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Combustion Thermodynamics
Combustion Thermodynamics
Combustion Thermodynamics
Introduction:
A fuel is a substance which releases energy in the form
of heat while undergoing combustion.
The fuels are classified as chemical fuels and nuclear
fuels.
A chemical fuel is a substance which releases energy in
the form of heat while undergoing combustion.
The main combustible elements in any chemical fuel
are carbon and hydrogen. Some fuel contains small
quantities of sulphur which is also combustible.
However presence of sulphur in fuel is considered
undesirable. Fuels are further classified as below;
1
TYPE OF FUEL PRIMARY FUEL SECONDARY
(WHICH OCCUR (PREPARED)
NATURALLY)
Solid Wood Coke
Peat Charcoal
Coal Briquettes
Liquid Petroleum (Crude Gasoline (Petrol)
Oil) Kerosene
Diesel oil
Fuel oil
Alcohol
Benzol
Shale oil
Gaseous Natural gas Petroleum gas
(LPG)
Producer gas
Coal gas
Coke-oven gas
Blast furnace gas
2
Combustion or burning is the chemical process in
which the inflammable matter in a substance
combines with oxygen at a temperature above the
spontaneous ignition temperature of that substance
and results in the evolution of heat and light.
The combustion process involves the oxidation of
constituents in the fuel, that are capable of being
oxidized and it can be represented by a chemical
equation.
These equations indicate the required amount of
oxygen combined with required amount of fuel.
In a chemical reaction the terms, reactants and the
products are frequently used.
Reactants comprise of initial constituents which start
the reaction while products comprise of final
constituents which are formed by the chemical
reaction. 3
The smallest particle which can take part in a chemical
change is called an atom.
It is rare to find elements to exist naturally as single
atom.
Some elements have atoms which exist in pairs, each pair
forming a molecule, and the atoms of each molecule are
held together by stronger inter-atomic forces.
The symbols and molecular weight of some important
elements, compounds and gases are given in table below:
4
Elements/ Molecule Atom
Compounds/
Gases Symbol Molecular Symbol Atomic weight
weight
Hydrogen H2 2 H 1
Oxygen O2 32 O 16
Nitrogen N2 28 N 14
Carbon 12 C 12
C
Sulphur 32 S 32
S
Water 18 - -
H2 O
Carbon monoxide 28 - -
CO
Carbon dioxide 44 - -
CO2
Sulphur dioxide 64 - -
Methane (Marsh SO2 16 - -
gas) CH4 28 - -
Ethylene C2H4 30 - -
Ethane C2H6 26 - -
Acetylene C2H2 44 - -
Propane
C3H8
5
Generally combustion requires reaction with an
oxidant or supporter of combustion.
Oxygen is the main oxidant, but the halogens
(chlorine and fluorine), hydrogen peroxide and
also nitric acid, may act as oxidants as in rocket
propulsion.
Air is the commonest oxidant because it is cheap
and readily available. The following analysis of air
is used in combustion calculations:
11
Theoretical Air and Excess Air:
The minimum amount of air that supplies sufficient oxygen
for the complete combustion of all the carbon, hydrogen,
and any other elements in the fuel that may oxidize is called
the theoretical air.
When complete combustion is achieved with theoretical air,
the products contain no oxygen.
Complete combustion is not attained in practice unless
more than the amount of theoretically required air is used.
The need of excess air is due to the difficulty of obtaining
intimate contact between the air and the fuel.
It is also partly due to the need to complete the
combustion within the combustion space.
The excess air is the amount of air supplied over and above
theoretical air. 12
The complete combustion of methane with minimum
amount of theoretical air and 150% theoretical air
respectively is written as:
15
Theoretical or stoichiometric or minimum air required for
complete combustion:
We know that fuel mainly consists of constituents like carbon,
hydrogen and sulphur and we also know that for combustion;
Carbon requires 2.67 times its own mass of oxygen
Hydrogen requires 8 times its own mass of oxygen
Sulphur require its own mass of oxygen
Now consider 1kg of fuel whose ultimate analysis gives:
Mass of carbon = C kg
Mass of hydrogen = H2 kg
Mass of sulphur = S kg
Then oxygen required to burn
C kg of carbon = 2.67C kg
H2 kg of hydrogen = 8 H2 kg
S kg of sulphur = S kg 16
Therefore total oxygen required for complete combustion
of 1 kg of fuel
= (2.67C + 8H2 + S) kg
As fuel already contains O2 kg of oxygen which we assume
can be used for combustion.
