Acetylene explosion

Polymerization and GycliZation. Acetylene polymerizes at elevated temperatures and pressures which do not exceed the explosive decomposition point. Beyond this point, acetylene explosively decomposes to carbon and hydrogen. At 600—700°C and atmospheric pressure, benzene and other aromatics are formed from acetylene on heavy-metal catalysts. 

Silver acetylide is a more powerful detonator than the copper derivative, but both will initiate explosive acetylene-containing gas mixtures [1]. It decomposes violently when heated to 120-140°C [2], Formation of a deposit of this explosive material was observed when silver-containing solutions were aspirated into an acetylene-fuelled atomic absorption spectrometer. Precautions to prevent formation are discussed [3], The effect of ageing for 16 months on the explosive properties of silver and copper acetylides has been studied. Both retain their hazardous properties for many months, and the former is the more effective in initiating acetylene explosions [4],... 

B. A. Ivanov, "Fizika Vzryva Atsetilina (Physics of Acetylene Explosions),... 

CH2=CHC = CCH = CH2. a colourless liquid which turns yellow on exposure to the air it has a distinct garlic-like odour b.p. 83-5°C. Manufactured by the controlled, low-temperature polymerization of acetylene in the presence of an aqueous solution of copper(I) and ammonium chlorides. It is very dangerous to handle, as it absorbs oxygen from the air to give an explosive peroxide. When heated in an inert atmosphere, it polymerizes to form first a drying oil and finally a hard, brittle insoluble resin. Reacts with chlorine to give a mixture of chlorinated products used as drying oils and plastics. 

Bromine. Slip the glass cover of a jar momentarily aside, add 2-3 ml. of bromine water, replace the cover and shake the contents of the jar vigorously. Note that the bromine is absorbed only very slowly, in marked contrast to the rapid absorption by ethylene. This slow reaction with bromine water is also in marked contrast to the action of chlorine water, which unites with acetylene with explosive violence. (Therefore do not attempt this test with chlorine or chlorine water.)... 

Certain mixtures of acetylene and air are explosive. All free flames in the vicinity must therefore be extinguished. 

The predetonation distance (the distance the decomposition flame travels before it becomes a detonation) depends primarily on the pressure and pipe diameter when acetylene in a long pipe is ignited by a thermal, nonshock source. Figure 2 shows reported experimental data for quiescent, room temperature acetylene in closed, horizontal pipes substantially longer than the predetonation distance (44,46,52,56,58,64,66,67). The predetonation distance may be much less if the gas is in turbulent flow or if the ignition source is a high explosive charge. 

The pressure developed by decomposition of acetylene in a closed container depends not only on the initial pressure (or more precisely, density), but also on whether the flame propagates as a deflagration or a detonation, and on the length of the container. For acetylene at room temperature and pressure, the calculated explosion pressure ratio, / initial > deflagration and ca 20 for detonation (at the Chapman-Jouguet plane). At 800 kPa (7.93... 

Liquid and Solid Acetylene. Both the Hquid and the soHd have the properties of a high explosive when initiated by detonators or by detonation of adjoining gaseous acetylene (85). At temperatures near the freezing point neither form is easily made to explode by heat, impact, or friction, but initiation becomes easier as the temperature of the Hquid is raised. Violent explosions result from exposure to mild thermal sources at temperatures approaching room temperature. 

Acetylene under piessuie fomis an explosive compound with copper when moist or when certain impurities are present. Cu are satisfactory under this use. When gas is not under pressure other copper alloys are satisfactory. 

Explosions in the Absence of Air Some gases with positive heats of formation can be decomposed explosively in the absence of air. Ethylene reacts explosively at elevatea pressure and acetylene at atmospheric pressure in large-diameter piping. Heats of formation of these materials are -t-52.3 and -t-227 kj/mol (-1-22.5 and -1-97.6 X 10 Btii/lb mol), respec tively. 

Explosion prevention can be practiced by mixing decomposable gases with inert diluents. For example, acetylene can oe made nonexplosive at a pressure of 100 atm (10.1 MPa) by including 14.5 percent water vapor and 8 percent butane (Bodurtha, 1980). One way to prevent the decomposition reaction of ethylene oxide vapor is to use methane gas to blanket the ethylene oxide hquid. 

Hydrochloric acid may conveniently be prepared by combustion of hydrogen with chlorine. In a typical process dry hydrogen chloride is passed into a vapour blender to be mixed with an equimolar proportion of dry acetylene. The presence of chlorine may cause an explosion and thus a device is used to detect any sudden rise in temperature. In such circumstances the hydrogen chloride is automatically diverted to the atmosphere. The mixture of gases is then led to a multi-tubular reactor, each tube of which is packed with a mercuric chloride catalyst on an activated carbon support. The reaction is initiated by heat but once it has started cooling has to be applied to control the highly exothermic reaction at about 90-100°C. In addition to the main reaction the side reactions shown in Figure 12.6 may occur. 

On acetylene service, use only approved fittings and regulators. Avoid any possibility of it coming into contact with copper, copper-rich alloys or silver-rich alloys. (In the UK use at a pressure greater than 600 mbar g must be notified to HM Explosives Inspectorate for advice on appropriate standards.)... 

Explosive reactions can occur between oxygen and a wide range of chemicals including organic compounds (such as acetone, acetylene, secondary alcohols, hydrocarbons), alkali and alkaline earth metals, ammonia, biological specimens previously anaesthetized with ether, hydrogen and foam rubber. 

Vapor Density (VD) — the mass per unit volume of a given vapor/gas relative to that of air. Thus, acetaldehyde with a vapor density of 1.5 is heavier than air and will accumulate in low spots, while acetylene with a vapor density of 0.9 is lighter than air and will rise and disperse. Heavy vapors present a particular hazard because of the way they accumulate if toxic they may poison workers if nontoxic they may displace air and cause suffocation by oxygen deficiency if flammable, once presented with an ignition source, they represent a fire or explosion hazard. Gases heavier than air include carbon dioxide, chlorine, hydrogen sulfide, and sulfur dioxide. 

Chemical Reactivity - Reactivity with Water Reacts vigorously with water to form highly flammable acetylene gas which can spontaneously ignite Reactivity with Common Materials Reacts with copper and brass to form an explosive formulation Stability During Transport Stable but in absence of water Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

Fabiano et al. (1999) describe an explosion in the loading section of an Italian acetylene production plant in which the installed flame arresters did not stop a detonation. The arresters were deflagration type and the arrester elements were vessels packed with silica gel and aluminum plates (Fabiano 1999). It was concluded that the flame arresters used were not suitable for dealing safely with the excess pressures resulting from an acetylene decomposition, and may not have been in the proper location to stop the detonation. 

Fabiano, B., Pastormo, R., and Solisio, C. 1999. Explosion at an Acetylene Plant A Methodological Approach to Accident Analysis. IChemE Loss Prevention Bnlle-tin. Issue 145 (February 1999). 

Fluormation likewise significandy destabilizes the multiple bonds in allenes and acetylenes [105] Fluoro- and difluoroacetylene are dangerously explosive, and hexafluoro-2-butyne is very susceptible to both concerted and biradical addition reacbons [106, 107] (see pp 757 and 767)... 

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