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Discussion

Fuel Energy
Definition of fuel is any substance that can provide heat and produce energy when it is burned.
This energy that releases is generally in the form of chemical energy or heat energy. The recent
invention of nuclear technology means now even nuclear energy may be released due
to nuclear fission or fusion. We obtain most of our energy by burning fossil fuels. Why does
burning fuels provide energy? Fuels are reduced forms of matter that burn readily in the
presence of oxygen, and combustion is an oxidation reaction.

Fuels are burned so that we may utilize the energy released from that process of some purpose.
We know that a chemical reaction involves the conversion of reactions into products. Chemical
bonds in the reactions be broken. Bond cleavage requires an energy input. This endothermic
process is represented in mathematical terms with a plus (+) sign by chemists. New chemical
bonds must be made as product is formed. The formation of chemical bonds releases energy,
and chemists represent this exothermic process in mathematical terms by a minus (–) sign.

This heat energy that fuels release is used for various purposes such as cooking, in heaters, for
many industrial and manufacturing purposes. At other times we use an engine to convert this
heat energy into mechanical energy. Like when we use petrol to run our cars. The oil which is
used to as fuel in the engine is known as Fuel oil.

And then there is the fuel our bodies use. Every cell requires energy to perform its functions.
They get this energy from organic molecules such as carbohydrates, fats etc. This process of
using fuels is known as cellular respiration. And these organic molecules are obtained
via nutrition, which is why we call food as the fuel of our bodies.

The energy changes associated with chemical reactions fall into three different categories:

Energy Is Consumed Overall – If the sum of the energies required to break bonds in the
reactants is greater than the energy released by all new bonds formed in the products, energy will
be consumed in the chemical reaction. The endothermic, bond-breaking process (+ sign) require
more energy than the exothermic, bond-forming processes (- sign) release, so the sum of these

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energy changes is endothermic overall (+ sign). This type of chemical reaction requires an overall
energy input, and, thus, such a reaction would not be useful as a source of energy.

Energy Is Released Overall – If the sum of the energies required to break bonds in the reactants
is less than the energy released by all new bonds formed in the products, energy will be released
in the chemical reaction. Thus, the endothermic, bond-breaking processes (+ sign) require less
energy than the exothermic, bond-forming processes (-sign) release, so the sum of these energy
change is exothermic overall (-sign). This type of chemical reaction produces energy overall, and
thus, might be a useful source of energy. In other words, the reactants might represent a usable
fuel. Factors other than the amount of energy released by combustion of a fuel may also be
important in determining its suitability as a fuel, however.

No Net Energy Change Occurs – If the sum of the energies required to break bonds in the
reactants is exactly equal to the energy released by all new bonds formed in the products, there is
no net energy change. Thus, the endothermic, bond-breaking processes (+ sign) require exactly
the same amount of energy released by the exothermic, bond-forming processes (-sign), so the
sum of these energy changes is zero. This is a relatively rare, although not impossible, occurrence
for a chemical reaction.

TABLE 1.1 Average Bond Energies

Bond Energy (kJ/mol)
C–H 416
O = O 498
C = O 803
O–H 467
C–C 356
H–H 436
C–O 336

The complete combustion of any hydrocarbon will produce only carbon dioxide and water, so it
is relatively simple matter to write such an equation for methane. By using the bond energies in
Table 1.1, we see that it take a total of 2660 kJ to break all the bonds in the reactants (one mole
of methane and two moles of oxygen). Since those processes are endothermic, we indicate this
energy requirement as +2660 kJ. Similarly, we see that the formation of all bonds in the product

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molecules releases 3474 kJ. We designate this exothermic process as –3474 kJ. The sum of
these two processes is –814 kJ (the negative sign indicates that the overall process is
exothermic). This is the amount of heat energy released in burning one mole of methane. The
heat released when a fuel is burned is known as the heat of combustion.

