Theory of Thermal Ignition

Ignition
Most of the energy released in a combustion

reaction is in thermal form while a fraction is

released in the form of light.
Emission
of light is either due to
incandescent solid particles such as carbon
in the flames (hot light = incandescence) or
due to some unstable (excited) intermediate
species (cold light = chemiluminence).
Of the heat generated, part is lost from the
reacting mixture and part is retained by it.

(a) Thermal Ignition

Under
certain conditions of heating
brought about by an external source of
energy such as a spark, hot vessel walls,
compression, etc., there is always some
temperature of the reacting mixture at
which the rate of heat generation exceeds
the loss rate.
The excess heat increases the mixture
temperature which in turn leads to higher
reaction rate. The mixture temperature
rises continuously and acceleratively until
a high heat evolution rate is attained.
Ignition is then said to have occurred.

In

reality, the accelerative rise of

temperature is quite abrupt; the previously
invisible slow reaction suddenly becomes
visible and measurable.

An uncontrollably fast reaction is known as

an explosion. Closed vessel explosions are

very common in practice.

At ignition, any combustion reaction seems

as though it were an explosion. For this

reason, superficially, the terms "explosion"
and "ignition" are used synonymously in
the combustion literature.

(b) Chemical Chain Ignition

If the combustion reaction involves intermediate
chain carriers, ignition is possible even under
isothermal conditions. If the rate of chain carrier
generation exceeds the rate of their
termination, the reaction becomes progressively
fast and subsequently leads to ignition.
The chain initiation itself may require an

external source of thermal or photon energy.

Once the chain is initiated, the external source
may be removed and ignition may be expected
if the above criterion of positive chain carrier
balance is fulfilled.

Determination of the conditions under which a

given combustible mixture ignites, is an

important topic in the design of combustion
engines as well as in fire prevention.

(c) Scope of the Present Chapter

A major part of the rest of this chapter
deals with ignition and extinction from a
thermal viewpoint.
The
concepts
of
ignition
delay,
flammability limits, and minimum ignition
energy are presented through this thermal
theory.

(d) Two Types of Ignition

Experience shows that there are two general
modes of ignition spontaneous and forced.
Spontaneous ignition
Spontaneous

ignition is sometimes called as

autoignition or selfignition. Spontaneous ignition
occurs as a result of raising the temperature of a
considerable volume of a combustible gas mixture
by containing it in hot boundaries or by subjecting
it to adiabatic compression.

Because the heat generation rate is a strong

exponential function of temperature whereas the

heat loss rate is a simple linear function, even a
slight increase in the temperature of the reacting
mixture would greatly increase the rate of its
temperature rise.

As a consequence, once the generation

rate exceeds the loss rate, ignition occurs

in
the
whole
volume
almost
instantaneously.
The reaction then proceeds by itself
without any further external heating.
Forced ignition
Forced ignition occurs as a result of local

energy addition from an external source

such as an electrically heated wire, an
electric spark, an incandescent particle, a
pilot flame, etc.

There are many instances in which a fuel

and an oxidant are rapidly mixed at a high

temperature which can result in a
spontaneous ignition.
For example, a spray of diesel fuel into the
hot compressed air is in part vaporized and
mixed with the air in a very short time.
Following a definite delay, the reaction
would proceed rapidly enough to be
considered a flame.
There are technically important instances
of spontaneous ignition where it is not
wanted, i.e. fire such as that occurring on
oil splashed on hot surfaces and the knock
in a gasoline engine.

