Combustion

Combustion, or burning,^[1] is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combustion does not always result in fire, because a flame is only visible when substances undergoing combustion vaporize, but when it does, a flame is a characteristic indicator of the reaction. While activation energy must be supplied to initiate combustion (e.g., using a lit match to light a fire), the heat from a flame may provide enough energy to make the reaction self-sustaining. The study of combustion is known as combustion science.

Combustion is often a complicated sequence of elementary radical reactions. Solid fuels, such as wood and coal, first undergo endothermic pyrolysis to produce gaseous fuels whose combustion then supplies the heat required to produce more of them. Combustion is often hot enough that incandescent light in the form of either glowing or a flame is produced. A simple example can be seen in the combustion of hydrogen and oxygen into water vapor, a reaction which is commonly used to fuel rocket engines. This reaction releases 242 kJ/mol of heat and reduces the enthalpy accordingly (at constant temperature and pressure):

${displaystyle {ce {2H_{2}(g){+}O_{2}(g) ightarrow 2H_{2}Ouparrow }}}$

Uncatalyzed combustion in air requires relatively high temperatures. Complete combustion is stoichiometric concerning the fuel, where there is no remaining fuel, and ideally, no residual oxidant. Thermodynamically, the chemical equilibrium of combustion in air is overwhelmingly on the side of the products. However, complete combustion is almost impossible to achieve, since the chemical equilibrium is not necessarily reached, or may contain unburnt products such as carbon monoxide, hydrogen and even carbon (soot or ash). Thus, the produced smoke is usually toxic and contains unburned or partially oxidized products. Any combustion at high temperatures in atmospheric air, which is 78 percent nitrogen, will also create small amounts of several nitrogen oxides, commonly referred to as NOx, since the combustion of nitrogen is thermodynamically favored at high, but not low temperatures. Since burning is rarely clean, fuel gas cleaning or catalytic converters may be required by law.

Fires occur naturally, ignited by lightning strikes or by volcanic products. Combustion (fire) was the first controlled chemical reaction discovered by humans, in the form of campfires and bonfires, and continues to be the main method to produce energy for humanity. Usually, the fuel is carbon, hydrocarbons, or more complicated mixtures such as wood that contain partially oxidized hydrocarbons. The thermal energy produced from the combustion of either fossil fuels such as coal or oil, or from renewable fuels such as firewood, is harvested for diverse uses such as cooking, production of electricity or industrial or domestic heating. Combustion is also currently the only reaction used to power rockets. Combustion is also used to destroy (incinerate) waste, both nonhazardous and hazardous.

Oxidants for combustion have high oxidation potential and include atmospheric or pure oxygen, chlorine, fluorine, chlorine trifluoride, nitrous oxide and nitric acid. For instance, hydrogen burns in chlorine to form hydrogen chloride with the liberation of heat and light characteristic of combustion. Although usually not catalyzed, combustion can be catalyzed by platinum or vanadium, as in the contact process.

Types[edit]

Complete and incomplete[edit]

Complete[edit]

In complete combustion, the reactant burns in oxygen and produces a limited number of products. When a hydrocarbon burns in oxygen, the reaction will primarily yield carbon dioxide and water. When elements are burned, the products are primarily the most common oxides. Carbon will yield carbon dioxide, sulfur will yield sulfur dioxide, and iron will yield iron(III) oxide. Nitrogen is not considered to be a combustible substance when oxygen is the oxidant. Still, small amounts of various nitrogen oxides (commonly designated NO
_x species) form when the air is the oxidative.

Combustion is not necessarily favorable to the maximum degree of oxidation, and it can be temperature-dependent. For example, sulfur trioxide is not produced quantitatively by the combustion of sulfur. NO_x species appear in significant amounts above about 2,800 °F (1,540 °C), and more is produced at higher temperatures. The amount of NO_x is also a function of oxygen excess.^[2]

In most industrial applications and in fires, air is the source of oxygen (O
₂). In the air, each mole of oxygen is mixed with approximately 3.71 mol of nitrogen. Nitrogen does not take part in combustion, but at high temperatures, some nitrogen will be converted to NO
_x (mostly NO, with much smaller amounts of NO
₂). On the other hand, when there is insufficient oxygen to combust the fuel completely, some fuel carbon is converted to carbon monoxide, and some of the hydrogens remain unreacted. A complete set of equations for the combustion of a hydrocarbon in the air, therefore, requires an additional calculation for the distribution of oxygen between the carbon and hydrogen in the fuel.

