N.

DARABIHA
Gnralits sur la
cintique de combustion
Samedi 29 Mai 2010, 11h00 12h30

Laboratoire d'Energtique Molculaire

et Macroscopique, Combustion
ECOLE
CENTRALE
PARIS

Nasser DARABIHA
nasser.darabiha@em2c.ecp.fr
http://www.em2c.ecp.fr
Tlphone : +33 1 41 13 10 72
Tlcopie : +33 1 47 02 80 35
1

Fluid
Mechanics

Ther

mody

nami

l
u
M

cs

h
p
ti-

Chemical
Kinetics

Combustion

e
s
a

w
o
fl

t
r
o
p
s
n
a
a
n
r
e
T
m
o
n
e
h
P
2

Why Chemical Kinetics?

Production and destruction of pollutants

Ignition,
Extinction,
Flame Structure,
..

Reacting mixture

Temperature

Collisions

Reaction

CONTENTS
- Some Definitions
- Thermodynamics
- Chemical kinetics
Arrhenius Law
Reaction rate
Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition
PSR

- Pollutants in atmosphere

Mixing of N species inside a volume

nk moles of species k ,

n=

k=1

1 mole = 6,02252*1023 molecules

mass :

m=

m = n

k=1

mk
Mass fraction Yk =
m
Mk
Yk = X k
M
!

k=1

k Mk

nk
Mole fraction X k =
n
N

m
Mixture Molar mass M = Xk Mk =
k=1
n
!
6

nk
Concentration Ck =
V

Density

n
" Ck = V # 1
k=1

mk
"k=
V

nk M k
"k =
= Ck M k
V!
Mass fraction

" = # "k
k=1

mk "k
Yk =
=
"
! m
7

Stoichiometric reaction
Enough oxidant O to burn all fuel F
FF + O O + N2

Products
mass stoichiometric coefficient

stoichiometric coefficient

F + S O + N2

Products
8

Stoichiometric reactions:
CnHm + (n+m/4) (O2 + N2)

nCO2 +(m/2) H2O + (n+m/4) N2

CH4 + 2 (O2 + N2)

CO2 +2 H2O + 2 N2

C3H8 + 5 (O2 + N2)

3CO2 +4 H2O + 5 N2

H2 + 1/2 (O2 + N2)

H2O + 1/2 N2

Mixture equivalence ratio

Stoichiometric reaction:
CH4 + S (O2 + N2)

Products

Any reaction ... :

CH4 + S( O2 + N2)

Mixture
equivalence ratio

Products
XCH4

XO2

XCH4
XO2

Stoich

1
S
"
S
=
=
1 S"
S
10

Any reaction ... :

S
CH4 + S (O2 + N2)
S"

Products

CH4 + S (O2 + N2)

Products

!
= 1

Stoichiometric mixture

> 1

Rich mixture

< 1

Lean mixture
11

Any reaction ... :

CH4 + S (O2 + N2)

Mixture
equivalence ratio

Products

YCH4

CH4 + S (O2 + N2)

YO2

YCH4
YO2

MCH 4
S " MO 2 S
=
=
MCH 4
S"
S MO 2

Stoich

Products
12

Air Factor
Any reaction ... :

CH4 + S (O2 + N2)

F=1/

Products

CH4 + F . S (O2 + N2)

Products

13

Air volume (excess)

CH4 + (1+ e ) . S (O2 + N2)

Products

e = F - 1 = (1 )/

e= 0

Stoichiometric mixture

e< 0

Rich mixture

e> 0

Lean mixture
14

CONTENTS
- Some Definitions
- Thermodynamics
- Chemical kinetics
Arrhenius Law
Reaction rate
Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition
PSR

