Pengkelasan dan perlabelan Bahan kimia KULIAH 2: Chemical Chemical is defined as a is a substance that is produced or used in a process involving

g changes to atoms or molecules The OSHA definition of chemical under the Hazard Communication Standard 29 CFR 1910.1200 "element, chemical compound or mixture of elements and/or compounds BLEVE (Boiling Liquid Expanding Vapor Explosion) IDLH = Immediately Dangerous to Life or Health A substance - a form of matter that has a definite (constant) composition and distinct properties. Substances differ from one another in composition and identified by their appearance, smell, taste and other properties e.g sodium chloride, water, ammonia, table sugar , gold, and oxygen Mixtures - a combination of two or more substances in which the substances retain their distinct identities. Mixtures do not have constant composition. e. g air, soft drinks, milk and cement Mixtures are either homogenous or heterogeneous e. g Homogenous mixture : water and methanol, Heterogeneous mixture : sugar and sand. Compound - a substance composed of atoms of two or more elements chemically united in fixed proportions e.g. a water molecule is a combination of two hydrogen atoms and one oxygen atom, a glucose molecule is made up of carbon, hydrogen and oxygen Element - a substance that cannot be separated into simpler substances by chemical means. To date , 113 elements have positively identified. e.g Hydrogen, sodium, uranium The matters are identified by their properties & composition. There are 2 categories of properties Physical properties The properties that can be measured and observed without changing or identity of a substance e.g. melting point, boiling point, vapor pressure, etc Chemical properties the properties that occur due to a chemical changes electron orbital changes e.g hydrogen gas burns in oxygen gas to form water. (H2 + O2 -> H2O) Factors affecting a chemical reaction 1. Phases (Gas, liquid or solid) 2. Temperature 3. Pressure 4. Catalyst Factors lead to chemical hazard 1. How chemicals get into the body 2. Their physical and chemical properties 3. How dangerous chemicals are, 4. Duration of exposure 5. The personal characteristics of the exposed individual : age, sex, health status and susceptibility to certain chemical Pengkelasan Bahan Kimia CPL 1997 and Guidelines for the classification Hazardous Chemicals (Classification, Packaging and Labeling of Hazardous Chemicals) Regulations 1997 [P.U. (A) 143]) DOT (Department of Transport) NFPA(National Fire Protection Agency) ANSI (American National Standard Institute) HMNIG(Hazardous Materials Identification Guide) Chemical companies

CPL 1997 and Guidelines for the classification Hazardous Chemicals (Classification, Packaging and Labeling of Hazardous Chemicals) Regulations 1997 [P.U. (A) 143]) Part A of Schedule 1 Physicochemical properties Explosive Oxidizing Extremely flammable Highly flammable Flammable Part B of Schedule I Health Effects properties Very toxic, toxic, harmful, corrosive, irritant, carcinogenic, Teratogenic mutagenic.

1. 2. 3. 4. 5.

1. 2. 3. 4. 5. 6. 7. 8.

DOT (Department of Transport) Classifications of hazardous materials 1. Class 1 Explosives; Divided in to 6 division Explosive materials are chemicals that cause a sudden, almost instantaneous release of large or small amounts of pressure, gas, and heat when subjected to sudden shock, pressure, or high temperature. Some substances, under certain conditions of shock, temperature, or chemical reaction, can explode violently. Such explosions present many hazards to laboratory personnel. Flying glass can seriously lacerate skin. Fires can result from burning gases. Corrosive or toxic substances can be liberated. 1.1 1.2 1.3 1.4 1.5 1.6 2. Class 2; Gases 2.1 2.2 2.3 Mass explosion hazard Projectile hazard Minor blast/projectile/fire Minor blast Insensitive explosives Very insensitive explosives Flammable gases; ex Acetylene, Vinyl chloride Non flammable compressed gases; ex Oxygen, Carbon dioxide, Nitrogen Poisonous gases; ex Phosgene, Methyl Mercaptan

3.

