C 4

The Discontinuous/Batch Reactor
A discontinuous or batch reactor has no fluid

streams flowing through. V(t)
Perfect mixed
medium
The total feed is introduced before start, and no

withdrawal is made until the reaction has reached XA(t) CA(t)
the degree of completion desired.
The mathematical model results from mass balances for all species
Input of mass to  Output of mass from  Accumulation of mass 
     
 the system during    the system during    within the system 
 the time period t   the time period t  during the time period t 
     
amount of mass  amount of mass 

   
in the system 
 in the system 
at time t  t  at time t 
 n   n 
June 5, 2008 FILS – Chemical Reactors 1
The Characteristic Equation
Rewriting the dynamic mass balance

tn  t
  Input of mass to the  Output of mass from the   Mass within the system  Mass within the system 

tn

 system per unit time

 
  system per unit time


dt  
 at time t n +Δt

  at time t n


 
tn t
 
   0  M A  rA  t   V  t   dt  M A  N A tn t  M A  N A tn
 
tn  Input of reactant A 
Output of reactant A by    
 per unit time 
mass of reactant A within mass of reactant A within
reaction per unit time the system at time t n t the system at time t n
tn t
 rA  t   V  t   dt  N A tn t N A tn
tn

dN A
Using the Mean Value Theorem of Integral Calculus   V  rA
S
dt
Single Reaction Chemical Process 
j 1
j A j  0
    
dN Aj  d  N A0  M A j / A  j X A    N A0 j dX A
dX A rA V
 
dN Aj   a  a
sign  Aj  V  rA j 
dt dt N A0
The Characteristic Equation
1
X Af dX A rA  V
t  N A0 
0 rA  V
Operating conditions
0
Performance XA
Initial conditions t
Reaction time Area 
N A0
R S
Multiple reactions chemical processes 

i 1 j 1
ij Aj  0
Rewriting the dynamic mass balance

Reaction rate with respect to Aj
dN Aj d  R
 R
  N Aj 0   ij  i   V  rAj  V   ij  ri Equivalent reaction
dt dt  i 1  i 1 rate for “i” reaction
Taking the derivative of the parenthesis
1 R d i R
 ij dt  
V i 1 i 1
 ij  ri
Holds for every term of the sum
1 d i
 ri   , i  1, 2, , R
V dt
The vector of extents of all reactions, kmol
The extent of reaction “i”, kmol

The Characteristic Equation and the Volume of Reaction
A) The volume of reaction is constant during the chemical process
1) Single reaction chemical process

XA C A
dX A dC A
t  C A0 
0
rA  X A 
 
CA 0 A  A 
r C
p
1 A
dp A
t  
Rgas pA 0 rA  p A   T
2) Multiple reactions chemical process
d V i
 ri V  , i  1, 2, , R
dt
The vector of volumic extents of all reactions, kmol∙m-3
The volumic extent of reaction “i”, kmol ∙m-3

The Characteristic Equation and the Volume of Reaction
B) The volume of reaction is variable during the chemical process
1) Single reaction chemical process
V  V0  1    X A 
XA dX A
t  C A0 
0
1    X A   rA  X A ,  
2) Multiple reactions chemical process
 d i 1 d i 1 d mi 1
 ri     ri     ri  m  , i  1, 2, , R
V dt m dt  dt 
The vector of mass
The mass extent of extents of all
reaction “i”, kmol ∙kg-1 reactions, kmol∙kg-1
Irreversible chemical processes

(the equilibrium constant has very
large values, thus the reverse
reaction is negligible)

The DC Reactor – Solving the Characteristic
Equation
Single reaction chemical process
Irreversible first order chemical processes A 

k
 products

dC A
CA t
  k  dt C A  C A 0  e  kt
0
rA  k  C A  k  C A0  1  X A 
CA0 C
A
XA dX A t
 0 1 X A
 k  dt
0
X A  1  e  kt

XA t
dX A
rA  k  C A  k  C A0
1 X A  1 X A
 k  dt
X A  1  e  kt
1   X A 0 1    X A  0
1   X A
Important Conclusion!! The volume behavior does not affect the performance

Common plot for a first-order irreversible reaction
X A  1  e kt
 ln 1 X A  The initial concentration
 ln  
CA
C A0
Slope = k does not affect the
performance of the first
order processes
0
C A  C A0  e kt
0 t

