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Rates of Reactions

Mechanism
Step 1: 2NO(g) → N2O2(g) (slow)
Step 2: N2O2(g) + O2(g) → 2NO2(g) (fast)
overall reaction 2NO(g) + O2(g) → 2NO2(g).
Species such as N2O2(g) that do not appear in the overall equation i.e. neither present at the
start as a reactant nor present at the end as a product are called intermediates.
A correct reaction mechanism must meet up with the following requirements:
-The sum of the elementary steps must give the overall balanced equation.
- The steps do not take place at the same rate. The rate determining step (slowest step) should
predict the same rate law as it is determined experimentally.
-All intermediates must cancel out as the elementary steps are summed up.
- An intermediate in the slow step does not appear in the rate law but replaced by the substances that
react to form it.
- If the slow step (rate determining step) is of the form: aX + bY → product, then the rate equation
for the reaction will be: Rate = k[X]a[Y]b if neither X nor Y is an intermediate.
-The catalyst must be regained in its initial form by the end.
Definition: The rate determining step of a reaction is the slowest step of the reaction.
Following the points above, the predicted rate expression or rate equation or rate law for the
reaction is: Rate = k[NO]2. This is because two molecules of NO appear in the slow step.
ACTIVITY 01: When a pure aluminium metal is dipped into a solution of copper (II) sulphate, the
overall ionic reaction that takes place is: 3Cu2+(aq) + 2Al(s) → 2Al3+(aq) + 3Cu(s). The reaction takes
place in two steps.

(a) What type of reaction is represented above? Explain.

(b) Suggest the two steps for the reaction
(c) What name is given to the two steps in (a) for the reaction: 3Cu 2+(aq) + 2Al(s) → 2Al3+(aq) + 3Cu(s)?
ACTIVITY 02: Consider the reaction between NO and O2 below that takes place in the following
two steps:
Equation for the reaction: 2NO(g) + O2(g) → 2NO2(g).
Mechanism
Step 1: 2NO(g) → N2O2(g) (slow)
Step 2: N2O2(g) + O2(g) → 2NO2(g) (fast)
overall reaction 2NO(g) + O2(g) → 2NO2(g).
(a) Suggest the main reason why the mechanism is correct.
(b) Suggest a rate equation for the reaction and give an explanation for your equation written.
(c) Identify an intermediate according to the reaction mechanism and explain why it is the
intermediate.
ACTIVITY 03: Consider the reaction between NO and O2 with a two step hypothetical mechanism
given below.
Equation for the reaction: 2NO(g) + O2(g) → 2NO2(g).
Mechanism
Step 1: 2NO(g) → N2O2(g) (fast)
Step 2: N2O2(g) + O2(g) → 2NO2(g) (slow)
overall reaction 2NO(g) + O2(g) → 2NO2(g).
(a) It is wrong to write the rate equation according to the mechanism above as:
Rate = k[N2O2][O2]. Explain.
(b) Write the correct rate equation and suggest a reason for the equation written.

ACTIVITY 04:
(a) The mechanism for a reaction with the rate equation: Rate = k[NO 2]2 is given below.
Mechanism
Step 1: NO2(g) + NO2(g) → NO(g) + NO3(g)
Step 2: NO3(g) + CO(g) → NO2(g) + CO2(g).
(i) Write down the overall equation for the reaction.
(ii) How would doubling the concentration of CO affect the rate of the reaction? Explain.

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A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
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Rates of Reactions

(iii) Identify an intermediate in the mechanism and explain why.

(iv) Identify the catalyst in the mechanism and explain why.
(v) Describe and explain the relative rates of steps 1 and 2.
(b) Fluorine combines with chlorine dioxide according to the balanced equation below.
F2(g) + 2ClO2(g) → 2FClO2(g).
The rate equation for the reaction is Rate = k[F2(g)][ClO2(g)]. Propose a mechanism for the
reaction.

ACTIVITY 04: The mechanism of a complex reaction is shown below.

Step I: 2NO(g) + H2(g) → N2(g) + H2O2(g) (slow)
Step II: H2O2(g) + H2(g) → 2H2O(g) (fast)
(a) Identify an intermediate.
(b) Write down a balanced overall equation for the reaction.
(c) Write down a rate expression for the reaction. Suggest a reason for your expression given.
(d) State and explain the effect on the rate of reaction on doubling the concentration of hydrogen gas .
(e) Suggest a reason why step I is the slowest step.

