1

Multiple Reactions

2
Definitions
There are four basic type of multiple reactions: series, parallel, complex, and
independent. These types of multiple reactions can occur by themselves, in pair,
or all together. When there is a combination of parallel and series reactions, they
are often referred to as a complex reactions.
Parallel reactions (competing reaction)
A
k
1
k
2 C
B
Series reactions (consecutive reaction)
A
k
1 k
2
C B
The reactant is consumed by two different
reaction pathways to form different products.
The reactant forms an intermediate product,
where reacts further to form another product.
3
Complex reactions
E C A
D C B A
+
+ +
O H H C CHO CH H C
H CHO CH OH H C
O H H C OH H C
2 6 4 3 4 2
2 3 5 2
2 4 2 5 2
+ +
+
+
Involving a combination of both series and
parallel reactions
Independent reactions
F E D
C B A
+
+
4 2 14 3 18 8
6 3 24 12 32 15
H C H C H C
H C H C H C
+
+
Occurring at the same time but neither the products
nor reactants react with themselves or one another.
formation of butadiene from ethanol
cracking of crude oil to form gasoline
4
Desired and Undesired Reactions
Of particular interest are reactants that are consumed in the formation of
a desired product, D, and the formation of an undesired product, U, in a
competing or side reaction.
U A
D A
U
D
k
k


For a parallel reaction sequence For a series reaction sequence
U D A
U D
k k

We want to minimize the formation of U
and maximize the formation of D because
the greater the amount of undesired
product formed, the greater the cost of
separating the undesired product U from
the desired product D (Figure 6-1).
As the cost of a reactor system increases
in a attempt to minimize U, the cost of
separating species U from D decreases.
5
Selectivity tells us how one product is favored over another when we have
multiple reactions. We can quantify the formation of D with respect to U by
defining the selectivity and yield of the system.
The instantaneous selectivity of D with respective to U is the
ratio of the rate formation of D to the rate of formation of U.
U rmationof rateoffo
D rmationof rateoffo
r
r
S
U
D
U / D
= =
t redproduc ofundesi flowrate Exitmolar
dproduct ofdesire flowrate Exitmolar
F
F
S
~
U
D
U / D
= =
Overall selectivity
for a batch reactor
U
D
U / D
N
N
S
~
=
6
Example 6-1
Develop a relationship between S
D/U
and for a CSTR.
U / D
S
~
U A
D A
U
D
k
k


Solution
Consider the instantaneous selectivity for the two parallel
reactions just discussed:
U
D
U / D
r
r
S =
U / D
U
D
U
D
U
D
U / D
S
r
r
V r
V r
F
F
S
~
= = = =
Overall selectivity
For a CSTR the overall and instantaneous selectivities are equal.
U D A
U D
k k

Carrying out a similar analysis of the series reaction
7
instantaneous yield
tA tan keyreac ateofthe reactionr
ct ivenprodu ateofag reactionr
r
r
Y
A
D
D
=

=
overall yield
reaction endofthe edatthe tAconsum tan c hekeyrea molesoft
ereaction endofth medatthe roductfor molesofp
Y
~
D
=
for a batch system
A 0 A
D
D
N N
N
Y
~

=
A 0 A
D
D
F F
F
Y
~

=
for a flow system
~Instantaneous yield and overall yield are identical
for a CSTR.
~From an economic standpoint, the overall selectivities
and yields are important in determining profits.
However, the rate-based selectivities give insights in
choosing reactors and reaction schemes that will help
maximize the profit.
~There often is a conflict between selectivity and
conversion (yield) because you want to a lot of your
desired product (D) and at the same time minimize
the undesired product (U). However, in many
instances, the greater conversion you achieve, not
only do you make more D, but you also form more U.
8
Parallel reactions
2 U
1 D
A U U
k
A D D
k
C k r ) undesired ( U A
C k r ) desired ( D A
o
o
=
=
rate of disappearance of A is
2 1
A U A D U D A
C k C k r r r
o o
+ = + =
0
0
2
1
> o
> o
instantaneous selectivity is
2 1
A
U
D
U
D
U / D
C
k
k

r
r
S
o o
= =
Case 1:o
1
>o
2
a
A
U
D
U / D
C
k
k
S =
0 a
2 1
> o o =
To make this ratio as large as possible, we want to carry out
the reaction in a manner that will keep the concentration of
reactant A as high as possible during the reaction.
If the reaction is carried out in the gas phase, we
should run it without inerts and at high pressures to
keep C
A
high.
If the reaction is in the liquid phase, the use of diluents
should be kept to a minimum.
A batch or pl ug
flow reactor should
be used in this case.
CSTR should not be
chosen under these
circumstances.
9
Case 2:o
2
>o
1
b
A U
D
A
U
D
U / D
C
1
k
k
C
1
k
k
S
2 2
= =
o o
0 b
1 2
> o o =
For this ratio r
D
/r
U
to be high, the concentration of
A should be as low as possible
This low concentration may be accomplished by diluting the feed
with inerts and running the reactor at low concentrations of A.
A CSTR should be used because the concentrations of reactants are
maintained at a low level.
A recycle reactor in which the product stream acts as a diluent
could be used to maintain the entering concentrations of A at a low
value.
10
Because the activation energies of the two reactions in case 1 and 2 are not
given, it cannot be determined whether the reaction should be run at high or
low temperatures.
The sensitivity of the instantaneous selectivity to temperature can be determined
from the ratio of the specific reaction rates,
] RT / ) E E [(
U
D
U
D
U / D
U D
e
A
A
k
k
S

= ~
Case 3:E
D
>E
U
A is the frequency factor
E is the activation energy
S
D/U
T

Case 4:E
U
>E
D
S
D/U
T

The reaction system should be operated at the
highest possible temperature to maximize S
D/U
.
The reaction system should be carried out at
a low temperature to maximize S
D/U
.
11
Example 6-2
Reactant A decomposes by three simultaneous reactions to form three products, one
that is desired, B, and two that are undesired, X and Y. These gas-phase reactions,
along with the appropriate rate laws, are called the Trambouze reactions.
2
A
3 2
A 3 Y A 3
k
A
1
A 2 B A 2
k
3
1 X A 1
k
C ) s mol / dm 008 . 0 ( C k r r Y A
C ) s 0015 . 0 ( C k r r B A
s dm / mol 0001 . 0 k r r X A
3
2
1
= = =
= = =
= = =

