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FIRE CHEMISTRY

OBJECTIVE Learning Outcome 5 Describe the Chemistry of Combustion.

Assessment Criteria 5

5.1

Define . 5.1.1 5.1.2 5.1.3 5.1.4 Flash Point Fire Point Spontaneous Ignition Temperature and Spontaneous Combustion.

5.2 5.3 5.4 5.5

List the classification of fire. Explain the transmission of heat. Explain the methods of extinguishing fires. Describe the chemistry of combustion.

REFERENCES a. Fire Service Manual Volume 1 Fire Service Technology, Equipment and Media Chapter 6. b. First Edition Essentials of Fire Fighting, INTERNATIONAL FIRE SERVICE TRAINING ASSOCIATION. c. MALAYSIAN STANDARD MS 566: PART 3:2003 SPECIFICATION FOR PORTABLE FIRE EXTINGUISHERS.

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FIRE CHEMISTRY
INTRODUCTION Chemistry is a complicated subject bristling with long and difficult names to pronounce, and with intricate formula used by the chemist. There are, of course, many text books available to the student on chemistry and, inpresenting an opening to the study of fire-firefighting techniques, it is difficult to decide exactly how much should be included. Many new processes and materials have become available in recent year. Firefighters are faced with so many new substances, particularly new building materials, during the course of their work, that they must have some idea how they will react when involved in fire. PRINCIPLES OF COMBUSTION The combustion process is a chemical reaction that produces energy in the form of heat and combustion products of different shapes and properties of the original material was burned. Combustion is defined as a process rapid oxidation of the ability to support himself, followed by heat and light. To produce flame (Ignition), three key elements required are: a. Fuel (Fuel) b. Heat (Heat) c. Oxygen or oxidation agents (Oxidizing Agent) These three elements are represented as triangles burning (Fire Triangle) as shown in Figure 1.

Figure 1 : The Fire Triangle was used to explain the Three components necessary for burning.

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FUEL (Reducing Agent) The fuel segment of both the fire triangle and tetrahedron is defined as "any material that can be oxidized." The term "reducing agent" has reference to a fuel's ability to reduce an oxidizing agent. OXYGEN (Oxidizing Agent) The term "oxidizing agent" helps explain how some materials, such as sodium nitrate and potassium chlorate, which release their own oxygen under certain conditions, can burn in an oxygen-free atmosphere. HEAT (Temperature) Heat and temperature are closely related and in some cases inseparable. Heat is a type of energy in disorder while temperature is a measure of the degree of that disorder. CHEMICAL CHAIN REACTION The vapors of gases which ate distilled during the burning process of a material are carried into the flame. These vapors contain atoms and molecules which have not yet been changed and they have an electrical charge which either attracts or repels other particles. The area between the flame and the fuel is called the "flame interface," a place where very little burning takes place. Oxygen is drawn into the flame area from the interface throughout it suppermost regions. Here the molecular structure of the material is broken down and the released atoms combine with other radicals to form new compounds, which are again broken down by the heat. Neither this description nor the reactions depicted in Figure 2 are a step-by-step process, because these reactions occur simultaneously in varying degrees.

