ChE 304: Reaction Engineering

Chapter 4: Stoichiometry
If you are thinking about someone while reading this book, you are
most definitely in love
—Tim Newberger, Undergraduate ChE Student W2013

Dr. Abdulrahman Almithn

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 Lecture 4
 Block 1
 Mole Balances (Chapter 1-2)
 Size CSTRs and PFRs given –rA=f(X)
 Block 2
 Rate Laws (Chapter 3)
 Reaction Orders
 Arrhenius Equation
 Block 3
 Stoichiometry (Chapter 4)
 Stoichiometric Table
 Definitions of Concentration
 Calculate the Equilibrium Conversion, Xe

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 Reaction Engineering

Mole Balance Rate Laws Stoichiometry

Chapters 1-2 Chapter 3 Chapter 4

These topics build upon one another

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Review Chapter 1
Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction A→B)
Reactor Differential Algebraic Integral
𝑁𝐴0
NA
𝑑𝑁𝐴
Batch dN A 𝑡1 = න
= rAV 𝑁𝐴1
−𝑟𝐴 𝑉
dt t
CSTR FA 0 − FA
V=
−rA
𝐹𝐴0
FA
PFR dFA 𝑑𝐹𝐴
= rA 𝑉1 = න
−𝑟𝐴
dV  𝐹𝐴1
V
𝐹𝐴0 FA
PBR dFA 𝑊1 = න
𝑑𝐹𝐴
= rA −𝑟𝐴′
4  dW 𝐹𝐴1

W
Review Chapter 2

a A + bB⎯
⎯→ c C + d D
Choose limiting reactant A as basis of calculation

b c d
A + B⎯
⎯→ C + D
a a a

moles A reacted
X=
moles A fed

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Review Chapter 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 න
−𝑟𝐴
dV 0

dX 𝑑𝑋
𝑋 X
PBR FA 0 = − rA 𝑊 = 𝐹𝐴0 න
 dW −𝑟𝐴′
0
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W
Review Chapter 2
Levenspiel Plots

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Review Chapter 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 Chapter 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 Chapter 3
Building Block 2: Rate Laws
Power Law Model:
  α order in A
− rA = kC A CB
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 A2CB
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2nd order in A, 1st order in B, overall third order
Review Chapter 3

The Reaction Rate Constant

k is the specific reaction rate (constant) and is
given by the Arrhenius Equation.
where:

k = Ae − E RT

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Review Chapter 3
Reaction Engineering

Mole Balance Rate Laws Stoichiometry

Chapters 1-2 Chapter 3 Chapter 4

These topics build upon one another

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 Building Block 3: Stoichiometry
Chapter 4: Summary

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 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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 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  NB 0 b 
N B = N B 0 − N A 0 = N A 0 − X
a  NA 0 a 
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 
15 a  a 
 Batch System - Stoichiometry Table
Species Symbol Initial Change Remaining
A A NA0 -NA0X NA=NA0(1-X)
B B NB0 -b/aNA0X NB=NA0(ΘB-b/aX)
C C NC0 +c/aNA0X NC=NA0(ΘC+c/aX)

D D ND0 +d/aNA0X ND=NA0(ΘD+d/aX)

Inert I NI0 -- NI=NI0
NT0 NT=NT0+δNA0X
Ni0 Ci 00 Ci 0 yi 0 d c b
Where: i = = = = and  = + − − 1
N A0 C A00 C A0 y A0 a a a
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δ = 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
NA N A 0 (1 − X )
CA = = = CA 0 (1 − X )
V V0
NB NA 0  b   b 
CB = =   B − X  = C A 0  B − X 
V V0  a   a 

etc.
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 Stoichiometry Constant Volume Batch
Suppose −rA = k A CA2 CB

Batch: V = V0

2 b 
− rA = k AC A0 (1 − X )   B − X 
 2

 a 

Equimolar feed: B = 1
b
Stoichiometric feed:  B =
a
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 Stoichiometry Constant Volume Batch
If − rA = k AC A2CB , then

