Hazardous Chemicals Awareness Level

Wes Adams Asheville-Buncombe Technical Community College

Note: Permission to use this presentation is granted as long as you give credit to the author, Wes Adams.

HAZMAT Awareness
1. 2. 3. 4. 5. 6.

Topics to be covered: MSDS Sheets NFPA System UN Identification Number Emergency Response Guidebook Factors Affecting the Rate of Reaction The DOT Hazardous Materials Classes along with the particular hazards of each class.

MSDS Sheets

An Material Safety Data Sheet (MSDS) is a technical bulletin containing detailed information about a hazardous substance. OSHA requires that manufacturers prepare an MSDS for each chemical that it sells. The MSDS contains more extensive information than is conveyed on the label. The MSDS must accompany each chemical it ships the first time that the chemical is shipped to that recipient.

MSDS Sheets
1.

2.

3.

The following minimum information must be provided in the MSDS: The identity of the product as used on the container label. The chemical and common name for all ingredients present in concentrations greater than 1% and 0.1% for a cancer causing substance (carcinogen). The physical and chemical properties of the hazardous components.

MSDS Sheets
4.

5. 6. 7.

8.

The physical and health hazards, including signs and symptoms of exposure and/or prior and/or existing conditions that can warn against exposure. Primary routes of entry into the body. Any known exposure limits. Whether the hazardous substance is a carcinogen. Precautions for safe handling and use.

MSDS Sheets
9. 10. 11. 12. 13.

Procedure for spill or leak cleanup. Control measures Emergency first-aid procedures.

The date of preparation

The name, address, and telephone number of the company or responsible employee distributing the MSDS.

NFPA System

The National Fire Protection Association (NFPA) recommends certain markings for use on storage tanks, exterior building walls, pipelines and other relevant locations. This procedure for identifying potential hazards associate with a chemical is called the NFPA 704 system. NFPA ratings can be found on the MSDS sheet.

NFPA System
1. 2.

3.
4.

The NFPA system uses a diamond with color coded: Blue is for the health hazard. Red is for the flammability hazard. Yellow is for the reactivity hazard. White is for special hazards. A number is placed in each section ranging from 0-4. A 0 means no hazard and a 4 means an extreme hazard.

NFPA System

1. 2.

The following seven symbols are employed in the white section of an NFPA diamond: A radiation hazard symbol is a three bladed propeller. The letter W with a line trough it is a caution against applying water.
The letters OXY indicate that the material is an oxidizer. The letter P indicates there is a potential for the material to under go auto-polymerization. The Word ACID indicate that the material is an acid. The letters ALK indicate that the material is an alkali (base). The letters COR indicate that the material is corrosive.

3. 4.

5. 6. 7.

NFPA System
4 = Severe 1 4 P 2 3 = Serious

2 = Moderate
1 = Slight 0 = None

Identification Number

UN or NA preceding a number indicates the identity of the chemical. UN indicates internationally transported chemicals while NA refers to those only transported in the US and Canada. In addition to these placards the UN number may also be inset into the appropriate placard.

Emergency Response Guidebook

Also Available on the Web

Emergency Response Guidebook

1.

2.

After obtaining the identification number consult the North American Emergency Response Guide Book: The yellow pages list the materials in numerical order by UN ID number. The blue pages list the materials in alphabetical order.

Emergency Response Guidebook

The orange bordered pages list 172 individual guide numbers listing emergency response actions for particular materials. The green bordered pages give initial isolation and protective distances for the highlighted entries in the yellow and blue sections.

Factors Affecting the Rate of Reaction

There are 5 important factors which affect rates of reactions:

Nature of the Material Reactant Concentration Temperature Action of Catalysts Surface Area

Factors Affecting the Rate of Reaction

Nature of the Material includes the chemical composition of the substance and the physical state in which it exists. For example white phosphorous ignites spontaneously in air while wood requires an ignition source and water will not burn. Generally reaction occurs fastest in the gas phase, the second fastest in the liquid phase, and much more slowly in the solid phase.

Factors Affecting the Rate of Reaction

Reactions in general go more quickly at higher concentrations. For example flammable materials burn much more quickly at high oxygen concentrations. Since air is 78% nitrogen and 21% oxygen by volume, nitrogen serves to lower the oxygen concentration and reduce the rate of combustion.

Factors Affecting the Rate of Reaction

As a general rule the rate of the reaction increases as the temperature increases. For example food spoils when not refrigerated. As a general rule the rate of a chemical reaction doubles for every rise of 18oF (10oC).

Factors Affecting the Rate of Reaction

Reactions also proceed more quickly in the presence of a catalyst. Catalysts speed up a reaction without being used up in the reaction. This is usually done by lowering the activation energy which is the energy required to initiate a chemical reaction. The combustion of hydrogen and oxygen will not occur without a spark unless a piece of platinum is added and then they explode violently.

Factors Affecting the Rate of Reaction

MnO2 causes the Catalytic Decomposition of H2O2 to liberate oxygen which will increase the combustion rate.

Factors Affecting the Rate of Reaction

Generally reactions occur more quickly with a greater surface area. For example a flammable liquid will burn more quickly in a container that will allow it to assume the largest surface area.

Factors Affecting the Rate of Reaction

Burning Licompodium Powder

Hazard Class
Class 1.1 1.2 1.3 1.4 1.5 1.6 2.1 2.2 2.3 3 Combustible Liquid 4.1 Label Explosive 1.1 Explosive 1.2 Explosive 1.3 Explosive 1.4 Explosive 1.5 Explosive 1.6 Flammable Gas Non-Flammable Gas Poison Gas Flammable Liquid (none) Flammable Solid Class 4.2 4.3 5.1 5.2 6.1 6.2 7 7 7 7 8 9 Label Spontaneously Combustible Dangerous When Wet Oxidizer Organic Peroxide Poison Infectious Substance Radioactive White-I Radioactive Yellow-II Radioactive Yellow-III Empty Corrosive Class 9

Class 1: Explosives
1.

There are two general types of explosive materials: Chemical explosives detonate as a result of the application of friction, mechanical impact, or heat; usually used for demolition and other destructive acts. It is distinguished from gasoline and flammable gases which will seem to explode when ignited. They are also distinguishable from nuclear explosives, which detonate by nuclear phenomena.

Class 1: Explosives
Some Explosive Articles (49 CFR 173.59)
Ammunition Black Powder Bombs Charges Flash Powder Smokeless Powder Fuse Primer Fuze (Ammo) Projectiles Igniters Propellants Sounding Devices Torpedoes Warheads

Fireworks Flares

Mines Powder cake

Rocket Motors Signals

Class 1: Explosives

The rapidly expanding gases often exceeds the speed of sound and cause shock waves. These shock waves are associated with the explosives shattering power called its brisance. The brisance is an important factor in choosing the correct explosive for a particular use, like clearing rock for a road. Sometimes so-called chemical explosives are a mixture of substances that appear to detonate which includes gunpowder and some blasting agents.

Class 1: Explosives

Nitrogen Triiodide is an explosive.

Class 2: Gases

1.

2.

A division 2.1 (flammable) gas is any material that is a gas at 68oF or less and 14.7 psi of pressure and is one of the following: Ignitable at 14.7 psi when in a mixture of 13% or less by volume with air. Possesses a flammable range at 14.7 psi of at least 12% regardless of the lower limit.

Class 2

A Bunsen Burner Flame is fueled by Natural gas. Different Metals in the flame will change the flame from blue to different colors. This also works for liquids.

Class 2: Gases

1.

2.

A division 2.2 (non-flammable) gas is any material or mixture that does one of the following: Exerts in its packaging an absolute pressure of 41 psi or greater at 68oF. Does not meet the definition of division 2.1 or 2.3

Class 2: Gases

A small amount of water is placed into a can and heated when rapidly cooled the water vapor condenses leaving a vacuum which allows the air pressure to crush the can.

Class 2: Gases

1.

2.

A division 2.3 (poison by inhalation) gas is a material that is a gas at 68oF or less at 14.7 psi and is one of the following: Known to be so toxic to humans as to pose a health hazard during transportation. In absence of data on human toxicity, is toxic to laboratory animals and has and LC50 (lethal concentration 50% of the time) less than 5000 mL/m3.

Class 2: Gases

Some examples of toxic gases are: Carbon Monoxide Hydrogen cyanide Sulfur dioxide Hydrogen Sulfide Nitrogen Dioxide Anhydrous Ammonia

Class 2: Gases

Copper and Nitric Acid generate Nitrogen Dioxide

Class 3: Flammable Liquids

1.

2.

