1 rate of reaction

1.3 The Collision Theory

 1.3 The Collision Theory
 1 According to the kinetic theory of
matter, all matter is made up of tiny,
discrete particles. These particles are
continually moving and so have
kinetic energy.
 1.3 The Collision Theory
 2 Based on the assumption that the particles in
matter are moving all the time and collide with
each other, the collision theory was introduced to
explain
 (a) how chemical reactions occur, and
 (b) the factors affecting the rates of reactions.
 1.3 The Collision Theory
 3. When the reactants are mixed, the reactant
particles (atoms, molecules or ions) collide with
each other. However, not all collisions will result
in a chemical reaction to form the products of the
reaction. It is likely that the particles collide but
are bounced back without producing any changes.
The collisions that are successful in producing a
chemical reaction are called the effective
collisions.
 1.3 The Collision Theory
 4 Collisions of particles that are unsuccessful in
producing a chemical reaction are called
ineffective collisions.
 1.3 The Collision Theory
 5 The collision theory states that for a
chemical reaction to occur, the reacting particles
must:
 (a) collide with each other so that the breaking
and formation of chemical bonds can occur.
 1.3 The Collision Theory
 5 The collision theory states that for a chemical
reaction to occur, the reacting particles must:
 (a) collide with each other so that the breaking
and formation of chemical bonds can occur.
 (b) possess energy that is equal to or more than
the minimum energy called the activation
energy.
 1.3 The Collision Theory
 5 The collision theory states that for a chemical
reaction to occur, the reacting particles must:
 (a) collide with each other so that the breaking
and formation of chemical bonds can occur.
 (b) possess energy that is equal to or more than
the minimum energy called the activation energy.
 (c) collide in the correct orientation.
 Activation Energy
 1 The activation energy is the minimum
energy that the reactant particles must possess
at the time of collision in order for a chemical
reaction to take place.
 Activation Energy
 2 The activation energy can also be
considered as an energy barrier that
must he overcome by the colliding particles
in order that collision will result in the
formation of product molecules.
 Activation Energy
 3 (a) If the two molecules with sufficient energy (that is,
energy equal to or more than the activation energy) collide
in the correct orientation, the chemical bonds in the
reactant molecules will break and reaction will occur to
form new bonds in the product molecules (Figure 1.35). For
example,
 Activation Energy
 3 (b) However, if two molecules, with energy equal to or
more than the activation energy, do not collide with each
other in the correct orientation, then reaction will not
occur.
 Activation Energy
 3 (c) If two reactant molecules, with
energy less than the activation energy,
collide in the correct orientation, then
reaction will also not occur. The colliding
molecules will simply rebound and move
away from each other.
 Relating the frequency of effective
collisions with factors influencing the
rate of reaction
 According to the collision theory, two important
factors that determine the rate of a chemical
reaction are:
 (a) the frequency of effective collisions and
 (b) the magnitude of the activation energy
 Relating the frequency of effective
collisions with factors influencing the
rate of reaction
 1 Frequency of effective collisions
 For a given reaction, if the frequency of collisions
between reactant molecules is high, it follows that
the frequency of effective collisions that causes a
reaction to occur will also be high. As a result, the
rate of reaction increases.
 Relating the frequency of effective
collisions with factors influencing the
rate of reaction
 2 Magnitude of activation energy
 Reactions that have high activation energy will occur at a
slow rate. This is because only a small fraction of the
molecules possess sufficient energy to overcome the
activation energy for the reaction to occur. In contrast,
reactions that possess low activation energy will occur at a
fast rate. This is because most of the molecules have
sufficient energy to overcome the activation energy and
this enables the reaction to occur.
 Relating the frequency of effective
collisions with factors influencing the
rate of reaction
 3 In general, any factor that increases the
rate of effective collisions will also increase
the rate of reaction.
 Effect of surface area on the
reaction rate
 1 The sodium chloride crystal as shown in Figure 1.29 (a)
has a surface area of 16 cm2. When this crystal is divided
into smaller crystals as shown in Figure 1.29 (b), the total
surface area is increased to 24 cm2.
 Surface area of the NaCl crystal =(1 x 2) x 4 + (2 x 2) x 2
=16cm2