Figure 2 : Chemical Chain Reaction

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FLASH POINT The liquid temperature at which application of an ignition source will cause a flame to flash across the liquid. This is a premixed flame moving through the vapour/air mixture but, just above the flashpoint, it burns out, or self-extinguishes, because it has consumed all the vapor. If heating is continued, a temperature will be reached at which ignition of the vapours will lead to a flash, followed by the development of the sustained diffusion flame at the surface flame. FIRE POINT The lowest temperature at which the rate of supply of fuel vapours (by evaporation) can sustain the flame. There are types of apparatus for determining the flash point of the liquid. The most comman is the Pensky-Martens closed cup test in which the vapours can not diffuse away from the surface, but can achieve a uniform concentration in the head space above the liquid surface. The Able apparatus is also a close cup test. The Cleveland open cup test gives a slightly higher flashpoint than the Pensky -Martens, but can be used to determine the firepoint. Clearly, it is always necessary to quote the method and type of apparatus used, and whether the result is an open cup or close cup flashpoint. Note that the flashpoint is affected slightly by pressure: values quoted in handbooks, etc.., are adjusted to normal atmospheric pressure. Corrections should be considered for high altitude applications. SPONTANEOUS IGNITION TEMPERATURE This is the lowest temperature at which the substance will ignite spontaneously, that is the substancewill burn without the application of a flame or ignition source. This is sometimes referred to as the auto-ignition temperature. For some materials, the ignition temperature may be so low that is a danger of them igniting under normal condition, or in the range of temperatures that the material would experience during day-to-day use. Such materials are normally well documented and information available regarding their safe handling. SPONTANEOUS COMBUSTION Spontaneous combustion should be considered as a possible cause of a fire for which there is no obvious ignition source, but it is necessary to show that the material involved has the propensity to self heat, and that a sufficient quantity has been stored in such a way as to provide the necessary thremalinsulation for the inside of the pile. A useful rule-of-thumb is that if the material does not produce a rigid char when it is heated, it is very unlikely to self heat ignition. CLASSIFICATION OF FIRES AND EXTINGUISHING METHODS According to the MS 1182: Classification of fires can be classified into 6 categories which are: CLASS A FIRES Fires involving ordinary combustible materials, such as wood, cloth, paper, rubber, and many plastics. CLASS A EXTINGUISHMENT Water is used in a cooling or quenching effect to reduce the temperature of the burning material below its ignition temperature Figure 5.1.

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Figure 5.1 : Most ordinary combustible materials are included in the definition of Class A fires. CLASS B FIRES Fires involving flammable liquids, greases, and gases. CLASS B EXTINGUISHMENT The smothering or blanketing effect of oxygen exclusion is most effective. Other extinguishing methods include removal of fuel and temperatur~ reduction Figure 5.2.

Figure 5.2 : Class B fires involve flammable liquids and gases. CLASS C FIRES Involving flammable gases such as methane and butane. The easiest way to remove the fire is the way starving. CLASS C EXTINGUISHMENT " Three groups of gaseous extinguishing agents may be used in portable extinguishers. The first is the halons, the use of which has been greatly restricted by the ratification of the Montreal Protocol. The second is carbon dioxide and the third group

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consists of more, complex mixtures of non halogen gases. AII of these groups are classified as clean agents.

Figure 5.3 : Class C CLASS D FIRES Fires involving combustible metals, such as magnesium, titanium, zirconium, sodium and potassium. CLASS D EXTINGUISHMENT The extremely high temperature of some burning ,metals makes water and other common extinguishing agents ineffective. There is no agent available that will effectively control fires in all combustible metals. Special extinguishing agents are available for control of fire in each of the metals and are marked specifically for that metal Figure 5.4.

Figure 5.4 : Combustible metals in Class D fires special extinguishing agents. CLASS F FIRES Fires involving fast and cooking oils. CLASS F EXTINGUISHMENT The selection of extinguishers should also take into account the likelihood of gaseous and/or electrical hazards in the same area. Multi-purpose types are especially suited to these positions. For deep fat frying situations class F extinguishers are recommended.

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THE TRANSMISSION OF HEAT Heat energy always flows from regions of high temperature to regions of lower temperature. Heat will always flow when there is a temperature difference, no matter how small that temperature difference is. There are three methods by which heat may be transmitted (Figure 5.5) : Conduction; Convection; and Radiation. Direct Flame Contact.

Figure 5.5 : Diagram illustrating conduction, convection and radiation. Conduction Heat may be conducted from one body to another by direct contact of the two bodies or by an intervening heat-conduction medium. The amount of heat that will be transferred and its rate of travel by this method depends upon the conductivity of the material through which the heat is passing. Not all rnaterials have the same heat conductivity. Aluminum, copper, and iron are good conductors. Other solids such as stone and wood are poor conductors. Fibrous materials, such' as felt, cloth, and paper, are poor conductors. Liquids and gases are poor conductors of heat because of the free movement of their molecules. Air is a very poor conductor. Certain solid materials, when shredded into fibers and packed into batts, make good insulation because' the material itself is a poor conductor and there are air pockets within the batting. Double building walls which contain. an air space provide additional insulation. The line drawing in Figure 5.6 illustrates heat transfer by conduction