The specific reaction rate are given at 300 K and the activation energies for reactions
(1), (2), and (3) are E
1
=10000 kcal/mol, E
2
=15000 kcal/mol, and E
3
=20000 kcal/mol.
How and under what conditions (e.g., reactor type(s), temperature, concentrations)
should the reaction be carried out to maximize the selectivity of B for an entering
concentration of A of 0.4M and a volumetric flow rate of 2.0 dm
3
/s.
12
Solution
The selectivity with respect to B is
2
A 3 1
A 2
Y X
B
XY / B
C k k
C k
r r
r
S
+
=
+
=
maximum
C
A
*=?
Because the concentration changes down
the length of a PFR, we cannot operate at
this maximum. As a result, a CSTR would
be used and operated at this maximum.
2
2
*
A 3 1
*
A 3
*
A 2
2
*
A 3 1 2
A
XY / B
) C k k (
) C k 2 ( C k ) C k k ( k
0
dC
dS
+
+
= =
3
3
3
3
1
*
A
dm / mol 112 . 0
) s mol / dm ( 008 . 0
) s dm / mol ( 0001 . 0
k
k
C
=

= =
The corresponding selectivity at C
A
* is
84 . 0
) 008 . 0 )( 0001 . 0 ( 2
0015 . 0

k k 2
k
k k
k
k
k
C k k
C k
S
3 1
2
1 1
3
1
2
2
*
A 3 1
*
A 2
XY / B
= =
=
+
=
+
=
13
2
A A 3 A A 2 A 1 A
2
A A 3 A A 2 A 1 A 3 A 2 A 1 A
C k C k k r
C k C k k r r r r
+ + =
= + + =
The net of formation of A from reactions (1), (2), and (3) is
The mole balance on a CSTR for this liquid-phase reaction (v=v
0
) is
2
*
A A 3
*
A A 2 A 1
*
A 0 A 0
A
*
A 0 A 0
C k C k k
) C C ( v
r
) C C ( v
V
+ +

=

=
2
*
A A 3
*
A A 2 A 1
*
A 0 A
0 C k C k k
C C
v
V
+ +

= = t
s 783
) 112 . 0 )( 008 . 0 ( ) 112 . 0 )( 0015 . 0 ( 0001 . 0
112 . 0 4 . 0
2
=
+ +

= t
3 3
0
dm 1566 ) s 783 )( s / dm 2 ( v V = = t =
14
(
(
(

+
= =
+
=
+
=
RT
E
2
E E
exp
A A 2
A
k k 2
k
k k
k
k
k
C k k
C k
S
2
3 1
3 1
2
3 1
2
1 1
3
1
2
2
*
A 3 1
*
A 2
XY / B
Maximize the selectivity wrt temperature
Case 1: If
2
3 1
E
2
E E
<
+
Run at as high a temperature as possible with existing
equipment and watch out for other side reactions that
might occur at high temperatures.
Case 2: If
2
3 1
E
2
E E
>
+
Run at low temperatures but not so low that a significant
conversion is not achieved.
For the activation energies given above
0 15000
2
20000 10000
E
2
E E
2
3 1
=
+
=
+
The selectivity for this combination of activation energies is
independent of temperature!
15
72 . 0
4 . 0
112 . 0 4 . 0
C
C C
X
0 A
*
A 0 A *
=

=
What is the conversion of A in the CSTR?
If greater than 72% conversion of A is required, then the CSTR operated with a reactor
concentration of 0.112 mol/dm
3
should be followed by a PFR because the concentration
and hence selectivity will decrease continuously from C
A
* as we move down the PFR to
an exit concentration C
Af
. Hence the system



would give the highest selectivity while forming more of the desired product B, beyond
what was formed at C
A
* in a CSTR.
Af
*
A
*
A
C
C C
PFR CSTR +
16
Optimum CSTR followed by a PFR
The exit concentrations of X, Y, and B can be found from the CSTR mole balances
1
X 0
X
X 0
k
C v
r
C v
V = =
*
A 2
B 0
B
B 0
C k
C v
r
C v
V = =
2
*
A 3
Y 0
Y
Y 0
C k
C v
r
C v
V = =
3 3
1
0
1
X
dm / mol 0783 . 0 ) s 783 )( s dm / mol 0001 . 0 ( k
v
V k
C = = t = =
s / mol 156 . 0 C v F
X 0 X
= =
3 3 1 *
A 2
0
*
A 2
B
dm / mol 132 . 0 ) s 783 ))( dm / mol 112 . 0 )( s 0015 . 0 ( C k
v
V C k
C = = t = =

s / mol 264 . 0 C v F
B 0 B
= =
3 2 3 3
2
*
A 3
0
2
*
A 3
Y
dm / mol 0786 . 0 ) s 783 ( ) dm / mol 112 . 0 )( s mol / dm 008 . 0 ( C k
v
V C k
C = = t = =
s / mol 157 . 0 C v F
Y 0 Y
= =
17
If 90% conversion were required then the exit concentration would be
C
Af
=(1-0.9)/(0.4 mol/dm
3
)=0.04 mol/dm
3
.
Y
Y
B
B
X
X
A
A A
0
r
d
dC
, r
d
dC
, r
d
dC
, r
d
dC
dV
dC
v =
t
=
t
=
t
=
t
=
The PFR mole balances for this liquid-phase reaction (v=v
0
) are
3
Y
2
A 3
Y
3
B A 2
B
3
X 1
X
3
A
2
A 3 A 2 1
A
dm / mol 0786 . 0 thenC , 0 at C k
d
dC
dm / mol 132 . 0 thenC , 0 at C k
d
dC
dm / mol 0783 . 0 thenC , 0 at k
d
dC
dm / mol 112 . 0 thenC , 0 at C k C k k
d
dC
= = t =
t
= = t =
t
= = t =
t
= = t =
t
At =0, the values of the entering concentrations to the PFR are
the exit concentrations from the CSTR.
18
3 3
0
dm 600 ) s 300 )( s / dm 2 ( v V = = t =
3
Y
3
B
3
X
3
A
dm / mol 090 . 0 C
dm / mol 160 . 0 C
dm / mol 110 . 0 C
dm / mol 037 . 0 C
=
=
=
=
3
Y
3
B
3
X
dm / mol 180 . 0 F
dm / mol 320 . 0 F
dm / mol 220 . 0 F
=
=
=
19
2 2 2
1 1 1
B A 2 U
k
B A 1 D
k
C C k r ) undesired ( U B A
C C k r ) desired ( D B A
| o
| o
= +
= +
2 1 2 1
B A
2
1
U
D
U / D
C C
k
k