 Effect of surface area on the
reaction rate
 Total surface area
 Effect of surface area on the
reaction rate
 2. The smaller the particle size, the greater the
total surface area exposed for reaction to occur.
 Effect of surface area on the
reaction rate
 3 In the reaction between hydrochloric acid and
marble chips (calcium carbonate),
 CaCO3(s) + 2HCl(aq)  CaCl2(aq) + H2O(l) +
CO2(g)
 the rate of reaction will increase if powdered
marble is used instead of marble chips.
Effect of surface area on the
reaction rate
 Effect of surface area on the
reaction rate
 4. The total surface area is larger in powdered
marble. With greater surface area exposed for
reaction with the acid (Figure 1.30), collisions
between reacting molecules become more
frequent.
 Effect of surface area on the
reaction rate
 5. This means that the frequency of
effective collisions (that is, collisions with
the correct orientation and with energy
equal to or greater than activation energy)
between reacting particles will increase. As
a result, the rate of reaction also increases.
 Effect of concentration on the
rate of reaction
 1 Magnesium reacts with dilute
hydrochloric acid according to the
equation:
 Mg(s) + 2HCl(aq)  MgCl2(aq) + H2(g)
 When the concentration of hydrochloric
acid increases, the rate of reaction also
increases.
 Effect of concentration on the
rate of reaction
 2 Figure 1.37 shows the arrangement of
particles in 1 mol dm-3 hydrochloric acid
and 2 mol dm-3 (more concentrated)
hydrochloric acid.
 Effect of concentration on the
rate of reaction
 When the concentration of hydrochloric
acid increases, the number of particles
per unit volume also increases and the
particles are closer together.

Same volume
 Effect of concentration on the
rate of reaction
 3 When the number of particles increases,
the frequency of collisions also
increases. As a result, the frequency of
effective collisions increases. This causes
the rate of reaction to increase.
Effect of pressure on the rate of
reaction
 1 In chemical reactions involving gases,
increasing the pressure increases the rate of
reaction. Conversely, decreasing the pressure
decreases the rate of reaction. For example, the
rate of reaction between nitrogen and oxygen to
produce nitrogen monoxide can be increased by
increasing the pressure.
 N2(g) + O2(g)  2NO(g)
Effect of pressure on the rate of
reaction
 2 At low pressures, the gaseous molecules are
spread far apart (Figure 1.32 (a)). When the
pressure is increased, the volume of the gas is
reduced (Figure 1.32(b)).

Number of particles same

Effect of pressure on the rate of
reaction
 This means that at high pressures,
 (a) the number of gaseous molecules per
unit volume is increased, and
 (b) the gaseous molecules are packed
closer together.

Number of particles same

Effect of pressure on the rate of
reaction
 3 As a result, increasing the pressure causes
the gaseous molecules to collide more frequently.
Consequently, the frequency of effective
collisions increases and the rate of reaction also
increases.
 Effect of temperature on the
rate of reaction
 1 Calcium carbonate reacts with
hydrochloric acid to form carbon dioxide
according to the following equation:
 CaCO3(s) + 2HCl(aq)  CaCl2(aq) + H2O(l) + CO2(g)
 Effect of temperature on the
rate of reaction
 Figure 1.33 shows the graphs of total volume of
carbon dioxide given off against the time taken for
the reaction between calcium carbonate and dilute
hydrochloric acid at 25 °C and 30 °C.
 Effect of temperature on the
rate of reaction
 2. At low temperatures, particles of reactants move at a
slower speed. However, when the temperature is
increased, the particles absorb the heat energy. As a
result, the kinetic energy of the particles increases. Hence,
 (a) the reacting particles move faster, and
 (b) the number of reacting particles with the activation
energy required increases.
 Effect of temperature on the
rate of reaction
 3 Consequently, the frequency of
effective collisions increases and hence,
the rate of reaction also increases.
 Effect of temperature on the
rate of reaction
 4 Temperature has a great effect on the
rate of reaction. For most reactions, the
rate of reaction approximately doubles
when the temperature of reaction increases
by 10 °C.
 Effect of catalysts on reaction
rates
 1 The decomposition of hydrogen peroxide to
water and oxygen occurs very slowly at room
temperature.

 2H2O2(aq)  2H2O(l) +O2(g).
 In the presence of a catalyst, the decomposition of
hydrogen peroxide occurs rapidly.
 Effect of catalysts on reaction
rates
 2 Figure 1.34 shows the rate of evolution of oxygen for
the decomposition of hydrogen peroxide without a catalyst
and in the presence of a catalyst such as manganese(IV)
oxide or iron(III) oxide.
 Effect of catalysts on reaction
rates
 3. A catalyst provides an alternative reaction route (or
pathway) for the reaction to occur. In the presence of a
positive catalyst, an alternative route has a lower
activation energy.
 Effect of catalysts on reaction
rates
 In other words, a positive catalyst lowers the activation
energy required for the reaction (Figure 1.34). As a
result, more reacting particles possess sufficient energy
to overcome the lower activation energy required for
effective collisions. Hence, the frequency of effective
collisions increases and the rate of reaction increases