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Figure 5.6 : Example of heat transfer by conduction. Heated steel beam conducts heat to other combustibles. Convention Convection is the transfer of heat by the movement of air or liquid. This movement is different from the molecular motion discussed in conduction. When liquids or gases are heated, they begin to move within themselves. For example, when water is heated in a glass container, an upward movement within the vessel can be observed through the glass. (The addition of some sawdust to the water will make this movement more apparent.) As the water is heated, it expands and grows lighter, causing the upward movement. In the same manner, heated air will expand, become lighter, and move upward. As the heated air moves upward, cooler air takes its place at lower levels. As previously mentioned, this is important for firefighters to remember, and is why you must remain low in this type of environment., Th~ spread of fire by convection has more influence upon the positions for fire attack and ventilation than either of the previously discussed methods of heat propagation. Heated air in a building will expand and rise. For this reason, fire spread by convection is mostly in an upward direction although air currents can carry heat in any direction. Convected heat currents are generally the cause of heat movement from floor to floor, from room to room and from area to area. The spread of fire through corridors, up stairwells and elevator shafts, between walls, and through attics is mostly caused by the convection of heat currents. the line drawing in Figure 5.7 illustrates heat transfer by convection.

Figure 5.7 : Heat transfer by convection, or the movement of air. Fire spread by convection will usually be in an upward direction.

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Radiation This method of heat transmission is known as radiation of heat waves. Heat and light waves are similar in nature but they differ in length. Heat waves are longer than light waves and they are sometimes called infrared rays. Radiated heat will travel through space until it reaches an opaque object. As the object is exposed to heat radiation it will in return radiate heat from its surface. Radiated heat is one of the major sources of fire spread and its importance demands an immediate defensive attack at points where radiation exposure is severe. Heat transfer by radiation is illustrated in Figure 5.8.

Figure 5.8 : Heat transfer by radiation, one of the major sources of fire spread. THE METHODS OF EXTINGUISHING FIRES Fire extinguishing methods often use more than one of these principles, but it will be convenient to group them according to the main principle involved. Starvation Fires can be starved of fuel (Figure 5.9, top) in three ways. By removing potential fuel from the neighbourhood of the fire. For example, by: Draining fuel from burning oil tanks; Working out cargo at a ship fire; Cutting treaches or creating fire breaks in, for example, peat, heath and forest fire, demolishing buildings to create a fire stops; and Counter-burning in forest fires.

Smothering Smothering is the principle behind snuffing out candles and capping oil well fires. The battening down of a ships hold when a fire breaks out below decks will sometimes hold the flame in check until port is reached. Small fires, such as those involving a persons clothing, can be smothered with a rug, blanket, etc., while the used of sand or earth on a small metal fire is a further instance of the same principle.

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Cooling Cooling the fuel is the main way in which water is used to extinguish fires. There are many variation: for example, a tank fire involving a high flashpoint oil (boiling point >> 100C) can be extinguished by a high velocity sprinkler spray which apparaently produses a water-in-oil emulsion at the surface, thus causing rapid cooling. This neatly avoids the problem of water sinking to the bottom of the tank before it has had much effect on the temperature of the surface layer. When it is applied to a fire, the extinguishing medium waterfor example itself undergoes changes as it absorbs heat from the fire: (1) (2) (3) (4) Its temperature will rise; It may evaporate (boil); It may chemically decompose (not water); and It may react chemically with the burning material.

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Figure 5.9 : The tringle of combustion Top : Starvation or the limition of the combustible material. Centre : Smothering or the limition of oxygen. Bottom : Cooling or the limition of temperature. CONCLUSION In order to be a successful fire fighter you must learn as much as possible about the characteristics and behaviour of fire, which were covered in this chapter. Within this chapter the different characteristics of solid, liquids, and gases were described. The conditions necessary for combustion to occur and the products of combustion were described.

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