r
r
S
| | o o
= =
maximizing S
D/U
The two reactions with recycle shown in (i) and (j) can be
used for highly exothermic reactions. Here the recycle stream
is cooled and returned to the reactor to dilute and cool the
inlet stream thereby avoiding hot spots and runaway
reactions. The PFR with recycle is used for gas-phase
reactions, and the CSTR is used for liquid-phase reactions.
The last two reactors, (k) and (I), are used for
thermodynamically limited reactions where
the equilibrium lies far to the left (reactant
side)
A+BC+D
and one of the products must be removed (e.g.,
C) for the reaction to continue to completion.
The membrane reactor (k) is used for
thermodynami cal l y l i mi ted gas-phase
reactions, while reactive distillation (I) is used
for liquid-phase reactions when one of the
products has a higher volatility (e.g., C) than
the other species in the reactor.
20
Example 6-3
2 2 2
1 1 1
B A 2 U
k
B A 1 D
k
C C k Ur B A
C C k Dr B A
| o
| o
= +
= +
For the parallel reactions
Consider all possible combinations of reaction orders and select the reaction scheme
that will maximize S
D/U
.
Solution
Case I:o
1
>o
2
, |
1
>|
2 2 1 2 1
andb a | | = o o =
b
B
a
A
2
1
U
D
U / D
C C
k
k

r
r
S = =
~A tubular reactor (Figure 6.3 (b))
~A batch reactor (Figure 6.3 (c))
~High pressures (if gas phase), and reduce inerts
To maximize the ratio r
D
/r
U
, maintain the concentration of both A and B as high as
possible. To do this, use
21
Case II:o
1
>o
2
, |
1
<|
2 1 2 2 1
andb a | | = o o =
b
B
a
A
2
1
U
D
U / D
C
C
k
k

r
r
S = =
~A semibatch reactor in which B is fed slowly into a large amount of A (Figure 6.3(d))
~A membrane reactor or a tubular reactor with side streams of B continually fed to
the reactor (Figure 6.3(f))
~A series of small CSTRs with A fed only to the first reactor and small amounts of B
fed to each reactor. In this way B is mostly consumed before the CSTR exit stream
flows into the next reactor (Figure 6.3(h))
To make S
D/U
as large as possible, we want to make the concentration of A high and
the concentration of B low. To achieve this result, use
22
Case III:o
1
<o
2
, |
1
<|
2 1 2 1 2
andb a | | = o o =
b
B
a
A 2
1
U
D
U / D
C C
1
k
k

r
r
S = =
~A CSTR (Figure 6.3(a))
~A tubular reactor in which there is a large recycle ratio (Figure 6.3(i))
~A feed diluted with inerts
~Low pressure (if gas pressure)
To make S
D/U
as large as possible, the reaction should be carried out at low concentrations
of A and B. To achieve this result, use
23
Case IV:o
1
<o
2
, |
1
>|
2 2 1 1 2
andb a | | = o o =
a
A
b
B
2
1
U
D
U / D
C
C
k
k

r
r
S = =
~A semibatch reactor with A slowly fed to a large amount of B (Figure 6.3(e))
~A membrane reactor or a tubular reactor with side streams of A (Figure 6.3(g))
~A series of small CSTRs with fresh A fed to each reactor (Figure 6-3(h))
To make S
D/U
as large as possible, run the reaction at high concentration of B and low
concentration of A. To achieve this result, use
24
Maximizing the Desired Product in Series Reactions
C B A
2 1
k k

For series of consecutive reactions, the most important variable is time: space-
time for a flow reactor and real time for a batch reactor. To illustrate the
important of the time factor, we consider the sequence
B is the desired product
~If the first reaction is slow and the second reaction is fast, it will be extremely
difficult to produce species B.
~If the first reaction (formation of B) is fast and the reaction to form C is slow,
a large yield of B can be achieved.
~However, if the reaction is allowed to proceed for a long time in a batch
reactor, or if the tubular flow reactor is too long, the desired product B will be
converted to the undesired product C.
25
Example 6-4
The oxidation of ethanol to form acetaldehyde is carried out on a catalyst of 4 wt %
Cu-2 wt % Cr on Al
2
O
3
. Unfortunately, acetaldehyde is also oxidized on this catalyst to
form carbon dioxide. The reaction is carried out in a threefold excess of oxygen and in
dilute concentration (ca. 0.1% ethanol, 1% O
2
, and 98.9% N
2
). Consequently, the
volume change with the reaction can be neglected. Determine the concentration of
acetaldehyde as a function of space-time,



The reactions are irreversible and first order in ethanol and acetaldehyde, respectively.
2
O
O H 2
3
O
O H
2 3
CO 2 CHO CH OH CH CH
2 2
5
2
2 2
1
2

