Lecture 4

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the
reactors in which they take place.

Lecture 4
Block 1
Mole Balances
Size CSTRs and PFRs given rA=f(X)

Block 2

Rate Laws
Reaction Orders
Arrhenius Equation

Block 3
Stoichiometry
Stoichiometric Table
Definitions of Concentration
Calculate the Equilibrium Conversion, Xe
2

Reactor Mole Balances

Review Lecture 2
Summary
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 2

Levenspiel Plots

FA 0
rA

Review Lecture 2

PFR

Review Lecture 2

Reactors in Series

moles of A reacted up to point i

Xi
moles of A fed to first reactor

Only valid if there are no side streams

6

Review Lecture 2

Reactors in Series

Review Lecture 2

rA f X
Two steps to get
Step 1: Rate Law rA g Ci

Step 2: Stoichiometry

Ci h X

Step 3: Combine to get rA f X

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 3

Arrhenius Equation

k Ae

E RT
k

E = Activation energy (cal/mol)

R = Gas constant (cal/mol*K)
T
T = Temperature (K)
A = Frequency factor (same units as rate constant k)
(units of A, and k, depend on overall reaction
order)

10

T k A
T 0 k 0
A 1013

Review Lecture 3

Reaction Engineering

Mole Balance

Rate Laws

Stoichiometry

These topics build upon one another

11

Review Lecture 3

Algorithm
How to find r

fX

Step 1: Rate Law rA g Ci

Step 2: Stoichiometry

Ci h X

Step 3: Combine to get rA f X

12

Stoichiometric Tables

13

Stoichiometric Tables are like account statements

of the reactors.
Very useful bookkeeping tool for writing rate laws
in terms of conversion.
Can be used for batch or flow reactors
Can be written in terms of N, C, or F
Table includes the following columns:
1. Particular species, reactant or product
2. Number of moles initially present
3. Change in number of moles due to the reaction
4. Number of moles remaining

Batch Reactor: Stoichiometric Tables

Consider: aA + bB cC + dD
A + b/a B c/a C + d/a D

Table

Species

Symbol
A
B
C
D
I
total

14

Initial
moles

Change
in moles

Remaining
moles

Batch Reactor: Stoichiometric Tables

Symbol
A
B

Initial
moles

Change in
moles

N AO

- ( N AO X )
b
- ( N AO X )
a
c
( N AO X )
a
d
( N AO X )
a
-

N BO B N AO

N CO C N AO

N DO D N AO

N IO I N AO

Total

15

N TO

Remaining moles
N A N AO (1 X )
b
N B N AO ( B X )
a
c
NC NAO ( c X )
a
d
ND NAO (D X )
a

N I N IO
N T N TO (

d c b
1) N AO X
a a a

How do we calculate Change?

16

Start with A (limiting reactant).

Change in moles of A = -N X
AO

For every mole of A converted, b/a

moles of B are converted
b
N AO X
Change in moles of B = a
Same for other species
ALL are in terms of N X
AO

Other Terms - Stoichiometric Tables

Change in the total number of moles:

d c b

1
a
a
a

Example: N 3H 2 NH
2
2
3
for H2 = (2/3) (1/3) - 1

Ratio of initial amount of species I, to initial

amount of species A
N
C

17

i0

i0

NA 0 C A 0

Practice - Stoichiometric table (Soap)

Write a stoichiometric table for the
following liquid-phase reaction:
Soap formation:

3NaOH + (C17H35COO)3C3H5
3 C17H35COONa + C3H5(OH) 3

Only reactants and water (inert) are

present initially
Use NaOH as the basis
A + 1/3 B C + 1/3 D

18

Stoichiometric Table (Soap)

A + 1/3 B C + 1/3 D

Species

Symbol
A
B
C
D
I
Total

19

Initial

Change

Remaining

Continuous Reactors: Stoichiometric

Tables
Symbol

Feed Flow
Rate
(mol/s)

Change
within
Reactor
(mol/s)

Effluent Rate from

Reactor
(mol/s)

A
B

FAO

- ( FAO X )

FBO B FAO

FCO C FAO

FA FAO (1 X )
b
FB FAO ( B X )
a

FDO D FAO

FIO I FAO

Total

FTO

20

b
( FAO X )
a
c
( FAO X )
a
d
( FAO X )
a
-

c
X)
a
d
FD FAO ( D X )
a
FC FAO ( c

FI FIO
FT FTO FAO X

If volume is constant, we can replace F with C

Continuous Reactors: Stoichiometric

Tables

Consider:
Ca(OH)2 + 2HCl CaCl2 + H2O

Species Symbol

Initial

Change

Remaining

A
B
C
D
I
Total

21

If volume is constant, we could replace F with C

Building Block 3: Stoichiometry

We shall set up Stoichiometry Tables using species
A as our basis of calculation in the following
reaction. We will use the stoichiometric tables to
express the concentration as a function of
conversion. We will combine Ci = f(X) with the
appropriate rate law to obtain -rA = f(X).

b
c
d
A B C D
a
a
a
A is the limiting reactant.
22

Stoichiometry

NA NA 0 NA 0 X

For every mole of A that reacts, b/a moles of B react. Therefore

moles of B remaining:

N B0 b
b
N B N B 0 N A0 X N A0
X
a
N A0 a
Let B = NB0/NA0
Then:

