COMBUSTION ENGINEERING

Dr. B.S.Samaga
Former Prof. of Mech. Engineering

sam.nmamit@yahoo.co.in


COMBUSTION AND THERMOCHEMISTRY
Definitions:

Mole of a gas: It is the quantity of any gas whose mass is
numerically equal to its molecular weight. Thus, 2 gm of
hydrogen, 32 gm of oxygen, 44 gm of carbon dioxide etc
are each one gram mole. When the molecular weight is
expressed in kg, it is called kg mole or kmole.
At NTP ( 273K and 1.01325 bar) one gm mole of each
gas will occupy a volume of 22.4 litres (one kg mole will
occupy 22400 litres)
Stoichiometry: It is the study of combustion reactions
converting reactants into products.
Mass conservation principle: Total mass of each
element is conserved during a chemical reaction. Also
total mass of reactants will be equal to total mass of
products. However, total number of moles of reactants
need not be the same as the total number of moles of
products. This means, there can be molecular
(volumetric) contraction or expansion due to the reaction.
Stoichiometric or theoretical air is the minimum amount
of air required for the complete combustion of the fuel.
Fuel air equivalence ratio is the ratio of actual fuel-air
ratio supplied for combustion to the stoichiometric fuel-
air ratio. Thus > 1 is rich and < 1 is lean mixture.
Enthalpy of Reaction and Enthalpy of Combustion:
Enthalpy of reaction is the difference between the
enthalpy of the products and the enthalpy of reactants
when a complete chemical reaction occurs at a specified
pressure and temperature. If complete combustion
occurs, this quantity is called Enthalpy of combustion.
Since the reactants and products are at the same
reference temperature, the enthalpy of reaction or
combustion are negative, as the products contain no
chemical energy. They are tabulated on mole basis and
the value depends on the state of the fuel (liquid or gas)
and the state of H
2
O formed (water or steam). Liquid fuel
and steam in the product give lower values due to the
latent heat absorbed by the fuel for its vaporization and
the latent heat held by the steam in the product.

Internal Energy of combustion: It is the difference
between the internal energy of products and reactants
when measured at the same reference state.
Enthalpy of Formation: It is the enthalpy change
associated with the formation of a chemical compound
from its elements, all at the standard reference state.
Enthalpy of all elements at the standard reference state
is assigned the value of zero.
Calorific (Heating) value: It is the enthalpy of combustion
on mass basis (per kg) with the sign changed, and is
defined as the energy liberated when unit mass of the
fuel undergoes complete combustion. We have higher
and lower values, depending on whether the steam in
the product is condensed or left out.
Standard Reference State chosen are 1 atm and 25C.
First Law applied to Reactive systems:
Q + H
R
= W + H
P
When there is no work involved, Q = H
P
H
R
, which is the
enthalpy of combustion.
Adiabatic Flame Temperature:
It is the maximum temperature that the combustion
products can attain with stoichiometric fuel-air mixture
when there is no heat loss from the system to the
surroundings during the combustion process. This
temperature is found out by trial and error by equating
the enthalpy of reactants at the standard state to the
sensible enthalpy of hot products at this temperature.
H
P
at T(adia) = H
R
at 298K
Second Law analysis of reactive systems
(Ref: Engg.Thermodynamics by E. Rathakrishnan)
The irreversibility associated with a chemical reaction is, I = T
o
S
gen
(kJ)
where T
o
is the temp of the surroundings and S
gen
is the entropy
generated.
For a steady flow combustion process, in the absence of kinetic and
potential energy changes, the max work available will be
W
rev
= N
r
( h
f
o
+ h- h
o
T
o
s )
rea
- N
p
( h
f
o
+ h- h
o
T
o
s )
pro
where N is
no of moles of each constituent, h
f
o
is the enthalpy of formation,
(h h
o
) is the increase in sensible enthalpy from the standard ref
temp to the actual reaction temp, all on mole basis, T
o
is the
surrounding temp and s is the entropy /mole of the constituent.
For a combustion system involving heat transfer Q
R
with a reservoir at
temp T
R
,
W
rev
= N
r
( h
f
o
+ h- h
o
T
o
s )
rea
- N
p
( h
f
o
+ h- h
o
T
o
s )
pro
Q
R
(1- T
o
/ T
R
)
Gibbs function:
Gibbs Function G = H - Ts
For the situation when both the reactants and products are at the
temperature of the surroundings T
o
, we have g
o
= (h-T
o
s)

, where
g
o
is the Gibbs function of unit mole of substance at T
o
. For this
case the maximum work,
W
rev
= N
r
( g
f
o
+ g - g
o
)
rea
- N
p
( g
f
o
+ g - g
o
)
pro

where, g
f
o
is the Gibbs function of formation, which is zero for all
stable elements at standard reference state (1 atm and 298K )like
enthalpy of formation.
Second Law Efficiency of a Reactive System:
For a fuel at T
o
, p
o
, the max available energy (chem.exergy) is the max
reversible work that can be obtained by reaction with oxygen from
the environment. But due to irreversibilities like heat loss and friction
the actual work will be less. The second law efficiency
Effy
II
= Actual work done / Max theoretical work
= W
act
/ ( m
fuel
x Chem.Exergy)

While implementing methods to improve the second law efficiency,
additional cost must be weighed against reduction in exergy losses.
CHEMICAL EQUILIBRIUM
The equilibrium criterion for reacting systems is based on the second
law of thermodynamics.
From the second law, dS
sys
Q / T
And for an adiabatic system dS
sys
0
A chemical reaction in an adiabatic chamber proceeds in the direction
of increasing entropy and when the entropy reaches a maximum the
reaction stops and equilibrium is achieved.
From the first and second laws we have,
Q = dU + pdV and dS Q / T Or, dU + pdV TdS 0(1)
At const T and p, Gibbs function is G = H TS
Therefore, (dG)
T,p
= dH TdS SdT = (dU+pdV+Vdp) TdS SdT
= dU + pdV TdS since T and p are constant.
From eqn (1) we get (dG)
T,p
0
Hence equilibrium criterion is S will be max or G will be min.

Criterion for chemical equilibrium at a given p and T
G
dG=0
dS=0
dG<0 dG>0
dS>0
dS<0
This part is
impossible since
it violates II law
Reaction coordinate
100%
reactants
100%
products
Chemical
equilibrium
composition

Pressure=p
Temperature =T
The effect of pressure and temp change on the chemical equilibrium
will be to drive the reaction in the direction to oppose the change.
EQUILIBRIUM CONSTANT
Consider a mixture of 4 components A,B,C and D which exist in
equilibrium at a specified p and T with N
A
, N
B
,N
C
and N
D
as their
respective number of moles. Now consider the reaction to occur to
an infinitesimal extent (at constant p and T) with differential amounts
of reactants A and B converted into products.
dN
A
A + dN
B
B dN
C
C + dN
D
D
For chemical equilibrium, (dG)
T,p
= (g
i
dN
i
)
T,p
= 0 where, i indicates
each constituent.
Or, g
A
dN
A
+ g
B
dN
B
+ g
C
dN
C
+ g
D
dN
D
= 0 .(1) where g is
the chemical potential or molar Gibbs function for each
component at T and p, dNs are differential changes in the number of
moles of the components. These changes in moles are proportional
to the stoichiometric coefts from the stoichiometric chemical
equation:

A
A +
B
B
C
C +
D
D ..(2) where s are the
stoichiometric coefficients.

Therefore, dN
A
= -
A
, dN
B
= -
B
, dN
C
=
C
and dN
D
=
D
where, is the proportionality constant which represents the extent
of reaction, the ve sign indicating the consumption of reactants.
Substituting in Eqn (1), we obtain,

C
g
C
+
D
g
D
-
A
g
A
-
B
g
B
= 0
This is the criterion for chemical equilibrium valid for any chemical
reaction regardless of the phases involved. It can be extended for
any number of reactants and products.
The Equilibrium Constant K
P
for Reaction shown in Eqn (2) is defined
as, K
P
= [(p
C
)

C

(p
D
)

D

]

/ [ (p
A
)

A
(p
B
)

B

] ..(3) where p is the partial
pressure of individual component in the mixture (atm) and is the
stoichiometric coefficient of the respective components.
At a given temperature, it can be shown that change in Gibbs function
with respect to pressure has a logarithmic relation as -
G
(T)
= - R
u
T. ln [(p
C
)

C

(p
D
)

D

]

/ [ (p
A
)

A
(p
B
)

B

]
Hence, K
P
= e
- G
(T)
/(R
u
T)
.(4)



Partial pressure of the component, p = (N
i
/ N
total
) x P,
Where, N
total
= total number of moles present in the chamber and P is
the total pressure. Substituting in Eqn (3) we can write,

K
P
= [(N
C
)

C

(N
D
)

D

]

/ [ (N
A
)

A
(N
B
)

B

] . [P/N
total
]
(
C
+
D
-
A

B
)
(5)



Simultaneous Reactions:
When more than one reaction is involved in the system the condition
dG
(T,p)
= 0 must exist for every reaction for chemical equilibrium.
Determination of equilibrium composition of a reacting mixture
requires that there should be as many equations as unknowns. The
mass balance for each element involved provides one equation and
the rest of the equations must come from K
P
relations written for
each reaction.
VARIATION OF K
P
WITH TEMPERATURE
From Eqn (4), we have ln K
P
= - G (T) /(R
u
T)
But G = H - T S Therefore we can write,
d(ln K
P
)/dT = H(T) /(R
u
T
2
) d (H(T)) /(R
u
TdT) + d(S
(T)
)/ R
u
dT,
where, R
u
= Universal gas constant.
At constant pressure the Tds relation: Tds = dh vdp becomes
Tds = dh. Therefore, Td (S) = d(H ).
Thus, the above relation becomes,
d(ln K
P
)/dT = H(T) / (R
u
T
2
) = h
R(T)
/ (R
u
T
2
) (6)
Where, h
R(T)
is the enthalpy of reaction at temperature T. This is
known as vant Hoff relation from which we can calculate the heat
of reaction for any given temp (range) from the K
P
value.
For small temp intervals h
R
can be taken as constant and vant Hoffs
eqn gives on integration, ln(K
P2
/K
P1
) (h
R
/R
u
).(1/T
1
1/T
2
)
It can be seen that for exothermic reactions, since h
R
is -ve K
P

decreases with increase in temperature.




Laminar Flame
Propagation
One dimensional adiabatic combustion wave
Structure of adiabatic combustion wave front
The Temp-Distance (T-x) and Conc-Diastance(C-x) Diagram
Temp-Distance(T-x) and Conc-Distance(C-x)
diagram across the laminar flame front
At point of
inflection
Mallard and Le Chateliers approach
Simplifying Assumptions:
1. No reaction occurs below ignition temperature T
i
.
2. Gas from T
o
(at x= - ) to T
i
gets heated only by conduction.
3. Reaction takes place from x
i
to x
f
without any heat loss.
4. C
p
and k are constant in the range of temp from T
o
to T
f
For an energy balance,
Sensible heat gain in the preheat zone = Heat conducted from the
reaction zone
C
p
(
o
.S
F
)(T
i
T
o
) = -k.dT/dx
|x=x
i

per unit area.
Assuming roughly a straight line temp variation,
-dT/dx (T
f
- T
i
)/(x
f
- x
i
)

Therefore, S
F
= k . (T
f
T
i
)
C
p
.
o
(x
f
x
i
) . (T
i
T
o
)
T
T
o
T
f
T
i
x
o
x
i
x
f
Preheat Reaction
zone zone
Thermal Model: Semenovs Equation


u
= Density of unburned gas (g/cc)
k
b
= Mean Thermal conductivity of burned gases (cal/s.cm.K)
T
b
and T
u
= Burned and Unburned gas Temp (K)
E
act
= Activation energy (cal/gmol)
k/( C
p
..D) =

