Chbi502 Chapter 6
Chbi502 Chapter 6
Chbi502 Chapter 6
2. Parallel Reactions
3. Complex Reactions:
Series and Parallel
4. Independent
None of the products or reactants
are common.
In series A
kD
D
kU
U
D
A Reactor Seperator
Seperator Cost
1
Selectivity and Yield
Selectivity tells us how one product is favored over another when multiple
rxns take place
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
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
rD k D
S D/U = = CA 1 2
rU k U
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
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)
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)
(6)
where the term in brackets is the left hand side of equation (1).
6
(which you should be able to evaluate, since you know f(z)), to yield
Derivation
f(t)=k2, so
The constant can be obtained from the intitial condition that at t=0, CB=0;
7
3. Algorithm for Multiple
Reactions
B B B C
D
A A
A 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
9
Species A rA = r1A + r2A
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
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
Relative rates
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
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
14
Concentration-
Concentration-Time Trajectories
Solution: Part 1
15
Solution: Part 2
16