Summary

Elementary (one step)

• Simple systems of elementary reactions reactions between stable
molecules are very rare.
• Open x Closed sequence of elementary steps Rather, a sequence of
elementary steps is
• Quasi Steady State Hypothesis necessary.
• Practically important examples
3. Systems of reactions. Reversible, parallel, consecutive reactions.
Complex reaction systems.

Examples
 Polymerization
 Catalytic and enzymatic reactions
 Combustion
 Catalytic reactions (homogeneous, heterogeneous)

Basic characteristics
 large number of species (N > 106 )
 complex mechanism
 effect of environment (e.g. effect of solid surface on reaction rate)
 highly exothermic or endothermic processes
Homework 3
Basic types of complex reactions To find c1(t), c2(t),c3(t) in the closed isotherm
1) Reversible reactions constant volume reaction system, in which the first
order irreversible consecutive reactions take place
2) Parallel reactions
A1  A2 rV 1  k 1 c1 t  0, c1  1 m ol/l, c 2  c 3  0
3) Consecutive reactions A2  A3 rV 2  k 2 c 2 t  (0; 5)
1 1
a ) k 1  2 m in , k 2  1 m in
1
b ) k 1  k 2  1 m in
c ) t opt for c 2
 A1  A2 rV 1  k 1 c1 t  0, c1  1 m ol/l, c 2  c 3  0
A 2  A3 rV 2  k 2 c 2 t  (0; 5)
HW 3 1
a ) k 1  2 m in , k 2  1 m in
1

1
b ) k 1  k 2  1 m in
c ) t o p t for c 2
LINEAR 1ST ORDER DIFFERENTIAL
S olu tion EQUATION INTEGRATION FACTOR
k1
a ) c 2  c1
o

k 2  k1
e  k1 t
e
 k2t

o  k1 t
b ) c 2  c1 k 1 t e

k 
ln  2  k2

k
 1  o
 k  k 2  k1
1
c ) k 1  k 2 , t opt   0.693, c 2 ( t opt )  c1  1   m ol/l
k 2  k1  k2  2
o
1 c1
k 1  k 2 , t opt   1, c 2 ( t opt )   0.368 m ol/l
k1 e

0.6

0.5 k1=2, k2=1

0.4

c2 0.3
mole/l
0.2 k1=1, k2=1
0.1

0
0 2 4 6
t/min
 Open x Closed sequence of elementary steps

• In the sequence of elementary steps, the reactants and products of these are not stable reactants or products
but are highly reactive intermediates.

• The reactive intermediates can be of several different chemical types : free radicals, free ions, solvated ions,
complexes at solid surfaces, complexes in homogeneous phase, complexes with enzymes.

• Many intermediates may be involved in a given reaction, however the advancement of the reaction can still
be described by means of a single parameter – extent of reaction or fractional conversion of key component.

• There are two types of sequences leading from reactants to products through intermediates: OPEN or CLOSED.

• An open sequence is one in which an intermediate is not reproduced in any other step of the sequence.

• A closed sequence is one in which an intermediate is reproduced so that a cyclic reaction pattern repeats itself
and a large number of molecules of products can be made through only one intermediate. (Catalysis)

O3( g ) O2( g )  O( g ) O 3 ( g )  C l( g ) C lO ( g )  O 2 ( g )
O3( g )  O( g )  2O 2( g ) C lO ( g )  O 3 ( g )  C l ( g )  2 O 2 ( g )
Open Closed
  (catalytic)
2 O 3 ( g )  3O 2 ( g ) 2 O 3 ( g )  3O 2 ( g )
 Quasi Steady State Hypothesis – QSSH

The concentrations of the intermediates remain low and constant  these

intermediate concentrations can be expressed using reactant and product
concentrations

Example
Fosgen (COCl2) is manufactured by gas phase reaction between CO and Cl2

CO(g) + Cl2(g)  COCl2(g)

It follows from experimental data :

3/ 2 3 1
rV  kc C O c C l2 [m ol.m .s ]

The proposed mechanism involves 2 intermediates Cl and COCl.

Reaction Kinetic equation

1. Cl2(g)  2Cl(g) 2
r1  k f ,1 c C l2  k b ,1 c C l
2. CO(g) + Cl(g)  COCl(g)
r2  k f , 2 c C O c C l  k b , 2 c C O C l
3. COCl(g) + Cl2(g)  COCl2(g) + Cl(g) r3  k f ,3 c C O C l c C l 2
 The balances of intermediates at steady state: Cl2 Cl CO COCl COCl2
R C l  2 r1  r2  r3  0  1 2 0 0 0
 
ν  0 1 1 1 0
R C O C l  r2  r3  0  
 1 1 0 1 1 

By adding above equations
2
2 r1  0  r1  k f ,1 c C l 2  k b ,1 c C l
1/ 2
 k f ,1 
cC l  c C l2 
 k
 b ,1 
Concentration of COCl:

R C O C l  r2  r3  k f ,2 c C O c C l  k b ,2 c C O C l  k f ,3 c C O C l c C l 2  0
1/ 2 1/ 2
 k f ,1   k f ,1 
 
1/ 2
k f ,2 c C O  c C l2  k f ,2   c C O c C l 2
k f ,2 c C O c C l  k b ,1   k b ,1 
cC O C l   
k b ,2  k f ,3 c C l 2 k b ,2  k f ,3 c C l 2 k b ,2  k f ,3 c C l 2
Rate of COCl2 production is given by equation (3) in which we substitute for COCl
concentration