Common plot for a first-order irreversible reaction
XA 1
0.5
k(T)
k(T-Ta) < k(T)
k(T+Ta) > k(T)
0
0 20 40 60 80 100
time, s

Equation
Irreversible second order elementary chemical processes A  B 
k
 products

rA  k  C A  C B  k  C A2 0  1  X A    M BA  X A 
XA t
dX A 1 Z1 Z2

0 1  X A  M BA  X A
 C A0  k   dt
0
 
1  X A  M BA  X A  1  X A M BA  X A
 1
 X  1  Z1 
M BA  1
A

Z1   M BA  X A   Z 2  1  X A   1 
X  M  Z   1
 A BA 2
M BA  1
M BA  1
M BA  X A
k  C A0   M BA  1  t  ln
M BA  1  X A 
M BA  1 XA
dX A
t
XA
 1  X 
0
2
 C A0  k   dt
0
k  C A0  t 
1 X A
A

Common plot for a irreversible second-order elementary reactions, MBA ≠ 1
Constant volume case
Slope= k (CB 0 - C A0 )
M BA  X A Intercept= ln( M BA )
ln
M BA 1 X A  CB
ln CA
CB C A0
ln
C AC B
0
Slope= k (CB 0 - C A0 )
0 0
0 t 0 t

CA0 = 0.5 CA0 = 1.5
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 k(T) 0.2 k(T)

k(T- a) < k(T) k(T- a) < k(T)
k(T+ a) > k(T) k(T+ a) > k(T)
0 0
0 20 40 60 80 100 0 20 40 60 80 100
time, s time, s
CA0 = 0.5 CA0 = 1.5
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 0.2
MBA = 2 MBA = 2
MBA = 4 MBA = 4
0 0
0 20 40 60 80 100 0 20 40 60 80 100
time, s time, s

Common plot for a irreversible second-order elementary reactions, MBA = 1
X 1
A Slope = kCA0
CA 1/CA0
1 X
A
Slope=k
0 0
0 t 0 t

CA0 = 0.5 CA0 = 1.5
0.8
0.8
0.6
0.6
XA
XA
0.4
0.4
0.2
k(T) 0.2 k(T)
k(T- a) < k(T) k(T- a) < k(T)
k(T+ a) > k(T) k(T+ a) > k(T)
0 0
0 20 40 60 80 100 0 20 40 60 80 100
time, s time, s

Equation
k
 products
rA  k  C A  CB  k  C A2 0
1  X A   M BA  X A 
1   X A 1   X A
XA dX A 1 XA 1    X A  dX A
t  C A0   0 1  X A  M BA  X A 
0 1  X A   M BA  X A  k  C A0
1    X A   k  C A2 0
1   X A 1   X A
1    X A  Z1 Z2
  Z1   M BA  X A   Z 2  1  X A   1    X A
1  X A  M BA  X A  1  X A M BA  X A
 1 
 X  1  Z   1  1 M BA 
 1   M BA 
1
1  M BA
A

  M BA  1  k  C A0t  ln    ln  
 X  M  Z  1    M BA  1 X A   M BA  X A 
 A BA 2
1  M BA

Variable volume case
CA0 = 0.5, MBA = 2 CA0 = 1.5, MBA = 2
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 0.2
eps = 0 eps = 0
eps > 0 eps > 0
eps < 0 eps < 0
0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
time, s time, s
CA0 = 0.5, MBA = 4 CA0 = 1.5, MBA = 2
0.8 0.8
0.6 0.6
XA
0.4 XA 0.4
0.2 0.2
eps = 0 eps = 0
eps > 0 eps > 0
eps < 0 eps < 0
0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
time, s time, s

Equation
k
 products
2
 1 X A 
M BA  1 rA  k  C A  CB  k  C A2 0   
 1    X A 
1 1    X A  dX A
XA 1   X A Z1 Z2  Z1  
t
k  C A0 0 1  X 2 1  X A 
2
 
