CHAPTER 3

Rate Laws and Stoichiometry

Lecture 4


Tell me and I'll forget; show me and I may remember;
involve me and I'll understand.
Chinese Proverb
CCB 3043 Kinetics and Reactor Design
Topics
Lecture 1: Basic definitions - Part 1
Types of reaction and relative rate of reaction
Lecture 2: Basic definitions - Part 2
Rate constant and activation energy
Lecture 3: Stoichiometric tables
Batch system
Consideration for constant volume system
Lecture 4:

Stoichiometric tables
Flow systems
Consideration for changing volume systems
CCB 3043 Kinetics and Reactor Design
Flow systems
D
a
d
C
a
c
B
a
b
A + +
F
A0
F
B0
F
C0
F
D0
F
I0
F
A
F
B
F
C
F
D
F
I
*PFR or CSTR
F
A0
F
B0
F
C0
F
D0
F
I0
F
A
F
B
F
C
F
D
F
I
D
a
d
C
a
c
B
a
b
A + +
CCB 3043 Kinetics and Reactor Design
Batch systems
at t = 0
N
A0
N
B0
N
C0
N
D0
N
I0
at t = t
N
A
N
B
N
C
N
D
N
I
CCB 3043 Kinetics and Reactor Design
Species Sym Initial Change Remaining
A A F
A0
- F
A0
X F
A
= F
A0
(1-X)
B B F
B0
= F
A0
O
B
-(b/a) F
A0
X F
B
= F
A0
[O
B
-(b/a)X]

C C F
C0
= F
A0
O
C
(c/a)F
A0
X F
C
= F
A0
[O
C
+(c/a)X]
D D F
D0
= F
A0
O
D
(d/a)F
A0
X F
D
= F
A0
[O
D
+(d/a)X]
Inert I F
I0
= F
A0
O
I
- F
I0
= F
A0
O
I

Total

F
T0
F
T
= F
T0
+ [d/a + c/a
b/a a]F
A0
X

F
T
= F
T0
+ oF
A0
X
Flow systems
CCB 3043 Kinetics and Reactor Design
Where:

Flow systems
v
F
C
1
a
b
a
c
a
d

y
y
C
C
F
F

i
i
0 A
0 i
A0
i0
A0
i0
i
=
+ =
= = =
Valid for constant
volume system
CCB 3043 Kinetics and Reactor Design
Flow system
Note that:
For liquid phase system (no phase change,
constant volume);



For gas phase system, the above is not true;
need to account for volume expansion
( ) X C C
v v
A A
=
=
1
0
0
CCB 3043 Kinetics and Reactor Design
Volume change with reaction (gas
phase): Batch Reactors
Occur when a system does not have an equal no of product
and reactant, (usually involve gas phase system) e.g.;
N
2
+ 3H
2
2NH
3

Combustion reaction
Need to take into account the expansion factor, c
X N
N N
T
T T
0
0

X; conversion any at or
reactor the to fed moles of number total
conversion complete for moles of number in total change

=
=
c
c
o c
0
0
0
1

A
T
A
y
N
N
a
b
a
c
a
d
=
|
.
|

\
|
+
=
CCB 3043 Kinetics and Reactor Design
CONSTANT VOLUME

BATCH FLOW
v
F
C
1
a
b
a
c
a
d

y
y
C
C
F
F

i
i
0 A
0 i
A0
i0
A0
i0
i
=
+ =
= = =
V
N
C
1
a
b
a
c
a
d

y
y
C
C
N
N

i
i
0 A
0 i
A0
i0
A0
i0
i
=
+ =
= = =
Reactor
Volume
Volumetric
flowrate
CCB 3043 Kinetics and Reactor Design
Volume change with reaction (gas
phase): Batch Reactors
Gas system; (Equation of state):

RT ZN PV
T
=
P = Total pressure, 1 atm
V = Volume, dm
3
Z = Compressibility factor
N
T
= Total number of moles

R = Gas constant,
0.08206 dm
3
.atm/mol.K
T = Temperature, K

CCB 3043 Kinetics and Reactor Design
At t = 0:
0 0 0 0 0
RT N Z V P
T
=
Volume change with reaction (gas
phase): Batch Reactors
RT ZN PV
T
=
0 0 0
0
0
0 0 0 0 0
T
T
T
T
N
N
Z
Z
T
T
P
P
V V
RT N Z V P
RT ZN PV
|
|
.
|

\
|
|
.
|

\
|
=
=
=
: rearrange
Divide
(1)/(2):
Remember? c=(N
T
-N
T0
)/N
T0
X
And for gas phase system, Z
0
~Z
( ) X
T
T
P
P
V V c +
|
.
|

