INDEX

FLAMES
Flame
Types of Flames
A-Stationary Flames
1-Premixed Flames
2-Diffusion Flames
B-Explosion Flames
Definitions:
1- Flame Front
2- Ignition Temperature
3- Flame Speed
4- Flame Stability
5- Flash-back
6- Blow-Off
7- Yellow Tips
Flammability limits
Flame Stability
-Flame Propagation
A- Stationary Flames
Theories of Flame Propagation
Theories of Laminar Flame Propagation
1- Theories based on thermal effect
a-Mallard-le Chatelier
b- General Case
SEMENOV solution for Flame Speed
Solution by Steve Turns
Experimental results:
Laminar flame speeds:
B- Flame Quenching
Effect of walls on flame structure
1-Thermal theory
2-Diffusion theory
Quench Distance (zone)
1. Thermal theory:
a. Work of R. Friedmen
b. Work of Potter and Berlad
c. Work of Von Karman
d. Work of Kurt Wohl
2. Diffusion theory-laminar flames
Work of Simon and Bells
Factors affecting flame quenching
1. Geometry of quenching surface
2. Fuel type
3. Inert diluents
4. Temperature
5. Pressure
6. Oxygen concentration

B-Explosion Flames
Gas Explosions
Explosion
- Deflagration
- Detonation
Mathematical treatment:
The Rankine-Hugoniot Curve:
Mathematical Solutions:
MathCad program :
Mitigation
Mixing
Helium injection
Deliberate Ignition
Recombiners
Venting
Inerting
Pre-Inerting
Partial Pre-Inerting
Post-Inerting
Halon Inerting
Water Fog and Foams
Sprays
Combustibility of Flammable mixtures in containment.
Flammability limits and correlation law
7-b. FLAMES
Flame may be visualized as gas rendered luminous by the liberation of chemical energy.
Flame front is the surface or area between the luminous region and the dark region of
unburned gas, which exists in all combustion reactions in the gaseous phase. Since the gases
may not become luminous instantly, it is expedient to visualize the burning zone as consisting
of a luminous zone and a reaction zone. Ignition and most of the oxidation occur in the
reaction zone. Completion of burning and emission of light take place in the luminous zone.
The continuance of luminosity, called after burning, is evident in various types of
combustion, especially in spark-ignition engines.

7-b-1.Types of Flames
A-Stationary Flames
Stationary flame may be defined as one in which a stream of combustible material flows
through a flame front maintained in a fixed position by some mechanical device usually
called a burner, flame is more or less stationary in space. Stationary flames can be classified
on the basis of whether or not part of their air required for combustion of the gas is mixed
with it before it emerges from the port.

1-Premixed Flames
Fuel is premixed with air before the combustion area. Flames of almost all domestic gas
appliances belong to this class, and also many laboratory burners, industrial and special
purpose burners, blow torches, welding torches...etc, in which the fuel gas is mixed with a
part or all of the air required for combustion before it emerges from the port. any of these
burners use part of the energy of the gas supplied to them under pressure to inject or inspirit
this primary air and assist in the mixing. Others have both gas and air supplied under
pressure, and the mixture is controlled by means of valves.

2-Diffusion Flames
Fuel and air enter the combustion area separately. Diffusion flames are all that flames in
which the fuel gases emerges from the burner as and when it becomes mixed with a sufficient
quantity of air. Such flames range from candle, wick lamp, gasoline flare. etc. In all these, the
process of liberating heat is limited in speed by the rate at which mixing take place between
the gas and air. The surface must extend itself until all the fuel gas has made contact with the
air required to burn it. In some, mechanical mixing plays a relatively important part. In
blowpipes and blast-lamp mixing is accelerated by forcing a jet of air through the emerging
gas.

B-Explosion Flames
Explosive burning occurs in homogeneous mixtures of fuel and air, and the flame front
progresses rapidly through the mixture.
1-Constant pressure
2-Constant volume
Detonation is a special type of explosion characterized by a tremendously increased reaction
rate accompanied by an ultra-high velocity percussion wave and an abnormal rate of pressure
rise.

Definitions:
1- Flame Front
The flame front is a zone of intense chemical reactions accompanied by the evolution of
thermal energy and the formation of products from the reacting mixture. There exist steep
gradients of temperature and concentrations from the flame to the unburned mixture. The
flame front is usually divided into two parts, the preheating zone and the reaction zone.
Ignition and most of the oxidation occur in the reaction zone. The preheating zone starts at the
beginning of the temperature rise and ends at the inflection point, where d2T/dx2=0. In this
region the temperature curve is convex towards the x-axis, d2T/dx2 > 0 , which means that the
gas molecules gain heat by conduction from the hotter molecules down streams faster than
they lose to the cooler ones upstream. The temperature continues to increase rapidly in the
reaction zone due to the reactions until the equilibrium flame temperature is reached. The
luminous part of the flame is due to the excitation of certain C-H groups which radiates heat
with some wave lengths in the visible regions. There are little chemical reactions before the
luminous zone. Calculations of Friedman and Burke showed that only 14% of the heat
released occurs before the luminous zone is reached. For a certain flame, the amount of heat
conducted to the cooler molecules is a function of the amount of heat liberated in the reaction
and the transport properties of the gases.

2- Ignition Temperature
When the unburned fuel air mixture reaches certain state that allows the initiation of chemical
reaction, the flame front propagates in the mixture and the stored energy is released in the
form of thermal energy. That state implies that the mixture reached a certain temperature
(called the ignition temperature), and some radicals and active molecules (e.g. O, H, OH),
diffused into the next unburned region to initiate a series of chemical reactions.

3- Flame Speed
Flame speed is expressed in terms of volume of combustible mixture per second divided by
the area of the flame surface. Both the actual integrated area of the flame surface and the area
of the geometrical cone having the port as a base are used. The cone may also be defined by
the area of the burner port and the angle.

4- Flame Stability
The flame is stable as long as it remains in space at a certain distance from the burner tip. The
limits of the stable range of operation are evidenced by the flame flashing back inside the port
at one extreme and being blown off the port by the stream of mixture at the other. Whether
the flame operates near one of these limits or the other depends on the relative magnitude of
the flame speed, and the velocity of flow of the mixture under the varied conditions of use.

5- Flash-back
At lower mixture velocity and higher percentage of primary air, flashback occurs as burning
velocity exceeds and overcomes the mixture velocity and the flame tends to propagate inside
the port.

6- Blow-Off
At higher mixture velocity, the flame is pushed back. As the mixture velocity exceeds the
burning the velocity blow-off occurs and the flame would be separated from the burner tip.

7- Yellow Tips
At low primary air, mixture is rich in fuel and turns to be yellow.

7-b-2. Flammability limits

Flame propagates through mixtures of fuel and air only within a range of mixture strength.
The lower limit < 1.0 is considered the leanest mixture that will allow steady flame
propagation, while the upper limit >1.0 represents the richest mixture. Flammability limits
are frequently quoted as percent fuel by volume in the mixture, or as a percentage of the
stoichiometric fuel required. = (F/A) / (F/A)st
 Table (7-b-1) Ignition limits of fuel gases in air at 20 oC
Fuel Flammability limits
min max (A/F)st
Acetylene C2H2 0.19 13.3
Carbon Monoxide CO 0.34 6.76 2.46
Ethane C2H6 0.5 2.72 16
Ethylene C2H4 0.41 >6.1 14.8
Hydrogen H2 0.14 2.54 34.5
Methane CH4 0.46 1.64 17.2
n-Octane C8H8 0.51 4.25 15.1
Propane C3H8 0.51 2.83 15.6

Table (7-b-2) Ignition limits of fuel gases in air and nitrogen

Fuel gas Ignition limit
Lower Upper
% by volume % by volume
Hydrogen 4.1 74.0
Carbon monoxide 12.5 74.0
Methane 5.3 13.9
Ethane 3.1 12.5
Propane 2.4 9.5
n-butane 1.9 8.4
Benzene 1.4 7.1

Figure (7-b-1): Ignition limits of fuel gases in air and nitrogen

 Figure (7-b-2): Ignition limits of fuel gases in air and carbon dioxide

7-b-3. Flame Stability

Flame stability limits
Starting with yellow flame, adding air to the mixture increases the flame speed and also the
velocity of flow. Increasing the flame speed tends towards flashback. Increasing mixture
velocity tends towards blow-off. With further addition of air stable operation continues with
both limits approaching each other. Further increase tends to blow-off the flame. There is no
definite relation between flame speed and average mixture velocity within the limits of stable
operation.

Figure (7-b-3): Effect of Primary air on flame stability

7-b-4. Flame Propagation

Flame propagation is an extremely important natural phenomenon, yet the theory of flame
structure has been very little developed. The difficulties in quantitative theoretical prediction
of the structure of any flame are the fact that very little of the necessary data are available for
any actual flame. These data are the rates of all the reactions occurring in the flame and their
dependence on temperature and concentration, and also the heat conduction and diffusion
constants of all the components of the mixture. Besides, the mathematical problem when
formulated is a difficult one for either analytical or numerical solution.

B- Stationary Flames
Theories of Flame Propagation
Due to the difficulties in solving the equations describing the chemical reactions along with
the energy equations and molecular diffusion dynamics, besides, the need to study the effect
of some factors on the speed of flame propagation, some simplified theories has been
proposed to handle a one dimensional flame propagation. Some theories showed the effect of
heat transfer to initiate ignition, other theories showed the effect of radical diffusion initiate
the chain of chemical reactions.
The published theories of laminar flame propagation are classified as:
-Comprehensive theory
-Thermal theory
-Diffusion theory

Comprehensive Theory:
In the comprehensive theories, an attempt is made to obtain a complete description of the
flame including expressions for the mass transport coefficients and concentrations of all
chemical species as a function of temperature and distance. Both diffusion of active particles
and heat conduction are considered important and necessary for the flame propagation. In the
thermal theory, the heat conducted back from the flame is regarded as sensitizing the
approaching gases so that these may join in the reaction when a suitability high temperature is
reached. The diffusion theory recognizes that some active species participate in the high
speed reaction are involved. It is assumed in this theory that the diffusion of such active
species into the unburned gas should be sufficient, both in number and rate to start many
reaction chains. In this case, the chemical process consists of a series of different reactions in
which intermediate products are formed in one step and destroyed in a succeeding step. These
intermediate products that help the reaction to completion are called chain carriers. The chain
carriers may be free atoms O,H .. or free radicals like OH, CHO, CH, ..etc. or some organic
compounds such as formaldehyde HCHO. A chain carrier is formed during the reaction and
instantly destroyed during the course of a chain reaction. The detection of the O-H radical in
the preheating zone by Gaydon and Wolfhard supported the diffusion theory for flame
propagation. Tanford and Pease, also supported the diffusion theory by assuming that H-
atoms diffuse from the burned gases into the reaction zone, where the rate is proportional to
the H-atom concentration. The calculations they made on the relation between rates of
diffusion, flame thickness and the flame speed, showed that the time of passage of the radicals
through the pre-heating zone is very much less than the induction period at the ignition
temperature. In the contrary, Minkoff and Tipper, mentioned that the concentration of H-
atoms, based initially on equilibrium values in the burned gas, could become much grater than
that caused by thermal dissociation.

