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HEALTH & SAFETY: 

HEALTH & SAFETY By Dr. Anna Dalipi

What is a Material Safety Data Sheet (MSDS)?: 

What is a Material Safety Data Sheet (MSDS)? An MSDS is a technical document which provides detailed and comprehensive information on a controlled product related to: health effects of overexposure to a substance; Hazard evaluation in relation to the product’s handling; storage or use; measures to protect people at risk of overexposure; and emergency procedures. The criteria for an MSDS are stated in the WHMIS legislation under the Hazardous Product Act/Controlled Product Regulation

What is the purpose of an MSDS?: 

What is the purpose of an MSDS? Intended to supplement the alert info provided on labels. It is a technical information reference, originally written for engineers, medical doctors, industrial hygienists. To educate people how to safely handle controlled products. An MSDS is NOT a document intended to represent all the information needed for safe use of a product. The variety of required protective measures cannot be anticipated through one sheet. It cannot foresee all possible types of worker exposure.

Info to be disclosed on an MSDS as per WHMIS:: 

Info to be disclosed on an MSDS as per WHMIS: Hazardous Ingredients Preparation Information Product Information Physical Data Fire or Explosion Hazard Reactivity Data Toxicological Properties Preventive Measures First Aid Measures

Hazardous Ingredients Section 2 in sample MSDS: 

Hazardous Ingredients Section 2 in sample MSDS This section lists the hazardous ingredients as per WHMIS criteria. Concentration of each ingredient in w/w, v/v, or w/v is given in certain ranges as per WHMIS criteria CAS NO, PIN NUMBER TLV, TWA LD50, LC50

Hazardous Ingredients cont’d. Classification as a Hazardous Ingredient: 

Hazardous Ingredients cont’d. Classification as a Hazardous Ingredient It meets one or more of WHMIS hazard criteria and is present in excess of 0.1% for carcinogens, teratogens, embryotoxins, reproductive toxins or respiratory tract sensitizers. All others such as oxidizers, corrosive, or flammables are reported when present in excess of 1%. If a given substance is on the WHMIS Ingredient disclosure list and it is a trade secret, then a special registration number is given. Nothing is known about a given ingredient.

Hazardous Ingredients cont’d. Material Identification (Section 1): 

Hazardous Ingredients cont’d. Material Identification (Section 1) Common chemical name, trade name, IUPAC name may be given. CAS Number - The identification number assigned to a chemical substance by the Chemical Abstracts Service Division of the American Chemical Society. The CAS number is unique to each ingredient. PIN is also given. This number is assigned to the product in the Transportation of Dangerous Goods Regulation.

Hazardous Ingredients cont’d. LD50/LC50?: 

Hazardous Ingredients cont’d. LD50/LC50? These values are measures of acute toxicity For materials causing immediate and serious health effects, these values - in part - further classify the material as being toxic or very toxic. LD = Lethal Dose. LC = Lethal concentration. It is the dose of the material which causes the death of 50% (one-half) of a group of test animals when given a single dose. It can be measured for different routes of exposure, but dermal and oral values are most relevant. How does it apply to humans?

Preparation Information (Section 1 in sample msds): 

Preparation Information (Section 1 in sample msds) The date the MSDS was prepared - As per WHMIS these documents must be reviewed every 3 years (not the case with American law - OSHA) or when a new hazard is reported. The name of the department and company that prepared this MSDS is given here. Any concerns - call the number to get further assistance.

Product Information cont’d.: 

Product Information cont’d. The name of the material including some of its other names like common names and trade name the material’s main use names addresses and emergency phone numbers of the manufacturer and supplier Example Name: Toluene Other Names: toluol, methylbenzene, phenylmethane, methyl benzol Use: Solvent for organic synthesis and explosive manufacture

Physical Data (Section 9 in sample msds): 

Physical Data (Section 9 in sample msds) This section includes physical characteristics of the material based on scientific knowledge and testing. Gas, liquid, or solid The physical state determines how the material may enter the body. In general gases enter the body by inhalation, liquids by ingestion or absorption and solids by ingestion. Dusts and fumes, which are solids, can also be inhaled.

Physical Properties cont’d.. Appearance and Odour: 

Physical Properties cont’d.. Appearance and Odour This subsection will describe the appearance and odour of the material. Solids are described as granular, powdery, crystalline. Liquids may be classified by their viscosity (thick or thin) Odour may be described as “fruity”, “sharp”, or “unpleasant”. For example, Ethyl acetate is a colourless liquid with a sweet fruity odour.

