30/01/2017

Intended Learning Outcomes:

At the end of this topic you should be
able to:
General Mole Balance
1. Explain the different terms in the
for Ideal Reactors
General Mole Balance equation for
Topic 2 reactors;
Ch.E. 422 2. Differentiate between Batch
Constant Volume/Pressure
Reactors, MFR or CSTR, and PFR in
terms of mole balances for a
specific participant in the reaction.

General Mole Balance for a Species J

General System Volume Around System Volume

+ - =

Input Rate of J + Generation Rate of J by Reaction

Fjo = Input or Entrance Rate of Species j - Exit Rate of J = Rate of Accumulation of J
Gj = Generation Rate of Species j inside volume
dN j
= Formation Rate of j Fjo  G j  Fj 
Fj = Output or Exit Rate of Species j dt

1
 30/01/2017

Generation Rate Term, Gj General Mole Balance:

Batch Reactors Constant Volume Batch Reactor

Constant Pressure Batch Reactor

2
 30/01/2017

Plug Flow Reactor (PFR)

MFR or CSTR Analysis Across Length, y

Steady State Flow:

Steady State Flow:

No spatial variation:

Plug Flow Reactor (PFR)

Analysis Across Length, y
Summary of Mole Balances

3
 30/01/2017

At the end of this topic, you should

be able to:
 Apply the general mole balance to
simple reactions for a batch reactor;
Analysis of Batch Reactors  Derive working equations for reaction
(Simple Reactions) time for constant volume and constant
pressure reactions;
Topic No. 3  Apply the working equations to solve
Ch.E. 422
batch reactor problems;
 Determine the order and rate
constants for simple reactions using
several mathematical methods.

Review of Mole Balances For Batch Reactors:

Differential Form:

dNA
rA V =
dt
Integral Form:
NA
dNA
t= 
0
rA V

4
 30/01/2017

Simple Reactions in Batch Reactor Operating Modes (Gas Phase Reactions)

 Single, Homogenous Reactions
• Decomposition: aA  Product(s)
• Combination: aA + bB  Product(s)
• Isomerization A  A’
• May be Elementary or Non-Elementary
 Operating Modes
• Constant Volume
o Usually for Liquid Reactions
o May be Constant/Variable Pressure for Gas Reactions Constant Volume Constant Pressure
• Constant Pressure
o Applied to Gas Reactions Only
o May be Constant or Variable Volume

Common Problem Types Constant Volume Equation

 Determination of Reaction Time or dNA
rA V =
Number of Batches per Day: dt
Unknown t or NB
 Determination of Percent Conversion per
Batch: Unknown %XA
 Determination of Percent Change in Total
dCA
NA CA
Pressure or Volume per Batch: dNA dCA CA

Unknown 100(∆P/Po) or 100(∆V/Vo)

t= 
0
rA V
= 
CAo
rA
 CAo rA
 Determination of Reactor Volume and/or
Amounts of Products per Batch:
Unknown V, NP

5
 30/01/2017

Decomposition Reaction (aAP) Decomposition Reaction (aAP)

dCA dCA
CA CA

t= 
CAo
rA
for n  1 t= 
CAo
k A CA

rA = k A CnA 1
  ln  CA  
CAo
n = order t=
kA  CA

CA
dCA 1  CA n1 
CA

t= 
CAo
n
k A CA
=  
k A  n  1  C t=
1 C
ln Ao
Ao
kA CA
1  1 1 
t=  n1 - n1  for n  1
(n  1) k A  A
C C Ao 

In terms of XA, Fractional Conversion In Terms of Half-Life (t1/2)

CA  CAo (1  XA ) At t = t1/2 ; CA = CAo / 2

for n  1 1  1 1 
t=  -  for n  1
  (n  1) k A  CnA1 CnAo1 
1 1
t=  -1 2n1 - 1
(n  1) k A CAo  1  XA 
n 1 n 1
 t1/2 =
 (n  1) k A CnAo1
for n  1 1 C for n  1
t= ln Ao
kA CA
1 1  ln(1  XA )
t= ln  ln 2
kA 1 - XA kA t1/2 =
kA

6
 30/01/2017

Combination Type: aA + bB P Combination Type: aA + bB P

dCA
CA
dCA
CA
t=  rA
rA = k A CA CB t= 
CAo k
CAo A
CA CB
Stoichiometry:
(CAo  CA ) (CBo  CB )
dCA
CA
b b
CB = C Ao (M  )  CA