1  X A 1  X A 2 
Z 2  1  
A

XA  1 
k  C A0  t  1     ln  
1 X A  1  X A 

Variable volume case CA0 = 0.5, k = 0.05 CA0 = 1.5, k=0.05
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 0.2
eps = 0 eps = 0
eps > 0 eps > 0
eps < 0 eps < 0
0 0
0 5 10 15 20 25 0 5 10 15 20 25
time, s time, s
CA0 = 0.5, k=0.075 CA0 = 1.5, k=0.075
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 0.2
eps = 0 eps = 0
eps > 0 eps > 0
eps < 0 eps < 0
0 0
0 5 10 15 20 25 0 5 10 15 20 25
time, s time, s

Equation
Irreversible second order chemical processes aA  bB 
k
 products

 b 
rA  k  C A  C B  k  C A2 0  1  X A    M BA  X A 
 a 
XA t
dX A
  b 
 C A0  k   dt
0
1  X A   M BA  X A  0
 a 
b
M BA  XA
M BA 
b
 b a
kC A0  M BA   t  ln
M BA 1  X A 
a
 a
b b XA
M BA  kC A0t 
a a 1 X A

Equation
Irreversible second order chemical processes aA  bB 
k
 products

1  X A    M BA  X A 
b
rA  k  C A  C B  k  C A2 0   a 
1    X A 
2
XA
1    X A  dX A t
  C A0  k   dt
1  X A   M BA  X A 
0
b 0
 a  a M BA
1
1
  b
M BA 
b  b  1   M BA 
k  C A0   M BA    t  ln    ln  
1 X A 
a
 a b
 M BA  X A 
 a 

b XA  1 
k  C A0  t  1   
b
M BA   ln  
a a 1 X A  1  X A 

Equation
Irreversible trimolecular type third-order reactions A  B  D 
k
 products
rA  k  C A  C B  C D  k  C A3 0  1  X A    M BA  X A    M DA  X A 
XA t
dX A

0 1  X A  M BA  X A  M DA  X A 
 C A2 0  k   dt
0
1 Y Z W
  
1  X A  M BA  X A  M DA  X A  1  X A M BA  X A M DA  X A
1 1 1
Y ; Z ; W 
 M BA  1 M DA  X A   M BA  M DA  M BA  1  M DA  1 M BA  M DA 
1 M BA M DA
ln ln ln
M BA  1 1 X A M BA  X A M DA  X A
kC A2 0 t   
M DA  1  M BA  1 M DA  1  M BA  M DA  M BA  1  M DA  1 M BA  M DA 
Common plot for a irreversible third-order elementary reactions, MBA > 1 , MDA > 1
Constant volume case CA0 = 0.5, MBA=2, MDA=2.5 CA0 = 0.5, MBA=4, MDA=5
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 k(T0) 0.2 k(T0)

k(T>T0) k(T>T0)
Drawback k(T<T0) k(T<T0)
0 0
0 50 100 150 200 250 0 5 10 15 20 25 30
Increasing MBA and/or time, s time, s
MDA results in large CA0 = 1.5, MBA=2, MDA=2.5 CA0 = 1.5, MBA=4, MDA=5
quantities of B & D
remained unreacted
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 k(T0) 0.2 k(T0)

k(T>T0) k(T>T0)
k(T<T0) k(T<T0)
0 0
0 5 10 15 20 25 0 0.5 1 1.5 2 2.5 3 3.5
time, s time, s

Equation
Irreversible trimolecular type third-order reactions A  B  D 
k
 products
rA  k  C A  C B  C D  k  C A3 0 
1  X A    M BA  X A    M DA  X A 
1    X A 
3
1    X A  dX A
XA 2 t
0 1  X A  M BA  X A  M DA  X A   C A0  k  0 dt
2
1    X A 
2
Y Z W
  
1  X A  M BA  X A  M DA  X A  1  X A M BA  X A M DA  X A
 1   M BA   M DA 
  1    M BA  1 ln     M DA  1 ln 
2 2 2
M BA  1 ln  
M DA  1 kC A2 0 t   1 X A    M BA  X A   M DA  X A 
 M BA  1 M DA  1  M BA  1 M BA  M DA   M DA  1 M BA  M DA 

