When both reactants and products are present in a vessel at a stated

temp, the system is either in equilibrium or not. This can be

determined by calculating the concentration term (reaction quotient)
and comparing it with the equilibrium value.

If the 2 are equal, the system is in equilibrium
If the concentration term is smaller than K
c
the system will react to
produce more products and the equilibrium moves to the right.
If the concentration term is greater than K
c
the system will react to
produce more reactants and the equilibrium moves to the left.

1. Effect on the equilibrium constant

For exothermic reactions, increasing temp results in lower K
c
and
K
p
values (we have explained this)

For endothermic reactions, increasing temp results in higher K
c

and K
p
values (we have explained this)

2. Effect on position of equilibrium
Exothermic
Increasing the temp causes the concentration term to be
bigger than K
c

The system reacts to make the concentration term smaller- by
forming more reactants until the concentration term = K
c
Therefore equilibrium shifts to the left
Endothermic
Increasing the temp causes the concentration term to be
smaller than K
c

The system reacts to make the concentration term larger- by
forming more products until the concentration term = K
c
Therefore equilibrium shifts to the right.

A decrease in temp has the opposite effect on exo and
endothermic reactions.
3. Effect on rate of reaching equilibrium

In a reversible reaction, an increase in temp increases the rate
of the forward and reverse reactions, but not equally.
Endothermic reactions have higher activation energies and so
its rate is increased more than the exothermic reaction.
Because the rates of both reactions are increased equilibrium
is reached more quickly.
1. Effect on the equilibrium constant

None

2. Effect on the position of equilibrium

This depends on the number of gas molecules on each side of
the equation





3. Addition of an inert gas

None: The number of moles and the volume of the reacting
species are not altered by the addition of an inert gas so the
value of the concentration term and K
c
are unaltered and
equilibrium does not change.

4. Effect on rate of reaching equilibrium

If the reaction is homogeneous the rate of collision increases
when pressure increases. This causes an increase in rate of
the forward and reverse reactions and equilibrium is reached
sooner.
1. Effect on the equilibrium constant

None

2. Effect on the position of equilibrium






1. Effect on the equilibrium constant

None

2. Effect on the rate of reaching of equilibrium

A catalyst speeds up both the forward and reverse reactions
equally. Therefore equilibrium is reached more quickly.




The aim is to:
Increase yield
Increase rate of reaction
Reduce costs
Increase atom economy
Continuous flow: The reactants are added continuously at one
end of the plant and the products are removed continuously at
the other.

Batch process: The reactants are added together in a reaction
vessel. When the reaction is complete the products are
separated from any catalyst, the solvent and any unused
reactants.
N
2(g)
+ 3H
2(g)
2NH
3(g)
H = -92 kJ mol
-1


Write the expression for K
c


The conditions are:
Temp of 400
0
C to 450
o
C
Pressure of 200atm
Catalyst iron promoted by traces of
aluminium and potassium oxides.
S
total

= S
system
+ S
surr
= S
system
- H/T

The haber process is exothermic so the value of - H/T and
hence S
surr
is positive. Any increase in temp will make the value
of - H/T less positive, which reduces the value of S
total

As ln K = S
total

this causes a fall in the value of the equilibrium
constant K
p


At room temp this reaction is so slow that almost no product is
formed. At high temps a low yield is achieved quickly. To
overcome this an iron catalyst is used which allows the reaction
to occur at 700K, a compromise temp of reasonable yield and
rate.



An increase in pressure does not alter the equilibrium constant,
but it causes the partial pressure expression to become smaller.
This means K
p
no longer = the partial pressure expression so the
system reacts making more ammonia until the values are again
equal. So equilibrium shifts to the right.

The rate of reaction is not altered by an increase in pressure as
the rate is controlled by active sites on the surface of the
catalyst.
Even under these conditions only about 30% of the hydrogen is
converted to Ammonia. This is because the rate is still too slow
for equilibrium to be reached in the catalyst chamber.

To obtain an economic overall yield with a high atom economy.
The ammonia is removed by cooling the gases leaving the
catalyst chamber. Unreacted Nitrogen and Hydrogen can be
recycled.
The crucial step in the manufacture of sulfuric acid is:

2SO
2(g)
+ O
2(g)
2SO
3(g)
H = -196 kJ mol
-1


Write the expression for K
c


The conditions are:
Temp of 425
o
C
Pressure of 2 atm
Catalyst vanadium (v) oxide
S
total

= S
system
+ S
surr
= S
system
- H/T

The process is exothermic so the value of - H/T and hence S
surr

is positive. Any increase in temp will make the value of - H/T
less positive, which reduces the value of S
total

As ln K = S
total

this causes a fall in the value of the equilibrium
constant K
p


A high temperature would mean a lower yield and a low temp
would mean an uneconomic rate. The catalyst allows a
compromise temp to be used that produces a high yield quickly.
An increase in pressure will drive equilibrium to the right as the
are more molecules on the left of the equation.

However this is unnecessary as yield is already high and
increasing pressure costs money.
The gases from the catalyst chamber are passed into
concentrated sulfuric acid which absorbs the sulfur trioxide from
the equilibrium mixture. The unreacted sulfur dioxide and air
are then passed through another bed of catalyst. This helps to
increase atom economy and reduce pollution.

The gases are passed through the first catalyst bed a temp of
698K. As the reaction is exothermic they heat up to 900K and
the conversion is only 60%. The gases are cooled to 700K and
passed through another bed of catalyst and the conversion is
now 95% and the mixture of sulfur trioxide, sulfur dioxide and
oxygen is passed through a tower containing concentrated
sulfuric acid. The sulfur trioxide form oleum and the remaining
gases pass through another catalyst bed and the overall
conversion is 99.5%
Hydrogen is made by reacting methane with steam over a nickel
catalyst at a temp of 1000K

CH
4(g)
+ H
2
O
(g)
CO
(g)
+ 3H
2(g)
H = +206 kJ mol
-1


Write the expression for K
p


This is a highly endothermic reaction and S
surr
is negative.

Increasing the temp causes the value of the equilibrium constant
to rise.
As most pharmaceutical substances decompose when heated
strongly, their manufacture is normally carried out between room
temp and 100
o
C. If energy is needed it can be provided by
absorbing microwaves
Enthalpy and entropy changes enable S
total
to be determined and
hence if it is thermodynamically feasable
An increase in temp of an exothermic reaction will result in a
decrease in equilibrium yield.
An increase in temp of an endothermic reaction will result in an
increase in equilibrium yield.
A decrease in temp will result in a lower rate, so a catalyst and
compromise temp may be used.
An increase in pressure will drive the equilibrium to the side of the
equation with fewer gas molecules. However, the use of high
pressure is expensive.
Unreacted reactants are recycled to increase atom economy and
reduce pollution
Many industrial processes are not true equilibrium systems
because the products are removed.
You can now try these:
Jan 2010 Q1,4,19,24
June 2010 Q15,16,19
Jan 2011 Q5,6,17d
June 2011 4,5,6,17c
Jan 2012 Q1,2,3,4,20
June 2012 Q3,4,17b
Jan 2013 Q6,17