EQUILIBRIUM

(Topics 7 & 17)

7.1 Dynamic equilibrium
7.1.1 Outline the characteristics of chemical and physical systems in a state of equilibrium









Dynamic Equilibrium: The state at which the rate of forward reaction is equal to the rate of
backwards reaction in a reversible reaction.
Concentration, pH, density and colour remain constant
Reversible Reaction: Reaction in which the newly formed products can convert back to the reactants
State of dynamic equilibrium can only exist in a closed system.


The reaction from A + B > C + D is the forward reaction, whilst the reaction C+D > A + B is the reverse
reaction.
Most reactions do not go through completion.
We cannot go to the reverse reaction until some of C and D have been formed.




7.2 The position of equilibrium
7.2.1 Deduce the equilibrium constant expression (K
c
) from the equation for a homogenous
reaction.
K
C
(Equilibrium constant) represents how far the reaction will proceed at a given temperature.

Only temperature will affect K
C
value direct relationship between increase temp & increase
K
C
and vice versa

K
C
= [products]/[reactants]

Exceptions: Do not count the following substances in an equilibrium expression
Solids
Liquid water IF some of the substances are aqueous

7.2.2 Deduce the extent of a reaction from the magnitude of the equilibrium constant
K
C
> 1 = products > reactants; when much greater than 1, reaction goes almost to
completion

K
C
< 1 = products < reactants; when approaching 0, reaction hardly proceeds

K
C
can NEVER be negative
7.2.3 Apply Le Chateliers principle to predict the qualitative effects of changes of temperature,
pressure and concentration on the position of equilibrium and on the value of the equilibrium
constant.
Change Effect on Equilibrium Effect K
c
?
Concentration
of products
Shift to OPPOSITE side
Reverse reaction will take place to make more
reactants
N
Concentration
of reactants
Shift to OPPOSITE side
Forward reaction will occur to make more
products
N
Pressure Shift to side with LEAST moles of gas N
Pressure Shift to side with MOST moles of gas N
Temperature Shifts in ENDOTHERMIC direction
Lowers temperature
Y
Temperature Shifts in EXOTHERMIC direction
Increases temperature
Y
+ Catalyst No effect
Rate of reaction increases, but no effect on
position of equilibrium
N

7.2.4 State and explain the effect of a catalyst on an equilibrium reaction
Catalyst has no effect on either K
C
or position of equilibrium

Only affects rate of reaction

Rate of forward and backwards reactions affected equally

7.2.5 Apply the concepts of kinetics and equilibrium to industrial processes
The Haber process
N
2(g)
+ 3H
2(g)


2NH
3(g)
-H = -92.4 kJ mol
-1

Process of manufacturing ammonia for industrial use
H obtained from normal air

N obtained from distillation of liquid air

More moles of gas on the left than the right greater yield will be produced at high
pressure (i.e. equilibrium position will life further to the right)

Reaction is exothermic, hence will give a greater yield at low temperatures (i.e. equilibrium
position shifts further to the right)

In actual practice, if low temperatures are used, then time taken for reaction to reach
equilibrium takes too long

An intermediate temperature is chosen (450C), which allows faster equilibrium time and
still has enough of the products in the equilibrium mixture.














Catalyst of finely divided iron is used to speed up the reaction (finely divided to maximise
surface area)

To make the process more efficient, ammonia produced at equilibrium is removed by first
cooling the mixture when ammonia turns into liquid, which can be tapped off.

Unreacted gases are mixed with fresh reactants and returned to chamber to re-establish
equilibrium, and the cycle is repeated continuously.

Summary:
High pressure
Low temperature, but the temperature has to be optimal.
Iron catalyst used.
Still, only 15% yield.

Contact Process
2 SO
2
(g) + O
2
(g) 2 SO
3
(g) : H = 197 kJ mol
1

This is the manufacture of Sulfuric Acid
Most industrially produced chemical, with production levels of over 150 million tonnes annually.
Used for fertilizers, detergents and etc.
Temperature
Similar to the Haber Process , enthalpy change is a negative value, so the reaction is exothermic.
As a result, a low temperature will be used to give a high yield of sulfuric acid. However, a high
temperature (approx. 450C) will be used to ensure a reasonable rate of reaction, so the yield
will be sacrificed to a certain extent.
Pressure
3 moles of reactants 2 moles of products
Manufacture takes place at high pressure, the reasons being similar to that of the Haber Process.
Essentially, high pressure is used to shift the reaction to the product side.
Catalyst
Vanadium Oxide is used.

HIGHER LEVEL
17.1 Liquid-vapour equilibrium
17.1.1 Describe the equilibrium established between a liquid and its own vapour and how it is
affected by temperature changes
Liquid enclosed in chamber will form an equilibrium with its own vapour

Fast moving particles in the liquid will escape from the surface and become vapour
H
2
O
(l)
H
2
O
(g)
Slow moving particles in the vapour will be captured by the liquid and become liquid again
(condensation)

At liquid-vapour (dynamic) equilibrium:

Rate of evaporation = rate of condensation

Effects of temperature:
As temperature increases, av. Speed of particles is greater

More particles will have sufficient speed to escape the liquid and fewer will be slow enough
to get recaptured

Therefore, as temperature increases, the equilibrium vapour pressure will also increase.

17.1.2 Sketch graphs showing the relationship between vapour pressure and temperature and
explain them in terms of kinetic theory