Thermal Theory:
Although both heat and active particles must flow from the flame, and even though the
transfer of both matter and heat are probably essential features of the basic mechanism of
flame propagation, the transfer of heat is considered in this study as the most important factor.
The equations describing the flame propagation are the conservation of mass and energy
together with the boundary conditions.
The following assumptions were considered in order to make the equations amenable to
solution:
-Laminar flow
-No pressure gradients
-No change in physical properties or molecular weight due to the reactions.
-Temperature is a function of the axial co-ordinate only.
-No reactions in the porous plate.
-Heat released from the reaction is conducted by the gases to the heating zone.
Theories of Laminar Flame Propagation
1- Theories based on thermal effect

a-Mallard-le Chatelier

. .
- q M hu M hi
dT -
kA A V (h i hu )
dx
-
A V C p (Ti Tu )
dT Tb Ti
Assume
dx b
T Ti -
k b V C p (Ti Tu )
b
- k Tb Ti
V
C p b Ti Tu
The first law of thermodynamics applied to the open system shown is

b- General Case
Assumptions:
-Plane flame front.
-Constant reaction rate.
-Constant ignition temperature.
 .
qx hx
q``` A x q x x hx x
dT
qx - k A
dx
d
qx x qx qx x
dx
d
hx x hx hx x
dx
dT - . dT d dT
-kA A V C p T q``` A x -kA -k A x
dx dx dx dx
- d -
A V Cp T A V Cp T x
dx
. d 2T - dT
q``` A x -kA x A V Cp x
2 dx
dx
. d 2T - dT
q``` - k V Cp
dx 2 dx
- -
2
d T V C p dT 1 . V Cp 1
q``` 0 Take and
2 k dx k k k
dx
2 .
d T dT
q``` 0
dx 2 dx
q"' may be released in one of the forms:
1- Heat is released in the reaction zone with a constant value.
2- Heat is released in the reaction zone with a constant rate.
3- Heat is released in the reaction zone with a rate proportional to the
distance (x) according to the following relation
. x
q``` 1 - cos 2
L

4- Heat is released in the heating zone proportional to the distance (x) according to the
relation
.
q``` e x/L
SEMENOV solution for Flame Speed

Assuming constant heat release rate ( i.e Q = constant ) the general differential equation is :
Where d = width of the reaction zone: Dividing by (d. k)

d 2T dT .
q``` 0
dx 2 dx
The general solution is :
. .
x q``` q```
T C1 C2 e x
k 2
k
Where
.
q``` H n`
H Enthalpy of combustion (kJ/mole)
n` Rate of reaction (mole/volume. sec)
To solve for C1 & C 2 set up boundary conditions :
When x - T Tu x 0 T Ti
Region I : Heating Zone
d 2T dT
2 dx
dx
T C1 C2 e x
x - T Tu Tu C1 C2 e - C1
x 0 T Ti Ti Tu C2 e 0
C2 Ti - Tu
T Tu Ti - Tu e x I
Region II :
H n` H n`
T C`1 C2 e x x
k 2
k
H n`
C1 C`1
2
k
H n` AV
T C1 C2 e x x But : H n` d Cp (Tb - Tu )
k A
H n` V C p Tb - Tu
Tb - Tu
k dk d
Tb - Tu
T C1 C 2 e x x
d
Boundary conditions to region II
x 0 T Ti Ti C1 C 2
x d T Tb Tb C1 C2 e d Tb - Tu
Tu C1 C2 e d
Ti C2 C2 e d Tu - Ti C2 e d 1
Tu - Ti
C2
e d 1
Tu - Ti
C1 Tu e d
d
e 1
Substitute for C1 & C 2
Tu - Ti Tu - Ti x
T Tu e d e x Tb - Tu
d d d
e 1 e 1
dT dT
at x 0 ) I, x 0 ) II, x 0
dx dx
Region I :
T Tu Ti Tu e x
dT
)x 0 Ti Tu e x x 0 Ti Tu
dx
Region II :
dT Tb - Tu e x Tb - Tu Ti Tu
)x 0 Ti Tu
dx d d d d
e 1 e 1
Tb - Tu Ti Tu
Equate I & II Ti Tu
d d
e 1
let d
(Ti - Tu )
(Ti - Tu ) (Tb - Tu ) -
e 1
(Tb - Tu )
-
(Ti - Tu ) e 1
(Tb - Tu ) 1- e
(Ti - Tu )
(Ti - Tu )
Case A : Ti Tu , 1.0 , large
(Tb - Tu )
(Ti - Tu ) 1 1 k 1
(Tb - Tu ) d V Cp V
Where V average velocity in reacting zone
time mixture speed in reacting zone
k (Tb - Tu )
V
C p (Ti - Tu )
(Ti - Tu )
Case B : Ti Tb , 1.0
(Tb - Tu )
x2 x3
Consider e x 1 x ...........
2! 3!
2
-
e 1
2
2
1 e-
1 e- dividing by 1
2 2
(Ti - Tu )
1
(Tb - Tu ) 2
(Tb - Ti )
2 (Tb - Tu )
d (Tb - Ti ) V Cp V 2 k (Tb - Ti )
V
2 2 (Tb - Tu ) k 2 C p (Tb - Tu )

Laminar Flame Speed,

Solution by Steve Turns
Laminar flame speed is calculated from the following relation:
.
2 A/F 1 M F
SL
u
Where:
SL : Laminar Flame Speed
: Average Thermal Diffusivity
A/F : Air to Fuel Ratio
o
M F : Average Reaction Rate
u : Density of Unburned Mixture

Procedure for Calculation

For any hydrocarbon fuel burns with air, the general combustion formula for excess air is;
CxHy + a (O2+3.76 N2) x CO2 + y/2 H2O + 3.76 a N2 + (a-x-y/4) O2
Givens
1. Fuel composition.
2. Air to fuel mass ratio. (A/F)
3. Temperature of unburned mixture. (Tu)
4. Pressure of the reaction. (P)
5. Table [1, p 137]:
i) Pre-exponential factor. (A)
ii) Activation Temperature. (Ea/Ru)
iii) Concentration indices. (m,n)
6. Temperature of burned products. (Tb).
Calculation Steps
- Calculation of the mean temperature
1 1
Tm Tb Tu Tb
2 2
- Mass fraction of fuel in unburned mixture
Mass of fuel in reactants
YFu
(Mass of fuel Mass of air)reactants
1 12x 1y
YFu
1 12x 1y a(32 3.76 * 28)
- Mass fraction of oxygen in unburned mixture
Mass of oxygen in reactants
YO 2 u
(Mass of fuel Mass of air) reactants
a 32
YO 2 u
1 12x 1y a(32 3.76 * 28)
- Mass fraction of fuel in burned mixture
Mass of fuel in products
YFb
Total mass of products
YFb 0 (in our example)
- Mass fraction of oxygen in burned mixture
Mass of oxygen in products
YO2b
Total mass of products
y
a x * 32
4
YO2b
y y
x(12 32) (2 16) 3.76a(28) a x * 32
2 4
- Average mass fraction of fuel
1
YF YFu YFb
2
- Average mass fraction of oxygen
1
YO 2 YO 2 u YO 2 b
2
- Average density
P
(R = 287 J/kg.K for simplification)
R Tm
- Average reaction rate (kg/m3.s)
Ea m n
o
m n A R u Tm YF YO2
MF (12x 1y) e
(1000)m n 1
(12x 1y) 32
- Average thermal diffusivity
k Tb Tu
k, C p @ , u for air @ Tu
u Cp 2
- Laminar Flame Speed
o
2 A/F 1 M F
SL
u
Some Results (At Chemically Correct Mixture):

Fuel Calculated Flame Speed From Above Guiding Values

Procedure
C6H6 33.15
C3H8 41.14 44
C2H2 101.34 136
C2H6 39.04 43
C2H4 58.95 67
CH4 7 40
Flame speed is in cm/sec.

Details for Methane

CH4 + 2 (O2+3.76 N2) CO2 + 2 H2O + 7.52 N2
Givens
1. Fuel composition. CH4
2. Air to fuel mass ratio. A/F)cc = 17.16
3. Temperature of unburned mixture. Tu=300 K
4. Pressure of the reaction. P=1 bar
5. Reference: Turns, Table [1, p 137]:
i) Pre-exponential factor. A=1.3*108
ii) Activation Temperature. Ea/Ru = 24358
iii) Concentration indices. M=-0.3, n=1.3
6. Temperature of burned products. Tb = 2326
Calculation Steps
- Calculation of the mean temperature
1 1
Tm 2326 300 2326 1819.5 K
2 2
- Mass fraction of fuel in unburned mixture
 1 12 *1 1 * 4
YFu 0.0551
1 * 12 * 1 1 * 4 2 * (32 3.76 * 28)
- Mass fraction of oxygen in unburned mixture
2 * 32
YO 2 u 0.22026
1 12 *1 1 * 4 2 * (32 3.76 * 28)
- Mass fraction of fuel in burned mixture
YFb 0
- Mass fraction of oxygen in burned mixture
YO 2 b 0
- Average mass fraction of fuel
1
YF 0.0551 0 0.02755
2
- Average mass fraction of oxygen
1
YO 2 0.22026 0 0.11013
2
- Average density
105
0.19155 kg/m 3
287 * 1819.5
- Average reaction rate (kg/m3.s)
24358
.
0.3 1.3 1.3 * 108 1819.5
MF (12 * 1 1 * 4) 0.19155 e
(1000) 0.3 1.3 1
- 0.3 1.3
0.02755 0.11013
*
(12 * 1 1 * 4) 32
-2.59 kg/m 3sec
- Average thermal diffusivity
2326 300
k 8.4 * 10- 2 W/m.K, C p 1200 J/kg.K @ 1313 K
2
u 1.1614 kg/m 3 for air @ Tu 300 K
-2
8.4 * 10
6.0272 * 10-5
1.1614 * 1200
- Laminar Flame Speed
2 * 6.0272 *10-5 17.16 1 ( 2.59)
SL 7 cm/sec approximately
1.1614

.
2 A/F 1 M F
SL
u
Note: Calculated value for Methane flame speed differs from the measured value. Professor
Turns indicated that the above equation is not valid for all fuels.
Experimental results:

Laminar flame speeds:

Figure (7-b-4): Effect of mixture ratio on flame speed

Figure (7-b-5): Effect of primary air on flame speed

 Figure (7-b-6):

B- Flame Quenching,[A]
Effect of walls on flame structure
The flame front is usually divided into two parts, the pre-heating zone and the reactions zone.
Ignition and most of the oxidation occur in the reaction zone. The pre-heating zone starts at
the beginning of the temperature rise and ends at the inflection point where:
2
T
0.0
x2
In this region the temperature curve is convex towards the x-axis, which means that the gas
molecules gain heat by conduction from the hotter molecules downstream faster than they
lose to the ones upstream. The temperature continues to increase rabidly in the reaction zone
due to the reactions until the equilibrium flame temperature is reached. The luminous part of
the flame is due to the excitation of certain C-H groups, which radiates heat with some
wavelengths in the visible region. There are little chemical reactions before the luminous
zone. Calculations of Friedman and Burke, showed that only 14 % of the heat released occurs
before the luminous zone is reached. Klaukens and Wolfhard , calculated the amount of heat
conducted to the pre-heating zone in an actual flat flame. From that they predicated the
amount of temperature rise due to the reaction. For a certain flame, the amount of heat
conducted to the cooler molecules is a function of the amount of heat liberated in the reaction
and the transport properties of the gases. In order to study the effect of a wall on flame
structure, let us assume a porous plate, through which the fuel and oxidizer molecules pass
freely, is placed somewhere in the flame front.

