Module 5: Combustion Technology

Lecture 32: Fundamentals of thermochemistry

Keywords : Heat of formation, enthalpy change, stoichiometric coefficients, exothermic
reaction.

Thermochemistry describes the thermal behaviour of a reacting system. The transfer of heat

energy between a system and its surroundings occurs by the difference of temperature . The

transfer of this energy takes place from a hotter body to a colder body until the temperatures

of the two bodies become equal or the molecular energies of the two bodies become the

same. The change of states also may happen due to this heat transfer. Combustion is a

chemical reaction between a fuel and oxygen. The heat energy generates from the combustion

of a fuel with air where the internal energy of the fuel species is the chemical energy. This

energy is associated with the chemical bonds and intermolecular attractions. During chemical

reaction, some chemical bonds are broken with the formation of new compounds with the

transfer of some heat energy between system and its surroundings. The heat of reaction is the

quantity of heat exchanged between a system and its surroundings during a chemical reaction

at a specified temperature. The heat of combustion is defined as the quantity of heat released

in combustion of a fuel with oxygen. Some important properties such as, pressure, volume,

temperature, internal energy, enthalpy, entropy and free energy are required for quantitative

analysis.

The properties, depending only on the final and initial conditions of that system, are called

state functions and they are independent of the path connecting with the initial and the final

state. The most important state function related with a chemical reaction system is enthalpy.

Enthalpy is usually evaluated at standard state, 1 atm pressure and 298 K of temperature. This

property is used to evaluate the heat or energy evolved or absorbed in a reaction. The

enthalpy of an element at standard state is assumed to be zero. The absolute value of the

enthalpy of a process cannot be determined, rather the enthalpy change of the process can be

determined. The enthalpy required to form a molecule from its constituent’s elements at
standard state is defined as the heat of formation, ∆Hfo . The standard enthalpy of formation

of any substance is defined as the enthalpy of that substance compared to the enthalpies of the

elements from which it is formed.

Fig. 1 Heat of reaction from standard heat of formatiom

Thus, the standard enthalpy change of formation of carbon dioxide by the reaction of

carbon and oxygen from their elemental forms is called the standard enthalpy of formation

of carbon dioxide or the heat of reaction for combustion (∆Hor) . The standard heat of

formation of each element of a fuel are required for determination of Heat of reaction for

the combustion. This can be explained by the diagram as shown in Fig.1.

This can be expressed by the equation

o
o L n ∆Ho
∆Hr L nj ∆Hformation i formation
products reactants

Where, ni and nj are the stoichiometric coefficients in the chemical reaction of reactants and

products respectively. Thus, the heat of reaction can be derived from the available heats of

formation data.

The reaction may be written as, C(graphite) + 02(g) → C02(g)

 o -1
∆Hf (i.e. the enthalpy change) at 298 K is -393.51 kJ mol .

The knowledge of thermochemistry is essential to determine the molar heat of reaction.

The amount of heat energy released during reaction will be obtained from the difference of

internal energy between products and reactants. The reaction where heat is released by the

reaction is called exothermic reaction. The combustion reactions are exothermic reactions.

The thermochemical calculation are performed either at constant volume or constant pressure.

The reactions are generally carried out at constant pressure.

We have H U + PV where H is the enthalpy, U is the internal energy and PV is pressure-

volume work.

The enthalpy change of a process is given by

∆H ∆U + P∆V.

From first law of thermodynamics, ∆U ∆Q w. In the present system, the work done

(w) in the system is the pressure volume work. However, because the system remains at a

constant volume, the work done P∆V w will be zero. ∆Q ∆U

At constant pressure process, assuming ideal gas law PV RT and ∆n V ∆V, we have

P∆V RT∆n. ∆n is the number of mole change in a reaction or,

∆H ∆U + RT∆n

The heat change at constant pressure process is ∆Q ∆H and, at constant volume is

∆Q ∆U. In liquid phase reaction the volume change is also negligible and ∆H is same as

∆U. Let us consider a reaction in a general form A + B → C + D

The heat change or the enthalpy change of the reaction is equal to the difference in enthalpies

of the products and reactants.

∆H Hproducts Hreactants (HC + HD) (HA HB)

The change in enthalpy of complete combustion of one mole of a substance for burning in

excess air is called the heat of combustion.

C(s) + 02(g) → C02(g) ∆H 394.5 k]/mole

C(s) + 1202(g) → C0(g) ∆H 108.8 k]/mole

Carbon monoxide also may oxidized as

C0(g) + 1202 → C02 ∆H 283.4 k]/mole

The quantity of heat is released depends on the enthalpy of the fuel and oxidant relative to

that of the enthalpy of the combustion products. Hydrocarbon fuels on combustion in oxygen

produce carbon dioxide and water with the release of heat.

The most relevant law for the evaluation of the energy of the reaction system is the Hess'

Law. This law states that the total amount of heat evolved or absorbed in a chemical reaction

is the same whether the process takes place in one or more steps. This is also known as the

law of constant heat summation. In order to explain the Hess' Law, the burning of carbon to

carbon dioxide reaction is used. The reaction may take place in two different ways:

1. Direct burning of carbon to carbon dioxide.

C(s) + 02(g) → C02(g) ∆H 393.5 k]/mole

 2. Carbon first burnt to CO and CO is further oxidized to CO2

C(s) + 1202(g) → C0(g) ∆H1 110.4 k]/mole

C0(g) + 102 → C02 ∆H2 283.2 k]/mole

2

Overall change of enthalpy= ∆H1 + ∆H2 110.4 283.2 393.6 k]/mole.

Hess’s law applied for these reactions may be explained in a diagram as shown in Fig.2.

Fig. 2 Application of Hess’s Law for the burning of pure carbon

Example1 : Determine the heat of reaction for C(s) + 2H2(g) → CH4 using the following

heat of reactions of the following reactions

C(s) + 02(g) → C02(g) ∆Hr,1 392.5 k]/mol (1)

H2(g) + 102(g) → H20(l) ∆Hr,2 284.6 k]/mol (2)

2

CH4(g) + 202(g) → C02(g) + 2H20(l) ∆Hr,2 885.6 k]/mol (3)

Eqn. (2) is multiplied by 2 and added to Eqn. (1),

C(s) + 2H2(g) + 202(g) → C02(g) + 2 H20(l) (4)

By subtracting Eqn. (3) from Eqn. (4), ∆Hr 961.7 + 885.6 76.1 k]/mol
Reference

1. Essentials of Physical Chemistry, B.S Bahl, G. D. Tuli and A. Bahl, S. Chand & Co. Ltd,

2004.

2. Fuels and Combustion, S. Sarkar, 3rd Edition, University Press, India,2009

3. Physical Chemistry, P. C. Rakshit, 6th Edition, Sarat Book Distributers, India, 2001

Module 5: Combustion Technology Lecture

33: Combustion air calculation

Keywords: Heat of combustion, stoichiometric air, excess air, natural gas combustion

Combustion air calculation

The reaction of fossil fuels such as, coal or natural gas with oxygen liberate heat and the heat is

used for various purposes. The main combustion products of burning of fuels are carbon dioxide

and water. Combustion is the reaction of a fuel substance with air or pure oxygen to form

combustion products. The combustion process is always exothermic and it liberates heat. The

combustion reaction may be written as:

Fuel + 02 → Products + Heat

In solid fuel, carbon is the main combustible component which is combined with an equivalent

amount of oxygen to form carbon dioxide. Carbon monoxide may also be formed for incomplete

combustion, which is further reacted to form carbon dioxide. The hydrogen and sulphur converts

to H2O vapour and sulphur dioxide respectively.

The various reactions observed in the combustion of coal are as follows:

C + 02 = C02 (1)

1
C + 0 = C0 (2)
2 2
 1
C0 + 0 = C0 (3)
2 2 2

1
H2 + 02 = H2 0 (4)
2

5 + 02 = 502 (5)
A definite amount of oxygen is required for the conversion of carbon to carbon dioxide. As per

the stoichiometry of equation (1), 32 kg of oxygen combines with 12 kg carbon in the first

reaction to form 44 kg of carbon dioxide. So, 1 kg of carbon requires 2.667 kg of oxygen.

