NUPT-215

Nuclear Plant Chemistry unit 5

Bismarck State college
Welcome to chemistry NUPT-215

Instructors name
Hazards of Chemicals and gases

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Desired Outcome for Unit five: State the hazards associated with the use of corrosives. State the general safety precautions necessary for the handling, storage, and disposal of corrosives.

LIST the general safety precautions regarding toxic compounds. LIST the criteria used to determine if a compound is a health hazard. STATE the methods by which toxic compounds may enter the body. SUMMARIZE the purpose and general contents of the following: Material Safety Data Sheets (MSDS) Toxic Substance List DEFINE the following terms: C om pressed gas Non-liquefied gases Liquefied gases Dissolved gases

STATE the five major families of gases.

STATE the general safety precautions regarding the use, handling, and storage of gases.
STATE the safety precautions for working with cryogenic liquids. LIST the physical properties and special precautions for the following gases: Hydrogen Oxygen Nitrogen

 DEFINE the following terms: Fl am m abl e l i qui d C om bust i bl e l i qui d STATE general safety precautions regarding the use, handling, and storage of flammable and combustible liquids. STATE the reasons for and techniques used in bonding and grounding of flammable liquid containers. LIST four sources of ignition of flammable liquids. STATE the health hazards associated with flammable and/or combustible liquids.

Nuclear power plant safety is of paramount concern for all personnel involved in the process of generating electric energy. The record of safety at nuclear plants is better than those of non-nuclear plants. This is because of the heightened concern for both nuclear safety and general safety for all plant personnel. The NRC has also weighed in on plant safety and has even established a line of communication with any whistle blowers to voice their concerns. It is the responsibility of every plant worker to not only affect his or her own safety, but that of others at the plant site.
Acids: Acids are corrosive in any form; H+ ions in solution. Can cause tissue damage in high concentrations and irritation with mild concentrations. Possible blindness if the eyes are effected. Damage to lung tissue may occur if fumes are inhaled. Can damage the throat and intestinal tract if swallowed and may be fatal. As operators, chemists, maintenance, and health physics personnel, you will be working with all types of corrosive materials while performing your jobs at the plant site. It is both managements and your responsibility to follow all precautions while performing work. When working with acids, eye protection, gloves, hard hat, respirator, and other protection may be required. An example of working with strong acids and caustic was covered in the last unit with the plant water demineralizers.

Alkalies (Strong Base): Are corrosive caustic substances that dissociate in water to yield OH- ions. Are more destructive to tissues than acids. Generates heat when dissolved in water which could cause boiling and splattering of solutions The same safety requirements for acids apply to Alkalies.

General safety: In areas where acids or caustics are handled, you will generally see an eye wash or shower unit in the vicinity. The picture below shows a typical eye wash station. The handle in yellow on the right side is pushed to turn on the spray.

 The picture below shows a shower unit with eye wash. Note it has the same handle to initiate eye wash and a pull handle for the shower.

If you think you have strong acid or caustic on your body dont be afraid to use this safety equipment. It is better to be safe than sorry. Speed in removing the corrosive is of utmost importance. After cleaning for 15 minutes, notify the control room of the event, you will probably be required to see a doctor as soon as possible.

Entering a confined space or tanks:

You may not enter a confined space or tank without several things taking place. Preplanning: this involves the why, who, what, where, and how question about the entry. The first step is to determine if the entry is even required and starts with the control room making the decision to do the entry. The tank will have to be drained, isolated (red/danger tagged), ventilated, sampled etc. prior to entry. Training and rescue procedures will be reviewed prior to entry. The entry permit will be filled out and properly approved. All protection equipment i.e. respirators, hard hat, safety goggles, protective clothing requirements, ventilation requirements etc. will be established and used. You may not enter a tank without someone outside of the tank monitoring the work inside the tank. If the tank is radioactive even more requirements will be put in place. A Radiation work permit (RWP) would also be required prior to entry with all of its listed requirements, precautions and approvals.