1. Thermal theory
According to the thermal theory, this wall acts as a heat sink. Its presence at this location will
increase the amount of heat conducted from the reaction zone assuming that its coefficient of
thermal conductivity is higher than that of the gases. At the same time, if its heat capacity is
also higher, its surface temperature will be lower than the gas temperature previously at this
location. These two factors will considerably reduce the gas temperature near the wall from
T1 to Tw, Fig. ( ). In order for the molecules near the wall to reach their previous
temperature, they have to be a certain distance (x1) from the wall. This will shift the flame
away from the wall without affecting its profile. The chemical reactions in this case start at
different temperature and concentration. According to that the reaction rate will be different
and this will change the slopes of both the temperature and concentration profiles of the
flame. As a result of these two factors, the flame will be shifted away from the wall and at
the same time, its temperature and concentration profiles will have different slopes in this
 region. Cooling or heating the wall will increase or decrease the distance from the wall. Also,
the higher the coefficient of thermal conductivity of the wall, the higher will be the amount of
heat conducted and the larger will be the distance of the flame from it. If this would be
applied to the cylinder walls of an I.C.E., the wall temperature at the flame arrival will be
higher if the wall has a lower coefficient of thermal conductivity. The instantaneous heat
transfer at the engine walls is reported in Ref.[E-1 ] for a clean wall and a deposited wall. The
deposits which have lower coefficient of thermal conductivity decreases the amount of heat
transfer to the wall. This will increase the instantaneous wall temperature at the flame arrival.

2. Diffusion theory
According to the diffusion theory, the wall acts as a chain breaker. Its action will decrease the
number of the effective collisions necessary for the reaction to continue. This will decrease
the amount of heat liberated from the reaction, which is necessary to raise the temperature of
the mass element in this region. In order to establish a flame at this condition, the flame has
to move away from the plate, Fig. ( ). The slopes of the temperature and concentration
profiles will also change due to the wall effect. The effect of the wall on the chain carriers is
not completely understood until now, Simon and Belles assumed that the wall has certain
efficiency in breaking chain carriers. It was not mentioned whether this efficiency varies with
temperature or not. Actually, the effect of both the thermal and diffusion will combine
together and keep the flame away from the wall. At the same time, its effect will change the
flame structure in this region. In order to study the effect of the wall on the flame structure
analytically, the following parameters have to be known:
1. Transport properties of the plate and their variations with temperature.
2. Efficiency of the wall in breaking the chain carriers and its dependence on
temperature.
3. Rates of the reactions occurring in the flame and their dependence on
temperature and concentration.
4. Transport properties of all the components of the mixture.
5. A mathematical solution for all these complicated equations.

Quench Distance (zone)

1. Thermal theory:
a. Work of R. Friedmen [A-5]
A simplified model for flame quenching based on thermal effects was developed. A flame
propagating between two parallel plates is assumed to be quenched when the rate of heat
generation in the reaction zone is equal to the rate of heat transfer from the flame to the walls.
The rate of heat generation is given by (see Fig.)

S = Mixture Velocity
And the rate of heat transfer to the wall may be roughly represented by
Tf To
2k Ld
fx

Where:
f = geometric factor = 1.0
By equating both equations, the quench distance is given by:
It is possible to eliminate d by using the Mallard-Le Chatelier equation for burning velocity,
k Tf Ti 1
S
C Ti To d
Solving for d and substituting in the equation for x* we get
1
2k 1 Tf Ti 2
x*
SC f Ti To

Therefore, the result of this simplified model indicates that the quench distance is a function
of the geometry, flame temperature, ignition temperature, thermal conductivity, flame speed
and heat capacity.

b. Work of Potter and Berlad ,[D-2]

This development was based on the assumption that for a flame to exist the heat retained by it
must be greater than a critical amount necessary for continued flame propagation which is
assumed to be a constant fraction of the total heat produced in the flame.
Hr
F
HT
Where:
HT = xf . H
And
xf = mole fraction of fuel in the fresh mixture.
H = heat of combustion per mole of fuel (assuming complete combustion)
Hr C P Tf To
Therefore,
CP Tf To F xf H
Assuming heat transfer by conduction only to the walls, where T = To
2
T k T
CP x2
Integrating and averaging
T
d2 d2 q
Tf To
Gi k Gi a
CP
a = thermal diffusivity.
Gi = geometric factor.
dT H w RT H w
q assumed constant
d CP N P CP N
N=Avogadro s Number Molecules/Mole

From (1) and (2)

F Gi a xf H
d2
CP q
dT
Substituting for q
d
Where:
w = is the rate of disappearance of fuel.
In order to apply the equation using experimental data, the rate controlling reaction must be
specified. Two choices were made:
1. The reaction between active particles and fuel. (Corresponding to the diffusion theory)
2. The reaction between O2 and fuel.
The two equations were tested using published data for the quenching of propane-oxygen-
nitrogen flames. The data selected included the effect on quench distance of O2-N2 ratio,
propane concentration, and initial temperature and pressure.
The equation using the active particle-fuel reaction did not correlate data for rich mixture;
the equation using the O2-fuel reaction, while correlating data for rich and lean mixtures,
showed a larger deviation from the predicted relation than the other equation. The quenching
diameter is given by either of the two equations depending upon how w is defined,
1. If the collision theory is used,
1
Er
w Bt a r c Tr2 exp
i i ,r
RTr

Where Tr = 0.7 Tf

so that
F Gi N kr xf F
d2 1 t
2
E B
C P ,r B t a r c
i i,r
Tr exp
RTr
2. Assuming the reaction in the combustion zone to be bimolecular and first order with
respect to fuel and oxygen, although it is probably that the real reacting species are not fuel
and oxygen molecules, then such an assumption is satisfactory if the concentrations of the
reacting species are proportional to the fuel and oxygen concentrations. In this case, the rate
of reaction is given by,
w = ks ar br
Where

1
2
Es
ks Bs T r exp
RTr

So that
F Gi N kr xf F
d2 1 s
2
Es Bs
C P ,r B s a r b r T r exp
RTr

c. Work of Von Karman [A-4]

In this derivation diffusion and the possible wall effect of breaking up chain reactions were
neglected. The wall was assumed to modify the flow through friction and the temperature
distribution through heat conduction. In order to eliminate the complications resulting from
the friction effect that extends ahead of the flame front, the flame was considered as
progressing in a large tube filled with the unburned mixture. The flow was considered In two
dimensions near the wall and in one dimension in the tube. To facilitate the solution the
viscous forces and pressure gradients were neglected, the reaction was assumed to be first
order and the rate assumed to follow the Arrhenius Law. Two domains were considered in the
solution for the temperature profiles. The first was where the temperature is below the
ignition temperature so that the problem was reduced to one of pure heat conduction and
convection. The second domain covered the region in which the temperature is above the
ignition temperature and where chemical reactions take place. From the continuity,
momentum, energy and reaction equations a solution was numerically computed for the
temperature distribution. The most important conclusion drawn from Table I, is that the
ratio between the dead space and the characteristic length, which is equal to flame
thickness, appears to be almost independent that the thermal conduction is the fundamental
process which determines the behavior of the flame near the wall.
k
l
CP

Table (7-b-3):
Gas l /l
CH4 0.3 0.05 5.9
Propane 0.28 0.044 6.36
Ethylene 0.18 0.027 6.66

It was stated that the values of the dead space measured by Kaskan and reported in a personal
communication to Von Karman agreed with those calculated.

d. Work of Kurt Wohl

By establishing a flame front parallel to a cool wall by passing a combustible gaseous mixture
through a cooled porous plate, the dead space (which is taken here to be the minimum
distance between the visible zone and the plate) was obtained by reducing the flow velocity,
causing the flame to approach the plate until the cooling effect extinguishes the flame. Only
thermal conduction was assumed between the flame and the plate.
Applying the conservation of energy and heat transfer equations, the relations
xl Su 1
ln 1
S
And
A
1
11
S 1 2
3
1
e
Su 1
Where obtained.
Tfa Tf
Degree of flame cooling
Ti Tu
7E
A
11R Tfa
Plotting (S/Su) against (x1/ ) yields two real values of (S/Su) greater than a critical reduced
distance (x1/ ) and no real values below this distance. Thus a well-defined dead space is
obtained which limits the approach of a flame front to a cool wall. The curves in Fig. ( )
indicate that with decreasing velocity of flow through the plate, the flame front approaches
the plate to a minimum distance and then moves away from it. As the velocity approaches
zero, the distance approaches infinity. The physical reason for this behavior was described as
follows. When the gas velocity, which is equal to the burning velocity, is gradually reduced,
the distance x1 decreases, and the portion of the heat transferred to the plate from the flame
increases with decreasing x1. Below a certain gas velocity the heat loss to the plate will
become so large that the gas cannot be heated to the ignition temperature so that a flame will
not be possible. In order to establish a flame at this gas velocity, the heat transferred to the
plate has to be reduced by increasing the distance x1.
2. Diffusion theory-laminar flames
Work of Simon and Bells ,[B-1,C-1]
An approximate equation was derived for quench distance based on the effect on the chemical
reaction and on flame propagation of the distribution of atoms and free radicals by the
surface. The derived equation is used in two ways to predict quench distance for propane-air
flames,
1. With one empirical constant derived from quenching data.
2. With a constant, which is, the quotient of the lean flammability limit and rate constant from
flame velocity measurement. A simple active particle mechanism of quenching is examined
in which active particles are considered to be generated in the gas and destroyed on the
container walls. Such a mechanism is shown to predict the existence of a limiting diameter for
flame propagation through a tube.
The equation for quench diameter was derived from the assumption that in order for the flame
to propagate through the tube, the number of effective collisions per unit volume necessary
for the flames to continue to propagate should be less than the total number of effective
collisions per unit volume before the chain carriers are destroyed at the wall. By equalizing
these two expressions, the general equation for the quench diameter is obtained and is given
by:
1
2

32 A P
d
Pi
i
Di t i E i

This mechanism of quenching indicates the importance of the nature of the surface. The
results of experiments to determine the effect of the nature of the surface on the quench
distance are conflicting. In general, the authors concluded that either no surface effect or only
a slight surface effect has been observed.

Comparison of thermal and diffusion theories with experimental results

An experimental study was made of the quenching of helium and argon-oxygen-propane
flames. It was found that a thermal quenching equation satisfactorily predicted the effect of
replacement of argon by helium on quench distance. A similar equation based on diffusion
effects did not give satisfactory results. The success of the thermal theory should not be
interpreted, as conclusion evidence that flame quenching is entirely a thermal process because
both thermal and diffusion equations are, in reality, quite approximate.

Factors affecting flame quenching

It has been found that flame quenching depends on many variables, mainly:
1. Geometry of quenching surface.
2. Fuel type and mixture ratio.
3. Inert diluents.
4. Temperature.
5. Pressure.
6. Oxygen concentration.

1. Geometry of quenching surface

Various cylindrical tubes and rectangular slits were used in studying the effect of geometry on
flame quenching. Fuels used were methane and propane in air at room temperature and
atmospheric pressure.
A geometric factor B was defined as:
 tube diameter d tube
B
slit diameter d slit
For lean to stoichiometric mixtures the average value of B is 1.25 for methane-air mixtures
and 1.45 for propane-air mixtures.
An extension of the study of geometry effects to include annuli and rectangular slots for
various length-to-width ratios is reported in, Ref. ( ). It was found that a very small center
body has a large quenching action in the annular case.

2. Fuel type
The quenching distance of mixtures of propane, benzene, n-heptane, and iso-octane in air
have been measured, by determining the smallest opening of a rectangular burner that will
permit a flame to flash back when the mixture flow is stopped Ref. ( ). It is shown that for
lean and stoichiometric mixtures the quenching distance decreases in the following order:
iso-octane > n-heptane > propane > benzene.
It was noted that this order is the same as the order of increasing burning velocities for the
four compounds. In the case of rich mixtures, no simple relation between quench distance and
burning velocities was found. However, results indicate that the quench distance for the
various compounds were a function of the molecular weights.