+

Solution
C B A
2 1
k k

C B ) 2 ( action Re
B A ) 1 ( action Re
2
1
k
k


O
2
in excess
26
Mole balance on A:
' r
dW
dF
A
A
=
A 1 A
C k ' r =
A 0 A A
C v vC F = =
A 1
A
0
C k
dW
dC
v =
t = = = t
b 0 b 0
v / V v / W '
A 1
A
C k
' d
dC
=
t
' k
0 A A
1
e C C
t
=
0 ' atW
C C
0 A A
= t =
=
Mole balance on B:
' r
dW
dF
net , B
B
=
B 2 A 1
B
0
C k C k
dW
dC
v =
B 2 A 1 2 rxn , B 1 rxn , B net , B
C k C k ' r ' r ' r = + =
B 0 B B
C v vC F = =
' k
0 A A
1
e C C
t
=
' k
0 A 1 B 2
B
1
e C k C k
' d
dC
t
= +
t
0
v / W ' = t
integrating factor
' ) k k (
0 A 1
' k
B
1 2
2
e C k
' d
) e C ( d
t
t
=
t
|
|
.
|

\
|

=
t t
1 2
' k ' k
0 A 1 B
k k
e e
C k C
2 1
0 ' atW
0 C
B
= t =
=
' k
2
e
t
27
Optimum yield
Mole balance on C:
|
|
.
|

\
|

= = =
t
t t
1 2
' k ' k
0 A 2 1 B 2 C
C
k k
e e
C k k C k ' r
' d
dC
2 1
)] e 1 ( k ) e 1 ( k [
k k
C
C
' k
1
' k
2
1 2
0 A
C
2 1
t t

=
0 ' atW
0 C
C
= t =
=
= t'
0 A C
C C =
B A 0 A C
C C C C =
|
|
.
|

\
|

+
= =
t
t t
1 2
' k
2
' k
1
0 A 1
B
k k
e k e k
C k 0
' d
dC
2 1
2
1
2 1
opt
k
k
ln
k k
1
'

= t
2
1
2 1
0
opt
k
k
ln
k k
v
W

=
) k k /( k
2
1
) k k /( k
2
1
' k
0 A
A 0 A
opt
1 2 1 2 1 1
opt 1
k
k
1
k
k
ln exp 1
e 1
C
C C
X

t
|
|
.
|

\
|
=
(
(

|
|
.
|

\
|
=
=

=
? k k
2 1
=
28
The yield has been defined as
thanolfed molesofe
einexit cetaldehyd molesofa
Y
~
A
=
shown as a function of conversion in Figure E6-4.2
Another technique is often used to follow the progress for two
reactions in series. The concentrations of A, B, and C are plotted
as a singular point at different space time (e.g., t
1
, t
2
) on a
triangular diagram (see Figure 6.-4). The vertices correspond to
pure A, B, and C.
For (k
1
/k
2
)>>1, a large quantity of B can be obtained.
For (k
1
/k
2
)<<1, very little B can be obtained.
29
Algorithm for Solution of Complex Reactions
~In complex reactions systems consisting of combination of parallel and
series reactions, the availability of software packing (ODE solvers) makes
it much easier to solve problems using moles N
j
or molar flow rates F
j

rather than conversion.
~For liquid systems, concentration is usually the preferred variable used in
the mole balance equations. The resulting coupled differential mole
balance equations can be easily solved using an ODE solver.
~For gas systems, the molar flow rates are usually the preferred variable in
the mole balance equation.
30
Mole Balances
Table 6-1 gives the forms of the
mole balance equation we shall
use for complex reactions
where r
A
and r
B
are the net
rates of formation of A and B.
31
We find the net rate of reaction
for each species in terms of the
concentration of the reacting
species in order to combine
them with their respective mole
balances.
32
Net Rates of Reaction
Consider the following reactions
2
C A A 2 A 2
k
B A A 1 A 1
k
C C k r E 3 C 2 A : ) 2 ( action Re
C C k r D C 3 B A : ) 1 ( action Re
A 2
A 1
= +
= + +
E 2 E 1 E
D 2 D 1 D
C 2 C 1 C
B 2 B 1 B
A 2 A 1 A
r r r
r r r
r r r
r r r
r r r
+ =
+ =
+ =
+ =
+ =
1
r
3
r
1
r
1
r
D 1 C 1 B 1 A 1
= =

3
r
2
r
1
r
E 2 C 2 A 2
=

2
C A A 2 E
B A A 1 D
2
C A A 2 B A A 1 C
B A A 1 B
2
C A A 2 B A A 1 A
C C k 3 r
C C k r
C C k 2 C C k 3 r
C C k r
C C k C C k r
=
=
=
=
=
B A A 1 A 1 D 1
B A A 1 A 1 C 1
B A A 1 A 1 B 1
C C k r r
C C k 3 ) r ( 3 r
C C k r r
= =
= =
= =
2
C A A 2 A 2 E 2
2
C A A 2 A 2 C 2
C C k 3 ) r ( 3 r
C C k 2 r 2 r
= =
= =
33
Example 6-5
Consider the following set of reactions:
2
O N O 3 O 3 2 2 2
2
NO N 2 N 2 2 2
5 . 1
NO NH NO 1 NO 1 2 2 3
2 2 2 2
2 2
3
C C k r NO 2 O 2 N : ) 3 ( action Re
C k r O N NO 2 : ) 2 ( action Re
C C k r O H 6 N 5 NO 6 NH 4 : ) 1 ( action Re
= +
= +
= + +
Write the rate law for each species in each reaction and then write the net rates of formation
of NO, O
2
, and N
2
.
Solution
Net Rates of Reaction
2 2
2 2 2
2 2
2 2 2 2
3 3
NO 3 NO
O 3 O 2 O
O H 1 O H
N 3 N 2 N 1 N
NH 1 NH
NO 2 NO 1 NO
r r
r r r
r r
r r r r
r r
r r r
=
+ =
=
+ + =
=
+ =
34
5 . 1
NO NH NO 1 NO 1 2 2 3
C C k r O H 6 N 5 NO 6 NH 4 : ) 1 ( action Re
3
= + +
Relative Rates of Reaction
6
r
5
r
4
r
6
r
O H 1 N 1 NH 1
NO 1 2 2 3
= =