Common plot for a irreversible third-order elementary reactions, MBA > 1 , MDA > 1
Variable volume case CA0 = 0.5, MBA=2, MDA=2.5, k=0.05 CA0 = 0.5, MBA=2, MDA=2.5, k=0.075
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 eps = 0 0.2 eps = 0

eps >0 eps >0
Drawback 0
eps < 0
0
eps < 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120
Increasing CA0 results time, s time, s
in faster reactions, but CA0 = 1.5, MBA=2, MDA=2.5, k=0.05 CA0 = 0.5, MBA=2, MDA=2.5, k=0.075
large reactants
quantities remaine
0.8 0.8
unreacted 0.6 0.6

XA
XA
0.4 0.4
0.2 eps = 0 0.2 eps = 0

eps >0 eps >0
eps < 0 eps < 0
0 0
0 5 10 15 20 0 2 4 6 8 10 12
time, s time, s

Equation
A  2 B 
k
 products
Irreversible third-order reactions of particular type
A  B 
k
 products
 k  C A3 0  1  X A    M BA  2 X A 2
rA  k  C A  C B2  
 k  C A 0  1  X A    M BA  X A 
3 2
XA t
dX A
b2  1  X A  M BA  b  X A 
 C A2 0  k   dt
0 0 b 1
M BA  1
M BA  2
1 1
M  2X A
1 2X A   2 k t
kC  M BA  2  t 
2
ln BA  2 2
C A C A0
M BA  M BA  2 X A 
A0
M BA  2 1 X A
M BA  2 M BA  1
2kC A2 0 t 
X A 2  X A 
k 1  M BA  t 
2 1  M BA  M BA  CB C A0 
 ln
CB
1  X A 
2
C B 0C B M BAC A
Equation
A  2 B 
k
 products
Irreversible third-order reactions of particular type
A  B 
k
 products
This case is homework

Equation
Empirical rate equations of nth order A 
k
 products
 k  C An 0  1  X A n , V  0

rA  k  C A  
n
 1 X A 
n
 k  C A0    , V  0
n
V  0   1    X A 
C 1An  C1A0n   n  1 kt , n  1 V  0
•The reactions with order n >1 can never go to

completion in finite time (but this is a
characteristic of first order chemical processes).
1    X A  dX A
XA n 1
•For orders n < 1, this rate form predicts that the k  C An 01  t  0 1  X n
reactant concentration will fall to zero and then A
become negative at some finite time

C1A0n
tmax 
1  n   k
Equation
Empirical rate equations of nth order A 
k
 products
CA0 = 0.5, k=0.05, n=1.75 CA0 = 0.5, k=0.05, n=0.05
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 k(T) 0.2 k(T)

k(T<T0) k(T<T0)
k(T>T0) k(T>T0)
0 0
0 500 1000 1500 2000 2500 3000 0 5 10 15 20 25 30 35
time, s time, s
CA0 = 0.5, n=0.25, k=0.05 CA0 = 1.5, n=0.25, k=0.05
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 eps = 0 0.2 eps = 0

eps >0 eps >0
eps < 0 eps < 0
0 0
0 5 10 15 20 0 10 20 30 40 50
time, s time, s

Equation
Reactions of Shifting Order A 
k
 products
A) Shift from low to high as the reactant concentration drops
k1  C A CA
rA 
1  k2  C A Zero order
•at high CA (or k2CA»1) - the reaction

rate is of zero order with rate constant First order
k1/k2.
•at low CA (or k2CA«1) - the reaction is t
of first order with rate constant k1. rA
k2 / k1
 1  Zero order
ln  
 1  X A    k  k1t
2
C A0 X A C A0 X A First order
CA

Equation
Reactions of Shifting Order A 
k
 products
B) Shift from high to low as the reactant concentration drops
(two competing reactions of different orders)
CA
rA  k1  k2C A Zero order
•at low CA - the reaction rate is of zero

First order
order with rate constant k1.
•at high CA- the reaction is of first order
with rate constant k2. rA
t
First order
k1  k2C A 0
 e  k2t Zero order
k1  k2C A
CA

Equation
Autocatalytic Reactions A  R 
k
R R
One of the products of reaction acts as a catalyst
r A  k  C A  CR  k  C A2 0  1  X A    M RA  X A 
The total number of moles of A and R remains unchanged
XA
C0  C A  C R  C A 0  C R 0 1 Low rate
There is a maximum, due to the antagonic effects High rate
rA
 k  C A2 0  1  M RA   2 X A   0
X A
0 Low rate
0 t
1  M RA rA
X Amax 
2
M RA  X A
Progress Start with some
 C A0   M RA  1 kt
in time
R present
ln
M RA  1  X A 
Parabolic
0
0 CA = C R 1 CA/CA0

