FLAMMABLE

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CHEMICAL ENGINEERING DEPARTEMENTSTATE OF POLYTECHNIC

FLAMMABLE

1. IntroductionManaging hazards associated with flammable and combustible liquids requires a comprehensive strategy tailored to the conditions of their use. While preventive measures, such as spill prevention and ignition control, should receive the utmost attention, measures to mitigate fires and explosions should also be addressed. A strategy relying solely on prevention could be ineffective as unforeseen circumstances may arise.The primary objective should minimize the life safety risk associated with the use of these materials. Other secondary consequences, such as environmental exposure, business interruption, and property damage, should also be factored into the strategy. This strategy should consider various scenarios, such as the potential for static pool fires, two dimensional flowing fires, three dimensional spill fires, as well as pressurized or spray fires. Also, explosions can result from combustion of vapors in either a confined or unconfined setting.2. Definition of FlammableA flammable material is any liquid, solid or gas that will ignite easily and burn rapidly. Materials that are flammable are of concern due to their ability to render damage to property and more importantly, to injure or cause death of workers.3. Classiication of flammability The US Government uses the Hazardous Materials Identification System (HMIS) standard for flammability ratings, as do many US regulatory agencies, and also the US National Fire Protection Association (NFPA).The NFPA 30 classification system is as follows: FlammableLiquidClass IA Flash Point < 73 F (22.8 C) & Boiling Point < 100 F (37.8 C)Class IB Flash Point < 73 F (22.8 C) & Boiling Point 100 F (37.8CClass IC Flash Point 73 F (22.8 C) & < 100 F (37.8 C) CombustibleLiquidClass II Flash Point 100 F (37.8 C) & < 140 F (60 C)Class IIIA Flash Point 140 F (60 C) & < 200 F (93 C)Class IIIB Flash Point 200 F (93 C)Table 1 lists ignition properties for a sample of flammable liquids and is sorted from lowest flash point to highest. Properties associated with electrostatic ignition include electrical conductivity, minimum ignition energy (MIE), and charge relaxation times. The auto ignition temperatures (AITs) are also shown.MaterialNFPA ClassFlash Point F (C)Boiling Temperature F (C)Electrical Conductivity (pS/m)MIE (mJ)Charge Relaxation Time (s)Auto Ignition Temperature F (C)

Diethyl EtherIA-49(- 45)95 (35)300.291.4356(180)

AcetoneIB- 4 (-20)133 (56)6 x 1060.193.2 x 10-5869(465)

HeptaneIB25 (-4)209 (98)< 1 x 1010.2~ 100399(204)

Isopropyl AlcoholIB53 (12)181 (83)3.5 x 1080.535 x 10-7750(399)

Ethyl AlcoholIB55 (13)173 (78)1.35 x 1050.231.6 X 10-3685(363)

Styrene MonomerIC88 (31)295 (146)102.2450(232)

Codes FlammabilityFor existing buildings, fire codes focus on maintaining the occupancies as originally intended. In other words, if a portion of a building were designed as an apartment, one could not suddenly load it with flammable liquids and turn it into a gas storage facility, because the fire load and smoke development in that one apartment would be so immense as to overtax the active fire protection as well as the passive fire protection means for the building. The handling and use of flammable substances inside a building is subject to the local fire code, which is ordinarily enforced by the local fire prevention officer.