Similarly, 1 kg of carbon requires 1.33 kg of oxygen to form 28 kg of carbon monoxide. 1 kg of

sulphur requires 1 kg of O2. The theoretical air can be calculated for a particular coal if carbon,

hydrogen, nitrogen, oxygen and sulfur contents in weight percent are known by ultimate

analysis.

Calculation of theoretical combustion air

Calculation on weight basis:

Let the ultimate analysis of a coal sample is as follows:

Carbon: 73%; hydrogen: 4.5%; oxygen 5.9%; nitrogen: 1.5%; sulphur: 5% ; water 2.1%; ash 8%

Oxygen required for burning of carbon, hydrogen and sulphur are as follows:

Basis: 1 kg coal burned

C: 0.73 × 2.667 kg = 1.9469 kg of oxygen

H: (0.045 × 8) - 0.059 = 0.301 kg of oxygen

(1 kg of hydrogen consumes 8 kg of oxygen and 0.059 kg of oxygen is initially present in

coal which should be subtracted from the total required oxygen)

S: 0.05×1 kg = 0.05 kg of oxygen

Total oxygen required to accomplish the complete burning = 1.9469+0.301+0.05 = 2.298 kg

Air contains Oxygen: Nitrogen in the proportion of 79:21 or 1 mole of oxygen is accompanied

by 3.762 mole of nitrogen. Total moles of air are equal to 4.762 moles.

One kg of oxygen equivalents to 4.762× 29/32=4.3155 kg ~ 4.32 kg of air, because, molecular

wt of air and oxygen are 29 and 32 respectively. Therefore, total amount air needed for the

burning of above coal sample will be 2.298 × 4.32 = 9.927 kg, which is the theoretical air

requirement.

Therefore, oxygen or theoretical air may be approximately determined by the general equations

as,

Oxygen required per kg coal = 2.667 C + (H×8- O) + S kg

Air required per kg carbon = 4.32× (C × 2.667 + (H×8- O) + S)

= 11.521 C + 34.56 H + 4.32(S-O) kg

Where C, H, O and S are weight on the basis of 1 kg fuel and the oxygen present in the fuel is

subtracted from the required oxygen for burning of fuel as shown in the equation.

Calculation on volume basis:

The volume of air requirements may also be determined in Nm3 per kg of fuel. 1 kmol is

equivalent to 22.4 Nm3.

1 kg of oxygen is equivalent to (1/32) kmol = (1/32)x 22.4 = 0.7 Nm3

So, 1 kg carbon required 32/12 kg oxygen = (32/12) x (1/32) x22.4 = 1.886 Nm3
Volume of oxygen required = (1.866C + 5.56H + 0.7S -0.7O) Nm3/kg

As the volume ratio of air: oxygen is 1: 0.21.

Therefore, the volume of air = Volume of oxygen /0.21

= (1/0.21) (1.866C + 5.56H + 0.7S -0.7O) Nm3/kg coal

= 8.89 (C+ 0.375S) + 26.5H -3.3O Nm3/kg coal

A common example of burning of gaseous fuel is the combustion of natural gas which mainly

contains methane. One molecule of methane reacts with two molecules of oxygen to produce one

molecule of carbon dioxide and two molecules of water vapor.

CH4 + 202 = C02 + 2H20 (6)

Excess air calculation

In a combustion process, the complete burning can not be accomplished with the exact

theoretical amount of air. Therefore it is essential to supply an excess amount of air for the

combustion of fuel. The volume of twice the theoretical air may be used; otherwise, it is decided

based on the nature of the fuel used and the method of burning process.

The valid reason for incomplete combustion of fuel in presence of theoretical amount of air may

be due to the fact that each particle of oxygen in the air does not have the intimate contact with

the fuel particles in the combustion process. Therefore an excess air is to be supplied.

It was observed that 50 per cent more than the theoretical amount of air is usually needed. If less

than this amount of air is supplied, the carbon burns to monoxide instead of dioxide.
An excess of air is also a source of waste, as the products of combustion will be diluted and carry

off an excessive amount of heat in the chimney gases, or the excess air will so lower the

temperature of the furnace gases as to delay the combustion to an extent that will cause carbon

monoxide to pass off unburned from the furnace.

Calculation flue gas volume of combustion of methane

Stoichiometric equation is CH4 + 202 = C02 + 2H20 with pure oxygen

CH4 + 202 + 7.524 N2 = C02 + 2H20 + 7.524 N2 (2 mole oxygen= 7.524 moles of nitrogen,

that means, 7.524+2=9.524 moles of air)

1 mole of methane requires 9.524 moles of stoichiometric air or 9.524 ml of air at STP per ml of methane.

Flue gas composition:

Example 1: In combustion of pure methane gas with 5% of excess air, determine the gas

composition of flue gas in volume %.

Solution:

Basis: 1 mole of methane burning

If 5% excess air is used, according to the following equation, oxygen in air is, 2+ 2×0.05=2.1

moles and nitrogen in air is, 7.7524+7.524×0.05=7.9 moles.

CH4 + 2.102 + 7.9 N2 = C02 + 2H20 + 7.9 N2 + 0.1 02

Total number of moles in flue gas = 1 mole CO2 + 2 moles H2O + 7.9 mole N2 + 0.1 mole O2 =

11 moles
Composition in volume percent is CO2=0.0909; H2O = 0.182; N2= 0.718; O2 = 0.00909

According to the wet (water is liquid) analysis.

Example 2 : Methane is burned with 18 % excess air in respect of volume. Determine the carbon

dioxide percentage in the flue gas dry basis.

Solution : The reaction is CH4 + 202 = C02 + 2H20

1m3 2m3 1m3 2m3

Basis: 1 m3 methane burning

The volume of stoichiometric air = 2/21 x 100 = 9.524 m3

The volume of actual air = 9.524 (1+0.18) m3= 11.238 m3

Volume of Nitrogen = 11.238 m3 x 0.79 = 8.878 m3

Volume of Carbon dioxide = 1m3

Volume of Oxygen = 2m3 x 0.18 = 0.36 m3, Total volume of flue gas = 10.238 m3

% of Carbon Dioxide = 1/10.238 x 100 = 9.767

Stoichiometric ratio

If the minimum air is used following the stoichiometry of the combustion reaction then the air is

called the stoichiometric air. The ratio of actual air to stoichiometric air is called stoichiometric

ratio. For example, soichiometric air for burning of methane is

 Actual air
5toichiometric ratio =
5tiochiometric air

Actual air - 5toichiometric air

Excess air =
5toichiometric air

Excess air = (5toichiometric ratio - 1) x 100 %

Example 3: Calculate the percentage excess air for methane burning. The flow rate of methane

and air are 25 and 290m3/h respectively.

Stoichiometric air for methane burning is 9.524 m3 /m3

Assuming the flow rate of methane = 25 m3/h

The flow rate of air = 290 m3/h

Air required = 25 x 9.524 =238.1 m3/h

290
Then 5toichiometric ratio = = 1.22
238.1
 Excess air = (1.22 – 1) x 100 % = 22 %
References

1. Applied Combustion, Second Edition, Eugene L. Keating, CRC Press (Taylor and

Francis Group), 2007, NY

2. Fuels and Combustion, S. Sarkar, 3rd Edition, University Press, 2009, India.
 Module 5: Combustion Technology

Lecture 34: Calculation of calorific value of fuels

Keywords : Gross calorific value, Net calorific value, enthalpy change, bomb calorimeter

5.3 Calculation of calorific value of fuels

The heating value or calorific value of a combustible material is an important property, which

may be used to evaluate its effectiveness for using as a fuel and also for the design of chemical

equipments where it is to be used. The calorific value may be defined as the quantity of heat

liberated by the complete burning of a unit mass of the fuel with oxygen at constant volume

process. In case of gaseous fuel, the heat released during the complete combustion of one cubic

meter of gas at N.T.P (normal temperature and pressure) i.e, 1 atm pressure at 0°C is the measure

of calorific value. Whereas, the calorific value for solid fuel is measured per gram or per kg of

solid fuel.