Thermal diffusivity, assumed to be 1
Concept of Diffusion Mechanism






The reasoning for a diffusional mechanism begins with the assumption
that potential chain carriers such as H, O and OH radicals are present
in the flame front in thermo-dynamic equilibrium concentration at the
maxmimum temperature. These active species, particularly hydrogen
diffuse so rapidly into the unburned gas region that their concentration
there is found to be far more than corresponding to the calculated
equilibrium conc. at the unburned gas temp. These chain carriers can
activate chemical reaction in the unburned gas without much aid of
temperature.
T
o
T
i
T
f
Temp
or
Conc
Distance x
unburned preheat reaction burned
gas zone zone gas
Since the concentration of active particles in the unburned gas
region is dependent on their equilibrium concentration at the flame
temperature and their diffusion rate, it is concluded that the flame
velocity should be related to these two factors, rather than the
heat transfer from burned to unburned gases.
Work of Tanford and Pease
Simplifying assumptions:
1. Chain branching (leading to explosion) does not take place.
2. Rate controlling step in the chemical reaction is the reaction of an
active species like H with the fuel molecule.
3. Rate of formation of comb.products per unit area of the flame
surface is the sum total of products formed from each active
species with their specific reaction rate constants.
4. The speed with which the unburned gas is converted into comb.
products per unit area of the flame surface is the flame velocity.
5. The combustion zone temp and diffusion coefts for each species
are assumed constant at their mean values in the reaction front.
Diffusion Model: Tanford and Pease Equation
a
t,m
. X
f,o
. K
i
.X
i,F
. D
i,m

Sf = ------------- i ------------------


m
2
. X
p
B
i
Where,
a
t,m
= Total mean concentration (moles/cc)
X
f,o
= Mole fraction of fuel in unburned gas;
m
= 0.7 T
F
/T
o

X
P
= Mole fraction of potential combustion products in the unburned
gas
X
i,F
= Calculated mole fraction of i
th
active species at equilibrium
flame temp, T
F
D
i,m
= Diffusion Coeft for i
th
species into the unburned gas at the
mean combustion zone temp (cm
2
/sec)
B
i
= Dimensionless factor which allows for radical recombination
(i.e., loss of active species due to reaction)
K
i
= Specific rate constant for the reaction of i
th
species
Comparison of Thermal and Diffusion Models
----------------------------------------------------------------------------------------------------------------
Hydrocarbon in air Burning Velocity (cm/s)
---------------------------------------------------------
Measured Diffusion Thermal
(Tanford and Pease) (Semenov)
-----------------------------------------------------------------------------------------------------------------------------------
Methane 33.8 33.9 40.2
Propane 39.0 37.7 39.0
Hexane 38.5 37.3 37.2
2,2,3 Trimethyl butane 35.8 36.6 37.0
Propene 43.8 45.3 48.9
1-Hexene 42.1 41.7 42.0
Propyne 69.9 61.3 64.9
Cyclohexane 38.7 37.4 38.3
Benzene 40.7 40.4 44.5
-----------------------------------------------------------------------------------------------------



Evaluation of Thermal and Diffusion Models
Equations based on thermal mechanism show a relation between flame
velocity and thermal conductivity, whereas those based on
diffusion mechanism relate flame velocity with diffusion
coefficients and equilibrium concentrations of active particles. A
critical evaluation of the two theories is therefore difficult for the
following reasons:
1. Equations of heat conduction are mathematically similar to those
of diffusion, and hence burning velocity relations based on the two
concepts are similar.
2. Equilibrium concentrations of active species as well as heat
conduction, both depend strongly on flame temperature.
3. Both the equations are based on broad simplifying assumptions
and their validity varies for different combustion systems.
4. Chemical kinetic factors used in the equations have not been
independently determined.

5. Thermal and transport properties of mixtures at high temperatures
and diffusion coefficients for atoms and free radicals used in the
equations are questionable.
6. The precision of burning velocity measurements is usually 2 to 5 %,
while the accuracy is probably much less.
Both the mechanisms have evidences as well as exceptions. Two
experimental observations which clearly appear to favour diffusion
mechanism are (i) increase in flame speed by the addition of
hydrogen or water to non-hydrogen containing fuels (ii) changes in
flame velocity caused by interchanging Helium and Argon as inert
diluents.
It is in fact probable that both heat conduction and diffusion contribute
to propagation of any flame. Modified comprehensive equations
including both these factors are therefore required which can give a
satisfactory solution.

Factors affecting laminar flame velocity
1. Mixture temperature:
40
80
200
160
120
S
F
(max)
(cm/s)
160 320 480 640
T
0
(K)
C
2
H
4
+ air

C
3
H
8
+ air

CH
4
+ air
For Paraffins Empirical relation: For T
0
= 200 to 615 K
S
F
(at T
0
) / S
F
(at 298K) = ( 25 + 0.00085 T
0
2
)/100
1(a) Effect of mixture temp.on burning velocity
X

1
0
3

2. Fuel-Air Equivalence Ratio:
100
50
0.5 1.0 1.5

S
F
/S
F(max)
%
1 atm, 25C
C
2
H
4
, C
3
H
6
, C
5
H
12
with air
Empirical eqn for the above fuels applicable in the lean region:
S
F
/ S
F(max)
= 2.6 log
10
+ 0.94
2(a)Effect of mix.strength on flame velocity
by vol
2(b) Fuel-air equivalent ratio and mix temp:

Temp
increasing
S
F
lean 1.0 rich
Max velocity shifts towards = 1 as temperature increases.
3. Mixture pressure:
0.2


0.0


-0.2
0.1


-0.1


-0.3


n
S
F
(cm/s)
10 100 1000
Cooler flames Hot flames
For different hydrocarbons
S
F1
/ S
F2
= (p
1
/ p
2
)
n
Pressure effect is not much pronounced. For very hot flames it slightly increases and for
cooler flames it slightly decreases as pressure increases. For oxy- acetylene flame it is
nearly constant, i.e., n = 0. For CH
4
+ air, n = -0.24 to 0.49 ; for C
3
H
8
+ air, n = - 0.3

V
4. Electric field and Acoustical disturbances:

No much effect of AC or DC field
was seen. Flame speed slightly
increased in the high voltage range
owing to intense ionization and
flame front break up.

In the audible range of acoustical
disturbances ( upto 20000 cps ) no
much effect was observed. Beyond
this flame speed may increase due turbulence until the
flame breaks up into islands and the flame speed cannot
be measured.


5. Mixture dilution:

O
2
conc
increasing
S
F
(cm/s)

lean 1.0 rich
Max velocity shifts towards = 1 as O
2
conc increases.
200


100


0
O
2
O
2
+N
2

5(a)
Effect of Nitrogen
Dilution on the
Flame Velocity
6. Hydrocarbon structure:
Short straight chain length, minimum chain branching, unsaturation and
small cyclo-alkane ring size increase flame speed. Oxygen containing
Compounds have higher flame speed. But alcohols have flame speeds
similar to alkanes.
In general, Alkenes > Aldehydes and Ketones > Alkanes

7.Additives:
a) For a fuel blend, empirically S
F(blend)
= S
F(a)
.X
(a)
+ S
F(b)
.X
(b)

Where, x is the mole fraction of the component. But actually it is found
to be slightly higher than that given by the simple mixing rule.
b) Moisture has slight inhibiting effect on hydrocarbons, bur increases
the flame speed of CO.
c) Anti-knock agents such as TEL, Ethyl nitrate etc did not show any
significant effect on flame speed of iso-octane or gasolene.
Additives contd
d) Inert diluents reduce flame speed in the following order: He, Ar, N
2

and CO
2,
Helium having the maximum reducing effect. This is due to
variations in the transport properties of the inert gases, such as
specific heat, thermal conductivity and diffusion coefts.
8. Wall surface:
Most wall surfaces of glass vessels and Bunsen tubes have a retarding
effect due to quenching and chain carrier adsorption, being less with
larger diameters. However, certain types of refractory surfaces are
found to have an accelerating effect on flame velocity, due to its
white hot surface inside the furnace or due to some catalytic action.
9. Turbulence:
Turbulence, by far, has the greatest effect on flame propagation.
Though the laminar speed does not change, the burning rate rapidly
increases due to turbulent wrinkling of the flame surface and
increase in the heat and mass transfer across the flame front.

TURBULENT FLAME PROPAGATION
Concept of turbulence:
Turbulent motion is a randomly fluctuating motion of small masses of
fluid superimposed over a mean flow.

Mathematically,
U = U
0
+ u, V = V
0
+ v and W = W
0
+ w , where, U
0
,

V
0
and

W
0
are
the time mean average values of flow velocities in the x,y and z
directions and u, v and w are the instantaneous deviations from the
mean velocity in the x, y and z directions.
By definition, u , v and w are all = 0. But we can define u, v and
w as u
2
, v
2
and w
2
which are components of turbulence
intensity in the 3 directions.
Turbulence intensity can also be defined as u/U
0
, v/V
0
and w/ W
0
.


U
0
u
Mechanism of burning velocity enhancement
due to turbulence

Burning rate increases with turbulence due to any or several
of the following reasons:
1. Increased burning area due to wrinkling of the flame front,
with the burning velocity remaining constant at the laminar
value normal to the flame front.
2. Increased rate of heat and mass transport due to eddy
movements across the flame front.
3. Increased rate of mixing of burned and unburned gases
due to eddy diffusion at the flame surface.
Damkohlers turbulent combustion wave model
U
o

+

u

U
o

+

u

U
o

Damkohlers theory of turbulent flame
propagation
Large scale turbulence distorts the instantaneous velocity profile from
the mean value with eddies (groups of molecules) randomly moving
in and out across the flame front. The flame front profile will be
similarly distorted forming +ve and ve cones, thus giving the
appearance of a wrinkled surface. This greatly enlarges the surface
area available for combustion per unit gas flow area and the flame
front can remain stationary only if the average gas velocity is
increased to a value S
T
, which is the turbulent flame velocity. It
should be noted that for any element of the distorted wave, the rate
of propagation normal to the wave is assumed to be still laminar.
Hence increase in flame area is an indication of increase in the
flame velocity.
In analogy to burner flames where the flame cone surface area is
proportional to the gas velocity, Damkohler assumes that cone
surface area in the turbulent flame front will be proportional to the
fluctuating velocity u. Hence S
T
u.
Now, by definition, in turbulent diffusion eddy diffusivity u.l, where
l is the scale of turbulence.
Thus for a given scale of turbulence, we can write S
T
.
But from the turbulence theory, R
e
. where is the kinematic
viscosity, which depends only on the nature of the gas.
Thus for a given gas and for a given scale of turbulence, S
T
R
e
.
However, to account for the effect of small scale turbulence which is
inherent in the system, Damkohler modified equation as -
S
T
= aR
e
+ B
Where, a is a constant and B is to account for small scale (micro)
turbulence to be determined experimentally.
Small scale turbulence:
Scale of turbulence is smaller than flame thickness and does not
produce any wrinkling of flame surface. But, the transfer processes in
the combustion wave increase. He suggested the eqn: S
T
= S
L
. R
e.

High discrepancy between calculated and measured values were
attributed to presence of eddy sizes.


