Chapter 5 & 6 Essentials of

Chemical Reaction Engineering

Isothermal Reactor DesignBatch, CSTR & PFRHomogeneous Reactions

Isothermal Design

Stoichiometry
Rate Laws
Mole Balance

Rate Laws

Mole Balance

Isothermal reactor design

These topics build upon one

Stoichiometry

Chemical Reaction Engineering

Review
Lecture 2
Building Block 1: Mole
Balances
in terms of conversion, X

Reactor

Batch

Differential

N A0

PBR

dX
t N A0
rAV
0
V

dX
FA 0
rA
dV
dX
FA 0
rA
dW

Integral
X

dX
r AV
dt

CSTR

PFR

Algebraic

X
t

FA 0 X
rA
X

dX
V FA0
rA
0
X

W FA0
0

X
dX
rA

Review Lecture 3

Building Block 2: Rate Laws

Power Law Model:

rA kC C
2 A B 3C

order in A
order in B
Overall Rection Order

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

rA k AC C B
2
A

2nd order in A, 1st order in B, overall third order

Review Lecture 4
Building Block 3:
Stoichiometry

L5-7

Review: Stoichiometric Tables

FA0
FB0
FC0
FD0
FI0

Feed rate
(mol/time)
FA0

Change in reactor
(mol/time)
-FA0XA

FA
FB
Out
FC
FD
FI
Effluent rate from
reactor (mol/time)
FA = FA0 (1XA)

FB0 = FA0

BFA0XA

FB = FA0 (+ BXA)

FC0 = CFA0

CFA0XA

FC = FA0 (C+ CXA)

FD0 = DFA0

DFA0XA

FD = FA0 (D+ DXA)

FI0 = IFA0

---

FI =FI0

Species

In

FT0
Total
Fj0
C j00
C j0
y j0
J

FA0 C A00 CA0 y A0

b
c
d
B C D
a
a
a

FA0XA

FT = FT0 + FA0XA
d c b
j stoichiometric coefficient
= 1
for products, for reactants
a a a

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

Review Lecture 5

French Menu Analogy

Building Block 4: Combine

Review Lecture 5

Building Block 4:
Combine

Objectives
Describe the algorithm that allows the reader to
solve chemical reaction engineering problems
through logic rather than memorization.
Sizing batch reactors, semi-batch reactors, CSTRs,
PFRs, and PBRs for isothermal operation given the
rate law and feed conditions.
Studying a liquid-phase batch reactor to determine
the specific reaction rate constant needed for the
design of a CSTR.
Design of a tubular reactor for a gas-phase reaction.
Account for the effects of pressure drop on
conversion in packed bed tubular reactors and in
packed bed spherical reactors.
The principles of unsteady operation and semi-batch
reactors.

Fig. 5-1
Isothermal
Reaction
Design
Algorithm
for Conversion

4.1 Design structure for isothermal reactors

Algorithm for isothermal reactor design
1. Mole balance and design equation
2. Rate law
3. Stoichiometry
4. Combine
5. Evaluate
We can solve the equations in the
combine step either
A. Graphically (Chapter 2)
B. Numerical (Appendix A4)
C. Analytical (Appendix A1)
D. Software packages (polymath)

Algorithm for Isothermal Reactors

L5-14

The Logic of Isothermal Reactor Design

1. Set up mole balance for In Out +Generation =Accumulation
V
dN j
specific reactor
Fj0 F j rjdV
dt

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)

Batch
t =NA0

XA

dX A

0 -rA V

rA kC jn

CSTR
F X
V = A0 A
-rA

PFR
X A dX
A
V =FA0
0 -rA

C j0 jCA0 X A P T0 Z 0
Cj

1 XA
Z
P0 T

C j0 jCA0 X A P T0 Z 0
rA k
P T Z
1

X

0
A

4. Plug rA into design eq and solve for the

time (batch) or volume (flow) required
for a specific XA

This week!