In general, the calorific value of a solid or liquid fuel is the gross calorific, which is determined

at constant volume for a liquid fuel and for gaseous fuels at constant pressure. If the water

formed and liberated during combustion is in the liquid phase, then the corresponding calorific

value is called gross calorific value. The net calorific value corresponds to the process when the

water formed during combustion remains as steam.

The calorific value of fuel depends on the type of exothermic reaction and the heat of reaction.

Heat of combustion is measured from the heat of reaction of the reaction. It is determined from

the value of enthalpy change for the reaction at constant pressure and temperature. At constant

pressure system, the enthalpy change is obtained from the equation.

∆H = ∆U + RT∆n (1)
Therefore, the enthalpy change for the reaction may be determined from the internal energy and

number of mole changes in the reaction. The internal energy change with the change of

temperature is given as

d∆
d = C or, = ∆C
dT P V dT V
P
T2
∆U - ∆U = I ∆C dT = ∆C (T -T ) (2)
2 1 Tl V V 2 1

dH
From the knowledge of thermodynamics, =C
dT P P

and
d(∆H) = ∆C = C -C (3)
dT P P,2 P,1
P

T
∆H - ∆H = I 2 ∆C dT = ∆C (T -T ) (4)
2 1 Tl P P 2 1

The heat of reactions may be determined from Eqn. (2) and (4), where the subscripts ‘1’ and ‘2’

are designated as reactants and products. T1 and T2 are the average temperature of reactants and

products respectively. CP and CV are the heat capacities at constant pressure and constant

volume respectively. The use of average heat capacities in the above equation is a well

approximation. The heat of reaction may be determined from the heat capacities of all reactants

and products. The heat capacity is usually the temperature dependent extensive property in

thermodynamics. It may be expressed as

CP = A + BT + CT2 + DT3

The values of the constants A, B, C, D….etc are available in the literature. The calorific value of

solid or liquid fuel may be measured by the bomb calorimeter.

From the summation of all heat of reactions of the possible reactions in the burning process of a

fuel may give an idea of the heating value or the calorific value of the fuel. This procedure is

easily applicable for the gaseous fuels. For gaseous fuels, such as, natural gas, LPG and producer

gas, the heat of combustion is sufficient to be used as an approximate calorific value for natural

gas.

The composition of the fuel gas should be known. Then the values for the heat of reaction for

oxidation of each constituent to CO2 and H2O at 250 C are to be determined. The heat of reaction

also can be determined from the standard heat of formation data of products and reactants. The

summation of all these heat of reactions are made to obtain the heat of combustion in kcal or kJ

per mole of the gas and further it may be converted in per unit mass or volume. The values of

the standard heat of formation (∆H°f) of reactants and products are available in the literature.

The water formed during combustion may be either in liquid phase and vapor state, an addition

amount of heat is required to vaporize the water present in the fuel. Then the heat generated by

combustion, known as the gross calorific value if water is in liquid state after condensing the

vapor. Otherwise, the water will be in the vapor state. Then the heating value is called the net

calorific value. This is called the net calorific value is obtained by subtracting the latent heat of

vaporization (∆Hv ) from the gross calorific value.

Example: Calculating the heating value of Methane

It may be assumed the methane is burnt in pure oxygen and does not contain any water vapor.

The reaction stoichiometry is CH4(g) + 2O2 (g) → CO2 (g) + 2H2 O(g)

The ∆Hcomb of methane at 298K is the heat of reaction between CH4 and O2 to form CO2 (g) and

H2O(g), The heat of formation data are as follows:

∆ H°f of CO2 (g)= –393.5 kJ/mol, ∆H°f of H2O(g) = –242.8 kJ/mol and

∆H°f of CH4(g) = 74.8 kJ/mol

Then the heat of combustion of methane is calculated from the equation

0 0 0
∆Hr = L ∆Hf,j - L ∆Hf,i
products reactants

∆Hr0 = -393.5 + 2(– 242.8) + 74.8 = -804.3 kJ/mol

So, the heat of combustion of methane at 298 K is 804.3 kJ/mol assuming water formed is in

vapor phase, this is same as the net calorific value of methane. If water is in the liquid phase,

then the heat ∆H0f of H2O(liquid) = -286.2 kJ/mol.

∆Hr0 = -393.5 + 2(-286.2) + 74.8 = -891.1 kJ/mol

The heating value or heat of combustion is 891.1 kJ/mol, which 86.8 kJ/mol more than the value

obtained for water in vapor phase. The heat of vaporization of water = 86.8/2=43.1 kJ/mol. This

heating value is identical to gross calorific value.

The calorific value for gaseous fuel may be experimentally determined using Junker’s gas

calorimeter. The calorimeter consists of a combustion cylinder surrounded by a water jacket

and fuel burner is kept below the combustion cylinder. The flow of cooling water may be

adjusted by a control valve. The temperature of the gas exhaust, cooling water inlet and outlet

temperatures are measured. The burner is set in such a way so that a complete combustion of the

gaseous fuel is occurred. The flow rate of water is then measured. Temperature of the exhaust

gas is brought down to the ambient temperature by the flow of cooling water. Water vapour
contained in the flue gas is condensed. The heat released by the combustion process is used to

heat up the gases inside the combustion chamber (i.e. air and fuel). Then the gases are cooled by

the cooling water and the outlet water temperature is increased. If the flue gas is cooled down to

ambient temperature, then the heat of the hot gas is completely transferred to the cooling water.

Assuming the continuous water flow rate, a steady state heat balance may be written as:

mF HF + mW . CW . (Two - Twi ) = Q

If the heat loss from the calorimeter body to surrounding is negligible for the temperature of wall

of the instrument is same as the ambient temperature. So,Q = 0.

Gross Calorific Value, HF = [mW CW . (Two - Twi )]/mF .

Where, mF and mW are the mass flow rate of fuel and water respectively. Two and Twi are outlet

and inlet temperature of water respectively. CW is the specific heat of water.

If water is condensed and collected from the gas outlet for a specified time interval,

then the net calorific value is HF,net = HF,gross - WChC where, WC = mass of water condensed,

and hC = heat of condensation of water vapor.

The calorific value of solid or liquid fuel may be experimentally determined in a bomb

calorimeter. The sketch of a bomb calorimeter is given in Fig.1 of Lecture-6 in Module-1. The

total quantity of heat generated by combustion including the heat needed to vaporize the water is

obtained, which is called gross calorific value. These measurements are obtained by burning a

representative sample in a high pressure oxygen atmosphere within a stainless steel pressure
vessel or bomb. The heat released by this combustion is absorbed by water within the calorimeter

and the resulting temperature change of water is noted.

(mw +W)Cw (T2 -Tl)

The heat absorbed by the water in the calorimeter, QV = m
F

Where, W = water equivalent of the calorimeter, mw = mass of water in the calorimeter, Cw =

specific heat of water, mF = mass of fuel , T1 = initial temperature of water and T2 = final

temperature of the water.

Reference

1. Fuels and Combustion, S. Sarkar, 3rd Edition, University Press, India, 2009.

2. Physical Chemistry, P. C. Rakshit, 6th Edition, Sarat Book Distributers, India, 2001

3. Chemical Process principles, Part-I, Materials and Energy Balances, O. A. Hougen, K.

M. Watson and R. A. Ragatz, 1st Edn, (Reprint), Asia Publishing House, Calcutta, 1976.
 Module 5: Combustion Technology

Lecture 35: Adiabatic flame temperature calculation

Keywords: Constant pressure adiabatic flame temperature, constant volume adiabatic flame

temperature

5.4 Adiabatic flame temperature calculation

The temperature of the products in an adiabatic combustion of fuel without applying any shaft

work, is defined as the “Adiabatic Flame Temperature”. In a combustion process the heat

produced during the exothermic chemical reaction is released to their product and the

temperature of the products is raised. There is no possibility for dissipation of the heat to the

surrounding and the process will be adiabatic as there is no heat loss to the surrounding. As a

result, the temperature of the products suddenly increases and it produces a flame. This will heat

up the product gases in flame region and the temperature rise will be maximum. This highest

temperature is known as the adiabatic flame temperature. The temperature rise depends on the

amount of excess air used or the air-fuel ratio. The flame temperature has the highest value for

using pure oxygen gas and it decreases by using air. So, the exact stoichiometric air is to be

supplied for better result. With too large amount of excess air the flame temperature will be

reduced. When the heat lose to the environment or diluted by the inert gases and there is an

incomplete combustion. So, the temperature of the products will be less. The flame temperature

is determined from the energy balance of the reaction at equilibrium. There are two type of

adiabatic flame temperature: constant pressure adiabatic flame temperature and constant volume

adiabatic flame temperature.