The amount of air required for complete combustion is known as the "theoretical air" or "stoichiometric air".^[3] The amount of air above this value actually needed for optimal combustion is known as the "excess air", and can vary from 5% for a natural gas boiler, to 40% for anthracite coal, to 300% for a gas turbine.^[4]

Incomplete[edit]

Incomplete combustion will occur when there is not enough oxygen to allow the fuel to react completely to produce carbon dioxide and water. It also happens when the combustion is quenched by a heat sink, such as a solid surface or flame trap. As is the case with complete combustion, water is produced by incomplete combustion; however, carbon and carbon monoxide are produced instead of carbon dioxide.

For most fuels, such as diesel oil, coal, or wood, pyrolysis occurs before combustion. In incomplete combustion, products of pyrolysis remain unburnt and contaminate the smoke with noxious particulate matter and gases. Partially oxidized compounds are also a concern; partial oxidation of ethanol can produce harmful acetaldehyde, and carbon can produce toxic carbon monoxide.

The designs of combustion devices can improve the quality of combustion, such as burners and internal combustion engines. Further improvements are achievable by catalytic after-burning devices (such as catalytic converters) or by the simple partial return of the exhaust gases into the combustion process. Such devices are required by environmental legislation for cars in most countries. They may be necessary to enable large combustion devices, such as thermal power stations, to reach legal emission standards.

The degree of combustion can be measured and analyzed with test equipment. HVAC contractors, firefighters and engineers use combustion analyzers to test the efficiency of a burner during the combustion process. Also, the efficiency of an internal combustion engine can be measured in this way, and some U.S. states and local municipalities use combustion analysis to define and rate the efficiency of vehicles on the road today.

Carbon monoxide is one of the products from incomplete combustion.^[5] The formation of carbon monoxide produces less heat than formation of carbon dioxide so complete combustion is greatly preferred especially as carbon monoxide is a poisonous gas. When breathed, carbon monoxide takes the place of oxygen and combines with some of the hemoglobin in the blood, rendering it unable to transport oxygen.^[6]

Problems associated with incomplete combustion[edit]

Environmental problems[edit]

These oxides combine with water and oxygen in the atmosphere, creating nitric acid and sulfuric acids, which return to Earth's surface as acid deposition, or "acid rain." Acid deposition harms aquatic organisms and kills trees. Due to its formation of certain nutrients that are less available to plants such as calcium and phosphorus, it reduces the productivity of the ecosystem and farms. An additional problem associated with nitrogen oxides is that they, along with hydrocarbon pollutants, contribute to the formation of ground level ozone, a major component of smog.^[7]

Human health problems[edit]

Breathing carbon monoxide causes headache, dizziness, vomiting, and nausea. If carbon monoxide levels are high enough, humans become unconscious or die. Exposure to moderate and high levels of carbon monoxide over long periods is positively correlated with the risk of heart disease. People who survive severe carbon monoxide poisoning may suffer long-term health problems.^[8] Carbon monoxide from the air is absorbed in the lungs which then binds with hemoglobin in human's red blood cells. This reduces the capacity of red blood cells that carry oxygen throughout the body.

Smoldering[edit]

Smoldering is the slow, low-temperature, flameless form of combustion, sustained by the heat evolved when oxygen directly attacks the surface of a condensed-phase fuel. It is a typically incomplete combustion reaction. Solid materials that can sustain a smoldering reaction include coal, cellulose, wood, cotton, tobacco, peat, duff, humus, synthetic foams, charring polymers (including polyurethane foam) and dust. Common examples of smoldering phenomena are the initiation of residential fires on upholstered furniture by weak heat sources (e.g., a cigarette, a short-circuited wire) and the persistent combustion of biomass behind the flaming fronts of wildfires.