5 . 1
NO NH NO 1
3
2
NO 1
3
2
NH 1
C C k ) r ( r
3 3
= =
5 . 1
NO NH NO 1
6
5
NO 1
6
5
N 1
C C k ) r ( r
3 2
= =
5 . 1
NO NH NO 1 NO 1 O H 1
C C k r r
3 2
= =
2
NO N 2 N 2 2 2
C k r O N NO 2 : ) 2 ( action Re
2 2
= +
1
r
1
r
2
r
2 2
O 2 N 2
NO 2
= =

2
NO N 2 N 2 NO 2
C k 2 r 2 r
2 2
= =
2
NO N 2 N 2 O 2
C k r r
2 2 2
= =
35
2
O N O 3 O 3 2 2 2
2 2 2 2
C C k r NO 2 O 2 N : ) 3 ( action Re = +
2
r
1
r
2
r
2 2 2
NO 3 N 3 O 3
=

2
O N O 3 O 3 NO 3
2 2 2 2 2
C C k r r = =
2
O N O 3
2
1
O 3
2
1
N 3
2 2 2 2 2
C C k ) r ( r = =
NO 2 NO 1 NO
r r r + =
2
NO N 2
5 . 1
NO NH NO 1 NO
C k 2 C C k r
2 3
=
2 2 2 2
N 3 N 2 N 1 N
r r r r + + =
2
O N O 3
2
1
2
NO N 2
5 . 1
NO NH NO 1
6
5
N
2 2 2 2 3 2
C C k C k C C k r + =
Net rate NO
Net rate N
2
2 2 2
O 3 O 2 O
r r r + =
Net rate O
2
2
O N O 3
2
NO N 2 O
2 2 2 2 2
C C k C k r =
36
Stoichiometry: Concentration
0
j
j
v
F
C =
for liquid-phase reactions, v=v
0
T
T
P
P
F
F
C
T
T
P
P
F
F
v
F
C
0
0 T
j
0 T
0
0 T
j
0
0 T
j
|
|
.
|

\
|
=
|
|
.
|

\
|
=
for gas-phase reactions

=
=
n
1 j
j T
F F
0
0
0 T
RT
P
C =
T=T
0
, P=P
0
|
|
.
|

\
|
=
T
j
0 T j
F
F
C C
|
|
.
|

\
|
= =
|
|
.
|

\
|
= =
T
j
0 T
T
2
0 T
T
1
0 T 2 n j 2 1 2 n 2
T
j
0 T
T
2
0 T
T
1
0 T 1 n j 2 1 1 n 1
F
F
C ,...,
F
F
C ,
F
F
C f ] C ... C , C [ f r
F
F
C ,...,
F
F
C ,
F
F
C f ] C ... C , C [ f r
where fn represents the functional dependence on
concentration of the net rate of formation
37
Multiple Reactions in a PFR/PBR
We now insert rate laws written in terms of molar flow rates into the mole balances.
After performing this operation for each species, we arrive at a coupled set of first-
order ordinary differential equations to be solved for the molar flow rates as a
function of reactor volume.
In liquid-phase reactions, incorporating and solving for total molar flow rate is not necessary
at each step along the solution pathway because there is no volume change with reaction.
|
|
.
|

\
|
= = =
|
|
.
|

\
|
= = =

=
=
T
j
0 T
T
2
0 T
T
1
0 T nj
q
1 i
ij j
j
T
j
0 T
T
2
0 T
T
1
0 T 1 n
m
1 i
1 i 1
1
F
F
C ,...,
F
F
C ,
F
F
C f r r
dV
dF
.
.
.
F
F
C ,...,
F
F
C ,
F
F
C f r r
dV
dF
Combi ng mol e
balance, rate laws,
and stoichiometry
T=T
0
, P=P
0
for gas-phase reactions
solved simultaneously with a numerical
package or by writing an ODE solver.
V=?
38
Example 6-6
2
O N O 3 O 3 2 2 2
2
NO N 2 N 2 2 2
5 . 1
NO NH NO 1 NO 1 2 2 3
2 2 2 2
2 2
3
C C k r NO 2 O 2 N : ) 3 ( action Re
C k r O N NO 2 : ) 2 ( action Re
C C k r O H 6 N 5 NO 6 NH 4 : ) 1 ( action Re
= +
= +
= + +
Consider again the reaction in Example 6-5. Write the mole balances on a PFR in terms of
molar flow rates for each species.
Solution
T
T
P
P
F
F
C C
0
0 T
j
0 T j
=
T=T
0
, P=P
0
T
j
0 T j
F
F
C C =
2 2 2 2 3
NO O O H N NH NO T
F F F F F F F + + + + + =
total molar flow rate of all the gases is
39
5 . 1
T
NO
T
NH
5 . 2
0 T NO 1 3
2
5 . 1
NO NH NO 1 3
2
NO 1 3
2
NH 1 NH
NH
F
F
F
F
C k
C C k r r r
dV
dF
3
3 3 3
3
|
|
.
|

\
|
|
|
.
|

\
|
=
= = = =
mole balance on NH
3
mole balance on H
2
O
5 . 1
T
NO
T
NH
5 . 2
0 T NO 1
5 . 1
NO NH NO 1 NO 1 O H 1 O H
O H
F
F
F
F
C k
C C k r r r
dV
dF
3
3 2 2
2
|
|
.
|

\
|
|
|
.
|

\
|
=
= = = =
2
T
NO 2
0 T N 2
5 . 1
T
NO
T
NH
5 . 2
0 T NO 1
2
NO N 2
5 . 1
NO NH NO 1 NO
NO
F
F
C k 2
F
F
F
F
C k
C k 2 C C k r
dV
dF
2
3
2 3
|
|
.
|

\
|

|
|
.
|

\
|
|
|
.
|

\
|
=
= =
mole balance on NO
40
2
T
O
T
N
3
0 T O 3
2
T
NO 2
0 T N 2
2
O N O 3
2
NO N 2 O
O
F
F
F
F
C k
F
F
C k
C C k C k r
dV
dF
2 2
2 2
2 2 2 2 2
2
|
|
.
|

