CHAPTER 5

REACTION
KINETICS

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CHAPTER 5: REACTION KINETICS

5.1 Rate of reaction

1. Rate of reaction is the change in concentration of a reactant or a product with time.
2. Consider a reaction: A→B
3. The rate of reaction tells us how the concentration of the reactants decreases with time
d[A] d[B]
(- ) or how the concentration of the products increases with time ( ).
dt dt

4. Usually the units used for rate of reactions are mol dm-3 time -1
5. Let’s say the concentration of A changes as follows:

Rate of reaction at time t1 = gradient

of tangent at t1

6. Instantaneous rate at a particular time is determined by drawing a tangent at the time on

the graph and calculating its gradient.
7. The rate of reaction decreases with time because the concentration of reactants is
decreases with time
8. Average rate is a measure of the overall change of concentration of reactant/product over a
period of time.

Average rate for time to to x2

= overall change of [A] from to to x2 total time
𝐶𝑥 – 𝐶0
=
𝑥2 – 𝑡0

9. The shorter the time taken to complete a reaction, the higher the rate of the reaction

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Rate Equation & Order of Reaction
1. A rate equation shows how reactant concentration(s) affects the rate of a reaction.
2. For the reaction aA + bB → products, the rate equation is as follows:
Rate = k [A]m [B]n
m = order of reaction with respect to A
n = order of reaction with respect to B
m + n = overall order of reaction
k = rate constant
a and b = stoichiometric coefficients
3. Half-life, t1/2 of a reaction is the time taken for the initial concentration/ amount of the
reactant to be halved
4. Rate determining step is the slowest step in the reaction mechanism
5. Activation energy is the minimum energy required for a chemical reaction to occur
6. Catalyst is the substance that increases the rate of reaction by providing an alternative
reaction pathway with lower activation energy

Collision Theory
1. An effective collision is one where:
a) the reactants must collide in a correct orientation
b) the reactants must have a minimum amount of energy called the activation energy (Ea)
2. The factors affecting the rate of reactions are:
a) concentration of reactant (or pressure of gases): As concentration increases, the number
of particles per unit volume increases. The frequency of collision increases and therefore
the frequency of effective collision increases. This results a higher rate of reaction
b) size of solid reactant: Smaller size particles has larger total surface area exposed. The
frequency of collision increases and therefore the frequency of effective collision
increases. This results a higher rate of reaction
c) temperature: As temperature increases, the number of particles that have energy more or
equal to activation energy increases. The frequency of collision increases and therefore
the frequency of effective collision increases. This results in an increase in rate of reaction

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 d) catalyst: Catalyst provides alternative route by lowering the activation energy. More
reactant particles acquire activation energy. The frequency of effective collision increases.
This results a higher rate of reaction.

Question 5.1 [2020, Question 20]

The data for the decomposition of NO2 at 380 °C is shown below.
2NO2 (g) → 2NO (g) + O2 (g)
Time (s) [NO2]/ moldm-3
0.0 0.1000
5.0 0.0905
10.0 0.0820
15.0 0.0741
20.0 0.0671
30.0 0.0549
40.0 0.0448
50.0 0.0368
80.0 0.0200

a) Plot a graph of concentration of NO2 against time for the above reaction. Determine
the initial rate and the rate of formation of oxygen at 35 s. [7 marks]
b) Using collision theory, explain how the rate of reaction is affected by the following
factors:
i)The increase in the partial pressure of reactant [2 marks]
ii) The increase in temperature [3 marks]

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Suggested answer
1.a) Concentration of NO2/ mol dm-3

Time/s

The initial rate = gradient at time =0

= 0.1000-0.0700
10.0
= 3.00 x 10-3 moldm-3s-1
The rate at 35s = 0.0640 -0.0340
50.0 - 20.0
= 1.00 x 10-3 moldm-3s-1
b) i) As partial pressure increases, the number of particles per unit volume increases. The rate
of collision increases and therefore the number of effective collision increases/ more
collisions can overcome the activation energy. This results in an increase in rate of reaction

ii)As temperature increases, the kinetic energy of the reactant molecules increases. More
molecules acquire activation energy. The rate of collision increases and therefore the number
of effective collision increases/ more collisions can overcome the activation energy. This
results in an increase in rate of reaction