Broken up flame islands in highly turbulent flow
Shelkins model for small scale (micro)
turbulence
Shelkin expanded Damkohlers thermal concept of turbulent
flame propagation and proposed the following model for
micro turbulence (i.e., eddy size L less than the flame
thickness):
S
T
/ S
L
= (1+ /) ,
Where, S
T
= Turbulent burning velocity
S
L
= Laminar burning velocity
= Thermal diffusivity = K
L
/(C
P
.
0
)
= Eddy diffusivity = K
T
/(C
P
.
0
)
K
L
= Molecular heat transfer coeft
K
T
= Turbulent heat transfer coeft

Shelkins model for large scale (macro)
turbulence (l > flame thickness)
Like Damkohler, Shelkin agrees that turbulence wrinkles
the flame front surface and increases the burning area.
He imagines that the flame surface consists of dancing
cones formed by burning eddies which move up and
down the flame surface. The cone base area is
proportional to l
2
where l is the cone dia, i.e., the eddy
size. The height of this cone = u.t where, u = average
turbulent fluctuating velocity and t = the time during
which an element of combustion wave is associated with
this eddy moving in the direction normal to the wave and
finally reducing it to zero size at the tip of the cone.
Hence, t = l/S
L
= time for the consumption of the eddy of
size l and height of the cone h = u. l/S
L
.
Shelkins model contd.
Cone base area = l
2
/4
Cone ht h = (u. l/S
L
)
Slant surface area = .(l/2).s
= .(l/2).(h
2
+ l
2
/4)

Shelkins theory:
S
T
/S
L
= Cone surface area/ Cone base area
= ( 1 + 4 h
2
/l
2
) = [ 1 + (2u/S
L
)
2
]
Allowing for the crudeness of the model, Shelkin prefers to
replace 2 by a const B which may be taken as 1.
Therefore, S
T
= S
L
. [ 1 + (B.u/S
L
)
2
]
Note: When u=0, S
T
=S
L
. When u >>1, S
T
u, independent of fuel, exactly
as Damkohler said, but is not fully supported by measured data.


h
l
Shelkins Model of
turbulent burning cone
FACTORS AFFECTING TURBULENT BURNING VELOCITY

1.Effect of mix.strength on turbulent burning velocity

2. Effect of equivalence ratio on burning velocity
/
max
0.6 0.8 1.0 1.2 1.4 1.6
1.0
0.5
0
SL / SL
max
And
ST / ST
max
Effect is similar for both laminar and turbulent flames
3. Effect of Mix. Strength on Reynolds Number
of pipe flow
0 5 10
Fuel %
Ethene-Air Mixture
Re = 33700

Re = 20000
Re = 10000
Re = 3000

100





50
S
T
4. Effect of turbulence intensity on turbulent burning velocity
PREMIXED AND DIFFUSION
FLAMES

Pre-mixed and Diffusion Flames
Pre-mixed flames:
Fuel and oxidant are mixed prior to arriving in the burning zone and
hence chemical reactions leading to combustion will be faster or the
burning zone will be shorter in length than diffusion flames.
Examples: Domestic LPG gas stove, Bunsen burner with the air valve
open, combustion in the S.I.Engine, explosion in mines etc.
Structure of Pre-mixed Flame:
Fuel
Oxygen
Products
Flame
front
Burner
Centreline
1750 C
1800 C
1850 C
Temp. Profiles Conc. Profiles
Flat flame burner; 0.755 x 2.19 cm
8.7% Natural gas in Air
Intermediate
products
Diffusion Flames (Jet Flames):

Fuel and oxidant arrive separately at the combustion zone
and mixing takes place in the reaction zone itself by
diffusion. Diffusion of oxygen into the fuel gas being a
slow process, carbon formation takes place which glows
to give a bright luminous flame. Diffusion rate depends on
nature of gases, pressure, density etc. Height of the flame
is decided by the gas flow rate and the oxygen diffusion
rate and is given by the point at which air just diffuses to
the axis of the flame. At higher flow rates soot formation
takes place and the flame tip will not be clearly defined.
The maximum soot free length of the flame is an
indication of the soot forming tendency of the fuel.
Examples: Candle flame, kerosene wick lamps, Bunsen
burner with air valve closed, Combustion in the diesel
engine, flames in furnaces etc.
Structure of Diffusion Flame:
Diffusion flame structure is influenced by the following factors-
(1) Width of the reaction zone (2) Radiation heat losses (3) Carbon
forming tendency of he fuel (4) Convective flow pattern (5) Momentum
Transfer (6) Diffusion Coefficient and (7) Air-fuel ratio.
C
2
H
2
-Air flame
Centre line
of flame
C
2
H
2
Complex HC
molecules
C CH
OH
O
2
N
2
2800C
Temp. profile
(Burner dia=24 mm)
Carbon
Zone
Reaction
Zone
Burner rim
Effect of air flow rate on flame boundary of jet flames
When air flow is in excess (Over ventilated)
More air will diffuse into the fuel and the
flame boundary will close at the top at a
Shorter distance.


When air flow is in deficit (Under ventilated)
Fuel gas diffuses more into the air and the
flame will flare up to the outer wall.


In both cases, flame height is definable.

Air Fuel
Under
ventilated
Over
ventilated
Distinction between pre-mixed and diffusion flames
Pre-mixed flames Diffusion flames
-----------------------------------------------------------------------------------------------
1. For a pure pre-mixed flame Fuel - Air True Fuel Air ratio cannot be defined
ratio is const at the molecular level, and since the mixing continues as the reaction
will not be altered by addition of, say, is in progress.
Oxygen from outside.
2. Burning velocity can be defined and Since the reaction rate is controlled by
Measured. diffusion rate, no burning velocity can be
adequately defined.
3. Flame is bluish and less luminous, Flame is luminous due to carbon formation
as carbon formation is less pronounced. from deficit oxygen on the fuel side, which
glows as bright yellow flame at high temp.
4. Pre - ignition reactions occur during Since the reaction begins and ends in the
premixing which causes some heat loss burning zone itself, the temperature in the
in the process. Hence flame temp will burning zone is near the theoretically max
be slightly less than the theoretical max. possible value.
------------------------------------------------------------------------------------------------


BURNING VELOCITY
MEASUREMENT
MEASUREMENT OF LAMINAR BURNING
VELOCITY OF PREMIXED FLAMES
1. Bunsen burner method:


U
g
= Gas velocity S
u
= Flame velocity
A
b
= burner area A
f
= flame cone area




Rate of gas flow through A
b
= Rate of burning over A
f

A
b
.U
g
= A
f
.S
u
Therefore, S
u
= (A
b
/A
f
).U
g
But A
b
= R
b
2
and A
f
= R
b
.l
A
b
/A
f
= R
b
/l = Sin ,where is half cone angle.
Thus, S
u
= U
g
Sin


A
b
A
f
R
b
burned
unburned
U
g
S
u
Parabolic
velocity
profile
Inner cone
(flame boundary)
l=slant length
Limitations of the Bunsen burner method:
1. U
g
is not uniform throughout the burner area, since the velocity profile
is parabolic (Poiseuille flow).
Soln: (a) Measure U
g
at a distance of

0.707 R
b
from the centre using a
pitot tube which represents the average velocity. (b) U
g
= V
g
/A
b
where,
V
g
is the measured volume flow rate of gas. (c) Divide the flame cone
into small horizontal segments and sum up the individual
surface areas of segments to get a more accurate value
for A
f
to be used in the eqn: S
u
= (A
b
/A
f
). U
g
A
f
=a
f

2. Actual wave shape will be different from right circular
cone, particularly for weak mixtures. The cone becomes
thin and pointed for higher gas velocities and becomes
blunter at the tip for low gas velocities.
Soln:
a
f
s
r
1
r
2
R
Select the mid region of the flame area, where the
slant surface is straight.
For cylindrical burners,

S
u
= 2U
m
(r
2
r
1
)[ 1 (r
2
2
r
1
2
)/(2R
2
) ] / s

Where, U
m
is the average gas velocity in the
burner of radius R, r2 and r1 are the radii at the
base and top of the frustrum, and s is the slant
height of the frustrum.

A further modification is to use rectangular ( flat ) burner tubes, in
which the combustion wave assumes the shape of two inclined
planes so that the concave curvature of the wave (which is a source
of error) is eliminated.
3. The change of burning velocity at the base (due to quenching effect
by the burner rim) and at the tip due to high temperature are not
taken into account.
4. Outward deflection of gas flow lines at the burner exit increases the
base radius of the flame cone.

The burner method is more accurate when a nozzle is used instead
of the cylindrical burner, since the nozzle yields more or less a
uniform velocity profile and hence, the errors due to distorted flame
geometry at the cone base are reduced.
Particle Track Method:
To visualize the flame cone profile more clearly, particle track can be
used which is developed by Lewis and von Elbe. The
track is traced using a stroboscopic disc by inter-
mittently illuminated MgO dust sent along with the fuel.


Flat burner
Illuminated
particles
2. Soap Bubble Method:
This is a spherical propagation velocity measurement, applicable for
mixtures having isotropic propagation.
.
Gas filling
tube
Gold wire ring
support
Soap
bubble
Electrode
Flame
front
d
D 30 50 70 90
Vol % of fuel in mixture
V
e
l
o
c
i
t
y
,

m
/
s

5
10
Burning velocity

(Transformation vel)
Spatial velocity
Soap bubble experiment:
Soap bubble is inflated with the combustible mixture to a dia of about
10 cm around the centrally located ignition electrode. When the
spark is created, a spherical flame moves and the bubble freely
expands ensuring const pressure combustion. Expansion of the
bubble and the flame front movement are photographed with high
speed photography.
If S
sp
is the spatial velocity as measured from the photograph, the true
burning velocity will be S
u
= S
sp
/ , where is the correction
factor for the forward transportation of the flame front due to the
expansion of gases behind the flame front. If d and D are the
initial and final bubble diameters at time 0 and any selected time t,
then = (D/d)
3
.
Thus, S
u
= S
sp
/(D/d)
3
Limitations: 1) Moisture in soap bubble affects the flame speed.
2) Expt must be done immediately after filling the bubble to avoid
diffusion of the gas through the soap film. 3) Method not suitable for
corrosive gases like H
2
-Cl
2
and H
2
-O
3
. 4) Bubble will not be truly
spherical due to buoyancy effects; hence may not be accurate.


3. Flame tube method:







Tube dia should be >> quenching dia, and length > 1 m for better
accuracy of time measurement. Too large a dia will cause gas
vibration and turbulence, which will enhance flame velocity. E.g, for
propane, for which d
q
is 0.3 cm, a tube dia of 3 cm is chosen. Time
interval t for the flame travel between the two marks is counted by
an electronic counter, which is triggered by sensors (photo cells or
ionization probes) when the flame moves across them. S
u
= L/ t .
Ignition is made from the open end to eliminate the effect of flame
transportation by the expanding gases behind the flame.
L
Initial
mark
Final
mark
Fuel Air
Spark
Pyrex tube: 2 cm dia and 3 m long
Porous plug
(flame arrester)
Mixing
chamber
The measured values from the flame tube method depends on the
orientation of the tube. The flame velocity is the highest for vertical
tubes with upward flame. This is due to the effect of buoyancy and
heat convection in the upward direction. For downward flame the
value is minimum and for horizontal movement it is in between the
two. Hence while reporting the values, it is necessary to mention the
orientation of the tube used in the experiment.
4. Constant volume bomb method:
A spherical steel vessel is filled with the mixture and fired by a spark from
the centre. The pressure is continuously recorded with respect to time
using a pressure probe. The progress of the spherical flame is
calculated using thermodynamically relating it to the rate of pressure
increase, and the flame velocity is estimated duly accounting for the
apparent effect of expanding gases on flame transportation.
S
u
= (dr
i
/dt).(r
i
/r
b
)
2
.(p
i
/p)
1/ku
), where, S
u
is the instantaneous flame
velocity at time t, r
i
is the initial flame radius at t (at p
i
), dr
i
/dt is
obtained from a plot of calculated r
i
vs t, r
b
is the flame radius at t + dt
(at p) and ku is the sp.heat ratio of unburned gas.
Comparison of different methods
A simple nozzle burner method is the best and most practical
(with a large flame, rim and tip effects are relatively small).
Cylindrical burners do not exhibit a right circular flame cone.
Flat burners are better as they have reduced rim effect.
Particle track technique is superior, but the procedure is
laborious without much improvement in accuracy.
Soap bubble technique suffers from moisture effect and
possible quenching at the electrode and give a reduced
value.
Spherical bomb method involves a pressure record.
Thermodynamic calculations being sensitive to the accuracy
of pressure values, it generally gives lower velocity values.
Measurement of premixed turbulent
flame speed in cylindrical burners
Burner tubes should be long enough to ensure
fully developed turbulent pipe flow. Flame height
decreases due to turbulence brush and the
average flame cone boundary is considered for
flame velocity calculation.