Physical Properties cont’d. Odour Threshold: 

Physical Properties cont’d. Odour Threshold This is the minimum concentration of the material that can be detected by the sense of smell. It is expressed in PPM. For example, ammonia can be detected at 1-5 PPM. Compare this value to the exposure values such as TLV or TWA. Example: Toluene diisocyante has an odour threshold of 0.4 to 2.4 PPM whereas the exposure limit (ACGIH or as specified in regulations) is considerably lower at 0.005 PPM. Varying individual sensitivity to smell is another reason why detection by odour should not be relied upon.

Physical Properties cont’d.: 

Physical Properties cont’d.

Physical Properties cont’d.: 

Physical Properties cont’d.

Physical Properties cont’d.: 

Physical Properties cont’d.

Fire or Explosion Hazard (Section 5 in sample msds): 

Fire or Explosion Hazard (Section 5 in sample msds) This subsection will indicate whether or not there is a danger of the material igniting and under what conditions. E.g. Vapours of toluene will ignite if they come into contact with a flame or spark. When a material is listed as flammable or combustible, precautions must be taken to prevent it reaching its flash point.

Fire or Explosion Hazard cont’d. Flash point: 

Fire or Explosion Hazard cont’d. Flash point It is the lowest temperature at which a sufficient amount of vapour is given off to create a mixture with air which is flammable on contact with open flame or spark. The lower the flash point the higher the risk of fire. E.g.. Styrene has a flash point of 31 Deg. C. If the temperature of the room reaches 31 Deg. C., a fire may begin if its vapours come into contact with an open flame or spark.

Fire or Explosion Hazard cont’d. Auto-Ignition Temperature: 

Fire or Explosion Hazard cont’d. Auto-Ignition Temperature The lowest temperature at which spontaneous ignition of the material in air begins in the absence of a flame or spark. The lower the auto-ignition temperature, the greater the risk of fire. E.g. Turpentine has an auto-ignition temperature of 253 Deg. C. It will, therefore, not ignite by itself unless it is heated to that temperature.

Fire or Explosion Hazard cont’d. Explosive limit: 

Fire or Explosion Hazard cont’d. Explosive limit LOWER explosive limit (L.E.L.) It is the LOWEST percent volume/volume ratio of a vapour or gas in air that can explode if ignited. Mixtures below L.E. L. are too “lean” to burn. E.g. Gasoline has an L.E. L. of 1.4%. If the conc of the vapours is <1.4% there is no risk. But when it reaches 1.4% (LEL) a spark or flame can cause the mixture to explode! UPPER explosive limit (U.E.L.) It is the HIGHEST percent volume/volume ratio of a vapour or gas in air that can explode if ignited. Mixtures above U.E. L. are too “rich” to burn. E.g. Gasoline has an U.E. L. of 7.4%. If the conc. of the vapours is >7.4% there is no risk. However, dilution will reduce the concentration to the explosive range.

Fire or Explosion Hazard cont’d. : 

Fire or Explosion Hazard cont’d.

Reactivity Data (Section 10 in sample msds): 

Reactivity Data (Section 10 in sample msds)

Toxicological Properties Fundamental “laws of toxicology” (Section 11 in sample msds): 

Toxicological Properties Fundamental “laws of toxicology” (Section 11 in sample msds) There is NO toxicity without exposure It is the DOSE that makes the poison -- one should be able to see clear evidence of a dose-response relationship. Generally, the lower the LD50, the more potent the toxicant is. Consider ethanol, dioxin, & botulinum toxin (botulism food poisoning). Their lethal potencies are: botulinum toxin >>dioxin>ethanol Yet ethanol is responsible for far more deaths in Canada than potent toxicants, because many people expose themselves to immoderate amounts of ethanol.

Toxicological Properties Routes of Entry: 

Toxicological Properties Routes of Entry Provides information about possible risks to health based on current scientific knowledge. Inhalation - Material in form of dusts, mists, vapours, gases and fumes can be inhaled. Some materials can damage the lungs (asbestos) and others may pass into the blood and be distributed to other parts of the body (toluene) Ingestion - Materials that pose a hazard when swallowed. Some materials can damage the stomach (acids) others may be absorbed into the bloodstream (alcohols).

Toxicological Properties cont’d. Routes of Entry: 

Toxicological Properties cont’d. Routes of Entry Absorption - indicates a possible hazard if absorbed into the bloodstream through intact skin (phenol) Skin contact - indicates that the material can corrode, sensitize, or irritate the skin but may not be absorbed (strong acids - H2SO4) Eye contact - indicates that the material may corrode or irritate the eye. It may also affect vision or cause cataracts.

