11.

Ignition Processes

11.1 Simplified Semenov Analysis of Thermal Explosions

Assumptions:
• closed reaction vessel, mixture at rest
• no spatial gradients in the system
• Newton's law of heat exchange with the surrounding
• one-step reaction of first order F → P without consumption of fuel

Heat loss to the vessel surface (linear temperatur dependence):

V = χ S (T - Tw) χ = heat transfer coeffiient

S = surface of the vessel
Tw = wall temperature

Heat release due to chemical reaction (exponential temperature dependence):

P = Z exp(-E/RT) (hP - hF)

P, V P1
P2
P3

unstable
stationary
point

stable stationary
point

T T T T

P1, P2, P3 are curves for different activation energies (E1 < E2 < E3)
stationary behaviour (i. e. no explosion) is only possible, if P and V compensate

P1: P > V for all T ⇒ permanent increase of temperature ⇒ explosion

P2: P = V for T2, P > V for T ≠ T2 ⇒ only in point T2 stationary behaviour
P3: P = V for T1 and T2
⇒ for T < T1 the system tends towards point T1
⇒ for T1 < T < T3 the system tends towards point T1
⇒ for T > T3 explosion occurs

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11.2 Autoignition - Ignition-Delay Time

In many cases autoignition takes place after a ignition-delay time or induction time. This is caused by the
nature of the process which is a radical-chain explosion. The induction time is the time which is necessary
to build up the radical concentrations through chain branching steps.
Due to the strong dependence of the temperature of the chemical reaction the ignition-delay time depends
strongly on the temperature.

log T log T

τind
t t
Thermal Explosion Chain explosion

log τ / μs

3.0

CH4 C2H5OH C2H6 C4H10 n-C7H16

2.0

C6H6

1.0
1000 K

0.5 0.6 0.7 0.8 0.9 1.0 T

Calculated (curves) and measured (points) ignition delay times in stoichiometric hydrocarbon-air mixtures

E g / RT
As a rough approximation we obtain: τ ∝e Eg = "apparent global activation energy"

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11.3 Autoignition: Ignition Limits

p / mbar

1000

Slow reaction

100

Explosion

10

Slow reaction
1
T/K
750 800 850

p-T-explosion diagramm for a stoichiometric mixture of hydrogen and air (Points: experiments; Curves:
Simulations).

Interpretation of the three ignition limits:

First ignition limit:

Competition of chain branching steps in the gas phase and diffusion of radicals to the wall with
following chain termination. Thus there is no explosion at low pressure, because the diffusion
coefficient in inversely proportional to the pressure, and diffusion of the radicals to the walls
becomes very fast at low pressures.

Second ignition limit:

almost exclusively governed by chemical reaction in the gas phase: At increasing pressure chain
termination due to H + O2 + M → HO2 + M dominates, at decreasing pressure chain branching (and
therefore explosion) due to H + O2 → OH + O dominates.

Third ignition limit:

thermal ignition limit which results from the competition of heat release due to chemical reaction
Σhjrj and the heat losses to the wall. The heat production per volume increases with increasing
pressure, such that a transition to explosion is observed.

Hydrocarbon-air-mixtures: similar, but much more complicated picture, (multistage-ignition, cool flames).

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