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5.2 Rate Law
1. Rate Law is an equation that gives the relationship between rate of a reaction and the
concentration of the reactants.
2. The order of a reaction can be determined by:
a) Initial Rate Method
b) Graphical Method (Integrated rate equation method- section 5.5)

The initial rate method

1. For the reaction aA + bB → products, we carry out two separate series of experiments,
one in which [A] is kept constant and [B] varied; the other in which [A] is varied and
[B] kept constant.
2. The initial rates for the two sets of experiments are then compared.
Experiment no. [A] / mol dm-3 [B] / mol dm-3 Initial rate / mol dm-3 s-1
1 0.100 0.010 2.4 x 10-3
2 0.100 0.040 9.6 x 10-3
3 0.300 0.010 2.16 x 10-2

Step 1: Write the general rate equation

rate = k [A]x [B]y

Step 2: Replace the value accurately in the rate equation based on the data given
Exp 1: 2.4 x 10-3 = k (0.100)x (0.010)y
Exp 2: 9.6 x 10-3 = k (0.100)x (0.040)y

Exp 1: 2.4 x 10-3 = k (0.100)x (0.010)y

Exp 3: 2.16 x 10-2 = k (0.300)x (0.010)y

Step 3: Determine the order of the reaction with respect to each reactant by solving the
simultaneous equation
x= 2
y=1

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 Step 4: Write the actual rate of reaction
Rate = k [A]2 [B]

Step 5: Determine the value of the rate constant, k if asked

Using experiment 1:
2.4 x 10-3 = k (0.100)2 (0.010)
k = 24 mol-2 dm6 s-1

Question 5.2 [2017, Question 20]

1. a) Define rate law for a chemical reaction [2 marks]
b) The combustion of nitrogen monoxide, NO produces nitrogen dioxide, NO2. The results of
three experiments carried out at constant temperature were given below.
Experiment [NO]/ mol dm-3 [O2]/ mol dm-3 Initial rate of reaction/ mol dm-3 s-1
1 0.800 0.160 6.62 x 10-4
2 0.200 0.160 4.14 x 10-5
3 0.800 0.320 1.33 x 10-3
i) Write the reaction equation for the combustion of nitrogen monoxide [1mark]
ii) Determine the rate law for the combustion of nitrogen monoxide and calculate the
rate constant [7 marks]
iii) Explain the effect on the reaction rate and rate constant when [NO] is tripled and [O2]
decreased eight times. [5 marks]
[2019, Question 17]
2. The reaction of nitric oxide with hydrogen at 1280 °C is given below.
2NO (g) + 2H2 (g) → N2(g) +2H2O (g)
Three experiments were carried out separately and the following data are collected.
Experiment [NO]/ mol dm-3 [H2]/ mol dm-3 Initial rate/ mol dm-3 s-1
1 1.0 x 10-2 2.0 x 10-3 5.0 x 10-5
2 1.0 x 10-2 4.0 x 10-3 1.0 x 10-4
-2 -3
3 2.0 x 10 8.0 x 10 8.0 x 10-4
a) Determine the order of the reaction with respect to H2 and NO [4 marks]
b) Write the rate equation for the reaction. [1 mark]
c) Calculate the rate constant, k. [2 marks]
d) Calculate the initial reaction rate when the concentration of both NO and H2 are 5.0 x 10-3
mol dm-3 [1 mark]