Spontaneous Ignition
Spontaneous Ignition Delay
(a) The Criterion
Consider a vessel of volume V and
surface S containing a combustible
mixture. Let T0 be the initial temperature
of the mixture. Assume that the
temperature at any later time in the
mixture is spatially uniform. Let the
vessel walls be kept at T0 for all times.

dT
&

Vq CV
0
dt
dT
&

Vq CV dt hS T To 0

(4.7)

(4.8)

Eq. (4.7) applies to adiabatic combustion

system
Eq. (4.8) takes into account the heat
transfer from flame to the wall
First term represents heat generation by
reactions
Second term represents accumulation of
heat in the vessel
Third term represents heat transfer

If the heat transfer coefficient is constant, at

a very low pressure the reaction rate will be

small because
the system then practically remains at T =
To
At a very high pressure, the heat generation
overwhelms the loss term (i.e. the system
approaches adiabatic conditions). The
temperature and the reaction rate, then,
enhance one another until spontaneous
ignition occurs.
Therefore, it is reasonable to expect that
there exists a critical pressure below which
the reaction behaves more like an
isothermal (non-explosive) process and
above which it behaves like a spontaneously

(b) Ignition delay

The criterion of positive heat balance is
required for spontaneous ignition
& hS T T
HVW
A
0

(4.14)

When the limiting case of adiabaticity is

approached, Eq. 4.8 with 3rd term = 0 can

be used to deduce the concept of ignition
delay (sometimes called ignition lag,
induction time, or ignition time).
The strong influence of temperature on a
simple thermal reaction rate is often
expressed by the conventional Arrhenius
exponential or by a simple power law.

WA kn C nA T

(4.15)

WA k n C nA eE / RT

(4.15a)

The power m is of the order 20 to 30 for

most combustible mixtures whereas the

activation energy E is of the order 20 to 60
kilocalories per mole.
Incorporating Eq. 4.15 into Eq. 4.7 and
1
integrating,
the
time
of

history

temperature
is obtained as
m1
T

To

C T0

n
m
m 1 H k C T

n
A0
0

(4.16)

Equation 4.16 indicates that as the time

C T0

t
m 1 H k Cn T m
n
A0
0

the temperature T of the reacting mixture

rises very steeply.
The critical time

ti

C T0

m 1 H kn CnA0 T0m

is called ignition delay

(4.17)

Eq. 4.17 shows that the ignition delay is short

if the mixture has a low volumetric heat

capacity, high temperature dependence of the
rate, high heat of combustion and high initial
reaction rate.

Incorporating Eq. 4.15a into Eq. 4.7 and

integrating,
the
time
history
of
temperature is obtained as with the
assumption
of
negligible
reactant
consumption during the ignition delay, the
2
time history
of temperature is t
T
exp E / RT0 T0 / T 1 1
ti
T0

(4.16a)

where

E / RT0

R T02
e
ti C

n
E H kn CA0

(4.17a)

Figure 4.5

illustrates
mixture
temperature
at fraction of
delay time
for various
values of E/RT0

Semenov Theory of Spontaneous

Ignition
Eq. 4.8dTcan be rewritten in the following eq.
&g q
&l
CV d t q
(4.8)
&g
q

Keeping the pressure fixed,

(T) will be a
rising function as shown in Figure
q&steeply
l

4.6(a)
q& l

(T) is a linear function of T with a slope

of hS cal/(sec K). Keeping hS fixed, three
different
(T) functions are also shown
in Figure 4.6(a) corresponding to three
values of the wall temperature T0. T is

Case: Wall temperature relatively low

&g
q& l
When T0 = T03,q
the
curve
and
line
intersect at two points, a and b; at a and b
thus dT/dt = zero.
&g q&l
q
If the starting (i.e., T at time t = 0) reacting
&g q
&l / dt
d q
mixture
temperature
T < Ta,
(and by Eq. 4.8, dT/dt) > 0 and
<
0. So, a mixture with T < Ta slowly heats
up until Ta (or dT/dt > 0), at a rate which
continuously decreases with time (d2 T/dt2
< 0). Curves of such heating for four
different values of the starting temperature
are shown in Figure 4.7(a).

If the starting temperature of the mixture is

&g q
&l / dt
d q
&l T , both
q
Ta <q&gT<
b

and

<0

so that the mixture cools down to Ta at a

continuously decreasing rate. Such cooling
curves are shown in Figure 4.7(a) for three
different values of the starting
temperature.
If the starting temperature of the mixture T

> Tb, both dT/dt and d2T/dt2 > 0 so that the

temperature of the reacting gases
increases at an accelerating rate as shown
by four curves in Figure 4.7(a).

