Lecture 20

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.
 Energy Balance Fundamentals
dE sys
 Fi 0 Ei 0   Fi Ei  Q  W 
dt

Substituting for

Q  W S   Fi 0 H i 0  Fi H i  0
2
 Reactors with Heat Exchange
User friendly Energy Balance Derivations
Adiabatic
Heat Exchange Constant Ta
Heat Exchange Variable Ta Co-current
Heat Exchange Variable Ta Counter Current

3
 Adiabatic Operation CSTR
FA0
FI

A B


Elementary liquid phase reaction carried out in a CSTR

The feed consists of both - Inerts I and Species A with

the ratio of inerts I to the species A being 2 to 1.

4
 Adiabatic Operation CSTR
Assuming the reaction is irreversible for CSTR,
A  B, (KC = 0) what reactor volume is necessary to
achieve 80% conversion?
If the exiting temperature to the reactor is 360K, what
is the corresponding reactor volume?
Make a Levenspiel Plot and then determine the PFR
reactor volume for 60% conversion and 95%
conversion. Compare with the CSTR volumes at these
conversions.
Now assume the reaction is reversible, make a plot of
the equilibrium conversion as a function of
temperature between 290K and 400K.
5
 CSTR: Adiabatic Example
(exothermic)
FA0
FI


A B
𝑇=?
FA 0 X
1) Mole Balances: V
 rA exit
6
 CSTR: Adiabatic Example
2) Rate Laws:  CB 
 rA  k C A  
 K C

E 1 1 
  
R  T1 T 
k  k1e

 H Rx  1 1 
K C  K C1 exp    
 R  T2 T 

3) Stoichiometry: C A  C A 0 1  X 

CB  CA0X
7
 CSTR: Adiabatic Example
4) Energy Balance
Adiabatic, ∆Cp=0

T  T0 
 H Rx X
T 
 H Rx X
0
  i C Pi C PA   I C PI

   20,000   20,000
T  300    X  300  X
164  2 18 164  36

T  300  100 X
8
 CSTR: Adiabatic Example
Irreversible for Parts (a) through (c)

 rA  kC A 0 1  X  (i.e., K C  )

(a) Given X = 0.8, find T and V

Calc Calc Calc Calc

Given X T k rA V
Calc KC
(if reversible)
9
 CSTR: Adiabatic Example
Given X, Calculate T and V
FA 0 X FA 0 X
V 
 rA exit kC A 0 1  X 

T  300  1000.8  380K

10,000  1 1 
k  0.1 exp     3.81
1.989  298 380 

V
FA 0 X

50.8
 2.82 dm 3
 rA 3.8121  0.8
10
 CSTR: Adiabatic Example
Given T, Calculate X and V
(b) Given X Calc
 T Calc
  k Calc
  rA Calc
 
 V
Calc K C
(if reversible)
 rA  kC A0 1  X  (Irreversible)
T  360 K
T  300
X   0.6
100
k  1.83 min 1

V 
50.6 
 2.05 dm 3
11 1.8320.4
 CSTR: Adiabatic Example
(c) Levenspiel Plot
FA 0 FA 0

 rA kC A 0 1  X 
T  300  100X

Calc Calc Calc FA 0

Calc
Choose X T k rA 
rA

12
 CSTR: Adiabatic Example
(c) Levenspiel Plot

13
 CSTR: Adiabatic Example
30
CSTR     X = 0.6     T = 360 K
25

20
-Fa0/Ra

15

10

CSTR 60%

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

CSTR     X = 0.95     T = 395 K

14
 CSTR: Adiabatic Example
30
PFR     X = 0.6
25

20

-Fa0/Ra
15

10

PFR 60%
5

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

PFR     X = 0.95

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 CSTR: Adiabatic Example - Summary

CSTR X = 0.6 T = 360 V = 2.05 dm3

PFR X = 0.6 Texit = 360 V = 5.28 dm3
CSTR X = 0.95 T = 395 V = 7.59 dm3
PFR X = 0.95 Texit = 395 V = 6.62 dm3