 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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 Batch Reactor – Example 4-1

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 Batch Reactor – Example 4-1

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 Batch Reactor – Example 4-1

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 Batch Reactor – Example 4-2

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 Batch Reactor – Example 4-2

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 Batch Reactor – Example 4-2

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 Batch Reactor – Example 4-2

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 Flow System – Stoichiometry Table

Species Symbol Reactor Feed Change Reactor Effluent

A A FA0 -FA0X FA=FA0(1-X)
B B FB0 -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 Table
Species Symbol Reactor Feed Change Reactor Effluent
C C FC0 +c/aFA0X FC=FA0(ΘC+c/aX)
D D FD0 +d/aFA0X FD=FA0(ΘD+d/aX)
Inert I FI0 -- FI=FI0
FT0 FT=FT0+δFA0X

Where: i = Fi 0 = Ci 0 0 = Ci 0 = yi 0 d c
and  = + − − 1
b
FA 0 C A 0 0 CA0 yA0 a a a
FA
Concentration – Flow System CA =
28 
 Flow System – Stoichiometry 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
Concentration – Flow System C A =
29 
 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
NA 0 
NB b   b 
CB = =   B − X  = C A 0  B − X 
 0  a   a 
etc.

We will consider CA and CB for gas phase

30 reactions in the next lecture
 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 CA =
31 
 Stoichiometry
FA
Concentration Flow System: C A =

Liquid Phase Flow System:  = 0

Liquid Systems => same as Batch

𝐹𝐴 𝐹𝐴0 1 − 𝑋
𝐶𝐴 = = = 𝐶𝐴0 1 − 𝑋 Flow Liquid Phase
𝜐 𝜐0

𝐹𝐵 𝐹𝐴0 𝑏 𝑏
𝐶𝐵 = = Θ𝐵 − 𝑋 = 𝐶𝐴0 Θ𝐵 − 𝑋
𝑉 𝑉0 𝑎 𝑎

etc.
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 Liquid Systems
If the rate of reaction were − rA = kC ACB

 b 
then we would have − rA = C A0
2
(1 − X )  B − X 
 a 

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
Taking the
FT P0 T
CT/CT0 Ratio  = 0
We obtain: 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 A0 X ) = 0 (1 +  X )
T0 P T0 P

Where  = y A0
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 For Gas Phase Flow Systems
FA
Concentration Flow System: CA =


 = 0 (1 + X )
T P0
Gas Phase Flow System:
T0 P

FA FA0 (1 − X ) C (1 − X ) T0 P
CA = = = A0
  0 (1 + X )
T P0 (1 + X ) T P0
T0 P

 b   b 
FA0   B − X  C A0   B − X 
CB =
FB
=  a 
=  a  T0 P
  (1 + X ) T P0 (1 + X ) T P0
0
37 T0 P
 For Gas Phase Flow Systems

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 For Gas Phase Flow Systems
If –rA=kCACB

  b  
 (1 − X )   B − a X   P T  2 
− rA = k AC A0 
2    0
 
 (1 + X ) (1 + X )  P0 T  
 

This gives us
FA0/-rA

39 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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 Gas Phase Flow System – Example 4-3

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 Gas Phase Flow System – Example 4-3

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 Gas Phase Flow System – Example 4-3

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 Gas Phase Flow System – Example 4-3

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 Gas Phase Flow System – Example 4-3

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 Gas Phase Flow System – Example 4-3

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 Gas Phase Flow System – Example 4-3

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 Gas Phase Flow System – Example 4-3

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 Gas Phase Flow System – Example 4-3

Now we have Ci(X) so we

can get –rA(X) then use
Chapter#2 to design the
reactor

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

Trial and error to find Xeb or use Polymath

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Equilibrium Conversion– Example 4-5

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 Building Block 3: Stoichiometry
Chapter 4: Summary

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64
 Heat Effects
Isothermal Design

Stoichiometry
Rate Laws
Mole Balance

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66
67
 End of Lecture 4

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