\
|
|
|
.
|

\
|

|
|
.
|

\
|
=
= =
mole balance on O
2

mole balance on NO
2

2
T
O
T
N
3
0 T O 3
2
O N O 3 O 3 NO 3 NO
NO
F
F
F
F
C k
C C k r r r
dV
dF
2 2
2
2 2 2 2 2 2
2
|
|
.
|

\
|
|
|
.
|

\
|
=
= = = =
2
T
O
T
N
3
0 T O 3
2
1
2
T
NO 2
0 T N 2
5 . 1
T
NO
T
NH
5 . 2
0 T NO 1
6
5
2
O N O 3
2
1
2
NO N 2
5 . 1
NO NH NO 1
6
5
N
N
F
F
F
F
C k
F
F
C k
F
F
F
F
C k
C C k C k C C k r
dV
dF
2 2
2 2
3
2 2 2 2 3 2
2
|
|
.
|

\
|
|
|
.
|

\
|

|
|
.
|

\
|
+
|
|
.
|

\
|
|
|
.
|

\
|
=
+ = =
mole balance on N
2

41
ODE solver algorithm is shown in Table E6-6.1
42
Table 6-2 shows the equation for
species j and reaction i that are
to be combined when we have q
reactions and n species.
43
Example 6-7
The production of m-xylene by the hydrodealkylation of mesitylene over a Houdry Detrol
catalyst involves the following reactions:
m-xylene can also undergo hydrodealkylation to form toluene:
The second reaction is undesirable, because m-xylene sells for a higher price than toluene
($1.32/lb vs. $0.30/lb). Thus we see that there is a significant incentive to maximize the
production of m-xylene.
The hydrodealkylation of mesitylene is to be carried out isothermally at 1500R and 35
atm in a packed-bed reactor in which the feed is 66.7 mol% hydrogen and 33.3 mol%
mesitylene. The volumetric feed rate is 476 ft
3
/h and the reactor volume (i.e., V=W/
b
) is
238 ft
3
.
44
The rate laws for reactions 1 and 2 are, respectively
5 . 0
H X 2 T 2
5 . 0
H M 1 M 1
C C k r
C C k r
=
=
where the subscripts are: M=mesitylene, X=m-xylene, T=toluene, Me=methane, and
H=hydrogen (H
2
).
At 1500R, the specific reaction rates are
h / ) lbmol / ft ( 20 . 30 k : 2 action Re
h / ) lbmol / ft ( 20 . 55 k : 1 action Re
5 . 0 3
2
5 . 0 3
1
=
=
The bulk density of the catalyst has been included in the specific reaction rate (i.e,
k
1
=k
1

b
).
Plot the concentration of hydrogen, mesitylene, and xylene as a function of space time.
Calculate the space time where the production of xylene is a maximum (i.e., t
opt
)
45
Solution
Me T H X : 2 action Re
Me X H M : 1 action Re
+ +
+ +
1.Mole balances:
Me
Me
T
T
X
X
M
H
H
H
r
dV
dF
: Methane
r
dV
dF
: Toluene
r
dV
dF
: Xylene
r
dV
dF
: Mesitylen
r
dV
dF
: Hydrogen
=
=
=
=
=
X
5 . 0
H 2 T 2
M
5 . 0
H 1 M 1
C C k r : 2 action Re
C C k r : 1 action Re
=
=
2.Rate laws and net rates:
X 2 H 2 Me 2 T 2
X 1 Me 1 M 1 H 1
r r r r
r r r r
= = =
= = =
46
X
5 . 0
H 2 T 2 T
X
5 . 0
H 2 M
5 . 0
H 1 T 2 M 1 Me 2 Me 1 Me
X
5 . 0
H 2 M
5 . 0
H 1 T 2 M 1 X 2 X 1 X
X
5 . 0
H 2 M
5 . 0
H 1 T 2 M 1 H 2 H 1 H
M
5 . 0
H 1 M 1 M
C C k r r
C C k C C k r r r r r
C C k C C k r r r r r
C C k C C k r r r r r
C C k r r
= =
+ = + = + =
= = + =
= = + =
= =
0
0
0 T
T
0
T
T
P
P
F
F
v v =
3.Stoichiometry:
0 2 2 2 2 = + = o
T=T
0
, P=P
0
0
v v =
) C C C ( V F F F F
) C C ( v F F C v F
C v F
C v F
C v F
X M 0 M 0 X M 0 M T
H 0 H 0 H 0 H Me 0 Me
X 0 X
M 0 M
H 0 H
= =
= = =
=
=
=
47
4.Combining:
X
5 . 0
H 2 M
5 . 0
H 1
X
X
5 . 0
H 2 M
5 . 0
H 1
H
M
5 . 0
H 1
M
C C k C C k
d
dC
C C k C C k
d
dC
C C k
d
dC
=
t
=
t
=
t
If we know C
M
, C
H
, and C
X
,
then C
Me
, and C
T
can be
calculated from the reaction
stoichiometry.
0
v
V
= t
5.Parameter evaluation:
3
3
0
0
0 T
ft / lbmol 032 . 0
) R 1500 (
R lbmol
atmft
37 . 0
atm 35
RT
P
C =

|
|
.
|

\
|

= =
3 3
0 T 0 H 0 H
ft / lbmol 021 . 0 ) ft / lbmol 032 . 0 )( 667 . 0 ( C y C = = =
3
0 H
2
1
0 M
ft / lbmol 0105 . 0 C C = =
0 C
0 X
=
h 5 . 0
h / ft 476
ft 238
v
V
3
3
0
= = = t
h / mol 23 . 15 ) h / ft 476 )( ft / lbmol 032 . 0 ( v C F
3 3
0 0 T 0 T
= = =
48
These equations can be solved analytically.
49
Multiple Reactions in a CSTR
j
j 0 j
r
F F
V

=
V r F F
j j 0 j
=
( )
N 2 1 j
q
1 i
ij j
C ,..., C , C f r r = =

=
=
n
1 j
j T
F F
~If there is no volume change with reaction, we use concentration, C
j
, as variables.
~If the reactions are gas phase and there is volume change, we use molar flow rates,
F
j
, as variables.
The total molar flow for n species is
|
|
.
|