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

L5-15

Isothermal Batch Reactor

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

L5-16

Batch Reactor Operation (1)

A B

-rA = kCA2

2nd order reaction rate

Calculate the time required for a conversion of XA in a constant V batch reactor

dX A
rA V
dt

Mole balance

NA0

Rate law

rA kC A 2

Stoichiometry (put CA in
terms of X)

C A C A0 (1 X A )

Combine

NA0

dX A
2
k CA 02 1 X A V
dt

Batch Volume is constant, V=V0

NA0

dX A
2
k C A02 1 X A V0
dt

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

L5-17

Batch Reactor Operation (2)

A B

-rA = kCA2

2nd order reaction rate

Calculate the time required for a conversion of XA in a constant V batch reactor

Evaluate

dX A
2
NA 0
kC A 02 1 X A V0
dt

dX A
dX A
2 1
2 V0
2

kC A02 1 X A

kC A0 1 X A
dt
CA 0
dt
NA0
dX A
2
Rearrange to get like variables together

kCA0 1 X A
dt

dX A

1 XA

Integrate

kC A0dt
XA

dX A
1
k is constant for an

dt

2
isothermal reaction
kC

A0 1 X A

dX A
1

2
kC

A0
0 1 XA

Time required to
1 XA
t achieve XA for
dt

kC A0 1 X A
0
2nd order rxn
t

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

L5-18

Batch Reactor Operation (3)

A B

-rA = kCA

1st order reaction rate

Calculate the time required for a conversion of XA in a constant V batch reactor

Mole balance

dX A
NA0
rA V
dt

Rate law

rA kCA

Stoichiometry (put CA in
terms of X)

C A C A0 (1 X A )

Combine

dX A
NA0
kC A 0 1 X A V
dt

Batch Volume is constant, V=V0

dX A

N
kC A 0 1 X A V0
Mole balance as a function of conversion
A0
dt
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L5-19

Batch Reactor Operation (4)

A B

-rA = kCA

1st order reaction rate

Calculate the time required for a conversion of XA in a constant V batch reactor

dX A
Mole balance as
NA 0
kC A0 1 X A V0
in terms of XA:
dt
V0
dX A

kC A0 1 X A
dt
NA0

dX A
k 1 XA
dt

dX A

kdt
1

Evaluate to solve for time

dX A
1
kC A0 1 X A
dt
CA0

Rearrange to get like variables together

dX A
1
k is constant for an

dt
isothermal reaction
k 1 X A

Time required to achieve

t
Integrate 1 X A dX A
1
1
dt ln
t XA for 1st order rxn

1 XA
k 0 1 X A 0
k
1
Remember: ln
ln 1 x

Confused about the integration? See the next slide

1 x

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

L5-20

Batch Reactor Operation (4)

A B

-rA = kCA

1st order reaction rate

Calculate the time required for a conversion of XA in a constant V batch reactor

t
Integrate 1 X A dX A
dt

k 0 1 X A 0

1
- ln 1 X A
k

XA
0

t
0

ln 1 X A
k

1
ln 1 0 t 0
k
0=ln(1)

1
1
1
ln 1 X A t ln
t
k
k
1

A
1
Remember: ln ln a
a
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

Batch Operation
Algorithm for isothermal reactor design
1. Mole balance and
design equation

2. Rate law
3. Stoichiometry
4. Combination

1 dN A

rA
V dt

1 dN A d N A / V0 dC A

rA
V0 dt
dt
dt

5. Analytical
Evaluation

rA kCA2

A B
dC A
kCA2
dt
dC A
kCA2

dC A

C A0

C A2

CA=CAo(1-X)
dX
CAo
=kCAo2(1-X)2
dt

dt

CA

1 1
1

k C A C A0

irreversible, 2nd order in A

t
X dX
1
kCAo 0 (1-X)2 = dt
0

dt

1
t=
kCAo

X
1-X

Batch Reaction Times (Table 5-1)

A B
Mole balance

r
dX
AV
dt
N A0
Second order

Rate law

Stoichiometry (V=V0)

rA kCA2
CA

NA
C A0 (1 X )
V0

Combine

dX
kCA0 (1 X ) 2
dt

Integration

X
kCA0 (1 X )

Batch Reaction Times- Example

1st - order (X 0.9, k 10 -4 s 1 )
tR

1
1
ln
k 1 X
1
1
ln
k 1 0.9

2.3

2.3
10

4 1

2nd order (X 0.9, kC A0 10 3 s 1 )

tR

X
kCA0 (1 X )

0 .9
kCA0 (1 0.9)

9
kCA0

9
10 3 s 1

23,000 sec

9,000 sec

6.4hr

2.5hr

Batch Reaction Times (Table 5-2)