\
|
= 1
0
0
0
Volume of gas for variable
volume batch reaction
CCB 3043 Kinetics and Reactor Design
Volume change with reaction (gas
phase): Batch Reactors
At any conversion;




o c
c
0
0
0
0
0
1
A
T
A
T
T T
y
N
N
a
b
a
c
a
d
X N
N N
=
|
.
|

\
|
+
=

=
X N
a
b
a
c
a
d
N N
From
A T T 0 0
1
|
.
|

\
|
+ =
: Table tric Stoichiome
F
T
= F
T0
+ [d/a + c/a b/a a]F
A0
X

OR

N
T
= N
T0
+ [d/a + c/a b/a a]N
A0
X
CCB 3043 Kinetics and Reactor Design
Volume change with reaction: BATCH
For batch system:




( )
0
0
0
T
T
X 1
P
P
V V c + |
.
|

\
|
=
o c
c
0
0
0
1

A
T
A
y
N
N
a
b
a
c
a
d
=
|
.
|

\
|
+
=
CCB 3043 Kinetics and Reactor Design
Volume change with reaction:
FLOW SYSTEM
|
.
|

\
|
|
|
.
|

\
|
=
T
T
P
P
F
F
C C
T
j
T j
0
0
0
D
a
d
C
a
c
B
a
b
A + +
|
|
.
|

\
|
|
|
.
|

\
|
=
0
0
0
0
T
T
P
P
F
F
T
T
u u
( )
|
.
|

\
|
|
|
.
|

\
|
+
+ O
=
T
T
P
P
X
X v C
C
j A
j
0
0
0
1 c
Can be used for membrane reactors
and multiple reactions
F
T
= sum of molar
flowrate from each
species
C
T
= sum of
concentration from
each specied
v
j
= stoichiometric
coefficient

v
A
= -1, v
B
= -b/a, v
C
= c/a, v
D
= d/a
Refer to
pg 113
( )
|
|
.
|

\
|
+ =
0
0
0
1
T
T
P
P
X c u u
CCB 3043 Kinetics and Reactor Design
VOLUME CHANGE
( ) X
T
T
P
P
V V c +
|
.
|

\
|
= 1
0
0
0
( )
|
|
.
|

\
|
+ =
0
0
0
1
T
T
P
P
X c u u
BATCH FLOW
P constant, T constant (isothermal):
( ) X V V c + = 1
0
( ) X c u u + = 1
0
BATCH FLOW
CCB 3043 Kinetics and Reactor Design
Volume change with reaction:
FLOW SYSTEM
Try to derive
those equations!!
(Hint: Use the
I deal gas law)
Refer to page
111(Fogler)
Read page 111 to
115, to make you
understand better

Where do we get those equations from???
CCB 3043 Kinetics and Reactor Design
Important notes for Rate Law and
Stoichiometry

IMPORTANT TABLES:
Table 3-3 (p101, Fogler): Stoichiometric
table for a BATCH system
Table 3-4 (p107, Fogler): Stoichiometric
table for a FLOW system
Table 3-5 (p114, Fogler): Concentrations in
a varible-volume gas FLOW system


CCB 3043 Kinetics and Reactor Design
Example 3.5: Determining the concentration of
species involved in a gas phase reaction
Consider the oxidation of SO
2
below. A mixture of 28%
SO
2
and 72% air is charged to a flow reactor in which
SO
2
is oxidized. Given that the total pressure of the
system is 1485 kPa and the temperature is constant at
227
o
C. Set up the stoichiometric table for the system and
evaluate the concentration of species presents in terms of
conversion. Plot the concentration profile of the species
with respect to conversion
2SO
2
+ O
2
2SO
3

CCB 3043 Kinetics and Reactor Design
Example 3.6: Calculating the equilibrium conversion
The reversible gas-phase decomposition of nitrogen tetroxide, N
2
O
4,
,


is carried out at constant temperature. The feed consists of pure N
2
O
4

at 340 K and 202.6 kPa (2 atm). The concentration equilibrium
constant K
c
, at 340 K is 0.1 mol/dm
3
.

a) Express the equilibrium conversion of N
2
O
4
in a constant-
volume batch reactor, in term of C
A0
and K
C
.

b) Express the equilibrium conversion of N
2
O
4
in a flow reactor, in
term of C
A0
and K
C

c) Assuming the reaction is elementary, express the rate of reaction
solely as a function of conversion for a constant-volume batch
and a flow system.

d) If k
A
is 0.5
min-1
and feed rate is 3 mol/min, determine the CSTR
volume necessary to achieve 80% of the equilibrium conversion
N
2
O
4
2NO
2

CCB 3043 Kinetics and Reactor Design
Checklist..
Mole balance
Rate Law
Stoichiometry
Do you have all these building blocks?
CCB 3043 Kinetics and Reactor Design