Equation
Autocatalytic Reactions A  R 
k
R R
CA0 = 0.5, k=0.075 CA0 = 1.5, k=0.075
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 MRA = 0.01 0.2 MRA = 0.01

MRA = 0.05 MRA = 0.05
MRA = 0.1 MRA = 0.1
0 0
0 50 100 150 200 250 0 20 40 60 80 100
time, s time, s
CA0 = 0.5,MRA = 0.01 CA0 = 1.5,MRA = 0.1
0.8 0.8
0.6 0.6
XA
XA
0.4 0.4
0.2 k(T0) 0.2 k(T0)

k(T<T0) k(T<T0)
k(T>T0) k(T>T0)
0 0
0 100 200 300 400 500 600 700 800 0 50 100 150 200
time, s time, s

Reversible chemical processes

(The complete conversion is never achieved,
due to the thermodynamic barriers)

Equation
First-order Reversible Reaction 
A P

kd
kr
 M PA 
1  
 1  KC  , K  kd
rA  kd C A  kr C P  kd C A0  1    X
 K C   1 
A
 C
kr
 1   
  K C  
At equilibrium
M
1  PA
dC KC C M  X Ae
rA   A  0  XA  0 K C  Pe  PA
dt 1 C Ae 1  X Ae
1
KC
The mass balance – applying the differential form of the characteristic equation
 
 
 1   K C  M PA   k  1  M PA   1  X A   k  1 
dX A
dt
 kd 1 
 K

C   1 
 X A
 d 
 K

C  X

Ae 
 XA 
 1   KC 
  K C  
Equation
First-order Reversible Reaction 
kd
A P

kr
dXˆ A ˆ  1  ˆ kd   M PA  1
dt

 k  1  Xˆ A  ln 
ˆ   kt 
 1 X A  M PA  X Ae
t
kd  M PA  1
 1  Slope 
ln  M PA  X Ae
1  ˆ 
 X A 

Equation
Second-order Reversible Reactions (V=ct) 
kd
R S
A  B  
kr
C A0  CB 0 & CR 0  CR 0  0   
kd
2 A  R S
2  1  2 2X A 1  kr
rA  kd C AC B  kd C R CS rA  kd C A 0 1   X A  1

1 


kd
 2R
 KC   1  1  2 A  
 K C 
kr
 KC
At equilibrium 
kd
A  B   2R

kr
2 X Ae 1 k
dC A
2
X Ae    0, K C  d
rA   0 1 1 kr
dt 1 1
KC KC
The integral form of the characteristic equation
XA
1   2 X Ae  1
X Ae  1 
ln  2k d   1 C Ao t
XA  X Ae 
1
X Ae

Equation
Second-order Reversible Reactions (V=ct)
1  X X 1 
 1 2 X Ae
ln    A Ae 
1
 1 X A X Ae 
 
 1

Slope=2 k d X Ae  1 C A0

Equation
Second-order Reversible Reactions (V=ct)
C A0  CB 0 & CR 0  CR 0  0
 
2  1   2 1  M BA  X A M BA 
rA  kd C AC B  kd C R CS rA  kd C A 0 1   X A  1

1

 KC   1 1 
 K C 
 KC
At equilibrium
1 1
 1   1  kd
rA  
dC A
0 X A  1  M BA   1 
2
 X A  M BA  1    0, K C 
dt 

KC   KC  kr
the roots are denoted q and p
p q  X A   1 
ln   p  q  kd C Ao  1  t
q p  XA  KC 

Equation 
A  B R S

kd
kr
Second-order Reversible Reactions (V=ct) 

kd
2 A  R S
kr
rA  kd C AC B  kd C R CS C A0  CB 0 & CR 0  CR 0  0 
kd
2 A   2R
kr


M 
M RA  M SA  
kd
A  B   2R

 M M  1  M BA  M RA  M SA  X A  BA
KC  kr
rA  k d C A2 0 1  RA SA   X A2  
 KC   1 1 
 1  1  
 KC KC 
 M RA  M SA 
1 
 M M   2  M RA  M SA  X A  KC 
rA  k d C A2 0 1  RA SA   X A2  
 KC   1 1 
 1 1 
 KC KC 
 2 M RA 
1
 M 2
  2 X A 1  M RA  KC  The solving procedure
rA  k d C A2 0 1  RA

