liquid or solid) to diminish its hazardous exposure e.g. caustic, lime, water etc. If this is not possible, proper absorbent may be used e.g. sand, sponge rubber etc. See Part 8.5 and Table 18.6 of this Chapter and Table-17 of Chapter-32 for scrubbers. 21. pH : It is a measure of the acidity or alkalinity (basicity) of a material when dissolved in water. It is expressed in a scale from 0 to 14 as under : pH 0 - 2 Strong acidic 3 - 5 Weak acidic 6 - 8 Neutral 9 - 11 Weak basic 12 - 14 Strong basic This information is useful to select a neutralising material for scrubbing or effluent treatment or spill control. 22. Flash Point : It is the lowest temperature at which a material gives off enough vapour near its surface to form a flammable air vapour (gas) mixture so that it can be ignited if a spark is available. The lower flesh point indicates higher hazard as it can cause fire at a lower temperature. It is expressed as Closed Cup (CC) or Open Cup (OC). CC value is slightly less than the OC value. 23. Autoignition Temperature : It is the lowest temperature at which a material begins to burn in air without any contact of spark or flame. During heating if the material decomposes, the decomposed chemical may auto-ignite at some other temperature. Different test methods give different auto-ignition temperatures for the same material. Therefore this value is an estimate. The material should be stored, processed or handled well below its auto-ignition temperature to avoid the risk of self fire or explosion. Substances liable to spontaneous combustion are those liable to spontaneous heating under normal conditions or to heating up on contact with air and being then liable to catch fire. 24. Flammable or Explosive Limits (LEL/UEL) : The lowest concentration (percentage in air) of gas or vapour which will burn or explode if ignited, is called the Lower Explosive (or Flammable) Limit i.e. LEL or LFL. The upper concentration (percentage in air) of gas or vapour which will burn or explode if ignited, is called the Upper Explosive (or Flammable) Limit i.e. UEL or UFL. The range between LEL and UEL is called the Explosive (or Flammable) Range. The fire or explosion risk lies within this range but not out of it. Below LEL the gas-air mixture is too lean to ignite and above UEL it is too rich to ignite. However the concentration above UEL should be considered dangerous as due to entrainment of fresh air, it may be diluted and enter the explosive range. Similarly after LEL if gas discharge is continued in the same air, it can also enter the explosive range. Thus explosive range can be reached depending on flow of gas and air affecting their concentration. Air and gas temperature may also affect. Therefore the range should be considered as approximate values. For gas/vapour it is expressed in % of air (1% = 10,000 ppm) and for powder in gm/m3 of air. This information is useful to avoid the conditions leading to the explosive range and to ascertain it before allowing any person to enter any vessel or confined space where such air-gas mixture is suspected. Explosimeters are available to detect this range. Detection should be of percentage of LEL and all safety devices (alarms, controls, trips etc.) should operate well below the LEL. Fire hazard should be prevented at pre-determined percentage of LEL. 25. TDG Flammability : Transport of Dangerous Goods (TDG) classifies the materials according to their flammability as under - 2.1 Flammable gas. 3 Flammable liquid (Subclasses 3.1, 3.2 and 3.3 based on flash point). 4.1 Flammable solid. 4.2 Spontaneously combustible material. 4.3 Material which gives off a flammable gas on contact with water. 26. Explosion Data (Sensitivity) : It gives explosive properties of a material e.g. low, moderate or high. It gives two types of sensitivity : Explosion Sensitivity to Impact - It indicates whether or not the material will burn or explode on shock or friction, and Explosion Sensitivity to Static Electricity - It indicates how readily the material can be ignited by an electric spark or static discharge. 27. Explosive Material : An explosive material is that material which can explode on impact or by electric spark. Schedule-1 of Manufacture, Storage and Import of Hazardous Chemicals Rules, 1989 defines 'Explosives' as those chemicals which explode under the effect of flame, heat or photo-chemical conditions or which are more sensitive to shocks or friction than dinitrobenzene (old definition) or pyrotechnic substance (firework) or which is capable of producing gas at such temperature, pressure and speed to cause damage to surroundings or exothermic reaction by heat, light, sound, gas, smoke or their combination (new definition). 28. Combustible and Flammable Material : Flammable solid, liquid or gas which can catch fire and burn rapidly or explosively are flammable materials. The terms combustible and flammable both indicates the ability of a material to burn. Any material that will burn at any temperature is combustible by definition. Flammable are a special group of combustible materials that ignite easily and burn rapidly. For example, NaCl, CCl4 and CO2 are non-combustible while sugar, cellulose and ammonia are combustible but non-flammable. The more readily ignition occurs, the more flammable the material, less easily ignited materials are said to be combustible, but the line of demarcation is difficult to decide. Normally combustible liquids are classified as those whose flash point is greater than 37.70C (100 0F). Flammable or Inflammable liquids are classified under MSIHC Rules as (1) Extremely flammable - having FP<230C and BP<350C (2) Very highly flammable liquids - having FP<230C and BP>350C (3) Highly flammable - having FP between 230C and 600C and (4) Flammable - having flash point between 600C and 900C. Thus liquids having flash point between 37.70C to 900C can be called combustible as well as flammable, while those having flash point greater than 900C should be called combustible. Flammable liquids are extremely hazardous, as they give off vapours at low temperature and these vapours by travelling to a source of ignition can cause flash back to the flammable liquid. It is difficult to extinguish a burning flammable liquid with water because water may not be able to cool the liquid below its flash point. Flammable gases (normally boiling point < 20 0C) are equally hazardous as flammable vapours as explained above. Confined flammable gases are most dangerous. Flammable gases are also defined as those which at 200C and at standard pressure of 101.3 KPa, have LEL 13% or less or a flammable range of 12% or more regardless of the LEL. Flammable solids can be ignited due to external heat, flame, process heating by interaction with water or other substances. Flammable solids are of various types (1) Dusts or fine powders e.g. cellulose, flour etc. (2) Spontaneously ignitable at low temperature e.g. yellow phosphorous (3) Those in which internal heat is built-up by microbial or other degradation activity e.g. fish meal, wet cellulosic material (4) Films, fibres and fabrics of low-ignition point materials. Flammable solids are readily combustible or may cause or contribute to fire through friction or which are liable to undergo a strong exothermic reaction. 