Chapter 7

Mole Balances
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 V = FA0 
dX
PFR FA 0 = −rA
dV  0
− rA
X
X
dX dX
PBR
 FA 0 = −rA W = FA0 
dW 0
− rA
W
Rate Laws
Power Law Model:
  α order in A
− rA = kC A C 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 A2 C B
2nd order in A, 1st order in B, overall third order
Stoichiometry
Combine
Example 1

 Example for Liquid Phase

(CH2CO)2O + H2O → 2CH3COOH
A + B → 2C
Entering
Volumetric flow rate v0 = 0.0033 dm3/s
Acetic Anhydride 7.8% (1M)
Water 92.2% (51.2M)
Elementary with k’ 1.95x10-4 dm3/(mol.s)

Case I conversion X1 in a CSTR V = 1dm3

Case II conversion X2 in a PFR V = 1dm3
Case III time for X1 and X2 in a Batch Reactor
 CSTR Laboratory Experiment
Example: CH3CO2 + H20 → 2CH3OOH

C A0 = 1M
C B 0 = 51.2 M
X=?
V = 1 dm 3
dm 3
 0 = 3.3 10−3
s
 2C
A+B→
FA0 X
1) MoleBalance: CSTR: V =
− rA
CSTR Laboratory Experiment
2) Rate Law: − rA = k AC AC B

3) Stoichiometry:
A FA0 -FA0X FA=FA0(1-X)
B FA0ΘB -FA0X FB=FA0(ΘB-X)

C 0 2FA0X FC=2FA0X
CSTR Laboratory Experiment
FA0 (1 − X )
= C A0 (1 − X )
FA
CA = =
 0

FA0 ( B − X )
CB = = C A0 ( B − X )
0

51.2
B = = 51.2
1

C B = C A0 (51.2 − X )  C A0 (51.2 )  C B 0
CSTR Laboratory Experiment
− rA = k ' C B 0 C A0 (1 − X ) = kC A0 (1 − X )

k

 0 kC A0 X V
kX V kX
V=  = = =
C A0 (1 − X )  0 (1 − X )  0 (1 − X )

k V
X =  = = 303s
1 + k v0

k= k’ *CB0= 0.009984 s-1 3.03

X= = 0.75
4.03
PFR Laboratory Experiment
A + B → 2C
dm 3
0.0033 1 dm3 X =?
s

1) Mole Balance: dX − rA
=
dV FA0

2) Rate Law: − rA = kC AC B

3) Stoichiometry: C A = C A0 (1 − X )
CB  CB0
PFR Laboratory Experiment
4) Combine: − rA = k ' C B 0C A0 (1 − X ) = kC A0 (1 − X )

dX kC A0 (1 − X )
=
dV C A00
dX k
= dV = kd
(1 − X ) 0

1
ln = k
1− X
X = 1 − e − k
PFR Laboratory Experiment
V 1dm 3
= = = 303 sec k = 0.009984 s −1
0 0.0033 dm sec
3

X = 1 − e − k X = 0.951

 for x=0.75?
1
ln
 = 1 − X = 139 s
k
Compared to 303s in CSTR
 Constant Volume Batch
Gas Phase A + B → 2C t=?

1) Mole Balance: dX = − rAV0 = − rA = − rA

dt N A0 N A0 V0 C A0
2) Rate Law: − rA = k ' C B 0 C A = kC A

k
3) Stoichiometry: V = V0

N A0 (1 − X )
CA = = C A0 (1 − X )
V0
 Constant Volume Batch
dX kC A0 (1 − X )
4) Combine: = = k (1 − X )
dt C A0

dX 1
= kdt ln = kt X = 1 − e − kt
(1 − X ) 1− X
1
ln 1
t for
t= 1 − X = 139 s t for ln
x=0.75 x=0.951 t= 1 − X = 303 s
k
k

For constant V or constant v reactions t in Batch Reactor   in PFR

Example 2
 Example for Gas Phase : PFR and Batch Calculation
2NOCl → 2NO + Cl2
2A → 2B + C
Pure NOCl fed with CNOCl,0 = 0.2 mol/dm3 follows an
elementary rate law with k = 0.29 dm3/(mol.s)
Case I PFR with v0 = 10 dm3/s
Find space time, 𝜏 with X = 0.9
Find reactor volume, V for X = 0.9
Case II Batch constant volume
Find the time, t, necessary to achieve 90%
conversion. Compare 𝜏 and t.
 Gas Flow PFR Example
2 NOCl → 2 NO + Cl2
2A → 2B + C
dm 3 dm 3 mol
 0 = 10 k = 0.29 C A0 = 0.2
s mol  s L
T = T0 P = P0 X = 0.9 V =?