Constant pressure adiabatic flame temperature:

From the first law of thermodynamics at constant pressure process

∆U = Qp - wp = Qp - p∆V

H = U + pV

At constant pressure, ∆H = ∆U + p∆V + V∆p = ∆U + p∆V

Under adiabatic condition, Qp = 0 , ∆H = 0,

For equilibrium reaction,

Hreactants = Hproducts

Fig. 1 Combustion of fuel

L Hreactants (Ti, p) = L Hproducts (T, p)

T
L Hproducts (Ti, p) = L ni Cpi dT + QVL
TR
Where, QVL = latent heat of vaporization or condensation for phase change of the product
during the change of temperature of from TR to T K.

Ti is the inlet temperature of fuel and air and TR is the reference temperature, 298 K.

Where, Cpi is the heat capacities which is expressed as

Cpi = Ai + Bi T + Ci T 2

Therefore,
Bi 2
Ci 2
0
L Hproducts (Ti , p) = L ni [∆Hf,i + Ai (T - TR ) + (T - TR ) + 3 (T - TR ) ]
2
The flame temperature, T may be calculated from the above equations. It is assumed that

QVL = 0. Also if the mean heat capacity data is used,

0
L Hproducts (Ti , p) = L ni [∆Hf,i --p-,-i (Tad - TRef )]
+C

Constant volume adiabatic flame temperature:

From the first law of thermodynamics,

QV = ∆U , and QV = QP - nRT = ∆HP - ∆nRT

In adiabatic process, QV = 0 = ∆HP - nRT

Hreactants (Ti, pi ) - Hproducts (Tad , pf ) - R(nreactants Ti - nproducts Tad ) = 0

Example 1 : Determine the constant pressure adiabatic flame temperature for the combustion of
methane with a stoichiometric air at 1 atm pressure. The reactant temperature at initial
condition, Ti=298 K. The reaction is CH4 + 2O2 + 7.52 N2 = CO2 + 2H2O + 7.524 N2 .Also,
determine the constant volume adiabatic flame temperature using the following Table 1.

(The problem may be solved by trial and error method if specific heats data are available as a
function of temperature. In the present problem, the specific heats of reactants are taken at an
average temperature between initial and final temperature which is (298+1850)/2 = 1074
K�1100 K. Where, the final temperature is assumed as the adiabatic flame temperature of 1850
K in air. )
Table:1

Species Standard Enthalpy of Average specific heat

Formation at 298 K

CH4 -72.1 kJ/mol -75.328 kJ/kmolK

CO2 -394.0 55.396 kJ/kmolK

H2O -244.5 42.44 kJ/kmolK

N2 0 33.0 kJ/kmolK

O2 0 ---

Solution:

Basis : 1 kmol of methane , TRef =298 K

At constant pressure process, we have Hreactants = Hproducts

Hreactants = -72100 + 2(0) + 7.524(0) = -72100 kJ/kmol

Hproducts = ∑ ni [∆Hf,i --p--,i ad
0
+ C (T - 298)] = [-394000 + 55.396(Tad -298)]

+[-244500 + 42.44(Tad -298)](2)

+[0.0 + 33.0(Tad -298)](7.52)

= -883000+388.436 (Tad -298) =Hreactants= -72100 kJ/kmol

Hence, Tad = 2385.6 K, So the adiabatic flame temperature is 2385.6 K.

At constant volume process, R(nreactants Ti - nproducts Tad ) is to add with the final enthalpy of

products, Hproducts . The constant volume adiabatic temperature will be larger than the constant

pressure adiabatic flame temperature.

Then we can write,

Hproducts = ∑ ni [∆Hf,i --p--,i ad

reactants i products ad
0 - 298)] - R(n T -n T )
+ C (T

As in the above reaction, nreactants = nproducts = 10.52 = constant

R(nreactants Ti - nproducts Tad ) = 8.314(10.52)(298 - Tad ) . For specific heat data slight

higher temperature may be assumed. The problem is solved considering same Cp data.

Hproducts = -883000+388.436 (Tad -298) + 8.314(10.52)(298- Tad ) = -72100 kJ/kmol

-810900 + (383.84 - 87.463)( Tad -298) =0 ,

Tad = adiabatic flame temperature at constant volume process = 2992.3 K

The constant volume adiabatic flame temperature is greater than the constant pressure value.

Determination of adiabatic flame temperature using heat of combustion of fuel

If the heat of combustion of the fuel is known and the heat capacity data of all products are

available, the adiabatic flame temperature can be calculated by using the following equation:

Tf
Qc = L CP,i dT
298 i

Where , Qc = ∆H0R= the heat of combustion of the gaseous fuel. The mean CP -values may be

used for the calculation. Average temperature may be used as, from the arithmetic mean of 298

and Tf .

Example 2: Determine the adiabatic flame temperature at constant pressure combustion of

propane gas using stoichiometric air. The heat of combustion of propane is 2220 kJ/mol.
Mean Cp data at 1200 K is available as

CO2 : 0.05632 kJ/mol-K; H2O : 0.04365 kJ/mol-K; N2 : 0.03371 kJ/mol-K

Solution:

Basis: 1 mol of propane burning with soichiometric air

Reaction Soichiometry: C3H8 (g) + 5O2 (g) = 3 CO2(g) + 4H2O (g) + 18.81 N2

---P-,-i (Tf - 298)

Qc = L C
i

∑i -C--P--,i (Tf - 298) = 3 x 0.05632 + 4 x 0.04365 + 18.81 x 0.03371 x (Tf - 298)

= 0.9777 x (Tf - 298)

0.9777 x (Tf - 298) = 2220, Tf = 2570 K

The adiabatic temperature is 2570 K with soichiometric air.

References

1. Chemical Process principles, Part-I, Materials and Energy Balances, O. A. Hougen, K.

M. Watson and R. A. Ragatz, 1st Edn, (Reprint), Asia Publishing House, Calcutta, 1976.

2. Physical Chemistry, P. C. Rakshit, 6th Edition, Sarat Book Distributers,India, 2001

 Module 5: Combustion Technology

Lecture 36: Mechanism and kinetics of combustion

Keywords: Chemical equilibrium, equilibrium composition, kinetics of combustion,

stoichiometric coefficients

5.5 Mechanism and kinetics of combustion

The most essential thermodynamic parameter is equilibrium constant as a function of

temperature which is required for the study of the kinetics of combustion reactions. Many

steps in the combustion reaction are reversible in nature. The knowledge of thermodynamics

can be applied to predict the details of chemical equilibrium of the balanced reactions.

For a gas phase chemical reaction

aA + bB 
cC + dD (1)
a b c d
the forward rate, r1 = k1pA pB and the backward rate, r2 = k2pCpD
a b c d
At equilibrium, k1pApB = k2pCpD

Where a, b, c and d are stoichiometric coefficients of the species A, B, C and D respectively.