Spontaneous[edit]

Spontaneous combustion is a type of combustion that occurs by self-heating (increase in temperature due to exothermic internal reactions), followed by thermal runaway (self-heating which rapidly accelerates to high temperatures) and finally, ignition. For example, phosphorus self-ignites at room temperature without the application of heat. Organic materials undergoing bacterial composting can generate enough heat to reach the point of combustion.^[9]

Turbulent[edit]

Combustion resulting in a turbulent flame is the most used for industrial applications (e.g. gas turbines, gasoline engines, etc.) because the turbulence helps the mixing process between the fuel and oxidizer.

Micro-gravity[edit]

The term 'micro' gravity refers to a gravitational state that is 'low' (i.e., 'micro' in the sense of 'small' and not necessarily a millionth of Earth's normal gravity) such that the influence of buoyancy on physical processes may be considered small relative to other flow processes that would be present at normal gravity. In such an environment, the thermal and flow transport dynamics can behave quite differently than in normal gravity conditions (e.g., a candle's flame takes the shape of a sphere.^[10]). Microgravity combustion research contributes to the understanding of a wide variety of aspects that are relevant to both the environment of a spacecraft (e.g., fire dynamics relevant to crew safety on the International Space Station) and terrestrial (Earth-based) conditions (e.g., droplet combustion dynamics to assist developing new fuel blends for improved combustion, materials fabrication processes, thermal management of electronic systems, multiphase flow boiling dynamics, and many others).

Micro-combustion[edit]

Combustion processes that happen in very small volumes are considered micro-combustion. The high surface-to-volume ratio increases specific heat loss. Quenching distance plays a vital role in stabilizing the flame in such combustion chambers.

Chemical equations[edit]

Stoichiometric combustion of a hydrocarbon in oxygen[edit]

Generally, the chemical equation for stoichiometric combustion of a hydrocarbon in oxygen is:

${displaystyle {ce {C}}_{x}{ce {H}}_{y}+left(x+{y over 4} ight){ce {O2->}}x{ce {CO2}}+{y over 2}{ce {H2O}}}$

For example, the stoichiometric combustion of methane in oxygen is:

${displaystyle {ce {{underset {methane}{CH4}}+ 2O2 -> CO2 + 2H2O}}}$

Stoichiometric combustion of a hydrocarbon in air[edit]

If the stoichiometric combustion takes place using air as the oxygen source, the nitrogen present in the air (Atmosphere of Earth) can be added to the equation (although it does not react) to show the stoichiometric composition of the fuel in air and the composition of the resultant flue gas. Treating all non-oxygen components in air as nitrogen gives a 'nitrogen' to oxygen ratio of 3.77, i.e. (100% - O2%) / O2% where O2% is 20.95% vol:

${displaystyle {ce {C}}_{x}{ce {H}}_{y}+z{ce {O2}}+3.77z{ce {N2 ->}}x{ce {CO2}}+{y over 2}{ce {H2O}}+3.77z{ce {N2}}}$

where ${displaystyle z=x+{y over 4}}$.

For example, the stoichiometric combustion of methane in air is:

${displaystyle {ce {{underset {methane}{CH4}}+ 2O2}}+7.54{ce {N2-> CO2 + 2H2O}}+7.54{ce {N2}}}$

The stoichiometric composition of methane in air is 1 / (1 + 2 + 7.54) = 9.49% vol.

The stoichiometric combustion reaction for C_αH_βO_γ in air:

${displaystyle {ce {C_{mathit {alpha }}H_{mathit {eta }}O_{mathit {gamma }}}}+left(alpha +{frac {eta }{4}}-{frac {gamma }{2}} ight)left({ce {O_{2}}}+3.77{ce {N_{2}}} ight)longrightarrow alpha {ce {CO_{2}}}+{frac {eta }{2}}{ce {H_{2}O}}+3.77left(alpha +{frac {eta }{4}}-{frac {gamma }{2}} ight){ce {N_{2}}}}$

The stoichiometric combustion reaction for C_αH_βO_γS_δ: