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FUELS AND COMBUSTION

Any material that can be burned to release thermal energy is called a fuel. Most familiar fuels
consist primarily of hydrogen and carbon. They are called hydrocarbon fuels and are denoted by the
general formula CnHm. Hydrocarbon fuels exist in all phases, some examples being coal, gasoline, and
natural gas.

The main constituent of coal is carbon. Coal also contains varying amounts of oxygen, hydrogen,
nitrogen, sulfur, moisture, and ash. It is difficult to give an exact mass analysis for coal since its
composition varies considerably from one geographical area to the next and even within the same
geographical location. Most liquid hydrocarbon fuels are a mixture of numerous hydrocarbons and are
obtained from crude oil by distillation.

Although liquid hydrocarbon fuels are mixtures of many different hydrocarbons, they are usually
considered to be a single hydrocarbon for convenience. For example, gasoline is treated as
octane, C8H18, and the diesel fuel as dodecane, C12H26. Another common liquid hydrocarbon fuel is
methyl alcohol, CH3OH, which is also called methanol and is used in some gasoline blends. The
gaseous hydrocarbon fuel natural gas, which is a mixture of methane and smaller amounts of other
gases, is often treated as methane, CH4, for simplicity.

Natural gas is produced from gas wells or oil wells rich in natural gas. It is composed mainly of methane,
but it also contains small amounts of ethane, propane, hydrogen, helium, carbon dioxide, nitrogen,
hydrogen sulfate, and water vapor. On vehicles, it is stored either in the gas phase at pressures of 150
to 250 atm as CNG (compressed natural gas), or in the liquid phase at 162°C as LNG (liquefied natural
gas). Over a million vehicles in the world run on natural gas. Liquefied petroleum gas (LPG) is a
byproduct of natural gas processing or the crude oil refining. It consists mainly of propane and thus LPG
is usually referred to as propane. However, it also contains varying amounts of butane, propylene, and
butylenes. Propane is commonly used in vehicles. Ethanol is obtained from corn, grains, and organic
waste. Methonal is produced mostly from natural gas, but it can also be obtained from coal and
biomass. Both alcohols are commonly used as additives in oxygenated gasoline and reformulated fuels
to reduce air pollution.

Vehicles are a major source of air pollutants such as nitric oxides, carbon monoxide, and
hydrocarbons, as well as the greenhouse gas carbon dioxide, and thus there is a growing shift in the
transportation industry from the traditional petroleum-based fuels such as gasoline and diesel fuel to the
cleaner burning alternative fuels friendlier to the environment such as natural gas, alcohols (ethanol and
methanol), liquefied petroleum gas (LPG), and hydrogen.

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A chemical reaction during which a fuel is oxidized and a large quantity of energy is released is
called combustion. The oxidizer most often used in combustion processes is air, for obvious
reasons—it is free and readily available. Pure oxygen O2 is used as an oxidizer only in some
specialized applications, such as cutting and welding, where air cannot be used. Therefore, a few
words about the composition of air are in order. On a mole or a volume basis, dry air is composed of
20.9 percent oxygen, 78.1 percent nitrogen, 0.9 percent argon, and small amounts of carbon
dioxide, helium, neon, and hydrogen. In the analysis of combustion processes, the argon in the air is
treated as nitrogen, and the gases that exist in trace amounts are disregarded. Then dry air can be
approximated as 21 percent oxygen and 79 percent nitrogen by mole numbers. Therefore, each mole
of oxygen entering a combustion chamber is accompanied by 0.79/0.21 3.76 mol of
nitrogen. That is,

During combustion, nitrogen behaves as an inert gas and does not react with other elements, other
than forming a very small amount of nitric oxides. However, even then the presence of nitrogen greatly
affects the outcome of a combustion process since nitrogen usually enters a combustion chamber
in large quantities at low temperatures and exits at considerably higher temperatures,
absorbing a large proportion of the chemical energy released during combustion. Throughout this
lecture, nitrogen is assumed to remain perfectly inert. Keep in mind, however, that at very high
temperatures, such as those encountered in internal combustion engines, a small fraction of nitrogen
reacts with oxygen, forming hazardous gases such as nitric oxide. Air that enters a combustion
chamber normally contains some water vapor (or moisture), which also deserves consideration. For
most combustion processes, the moisture in the air and the H2O that forms during combustion can also
be treated as an inert gas, like nitrogen. At very high temperatures, however, some water vapor
dissociates into H2 and O2 as well as into H, O, and OH. When the combustion gases are cooled below
the dew-point temperature of the water vapor, some moisture condenses. It is important to be able to
predict the dew-point temperature since the water droplets often combine with the sulfur
dioxide that may be present in the combustion gases, forming sulfuric acid, which is highly

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corrosive.

