Chemical Equilibrium

COLLISION THEORY
Correct Orientation
• Molecules need to collide with an orientation that allows for
the breaking of existing chemical bonds and formation of new
chemical bonds.
 COLLISION THEORY
• Molecules that give small number of successful collision:
• Large or complex molecules – reactive sites represent only
a small part of the whole molecule.
• Molecules with extensive structures – reactive sites are
obscured from colliding with other reactant particles.

• Orientation of colliding particles is the result of random

motion and is not something that can be easily modified.

• Hence, it’s easier to increase the reaction rate by modifying

the energy of particles.
 COLLISION THEORY
Sufficient Energy
• Particles colliding in the correct orientation still need to have a
certain amount of kinetic energy for the collision to be
successful.

Activation energy, Ea, is

• At any given temperature, the energies possessed by the

particles are not all the same due to the different velocities of
the particles.
 COLLISION THEORY
• This range of kinetic energies is illustrated by a probability
distribution called Maxwell-Boltzmann distribution curve.

Amount of energy possessed by the greatest number of

particles in the substance
 COLLISION THEORY
• When the energy of a collision is equal to, or greater than, the
activation energy, there is potential for a reaction to occur.
 COLLISION THEORY
• The activation energy of a reaction can also be illustrated by
energy profile diagram.
Highly energized and highly
unstable arrangement of reactant
particles where bond breaking, and
formation takes place.

exothermic endothermic
Chemical Equilibrium
 COLLISION THEORY
• The energy profile diagram shows the reaction journey of
individual atoms, ions or molecules, whereas the kinetic
energy distribution diagram shows the overall picture of all
particles potentially involved in a reaction.

• The magnitude of a reaction’s activation energy determines the

ease with which a given reaction occurs.

Chemical Equilibrium
 1. What are the two criteria required for a collision to be successful?

2. Draw a fully labelled Maxwell-Boltzmann distribution curve to represent the

Progress check 1

range of kinetic energies possessed by the particles in a substance at a certain

temperature. Indicate the position of activation energy.
 REACTION RATE

The rate of reaction,

change in amount of reactants or products

Rate =
time

Formation of
precipitation Change
Colour Gas
in mass
change released

Chemical Equilibrium
 REACTION RATE

These factors can either

(i) generate a greater

number of collisions
(both successful and
unsuccessful) per unit
Factors time
affecting
Reaction Rate OR

(ii) increase the

probability that any
given collision will
be successful

Chemical Equilibrium
 REACTION RATE
Increasing Collision Frequency
• Increasing the overall frequency of collision can increase the
total number of successful collision per unit of time.

a) Surface area of solid reactants

• When the size of the particles of a substance is reduced,
the total surface area of the substance increases.

Chemical Equilibrium
 REACTION RATE
• Increasing the surface area of the solid reactants exposes a
greater number of reacting particles to the possibility of a
collision.
• This increased frequency of collision results in a higher
number of successful collisions per unit of time and hence
an increased reaction rate.

Why is it dangerous to throw water on a fat, oil

or grease fire in the kitchen?

Chemical Equilibrium
 REACTION RATE
b) Concentration
• The concentration of a substance is the number of particles per
unit volume.
• At higher concentration (or higher pressure for gaseous
reaction), the rate of collisions between the particles increases,
resulting in a greater number of successful collision per unit of
time and hence, a faster reaction rate.

Chemical Equilibrium
 REACTION RATE
c) Pressure
• Pressure is the force per unit area that gas particles exert when
they collide with the walls of their container.
• When more gas particles are introduced into a given volume,
raising the pressure, the frequency of collisions per unit time
increases. This results in a greater number of successful
collisions per unit of time and hence, a faster reaction rate.

Chemical Equilibrium
 REACTION RATE
• For mixture of gases, such as air, the total pressure exerted by
the mixture is the sum of the individual pressures of the
composite gases.

• The partial pressure of a gas in a mixture of gases can be

considered as the equivalent of the concentration of a solute in
a solution.

• If two reacting gases are in a vessel of fixed volume, and the

total pressure is increased by adding an inert gas, the partial
pressure of the two reacting gases does not change, and hence
reaction rate remains unchanged.

