Chemical Kinetics

1
Global vs. Elementary Reactions

Law of Mass Action

Arrhenius Law

Relation between forward and reverse reaction rates

Steady State approximation
from S.R Turns
Hydrocarbon Combustion (Turns p. 157)
2
H
2
-O
2
Combustion (Turns p. 117)
3
4
Reactor models
Constant pressure reactor
T = T(t)
[X
i
] = [X
i
](t)
V = V(t)
Constant volume reactor
T = T(t)
[X
i
] = [X
i
](t)
P = P(t)
5
Reactor models (contd.)
Well-stirred reactor
T = constant
[X
i
] = constant
P = constant
Plug-flow reactor
T = T(x)
[X
i
] = [X
i
](x)
P = P(x)
V = V(x)
6
Assumptions:
No temperature gradients
No composition gradients
i.e. T and [X
i
] are functions of time
Known:
| | | |
0
0
) 0 (
) 0 (
i i
X t X
T t T
= =
= =
Constant Pressure Reactor
7
Conservation of energy (First Law of Thermodynamics):
|
.
|

\
|
+ =
+ =
dt
dv
P
dt
dh
m
dt
dv
mP
dt
du
m W Q

dt
dh
m
Q
=

Constant Pressure Reactor

Expressing system chemical enthalpy in terms of chemical composition,
m
h N
m
H
h
i
i i
= =
8
(

|
|
.
|

\
|
+
|
.
|

\
|
=

i i
i
i
i
i
dt
h d
N
dt
dN
h
m dt
dh 1
Assuming Ideal Gas behavior (h is a function of T only) :
dt
dT
c
dt
dT
T
h
dt
h d
i p
i i
,
=
c
c
=
Constant Pressure Reactor (contd.)
9
( ) | |
[
= =
|
|
.
|

\
|
=
N
j
i
M
k
u
ak
k k i k i i
k j
k
X
T R
E
T A
1 1
'
,
"
,
,
'
exp
v
o
v v e

The rate of change of N

i
:
[ ]
i
i i i
dN
N V X V
dt
e =
Where,
Substituting these expressions in the First Law,
| | ( )

|
|
.
|

\
|
=
i
p i
i
i i
i
c X
h
V
Q
dt
dT
e

Constant Pressure Reactor (contd.)

1
10
Where,
| | ( )

=
i
i i
MW X
m
V
}
+ =
T
T
i p i f i
ref
dT c h h
,
0
,
Constant Pressure Reactor (contd.)
| |
| |
dt
dV
V
X
dt
dV
V
N
dt
dN
V dt
V
N
d
dt
X d
i i i
i
i
i
1 1 1
2
= =
|
.
|

\
|
= e

The rate of change of [X

i
] is given by :
11
| |
| |
| |
(
(
(

+ =

dt
dT
T X
X
dt
X d
i
i
i
i
i i
i
1
e
e

By using the ideal gas law :

dt
dT
T dt
dN
N dt
dV
V
i
i
i
i

+ =
1 1 1
Constant Pressure Reactor (contd.)
2
i u
i
PV N R T =

Differentiating
12
Constant Pressure Reactor (contd.)
Solution Methodology:

System of First order ODEs

Integration routine capable of handling stiff equations


13
Assumptions:
No temperature gradients
No composition gradients
i.e. T and [X
i
] are functions of time
Known:
| | | |
0
0
) 0 (
) 0 (
i i
X t X
T t T
= =
= =
Constant Volume Reactor
14
Conservation of energy (First Law of Thermodynamics):
dt
du
m W Q + =

dt
du
m
Q
=

Constant Volume Reactor

Expressing system chemical internal energy in terms of chemical
composition,
| |( ) ( )

+
|
|
.
|

\
|
=
i
u p i
i
i i
i
i u
R c X
h T R
V
Q
dt
dT
i
e e

1
15
Constant Volume Reactor (contd.)
Also, the rate of change of pressure (using Ideal Gas Law):
The rate of change of [X
i
] is given by :
| |
i
i
dt
X d
e