The order of magnitude of time
to achieve 90% conversion
For first- and second-order irreversible batch reactions
1st-order
k (s-1)

2nd-order
kCA0 (s-1)

Reaction time
tR

10-4

10-3

Hours

10-2

10-1

Minutes

10

Seconds

1,000

10,000

Milliseconds

Reaction Time in Batch Operation (Table 5-3)

1 1
1
t

k C A C A0

2nd order
Isothermal
Liquid-phase
Batch reaction

This time is the time t needed to reduce the reactant

concentration in a batch reactor from an initial value C A0 to
some
specified
value
CAfor
. a batch polymerization process
Typical
cycle
times

tt = t f + t e + t R + t c
1.
2.
3.
4.

Activity

Time (h)

Heat to reaction temperature, te

Charge feed to the reactor and agitate, tf
Carry out reaction, tR
Empty and clean reactor, tc

1.5-3.0
1.0-2.0
Varies (5-60)
0.5-1.0

Total cycle time excluding reaction

3.0-6.0

Decreasing the reaction time with a 60-h reaction is a critical problem. As

the reaction time is reduced, it becomes important to use large lines and
pumps to achieve rapid transfer and to utilize efficient sequencing to

L5-26

Isothermal CSTR

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

L5-27

CSTR Operation (1)

A B

-rA = kCA

Liquid-phase 1st order reaction rate

Calculate the CSTR volume required to get a conversion of XA

FA0 X A
rA

Mole balance

Rate law

rA kC A

Stoichiometry (put CA in
terms of X)

C A CA0 (1 X A )

Combine

FA0 X
kC A0 1 X A

Put FA0 in
terms of CA0

Volume required
C A00 X A
0 X A
V
V
to achieve XA for
kC A0 1 X A
k 1 XA
1st order rxn
(at
)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois
Urbana-Champaign.

L5-28

Scaling CSTRs
Chemical engineers are involved in scaling up a laboratory scale reaction
to the pilot plant scale or full-scale reactor
If one knows the volume of the pilot-scale reactor required to achieve X A,
how is this information used to achieve XA in a larger reactor?
Suppose for a 1st order irreversible liquid-phase reaction:
0 X A
0 X A
known: Vsmall
want: Vbigger
k 1 XA
k 1 XA
Want XA in the small reactor to be the same as XA in the bigger reactor
k in the small reactor is the same as k in the bigger reactor
0 in the small reactor must be different from 0 in the bigger reactor
So the reactor volume V must be proportional to the volumetric flow rate 0
XA
V
0 X A
How?
Separate variables we will

V
0 k 1 X A
k 1 X A vary from those held constant

V 0

XA
k 1 XA

Space time (residence time) required to

achieve XA for 1st order irreversible rxn

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

L5-29

Scaling CSTRs with Spacetime

XA
k 1 XA

Space time (residence time) required to

achieve XA for 1st order irreversible rxn
A B

-rA = kCA

1st order reaction rate

So if you know the spacetime required to get a conversion of XA in a

CSTR, you can use that to achieve the same XA in a different size CSTR
What is required to achieve a specific XA?
Rearrange to get XA
in terms of
k kX A X A

XA
1 k

XA

k 1 XA
k X A kX A

XA
1 XA

k XA 1 k

CSTR relationship between and

XA for 1st order liquid-phase rxn
(isothermal and V = V0)

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

L5-30

Damkhler Number, Da
rA0 V rate of reaction at entrance
reaction rate
Da

FA0
entering flow rate of A
convection rate
Estimates the degree of conversion that can be obtained in a flow reactor
First order irreversible reaction:
r V kC A0 V
kV
Da
Da A0
0
FA0
C A00

1st order
Da k irreversible
reaction

V 0 Substitute
Second order irreversible reaction:

nd
2
order
kC
V
rA0 V kCA 0 V
A
0
Da
Da

Da kC A0 irreversible
0
FA 0
CA00
reaction

How is XA related to Da in a first order irreversible reaction in a flow reactor?