Then total oxygen required for complete combustion of 1
kg of fuel is,
= (2.67C + 8H2 + S – O2) kg
Since air contains 23% of oxygen on mass basis, i.e. 1 kg
of oxygen is associated with 100/23 = 4.35kg of air.
Therefore,
Minimum or theoretical air required for complete
combustion of 1kg of fuel,
= 100/23 (2.67C + 8H2 + S – O2) kg
17
Theoretical or stoichiometric or minimum air required
for complete combustion:
Consider 1m3 of gaseous fuel whose ultimate volume analysis is:
Volume of carbon monoxide = CO m3
Volume of hydrogen = H 2 m3
Volume of methane = CH4 m3
Volume of ethylene = C2H4 m3
Then oxygen required to burn
CO m3 of carbon = 0.5 CO m3
H2 m3 of hydrogen = 0.5 H2 m3
CH4 m3 of sulphur = 2CH4 m3
C2H4 m3 of hydrogen = 3C2H4 m3
Therefore total oxygen required for complete combustion of 1 m3
of fuel
= (0.5CO + 0.5H2 + 2CH4 + 3C2H4) m3
18
As fuel already contains O2 m3 of oxygen which we
assume can be used for combustion.
Then total oxygen required for complete
combustion of 1 kg of fuel is,
= (0.5CO + 0.5H2 + 2CH4 + 3C2H4 – O2) m3
Since air contains 21% of oxygen on volume basis,
i.e. 1 m3 of oxygen is associated with 100/21 =
3.76m3 of air.
Therefore,
Minimum or theoretical air required for complete
combustion of 1kg of fuel,
= 100/21 (0.5CO + 0.5H2 + 2CH4 + 3C2H4 – O2) kg
19
Air-fuel Ratio from analysis of products of combustion:
By making analysis of the combustion products, the air-
fuel ratio can be calculated by the following methods.
1. When fuel composition is known
i) Carbon Balance Method- Quite accurate when
combustion takes place with excess air and when no
free (solid) carbon is present in the products.
ii) Hydrogen Balance Method- Suitable when solid carbon
is suspected to be present in the products.
iii) Carbon-Hydrogen Balance Method- Used when there
is some uncertainty about percentage of N2 present.
2. When fuel composition is unknown
Only Carbon-Hydrogen Balance Method can be
employed. 20
Analysis of exhaust (flue) gas:
The combustion products are mainly gaseous.
When a sample is taken for analysis it is usually cooled down to
a temperature which is below the saturation temperature of
the steam present.
The steam content is therefore not included in the analysis,
which is quoted as the analysis of the dry products.
Since the products are gaseous, it is usual to quote the analysis
by volume.
An analysis which includes the steam in the exhaust is called a
wet analysis.
Practical analysis of combustion products:
The most common means of analysis of the combustion
products is the Orsat analysis using Orsat apparatus.
It gives an analysis of dry products of combustion. 21
1. A burette- used to measure the volume of the exhaust gas
sample inside the apparatus at any time.
2. A gas cleaner- to filter out solid particles in the exhaust gas
sample.
3. A leveling bottle partly filled with water and connected to
the bottom of the burette by tubing.
4. Three absorption pipettes- each containing different
absorbent chemical solutions used to absorb different
constituents of the gas sample.
The pipettes are interconnected by means of a manifold
fitted with cocks with S1, S2, S3 and contain different
chemicals to absorb CO2, CO and O2. Each pipette is also
fitted with a number of small glass tubes which provide a
greater amount of surface. These tubes are wetted by
absorbing agents and are exposed to the gas under analysis. 22
The pipette 1, 2, 3 contain the following chemicals:
Pipette 1: caustic soda (KOH) to absorb CO2
Pipette 2: alkaline solution of pyrogallic acid to absorb O2
Pipette 3: acid solution of cuprous chloride to absorb CO
Further-more the apparatus has a leveling bottle and a
three way cock to connect the apparatus either to gases
or atmosphere. The procedure is as follows:
100cc of gas whose analysis is to be made is drawn into
the bottle by lowering the leveling bottle. The stop cock S1
is then opened and the whole flue gas is forced to pipette
1. The gas remains in this pipette for some time and most
of the CO2 is absorbed. The leveling bottle is then lowered
to allow the chemical to come its original level.