4. Example, and Properties of Flammable Materials Examples of flammable substancesFlammable substances include, but are not limited to:1. Gasoline - Petrol / a complicated mixture of hydrocarbons that includes isomers of octane, C8H182. Ethanol / CH3CH2OH3. Rubber4. Isopropyl alcohol / CH3CH(OH)CH35. Methanol / CH3OH6. Wood7. Acetone / CH3COCH38. Paper9. Nitromethane / CH3NO2 Properties of Flammable MaterialsFlammable substances are those gases, liquids and solids that will ignite and continue to burn in air if exposed to a source of ignition. Many flammable and combustible liquids and solids are volatile in nature; that is, they evaporate quickly and are continually giving off vapours. The rate of evaporation varies greatly from one liquid to another and increases with temperature. It is their vapours combined with air, not the liquid or solids themselves, that ignite and burn. In many instances, an increase in temperature creates a more hazardous condition because of the increase in the rate at which vapours are evolved. Flash Point This is the lowest temperature of the liquid at which it gives off enough vapour to form an ignitible mixture of vapour and air immediately above the liquid surface. A liquid is classified as flammable or combustible depending on its flash point. A flammable liquid has a flash point below 37.8 C while a combustible liquid has a flash point greater than 37.8 C. Example: Flash point of Acetone is - 17.8 C (*closed cup) and that of Aniline is 70.0 C (*closed cup). The lower the flash point, the greater the potential fire hazard. Flammable (Explosive) Range This is the range between the lowest explosive limit (LEL) and the upper explosive limit (UEL). The LEL is the lowest concentration of vapour in air which will burn or explode upon contact with a source of ignition. Below the LEL, the mixture is too lean (i.e. there is insufficient fuel). The UEL is the highest concentration of vapour in air which will burn or explode upon contact with a source of ignition. Above the UEL, the mixture is too rich to burn (i.e. there is insufficient oxygen). The LEL and UEL are usually indicated by the percentage by volume of vapour in air.

Example - For diethyl ether, the LEL is 1.9% and the UEL is 36% by volume of air. This range becomes wider with increasing temperature and in oxygen-rich atmospheres. For most solvents the LEL lies in the range 1-5% in air and therefore good ventilation is essential in order to minimize the risk of forming a flammable or explosive atmosphere when such substances are used. However, it is significant that the LEL for most substances is considerably greater than the recommended hygiene standards for the concentration of vapour in the workroom air. Auto-Ignition TemperatureThe autoignition temperature of a substance is the minimum temperature required to initiate or cause self-sustained combustion, in the absence of a spark or flame. Example: 1. A steam line or a glowing light bulb may ignite carbon disulphide (autoignition temperature is 100 C). 2. Diethyl ether (autoignition temperature is 160 C) can be ignited by the surface of a hot plate. Vapour Density The vapour density is the ratio of the density of the gas or vapour to the density of air (vapour density of air = 1). Generally, vapours from flammable liquids are denser than air and thus tend to sink to ground level where they can spread over a large area. Example:- Vapour density of ethyl alcohol is 1.59. Sources of IgnitionA source of ignition represents a sufficiently high enough temperature to ignite a fuel. Common sources of ignition include:- open flames, hot surfaces, static electricity, smoking material, cutting and welding operations, radiant heat, frictional heat, electrical and mechanical (frictional) sparks, spontaneous combustion, and heat-producing chemical reactions. Examples of generation of static electricity:- 1. A rapidly moving belt develops static electricity by coming in contact with the pulley and then moving away from it. 2. Paper and cloth take on static charges when passing through machines. 3. Paint spraying generates static. 4. Static charges are produced by the flow of flammable liquids into or from tanks or other containers through pipes, hose, or even air, or by pouring from one container to another. Static electricity accumulations sufficient to cause a spark can, however, be prevented by grounding, bonding, or humidification. The danger of fire and explosion presented by flammable liquids, generally, can be eliminated or minimized by strict observance of safe storing, dispensing, and handling procedures.5. Handling PrecautionsThe main objective in working safely with flammable liquids is to avoid accumulation of vapors and to control sources of ignition. Besides the more obvious ignition sources, such as open flames from Bunsen burners, matches and cigarette smoking, less obvious sources, such as electrical equipment, static electricity and gas-fired heating devices should be considered. Accounts of a few of the fires that have occurred in our laboratories may be found inAnecdotes.Some electrical equipment, including switches, stirrers, motors, and relays can produce sparks that can ignite vapors. Although some newer equipment have spark-free induction motors, the on-off switches and speed controls may be able to produce a spark when they are adjusted because they have exposed contacts. One solution is to remove any switches located on the device and insert a switch on the cord near the plug end.Pouring flammable liquids can generate static electricity. The development of static electricity is related to the humidity levels in the area. Cold, dry atmospheres are more likely to facilitate static electricity. Bonding or using ground straps for metallic or non-metallic containers can prevent static generation.1. Control all ignition sources in areas where flammable liquids are used. Smoking, open flames and spark producing equipment should not be used.2. Whenever possible use plastic or metal containers or safety cans.3. When working with open containers, use alaboratory fume hoodto control the accumulation of flammable vapor.4. Use bottle carriers for transporting glass containers.5. Use equipment with spark-free, intrinsically safe induction motors or air motors to avoid producing sparks. These motors must meet National Electric Safety Code (US DOC, 1993) Class 1, Division 2, Group C-D explosion resistance specifications. Many stirrers, Variacs, outlet strips, ovens, heat tape, hot plates and heat gunsdo notconform to these code requirements.6. Avoid using equipment with series-wound motors, since they are likely to produce sparks.7. Do not heat flammable liquids with an open flame. Steam baths, salt and sand baths, oil and wax baths, heating mantles and hot air or nitrogen baths are preferable.8. Minimize the production of vapors and the associated risk of ignition by flashback. Vapors from flammable liquids are denser than air and tend to sink to the floor level where they can spread over a large area.9. Electrically bond metal containers when transferring flammable liquids from one to another. Bonding can be direct, as a wire attached to both containers, or indirect, as through a common ground system.10. When grounding non-metallic containers, contact must be made directly to the liquid, rather than to the container.11. In the rare circumstance that static cannot be avoided, proceed slowly to give the charge time to disperse or conduct the procedure in an inert atmosphere.6. Storage of Flammable and Combustible LiquidsThis material should be stored in a cool, because if stored in hot areas can cause fires, the air circulation it should be quite separate from oxidizing materials, available fire extinguisher nearby, away from sources of fire, where he provided a tool fire / smoke detectors automatically.Flammable and combustible liquids should be stored only in approved containers. Approval for containers is based on specifications developed by organizations such as the USDepartment of Transportation(DOT),OSHA, theNational Fire Protection Agency(NFPA) orAmerican National Standards Institute(ANSI). Containers used by the manufacturers of flammable and combustible liquids generally meet these specifications