Example of a confined space entry permit:

CONFINED SPACE ENTRY PERMIT This permit must be completed prior to entry into the confined space. Entry cannot be performed if any boxes are marked "No." This permit is valid for only 8 hours only. Date of entry: Time of Entry: Location: ________________________________ Type of space:_______________________ Equipment to be worked on: Work to be performed: Anticipated time needed to complete work:_________________________________________ Anticipated Harzards:__________________________________________________________ Entry personnel: _____________________________________________________________________ Attendants: Acceptable conditions 1. Atmospheric checks: Oxygen % O2 19.5 % to 23.5 % Explosive % L.F.L. 10% L.E.L./L.F.L. Toxic ppm 0-35 ppm Carbon Monoxide 0-10 ppm Hydrogen Sulfide Atmospheric Tester's Initials:_____________________ Time:_____________________ 2. Isolation of pumps/lines: N/A Yes No Pumps or lines blocked, ( ) ( ) ( ) blinked, or disconnected 3. Ventilation: N/A Yes No Mechanical ( ) ( ) ( ) Natural ventilation only ( ) ( ) ( ) 4. Hot work permit required ( ) ( ) ( ) 5. Atmospheric checks after isolation and ventilation, if applicable: Oxygen: % O2 Explosive: % L.E.L Toxic: PPM 6. Communication procedures: 7. Lockout procedures, if applicable: 8. Entrant(s), attendant(s), and rescue personnel (if applicable) have Yes No successfully completed required training. ( ) ( ) 9. Equipment: N/A Yes No Direct reading sampling device which is properly calibrated ( ) ( ) ( ) Safety harnesses and lifelines for entrants and attendants ( ) ( ) ( ) Mechanical retrieval/hosting equipment ( ) ( ) ( ) Communication equipment ( ) ( ) ( ) SCBA or Type C air line respirator ( ) ( ) ( ) Personal protective equipment and clothing ( ) ( ) ( ) Electrical equipment/Lighting/Non sparking Tools ( ) ( ) ( ) Traffic barriers/entrance covers ( ) ( ) ( ) I have reviewed the work authorized by this permit and the information pertaining to each item. Safety procedures have been received and are understood by all personnel. Entry Supervisor: ______________________________________________Date: ________________

What are the basic safety procedures concerning corrosives? Following these basic safe practices will help protect you from the hazards of corrosive materials: Show up for work in a good physical and mental state. No drugs or alcohol. Obtain and read the Material Safety Data Sheets (MSDSs) for all of the materials you work with. Be aware of all of the hazards (fire/explosion, health, chemical reactivity) of the materials you work with. Know which of the materials you work with are corrosives. Store corrosives in suitable labeled containers away from incompatible materials, in a cool, dry area. Store, handle, and use corrosives in well-ventilated areas. Inspect containers for damage or leaks before handling. Never use containers that appear to be swollen. Handle containers safely to avoid damaging them. Dispense corrosives carefully and keep containers closed when not in use. Stir corrosives slowly and carefully into cold water when the job requires mixing corrosives and water. Handle and dispose of corrosive wastes safely. Practice good housekeeping, personal cleanliness and equipment maintenance. Wear the proper personal protective equipment for each of the jobs you do. Know how to handle emergencies (fires, spills, personal injury) involving the corrosive materials you work with. Follow the health and safety rules that apply to your job. Flush contaminated eyes or skin with water for at least 15 minutes, sometimes longer, in case of accidental contact. Call immediately for medical assistance. Know where to closest eyewash station and safety showers are located, and how to use them. Do not reuse empty containers -- the residue may be hazardous. Never return unused material to the original container. It may contain traces of contamination which may cause a chemical reaction.

Storage of acids and caustics: Storage areas of acids and caustics are designated by the plant safety committee or equivalent staff. Areas are well ventilated and of corrosion and fire resistant materials with directed drains. Lighting and wiring are protected from fumes and corrosives. Area should be cool and dry. Face/eye and shower facilities should be in the area. Hand trucks or fork lifts will have protective devices to prevent damaging the containers. 10 CFR 29-1910 is controlling document

Storage cabinets should be closable and secured for the specific types of corrosive to be stored.

