Lecture 5

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 5 – Thursday 1/24/2013
Block 1: Mole Balances
Block 2: Rate Laws
Block 3: Stoichiometry
Stoichiometric Table: Flow
Definitions of Concentration: Flow
Gas Phase Volumetric Flow Rate
Calculate the Equilibrium Conversion Xe

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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 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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Review Lecture 3
Reaction Engineering

Mole Balance Rate Laws Stoichiometry

These topics build upon one another

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 Flow System Stoichiometric 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 Ci 0 0 Ci 0 y d c b
Where: i     i0 and    1
FA0 C A0 0 C A0 y A0 a a a

FA
Concentration – Flow System C A 
6 
 Stoichiometry
FA
Concentration Flow System: C A 

Liquid Phase Flow System:   0

Liquid Systems
FA FA0 1  X 
CA    C A 0 1  X  Flow Liquid Phase
 0
N B N A0  b   b 
CB     B  X   C A0   B  X 
V V0  a   a 
etc.
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 Liquid Systems
If the rate of reaction were  rA  kC AC B

2 æ b ö
then we would have - rA =kC ( 1- X ) çQ B - X ÷
A0
è a ø

This gives us  rA  f  X 
FA0
 rA

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X
 Stoichiometry
for Gas Phase Flow Systems
Combining the compressibility factor
equation of state with Z = Z0
P
Stoichiometry: CT 
ZRT
P0
CT 0 
Z 0 R0T0
FT  CT
FT 0  CT 0 0
We obtain:
FT P0 T
  0
FT 0 P T0
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 Stoichiometry
for Gas Phase Flow Systems
FA  P   T0  FT 0 FA  P   T0 
C A  FA         
 FT   P0   T  0 FT  P0   T 
0  
 F0 
Since CT 0  FT 0  0 ,

FA  P   T0 
C A  FA   CT 0   
FT  P0   T 

Using the same method,

 FB  P  T0 
C B  CT 0    
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 FT  P0  T 
 Stoichiometry
for Gas Phase Flow Systems
The total molar flow rate is: FT  FT 0  FA0X

Substituting FT gives:

 FT 0  FA0 X  T P0  FA0  T P0
  0    0  1  X
 FT 0  T0 P  FT 0  T0 P

T P0 T P0
 0  1  y A 0 X   0  1   X 
T0 P T0 P

Where   y A 0
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 For Gas Phase Flow Systems
FA
Concentration Flow System:C A 


T P0
Gas Phase Flow System:    0  1  X 
T0 P

FA FA0 1  X  C 1  X  T0 P
CA    A0
  1  X  T P0 1  X  T P0
0
T0 P

 b   b 
FA0   B  X  C A0   B  X 
FB  a   a  T0 P
CB   
   1  X  T P0  1  X  T P0
0
12 T0 P
 For Gas Phase Flow Systems
If –rA=kCACB

  b  
 1  X   B  X  2

 a 
 P T 
 rA  k AC A0 
2 0
 
 1  X  1  X   P0 T  
 

This gives us
FA0/-rA

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X
 For Gas Phase Flow Systems
where
d c b
    1
a a a
change in total number of moles

mole of A reacted
 d c b  FA0
      1  y A0
 a a a  FT 0

  y A0

change in total number of moles for complete conversion


total number of moles fed to the reactor
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 Example: Calculating the equilibrium
conversion (Xef) for gas phase reaction in a
flow reactor

Consider the following elementary reaction where

KC=20 dm3/mol and CA0=0.2 mol/dm3.

Calculate Equilibrium Conversion or both a batch

reactor (Xeb) and a flow reactor (Xef).

 2 CB 
2A  B  rA  k A C A 


KC 
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 Gas Flow Example (Xef)
2A  B
X eb  0.703
X ef  ?

Solution:

 2 CB 
 Rate Law:  rA  k A C A  
 KC 

1
A B
2
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 Gas Flow Example (Xef)

Species Fed Change Remaining

A FA0 -FA0X FA=FA0(1-X)
B 0 +FA0X/2 FB=FA0X/2
FT0=FA0 FT=FA0-FA0X/2

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 Gas Flow Example (Xef)
A FA0 -FA0X FA=FA0(1-X)
B 0 FA0X/2 FB=FA0X/2

Stoichiometry: Gas isothermal T=T0

Gas isobaric P=P0
  0  1   X 
FA0  1  X  C A0  1  X 
CA  
0  1   X   1  X 
FA0 X 2 C A0  1  X 
CB  
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0  1   X  2  1   X 
 Gas Flow Example (Xef)
 C 1  X   2 C X 
 rA  k A  A0   A0

 1  X   21  X  K C 

Pure A  yA0=1, CA0=yA0P0/RT0, CA0=P0/RT0

1  1
  y A0  1   1  
2  2
At equilibrium: -rA=0

X e  1  X e 
2 K C C A0 
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1  X e  2
 Gas Flow Example (Xef)
 dm 3  mol 
2 K C C A0  2 20  0.2 3   8
 mol  dm 

1  1
  y A 0  1 1 
2  2
X e  0.5X e 2
8
1  2X e  X e 2 
2
8.5X e 17X e  8  0

Flow: X ef  0.757 Recall Batch: X eb  0.70

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 End of Lecture 5

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