Self ignition temperature

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
auto‑ignition or self‑ignition. 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.
 A flame is initiated locally near the ignition source
and it propagates into the rest of the mixture.
 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 vvanted, i.e. fire
such as that occuring 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
V q   C V 0 (4.7)
dt
V q   C V dt  h S  T  To   0
dT
 (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
  C n  P n
q   WA A
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
exploding (abrupt temperature) adiabatic process.
Semenov Theory of Spontaneous Ignition
 Eq. 4.8 can be rewritten in the following eq.
dT
 CV dt
 q g  q l (4.8)
g
q
 Keeping the pressure fixed, (T) will be a steeply
rising function as shown in Figure 4.6(a)
q l
 (T) is a linear function of T with a slope of hS
l
q
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 mixture temperature.
 The right hand side of Eq. 4.8 as a function of T is
shown in Figure 4.6(b) for the three values of T0
Case: Wall temperature relatively low
q g
 When T0 = T03, the curve and line qintersect
l at
two points, a and b; at a and b thus dT/dt = zero.
 If the starting (i.e., T at time t = 0) reacting mixture
temperature T < Ta, (and by q g Eq.
q l 4.8, dT/dt) >
0 and < 0. So, a mixture d qwith  /<
g  q lT dt 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 Ta < T <
Tb, both and q g  q lq g that
< 0dso  q l  /the
dt 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
 When T = T , q
o o1
 curve
g and lineq l never intersect.
Thus, is alwaysq>g 0.
 qAs
l shown in Figure 4.7(c), the
temperature of the gases increases acceleratively.
Case: Wall temperature moderate:
 As the wall temperatures progressively > T are
03
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 T is a limiting one beyond
02
which the reaction progressively accelerates. The
corresponding temperature Tc is called
spontaneous ignition temperature of the reactant
gas mixture in the given vessel.
 T is not a fundamental property of the given
c
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 is given by the following two
equations.
q g c  q l c (4.18)
 d q g   d q l 
    (4.19)
 d T c  d T c

 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 law, Eqs.
4.18 and 4.19 become

n E /RTc
 H V kn C e
Ac 
 h s Tc  T0 c  (4.18a)

n E /R Tc  E 
 H V kn C e
Ac  2   hS (4.19a)
 R Tc 
 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  (4.20)
E
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)
E / R  Tc  R Tc2 / E 
 H V k 2 C 2A c e  
 h S R Tc / E 4.22 
 Since RTc/E << 1,
 H V k2 C e 2 E /RTc
Ac  h S R Tc /E 4.22a 
 If the gases are assumed perfect and if Pc and PA are
respectively the total pressure and the species A
partial pressure, P X P
Ac Ac c
CAc  
R Tc R Tc

where XA is the mole fraction of the species A.

 Equation 4.22 thus becomes,

 H V k 2  X AcPc /RTc  e
2 E /RTc
 h S R Tc /E 4.23
 If the composition X, is kept fixed, Eq. 4.23 relates
the critical pressure with the critical temperature.

P 2c  h S R3  E / RTc
4
 2 e
Tc  H V k2 X A E 
 Logarithmically,

0.5
P 
2
 hS R 3
 E
ln    ln 
c
4 2 
 (4.24)
T
 
c   HV k 2 X AE  2R Tc
 Eq. 4.24 is known as Semenov Equation. Plotting ln
(Pc/Tc2) on the y‑axis and (I/Tc) on the x‑axis, 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 U‑shaped. 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 fuel‑lean or too
fuel‑rich, 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.
 References

 “Combustion” by Irvin Glassman

 “Fuels and combustion” by Sharma and
Chander Mohan
 “Introduction to combustion” by
Stephen.R.Turns