29. Corrosive Material : It can attack (corrode) metals or human tissues such as skin or eyes. Structure or metal container may become weak and eventually collapse or leak. Skin, eyes or other body parts can be badly affected (burning) by corrosive materials. Acids, halogen gases, chlorides, caustic, phenol etc. are corrosive. 30. Hazardous Polymerisation : A polymer is a natural or man-made material formed by combining units called monomers, into long chains. e.g. styrene is the monomer for polystyrene. Polymerisation is the process of forming a polymer by combining monomers into long chains. Uncontrolled polymerisation can be hazardous, as it can cause heat, pressure or explosion. Some chemicals can polymerise on their own without warming, others upon contact with water, air or common chemicals. Vinyl chloride rapidly polymerises in presence of light, air or heat. Therefore polymerising conditions should be controlled properly. Inhibitors(negative catalysts or compounds that retard or stop an undesired chemical reaction such as polymerisation, oxidation, corrosion etc.) are normally added to products to reduce or eliminate the possibility of hazardous polymerisation. 31. Pyrophoric Material : Any liquid or solid that will ignite spontaneously in air at about 54.4 0C (130 0F). Titanium dichloride and phosphorous are examples of pyrophoric solids, tributylaluminium and related compounds are pyrophoric liquids. Sodium, butyllithium and lithium hydride are spontaneously flammable in moist air as they react exothermically with water. Such materials must be stored in inert gas or under kerosene. Some alloys (barium, misch metal) are called pyrophoric because they spark when slight friction is applied. Pyrotechnic materials mean fireworks. Catalysts of pyrophoric material which can burn in normal air, are replaced in the atmosphere of nitrogen blanketing. The workers have to wear self-breathing apparatus while doing such job, because in the atmosphere of about 90% nitrogen, oxygen is insufficient for breathing. 32. Oxidiser and Peroxide : It is a compound that spontaneously evolves oxygen either at room temperature or under slight heating. Oxidisers include peroxides, chlorates, perchlorates, nitrates and permanganates. These can react vigorously at ambient temperatures when stored near or in contact with reducing materials (that will remove oxygen or add hydrogen) such as cellulosic and other organic compounds. Storage areas should be well ventilated and kept as cool as possible. Peroxides release atomic (nascent) oxygen readily. They pose fire hazards in contact with combustible materials, especially under high temperature conditions. They are used as oxidising agents, bleaching agents and initiators of polymerisation. Oxidizing substances are not necessarily combustible in themselves but by giving oxygen they contribute to combustion of other materials. Organic Peroxides contain bivalent 0-0-structure, are thermally unstable and may undergo exothermic self-accelerating decomposition. 33. Chemical Stability : A stable compound does not easily decompose or react readily. Chemical stability is the ability of a material to remain unchanged in the presence of heat, moisture or air. An unstable compound may decompose, polymerise, burn or explode under normal environmental conditions. Special precautions are required to store or handle unstable materials. For examples, CS2 decomposes in light and burns due to heat, spark, flame or friction and gives off toxic fumes of SOx. Caprolectum liberates NOx fumes due to heating. TNT explodes due to heavy shock or by heating. Thus conditions disturbing stability must be known. 34. Incompatibility : Compatibility means the ability of two or more materials to exist in close and permanent association indefinitely. Liquids and solids are compatible if the solid is soluble in the liquid. Water is compatible with alcohol (because it is miscible) but not with gasoline (e.g. petrol). Incompatibility means disability to co-exist permanently. Therefore incompatible materials should not be stored or kept together. For example, toluene reacts violently with some acids, plastic or rubber, therefore, these substances should be kept away. Incompatible materials can cause a fire, explosion, toxic release, violent reaction, polymerisation or destroy the structure or function of a product. This information is useful for storage and handling purposes. 35. Reactivity : Two or more chemicals can react with each other and give reaction products. e.g. 2H2 + O2 = 2H2O. A single chemical can react with air or water (which are also chemicals) and give the product. e.g. phosphorous burns in air and gives its oxides (P2O3, P2O5), sulphur burns and gives SO2 etc. Reactions are exothermic when they evolve heat and are endothermic when they need heat to maintain them. A reversible reaction is one in which the reaction product is unstable and goes back to the original substance spontaneously. In MSDS we are concerned with the hazardous reaction or reactive material which can cause fire, explosion, toxic release or violent reaction with air, water or common chemicals or under environmental conditions. Phosphorous, CS2, Sodium metal, acids (reactive with metals) etc. are known for their reactivity. This information is useful for storage, handling and process safety purposes. 36. Hazardous Reaction Products : These must be known for the safety of process, workers and environment. Here products are more important than the reaction because of their hazardous nature. e.g. Chlorine reacts with alcohol and forms explosive alkyl hypochlorite. If toxic fumes are to be generated, scrubbers are required, if flammable vapours are generated, inert gas blanketing is required and earthing of the vessel also becomes necessary. If reaction products are highly poisonous like NaCN, HCN etc., they are to be handled in a closed system. 37. Health Hazard Data : For TLV, STEL, IDLH, LD/LC etc. see Part 6.8, for routes of entry see Part 6.6, for effects of exposure see Part 6.7, for engineering controls see Part 6.12.2 and for health hazards see Part 6.1, all of Chapter-24. For emergency and first aid treatment and antidotes see Chapter-26, for fire and NFPA (National Fire Protection Association of USA) Code see Part 4.4 of Chapter-13, for ventilation see Chapter 10 and for personal protective equipment see Chapter-25. TLV and STEL are given in 2nd Schedule of the Factories Act. LD50 and LC50 are given in 1st Schedule of the MSIHC Rules for the purpose of major accident hazard. LD50 for insecticides are given in Rule 19 of the Insecticide Rules for labelling purpose. Lower these values, higher the toxicity. LD50 up to 200 mg/kg and LC50 up to 10 mg/l can cause major hazard. By local exhaust ventilation toxic gas, dust or vapour must be captured and effective PPE must be worn by the workers. Above STEL, SBA is desirable. 38. Tremcard : Transport Emergency Cards are to be given to the drivers carrying dangerous goods for emergency information which may be needed at any time during journey. The cards contain short information on nature of chemical, hazards involved, protective devices, emergency action for fire, spillage, leakage, first-aid etc.