16
 Energy Balance in terms of Enthalpy

F Hi i V   Fi H i  UaTa  T V  0
V  V

 d  Fi H i
 UaTa  T   0
dV

 d  Fi H i  dH i dFi 
   Fi   Hi 
dV  dV dV 

17
 PFR Heat Effects
dFi
 ri  i  rA 
dV
H i  H i0  C Pi T  TR 

dH i dT
 C Pi
dV dV

 d  Fi H i  dT 
   Fi C Pi   H ii  rA 
dV  dV 
i H i  H R x
18
 PFR Heat Effects

19
Need to determine Ta
 Heat Exchange:

dT  rA  H Rx   UaT  Ta 

dV  Fi C Pi

Need to determine Ta
20
 Heat Exchange Example:
Case 1 - Adiabatic

Energy Balance:

Adiabatic (Ua=0) and ΔCP=0

T  T0 
 H Rx X
(16A)
 i C Pi

21
 User Friendly Equations
A. Constant Ta e.g., Ta = 300K

B. Variable Ta Co-Current
dTa UaT  Ta 
 ,V  0 Ta  Tao (17C )
dV m C Pco o l

C. Variable Ta Counter Current

dTa UaTa  T 
 V  0 Ta  ? Guess
dV m C Pcool
Guess Ta at V = 0 to match Ta0 = Ta0 at exit, i.e., V = V
22
 Heat Exchanger Energy Balance
Variable Ta Co-current
Coolant Balance:
In - Out + Heat Added = 0

m C H C V
 m C H C V  V
 UaV T  Ta   0
dH C
 m C  UaT  Ta   0
dV
H C  H 0C  C PC Ta  Tr 

dH C dTa
 C PC
dV dV

dTa UaT  Ta 
 , V  0 Ta  Ta 0
23 dV m C C PC
 Heat Exchanger Energy Balance
Variable Ta Counter-current

In - Out + Heat Added = 0

m C H C V  V  m C H C V  UaV T  Ta   0

dH C
m C  UaT  Ta   0
dV

dTa UaTa  T 

dV m C C PC
24
 Heat Exchanger – Example
Case 1 – Constant Ta

Elementary liquid phase reaction carried out in a PFR

Heat Exchange
c
m Fluid
Ta
FA0 T
FI AB

The feed consists of both inerts I and species A

ratio of inerts to the species A being 2 to 1.
with the
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 Heat Exchanger – Example
Case 1 – Constant Ta

1) Mole Balance: dX
(1)   rA FA 0
dV
 CB 
2) Rate Laws: (2) rA  k C A  
 KC 
 E  1 1 
(3) k  k1 exp    
 R  T1 T 
 H Rx  1 1 
(4) K C  K C 2 exp    
 R  T2 T 
26
 Heat Exchanger – Example
Case 1 – Constant Ta

3) Stoichiometry: C A  C A 0 1  X  5

CB  CA0X 6
4) Heat Effects: dT H R  rA   UaT  Ta 
 7 
dV FA0   i C Pi

C P  0
kC
X eq  8
1 kC

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 C i Pi  C PA   I C PI 9
 Heat Exchanger – Example
Case 1 – Constant Ta

Parameters: H R , E , R, T1 , T2 ,
k1 , kC 2 , Ua, Ta , FA0 ,
C A0 , C PA , C PI ,  I ,
rate  rA

28
 PFR Heat Effects
Heat Heat
generated removed

dT Q g  Q r

dV  Fi C Pi

29
 Heat Exchanger – Example
Case 2 – Adiabatic
dX rA
Mole Balance: 
dV FA 0
Energy Balance:
Adiabatic and ΔCP=0
Ua=0 
T  T0 
 H Rx X
(16A)
 i C Pi
Additional Parameters
(17A) & (17B)
30 T0 ,  i C Pi  C PA   I C PI
 Adiabatic PFR

