Chemical Reaction Engineering (CRE)

is the field that studies the rates and

mechanisms of chemical reactions and
the design of the reactors in which they
take place.

Lecture 4
Lecture 4 Tuesday 1/18/2011
Block 1
Size CSTRs and PFRs given r
A
=f(X)
Block 2

Reaction Orders
Arrhenius Equation
Block 3

Stoichiometric Table
Definitions of Concentration
Calculate the Equilibrium Conversion, X
e

2





Reactor

Differential

Algebraic

Integral













A
A
r
X F
V

=
0
CSTR
A A
r
dV
dX
F =
0 }

=
X
A
A
r
dX
F V
0
0
PFR
V r
dt
dX
N
A A
=
0

0
0
}

=
X
A
A
V r
dX
N t
Batch
X
t
A A
r
dW
dX
F
'
=
0
}
'

=
X
A
A
r
dX
F W
0
0
PBR
X
W
3
Review
Lecture 2


F
A0
r
A

X
Review
Lecture 2

F
A0
r
A
Area = Volume of PFR

V =
0
X
1
}
F
A0
r
A
|
\

|
.
|
dX

X
1
Review
Lecture 2

6
reactor first to fed A of moles
i point to up reacted A of moles
X
i
=
Only valid if there are no side streams
Review
Lecture 2
7

Review
Lecture 2

Two steps to get

Step 1: Rate Law


Step 2: Stoichiometry


Step 3: Combine to get



r
A
= f X
( )

r
A
= g C
i
( )

C
i
( )
= h X
( )

r
A
= f X
( )
Review
Lecture 2
| o
=
B A A
C kC r

+ = Order Rection Overall

B in order
A in order

Power Law Model
9
C 3 B A 2 +
A reactor follows an elementary rate law if the
reaction orders just happens to agree with the
stoichiometric coefficients for the reaction as written.
e.g. If the above reaction follows an elementary rate
law

2nd order in A, 1st order in B, overall third order
B
2
A A A
C C k r =
Review
Lecture 3




E = Activation energy (cal/mol)
R = Gas constant (cal/mol*K)
T = Temperature (K)
A = Frequency factor (same units as rate constant k)
(units of A, and k, depend on overall reaction order)
10
RT E
Ae k

=

T k A
T 0 k 0
A ~10
13

T
k
Review
Lecture 3
These topics build upon one another
Mole Balance Rate Laws Stoichiometry

11
Review
Lecture 3

r
A
= f X
( )

r
A
= g C
i
( )
Step 1: Rate Law

C
i
( )
= h X
( )
Step 2: Stoichiometry

r
A
= f X
( )
Step 3: Combine to get
12
Review
Lecture 3

We shall set up Stoichiometry Tables using species
A as our basis of calculation in the following
reaction. We will use the stochiometric tables to
express the concentration as a function of
conversion. We will combine C
i
= f(X) with the
appropriate rate law to obtain -r
A
= f(X).




D
a
d
C
a
c
B
a
b
A + +
A is the limiting Reactant.
13

N
A
= N
A0
N
A0
X

N
B
= N
B0

b
a
N
A0
= N
A0
N
B0
N
A0

b
a
X
|
\

|
.
|
For every mole of A that react, b/a moles of B react.
Therefore moles of B remaining:

Let
B
= N
B0
/N
A0

Then:

N
B
= N
A0
O
B

b
a
X
|
\

|
.
|

N
C
= N
C0
+
c
a
N
A0
X = N
A0
O
C
+
c
a
X
|
\

|
.
|
14
Specie
s
Symb
ol
Initial Change Remaining
B B N
B0
=N
A0

B
-b/aN
A0
X N
B
=N
A0
(
B
-
b/aX)
A A N
A0
-N
A0
X N
A
=N
A0
(1-X)
Inert I N
I0
=N
A0

I
---------- N
I
=N
A0

I

F
T0
N
T
=N
T0
+N
A0
X
Wher
e:
0
0
0
0
0 0
0 0
0
0
A
i
A
i
A
i
A
i
i
y
y
C
C
C
C
N
N
= = = = O
u
u
1 + =
a
b
a
c
a
d
o
and
C C N
C0
=N
A0

C
+c/aN
A0
X N
C
=N
A0
(
C
+c/aX
)
D D N
D0
=N
A0

D
+d/aN
A0
X
N
D
=N
A0
(
D
+d/aX)
15
= change in total number of mol per mol A
reacted
Note: If the reaction occurs in the liquid phase
or
if a gas phase reaction occurs in a rigid (e.g. steel)
batch reactor

V =V
0
Then

C
A
=
N
A
V
=
N
A0
1 X ( )
V
0
= C
A0
1 X ( )

C
B
=
N
B
V
=
N
A0
V
0
O
B

b
a
X
|
\

|
.
| = C
A0
O
B

b
a
X
|
\

|
.
|
etc.
16
Suppose

r
A
= k
A
C
A
2
C
B
Batch:
0
V V =
17

r
A
= k
A
C
A0
2
1 X ( )
2
O
B

b
a
X
|
\

|
.
|
Equimolar feed:

