Chapter 6 MULTIPLE REACTIONS

If there are multiple rxns, use concentrations not conversions.

intermediate

1. Series Reactions Consecutive rxns

2. Parallel Reactions

3. Complex Reactions:
Series and Parallel

4. Independent
None of the products or reactants
are common.

These might occur in combination or by themselves.

Desired & Undesired Rxns

We want to get the desired product, D and avoid the formation of
undesired one, U.
In the parallel rxn A
kD
D
A
kU
U

In series A
kD
D
kU
U
D

Cost Total Cost Reactor Cost

A Reactor Seperator
Seperator Cost

U Low Efficiency High

1
 Selectivity and Yield
Selectivity tells us how one product is favored over another when multiple
rxns take place

Exit flow rate

~ ND
For batch S DU =
NU tend

Reaction yield = ratio of the

rxn rate of a given product to
the rxn rate of key reactant A.

Determine the instantaneous selectivity, SD/U, for the liquid phase reactions:
A+B
D rD = k 1 C A C B
2

A+B
U 1 rU 1 = k 2 C A C B
A+B
U 2 rU 2 = k 3 C A C B
3

Sketch the selectivity as a function of the concentration of A. Is there an

optimum and if so what is it?
2
rD k1C A C B k1C A
SD/U1U 2 = = =
rU1 + rU 2 k 2 C A C B + k 3C A 3C B k 2 + k 3C A 2

Find the optimum

concentration
dS
dC A
[ ]
= 0 = k1 k 2 + k 3C A k1C A 2k 3C A
*2 *
[
*
]
k2
CA =
*

k3

2
Parallel Rxns:
For the following competing rxns

1
A
kD
D (desired) rD = k D C A
2
A
kU
U (undesired ) rU = k U C A

Rate of disappeara nce of A

2
- rA = rD + rU = k D C A 1 + k U C A
where 1 and 2 are positive rxn orders.

rD k D
S D/U = = CA 1 2
rU k U

Maximizing the Desired Product for one Reactant

Case1:
kD
If 1 > 2 SD/U = CA 1 2 SD/U as C A
kU

Case2:
kD 1
If 1 < 2 SD/U = SD/U as C A
k U C A 2 1

In Case 1: If gas rxn, we should run it without any inerts and at high
pressures to keep CA high.
If liquid phase rxn, the diluents should be minimum. CSTR should not be
used, batch or plug flow should be used.
In Case 2: Dilute the feed with inerts. CSTR should be used, because CA
decreases rapidly.

3
Effect of Temperature on Selectivity
It can be determined from
k D A D -([E D -E U ]/RT)
SD/U ~ = e
kU AU
where A : freq factor, E : activation energy

SD/U
Rxn should be operated at the highest
possible T to max. SD/U
ED > EU
T

SD/U

ED < EU

2. Series Reactions

This series reaction could also be written as

Reaction (1)
Reaction (2)

Species A:

Species B:

4
Using the integrating factor, i.f.:

at t = 0, CB = 0

When should you stop the reaction to obtain the maximum amount of B?
Let's see

Then

And

5
The Integrating Factor
(1)

If you only had an expression of the form

(2)

things would be much easier, then you could integrate with respect to z
and find y(z).
(3)
then you could manipulate equation (3):

(4)

where the term in brackets is the left hand side of equation (1). You need
du/dz = u f(z). Recall
(5)

If you define and f(z) = dq/dz (i.e. , then

(6)

This satisfies the condition that du/dz=u f(z). Therefore,

and substituting into equation (4),
(7)

where the term in brackets is the left hand side of equation (1).

CONCLUSION: If your problem is of the form

you can multiply both sides of the equation by the

6
 (which you should be able to evaluate, since you know f(z)), to yield

or, substituting from equation (7)

Derivation

f(t)=k2, so

From equation (12), the solution is then

The constant can be obtained from the intitial condition that at t=0, CB=0;

7
 3. Algorithm for Multiple
Reactions

Reactor Selection & Operating Conditions:

Consider two simultaneous rxns
1
A + B
k1
D rD = k 1C A 1 C B
2
A + B
k2
U rU = k 2 C A 2 C B
rD k 1 ( ) ( )
S D/U = = CA 1 2 CB 1 2
rU k 2
We usually want to max SD/U. So the reactors should be designed to max SD/U
B
H>>0
B
A
A

B B B C
D
A A
A D

H>>0 Thermodinamically limited rxns A + B <-> C + D

8
 Algorithm for Solution of Complex Reactions:
In combinations of parallel and series rxns, ODE solver packages
make life easier.
Write the rxns
Write the mole balances
Net rate laws
Stoichiometry
Combine & Solve

4. Applications of Algorithm

NOTE: The specific reaction rate k1A is

(1) defined with respect to species A.

