You are on page 1of 24

Module II

Reaction Mechanisms for


non-elementary reactions
Dr. Udaya Bhaskar Reddy Ragula
Associate Professor
Department of Chemical Engineering & Materials Science
Amrita Vishwa Vidyapeetham
Coimbatore 641 112
u_bhaskarreddy@cb.amrita.edu

1
Reaction Mechanisms
 Reaction mechanism is the
path followed by the reaction to
convert reactants to products
A   R  Elementary rxn. A   B  R
k k1 k2

 rA 
dC A  Elementary 
dt dC A
 rA 
For a first order reaction dt
 rA  kC A For a first order reaction
rR  kC A  rA  k1C A
rB  k1C A  k 2C B
2 rR  k 2CB
Single and Multiple Reactions
 Series Reactions
 A →B →R
 Parallel Reactions
 A →B
 A →R
 Series-parallel reactions
 A+B → R
 A+R→ S

 Reaction is in series with respect to R and parallel


with respect to A

3
Why non-elementary reactions
exist?
 As discussed in Transition state theory,
intermediates will be formed during the
reaction.
 The rate of formation of intermediates cannot
be measured (Because of their high
reactivity)
A2  B2  2 AB
Re action mechanism for a non  elementary reaction
A2  2 A *
A *  B2  AB  B *
A *  B*  AB

4
A *&B * are intermediates
Types of intermediates
 Free radicals
.
 CH3 , C2H5
.
 Ions and polar substances
 Na+, Cl-, CH3COO-
 Molecules
 A → B → R (If B is highly reactive, then its
existence cannot be measured)
 Transition Complexes
 Unstable form or Unstable association of
molecules

5
Reaction mechanisms for
formation of intermediates
Non-Chain mechanism

Reactants  Intermediates * Initiation 


Intermediates*  Products Termination 

Chain mechanism
Reactants  Intermediates * Initiation 
Intermediates *  Reactants  Products  Intermediates * Propagation 
Intermediates*  Products (Termination)

6
Free radicals in a chain
reaction -1
H 2  Br2  2 HBr
The experimental rate of reaction is found to be
k1[ H 2 ][ Br2 ]1/ 2
rHBr 
[ HBr ]
k2 
[ Br2 ]
This involves the formation of Intermediates H  and Br 
The following mechanism has been proposed
Br2 
k1

k 1
2 Br 
Br   H 2 
k2

k 2
HBr  H 
H   Br2 
k3
HBr  Br 

7
Free radical chain mechanism
-1 contd..
rHBr  k 2 [ Br  ][ H 2 ]  k  2 [ HBr ][ H  ]  k3 [ H  ][ Br2 ]
Since , the [ H  ] & [ Br  ] cannot be measured
[]  Concentration of the substance
[ H  ] & [ Br  ] in terms of [ H 2 ], [ Br2 ] and [ HBr ]
Pseudo  Steady State Hypothesis
rH   0 & rBr   0
rH   k 2 [ Br  ][ H 2 ]  k  2 [ HBr ][ H  ]  k3 [ H  ][ Br2 ]  0
rBr   k1[ Br2 ]  k 1[ Br  ]2  k 2 [ Br  ][ H 2 ]
 k  2 [ HBr ][ H  ]  k 3 [ H  ][ Br2 ]  0

8
Free radical chain mechanism-
1 contd..

rH   rBr   k1[ Br2 ]  k 1[ Br  ]2  0


k1
k 1[ Br  ]2  k1[ Br2 ]  [ Br  ]  [ Br2 ]
k 1
rH   k 2 [ Br  ][ H 2 ]  k  2 [ HBr ][ H  ]  k3[ H  ][ Br2 ]  0
 [ H  ]k  2 [ HBr ]  k3[ Br2 ]  k 2 [ Br  ][ H 2 ]
 k 2 [ Br  ][ H 2 ]
 [H ] 
k 2 [ HBr ]  k3[ Br2 ]

9
Free radical chain mechanism
– 1 contd..
Substituting [ Br  ]
k1
k2 [ Br2 ] [ H 2 ]
k 1
[H  ] 
k 2 [ HBr ]  k3[ Br2 ]
Substituting [ H  ] &[ Br  ] in rHBr