3. Inert diluents
The effect of inert gases on quenching is reported in Ref. ( ). Inert gases used were helium,
argon, nitrogen and carbon dioxide. Mixtures of hydrogen and oxygen and inert gas were
prepared such that the calculated flame temperatures of the stoichiometric mixtures were the
same in all four cases. It is shown that for a given mixture, the quench distance decreases with
inert diluents used in this order:
Helium > argon > nitrogen > carbon dioxide
Analogous results for hydrocarbon fuels were found for methane Ref. ( ) and for propane Ref.
( ). Replacement of rare gases by nitrogen affects not only the transport coefficients but also
the temperature and reaction rates in the flame. In this case not only the transport process but
also the rate controlling reactions must be specified. For the ox-hydrogen quenching it was
considered unlikely that low concentrations of H2O have any abnormal effect on the result. It
has been stated that no conclusion could be drawn, active particles to the walls might be
important Ref. ( ). In Ref. ( ) it was hoped that a decision could be reached as to the
importance of loss of heat as opposed to loss as active particles at the walls. Table II
compares the observed ratios of quenching distances at atmospheric pressure for propane-
oxygen-argon and propane-oxygen-helium mixtures with ratios predicted by diffusion and
thermal theories.

Table (7-b-4):
Stoichiometric Fuel-Oxidant Ratio
Percent Observed Thermal Diffusion
73.8 0.35 0.47 0.67
100.0 0.41 0.48 0.68
149 0.44 0.50 0.72
The observed ratios are in better agreement with the results of the thermal theory than with
the diffusion theory.

4. Temperature
The effect of temperature on quenching distance has been studied Ref. ( ). Increased
temperature decreases the quench distance. The results given for propane-air mixtures at
about 1 atmosphere are consistent with the general observation that chemical reactions are
promoted by increase in temperature. The magnitude of the temperature effect varies with
mixture composition. For rich and stoichiometric propane-air mixtures, quench distance is
approximately proportional to the 0.5 power of the absolute temperature, while for lean
mixtures, the exponent increases.

5. Pressure
Quenching distance increases with decreasing pressure Ref. ( ). It is pointed out that d Pn
where n is a negative number, increasing from lean to stoichiometric mixtures and reaching
a maximum somewhat rich of stoichiometric. n usually decreases again the mixture
becomes very rich. The pressure exponent of the quench distance is the sum of two terms: one
is one half the order of the reaction and the other is a function of the pressure dependence of
the flame temperature. The effect of the pressure on quench distance of propane, benzene, n-
heptane and iso-octane-air flames was reported in Ref. ( ). The value of n for the propane
concentration corresponding to the minimum quench distance was 0.91.
Table III shows the variation of the pressure dependence of quench distance of propane-air
flames with fuel concentration.

Stoichiometric n Reference
. Fuel-air ratio
(percent)
74 -0.83 K-11
74 -0.85 D-2
86 -0.84 D-2
87 -0.85 K-11
100 -0.88 K-11
100 -0.89 D-2
110 -0.91 D-1
124 -0.95 D-2
149 -0.98 D-2

6. Oxygen concentration
The effect of pressure on the quench distance of flames in various propane-oxygen-
nitrogen systems is reported in Ref. ( ). Five oxidant atmospheres were used, containing 17,
21, 30, 50, and 70 percent oxygen by volume. At any given pressure and percent
stoichiometric propane, the quenching distance decreases as the oxygen concentration is
increased.

Reference: Gad ElMawla, Ahmed El Said, Ph.D. Thesis, University of Michigan, 1965

B-Explosion Flames
Combustion
The burning of gas, liquid, or solid in which fuel is oxidized involves heat release and
often light emission. Combustion of methane (CH4) in air can be described by the chemical
equation:

CH4 + 2 (O2 + 3.76 N2 ) CO2 + 2H2O+ 2 (3.76 N2 ) + Energy

The chemical products from complete combustion of a hydrocarbon fuel are mainly CO2 and
H2O (vapor). The combustion process will result in increased temperature due to the
transformation of chemically bound energy into heat. It should be emphasized that the above
equation constitutes a strong simplification of the real combustion process.
Combustion of gaseous fuel in air can occur in two different modes. One is the fire, where
fuel and oxygen is mixed during the combustion process. In the other case the fuel and air (or
another oxidizer) is premixed and the fuel concentration must be within the flammability
limits. In general the premixed situation allows the fuel to burn faster, i.e. more fuel is
consumed per unit time.
 No Ignition

Immediate Fire
Ignition
Release of
Gas and/or Damage
Liquid Formation of Ignition Gas
Combustible (delayed) Explosion Fire
Fuel-Air
Cloud
Figure (7-b-7): An event tree showing typical consequences of accidental releases of
combustible gas or evaporating liquid into the atmosphere.

Gas Explosions
Explosion
An explosion in general is an event leading to a rapid increase of pressure. This pressure
increase can be caused by: nuclear reactions, loss of containment in high pressure vessels,
high explosives, metal water vapor explosions, run-a-way reactions, combustion of dust, mist
or gas (incl. vapors) in air or in other oxidizers.
Figure ( ) shows what can happen if combustible gas or evaporating liquid is accidentally
released into the atmosphere. If the gas cloud, formed from the release, is not within the
flammability limits or if the ignition source is lacking, the gas cloud may be diluted and
disappear.
Ignition may occur immediately , or may be delayed by up to tens of minutes. In case of an
immediate ignition( i.e. before mixing with air or oxidizer has occurred) a fire will occur.
The most dangerous situation will occur if a large combustible premixed fuel-air cloud is
formed and ignites. The time from release start to ignition can be from a few seconds up to to
tens of minutes. The amount of fuel can be from a few kilograms up to several tons.
The pressure generated by the combustion wave will depend on how fast the flame propagates
and how the pressure can expand away from the gas cloud( governed by the confinement).
Gas explosion is a process where combustion of a premixed gas cloud, i.e. fuel-air or fuel-
oxidizer, is causing rapid increase of pressure. Gas explosions can occur inside process
equipment or pipes, in buildings or offshore modules, in open process areas or in unconfined
areas.
The consequences of a gas explosion will depend on the environment in which the gas cloud
is contained :
Type of fuel and oxidizer
Size and fuel concentration of the combustion cloud
Location of the ignition point
Strength of the ignition source
Size, location and type of explosion vent areas
Location and size of structural elements and equipment
Mitigation scheme
When a cloud is ignited the flame can propagate in two different modes through the
flammable parts of the cloud. These modes are :
- Deflagration
- Detonation
Therefore it has been common to classify a gas explosion from the environment where the
explosion takes place:
i) Confined Gas Explosions within vessels, pipes, channels or tunnels.
ii) Partly Confined Gas Explosions in a compartment, buildings or off-shore modules and,
iii) Unconfined Gas Explosions in process plants and other unconfined areas.
It should be pointed out that these terms are not strictly defined. In an accidental event it may
be hard to classify the explosion. As an example an unconfined explosion in a process plant
may also involve partly confined explosions in compartments into which the gas cloud has
leaked.
i) Confined Gas Explosions
Confined gas explosions are explosions within tanks, process equipment, pipes, in culverts,
sewage systems, closed rooms and in underground installations. Confined explosions are also
called internal explosions.

Deflagration
A deflagration is the most common mode of flame propagation in accidental gas
explosions. It is defined as an explosion where the combustion wave propagates at subsonic
velocities relative to the unburned gas immediately ahead of the flame (which itself is set in
motion by the expanding combustion products). In the deflagrative mode the flame speed
ranges from a few m/s up to 500-1000 m/s. The explosion pressure will range from a few
mbar to several bar, depending on the flame speed.
The flame speed and explosion pressure will strongly depend on the gas cloud and the
geometrical conditions within the cloud (i.e. process equipment, piping etc.) or geometries
confining the cloud (i.e. buildings etc.). To predict the flame speed and explosion pressure for
a deflagration is not a simple task, even if scenario parameters such as cloud size, fuel
concentration and ignition point are known. The phenomenon of flame acceleration is a
mathematically stiff problem, i.e. the result is very sensitive to variation of specific
parameters.
Deflagration Waves and Explosion Pressure
Deflagration wave is a gas explosion where the flame front propagates at subsonic speed
relative to the unburned gas immediately ahead of the wave. In a gas explosion the
propagating velocity can span more than three orders of magnitude. The mechanism of flame
propagation will be quite different in the different velocity regimes.

Figure (7-b-8): Illustration of the structure of a laminar flame front in a premixed gas

When the cloud is ignited by a weak ignition source (i.e. a spark or a hot surface) the flame
starts as a laminar flame. For a laminar flame the basic mechanism of propagation is
molecular diffusion of heat and mass. The laminar flame structure is illustrated in Figure.
This diffusion process of heat and mass into the unburned gas is relatively slow and the
laminar flame will propagate with a velocity of the order of 3-4 m/s.
The propagation velocity of the laminar flame depends on the type of fuel and the fuel
concentration. Figure shows the laminar burning velocity for methane-, ethylene-and
hydrogen-air. Methane has a maximum burning velocity of about 0.4 m/s. Maximum laminar
burning velocities of 0.4-0.5 m/s are typical for hydrocarbons. Ethylene, acetylene and
hydrogen have higher burning velocities due to fast chemical kinetics and high molecular
diffusivity.

Figure (7-b-9): Laminar burning velocity for methane-air, ethylene-air and hydrogen-air

In most accidental explosions the laminar flame will accelerate and transit into a turbulent
deflagration (i.e. turbulent flame), since the flow field ahead of the flame front becomes
turbulent. The turbulence is caused by the interaction of the flow field with process
equipment, piping, structures etc.
One of the mechanisms causing the increased burning rate in turbulent deflagrations is the
wrinkling of the flame front by large turbulent eddies.

Figure (7-b-10): Wrinkled flame front when size of turbulent eddies.

Turbulent flame brush when size of turbulent eddies

For this combustion regime the increased flame surface area is causing the burning rate to
increase. This regime is characterized by the turbulent integral length scale, lt , being
significantly larger than the thickness of the flame front. When the turbulent integral length
scale, lt , is of the order of the thickness of the flame front or smaller, the flame becomes a
thick turbulent flame brush. In this regime the turbulence is causing increased diffusion of
heat and mass and thereby a high burning rate. When a flame propagates through a premixed
gas cloud there are two mechanisms causing pressure build-up. These are:
i) fast flame propagation
ii) burning in a confined volume
In most accidental explosions a combination of these two effects causes the pressure build-up.
Here we will use a flame propagating in a pipe and an explosion in a vessel as examples. At
the location of the flame front there will be a small pressure drop. This drop in pressure is
required in order to satisfy the conservation equations across the flame front.
 Figure (7-b-11) Pressure-distance profile for a deflagration propagating in a tube.

The pressure behind the flame (in the burnt gas) will gradually decay away from the flame.
This pressure decay will mainly depend on the boundary conditions on the left end of the tube
(i.e. open or closed tube) and on the flame velocity.
Since the flame front is a subsonic combustion wave, the burning will influence the flow
ahead of the flame. In Figure 5.4 this is illustrated by a decaying pressure and shock wave in
the unburned mixture. The pressure profile ahead of the flame will depend on the flame
acceleration and speed. In order to obtain a shock wave ahead of the flame, a high flame
speed is required. Figure 5.5 shows the maximum overpressure versus flame velocity in two
modes of flame propagation; i) planar mode, i.e. flame propagating in a tube and ii) spherical
mode, i.e. flame propagating in an unconfined cloud. The spherical mode of flame
propagation requires a higher flame velocity than the planar mode in order to obtain the same
explosion pressure. This can be explained by the fact that gas can expand more freely in a
spherical mode than in a planar mode. From Figure 5.5 one sees that a flame velocity of the
order of 100 m/s is required to produce pressure waves of a significant strength (~0.1 barg).
The pressure in a deflagration is strongly linked to the flame velocity and burning rate.
Explosion pressures for constant velocity flames have been predicted by several researchers,
among them Guirao et al. (1976) and Strehlow et al. (1979). The results of such predictions
are shown in Figure 5.5.