EXAMPLE:
CH4 + 2 O2 O2 + 2 H2O
H
|
H–C–H +2O = O O = C = O + 2H–O–H
|
H
Bond Broken Bond Formed
endothermic exothermic
+ –

Bond Broken:
4 (C – H) = 4 mol (416 kJ/mol) = +1664 kJ
2 (O = O) = 2 mol (498 kj/mol) = + 996 kJ
+ 2660 kJ

Bond Formed:
2 (C = O) = 2 mol (–803 kJ/mol) = –1606 kJ
4 (O – H) = 4 mol (–467 kJ/mol) = –1868 kJ
–3474 kJ

Net = +2660 kJ + (–3474 kJ)

Net = –814 kJ

? SAQ 1
A. Calculate the bond energy in the combustion of one mole of pentane.
C5H12 + 8 O2 5 CO2 + 6 H2O

SAQ 2
B. Determine the average bond energy of the combustion of one mole of methanol (CH3OH).
CH3OH + 3/2 O2 CO2 + 2 H2O

Petroleum Refining
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The refining of petroleum begins with the separation of fractions according to boiling point
ranges by a process called fractional distillation. The difference between simple distillation
and fractional distillation is the degree of separation achieved for the mixture being distilled. For
example, water that contains dissolved solids or other liquids can be purified by simple
distillation. The impure solution is heated to boiling; the water vapor is condensed and collected
in a separate container. Since petroleum contains thousands of hydrocarbons, separation of the
pure compounds is not feasible or even necessary. The product obtained from distillation of
petroleum are still mixtures of hundreds of hydrocarbons, so they are called petroleum
fractions.

Figure 1.1 illustrates a fractional distillation tower used in the petroleum-refining process. The
crude oil is first heated to about 400 ºC to produce a hot vapor and liquid mixture that enters the
fractionating tower. The vapor rises and condenses at various points along the tower. The lower
boiling petroleum fractions (those that are more volatile) will remain in the vapor stage longer
than the higher boiling fractions. These differences in boiling point ranges allow the separation
of fractions. Some of the gases do not condense and are drawn off the top of the tower, while
the unvaporized residual oil is collected at the tower. Typical products of the fractional distillation
of petroleum are listed in Table 1.2.

FIGURE 1.1 Petroleum fractionation.

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Crude oil is first heated to 400 ºC in the pipe still. The vapors then enter the fractionation tower.
As rise in the tower, the vapors cool down and condense so that different fractions can be
drawn off at different heights. This show how the rising vapor is repeatedly condensed and
collected at the numerous bell caps.

TABLE 1.2 Hydrocarbon Fractions from Petroleum

Fraction Size Range of Boiling Point Range Uses
Molecules (ºC)
Gas C1 – C4 0 – 30 Gas fuels
Straight-run gasoline C5 – C12 30 – 200 Motor fuel
Kerosene C12 – C16 180 – 300 Jet fuel, diesel oil
Gas oils C16 – C18 Over 300 Diesel fuel, cracking stock
Lubricants C18 – C20 Over 350 Lubricating oil, cracking stock
Paraffin wax C20 – C40 Low-melting solids Candles, wax paper
Asphalts Above C40 Gummy residues Road asphalt, roofing tar

Octane

Octane and 2, 2, 4 – trimethylpentane (both of which have the same formula. C 8H18, a molecular
weight of 114 g/mol) release similar amounts of energy (roughly – 5049 kJ/mol or – 44.3 kJ/g)
upon combustion. Both reactions involve the breaking and formation of exactly the same types
of numbers of bonds, but because it is easier to break branched-chain bonds than straight-chain
bonds, the combustion of 2, 2, 4 – trimethylpentane releases slightly more energy. Note in the
following analysis that the balanced equation initially gives the amount of energy for combustion
of two mole of octane, so we must divide the value obtained by 2 to arrive at the heat of
combustion per mole.

Octane is a very poor fuel and 2, 2, 4 – trimethylpentane is a very good fuel even though they
release similar amounts of energy upon combustion. Why is that? Clearly the quality of a fuel
must be related to more than its energy content.

