Topic 2.

3: Kinetics I
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2.3 (a) Factors affecting the rate of reaction

 Temperature: An increase in temperature increases the rate of reaction.
 Concentration: An increase in the concentration of a solution of reactants
increases the rate of reaction.
 Pressure: Increasing the pressure of a gas involved in a reaction increases the
rate of reaction. Increasing a gas pressure is like increasing the concentration
of the gas.
 Surface area of reactants: An increase in the surface area of a solid reactant
increases rate of reaction. The surface area of a solid is increased if it is
broken into smaller pieces.
 Catalyst: The use of a catalyst increases the rate of reaction.
Task 2.3a Complete and extend the table below:
variable (factor) value high or low rate
2.3 (b) Explanations using collision theory
The collision theory is used to explain changes in reaction rate. In a reaction
between 2 gaseous substances A and B, a molecule of A must collide with a
molecule of B before reaction can occur. The number of collisions in a given time,
the collision frequency, controls the rate of reaction. The greater the collision
frequency the greater the rate of reaction. Not every collision leads to a reaction.
A reaction takes place during a collision if the molecules hit at the correct angle or
orientation and if they have enough energy. This amount of energy per mol of
molecules is called the activation energy. The theory is extended to cover liquids
and solids.
Temperature
Increasing the temperature increases the speed of the reacting particles and faster
particles collide more often than slow ones. The increase in the number of
collisions leads to an increase in the collision frequency and rate of reaction.
Increasing the temperature also gives the particles more energy so that they collide
with more violence. Energetic particles have a better chance of their collisions
leading to a reaction.
Concentration
The concentration of a substance, normally a solution, is the amount in a given
volume.
concentration = amount {units = mol/dm3 or M}
volume
In a higher concentration solution there are more particles to react therefore there
are more collisions and a higher collision frequency. As a reaction depends on
collisions happening, a higher collision frequency leads to a faster reaction rate. If
we were doing a reaction with acid and we double the number of acid particles, we
double the number of collisions and therefore are likely to double the reaction rate.
Pressure
Increasing the pressure of a gas puts more gas molecules into a given volume.
There will be more collisions and a higher collision frequency leading to a higher
rate of reaction.
Surface area
Surface area is controlled by the particle size of a solid. A powder has a higher
surface area than lumps and therefore a powder has more atoms or ions exposed on
its surface in a position to react. More collisions take place between the ions or
molecules in the surrounding liquid. The collision frequency in increased and so
is the rate of reaction.
Task 2.3b Draw diagrams to show slow and fast reactions caused by changing the
factors above.
2.3 (c) Maxwell-Bolzmann distribution

As the temperature is raised the average energy of the molecules increases. The
proportion of molecules with the activation energy (see section under graph) is
greater at higher temperatures. A small increase in temperature gives a large
increase in reaction rate. Simulation of change in temperature requires Microsoft
Excel (source www.chemit.co.uk )
2.3 (d) Activation energy
Activation energy is a measure of the energy needed, when molecules collide, to lead
to a reaction. The lower the activation energy the more molecules at a particular
temperature will have enough energy to react when they collide. As the temperature
increases more molecules will have an amount of energy equal to or more than the
activation energy. At a high temperature more collisions therefore lead to reaction.
2.3 (e) Catalysts and activation energy
Catalysts alter the rate of a chemical reaction without being consumed in the
reaction. (e.g. the catalyst may end up in the oxidation state it began with). A
catalyst reduces the activation energy for a reaction by providing an alternative
mechanism for the reaction.
Homogeneous catalysts can form intermediates which contain the catalyst but then
decompose to form products. For the reaction
A -----> B + C high activation energy
A + catalyst -----> A-catalyst low activation energy
A-catalyst -----> B + C + catalyst low activation energy
The catalyst may change oxidation state during the reaction see
http://www.wbateman.demon.co.uk/newsums/sum5.2/sum5.2.htm
Heterogeneous catalysts such as surface catalysts involve steps such as; diffusion to
surface, adsorption on surface, reaction at surface, deadsorption from surface,
diffusion from surface.
If two reactant molecules collide they may react if they have enough energy. If they
are brought together on the surface of a catalyst the activation energy may be lower
so at a given temperature the reaction will be faster.

The reaction profile for a catalysed and an uncatalysed reaction is shown below.

2.3 (f) Thermodynamic and kinetic stability

One system is thermodynamically stable with respect to a second one if the first one
is lower than the second on an enthalpy level diagram.
e.g. Oxygen is energetically stable with respect to ozone.
ozone (unstable)
|
|
oxygen \/ (stable)
Even if a system is thermodynamically unstable and is expected to react to form a
stable one the system may not react. The system will not react if it is kinetically
stable. This means that the reaction proceeds too slowly for any reaction to be seen.
If kinetically unstable, a reaction is fast and observations can be made. When a
system is thermodynamically unstable but kinetically stable, the reaction is likely to
be seen but only under favourable conditions. Sugar and oxygen is a system like this
with respect to carbon dioxide and water. A bowl of sugar on the table does not
react but if heated an exothermic reaction takes place.