Figure (7-b-12): Maximum overpressure vs. flame velocity for planar and spherical flames
(Moen and Saber, 1985).

If the explosion happens inside a closed vessel, fast flame propagation is not required to
obtain high pressures. A vessel as shown in Figure 5.6 will prevent the expansion of the gas
when it burns and lead to pressure increase. A Stoichiometric fuel-air cloud in a closed vessel
will give up to 8 to 9 bar when exploding. By opening up part of the vessel wall, relief will be
provided and the pressure will be reduced. The reduction will depend mainly on how fast the
flame is burning in the vessel and the location and size of the vent area.

Figure (7-b-13): Explosion in a closed vessel

The main factors determining the consequences of deflagrations are:

Type of fuel
Fuel concentration
Size and location of the cloud
Location and strength/type of the ignition source
Obstacle number and size + orientation/location
Confinement and venting (size and position of vent area)
Scale
In order to evaluate the consequences of a deflagration all of these factors have to be taken
into account.
The consequences of a gas explosion depend strongly on the venting arrangements and the
geometrical layout (i.e. arrangement of process equipment, piping, etc.). Small changes in the
geometry can change the explosion pressure significantly. It is therefore important to
understand the mechanisms of flame acceleration and pressure build-up. Based on this
knowledge it is often possible to suggest changes in the layout that will affect the explosion
behavior significantly and hence improve overall safety.
A deflagration in a truly unconfined cloud will propagate slowly and only produce small
overpressure. Deflagrations produce high pressures when they propagate in an obstructed,
partly confined area or confined volume.
When evaluating the consequences of deflagrations, not only peak pressure should be
considered, but also the rise time, the duration and the impulse.

Detonation
A detonation is a combustion wave that travels at sonic speeds relative to the unburnt gas in
front of it. The front of the detonation wave resembles a shock wave traveling in a natural
gas, with a rapid chemical reactions occurring behind the shock front. A detonation can be
initiated with a region of burning gas of sufficient size and intensity to cause a localized
explosion and a propagating blast wave.
A detonation is the most devastating form of gas explosion. Unlike the deflagration, a
detonation does not require confinement or obstructions in order to propagate at high velocity.
Particularly in an unconfined situation, the behavior of a detonation is quite different from a
deflagration. A detonation is defined as a supersonic combustion wave (i.e. the detonation
front propagates into unburned gas at a velocity higher than the speed of sound in front of the
wave). The gas ahead of a detonation is therefore undisturbed by the detonation wave. In fuel-
air mixtures at atmospheric pressure, the detonation velocity is typically 1500 - 2000 m/s and
the peak pressure is 15-20 bar.
Transition to detonation, propagation and transmission of detonation waves, depend strongly
on the reactivity of the gas cloud.

Shock wave
Formation of a shock wave in an ideal gas.
The propagation of an ordinary sound or acoustic wave in a gas is accompanied by small
amplitude longitudinal displacements of molecules; there is no net flow of gas, and any
physical changes in the gas are small and reversible. The velocity of such a wave, termed the
local sound speed of the gas, is determined by the collision rate between gas molecules; it is
therefore approximately equal to the mean kinetic velocity of the molecules and is primarily
determined by the temperature of the gas.
A totally different situation arises when a disturbance is forced through the gas at a speed
greater than the local molecular velocity. In this case it is evident that a wave of a very
different nature is established in the gas. Since the molecules can only move away from the
supersonic (i.e. greater than the sound speed) disturbance at the sound speed, then the
pressure, density and temperature must all build up ahead of this disturbance. This situation is
analogous to the case of a ship moving through water at a speed greater than the velocity of
the surface waves on the water; the water tends to pile up ahead and to both sides of the bows,
forming a steep wave of large amplitude known as a bow-wave. This wave is stationary
relative to the ship, diverges linearly, and becomes attenuated with increasing distance
backwards from the bows. Such a wave, when generated in a gas by a supersonic disturbance,
which might be a solid piston or a sharp interface, is termed a shock wave and at its front very
steep gradients of pressure, density and temperature occur.

The Becker Model

One of the simplest models which illustrate shock-wave formation is due to Becker [1] and is
shown in figure 1. Here, a rigid piston accelerates into a motionless gas in a duct; the
acceleration is approximated by a series of small instantaneous increases of velocity occurring
after short, finite time intervals. After the first impulsive acceleration at say t=1, a pressure
wave (shown as a vertical line) moves along the duct and affects a mass a of gas. This mass
starts to move at the piston velocity and has its pressure increased slightly; between t=1 and
t=2, the pressure and velocity of a is further increased due to the second acceleration of the
piston, the original wave has by now reached b and imparts a pressure and velocity pulse to
this mass. This process then continues as shown in the diagram, each pressure wave moving
at the local sound speed with respect to the gas through which it passes. However, the masses
nearest the piston have both higher velocities and higher temperatures (due to higher
pressures) and consequently much higher pressure-wave speeds relative to the duct than
masses further away. This causes the pressure waves nearer the piston to overtake those
further downstream; eventually all the pressure waves coalesce to form a single steep pressure
gradient or shock-wave.
Unlike a sound wave, this large amplitude disturbance changes the physical nature of its
supporting gas and so it acquires non-linear characteristics; it also travels at supersonic speed
relative to the gas in front. From simplified theory, these large pressure, density and
temperature gradients should become infinite; however before this occurs, viscous and heat
conduction effects intervene to produce a shock with large, but finite gradients across it.
By applying a similar argument to that given above to the gas behind an accelerating piston, it
can be shown that in this region a series of weak expansion waves propagate into the gas and
travel at the local sound speed away from the piston. However, in this case each wave travels
into a cooling gas with continually decreasing sound speed. Hence, these waves have
continuously decreasing speeds and form a gentle and continuously decreasing gradient of
pressure, density and temperature, termed the "rarefaction fan".
What is a Detonation Wave?
Detonation waves are perhaps the most extensively studied and severe of all the combustion
processes and were discovered over a century ago when Mallard and LeChatelier and
Berthelot and Vielle discovered that low velocity flames propagating in a reactive gaseous
mixture could suddenly acquire very high velocities accompanied by substantial increases in
temperature and pressure near the flame front. It was then realized that this supersonic
combustion consisted of a shock front closely followed by a reaction - the two components of
a detonation wave.
Characteristics of a detonation wave
In a simple one dimensional theory, a detonation wave can be regarded as consisting of an
extremely strong shock wave closely followed by an exothermic reaction capable of
providing enough energy to sustain the wave. It is far more violent and destructive than a
shock wave due to the presence of a greater amount of energy produced from the reaction,
and the chemical combustion is continuously initiated by the adiabatic compression and
heating of the gaseous medium behind the shock front. Two of the main characteristics of a
detonation are that it propagates with a steady constant velocity and a sharp peak in pressure
called the Von Neumann spike is observed at the detonation front. This is associated with the
finite rate chemistry which takes place after an extremely short induction time. High
instantaneous over-pressures are therefore associated with detonations, particularly in the
transition to detonation process.
Initiation of a detonation
Detonations may be initiated by a variety of techniques, in all of which the degree of
confinement or the geometry of the container play a dominant role. These include initiation
from an accelerating flame (deflagration to detonation transition), direct initiation by a high
energy spark, or by shock wave initiation. In the latter method, if the induced chemical
reactions are extremely exothermic, then the shock wave may accelerate and use the chemical
energy released from the reactions to undergo some form of explosive transition. Equilibrium
is then reached, the shock wave is self supporting, and a detonation wave traveling at a
characteristic velocity
is established.

Detonation Waves
Detonation waves were observed experimentally more than 100 years ago. Chapman and
Jouguet were the first to present a theory describing this supersonic combustion wave,
propagating at a unique velocity. The C-J (Chapman-Jouguet) theory (Fickett and Davis,
1979) treats the detonation wave as a discontinuity with infinite reaction rate. The
conservation equations for mass, momentum and energy across the one-dimensional wave
gives a unique solution for the detonation velocity (CJ-velocity) and the state of combustion
products immediately behind the detonation wave. Based on the CJ-theory it is possible to
calculate detonation velocity, detonation pressure etc. if the gas mixture is known. The CJ-
theory does not require any information about the chemical reaction rate (i.e. chemical
kinetics).

Table (7-b-5): CJ-pressure and CJ-detonation velocity for some fuel-air mixtures.
Initial 25°C and 1.013 bar (Baker et al. 1983)
Hydrogen Ethylene Propane Methane
CJ-Pressure, bar 15.8 18.6 18.6 17.4
CJ-Velocity, m/s 1968 1822 1804 1802

During World War II, Zeldovich, Döring and von Neumann improved the CJ-model by taking
the reaction rate into account. As shown in Figure 6.2 the ZND-model describes the
detonation wave as a shock wave, immediately followed by a reaction zone (i.e. flame). The
thickness of this zone is given by the reaction rate. The ZND-theory gives the same
detonation velocities and pressures as the CJ-theory, the only difference between the two
models is the thickness of the wave.

Figure (7-b-13): CJ detonation velocity and pressure for ethylene-air.

An actual detonation is a three-dimensional shock wave followed by a reaction zone. The

leading shock consists of curved shock segments. At the detachment lines between these
shock segments, the shock wave interacts in a Mach stem configuration. A two-dimensional
illustration of the actual structure is given in Figure 6.2. The characteristic length scale of the
cell pattern, the cell size, is shown in the figure.

Figure (7-b-14): ZND structure and pattern of an actual structure of a detonation front.

The size of the fish shell pattern generated by the triple point (Mach stem) of the shock wave
is a measure of the reactivity of the mixture representing a length scale characterizing the
overall chemical reaction in the wave (Lee, 1984). This length scale, , is often the cell size or
the cell width. The more reactive the mixture, the smaller the cell size. Figures 6.3 and 6.4
show the detonation cell size versus fuel concentration for several fuel-air mixtures.
 Figure (7-b-15): Cell size vs. fuel concentration for acetylene, ethylene and hydrogen in air
(25°C and 1 atm) (Shepherd et al., 1991).

Figure (7-b-16): Cell size vs. fuel concentration for ethylene, propane and methane in air
(25°C and 1 atm) (Shepherd et al., 1991).

The cell size is measured experimentally and there are some variations in the reported results.
Variations of a factor of two is not uncommon.
The cell size, , is a parameter which is of practical importance. The transition from
deflagration to detonation, propagation and transmission to detonation, can to some extent be
evaluated based on the knowledge of the cell size of the mixture.
The probability of occurrence of a detonation in fuel-air mixtures depends strongly upon the
type of fuel. Very reactive fuels, such as hydrogen, acetylene or ethylene, may detonate in an
accident situation.
Other fuels are less likely to detonate. In particular no data exist on detonations involving
pure methane-air.
Presently the most effective way of mitigating the occurrence of a detonation is to avoid
situations where the deflagration can accelerate to a condition where transition from
deflagration is possible, i.e. high pressure deflagrations.
The CJ-detonation pressure can be calculated by codes like STANJAN. Such data can be used
for stable detonation waves. However, in the event of transition from deflagration to
detonation, pressure spikes much higher than the CJ-values appear.
Propagation and transmission of detonation waves depend mainly on the cell size (i.e. type of
fuel and fuel concentration) and geometrical conditions. By operating with geometrical
dimensions (d, w, h) smaller than the limits indicated in Figures 6.8-6.10, it is very unlikely
that a stable detonation will occur.
The cell size as a measure of detonability is not an exact number. In the literature a variation
of a factor of two is often found. When using cell sizes for estimation of limiting conditions
for successful propagation or transmission, they should be regarded as approximate values.
Hence safety factors should be used.