Safety Cans and Closed Containers

Many types of containers are required depending on the quantities and classes of flammable or combustible liquids in use. A safety canis an approved container of not more than 5 gallons capacity that has a spring closing lid and spout cover. Safety cans are designed to safely relieve internal pressure when exposed to fire conditions. A closed containeris one sealed by a lid or other device so that liquid and vapor cannot escape at ordinary temperatures.Colors are used to designate what type of liquid is being stored so it can be quickly and visually identified without label reading. Using colors to differentiate between various types of liquids helps avoid costly errors when more than one type of liquid is present at a worksite. It reduces errors because content identification is easier.Red Flammable Liquids General flammable liquids storage - Red is the most widely used (and OSHA-accepted) color for flammable liquid safety cans. Heavy-duty, high grade coated steel construction features special reinforcing ribs to strengthen sidewalls for extra "bumper guard" protection. The self-closing, leakproof lid helps prevent spills and leaks.

Green (Oils) Green flammable liquid safety cans for oils storage - Using colors to differentiate between various types of liquids helps avoid costly errors when more than one type of liquid is present at a worksite. Unique counterbalance, ergonomic design with full-fisted grip handle offers gravity-assisted pouring.Blue (Kerosene) Blue safety cans for kerosene storage - Colors are used to designate what type of liquid is being stored so it can be quickly, visually identified without label reading. To protect against rupture or explosion, positive pressure relief mechanism automatically vents between 3 and 5 psig.Yellow (Diesel) Yellow safety cans are used for diesel fuel (although like all Type I cans, they can handle any flammable liquid). Finished in a tough powder coat paint, these cans resist chemicals and standup to heavy abuse. Safety can meets OSHA and NFPA requirements, and carries an exclusive Justrite Ten-Year Warranty.Polyethylene Excellent for corrosives - Choose Type I nonmetallic, high-density polyethylene Safety Cans when dent and chemical resistance are vital. Polyethylene construction means it is inert, so it stands up to tough acids and corrosives as well as heat. Its dent, puncture and chip resistant. Flammable Liquid Storage CabinetsAflammable liquid storage cabinetis an approved cabinet that has been designed and constructed to protect the contents from external fires. Storage cabinets are usually equipped with vents, which are plugged by the cabinet manufacturer. Since venting is not required by any code or the by local municipalities and since venting may actually prevent the cabinet from protecting its contents, vents should remain plugged at all times. Storage cabinets must also be conspicuously labeled"FLAMMABLE KEEP FIRE AWAY".Storage Considerations Quantities should be limited to the amount necessary for the work in progress.