Class 3; Flammable and Combustible Liquids Gases 3.1 Flammable flash point below 141F (60 C) 3.2 Combustible flash point 141-200F (60 93 C) Flammability Flammability is a measure of how easily a gas, liquid, or solid will ignite and how quickly the flame, once started, will spread. The more readily ignition occurs, the more flammable the material. Flammable liquids themselves are not flammable; rather, the vapor from the liquids are combustible. There are two physical properties of a material which indicate its flammability: flash point and volatility (boiling point). Flash point The flash point of a material is the temperature at which a liquid (or volatile solid) gives off vapor in quantities significant enough to form an ignitable mixture with air. Given an external source of ignition (i.e., spark, flame), a material can ignite at temperatures at or above its flash point. Flammable gases have no flash point, since they are already in the vapor phase.

Volatility Volatility of a material is an indication of how easily the liquid or solid will pass into the vapor stage. Volatility is measured by the boiling point of the material - the temperature at which the vapor pressure of the material is equal to the atmospheric pressure. The term volatility is often mistakenly used as a synonym for flammability. There are some materials that are volatile but not flammable, such as water, chloroform, and mercury. Pyrophoric Some materials are pyrophoric, They can ignite spontaneously with no external source of ignition. Potassium metal, for example, can react with the moisture in air. This reaction causes hydrogen gas to be evolved, and the heat generated by the reaction can be hot enough to ignite the hydrogen. 4. Class 4; Flammable Solids 4.1 Flammable solids 4.2 Spontaneously combustible 4.3 Dangerous when wet Oxidizers and Organic Peroxides 5.1 Oxidizer 5.2 Organic Peroxide Oxidizers An oxidizing agent is a chemical used to provide oxygen for chemical reactions. - Oxidizers spontaneously evolve oxygen at room or slightly elevated temperatures, and can explode violently when shocked or heated. - Because oxidizers have varying degrees of chemical instability, oxidizing agents are explosively unpredictable and, therefore, represent a particularly hazardous safety threat. Examples of oxidizing agents: peroxides hyperperoxides peroxyesters Oxidizers can react violently when in contact with organics. For this reason, avoid interactions between oxidizers and organic materials. (compatibility) Examples of organic-reactive oxidizers include nitric acid, chromic acid, and permanganates. Peroxides Some organic compounds, such as ethers, can react with oxygen from the air, forming unstable peroxides. Peroxide formation can occur under conditions of normal storage, when compounds become concentrated by evaporation, or when mixed with other compounds. The accumulated peroxides can then violently explode when exposed to shock, friction, or heat. Pure compounds will accumulate peroxides more readily than compounds containing impurities 6. Poisons 6.1 6.2 Material that is poisonous Infectious Agents

5.

7. Radioactives 8. 9. Corrosives 10. Miscellaneous (Other Reactive Materials)

NFPA; Each hazard class uses a different color and a rating scale from 0 - 4. 1. BLUE; Flammable Materials 2. RED; Health Hazard a. Carcinogens b. Mutagens c. Teratogens 3. WHITE; Specific Hazard a. Corrosive materials b. Oxidisers 4. YELLOW; Reactivity a. Explosive Materials

Toxicology The science of adverse effects of chemical substances on living organisms. There are no safe substances, but they can be used safely. The effect depends on The dose Exposure. Information required to predict whether a substance can give adverse effect: 1. Its chemical and physical properties 2. The biological system affected 3. The effects or response caused by the substance 4. The exposure (dose, time, situation) These information are obtained from - from laboratory tests with cells, bacteria, animals and - from accidents involving the substance. Chemical routes of entry Breathing Skin contact Swallowing (eating and drinking) (Others : injection, enter through eyes, accidents Breathing (Air dust, vapor, gases or mists) Air enter through nose, passes through the larynx, then enter the trachea, a long tube at its end to two the tubes called bronchi Depending on their composition, gases and vapors may be absorbed in the blood, e.g Cigarette tar deposit on lung layer The smaller the size of the particles we breathe, the more deeply the are likely to penetrate into the respiratory system Some particles are attacked by the bodys dependence cells called macrophages and may be either destroyed or converted into more harmful substances Amount of chemical and the longer exposure would determine the seriousness of the health effect. Generally, Children, the elderly and pregnant women and those weakened by illness are at high risk from the unhealthy of chemicals. For Aerosols (dust, mist, fog, smoke or other kinds of particles suspended in air) penetrate the respiratory system depends - The particle size,

Physical shape Properties of chemical.