23
The volume of gas thus absorbed is read on the scale of
the measuring bottle.
The flue gas is then forced through pipette 1 for a number
of times to ensure that the whole of the CO2 is absorbed.
Further the remaining flue gas is then forced to pipette 2
which absorb whole of O2.
The reading on the measuring bottle will be the sum of
volume of CO2 and O2.
The oxygen content then is found by subtraction. Finally,
as before the sample of gas forced through the pipette 3
to absorb CO completely.
The amount of N2 in the sample can be determined by
subtracting from total volume of the gas the sum of CO2,
CO and O2 contents.
24
Enthalpy of formation (ΔHf):
A combustion reaction is a particular kind of reaction in which
the products are formed from reactants with the release or
absorption of energy as heat is transferred to and from the
surroundings. In some substances like hydrocarbon fuels the
heat of reaction or combustion may be calculated on the
basis of known values of the enthalpy of formation, ΔHf of the
constituent of the reactants and products at the temperature
T0 (reference temperature). The enthalpy of formation (ΔHf)
is the increase in enthalpy when a compound is formed from
its constituent elements in their natural form and in a
standard state. The standard state is 250C, and 1 atmospheric
pressure.
Therefore the enthalpy of combustion at T0 or the constant
pressure heat of combustion at T0, may be given as:
25
Enthalpy of reaction:
The enthalpy of reaction hR, is defined as the difference
between the enthalpy of products at a specified state
and the enthalpy of the reactants at the same state for
a complete reaction.
For combustion processes, the enthalpy of reaction is
usually referred as the enthalpy of combustion hC,
which represents the amount of heat released during a
steady flow combustion process when 1 k-mol (or 1 kg)
of fuel is burned completely at a specified temperature
and pressure (Fig. below).
26
It is expressed as
hR = hC = Hprod - Hreact
Which is -393.520 kJ/k-mol for carbon at the standard
reference state.
The enthalpy of combustion of a particular fuel is
different at different temperatures and pressures
27
Internal energy of reaction:
When the combustion process is carried out at constant volume, the
non-flow energy equation, Q = (U2 – U1) + W, can be applied to give
Q = (UPo – URo)
Where, W = 0 for constant volume combustion
U1 = URo
U2 = UPo
The internal energy change is independent of the path between the
two states and depends only on the initial and final values and is
given by the quantity Q. The heat transferred during this constant
volume process is called the internal energy of combustion at T0 (or
constant volume heat of combustion), and is denoted by . Thus
29
In case of steam generator or boiler
30
Adiabatic flame temperature:
In a given combustion process that takes place
adiabatically and with no work or changes in kinetic
or potential energy involved, the temperature of
the products is referred to as adiabatic flame
temperature.
With the assumption of no work and no changes in
K.E or P.E, this is the maximum temperature that
can be achieved for the given reactants because
any heat transfer from the reacting substances and
any incomplete would tend to lower the
temperature of the products.
31
The following points to be noted:
1. The maximum temperature achieved through
adiabatic complete combustion varies with the
type of reaction and percent of theoretical air
supplied. An increase in the Air-Fuel ratio will
affect a decrease in the maximum temperature.
2. For a given fuel and given pressure and
temperature of the reactants, the maximum
adiabatic flame temperature that can be achieved
is with a stoichiometric mixture.
3. The adiabatic flame temperature can be controlled
by the amount of excess air that is used.
32
Heating values of the fuel:
In case of a constant pressure process (steady
flow process), the negative of the enthalpy of
combustion is called heating value at constant
pressure.
This represents the heat evolved during the
combustion at constant pressure.
Similarly, the negative of the internal energy of
combustion is called the heating value at
constant volume and it represents the heat
released during the constant volume
combustion process.
33
In general, the heating value also called calorific
value of a fuel is the quantity of heat energy
released by the combustion of the fuel.