\
|
= = =
|
|
.
|

\
|
= = =
|
|
.
|

\
|
= = =

=
=
=
T
N
0 T
T
2
0 T
T
1
0 T N
q
1 i
iN N N 0 N
T
N
0 T
T
2
0 T
T
1
0 T j
q
1 i
ij j j 0 j
T
N
0 T
T
2
0 T
T
1
0 T 1
q
1 i
1 i 1 1 10
F
F
C ,...,
F
F
C ,
F
F
C Vf r V V r F F
F
F
C ,...,
F
F
C ,
F
F
C Vf r V V r F F
F
F
C ,...,
F
F
C ,
F
F
C Vf r V V r F F
50
Example 6-8
For the multiple reactions and conditions described in Example 6-7, calculate the conversion
of hydrogen and mesitylene along with the exiting concentrations of mesitylene, hydrogen,
and xylene in a CSTR.
Solution
0
v v =
A 0 A A
C v vC F = =
V r C v : Methane
V r C v : Toluene
V r C v : Xylene
V r C v C v : Mesitylen
V r C v C v : Hydrogen
Me Me 0
T T 0
X X 0
M M 0 0 M 0
H H 0 0 H 0
=
=
=
=
=
X
5 . 0
H 2 M
5 . 0
H 1 X
X
5 . 0
H 2 M
5 . 0
H 1 H
M
5 . 0
H 1 M
C C k C C k r
C C k C C k r
C C k r
=
=
=
t =
t + =
t =
) C C k C C k ( C
) C C k C C k ( C C
C C k C C
X
5 . 0
H 2 M
5 . 0
H 1 X
X
5 . 0
H 2 M
5 . 0
H 1 H 0 H
M
5 . 0
H 1 M 0 M
Me T H X : 2 action Re
Me X H M : 1 action Re
+ +
+ +
51
X X
5 . 0
H 2 M
5 . 0
H 1 X
X
5 . 0
H 2 M
5 . 0
H 1 0 H H H
M
5 . 0
H 1 0 M M M
C ) C C k C C k ( 0 ) C ( f
) C C k C C k ( C C 0 ) C ( f
C C k C C 0 ) C ( f
t = =
t + + = =
t + = =
h 5 . 0
h / ft 476
ft 238
v
V
3
3
0
= = = t
72 . 0
0105 . 0
0029 . 0 0105 . 0
C
C C
F
F F
X
: Mesitylene
58 . 0
021 . 0
0089 . 0 021 . 0
C
C C
F
F F
X
: Hydrogen
0 M
M 0 M
0 M
M 0 M
M
0 H
H 0 H
0 H
H 0 H
H
=

=
=

=
52
The moles of hydrogen consumed in reaction 1 are equal to the moles of mesitylene
consumed. Therefore, the conversion of hydrogen in reaction 1 is
36 . 0
021 . 0
0029 . 0 0105 . 0
C
C C
X
0 H
M 0 M
H 1
=

=
The conversion of hydrogen in reaction 2 is just the overall conversion minus the
conversion in reaction 1; that is,
22 . 0 36 . 0 58 . 0 X X X
H 1 H H 2
= = =
The yield of xylene from mesitylene based on molar flow rates exiting the CSTR for
t=0.5 is
ed lenereact molmesity
producted molxylene
41 . 0
0029 . 0 0105 . 0
00313 . 0
C C
C
F F
F
Y
~
M 0 M
X
M 0 M
X
X / M
=

=
The overall selectivity of xylene relative to toluene is
d eproducte moltoluen
producted molxylene
7 . 0
00313 . 0 0029 . 0 0105 . 0
00313 . 0

C C C
C
C
C
F
F
S
~
X M 0 M
X
T
X
T
X
T / X
=

=

= = =
53
Membrane Reactor to Improve Selectivity in Multiple Reactions
~In addition to using membrane reactors to remove a reaction product in order to
shift the equilibrium toward completion, we can use membrane reactor to
increase selectivity in multiple reactions.
~This increase can be achieved by injecting one of the reactants along the length of
the reactor.
~It is particularly effective in partial oxidation of hydrocarbons, chlorination,
ethoxylation, hydrogenation, nitration, and sulfunation reactions.
By keeping one of the reactants
at a low concentration, we can
enhance selectivity. By feeding a
reactant through the sides of a
membrane reactor, we can keep
its concentration low.
54
Example 6-9
The reactions
s mol / dm 3 k C C k r U B A ) 2 (
s mol / dm 2 k C C k r D B A ) 1 (
2 6
A 2
2
B A A 2 A 2
2 6
A 1 B
2
A A 1 A 1
= = +
= = +
take place in the gas phase. The overall selectivities, , are to be compared for a membrane
reactor (MR) and a conventional PFR. First, we use the instantaneous selectivity to determine
which species should be fed through the membrane



We see that to maximize S
D/U
we need to keep the concentration of A high and the
concentration of B low; therefore, we feed B through the membrane. The molar flow rate of A
entering the reactor is 4 mol/s and that of B entering through the membrane is 4 mol/s as
shown in Figure E6-9.1 For the PFR, B enters along with A.