[ Br2 ][ H 2 ]  k3 [ Br2 ]  k  2 [ HBr ][ H  ]


k1
rHBr  k 2
k 1
k1
k2 [ Br2 ] [ H 2 ]
k 1
[ Br2 ][ H 2 ]  k3 [ Br2 ]  k  2 [ HBr ]
k1
rHBr  k 2
k 1 k 2 [ HBr ]  k3[ Br2 ]
10
Free radical chain mechanism-
1 contd..

k1  k3 [ Br2 ]  k  2 [ HBr ] 
rHBr  k 2 [ Br2 ][ H 2 ]
 1  
k 1  k  2 [ HBr ]  k3 [ Br2 ] 

k1  2k3[ Br2 ] 
rHBr  k 2 [ Br2 ][ H 2 ]
 k [ HBr ]  k [ Br ] 

k 1  2 3 2 
 Through out by [ Br2 ]
 
 
[ Br2 ][ H 2 ] 
k1 1
rHBr  2k 2 k3
k 1  k  2 [ HBr ] 
 k3  
 [ Br2 ] 

11
Free radical chain mechanism-
1 contd..
Rearranging above equation
k1 k k1
2 k 2 k3 [ Br2 ]1 / 2 [ H 2 ] 2 2 k3 [ Br2 ]1 / 2 [ H 2 ]
k 1 k 2 k 1
rHBr   rHBr 
k [ HBr ] k3 [ HBr ]
k3   2 
[ Br2 ] k 2 [ Br2 ]
c1[ Br2 ]1 / 2 [ H 2 ]
rHBr 
[ HBr ]
c2 
[ Br2 ]
k2 k1 k
Where , c1  2 k3 & and c 2  3
k 2 k 1 k 2

12
Free Radical Chain
mechanism -2
Thermal Decomposition of EthaneC 2 H 6 
Products : Hydrogen , Methane , Ethylene, and Butane
The mechanism proposed is
Initiation
2CH 3
k
C 2 H 6 
1

Propagation
CH 3  C 2 H 6  CH 4  C 2 H 5
2 k

C 2 H 5  C2 H 4  H 
k 3

H   C 2 H 6  H 2  C 2 H 5
4k

Termination
2C 2 H 5 
5k
C 4 H10
Determine the rate expression for the formtion of Ethylene

13
Free Radical Chain
mechanism -2 contd…

Solution
Free radicals that are being formed C 2 H 5 , CH 3 , H 

rC 2 H 4  k3 C 2 H 5 
 k CH C   k3 C 2 H 5  k 4 H  C 2 H 6   k5 C 2 H 5   Eqn.  1
 2
rC  2 3 2H6
2 H5

rCH   
 k1C 2 H 6   k 2 CH 3 C 2 H 6  Eqn.  2 

   
3

rH   k3 C 2 H 5  k 4 H  C 2 H 6  Eqn.  3
According to PSSH , rC   0, rCH   0 & rH   0
2 H5 3