The standard free energy change of the reaction is given by

c d
pc pD
-∆GO = RT ln [ ] (2)
a b
pA pB

c d
k pc pD
Where, K
p
=kl = pa pb
= Chemical equilibrium constant of Eqn. (1)
2 A B

Hence, -∆GO = RT ln Kp and Kp = exp (- ∆GO⁄RT) (3)

d ln Kp -∆HO (4)
dT = RT 2

∆H O 1 1
K
ln [Kp2 ]=- [ - ] (5)
pl R T2 Tl

Eqn. (4) may used to calculate the equilibrium constant

The examples of some equilibrium reactions of combustions are

 1 1
H + 0 
0H (6)
2 2 2 2
1
H 
H (7)
2 2
1
H2 + 2 02H20 (8)

The equilibrium constants for the above reactions are

p0H pH pH20
Kp,0H = l/2 l/2
, Kp,H = l/2 and Kp,H20 = .
l/2
pH2 p02 pH2 pH2p02

Using the above relations the equilibrium constant for the reaction, H20
H + 0H can be
determined as
l/2 l/2 l/2
pH p0H Kp,H pH Kp,0H pH2 p02 Kp,HKp,0H
2
Kp,H20 = = l/2 = (9)
p H2 0 Kp,H20 pH2 p0 Kp,H20
2

Thermodynamics can describe the composition of the species of equilibrium steps in the

overall mechanism, but it cannot predict the speed of the reaction. So, the knowledge of

chemical kinetics is essential. The equilibrium constant may be required in the overall

mechanism.

Mechanism of Combustion

A combustion reaction has a particular speed at a specified temperature. In many cases, the

mechanism of combustion follows the complex kinetics phenomena with several elementary

steps. In the preliminary study, the possible steps on the overall reaction are to be assumed.

For kinetically controlled reactions, a large number of elementary reaction steps involving

large number of intermediates are possible and it is very difficult to formulate the overall rate

equation. For example, a large number of species are involved in the combustion of simple

hydrocarbons.

The combustion can be explained by radical mechanism usually consisting of initiation,

propagation, branching and termination. It can be explained by the combustion of methane as

follows.
Initiation:

1. CH4 → C H3 + H

2. 02 → 20

3. 0 + H → H0

Chain propagation:

4. CH4 + H → C H3 + H2

5. CH4 + H0 → C H3 + H20

6. C H3 + 0 → CH20 + H

7. CH20 + H0 → H20 + CH0

8. CH20 + H → H2 + CH0

9. CH0 → C0 + H

10. C0 + H0 → C02 + H

Branching :

11. C0 + H + 02 → H0 + 0

Termination:

12. H + R + M → RH + M

M is a third body in the system, which is non-reacting.

The derivation of rate of formation of carbon dioxide is difficult as there are 11 steps, which

needs 11 independent rate equation and elimination of free radicals containing terms.

Combustion of hydrogen is therefore chosen to explain the derivation of rate equation for the

combustion. Though the reaction seems to be very simple but its mechanism is very complex

one. The steps are formulated by considering branched chain reactions with the formation of
H , 0 H, 0" radicals. In the rate equation H , 0 H, and 0" radicals are designated by as H,

OH and O respectively.

The overall reaction : 2H2 + 02 → 2H20

The mechanism is given as follows:

Initiation

kO
1. H2 + wall → 2H + wall

Branching
kl
2. 02 + H → 0H + 0
k2
3. 0 + H2 → 0H + H

Propagation
k3
4. 0H + H2 → H20 + H
k4 1
5. H + Wall → H
2 2

Termination
kS
6. H + 02 + M → H02 + M

In steps 2 and 3 one radical produces two radical chain carriers. These two steps are called

branching steps. At very low pressures, the mean free path in the gas is large, and chain

carriers can reach the walls and combine. Collisions with walls are similar to those of

bimolecular collision. In this condition a steady state will attain. At high pressure, the chain

carriers react more predominately in the branching reactions than reacting with the wall. So,

an explosion will occur. Wall act as a third colliding partner and it is represented by M.

The individual rates may be derived as follows:

d[H]
= k [H ] - k [0 ][H] + k [0][H ] + k [0H][H ] - k [H] - k [H][0 ][M] [10]
O 2 1 2 2 2 3 2 4 5 2
dt
d[0H]
= k [0 ][H] + k [0][H ] - k [0H][H ] [11]
1 2 2 2 3 2
dt
d[0]
= k [0 ][H] - k [0][H ] [12]
dt 1 2 2 2

d[0H] d[0]
At steady state, and are zero.
dt dt

d[0H] d[0]
So, dt = dt :::
kl[02][H]
Then, [0] = [13]
k2[H2]

kl[02][H]+k2[0][H2]
[0H] = k3[H2]
[14]

substituting [0]

[02][H]+kl[02][H] 2kl[02][H]
[0H] = kl k3[H2]
= k3[H2]
[15]

d[H]
= k [H ] + {2k [0 ] - k - k [0 ][M]}[H] [16]
O 2 1 2 4 5 2
dt

Let, n = kO[H2] m = 2k1[02] p = k4 + k5[02][M]

For constant
d[H]
So, = n + {m - p}[H] [17]
dt

On integration of Eqn.(17), one can determine the concentration of hydrogen radical.

References

1. Combustion, Irivin Glassman, 2nd Edition, Academic Press, 1987.

2. Fuels, combustion, and furnaces, John Griswold, McGraw-Hill Book Company, Inc.,

1946.

3. Fuels and Combustion, Marion L. Smith and Karl W. Stinson, 1st Edition, New York,

1952.
Module 5: Combustion Technology

Lecture 37: Flame Properties

Key words: Flammability, premixed flame, diffusion flame, flame front, velocity of flame

propagation

5.6 Flame properties

Formation of Flame

If the combustible substances produce vapour during burning process, a flame is produced.

Flame is a luminous zone of the rapid exothermic reaction in combustion of vapour with the

formation of light and heat energy. A non-luminous region is appeared just after the flame

where the temperature is slightly reduced. A flame is bounded between the iginition zone

and a non-luminous gaseous zone. The combustion of gaseous fuels in a flame need the

intimate contact of fuels with an oxidant, either oxygen or air prior to the reaction. The

ranges of flammability and the point at which the mixture spontaneously ignites must be

known. They must be heated to the combustion temperature and the flame produced will be

at a high temperature. Then the reaction take place in within a narrow zone or region in the

flame. This combustion zone is called the flame front with this mixture is often several

thousand degrees.

Types of Flames

Flames may be of different types depending on the extent of mixing of fuel and oxidizer or

how the mixture reach the reaction zone. The flow patterns in the reaction vessel, such as

well mixed and plug flows are the major tools to classify the flames in different types. The

flame may be turbulent and laminar types depending on the flow behaviour of the

combustion gases.

In a premixed flame the fuel and the oxidant are molecularly mixed before the combustion

process takes place.

The flames are mainly classified as:

i) Non -Premixed or Diffusion Flames and ii) Premixed flames. These flames may be both

laminar or turbulent types.

Non-Premixed Flames

In many combustion processes, the fuel and air are often initially not mixed. The fuel and

oxidizer are kept on either side of the reaction zone and moved to the reaction zone. The

resultant flame is termed as the diffusion or non-premixed flame. In some cases, the gas and

air are injected in a coaxial parallel tubes and ignited. The flow behaviour of the non-

premixed flame is laminar type. Molecular or turbulent diffusion is responsible for the mixing

of the gases in non-premixed flames.

In a laminar flow region, the reach the reaction front by diffusion, before the reaction takes

place. The products of combustion also diffuse to come out from the reaction zone. The flame

is also called Laminar Non-Premixed Flames or Diffusion Flame. The diffusion flame occurs

at the interface of the gaseous fuel and air. With the progress of time as the flame

propagates, the thickness of the reaction zone increases. In diffusion flame the combustion

rate will solely controlled by the diffusion rate, not by the kinetic rate of reaction. The

mechanism of this flame is very complicated. The fuel approaches gradually towards the

flame zone, there is a deficiency of oxygen and it is pyrolysed to smaller molecules or

radicals. Then, there will be the formation of carbon soot and fuel burns with a bright

luminous yellow flame.

As the flame propagates, the oxygen concentration in the zone increases and the product of

pyrolyzed products are further reacted. Gradually the reaction occurs under the stoichiometric

proportion of oxygen and combustible. Under this circumstances, the total enthalpy of the

reactants will be equal to the total enthalpy of the products and the energy losses. The non-
premixed flames at stoichiometric conditions optimize the flame temperature with a definite

fuel-air ratio.

Premixed Flames

In this type, the fuel and oxidant gas are mixed together at ambient condition before being

delivered to the flame zone. As the mixture approaches the flame front, it is heated by

conduction and radiation. A reaction takes place before reaching the flame front. Gradually

the mixture is sufficiently heated at the reaction front and the chemical reaction takes place.