1/ 2
 k f ,1 
 
3/ 2
k f ,3 k f , 2   c C O c C l 2
 k b ,1 
R C O C l 2  r3  k f ,3 c C O C l c C l 2 
k b , 2  k f ,3 c C l 2

If Cl2 concentration is low or k b , 2   k f ,3 is valid, we get

1/ 2
k f ,3 k f ,2  k f ,1 
   
3/ 2 3/ 2
R C O C l2    c C O cC l2  kc C O c C l 2
k b ,2  k b ,1 
1/ 2
k f ,3 k f ,2  k f ,1 
k   
k b ,2  k b ,1 
Validity of QSSH

Isothermal batch constant volume reactor

1/ 2
k f ,3 k f , 2  k f ,1  3 -1 3/2 -1
k     0.07 (m m ol ) s
k b , 2  k b ,1 
Kinetic parameters used in numerical simulation
Concentration profiles of COCl2
Homework 4 (due after Chapter 4)

Calculate volumes of CSTR a PFR working at 150 oC and 300 kPa to produce 1 t COCl2/day with CO
conversion equal to 95 %. A mixture of CO and Cl2 (molar ratio 1:1) is fed at 300 kPa and 150 oC.
Data
k(423 K) = 0.07 (m3mol-1)3/2.s-1
MCOCl2 = 98.92 kg/kmol.

Answer:

VCSTR = 0.053 m3 VPFR = 0.0021 m3

 c( N O )2
K1  2
c NO
Example
r2  k f ,2 c ( N O ) 2 c O 2  k b ,2 c N O 2  k f ,2 K 1 c N O c O 2  k b ,2 c N O 2  k f c N O c O 2  k b c N O 2
2 2 2 2 2
2NO(g) + O2(g)  2NO2(g)
E f ,2  r G1
o
 r S1
o
E f ,2   r H 1
o
 E f
   
Mechanism: k f  k f ,2 K 1  Aof ,2 e RT
e RT
 Aof ,2 e R
e RT
 Aof e RT

2NO(g)  (NO)2(g) equlibrium(1)  r S1

o

(NO)2(g) + O2(g)  2NO2(g) (2) Aof  Aof ,2 e R

, E f  E f ,2   r H 1
o

Max Bodenstein, 1941

Radical polymerization
Inicialization
k
I 
d
2R  rd  k d c I

R   M 
i
P1 
k
rinit  k i c R  c M

Propagation

P1   M 
p k
P2  r1  k p c P1  c M

P2   M 
p k
P3  r2  k p c P2  c M

. .
. .
kp
Pi 1   M  Pi  ri 1  k p c Pi 1  c M
. .

Termination

Pk   Pl   
t k
 Pk  l rt , k  l  k t c Pk  c Pl 
Intermediates
dc Pi  dc R 
 0
dt dt

Balance of initiator
2 rd  rinit  0
2 k d cI  kicRcM
2kd cI
cR 
kicM

Balance of P1 


R P1   rinit  r1  rt ,1  k i c R  c M  k p c P1  c M  k t c P1   c P j   0
j 1

Balance of Pk  , k  2, 3, ...


R Pk   k p c Pk 1  c M  k p c Pk  c M  k t c Pk   c P j   0
j 1

By summing the last equation from k=2,3,… and adding balance

equation of P1 
2 
   kicRcM 2kd cI
k ic Rc M  k t   c Pj    0
  c Pj 

kt

kt
 j 1  j 1
 Monomer consumption

 

R M   rinit  k p c M c Pj 
   kicRcM  k p cM c Pj  
j 1  j 1 
 2kd cI  2kd cI
   2kd cI  k p cM    k p cM
 kt  kt
 

Polymer Pn production
n 1
1 Homework 5: to justify these equations
R Pn 
2
 kc t Pn  k 
c Pk 
k 1

From balance of Pk 
k 1
k p c Pk 1  c M k p c Pk 1  c M 2kd cI  k p cM 
c Pk   c Pk     
k p cM  2kt kd cI k p cM  2kt kd cI k pcM  2 k t k d c I  k p c M  2 k t k d c I 

2 n2
1 n 1
( n  1) k t  2kd cI   k p cM 
R Pn  kc t Pn  k 
c Pk      
2 k 1 2  k p c M  2 k t k d c I   k p c M  2 k t k d c I 
 o
c M [m ol/dm ]
3
3.0 o
c I [m ol/dm ]
3
1.0x10-2
kd [s-1] 1.45x10-5 kt [dm3.mol-1.s-1] 1.2x106
3.5 1.4E-05
kp [dm3.mol-1.s-1] 4.4x102

3.0 1.2E-05

2.5 1.0E-05

2.0 8.0E-06

cM CPn cM

[mol/dm3] [mol/dm3]
n=25
1.5 6.0E-06

n=45

n=70
1.0 4.0E-06

n=100

0.5 2.0E-06

0.0 0.0E+00
0.E+00 5.E+03 1.E+04 2.E+04 2.E+04 3.E+04 3.E+04 4.E+04 4.E+04
t [s]
Summary
• Simple systems of elementary reactions
• Open x Closed sequence of elementary steps
• Quasi Steady State Hypothesis
• Practically important examples