Decomposition, flammability

Bromine is used in the manufacture of many important organic compounds including 1,2-dibromoethane (ethylene dibromide), added to petrol to prevent lead deposition which occurs by decomposition of the anti-knock —lead tetraethyl bromomethane (methyl bromide), a fumigating agent, and several compounds used to reduce flammability of polyester plastics and epoxide resins. Silver(I) bromide is used extensively in the photographic industry... 

Antimony Oxide as a Primary Flame Retardant. Antimony oxide behaves as a condensed-phase flame retardant in cellulosic materials (2). It can be appHed by impregnating a fabric with a soluble antimony salt followed by a second treatment that precipitates antimony oxide in the fibers. When the treated fabric is exposed to a flame, the oxide reacts with the hydroxyl groups of the cellulose (qv) causing them to decompose endothermically. The decomposition products, water and char, cool the flame reactions while slowing the production and volatilization of flammable decomposition products (see Flaa retardants for textiles). 

In the flame phase the water vapor forms an envelope around the flame, which tends to exclude air and dilute the flammable gases. The water vapor reacts endothermically with the flame radicals. The alumina residue becomes a conduit through which heat is conveyed away from the flame area, slowing down polymer decomposition. 

Dehydration or Chemical Theory. In the dehydration or chemical theory, catalytic dehydration of ceUulose occurs. The decomposition path of ceUulose is altered so that flammable tars and gases are reduced and the amount of char is increased ie, upon combustion, ceUulose produces mainly carbon and water, rather than carbon dioxide and water. Because of catalytic dehydration, most fire-resistant cottons decompose at lower temperatures than do untreated cottons, eg, flame-resistant cottons decompose at 275—325°C compared with about 375°C for untreated cotton. Phosphoric acid and sulfuric acid [8014-95-7] are good examples of dehydrating agents that can act as efficient flame retardants (15—17). 

In the absence of air, TEE disproportionates violently to give carbon and carbon tetrafluoride the same amount of energy is generated as in black powder explosions. This type of decomposition is initiated thermally and equipment hot spots must be avoided. The flammability limits of TEE are 14—43% it bums when mixed with air and forms explosive mixtures with air and oxygen. It can be stored in steel cylinders under controlled conditions inhibited with a suitable stabilizer. The oxygen content of the vapor phase should not exceed 10 ppm. Although TEE is nontoxic, it may be contaminated by highly toxic fluorocarbon compounds. 

Diketene is a flammable Hquid with a flash point of 33°C and an autoignition temperature of 275°C. It decomposes rapidly above 98°C with slow decomposition occurring even at RT. The vapors are denser than air (relative density 2.9, air air = 1). The explosive limits in air are 2—11.7 vol % (135). In case of fire, water mist, light and stabilized foam, as well as powder of the potassium or ammonium sulfate-type should be used. Do not use basic extinguisher powders and do not add water to a closed container. 

ButyUithium is available as a 15—20 wt % solution in //-pentane or heptane. Noticeable decomposition occurs after alb reflux in heptane (bp 98.4°C) but not after a 15 min reflux in ben2ene (bp 80.1°C) or hexane (bp 68°C). /-ButyUithium in pentane or heptane is more stable than //-butyUithium in hexane (125). Solutions of /-butyUithium in pentane and heptane are flammable Hquids and are considered pyrophoric. The /-butyl compound is more reactive than either the n- and sec-huty. Di-//-butylether is cleaved by /-butyUithium in 4—5 h at 25°C, compared to the 2 d for j iZ-butyUithium and 32 d for //-butyUithium (126). /-ButyUithium can be assayed by aU of the techniques used for //-butyUithium. /-ButyUithium is a useful reagent in syntheses where the high reactivity of the carbon—lithium bond and smaU si2e of the lithium atom promote the synthesis of stericaUy hindered compounds, eg,... 