Mathematical treatment:
The Rankine-Hugoniot Curve:
For a fixed energy released, all possible solutions of the overall conservation equations for
mass, momentum, and energy are given by an expression known as the Rankine-
Hugoniot Equation.
Examination of the Hugoniot Equation shows the possible existence of two types of
solutions, those corresponds to:
Detonation
or Deflagration
Stable detonation occurs only under such condition that the entropy of the burnt gas is a
relative minimum along the Hugoniot curve.
The tangent from the initial state to the upper part of this curve, for which the final
pressure exceeds the initial pressure, meets the Hugoniot curve at the upper Chapman-
Jouguet point, which corresponds to point of stable detonation in monoatomic gases.
For deflagration (laminar flame propagation), the final pressure is smaller than the initial
pressure before combustion. The entire lower H-C. between constant pressure
deflagration and the lower C-J point corresponds to possible and states for deflagration.

The Hugoniot Curve

____________________________________

Reactants, Po,To, o D' Products

u Pf, Tf, f

____________________________________

u = mixture velocity.
D' = velocity of reaction front.
v =u-D
= velocity of gases relative to reaction front.

Mass: v o vo f vf m 1
2 2
Momentum: P v2 Po o vo Pf f vf 2
Po 1 2 Pf 1 2
Energy: vo eo vf ef q 3
o 2 f 2
e = internal energy per gm gas mixture.
q = heat evolved per gm of reactant.
From Eq. 1,
1 vf

f
m
1 vo
o m
 1 1 1
(v - v o ) (1-a)
f o m f

From Eq. 2,
Pf - Po m(v o vf ) (2-a)
Dividing Eq. 2-a by Eq. 1-a , leads to the relation,
Pf - Po
m2 2 2
v 4
1 1
f o
From Eq. 3,
Po Pf 1
q ef eo vo2 vf 2 (3-a)
o f 2
m
vo
o
(1-b)
m
vf
f
From Eq. [3-a] and [1-b]
2 2
Po Pf m2 1 1
q ef eo
o f 2 o f
Or
Po Pf m2 1 1 1 1
q ef eo 5
o f 2 o f o f
1 1
Replacing in Eq. 5 by using Eq. 4
o f
Po Pf 1 1 1
q ef eo Pf Po
o f 2 o f
1 1 1
q ef eo Pf Po 6
2 f o
Pf
hf ef
f
Po
ho eo
o
It follows from Eq. 6 that,
1 1 1
q hf ho Pf Po 7
2 f o
 Figure (7-b-17): Hugoniot Curve

Region I-II corresponds to detonation.

Stationary solution at point Upper C-J.
1 1
Pf Po
f o
P -P
vf vo - f o
m
Entropy of burnt Gas is minimum at "Upper C-J"
h = f (P, v)

h h
dh ) v .dP ) P .dv
P v
h h
dh ) P .dv Tds vdP ) P .dv
dP v v
h h
)v )v
P P
On a Hugoniot curve
1
q h2 h1 P2 P1 v1 v
2
q = constant
h 1
)P P P1
v 2
h 1
)v v1 v
P 2
1
Tds vdP P - P1 .dv
dP 2
1
v1 v
2
 ds dP 1
T v P - P1
dP dv dv 2
Slope
dv 1
v1 v
2

1 dP ds 1
v1 v T P - P1
2 dv dv 2
ds
T
dP dv P - P1
dv 1 v1 v
v1 v
2
at Chapman-Jouget point
ds
T
dP P2 - P1 dv P2 - P1
dv v1 v 2 1 v1 v 2
v1 v
2
ds = 0 Point at minimum entropy.

Speed of burnt gas relative to the reaction front

vf = uf - D' equals speed of sound.

For ideal gas, and adiabatic process P v k constant

C
P
vk
dP2 P2
P2 v 2 k kv 2 ( k 1) k
dv 2 v2
at C - J point
dP2 P2 P1
dv 2 v2 v1
P2 P1 P2
k
v2 v1 v2
P2 P1
v2 k P2 v 2
v2 v1
P2 P1
v2 k RT
v2 v1

From Eq. [ 4 ]
1/ 2
P P
u2 v2 2 1
v1 v 2
u2 a 2 (Speed of sound)
Relation between Pressure and temperature after detonation wave & initial conditions
 dPf dTf Po Pf
2Cp 9
1 1 1 1
d( ) d( )
f f f o

Pf RT 10

dTf f Tf dPf
11
1 R Pf 1
d( ) d( )
f f

9 & 10

dPf 2 CpPf Po Pf
1 R 1 1 2 CpTf
d( )
f f o Pf

1 1
Equation of straight line passing through points: ( Po , ) and ( Pf , )
o f
Po Pf
k f Pf
1 1
f o
2 2
f vf k f Pf
- vf -u f D & Cf k R Tf 1/2
10 & 13

Po Pf k Pf 1 f
o
P P P T
1- f k f 1 f o
Po Po Po Tf

2
Mf T Pf Pf
k o 1 k 1 0
Mo Tf Po Po

T M
1 k 1 k 2 4k o f
Pf Tf M o
Po T M
2k o f
Tf M o
Example:
Calculate the detonation velocity for stoichiometric mixture of H2 & O2, if the initial pressure
is 1.0 atm and the initial temperature 291 K.
Governing Equations:
f R
D vo kf Tf
o M
T M
1 k 1 k 2 4k o f
Pf Tf M o
Po T M
2k o f
Tf M o
Po
(1 k)
Pf Pf
Po k

Po
2k 1
Pf Pf Po
1 2 q hf ho
Po Po Po
1 k
Pf
where :
M f , M o : Molecular weight of product & reactants.
q: Heat release per gram.
h: Enthalpy per gram.
D: Detonation wave velocity.

To calculate the detonation velocity D, ( f , M f , k f , Tf ) should be known, that means the

equilibrium temperature and the number of molecules of the product should be known.
Procedures:
-Estimate: M , k , T .
-Solve for P .
-Calculate n .
-Correct first estimate of M , k.
-Solve for P.
-Calculate n.
-Check in energy equation.
-Calculate D.
2 H2 + O2 nO. O + nH. H + nOH. OH + nH2O. H2O + nO2. O2 + nH2. H2

Equilibrium Reactions:

P
1/2 O2 O, nO Kp1 * ( t ) 0.5 * nO 2 0.5 1
n tc
P
1/2 H2 H, nH Kp 2 * ( t ) 0.5 * nH 2 0.5 2
n tc
1/2 H2 + 1/2 O2 OH , nOH Kp 3 * nO 2 0.5 * nH 2 0.5 3
 P
H2 + 1/2 O2 H2O , nH 2 O Kp 4 * ( t ) 0.5 * nO 2 0.5 * nH 2 4
n tc

NH = nH + nOH + 2 nH2 + 2 nH2O 5

NO = nO + nOH + nH2O + 2 nO2 6

From the above equations, we get:

First, a relation between nH2, nO2

NH 2nH 2 Kn 2 * nH 2 0.5
nO 2 0.5
2Kn 4 * nH 2 Kn 3 * nH 2 0.5 Kn 3 * nH 2 0.5
Then, a check for the number of oxygen atoms
NO Kn 4 * nH 2 Kn 3 * nH 2 0.5 Kn1 nO 2 0.5 2nO 2
First trial :
Assumptions :
T = 3600 K
n = 2.326 > 2.0
kf = ko = 1.2
Mf = Mo = 12.0 gm/mole
substitute and calculate Pf /Po

Pf /Po = 22.4 Pf = 22.4 ats.

From tables :
Kp1 = 0.625, Kp2 = 0.734, Kp3 = 1.34, Kp4 = 4.03
Kn1 = 0.205, Kn2 = 0.237, Kn3 = 1.34, Kn4 = 12.5

assume: nH 2 0.5 0.33 , nH2 = 0.5744

NH 2nH 2 Kn 2 * nH 2 0.5
nO 2 0.5
2Kn 4 * nH 2 Kn 3 * nH 2 0.5 Kn 3 * nH 2 0.5

4 2 * 0.33 0.237 * 0.5744

nO 2 0.5 0.355
2 * 12.5 * 0.33 1.34 * 0.5744 1.34 * 0.5744
nO2 = 0.1225
Check for NO
NO Kn 4 * nH 2 Kn 3 * nH 2 0.5 Kn1 nO 2 0.5 2nO 2
NO 12.05 * 0.33 1.34 * 0.5744 0.205 * 0.355 .1225 2.055
But, N = 2.0
Error = [2.055 2.0]/2 = 2.75 %
Number of moles of species

P
nO Kp1 * ( t ) 0.5 * nO 2 0.5 = 0.205 x 0.355 = 0.0727
n tc
P
nH Kp 2 * ( t ) 0.5 * nH 2 0.5 = 0.136
n tc
nOH Kp 3 * nO 2 0.5 * nH 2 0.5 = 0.237 x 0.5744 = 0.279
 P
nH 2 O Kp 4 * ( t ) 0.5 * nO 2 0.5 * nH 2 = 12.5 x 0.33 x 0.355 = 1.464
n tc

Check ntc = nO + nH + nOH + nH2O + nH2 + nO2

= 0.0727 + 0.136 + 0.279 + 1.464 + 0.33 + 0.1225
= 2.4042
error = [2.4042-2.326]/2.326 = 3.36 %

Calculation of Mf , kf

Item No.of Molecular Mass Mole Mass Cp x.Cp

moles .Weight M fraction fraction Cal/mole.C
N M x x.M
O 0.072 16 1.152 0.0299 0.4784 5.05 0.15
H 0.136 1.008 0.137 0.0566 0.05705 4.968 0.28
OH 0.279 17.008 4.745 0.1162 1.976 8.955 1.04
H2O 1.464 18.016 26.375 0.609 10.971 13.2 8.03
H2 0.33 2.016 0.665 0.137 0.276 8.99 1.23
O2 0.1225 32.00 3.92 0.051 1.63 9.79 0.499
= =36.9 =15.39 =11.23
2.4

error in mass = (36.9-36)/36

= 0.9/36 = 2.5 %

Molecular wt. = 15.39 assumed to be 12.0

k/(k-1) = Cp/R
= 11.23/1.987 = 5.65
k = 1.215, assumed 1.2

Recalculate Pf /Po

291 15.39
1 1.215 1 1.215 2 4 * 1.215
Pf 3600 12
17.117
Po 291 15.39
2 * 1.215
3600 12
Pf = 17.117 atm
Recalculate new equilibrium constants Kn`s

Kn1 = 0.625*(17.117/2.4)-0.5 = 0.234

Kn2 = 0.734*(17.117/2.4)-0.5 = 0.274
Kn3 = 1.34 * 1 = 1.34
Kn4 = 4.03 *(17.117/2.4) 0.5 = 10.762

Estimate nH 2 0.37 , nH20.5 = 0.608

4 2 * 0.37 0.274 * 0.608
nO 2 0.5 0.352
2 * 10.762 * 0.37 1.34 * 0.608

nO2 = 0.1239
NO 10.762 * 0.37 1.34 * 0.608 0.234 * 0.352 2 * 0.1239 2.017

error = ( 2.017 2.0 )/ 2.0 = 0.85 %

nO = 0.234 x 0.352 = 0.0823
nH = 0.274 x 0.608 = 0.1665
nOH = 1.34 x 0.352 x 0.608 = 0.2867
nH2O = 10.762 x 0.37 x 0.352 = 1.401
nH2 = 0.37
nO2 = 0.1239
ntc = n
= 2.43
error = 0.03/2.4 = 1.25 %

Check Hugoniot Equation

Po
2k 1
Pf Pf Po
1 2 q hf ho
Po Po Po
1 k
Pf
1
21.215 1
17.117
LHS 17.117 1 25.197
1
1 1.215
17.117
RHS
-q = ( Hf - Ho )
= nO HO + nH H.H + nOH H.OH + nH2O H.H2O
= 0.0823 x 59.56 + 0.1665 x 752.102 + 0.2867 x 9.33 + 1.41 x -57.79
= 4.9 + 8.674 + 2.674 - 81.48
= -65.2359

hf = 0.0823 x 16.537 + 0.1665 x 16.4 + 0.32 x 26.7

+ 1.41 x 38.3 + 0.37 x 26.616 + 0.1239 x 29.254
ho = - 0.146
-q + hf - ho = 80.105 + 0.146 - 65.1259
= 15.015
2* /Po = (2/R.To) [(-q + hf - ho)/Mf]
where Mf = 36.9

Mf (R/M)* To = 36.9 x (1.98/12) x 291 x (1/1000) kCal.

