REACTION

MECHANISM
Consider the gas-phase reactions  
2NO2 + O3 N2O5 + O2

The forward reaction consist of the

following steps
 
NO2 + O3 NO3 + O2……..(1)
 
NO3 + NO2 N2O5……………(2)
The steps constitute the proposed
mechanism of the reaction.

NO3 is a reactive intermediate.

Step 1 and 2 - elementary

step/process
  Its classify by its molecularity-
◦ §     Unimolecular
◦ §     Bimolecular
◦ §     Termolecular
Reaction mechanism and Rate Law

H2 + I2 2HI
The mechanism cannot be
deduce from a rate law
A proposed mechanism consist of
elementary steps.
Rate Laws for consecutive, parallel
and reversible elementary reactions

Consider the set of elementary

reactions
1. A + B C
2. 2C A+ D
3. A + D 2C
4. 2B E
Step 1

d [C ]
 k1[ A][ B ]
dt
step 2

1 d [C ] d [C ]
  k 2 [C ] 2   2 k 2 [C ] 2
2 dt dt
Step 3

1 d [C ] d [C ]
 k 3 [ A][ D]  2 k 3 [ A ][ D ]
2 dt dt

step 4

d [C ]
 0
dt
The total rate change of
concentration of C
d[C]
 k1[A][B]  2k2[C]2  2k3[A][D]
dt

The rates disappearance of A and

B  d [ A]  k [ A][ B ]  k [C ] 2  k [ A][ D ]
1 2 3
dt
and

d [ D]
 k 2 [C ] 2  k 3 [ A][ D ]
dt

and
d[E ]
 k 4 [ B] 2

dt
consecutive reactions -which the
product of one reaction is the
reactant for the next
reactions 1 and 2

I2 2I
I + CH3CHO HI +
CH3CO
The rate

d [ I ]
 2k1 [ I 2 ]  k 2 [ I ][CH 3 CHO]
dt
parallelor concurrent-If a
reactant can undergo two
independent reactions
concurrently
 reversible -a particular
elementary reaction occurs in
both directions
H2 + I 2 2HI
d[H2 ] d[I 2 ] 1 d[HI]
    k1[H2 ][I 2 ]  k1[HI]2

dt dt 2 dt
Thus at equilibrium where [H2] =
[H2]e , [HI] = [HI]e;

d [ H 2 ] 1 d [ HI ]
   k1[ H 2 ]e [ I 2 ]e  k1[ HI ]e2  0
dt 2 dt

and therefore

[ HI ] e2 k1
  K
[H 2 ]e [I 2 ]e k 1
The Rate Limiting Step
Approximation
  Let us assume that;

NO2 + O3 NO3 +
O2……..1
NO3 + NO2 N2O5
……………..2

·        that k2 >> k1

The slow first step is the rate-
limiting or rate determining step
 Example;

O3 + M O2 + O +
M……..fast
O + O3 2O2
……..slow

1 d [O 2 ]
Rate  k 2 [ O 3 ][ O ]
2 dt
 Example:

Find the rate law for the forward rate of the

gaseous reaction.
2NO + 2H2 N2 + 2H2O
 
assuming the mechanism
(1) 2NO + H2 N2 + H2O2
(slow)
(2) H2O2 + H2 2H2O
(fast)
 The Steady State
Approximation Theory (SSAT)

d[I ] d[I ]

dt dt

d[I ]
0
dt
 Example:
The following mechanism is a gas-phase
reaction, proposed by Ogg. Stoichiometry:

2N2O5 4NO2 + O2
 
Mechanism;
N2O5 NO2 + NO3
NO2 + NO3 NO + O2 + NO2
NO + NO3 2NO2

Find the rate law using the steady state

approximation theory (SSAT)
 Answer
1. Identify the intermediates
NO and NO3

2. Write the initial rate law

(1)

3. Find the expression for intermediates in initial rate

law
Chain Reaction

The step consist of initiation,

propagation, termination and inhibition.
Br2 2Br Initiation
Br + H2 HBr + H Chain
H + Br2 HBr + Br
propagation
(-2)H + HBr H2 + Br

(-1)2Br Br2 Termination/chain

ending
 The net rate of HBr

d[HBr]
 k2[Br][H2 ]  k3[H ][Br2 ]  k4[H ][HBr]
dt
 Example
The proposed mechanism are for the
decomposition of ethanal (acetaldehyde)
into methane and carbon monoxide.

CH3CHO CH3 + CHO

CH3 + CH3CHO CH4 +
CH3CO
CH3CO CH3 + CO
CH3 + CH3 C2H6
Use steady-state approximation for the rate
law of formation of methane.
Two mechanism for one reaction

Example :
Consider a following reaction
 2NO + O 2NO2
2

Experimentally rate law;

d [ NO2 ]
 k[ NO ] [O2 ]
2

dt
The two proposed mechanism;

1. NO + NO N2O2
Fast
N2O2 + O2 2NO2
Slow

2. NO + O2 NO3 Fast
NO + NO3 2NO2
Slow
Effect of catalyst and temperature in
reaction mechanism.
 
1.     Temperature
Consider the following reaction
which occur at 250C
NO2 + CO CO2 + NO

The rate law equation

d [CO2 ]
 k[ NO2 ][CO]
dt
The proposed mechanism
NO2 + CO [N-O-O-C-O]‡
[N-O-O-C-O]‡ CO2 + NO

lower temperature, < 250C

The rate law equation
d [CO2 ]
 k[ NO2 ] 2

dt
The proposed mechanism
NO2 + NO2 NO3 + NO
Slow
NO3 + CO CO2 + NO2
Fast
2. Catalyst
to accelerate the reaction by
increasing the collision
frequency

It’s chemical properties does not

change before and after the
reaction.
Example:
The reaction between Ce4+ and
Ti+
Without catalyst ;
2Ce4+ + Ti+ 2Ce3+ +
Ti3+

a termolecular collision
With Mn2+ catalyst
Ce4+ + Mn2+ Ce3+ +
Mn3+
Ce4+ + Mn3+ Ce3+ +
Mn4+
Mn4+ + Ti+ Mn2+ +
Ti3+

dwimolecular collision.
 Example :
The decomposition of peroxide
Without catalyst;
H2O2 2OH
OH + H2O2 H2O + HOO
HOO + H2O2 O2 + H2O +
OH
2OH H2O2
OH + HOO H2O + O2
Catalyst;

Fe2+ + H2O2 Fe3+ + OH + OH

fast
OH + H2O2 H2O + HOO
HOO + H2O2 O2 + H2O + OH
2OH H2O2
OH + HOO H2O + O2
Fe3+ + OH Fe2+ + OH