From
k
Da
X

A
A
previous
1 k
1 Da
slide:
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L5-31

Damkhler Number, Da
rA0 V rate of reaction at entrance
reaction rate
Da

FA0
entering flow rate of A
convection rate
Estimates the degree of conversion that can be obtained in a flow reactor
Relate XA to Da for a 1st
order irreversible rxn in
a flow reactor:

XA

1 k

Da k
1 order
irreversible rxn
st

XA

Da

1 Da

If Da=0.1 for this 1st order irreversible rxn in a flow reactor, then
Da
0.1
XA
XA
0.091
1 Da
1 0.1
If Da=10 for this 1st order irreversible rxn in a flow reactor, then
XA

Da
10

XA
0.91
1 Da
1 10

Da 0.1 will usually give less than 10% conversion.

Da 10.0 will usually give greater than 90% conversion.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L5-32

Sizing CSTRs for 2nd Order Rxns

AB

-rA = kCA2

Liquid-phase 2nd order reaction rate

Calculate the CSTR volume required to get a conversion of XA

FA0 X 0CA0 X

rA
rA

Mole balance

Rate laws

rA kCA 2

Stoichiometry

C A CA0 (1 X)

Combine

0CA0 X

kCA 02 1 X

In terms of conversion?
2nd order liquid
irreversible reaction

Da kC A0

In terms of space time?

V
X

2
or 0
kC 1 X
A0

1 2 kC A0

In terms of XA as a
function of Da?

1 4 kC A0

2 kC A0

1 2Da

1 4Da

2Da

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

A Second-Order Reaction in a CSTR

0.88
0.67

60

L5-34

CSTRs
in
Series
C
A0 0

CA1

CA2

Effluent of reactor 1 is input for

reactor 2, no change in

A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and and k are the same in both reactors (& k1 = k2 = k)
Determine V1 for 1st CSTR using our standard procedure. For 2nd CSTR:
FA1 FA2
1. Mole balance CSTR2 V
rA2
2. Rate law CSTR2

rA2 kC A2

3. Stoichiometry CSTR2 Skip this step for now.

4. Combine for CSTR2
Relate CA2 to
CA1, k, &

CA1 CA2
kCA2

0 CA1 CA2
C A1 C A2

V
or =
kC A2
kC A2
kC A2 C A1 C A2 kC A2 C A2 C A1

C A2 k 1 CA1 CA2

C A1
k 1

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

L5-35

CSTRs
in
Series,
C
A1
C
A0 0

CA1

CA2

Effluent of reactor 1 is input for

reactor 2, no change in

A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and and k are the same in both reactors (& k1 = k2 = k)
What is CA1 in terms of and k?
XA

We know for a single CSTR:

st
k Put XA for 1 C C (1 X ) CA1 1 X X 1 CA1

A1
A0
A1
A1
A1
CSTR in
CA0
CA0
1 k

terms of CA1:

CA1 Solve
C A1
k
k

1 k
Substitute:

A1
1 k
1 k
CA0 for CA1:
C A0

C A1 CA1
C A1
C A1 CA1
k 1 k

1
1 k 1

CA0 C A0
C A0
C A0 CA0
C A1
1

C A0 1 k

C A1

C A0
1 k

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

L5-36

CSTRs in Series, CA2

CA00

CA1

CA2

Effluent of reactor 1 is
input for reactor 2

A first order reaction is carried out isothermally using 2 CSTRs that are the
same size, and and k are the same in both reactors (& k1 = k2 = k)
CA0
C A1
& CA1
Relate CA2 to k & CA2
k 1
1 k
Substitute

CA2

CA0

CA 0 1
CA 2
k 1
1

1 k 2

1st order irreversible

rxn with V1 = V2,
and k1 = k2

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

L5-37

n CSTRs in Series
CA00

CA1

CA2

1st order irreversible liquid-phase rxn run in n CSTRs with identical V, and k
For n identical CSTRs, then: C An

CA0

1 k n

Rate of disappearance of A in the nth reactor:

C A0
rAn kCAn k
1 k n
How is conversion related to the # of CSTRs in series?
C A0
1
Put CAn in terms of XAn
1 X An
C 1 X An
n
(XA at the last CSTR): A0
1 k n
1 k
1

1 k

X An or 1

1 Da

X An

1st order irreversible liquid phase

rxn run in n CSTRs with identical
V, and k

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

CSTRs in Series
Solving for CA2, the concentration exiting the second reactor, we get

