# 4.9 What energy is released when gasoline is burned?

It is important to note that the theoretical energy content of gasoline
when burned in air is only related to the hydrogen and carbon contents.
The energy is released when the hydrogen and carbon are oxidised (burnt),
to form water and carbon dioxide. Octane rating is not fundamentally
related to the energy content, and the actual hydrocarbon and oxygenate
components used in the gasoline will determine both the energy release and
the antiknock rating.

Two important reactions are:-
C + O2 = CO2
H + O2 = H2O
The mass or volume of air required to provide sufficient oxygen to achieve
this complete combustion is the "stoichiometric" mass or volume of air.
Insufficient air = "rich", and excess air = "lean", and the stoichiometric
mass of air is related to the carbon:hydrogen ratio of the fuel. The
procedures for calculation of stoichiometric air-fuel ratios are fully
documented in an SAE standard [35].

Atomic masses used are:- Hydrogen = 1.00794, Carbon = 12.011,
Oxygen = 15.994, Nitrogen = 14.0067, and Sulfur = 32.066.

The composition of sea level air ( 1976 data, hence low CO2 value ) is
Gas Fractional Molecular Weight Relative
Species Volume kg/mole Mass
N2 0.78084 28.0134 21.873983
O2 0.209476 31.9988 6.702981
Ar 0.00934 39.948 0.373114
CO2 0.000314 44.0098 0.013919
Ne 0.00001818 20.179 0.000365
He 0.00000524 4.002602 0.000021
Kr 0.00000114 83.80 0.000092
Xe 0.000000087 131.29 0.000011
CH4 0.000002 16.04276 0.000032
H2 0.0000005 2.01588 0.000001
---------
Air 28.964419

For normal heptane C7H16 with a molecular weight = 100.204

C7H16 + 11O2 = 7CO2 + 8H2O

thus 1.000 kg of C7H16 requires 3.513 kg of O2 = 15.179 kg of air.

The chemical stoichiometric combustion of hydrocarbons with oxygen can be
written as:-
CxHy + (x + (y/4))O2 -> xCO2 + (y/2)H2O
Often, for simplicity, the remainder of air is assumed to be nitrogen,
which can be added to the equation when exhaust compositions are required.
As a general rule, maximum power is achieved at slightly rich, whereas
maximum fuel economy is achieved at slightly lean.

The energy content of the gasoline is measured by burning all the fuel
inside a bomb calorimeter and measuring the temperature increase.
The energy available depends on what happens to the water produced from the
combustion of the hydrogen. If the water remains as a gas, then it cannot
release the heat of vaporisation, thus producing the Nett Calorific Value.
If the water were condensed back to the original fuel temperature, then
Gross Calorific Value of the fuel, which will be larger, is obtained.

The calorific values are fairly constant for families of HCs, which is not
surprising, given their fairly consistent carbon:hydrogen ratios. For liquid
( l ) or gaseous ( g ) fuel converted to gaseous products - except for the
2-methylbutene-2, where only gaseous is reported. * = Blending Octane Number
as reported by API Project 45 using 60 octane base fuel, and the numbers
in brackets are Blending Octane Numbers currently used for modern fuels.
Typical Heats of Combustion are [36]:-

```Fuel     State  Heat of Combustion      Research        Motor
MJ/kg                Octane         Octane
n-heptane  l        44.592                  0              0
g        44.955
i-octane   l        44.374                100            100
g        44.682
toluene    l        40.554                124* (111)     112*  (94)
g        40.967
2-methylbutene-2    44.720                176* (113)     141*  (81)
```

Because all the data is available, the calorific value of fuels can be
estimated quite accurately from hydrocarbon fuel properties such as the
density, sulfur content, and aniline point ( which indicates the aromatics
content ).

It should be noted that because oxygenates contain oxygen that can
not provide energy, they will have significantly lower energy contents.
They are added to provide octane, not energy. For an engine that can be
optimised for oxygenates, more fuel is required to obtain the same power,
but they can burn slightly more efficiently, thus the power ratio is not
identical to the energy content ratio. They also require more energy to
vaporise.

```            Energy Content   Heat of Vaporisation   Oxygen Content
Nett MJ/kg          MJ/kg                   wt%
Methanol        19.95             1.154                  49.9
Ethanol         26.68             0.913                  34.7
MTBE            35.18             0.322                  18.2
ETBE            36.29             0.310                  15.7
TAME            36.28             0.323                  15.7
Gasoline       42 - 44            0.297                   0.0
```

Typical values for commercial fuels in megajoules/kilogram are [37]:-

```                                Gross        Nett
Hydrogen                        141.9       120.0
Carbon to Carbon monoxide        10.2          -
Carbon to Carbon dioxide         32.8          -
Sulfur to sulfur dioxide          9.16         -
Natural Gas                      53.1         48.0
Liquified petroleum gas          49.8         46.1
Aviation gasoline                46.0         44.0
Automotive gasoline              45.8         43.8
Kerosine                         46.3         43.3
Diesel                           45.3         42.5
```

Obviously, for automobiles, the nett calorific value is appropriate, as the
water is emitted as vapour. The engine can not utilise the additional energy
available when the steam is condensed back to water. The calorific value is
the maximum energy that can be obtained from the fuel by combustion, but the
reality of modern SI engines is that thermal efficiencies of only 20-40% may
be obtained, this limit being due to engineering and material constraints
that prevent optimum thermal conditions being used. CI engines can achieve
higher thermal efficiencies, usually over a wider operating range as well.
Note that combustion efficiencies are high, it is the thermal efficiency of
the engine is low due to losses. For a water-cooled SI engine with 25%
useful work at the crankshaft, the losses may consist of 35% (coolant),
33% (exhaust), and 12% (surroundings).

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