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Octane Rating
The burning properties of hydrocarbons depend on their structure. Isooctane (2, 2, 4 –
trimethylpentane) is the standard used to assign octane ratings. The octane rating is an arbitrary
scale for rating the relative knocking properties of gasolines, and it is based on the operation of
a standard test engine. Heptane knocks considerably and is assigned an octane rating of 0,
whereas 2, 2, 4 – trymethylpentane burns smoothly and is assigned an octane rating of 100.
The octane rating of a gasoline is determined by first using the gasoline in a standard engine
and recording its knocking properties. The test results are then compared with the behavior of
mixtures of heptane and isooctane in the mixture with identical knocking properties is called the
octane rating of the gasoline. Thus if a gasoline has the same knocking characteristics as a
mixture of 13 % heptane and 87 % isooctane, it is assigned an octane rating of 87. This
corresponds to regular unleaded gasoline. Other higher grades of gasoline available at gas
stations have octane ratings of 89 (regular plus) and 92 (premium):

The “straight-run” gasoline fraction obtained from the fractional distillation of petroleum has an
octane rating of only 55 and needs additional refinement because it contains primarily straight-
chain hydrocarbons that burn too rapidly to be suitable for use as a fuel in internal combustion
engines. Rapid burning causes uncontrolled explosion of the fuel as evidenced by a “knocking”
and “pinging” sound in engine. This reduces engine power and may damage the engine.

The octane rating of a gasoline can be increased either by increasing the percentage of
branched-chain and aromatic hydrocarbon fractions or by adding octane enhancers (or a
combination of both). Since the octane rating scale was established, fuels superior to isooctane
have been developed, scale has been extended well above 100. Table 1.3 lists octane ratings
for some hydrocarbons and octane enhancers. Note that the octane rating of a fuel is not a
measure of the energy content of the fuel. For instance, octane (a poor fuel) and isooctane or 2,
2, 4 – trimethylpentane (a good fuel) release the same amount of energy but burn at different
rates. One cannot merely find the fuel with the highest octane rating and decide that is the best
fuel. Toluene, for instance, has a very high octane rating (118), but when other properties of
toluene, including its energy content, considerable toxicity, combustion properties, and cost are
considered, it is not the fuel of choice. However, most gasoline mixtures do contain about 5 % to
7 % toluene.

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Table 1.3 Octane Numbers of Some Hydrocarbons and Gasoline Additives

Name Octane Number

Octane – 20
Heptane 0
Pentane 62
1 – Pentene 91
2, 2, 4 – trimethylpentane (isooctane) 100
Benzene 106
Methanol 107
Ethanol 108
Tertiary-butyl alcohol 113
Methyl tertiary-butyl ether (MTBE) 116
Para-xylene 116
Toluene 118

Catalytic Cracking
Part of the petroleum refinement process involves adjusting the percentage of each
hydrocarbon fraction to match commercial demand. For example, the demand for gasoline is
higher than that for kerosene. As a result, chemical reactions convert the larger kerosene-
fraction molecules into molecules in the gasoline range in a process called cracking. The
catalytic cracking process uses a zeolite catalyst and involves heating saturated
hydrocarbons under pressure in the absence of air. The hydrocarbons break into shorter chain
hydrocarbons – both alkanes and alkenes, some of which will be in the gasoline range.

Pressure
C16H34 C8H18 + C8H16
Heat
An alkane An alkane An alkene
in the gasoline range

Since alkenes have higher octane rating than alkanes, the catalytic cracking process also
increases the octane rating of the mixture. Catalytic cracking is also important for the production
of alkenes used as starting materials in the organic chemical industry.

