AUTE3450U

Combustion and Engines

Basic Thermochemistry Principles as
Applied to IC Engines
Anand Joshi
Academic Associate, UOIT

Thermochemistry: Chemical Reaction

Most IC engines obtain their energy from the combustion of a hydrocarbon fuel
with air, which converts chemical energy of the fuel to internal energy in the
gases within the engine.
There are many thousands of different hydrocarbon fuel components, which
consist mainly of hydrogen and carbon but may also contain oxygen (alcohols),
nitrogen, and/or sulfur, etc.
The maximum amount of chemical energy that can be released (heat) from the
fuel is when it reacts (combusts) with a stoichiometric amount of oxygen.
Stoichiometric oxygen (sometimes called theoretical oxygen) is just enough to
convert all carbon in the fuel to CO2 and all hydrogen to H2O, with no oxygen left
over.

Thermochemistry: Chemical Reaction

The balanced chemical equation of the simplest hydrocarbon fuel, methane CH4,
burning with stoichiometric oxygen is:
CH4 + 2O2 = CO2 + 2H2O
It takes two moles of oxygen to react with one mole of fuel, and this gives one
mole of carbon dioxide and two moles of water vapor.
If isooctane is the fuel component, the balanced stoichiometric combustion with
oxygen would be:
C8H18 + 12.5O2 = 8CO2 + 9H2O
Molecules react with molecules, so in balancing a chemical equation, molar
quantities (fixed number of molecules) are used and not mass quantities. One
kgmole of a substance has a mass in kilograms equal in number to the molecular
weight (molar mass) of that substance. In English units the lbmole is used.
m = NM
(4-1)

Thermochemistry: Chemical Reaction

Thermochemistry: Chemical Reaction

The components on the left side of a chemical reaction equation which are
present before the reaction are called reactants, while the components on the
right side of the equation which are present after the reaction are called products
or exhaust.
Very small powerful engines could be built if fuel were burned with pure oxygen.
However, the cost of using pure oxygen would be prohibitive, and thus is not
done. Air is used as the source of oxygen to react with fuel.
Atmospheric air is made up of about:
78% Nitrogen by mole
21% Oxygen
1% Argon, traces of C02, Ne, CH4, He, H20, etc.

Thermochemistry: Chemical Reaction

Nitrogen and Argon are essentially chemically neutral and do not react in the
combustion process.
Their presence, however, does affect the temperature and pressure in the
combustion chamber.
To simplify calculations without causing any large error, the neutral argon in air is
assumed to be combined with the neutral nitrogen, and atmospheric air then can
be modeled as being made up of 21% oxygen and 79% nitrogen.

Thermochemistry: Chemical Reaction

For every 0.21 moles of oxygen there is also 0.79 moles of nitrogen, or for one
mole of oxygen there are 0.79/0.21 moles of nitrogen.
For every mole of oxygen needed for combustion, 4.76 moles of air must be
supplied: one mole of oxygen plus 3.76 moles of nitrogen.
Stoichiometric combustion of methane with air is then:
CH4 + 2O2 + 2(3.76) N2 = CO2 + 2H2O + 2(3.76) N2
and of isooctane with air is:
C8H18 + 12.5 O2 + 12.5 (3.76) N2 = 8 CO2 + 9 H2O + 12.5 (3.76) N2

Thermochemistry: Chemical Reaction

The energy released by the reaction will thus have units of energy per kgmole of
fuel, which is easily transformed to total energy when the flow rate of fuel is
known.
Molecular weights can be found in Table 4-1 and Table A-2 in the Appendix.
Example: The molecular weight of 29 will be used for air.
Combustion can occur, within limits, when more than stoichiometric air is present
(lean) or when less than stoichiometric air is present (rich) for a given amount of
fuel.
If methane is burned with 150% stoichiometric air, the excess oxygen ends up in
the products:

Thermochemistry: Chemical Reaction

Table A-2

Carbon Monoxide

Equivalence Ratio

Example Problem 4.1

Example contd

 Even when the flow of air and fuel into an engine is controlled exactly at stoichiometric
conditions, combustion will not be "perfect," and components other than CO2, H2O, and
N2 are found in the exhaust products.
One major reason for this is the extremely short time available for each engine cycle,
which often means that less than complete mixing of the air and fuel is obtained.
Some fuel molecules do not find an oxygen molecule to react with, and small quantities
of both fuel and oxygen end up in the exhaust.

