L9-1

Review: Isothermal Reactor Design

1. Set up mole balance for
specific reactor

2. Derive design eq. in

terms of XA for each
reactor
3. Put Cj is in terms of
XA and plug into rA
(We will always look
conditions where Z0=Z)

In - Out +Generation = Accumulation

V
dN j
Fj0 F j rjdV
dt
Batch
t =NA0

CSTR
F X
V = A0 A
-rA

XA

dX A

0 -rA V

rA kC jn

PFR
X A dX
A
V =FA0
0 -rA

C j0 jCA0 X A P T0 Z 0
Cj

1 XA
Z
P0 T

Reaction order
n
needs to be
C j0 jC A0 X A P T0
determined.
rA k

4. Plug rA into design eq & solve for the time

(batch) or V (flow) required for a specific XA
or the XA obtained for given V , 0, time, etc

1 X A

P0 T

Be able to rearrange
equations & integrate for Q2

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-2

Review: Analysis of Rate Data

Goal: determine reaction order, , and specific reaction rate constant, k
Data collection is done in the lab so we can simplify BMB, stoichiometry,
and fluid dynamic considerations
Want ideal conditions well-mixed (data is easiest to interpret)
Constant-volume batch reactor for homogeneous reactions: make
concentration vs time measurements during unsteady-state operation
Differential reactor for solid-fluid reactions: monitor product concentration
for different feed conditions during steady state operation

Method of Excess
Differential method
Integral method
Half-lives method
Initial rate method
Differential reactor
More complex kinetics

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-3

Review: Method of Excess

A + B products

Suspect rate eq. -rA = kCACB

1.Run reaction with an excess of B so CB CB0

2.Rate equation simplifies to rA = kCA where k=kACB k=kACB0and
can be determined
3.Repeat, but with an excess of A so that CA CA0
4.With excess A, rate simplifies to rA = kCB where k=kACA k=kACA0
5.Determine kA by measuring rA at known concentrations of A and B, where
kA

rA

dm mol

C A CB

1

s

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-4

Review: Differential Method

d
dC j
Fj0 Fj rj V N j
rj
dt
dt
0 0
Average slope
1. Plot CA/t vs t

alpha power

Where rA = kCA

Curved line
2. Determine dCA/dt from plot by
represents
graphical or numerical methods
dCA/dt
a) Draw rectangles on the graph.
Then draw a curved line so that
the area above the curve that is
cut off of each rectangle
approximately fills the unfilled
area under the curve
b) -dCA/dt is read using the value
dCA dt
where the curve crosses a
k

Slope of line =
C A
specified time
dCA
Insert , dCA,p/dt, &
3. Plot ln(-dCA/dt) vs ln CA
ln
lnk lnCA

dt
corresponding CA,p
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-5

Review: Integral Method

A trial-and-error procedure to find reaction order
Guess the reaction order integrate the differential
equation
Method is used most often when reaction order is known
and it is desired to evaluate the specific reaction rate
constants (k) at different temps to determine the activation
energy
Looking for the appropriate function of concentration
corresponding to a particular rate law that is linear with time

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

For the reaction

A products

For a zero-order reaction

Plot of CA vs
t is a straight
line

dC A
rA
dt
dC A
k
dt

-rA = k

L9-6

CA

CA CA0 kt
t

For a first-order reaction

- r A = k CA

ln (CA0/CA)
Plot of ln(CA0/CA)
vs t is a straight
line

For a second-order reaction - rA = k CA2

1/CA
Plot of 1/CA vs t
is a straight line

dC A
kC A
dt
CA0
ln
kt
CA
dCA
kCA 2
dt
1
1

kt
CA CA0

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-7

Review: Method of Half-lives

Half-life of a reaction (t1/2): time it takes
for the concentration of the reactant to
drop to half of its initial value

ln (t1/2)
Slope = 1-

A products dCA kC
A

dt
rA kC A

1
1
1
t

1
k 1 C A
CA0

1
CA C A0 at t = t1 2
2
t1 2

ln CA0
Plot ln(t1/2) vs ln CA0. Get a straight
line with a slope of 1-

ln t1 2

2 1 1
1

k 1 CA0 1

2 1 1
ln
1 lnCA0
k 1

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-8

Review: Method of Initial Rates

When the reaction is reversible, the method of initial
rates can be used to determine the reaction order and
the specific rate constant
Very little product is initially present, so rate of reverse
reaction is negligible
A series of experiments is carried out at different initial
concentrations
Initial rate of reaction is determined for each run
Initial rate can be found by differentiating the data and
extrapolating to zero time
By various plotting or numerical analysis techniques relating -rA0
to CA0, we can obtain the appropriate rate law:

