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COMBUSTION

The objective of this chapter is to study systems involving chemical reactions. Since the combustion of
hydrocarbon fuels occurs in most power-producing devices combustion is emphasized.

COMBUSTION FUNDAMENTALS

When a chemical reaction occurs, the bonds within molecules of the reactants are broken, and
atoms and electrons rearrange to form products. In combustion reactions, rapid oxidation of
combustible elements of the fuel results in energy release as combustion products are
formed. The three major combustible chemical elements in most common fuels are carbon,
hydrogen, and sulfur. Sulfur is usually a relatively unimportant contributor to the energy released,
but it can be a significant cause of pollution and corrosion problems.

Combustion is complete when all the carbon present in the fuel is burned to carbon dioxide, all the
hydrogen is burned to water, all the sulfur is burned to sulfur dioxide, and all other combustible
elements are fully oxidized. When these conditions are not fulfilled, combustion is incomplete.
Combustion reactions expressed by chemical equations of the form

When dealing with chemical reactions, it is necessary to remember that mass is conserved, so the
mass of the products equals the mass of the reactants. The total mass of each chemical
element must be the same on both sides of the equation, even though the elements exist in
different chemical compounds in the reactants and products. However, the number of moles of
products may differ from the number of moles of reactants.

For example... consider the complete combustion of hydrogen with oxygen

In this case, the reactants are hydrogen and oxygen. Hydrogen is the fuel and oxygen is the
oxidizer. Water is the only product of the reaction. The numerical coefficients in the equation, which
precede the chemical symbols to give equal amounts of each chemical element on both sides of the
equation, are called stoichiometric coefficients. In words, states

Note that the total numbers of moles on the left and right sides of are not equal. However, because
mass is conserved, the total mass of reactants must equal the total mass of products. Since 1 kmol of
H2 equals 2 kg, kmol of O2 equals 16 kg, and 1 kmol of H2O equals 18 kg, this can be interpreted as
stating

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In the remainder of this lecture, consideration is given to the makeup of the fuel, oxidizer, and
combustion products typically involved in engineering combustion applications.

FUELS

A fuel is simply a combustible substance. In this lecture emphasis is on hydrocarbon fuels, which
contain hydrogen and carbon. Sulfur and other chemical substances also may be present. Hydrocarbon
fuels can exist as liquids, gases, and solids.

Liquid hydrocarbon fuels are commonly derived from crude oil through distillation and cracking
processes. Examples are gasoline, diesel fuel, kerosene, and other types of fuel oils. Most liquid
fuels are mixtures of hydrocarbons for which compositions are usually given in terms of mass fractions.
For simplicity in combustion calculations, gasoline is often modeled as octane, C8H18, and diesel
fuel as dodecane, C12H26.

Gaseous hydrocarbon fuels are obtained from natural gas wells or are produced in certain chemical
processes. Natural gas normally consists of several different hydrocarbons, with the major constituent
being methane, CH4. The compositions of gaseous fuels are usually given in terms of mole
fractions. Both gaseous and liquid hydrocarbon fuels can be synthesized from coal, oil shale, and tar
sands.

Coal is a familiar solid fuel. Its composition varies considerably with the location from which it is mined.
For combustion calculations, the composition of coal is usually expressed as an ultimate analysis.
The ultimate analysis gives the composition on a mass basis in terms of the relative amounts of
chemical elements (carbon, sulfur, hydrogen, nitrogen, oxygen) and ash.

MODELING COMBUSTION AIR

Oxygen is required in every combustion reaction. Pure oxygen is used only in special applications
such as cutting and welding. In most combustion applications, air provides the needed oxygen..
For the combustion calculations of this lecture, the following model is used for simplicity:

All components of air other than oxygen are lumped together with nitrogen. Accordingly, air is
considered to be 21% oxygen and 79% nitrogen on a molar basis. With this
idealization the molar ratio of the nitrogen to the oxygen is 0.79/0.21 = 3.76. When air
supplies the oxygen in a combustion reaction, therefore, every mole of oxygen is
accompanied by 3.76 moles of nitrogen.
We also assume that the nitrogen present in the combustion air does not undergo chemical
reaction. That is, nitrogen is regarded as inert. The nitrogen in the products is at the same
temperature as the other products, however, so the nitrogen undergoes a change of state if the
products are at a temperature other than the air temperature before combustion. If high
enough temperatures are attained, nitrogen can form compounds such as nitric
oxide and nitrogen dioxide. Even trace amounts of oxides of nitrogen appearing in the
exhaust of internal combustion engines can be a source of air pollution.