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Toxic compounds and MSDS: Toxicity is the capacity of a material to produce injury or harm to a living organism. Toxic compounds are abundant at nuclear power plants. Handling of the different toxic compounds varies with the specific job you hold at the plant. Maintenance people use certain types as chemists handle other types. Operators us acids and caustics as well as boric acid and LiOH. In order to keep all hazardous and toxic chemicals under control, Material Safety Data Sheets (MSDS) are required. The MSDS sheets should be consulted prior using any chemical that you are not familiar with or have not used recently. An Example of a MSDS sheet is in the docsharing file under MSDS. Review it and be able to answer general questions about it on the quiz. Remember, Hydrazine is the oxygen control agent For the RCS when primary temperature is less than 2000F and must be manually loaded into the chemical addition tank. MSDS note books containing all toxic chemicals are maintained in yellow folders for use in the plant. Hazard: is the possibility that the material will cause injury when a specific quantity is used under specific conditions. Elements considered when evaluating the hazard: Toxicity of the materials used. Physical properties of the material. Absorption probabilities of the material by individuals. Extent and intensity of exposure to the material. Control measures used.

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The image on the left is used by MSDS for numbering the levels of different concerns under each category. on the next pages are a listing of the levels and more information on MSDS
k

0
Physical Hazard

The reactivity section is now obsolete but is still in use at the plants where they have not been updated. The new color is orange and the section is now called physical hazard. It uses OSHA standards not NFPA. Because you may see the reactivity listed on the warning, I have added them below. Note the higher the number the more hazardous.

Reactivity or instability Identical to National Fire Protection Association (NFPA)

Readily capable of detonation or of explosive decomposition or reaction at normal temperatures and pressures Capable of detonation or explosive reaction, but requires a strong initiating source or must be heated under confinement before initiation, or reacts explosively with water. Normally unstable and readily undergo violent decomposition but do not detonate. Also: may react violently with water or may form potentially explosive mixtures with water. Normally stable, but can become unstable at elevated temperatures and pressures or may react with water with some release of energy, but not violently. Normally stable, even under fire exposure conditions, and are not reactive with water.

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Health The Health section conveys the health hazards of the material. In the latest version of HMIS, the blue Health bar has two spaces, one for an asterisk and one for a numeric hazard rating. If present, the asterisk signifies a chronic health hazard, meaning that long-term exposure to the material could cause a health problem such as emphysema or kidney damage. NFPA lacks this important information because the NFPA system is meant only for emergency or acute (short-term) exposures.

According to NPCA, the numeric hazard assessment procedure is different than that used by NFPA. Here are the numeric rankings for the HMIS system:
4 Life-threatening, major or permanent damage may result from single or repeated overexposures.

3
2 1 0

Major injury likely unless prompt action is taken and medical treatment is given.
Temporary or minor injury may occur. Irritation or minor reversible injury possible. No significant risk to health.

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Flammability For HMIS I and II, the criteria used to assign numeric values (0 = low hazard to 4 = high hazard) are identical to those used by NFPA. In other words, in this category, the systems are identical. For HMIS III, the flammability criteria are defined according to OSHA standards:

Flammable gases, or very volatile flammable liquids with flash points below 73 F, and boiling points below 100 F. Materials may ignite spontaneously with air. (Class IA) .
Materials capable of ignition under almost all normal temperature conditions. Includes flammable liquids with flash points below 73 F and boiling points above 100 F, as well as liquids with flash points between 73 F and 100 F. (Classes IB & IC). Materials which must be moderately heated or exposed to high ambient temperatures before ignition will occur. Includes liquids having a flash point at or above 100 F but below 200 F. (Classes II & IIIA). Materials that must be preheated before ignition will occur. Includes liquids, solids and semi solids having a flash point above 200 F. (Class IIIB). Materials that will not burn.