rA0 kCA0

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-9

Review: Differential Catalyst Bed

Conversion of reactants
& change in reactant
concentration in the bed
is extremely small

rA: rate of reaction per unit mass of catalyst

flow in - flow out + rate of gen = rate of accum.

FA0 FAe rA W 0

FAe

FA0
CA0

Cp
Fp

FA0 FAe 0CA0 CAe

rA

W
W
When constant flow rate, 0 = :

0 C A0 CAe 0Cp Product

rA

concentration
W
W
The reaction rate is determined by measuring
product concentration, Cp

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9: Reactor Design for Multiple

Reactions

L9-10

Usually, more than one reaction occurs within a chemical reactor

Minimization of undesired side reactions that occur with the desired
reaction contributes to the economic success of a chemical plant
Goal: determine the reactor conditions and configuration that
maximizes product formation
Reactor design for multiple reactions
Parallel reactions
Series reactions
Independent reactions
More complex reactions
Use of selectivity factor to select the proper reactor that minimizes
unwanted side reactions

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-11

Classification of Multiple Reactions

1) Parallel or competing reactions
A

k1
k2

2) Series reactions

Desired product
k1

k2

Desired product

3) Independent reactions
A

k1

4) Complex reactions

Crude oil cracking

k2

A B

k1

C D

AC

k2

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-12

Parallel Reactions

Purpose: maximizing the desired product in parallel reactions

kD

(desired)

rD kDCA1CB 1

rD

ED
AD e RT C A1CB 1

rU

EU
AUe RT CA 2 CB 2

A+B
kU

k T

U (undesired)

E
AeRT

rU kUC A 2 CB 2

Rate of disappearance of A: rA rD rU
rA

EU
ED
ADe RT C A1CB 1 AUe RT C A2 CB 2

Define the instantaneous rate selectivity, SD/U

SD U

SD U

rate of formation of D rD

rate of formation of U rU

sD U

AD e
A Ue

ED EU
AD
e RT

kD
CA1 2 CB 1 2 SD U
kU
AU

ED
RT

EU
RT

C A 1CB1

C A 2 CB2

CA12 CB12

Goal: Maximize SD/U to maximize production of the desired product

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

Maximizing SD/U for Parallel

Reactions: Temperature Control
SD U

ED EU
AD
e RT

AU

L9-13

C A12 CB 1 2

What reactor conditions and configuration maximizes the selectivity?

Start with temperature (affects k):
b) If ED < EU

a) If ED > EU
ED EU
0
RT

ED EU
e RT

Specific rate of desired reaction

kD increases more rapidly with
increasing T
Use higher temperature to favor
desired product formation

ED EU
0
RT

ED EU
e RT

Specific rate of desired reaction kD

increases less rapidly with
increasing T
Use lower T to favor desired
product formation (not so low that
the reaction rate is tiny)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-14

Maximize SD/U for Parallel Reactions

using Temperature
A

kD

SD U
kU

ED EU
AD
e RT CA12
AU

U
What reactor temperature maximizes the selectivity?

ED = 20 kcal/mol, EU = 10 kcal/mol, T = 25 C (298K) or 100 C (373K)

cal
cal

a) ED > EU
T = 25 C
20,000
10,000
(298K):

A
SD U D e
AU

mol
mol
cal

1.987

298K
molK

C A12

cal
cal

20,000
10,000
mol
mol

cal

1.987

373K
AD
mol

e
CA1 2
AU

A
SD U D 4.6 10 8 C A1 2
AU

T = 100 C
(373K):

kD/U

A
SD U D 1.4 10 6 C A1 2
AU
SD/U is greater at 373K, higher temperature to favors desired product formation
SD U

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-15

Maximizing SD/U for Parallel

Reactions: Concentration
kD

SD U

A+B
kU

ED EU
AD
e RT

AU

CA12 CB 1 2

What reactor conditions and configuration maximizes the selectivity?