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AIRFUEL RATIO

Two parameters that are frequently used to quantify the amounts of fuel and air in a particular
combustion process are the airfuel ratio and its reciprocal, the fuelair ratio. The airfuel ratio is
simply the ratio of the amount of air in a reaction to the amount of fuel. The ratio can be written on a
molar basis (moles of air divided by moles of fuel) or on a mass basis (mass of air divided by
mass of fuel). Conversion between these values is accomplished using the molecular weights of the
air, Mair, and fuel, Mfuel,

where is the airfuel ratio on a molar basis and AF is the ratio on a mass basis. For the combustion
calculations of this lecture the molecular weight of air is taken as 28.97.

THEORETICAL AIR

The minimum amount of air that supplies sufficient oxygen for the complete combustion of
all the carbon, hydrogen, and sulfur present in the fuel is called the theoretical amount of air. For
complete combustion with the theoretical amount of air, the products would consist of carbon dioxide,
water, sulfur dioxide, the nitrogen accompanying the oxygen in the air, and any nitrogen contained in
the fuel. No free oxygen would appear in the products.

For example, let us determine the theoretical amount of air for the complete combustion of methane.
For this reaction, the products contain only carbon dioxide, water, and nitrogen. The reaction is

where a, b, c, and d represent the numbers of moles of oxygen, carbon dioxide, water, and
nitrogen. In writing the left side of the equation 3.76 moles of nitrogen are considered to
accompany each mole of oxygen. Applying the conservation of mass principle to the carbon,
hydrogen, oxygen, and nitrogen, respectively, results in four equations among the four unknowns

Solving these equations, the balanced chemical equation is

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The coefficient 2 before the term (O2 + 3.76N2) in the above equation is the number of moles of
oxygen in the combustion air, per mole of fuel, and not the amount of air. The amount of combustion
air is 2 moles of oxygen plus 2 3.76 moles of nitrogen, giving a total of 9.52 moles of air per mole of
fuel. Thus, for the reaction above the airfuel ratio on a molar basis is 9.52. To calculate the airfuel
ratio on a mass basis, we write

Normally the amount of air supplied is either greater or less than the theoretical amount. The
amount of air actually supplied is commonly expressed in terms of the percent of theoretical air.
For example, 150% of theoretical air means that the air actually supplied is 1.5 times the theoretical
amount of air. The amount of air supplied can be expressed alternatively as a percent excess or a
percent deficiency of air. Thus, 150% of theoretical air is equivalent to 50% excess air, and 80% of
theoretical air is the same as a 20% deficiency of air.

For example, consider the complete combustion of methane with 150% theoretical air (50% excess
air). The balanced chemical reaction equation is

In this equation, the amount of air per mole of fuel is 1.5 times the theoretical amount. Accordingly,
the airfuel ratio is 1.5 times the airfuel ratio. Since complete combustion is assumed, the products
contain only carbon dioxide, water, nitrogen, and oxygen. The excess air supplied appears in the
products as uncombined oxygen and a greater amount of nitrogen based on the theoretical
amount of air.

The equivalence ratio is the ratio of the actual fuelair ratio to the fuelair ratio for complete
combustion with the theoretical amount of air. The reactants are said to form a lean mixture
when the equivalence ratio is less than unity. When the ratio is greater than unity, the
reactants are said to form a rich mixture.

EXAMPLE: Determining the AirFuel Ratio

Determine the airfuel ratio on both a molar and mass basis for the complete combustion of octane,
C8H18, with (a) the theoretical amount of air, (b) 150% theoretical air (50% excess air).

SOLUTION

Known: Octane, C8H18, is burned completely with (a) the theoretical amount of air, (b) 150%
theoretical air.

Find: Determine the airfuel ratio on a molar and a mass basis.