SI engines have a combustion efficiency in the range of 95% to 98% for lean mixtures and
lower values for rich mixtures, where there is not enough air to react all the fuel (Fig. 41).
CI engines operate lean overall and typically have combustion efficiencies of about 98%.

Combustion Efficiency

Chemical Equilibrium

Chemical Equilibrium
Equilibrium constants for many reactions can be found in thermodynamic
textbooks or chemical handbooks, tabulated in logarithmic form (In or Log ke)'An
abbreviated table can be found in the Appendix of this book (Table A-3).
Ke is very dependent on temperature, changing many orders of magnitude over
the temperature range experienced in an IC engine.
As Ke gets larger, equilibrium is more towards the right (products).
This is the maximizing of entropy. For hydrocarbon fuels reacting with oxygen (air)
at high engine temperatures, the equilibrium constant is very large, meaning that
there are very few reactants (fuel and air) left at final equilibrium.
However, at these high temperatures another chemical phenomenon takes place
that affects the overall combustion process in the engine and what ends up in the
engine exhaust.

Table A-3
Chemical
Equilibrium
Constants

Chemical Equilibrium
Examination of the equilibrium constants in Table A-3 shows that dissociation of
normally stable components will occur at these high engine temperatures.
CO2 dissociates to CO and O, O2 dissociates to mono-atomic O, N2 dissociates to
mono-atomic N, etc.
This not only affects chemical combustion, but is a cause of one of the major
emission problems of IC engines.
Nitrogen as diatomic N2 does not react with other substances, but when it
dissociates to monatomic nitrogen at high temperature it readily reacts with
oxygen to form nitrogen oxides, NO and NO2, a major pollutant from
automobiles.

Chemical Equilibrium
To avoid generating large amounts of nitrogen oxides, combustion temperatures
in automobile engines are lowered, which reduces the dissociation of N2.
Unfortunately, this also lowers the thermal efficiency of the engine.
Exhaust Dew Point Temperature
When exhaust gases of an IC engine are cooled below their dew point
temperature, water vapor in the exhaust starts to condense to liquid.
It is common to see water droplets come out of an automobile exhaust pipe
when the engine is first started and the pipe is cold.
Very quickly the pipe is heated above the dew point temperature, and
condensing water is then seen only as vapor when the hot exhaust is cooled by
the surrounding air, much more noticeable in the cold winter time.

Example Problem 4.2

Example contd

Saturated Water
Pressure Table

Ref: Heat and Mass Transfer:

Fundamentals & Applications, Y.A.
Cengel, A.J. Ghajar, 4th ed.,
McGraw-Hill, New York (2010).

Example contd

Saturated Water
Temperature Table

Ref: Heat and Mass Transfer:

Fundamentals & Applications, Y.A.
Cengel, A.J. Ghajar, 4th ed.,
McGraw-Hill, New York (2010).

Example contd

Combustion Temperature

Combustion Temperature

Heat Input

Adiabatic Flame Temperature

Adiabatic Flame Temperature

Engine Exhaust Analysis

It is common practice to analyze the exhaust of an IC engine.
The control system of a modern smart automobile engine includes sensors that
continuously monitor the exhaust leaving the engine.
These sensors determine the chemical composition of the hot exhaust by various
chemical, electronic, and thermal methods.
This information, along with information from other sensors, is used by the
engine management system (EMS) to regulate the operation of the engine by
controlling the air-fuel ratio, ignition timing, inlet tuning, valve timing, etc.

Engine Exhaust Analysis

Repair shops and highway check stations also routinely analyze automobile
exhaust to determine operating conditions and/or emissions.
This is done by taking a sample of the exhaust gases and running it through an
external analyzer.
When this is done, there is a high probability that the exhaust gas will cool below
its dew point temperature before it is fully analyzed, and the condensing water
will change the composition of the exhaust.
To compensate for this, a dry analysis can be performed by first removing all
water vapor from the exhaust, usually by some thermo-chemical means.

Example Problem 4-4

Example contd

Example contd

Table A-2

Reference:
Engineering Fundamentals of the Internal Combustion Engines, by W. W.
Pulkrabek, 2nd edition, Prentice Hall, Upper Saddle River (2004).