No more than 10 gallons of flammable and combustible liquids, combined, should be stored outside of a flammable storage cabinet unless safety cans are used. When safety cans are used up to 25 gallons may be stored without using a flammable storage cabinet.

Storage of flammable liquids must not obstruct any exit.

Flammable liquids should be stored separately from strong oxidizers, shielded from direct sunlight, and away from heat sources because can to be fire.

Handling PrecautionsControl all ignition sources in areas where flammable liquids are used. Smoking, open flames and spark producing equipment should not be used.

Whenever possible use approved safety cans, plastic or metal containers.

When working with open containers, use a laboratory fume hood to control the accumulation of flammable vapor.

Use bottle carriers for transporting glass containers.

Electrically bond metal containers when transferring flammable liquids from one to another. Bonding can be direct, as a wire attached to both containers, or indirect, as through a common ground system.

Flammable AerosolsFlammable aerosols are in pressurized containers that may rupture when exposed to fire. As with flammable liquids, these should be stored in a flammable storage cabinet. RefrigeratorsUse only those refrigerators that have been designed and manufactured for flammable liquid storage. Standard household refrigerators must not be used for flammable storage because internal parts could spark and ignite. Refrigerators must be prominently labeled as to whether or not they are suitable for flammable liquid storage.Storage Considerations:1. Quantities should be limited to the amount necessary for the work in progress.2. No more than 10 gallons of flammable and combustible liquids, combined, should be stored outside of a flammable storage cabinet unless safety cans are used. When safety cans are used, up to 25 gallons may be stored without using a flammable storage cabinet.3. Storage of flammable liquids must not obstruct any exit.4. Flammable liquids should be stored separately from strong oxidizers, shielded from direct sunlight, and away from heat sources. See Anecdotesfor a description of an incident involving a flammable material stored near a hot plate.7. Safe Working with Flammable SubstancesThe Health and Safety Executive is the principle authority on flammable substances with Fire and Local authorities taking a secondary role never the less working very closely together. Small quantities of dangerous goods can be found in most workplaces. Whatever they are used for, the storage and use of such goods can pose a serious hazard unless basic safety principles are followed. If you use one particular group of dangerous goods flammable and explosive substances this guidance will help you to:1. be aware of the hazards of various types of flammable substance2. be aware of the basic standards which apply to safe handling and storage of flammable substances3. introduce procedures to prevent accidents and protect people from the hazards of flammable substances4. find more detailed information when you need itThere is an enormous variety of flammable substances to be found in the workplace. They range from the obvious, e.g. petrol, paint thinners, welding gases and heating fuels, to the not so obvious, e.g. packaging materials, dusts from woodworking and dusts from food stuffs such as flour and sugar etc. Three ingredients are needed for a fire: a fuel at the right concentration, a good supply of air, and a source of ignition. If you control these ingredients, fires can be prevented. Safety PrinciplesBy applying the following five principles you will be well on the way to making sure that you are working safely with flammable substances.Think V.I.C.E.S and keep a strong grip on your workplace safety.

VentilationIs there plenty of fresh air where flammable liquids or gases are stored and used? Good ventilation will mean that any vapours given off from a spill, leak, or release from any process, will be rapidly dispersed. IgnitionHave all the obvious ignition sources been removed from the storage and handling areas? Ignition sources can be very varied and they include sparks from electrical equipment or welding and cutting tools, hot surfaces, open flames from heating equipment, smoking materials etc. ContainmentAre your flammable substances kept in suitable containers? If you have a spill will it be contained and prevented from spreading to other parts of the working area? Use of lidded containers and spillage catchment trays, for example, can help to prevent spillages spreading. ExchangeCan you exchange a flammable substance for a less flammable one? Can you eliminate flammable substances from the process altogether? You may be able to think of other ways of carrying out the job more safely. SeparationAre flammable substances stored and used well away from other processes and general storage areas? Can they be separated by a physical barrier, wall or partition? Separating your hazards in this manner will contribute to a safer workplace.Think about the flammable substances you have in the workplace and apply these five principles wherever possible. Tell workers, and others who need to know, about the hazards and how they should control them.