 A X 2
  
 KC  1
1
1
1  remains the same; case
 
 KC KC  should be taken when
 2 M RA  computing the roots of
 M BA  
 M 2
 1  M BA  2M RA  X A  KC
rA  k d C A2 0 1  RA
 X A 
2
1 1
 the equilibrium equation.
 KC  1 1 
 
 KC KC 
Equation
Second-order Reversible Reactions (V≠ct) 
kd
A  B  RS

kr
rA  kd C AC B  kd C R CS C A0  CB 0 & CR 0  CR 0  0
M RA M SA  M RA  M SA 
1  M  
rA  kd C A 0
2 KC
 X 2

1  M BA  M RA  M SA  X A

BA
KC

 A
1 1
2 A
1   X  1  1  
 
 KC KC 
 M M 
kd C A0  1  RA SA  t  
XA 1   X A  dX A
 KC  0
 X A  p  X A  q 
 M RA M SA   p q  X A     q   p 
kd C A0  1    p  q  t  ln      q ln    p ln  
 K C  
 q  p  X 
A    q  X A   p  X A 

Equation
Multiple reactions chemical processes

Equation
A 
k1
 R, r1  k1C A
Irreversible Reactions in Parallel (V=ct)
A 
k2
 S , r2  k2C A
2
dC A
 rA   ij ri   k1C A  k2C A    k1  k2  C A
dt i 1
dCR
 rR  k1C A
dt
The integration of equations gives
CA
  k1  k2  t
  k1  k2 t
 ln  C A  C A0 e
C A0
dCR
dt
C
 k1C A  k1C A0 e  1 2   R 
 k k t k1
C A 0 k1  k2
1 e  1 2
 k k t
 
C A 0  C R 0  CS 0  C A  C R  CS 
CS

k2
C A0 k1  k2
1 e  1 2
 k k t


Equation
A 
k1
 R, r1  k1C A
Irreversible Reactions in Parallel (V=ct)
A 
k2
 S , r2  k2C A
CA0
CA
CR
0 CS
0 t
Equation
Irreversible Reactions in Series (V=ct) A 
k1
 R 
k2
S
2
dC A
 rA   ij ri   k1C A
dt i 1
2
dCR
 rR   ij ri  k1C A  k2CR
dt i 1
The integration of equations gives

CA CA
 ln  k1t   e  k1t
C A0 C A0
dCR
 k2CR  k1C A 0 e  k1t
CR

k1
C A 0 k1  k2

e  k2t  e  k1t 
dt
C A0  C A  CR  CS 
CS
 1

k2 e  k1 t  k1e  k2 t 
C A0 k1  k2

Equation
Irreversible Reactions in Series (V=ct) A 
k1
 R 
k2
S
ln  k2 / k1 
tmax 
k2  k1
k2 /  k2  k1 
CR ,max  k1 
 
C A0  k2 

Polymerization in Batch Reactors
Calculation of molecular weight

distribution in a batch thermal
polymerization of styrene

Polymer molecular weight distribution (MWD) is one of the most important
polymer properties that dictate the physical, mechanical, and rheological
properties of industrial polymers. These are commonly used:
• Molecular weight averages
•Average/mean molecular number
•Average/mean molecular mass
• Polydispersity - ratio of mean molecular mass and mean molecular number
There are cases of two polymers of different chain length distribution having
identical molecular weight averages.
Sometimes, a slight variation in high or low molecular weight fractions of

polymer causes a significant difference in the polymer’s enduse properties.
In practice, it is desired to predict or control the entire chain length

distribution instead of molecular weight averages.

In modern industrial polymerization processes, polymerization process

conditions are designed and operated to produce the polymers of desired
molecular weight properties with minimum variance from their target values.
To do so, it is required that the relations between the polymer’s molecular

weight properties and reaction conditions be quantitatively established.
A detailed polymerization process model can be utilized for such purposes.
If the main goal is to predict and control polymer molecular weight distribution
in a given polymerization process, it will be necessary to have available an
appropriate computational method to predict the chain length distribution
during the progress of reaction.