Now evaluate concentration:
a) 1 2 1 2 0
b) 1 2 1 2 0
CA1 2

CA1 2

Use large CA

Use small CA

c) 1 2 1 2 0

d) 1 2 1 2 0

CB 1 2

CB 1 2

Use large CB

Use small CB

How do these concentration requirements affect reactor selection?

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

Concentration Requirements &

Reactor
Selection
k
D

A+B
kU

How do concentration requirements play

into reactor selection?
CA00
CB00

PFR
PFR (or PBR): concentration is
high at the inlet & progressively
drops to the outlet
concentration

CA(t)
CB(t)

L9-16

Batch:
concentration is
high at t=0 &
progressively drops
with increasing time

CB0

CA

CA0
CB0

CSTR:
concentration is
always at its
lowest value
(that at outlet)

Semi-batch: concentration
of one reactant (A as
shown) is high at t=0 &
progressively drops with
increasing time, whereas
concentration of B can be
kept low at all times

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

kD
A+B

kU

High CA favors undesired

High
C
favors
desired
A

product formation
product formation
U
(keep CA low)

High CB
favors
desired
product
formation

L9-17

Batch reactor
When CA & CB are low (end time
or position), all rxns will be slow

PFR/PBR
High P for gas-phase rxn, do not
add inert gas (dilutes reactants)

PFR/PBR
Side streams feed low CA
CA
Semi-batch
reactor slowly feed
High CB
A to large amt of B
CA
CA
CA
CSTRs in
series
CA00
CB00

CA0
CB

CSTR

PFR/PBR w/ side streams feeding

High CB
low CB
CB
favors
Semi-batch
High CA
PFR/PBR
undesired reactor, slowly
PFR/PBR
w/ high
feed B to large amount of A
product
recycle
CB
CB
CB
formation
CSTRs in
Dilute feed with inerts that are
(keep CB series
easily separated from product
low)
B consumed
before&leaving
CSTR
Low
P if gas
phaseUrbana-Champaign.
Slides courtesy of Prof
M L Kraft, Chemical
Biomolecular
Engr
University
of Illinois,
n Dept,

L9-18

Different Types of Selectivity

rate of formation of D rD

instantaneous rate selectivity, SD/U

rate of formation of U rU
overall rate selectivity,S%
SD U

DU

F
Exit molar flow rate of desired product
S%D U D
FU Exit molar flow rate of undesired product
N
Final moles of desired product
S%D U D
NU Final moles of undesired product
instantaneous yield, YD
(at any point or time in reactor)

YD

r
rate of formation of D
D
rate of consumption of A rA

%
overall yield, Y
D
% FD
Y
flow D F F
A0
A

Evaluated
at outlet

batch Y%
D

ND
NA0 NA

Evaluated
at tfinal

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-19

Series (Consecutive) Reactions

A

k1

k2
U
D
(desired) (undesired)

Spacetime for a flow reactor

Time is the key factor here!!!

Real time t for a batch reactor

To maximize the production of D, use:

CSTRs in series

Batch
or

PFR/PBR

or
n

and carefully select the time (batch) or spacetime (flow)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-20

Concentrations in Series Reactions

k1

k2

-rA = k1CA
rB,net = k1CA k2CB

How does CA depend on ?

dFA
dC A
k1C A 0
k1C A C A C A0e k1
dV
dV
How does CB depend on ?
dFB
dCB
k1C A k 2CB 0
k1 C A0e k1 k 2CB
dV
dV

Substitute
0

dCB
dCB
k1 C A0ek1 k 2CB
k 2CB k1 CA0e k1
d
d

Use integrating
factor (reviewed
on Compass)

d CBek 2
d

k C
1

ek1 ek 2
k 2 k1 CB k1CA0

A0
k

k
2
1

CC CA0 CA CB
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L9-21

Reactions in Series: Cj & Yield

CA CA0ek1

B
C

ek1 ek 2
CB k1C A0

k
2
1

CC CA0 CA CB

opt

The reactor V (for a given 0) and that maximizes CB occurs when dCB/dt=0

dCB k1CA0
k1
k 2

k
e

k
e
0
1
2

d
k 2 k1

opt

k
1
ln 1
k1 k 2 k 2

V
so Vopt 0 opt
0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.