1 0

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Physical Hazard (HMIS III) o Reactivity hazard are assessed using the OSHA criterion of physical hazard. Seven such hazard classes are recognized:

Water Reactive Organic Peroxides Explosives Compressed gases Pyrophoric materials. Oxidizers Unstable Reactive

This version replaces the now-obsolete yellow section titled Reactivity - see the previous section for more information. As with the Health and Flammability sections, the level of hazard is indicated using numeric values (0 = low hazard to 4 = high hazard):
4 Materials that are readily capable of explosive water reaction, detonation or explosive decomposition, polymerization, or self-reaction at normal temperature and pressure. Materials that may form explosive mixtures with water and are capable of detonation or explosive reaction in the presence of a strong initiating source. Materials may polymerize, decompose, self-react, or undergo other chemical change at normal temperature and pressure with moderate risk of explosion. Materials that are unstable and may undergo violent chemical changes at normal temperature and pressure with low risk for explosion. Materials may react violently with water or form peroxides upon exposure to air. Materials that are normally stable but can become unstable (self-react) at high temperatures and pressures. Materials may react non-violently with water or undergo hazardous polymerization in the absence of inhibitors. Materials that are normally stable, even under fire conditions, and will not react with water, polymerize, decompose , condense, or self-react. Non-explosives.

1 0

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Personalprotection Personal Protection

We present the lettering scheme here, along with a series of graphics meant to reinforce the meaning of each letter: Letter Required Equipment

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L through Z

Site-specific label. Ask your supervisor or safety specialist for handling instructions

Compressed gases:

At nuclear power plants there are many forms of compressed gas. Those used by operations personnel, chemists, maintenance, and trades personnel. Welding, brazing, chemistry control, calibrations of instrumentation just to name a few. The gauges on compressed gas systems normally read in absolute pressure which is equal to atmospheric pressure (14.7 psi) plus the pressure of the gas.

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Compressed gas can be in liquid or non-liquid phase, may come with MSDS papers depending on the type of gas.

Upright cylinder tanks found around the plant must be chained in position. Any bottles not chained should be reported to the control room.

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Almost all gasses can act as asphyxiants by displacing the air in a non-ventilated space. Please do not inhale helium and try to run to the control room to be funny, you can pass out doing this and harm yourself or others. For oxygen tanks do not use any grease or oils on the fittings and keep bottles at least 20 feet away from any form of flammable substances, including grease and oils. Note: The text book says 10 feet, this is not correct. OSHA requirement is 20 feet. High pressure tanks can become missiles if the valve is knocked off resulting in damage to structures and possible death. All high pressure bottles should be handled with the appropriate hand truck with chains installed. All high pressure tanks should be stored with the protective cap installed to prevent damage to the tanks valve. No smoking signs should be posted in the area of all combustible gas bottles or tanks. There are also requirements for bulk storage of bottles including number or bottles per fire wall separation (cuft of flammable gas) to prevent cascade explosions in the case of fire. The plants safety officer is required to train all personnel in the safety issues regarding the cylinders and gasses.

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Cryogenic Liquids: You will not normally be using cryogenic liquids at the power plant unless specifically trained to do so. The only time you may come into contact with these fluids is when a freeze seal is being applied to a pipe for repair of a leak on an operating system which cannot be isolated. Note the freeze plug or seal applied to this 6 inch line. The frozen water blocks the pressure from causing a flood while making repairs on the valves. Cryogenic liquid is pumped into the casing device. Normally, it is liquid nitrogen. Note hard hats, safety glasses, and cloves. If you are not specifically involved with work like this, just stay out of the area and obey any posted signs. Do not touch any piping or parts around this type of work. If for some reason you do come into contact (bare skin), contact the control room or your supervisor for medical attention.

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Specific properties of selected gasses: Hydrogen: The primary physical hazards associated with hydrogen gas are its flammability and explosivity. This is because hydrogen can form a flammable mixture with air over a wide range of concentrations (4% 75%), and very low energy is needed to ignite hydrogen-air Mixtures. Once hydrogen is ignited, it burns with an almost invisible flame. A low-energy ignition source is possible in hydrogen-air mixtures of 18 60% Vol that are well mixed and confined. Although hydrogen air mixtures have the same calorific value per pound as TNT; the rate of energy release is much slower for hydrogen-air mixtures. Hydrogen detonations, although rare, are characterized by pressure increases so rapid that pressure-relief devices are usually ineffective. When using hydrogen in enclosed areas, consult your plant safety officer. Hydrogen is nontoxic. The primary health effect associated with hydrogen is the possibility that it could displace air in a poorly ventilated or confined space, resulting in asphyxiation. However, because it is flammable at only 4% in air, the most significant concern should be the physical hazard of flammability and the possibility of burns resulting from fires and explosions. When working with liquid hydrogen, there is an additional health hazard of cryogenic burns.