Methods to calculate S
T
:

1. S
T
= U Sin , where U is the mean gas flow
velocity, is the half angle of average turbulent
cone.
2. S
T
= (A
p
/A
f
).U where A
f
is the flame surface
area = (4/3).r
p
.b
f
, calculated by assuming the
flame surface as a paraboloid of revolution (rather than a cone), where b
f

is the mean height of the flame and r
p
is the port radius and A
p
is the port
area.
Laminar
flame cone
Average
Turbulent
flame cone
Turbulent
brush
r
p
b
f
LAMINAR JET (DIFFUSION) FLAMES
Flame lengths for circular port and slot burners
Ropers Correlations:
Ropers experimental results are applicable for jet flames emerging into
either a quiescent oxidiser or a coflowing oxidiser stream, so long as
the oxidiser is in excess ( i.e., flame is not under-ventilated )
Circular port:
L
f
= 1330.Q
F
(T

/T
F
) / ln(1 + 1/S) where L
f
is the length of the
jet flame (m), S is the molar stoichiometric oxidiser-fuel ratio, T

and T
F
are the oxidiser stream and fuel stream temperatures (K), Q
F

is the flow rate of fuel gas (m
3
/s).
Ropers theoretical equations include mean diffusion coefts as well as
flame temperatures both of which can only be calculated with limited
accuracy. Hence experimental formulae are preferred.
Square Port:
L
f
= 1045 Q
F
(T

/T
F
) / [ inverf { (1 + S)
-0.5
}]
2
where, inverf is the
inverse error function.

Sample error function table
erf erf erf
0.00 0.00000 0.36 0.38933 1.04 0.85865
0.04 0.04511 0.40 0.42839 1.12 0.88679
0.08 0.09008 0.48 0.50275 1.20 0.91031
0.12 0.13475 0.56 0.57162 1.40 0.95228
0.16 0.17901 0.64 0.63459 1.60 0.97635
0.20 0.22270 0.72 0.69143 1.80 0.98909
0.24 0.26570 0.80 0.74210 2.00 0.99532
0.28 0.30788 0.88 0.78669 2.40 0.99931
0.32 0.34913 0.96 0.82542 2.80 0.99992
E.g. : inverf (0.2657) is value of for which erf is 0.2657, i.e., = 0.24
Slot burner Momentum controlled ( Flame Froude No >>1):
L
f
= 8.6x10
4
(T

/T
F
)
2
. (b
2
Q
F
)/(hIY
f,stoic
)
where, b and h are the slot width and length,
and function = 1/ { 4 inverf [1/( 1 + S )] } and I is the ratio of
actual initial flow momentum from the slot to that of uniform flow, = 1
for uniform flow and = 1.5 for fully developed flow with parabolic exit
velocity profile and Y
f,stoic
is oxidiser/fuel ratio by mass in stoichio-
metric mixture (to be checked)
Slot burner Buoyancy controlled ( Flame Froude No. << 1):
L
f
= 2000 [ (
4
Q
F
4
T

4
) / (a h
4
T
F
4
) ]

, where, a is the mean

buoyant acceleration = 0.6 g (T
f
/T

- 1), g being the accln due to

gravity and T
f
is the flame temperature, assumed to be 1500K. In
the above expression b is neglected relative to h, assuming h >>
b.
Slot burner Transition Regime (Flame Froude No. 1):
Roper proposes an expression to find an intermediate average value
from the above two calculated flame lengths.
Mechanism of soot formation in jet flames
Soot formation in jet (diffusion) flames is basically due to lack of
oxidiser reaching the right zone at the right time. It is generally
agreed that soot is formed over a temperature range of 1300 to
1600 K within the flame. The soot particles radiate light
particularly in the infrared region of the spectrum and make it look
bright readable light. Soot formation is believed to take place in
four sequential steps:
1. Formation of polycyclic aromatic hydrocarbons as intermediates
between the original fuel molecule and the primary soot particle.
2. Formation of small primary soot particles of critical size (3000 to
10000 atomic mass units) from growth by both chemical process
and coagulation.
3. Further surface growth and agglomeration of these primary soot
particles due to exposure to the pyrolizing fuel as they travel
through the flame.



4. At some point further these soot particles will pass through an
oxidizing region of the flame, namely, the flame tip where they get
an opportunity to get oxidized. When all the soot is oxidized, it
results in a non-sooting flame, while incomplete oxidation causes a
sooting flame.
The amount of soot formed depends on the type of fuel and the fuel
flow rate. The minimum flow rate at which smoke is observed to
escape from the flame tip is a measure of the smoke point. The
maximum flame height of a non-sooting flame is also taken as a
measure of the smoking tendency of the fuel. Non-sooting fuels will
have a higher non-smoking flame length and a higher flow rate at
the smoke point.
The sooting tendency of fuels from least to greatest is found to be in
the order of alkanes, alkenes, alkynes and aromatics. Also in a
given grouping, the sooting tendency generally increases with the
number of carbon atoms.
FLAME STABILIZATION
IN LAMINAR FLOW
THE TUBE BURNER
Combustion in a tube burner involves fuel gas flow, combustion and
quenching at the burner rim. Let T
u
,
T
i
* and T
b
* be the isotherms for the
plane adiabatic combustion wave.
The gas flow lines diverge at the
open end due to heating and expan-
sion effect while the solid rim acts as
a heat sink to quench the flame by
absorbing heat and chain carriers.
The quenching effect decreases as
the distance from the rim increases.
Near the rim the actual T
i
and T
b

surfaces diverge from T
i
* and T
b
*
T
i
*
T
b
*
T
i
T
b
T
u
Reaction zone
Gas flow lines
Dead space
Burner
rim
due to rim quenching effect. Heat loss to the rim reduces the T
b

surface temperature below T
b
*. The T
i
surface, which marks the
starting point of chemical reactions will have to be higher than T
i
*
since some of the chain carriers (active species) are lost to the sink.
As such the burned gas temperature T
b
isotherm and the inflexion
point temperature T
i
isotherms will merge together in the vicinity of
the rim. Hence due to this rim effect the burning velocity decreases
below its standard value S
u
* (away from the rim) to zero near the
sink at the merging point where the unburned gas flow into the
reaction zone will also reduce to zero. This region of the vanishing
burning velocity is considered as the fringe of the combustion
wave. The region between the fringe and the rim is called the dead
space which shows the closest possible approach of the reaction
zone to the sink.
For the flame to be stably anchored to the rim, the flame velocity should
equal the flow velocity in opposing directions. This happens only at
one point near the fringe and at all other points on the wave the gas
velocity exceeds flame velocity making the wave surface inclined.

Stabilization of flame in a laminar jet
S
u
* is the standard burning
velocity of the mixture, away
from the quenching effects of
the burner rim. Consider the
fringe of the wave near the
burner rim ( 1 mm above
the rim for a slow burning
mixture like methane + air).
For relatively large burner
dimensions, the gas velocity
profile can be assumed to be
linear at the burner tube wall
(Poiseuille flow). Consider 3
positions of the wave profile.

S
u
*
S
u
*
S
u
*
S
u
*
S
u
*
S
u
*
Open
atmos
U
g
S
u
=U
g
S
u
>U
g
S
u
<U
g
Gas vel. profile
Solid
rim
3
2
1
Position 1: Combustion wave is too close to the rim. Quenching effect
is predominant. Gas velocity exceeds the burning velocity every
where. The flame is driven back (upwards).
Position 2: Equilibrium and stable position. The increased distance
from the solid rim reduces quenching and the burning velocity
increases. At some point it equals the gas velocity, and the flame
gets anchored to the burner. At the outermost region of the fringe
excessive dilution by diffusion of atmospheric air decreases the
burning velocity and the flame profile will be driven back (curved).
Position 3: Wave is too far from the rim. The burning velocity
exceeds the gas velocity and the flame moves towards the
equilibrium position 2.

(Note: At all points away from the rim all along the wave profile, the gas
velocity exceeds the burning velocity and therefore the wave profile
is inclined to the gas flow vector at an angle governed by the relation
S
u
* = U
g
Sin where is half the cone apex angle.)
Flash back and blow off principle
Case I: Flame inside the burner tube - Fig [ I ]
Velocity gradient is assumed to be linear from the burner wall towards
the centre such that U
g
= g.y , where g = boundary velocity gradient
dU/dy and y is the distance from stream boundary. Till certain
distance from the wall, flame does not exist due to wall quenching
effect. The flame velocity gradually increases till it reaches S
u
* away
from the wall and remains steady at this value towards the centre. 1,2,3
are three boundary velocity gradients
shown for the gas flow. For gradient 1,
there is a region where the flow velo-
city is less than the burning velocity.
Thus flash back occurs. For gradient 3,
the flow velocity at all points exceeds
the burning velocity and the flame will
S
u
*
S
u
=U
g
Dead space
X
pen,F
Gas vel profile
U
g
Burner rim
Critical g
F
condition
at flame flash back
be lifted up towards the free stream. Gradient 2 is at a tangent to the
S
u
curve and defines the upper limit of gas flow at which flash back just
occurs. This gradient is called the critical boundary velocity gradient for
flash back g
F
. Penetration distances X
pen,F
and X
pen,B
are arbitrary
defined quantities used to illustrate the effect of wall quenching (in flash
back) and secondary air dilution (in blow off) and is equal to the ratio of
fundamental flame velocity to the critical velocity gradient.
X
pen,F
= S
u
*/ g
F
and X
pen,B
= S
u
*/ g
B
.

The penetration distance represents
the distance from the burner wall, at
which the local gas stream velocity
equals local burning velocity and is
defined only for flash back and blow
off conditions. Dead space indicates
wall quenching distance during flash
back similar to that seen above the rim for a normal stable flame.


X
pen,B
Dead
space
Diffusing
air
Critical g
B
condition
at flame blow off
U
g
Gas vel profile
S
u
*
S
u
=U
g
Case II: Flame in free jet - Fig [ II ]
Consider a stable flame in free jet above the burner rim. Curves A, B
and C show flame velocity variations on three different wave profiles at
different distances above the rim. Each of these curves start at a
distance = quench distance from the stream boundary which decreases
as the distance of the wave above the burner rim increases. They end
up with the standard S
u
* value beyond the quench free distance along
the wave profile.
Lines 1,2,3,4 and 5 represent 5 different increasing gas velocity profiles
corresponding to 5 different boundary velocity gradients. When the gas
flow is reduced, g decreases and the equilibrium flame position shifts
closer to the solid rim. Position 2 represents critical boundary velocity
gradient for flash back g
F
, below which (e.g.,line 1) a flash back occurs,
i.e., the flame will move into the burner tube.

When the gas flow is increased, the equilibrium position of the flame
shifts upwards away from the burner rim. Flame position B represents
stable position for the flame. However, with increasing lift, the mixture
becomes progressively diluted due to inter-diffusion of air from the
surrounding atmosphere and the burning velocity in the outermost
region of the wave fringe decreases considerably. At the boundary
velocity gradient given by line 4 the wave profile will be lifted to a critical
position C beyond which the excessive dilution effect will more than
offset the burning velocity improvement due to increased distance from
the rim and the flame blows off. The boundary velocity gradient corres-
ponding to this position is called the critical boundary velocity gradient
for blow off g
B
. For a velocity gradient > g
B
, such as line 5, the wave
will be driven upwards and blown off.
Critical Boundary Velocity Gradients
for Flash back and Blow off
Fig I Fig II
1
CRITICAL FLOWS FOR FLASH BACK IN TUBES

stoichiometric
On-set of flash back near critical flow
Critical flow for blow off in cylindrical tubes
to the right
of dotted line



Stability regime between flash back and blow off
Stability diagrams for different tube diameters

Characteristic Stability Diagram for
open Flames
The characteristic stability diagram is a plot of gas velocity versus
mixture strength indicating regions of stable flame, flash back, blow
off, lifted flame and blow out (i.e., blow off from lifted flame position).
Flash back curve ABC: This occurs at low gas velocities and relatively
low mixture strengths. Maximum tendency for flash back occurs for
a mixture slightly richer than stoichiometric, which would correspond
to maximum flame velocity mixture. Beyond 8% butane ( 2.6) the
rich mixture does not support a flame to flash back into the burner
since no additional air is available inside the burner tube to diffuse
into the mixture. But the flame sustains itself at the port as a stable
flame due to oxygen diffusion from outside, which makes the mixture
combustible. To the left of A the mixture is so lean that no flame can
exist at any flow velocity.