C k
C k

C C k
C C k
S
B A 2
A A 1
2
B A A 2
B
2
A A 1
U / D
= =
U / D
S
~
The reactor volume is 50 dm
3
and the entering
total concentration is 0.8 mol/dm
3
. Plot the
molar flow rates and the overall selectivity, ,
as a function of reactor volume for both the MR
and PFR.
U / D
S
~
55
Solution
Mole Balances for both the PFR and the MR
U
U
U
U
D
D
D
D
B B
B
B
B
A
A
A
A
r
dV
dF
r
dV
dF
) 4 ( : SpeciesU
r
dV
dF
r
dV
dF
) 3 ( : SpeciesD
R r
dV
dF
r
dV
dF
) 2 ( : SpeciesB
r
dV
dF
r
dV
dF
) 1 ( : SpeciesA
MR PFR
= =
= =
+ = =
= =
Net Rates and Rate Laws
C C k r r
C C k r r
C C k C C k r r r
C C k C C k r r r
2
B A A 2 U 2 U
B
2
A A 1 D 1 D
2
B A A 2 B
2
A A 1 B 2 B 1 B
2
B A A 2 B
2
A A 1 A 2 A 1 A
= =
= =
= + =
= + =
56
Transport Law
The volumetric flow rate through the membrane is given by Darcys Law:
t t s m
A ) P P ( K v =
K is the membrane permeability (m/skPa) and P
s
(kPa)
and P
t
(kPa) are the shell and tube side pressures, and
A
t
is the membrane surface area (m
2
).
t t
aV A =
t B t t s 0 B m 0 B 0 B
V R aV ) P P ( K C v C F = = =
The molar flow rate of B per unit volume of reactor is
t
0 B
B
V
F
R =
Stoichiometry
T
U
0 T U
T
B
0 T B
T
D
0 T D
T
A
0 T A
F
F
C C
F
F
C C
F
F
C C
F
F
C C
= =
= =
no pressure drop
isothermal operation
Combining
Polymath
F
i
vs. V
S
D/U
vs. V
57
We can easily modify the program,
Table E6-9.1, for the PFR simply by
setting R
B
equal to zero (R
B
=0) and
the initial condition for B to be 4.0.
Notes that the enormous enhancement in selectivity the MR has over the PFR.
U
D
U / D
F
F
S
~
=
58
Example 6-10
The following gas-phase reactions take place simultaneously on a metal oxide-supported
catalyst:




Writing these equations in terms of symbols yields
O H 6 N 4 NO 6 NH 4 . 4
NO 2 O NO 2 . 3
O H 3 N O 5 . 1 NH 2 . 2
O H 6 NO 4 O 5 NH 4 . 1
2 2 3
2 2
2 2 2 3
2 2 3
+ +
+
+ +
+ +
min / ) kmol / m ( 0 . 5 k C C k r D 6 E 5 C 6 A 4 : 4 action Re
min / ) kmol / m ( 0 . 10 k C C k r F 2 B C 2 : 3 action Re
min kmol / m 0 . 5 k C C k r D 3 E B 5 . 1 A 2 : 2 action Re
min / ) kmol / m ( 0 . 5 k C C k r D 6 C 4 B 5 A 4 : 1 action Re
3 / 2 3
C 4
3 / 2
A C C 4 C 4
2 3
B 3 B
2
C B 3 B 3
3
A 2 B A A 2 A 2
2 3
A 1
2
B A A 1 A 1
= = + +
= = +
= = + +
= = + +
Determine the concentrations as a function of position (i.e., volume) in a PFR.
Addition information: Feed rate = 10 dm
3
/min; volume of reactor = 10 dm
3
; and C
A0
=
C
B0
= 1.0 mol/dm
3
, C
T0
= 2.0 mol/dm
3
59
Solution
F
F
E
E
D
D
C
C
B
B
A
A
r
dV
dF
: SpeciesF
r
dV
dF
: SpeciesE
r
dV
dF
: SpeciesD
r
dV
dF
: SpeciesC
r
dV
dF
: SpeciesB
r
dV
dF
: SpeciesA
=
=
=
=
=
=
Mole Balances
F E D C B A T
F F F F F F F : Total + + + + + =
Stoichiometry
6
r
5
r
6
r
4
r
: 4 action Re
2
r
1
r
2
r
: 3 action Re
3
r
1
r
5 . 1
r
2
r
: 2 action Re
6
r
4
r
5
r
4
r
: 1 action Re
D 6 E 5 C 4 A 4
F 3 B 3 C 3
D 2 E 2 B 2 A 2
D 1 C 1 B 1 A 1
= =

= =

= =

relative rates
concentration

F
F
C C
T
j
0 T j
=
no pressure drop
isothermal operation
60

F
F F
C k r

F
F F
C k r

F
F F
C k r

F
F F
C k
F
F
C
F
F
C k C C k r
3 / 5
T
3 / 2
A C 3 / 5
0 T C 4 C 4
3
T
B
3
C 3
0 T B 3 B 3
2
T
B A
2
0 T A 2 A 2
3
T
3
B A
3
0 T A 1
2
T
B
0 T
T
A
0 T A 1
2
B A A 1 A 1
=
=
=
=
|
|
.
|

\
|
|
|
.
|

\
|
= =
B 3 F
C 4 6
5
A 2 2
1
E
C 4 A 2 A 1 D
C 4 B 3 A 1 C
B 3 A 2 A 1 B
C 4 3
2
A 2 A 1 A
r 2 r : SpeciesF
r r r : SpeciesE
r r 5 . 1 r 5 . 1 r : SpeciesD
r r 2 r r : SpeciesC
r r 75 . 0 r 25 . 1 r : SpeciesB
r r r r : SpeciesA
=
=
=
+ + =
+ + =
+ + =
D 6 E 5 C 6 A 4 : 4 action Re
F 2 B C 2 : 3 action Re
D 3 E B 5 . 1 A 2 : 2 action Re
D 6 C 4 B 5 A 4 : 1 action Re
+ +
+
+ +
+ +
61
Notes that there is a maximum in the concentration of NO (i.e., C) at approximately 1.5 dm
3
.
62
Closure
~After completing this section, the student should be able to describe the
different types of multiple reactions (series, parallel, complex, and independent)
and to select a reaction system that maximizes the selectivity.
~The student should be able to write down and use the algorithm for solving
CRE problems with multiple reactions.
~The student should also be able to point out the major differences in the CRE
algorithm for the multiple reactions from that for the single reactions, and then
discuss why care must be taken when writing the rate law and stoichiometric
steps to account for the rate laws for each reaction, the relative rates, and the
net rates of reaction.
~Finally, the student should feel a sense of accomplishment by knowing they
have now reached a level they can solve realistic CRE problems with complex
kinetics.
63
Homework-4
Due 2007.11.26
In Int. J. Chem. Kinet., 35, 555 (2003), does the model overpredict the
orthodiethyl benzene concentration? Please give a reason.