Thermal runaway

Thermal runaway occurs in situations where an increase in temperature changes the conditions in a way that causes a further increase in temperature, often leading to a destructive result. It is a kind of uncontrolled positive feedback. Thermal runaway occurs in situations where an increase in temperature changes the conditions in a way that causes a further increase in temperature, often leading to a destructive result. It is a kind of uncontrolled positive feedback. In other words, 'thermal runaway' describes a process which is accelerated by increased temperature, in turn releasing energy that further increases temperature. In chemistry (and chemical engineering), it is associated with strongly exothermic reactions that are accelerated by temperature rise. In electrical engineering, thermal runaway is typically associated with increased current flow and power dissipation, although exothermic chemical reactions can be of concern here too. Thermal runaway can occur in civil engineering, notably when the heat released by large amounts of curing concrete is not controlled. In astrophysics, runaway nuclear fusion reactions in stars can lead to nova and several types of supernova explosions, and also occur as a less dramatic event in the normal evolution of solar mass stars, the 'helium flash'. There are also concerns regarding global warming that a global average increase of 3–4 degrees Celsius above the preindustrial baseline could lead to a further unchecked increase in surface temperatures. For example, releases of methane, a greenhouse gas more potent than CO2, from wetlands, melting permafrost and continental margin seabed clathrate deposits could be subject to positive feedback. Thermal runaway is also called thermal explosion in chemical engineering, or runaway reaction in organic chemistry. It is a process by which an exothermic reaction goes out of control: the reaction rate increases due to an increase in temperature, causing a further increase in temperature and hence a further rapid increase in the reaction rate. This has contributed to industrial chemical accidents, most notably the 1947 Texas City disaster from overheated ammonium nitrate in a ship's hold, and the 1976 explosion of zoalene, in a drier, at King's Lynn. Frank-Kamenetskii theory provides a simplified analytical model for thermal explosion. Chain branching is an additional positive feedback mechanism which may also cause temperature to skyrocket because of rapidly increasing reaction rate. Chemical reactions are either endothermic or exothermic, as expressed by their change in enthalpy. Many reactions are highly exothermic, so many industrial-scale and oil refinery processes have some level of risk of thermal runaway. These include hydrocracking, hydrogenation, alkylation (SN2), oxidation, metalation and nucleophilic aromatic substitution. For example, oxidation of cyclohexane into cyclohexanol and cyclohexanone and ortho-xylene into phthalic anhydride have led to catastrophic explosions when reaction control failed. Thermal runaway may result from unwanted exothermic side reaction(s) that begin at higher temperatures, following an initial accidental overheating of the reaction mixture. This scenario was behind the Seveso disaster, where thermal runaway heated a reaction to temperatures such that in addition to the intended 2,4,5-trichlorophenol, poisonous 2,3,7,8-tetrachlorodibenzo-p-dioxin was also produced, and was vented into the environment after the reactor's rupture disk burst. Thermal runaway is most often caused by failure of the reactor vessel's cooling system. Failure of the mixer can result in localized heating, which initiates thermal runaway. Similarly, in flow reactors, localized insufficient mixing causes hotspots to form, wherein thermal runaway conditions occur, which causes violent blowouts of reactor contents and catalysts. Incorrect equipment component installation is also a common cause. Many chemical production facilities are designed with high-volume emergency venting, a measure to limit the extent of injury and property damage when such accidents occur. At large scale, it is unsafe to 'charge all reagents and mix', as is done in laboratory scale. This is because the amount of reaction scales with the cube of the size of the vessel (V ∝ r³), but the heat transfer area scales with the square of the size (A ∝ r²), so that the heat production-to-area ratio scales with the size (V/A ∝ r). Consequently, reactions that easily cool fast enough in the laboratory can dangerously self-heat at ton scale. In 2007, this kind of erroneous procedure caused an explosion of a 2,400 U.S. gallons (9,100 L)-reactor used to metalate methylcyclopentadiene with metallic sodium, causing the loss of four lives and parts of the reactor being flung 400 feet (120 m) away. Thus, industrial scale reactions prone to thermal runaway are preferably controlled by the addition of one reagent at a rate corresponding to the available cooling capacity. Some laboratory reactions must be run under extreme cooling, because they are very prone to hazardous thermal runaway. For example, in Swern oxidation, the formation of sulfonium chloride must be performed in a cooled system (–30 °C), because at room temperature the reaction undergoes explosive thermal runaway.