Combustion - Reaction Mechanism

Reaction Mechanism

Combustion in oxygen is a chain reaction where many distinct radical intermediates participate. The high energy required for initiation is explained by the unusual structure of the dioxygen molecule. The lowest-energy configuration of the dioxygen molecule is a stable, relatively unreactive diradical in a triplet spin state. Bonding can be described with three bonding electron pairs and two antibonding electrons, whose spins are aligned, such that the molecule has nonzero total angular momentum. Most fuels, on the other hand, are in a singlet state, with paired spins and zero total angular momentum. Interaction between the two is quantum mechanically a "forbidden transition", i.e. possible with a very low probability. To initiate combustion, energy is required to force dioxygen into a spin-paired state, or singlet oxygen. This intermediate is extremely reactive. The energy is supplied as heat. The reaction produces heat, which keeps it going.

Combustion of hydrocarbons is thought to be initiated by hydrogen atom abstraction (not proton abstraction) from the fuel to oxygen, to give a hydroperoxide radical (HOO). This reacts further to give hydroperoxides, which break up to give hydroxyl radicals. There are a great variety of these processes that produce fuel radicals and oxidizing radicals. Oxidizing species include singlet oxygen, hydroxyl, monatomic oxygen, and hydroperoxyl. Such intermediates are short-lived and cannot be isolated. However, non-radical intermediates are stable and are produced in incomplete combustion. An example is acetaldehyde produced in the combustion of ethanol. An intermediate in the combustion of carbon and hydrocarbons, carbon monoxide, is of special importance because it is a poisonous gas, but also economically useful for the production of syngas.

Solid and heavy liquid fuels also undergo a great number of pyrolysis reactions that give more easily oxidized, gaseous fuels. These reactions are endothermic and require constant energy input from the combustion reactions. A lack of oxygen or other poorly designed conditions result in these noxious and carcinogenic pyrolysis products being emitted as thick, black smoke.

The rate of combustion is the amount of a material that undergoes combustion over a period of time. It can be expressed in grams per second (g/s) or kilograms per second (kg/s).

Read more about this topic:  Combustion

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