Mechanisms of

reactions
Rates of chemical Reactions
Mechanisms of Reactions
An elementary reaction: An elementary step is an equation that
describes an actual molecular level reaction.

 Mechanism: A description of the sequence of elementary steps by

which a reaction occurs is called the mechanism for the reaction.
 The sum of the elementary steps must give the overall balanced
equation for the reaction. If this happens the mechanism is said to
be plausible (not proven).
 One way to check this is to add the sequence of elementary steps
for the reaction. If the sum yields the overall equation for the
reaction than the reaction is plausible.

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Example
 The overall reaction that describes the decomposition of ozone is
2O3(g) → 3O2(g)
 One proposed mechanism involves two steps.
Step1: O3 →O2 + O
Step 2: O + O3 →2O2
 Adding steps 1 and 2 gives the overall equation for the reaction
2O3(g) → 3O2(g)

 In this mechanism, oxygen is a reaction intermediate. It is

produced in the first step, and consumed in the second, and is not
observed among the products in the overall reaction.
Intermediates generally do not appear in the overall rate law of
the reaction.

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Graph showing intermediate

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Examples
1.The reaction of nitrogen dioxide with fluorine to form nitrosyl
fluoride, NO2F.
 The following mechanism has been proposed:
NO2(g) + F2(g) → NO2F(g) + F(g) Step 1
NO2(g) + F(g) → NO2F(g) Step 2
 a) Determine whether the mechanism is correct.
 b) Identify any intermediates.

2. Consider the mechanism of the following reaction

NO2 + NO2 → NO3 + NO Step 1
NO3 + CO → NO2 + CO2 Step 2
 Write the overall equation for the reaction
 Identify the intermediate in the reaction and explain your choice

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DEDUCTION OF RATE LAWS FROM
ELEMENTARY REACTIONS
Deduction from a single step elementary reaction
 For a one- step elementary reaction, the coefficients of the
reactants constitute the orders with respect to these reactants.
A + 2B →C + D
 The coefficients of A is 1, while that of B is 2, thus the rate
expression is

 Rate = k[A][B]2

Try: The reaction of carbon monoxide with nitrogen(IV)oxide

occurs in one step at 500K:
CO+NO  NO+CO
2 2

 Deduce the rate expression for this reaction.

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Deduction of rate law from reactions
involving multiple steps
 When a reaction takes place through a series of steps, the
coefficients of the reactants in the rate determining slow step are
the orders of the reaction, and these appear in the rate
expression.
 1. If the slow rate determining step is the first step, the orders
with respect to the reactants are read directly from the
coefficients in the rate determining step.

 II. If the slow rate determining step is not the first step, but
involves an intermediate, the intermediate must be expressed in
terms of the reactants before the actual rate expression can be
derived.

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Example 1. Slow first step
 Nitrogen(IV) oxide reacts with carbon monoxide gas to produce
NO and CO2 according to the equation,
 NO2 + CO →NO + CO2
 The following mechanism has been proposed:

2NO 
 NO +NO(slow)
2
k1
3

3

NO +CO  NO +CO

K2

2 2
k -2

 Deduce the rate expression for this reaction

 Solution
 The first step is slow. Thus the rate of the reaction depends only
on the first step.The coefficients in this first step represent the
orders with respect to the reactants. Thus the rate law is
 Rate = K[NO2]2

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TRY
Consider the reaction of NO with F2 to form ONF:
2NO(g) + F2(g) → 2ONF(g)

The following mechanism has been proposed

NO + F2 → ONF + F Step1 Slow
NO + F → ONF Step 2 Fast

 Deduce the rate expression and the overall equation for the
reaction.

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Deduction of rate law from reactions
involving multiple steps
 When a reaction takes place through a series of steps, the
coefficients of the reactants in the rate determining slow step are
the orders of the reaction, and these appear in the rate
expression.
 1. If the slow rate determining step is the first step, the orders
with respect to the reactants are read directly from the
coefficients in the rate determining step.

 II. If the slow rate determining step is not the first step, but
involves an intermediate, the intermediate must be expressed in
terms of the reactants before the actual rate expression can be
derived.

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Multistep reactions involving
intermediates in the rate determining step
 The intermediate is eliminated from the final rate expression, by
expressing the concentration of the intermediate in terms of the
stable reactants.
 Consider the reaction A + B →2D
 That takes place in two steps in which the slow step involves an
intermediate:

Step1:A X

k1

k -1
fast

Step 2:B+X 
 2D Slow
k2

 The rate of the reaction will be determined by the slow second

step:
 Rate = k2[B][X]
 But X is not a reactant in the equation for the reaction, hence
must be eliminated in the rate equation.

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How to eliminate X
 For the reversible reaction in step 1,
 Rf = k1[A] Rf = rate of forward reaction Equation 1
 Rr = k-1[X] Rr = rate of reverse reaction Equation 2

 For a reversible reaction at equilibrium, the rate of the forward

reaction is equal to the rate of the reverse reaction

 k [A]=k [X] equation 3

1 -1

 We then express the concentration of the intermediate X in

terms of the concentration of A by making [X] the subject of
equation 3.

k [A]
[X]  1

k 1

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 The overall rate of the reaction is determined by the slow rate
determining step 2 as above
 Rate = k2[A][X]
 Substituting the value of [X] into this equation eliminates it.

k [A]
Rate  k 2
1
[B]
k 1

 Combining all the constant into one rate constant K, gives the
rate as
 Rate = k[A][B]

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 END

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