Characteristic stability diagram for butane-air open flames
(Butane % by vol)
0 10 20
(
m
/
s
)






30




20




10
(
3
.
1
3

%

b
y

v
o
l
)

G
H
Blow off and lift curve ADE:
The stream velocity, and hence the boundary velocity gradient is so
high that the flame has to be blown off. However entrainment of
ambient air at the stream boundary produces a more favourable
combustible mixture extending to some depth into the stream and
also decreases the average gas velocity due to momentum loss at
the interaction zone. Hence at some height from the rim the gas
velocity and the burning velocity become equal and the flame finds
itself stable in this lifted position. The lifted position is possible only
for very rich mixtures as it can be made combustible by diffusion of
diluting air. To the left of D, where the mixture is relatively lean, it
will be further leaned by air diffusion and the flame, therefore, simply
blows off without a lifted position. The lift will be higher if the flow
continues to remain laminar, and will decrease if the flow turns out to
be turbulent (due to higher flame speed).
Blow out curve DF:
This corresponds to the gas velocity required to remove a lifted flame
down stream causing a blow out. This rises very steeply with mixture
strength, and possibly no blow out may occur for highly rich mixtures
or pure fuel gas when it will burn like a pure lifted diffusion flame.
The dashed line DG is a continuation of the blow out limit. For mix-
ture composition between D and G, the flame may be removed from
the stream either by blow out or by blow off. However, the lifted
flames are more vulnerable (for removal by blow out), than the
seated flames (by blow off).
Drop back curve GH :
When the stream velocity is decreased for a lifted flame, it may drop
back to the burner rim and there is a region between the lift and drop
back limit in which the flame has a choice between these two
positions of stability, one the lifted and the other seated. Inter-
shifting between these positions is possible by introducing some
disturbances in the flow stream.
Below the drop back limit, the flame remains stably seated on the rim at
all mixture strengths beyond the flash back regime.
Flame stabilization in
high speed flow
Low velocity flow over a bluff body
Effect of bluff body on high speed flow

High speed flow over a rod with and
without combustion
Flame anchored to the bluff body

Characteristics of bluff body flame holders
Some practical schemes of flame stabilization
in high speed flow

Flow Pattern in a Jet Engine Combustor
Stability Characteristics of Gas Turbine
Combustion Chambers
Due to high velocity of air in the ignition zone, it is difficult to form
homogeneous mixing with the injected fuel in such a short available
time. Therefore, actual strength and limits measured in the expt will
indicate higher air/fuel ratios since some of the air will flow past the
ignition zone without mixing with the fuel.
The nearly horizontal portions of the stability curve correspond to rich
(A-B) and lean (D-E) limits of mixture strengths in the primary zone
because, the air-fuel ratios are constant irrespective of flow velocity.
Point C corresponds to a mixture strength in the primary zone giving
the maximum flame velocity.
At still lower velocities, the rich and lean limits deviate. Along the lean
stability limit, the flame moves towards the spray cone and sticks to it
where it finds the desired mixture strength. Irrespective of the A/F, a
small flame remains stuck to the spray cone.
Stability Characteristics of Gas Turbine Flames
A
B
C
D
E
Theoretical
Along the rich limit 1, the flame moves towards the secondary zone (the
primary zone being over rich) and stabilizes at the interface between
the vortex and the secondary zone where the desired strength is
possible. (This cannot occur in the rich limit 2, since the flow velocity
at the interface is high which will blow off the flame).
At the rich limits the system is found to be susceptible to pulsating
combustion and explosion blow out. This is because, at the rich limit
flame is sensitive to the rate of air supply to the vortex and a
temporary dynamic disturbance can cause a momentary decrease in
heat liberation so that a strong feed back exists between the flame
and the disturbance. The flame may then decrease to such an
extent that substantial quantities of explosive mixture accumulate in
the duct which will get ignited with violent effects by the residual
flame. On the lean side the flame is relatively insensitive to air flow
and such disturbances are not observed.
With increase in temp, pr and atomization of fuel, the stability limits are
enlarged. With decrease in pressure the rich and lean limits
approach each other, and below a critical pressure the combustor
fails to support a flame.
LIMITS OF
INFLAMMABILITY
Limit of inflammability pertains to condition at which the mixture cannot
be ignited, or if ignited, it is incapable of sustained burning. This is
because, the flame at its flammability limit becomes fairly weak
and vulnerable due to its low burning velocity, and the heat
released becomes less than the heat dissipated by convection
and radiation to the unburned gas which quenches the flame.
Factors affecting the flammability limits:
1. Tube diameter:
Tube dia should be more than the
quenching dia to eliminate direct
flame quenching due to heat and
active mass loss to the walls.
Flammable range widens upto
5 cm dia due to reduced quench-
ing effect of the wall.
40
30
20
10

M
i
x
.
P
r
e
s
s
u
r
e

(
c
m
.
H
g

a
b
s
)

1 2 3 4 5 6 7
C
3
H
8
in air (% by Volume)
Lean limit Rich limit
Flammability region
Tube dia
1.6 cm
2.2
2.8
4.7
6.6
=1
2. Mixture Pressure:
(i) Flammability range widens with increase of pressure. In most
cases this variation is small.
(ii) The pressure for any given rich or lean limit mixture decreases
with increase in tube diameter.
(iii) As the pressure decreases, the lean and rich limits progressively
converge for all diameters.
(iv) Flammable range at any given pressure is wider for larger tubes
at least near the quenching diameter.
3. Mixture Temperature:
Increased mixture temperature
improves the flammability limits
at any given pressure.


Natural gas % by Vol
Mix
temp
Flammability
Range
4. Ignition energy:
Ignition energy must be sufficient so that no limitation is caused on
flame development on account of it. A strong ignition source or a
small naked flame will give true results.
5. Fuel type:
Branched chain hydrocarbons have some what smaller inflammable
range than the corresponding straight chain fuels. Benzene has
still a smaller range.
6. Inert Diluents:
Effectiveness of inert gases on flame
extinction increases in the order of
N
2
, Exh.gas, CO
2
, CCl
3
F, CH
3
Br.
Flame cannot be sustained when %
of CCl
3
F (tri-chlorofluoromethane) in
the mixture exceeds 11%, while with
N
2
,

flames can propagate upto 43%.
0 2 4 6 8 10
Gasolene vapor, % by vol in air
40





30
20
10
I
n
e
r
t

g
a
s
,

%

b
y

v
o
l

N
2
Exh.gas

CO
2

CCl
3
F
CH
3
Br

7. Velocity and Turbulence:
Opinions differ in this respect. For CH
4
+ Air , limits are widened,
where as for C
3
H
8
+ Air, limits are narrowed. Generally upto a
certain level of turbulence limits may widen; beyond this limits are
narrowed.
8. Orientation of Experimental Combustion tube:
In vertical tubes, the limits are observed to be wider when the flame
travels up compared with when the flame travels down. This is
because the buoyancy effect (low density hot gases moving up)
enhances heat transfer to the unburned gas which helps the
upward flame movement. For horizontal tubes the limits ar found
to be in between the above two values.
Typical observations with some mixtures are given below:
CH
4
+ Air C
2
H
6
+ Air C
6
H
6
+ Air
Lean Rich Lean Rich Lean Rich
Upward 0.54 1.7 0.54 2.9 0.53 2.9
Downwards 0.60 1.5 0.56 1.9 0.54 2.1
Horizontal 0.54 1.6 0.54 2.5 0.53 2.6

Important factors to be considered for determining the
true limits of inflammability :
1. Strong ignition source (or a small naked flame) should
be used to ignite the mixture.
2. Pyrex glass may be chosen for the flame tube and its
diameter should be far larger than quenching diameter
(5 cm or more).
3. Large tube length should be used (1.3 m or more) to
enable the flame to travel steadily and indefinitely.
4. Direction of flame movement in the flame tube should
be specified (upward, downward or horizontal).
5. Ignition end of the tube should be open to equalize the
pressure with the ambient atmosphere.
FLAME QUENCHING
AND
QUENCHING DISTANCE
Flame quenching
Flames can be quenched in the following ways:
1. Excessive loss of heat and active mass to the surrounding surface
2. Flame stretch due to divergent flow
3. Diffusional stratification in fuel-air strength, particularly with limit
mixtures
4. Excessive turbulence causing rapid heat dissipation to the
surrounding gas.
Definition of Quenching distance and Quenching diameter:
The minimum distance between the walls of a slit or the minimum tube
diameter, which can just permit a laminar flame to propagate
through it, is called the quenching distance (d
q
) or quenching
diameter(D
q
).
Application of quenching distance: (1) Davy lamp used in mines.
(2) To estimate UBHC emission from combustion engines.
Measurement of Quenching Distance

1. A strong spark is generated at the centre of a pair of parallel plates
with adjustable distance between them, containing the test mixture.
The minimum distance at which the flame just propagates from the
source is the quenching distance.
2. A rectangular burner with adjustable width is used and the flame is
established above the burner. The gas flow is suddenly stopped.
The flame will now strike back through the tube. The maximum width
through which the flame does not strike back is measured as the
quenching distance.
3. Similarly experiments can be conducted on tube burners with
variable mouth diameters. The minimum diameter through which the
flame is just able to pass is measured as quenching diameter.





Factors affecting quenching distance
1. Geometry of the measuring device (whether rectangular or
circular).
Geometrical factor B = d
tube
/d
slit
= 1.25 for CH
4
+ air
= 1.45 for C
3
H
8
+ air
2. Nature of surface ( whether glass, metal, etc):
No significant effect was noticed, because conductivity of the gas
layer is far less than that of solids.
3. Type of fuel:
Quenching distance decreased in the following order:
Iso-octane > n-heptane > propane > benzene, when looked up
from the lean side. This is attributed to the decreasing thermal
conductivity of the fuel mixture in the above order. On the rich
side some overlap was observed.
Fuels having higher flame velocities like hydrogen, acetylene
etc have lower quenching distance. So also fuel + O
2
mixtures
have lower quenching distance relative to fuel + air mixtures.











4. Min. Ign. Energy:
d
q
increases with increase in E
min

requirement for the mixture.
E
min
d
q
2
(Ref: Strehlow, p 234)
This relation holds good for a
good number of hydrocarbons.
4.5

3.0

1.5
0.6 0.8 1.0 1.2 1.4 1.6 1.8

D
q
(mm)
Iso-octane
n-heptane
propane
benzene
H
2
E
min

(mJ)
d
q
(cm)
0 1.0 2.0
10

1.0

0.1
HC1 HC2
5. Mixture strength:
Quenching distance increases as the limits of inflammability are
approached. Minimum d
q
exists for the fastest burning mixture.

Stoichiometric strength
6. Initial temperature:
d
q
decreases with increase
of temperature.


7. Mixture pressure:
d
q
decreases with increase of mixture pressure since quantity of
mixture available is more in the slot at higher pressures. Expts
have shown that d
q
1/p
-0.9
holds good for several

hydrocarbons.



0.6 0.8 1.0 1.2 1.4 1.6

Dq
(mm)
5
4
3
2
1

27C
127C
210C
285C
(C
3
H
8
+ Air)
0.8 1.0 1.2 1.4

20

15

10

5

0




D
q

(mm)
(C
3
H
8
+ Air Temp = 24C)
6.3 cm.Hg

16.4cm.Hg

27.3cm.Hg
76 cm.Hg
Log-log plot
d
q
Mix. pressure
8. Inert diluents:
Experiment was conducted by choosing the proportion of diluents
to give the same flame temp (2340C) so that the sole effect of
diluent properties on d
q
could be singled out. Quenching distance
varies as He > A > N
2
> CO
2
, chiefly due to thermal and transport
property variations among these gases.
2.5

2.0

1.5

1.0

0.5

0.6 0.8 1.0 1.2 1.4 1.6
D
q
(mm)

He

A

N
2

CO
2
H
2
+ O
2
Mixture
Atmos. pressure
and Temperature

9. Oxygen concentration:
Quenching distance decreases
as the oxygen concentration
increases. This is due to better
combustibility with higher oxygen
concentration.


10. Turbulence:
With increased turbulence heat loss to the wall increases, and
hence, quenching possibilities increase. When the turbulence is
very high, the unburned gas may act as a sink for heat and chain
carriers thereby causing homogeneous quenching by excessive
heat dissipation to the unburned gas itself.

10


1.0


0.1
CH
4
% by volume
D
q

(mm)
0 20 40 60
O
2
/(O
2
+N
2
)
=1.0

0.21 0.35 0.5 0.67
(Pr = 1 atm)
Models for flame quenching
Models based on thermal and diffusional mechanisms have been
developed by various scientists. Predicted values are shown in the
table.
________________________________________________________
Fuel/O
2
ratio Observed d
q
(cm) Predicted d
q
(cm)

(% stoichiometric) Thermal Diffusional
------------------------------------------------------------------------------------
73.8 0.35 0.47 0.67

100 0.41 0.48 0.68

149 0.44 0.50 0.72
_________________________________________________________
Values predicted by thermal theory are more near to measured values.