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Nitrogen: Rapid release of nitrogen gas into an enclosed space can displace oxygen, and therefore represents an asphyxiation hazard. This may happen with few warning symptoms, An example occurred shortly before the launch of the first Space Shuttle mission in 1981, when two technicians lost consciousness (and one of them died) after they walked into a space located in the Shuttle's Mobile Launcher Platform that was pressurized with pure nitrogen as a precaution against fire. The technicians would have been able to exit the room if they had experienced early symptoms from nitrogen-breathing. When inhaled at high partial pressures (more than about 4 bars, encountered at depths below about 30 m in scuba diving) nitrogen begins to act as an anesthetic agent. It can cause nitrogen narcosis, a temporary semi-anesthetized state of mental impairment similar to that caused by nitrous oxide. Nitrogen also dissolves in the bloodstream and body fats. Rapid decompression (particularly in the case of divers ascending too quickly, can lead to a potentially fatal condition called decompression sickness (the "bends"), when nitrogen bubbles form in the bloodstream, nerves, joints, and other sensitive or vital areas. Direct skin contact with liquid nitrogen will eventually cause severe frostbite (cryogenic "burns"). This may happen almost instantly on contact, or after a second or more, depending on the form of liquid nitrogen. Full "contact" between naked skin and large collected-droplets or pools of liquid nitrogen may be prevented for second or two, by a layer of insulating gas from the Leiden frost effect. This may give the skin a second of protection from nitrogen bulk liquid. However, liquid nitrogen applied to skin in mists (such as spray from liquid cylinder and on fabrics, bypasses this effect, and causes local frostbite immediately.

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Oxygen: Oxygen is a re hazard because it promotes combustion. The serious consequences of res in air, which contains only 21 % oxygen, are well known. Increasing the oxygen concentration to more than 21 % greatly increases the re hazard. Many materials that may not be combustible in atmosphere will burn in an oxygen-enriched atmosphere. Combustible materials are easier to ignite and burn faster and hotter. Fires spread more rapidly, often with seemingly explosive results. Ignition sources that have no effect in air can be of critical importance in oxygen systems.

Sources of ignition:

Static electricity is generated by a change in relative position of contacting surfaces and may be found throughout industry in the following situations: Product flow in piping. Mixers blending solids into liquids in a partially filled tank or vessel constructed of a nonmetallic material or lined with a non-conducting material. Particulates passing through chutes or pneumatic conveyors. Container splash filling operations. Steam, air, or gas flowing from any opening in a pipe or hose, when the stream is wet or the air or gas stream contains particulate matter. Nonconductive belts in motion. Personnel wearing nonconductive shoes.

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Electrical devices in the area such a pump motors, contactors, switches, lighting fixtures, welders, etc. Spontaneous ignition on oily rags and high oxygen concentrations. Hand tools creating sparks when struck. Smoking and cigarette lighters.

Flammable and combustible liquids: On the drawing below, is a graphic display of the classes for various liquids by flash point and boiling points. Flash point: is minimum temperature at which a liquid gives off vapor within a vessel in sufficient concentration to form an ignitable mixture with air near the surface of the liquid. Boiling point: is the point of a liquid at a pressure of 14.7 psia and temperature such that it will begin to boil. This pressure is equivalent to 760 millimeters of mercury.

