Science Fair Project Encyclopedia
Halons are a group of compounds obtained by replacing the hydrogen atoms of a hydrocarbon with halogen atoms, such as bromine or fluorine. Halon 1211 is bromochlorodifluoromethane (CF2BrCl) and Halon 1301 is bromotrifluoromethane (CF3Br). Halons are very stable and are widely used in fire extinguishers where water and other alternatives would be ineffective and dangerous (e.g. when dealing with oil fires) or cause unacceptable collateral damage (e.g. with electronic equipment.)
At high temperatures, halons decompose to release halogen atoms that combine readily with active hydrogen atoms, quenching the flame propagation reaction even when adequate fuel, oxygen and heat remains. The chemical reaction in a flame proceeds as a free radical chain reaction; by sequestering the radicals which propagate the reaction, halons are able to "poison" the fire at much lower concentrations than are required by fire suppressants using the more traditional methods of cooling, oxygen deprivation, or fuel dilution.
For example, Halon 1301 flood systems are typically used at concentrations no higher than 6% v/v in air, and can suppress many fires at 2.9% v/v. By contrast, carbon dioxide fire suppression flood systems are operated from 34% (surface-only combustion of liquid fuels) up to 75% (dust traps). Carbon dioxide can cause severe distress at concentrations of 3 to 6%, and has caused death by respiratory paralysis in a few minutes at 10% concentration. Halon 1301 causes only slight giddiness at its effective concentration of 5%, and even at 15% persons remain conscious but impaired, and suffer no long term effects. (Experimental animals have also been exposed to 2% concentrations of Halon 1301 for 30 hours per week for 4 months, with no discernible health effects at all.) Halon 1211 also has low toxicity, although it is more toxic than Halon 1301, and thus considered unsuitable for flooding systems.
However, halon fire suppression is not completely non-toxic; very high temperature flame, or contact with red-hot metal, can cause decomposition to toxic byproducts. The presence of such byproducts is readily detected because they include hydrobromic acid and hydrofluoric acid, which are intensely irritating. Halons are very effective on Class A (organic solids), B (flammable liquids and gases) and C (electrical) fires, but they are totally unsuitable for Class D (metal) fires, as they will not only produce toxic gas and fail to halt the fire, but in some cases pose a risk of explosion. Halons can be used on Class K (kitchen oils and greases) fires, but offer no advantages over specialised foams.
Halons are referred to by a system of code numbers similar to (but simpler than) the system used for freons. The first digit specifies the number of carbon atoms in the molecule, the second is the number of fluorine atoms, the third is the chlorine atoms, and the fourth is the number of bromine atoms. If the number includes a fifth digit, the fifth number indicates the number of iodine atoms (though iodine in Halon is rare). (Note that the various atomic species are listed in order of increasing atomic number.) Any bonds not taken up by halogen atoms are then allocated to hydrogen atoms.
For example, consider Halon 1211:
C F Cl Br 1 2 1 1
Halon 1211 has one carbon atom, two fluorine atoms, one chlorine atom and one bromine atom. A single carbon only has four bonds, all of which are taken by the halogen atoms, so there is no hydrogen. Thus its formula is CF2BrCl, and its IUPAC name is therefore bromochlorodifluoromethane.
Halon 1211 is typically used in hand-held extinguishers, in which a stream of liquid halon is directed at a smaller fire by a user. The stream evaporates under reduced pressure, producing strong local cooling, as well as a high concentration of halon in the immediate vicinity of the fire. In this mode, extinguishment is achieved by cooling and oxygen deprivation at the core of the fire, as well as radical quenching over a larger area. After fire suppression, the halon moves away with the surrounding air, leaving no residue.
Halon 1301 is more usually employed in flooding systems. In these systems, banks of halon cylinders are kept pressurised to about 4 MPa (600 PSI) with compressed nitrogen, and ducts lead to the protected enclosure. On triggering, the entire measured contents of one or more cylinders are dumped into the enclosure in a few seconds, through nozzles designed to ensure uniform mixing throughout the room. The quantity dumped is pre-calculated to achieve the desired concentration, typically 3-5% v/v. This level is maintained for some time, typically twenty minutes, to ensure all items have cooled so reignition is unlikely to occur, then the air in the enclosure is purged. During this time the enclosure may be entered by persons wearing SCBA. (There exists a common myth that this is because halon is highly toxic; in fact it is because it can cause giddiness and mildly impaired perception, and also due to the risk of combustion byproducts.)
Flooding systems may be manually operated or automatically triggered by a VESDA. In the latter case, a warning siren and strobe lamp will first be activated for a few seconds to warn personnel to evacuate the area. The rapid dumping of halon and consequent rapid cooling fills the air with fog, and is accompanied by a loud, disorienting noise.
There is concern that halons are being broken down in the atmosphere to bromine, which reacts with ozone, leading to depletion of the ozone layer (this is similar to the case of chlorofluorocarbons such as freon). These issues are complicated: the kinds of fires that require halon extinguishers to be put out will typically cause more damage to the ozone layer than the halon itself, not to mention human and property damage. However, fire extinguisher systems must be tested regularly, and these tests may lead to damage. As a result, some regulatory measures have been taken, and halons are being phased out in most of the world.
Carbon tetrachloride was used in fire extinguishers and glass (anti)-"fire grenades" from the late nineteenth century until around the end of World War II. Experimentation with halogenated hydrocarbons for fire suppression on military aircraft began at least as early as the 1920s. During World War II, various early halons were in standard use in aircraft by some combatants, but these early halons suffered from excessive toxicity. Nevertheless after the war they slowly became more common in civil aviation as well.
In the 1960s, fluorinated halons became available, and were quickly recognised as one of the most effective fire fighting materials discovered. Much early research with Halon 1301 was conducted under the auspices of the US Armed Forces, while Halon 1211 was initially mainly developed in the UK. By the late 1960s, they were standard in many applications where water and dry powder extinguishers posed a threat of damage to the protected property, including computer rooms, telecommunications switches, laboratories, museums and art collections. Beginning with warships in the 1970s, halons also progressively came to be associated with rapid knockdown of severe fires in confined spaces with minimal risk to personnel.
By the early 1980s, halons were in common use on aircraft, ships and large vehicles, as well as in computer facilities and galleries. However, concern was beginning to be felt about the possible impact of chlorinated and brominated hydrocarbons on the ozone layer. The Vienna Convention on Ozone Layer Protection did not cover halons, as it was felt that emergency discharge of systems was too small in volume to produce a significant impact, and too important to human safety for restriction. However, by the time of the Montreal Protocol it was realised that discharges during system tests and maintenance accounted for substantially larger volumes than emergency discharges, and so halons were brought into the treaty, but with many exceptions.
Halons have been generally phased out and the possession of halon equipment is prohibited in some countries like the Netherlands and Belgium from January 1, 2004, based on the Montreal Protocol and guidelines of the European Union. Production of new stocks has ceased in most (probably all) countries as of 1994. However many countries still require aircraft to be fitted with halon fire suppression systems, as no safe and completely satisfactory alternative has been discovered for this application. There are also a few other highly specialised users. These programs recycle halon through "halon banks", coordinated by the Halon Recycling Corporation, to ensure that discharge to the atmosphere occurs only in a genuine emergency, and to conserve remaining stocks.
- History of Halon use by the US Navy
- MSDS for Halon 1301 (PDF file)
- Halon and CFC code numbers
- Class I Ozone-Depleting Substances
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