14
Free Radical Chain
mechanism -2 contd…
From Eqn. 3
   
0  k3 C 2 H 5  k 4 H  C 2 H 6   k 4 H  C 2 H 6   k3 C 2 H 5    
H   kk CC HH 

 3 2 5
4 2 6
From Eqn. 2 
  
0  k1 C 2 H 6   k 2 CH 3 C 2 H 6   k 2 CH 3 C 2 H 6   k1 C 2 H 6  
CH   kk3
 1
2


Substituting , H  & CH 3 in Eqn. 1   
   
0  k 2 CH 3 C 2 H 6   k3 C 2 H 5  k 4 H  C 2 H 6   k5 C 2 H 5    
2

15
Free Radical Chain
mechanism -2 contd…

0  k2
k1

C 2 H 6   k3 C 2 H 5  k 4


k3 C 2 H 5   
C 2 H 6   k5 C 2 H 5 
2

k2 k 4 C 2 H 6 

0  k1C 2 H 6   k5 C 2 H 5  
2


k5 C 2 H 5 
2
 k1C 2 H 6 

C 2 H5

 k1
k5
C 2 H 6 

 
rC 2 H 4  k3 C 2 H 5  rC 2 H 4  k3
k1
k5
C 2 H 6 

16
Problems on non-elementary
kinetics
Showthat the following scheme

N 2O5 
k

k
NO2  NO3
1
2


NO3 
k
NO   O2 3


NO3  NO  
k
2 NO2 4

proposed is consistent with the obesrved first order decomposition of N 2O5


Solution
rN 2 O5
  k1 N 2O5   k 2 NO2  NO3  


Intermediates  NO3 &NO 
According to PSSH , rNO   0 & rNO  0 

     NO 1
3

 k1 N 2O5   k 2 NO2  NO3  k3 NO3  k 4 NO3


   
rNO 

   NO 2
3

 
rNO  k3 NO3  k 4 NO3

17
Problems on non-elementary
kinetics contd..

From 2 

0  k 3 NO3  
 k NO NO   NO   kk
4 3
   3

From 1

0  k1 N 2O5   k 2 NO2  NO3   k NO  k NO  kk



3 3

4 3
 3

0  k1 N 2O5   k 2 NO2 NO  2k NO 


3

3 3

NO k NO   2k   k N


3

2 2 3 1 2 O5 
N O 
NO   k kNO
 1 2 5
3
  2k 
2 2 3

18
Problems on non-elementary
kinetics contd..


Substituting NO3 in



rN 2O5  k1 N 2O5   k 2 NO2  NO3


k1 N 2 O5 
rN 2O5  k1 N 2O5   k 2 NO2 
k 2 NO2   2k3 
 k 2 NO2  
rN 2O5  k1 N 2O5 1  
 k 2 NO 2   2 k 3 

2k1k 3 N 2O5 
rN 2O5 
k 2 NO2   2k 3

19
The Rate Determining Step
 This depends on the values of reaction rate
constants
 The rate determining step is the slowest step in
a series or series-parallel reaction.
 If the reaction is non-elementary, the step in
which an intermediate with highest energy
formed is the rate-determining step
 It doesn’t mean that rate-determining step is
always the forward reaction in a reversible
reaction, It could also be the reverse step
 There could be some other processes like
external diffusion, product desorption in a
catalytic system.

20
Guidelines for Formulating a
Mechanism
 The number of elementary reactions employed
must be sufficient to provide a complete path
for the formation of all observed products.
 All the intermediates produced by the
elementary reactions must be consumed by
other elementary reactions so that there will
be no net production of intermediate species.
 The majority of known elementary steps are
bimolecular, the remainder being
unimolecular.
 A postulated mechanism for a reaction in the
forward direction must also hold true for the
reverse reaction.

21
Guidelines for Formulating a
Mechanism contd…
 In general, the transitory intermediates involving highly reactive
species do not react preferentially with one another rather, they try
to react with stable species (Except in the termination step).
 When the overall order of a reaction is greater than three, the
mechanism probably has one or more equilibria and intermediates
prior to the rate-determining step. (Formation of the Product)
 Inverse orders (during product formation) arise from rapid
equilibria during rate determining step. This means that there
exits a faster reaction equilibrium during product formation.
 A higher order for a particular species tell us that more than one
molecule is combining before the rate determining step
 Whenever a rate law contains non-integers orders, there are
intermediates present in the reaction sequence. When a fractional
order is observed in an empirical rate expression for a
homogeneous reaction, it is often an indication that an important
part of the mechanism is the splitting of a molecule into free
radicals or ions.

22
Guidelines for Formulating a
Mechanism contd…
 If the magnitude of the Stoichiometry coefficient of a reactant
exceeds the order of reaction w.r.to species, there are one or
more intermediates and reactions after the rate determining
step. Before applying this rule, the stoichiometric equation
must be formulated for the reaction such that all coefficients
are integers.
 If the order of a reaction with respect to one or more species
increases as the concentration of those species increases, it is
an indication that the reaction may be proceeding by two or
more parallel paths.
 If there is a decrease in the order of a reaction with respect to
a particular substance as the concentration of that species
increases, the dominant form of that species may be
undergoing a change caused by the change in concentration
 A decrease in reaction order with respect to hydrogen ion
concentration with increasing acidity has frequently been observed
for reactions involving weak acids.
23
Ozone Decomposition
Reaction

Propose a mechanism for the Ozone decomposit ion


which is in consistent with the rate law
 rO3  k O3 2 O2 1

Note : Please refer to the guidelines on formulation of


reaction mechanism

24