For solid and liquid fuels it is expressed in kJ/kg of
fuel, while for gaseous fuels the unit used is kJ/m 3
of fuel at standard temperature and pressure.
Heating values of fuel can be experimentally
determined using calorimeters.
E.g., Bomb calorimeter, Boyce calorimeter and
Junkers gas calorimeter.
34
The Higher Heating Value (HHV) or Higher Calorific
Value (HCV) is the heat released when H2O in the
products of combustion is in the liquid state.
The Lower Heating Value (LHV) or Lower Calorific
Value (LCV) is the heat released in the reaction
when H2O in the products is in the vapor state.
Therefore,
LCV = HCV – mH2O.hfg
Where, mH2O is the mass of water formed during the
combustion
hfg is the latent heat of vaporization.
35
Example 1
Calculate the minimum volume of air required to burn one
Kg of coal having the following composition by weight
C = 72.4%, H2 5.3%, N2 = 1.81, O2 = 8.5%, moisture 7.2%
S = 0.9% and ash 3.9%
On weight basis:
Taking 1kg coal as basis weight of oxygen required to burn 1kg
of coal
C + O2 → CO2
0.724 x 32/12 = 1.93 kg
0.53x 16/2 = 0.424 kg
0.009x32/32 = 0.009 kg
Total O2 = 2.363 kg per kg of coal 36
But 0.085kg O2 is available in coal, therefore O2 required
= 2.363 – 0.085 = 2.278kg per Kg of coal.
Air contains 23% of oxygen by weight.
Therefore the weight of the air supplied is
2.278x 100/23 = 9.9 kg per kg of coal
Density of air required at NTP
P v = mRT
P= m/v RT = ρRT,
ρ = Molecular weight
Volume = P/RT = 1.013x105/287x273 = 1.29 kg/m3
Therefore volume of air required = 9.9(kg)/1.29(kg) = 7.67 m 3
37
On mole basis Consider 100kg of coal
C = 72.4/12= 6.03K mol, O2 = 8.5/32 = 0.265K mol
H2 = 5.3/2 = 2.65K mol, H2O = 7.2/18 = 0.4K mol
N2 = 1.8/28 = 0.064K mol, S = 0.9/32 = 0.028K mol
1K mol C + 1K mol O2 → 1Km CO2
Therefore 6.03 K mol of carbon requires 6.03 K mol of oxygen
1 K mol H2 + ½ K mol O2 → 1K mol H2O
H2 - 2.65 x ½ = 1.325K mol,S -0.028x1 = 0.028
Total O2 required 6.03 + 1.325 + 0.028 = 7.383
The oxygen present in coal 0.265K mol
Net O2 required = 7.383 – 0.265 = 7.118K mol
Air required
7.118x100/21= 33.89K mol / 100kg of coal = 0.3389K mol / 1kg coal
Volume of air supplied
38
0.3389K mol/kg X 22.4m = 7.59m /kg of coal
3 3
Example 2
Calculate the volumetric analysis of the flue gases when
coal burns with 20% excess air from the previous calculation
the actual air required 33.89K mol/100kg coal.
Therefore the actual air is
33.89 x 120/100=40.67K mol/ 100 kg coal
The amount of N2 associated with this
40.67 x 79/100 = 32.13K mol
The amount of O2 present
40.67 x 21/100 = 8.54K mol
The actual amount of O2 required was 7.118K mol excess O2
will appear in exhaust gas
= 8.54 – 7.118 = 1.422K mol. 39
Therefore:
CO2 = 6.03K mol
SO2 = 0.028K mol
N2 = 32.13K mol (air) + 0.064 (fuel)
= 32.194K mol
O2 = 1.422K mol os excess oxygen.
Therefore the Total volume
= (6.03 + 0.028 + 32.194 + 1.422)
= 39.674K mol
The volumetric composition of the gas
CO2= (6.03/39.674) x 100 = 15.12%
SO2=(0.028/39.674) x 100 = 0.07%
N2 = (32.13/39.674) x 100 = 81.15%
O2= (1.422/39.674) x 100 = 3.58% 40
3. The composition of dry flue gases obtained by burning
a liquid fuel containing only hydrogen and carbon is CO2
10.7%, O2 5.1%, N2 84.2%. Calculate the composition of
fuel by weight and excess air used.