Through the Skin Chemicals enter through the skin, then they may be carried away by the blood stream, causing harm to organs or to bodily function related to breathing, the nervous system, and etc. Some chemicals such as acid and alkaline have corrosive action on the skin, cause physical injuries If the skin is damaged by cuts, burns or others, it is most likely to be penetrated by chemicals Many pesticides cause skin and other health problems. Swallowing (Eating and drinking) - Chemicals in food and drink - Contaminated food - Water Exposure To have an adverse effect a substance must be able to enter the system. The exposure depends of the amount of substance and the period during which it affects the target, e.g. humans, animals or bacteria. The assessment of how a human system would react is not straightforward estimation from the animal tests. -The animal test gives an idea of the level of the toxic effects. In toxicological animal experiments the routes of exposure may be: - Inhalation (breathing in) - Absorption (through the skin or eyes) - Ingestion, oral (eating, swallowing) - Transfer across the placenta to the unborn baby - Intravenous (injection into the vein) - Intramuscular (injection into the muscle) - Subcutaneous (injection under the skin) - Intraperitoneal (injection inside the membrane that lines the interior wall of the abdomen) LD50 and LC50 For different substances the doses needed to produce an adverse effect varies widely. These values are used to compare acute toxicity. LD 50 - The dose which kills 50% of the test population. - Expressed in milligrams per kilogram of body weight of the test animal (which must be mentioned). LC50 - The exposure concentration of a toxic substance lethal to half of the test animals. - Expressed in milli litres per kilogram of body weight of the test animal (which must be mentioned), exposed to the substance by inhalation during a specified period. The numerical values of LD50 and LC50 depend on several factors, such as the biological system or animal, strain, sex, age and diet. Examples -The LD50 of DDT insecticide administered orally is 87 mg/kg of body weight for a rat but 150 mg/kg of body weight for a dog. Limit values to control toxic effects, there is a need to set priorities, goals and strategies. In places of work one way is to set limit values to guide the users. Occupational limit values are based on the best available information from industrial experience, from experimental laboratory studies and from accidents. They are informed and negotiated compromises, not fixed safety standards There are different kinds of limit values.The TLVs (Threshold Limit Values) are published by the American Conference of Governmental Industrial Hygienists (ACGIH) and concern the airborne concentrations of hazardous substances. They set a limit concentration below which

it is believed that nearly all workers can be repeatedly exposed day after day without adverse effect 1. TLV-TWA (Threshold Limit Value) Threshold Limit Value for the Time Weighted Average 8 hour day. Time Weighted Average(TWA) is a time-weighted average concentration for an eight hour working day or 40 hours a week to which nearly all workers may be repeatedly exposed without adverse effect. 2. TLV-STEL (Threshold Limit Value) Short Term Exposure Limit is the concentration to which workers may be exposed for a short time (usually 15 minutes) without suffering from irritation, long-term or irreversible tissue damage or impairment likely to increase accidental injury, affect self-rescue or reduce work efficiency. However daily TLV-TWA values should not be exceeded. 3. TLV-C (Threshold Limit Value - Ceiling) - a concentration that should not be exceeded at all during work exposure. Responses of a system The adverse effect is strongly related to the dose. The ultimate effect is death. The effects of toxic chemicals are less severe, from altered food consumption to serious health problems. 1. Human body The effects may be immediate or delayed, and they may be reversible or irreversible toxic effects Local/systemic Effects Local effects - occur at the area of the body which has been in contact with the chemical. Examples are injuries from acids or lung injuries from inhaled reactive gases. Systemic effects - occur after the chemical has been absorbed and distributed from the entry point to other parts of the body. Most substances produce systemic effects, but some substances may cause both types of effects. Both effect; Ex Tetraethyl lead - a gasoline additive and produces skin effects at the contact site. - absorbed and transported into the body causing typical effects on the central nervous system and on other organs. Effects on Target Organ The degree of the toxic effect is not the same in all organs. There are one or two organs which show the major toxic effect. These are referred as target organs of toxicity of the particular substance. The central nervous system is the target organ of toxicity most frequently involved in systemic effects. The blood circulation system, liver, kidneys, lungs and skin follow in frequency of systemic effects. Muscle and bones are the target organs for a few substances. The reproduction systems are vulnerable to many substances. a. Skin the largest organ in the human body, 1.5-2 m2 in area. provides a protective cover to the body but can fail if the load is overwhelming. a number of substances can penetrate healthy intact skin and enter the blood circulation. The vast majority of work-related skin diseases are contact eczemas, irritation and inflammation of the skin. This condition can be either a non-allergic or allergic reaction to exposure to chemical substances. Examples of common contact sensitizers are several colorants and dyes, metals e.g nickel and its salts, chromium and cobalt salts and organomercuric compounds, monomers of a number of acrylates and methacrylates,