(2) NOTE: The specific reaction rate k2C is

defined with respect to species C.
Case 1: PFR
Mole Balances Rate Laws
dF A
A: = rA
dV
dF B
B: = rB
dV
dF C
C: = rC
dV
dF D
D: = rD
dV

9
Species A rA = r1A + r2A
r1A = -k 1A C A C B
2

For reaction (1):

r1B = 2r1A
r1C = -r1A
r1A = -k 1A C A C B
2

- r2A -r
For reaction (2): = 2C
2 3
2 2
r2A = ( -r2C ) = k 2C C C C A
3 2

3 3
1
r2D = r2C
3
2
rA = k 1A C A C B k 2C C C C A
2 3 2
Species A
3
rB = r1B = 2 k 1A C A C B
2
Species B
rC = k 1A C A C B k 2C C C C A
2 3 2
Species C

Species D r2C 1
rD = r2D = = k 2C C C C A
3 2

3 3

Writing the net rates

Stoichiometry liquid : v = v0
FA = CAv0
Combine
dC A rA
Species A =
dV v 0
2
k1A C A C B k 2C C C C A
2 3 2
dC A 3
=
dV v0 Evaluate solution using Polymath of
dC B rB MatLab
Species B =
dV v 0 k1A = 0.5
dC B 2k1A C A C B
2
= k2C = 2.0
dV v0
v0 =5.0
dC C rC
Species C =
dV v 0 @ t=0; V=0, CA0=4, CB0=4, CC0=0, CD0=0
dCC k1A C A C B k 2C C C C A Vf = 5 dm3
2 3 2
=
dV v0
dC D rD
Species D =
dV v 0
3 2
dC D 1 k 2C C C C A
=
dV 3 v0

10
Case 2: CSTR

(FA0 - FA ) v 0 (C A0 - C A )
Species A V= =
- rA 2
k1A C A C B + k 2C C C C A
2 3 2

3
( F - F ) v (C - C )
Species B V = B0 B = 0 B0 B2
- rB 2k1A C A C B
(FC0 - FC ) FC v 0CC
Species C V= = =
- rC rC k1A C A C B 2 k 2C C C 3C A 2
(FD0 - FD ) FD v 0C D
Species D V= = =
- rD rD 1 k C 3C 2
2C C A
3

We will specify V, CA0, CB0 along with the specific reaction rates kij.
This formulation leaves us with four equations and four unknowns (CA,
CB, CC and CD)

2 2
f(C A ) = - V k 1A C A C B + k 2C C C C A + v 0 (C A0 - C A )
2 3

3
[ ]
f(C B ) = - V 2k 1A C A C B + v 0 (C B0 - C B )
2

[
f(C C ) = V k 1A C A C B k 2C C C C A v 0 C C
2 3 2
]
1 2
f(C D ) = V k 2C C C C A v 0 C D
3

11
Case 3: Semibatch Liquid Phase
dC A 2 vC
= k 1A C A C B k 2C C C C A 0 A
2 3 2
Species A
dt 3 V
dC B v0 [C B0 C B ]
= 2 k 1A C A C B
2
Species B
dt V
dC C vC FB0
= k 1A C A C B k 2C C C C A 0 C
2 3 2
Species C
dt V
dC C 1 v0 C D
= k 2C C C C A
3 2
Species D
dt 3 V A

V = V0 +v 0 t

Parameters dm 6 dm 2
k1A = 0.5 k 2C = 2
mol2 hr mol4 hr
dm 3 mol
v 0 = 1.2 C B0 = 4 V0 = 2dm 3
hr dm 3
Initial conditions C Ai = 4 C Bi = 0 C Ci = 0 C Di = 0 t f = 8 hr

PolyMath Solutions

12
THE ALGORITHM

Mole balances Rate Laws

Relative rates

Rxn (1) A + 2B ->C

Net rates Rxn (2) 2A + 3C ->D

Species A
Species B

Species C
Species D

2
rA = k 1A C A C B
2 3 2
Species A k 2C C C C A
3
rB = r1B = 2 k 1A C A C B
2
Species B
rC = k 1A C A C B k 2C C C C A
2 3 2
Species C
r2C 1
rD = r2D = = k 2C C C C A
3 2
Species D
3 3

Stoichiometry FT0 FA0 P T0 F P T

CA = = C T0 A0 0
v 0 FT0 P0 T FT0 P0 T

13
 Combine P = 0, P = P0 , T =T0
Fi
Ci =C T0
FT
dFA 2
= k1A C A C B k 2C C C C A
2 3 2
Species A
dV 3
2
dFB 3 F F
Species B = 2k1A C T0 A B
dV FT0 FT0
2 3 2
dFC 3 F F 1 5 F FA
Species C = k1A C T0 A B k 2C C T0 C
dV T0 T0
F F 3 FT0 FT0
3 2
Species D dFD 1 5 F FA
= k 2C C T0 C
dV 3 FT0 FT0
FT = FD +FC + FB +FA
Parameters k1A = 0.05, k 2C = 1.3 C T0 = 0.8
Initial Cond. V = 0, FA = 10, FB = 20, FC = 0, FD = 0, Vf = 200

For a CSTR
(FA0 - FA )
Species A V=
- rA
(FB0 - FB )
Species B V=
- rB
(FC0 - FC )
Species C V=
- rC
(FD0 - FD )
Species D V=
- rD
Total : FT = FD +FC + FB +FA

Five equations five unknowns

FA0 - FA
X=
FA0

14
Concentration-
Concentration-Time Trajectories

1. The following concentration-time trajectories were observed in a batch

reactor

Which of the following reaction pathways best describes the data

2. Sketch the concentration-time trajectory for the reaction

Solution: Part 1

Choice B is the answer. Choices A and C are incorrect because they

show species B eventually consumed, which is clearly not the case

15
Solution: Part 2

(1) B virtually consumed so no more D can be produced in reaction 2.

(2) Rates of Consumption of A and Ba are virtually the same.
(3) Rate of consumption of B greater than that of A owing to Reaction 2

16