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Suggested answer
1) a) Rate law is an equation that gives the relationship between rate of reaction
and the concentration of reactant
b) i) 2𝑁𝑂 + 𝑂2 → 2𝑁𝑂2
ii) Let the rate equation be as follows:
𝑟𝑎𝑡𝑒 = 𝑘 [𝑁𝑂]𝑥 [𝑂2 ]𝑦
Exp 1 6.62 𝑥 10−4 𝑘 0.800𝑥 0.160𝑦
: 4.14 𝑥 10 −5 = 𝑘 0.200𝑥 0.160𝑦
𝐸𝑥𝑝 2
𝑥=2
Exp 3 1.33 𝑥 10−3 𝑘 0.320𝑦 0.160𝑦 0.800𝑥
: = 𝑘 0.160𝑥 0.160𝑦 0.800𝑥
𝐸𝑥𝑝 1 6.62 𝑥 10 −4
𝑦=1
The rate equation is:
𝑟𝑎𝑡𝑒 = 𝑘 [𝑁𝑂]2 [𝑂2 ]
Using experiment 1:
6.62 𝑥 10−4 = 𝑘 (0.800)2 (0.160)
𝑘 = 6.46 𝑥 103 𝑚𝑜𝑙 −2 𝑑𝑚6 𝑠 −1
iii) Let the original rate be r 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1
𝑟𝑎𝑡𝑒 = 𝑘 [𝑁𝑂]2 [𝑂2 ]
Under new condition:
1
New rate = k(3[NO])2 8[O2]
9
= 8 𝑘 [𝑁𝑂]2 [𝑂2 ]
9
= 8 r 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1
9
Rate of reaction increase by times
8
The rate constant remains unchanged because the temperature does not change
2) a) Let the rate equation be as follows
𝑟𝑎𝑡𝑒 = 𝑘 [𝑁𝑂]𝑥 [𝐻2 ]𝑦
Exp 2 1.0 𝑥 10−4 𝑘 (1.0 𝑥 10−2 )𝑥 (4.0 𝑥 10−3 )𝑦
: 5.0 𝑥 10 −5 = 𝑘 (1.0 𝑥 10−2 )𝑥 (2.0 𝑥 10−3 )𝑦
𝐸𝑥𝑝 1
𝑦=1
Exp 3 8.0 𝑥 10−4 𝑘 (2.0 𝑥 10−2 )𝑥 (8.0 𝑥 10−3 )
: 1.0 𝑥 10 −4 = 𝑘 (1.0 𝑥 10−2 )𝑥 (4.0 𝑥 10−3 )
𝐸𝑥𝑝 2
𝑥=2
It is first order with respect to [H2] and second order with respect to [NO]
b) 𝑟𝑎𝑡𝑒 = 𝑘 [𝑁𝑂]2 [𝐻2 ]
c) Using experiment 1:
5.0 𝑥 10−5 = 𝑘 (1.0 𝑥 10−2 )2 (2.0 𝑥 10−3 )
𝑘 = 2.5 𝑥 10−2 𝑚𝑜𝑙 −2 𝑑𝑚6 𝑠 −1
d) By substitution:
𝑟𝑎𝑡𝑒 = 𝑘 [𝑁𝑂]2 [𝐻2 ]
= (2.5 𝑥 10−2 )(5.0 𝑥 10−3 )2 (5.0 𝑥 10−3 )
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= 3.1 𝑥 10−9 𝑚𝑜𝑙𝑑𝑚−3 𝑠 −1

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5.3 The Effect of temperature on reaction kinetics
1. The relationship of the rate constant, k, with T and Ea is shown in the Arrhenius equation:
k = Ae –Ea/ R T
where A = Arrhenius constant
R = gas constant (must use the value 8.31 J mol-1 K-1),
Ea = activation energy (in J mol-1)
T = temperature in Kelvin
e –Ea/RT represents the fraction of reactant particles possessing sufficient energy for the reaction.
2. Modifying Arrhenius’equation we have:
𝐸𝑎 1
ln k = ln A - (𝑇 )
𝑅

3. Plot graph of ln k versus 1/ temperature

(K-1)

4. If Ea has a large value, then k is small. If Ea is small, k is large.

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Maxwell-Boltzmann Distribution
1. Explains the distribution of molecular energy
2. Based on distribution of energy among reacting molecules under different conditions

3. The effect of temperature

• As temperature increases, more molecules acquire activation energy resulting in the

increase of frequency of effective collision
4. The effect of catalyst

• When the catalyst is added, the activation energy is lowered.