Minimum Ignition
Energy
Minimum ignition energy E
min
is the minimum energy to be imparted by
a spark (in milli Joules) so as to cause a stable combustion wave
capable of self propagation.
The electric spark can be either a capacitive or inductive and is a very
hot and fast discharging source (10
-8
to 10
-7
sec). Chances of
ignition of the mixture depend on the following factors:
(i) Ignition energy supplied
(ii) Ignition limits (flammability limits) of the mixture,
(iii) Flame quenching possibilities
(iv) Ignition temperature of the mixture ( i.e., the lowest temperature at
which heat loss from the gas is over-balanced by the heat generated
by the chemical reaction)
(v) Duration of contact of the source with the mixture.
E
min
can be measured by the arrangement shown in the diagram.
Capacitance can be varied from 100 to 5000 F in the capacitance
bank.


Set up to determine minimum Ignition Energy
for Mixtures
Desired electrode gap is set and the capacitors are slowly charged.
Voltage V at which spark occurs is noted. If no flame occurs,
capacitance is increased in steps, until the critical capacitance C at
which ignition occurs is found.
E
min
= C V
2
, where V is the voltage value at
the threshold of ignition.
Similarly, if inductive spark is used, E
min
= Li
2
, where, L is the
inductance (Henry) and i is the current (Amp) in the circuit.
Factors affecting Min. Ign. Energy
1. Electrode Gap:
Too small gaps require higher energy due to quenching effect and due
to lack of mixture quantity in the path of discharge. For flanged
electrodes this increase is very sharp below 2mm gap, which
correspond to quenching distance d
q
. For larger gaps E
min
is
fairly constant. When the gap is very large, spark becomes less
intense since its energy is distributed over a longer spark length,
which increases E
min
.
Too high a spark energy will increase turbulence and hence quenching
effects which fails to generate a flame. --------------
Free electrode tips
Glass flanged tips
0 1 2 3 4

16



4
12
8
E
min

(mj)
Elecrode gap (mm)
G
l
a
s
s

f
l
a
n
g
e
d

t
i
p
s

E
min

(mj)
Electrode gap (mm)
100

10

1.0

0.1
2 2.5 3
Ignition
region
Effect of Pressure on Min. Ign. Energy
at Different Electrode Gaps
2. Pressure:
As the pressure decreases, the Min.ign energy requirement increases
since quantity of mixture available in the gap to support the flame
becomes less at reduced pressure.
Similarly at any given pressure, once the electrode gap exceeds the
quenching distance, the mini. Ign. energy remains fairly constant as
the gap increases, but increases at very large gaps due to weaker
spark intensity.
3. Effect of dilution (Oxygen concentration):
Min. ign. energy increases with dilution by inert gases. This is due to
reduction in oxygen concentration due to dilution. The effect is
minimum with Argon. Next comes nitrogen and CO
2
. Maximum
effect is seen with Helium. Though all these diluents are inert, the
difference in their effect on min. ign. energy is due to the difference
in their transport and thermal properties such as specific heat,
thermal conductivity, diffusion coefficient etc.
Effect of dilution on Min.Ign Energy
at different pressures
4. Inert gas dilution:
O
2
/ (O
2
+ Inert gas)=0.21
He
CO
2
N
2
A
E
min
(mJ)
with H
2
as fuel
Lean 1.0 rich
0.01
0.02
0.04
0.045
The effect of inert gases in increasing the min. ign. energy, increases
in the order of A,N
2
,CO
2
and He, which is chiefly attributable to (i)
high thermal conductivity of He (ii) larger specific heat of CO
2
relative
to N
2
. The other transport properties too have some small effects.
5. Mixture strength:
0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
2.5
2.0
1.5
1.0
0.5
0

E
min

(mJ)
Pr = 1 atm
CH
4 C
3
H
8
C
7
H
16
The minimum energy value is fairly the same for all the three hydrocarbons,
apprx. 0.2 mJ., but the mixture strength at which it occurs goes on increasing
as the number of Carbon atoms in the fuel increases. This is presumed to be
due to the diffusion processes giving rise to non-isotropic flame propagation
with heavier hydrocarbons.
Methods of Ignition
1. Spark Ignition: Most commonly used as it is very quick.
2. Ignition by hot wires: If electrically heated, E = i
2
Rt, where i is
the current, R is the resistance and t is the time period required.
This is a relatively slow process requiring more contact time.
3. Ignition by large heated bodies: Due to high heat capacity a hot
solid bar maintains a constant surface temperature. Ignition is
more reliable due to large surface contact area.
4. Ignition of high velocity streams by hot bodies: The process
involves igniting and stabilizing the flame. Large spheres or
cylinders internally electrically heated can ignite the flame and
stabilize the flame in the wake of the flow stream.
5. Ignition by pilot flames: Heat energy is continuously provided by
a small pilot flame. Governing factors are:

(a) Temp. of pilot flame: Higher the temperature, quicker the ignition.
(b) Size of the flame: Larger flame height requires shorter period of
contact for ignition.
(c) Duration of contact: Depends on flame size and mixture strength,
being minimum for a mixture slightly richer than stoichiometric.
(d) Mixture strength: Slightly richer than stoichiometric strength will
give quickest ignition.
(e) Pressure of the mixture: Higher pressure requires shorter period of
contact.
(f) Diluents in the mixture: They reduce the ignitability.

6. Ignition by hot air (or gas): Fuel gas is quickly mixed in hot air (in
about 6 ms) and ignition occurs after the elapse of ignition lag.
Influencing factors are (i) mixing process (ii) Physico-chemical
nature of the fuel (iii) Temp and pressure of the hot air (iv) Fuel
concentration (v) Thermal cracking of fuel.
7. Ignition by adiabatic compression: Fuel is injected in a finely
atomized form into the hot compressed air. Auto ignition takes
place after the elapse of delay period. Method is used in diesel
engines. Influencing factors are (i) Cetane number of the fuel (ii)
Temperature Pressure and Density of air (iii) Mixing process (iv)
Fuel injection characteristics.
8. Ignition by shock waves: A shock wave is generated within a
tube containing an ignitable mixture, by rupturing a diaphragm
across a pressure differential which travels with supersonic
velocity. It creates a pressure and temperature jump when it gets
reflected at the tube end. This temperature jump will ignite the
mixture. The time interval between the point of reflection and point
of ignition (as sensed by a photocell) gives the ignition delay.
Some calculated theoretical results are given below:
Ratio of pressures Shock velocity (m/s) Temp behind shock C Adiabatic compr Temp.C
(given for comparison)
2 452 62.8 57.2
10 978 432.2 242.2
100 3021 3587.7 676.6
1000 10122 18813.7 1437.7
DROPLET
COMBUSTION
Model of single droplet combustion
do
f
Tg, g
Ts
Tf
Liquid
droplet
Vapour
envelope
Oxidiser gas
(air)
Burning time of the droplet increases with surface area and fuel
density, but decreases with the surrounding gas (air) density,
diffusion rate between vapour and air and the rate of mass transfer
from the liquid droplet.

Thus burning time t
b
(sec) = (d
o
2
.
f
) / [ 8 log
e
(1+B). ], where,
d
o
= initial dia. of the droplet (cm) or [m]

f
= fuel density, (g/cc) or [ kg/m
3
]
(gamma) = D.
g
= Exchange coeft (g/cm.s) or [ kg/m.s]
D = diffusion coeft. - vapour to air (cm
2
/s) or [ m
2
/s]

g
= gas density, (g/cc) or [ kg/ m
3
]

B = Transfer number, which represents the rate of mass transfer from
the droplet, which in turn increases with temp.difference (T
g
-T
f
),
heating value of the fuel, oxygen concentration and decreases with
increase in latent heat and boiling point of the fuel.



Transfer number:
For liquid droplets :
B = [ (H. m
O
2
,g
) / r + C
p
(T
g
T
s
) ] / Q where,
H = heat of combustion of the fuel (calorific value) (cal/g) or [ kJ/kg ]
m
O
2
,g
= mass concentration of oxygen in the gas
= 1.0 if the oxidiser gas is only oxygen,
= 0.232 if the gas is air
r = mass ratio of oxygen to fuel in the chemical reaction equation
C
p
= Sp. heat of gases at const pressure (Cal/gC) or [ kJ/kg.K]
T
g
= gas temp. (C)
T
s
= droplet surface temp. (C) which is always boiling point of fuel.
Q = Heat required to vaporize unit mass of fuel = Latent heat of fuel if
the droplet is at boiling point (Cal/g) or [ kJ/kg ]

(Note: Set of SI units given in Sq. brackets will also give dimensional consistency)

For Solid fuels :
T
s
will reach T
g
.
B = m
O
2
,g
/ r, where r = 16/12 for the reaction C + O = CO
and r = 32/12 for the reaction C + O
2
= CO
2


Combustion of cluster of droplets
In a cluster of droplets, as in diesel engine or gas turbine combustion,
burned gases produced from the combustion of one droplet will
affect the combustion of the neighboring droplet due to oxygen
dilution by inert products of combustion. Hence modeling for cluster
of droplets becomes more involved and single droplet model cannot
be directly applied. Particularly when gas turbulence is present, only
empirical models are possible which have to be validated with
experimentally measured results.

COMBUSTION IN
PRACTICAL
SYSTEMS

COMBUSTION OF SOLID COAL

Traveling chain grate over feed stoker
Combustion in Over feed fuel bed
Diagramatic cross section of over feed fuel bed
Primary air
Overfeed Coal Combustion Scheme
Typical under feed stoker
Underfeed Coal Combustion Scheme
Cyclone Furnace for
Pulverized Coal Combustion
The Cyclone Furnace
Oil Burner for Power Plants
Pressure Jet Oil Burner
Steam atomized Oil Burner
Atmospheric Gas Burner
Gas Turbine Combustors
Principal requirements are:
1. Low weight and small frontal area
2. Low pressure loss
3. Stable and efficient combustion over the operating flight altitudes
and speeds
4. Reliability, serviceability and reasonably long life
5. Thorough mixing of hot and cold fluids to give a final temperature
sustainable by the blades without warping or mechanical damage
A compromise will have to be sought in the design since some of the
requirements are conflicting. E.g., large ducts and pipes reduce
pressure drop but increase size, weight and frontal area. Addition
of diluting air is a thermodynamic loss, but is needed to prevent
mechanical damage to the blades.
A/F ratio may vary from 50:1 to 150:1, while primary air (25% of total
air), is properly controlled with load to avoid rich or lean blow out.
Straight through combustion system
(Can or Tubular type design)
Ign.zone Reaction zone Quenching &
mixing zone
Compressor
Turbine
Fixed blades
Moving blades
Exh. Jet
Ign
torch
Primary
air
Secondary
dilution air
Shaft cL
Fuel
line
Nozzle
Return flow combustion system
(Industrial type design)
Compressed air
from compressor
Turbine
Shaft cL
Nozzle
Exh. Jet
Fixed blades

Moving blades
mixing zone reaction Ign
zone zone
Fuel line
Ign
torch
Primary air
Secondary air
Annular combustion system
(used in Aircrafts)
Fuel line
C.C.
C.C.
Compressor
inlet
Nozzle
Ign Reaction Quenching and
zone zone mixing zone
Gas
Turbine
Exh.
Jet
Fixed blades
Moving blades
Turbo-compressor shaft
Comparison of return flow and straight through combustors
Return flow Straight through
-------------------------------------------------------------------------------------------
1. --------- Requires a longer shaft involving a third
bearing and a flexible coupling.
2. Permits automatic compensation of Requires expansion joints to allow
expn without any special joints. differential expansion.
3. Turbine stator and rotor blades are High blade temperature may exist due to
shielded from high temp flame ra- direct flame radiation requiring special
diation. cooling.
4. Involves two 180 bends in the path Involves no bends and hence less press-
of the gas and hence higher pr loss. ure loss.
5. ---------- Allows a greater cross sectional area for
combustion within a given overall dia.
6. Larger frontal area. ---------
7. ---------- Simpler to manufacture.
8. Easier assembly and dissembly. ---------
9. Chances of uneven air distribution. Provides more even air distribution.
----------------------------------------------------------------------------------------------------