O
B
=1
Stoichiometric feed:

O
B
=
b
a

r
A
= f X ( )
and we have
if

r
A
= k
A
C
A
2
C
B
then

r
A
= C
A0
3
1 X ( )
2
O
B

b
a
X
|
\

|
.
|
Constant Volume Batch
18
A
r
1
X
Consider the following elementary reaction with
K
C
=20 dm
3
/mol and C
A0
=0.2 mol/dm
3
.
X
e
for both a batch reactor and a flow reactor.
Calculating the equilibrium conversion
for gas phase reaction,X
e

(

=
C
B
2
A A A
K
C
C k r
B A 2
19

Step 1:

dX
dt
=
r
A
V
N
A0
3
0
2 . 0 dm mol C
A
=
mol dm K
C
3
20 =
Step 2: rate law,
B B
2
A A A
C k C k r =
Calculate X
e

B
A
C
k
k
K =
(

=
C
B
2
A A A
K
C
C k r
20

Symb
ol
Initial Change Remaining
B 0 N
A0
X N
A0
X/2
A N
A0
-N
A0
X N
A0
(1-X)
Totals: N
T0
=N
A0

N
T
=N
A0
-N
A0
X/2

@ equilibrium: -r
A
=0
C
Be
2
Ae
K
C
C 0 =

K
e
=
C
Be
C
Ae
2

C
Ae
=
N
Ae
V
=C
A0
1 X
e
( )

C
Be
=C
A0
X
e
2
21
Calculate X
e

Species Initial Change Remaining
A N
A0
-N
A0
X N
A
=N
A0
(1-X)
B 0 +N
A0
X/2 N
B
=N
A0
X/2
N
T0
=N
A0
N
T
=N
A0
-N
A0
X/2
Solution:
2
Ae
Be
C
C
C
K =
(

= =
C
Be
2
Ae A A
K
C
C k 0 r
At equilibrium
0
V V =
2 / B A Stoichiometry

Constant
volume
Batch
Calculating the equilibrium conversion
for gas phase reaction
22

( ) | | ( )
2
e 0 A
e
2
e 0 A
e
0 A
e
X 1 C 2
X
X 1 C
2
X
C
K

=
( )
( )( ) 8 2 . 0 20 2
X 1
X
C K 2
2
e
e
0 A e
= =

=

X
eb
=0.703
23

A A F
A0
-F
A0
X F
A
=F
A0
(1-X)
Specie
s
Symb
ol
Reactor
Feed
Chang
e
Reactor
Effluent
B B F
B0
=F
A0

B
-
b/aF
A0
X
F
B
=F
A0
(
B
-b/aX)

O
i
=
F
i0
F
A0
=
C
i0
u
0
C
A0
u
0
=
C
i0
C
A0
=
y
i0
y
A0
Where:

Flow System Stochiometric Table
24
Specie
s
Symb
ol
Reactor
Feed
Chang
e
Reactor
Effluent
0 A
0 i
0 A
0 i
0 0 A
0 0 i
0 A
0 i
i
y
y
C
C
C
C
F
F
= =
u
u
= = O
Where:
Inert I F
I0
=
A0

I
---------- F
I
=F
A0

I

F
T0
F
T
=F
T0
+F
A0
X
C C F
C0
=F
A0

C
+c/aF
A0
X F
C
=F
A0
(
C
+c/aX)
D D F
D0
=F
A0

D
+d/aF
A0
X F
D
=F
A0
(
D
+d/aX)
1
a
b
a
c
a
d
+ = o
and
u
=
A
A
F
C Concentration Flow System
25

Flow System Stochiometric Table
Species Symbol Reactor Feed Change Reactor Effluent
A A F
A0
-F
A0
X F
A
=F
A0
(1-X)
B B F
B0
=F
A0

B
-b/aF
A0
X F
B
=F
A0
(
B
-b/aX)
C C F
C0
=F
A0

C
+c/aF
A0
X F
C
=F
A0
(
C
+c/aX)
D D F
D0
=F
A0

D
+d/aF
A0
X F
D
=F
A0
(
D
+d/aX)
Inert I F
I0
=F
A0

I
---------- F
I
=F
A0

I

F
T0
F
T
=F
T0
+F
A0
X
0 A
0 i
0 A
0 i
0 0 A
0 0 i
0 A
0 i
i
y
y
C
C
C
C
F
F
= =
u
u
= = O 1
a
b
a
c
a
d
+ = o Where: and
u
=
A
A
F
C
Concentration Flow System
26
u
=
A
A
F
C Concentration Flow System:
0
u = u Liquid Phase Flow System:

C
A
=
F
A
u
=
F
A0
1 X ( )
u
0
= C
A0
1 X ( )

C
B
=
N
B
u
=
N
A0
u
0
O
B

b
a
X
|
\

|
.
| = C
A0
O
B

b
a
X
|
\

|
.
|
Flow Liquid Phase
etc.
27
We will consider C
A
and C
B
for gas phase
reactions in the next lecture
Mole Balance
Rate Laws
Stoichiometry
Isothermal Design
Heat Effects
28
End of Lecture 4
29