- Pollutants in atmosphere

15

Thermodynamics
First principle
(no variation of kinetic and potential enery) :
dU = dQ + dW

dW

dW = -PdV
dU = dQ -PdV

dQ

dU

Constant volume reaction:

dU = dQ
Constant pressure reaction:
H=U + PV

dH=dU + VdP + PdV= dQ + dW + PdV

dH = dQ

16

Thermodynamics

Adiabatic Constant volume

reaction:

dU = 0

dW
0
dQ

dU

Adiabatic Constant pressure

reaction:

dH = 0
17

Thermodynamics
Species enthalpy

chemical

sensible

Mixture enthalpy

18

Thermodynamics

Mixture enthalpy :

chemical

sensible

with

19

Initial state - final state

T

final state: 2

P1
T1
Y1k

initial state : 1

YCO2

P2
T2
Y2k

If time is infinite
Final state = Equilibrium

Gibbs energy: G = H - TS
Equilibrium is reached when G is minimal (S is maximal)
20

Thermodynamic Equilibrium
CH4 + 2(O2

+ 3,76

N2)

Final equil. products

At the equilibrium state, burnt gases are composed of:

CO2 , H2O , N2 , CO, CH2 , CHi , H, H2 , OH ,
, O , O2 ,.,.,. , NO , NO2 ,.,.,.
Mathematically, the equilibrium composition
is obtained by minimizing G
21

Equilibrium burnt gases temperature

adiabatic constant pressure : H = cst
N

$# " A
k

$# "" A
k

k=1

k=1

initial state : 1

final state: 2

Adiabatic:

The only unknown

"Y

1k

k=1

hk (T1,P) = "Y2k hk (T2 ,P)

k=1
22

Equilibrium burnt gases temperature

adiabatic constant pressure
T1

"Y

1k

hk (T0 ,P) +

$ "Y

1k

c pk (T #,P) dT # =

T0 k=1

k=1

T2 N

"Y

2k

k=1

hk (T0 ,P) +

$ "Y

2k

c pk (T #,P) dT #

T0 k=1

c p 2 (T ")
23

Burnt gases temperature

constant pressure
Unknown
T2

#c

T1
p2

(T ") dT " $

T0

#c

T0

p1

(T ") dT " =
N

# (Y

1k

" Y2k ) hk (T0 ,P)

k=1

Heat released by the

combustion

!
!

24

c p1 (T,P) = "Y1k c pk (T,P)

CO

k=1

CO2

25

Burnt gases temperature

constant pressure
Assume all cpk = cst = cp and not temperature dependent

c p (T2 " T1 ) = # (Y1k " Y2k ) hk (T0 )

k=1

Unknown
Heat released by the combustion
26

Calorific value
It is the quantity of heat that can theoretically be
released per unit mass of fuel
Calorific value at constant pressure :
N

(PC) p = # (Y1k " Y2k ) hk (T0 , p0 )

k=1

(PC) p = h1 (T0 , p0 ) " h2 (T0 , p0 )

!
!

Calorific value at constant volume:

(PC) v = U1 (T0 , p0 ) " U 2 (T0 , p0 )

27

Calorific value
Calorific value: The quantity of heat released by the
complete combustion, per unit mass of a fuel, the vapor
produced by the combustion of the gas being assumed
to remain as a vapour.
High calorific value: The amount of heat released by
complete combustion, per unit mass of a fuel, the vapor
produced by the combustion of the gas being assumed
to be completely condensed and its latent heat released.

28

CONTENTS
- Some Definitions
- Thermodynamics
- Chemical kinetics
Arrhenius Law
Reaction rate
Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition
PSR

- Pollutants in atmosphere

29

Reacting mixture

Temperature

Collisions

Reaction
30

Collision frequency
Motion molecular velocity

Kuo, 2005

Volume through which the molecule

sweeps in 1s
For one molecule (if all other
molecules are motionless)
31

Collision frequency

32
Kuo, 2005

Collision frequency

A+A

A+B

2A + 3B

P
2

But all collisions do not lead to reaction

33

Arrhenius Law
Only molecules with E > Ea will react ...
Ea =Activation Energy
Svante Arrhenius (1859-1927)

dCB
= " fc P e
dt

Ea
"
RT

steric factor (depends on the

orientation of the colliding
molecules)

collision frequency

Boltzmann factor

with
R
34

Order of reaction
N

$# " A
k

$# "" A

k=1

dCM k
!