In both return flow and straight through systems, several combustion
chambers are symmetrically disposed around the turbine inlet. The
length to dia ratio of C.C.s may vary from 2.25 to 5 and the heat
release rates may vary from 50 to 130 x10
6
kJ/m
3
Hr.
Annular combustion chamber is more compact than multi-cell burner
arrangement with a smaller overall dia (frontal area). Both single or
multiple ignition points can be used to initiate combustion. Uniform
mixing and cooling is more difficult to accomplish and also it is
difficult to vary primary and secondary air as precisely as is possible
with other unitary designs. Chances of serious warpage of the
combustion chamber exists due to the above.
Flame stability can be achieved by creating a recirculation zone in the
flow path after the primary air entrance by any of the techniques
discussed earlier.
To increase the jet thrust, an after burner is placed in the exit stream of
the gases where extra fuel is burned using the excess air present.
Combustion in rocket motors

Rockets work in space where there is no air available to supply the
required oxidant. Hence rockets have to carry fuels and oxidants on
board. These are burned in a simple combustion chamber at an
enormous rate to produce the required jet thrust through the exhaust
nozzle at supersonic flow velocities. Despite the simplicity in its
principle, the development of a reliable rocket jet-propulsion system
encounters several perplexing problems. The system should be light
in weight, the rocket motor (rocket engine) must be capable of
sustained operation in contact with gases at above 20 bar pressure
and 2800C. Hence major problems encountered are choice of
material, techniques of construction, method of propellant
admission, ignition for smooth start up, thrust control, cooling
methods, control of combustion instabilities and design of reliable
electronic remote control systems.
Bi-propellant Rocket Motor system
Fuel
Oxidiser
Thrust
P
c
, T
c

Comb. Chamber
Exh.
Jet
Nozzle
Throat
The propellants employed may be a solid, two liquids (fuel + oxidiser)
or mono-propellants (materials containing adequate supply of
oxygen in their chemical composition.

Solid Propellant rocket motor system:





No cooling required since it is supposed to burn off after its period of
operation (45 to 80 sec). Used for projectiles, missiles, assisted take
off of air crafts etc.
Propellants used are mono-propellants like,
nitroglycerin(C
3
H
5
(ONO
2
)
3
), picric acid, TNT (tri-nitro toluene),
nitromethane etc.

Solid Propellant stick
Flexible liner to ensure uniform burning
Steel wall
Direction of burning
Exh.Jet Thrust
Bi-propellant liquid rocket propulsion
Remotely operated
propellant control valve
Fuel
tank
Oxidiser
tank
Pressure feed (using mech. pumps or high
pressure inert gas storage)
Propellant control


Injection

Combustion


Exhaust from nozzle
Rocket
motor
Liquid propellant systems can be operated for longer durations
depending on the quantity of propellant storage. Thrust control is
possible by remote control of propellant flow.
Propellant injection comprises several pairs of fuel and oxidant
streams impinging on each other as follows:
Arrangement of Injector
Oxidant jets
Fuel jets
Arrangement of jets
i) Like on like
ii) Shower head
iii) Impinging triplets
(Like-on-unlike is not much favoured due to possibility
of aerodynamic disturbance causing combustion
instability)
Fuel oxidiser combinations for bi-propellant
systems
Liquid Oxygen with..
Liquid hydrogen, Gasolene, Ethanol, Methanol, Hydrazine (N
2
H
4
),
Liquid Ammonia (NH
3
), UDMH (Unsymmetrical Di-Methyl Hydrazine:
(CH
3
)
2
N:NH
2

Nitric Acid(HNO
3
) with ..
Aniline (C
6
H
5
NH
2
), Furfuryl alcohol (C
4
H
3
OCH
2
OH), Monoethylaniline
(C
2
H
5
C
6
H
4
NH
2
)

Hydrogen Peroxide(H
2
O
2
) with ..
Ethanol, Methanol, Hydrazine, Ethylene Diamine (C
2
H
4
N
2
H
4
)

Ignition and Starting Methods for Rocket Motors
Ignition should be quick, since otherwise, large accumulation of
unburned propellants may cause chamber pressures far in excess
of design pressures when the combustion starts. If one of the
propellants is cryogenic liquid, it is usually chosen as the leader
since it prevents accumulation due to rapid evaporation.
Ignition methods:
1. Pyrotechnic device such as a large fire work, which is fired
electrically via a small priming charge providing a shower of
incandescent particles for a few seconds.
2. A spark discharge or a glow plug, either of which is effective only
at low flows and thus may require a pre-combustion chamber.
3. For hypergolic propellants (self igniting when come in contact) no
external source of ignition is necessary.
4. Initial addition of a spurt of hypergolic material via one of the main
propellant flows.
Rocket motor cooling
Cooling methods:
1. Suitable choice of material and thickness of the wall so as to
absorb the heat during the period of operation (used only in solid
propellant motors of short duration)
2. One of the propellants is circulated around the walls, called the
regenerative system.
3. High temperature resistant refractory material lining is used. This
is generally combined with method 2.
4. Film cooling can be effectively applied. A complete film of fuel is
formed over the inside wall of the chamber which by its evapora-
tion keeps the surface cool. In one German design, 7% of total
fuel was used for this purpose.
About 5% of heat liberated by combustion is dissipated through the
chamber and the nozzle walls, which is about 120 to 200 kJ/sec.

Combustion Instability in rocket motors
Low frequency (50 250 cps) Chugging:
This form of combustion instability appears to be connected with the
finite time which elapses between the injection of liquid propellants
and starting of combustion, i.e., the combustion delay. This is due to
the time required for the atomization, heating, ignition and burning
and is of the order of a few milliseconds. Because of this delay, the
adjustments in burning rate will cause a mass variation and hence
pressure fluctuation within the combustion chamber, which in turn,
causes changes in propellant inflow that lags behind it and so
oscillations may be set up.

The consequences of chugging is not usually disastrous and can be
controlled by throttling the propellant flow through a higher pressure
difference, thereby making it more insensitive to chamber pressure
variations.

High frequency (1000 to 2000 cps) Screaming:
The mechanism of screaming is not well understood. It is generally
agreed to be an acoustic disturbance of such a high frequency that
the propellant inflow is virtually unaffected. These oscillations are
generally tangential and correspond to a pressure wave moving to
and fro across a diameter or round and round the circumference of
the chamber. One plausible theory is that the circumferential (and to
some extent radial) gas velocities associated with the resonance
disturb the propellant droplets, thereby affecting the mixing and
combustion rates. This suggests that critical injection arrangements
such as impinging triplets which are easily disturbed by cross
currents should be avoided.
Chambers of large size are more prone to screaming, probably due to
reduced damping effect of friction at the walls. The results of
screaming are generally devastating, resulting in rapid failure of
thrust chamber on account of high rates of mixing, heat release and
heat transfer to the chamber walls.
PRACTICAL APPLICATIONS
OF COMBUSTION STUDY
SOME PRACTICAL APPLICATIONS OF COMBUSTION STUDIES
Premixed Flames: Domestic stoves, S. I. engines, Mine explosions
Diffusion Flames: Candle light, Reading lamps, Diesel engine
Flame Propagation Models: S.I. engines and Industrial burners
Turbulent flame Models: S.I. engines, Gas Turbine Combustion
Flammability Limits: Identification of fire hazards at coal mines, petrol
car garages, LPG kitchens with possible fuel leakages
Flame Quenching: Davy lamp, Prevention of fire spreading
Min.Ign.Energy: Design of Ign. system for SI engines and Gas lighters
Ignition Methods: I.C.Engines, Gas turbines, Rocket motors, Domestic
Gas Stoves, Industrial Furnaces
Flame Stability: Bunsen burner, Gas welding torch, Domestic burners
Flame Stability in High Speed Flow: Gas turbines, Rocket Motors
Droplet Combustion: Diesel engines, Gas turbines, Pulverized coal
Combustion systems
Basic Reaction Kinetics: Research on chemistry of reaction rates


Elements of Organic
Chemistry

Organic chemistry is the chemistry of compounds containing Carbon.
Hydrocarbons are compounds containing Carbon and Hydrogen and in
addition may also contain elements like N, O, S, P etc.
Carbon can combine with other atoms in a serial way, giving rise to
side chain, branched chain and ring structures.
Aliphatic compounds are those which contain only C & H with open
chain structure.
Aromatic compounds are those which have a ring structure.
Compounds of homologous series are those whose composition can be
represented by a general formula.
Homologous Series:
Alkanes (paraffins) : C
n
H
2n+2
CH
4
, C
2
H
6
,.. C
8
H
18
, C
16
H
34
All
carbon valences satisfied, hence the name-saturated hydrocarbons.
e.g., methane, ethane, propane, butane, pentane, hexane, heptane,
octane, nonane, decane, cetane (hexa decane), etc
Alkenes (Olefines) : C
n
H
2n
C
2
H
4
, C
3
H
6
, C
8
H
16
(Double bond)
e.g., ethene(ethylene), propene, butene, . etc.
Alkines: C
n
H
2n-2
C
2
H
2
, C
3
H
4
, C
4
H
6
C
8
H
14
(Triple bond)
e.g., Ethyne (acetylene), propyne, butyne etc.
Aromatic series: C
n
H
2n-6
C
6
H
6
, C
7
H
8
, C
8
H
10
(ring structure)
e.g., benzene, toluene, xylene etc.


-C-C-C-H -C-C=C -C C-C-
C
C C
C C
C
C
C C
C C
C
C
propane propene propyne benzene toluene
H H H
H
H H H
Hydrocarbon derivatives:
1. H atom or group of atoms is replaced by another atom: e.g., CH
3
I,
C
2
H
5
Cl where CH
3
,

C
2
H
5
are called Alkyl radicals R.
2. H atom is replaced by a hydroxyl group to give an alcohol. e.g.,
CH
3
OH, C
2
H
5
OH etc.
Compd General formula Functional group

Alcohol R - OH Hydroxyl group
Aldehydes R - C=O Aldehyde group
H
Ketones R - C- R Carbonyl group
O
Esters R - C-O-R Ester group
O
Acid R - C=O Carboxyl group
OH
Peroxide R - O-O-R Peroxide group
Isomers:
These are compounds having the same chemical formula, but different
chemical structure and hence different properties.

Normal Octane: C
8
H
18
. - C-C-C-C-C-C-C-C-
-C-
Iso-Octane : C
8
H
18
-C-C-C-C-C-
-C- -C-

Similarly, Isomers of HC derivatives:

Ethyl alcohol: C
2
H
6
O -C-C-O-

Dimethyl ether: C
2
H
6
O -C-O-C-


Some Commonly known Hydrocarbon Derivatives

Alcohols: CH
3
OH(Methanol), C
2
H
5
OH(Ethanol), C
4
H
9
OH(Butyl
alcohol), C
6
H
5
OH(Phenol)(carbolic acid)
Acids: HCOOH(formic acid), CH
3
COOH(Acetic acid)
Aldehydes: HCHO(formaldehyde), CH
3
CHO(acetaldehyde), C
6
H
5
CHO
(benzaldehyde)
Esters: HCOOCH
3
(methyl formate)
Ethers: (C
2
H
5
)
2
O(Diethyl ether), (C
6
H
5
)O(C
3
H
5
)(propyl phenyl ether)
Ketones: (CH
3
)
2
CO(acetone)(dimethyl ketone), (C
2
H
5
)CO(C
4
H
9
)(ethyl
butyl ketone)
Peroxides: HOOH = H
2
O
2
(hydrogen peroxide), R-O-O-R (organic
peroxides)
Amines: R-NH
2
Nitro alkyl compounds: R-NO
2

BASIC
REACTION KINETICS
Chemical Kinetics
Chemical kinetics is that branch of physical chemistry which deals with
the factor of reaction velocity in chemical processes. It seeks to
define the rate of reaction in terms of several possible variables
such as temperature, pressure, composition, state of agregation,
external energy sources and presence or absence of catalysts.
Rate of reaction:
It is measured by the rate of decrease of concentration of reactants or
by the rate of increase of concentration of products.
Rate = - dC/ dt , (mole/litre.sec) where C is the concentration of
the reactant under consideration at time t.
C = n/V (mole/litre) where n is the number of moles of the reactant
present in volume V.
Note: One Mole of a gas = Quantity of the gas whose wt numerically =
molecular weight. Volume occupied by 1 mole of any gas = 22.4
litres per gm.mole (or 22400 litres/ kmol) at NTP (273K & 1 atm.pr).