Chemical Equilibrium
 REACTION RATE
Increasing Collision Probability
• Most collisions between reactant particles are unsuccessful as
the particles may not have the required activation energy.
• Increasing the temperature and the presence of catalyst can
increase the probability of a given collision being successful
and hence, increase the reaction rate.

a) Temperature
• Raising the temperature of a reaction mixture always
increases the reaction rate (for both exothermic and
endothermic reaction).
• At higher temperature, particles on average have a greater
kinetic energy.

Chemical Equilibrium
 REACTION RATE
• The average collision energy of reacting particles in a
reaction mixture increases.
• Greater percentage of collisions will have sufficient energy
(≥ Ea) to form activated complex.
• Greater percentage of collisions are successful and hence,
reaction rate increases.
• Effect of increased rate of collision between particles is
minor.

Chemical Equilibrium
REACTION RATE

Chemical Equilibrium
REACTION RATE

Chemical Equilibrium
 REACTION RATE
b) Presence of Catalyst

• Catalyst – substances that speed up a chemical reaction while

remaining chemically unchanged at the end of the reaction.
• Mostly transition metals: Mn, Pt, Pd, Au, Rh
• Provides an alternative reaction pathway with lower
activation energy.
• Greater proportion of the reactant particles will have enough
energy to overcome the, now reduced, activation energy.
• Greater percentage of collisions are successful; hence rate of
reaction increases.

Chemical Equilibrium
REACTION RATE

Chemical Equilibrium
 REACTION RATE
• Catalysts are specific to a certain reactions. They are not
consumed in the reaction but can be deactivated or poisoned.
• The alternative reaction pathway with a lower activation
energy can be illustrated on a reaction energy profile as
shown.

Chemical Equilibrium
 1. Which of the following would not be a suitable method to measure the
rate of reaction between zinc metal and hydrochloric acid?

A. Loss of mass from the reaction vessel

B. Mass of hydrogen gas produced
C. The concentration of zinc metal remaining
Progress check 2

D. The volume of hydrogen gas produced

2. According to the collision theory, which one of the following is not

essential for a reaction to occur?

A. Molecules must collide to react

B. The reactant particles should collide with the correct orientation
C. The reactant particles should collide with enough energy to
overcome the activation energy barrier
D. The reactant particles should collide with double the energy of the
activation energy

Chemical Equilibrium
 3. Which one of the following correctly explains why a sample of
magnesium reacts more rapidly with 1.0 mol L-1 HCl than with 0.10
mol L-1 HCl?

A. The energy of collisions between reactant particles is greater for the

reaction containing 1.0 mol L-1 HCl.
Progress check 2

B. The rate of collisions between reactant particles is greater for the

reaction containing 0.10 mol L-1 HCl.
C. There are more collisions between the magnesium and 1.0 mol L-1
HCl.
D. The frequency of collisions between reactant particles is greater for
the reaction containing 1.0 mol L-1.

Chemical Equilibrium
 4. What is meant by a successful collision between reacting particles?
Progress check 2

5. Catalysts are usually in the form of powders or fine wire mesh. Why is this?

6. An increase in temperature of only 10 oC can markedly increase reaction rate.

Explain the main reason for this.

Chemical Equilibrium
 7. The effect of particle size on the reaction rate between marble chips and hydrochloric
acid was examined. Carbon dioxide gas was collected by the downward displacement of
water and its volume measured at regular intervals until the reaction had stopped. The
results are given in the following graph.
Progress check 2

a) What does the steeper gradient of the small marble chips signify?

b) What does the region of zero gradient on the curve represent?

c) Why do both curves plateau at the same point?

 8. Consider the reaction between solution V and W that produces X and Z according to the
equation:
V(aq) + W(aq) ⟶ X(aq) + Z(aq)
The energy profile diagram for this process is shown below:
Progress check 2

a) Is the reaction endothermic or exothermic?

b) What does A represent for forward reaction?
c) What does B represent for forward reaction?
d) What does B represent for reverse reaction?
e) What does C represent for reverse reaction?
 9. In what way do the Maxwell-Boltzmann distribution curve for an uncatalysed and
catalysed reaction on the same set of axes differ?
Progress check 2

10. Nitroglycerin is an unstable compound that explode easily even with a small bump.
Sketch the energy profile diagram that shows the instability of this compound.