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Question 5.3 [2015, Question 19]
Variation of the rate constant with temperature for the reaction is given in the table below
A → 2B +C
Temperature /K Rate constant, k/ s-1
298 1.74 x 10-5
308 6.61 x 10-5
318 2.51 x 10-4
328 7.59 x 10-4
338 2.40 x 10-3
1
a) By plotting a graph of ln k against 𝑇, determine the activation energy for the reaction above

[8 marks]
b) Based on the graph which you have plotted, calculate the half-life of the above reaction at
300K. [4 marks]

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Suggested answer
1
a) A graph of ln k versus 𝑇 gives a straight line with gradient that is equal to –Ea/RT

Temperature/K 1 Rate constant/ s-1 ln k

(𝑥 10−4 𝐾 −1 )
𝑇
298 33.6 1.74 x 10-5 -11.0
308 32.5 6.61 x 10-5 -9.62
318 31.4 2.51 x 10-4 -8.29
328 30.5 7.59 x 10-4 -7.18
338 29.6 2.40 x 10-3 -6.03
ln k

1/T (x10-4 K-1)

Arrhenius equation:
ln k = ln A - Ea/RT

Gradient = - [(10-6.5)/ (32.8-30.0) x 10-4]

= - 1.25 x 104
-Ea/R= -12.5 x 104
Ea= 1.04 x 105 Jmol-1/ 104 kJmol-1

b) At 300 K (1/T = 33.3 x 10-4 s-1)

ln k = -10.6
k= 2.4916 x 10-5s-1
using the expression:
t1/2 = ln 2/ k
= ln2 / 2.4916 x 10-5
= 2.78 x 104 s

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5.4 The role of catalysts in reactions
1. A catalyst provides an alternative route or pathway for a reaction via which the activation
energy required is lower. The result is a higher percentage of reactant particles having
Ea, hence a higher frequency of effective collisions.
2. Important features of catalysts
a) They do not alter the enthalpy change of a reaction.
b) They do not alter the stoichiometry of a reaction.
c) They may change the mechanism through which a reaction occurs
d) They may change the order of a reaction.
e) They are specific. Every reaction is catalysed by a particular catalyst.
f) Catalysts increase the value of the rate constant, k.
g) For reversible reactions, the catalyst alters the value of the rate constants, k1 and
k-1, for both the forward and backward reactions. ***
h) Catalysts cannot alter the concentrations of products and reactants (will not affect
the yield) in a reversible reaction, that is they do not alter the equilibrium constant,
Kc or Kp. ***Catalysts merely help to achieve equilibrium faster.
i) Catalysts are involved only temporarily in a chemical reaction; hence they emerge
again at the end of the reaction. Catalysts are recycled. This explains why only a small
quantity of catalysts is sufficient for a reaction.
3. Homogeneous catalysts - reactants and catalyst are in the same phase
4. Works by transition metal’s varying oxidation state
5. For example

a) Reaction is slow because the negative ions repel.

b) Reaction is faster with the presence of catalyst, Fe2+

6. Heterogeneous catalysts - the reactants and catalyst are not in the same phase.
7. Usually the catalyst is in the solid state, while the reactants are either liquids or gases.

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8. An example of heterogeneous catalyst is the conversion of sulphur dioxide to sulphur
trioxide in the Contact process given by the equation:

V2O5
2SO2 (g) + O2 (g) 2SO3 (g)
Diagram Explanation
SO2 and O2 diffused towards the active sites
on the catalyst, V2O5 surface

Adsorption: SO2 and O2 adsorbed on the

surface of the catalyst. This causes O-O bond
to weaken

The neighbouring SO2 and O2 molecules

form S-O bonds with one another

Desorption: The completed SO3 molecules

break away from the surface of the catalyst.
The surface of the catalyst is now free for
further of SO2 and O2 molecules