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Assumptions:

1. Each mole of oxygen in the combustion air is accompanied by 3.76 moles of nitrogen.

2. The nitrogen is inert.

3. Combustion is complete.

Analysis:

(a) For complete combustion of C8H18 with the theoretical amount of air, the products contain carbon
dioxide, water, and nitrogen only. That is

Applying the conservation of mass principle to the carbon, hydrogen, oxygen, and nitrogen,
respectively, gives

Solving these equations, a=12.5, b=8, c=9, d=47. The balanced chemical equation is

The airfuel ratio on a molar basis is

The airfuel ratio expressed on a mass basis is

(b) For 150% theoretical air, the chemical equation for complete combustion takes the form

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DETERMINING PRODUCTS OF COMBUSTION

In each of the illustrations given above, complete combustion is assumed. For a hydrocarbon fuel, this
means that the only allowed products are CO2, H2O, and N2, with O2 also present when excess air is
supplied. If the fuel is specified and combustion is complete, the respective amounts of the products
can be determined by applying the conservation of mass principle to the chemical equation. The
procedure for obtaining the balanced reaction equation of an actual reaction where combustion is
incomplete is not always so straightforward.

Combustion is the result of a series of very complicated and rapid chemical reactions, and the
products formed depend on many factors. When fuel is burned in the cylinder of an internal
combustion engine, the products of the reaction vary with the temperature and pressure in the
cylinder. In combustion equipment of all kinds, the degree of mixing of the fuel and air is a controlling
factor in the reactions that occur once the fuel and air mixture is ignited. Although the amount of air
supplied in an actual combustion process may exceed the theoretical amount, it is not uncommon for
some carbon monoxide and unburned oxygen to appear in the products. This can be due to incomplete
mixing, insufficient time for complete combustion, and other factors. When the amount of air supplied
is less than the theoretical amount of air, the products may include both CO2 and CO, and there
also may be unburned fuel in the products. Unlike the complete combustion cases considered above,
the products of combustion of an actual combustion process and their relative amounts can be
determined only by measurement. Among several devices for measuring the composition of products
of combustion are the Orsat analyzer, gas chromatograph, infrared analyzer, and flame
ionization detector. Data from these devices can be used to determine the mole fractions of the
gaseous products of combustion. The analyses are often reported on a dry basis. In a dry product
analysis, the mole fractions are given for all gaseous products except the water vapor.

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Since water is formed when hydrocarbon fuels are burned, the mole fraction of water vapor in the
gaseous products of combustion can be significant. If the gaseous products of combustion are cooled
at constant pressure, the dew point temperature is reached when water vapor begins to
condense. Since water deposited on duct work, mufflers, and other metal parts can cause corrosion,
knowledge of the dew point temperature is important.

EXAMPLE: Using a Dry Product Analysis

Methane, CH4, is burned with dry air. The molar analysis of the products on a dry basis is CO2, 9.7%;
CO, 0.5%; O2, 2.95%; and N2, 86.85%. Determine (a) the airfuel ratio on both a molar and a mass
basis, (b) the percent theoretical air, (c) the dew point temperature of the products, in oC, if the
mixture were cooled at 1 atm.

SOLUTION

Known: Methane is burned with dry air. The molar analysis of the products on a dry basis is provided.

Find: Determine (a) the airfuel ratio on both molar and mass basis, (b) the percent theoretical air,
and (c) the dew point temperature of the products, in oC, if cooled at 1 atm.

Assumptions:

1. Each mole of oxygen in the combustion air is accompanied by 3.76 moles of nitrogen, which is inert.

2. The products form an ideal gas mixture.

Analysis:

(a) The solution is conveniently conducted on the basis of 100 kmol of dry products. The chemical
equation then reads

In addition to the assumed 100 kmol of dry products, water must be included as a product.

Applying conservation of mass to carbon, hydrogen, and oxygen, respectively

Solving this set of equations gives a=10.2, b=23.1, c=20.4. The balanced chemical equation is

On a molar basis, the airfuel ratio is

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On a mass basis

(b) To determine the dew point temperature requires the partial pressure of the water vapor pv. The
partial pressure pv is found from pv=yvp, where yv is the mole fraction of the water vapor in the
combustion products and p is 1 atm. Referring to the balanced chemical equation of part (a), the
mole fraction of the water vapor is

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EXAMPLE: Burning Natural Gas with Excess Air

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