C A2

C A0
C A1

1 2 k 2 1 2 k 2 1 1k1

If instead of two CSTRs in series we had n equal-sized CSTRs connected in

series (1 = 2 = = n = i = (Vi/v0)) operating at the same temperature (k1 =
k2 = = kn = k), the concentration leaving the last reactor would be

C An

C A0

1 k n

C A0

1 Da n

The conversion and the rate of disappearance of A for these n tank reactors
in series would be

X 1

1 k

X= 1-CA/CAo
1
=1(1+Da)n

rAn kCAn

kCA0

1 k n

Conversion as a Function of Reactors in Series

for different Damkohler numbers for a first-order recation
Da=k=1
Da=k=0.5

Da=k=0.1

Da 1, 90% conversion is achieved in two or three reactors;

thus the cost of adding subsequent reactors might not be justified
Da ~0.1, the conversion continues to increase significantly with each reactor added

L5-40

Isothermal CSTRs in Parallel

Mole Balance
X Subscript i
Vi FA0i Ai
rAi denotes reactor i

FA01
FA0
FA02

same T, V,
FA01 = FA02 = FA0n

X A

rA

V FA0

V total volume of all CSTRs

Vi
n
# of CSTRs
Volume of each CSTR
FA0i

FA0 total molar flow rate

n
# of CSTRs

Molar flow rate of each CSTR

X1 =X 2 =... =Xn =X
rA1 rA2 ... rAn rA

V FA0 X Ai

n
n rAi

X A

r
A

V FA0

Conversion achieved by any one of the reactors in parallel is the

same as if all the reactant were fed into one big reactor of volume
Slides courtesy
of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
V

CSTRs in Parallel
A balance on any reactor i, gives the individual
reactor volume

FA0

Xi
Vi FA0i
rAi

FA0 i

-rA1, V1, X1

X1 X 2 X n X

rA1 rA2 rAn rA

The volume of each individual reactor, Vi, is
related to the total volume, V, of all the reactors,
and similar relationship exists for the total molar
flow rate
FA 0
V
Vi
FA 0 i

-rAi, Vi
n

-rAn, Vn

CSTRs in Parallel
Substituting these values into Eq (4-12) yields
F
FA 0 i A0
n
V

Vi

FA0

Xi
Vi FA0i
rAi

FA01

FA0i

-r-rA1, ,VV1, X1
A1

V F A0 X i

n
n rAi
V

FA0n

-r-rAiAi, ,VVi,i Xi

FA 0 X i FA 0 X

rAi
rA

The conversion achieved in any one of the reactors in

parallel is identical to what would be achieved if the
reactant were fed in one stream to one large reactor of
volume V

-r-rAn, ,VVn, Xn
An

Isothermal PFR/PBR

L6-44

Be able to do these 4 steps,

integrate & solve for V for ANY
ORDER RXN

Liquid Phase Reaction in PFR

LIQUID PHASE: Ci f(P) no pressure drop
2A B -rA = kCA2 2nd order reaction rate
Calculate volume required to get a conversion of XA in a PFR
dX A rA

Mole balance
dV
FA0
Rate law

rA kC A 2

Stoichiometry (put CA in
terms of X)

C A C A0 (1 X A )

dX A

dV

Combine

FA0

k C A0

XA

dX A

1 XA

See Appendix A for integrals

frequently used in reactor design

dV
0

k C A02 1 X A

FA0

k CA02

FA0

XA
1 X V

Liquid-phase 2nd order reaction in PFR

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

L6-45

Liquid Phase Reaction in PBR

Be able to do these 4 steps, integrate
& solve for V for ANY ORDER RXN

LIQUID PHASE: Ci f(P) no pressure drop

2A B -rA = kCA2 2nd order reaction rate
Calculate catalyst weight required to get a conversion of XA in a PBR
dX A r ' A

Mole balance
dW
FA0
r 'A kCA 2

Rate law

CA C A0 (1 X A )

Stoichiometry (put CA in
terms of X)

dX A

dW

Combine

FA0

k CA0

XA

dX A

1 XA

dW
0

k CA02 1 X A

FA0

k CA02

FA0

XA
1 X W

Liquid-phase 2nd order reaction in PBR

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

L6-46

Isobaric, Isothermal, Ideal gas Rxns

in Tubular Reactors
Gas-phase reactions are usually carried out in tubular reactors (PFRs & PBRs)
Plug flow: no radial variations in concentration, temperature, & -rA
No stirring element, so flow must be turbulent