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9. Enzymes are biological catalysts made of proteins.
10. Enzymes work well only within a narrow pH and temperature range, their most
effective temperature being 37o C. At high temperatures enzymes become denatured.
11. An example of biological catalyst is maltase that catalyses the hydrolysis of maltose:

maltase
C12H22O11 (aq) + H2O (l) 2C6H12O6 (aq)
12. Oxidation of sulphur dioxide gas to sulphur trioxide catalysed by nitrogen dioxide gas
according to the following equation:
2SO2 (g) + O2 (g) + H2O (g) →H2SO4 (g)

a) The nitrogen dioxide, NO2 oxidises sulphur dioxide, SO2 to sulphur trioxide, SO3.
In this process, nitrogen dioxide, NO2 reduced to nitrogen monoxide, NO.
SO2 (g) + NO2 (g) → SO3 (g) + NO (g)

b) Then, the nitrogen monoxide, NO is converted to nitrogen dioxide, NO2 by reacting

with oxygen
2NO (g) + O2 (g) → 2NO2 (g)

c) Now, the nitrogen dioxide, NO2 is regenerated at the end of the reaction and
catalyses other molecules of SO2 and O2

d) Sulphuric acid is formed as tiny droplets in atmosphere and brought to the ground
by water known as acid rain

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Question 5.4
a) Using collision theory, explain how the rate of reaction is affected by the addition of
catalyst [2 marks]
b) Explain how Fe2+ ion catalyses the reaction between I- and S2O82- [5 marks]

Suggested answer
a) Catalyst provides alternative route by lowering the activation energy. Number of
molecules acquire activation energy increases. The number of effective collision increases/
more collisions can overcome the activation energy. This results in an increase in rate of
reaction
b) Fe2+ is a homogeneous catalyst.
It provides alternative pathway for I- and S2O82- to react as shown below:

Collision between two oppositely charged ions takes place easily (thus Ea is lowered)
compared to the collision between I- and S2O82- that require higher Ea to overcome the
repulsive force.

5.5 Order of the reactions and rate constants

a) Graphical method (Integrated rate equation method)
b) Integrated rate equations for zero order, first order and second order

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ii) Graphs for zero order, first order and second order
Order of the Zero order First order Second order
reaction
Graph of Rate
vs
concentration

Graph for the

[𝐴]0
integrated rate 𝑙𝑛
[𝐴]𝑡
equations Gradient = -k
Gradient = -k
Gradient = -k

[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0 [𝐴] 1 1

𝑙𝑛 [𝐴]0 = 𝑘𝑡 = 𝑘𝑡 +
𝑡 [𝐴] [𝐴]0

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 Graph of
Concentration Concentration
Concentration

vs time
Time
Time

𝑡1 is constant Second 𝑡1 = 2 first 𝑡1

2 2 2

Reaction Mechanisms
1. The rate of a chemical reaction is determined by the slowest step in the mechanism which
is known as the rate determining step.
2. Hence the order of a reaction is deduced from the slowest step of a mechanism.
3. Example 1: Consider the reaction mechanism as given below:

slow
2A + 3B → D + E …. Step 1

fast
A+E+C→F …. Step 2
4. Since step 1 is the slowest step, it is the rate determining step.
5. Hence, the rate equation is: 𝑅𝑎𝑡𝑒 = 𝑘 [𝐴]2 [𝐵]
6. The overall equation can be obtained by adding step 1 and step 2
2A + 3B → D + E …. Step 1
A+E+C→F …. Step 2
3A + B + C → D + F
7. Species E is the intermediate species which is unstable and short-lived

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Question 5.5
For the reaction of reagent X in solution to give products, the following data were obtained.
Time, t/min Concentration, [X]/moldm-3
0.0 0.58
9.0 0.34
12.0 0.26
14.0 0.22
18.0 0.17
20.0 0.13
24.0 0.12
a) Determine graphically the order of reaction [5 marks]
b) calculate the value of rate constant [2 marks]

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Suggested answer

[X]/ moldm-3

Labelled axes- 1
Points-1
Shape of the graph- 1

Since half-life, t1/2 is constant, the reaction is first order.

Mean t1/2 = 11.0 +9.0 +11.5/3
= 10.5 min
b) Rate constant, k = ln 2/ t1/2
= ln 2/ 10.5
= 0.066min-1

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