In particular, PB and PMP are inert materials and usually present no health hazard. PMP is employed extensively for a number of medical and food packaging appHcations. Several grades conform to FDA regulations and to the health standards of other countries. Flammability of polyolefin resins is equal to that of PP, around 2.5 cm /min (ASTM D635). However, during combustion or pyrolysis, smoke, fumes, and toxic decomposition products are formed and can pose a health hazard. 

Oxahc acid is not flammable but its decomposition products, both formic acid and carbon monoxide, are toxic and flammable. Its dust and mist are irritating, especially under prolonged contact. Personnel who handle oxahc acid should wear mbber gloves, aprons, protection masks or goggles, etc, to avoid skin contact and inhalation. Adequate ventilation also should be provided in areas in which oxahc acid dust fumes are present. 

PTMEG is a polymeric ether susceptible to both thermal and oxidative degradation. It usually contains 300—1000 ppm of an antioxidant such as 2,6-di-/ f2 -butyl-4-hydroxytoluene (BHT) to prevent oxidation under normal storage and handling conditions. Thermal decomposition in an inert atmosphere starts at 210—220°C (410—430°E) with the formation of highly flammable THE. In the presence of acidic impurities, the decomposition temperature can be significantly reduced contact with acids should therefore be avoided, and storage temperatures have to be controlled to prevent decomposition to THF (261). 

Titanium Dibromide. Titanium dibromide [13873-04-5] a black crystalline soHd, density 4310 kg/m, mp 1025°C, has a cadmium iodide-type stmcture and is readily oxidized to trivalent titanium by water. Spontaneously flammable in air (142), it can be prepared by direct synthesis from the elements, by reaction of the tetrabromide with titanium, or by thermal decomposition of titanium tribromide. This last reaction must be carried out either at or below 400°C, because at higher temperatures the dibromide itself disproportionates. 

Solutions of these fire retardant formulations are impregnated into wood under fliU cell pressure treatment to obtain dry chemical retentions of 65 to 95 kg/m this type of treatment greatly reduces flame-spread and afterglow. These effects are the result of changed thermal decomposition reactions that favor production of carbon dioxide and water (vapor) as opposed to more flammable components (55). Char oxidation (glowing or smoldering) is also inhibited. 

Stabilized tetrachloroethylene, as provided commercially, can be used in the presence of air, water, and light, in contact with common materials of constmction, at temperatures up to about 140°C. It resists hydrolysis at temperatures up to 150°C (2). However, the unstabilized compound, in the presence of water for prolonged periods, slowly hydrolyzes to yield trichloroacetic acid [76-03-9] and hydrochloric acid. In the absence of catalysts, air, or moisture, tetrachloroethylene is stable to about 500°C. Although it does not have a flash point or form flammable mixtures in air or oxygen, thermal decomposition results in the formation of hydrogen chloride and phosgene [75-44-5] (3). 

Hot bearing/seals causing ignition of flammables in vapor space. Localized initiation and possible propagation of decomposition or loss of containment. 

Eriction from contact of moving parts, tramp metal, bearings or seals initiating thermal decomposition or igniting flammable vapors. 

While this book does not cover shock-sensitive powders, such as primary explosives, UN-DOT Class 4.1 Flammable Solids are within its scope. These include thermally unstable powders that can both deflagrate in an oxidant and decompose in bulk. Examples include some nitrogen blowing agents. Should ignition occur at any point, a propagating decomposition... 

Calcium hypochlorite Ca(CIO), Water soluble white crystals or powder with strong chlorine odour Non-flammable but can evolve Cb and O2 May undergo decomposition Water spray may be used but evolves Cb gas freely at ordinary temperatures with moisture... 

Special Hazards of Combustion Products Not pertinent Behavior in Fire May explode in fires Ignition Temperature Not flammable Electrical Hazard Not pertinent Burning Rate Not flammable. Chemical Reactivity - Reactivity with Water No reaction Reactivity with Common Materials Dirt and metals can cause rapid decomposition with the liberation of oxygen gas Stability During Transport Pure grades are stable, but contamination by dirt and metals can cause rapid or violent decomposition Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

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