KINETICS

Kinetics is the study of the movement of reacting particles (substances). For

substances to react together.

(a) They must collide with one another.

(b) They must have sufficient energy.
(c) They must collide in correct or proper orientation.

If particles with less energy collide, they will not react to form a new substance even
if the orientation is correct. Such particles bounce back and only react if all the
factors listed above are achieved.

Rate of Chemical Reaction

Rate of chemical reaction is the change in concentration of a reactant or product in a

unit time.

change in concentration of reac tan t

Rate 
change in time

change in concentration of product

Rate 
change in time

When a chemical reaction is taking place the concentration of the reactant

decreases and that of the product increases, therefore, rate can be defined as the
decrease in concentration of the reactant in a unit or time increase in the
concentration of the product in a unit time.

decreasein concentration of reac tan t

Rate 
time

increase in concentration of product

Rate 
time

If the concentration is in mol dm3 and time in seconds, then the units of rate of
reaction are mold dm3s1.

Example

The concentration of hydrochloric acid decreased from 20 mol dm3 to 0.5 mol dm3
in a reaction with calcium carbonate. The reaction lasted 1 minute. Calculate the rate
of the chemical reaction.

2.0 mol dm 3  0.5 mol dm 3

Rate 
60 sec

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 1.5 mol dm 3

60 sec

 0.025 mols dm3 s 1

Factors that affect the rate of reactions

For a chemical reaction to occur, there must be collisions between the particles.
Therefore, any factor which will affect the frequency of collisions between the
particles, will have an effect on the rate of reaction. The following are the factors that
affect the rate of reaction:

a. Temperature
b. Concentration
c. Surface area
d. Catalyst
e. Pressure
f. Light

(a) Temperature

Increasing the temperature increases the rate of a chemical reaction because,

the particle gain more kinetic energy hence frequency of collisions increases
and more particles overcome the activation energy (energy barrier).

(b) Concentration

Concentration is the number of particles in a unit volume of solution.

Number of particles
Conc 
Volume

n m
C or C 
v v

Increasing the concentration of a solution increases the rate of the chemical

reaction because there are more particles present in a limited volume and the
particles collide more frequently with other reaction substances.

Example

1. Two students carried out an experiment to determine the rate of reaction.

- Student A reacted 1 g of magnesium ribbon with an excess of 2 M

hydrochloric acid.
- Student B reacted 1 g of magnesium ribbon with an excess of 1 M
hydrochloric acid.

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 The two students were asked to sketch their results on the same grid by
plotting the volume of hydrogen gas collected against time.

The sketch was as shown below:

A
Volume of
hydrogen
B
gas
collected

Time
Study the two reactions below and sketch the graph on the same grid
provided.

Reaction 1

10 g of produced calcium carbonate was reacted with 100 cm3 of 1 M

hydrochloric acid.

Reaction 2

10 g of produced calcium carbonate was reacted with 100 cm 3 of 2 M

hydrochloric acid. The equation of the reaction is

CaCO3 + 2HCl  CaCl2 + H2O + CO2

(c) Surface Area

Surface area of a substance is the surface that is exposed to react with other
substances. Increasing the surface area, increases the rate of a chemical
reaction because reacting particles collide more frequently. Surface area is
only applicable to substances in solid state e.g. two students carried an
experiment to determine the rate of the reaction between marble chips and
dilute hydrochloric acid.

CaCO3 + 2HCl  CaCl2 + H2O + CO2

- Student 1 used 2 g of a lump of marble chips and reacted it with 100

cm3 of 0.2 M hydrochloric acid.
- Student 2 used 2 g of powdered marble chips and reacted it with
100 cm3 of 0.2 M hydrochloric acid.

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 Sketch the graphs of the results for the two reactions on the same grid and
interpret the graphs.

Reaction 2

Volume of
CO2 Reaction 1
collected

t2 t1
Time

- The reaction 2 is faster than reaction 1 because powdered marble

chips have a larger surface area than the lumps of marble chips.
- The volume of CO2 collected by both students is the same because
they used the same quantity of the reactant.
- The slope at the beginning is steeper because there are more particles
to be reacted at the beginning of the reaction.

(d) Catalyst

A catalyst is a substance that alters the rate of a reaction without itself being
permanently changed chemically.