dt

k=1
N

= (# "k" $ # "k ) k f

% (C

Mk

# "k

k=1
N

Overall order of reaction :

m = $# "k
k=1
35

First order reactions

! Valid only for
elementary reactions

36

Second order reactions

AB

37

Third order reactions

Third order reactions

--> Becomes a 2nd order

reaction if CM38 is cst

Consecutive reactions
k1

k2

39

Parallel reactions
Twin reactions
k1

A + B ""# C
k2
A + B ""# D
dCC
= k1 CA CB
dt
dCD
= k2 CA CB
dt

CC k1
"
=
CD k2
40

Parallel reactions
Competitive reactions
k1

A + B ""# C
k2
A + E ""# D
dCC
= k1 CA CB
dt
dCD
= k2 CA CE
dt

CB 0

CE 0
k1
" ln
= ln
CB 0 # CC k 2 CE 0 # CD
41

Opposing (or reverse) reactions

N

kf

%%&
$# "k Ak '%%
k=1
kb

$# "" A
k

k=1

42

Opposing (or reverse) reactions

But complex mechanisms:
N species, I reactions :
kf

%%&
$# "k,i Ak '%%
k=1
kb
Each reaction

$# ""

k,i

Ak

for i = 1,.....,I

k=1

is characterized by a rate of progress

43

qi

General expression of reaction rates

Reaction rate of species k in the ith reaction is:

Reaction rate of species k for the overall mechanism is:

.
44

General expression of reaction rates

Molar reaction rate:

# mole
&
%
3 (
m s'
$

# kg
&
%
3 (
$ m s'

dCk
= "k
dt

dCk M k
= Mk "k
dt
!
as

!
!

Ck M k = " k = " Yk

d"Yk
= Mk #k
dt

Mass reaction rate

45

General expression of reaction rates

d"Yk
= Mk #k
dt
N

d"Yk
# dt = # M k $ k
k=1
k=1
N

Then:

# M "k = 0
k

k=1

Conservation
of mass
46

CHEMKIN
Thermodynamics
Data Base

Kinetics Scheme

CHEMKIN
Interpreter

LINK file

Set of CHEMKIN
Routines :
CKXTY
CKYTX
CKXTC
CKCPY
CKWXP
CKWYP
.
.

Users program (x. : equil, .)

47

CONTENTS
- Some Definitions
- Thermodynamics
- Chemical kinetics
Arrhenius Law
Reaction rate
Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition
PSR

- Pollutants in atmosphere

48

DETAILED CHEMISTRY

H2 + 1/2 O2
CH4 + 2O2

CH4 + 2 O2

H2O
CO2 +2 H2O

Products

Even at the equilibrium state, burnt gases are composed

of:
CO2 , H2O , CO, CH2 , CHi , H, H2 , OH ,
, O , O2 ,.,.,.,.,.,.
49

Chain reactions
Series of competitives, consecutives and opposing reactions
Apparition of intermediate species
Importance of free radicals
Radicals: highly reactive molecules or atoms
A2 + M " 2A + M

A + B2 " AB + B
B + A2 " AB + A
A + AB " A2 + B
B + AB " B2 + A
2A + M " A2 + M
2B + M " B2 + M

Chain-initiation reaction (A2 has a

lower Ea than B2)
Chain-carrying reactions:
radical -> radical (fast propagation)

Chain terminating reaction

50

H2 / O2 combustion

51

DETAILED CHEMISTRY
(H2 - O2 combustion)
Temperature

Collisions

O2 + M

2O +M

H2 + M

2H +M

Chain-Initiating
reactions

M denotes all other species as third body (O2, H2O, )

Delivering its energy to O2 and H2 helping them to dissociate

INITIATION : free - radical production

52

DETAILED CHEMISTRY
Chain-branching reaction : Radicals are more produced than
consumed
O + H2

H + OH

H + O2

O + OH

Very fast reactions

53

Example :
A 1 cm3 container with n =1019 molecules
and fc = 108 collisions / s
1 free radical per cm3

Chain-carrying:
time for all molecules to react = 1019/108 = 30,000 years

54

Chain reactions

Assume chain-branching reactions

1 radical --> 2 radicals

Chain-branching:
1 + 2 + 22 + + 2L= (2L+1-1)/(2-1) = 1019 molecules
after L=64 generations
Time to react = 64 / 108 1 s
Extremely fast reaction ....

