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.
 Chapter 4

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
Review Lecture 2
Reactor Mole Balances Summary
in terms of conversion, X
Reactor Differential Algebraic Integral

X
X
dX
Batch N A0
dX
  r AV t  N A0 
dt 0
 rAV
t
FA 0 X
CSTR V
rA
X
dX dX
PFR FA 0  rA V  FA0 
dV  0
 rA

X
X
dX dX
PBR
 FA 0   rA W  FA0 
3 dW 0
 rA
W
Review Lecture 2
Levenspiel Plots

FA 0
rA

 X

4 
Review Lecture 2
PFR

5
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

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Review Lecture 2
Reactors in Series

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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 

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Review Lecture 3
Building Block 2: Rate Laws
Power Law Model:
 rA  kC C   α order in A
A B
β order in B
Overall Rection Order  α  β
2 A  B  3C
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

9
2nd order in A, 1st order in B, overall third order
Review Lecture 3
Arrhenius Equation
k  Ae  E RT
k
T  k  A
T 0 k 0
E = Activation energy (cal/mol)
A  1013
R = Gas constant (cal/mol*K)
T = Temperature (K) T
A = Frequency factor (same units as rate constant k)
 order)
(units of A, and k, depend on overall reaction

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Review Lecture 3
Reaction Engineering

Mole Balance Rate Laws Stoichiometry

These topics build upon one another

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Review Lecture 3
Algorithm
How to find  rA  f  X 

Step 1: Rate Law  rA  g  Ci 

Step 2: Stoichiometry  Ci   h  X 

Step 3: Combine to get  rA  f  X 

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 Chapter 4

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.
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 Chapter 4

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:
b æ N B0 b ö
N B =N B0 - N A0 X =N A 0 ç - X÷
a è N A0 a ø
Let ΘB = NB0/NA0
Then:
 b 
N B  N A0   B  X 
 a 
c  c 
NC  NC 0  N A 0 X  N A 0 C  X 
14 a  a 
 Chapter 4

Batch System - Stoichiometry Table

Species Symbol Initial Change Remaining
A A NA0 -NA0X NA=NA0(1-X)
B B NB0=NA0ΘB -b/aNA0X NB=NA0(ΘB-b/aX)

C C NC0=NA0ΘC +c/aNA0X NC=NA0(ΘC+c/aX)

D D ND0=NA0ΘD +d/aNA0X ND=NA0(ΘD+d/aX)

Inert I NI0=NA0ΘI ---------- NI=NA0ΘI
FT0 NT=NT0+δNA0X
Ni0 Ci 00 Ci 0 yi 0 d c b
Where: i         1
N A0 C A0 0 C A0 y A0 and a a a
15
δ = change in total number of mol per mol A reacted
 Chapter 4

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
NA N 1  X 
CA   A0  CA 0 1  X 
V V0
NB N A 0  b   b 
CB  
 B  X  CA 0 B  X 
V V0  a   a 

etc.
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
 Chapter 4

Stoichiometry Constant Volume Batch

Suppose rA  k A CA CB
2

Batch: V  V0

- r =k C 3 ( 1- X ) 2 æ b ö
çQ B - X ÷
A A A0
è a ø

Equimolar feed: B  1
b
Stoichiometric feed:  B 
a
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 Chapter 4

Stoichiometry Constant Volume Batch

If  rA  k AC AC B , then
2

 b 
 rA  C A0
3
1  X    B  X  Constant Volume Batch
2

 a 

and we have  rA  f  X 

1
 rA

X
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 Chapter 4

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
 2 CB 
 rA  k A C A  
 KC 
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 Chapter 4

Batch Reactor - Example

Calculate Xe C A0  0.2 mol dm 3
K C  20 dm 3 mol
dX  rAV
Step 1: 
dt N A0
Step 2: rate law:  rA  k A C A  k B C B
2

 2 CB 
 rA  k A C A  
 KC 
kA
KC 
kB
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 Chapter 4

Batch Reactor - Example

Symbol Initial Change Remaining
A NA0 -NA0X NA0(1-X)
B 0 ½ NA0X NA0 X/2

Totals: NT0=NA0 NT=NA0 -NA0 X/2

C Be
@ equilibrium: -rA=0 0C 2
Ae
KC
CBe N Ae
Ke  2 CAe   CA 0 1  X e 
CAe V
Xe
CBe  CA 0
21 2
 Chapter 4

Batch Reactor - Example

Solution:
 2 C Be  C Be
At equilibrium  rA  0  k A C Ae   KC  2
 K C  C Ae

Stoichiometry: A  B/ 2
Constant Volume: V  V0

Batch
Species Initial Change Remaining
A NA0 -NA0X NA=NA0(1-X)
B 0 +NA0X/2 NB=NA0X/2
NT0=NA0 NT=NA0-NA0X/2
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 Chapter 4

Batch Reactor - Example

Xe
CA0
2 Xe
Ke  
 C A 0 1  X e   2C A 0 1  X e 
2 2

Xe
2K e C A 0   2 20  0.2   8
1  X e  2

X eb  0.703

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 Flow System – Stoichiometry Chapter 4

Table

Species Symbol Reactor Feed Change Reactor Effluent

A A FA0 -FA0X FA=FA0(1-X)

B B FB0=FA0ΘB -b/aFA0X FB=FA0(ΘB-b/aX)

Where: i  Fi0  Ci0 0  Ci0  y i0

FA 0 CA 0 0 CA 0 yA 0
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 Flow System – Stoichiometry Chapter 4

Table
Species Symbol Reactor Feed Change Reactor Effluent
C C FC0=FA0ΘC +c/aFA0X FC=FA0(ΘC+c/aX)
D D FD0=FA0ΘD +d/aFA0X FD=FA0(ΘD+d/aX)
Inert I FI0=A0ΘI ---------- FI=FA0ΘI
FT0 FT=FT0+δFA0X

d c b
Where: i  Fi 0  Ci 0 0  Ci 0  yi 0 and      1
FA 0 C A 0 0 CA0 yA0 a a a
FA
Concentration – Flow System CA 
25 
 Flow System – Stoichiometry Chapter 4

Table

Species Symbol Reactor Feed Change Reactor Effluent

A A FA0 -FA0X FA=FA0(1-X)
B B FB0=FA0ΘB -b/aFA0X FB=FA0(ΘB-b/aX)
C C FC0=FA0ΘC +c/aFA0X FC=FA0(ΘC+c/aX)
D D FD0=FA0ΘD +d/aFA0X FD=FA0(ΘD+d/aX)
Inert I FI0=FA0ΘI ---------- FI=FA0ΘI
FT0 FT=FT0+δFA0X
Fi 0 C  C y d c b
Where: i   i0 0  i0  i0 and    1
FA 0 C A 0 0 C A 0 y A 0 a a a
FA
CA 
Concentration – Flow System
26 
 Chapter 4

Stoichiometry
FA
Concentration Flow System: CA 

Liquid Phase Flow System:   0
FA FA 0 1  X 
CA    CA 0 1  X  Flow Liquid Phase
 0
N B N A 0  b   b 
CB   B  X  CA 0 B  X 
  0  a   a 
etc.

We will consider CA and CB for gas phase

27 reactions in the next lecture
 Algorithm

Heat Effects
Isothermal Design

Stoichiometry
Rate Laws
Mole Balance

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 End of Lecture 4

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