• Directorate Industrial Safety and Health is a part of Labour and Employment Department, Govt. of Gujarat. Directorate Industrial Safety and Health, Govt. of Gujarat. previously was known as Factory Inspectorate, but after declaration of new designations for Factory Inspectors by state govt; this administration is now Directorate Industrial Safety and Health. It is functioning under direct control of Director Industrial Safety and Health, Gujarat State. For efficient administration and effective control, state is divided in to four administrative regions namely Ahmedabad , Vadodara, Surat and Rajkot. These regions are under control of Jt. Director Industrial Safety and Health for relevant region.The Directorate Industrial Safety and Health looks after the implementation of following statues

• The Factories Act 1948 and Gujarat Factories Rules, 1963
• The Environment Protection Act, 1986
• The Manufacture, Storage and Import of Hazardous Chemical Rules, 1989
• Chemical Accidents (Emergency Planning, Preparedness and Response ) Rules, 1996
• The Building and Other Construction Workers (Regulation of Employment and
   Condition of Service) Act, 1996
• Gujarat Building and Other Construction Workers (Regulation of Employment and
  Condition of Service) Rules-2003
• The Payment of Wages Act, 1936 and Rules there under
• The Maternity Benefit Act, 1961 and Rules there under
• The Gujarat Physically Handicapped Persons (Employment in Factories) Act, 1982
• The Gujarat Payment of Unemployment Allowance to workmen (In Factories) Act,
   1981
• The Cotton Ginning and Pressing Factories Act, 1925