Specific materialsThe following sections deal with specific types of flammable substances. The precautions mentioned need to be considered in addition to the VICES principles just described. Flammable liquidsFlammable liquids can give off large volumes of flammable vapours at room temperature. These vapours, when mixed with air, can ignite, often violently. Spilled flammable liquids can, if not contained, flow a long way to an ignition source, and then flash back to the source of the leak. Spills on clothing can represent a serious risk of injury if ignited. To help control these risks:1. store flammable liquids in a separate storage area, or in a purpose-made bin or cupboard2. dispense and use them in a safe place where there is good ventilation and no source of ignition3. keep containers closed when not in use. If possible, use safety containers which have self-closing lids4. dispense liquids over a tray and keep some non-flammable absorbent material handy to mop up spills5. dispose of contaminated materials safely or call in disposal experts. Flammable dustsFinely divided flammable dusts dispersed in the workplace atmosphere can, if ignited, explode violently and cause a lot of damage. If you handle flammable dusts you need to remember the following:1. keep plant dust-tight;2. keep the working area dust-free by regular cleaning, and vacuuming spillages as they occur3. some dust handling plant has special safety features built in. The purpose of these needs to be properly understood, and they should be maintained in good working order. Flammable solidsSome types of plastic foam, packaging materials, polyester wadding and textiles will ignite easily and burn fiercely, giving off a lot of dense black smoke. Remember:1. do not store these materials close to heaters or electrical equipment which could run hot and act as a local ignition source;2. make sure that gangways and exits from storage and working areas are kept clear of packaging materials, finished products containing flammable solids etc. In the event of fire, gangways and exits could become obscured by smoke, so the easier they are to find, the better. Flammable gasesGases in cylinders are often stored at very high pressures, and so their uncontrolled release can be physically dangerous. A small amount of released gas can fill a large area with a potentially explosive mixture. This is particularly true of liquefied gases such as LPG. The following points need to be considered:1. stored cylinders need to be suitably restrained and their valves protected from impact damage2. gas cylinders may need special valves, fittings and hoses. Always check the manufacturers or suppliers instructions and fit the correct equipment3. protect hoses from potential causes of damage that could cut, scuff or weaken them. Examine them regularly and replace them if they show signs of damage or wear that could give rise to a leak. OxygenAlthough oxygen is necessary for life and is an essential ingredient in controlled burning, such as in a gas fire or oxy-fuel gas welding and cutting, its misuse can lead to serious consequences. Materials that ordinarily will burn only slowly will burn very vigorously in an oxygen-enriched atmosphere. Others such as greases and oils may burst into flames in this kind of atmosphere. As well as the precautions outlined above for flammable gases, the following points should be remembered:1. never use oxygen instead of compressed air2. never use oxygen to sweeten the air in a working area or confined space3. never use grease or oil on equipment containing oxygen. Reactive chemicalsSome products contain chemicals, such as organic peroxides, which can explode if they are not stored and handled correctly. Other substances can react vigorously with incompatible materials or contaminants. For example, oxidising chemicals can cause flammable materials to ignite, and some substances, such as sodium, react violently with water and can ignite. The following points need to be considered:1. storage and process temperatures may need to be carefully controlled to prevent dangerous decomposition or reaction;2. check labels and safety data sheets for physical properties and incompatibility with other materials. EmergenciesWhenever you work with flammable substances, there is the potential for something to go wrong. You need to think about possible problems and make sure everyone knows what to do in an emergency. Instructing staff in emergency procedures is an important part of their job training, and should be ongoing. Examples of things to think about are:1. make sure workers know enough to prevent the mixing of incompatible chemicals;2. lay down the procedures to be followed if there is a leak or spill of flammable material and make sure people know and understand them;3. if special first-aid facilities or equipment are required, then staff need to be trained in their use.

Further InformationThe guidance leaflet safe working with flammable substances will give you some basic guidance on the safe storage and use of flammable substances. Health and safety inspectors who might visit your premises will be looking to see how you have applied this guidance to help prevent fires. You may also have a visit from the Fire Safety Officer of your local Fire and Rescue Service who will want to ensure that that you comply with the The Regulatory Reform (Fire Safety) Order 2005. This includes checking if a fire risk assessment has been completed which should have considered the safe working with flammable substances.HSE priced and free publications are available at HSE BooksThis leaflet contains notes on good practice which are not compulsory but which you may find helpful in considering what you need to do.