=
| |

+ =
i
i u
i
i u
dt
dT
X R T R
dt
dP
e

2
16
Well-stirred reactor
Conservation of species for the integral CV :
Assumptions:
Steady state operation
Steady flow operation
System is perfectly mixed and
homogenous in composition
in i
in i
h
Y
m
,
,

out i
out i
h
Y
m
,
,

out i in i i
cv i
m m V m
dt
dm
, ,
"' ,
+ =
Rate of
accumulation
of mass i in
CV
Rate of
generation of
mass i in CV

Mass
flow of i
into CV
Mass flow
of i out of
CV
Known:
in i
Y V m
,
, ,
17
Well-stirred reactor (contd.)
Since diffusional mass flow rate is negligible,
0 ) (
, ,
"'
= +
out i in i i
Y Y m V m
( ) | |
[
= =
|
|
.
|

\
|
=
' ' '
N
j
i
M
k
u
ak
k k i k i i i
k j
k
X
T R
E
T B MW m
1 1
'
,
"
,
,
'
exp
v
o
v v
Where,
i i
Y m m =
Hence, conservation of mass :
for i = 1,2,,N
Since the reactor is homogeneous, the mass fraction at the outlet is
equivalent to that inside the reactor
| | ( ) | | ( ) T X f T X f V m
out
i
cv
i i
, ,
"'
= =
18
Well-stirred reactor (contd.)
Conservation of Species provides N equations with N+1 unknowns
Additional equation from conservation of energy

( )
in out
h h m Q =

| |
| |

=
=
N
j
j j
i i
i
MW X
MW X
Y
1
Where, [X
i
]and Y
i
are related as
Conservation of energy for steady state,
steady flow conditions:
In terms of individual species :
( ) ( )|
.
|

\
|
=

= =
N
i
in i in i
N
i
i out i
T h Y T h Y m Q
1
,
1
,

19
Well-stirred reactor (contd.)
( )
}
+ =
T
T
i p i f i
ref
dT c h T h
,
0
,
Where,
Conservation of mass and conservation of energy are simultaneously
solved for T and Y
i,out
Solution Methodology:
Coupled non-linear algebraic equations, rather than system of ODEs

Mass generation rate depends only on Y
i
or [X]
i

Generalized Newtons method used to solve the system
"'
i
m
Mean residence time, t
R

m V t
R
/ =
20
Plug flow reactor
Assumptions:

Steady state and steady flow operation

No mixing in the axial direction

Uniform properties in direction perpendicular to flow

Ideal frictionless flow

Ideal gas behavior
X
x
21
Plug flow reactor (contd.)
Conservation of mass :
Known quantities :
"
, ( ), ( ) (nozzle or diffuser), ( )
i
m k T A x Q x
( )
0 =
dx
uA d
Conservation of momentum:
0 = +
dx
du
u
dx
dP

Conservation of energy:
( )
2
"
2
0
m
u
d h
Q P
dx m
+
+ =
(P
m
= perimeter)
Conservation of species:
( )
"'
i
i
m
dx
u Y d
=

for i = 1,2,,N
22
Plug flow reactor (contd.)
Ideal gas equation of state:
1
1

=
(

=
=

N
i
i
i
mix
mix
u
MW
Y
MW
MW
T R
P

Where,
Hence, N+4 unknowns (Y
i
s, , P, T, u)
with N+4 equations
Usable forms of equations
0
1 1 1
= + +
dx
dA
A dx
du
u dx
d

From conservation of mass

23
Plug flow reactor (contd.)
0 = +
dx
du
u
dx
dP

0
"
= + +
m
P Q
dx
du
u
dx
dh

dx
dY
h
dx
dT
c
dx
dh
i
N
i
i p
=
+ =
1
From ideal gas calorific
equation of state h=h(T, Y
i
)
0
1 1 1 1
= + =
dx
dMW
MW dx
dT
T dx
d
dx
dP
P
mix
mix

From conservation of momentum

From conservation of energy
From ideal gas law
dx
dY
MW
MW
dx
dMW
i
N
i
i
mix
mix

=
=
1
2
1
From MW
mix
24
Combustion system modeling
Conceptual drawing of a Gas turbine combustor
Fuel
Air
Products
WSR
1
WSR
2
PFR