If 1% of the reactions are chain-branching:

t 40 s
55

DETAILED CHEMISTRY
Chain-carrying : Radicals and final products

OH + H2

H2 O + H

O + H2O

2 OH

56

DETAILED CHEMISTRY
Chain-terminating steps : recombination mechanism
H+H+M

H2 + M

O+O+M

O2 + M

H+O+M

OH + M

H + OH + M

H2O + M
57

COMBUSTION of H2 / O2
H2 + O2
H2 + OH
O + OH
O + H2
H + O2 +M
OH + HO2
H + HO2
O + HO2
OH + OH
H+H+M
H + H + H2
H + H + H2O
H + OH + M
.
.

2 OH
H2 O + H
H + O2
OH + H
HO2 + M
H 2 O + O2
2 OH
O2 + OH
O + H2O
H2 + M
H2 + H2
H2 + H2O
H2 O + M

>10 species
>40 reactions

58

COMBUSTION of CH4 / O2
C2H6
CH4

C2H5

C3...
C3...

C2H4

CH3

C2H3

CH2O

C2H2
HCO

CH2
CH
CO

CO, CO2

59

OXYDATION of CO
Chain-terminating steps:
CO + OH

CO2 + H

CO + O2

CO2 + O

Main OH production reactions:

O + H2O

2 OH

H + O2

OH + O

At the flame front:

CO + HO2

CO2 + OH
60

CONTENTS
- Some Definitions
- Thermodynamics
- Chemical kinetics
Arrhenius Law
Reaction rate
Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition
PSR

- Pollutants in atmosphere

61

Application of spontaneous combustion

Hypersonic combustion (SCRAMJET)
Diesel engines
To be avoided in :
Safety characteristic length of fuel tanks
Semenov theory
Spark ignition engines (avoid pinking)

62

Spontaneous combustion

Adiabatic, constant pressure

63

Auto-ignition of a reactive mixture

Adiabatic, constant pressure

Initial conditions :
64

Auto-ignition of a reactive mixture

Auto-igniting
delay time

T0 > Ti

65

Auto-ignition delay time

i decreases exponentially with T0
i
ms

40

CH4

C2H2

10

Kerosene

CO
H2

1
0.5
1100

T C
1000

900

800

700

600

i changes as P01-n
Influence of equivalence ratio and dilutant66(YN2)

Spontaneous combustion
T = ambient: metastable state, reaction rate is
almost null
When T increases:
If T > Ti Beginning of exothermic oxidation
reaction:
production of enough radicals to ignite
If T < Ti Heat released is not sufficient to
increase the temperature, because endothermic
reactions absorb the heat to crack the fuel:
not enough radicals are produced to ignite
67

Spontaneous combustion
Container with constant volume with
isothermal wall (Tw) and a wall surface S

V
YF

S
Tw

T
YO

Heat losses Q
Container balance energy equation .
68

Spontaneous combustion

d"VYk
= V Mk #k
dt
d"VU
= # K S (T # Tw )
dt

U = " YkU k
k=1

dU k
dYk
# (" VYk dt + U k " V dt ) = $ K S (T $ Tw )
k=1
!
N
dU k
$ (" VYk dt + U kV M k # k ) = % K S (T % Tw )
k=1
69

Spontaneous combustion
N

dT
" V cv
= # % (V M k U k $ k ) # K S (T # Tw )
dt
k=1

dT
" V cv
= V # F Qv 0 $ K S (T $ Tw )
dt

Production

Heat loss

Fuel consumption rate modeling:

!
70

Semenov theory
Auto-ignition conditions

Production >

" F Qv 0

y1 (T )
!