= 1.77 kCal.

[(2*15.015)/(Mf*R*To)]= (2*15.015)/1.77
= 16.966 kCal

L.H.S. does not equal to R.H.S.

Rise estimated temperature to 3650 K.

Mathematical Solutions:
Math Cad program : (Gad ElMawla)
A program was constructed to solve for the detonation velocity.
Results were compared with published values are shown in the following table
Comparison of calculated results by different methods:

H2-Air C2H2-Air C3H8-Air CH4-Air

P bar 15.8 18.6 18.6 17.4
V m/s 1968 1822 1804 1802

Math Cad Program ( Gad ElMawla)

H2-O2 H2-Air C2H2-Air C3H8-Air CH4-Air

Hf, J/mole 0 0 226899.4 -103916.4 -74997.7
Detonation 2806 1945 1874 1822 1815
Velocity
V, m/s
P, bar 18.056 15.899 20.638 20.155 18.689
Tf, K 3635 2899 3148 2892 2824
Mi, 12.01 20.913 28.635 29.46 27.635
M 14.67 23.985 28.385 27.572 27.028
K 1.169 1.071 1.016 1.008 1.019
nt 1.228 2.947 13.013 26.505 10.756
nH2 0.195 0.084 0.084 0.22 0.1
nO2 0.058 0.021 0.289 0.336 0.11
nCc 0 0 6.434*10-7 5.724*10-7 1.755*10-7
nN2 0 1.869 9.283 18.667 7.476
nO 0.043 0.004913 0.079 0.051 0.015
nH 0.091 0.014 0.056 0.06 0.021
nOH 0.162 0.048 0.199 0.309 0.115
nH2O 0.676 0.888 0.788 3.603 1.84
nN 0 4.17*10-6 4.61*10-5 3.388*10^-5 9.052*10-6
nNO 0 0.021 0.235 0.265 0.087
nCg 0 0 1.45*10-10 1.1*10-11 1.84*10-12
nCO 0 0 0.88 0.894 0.269
nCO2 0 0 1.12 2.109 0.732
"Fuels and Combustion" Results

V, m/s P, bar T
H2/O2 2806 18.05 3583

"Flame and Combustion" Results

H2/O2 H2/Air C2H2/Air C3H8/Air CH4/Air

V, m/s 2825 1940 1900 1800 1800
P, bar 18.05 15.6 19 17.2 18.3
Tf, K 3700 2950 3100 2740 2820

"Stanjan" Results

V, m/s P, bar T, K
H2-O2 2840.5 18.716 3681.5
H2-Air 1978.2 15.6 2968.9
Mitigation
The term mitigation is used to indicate measures that can be employed to limit the expected
combustion of a fuel air mixture cloud in a containment. A narrower definition refers to
technical means, ( hardware, strategies, actuation criteria, ..etc ) that can be used to reduce the
probability of containment failure due to combustion. A plant-specific mitigation strategy
may use one or more of the mitigation systems and equipment that is suitable for a specific
mitigation, depending on the actual state of the plant during and after the accident.
In order to limit the combustibles (fuel) concentration and prevention of ignition, different
methods are used , mainly :

Mixing
Mixing devices are installed in many plants, primarily intended for the removal of heat from
the containment atmosphere during normal operation and/or following an accident. Mixing
can reduce high local concentration of fuel mixtures and prevent the occurrence of flammable
mixtures in localized regions of containment atmosphere or in compartments, provided the
ratio of the fuel volume present or generated is small compared to total containment volume.
The intent of mitigation by mixing is to dilute the mixture such that the lower flammability
limit is not exceeded. The mixing systems consist of redundant fan units which may, or may
not, be connected to a system of ducts to take the atmosphere from one containment region
and blow it into a different, and sometimes remote regions.
Advantage of individual fan mixing systems are plant specific. In general, systems with high
flow rates will ensure rapid mixing, but could also lead to turbulence, rapid changes of
atmosphere condition (possible inerting or de-inerting) and possibility to static conditions.
The disadvantage of these systems is their dependence on the availability of electrical power,
which may not be ensured during severe accidents.

Helium injection
Local accumulation of fuel (hydrogen) may occur due to temperature inversions. When the
density of the atmosphere in the upper part of the containment is sufficiently low, natural
convection mixing is limited essentially to the lower compartments. Convection could be
extended into the upper compartment region by injection of helium into a lower compartment,
thus reducing the density. The advantage of the helium method is that it needs limited electric
power , it also has an inerting effect. The disadvantage is that the mixing may not be achieved
as fast as with the fans and,
it may be designed to address only certain specific accident conditions and plant geometries.
Deliberate Ignition
The philosophy behind this type of mitigation scheme is to keep the combustible-air mixture
concentration below the flammability limit. Deliberate ignition schemes initiate controlled
combustion as near as possible to the flammability limits in order to :
a- avoid spurious burns
b- promote spatial and temporal distribution of the energy release associated with the
combustion.
Ignition may be initiated by manual control of glow plugs from control room. Deliberate
ignition systems have been installed in a number of containment buildings in nuclear plants.
Recombiners
A recombiner is a device that reduces the hydrogen concentration in the containment
atmosphere by combining free hydrogen and oxygen to form water. All the three types (
flame, thermal, and catalytic) perform the same function, they differ primarily in the way that
they initiate the recombination reaction:
- Catalytic recombiners use a precious-metal catalyst bed to induce recombination reaction
at relatively low temperatures.
- Thermal recombiners use radiant heat to bring about the recombination.
- Flame recombiners depend on self-maintaining, exothermic combustion process.
- Chemical absorption in liquid or solid substances.
Venting
Venting is an effective and commonly used technique to limit the combustion overpressures
resulting from deliberate or accidental combustion. To limit these overpressures, a vent
opening is provided on one of the side walls or the top of the building to be protected. The
vent is normally covered with panel or a rupture disk which bursts open on or near a
predetermined pressure differential. The peak pressure developed during venting depends on
several factors such as :
Mixture composition, igniter location, vent area, vent panel design pressure, and turbulence
generated in the building by fan and obstacles. Filtered containment venting schemes have
been adopted for application to certain nuclear reactors accident situations where it is
preferable to avert containment over-pressurization failure by allowing a small release of
radio nuclides in order to preserve to containment integrity. A containment failure can be
averted by relieving a gas at moderate flow rates through a filter system into the environment.

Inerting
One of the commonly used methods in fire suppression is dousing the flame with an inert gas
such as carbon dioxide. A mixture is inert if a flame cannot propagate through it. A mixture
may be inert due to lack of combustible (fuel) or oxygen or due to an excess of a diluent gas
such as steam. The main mechanism of suppression generally is the displacement of oxygen
with an inert gas. In gaseous fuel-air mixtures, the inert plays a different role : it extracts
energy from the combustion of fuel and reduces the peak flame temperature and pressure.
This in turn reduces the burning velocity of the mixture. Carbon dioxide and steam are more
effective as diluents than many other common gases such as nitrogen because of their high
molar heat capacities. Carbon dioxide reduces the flame velocity by reducing the flame
temperature as well as mass and thermal diffusivities of the mixture. It also effectively
scavenges active radicals, therefore, reducing the concentrations of the radical species
responsible for flame propagation. Steam inhibits combustion by reducing the flame
temperature. However, it also enhances combustion by its high third-body effectiveness in
radical-radical recombination reactions. The net effect of steam dilution on burning velocity is
about the same as that of nitrogen dilution.
The addition of large amounts of diluents may reduce the flame temperature nd burning
velocity to such an extent that flame propagation would be suppressed completely. The
amount or concentration of diluent required to completely suppress combustion is determined
by the flammability limits. As an example Figure ( ), shows the flammability limits for
hydrogen-air-carbon dioxide and hydrogen-air-nitrogen mixtures plotted as a function of the
diluent concentration.
Pre-Inerting
Is a hydrogen mitigation scheme that has been employed in nuclear power plants
containments . The concept is simply to inert the containment atmosphere with nitrogen
during operation, therefore eliminating the possibility of hydrogen combustion following a
loss of coolant accident LOCA. This method of control is particularly suited in small volume
containments for two main reasons:
First, larger containments must be accessible during operation, and accessibility is facilitated
by having a breathable atmosphere in containment. Second, the containments are so large
that, maintaining a nitrogen atmosphere during normal operation is difficult and expensive.
Partial Pre-Inerting
It means less gas is injected than necessary for a full suppression of combustion. Deflagration
is, therefore, still possible, but it was aimed that sufficient dilution would occur, so that
eventual deflagration would be mild and no significant loadings from combustion would
arise.
The partial pre-inerting, with nitrogen, of the containment atmosphere during operation is to
about 14% to 15% oxygen. The normal oxygen content of air is about 21%, so this represents
a gaseous mixture that is roughly 70% air and 30% added nitrogen. An atmosphere with this
composition is breathable. If partial pre-inerting is used in a situation where post inerting is
also employed, it provides a significant "head start" in case of an accident. The lower oxygen
concentration also promotes slower and weaker combustion. An advantage for partial pre-
inerting is that the containment pressure would not increase so much by the addition of inert
gases, as would be the case for full post-accident inertization.
Post-Inerting
Involves injection of noncombustible or combustion-inhibiting gases into the containment
atmosphere following the onset on an accident (but before release of significant quantities of
hydrogen). Post-accident inerting could be accomplished either through oxygen depletion or
through the addition of a diluent. Nitrogen and carbon dioxide have been considered as
candidate noncombustible (diluent) gases. The major concern with such a system would be
the time required to inert the containment after the onset of the accident . The device could be
located external to containment (connected by piping) or inside of containment with cooling
provided to prevent excessive heating of the atmosphere. The quantity of gas to be injected
depends on the inerting characteristics of the gas. Carbon dioxide seems to be the best at the
moment, as it has a greater specific heat than Nitrogen and a greater chemical stability than
Halon.
Deliberate ignition or post-accident inerting may be coupled with partial pre-inerting. For
post-accident inerting, partial pre-inerting would provide a significant head start and reduce
the time required to achieve an inserted condition. Post-inerting and partial-inerting schemes,
have, so far, not been applied in any nuclear power plant.
Steam will be released into the free containment volume during the blowdown phase and later
during the phase of core degradation. The partial pressure of the released steam determines
the over-pressurization of the containment during the accident. Steam will condense on all
containment internal surfaces, initially at ambient temperature. After termination of the blow
down and under conditions of moderate subsequent steam release from the primary system,
the partial pressure of steam finally may decrease below the minimum threshold for complete
suppression of flammability.
A post-inertisation system should be able to replace condensing steam as the primary inerting
agent and to preserve a sufficiently high inertisation degree.
In the case of scenarios with long lasting blowdown, phases inertisation should be initiated by
injecting only a part of the stored diluents gases (because steam will be released into the free
volume during this phase). To allow this flexibility the diluents storage should be divided
into several tanks. If necessary, additional tanks may be activated later. The necessary
information for an operator to continue with the injection could be provided by the accident
monitoring system, which supports any accident management measure.
In order to make post-inerting completely efficient in any accident scenario, steam or other
inert gases produced during the accident must be not considered . The presence of steam in
the H2/inert mixture was deleted after some consideration as stream is recognized to have
some considerable inerting effects. It was argued that the steam production and dispersion is
not controllable in an accident and that, therefore, a protective measure based on post-
inertisation should not incorporate the presence of seam but should be based on the presence
of hydrogen(combustible) only .
Injection of liquid carbon dioxide from pressure-resistant storage tanks is a proven technique.
Insurance companies have established rules for the proper design of pipe systems and spray
nozzles, including precautions against freezing of the nozzles . Injection of liquid carbon
dioxide released from a high-pressure storage tank is a proven technique. Immediately upon
discharge into the containment the temperature of the evaporating CO2 will be in the range of
2000K (-730C) providing a considerable driving head for buoyancy natural convection if
injected at proper locations into the upper dome of a containment building .
Severe analyses of nuclear plants accidents indicate that hydrogen formation may be expected
not before approx. 60 minutes after the initiating LOCA has occurred. Fire fighting
experience with liquid carbon dioxide injection shows that a time window of 30 minutes
should be sufficient to achieve total inertisation within a large volume compartment system .
Due injection of the inertisation gas the pressure level inside the containment should not
exceed the level reached during a coolant blowdown, thus remaining well below the design
pressure of the containment. If necessary, filtered venting may be finally activated to prevent
slow over-pressurization late in the course of a severe accident .
One way to reduce the pressure rise would be to use coupled volumes. The diluent gas would
be contained either in an adjoining building or in large gas bags within containment. During
an accident, the volumes would be connected and diluent gas and air would mix with a much
lower or negligible pressure rise .
Post-inertisation may also be applied in conjunction with the installation of catalytic
recombiners. Sufficient Oxygen will be available although at low partial pressure allowing a
continuous recombination of released hydrogen by catalytic recombiners.
A possible threat to vital containment-internal equipment by cold shocks stemming from
injected carbon dioxide snow has shown not be a real problem. Pipe systems are normally
protected by insulation. Other important aggregates like pumps etc. should not be target of
the injection nozzles as well as vital instrumentation and monitoring systems which may more
easily survive a period of lower temperatures than a period of very high temperatures caused
by a hydrogen fire .

