CHE 631: Chemical Reaction CHE 631: Chemical Reaction Engineering

CHE 631: Chemical Reaction
Engineering
Animangsu
g Ghatak
Department of Chemical Engineering, IIT Kanpur

Lecture 3
Free radical Polymerization
kd
Initiation I  2R0
k1
R0  M 1  R1
kp
Propagation R1  M1  R2
kp
Rn1  M1 Rn
Termination
Combination Rn  R m 
k Tc
Pn  m
kTd
Disproportionation Rn  Rm  Pn  Pm
Example
k1

Initiation Initiator( I )  CH 2  CHX  I  CHX  CH 2
 
I  CHX  CH2  CH2  CHX  I  CHX  CH2  CHX  CH2
CH2 
CHX
  (CHX  CH2 )n  CHX  CH2
 
Propagation  (CHX  CH2 )n  CHX  CH2  (CHX  CH2 )m  CHX  CH2
 (CHX  CH2 )n  CHX  CH2  CHX  CH2  (CHX  CH2 )m 
Termination
 
Combination  (CHX  CH2 )n  CHX  CH2  (CHX  CH2 )m  CHX  CH2
 (CHX  CH2 )n  CX  CH2  (CHX  CH2 )m  CHX  CH3
 
Disproportionation  (CHX  CH2 )n  CHX  CH2  (CHX  CH2 )m  CHX  CH2
 (CHX  CH2 )n  CX  CH2  (CHX  CH2 )m  CHX  CH3
Rate of appearance/disappearance of reactants/radicals
R1 , R2 ,  , Rn 1 , Rn , Rm Micro & macro-radicals containing 1, 2, …, (n-1), n

monomer units
Pn , Pm , Pn  m Dead polymers
M1 Monomer
These symbols will also represent the respective concentrations

kd
dI
Initiation I  2R0 Rate of dissociation of initiator:   kd I
dt
k1
dR 0
R0  M 1  R1 Rate of appearance of radical R0  2 fk d I  k i R0 M 1
dt
Efficiency of splitting initiator
dR 1
Rate of appearance of radical R1  k i R 0 M 1  k p R1 M 1  ( k Tc  k Td ) R1 R
dt

R R
n 1
n
Total concentration of radicals
dR 2
Rate of appearance of radical R2  k p M 1 ( R1  R 2 )  ( k Tc  k Td ) R 2 R
dt
dR n
Rate of appearance of radical Rn  k p M 1 ( R n 1  R n )  ( k Tc  k Td ) R n R
dt
dR1  dR n
Total rate of   k i R0 M 1  0  kTc  kTd R R1  R2   Rn 
appearance of radicals dt n  2 dt
 k i R0 M 1  0  kTc  kTd R 2
dM 1
Rate of appearance of monomer   k i R0 M 1  k p R1 M 1  k p R 2 M 1    k p R M 1
dt
dM 1
   k i R0 M 1  k p RM 1
dt
For dead monomer,
dPn
 ktc Rn1R1  ktc Rn1R2   ktd Rn R1  ktD Rn R2  
dt
 ktc [ Rn1R1  Rn1R2  R1Rn1 ]  ktd [ R1  R2  ]Rn
n 1
 ktc  Rnm Rm  ktd Rn R
n1
Assuming pseudo-steady state for radicals

dR0
 0  2 fkd I  ki R0M1  2 fkd I  ki R0M1
dt
dR d
 Ri  0
dt dt
ki R0M1  (kTc  kTd )R2  0  ki R0M1  (kTc  kTd )R2  0
1/ 2
 2 fk d I 
R  
k
 Tc  k Td 
dRn
For n-th radical:  0  k p M 1 ( Rn 1  Rn )  ( kTc  kTd ) Rn R
dt
Substituting the expression for R:
 (ktc  ktd )R   k1M 1 

Rn-1  1   Rn  Rn  α Rn-1    Rn 1
 k p M 1   k p M 1  (ktct  ktd )R 
probability of propagation
dR1
0 Solving for : R1  R 1-α 
For radical R1:
dt
Since, Rn  α Rn-1
 ki R0 M 1  k p R1M 1  (kTc  kTd ) R1R
Rn  α Rn-1  Rn  α 2 Rn- 2 
 (kTc  kTd ) R  k p R1M 1  [(kTc  kTd ) R1 ]R
2
  Rn  α n 1 R1
k p M1
 (kTc  kTd ) R   Rn  α n 1 R1-α 
2
R1

Rn  α n 1 R1-α
α
Above relation depicts the concentration distribution of macro-radical
with
ith respect
e e t to
t the chain
h i length,
le th made
de up off n-monomere units.
it
Evolution with time of various species,

dI
  k d I  I  I 0 exp  k d t 
dt
dM 1
  k i R0 M 1  k p RM 1
dt
1/ 2
 2 fk d I 
  2 ffk d I  k p M 1  
k
 Tc  k Td 
1/ 2
 2 fk d   kd t 
  2 ffk d I 0 expp  k d t   k p M 1   I 12
0 expp   
k
 Tc  k Td   2 
12
 2k p 2 fk d I 0    kd t  
Solving for M1, M 1  M 10 exp  .   exp    1
k
 d Tc k  k Td    2  
n 1
dPn
 k tc  R n  m R m  k td R n R
dt n 1
n 1
dPn
  k tc  R n  m R m  k td  n 1 R(1 -  ) R
dt n 1
Since, Rn  n1 R1- , Rm  m1 R1- 

So Rnm  nm1 R1- 
RnmRm  n2 R2 1- 
2
n1 n1
 nm m  R 1-
 n2 2 2
R R 
m1 m1
n -1 n2 2
  R 12
2
dPn n -1 n2 2
Then
Then,  k tc  R (1   ) 2  k td  n 1 R(1 -  ) R
dt 2
To be solved numerically

CHE 631: Chemical Reaction CHE 631: Chemical Reaction Engineering

Uploaded by

Copyright:

Available Formats

CHE 631: Chemical Reaction CHE 631: Chemical Reaction Engineering

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

CHE 631: Chemical Reaction CHE 631: Chemical Reaction Engineering

Uploaded by

Copyright:

Available Formats

CHE 631: Chemical Reaction

Department of Chemical Engineering, IIT Kanpur

R1 , R2 ,  , Rn 1 , Rn , Rm Micro & macro-radicals containing 1, 2, …, (n-1), n

These symbols will also represent the respective concentrations

Assuming pseudo-steady state for radicals

Substituting the expression for R:

 (ktc  ktd )R   k1M 1 

Evolution with time of various species,

Since, Rn  n1 R1- , Rm  m1 R1- 

You might also like