When a polymerization kinetic model is available, molecular weight averages
and MWD can be calculated by:
• numerical integration of the polymer population balance equations
• using a moment generating function
• z-transform
• continuous variable transformation
• the method of molecular weight moments
• Markov chain approaches
• integrating an instantaneous chain length distribution to a desired
conversion
• fitting a pre-specified chain length distribution function with molecular
weight averages
• Monte Carlo simulation techniques, for free radical polymerization
• discrete weighted Galerkin methods, with expansion of a chain length
distribution into certain orthogonal polynomials.

The Method of Finite Molecular Weight Moments (MFMWM)
• Calculate the chain length distribution in free radical polymerization where
chain termination is via disproportionation and combination mechanisms.
• Instead of calculating the concentration or weight fraction of polymer with a
certain chain length, the weight fraction of polymers in a finite chain length
interval is calculated.
• The function that defines the weight fraction of polymer in a certain chain
length interval is analytically represented from the reaction kinetic model.
In MFMWM, a quasi-steady state approximation is used for live polymer

radicals and the resulting recursive relationship between the concentrations of
live polymer chains is used to derive the expressions for polymer weight
fractions.
The major advantage of the method of finite molecular weight moments is that
the differential equation for the weight fraction of any finite chain length interval
is explicitly expressed in terms of process variables.
This method is different from simply discretizing the polymer population
balance equations to finite difference form for numerical calculations.

The method of finite molecular
weight moments
Thermal polymerization of styrene
The kinetic scheme Thermal initiation
3M 
ki
 2 R1
R1  M   R2
k
p Propagation
Ri  M   Ri 1
p k
Ri  M  Pi  R1
fin k
Ri  R j 
kt
 Pi  j Termination thru
•Disproportionation
•Combination

weight moments
Applying the quasi-steady state approximation to live polymers (radicals) →
The concentrations of radicals (live polymers)
1/ 2
R1  1    R  2 ki M 3
R 
 k t 
kpM Total live polymer
 concentration
k p M  k fin M  kt M
The probability of propagation
The chain length i
Ri  1     i 1 R
The Schulz-Flory Most Probable Distribution
weight moments
The mass balance equation for polymer of chain length i
dPi kt
 k fin M 1     R   i  11     i  2 R 2
i 1 2
dt 2
The molecular weight averages can be conveniently calculated using the
method of moments
 
R

  i Ri 
1   R
   Ri  R 1R   iRi  
R R 2
 
2 2
1 
0
i 1 i 1 i 1 1 
 
P

  i Pi 
1   P
   Pi  P 1   iPi  
P P P 2
1   
2 2
1
0
i 1 i 1 i 1

weight moments
The moments equation for polymer of chain length i
d 0P 1
 kt R 2  k fin MR
dt 2
d 1P 1
  kt R 2  k fin MR  2    
dt 1
d 2P 1
  kt R 2   2   k fin MR  2  3  4  
dt 1  

weight moments
The number-average and weight-average chain lengths
1P  1R 1P

Xn  P  P
0  0 0
R
2P  2R 2P

Xw  P  P
1  1 1
R
X w 2P
Polydispesity   P
X n 0

weight moments
For the calculation of a complete polymer chain length distribution, the
polymer population balance equations need to be solved.
The method of integrating the ODE system for “all i” to compute the
polymer molecular weight distribution is impractical because of the very
large value of i.
Simpler is the method of finite molecular weight moments.
Definition
n
 iP i
Weight of polymer chain lenght from m to n
f  m, n   im


Total weight of polymer
 iP
i 2
i

weight moments

weight moments
Having defined the function f (m, n), the following equation is derived
df  m, n  1 n
dPi f  m, n  d 1P
dt
 P
1

i m
i
dt

dt dt
   m 1   n  m  1  m 1  n n  
 k fin M 1    R    
 1    1
2
df  m, n  1   
 P 
dt 1  k 1  n  n  1   2  n  1 n  1   n  n  1    
n 1 n n 1
2
 R
t
 
m2 
   m  1 m  2    2m  m  2    m  m  1   
m 1
 2 1 m
f  m, n 
 P  kt R 2  k fin MR  2    
1 1   

weight moments
Batch near-isothermal bulk polymerization of 150oC
The reaction temperature reaches 150oC after about 60 min, during which
period, the monomer conversion is quite low.
This operation as a “near” isothermal operation.
As expected, the molecular weight averages reach their stationary values
when the monomer conversion exceeds about 50%.
weight moments
Weight chain length distribution for near-isothermal polymerization at 150oC
Notice that after 3 h

of reaction, the chain
length distribution is
almost time invariant.