If the fuel and the oxidant gas are thoroughly mixed prior to reaching the flame front, the

location of the flame front does not depend on the diffusion of reactants. The flame speed or

the velocity of the reactants in the reaction zone is important. In another case, the fuel is

injected into the oxidant gas flow in the upstream side of the flame front but the mixing is

improper.

The turbulent pre-mixed flame plays an important role in the various practical applications

because, it increases the ignition of fuel with the reduction in the emission of gases. Both the

laminar premixed or laminar non-premixed flames (diffusion flame) are slow processes and

not economic. Turbulence actually results in a reduction in flame length. The turbulence can

be increased by recirculation of the fuel-air mixture.

Flame Structure

The example of the laminar premixed flame is the flame in a Bunsen Burner as shown in

Fig.1. In the premixed type, the laminar flame is the most simple type. The structure of the

flame may be analysed by a flame in the burner. The flame consists of four distinct regions

as shown in Fig 1.
1. Zone containing unburnt gases, 2. Reaction zone, 3. Incomplete combustion zone, and 4.

Complete combustion zone. The idealized shape of the reaction zone of a laminar premixed

flame is a cone. The height of the cone represents the flame length, and depends on the

velocity at the burner outlet.

Flame Propagation

Fig.1 Laminar premixed flame in a Bunsen Burner.

Since the flame front is stationary, the velocity of flame propagation vp , with respect to the

unburnt mixture will be equal to the flow velocity of the unburnt mixture normal to the flame

front . This is also called burning velocity.

Velocity of flame propagation , vp = vx Sin α

Where, α = flame cone angle and vx is the velocity air fuel mixture.
Velocity of flame propagation depends on the properties of the fuel-air mixture, pressure and

temperature of the process. A premixed flame of a particular fuel-air combination is

characterized by three main parameters, the burning velocity, flame temperature and

flammability limit, which are also determined by the pressure, temperature and, air-flue ratio.

Dilution of the burning mixture with an inert gas, such as helium or nitrogen, lowers the

temperature and, consequently, the reaction rate. Higher amounts of inert gas extinguish the

flame.

The Propagation Velocity in a Tube

The propagating flame along a vortex axis is completely different from the ‘normal’ flames,

which propagate in a tube or expand spherically from an ignition point. Its propagating speed

is nearly equal to the maximum tangential velocity in the vortex.

For a fuel oxidizer mixture enclosed in cylindrical tube whose one end is closed while other

end is opened, let us consider the flame front is perpendicular to the direction of flow.

For the premixed gases in a laminar flow, the flame speed Vf is obtained from the burning

velocityVb . Burning velocity is equal to normal velocity of flame propagation.

In the case of a flame propagating in a tube, the flame speed or outlet gas velocity is given as

Sf
V =V . Where S and S are the cross section of flame and tube respectively.
f bS f f
t

Also for a spherically expanding flame propagating axially in a cylinder, the flame speed is

given by

i
V =V . Where, Vb is the burning velocity relative to unburnt gas velocity, i and o
f b
0

are densities of inlet and outlet gases. As i ≫ o , Vf ≫ Vi . It is observed that the gas

velocity will change across the flame front by the changes of gas concentration, temperature
and density. In the explosive flame, the velocity of flame front will be obtained from the

algebraic sum of normal velocity of flame propagation and gas velocity.

Flammability limit

A spontaneous or explosive reaction of fuel may be possible when ignited in presence of

either air or oxygen for a particular range of gas composition at fixed temperature and

pressure. Flammability limits describe the range of fuel concentration in terms of volume %

and this reaction may occur even when the mixture is cold. For example, the lower

flammability limit for aviation kerosene is about 0.7% by volume and the higher flammability

limit is about 5% by volume. For hydrogen gas, lower limit 4%, and higher is 75%.

Flammability limits also are much wider in oxygen than in air. So it highly depends on the

burning atmosphere, pressure, temperature, and on the ignition source.

References

1. Fuels and Combustion, S. Sarkar, 3rd Edition, University Press, India, 2009.

2. A to Z guide to Thermodynamics, Heat & Mass Transfer, and Fluids Engeering,

Flames, A. Williams, Thermopedia, http://www.thermopedia.com/content/766/

3. Experimental investigation of flame propagation in long, narrow tubes, Thomas

A. Connelly,M.S thesis, University of Illinois at Urbana-Champaign,

http://hdl.handle.net/2142/44154
Module 5: Combustion Technology

Lecture 38: Combustion Burners

Keywords : Atmospheric burner, atomizer, rotating cup burner, swirl type burner, nozzle design

5.7 Combustion Burners

Types of Burner

The basic combustion theory and laws are applied for the design of burning equipments

depending on the type of fuels , such as gaseous or liquid fuels. Theses burning equipments are

called burners. There are different liquid fuel and gaseous fuel burners. There are some

similarities in their design but it depends on the type and properties of fuel in addition to their

type of applications. Although many designs are available, but they are common in one aspect of

requiring proper mixing of air and fuel prior to their combustion. These oil or gas burners are

used in furnaces.

Gas Burners

Gas burners are usually classified based on their operating gas pressure. They are operated both

atmospheric and high-pressure conditions. The gases are supplied in different ways depending on

the pressure. In low pressure burner, the gas pressure varies from 1 to 4 kPa. Whereas, high

pressure burners the pressure varies from 7 to 70 kPa.

Oil Burners

The oldest burning process of fuel oil is the pot type burner in which the oil is first vaporized by

applying heat. After vaporization, the oil vapors are mixed with excess air and then burned. As

oil is vaporized at a slower rate than the rate of combustion reaction, the process is modified by

using atomizer to form tiny droplets of oil before its ignition. The droplets can be vaporized

easily. The atomization is carried out by either a mechanical device or applying a fuel jet. The

nozzles are designed in such a way so that, it can be used to atomize oil at an elevated oil
pressure at about 100 psi. The process can produce oil droplets in the range from 0.0002 inch to

1.10 inch. Quick ignition of relatively smaller droplets results in the rapid flame formation.

Proper designing of nozzle is required to deliver droplets at a uniform rate for a particular burner.

Oil is also atomized by using a rotating cup, rotating disc and swirling method. The examples of

some oil burners are described in this section.

Swirl Oil Burner

. The liquid oil is first pressurized at about 100-150 psi by a pump. In the swirl oil burner, the

pressurized liquid fuel enters tangentially through the slots at a high velocity in the oil swirl

chamber. It flows in the form of a vortex and escapes through a nozzle at the other end of the

chamber. The sketch of a swirl type burner is shown in Fig.1. The centrifugal force is exerted on

to the oil and it moves forward in the shape of a hollow tube. Air enters to the annular space

and moves forward. Then the fine droplets emerge at the exit of the chamber in the form of a

spray.

Fig. 1 Swirl oil burner

The nozzle design is mainly based on mass balance in the burner.The diameter of oil tube may

be determined from the equation

2
rr O
pVoil = m· oil
4
4 moil O.5 m· oil
Do =[ ] = 18.8 (1)
36OO np Voil p V oil

Do = diameter of oil tube in mm

m· oil = mass flow rate of oil in kg/hr.

Voil = allowable velocity through the tube in m/s

p = oil density in kg/m3

The velocity through the orifice is related with oil pressure by the following equation

m· oil = 3600CO AO J2pPO (2)

PO = oil pressure in pascal

AO = nozzle area in mm2

CO = flow coefficient.
n 2 196 m· oil
AO = 4 Dn = C
(3)
2pP
oJ o

The diameter of nozzle , Dn = 1.128 JAO

Rotary Cup Burner

The rotary cup burners are usually used in industry as well as for domestic purpose. A sketch of

the rotary cup burner is shown in Fig.2. The capacity of fuel varies in wide range. The device

consists of a rotating cup and a fan. Both the cup and the fan are rotated by an electric motor( not

shown in figure) with a shaft. Oil is fed to the oil distributer to throw at the inner surface of the

cup. The cup is rotated at a speed of about 3600 rpm. Then oil flows in a swirling motion and is

thrown as fine droplets at the other end. The primary air is supplied by a fan or blower in a

whirling motion opposite to the oil motion. This helps to further disintegrate the oil particles and

finally to reach the combustion chamber.