Case: Wall temperature relatively high

&l
&g
q
q
When To = T
curve and line
o1,
&g q
&l
q
never intersect. Thus,
is always > 0.
As shown in Figure 4.7(c), the temperature
of the gases increases acceleratively.
Case: Wall temperature moderate:
As the wall temperatures progressively >
T03 are considered, the points a and b
approach one another when ultimately they
coincide at the point c corresponding to a
critical wall temperature T02 in Figure 4.6(a).
The heat balance curve for this situation is
shown in 4.6(b). The heating curves are
shown in Figure 4.7(b).

Important criteria concerning spontaneous

ignition
The wall temperature T02 is a limiting one
beyond which the reaction progressively
accelerates. The corresponding temperature
Tc is called spontaneous ignition temperature
of the reactant gas mixture in the given
vessel.
Tc is not a fundamental property of the given
fuel/oxidant mixture. The vessel in which such
a mixture is contained has quite a strong
influence on it.

At the critical point, c, the curve and the

line are tangential. The interrelationship

between pressure, temperature and
composition at the ignition threshold hence
&g
&l following two equations.
dq
dq
is given
by
the

(4.19)

dT

dT

q&g c q&l c

(4.18)

In the above analysis, the pressure (i.e. the

reaction) and the heat transfer coefficient

are kept fixed and the critical wall
temperature is deduced

Keeping the reaction (=pressure) and wall

temperature fixed while seeking for the

critical heat transfer coefficient results in
Fig. 4.8

Keeping the wall temperature and the heat

transfer coefficient fixed and while seeking

for the critical reaction (=critical pressure)
results in Fig. 4.9

Application of Semenov Theory to

Predict
Ignition Range
The critical point c in Figure 4.6(a) marks
the transition of a slow stable reaction into
one that is explosive. Assuming Arrhenius
type rate nlaw,
4.18 and 4.19 become
E / RTEqs.
c

H V kn C Ace

n E / R Tc
Ac

H V kn C e

hs Tc T0c

E
hS

2
RTc

(4.18a)

(4.19a)

Eliminating H Vkn CAcn/hS from these two

equations and with an assumption that the

amount of reactant consumed in the ignition
delay is negligible,
RTc2
Tc T0c
E

(4.20)

This quadratic has two roots; the lower one

applies to ignition and the upper one to
extinction.

Substituting Eq. 4.20 in Eq. 4.18(a) we obtain

for a simple second order thermal reaction

(applies to most of HC/air reactions)

H V k2 C e
2
Ac

E / R Tc RTc2 / E

Since RTc/E << 1,

2 E / RTc
Ac

H V k2 C e

h SR Tc / E

h SR Tc / E

4.22

4.22a

If the gases are assumed perfect and if Pc and

PA are respectively the total pressure and the

species A partial pressure,
PA c
XA cPc
CAc

RTc
RTc

where XA is the mole fraction of the species A.

Equation 4.22 thus becomes,

E / RTc

H V k2 XAcPc / RTc e

4.23

hSR Tc / E

If the composition X, is kept fixed, Eq. 4.23

relates the critical pressure with the critical

temperature.

P2
hSR3
E / RT
T

c
4
c

e
HVk2 X E

2
A

Logarithmically,

hSR
ln ln
2
HVk2 X A E
T
2
c
4
c

0.5

2RTc

(4.24)

Eq. 4.24 is known as Semenov Equation.

Plotting
ln (Pc/Tc2) on the yaxis and (I/Tc) on the
xaxis, Eq. 4.24 gives a straight line with a
slope of E/2R (see Figure 4.10).

 Pc Tc plane, as shown in Figure 4.11, delineates

the ignitable from non-ignitable conditions.

At low pressures, very high temperatures are
needed to accomplish ignition and vice versa.