ACTIVITY 05: Iodine is liberated when hydrogen peroxide (H2O2) reacts with iodide ions in acidic
medium. The ionic equation for the reaction is: H2O2(aq) + 2H+(aq) + 2I–(aq) → I2(aq) + 2H2O(l).
Initial concentration of reactants
Exp’t [H2O2(aq)] /moldm-3 [H+(aq)] /moldm-3 [I–(aq)] /moldm-3 Initial rate in moldm-3s-1
1 0.01 0.01 0.01 1.75 x 10-6
2 0.02 0.01 0.01 3.50 x 10-6
3 0.01 0.01 0.04 7.00 x 10-6
4 0.01 0.02 0.01 1.75 x 10-6
(a) Using the data given above, deduce:
(i) State any two methods by which the progress of the above reaction can be followed. State
why the method chosen is suitable.
(ii) the order of the reaction with respect to reactant H2O2(aq).
(iii) the order of the reaction with respect to reactant H+(aq).
(iv) the order of the reaction with respect to reactant I–(aq).
(v) the overall order of the reaction.
(v) Write down the rate equation for the reaction.
(b) The mechanism proposed for the reaction is:
Step I: H2O2(aq) + I–(aq) → H2O(l) + IO–(aq), (slow step)
Step II: IO–(aq) + H+(aq) → HOI(aq), (fast step)
Step III: HOI(aq) + H+(aq) + I–(aq) → I2(aq) + H2O(l) (fast step)
(i) Suggest a rate equation in accordance with the reaction mechanism.
(ii) Is the above mechanism consistent with the experimental data in the table above for the
reaction? Suggest two reasons to support your answer.
Reasons:
(i) Write down a rate equation for the reaction considering step II to be the slow step.
(ii) Write down a rate equation for the reaction considering step III to be the slow step.
ACTIVITY 06:
An energy profile diagram for a reaction with multiple step mechanism is given below.
(a) How many steps make up
the reaction mechanism?
Explain.
(b) Is the reaction exothermic or
endothermic? Explain.
(c) Which step in the
mechanism is the rate
determining step? Explain.

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A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
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Rates of Reactions

ACTIVITY 07:
The mechanism proposed for the reaction is:
Step I: ClO–(aq) + H2O(l) → HOCl(aq) + OH–(aq).
Step II: Br–(aq) + HOCl(aq) → HOBr(aq) + Cl–(aq).
Step III: HOBr(aq) + OH–(aq) → BrO–(aq) + H2O(l).
(a) Write down the overall balanced equation for the reaction.
(b) What general name is given to the three steps I. II and III put together? Explain.
(c) Identify the intermediates and explain your choice of answer.
(d) What is the function of water in the mechanism? Explain.

Differences between activated complex and intermediate

Activated complex Intermediate
1 It is short-lived. It has a time limit
2 It occurs at a maximum potential energy It occurs at a minimum potential energy
It exists part way in every step of a reaction It is formed in one step and consumed in
3
the other
Molecularity
Each step of a reaction has number of particles colliding. This number of particles colliding
in that step is called the molecularity of that step.
Definition: Molecularity of a reaction is the number of reacting species that collide to form
the activated complex.
If an elementary step involves only one molecule, then the reaction will be called
unimolecular e.g SN1 in organic reactions. If two molecules collide in an elementary step to
form the activated complex, then the reaction is termed bimolecular e.g SN2 in organic
reactions. If three molecules collide in an elementary step to form the activated complex,
then the reaction is termed termolecular. Some elementary step reactions are shown below
and their respective molecularities.
A→P e.g N2O4(g) → 2NO2(g) Unimolecular
2A → P e.g 2NO2(g) → N2O4(g) Bimolecular
A+B→P e.g N2O2(g) + O2(g) → 2NO2(g) Bimolecular
3A → P e.g Termolecular
2A + B → P e.g 2NO(g) + O2(g) → 2NO2(g) Termolecular
A+B+C→P e.g Termolecular

Termolecular reactions are rare because the probability of three or more particles colliding
at the same time with the right energy and right orientation is very rare.
Differences between order of a reaction and molecularity of a reaction
Comparison between order and molecularity of a reaction is shown on table 12.11 below.
Table 12.11
Order of a reaction Molecularity of a reaction
It is the sum of the powers of the It is the number of reacting species
1 concentration terms in the rate equation. undergoing simultaneous collisions in the
elementary or simple reaction
2 It is determined experimentally It is a theoretical concept
3 It can be a fraction or a whole number: ½,1... It is usually a whole number like: 1, 2, .....
4 It can be zero for a reaction It cannot be zero for a reaction
5 It can be 3 or more It is rarely 3 or greater than 3.

Order of a reaction (overall order) should not be confused with order of a reaction with
respect to a particular reactant.

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A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N