REACTION MECHANISM

Consider the gas-phase reactions 2NO2 + O3 N2O5 + O2 The forward reaction consist of the following steps NO2 + O3 NO3 + NO2 NO3 + O2..(1) 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 ] 2 k 2 [C ] 2 dt

d [C ] 2k 2 [C ]2 dt

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

step 4
d [C ] 0 dt

The total rate change of concentration of C

d[C ] k1[ A][B] 2k 2 [C ]2 2k 3 [ A][D] dt

The rates disappearance of A and B

d [ A] 2 k1[ A][B] k 2 [C ] k 3 [ A][D] dt

and
d [ D] k 2 [C ]2 k 3 [ A][D] dt

and

d[ E ] 2 k 4 [ B] dt

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

I2 I + CH3CHO CH3CO

2I HI +

The rate
d [ I ] 2k1[ I 2 ] k 2 [ I ][CH 3CHO] dt

parallel or concurrent-If a reactant can undergo two independent reactions concurrently

reversible -a particular elementary reaction occurs in both directions H2 + I2 2HI

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

and therefore
2 [ HI ]e k1 K [ H 2 ]e [ I 2 ]e k 1

The Rate Limiting Step Approximation

Let us assume that; NO2 + O3 NO3 + NO2 NO3 + O2..1 N2O5 ..2

that k2 >> k1 The slow first step is the rate-limiting or rate determining step

Example; O3 + M M..fast O + O3 ..slow Rate O2 + O + 2O2

1 d [O2 ] k 2 [O3 ][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 + (2) H2O2 + H2 (fast)

H2O2

(slow) 2H2O

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
Mechanism; N2O5 NO2 + NO3 NO + NO3

4NO2 + O2

NO2 + NO3 NO + O2 + NO2 2NO2

the steady state

Find the rate law using 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

(2)

(3) (4) 3. Insertion of eq (4) into (2)

(5)

5. Insertion of eq (5) into (1) (6)

6. Simplified eq (6)

Actual rate law

Where,

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][H 2 ] 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.

Answer
Identify the intermediates CH3 , CH3CO 2. Write an initial rate law
1.

(1) 3. Find an expression for intermediates in initial rate law

(2)

(3)
3.Combine eq (2) and (3)

(4) 4.Insertion of eq (4) into (1) (5) 5.Simplified eq (5)

Where,

Two mechanism for one reaction

Example : Consider a following reaction 2NO + O2 2NO2

Experimentally rate law;

d [ NO2 ] 2 k[ NO] [O2 ] dt

The two proposed mechanism;

1. NO + NO N2O2 + O2 2. NO + O2 NO + NO3 N 2O 2 2NO2 Fast Slow

NO3 Fast 2NO2 Slow

Effect of catalyst and temperature in reaction mechanism.

1. Temperature Consider the following reaction which occur at 250C 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, < 250C The rate law equation

d [CO2 ] 2 k[ NO2 ] dt

The proposed mechanism NO2 + NO2 NO3 + NO NO3 + CO CO2 + NO2

Slow Fast

2. Catalyst to accelerate the reaction by increasing the collision frequency Its 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+ Ce4+ + Mn3+ Mn4+ + Ti+

Ce3+ + Mn3+ Ce3+ + Mn4+ Mn2+ + Ti3+

dwimolecular collision.

Example :
The decomposition of peroxide Without catalyst; H 2O 2 2OH OH + H2O2 H2O + HOO HOO + H2O2 O2 + H2O + OH 2OH H2O2 OH + HOO H2O + O2

Catalyst; Fe2+ + H2O2 fast OH + H2O2 HOO + H2O2 2OH OH + HOO Fe3+ + OH

Fe3+

+ OH + OH

H2O + HOO O2 + H2O + OH H2O2 H2O + O2 Fe2+ + OH