FA0

FA

C j0 jCA0 X A
C j0 jCA0 X A P T0 Z 0
Cj
GAS PHASE: C j

1 XA
1 XA
Z
P0 T
1

Stoichiometry for basis species A:

C A0 1 X A
C A0 CA0 X A
CA
CA
1 XA
1 XA
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

L6-47

Isobaric, Isothermal, Ideal Rxn in PFR

GAS PHASE: Ci = f() no P, T, or Z
2A B -rA = kCA2 2nd order reaction rate
Calculate PFR volume required to get a conversion of XA
dX A rA

Mole balance
dV
FA0
rA kC A 2

Rate law
Stoichiometry (put CA in
terms of X)

C A0 1 X A
CA
1 X A
2

Combine
V
V

FA0

k CA0

FA0

k CA0

XA

1 X A dX
A
2
1 XA

2 1 ln 1 X A

dX A k C A0 1 X A

dV
1 X 2 F
A

A0

Integral A-7 in appendix

1 2 X
A
2XA

1 X A

Gas-phase 2nd
order rxn in PFR
no P, T, or Z

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

Effect of on and XA

L6-48

NTf NT0 Change in total # moles at X A 1

NT0
total moles fed

: expansion factor, the fraction of change in V per mol A reacted

0: volumetric flow rate
varies if gas phase & moles product 1 X Z T P0

0
A
moles reactant, or if a P, T, or Z occurs
Z0 T
0 P
No P, T, or Z occurs, but moles product moles reactant
0 1 X A
= 0 (mol product = mol reactants): : constant volumetric flow rate as XA
increases
< 0 (mol product < mol reactants): volumetric flow rate decreases as
XA increases
Longer residence time than when
Higher conversion per volume of reactor (weight of catalyst) than if 0
> 0 (mol product > mol reactants): with increasing XA
Shorter residence time than when
Lower conversion per volume of reactor (weight of catalyst) than if 0
Slidescourtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.

Tubular Reactors
- 2nd-order gas-phase reaction
- Turbulent
- No dispersion
- No radial gradients in T, u, or C
PLUG-FLOW REACTOR
PFR mole balance

FA 0

dX
rA
dV

must be used when there is a P or

heat exchange between PFR & the
surrounds. In the absence of P or
heat exchange, the integral form of
the PFR design equation is used.

V FA 0

dX
rA

Rate law

V FA0

dX

kCA2

For Liquid-Phase Reaction

V FA0

dX

1
V/vo= = kC
Ao

X=

= FAo

kCA2

kCAo2(1-X)2

vo
=
kCAo
X
1-X

dX

X
1-X

Da2
kCAo
=
1+kCAo 1 + Da2

(Da2=Damkhler number for a 2nd-order RXN

For n-th order RXN, Dan=kCAon-1

For Gas-Phase Reaction

V FA0

dX
kCA2

Conversion as a Function of Distance Down the Reactor

v=vo(1+X)

v (1 0.5 X )v0
the reactant spends more time

v (1 2 X )v0
the reactant spends less time

V(m3)
The volumetric flow rate decreases with increasing conversion, and the reactant
spends more time in the reactor than reactants that produce no net change in the
total number of moles.

Change in Gas-Phase Volumetric Flow Rate Down the Reactor

v=vo(1+X)

Pressure Drop in Reactors

In liquid-phase reactions
- the concentration of reactants is insignificantly affected by even
relatively large change in the total pressure =>
- Hence, the effect of pressure drop on the rate of reaction can be ignored
when sizing liquid-phase chemical reactors
In gas-phase reactions,
the concentration of the reacting species is proportional to the total
pressure
- the effects of pressure drop on the reaction system are a key factor
in the success or failure of the reactor operation
- that is, pressure drop may be very important for gas-phase reactions

Pressure Drop and Rate Law

For an ideal gas,

Fi
FA 0 i vi X
Ci

v v0 (1 X )( P0 / P )(T / T0 )

(4-18)

i vi X
C i C A0
1 X

P To

P0 T

- determine the ratio P/P0 as a function of V or W

- combine the concentration, rate law, and design equation
- the differential form of the mole balance (design equation) must be used