23

b
N B N A0 B X
a

c
c
NC NC 0 N A 0 X N A 0 C X

a
a

Batch System - Stoichiometry Table

Species

Symbol

Initial

Change

NA0

-NA0X

NB0=NA0B

-b/aNA0X

NC0=NA0C

ND0=NA0D

Inert

NI0=NA0I
NT0

Where:
24

Remaining

NA=NA0(1-X)

NB=NA0(Bb/aX)
+c/aNA0X NC=NA0(C+c/aX
)
+d/aNA0 ND=NA0(D+d/aX
X
)
---------NI=N
A0 I
NT=NT0+NA0X

Ni0
Ci 0 0
Ci 0
yi 0
d c b
i

1
N A0 C A0 0 C A0 y A0 and
a a a

= change in total number of mol per mol A reacted

Stoichiometry Constant Volume Batch

Note: If the reaction occurs in the liquid phase
or
if a gas phase reaction occurs in a rigid (e.g. steel)
batch reactor
Then V V0
CA

NA
N 1 X
A0
CA 0 1 X
V
V0

NB
N A 0
b
b

CB

B X CA 0 B X

V
V0
a
a

25

etc.

Stoichiometry Constant Volume Batch

2
Suppose rA k A CA CB

Batch: V V0

b
3
2

rA k AC A0 1 X B X
a

Equimolar feed:

B 1

b
Stoichiometric feed: B
a
26

Stoichiometry Constant Volume

Batch
2
If rA k AC AC B , then

rA C A0

b
1 X B X Constant Volume Batch
a

and we have rA f X

27

1
rA
X

Batch Reactor - Example

Calculate the equilibrium conversion for gas phase reaction,
Xe .
Consider the following elementary reaction with
KC=20 dm3/mol and CA0=0.2 mol/dm3.
Find Xe for both a batch reactor and a flow reactor.

2A B

rA k A C A

28

CB

KC

Batch Reactor - Example

Calculate Xe

C A0 0.2 mol dm 3
K C 20 dm 3 mol

dX rAV
Step 1:

dt
NA 0
2
rA k A C A k BC B
Step 2: rate law:

rA k A C A

KC

29

kA
kB

CB

KC

Batch Reactor - Example

Symbol

Initial

Change

Remaining

NA0

-NA0X

NA0(1-X)

NA0X

NA0 X/2

Totals: NT0=NA0

NT=NA0 -NA0 X/2

@ equilibrium: -rA=0

CBe
Ke 2
CAe
30

C Be
0C
KC
2
Ae

CAe
CBe

N Ae

CA 0 1 X e
V
Xe
CA 0
2

Batch Reactor - Example

Solution:
At equilibrium

rA 0 k A C Ae

Stoichiometry:
Constant Volume:

C Be

KC

C Be
KC 2
C Ae

A B/ 2
V V0

Batch
Species
A

Initial
NA0

Change
-NA0X

Remaining
NA=NA0(1-X)

+NA0X/2

NB=NA0X/2

NT0=NA0
31

NT=NA0-NA0X/2

Batch Reactor - Example

Xe
CA0
Xe
2
Ke

2
2
C A 0 1 X e 2C A 0 1 X e
2K e C A 0

Xe

2 20 0.2 8
2
1 X e

X eb 0.703

32

Flow System Stoichiometry

Table

Species

Symbol

Reactor Feed

Change

Reactor Effluent

FA0

-FA0X

FA=FA0(1-X)

FB0=FA0B

b/aFA0X

FB=FA0(Bb/aX)

Where: i Fi0 Ci0 0 Ci0 y i0

FA 0

33

CA 0 0

CA 0

yA 0

Flow System Stoichiometry

Table
Species

Symbol

Reactor Feed

Change

FC0=FA0C

+c/aFA0X

FC=FA0(C+c/aX)

FD0=FA0D

+d/aFA0X

FD=FA0(D+d/aX)

Inert

FI0=A0I

----------

FI=FA0I

FT0

FT=FT0+FA0X

Where: i Fi 0 Ci 0 0 Ci 0 y i 0
FA 0

C A 0 0

CA0

yA0

Concentration Flow System

34

Reactor Effluent

d
a

c
a

b
a

and 1
CA

FA

Flow System Stoichiometry Table

Species

Symbol

Reactor Feed

Change

Reactor Effluent

FA0

-FA0X

FA=FA0(1-X)

FB0=FA0B

-b/aFA0X

FB=FA0(B-b/aX)

FC0=FA0C

+c/aFA0X

FC=FA0(C+c/aX)

FD0=FA0D

+d/aFA0X

FD=FA0(D+d/aX)

Inert

FI0=FA0I

----------

FI=FA0I

FT0

FT=FT0+FA0X

Where: Fi 0 Ci 0 0 Ci 0 y i 0
i

FA 0

35

C A 0 0

CA0

and

yA0
F

Concentration Flow SystemC A A

d c b
1
a a a

Stoichiometry
Concentration Flow System:

FA
CA

Liquid Phase Flow System:

FA FA 0 1 X
CA

CA 0 1 X Flow Liquid Phase

0
FB FA0
b
b

CB

B X C A0 B X

0
a
a

etc.

36

We will consider CA and CB for gas phase

reactions in the next lecture

Heat Effects
Isothermal Design

Stoichiometry
Rate Laws
Mole Balance

37

End of Lecture 4

38