Heat loss

S
# K (T $ Tw )
V

y 2 (T )
71

y(T)

Y1(T)

" F Qv 0
Production
(chemical)

T
72

Y (T)

Y2 (T)
Heat loss

S
K (T " Tw )
V

Tw

T
73

y1 y
2

Case 1: T0 high,

Tw

Auto-ignition

74

y1 y
2

Case 2: two curves are tangent

Tw

If T < Tc,

Tc

The temperature increases up to T=Tc

dT/dt =0 (unstable)
T = Tc + , Ignition

If T > Tc,

Auto-ignition
75

y2
y

y1

Case 3:
a
If T < Ta ,

Tw

the temperature
increases up to Ta and remains stable

If Ta < T < Tb , the temperature

decreases to Ta and remains stable
If T > Tb,

Auto-ignition
76

Varying K or (S/V)

The critical temperature

Tc is not an intrinsic
mixture property.
Indeed, it is function
of K and (S/V)

K
(S/V)
Tw

If the system is well insulated, K decreases,

and it increases the risk of auto-ignition
S/V=1/L
If L goes up, S/V decreases and it Increases
the risk of auto-ignition
77

Varying P

w
There exists a critical pressure Pc above which
there is always mixture auto-ignition.
78

Determination of ignition limits (Pi, Ti)

y

y1 y
2

Y1 = " F Qv 0
C

Tw

Ti

S
Y2 = K (T " Tw )
V
T

At the critical point C:

!
79

One shows that:

80

Determination of ignition limits (Pi, Ti)

Ignition

no combustion
Lean limit

Rich limit

Equivalence ratio

Ignition

no combustion
Lean limit

Rich limit

81
Equivalence ratio

Determination of ignition limits (Pi, Ti)

Ignition

no combustion

82

Hydrocarbons ignition limits

83

Temperature (K)

Influence of T0 on ignition (C7H16-air)

Time (s)

P0 =30 bars, =0.5

84

Influence of T0 on ignition (C7H16-air)

Ignition delay (s)

Cold flame
Principal ignition

Initial temperature (K)

P0 =30 bars, =0.5

85

CONTENTS
- Some Definitions
- Thermodynamics
- Chemical kinetics
Arrhenius Law
Reaction rate
Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition
PSR

- Pollutants in atmosphere

86

Perfectly stirred reactor (PSR)

Yk , hk, T
Volume V
INLET

m , Yk0 , hk0, T0

OUTLET

Yk , hk, T

!
Feed at the inlet at the state: X0
Homogeneous combustion
Burnt gases at the outlet

Residence time

Species mass balance equation :

IN

OUT

PRODUCTION
.

.
dYk
"V
= m Yk 0 # m Yk + $ k M k V
dt

k = 1,...,N

88

Enthalpy balance:
N

dh
"V
= m #Yk 0 hk 0 $ m #Yk hk $ Qh
dt
k=1
k=1

with h =

"Y

k=1

!
!

hk

" dhk %
dh
= ($Yk
' +
dt k=1 # dt &

dhk
dT
= C pk
dt
dt

dh
dT
= Cp
+
dt
dt
!

" dYk %
($# hk dt '&
k=1
N

C p = "Yk C pk
k=1

dYk
" hk dt
k=1

89

Enthalpy balance:
N

dT
" V Cp
= m #Yk 0 hk 0 $ m #Yk hk $ Qh
dt
k=1
k=1

%N
dYk (
$ '# hk " V
*
dt )
& k=1

dYk
"V
= m Yk 0 # m Yk + $ k M k V
dt

dT
" V Cp
= m #Yk 0 hk 0 $ m #Yk hk $ Qh
dt
k=1
k=1

& N
)

$ m #Yk 0 hk + m #Yk hk + ($#V 90hk % k M k +

' k=1
*
k=1
k=1

Balance Equations

dYk
"V
= m Yk 0 # m Yk + $ k M k V
dt

k = 1,...,N

N
&
)

dT
" V Cp
= m #Yk 0 hk 0 $ m #Yk 0 hk $ Qh + V ( $# hk % k M k +
dt
' k=1
*
k=1
k=1

Heat release rate

h
91

ATTENTION

dT
" V Cp
= m #Yk 0 hk 0 $ m #Yk hk $ Qh + h
dt
k=1
k=1

dT
" V Cp
= m #Yk 0 hk 0 $ m #Yk 0 hk $ Qh + h
dt
k=1
k=1

dh
"V
= m #Yk 0 hk 0 $ m #Yk hk $ Qh
dt
k=1
k=1

92

Application example

dYk 1
$k Mk
= (Yk 0 # Yk ) +
dt "
%
N

dT 1
1
Cp
= #Yk 0 hk 0 $
dt " k=1
"

k = 1,...,N

Qh h
#Yk 0hk $ %V + %
k=1

at t=0 , Yk(0)=Yk0 , T(0) = Ti

!