Solution:
consider 100K mol of dry flue gases. They will contain
10.7K mol of O2 (from CO2) + 5.1K mole of (as max.
oxygen) = 15.8K mol
Using nitrogen balance the actual air used 84.2 x 100/79
= 106.58K mol of dry flue gases and oxygen in the air
supplied 106.58 x 21/100 = 22.38K mol. Therefore the
amount of O2 present in the water produced by the
combustion of H2 is 22.38 – 15.8 = 6.58K mol O2.
41
We know that 1 K mole of H2 combines with ½ K mol O2 to
produce water. Therefore the amount of hydrogen present is
6.58x2 = 13.16K mol/100K mol of dry flue gases, and the carbon
present is 12X10.7 = 128.4kg/100K mol of dry flue gas.
Therefore the composition of fuel (by weight) is 128.4kgC and
26.32Kg H2 on the %age basis.
C = (128.4/(128.4+26.32) x 100 = 82.99%
H = (26.32/(128.4+26.32) x 100 = 17.01%
Excess air supplied
The amount of O2 required to burn 10.7K mol C is 10.7K mol and
to burn 13.16K mol H2 is 13.16 X ½ = 6.58
Total O2 required = 10.7 + 6.58 = 17.28K mol/100K mol of dry
flue gases
%age of excess air = (22.38 – 17.28)/(17.28) x 100 = 29.5%
42
Example 4
A blast furnace gas has the following volumetric
analysis H2 CO-24%, CH4 – 2%, CO2-6%, O2-3%
and N2-56%
Determine the Ultimate gravimetric analysis
Given volumetric analysis, H2 – 9%, CO-24%,
CH4 – 2%, CO2-6%, O2-3% and N2-56%
50
Solution: For complete combustion.
O2 required is
For carbon - 0.82 = 2.186 kg of O2
For hydrogen - 0.006 = 0.48 kg of O2
Total O2 required = 2.666kg.
Net O2 supplied = Total O2 required – O2 present in the fuel
= 2.66 – 0.004 = 2.662 kg/kg of coal
Theoretical minimum air required for complete
combustion [C burns to CO2 totally]
Air supplied = 2.626x100/23 = 11.417 kg/kg of coal
Flue gas analysis:
But actually only 80% carbon is burns to CO 2
CO2 = 0.8 x 0.82 x44/12 = 2.405kg of CO2 51
20% carbon is burnt to CO
CO = 0.2 x 0.82 x 28/12= 0.383 kg of CO
O2 actually required for 80% carbon burnt to CO 2
= 0.8 x 0.82 x 3232/12 = 1.749 kg of O2
O2 actually required for 20% carbon burnt to CO
= 0.2 x 0.82 x 16/12 = 0.219 kg of O2
O2 required by Hydrogen:
= 0.06 x 8 = 0.48 kg of O2.
H2O produced = 0.06 x 9 = 0.54 kg of H2O
But actual air supplied = 18kg
Actually O2 supplied = 18 x23/100 = 4.14 kg of O2
Free O2 in the flue gas = 4.14 + 0.04 – 1.749 – 0.219 – 0.48 =
1.732 kg of O2/kg of coal
N2 in the flue gas = 18x77/100 = 13.86 kg/kg of coal 52
Volumetric analysis of the dry products of combustion.
CO2 = (2.405/44)x 100 = 0.0546m3/K. mol
CO = (0.383/28) x 100=0.0137 m3/K.mol
O2= (1.732/32)x 100 = 0.0541m3/K.mol
N2 = (13.86/28)x 100 = 0.495m3/K.mol
In % of volume:
CO2= (0.0546/0.6174)x 100 = 8.84%
CO = (0.0137/0.6174)x 100 = 2.22%
O2 = (0.0541/0.6174)x 100 = 8.76%
N2 = (0.495/0.6174)x 100 = 80.70%
53
8.Consider the following reaction, which occurs in a steady
state, steady flow processes.
CH4 + 2O2 → CO2 + 2H2O (l)
The reactants and products are each at total pressure of
0.1Mpa and 25oC. Determine the heat transfer for per K
mol of fuel entering the combustion chamber.