31
 Example: Adiabatic
Find conversion, Xeq and T as a function of reactor volume

Xeq
X T rate
X

V V V

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 Heat Exchange
dT  rA  H Rx   UaT  Ta 

dV  Fi C Pi

dT  rA  H Rx   UaT  Ta 
 (16B)
dV FA 0   i C Pi
Need to determine Ta
33
 User Friendly Equations
A. Constant Ta (17B) Ta = 300K

Additional Parameters (18B – (20B):

Ta ,  i C Pi , Ua
B. Variable Ta Co-Current

dTa Ua T  Ta 
 V 0 Ta  Tao (17C )
dV m C Pcool
C. Variable Ta Countercurrent

dTa UaTa  T 
 V 0 Ta  ?
dV m C Pcool
34 Guess Ta at V = 0 to match Ta0 = Ta0 at exit, i.e., V = Vf
 Heat Exchange Energy Balance
Variable Ta Counter-current
Coolant balance:
In - Out + Heat Added = 0

m C H C V  m C H C V  V  UaV T  Ta   0
dH C
 m C  UaT  Ta   0
dV
All equations can be
H C  H  C PC Ta  Tr 
0
C used from before
except Ta parameter,
dH C dTa
 C PC use differential Ta
dV dV
instead, adding mC
dTa UaT  Ta 
 , V  0 Ta  Ta 0 and CPC
35 dV m C C PC
 Heat Exchange Energy Balance
Variable Ta Co-current

In - Out + Heat Added = 0

m C H C V  V  m C H C V  UaV T  Ta   0
dH C dTa UaTa  T 
m C  UaT  Ta   0 
dV dV m C C PC

All equations can be used from before except dTa/dV

which must be changed to a negative. To arrive at the
correct integration we must guess the Ta value at V=0,
integrate and see if Ta0 matches; if not, re-guess the
value for Ta at V=0
36
 Derive the user-friendly Energy Balance
for a PBR

W
Ua
0 B Ta  T dW   Fi0 H i0  Fi Hi  0

Differentiating with respect to W:

Ua dFi dH i
Ta  T   0   H i   Fi 0
B dW dW

37
 Derive the user-friendly Energy Balance
for a PBR

Mole Balance on species i:

dFi
 ri  i   rA 
dW  

Enthalpy for species i:

T
H i  H i TR    C Pi dT


TR

38
 Derive the user-friendly Energy Balance
for a PBR

Differentiating with respect to W:

dH i dT
 0  C Pi
dW dW

Ua dT
Ta  T   rA  i H i   Fi C Pi
 0
B dW

39
 Derive the user-friendly Energy Balance
for a PBR
Ua dT
Ta  T   rA  i H i   Fi C Pi
 0
B dW

 H i i  H R T 

Fi  FA 0 i  i X 
Final Form of the Differential Equations in Terms of Conversion:

A:

40
 Derive the user-friendly Energy Balance
for a PBR
Final form of terms of Molar Flow Rate:

Ua
Ta  T   rAH
dT  B

dW Fi C Pi

B: dX  rA
  gX, T 
dW FA 0

41
 Reversible Reactions
AB CD
The rate law for this reaction will follow an elementary rate law.

 CCC D 
 rA  k C A C B  
 KC 

Where Ke is the concentration equilibrium constant. We know from Le

Chaltlier’s law that if the reaction is exothermic, Ke will decrease as
the temperature is increased and the reaction will be shifted back to
the left. If the reaction is endothermic and the temperature is
increased, Ke will increase and the reaction will shift to the right.

42
 Reversible Reactions
KP
KC 
RT 

Van’t Hoff Equation:

d ln K P H R T  H R TR   Ĉ P T  TR 

 2

dT RT RT 2

43
 Reversible Reactions
For the special case of ΔCP=0

Integrating the Van’t Hoff Equation gives:

 H  R TR   1 1 
K P T2   K P T1 exp    
 R  T1 T2 

44
 Reversible Reactions

Xe KP
endothermic endothermic
reaction reaction

exothermic exothermic
reaction reaction

T T

45
 End of Lecture 20

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