weight moments
The reactor temperature set point is changed from 150oC to 180oC at t = 120 min
With an increase in the reactor temperature, the polymer molecular weight

decreases slightly and the polydispersity increases slightly.

weight moments
Weight chain length distribution for non-isothermal polymerization
Although the polymer

chain length distribution
curves look quite similar,
there is a distinct diffe-
rence in the final chain
length distributions bet-
ween the two cases

weight moments
Differential and cumulative chain length distributions for near-isothermal
and nonisothermal polymerizations
The temperature variations yield a subtle but clear difference in the chain length
distributions of the two polymers → a difference in the enduse properties.
If the polymer chain length distribution can be computed with a kinetic model, it
is possible to discern the difference in the polymer molecular weight properties,
otherwise difficult to do with molecular weight averages only.

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The Discontinuous/Batch Reactor

A discontinuous or batch reactor has no fluid

The total feed is introduced before start, and no

amount of mass  amount of mass 

Rewriting the dynamic mass balance

June 5, 2008 FILS – Chemical Reactors 2

Multiple reactions chemical processes 

Rewriting the dynamic mass balance

Holds for every term of the sum

The extent of reaction “i”, kmol

A) The volume of reaction is constant during the chemical process

1) Single reaction chemical process

2) Multiple reactions chemical process

The volumic extent of reaction “i”, kmol ∙m-3

B) The volume of reaction is variable during the chemical process

1) Single reaction chemical process

Irreversible chemical processes

June 5, 2008 FILS – Chemical Reactors 7

Irreversible first order chemical processes A 

A) The volume of reaction is constant during the chemical process

B) The volume of reaction is variable during the chemical process

June 5, 2008 FILS – Chemical Reactors 8

June 5, 2008 FILS – Chemical Reactors 9

June 5, 2008 FILS – Chemical Reactors 10

A) The volume of reaction is constant during the chemical process

June 5, 2008 FILS – Chemical Reactors 11

June 5, 2008 FILS – Chemical Reactors 12

0.2 k(T) 0.2 k(T)

CA0 = 0.5 CA0 = 1.5

June 5, 2008 FILS – Chemical Reactors 13

June 5, 2008 FILS – Chemical Reactors 14

June 5, 2008 FILS – Chemical Reactors 15

June 5, 2008 FILS – Chemical Reactors 16

CA0 = 0.5, MBA = 4 CA0 = 1.5, MBA = 2

June 5, 2008 FILS – Chemical Reactors 17

June 5, 2008 FILS – Chemical Reactors 18

CA0 = 0.5, k=0.075 CA0 = 1.5, k=0.075

June 5, 2008 FILS – Chemical Reactors 19

A) The volume of reaction is constant during the chemical process

June 5, 2008 FILS – Chemical Reactors 20

B) The volume of reaction is variable during the chemical process

June 5, 2008 FILS – Chemical Reactors 21

A) The volume of reaction is constant during the chemical process

0.2 k(T0) 0.2 k(T0)

Increasing MBA and/or time, s time, s

0.2 k(T0) 0.2 k(T0)

June 5, 2008 FILS – Chemical Reactors 23

B) The volume of reaction is variable during the chemical process

June 5, 2008 FILS – Chemical Reactors 24

0.2 eps = 0 0.2 eps = 0

Increasing CA0 results time, s time, s

unreacted 0.6 0.6

0.2 eps = 0 0.2 eps = 0

June 5, 2008 FILS – Chemical Reactors 25

This case is homework

June 5, 2008 FILS – Chemical Reactors 27

•The reactions with order n >1 can never go to

become negative at some finite time

0.2 k(T) 0.2 k(T)

CA0 = 0.5, n=0.25, k=0.05 CA0 = 1.5, n=0.25, k=0.05

0.2 eps = 0 0.2 eps = 0

June 5, 2008 FILS – Chemical Reactors 29