Toxicological Properties cont’d. : 

Toxicological Properties cont’d. Irritancy of Product - whether or not the material may cause irritation and possible damage to the skin or eyes. Sensitization of Product -information on whether the material can cause an allergic respiratory or skin reaction.

Toxicological Properties cont’d.: 

Toxicological Properties cont’d. Effects of Acute Exposure - Information on the acute effects of overexposure (higher than allowable limits) to the material. Acute effects are effects which may be felt within a few minutes, hours, or days. E.g.. An exposure to high concentrations (above legally set TWA) of hexanes may lead to dizziness, lack of co-ordination and narcosis (drowsiness). Effects of Chronic Exposure - Possible health problems due to repeated overexposure to a material over a long period of time. These effects may be felt months or years afterwards E.g. Chronic exposure to n-hexane may produce numbness, tingling in the hands and feet and weakness in the arms and thighs. Type of chronic effects - carcinogenic, reproductive, mutagenic, teratogenic.

Toxicological Properties cont’d. Carcinogenicity: 

Toxicological Properties cont’d. Carcinogenicity Substances are classified as carcinogens as per WHMIS only if a compound is listed in one of two publications. ACGIH TLV booklet; A1 (confirmed) or A2 (suspected) human carcinogen, or IARC monographs; group 1 (sufficient evidence) or group 2 (probably carcinogenic) Both agencies base classification on animal testing results and/or epidemeology (study of human population). Risk factors are used to allow for differences between species. E.g. A material is classified as carcinogenic when the risk to humans is 1 to 1,000, 000.

Toxicological Properties cont’d.: 

Toxicological Properties cont’d. Reproductive toxicity: Reports material that may cause sterility or another adverse effect on reproduction E.g.Dibromochloropropane (DBCP), a pesticide, has been shown to decrease fertility (low sperm count) Mutagenicity Possible hereditary changes made by a chemical to the DNA which make up the chromosomes. These changes affect genetic information passed to the offspring (offspring of both sexes can be affected) which may result in birth defects or the development of a disease such as cancer. E.g. Toluene-2,4-diamine has been shown to be mutagenic.

Toxicological Properties cont’d. Teratogenicity: 

This information is directed specifically toward women of childbearing age who are exposed to these kinds of materials. A material is classified as teratogenic if it causes one of the following: causes death, malformation, permanent metabolic or physiological dysfunction, growth retardation, psychological or behavioral alteration to the baby during pregnancy, at birth or in the postnatal period. E.g. Dimethyl Mercury is a proven teratogen. Toxicological Properties cont’d. Teratogenicity

Toxicological Properties cont’d. Synergistic Products: 

Synergism is the term used to describe the cooperative action of substances whose total effect is greater than the sum of their separate effects. E.g. Exposure to alcohols and chlorinated solvents (CH2Cl2) simultaneously will result in more severe nervous system effects than when one is exposed to each material separately E.g. Cancer risk for a smoker is 10x greater than for a non smoker. Cancer risk for a non smoker who works with asbestos is 5x greater than one who has no exposure to asbestos. Cancer risk for a smoker who works with asbestos is 50x greater (not 15x). Toxicological Properties cont’d. Synergistic Products

Toxicological Properties cont’d. Exposure Limits: 

Toxicological Properties cont’d. Exposure Limits Exposure limits are airborne concentrations of a material to which (it is believed) people may be exposed without adverse effects. Exposure limits known as TLV’s are published by the ACGIH and these limits are most likely to be found on MSDSs. There are 3 different type of TLV’s. Time Weighted Average (TLV) concentration for a normal 8 hr workday and a 40 hr workweek, to which nearly all workers may be exposed, day after day, without adverse effects. Short Term Exposure Limit (STEL) - A 15 min time weighted average exposure which should not be exceeded. Threshold Limit Value - Ceiling (TLV-C) - The concentration that should not be exceeded at any time.

Preventive Measures (Section 5, 6, 7, 8 in sample msds ): 

Preventive Measures (Section 5, 6, 7, 8 in sample msds ) Most important MSDS section. Contains info on how one should be protected when: handling, using or storing the material. clean up and disposal measures are given to prevent overexposure fire and damage to equipment

Preventive Measures cont’d.: 

Engineering Controls - Control measures that prevent the release of a material into the common air. E.g. ventilation system general and local (refers to fumehood), gloveboxes, etc. In chm247 much of the work will be done in the fumehood. Personal Protective Equipment (PPE) Gloves, Respirators, Eye Protection, Clothing, Other Equipment. Preventive Measures cont’d.