The DOT defines a flammable liquid as either of the following: Any liquid having a flash point not more than 141oF. Any liquid with a flash point at or above 100oF that is intentionally heated and offered for transportation or transported at or above its flash point within bulk packaging. A combustible liquid has a flash point above 141oF and below 200oF

Flammability

Burning Methanol

Storage and Transport of Compresses Gases

Large amounts of compressed gases or liquefied gases are transported in large tanks pulled behind the vehicle or as its own separate rail car. Such a tank exposed to direct flames will rupture. If a liquefied gas is flammable a Boiling Liquid Expanding Vapor Explosion (BLEVE) can occur. A BLEVE occurs when a released liquid is rapidly heated to temperature above its boiling point. Some BLEVEs have resulted in fireballs with radii of 900 ft.

Storage and Transport of Compresses Gases

Class 4: Flammable Solids

1. 2.

3.

The DOT defines a flammable solid as any of the following: Any of several wetted explosives Any of several self-reactive materials that are thermally unstable and can undergo a strongly exothermic (gives off heat) decomposition even without the participation of atmospheric oxygen A readily combustible solid.

Class 4: Flammable Solids

Burning Magnesium in the presence of Carbon dioxide.

Class 4: Flammable Solids

1.

2.

The DOT defines a spontaneously combustible material as either of the following: A pyrophoric material is a liquid or solid that even in small quantities and without external ignition source can ignite within five minutes after coming in contact with air. A self-heating material is a material that when in contact with air and without an energy supply is liable to self heat.

Class 4: Flammable Solids

Phosphorus in Air

Class 4: Flammable Solids

The DOT defines a dangerous when wet material as a material that, by interaction with water, is likely to become spontaneously flammable or to release a flammable or toxic gas or vapor at a rate greater than 28 in3/lb (1 L/kg) per hour.

Class 4: Flammable Solids

Calcium Carbide and Water liberate flammable acetylene gas.

Class 5: Oxidizers and Organic Peroxides

1.

The DOT defines two classes of oxidizers: An oxidizer (division 5.1) is a material that can cause or enhance the combustion of materials, generally by yielding oxygen.

Class 5: Oxidizers and Organic Peroxides

Potassium Chlorate and Gummy Bear

Copper Silver Redox

Ammonium Nitrate Zinc and Water

Class 5: Oxidizers and Organic Peroxides

An organic peroxide (division 5.2) is an organic compound containing oxygen in the bivalent OO structure. Organic peroxide formation is especially susceptible in some ethers especially: diglyme, diethyl ether, dioxane, glyme, isopropyl ether, tetrohydrofuran.

Class 5: Oxidizers and Organic Peroxides

Test for organic peroxides at the neck of old ether bottles before opening.

Class 6: Poisonous and Infectious Materials

1.

a.

b.

The DOT defines poisonous and infectious materials as follows: A poisonous material is a material other than a gas that is known to be toxic to humans to present a hazard during transport or: Is presumed to be toxic because of data obtained from tests performed on animals. Is an irritating material with properties similar to tear gas and causes extreme irritation, especially within confined spaces. Examples include cyanide containing salts, asbestos, and pesticides.

Class 6: Poisonous and Infectious Materials

2.

An infectious material is a viable micro organism or its toxin that causes or can cause disease in humans or animals. Potentially infectious substances include: Blood and blood products Saliva, vomit, urine Semen or vaginal secretions Skin, tissue, cell cultures Other body fluids (particularly if blood is visible).

Class 6: Poisonous and Infectious Materials

Class 7: Radioactive Materials

A radioactive material is any material or any combination of materials that spontaneously emits ionizing radiation having a specific activity greater than 70 Becquerels per gram. Radioactive White-I, Yellow-II, and Yellow-III alerts emergency response workers to increasing radioactivity. White-I is the least radioactive and Yellow-III is the most radioactive.

Class 7: Radioactive Materials

A Geiger Counter is used to measure radioactivity.

Class 8: Corrosive Materials

1.

2.

A corrosive material is both of the following: A liquid or solid that causes visible destruction or irreversible alterations in skin tissue at the site of contact. A liquid that has a severe corrosion rate on steel or aluminum, as measured in accordance with certain prescribed DOT testing procedures.

Class 8: Corrosive Materials

Sodium Biarbonate + HCl liberates CO2 gas.

Magnesium + HCl liberates H2 gas

Class 9: Miscellaneous Hazardous Materials

The DOT defines a miscellaneous hazardous material as a material that presents a hazard during transportation, but is not included in any other hazard class. These materials are any material that has anesthetic, noxious, elevated-temperature substances, hazardous wastes and marine pollutants, and magnetized materials. ORM-D materials are also class 9.

Class 9: Miscellaneous Hazardous Materials

Hot water when transported is an elevated temperature material an is therefore Class 9

Questions?