Fig.2 Rotary cup burner

Gas Burners

Gaseous fuel burners are classified based on the air and fuel mixing phenomena. They are

either premixed type or diffusion type. If the fuel and gas are premixed before passing through

the burner nozzle it is called premixed type. In diffusion type, a small quantity of air is mixed in

the flow of gas and there will be diffusion between them. Industrial burners for gaseous fuel are

diffusive type. In diffusion burner air and gaseous fuel are supplied separately in the furnace.

These burners are also used as for domestic purposes. The mixing rate between air and

fuel controls the combustion process. The burners are also categorized based on the applied gas

pressure. The gas burners may be either atmospheric or high pressure type. In the atmospheric

type burner, the gas pressure varies from 2 to 12 in water gauge. Whereas, in the high pressure

type, 0.5 to 40 psi gas pressure is used with a large combustion chamber. The construction of an

atmospheric burner is described in Fig.3. The design and operation is similar to the Bunsen

burner.

Fig.3 Atmospheric gas burner

Air for combustion is supplied in the furnace chamber. In these burners small portion of air is

mixed with fuel as primary air and the rest amount, known as secondary air, is supplied above

the burner port. Figure 3 shows an atmospheric gas burner where, the mass of air is about 10

times than that of fuel. Some fraction of total air is mixed with the fuel and this air supplied with

the fuel is called the primary air. The secondary air is further added in the combustion point in

the furnace. Mixing and combustion take place simultaneously. A free jet is produced in the

downstream side of the burner during the discharge of fuel. The gas velocity at the orifice will be

proportional to the square root of the differential pressure across the orifice. The venture tube is

provided for better mixing. When a mixture of air and gaseous fuel passes through the nozzle of

the burner, they mixed thoroughly in the divergent section of the venture. In this section pressure

increases gradually as the velocity head is converted to the pressure head. The secondary air is

supplied to the flame to complete combustion of the fuel.

References

1. Fuels, combustion, and furnaces, John Griswold, McGraw-Hill Book Company, Inc.,
1946
2. Fuels and Combustion, Marion L. Smith and Karl W. Stinson, 1st Edition, New York,
1952

3. Combustion Equipment, Colin French, http://203.158.253.140/media/e-

Book/Engineer/Power%20Plant/Plant%20Engineer%27s%20Reference%20Book/44524_
11.pdf.
Module 5: Combustion Technology

Lecture 39: Combustion Furnaces

Keywords : Gas combustion, Chimney, reheating furnace, smelting, cupola cup and cone feeder

5.8 Combustion Furnaces

Classification of Furnaces

Furnaces are used for different thermal processes where heat is produced and transmitted to the

solid or liquid material for their processing. The device consists of a furnace with a naturally

aspirating gas burner. The produced heat in the furnace may be applied directly to the body of

mass to be processed or externally to a separate place. Industrial furnaces are classified

according to their uses in various processes such as, smelting, roasting, petroleum refineries

different chemical process industries. In general they may be broadly classified as combustion

furnace or electric furnaces. The combustion furnaces may be of different types depending upon

the kind of combustion, it can be broadly classified as oil fired, coal fired or gas fired. Various

furnaces are made with tube bundles inside it and the combustion gases produced in a separate

chamber by burning of liquid or gaseous fuels are passed through the tubes. The furnaces may be

batch or continuous type according to the requirements.

Gas Combustion Furnaces

In a conventional gas-combustion furnace, air is forced to flow through the gas burners. The fuel

gases are allowed to flow through the furnace. Natural gas is used as the fuel where the

combustion products are carbon dioxide, water vapor and other compounds. The combustion

gases pass through the furnace where they give up heat across a heat exchanger and are vented

out through chimney. A circulating fan passes cooled house air from the return ducts over the

furnace heat exchanger, where the air is warmed up and passed into the ductwork that distributes
the heated air around the house. An example of gas combustion furnace is the reheating furnace

for steel plants

The Reheating Furnace

The reheating furnace operated in a gas heating system is shown in Fig. 1. In this furnace the

steel blocks are heated at a desired temperature to bring them in plastic state so that the blocks

can be rolled to the desired shape. The temperature usually varies in the range of 900 - 12500C .

The furnace consists of a properly insulated heating chamber made of refractory bricks. This is

used for continuous reheating of the stocks.

Fig.1 Gas combustion furnace

The steel stocks enter at one end and exit from the other end. Gas burners are fitted in the

furnace. The chimney is provided for removing the combustion gases from the chamber.
The Cupola Furnace

The coke fired cupola is used in iron foundries for the manufacture of cast iron with a feed of

scrap iron or pig iron since ancient times. The cupola furnace has several unique characteristics

which are responsible for its widespread use as a melting unit for cast iron. Cupolas is used to

melt pig iron or scrap iron with coke and flux. The construction of a conventional cupola

consists of a vertical steel shell which is lined with a refractory brick. The charge is introduced

into the furnace through a side door situated at middle. The internal diameter of cupolas varies

from 450 to 2100 mm with a melting rate of 1 to 30 tons per hour.

The use of any cheaper iron scrap as raw feed is an advantage of the process. Where coke is

expensive, the gas fired cupola are used. However, the cost of gaseous fuel must be cheaper than

coke. The coke-less cupola is very similar to a conventional coke fired cupola. It is an echo

friendly process and it was developed since 2003. Instead of coke, light diesel oil or liquefied

petroleum gas is used. The natural gas fired cupola is shown with a schematic diagram in Fig.2.

Raw materials are charged on the bed of ceramic beads. Ceramic bed is supported on water

cooled grate. The fuel is burnt in air in the burners provided at the bottom of the furnace. Slag is

withdrawn by suction process. The furnace is initially heated after the arranging ceramic bed on

the water-cooled grate. Then the furnace is charged with the iron raw materials with slag-

forming substances. Natural gas and air mixture is burned in the burners. Hot flue gas is used to

heat and melt the materials. The use of a gas instead of coke drastically reduces the slag

formation. The hot exhaust gas transfers the heat to air in a heat exchanger.
 Fig.2 Natural gas fired cupola

The molten iron and slug comes out at the bottom. The slag is separated from metal by siphon

and suction arrangement.

Blast Furnace

Blast furnaces are vertical tall steel vessel lined with refractory brick. It is major unit of a steel

plant which is used for smelting iron ore to form molten pig iron. The approximate height of the

furnace and diameter are 90 and 20 ft respectively. The mixture of iron ore, limestone and coke

is charged into furnace through the hopper situated at the top. . The coke in the charge serves as

fuel as well as a reducing agent. The pre heated air at 950 K from the stoves is distributed

through the opening at the bottom of the shaft. These openings are called tuyeres (a tube, nozzle
or pipe for blowing air into a furnace). The residence time of the charge materials is about 8 hrs.

The bottom product is the slag and molten iron. This liquid product accumulates in a vessel

which is drained from the furnace intermittently though the outlet. The flue gas from the top of

the furnace is cleaned by separating particulate matter from it. Then the energy of the gas is used

to preheat the air. Blast furnace is usually operated continuously for 4-10 years.

Fig. 3 Blast Furnace

Low iron containing ore are purified to increase the iron content. The coal is converted to coke

by carbonization by removing volatile matter in a coke oven plant. The coke is cooled and

screened into pieces ranging from one inch to four inches. Limestone forms the slag containing

the sulfur compounds. Slag formation starts at 1100 0C onwards.

The reactions occuring in a blast furnace are as follows:

1. 3 Fe2O3 + CO → CO2 + 2Fe3O4 at 400-600 0 C

2. Fe3O4 + CO → CO2 + 3FeO at 600-800 0 C

3. CO → C + CO2 at 540-650 0 C

4. FeO + CO → Fe + CO2 at 800-1100 0 C

5. CaCO3 → CaO + CO2 at 900 0 C

Reductions of metal oxides at 1200-2000 0 C

6. FeO + C → Fe +CO

7. SiO2 + 2C → Si +2CO

8. MnO + C → Mn + CO

9. P2O5 +5C → 2P +5CO

10. S + CaO + C → CaS + CO

11. CO2+ C → 2CO

The slag formed mainly contains the four oxides, CaO, MgO, SiO2 and Al2O3 which remain in

molten condition at 1200 to 14000 C.