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Other definitions: Auto-ignition temperature: of a substance is the lowest temperature at which it will spontaneously ignite in a normal atmosphere without an external source of ignition, such as a flame or spark. This temperature is required to supply the activation energy needed for combustion. The temperature at

which a chemical will ignite decreases as the pressure increases, or oxygen concentration increases. It is usually applied to a combustible fuel mixture. Auto-ignition temperatures of liquid chemicals are typically measured using a 500 mL flask placed in a temperature controlled oven in accordance with the procedure described in ASTM E659. Below is a list of auto-ignition temperatures for various items found around a nuclear plant. Diesel 210 C (410 F) Gasoline: 246280 C (475536 F) Butane: 405 C (761 F) Paper: 450 C (842 F) Hydrogen: 536 C (997 F)

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Flammable limits: Also called explosive limits, refer to the conditions under which a mixture of a flammable material and air will catch fire or explode. If the percentage of flammable material in the air is between the minimum and maximum limits, the presence of a flame or a source of ignition will likely lead to

rapid combustion or explosion

Simply put, the lower flammable limit (LEL) is the concentration below which a flame will not propagate; the upper flammable limit (UEL) is the concentration above which a flame will not propagate. A change in temperature or pressure may vary the limits. On the next slide are some examples of flammable limits and other information.

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LFL/LEL in % Substance

UFL/UEL in % NFPA Class Flash point

Minimum Ignition Energy in mJ expressed as percent by volume in air

by volume of by volume of air air

Auto-ignition Temperature

Acetaldehyde 4.0 Acetic acid (glacial) 4

57.0 19.9

IA II

-39C 39C to 43C

0.37

175C 463C

Acetone Acetonitrile Acetyl chloride

2.6 - 3

12.8 - 13

IB IB

-17C 2C 5C

1.15 @ 4.5%

465C, 485C [2] 524C 390C

7.3

19

IB

Acetylene

2.5

82

IA

-18C

0.017 @ 8.5% (in pure oxygen 305C 0.0002 @ 40%)

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Flammable range: Is the range over which a gas will form a flammable mixture with air. The flammable range varies with different flammable liquids. Gasoline has a flammability range of 1.4 to 7.6 percent. This means it will ignite when there is 1.4 parts of gasoline mixed with 100 parts air. It is the numerical difference between the lower and upper flammable limits expressed in percentage of vapor or gas in air by volume.

Also called the explosive range. Propagation of flame: the spread of flame through the entire volume of the flammable mixture from a single ignition source. Oxygen limits: the concentration of oxygen below which a normally flammable mixture will not ignite. Rate of diffusion: The rate at which two gases mix. The rate at which gases diffuse is inversely proportional to the square root of their densities.

Rate of diffusion

Vapor pressure: the pressure exerted by a volatile liquid under any conditions of equilibrium that may exist between the vapors and the liquid. Oxygen deficiency:
The Occupational Safety and Health Administration (OSHA) respiratory protection standard (29CFR1910.134) defines an oxygen-deficient atmosphere as an atmosphere with an oxygen content below 19.5% by volume.

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Note: The text book states that the limit is <21%, since federal laws apply to nuclear plants, the 19.5 % in fact the true limit. However, it is true a deficiency exists when the concentration of O2 is less than 21%. If a question is presented by use of the federal or OSHA standard, the answer would be the 19.5 %.

Bonding and grounding:

Whenever flammable liquids or explosive gas mixtures are involved by storage systems or supply systems you will find that a precaution called bonding is employed to prevent potential differences from existing by electrically connecting two systems by wire or metal straps. This is called bonding. You will also find that a grounding wire or metal strap is attached that shunts the charges to ground preventing a charge build up and thus eliminating sparks from static charge. This does not mean however, that you dont have a static charge on your body. It is best to ground yourself prior to operating the system containing the volatile liquid or gas. This can be done by touching the ground wire or strap or actually attaching a grounding wire to your body and maintaining the ground prior to performing any operations. This is particularly true when working in the safeguard battery rooms because of the presence of hydrogen gas.

Note the grounding system used on the tanks in the next slide.

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Note that not only are the tanks grounded, but are also bonded. When using 55 gallon drums of flammable liquid, follow the precautions as shown on page 38 of your text.

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Storage areas and storage:

It is the responsibility of the site safety officer (or equivalent), engineering, and management for setting up storage areas and flammable liquid tank installations. It is your responsibility is to insure you follow plant procedures while performing any work with flammable liquids. The text has a review of requirements involved with storage of volatile substances but realize the requirements vary from plant to plant, state to state, and federal requirements can change at any time. When you are hired by a nuclear plant, you will receive additional training on all the requirements at the plant site.

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