Molecularity of a reaction:
It is based on the number of molecules participating in a chemical
reaction.
1. Uni-molecular reaction (mostly decomposition reactions):
A Products e.g., Br
2
Br + Br
2. Bi-molecular reaction ( most common reaction):
A + B Products e.g., H
2
+ Br
2
2HBr
3. Tri-molecular reaction (very rare since ternary collisions are very
difficult to occur):
A + B + C Products e.g., 2NO + O
2
2NO
2
Note: In some cases when two atoms collide with each other the sum of the energy of reactions and
the K.E. of collision will be more than the dissociation energy of the formed diatomic molecule,
and hence in effect no reaction occurs. Such a reaction may be effected by using a third body
which mainly functions as an energy absorbent and keeps the product alive. The third body
can be any other molecule of inert gas or solid metal surface. In the case of two poly-atomic
molecules colliding with each other, a third body may not be necessary for the reaction, since
this energy of reaction is distributed among the various number of degrees of freedom
(translational, rotational, vibrational..) and is no longer concentrated in any one bond.
Law of mass action:
The rate of chemical reaction is proportional to the active masses (i.e.,
concentration) of the participants.
Thus, for the reaction A B, Rate r = - dC
A
/ dt is C
A
= k. C
A
Where, k = rate constant or specific reaction rate.
For the reaction 2H
2
+ O
2
2H
2
O
Rate r = k. C
H2
. C
H2
. C
O2
= k. C
H2
2
. C
O2

Similarly, for the reaction aA + bB + Products,
Rate r = k. C
A
a
. C
B
b
. .

Order of the reaction:
Order indicates the manner in which the rate of reaction varies with the
concentration of the reacting substance.
Thus, the above reaction is said to be of the a
th
order w.r.t. A, b
th
order
w.r.t. B and so on. The overall order of the above reaction is a + b +

In complex reactions involving a number of steps, the rate can be a
complex function of concentrations involving terms in the denominator
also. The order of reaction is strictly an experimental quantity and
merely provides information about the way in which the rate depends
on concentration.
In complex reactions molecularity may not be equal to the order of the
reaction. They are the same only for elementary reactions.
Rate Constant k :
Consider the reaction aA + bB + . . . Products
Reaction rate = k. C
A
a
. C
B
b
. .
Or, k = Rate / C
A
a
. C
B
b
. . (mole/litre.sec) / (mole/litre)
n

mole
(1-n)
.litre
(n-1)
.sec
-1
Where n = a + b + . . . = overall order.
Thus for 1
st
order reaction k will be in sec
-1
For 2
nd
order reaction k will be in litre.mole
-1
.sec
-1


Representation of 1
st
order reaction
A Products
Rate of reaction = -dC
A
/dt where C
A
is the conc. of A at time t.
Therefore, -dC
A
/dt = k C
A
Integrating,
- dC
A
/C
A
= k dt or, - lnC
A
= k t + const
Or, log C
A
= -kt / 2.303 + Const
If C
A
= a = initial conc. at t = 0, we get Const = log a.
Substituting, we get log C
A
= log (a-x) = -kt / 2.303 + log a
Or, k = (2.303/ t). log [a/(a-x)], where x is the no. of moles reacted at
time t.
Half life of a reaction is the time required to reduce the concentration
to half its initial value. Therefore by putting x=a/2,
we get Half life of 1
st
order reaction t

= 0.693/k (sec)


logCA
t
a
a/2
t
1/2
c
o
n
c

time
Representation of 2
nd
order reaction
A + B Products
Rate of reaction = -dC
A
/dt = -dC
B/
dt = kC
A
.C
B
, from the law of
mass action.
Let a be the initial conc of A, b initial conc of B at t = 0.
Then at time t, C
A
= a x and C
B
= b x, where x is the no. of moles
of A or B reacted at time t.
- d(a-x)/dt = dx/dt = k(a-x).(b-x)
Case(i): Equal initial concentrations: a = b
dx/dt = k(a-x)
2
Integrating,
dx/(a-x)
2
= k dt from which, 1/(a-x) = kt + C
At t = 0, x = 0. Hence C = 1/a
Therefore, 1/(a-x) = kt + 1/a
Hence, k = x / [t.a(a-x)] ( litre.mol
-1
.sec
-1
)
Putting, x = a/2, we get Half life = t

= 1 /(k.a)
C
A
t
hyperbolic
1/C
A
t
2
nd
order reaction with unequal initial concentrations:
k = {2.303 / [t.(a-b)] }. log [b(a-x)/ a(b-x)]

3
rd
order reaction with equal initial conc. of all
three reactants:
A + B + C Products
We obtain,
1/C
A
2
= 2kt + 1/a
2
from which
k = (2ax x
2
) / [2 t a
2
(a x)
2
]

Half life of n
th
order reaction with equal initial conc. of
all reactants:
t

= (2
n-1
-1) / [(n-1)k.a
n-1
]
Slope=2k 1/C
A
2
t
Arrhenius Rate Equation
Rate constant is independent of the concentration of reactants. All
other factors that affect the reaction rate, in general, also affect the rate
constant.
The temperature dependence of k was studied by Arrhenius (in 1889)
who proposed the relationship
Reaction Rate = Z.P.e
Ea/RT
, where Z is the number of
collisions/sec, P is the Steric factor, Ea is the activation energy
(cal / gm.mole or kJ / kg.mole), R is the Universal gas constant (8.314
kJ/ kmol.K), T is the temperature in K.
But, Rate = k.N
1
.N
2
where N
1
and N
2
are concentrations of the two
reactants in the bi-molecular reaction (from law of mass action).
Therefore, k = [(Z.P) / (N
1
.N
2
)].e
Ea/RT

For hydrocarbons, Ea 40,000 cal/gm.mole = 1,67,440 kJ/ kmole.
Meaning of Steric factor:
Collision geometry unfavorable:

Collision geometry favorable:

The physical concept of rate equation is that successful collisions
between two reaction partners result if the two colliding molecules
possess in a specific degree of freedom an energy equal to or more
than the activation energy Ea, and if the geometry of collision (line of
approach of the colliding molecules) is favorable for their interaction.
The latter condition is expressed as Steric factor, whose value is
undefined by theory, except that it should be < 1. The Arrhenius
factor e
Ea/RT
represents the fraction of collisions involving
molecules possessing an energy more than the activation energy.
When the temp. is increased the velocity and hence the K.E.of the
molecule increases and therefore the rate constant increases.

H
I
No Reaction
H H
I I
Reaction occurs: 2HI H
2
+ I
2
Experimental determination of Activation Energy
Determine the rate constant values for a reaction at two different
temperatures. From these values Ea for this temperature range can be
worked out.
k = A. e
Ea/RT
ln k = -Ea/RT + ln A
Or, log k = (-Ea/RT)/2.303 + log A

For the given temp range of T
1
to T
2
,
log k
1
= (-Ea/RT
1
)/2.303 + log A and log k
2
= (-Ea/RT
2
)/2.303 + log A
we can show that
log(k
1
/k
2
) = (Ea / 2.303R) . [(T
1
-T
2
)/T
1
T
2
]
from which Ea can be worked out for the temp range T
1
to T
2
Log k
1/T
Concept of Activated Complex
The classical collision theory has been supplanted by a more
sophisticated rate theory based on the concept of activated collision
complexes and their statistics. The collision theory equations remain
valid for reactions of atoms and simple molecules. However for large
molecules this theory becomes grossly inadequate as the Steric
factor becomes unrealistically high or low.
Activated Complex Theory:
This theory considers an intermediate
configuration of atoms with the highest
energy level on the reaction path way.
The concept has enabled to develop
more satisfactory equations to evaluate
reaction rates in complex reactions.
Reactants Activ.complexProducts


A
B
C
Activated complex
(Transition state)
Reactant
Product
Ea
H
Ha
Reaction coordinate
E
n
e
r
g
y

HI + HI H - H H
2
+ I
2
(slow) I - I (fast)
AB: energy required for activation
BC: energy released when activated
complex breaks down into products
H is the Heating value
Study of fast reactions
All chemical reactions are studied at constant temperature to eliminate
the variable temperature effect on the reaction rates.
Slow reactions:
Static method: Reactants are introduced into a bulb (reaction vessel)
maintained at the desired temperature. Composition of samples are
determined at intervals either directly by chemical analysis or indirectly
by pressure measurements (for reactions involving change in total
number of moles).
Dynamic method: Sample tubes are attached at the entrance and exit of
the reaction vessel to measure the concentration changes. The
residence time in the reaction vessel is calculated by knowing the flow
rate and the vessel volume. Experiment is repeated for various flow
rates.
Chemical analysis of sampled gas can be done using (i) Mass spectro-
scopy (ii) Chromatography or (iii) Spectrophotometers.

Fast Reactions:
The static and dynamic methods described earlier can be used only for
slow reactions with half life of the order of at least a few minutes. For
faster reactions continuous recording of variables (concentration,
pressure, radiation etc) is required using oscillographs, spectrophoto
-meters etc with sophisticated electronic instrumentation.
Stopped flow technique:
In this method, the flow into the reaction vessel is suddenly stopped
and spectrophotometric measurements of concentration are
recorded continuously.
Study of fast reactions require techniques of instantaneous starting of
the reactions for counting the time to follow the reaction velocity.
Following techniques have been developed for various reactions:
Relaxation method (1960s) :
The reaction is first allowed to go to equilibrium. It is then instantly
disturbed by pressure jump or temp. jump technique using large
currents. The approach to equilibrium (relaxation time) is then
followed by high speed techniques.

Shock tube technique: (1960s)
A supersonic shock wave is generated by breaking a diaphragm
through a shock pressure ratio. As the wave traverses an element of
gas it instantly raises it to high temperature and reaction occurs in
and behind the shock front. The course of reaction is followed by
fast techniques.
Flash Photolysis: (1956)
A light flash of very high intensity and very short duration (1s) is
produced in the neighbourhood of the reaction vessel. Under
suitable conditions this will produce atoms, free radicals and excited
species in the system which will initiate further reactions and can be
followed by spectroscopic means. This method is also known as
kinetic spectroscopy and is used for the study of Cl
2
+ H
2
reaction.
Reactions in molecular beams:
It is a recently developed technique in which mono-energetic molecular
beams are produced. By allowing two molecular beams impinge on
each other it has been possible to study the kinetics of bi-molecular
reactions such as K + HBr KBr + H.
Summary of Fast Reaction Study Techniques
Method Range of half life (sec)

1. Conventional 10
2
- 10
8
(3.2 yr)

2. Flow 10
-3
- 10
2
3. Relaxation method:
Pr. Jump 10
-6
- 1
Temp. Jump 10
-7
- 1
Field Pulse 10
-10
- 10
-4
4. Shock Tubes 10
-9
- 10
-3

5. Kinetic Spectroscopy 10
-15
- 10
-10
REFERENCES
1. Kenneth Wark Jr., Thermodynamics, 5
th
Ed.,Mc Graw Hill, 1989.
2. P.K.Nag, Engineering Thermodynamics, 3
rd
Ed.,TMH., 2005.
3. S.P.Sharma and Chander Mohan, Fuels and Combustion, TMH.,
1984.
4. Stephen R.Turns, An Introduction to Combustion (Concepts and
Applications), 2
nd
Ed., Mc Graw Hill, 2000.
5. H.N.Gupta, Fundamentals of Internal Combustion Engines,
Prentice Hall, EEE Edition, 2006.
6. M.J.Zucrow, Principles of Jet Propulsion and Rocket Systems,
John Wiley.
7. B.Lewis and G.von Elbe, Combustion, Flames and Explosion of
Gases, Academic Press Inc., NY, 1961.

CHAIN REACTION AND
COOL FLAMES