References

1. Fuels, Combustion and Furnaces, John Griswold, McGraw-Hill Book Company, Inc,1946

2. Atlas Foundry Company, http://www.atlasfdry.com/cupolafurnace.htm

3. Handbook of Thermoprocessing Technologies: Fundamentals, Processesing

Technology, Edited by Axel von Starck, Alfred Mühlbauer, Carl Kramer, Vulkan-

Verlag,GmbH, Germany, 2005.

4. Bureau of Energy Efficiency,

http://www.beeindia.in/energy_managers_auditors/ documents/guide_books/2Ch4.pdf
 Module 5: Combustion Technology

Lecture 40: Internal Combustion Engine

Keywords: Petrol engine, diesel engine, clearance volume, top dead center, bottom dead center,

crankshaft, Otto cycle, Diesel cycle

5.9 Internal Combustion Engine

Historical background

In the internal combustion(IC) engine, the gases produced from the combustion of gaseous or

liquid fuels at high pressure are expanded in a piston cylinder arrangement which helps to

transmit the mechanical energy to the crankshaft. Therefore, this device is used to convert

thermal energy to mechanical energy. In 1860, J. J. E. Lenoir developed the commercial IC

engine where coal gas- air mixture was used as a fuel. The four stroke engine first developed by

N. A. Otto in 1867 and the two stroke commercial engine first introduced in 1881 by D. Clerk.

Thereafter, Rudolf Diesel invented a different form of internal combustion engine in 1892.

Continuous efforts have been given by the researchers for the improvements of the IC engines.

Classification of Internal Combustion Engine

The engines are classified as the two strokes engine and four strokes engine by the operating

principles. The process of ignition and mixing of air and fuel are carried out in two different

ways in Otto and Diesel’s engines.

In Otto engine, air and fuel are premixed together in the approximate ratio of 15:1 in the

carburetor and then introduced into the cylinder for compression. In this engine petrol or gas can

be used. Then the mixture is ignited by an electric spark plug and the a flame front progresses

across the combustion chamber. So it’s another name is Spark Ignition Engine(SI-engine).

In Diesel engine, pure air is compressed first and the fuel is injected in the form of droplets at the

front of the compressed air. Then the temperature of air increases with the heat of compression
and the ignition starts. It is also called as Compression Ignition Engine (CI-engine) . Air fuel

ratio varies from 20:1 to 100:1. In this engine diesel oil is used as a fuel.

Four Stroke Engine

The four strokes of engines are as follows:

1. First stroke: the intake of fuel-air mixture.

2. Second stroke: the compression stroke followed by ignition

3. Third stroke: the expansion of the combustion gases are work is delivered to the

crankshaft

4. Fourth stroke: The exhaust of the flue gases.

Operation of Four Strokes Engine

The four stroke engine operates on a reciprocating motion of the piston in a cylinder. By the to

and fro motion of the piston in a cylinder, the power is transmitted to the crankshaft as shown in

Fig. 1. The minimum cylinder volume is called the clearance volume( VCl ) when the piston is

closed to the valves end. The volume swept out by the piston is called the swept volume( VS ).

Where, VS = Vtot - VCl and Vtot = total volume of the cylinder.

In the first stroke of the engine, the inlet valve opens and oil-air mixture enters the cylinder. This

stroke continues from the valve end to the other end. When the piston moves the full length of

the cylinder, the inlet valve closes. Then the mixture is compressed by the reverse movement of

the piston, which is the second stroke. The oil is ignited at this high pressure by applying a spark

when the piston reaches near the end of the cylinder which is called the top dead center (TDC).

Then the combustion starts and the gases are expanded in the cylinder. Then both the valves are
closed and both the pressure and temperature of the gases increase. In the third stroke of the

piston, the gases expand and the piston moves. The crankshaft starts to rotate and at the end of

expansion, the pressure decreases. The outlet valve opens to exit the gases from the cylinder and

then the outlet valve closes. In the last stage, the rest of the flue gas escapes from the cylinder

and the outlet valve closes. Now the inlet valve opens and the cycle continues by the intake of

the fresh air-fuel mixture. All strokes of the pistons are described in Fig.1
 Fig.1 Operation of four stroke engine

Ideal Engine Cycles

Otto Cycle

The Otto cycle consists of a four internally reversible processes by which the operation of a

petrol engine can be analyzed. The cycle is represented in both the P-V and T-S diagrams. The

cycle starts at Top Dead Centre (TDC) and ends at the Bottom Dead Centre (BDC). The

distance travelled by the piston from TDC to BDC is called a stroke. The clearance volume(VCl )

is measured after the TDC .The four stroke engine in Otto cycle may be represented as follows:

1. The compression from state 1 to state 2 in a constant entropy process.

2. The constant volume (Isochoric) process from 2 to 3, where the heat (Qh) is added to the

system and the gas-fuel mixture is ignited. Both the pressure and temperature increases.

3. The reversible and adiabatic (isentropic) expansion process occurs from 3 to 4. Work is

done on the piston by the expansion of gas mixtures. Both the pressure and temperature

decrease.
 Fig. 2 Otto cycle on P-V and T-S diagrams

4. The process 4 to 1 is constant volume cooling, i.e. the heat (Qc ) is removed from the

gases.

Considering unit mass of oil-air mixture, the heat and work relation can be explained by

the above two diagrams.

Heat transfer to the gas mixture (heating) per unit mass =

3
Qh = f Tds = area of 23A 2A 12 (Fig 2.)
2

Heat transfer by the gas mixture to surrounding (cooling) per unit mass =
1
Qc = f Tds = area of 41A 1A 24 (Fig 2.)
4

The net heat added to the cycle per unit mass = Qh - Qc

Similarly from p-V diagram, it may be observed that the work done to the fuel-air mixture per
2
unit mass = f PdV = Area of 12L 2L 1 1
1
4
And work delivers by the engine per unit mass = f PdV = Area of 34L1 L2 3
3

The net work done by the engine = area enclosed by the curves in P-V diagram.
 T2 V2
In an isentropic process ∆S = 0 = CV ln + Rln (1)
T1 V1

It is an adiabatic and reversible process.

CP
For ideal gas assuming CP and CV are constant, then CP -C V = R and =k
Cv

R R T2 V2
= -Rln
We have, CV = k-1 From eqn. (1) k-1 ln T1 V1

R
T2 1 V1 R
=
T1 V2

k-1
T2 V1
Or, = (2)
T1 V2

The efficiency in this cycle is given by

T2 - T1 T1
1= = 1-
T2 T2
1-k V1
V1
1 =1- also, = compression ratio = 1
V2 V2

Diesel Cycle

Diesel cycle is an ideal cycle by which the working principle of a diesel engine can be

represented. In this cycle, air is first compressed to a high pressure and then fuel injected to the

cylinder where the fuel is self ignited due to high temperature by compression. The process is

thus called as compression ignition. In this cycle, the heat is transferred to the fluid at constant

pressure.
 Fig.2 Diesel cycle on P-V and T-S diagram

In Diesel cycle, air is taken into the cylinder and is undergone reversible and adiabatic reversible,

i.e. isentropic compression from state-1 to state-2. It is shown in the P-V and T-S diagrams.

Then oil is sprayed into the cylinder and it ignites. In the process from state-2 to state-3, it

receives the heat qh at constant pressure. Then the combustion gases undergo the isentropic

expansion from state-3 to state-4 with the increase in volume. In the next stroke, the constant

volume cooling is performed from 4 to 1 by removing heat (qc). Next the cycle is continued. In

Diesel engine, the amount of work required will be less by the area 23’3 in the P-V diagram. So

this engine is economic.

References

1. Internal Combustion Engine Fundamentals, John B. Heywood, McGraw-Hill, Inc.,New

York. 1988.

2. Fundamental of Engineering Thermodynamics, John R. Howell and Richard O. Buckius,

McGraw-Hill Book Company, New York, 1987