T0 = 300 K

Inlet

H2/Air mixture
Pressure= 1 atm

Volume V

Outlet
Yk (t),
hk (t),
T(t)
93

Stoic. H2/Air
T0 = 300 K
Pressure= 1 atm
Ti = 4000K

=0,01 s

94

Influence of
Ti = 4000K

Time (s)

95

Influence of
Ti = 4000K

Time (s)

96

Influence of
Ti = 4000K

Residence time (s)

97

Influence of Ti

=0,01 s

Time (s)

98

Influence of Ti

=0,01 s

Time (s)

99

CONTENTS
- Some Definitions
- Thermodynamics
- Chemical kinetics
Arrhenius Law
Reaction rate
Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition
PSR

- Pollutants in atmosphere

100

 CO2, H2O
CO

(vegetations, combustion)
CH4 (Rice, Ruminants., combustion)
CHx
Soot
NOx (Lightning, combustion)
COV (combustion)
SOx
Cl
Br.
..
..
101

Impact of Pollutants
on the atmosphere

102

Troposphere : Altitude < 10-15 km,

T 220K
NO2
O2 + O +M
NO + O3

k1
k2
k3

day
NO + O

k1 (h)

!>

night

k2 very fast

O3 + M
NO2 + O2

=> Fragile equilibrium

Production of O3
If steady state for NO:

O3

k1 C NO

k3 C NO

If NO decreases and NO2 increases : Increase of O3

Effect of CO
CO + OH CO2 + H
H + O2 + M OH2 + M

Importance of OH :
Initiation of the
process

104

Effect of CO
If [O3] / [NO] < 5000
HO2 + NO NO2 + OH
NO2 + h NO + O
O2+O+M O3 +M

If [O3] / [NO] > 5000

HO2 + O3 OH + 2 O2

( > 420 nm)

Balance :
CO +2 O2 CO2 + O3

Formation of O3

Balance :
CO + O3 CO2 + O2

Destruction of O3
105

Effect of CH4
CH4 + OH CH3 + H2O
CH3 + O2 + M CH3O2 + M
CH3O2 + NO CH3O + NO2
CH3O + O2 CH2O + HO2
CH2O + O2 HCO + HO2
2 HO2 + 2 NO 2 NO2 + 2 OH
HCO + OH CO + H2O
3NO2 + h 3NO + 3O ( > 420 nm)
3O2+3O+3M 3O3 +3M

Balance :
CH4+ 6 O2 CO + 2 H2O + 3 O3

20%
106 - 50% of CO
in atmosphere

NO - NO2 Photochemical Cycle

< 420nm

NO

NO2

O2

O2
O3

Day time
Solar radiation allows
formation of O
Formation of O3 (O + O2)
Produced NO reacts with O3
and forms O2 et NO2
Establishment of equilibrium
Night
no production of O
Consumption of O3 by NO
emitted by cars (unless the
wind has moved O3 away)

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NO - NO2 Photochemical Cycle

in polluted atmosphere
Day time
New mechanism of NO2 /
RH formation
No consumption of O3
Continuous increase of O3

< 420nm

NO

NO2
RO2

+RH
O2

O2
O3

Night
no production of O
Consumption of O3 by NO
emitted by cars (unless the
wind has moved O3 away)
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Troposphere : < 10-15 km, T

acid rain
NO2 + OH

HNO3

220K

Stratosphere : > 10-15 km, T

Ozone layer :

O2

k1

O + O2

2 O

270K

k1 (h)

O3

Destruction of O3 by X : NO, OH, Cl, Br, .....

X + O3
XO + O
O3 + O

XO + O2
X + O2
2 O2

Direct Effects of NOx on

atmospheric equilibrium
NOx participate in the formation of ozone
in the troposphere : Smog
NOx participate in the destruction of the
ozone layer in the stratosphere

111