The history of Factories Act is more than 100 years old. First time the Indian Factories Act was enacted in 1881.After independence, 'The Factories Act, 1948' was made applicable in the country mainly to regulate health, safety, welfare and working conditions of Industrial workers. It has been amended from time to time, but the major amendments were enacted in 1976 and in 1987, wherein emphasis has been laid on safety in general and chemical safety in particular. To strengthen safety in chemical factories, Government of Gujarat amended the 'Gujarat Factories Rules, 1963' in February 1995.

The departmental Hierarchy is Director Industrial Safety and Health > Joint Director Industrial Safety and Health >Deputy Director Industrial Safety and Health > Assistant Director Industrial Safety and Health > Industrial Safety and Health Officer
To look after welfare of female workers, Lady Inspector of Factories has also been appointed under the Factories Act, 1948.

All the inspecting officers have been declared as Assistant Public Prosecutors for purpose of Factories Act.The Directorate Industrial Safety and Health, Gujarat State has also been declared authority under certain section of Environment Protection Act, 1986 and Manufacture, Storage, Import of Hazardous Chemicals, Rules, 1989, as amended in 1994.

Under Environment Protection Act, 1986, the Government of India has framed chemical Accidents (Emergency Planning, Preparedness and response) Rules, 1996, where the Inspector of factories performs the duties as member secretary of various crisis groups constituted under these rules through out the state.

The Directorate Industrial Safety and Health officers have also been appointed as inspectors under The Building and Other Construction Workers (Regulation of Employment and Condition of Service) Act, 1996.

Construction sector has huge employment and the newly given responsibility is a real big challenge for the wing. Implementation of the new legislation is recently started.

The Directorate Industrial Safety and Health officers have also been appointed as inspectors under the Payment of Wages Act, 1936, so far as the factories registered under the Factories Act, 1948 are concerned. For effective implementation of the Act, Payment of Wages Inspector is also appointed.

The officers of this wing have also been notified as Inspectors under Maternity Benefit Act, 1961.

The Government of Gujarat has enacted Gujarat physically Handicapped persons (Employment in Factories) Act, 1982. Under this legislation all Inspecting officers under DISH have been appointed as Inspector for implementation of this Act.

The Government of Gujarat has also enacted "The Gujarat Payment of Unemployment Allowances to Workmen (in Factories) Act, 1981". The employer is required to pay 50% wages to workers in the event of power-cut, if he is unable to provide alternative employment to workers within 8 Kms form the normal working place provided that the power cut is notified by Government. This wing also looks after the implementation of this Act.

The Directorate Industrial Safety and Health implements technical in nature, the officers appointed are mostly engineers, qualified in various disciplines of engineering. Looking to major concentration of chemical factories in the state, the Directorate Industrial Safety and Health has constituted a multi-disciplinary specialist cell in each region headed by Joint Director Industrial Safety and Health. Moreover one Assistant Director Industrial Safety and Health (chemical) has been appointed for assisting and advising Chief Inspectors of Factories about hazards and safety in chemical factories.

To assist legal matters, Law officers have been appointed in Ahmedabad and Vadodara Regions.To measure and monitor the ill effects of chemicals, cotton dust, Asbestos dust and Silica dust etc., Industrial Hygiene Laboratory has been established under the Chief Inspector of Factories. It is headed by Dy. Director of occupational health and consists of Medical Inspectors of Factories, Certifying Surgeons and other technical staff.