Equation

4.24 can also be used to

construct the ignition ranges on a T XA
plane at a fixed total pressure and on a P
XA plane at a fixed temperature (see
Figures 4.12 and 4.13)
In general, these graphs are Ushaped. The
conditions lying inside the U result in an
ignition whereas those lying outside, do
not.
Several inferences can be drawn from
these figures (see T XA relation given by
Figure 4.12)

1. Firstly,

there exist a lower and an upper

concentration limits for ignition; if the mixture is
too fuellean or too fuelrich, ignition is not
possible no matter what the temperature is. The
critical fuel concentration, below which ignition
is impossible, is known as the lower limit of
ignitability; and that above which ignition is
impossible, is known as the upper limit.

2. Secondly, as the temperature is lowered, these

two limits approach one another, thus narrowing

the range of ignition.
3. Thirdly, if the temperature is very low, ignition is

impossible at any composition.

Forced Ignition
Some Preliminary Concepts
When a cold reactant mixture is rapidly and locally

heated by a heat source (an incandescent solid

particle, a heated electrical filament or a spark, a
pocket of hot gas, or a pilot flame), a flame can be
initiated in the vicinity of the heat source and
propagated into the rest of the cold mixture. Such
an initiation of a propagating flame is defined as
forced ignition.

Both spontaneous and forced ignition share the

common
virtue
of
selfacceleration
and
autocatalytic behavior motivated by thermal
and/or chain branching reactions.

Initial provocation by an external source of energy

is necessary for both types of ignition.

The

phenomenon of forced ignition is

considered in this section in a thermal
viewpoint in order to systematically
develop
some
simple
relationships
between the critical physicochemical
properties of the system.

Let us examine the definition of forced

ignition by a hot particle. Consider as

shown in Figure 4.17 an incandescently hot
metal particle (whose temperature is Tw)
located in an infinite combustible mixture
(whose temperature T0 < Tw). Tw: wall
temperature of hot particle.

Case: Tw is moderate (see Fig. 4.17)

A steady state temperature profile T = T(x)

is established in such a way that the

steepest
temperature
gradients
are
confined to a thin boundary layer around
the particle.
Profile
(a)
when
the
mixture
is
noncombustible and (b) when it is
combustible.
The difference between these two profiles
is due to the heat release in chemical
reaction. In terms of the temperature
gradients at the wall, the heat flow from
the wall to the mixture is lower when the

Case : Tw is high (see Fig. 4.18)

The higher Tw, the lower the heat flux from

the wall (the rate of reaction is even

higher).
At a critical particle temperature Tc, the
heat flux from the wall to the reactive
mixture is zero.
If the particle temperature is even slightly
> Tc, the enhanced reaction in the mixture
shows a maxima of temperature (Tmax) of
the flame a small distance away from the
particle surface. Heat flows then partly to
the particle and mostly to the reservoir of

The higher Tw, the higher the exothermic heat of the

reaction rendering one time Treaction > Tw.

When dT/dx at and normal to the igniting particle

surface = 0, the reaction layer of gas (i.e., the flame)

begins to propagate into the unburnt mixture.

The

onset of this propagation is conveniently

considered as the criterion for forced ignition.

dT/dx in a reacting mixture are always accompanied

by composition gradients (dC/dx)

In the immediate vicinity of the particle,

the concentration of the reactants will be

the lowest and that of the products will be
the highest
Far away from the particle, the product
concentration will be zero and the reactant
concentration will be equal to the initial
value
As a result of the concentration gradients,
the products diffuse away from the particle
whereas the reactants diffuse towards the
particle to replenish the depleted mixture
with fresh new reactants.

Propagation of flame (see Fig. 4.19)

The fundamental flame speed (uo) is defined as
the speed at which the flame front travels in a
direction normal to itself and relative to the speed
of the unburnt mixture.
The temperature across the flame front varies from

the flame temperature Tf behind the front to the

initial mixture temperature T0 ahead of the front.
The flame thickness f is defined as the ratio of the

maximum temperature difference to the maximum

temperature gradient

Tf T0

dT / dx max

4.33

Phenomena of propagation
Heat is generated by combustion in a layer
of gas mixture of thickness f.
Due to the temperature gradient, the heat
so generated is transferred by conduction
to the unburnt gases.
Utilizing this heat, the unburnt mixture
heats up so that the combustion front
progresses forward at a velocity u0.