1) Mole Balance: dX − rA
=
  dV FA0

2) Rate Law: − rA = kC A2
Gas Flow PFR Example
3) Stoichiometry:  = 0 (1 + X )
(Gas Flow)
C A0 (1 − X )
CA =
(1 + X )
A → B + ½C
kC (1 − X )
2 2
4) Combine: − rA = A0

(1 + X )2
kC A2 0 (1 − X )
2
dX
=
dV C A00 (1 + X )2
Da
X
(1 + X )
2 V
kC A0 kC A0V 
 0 (1 − X )2 dX = 
0
0
dV =
0
= kC A0
Gas Flow PFR Example

kC A0 = 2 (1 +  ) ln (1 − X ) +  X +
2 (1 +  )2
X
1− X

1 1
 = y A0 = (1)  = kC A0 = 17.02
2 2

17.02
= = 294 sec
kC A0 V = v0 = 2940 L
Constant Volume Batch Example
Gas Phase 2A → 2B + C t=?

1) Mole Balance: dX = − rAV0 = − rA = − rA

dt N A0 N A0 V0 C A0

2) Rate Law: − rA = kC A2

3) Stoichiometry: V = V0

N A0 (1 − X )
CA = = C A0 (1 − X )
V0
− rA = kC 2
A0 (1 − X )
2
Constant Volume Batch Example

dX kC (1 − X )
2 2
4) Combine: = = kC A0 (1 − X )
A0 2

dt C A0

= kC A0 (1 − X )
dX 2

dt
dX
= kC A0 dt
(1 − X )2

1
= kC A0t
1− X

t = 155 sec
22
California Professional Engineering
Exam

5.8
 General Guidelines for the California
Professional Engineering Exam
Some hints:
1. Group unknown parameters/values on the same
side of the equation
example: [unknowns] = [knowns]
2. Look for a Case 1 and a Case 2 (usually two
data points) to make intermediate calculations
3. Take ratios of Case 1 and Case 2 to cancel as
many unknowns as possible
4. Carry all symbols to the end of the manipulation
before evaluating, UNLESS THEY ARE ZERO
24
 Solution

A B K C = 5 .8

Total moles reacted at Point 2

X2 =
Mole fed to first reactor

Knowns: Intermediate Conversion, X1, KC, and W1 = W2

Unknowns: FA0, W1, CA0
25
 P. E. Example
dX − rA
1) Mole Balances =
dW FA0
2) Rate Laws  CB 
− rA = k C A − 
 KC 

3) Stoichiometry
FA0 (1 − X )
Liquid,  = 0
= C A0 (1 − X )
FA
CA = =
0 0
FB FA0 X
CB = = = C A0 X
26
0 0
 P. E. Example
4) Combine
 X 
− rA = kC A0 1 − X − 
 K C 

dX − rA kC A0   1  
= = 1 − 1 +  X 
dW FA0 FA0   KC  

5) Evaluate W1 = W2
FA0 X dX FA0 X2 dX
W1 =
kC A0 
0   1  
= W2 =
kC A0 
X1   1  
1 − 1 +  X  1 − 1 +  X 
  KC     KC  

27
 P. E. Example   1  
1 −  1 + 
  K  X 1 
FA0 1 1 FA0 1   C  
W1 = ln = ln
kC A0  1   1  kC A0  1    1  
1 +  1 − 1 +  X 1 1 +  1 − 1 +  X 2 

 KC   KC   K C    K C  


Cancel unknowns FA0, k and CA0

   1  
2

1 − 1 − 1 +  X 1  
   K C  
 
X2 =  
1
1+
KC
Substitute X1 = 0.55 and KC = 5.8

X 2 = 0.745
28
 P. E. Example
Part 2

FA0 − FA 2
X overall = FA 2 = FA1 (1 − X 2 )
FA0
Conversion X¢2 based on FA1

29
 P. E. Example
FA0 1 1
W1 = ln
kC A0  1   1 
1 +  1 − 1 +  X1
 KC   KC 
FA1 X 2 dX FA1 1
W2 =
kC A0 0   1  
=

ln
1    1  
1 −  1 +  X  kC A0  1 + K   1 − 1 +  X 2 
  KC    C    KC  
W1 = W2
FA1 = FA0 (1 − X 1 )

Substitute for FA1 and cancel FA0, CA0, k

1 1
ln = (1 − X 1 ) ln
  1    1 
1 − 1 +  X1  1 − 1 +  X 2
  KC    KC 

30
X 1 = 0.55 K C = 5.8
 P. E. Example

One equation and one unknown

Solving for X 2
X 2 = 0.768

FA0 − FA 2 FA0 − FA1 (1 − X 2 ) FA0 − FA0 (1 − X 1 )(1 − X 2 )

X overall = = =
FA0 FA0 FA0

= 1 − (1 − X 1 )(1 − X 2 ) = 0.895

X overall = 0.895
31