A catalyst that speed up the rate of the chemical reaction is called a promoter.
A catalyst that slows down the rate of a chemical reaction is called an
inhibitor.

A catalyst participates in a chemical reaction by bringing the reacting

substances together and form a low energy activated complex. The activated
complex is an intermediate (transmission) substance in a chemical reaction.
Once the catalyst has achieved its purpose it come out of the activated
complex chemically unchanged.

Characteristics of Catalysts

i. They are usually transition metals or compounds of transition metals.

ii. They are required in very small amounts to take up little space.
iii. They remain unchanged chemically after the reaction.
iv. They usually speed up the rate of the chemical reaction.
v. They are specific in their action i.e. there is the universal catalyst.

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(e) Pressure

Pressure affects substances that are in gaseous state. It has no effect on

solids, liquids and aqueous solutions.

Increasing the pressure of gaseous particles increases the concentration

because the particles are compressed in a small volume. This increases the
frequency of collisions between particles and hence increasing the rate of a
chemical reaction.

(f) Light

Certain chemical reactions are catalysed by light. Such chemical reactions are
called photo catalysis reactions e.g.

- Substitution reactions of alkanes.

- Photosynthesis
- Photography etc.

Increasing the intensity of light for photo catalysis reactions, increase the rate
of a chemical reaction.

Note: One or more of the factors listed above can affect the rate of a
particular
chemical reaction e.g. list down the factors that can affect the reaction
below.

CaCO3 (s) + 2HCl (aq)  CaCl2 (aq) + H2O (l) + CO2 (g)

- Surface area of CaCO3

- Concentration of HCl
- Temperature
- Catalyst

Pressure cannot affect the above reaction.

Measuring the Volume of Gas in a Reaction.

The rate of a chemical reaction in which a gas is produced can be monitored

by using the volume of the gas at regular time intervals. The volume of gas
can be collected using

a. Gas syringe
b. Graduated gas jar

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Illustrations

The rate of a chemical reaction can also be monitored by measuring the

decrease in mass of the reaction mixture if the gas produced is allowed to
escape. The decrease in mass is measured at time intervals to obtain a series
of results. The following apparatus is used

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Other Methods of determining rate of reactions

(a) Titrimetric analysis

Titrimetric analysis is an analytical method used to determine the rate of a

chemical reaction. In this process small portions of the reaction mixture
called aliquots are removed using a leaf pipette. The aliquots are reacted
with other substances in to stop them from undergoing any further change
in concentration. This process is called quenching. The quenched aliquot
are titrated with a standard solution to determine their concentration and
then the rate of reaction.

(b) Calorimetric analysis

Calorimetric analysis is used to monitor the rate of reaction in which there

is a coloured reactant or coloured product. A photoelectric calorimeter is
used to measure the colour of the substance. The intensity of the colour is
related to the concentration of the substance. If the concentration of either
the reactant or product is known at a particular time, then the rate of a
chemical reaction can be calculated.

(c) Conductimetric analysis

Conductimetric analysis is used to measure the rate of chemical reactions

in which there are mobile ion such as aqueous or molten ionic compounds.
The number of ions in solution is related to the concentration of the
solution. If the conductivity of a solution is determined, the rate of a
chemical reaction can also be determined. As the number of ions
decreases, the concentration also decreases and the conductivity also
decreases. This is usually applied in electrolytic process.

Activation Energy

Activation Energy is the minimum amount of energy that is required to

initiate a chemical reaction. When particles (substances) are reacting
together, not all of them will have the same amount of energy, a few will
have very little energy and a few will have very high energy. The majority
of the particles will have average energy only the particles with high
energy will overcome the activation energy and be converted into the
desired results. The curve below shows the distribution of particles in a
chemical reaction. It is called the Maxwell-Boltzman distribution curve.

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Number of
particles with
energy

Kinetic Energy EA

To increase the number of particles with enough energy to overcome the

activation energy, factors such as temperature, concentration etc are
introduced in the chemical reaction.

Number of
particles

Ea

Energy (E)

Although the energy of most of particles has not increased much, there is
a large increase in the number of particles with energies equal to or
greater than activation energy.

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The sketch of Maxwell-Boltzman distribution curve to show the effect of
using a catalyst.

