AS Chemistry Kinetics and chemical Equilibrium Tutorial 3

Redington College Kajana Sivarasa 1

Kinetics I

Factors affecting rate of reaction:

o Temperature: An increase in temperature increases the rate of reaction.

o Concentration: An increase in the concentration of a solution of reactants
increases the rate of reaction.

o 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.

o 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.

o Catalyst: The use of a catalyst increases the rate of reaction.


Changes in rate using collision theory:

o For a reaction to take place, particles must collide.
o However, they must do so in the correct orientation and with sufficient energy:
the activation energy. Activation energy is the minimum energy required for a
reaction to take place.
o The more frequently collisions take place, the faster the rate of reaction.


o Temperature:
! Increasing the temperature causes an increase of the rate of a chemical
reaction (exo- and endothermic).
! This is because particles have more kinetic energy, and more of them
have energy greater than the activation energy. Hence, there will be
more successful collisions, with the required energy for reaction.

o Concentration:
! Increasing the concentration of reactants causes an increase of the rate
of a chemical reaction.
! The particles are closer together and so there are more collisions.
! With acid, if we double the number of acid particles, we double the
number of collisions and therefore are likely to double the reaction rate.

o Pressure:
! Increasing the pressure of gases causes an increase of the rate of
reaction
! Again, due to the fact that molecules are close


AS Chemistry Kinetics and chemical Equilibrium Tutorial 3

Redington College Kajana Sivarasa 2

o Surface area:
! Increasing the surface area of reactants causes an increase of the rate of
reaction.
! This is because a greater surface area allows for more frequent
collisions.

o Catalyst:
! Using a catalyst speeds up a reaction, without being used up.
! The catalyst provides an alternative route for the reaction, of lower
activation energy, so more particles at a certain temperature will be
able to react.


The Maxwell-Boltzmann Distribution.

o The Maxwell-Boltzmann Distribution is a plot of the number of particles
having each particular energy.
o The area under the curve is an indication of the number of particles present







To speed up the reaction, you need to increase the number of the very energetic
particles - those with energies equal to or greater than the activation energy. Increasing
the temperature does this and changes the shape of the graph:











AS Chemistry Kinetics and chemical Equilibrium Tutorial 3

Redington College Kajana Sivarasa 3




The curve peak shifts to the right and lowers. The area under the higher temperature
curve to the right of the activation energy has doubled - therefore doubling the rate of
the reaction.
A small increase in temperature gives a large increase in reaction rate.



Catalysis.

o Catalysts alter the rate of a chemical reaction
without being consumed in the reaction. A catalyst
reduces the activation energy for a reaction by
providing an alternative path for the reaction.
o This can be illustrated on a Maxwell-Boltzmann
distribution:








o The effect of a catalyst can also be shown on a reaction profile:


AS Chemistry Kinetics and chemical Equilibrium Tutorial 3

Redington College Kajana Sivarasa 4


o There are two types of catalysis

! Homogeneous catalysis: The catalyst in the same phase as the
reactants. Usually everything will be a gas or a liquid.

! Heterogeneous catalysis: This involves the use of a catalyst in a
different phase from the reactants. These involve a solid catalyst with
the reactants as either liquids or gases. Reaction examples include: the
Contact Process, catalytic converters, hydrogenation etc.

Heterogeneous catalysis takes places in stages:
o One or more of the reactants are adsorbed on to the
surface of the catalyst at active sites. An active site is a
part of the surface, which is particularly good at
adsorbing things and helping them to react.
o The reaction happens.
o The product molecules are desorbed i.e. leave the active
site available for a new set of molecules to attach to and
react.
A good catalyst does not absorb too strongly or too weakly.


Thermodynamic and kinetic stability:

o 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. I.e. the reaction
must be exothermic " The products have a lower energy overall. 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.

o Kinetically stable 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.

o NOTE: When a system is thermodynamically unstable but kinetically stable,
the reaction is likely to be seen but only under favourable conditions.













AS Chemistry Kinetics and chemical Equilibrium Tutorial 3

Redington College Kajana Sivarasa 5


Chemical equilibrium I

Dynamic equilibrium:

o A reversible reaction is one that can be made to go in either direction
depending on the conditions.
o A closed system is one in which no substances are either added to the system
or lost from it. Energy can, however, be transferred in or out at will.
o A dynamic equilibrium means that the rates of the forward and reverse
reactions are equal and so the concentration of each species remains constant.
o Homogeneous equilibrium: reactants and products are all in the same phase.

Le Chateliers principle:

o If a system in a state of dynamic equilibrium is disturbed, the equilibrium
position shifts in the direction which reduces the disturbance and restores the
equilibrium (i.e. oppose the change).

Changes in a system in equilibrium:


Factor Effect
Temperature
Increasing the temperature favours the endothermic reaction
Decreasing the temperature favours the exothermic reaction
If the temperature of an exothermic forward equilibrium reaction
is increased,the reaction will respond by going in the direction that
lowers the temperature and the reverse reaction will be favoured.
If the temperature of an endothermic forward equilibrium reaction
is increased,the reaction will respond by going in the direction that
lowers the temperature and the forward reaction will be favoured.
Pressure
Increasing pressure causes eq. to shift in direction of fewer moles
of gas.
Decreasing pressure causes eq. to shift in direction of more moles
of gas.
Concentration
Increasing concentration of reactants or decreasing conc. of
products shifts equilibrium to the right (towards the products)
Increasing concentration of products or decreasing con. of reactants
shifts eq. to the left (towards the reactants).
Increasing the concentration of a reactant makes the equilibrium
move in the direction that decrease the concentration of the
reactant.






AS Chemistry Kinetics and chemical Equilibrium Tutorial 3

Redington College Kajana Sivarasa 6


A catalyst does not alter the position of equilibrium or yield. It helps to establish
the equilibrium position at a faster rate.

An example of the importance of temperature control in industrial processes involving
equilibrium (e.g. the Haber Process, the Contact process) is: in the Haber process a
moderately high temperature of around 500
o
C is used to speed the rate at which
equilibrium is reached. This temperature is chosen in spite of the fact that a lower
temperature gives a higher yield.


Example

State the theoretical conditions of temperature and pressure that favour the production of
sulphur trioxide from sulphur dioxide and oxygen:

2SO
2(g)
+ O
2(g)
2SO
3(g)