Preventive Measures cont’d.: 

Preventive Measures cont’d. Leak and Spill Procedures - Measures to be taken in case of a leak or spill involving this material and the methods of disposal under these circumstances. E.g. Toluene: Remove all sources of ignition, stop leak if safe to do so, absorb with paper, sand or sawdust --> Where would you throw this waste away? Would you use such material to absorb nitric acid and why? Waste Disposal - Appropriate waste handling requirements. Generally not much info because they depend on local by-laws. Need to check these laws!

Preventive Measures cont’d.: 

Handling Procedures & Equipment: Info on how to handle material and specifies if special equipment is needed. E.g. Toluene - Wear splash proof goggles or a face shield. Avoid all skin contact. Provide adequate ventilation or wear appropriate respiratory equipment. Storage requirements - Provides info for safe storage of the material. E.g. Toluene - Store in a tightly sealed container in a well ventilated area. Keep away from sources of ignition and heat. Keep away from oxidizing substances such as KMNO4. Shipping - PIN number & other info required by TDG Reg. Preventive Measures cont’d.

First Aid Measures (Section 4 in sample msds): 

First Aid Measures (Section 4 in sample msds) This is the section you check in case of accidental overexposure to the material. E.g. Xylene: Eye contact - Flush eyes with plenty of water for at least 20 minutes, then see a physician. Skin contact - Quickly remove contaminated clothing. Wash skin with soap and water and rinse with water for 20 min., then see a physician. Ingestion - Do not induce vomiting. Contact a physician immediately. Inhalation - Remove victim to a well ventilated area. If breathing has stopped, perform artificial respiration. Contact a physician.

Health & Safety Prep for Each Experiment: 

Health & Safety Prep for Each Experiment Prepare a table of physical constants and make sure you do all of the calculation conversion mole --> gm or ml etc. Obtain an MSDS or info on safety hazards & health effects for all chemicals used. The following websites may be useful: www. Chem.utoronto.ca/health/msds http://www.sigmaaldrich.com/homepage.html (click on login and register for free) www.emdchemicals.com (no registration required)

Health & Safety Prep contd.: 

Health & Safety Prep contd. www.hc-sc.gc.ca/ehppsb/whmis www.gov.on.ca/lab/ohs/ohse http://www.iarc.fr/ http:/chemfinder.cambridgesoft.com www.cdc.gov.niosh www.ccohs for others search www.google.com

SAFETY AND LABORATORY RULES: 

SAFETY AND LABORATORY RULES Work is only permitted during SCHEDULED LABORATORY PERIODS. Know the location of FIRE EXTINGUISHERS, SAFETY EQUIPMENT, AND THE NEAREST EXIT. Approved SAFETY GOGGLES, A LAB COAT, must be worn at all times. Use of NITRILE RUBBER GLOVES is recommended to avoid contact of chemicals with skin. NO FOOD, DRINKS OR SMOKING ARE ALLOWED SHOES MUST BE WORN. TIE LONG HAIR BACK NEVER TASTE OR SMELL CHEMICALS DISPOSE OF CHEMICAL WASTE IN PROPER CONTAINER. Waste containers may not be always in the same fumehood.

MOST COMMON DANGERS IN AN ORGANIC LABORATORY: 

MOST COMMON DANGERS IN AN ORGANIC LABORATORY FIRE AND EXPLOSION CHEMICALS GLASSWARE

FIRE & EXPLOSION See Suppl. Lab Manual : 

FIRE & EXPLOSION See Suppl. Lab Manual Never use an open flame! Never smoke! Read the msds and lab instructions to make sure that you are using the right heat source. Use one of heating mantles, hot plates (never use for ether), or steam bath. Heat flammable solvents in a flask (not beakers) in the fumehood! Evaporate organic solvents in the fumehood Familiarize yourself with location of fire equipment.

EMERGENCY PROCEDURE IN CHEMICAL INJURY: 

EMERGENCY PROCEDURE IN CHEMICAL INJURY Go immediately to the nearest tap or shower and flood affected area with copious amounts of water. Speed is imperative. If you notice a fellow student needs assistance, help him/her. Once you have started emergency treatment call a TA. Yell loudly! REPORT ALL INJURIES TO THE PREP ROOM IMMEDIATELY! PRECAUTION: Read the safety pages of Suppl. Lab Manual.

GLASSWARE PRECUATION: 

GLASSWARE PRECUATION Handle glassware gently. Be especially careful when inserting glass tubing into a hole. It helps if the glass is wet (lubricated). Hold the glass with a paper towel or j -cloth and insert it with a gentle twisting motion with your driving hand close to the hole. REPORT ALL INJURIES TO THE PREP ROOM IMMEDIATELY!

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