Number of
particles

Ea2 Ea1
Energy (E)

Chemical Equilibria

Chemical Equilibria is the study of reversible chemical reactions. A

reversible reaction is a reaction that proceeds either i.e. the reactants
react to form products and the products react back to form reactants. The
reversible symbol ( ) is used to represent such reactions.

At the start of the reaction, the concentration of the reactants is maximum

or highest and the concentration of the products is zero because the
products are not in existence. As the reaction progresses, the
concentration of the reactants steadily decreases while that of the
products steadily increases. After sometime, the concentration of both the
reactants and products balance. This is because the rate at which the
forward reaction progresses become equal to the rate at which the reverse
reaction occurs. This state is called the state of dynamic equilibrium.

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 Forward reaction (rate decreasing)
Rf

Equilibrium Rr = Rf
Rate of
reaction

Reverse reaction (rate increasing) Rr

Rr

Time

When a state of dynamic equilibrium is reached, the reaction appears to

have come to a stop because no visible change is noticed. However, a
reversible reaction never come to a stop unless one of the substances
involved in the reaction is removed.

Factors that affect the state of dynamic equilibrium

When a reaction is in a state of dynamic equilibrium, the rate of the

forward reaction is equal to the rate of the reverse reaction. Any external
factor that is introduced to the reaction in dynamic equilibrium will be
opposed by the reaction. This principle is called Le Chatelier’s principle. Le
Chateliers principle states that when an external factor is introduced to a
reaction in dynamic equilibrium, the reaction shifts the position of
equilibrium so as to oppose the change and re-establish the state of
dynamic equilibrium.

To illustrate Le Chateliers principle, the Haber process can be used. In the

Haber process, hydrogen gas and nitrogen gas are reacted to form
ammonia. A reversible reaction occurs.

3H2 + N2 2NH3

The forward reaction is exothermic (bond formation) and the reverse is

endothermic (bond breakage).

a. Temperature

Increasing the temperature in the Haber process favours the reverse

reaction. More ammonia will be decomposed (broken down) to form
hydrogen and nitrogen. This means therefore, that the position of
equilibrium will shift towards the left. When more ammonia is broken
down into hydrogen and nitrogen, the concentration of the reactants

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 increases hence increasing the rate of the forward reaction and re-
establishing of the state of dynamic equilibrium.

b. Pressure

Pressure affect substances that are in gaseous state.

3H2 (g) + N2 (g) 2NH3 (g)

When pressure is changed in a reversible reaction, the total number of

moles of gaseous substances on either side should be considered.
There are four moles of gases on the left hand side and two moles of
gases on the right hand side of the equation.

Increasing the pressure in the Haber process favours the forward

reaction. This is because there are more number of moles of gases on
the left hand side. The position of equilibrium will therefore shift
towards the right i.e. more production of ammonia will take place.

c. Concentration

The increase in concentration favours the forward reaction hence more

products are produced. The position of equilibrium will therefore shift
towards the left. The increase of particle in the reactants leads to the
faster frequency of collision hence increasing the rate of reaction of the
forward reaction. The equilibrium shifts to the left due to the faster
production of ammonia. Hence the ammonia begins to decompose
faster causing a dynamic equilibrium.

3H2 (g) + N2 (g) 2NH3 (g)

d. Catalyst

A catalyst does not affect the position of equilibrium in a reversible

reaction. This is because a catalyst catalyses both the forward and the
reverse reactions equally. A catalyst helps a reversible reaction reach
dynamic equilibrium faster.

The reaction conditions in the Haber process

- Temperature: 450oC
- Pressure: 200 atm
- Catalyst: Finely powdered iron

The reversible reaction is discouraged by removing the ammonia when

produced. This is done by liquidifying the ammonia.

Exercise

1. 3H2 + N2 2NH3 H = 92 kJ/mol

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 i. Is the forward reaction exothermic or endothermic?
ii. Will heating the mixture give an equilibrium mixture with more or
less ammonia?
iii. Are there more gas molecules of reactant or product?
iv. Will raising the pressure give an equilibrium mixture with more
or less ammonia?

2. The Contact process

2SO2 (g) + O2 (g) 2SO3 (g) H = 196 kJ/mol

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