During a combustion process, the components that exist before the reaction are called reactants
and the components that exist after the reaction are called products. Consider, for example, the
combustion of 1 kmol of carbon with 1 kmol of pure oxygen, forming carbon dioxide,

Here C and O2 are the reactants since they exist before combustion, and CO2 is the product since it
exists after combustion. If carbon is burned with air instead of pure oxygen, both sides of the
combustion equation will include N2. That is, the N2 will appear both as a reactant and as a product. We
should also mention that bringing a fuel into intimate contact with oxygen is not sufficient to
start a combustion process. (Thank goodness it is not. Otherwise, the whole world would be on fire
now.) The fuel must be brought above its ignition temperature to start the combustion. The
minimum ignition temperatures of various substances in atmospheric air are approximately 260°C for
gasoline, 400°C for carbon, 580°C for hydrogen, 610°C for carbon monoxide, and 630°C for methane.
Moreover, the proportions of the fuel and air must be in the proper range for combustion to begin. For
example, natural gas does not burn in air in concentrations less than 5 percent or greater than about 15
percent. As you may recall from your chemistry courses, chemical equations are balanced on the
basis of the conservation of mass principle (or the mass balance), which can be stated as follows:
The total mass of each element is conserved during a chemical reaction. That is, the total mass of each
element on the right-hand side of the reaction equation (the products) must be equal to the total mass
of that element on the left-hand side (the reactants) even though the elements exist in different
chemical compounds in the reactants and products. Also, the total number of atoms of each element is
conserved during a chemical reaction since the total number of atoms is equal to the total mass of the
element divided by its atomic mass. It is common practice to round the molar masses to the nearest
integer if great accuracy is not required. However, notice that the total mole number of the reactants is
not equal to the total mole number of the products. That is, the total number of moles is not
conserved during a chemical reaction.

A frequently used quantity in the analysis of combustion processes to quantify the amounts of fuel and
air is the air–fuel ratio AF. It is usually expressed on a mass basis and is defined as the ratio of the
mass of air to the mass of fuel for a combustion process. That is,

The mass m of a substance is related to the number of moles N through the relation m = NM, where M
is the molar mass. The air–fuel ratio can also be expressed on a mole basis as the ratio of the mole
numbers of air to the mole numbers of fuel. But we will use the former definition. The reciprocal of
air–fuel ratio is called the fuel–air ratio.

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Example 1:

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THEORETICAL AND ACTUAL COMBUSTION PROCESSES

Combustion process is complete if all the carbon in the fuel burns to CO2, all the hydrogen burns
to H2O, and all the sulfur (if any) burns to SO2. That is, all the combustible components of a fuel are
burned to completion during a complete combustion process. Conversely, the combustion process is
incomplete if the combustion products contain any unburned fuel or components such as C, H2,
CO, or OH. Insufficient oxygen is an obvious reason for incomplete combustion, but it is not the
only one. Incomplete combustion occurs even when more oxygen is present in the combustion chamber
than is needed for complete combustion. This may be attributed to insufficient mixing in the
combustion chamber during the limited time that the fuel and the oxygen are in contact.

Another cause of incomplete combustion is dissociation, which becomes important at high

temperatures. Oxygen has a much greater tendency to combine with hydrogen than it does with carbon.
Therefore, the hydrogen in the fuel normally burns to completion, forming H2O, even when there is less
oxygen than needed for complete combustion. Some of the carbon, however, ends up as CO or just as
plain C particles (soot) in the products. The minimum amount of air needed for the complete
combustion of a fuel is called the stoichiometric or theoretical air. Thus, when a fuel is completely
burned with theoretical air, no uncombined oxygen is present in the product gases. The
theoretical air is also referred to as the chemically correct amount of air, or 100 percent theoretical
air. A combustion process with less than the theoretical air is bound to be incomplete. The ideal
combustion process during which a fuel is burned completely with theoretical air is called the
stoichiometric or theoretical combustion of that fuel. For example, the theoretical combustion of
methane is

Notice that the products of the theoretical combustion contain no unburned methane and no C, H2, CO,
OH, or free O2. In actual combustion processes, it is common practice to use more air than the
stoichiometric amount to increase the chances of complete combustion or to control the temperature of
the combustion chamber. The amount of air in excess of the stoichiometric amount is called excess air.
The amount of excess air is usually expressed in terms of the stoichiometric air as percent excess air
or percent theoretical air. Of course, the stoichiometric air can be expressed as 0 percent excess air or
100 percent theoretical air. Amounts of air less than the stoichiometric amount are called deficiency of
air and are often expressed as percent deficiency of air. The amount of air used in combustion
processes is also expressed in terms of the equivalence ratio, which is the ratio of the actual fuel–
air ratio to the stoichiometric fuel–air ratio.

Predicting the composition of the products is relatively easy when the combustion process is assumed to
be complete and the exact amounts of the fuel and air used are known. All one needs to do in this case

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is simply apply the mass balance to each element that appears in the combustion equation, without
needing to take any measurements. Things are not so simple, however, when one is dealing with actual
combustion processes. For one thing, actual combustion processes are hardly ever complete, even in the
presence of excess air. Therefore, it is impossible to predict the composition of the products on the basis
of the mass balance alone. Then the only alternative we have is to measure the amount of each
component in the products directly.

A commonly used device to analyze the composition of combustion gases is the Orsat gas analyzer. In
this device, a sample of the combustion gases is collected and cooled to room temperature and
pressure, at which point its volume is measured. The sample is then brought into contact with a
chemical that absorbs the CO2. The remaining gases are returned to the room temperature and
pressure, and the new volume they occupy is measured. The ratio of the reduction in volume to the
original volume is the volume fraction of the CO2, which is equivalent to the mole fraction if ideal-gas
behavior is assumed. The volume fractions of the other gases are determined by repeating this
procedure. In Orsat analysis the gas sample is collected over water and is maintained saturated at all
times. Therefore, the vapor pressure of water remains constant during the entire test. For this reason
the presence of water vapor in the test chamber is ignored and data are reported on a dry basis.
However, the amount of H2O formed during combustion is easily determined by balancing the
combustion equation.

Example 2:

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Example 3:

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Example 4:

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