2.

3.

 b. o o o

rubber additives and pesticides.

The nervous system sensitive to the hazardous effects of organic solvents. Some metals affect the nervous system, especially heavy metals such as lead, mercury and manganese. Organophosphate insecticides such as malathion and parathion interfere severely with information transmission (chemical neurotransmitter function) in the nervous system, leading to weakness, paralysis and sometimes death. The blood circulation The blood circulation is a target for the adverse effects of solvents. Blood cells are mainly produced in the bone marrow. Benzene affects the bone marrow; the first sign is mutation in the blood cells called lymphocytes. To study mutation, lymphocytes are cultured in the laboratory to observe specific types of cellular changes. Lead, in the form of the metal or its compounds, is another classic example of a chemical that may cause blood problems. Example Lead in the blood may inhibit certain enzyme activities involved in the production of hemoglobin in red blood cells. Chronic lead poisoning may result in a reduced ability of the blood to distribute oxygen through the body, a condition known as anaemia. Liver The liver is the largest of the internal organs in the body and has several important functions. It is a purification plant which breaks down unwanted substances in the blood. The liver has a considerable reserve capacity; symptoms of liver disorder appear only in serious diseases. Solvents such as carbon tetrachloride, chloroform and vinyl chloride, as well as alcohol, are hazardous to the liver. Kidneys The kidneys are part of the body's urinary system. the task of excreting the waste products that the blood has transported from various organs of the body, of keeping the fluids in balance and of ensuring that they contain an adequate blend of various necessary salts. They also maintain the acidity of the blood at a constant level. Solvents may irritate and impair kidney function. Carbon tetrachloride is a hazardous chemicals to the kidneys Turpentine in large quantities is also harmful to the kidneys: `painter's kidney' is a known condition related to occupational exposure. Others : lead and Cadmium

c.

d. e.

Allergic reactions and sensitization May appear after repeated contact to a substance. Once the sensitization has been produced, even very low doses can provoke a reaction. The different allergies are numerous, varying from minor skin irritation to very severe or even fatal reactions. The pattern of sensitization varies according to the species. In humans, the skin and the eyes are the most common areas of allergic response, In the guinea pigs reactions are more common in the respiratory system. Interactions The effect of simultaneous exposure to two or more substances may differ from a simple additive effect (1+1=2).

Organophosphate pesticides, such as parathion, is an example of chemicals where the combined effect is the sum of the effects observed when the chemicals act individually. The effect can be more than the sum of the individual effects of two chemicals (synergy); An example of an increase in risk is with asbestos fibers and cigarette smoking. They act together: the risk of developing lung cancer after exposure to asbestos fibers is forty times greater for a smoker than for a non-smoker. Another pair of the chemicals where the combined risk is greater than a mere additive effect are the solvents, trichloroethylene and styrene.