The heat generation rate is given by

&. .A
&g H.W
q
f

4.34

where W"' is the rate of combustion

averaged over the flame thickness, f and
the area of cross section considered, A.
The rate of conduction heat transfer is
given approximately by
q&k K A Tf T0 / f
4.35
K = thermal conductivity of unburnt gas

The rate of heating to raise the

temperature of a unit mass of the unburnt

mixture from T0 to Tf is C (Tf T0) cal/gm.
q&h 0 u0 AC Tf T0
4.36
where 0 is the density of the unburnt
&is
q
K the specific heat of
mixtureq&and
C
g
unburnt gas.
Equating
and
,
1/ 2
K Tf T0
f
(4.37)
&
H W

Eq. 4.37 shows that the flame thickness is

larger if the mixture conductivity is larger,

(Tf T0) is greater and the average heat
q& K rate isq& h lower
production
Equating
0 K / 0C and recalling the
and
definition
0 of thermal diffusivity
f
(4.38)
u0

&g
q
Equating

q& h
and

0u0C Tf T0
f
&
H W

4.39

Eliminating f from Eqs. 4.37 and 4.39,

1
u0

0C

1/ 2
&
K H W

Tf T0

4.40

The flame speed is greater if the mixture

conductivity is greater, mean heat production rate
HW"' is greater, the volumetric specific heat of
the original mixture is lower and (Tf T0) is lower
Effect of pressure on the flame speed

u0 P(n2) / 2

(4.41)

For most HC fuels burning in air or O 2, n is 2 so

that the fundamental flame speed is nearly
independent of the total pressure
So, a good fire extinguisher is that has low thermal
conductivity and high heat capacity

The most conducive conditions for ignition

(u0
high) are provided by
A low flame temperature
A high initial temperature
A high heat of combustion
A high mean reaction rate
A low volumetric heat capacity
A high thermal conductivity
A high total pressure
A mixture whose composition is nearly
stoichiometric
A low gas velocity (for flame stabilisation)
A low intensity of turbulence, if the flow is
turbulent

Range of ignition
Fig. 4.24 indicates that Emin is the least for

a
mixture
whose
composition
is
stoichiometric (or nearly stoichiometric).
If the mixture gets "leaner" or "richer," the
Emin increases first gradually and then
abruptly.
The abrupt rise of Emin suggests that when
the mixture is too "lean" (i.e. if the fuel
content < l % in Figure 4.24) or too "rich "
(i.e. if the fuel content > r % in Figure 4.24)
ignition is possible only if "infinite" amount
of energy is supplied through the igniter

Some relevant matters on Fig. 4.24

All
the
energies
and
compositions
corresponding to the area lying inside the
U result in an ignition whereas those lying
outside do not.
Ignition is impossible if the mixture is too
lean or too rich. The upper and lower limits
of flammability (corresponding to
r
and l in Figure 4.24) are characteristic of
the nature of fuel/oxidant combination.

For any given energy Eig, all mixtures, lying

between an upper (B) and a lower (A)

limits of composition, can be ignited. All
the mixtures lying outside these limits
cannot be ignited.
The range of ignitionABis narrowed if Eig
is chosen smaller. If Eig < Emin, ignition is
impossible for any mixture.

Flammability curves found extensively in

the combustion literature delineate the

ignitible and nonignitible domains on a
pressure (or temperature) and composition
plot. These curves are similar to Figures
4.12 and 4.13. It was found that as the
pressure is decreased, the Ucurve of
Figure
4.24
progressively
becomes
narrower, the upper and lower limits
ultimately coinciding as the minimum
pressure is approached.

If the initial temperature of the mixture is

raised, it is wellknown that the ignition

range is broadened for most HC/air
mixtures. That is, the lower limit is
decreased and the upper limit is raised.
Addition of inert gases to the combustible
mixtures narrows the ignition range, such a
narrowing being mainly due to a decrease
in the upper limit. The maximum amount
of the inert gas necessary to eliminate
ignition altogether is a matter of
importance in the extinguishment of
accidental fires.