=
t= a b a a
k
CAo A
CA CB b
CB = CBo - (CAo  CA )
a
dCA
CA
CBo
Let M =
CAo
; CBo = M CAo t=   b b



C Ao (M  )  C A 
CAo
b b b kA C
CB = MCAo - (CAo  CA ) = C Ao (M  )  C A
A
 a a 
a a a

In Terms of Fractional Conversion, X A Simplest Case: a=α=b=β=1 & M=1

CA
dCA A + B  Products: elementary, CBo = CAo or M=1
t=  k CA CB
CA  CAo (1  XA ) dCA  CAodXA
CA
dCA

CAo A
CAo  CA  CAo XA t= 
  b b 
C Ao (M  )  C A 
CAo
kA C A
CB = CBo -
b b b
(CAo  CA )  MCAo  (CAo  CA )  CAo (M  X A )  a a 
a a a CAo
dCA
CA
CAo dX A t=  1
t=   b 

CA  1 1 
k A C1A C Ao (1  )  C A 
k A C Ao (1  X A )  1 1 

C Ao (M  X A )
CAo
CAo
 a  dCA
CA
dX A
t=  k A C2A
or same as 2nd order decomposition type


CA
t=
 b 

1  1 1  CAo  CA XA
k A CAon1 1  X A    

CAo
M  X A  t= 
 a  k A  C A C Ao  k A C A C Ao k A C Ao (1  X A )

7
 30/01/2017

Derive the time Equation in terms

Change in Total Pressure, P with time
of CA and XA for the ff:
 2A + B  Products: Elementary,
for CAo = CBo and CAo = 2CBo
 A + 1.5B  Products: Elementary
for CAo = CBo and1.5 CAo = CBo
Derive also the half-life equation
for the above cases.
 Applicable only to Gas reactions
 Happens when sum of
coefficients of reactants is not
equal to sum of coefficient of
products in the balanced
chemical equation.
 Ex: aA + bB  cC + dD
• If (a+b) = (c+d), then P= constant
• If (a+b) > (c+d), then P decreases
• If (a+b) < (c+d), then P increases

Analysis of ∆P/Po Analysis of ∆P/Po

P  Po + (c+d)-(a+b) x
aA + bB  cC + dD PAo  PA
PAo  ax  PA x
a
A B C D
P  Po +
(c+d)-(a+b) (P  PA )
i PAo PBo PCo PDo a
Ao

∆ -ax -bx +cx +dx

Let A 
(c+d)-(a+b) and PAo  y AoPo
t PA PB PC PD a
P  PAo  PBo  PCo  PDo + (c+d)-(a+b) x PAo  PA  PAo XA

P  Po + (c+d)-(a+b) x PAo  ax  PA P  Po +APAo XA  Po +A y AoPo XA  Po (1  A y Ao X A )

8
 30/01/2017

Constant Pressure (Variable Volume)

Analysis of ∆P/Po Gas Phase Reactions
P  Po +APAo XA  Po +A y AoPo XA  Po (1  A y Ao X A ) NA
dNA dNA
rA V =
dt
t= 
0
rA V
Let A  y AoA P  Po (1  A XA )
NA  NAo (1  XA ) dNA  NAodXA

P P  Po P By Analogy with Variable P (for derivation:

1   A XA
Po Po Po V  Vo (1  A XA )

NAo dX A
XA X
A
CAo dX A
t= 
0

rA Vo (1   A X A ) 0 rA (1   A X A )

Decomposition Reaction (aAP) Decomposition Reaction (aAP)

NAo dX A
XA X XA
A
CAo dX A CAo dX A
t=  r V (1  
0 A o X
A A )

0
rA (1   A X A )
t= 
0  C (1  X A ) 
n

k A  Ao  (1   A X A )
 1  A XA 
n n
 N (1  X A )   CAo (1  X A ) 
n
N 
rA  k A  A   k A  Ao   kA  
 V   Vo (1   A X A )   1  A XA 
(1   A X A )n1 dX A
XA
1
XA
CAo dX A t= 
t= 
0  C (1  X A ) 
n
k A CnAo1 0
(1  X A )n
k A  Ao  (1   A X A )
 1  A XA 

9
 30/01/2017

Decomposition Reaction (aAP) Decomposition Reaction (aAP)

(1   A X A )n1 dX A (1   A X A )n1 dX A
XA XA
1 1
t=
k A CnAo1 
0
(1  X A )n
t=
k A CnAo1 
0
(1  X A )n
For n = 0 For n = 1
 ln(1  X A )
XA
1 dX A
 1 X
XA XA
1 C dX A t= 
0 (1  A XA ) dX A  kAoA 
1 Same as CV!
t= kA kA
k A CAo1 0
1  A XA 0 A