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Octane Enhancers
The octane number of a given blend f gasoline can also be increased by adding antiknock
agents, or octane enhancers. Prior to 1975, the most widely used antiknock agent was
tetraethyllead, (C2H5)4 Pb. The addition of 3 g of (C2H5)4 Pb per gallon increases the octane
rating by 10 to 15. Before the Environmental Protection Agency (EPA) required reductions in
lead content, both regular and premium gasoline contained an average of 3 g (C 2H5)4 Pb or
tetramethyllead. (CH3)4 Pb, per gallon. However, the Clean Air Act of 1970 required that 1975 –
model cars emit no more than 10 % of carbon monoxide and hydrocarbons emitted by 1970
models. The platinum – based catalytic converter chosen to reduce emissions of carbon
monoxide and hydrocarbons required lead – free gasolines, since lead deactivates the platinum
catalyst by coating its surface. For this reason, and the fact that lead released into the
environment is a neurological poison, automobiles manufactured since 1975 have been
required to use lead – free gasoline to protect the catalytic converter.

Since tetraethyllead can no longer be used, other octane enhancers must be added to
gasoline to increase the methyl tertiary – butyl ether (MTBE), methanol and ethanol.

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Summary
Energy from Fuels
Fuels are burned so that we may utilize the energy from that process for some purpose.
In chemical reactions, energy can be consumed or released or no net change may
occur at all. Endothermic cleavages are represented in mathematical terms with a plus
sign (+) by chemists. Exothermic bonding is represented in mathematical terms by a
minus (–). Different types of fuels have different heats of combustion, but all
hydrocarbons release about the same amount of heat per gram.

Heat of combustion
The quantity of heat released when a fuel is burned.

Fractional distillation
Separation of a mixture into fractions that differ in boiling points.

Catalytic cracking process

Process by which larger kerosene fractions are converted into hydrocarbons in the
gasoline range.

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References

Brown, Le May and Bursten, Burdge, 2004, Chemistry The Central Science (9 th edition),
Pearson Education (Asia) Pte Ltd.

Cengage Learning Asia Ltd., 2019, General Chemistry 2 (Philippine edition),

Rex Book Store Inc.

Malone, Leo J., Dolter, Theodore D., 2010, Basic Concepts of Chemistry (8th edition),
John Wiley and Sons, Inc.

Masterton, William L., Hurley, Cecile H., Peterson, James F., Sack, Dorothy. Gabler,
Robert E., 2018, Chemistry for Engineering Students (Philippine edition),
C & E Publishing, Inc.

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Answer of Self-Assessment Questions

(ASAQ)
SAQ 1
A. C5H12 + 8 O2 5 CO2 + 6 H2O

H H H H H
| | | | | spark
H–C–C–C–C–C–H + 8O = O 5O = C = O + 6H–O–H
| | | | |
H H H H H

Bond Broken:
5 (C – C) = 5 mol (356 kJ/mol) = +1780 kJ
8 (O = O) = 8 mol (498 kJ/mol) = + 3984 kJ
12 (C – H) = 12 mol (416 kJ/mol) = + 4992 kJ
+10756 kJ
Bond Formed:
10 (C = O) = 10 mol (–803 kJ/mol) = –8030 kJ
12 (O – H) = 12 mol (–467 kJ/mol) = –5604 kJ
–13634 kJ
Net = +10756 kJ + (–13634 kJ)
Net = – 2878 kJ

SAQ 2
B. CH3OH + 3/2 O2 CO2 + 2 H2O
H
|
H – C – O – H + 3/2 O = O O=C=O + 2H–O–H
|
H
Bond Broken:
3 (C – H) = 3 mol (416 kJ/mol) = + 1248 kJ Net = + 2462 kJ + (–3474
kJ)
1 (O – H) = 1 mol (467 kJ/mol) = + 467 kJ Net = – 1012 kJ
3/2 (O = O) = 3/2 mol (498 kJ/mol) = + 747 kJ
+ 2462 kJ
Bond Formed:
2 (C = O) = 2 mol (–803 kJ/mol) = –1606 kJ
4 (O – H) = 4 mol (–467 kJ/mol) = –1868 kJ

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–3474 kJ

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