Halon Inerting
Halon is a general term used to identify any of several halogenated hydrocarbons comprising
a group of gaseous fire-extinguishing agents.Among these, Halon 1301
(Bromotrifluoromethane CF3Br) exhibits good flame quenching capabilities. A key feature
of Halon is that it acts by chemically interrupting the combustion process, whereas regular
inerting materials (such as nitrogen and carbon dioxide) work by simply diluting the oxygen
concentration below the flammability limits and by providing a thermal heat sink. For this
reason, inerting can be achieved with significantly smaller amounts of Halon suppressing is to
chemically inert the containment atmosphere at some time after a serious accident begins and
before significant quantities of hydrogen are generated. The Halon would be stored in liquid
form in several storage vessels near containment and discharged, either automatically or
manually, into containment. Upon introduction into containment, the liquid Halon will
depressurize and immediately turn into a gas, thereby inerting the containment atmosphere
and preventing any hydrogen combustion .
The long-term effects of corrosion within the containment (due to CF3Br daughter species
created by the ionizing radiation from fission products) appear to be quite harmful. Despite
the problems associated with Halon inerting, it is widely employed in industry as a fire
suppressant and its use in nuclear applications promises to become more widespread.

Water Fog and Foams

Water can be used to cool the containment air, as well as equipment within the containment,
and thus mitigate the effects of hydrogen combustion. Consequently, water injection (in
several forms) has been proposed and studied as a mitigation scheme, either alone or
combined with deliberate ignition .

Sprays
Spray systems are capable of injecting very large flow rates of water into the containment
atmosphere. They are generally located in rings attached to the containment dome. The
initial distribution of spray droplet diameter is centered around 0.2-0.3 mm, but it contains a
significant spread, especially towards larger diameter drops. A theoretical upper limit for the
mitigating effects of water on hydrogen combustion can be calculated by assuming that a
certain volumetric fraction of the containment atmosphere is occupied by water that will be
heated and then evaporated very rapidly (compared to the burn propagation time throughout
the containment building). Unfortunately, the full beneficial effects of water cannot be
realized unless the droplets are quite small and the density is quite high (it is very difficult to
attain 0.5% volumetric water density with standard spray nozzles). Consequently, most of the
benefit of water sprays will be in cooling the containment atmosphere and contents after the
burn, rather than significantly decreasing the peak combustion pressure. The use of sprays
may in fact increase the peak combustion pressure due to turbulent, large-scale motions
generated by the injection process and local flame acceleration caused by the droplets
themselves. The mitigation effects of water sprays on diffusion flame combustion will be
very geometry specific , no benefit or great benefit may be derived.

Fogs
Water fogging involves the generation and dispersal of very small (diameters about 0.1 mm)
drops in a fine mist. Such a system would allow a much closer approach to the theoretical
pressure mitigation. A spinning disk device has in fact been constructed and used to create a
fine mist of 0.1-mm diameter droplets. This size distribution of droplets produced by this
device is quite narrow, which aids in suspending a relatively high density (volume fraction) of
droplets in the atmosphere. Fog generators are currently in use in nuclear containment
buildings.

Foams
Water-based foams are used routinely to mitigate or extinguish fire in buildings. Foam
generator systems are capable of creating dense foams (volumetric water contents > 0.1%)
very rapidly. These dense foams are fairly rigid and can in fact be loaded to a height of many
meters without a significant increase in breakup rate.
Several experimental studies have shown that this effect is true only for low concentration of
hydrogen. While foam appears to be beneficial at 10 and 15% hydrogen, at 20% hydrogen
the combustion was extremely violent with foam present. The foam generator was damaged
significantly by this 20% hydrogen test and it is possible that the mixture even detonated near
the end of the burn. The increase in scale that associated with a nuclear containment building,
coupled with the fact that a foam injected system might well create local high-concentration
pockets of hydrogen, have led to dismissal of foams as a viable scheme to mitigate hydrogen
combustion.

Combustibility of Flammable mixtures in containment.

Conditions of containment atmosphere under which mixtures may combust are governed by
flammability limits. Mass and energy equations are applied in order to govern the
containment pressure and temperature.

Flammability limits and correlation law

Flammability data exists for many ternary mixtures of fuel, oxidant, and a single inertant.
Those of importance include Hydrogen as fuel, Air as the oxidant, and Steam, Nitrogen and
Carbon dioxide as inertant. A sample flammability limit curves, figures below, show the
characteristic shape of a ternary flammability limit diagrams, for H2-Air-H2O & H2-Air-N2 ,
indicating lean and rich limits of fuel concentration with zero intertant ( vertical axis
intercepts) and an inertant concentration that prohibits burning for any fuel concentration ( the
tip of the nose formed by the flammability locus.
Generally, data are independently available for the flammability limits of ternary fuel-air-
intertant systems, and these must be combined empirically. The combined procedure, Le
Chatelier's law , is a valid approximation for systems of roughly similar flammability limits.
Data are not generally available for ternary systems except at a single temperature or along a
saturation line required to add the inertant.
A correlation for generalized H2-Air -H2O,CO2&N2 flammability limits from standard
temperature conditions to the auto-ignition temperature was developed by Plys et al. This
correlation is summarized in the following equations:
For ternary system, the flammability relation between the fuel concentration X and the
inertant concentration Y ( in mole fraction) is given by :
For H2-Air-H2O :

1
2.057
2.057 2.057
1 1
y 1.041
22.5 ( x 0.045) 0.8452 ( x .78)
For H2-Air-N2

1
1.42
1.42 1.42
1 1
y 1.023
1000 ( x 0.045) 1 (x .78)

Flammability limit correlation H2-Air-H2O Flammability limit correlation, H2-Air-N2

0.9

0.9

0.8

0.8

0.7
0.7
Fuel, (H2), mol/mol of mixture

Fuel, ( H2 ), mol/mol of mixture

0.6
0.6

0.5
0.5
Series1
Series1

0.4
0.4

0.3 0.3

0.2 0.2

0.1
0.1

0
0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0 0.1 0.2 0.3 0.4 0.5 0.6

Inertant, (H2O), mol/mol of mixture Inertant, ( N2 ), mol/mol of mixture

These flammability limit correlations are quite useful for severe accident analysis because the
entire anticipated concentration and temperature range is succinctly considered.
References :
A. Theory of Flame Quenching
1. Theory of Ignition, Quenching, and Stabilization of Flames of Non-Turbulent Gas Mixture,
Lewis, B. And G. Von Elbe
Third Symposium on Combustion, 1953, pp. 68-79
2. Quenching, Flash Back, Blow-off, Theory and Experiment,
Wohl, Kurt
Fourth Symposium on Combustion, 1953
3. A Thermal Equation for Flame Quenching,
Potter, A.E. , and Berlad, A.L.
NACA Report 1264, 1956
4. Thermal Theory of a Laminar Flame Front Near A Cold Wall,
Von Karman, and Gregorio Millan,
5. Quenching of Laminar Oxy-Hydrogen Flames by Solid Surfaces,
Friedman, Raymond,
Third Symposium on Combustion, 1949.
B. Diffusion Theory
1. An Active Particle Diffusion Theory of Flame Quenching for Laminar Flames,
Simon, D. And F.Belles,
NACA RM E51L18, 1952
C. Kinetics
1. Chain Breaking and Branching in the Active Particle Diffusion Concept of
Quenching,
Belles, F. and A. L. Berlad
NACA TN 3409, 1955
D. Effect of Some Variables on Flame Quenching
1. The Wall-Quenching of Laminar Flames as a Function of Pressure, Temperature, and
Air-Fuel Ratio,
Friedman, R. ,
Journal of Applied Physics, Vol. 21, No. 8, 1950, pp 795-797
2. The Effect of Fuel Type and Pressure on Flame Quenching,
Potter, A.E. , and Berlad, A.L
Six Symposium on Combustion, 1957
3. Relation of Boundary Velocity Gradient and Flash-Back to Burning Velocity
and Quenching Distance,
Potter, A.E. , and Berlad, A.L
Combustion and Flame, Vol. 1, No. 1, 1954,pp 127
4. Burning Velocities, Quenching and Stability Data on Non-Turbulent Flamed of
Methane and Propane with Oxygen and Nitrogen,
Harris, M.W. , J. Grumer, G. Von Elbe, and B. Lewis,
Third Symposium on Combustion, 1949
5. A relation between Burning Velocity and Quenching Distance,
Potter, A.E. , and Berlad, A.L ,
NACA TN3882, 1956.
6. Ignition and flammability of Hydrocarbon Fuels,
Belles w, F. , C. Swett,
NACA Report 1300, 195
7. Effect of Inert Gases on Some Flame Phenomena,
Mellish, C. E. , Linnett, J.W. ,
Fourth Symposium on Combustion, 1953
8. Chemical Action of Halogenated Agents, in Fire Extinguishing,
Belles, F.
NACA TN3565, 1955
9.Pressure Dependence of Quenching Distance,
Friedman, R. and Johnson,
Journal of Chemical Physics, Vol. 20, No 5, May 1952.
E. Quenching Distance
1. Flame Quenching at the Walls of an Internal Combustion Engine,
Daniel, W. A. ,
Sixth Symposium on Combustion
F. Burning Velocity.

K. Flame Propagation and Stability

1. Investigation and Interpretation of the Flammability Region for some
Lean Hydrocarbon-Air Mixture,
Simon, D., and F. Belles,
Fourth Symposium on Combustion, 1953
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