For n = 2
XA
(1   A X A )dX A
XA
CAo dX A C C V
 1   Ao ln(1   A X A )  Ao ln 1
t=
kA 0
X
A A k 
A A k 
A A Vo
t=
k A CAo 
0
(1  X A )2
Integrable by PF

For Additional Derivations: Combination Type: aA + bB P

 Constant Volume  
XA
CAo dX A N  N 
• Equations 18 & 19/45 (Lev)
t=  r
0 A (1   A X A )
rA = k A  A   B 
 V   V 
• Equations 23 & 24/46 (Lev) (NAo  NA ) (N  NB )
Stoichiometry: = Bo
 Constant Pressure a b
b
• Equation 73/71 (Lev) NB = NBo - (NAo  NA ) NA  NAo (1  X A )
a

NAo  NAo  NAo XA V  Vo (1   A X A )

10
 30/01/2017

Combination Type: aA + bB P Combination Type: aA + bB P

XA
CAo dX A
 r (1  
XA  
CAo dX A  NA   NB  t=
t= 
0
rA (1   AX A)
rA = k A  V   V 
    0 A AX A)
 
N  N  kA  
rA = k A  A   B  rA = N AN
NA  NAo (1 X A) NAo  NAo  NAo XA Vn
B
 V   V 

 b a 
NAo (1  XA )

MNAo a ( b  XA
NBo
Let M = ; NBo = M NAo )
NAo
rA = k A 
 Vo (1  A XA )
n
b b b
NB = MN Ao- (N Ao  A) =MN
N Ao N Ao
X A N Ao(M X )A
a a a

a 
1  XA 
b 
NB  NAo (M  X A)
a  b

 b  X A 
rA = k A CnAo M 
 a 1  A XA 
n

Combination Type: aA + bB P Simplest Case: a=α=b=β=1 & M=1

XA A + B  Products: elementary, M = 1
CAo dX A
t=  r (1  
1  A XA 
n 1
AX A)
XA
0 A 1 dX A
XA
CAo dXA
t=
 b
  a 


 1  XA 

t=  k A CnAo1 M  0
 b  XA 
a   a  
1  XA 

 b  XA 
0

 b  
n
k A C M  (1   A X A )
1  A XA  1  AXA dX A
Ao
 a
n
XA
1
t=
k A CAo  1  XA 
2

1  A XA 
XA n 1 0
1 dX A
t=
k A CnAo1   b 

Same as 2nd order decomposition case
1  XA 

M  a X A 
0

 

11
 30/01/2017

Derive the time and half-life Derive the time and half-life
equations for the ff: equations for the ff:
 2A + B  Products: Elementary,  A + 1.5B  Products: Elementary
for NAo=NBo or M = 1 for NAo = NBo or M = 1
1  A XA  1  A XA 
XA n 1 XA n 1
1 dX A 1 dX A
t=
k A CnAo1   b 

t=
k A CnAo1   b 


1  XA  1  XA 
 
M  a X A  M  a X A 
0 0

   
1  A XA 
XA 2
2 dXA
 1  X  2  X  1  A XA  dXA
t= XA 1.5
k A C2Ao 2 1
0

2
A A t=
k A CAo1.5 0 1  X 1  1.5 X 1.5
A A
2 XA 1  A XA  dX A
t
k A C2Ao 0

 1  XA 

2  XA 
Integrable by PF

Decomposition Equations Summary Combination Equations Summary

Constant Volume Constant Volume
XA
  1 dX A
 ln(1  X A ) n 1 
1 1 t= NBo CBo
t=  - 1  or t   M= =
1  XA  M  a XA 
k A CAo 0   b
(n  1) k A CnAo1  1  XA n1  kA NAo CAo

 
Variable Pressure (Gas Only) Variable Pressure (Gas Only)
ΔP ΔP NBo yBo PBo
P = Po (1  ξ A XA ) XA  P = Po (1  ξ A XA ) XA  M=  =
Poξ A Poξ A NAo y Ao PAo
Constant Pressure (Gas Only) Constant Pressure (Gas Only)
V = Vo (1  ξ A XA )
1  A XA  V = Vo (1  ξ A XA )
n 1 n 1
(1   A X A ) dX A
XA XA
1 1 dX A
t=
k A CnAo1  (1  X A )n ΔV
t=
k A CnAo1  
ΔV
XA   b 
1  XA 
0  XA 
M  a X A 
0
Voξ A Voξ A
 

12