Part II: Le Chteliers Principle

Recall:

Reversible reaction.

Dynamic equilibrium

Equilibrium constant, Kc

ICE table

Solubility product, Ksp

Predict how changes in concentration, pressure
and temperature affect equilibrium position of an
equilibrium system using Le Chateliers principle.

Recognise temperature as the only factor that
changes value of Kc.

Use Haber process as case study, explain how Le
Chatelier principle is used in industry and its
constraints.

Describe the effect of common ion on the
solubility of salt.
Manufacture of Ammonia



To produce more ammonia, we need to
choose conditions that move the
equilibrium position to the right (favour
forward reaction).

Le Chateliers Principle describes how an
equilibrium system shifts to response to a
stress or disturbance introduced in the
system.

If a stress is applied to a
system at equilibrium, the
system shifts in the
opposite direction that
reduce the stress in order
to restore equilibrium.

A stress is any kind of
In 1888, French chemist Henri- change in a system that
Louis Le Chatelier discovered
there are ways to control upset the equilibrium.
equilibria to make reactions more
productive.
Copyright Cengage Learning.
All rights reserved 7

Increase concentration, the equilibrium
position shifts to opposite direction.
Increase [reactant], equilibrium position shifts
to right (forward reaction).
Increase [product], equilibrium position shifts
to left (reverse reaction).
 N2(g) + 3H2(g) 2NH3(g)

Use Le Chateliers principle to predict how

each of these changes would affect the
amount of ammonia equilibrium
system.
(a)Adding hydrogen to the system.
(b)Removing ammonia from the system.
(c)Removing nitrogen from the system.
 N2(g) + 3H2(g) 2NH3(g)

Increase [H2], will shift the equilibrium

position to right in order to consume the
extra H2 added.

Therefore the amount of NH3 will
increase.
 N2(g) + 3H2(g) 2NH3(g)

Remove NH3 will shift the equilibrium

position to right in order to replace the
NH3 removed.

Therefore the amount of NH3 will
increase.
 N2(g) + 3H2(g) 2NH3(g)

Remove N2 will shift the equilibrium

position to left in order to replace the
amount of N2 reduced.

Hence the amount of ammonia will
decrease.

Because Kc is a constant at a given
temperature.

If [H2] increases, Kc value will decrease.

The position of equilibrium has to shift to
right (produce more NH3, reduce more
H2) in order to restore the Kc.
According to Le Chateliers principle:

When increase pressure, the system will move
from more moles side to fewer moles side to
reduce the pressure of the system.

If pressure is decreased, then system will move
to the direction involves increase in number of
moles of gas.

If both sides of reaction have equal number of
moles of gas, then no change in equilibrium
position.
 N2(g) + 3H2(g) 2NH3(g)

(a) Which reaction in the Haber process,

forward or reverse is favoured if the
volume of container is halved?
(b) Explain why.
 N2(g) + 3H2(g) 2NH3(g)
(4 moles of gas) (2 moles of gas)

(a) When volume is halved, pressure is

increased, the system will move to right.
(b) There are more moles of gas on the left
hand side of the equation.

How would decreasing the volume of the
reaction vessel affect each of the these equilibria?

(a)2SO2(g) + O2(g) 2SO3(g)

(b)H2(g) + Cl2(g) 2HCl(g)
(c)UO2(s) + 4HF(g) UF4(g) + 2H2O(g)
 2SO2(g) + O2(g) 2SO3(g)
(3 moles) (2 moles)

Decrease in volume will increase the pressure of
system.

Increase pressure of system will shift the
equilibrium position to right as there are more
moles of gas on the left hand side of the
equation.

As a result of equilibrium shift, amount (yield) of
SO3 will increase.
 H2(g) + Cl2(g) 2HCl(g)
(2 moles) (2 moles)

There are same number of moles of gas on both
sides of the equation.

Increase pressure of system will not change the
position of equilibrium.

No change in yied.
UO2(s) + 4HF(g) UF4(g) + 2H2O(g)
(4 moles) (3 moles)

Increase pressure of system will affect only the
gaseous molecules.

The equilibrium position will move to right as
there are fewer moles of gas one the right hand
side.

Yield of products will increase.

Exothermic reaction will release heat as a
product.
A
B + heat H = -ve
Increase temperature (addition of heat) will
shift the equilibrium position to left.
Decrease temperature (removal of heat) will
shift the equilibrium position to right.

Endothermic reaction will absorb heat,
assuming heat as a reactant:
A + heat
B H = +ve
Increase temperature (addition of heat) will
shift the equilibrium position to right.
Decrease temperature (removal of heat) will
shift the equilibrium position to left.
 N2(g) + 3H2(g) 2NH3(g) H=-92 kJ

a) Should we use higher or lower

temperature if we want to increase the
yield of ammonia?
b) Justify your choice.
 N2(g) + 3H2(g) 2NH3(g) + heat

a) A lower temperature should be used to

shift the equilibrium position to right in
order to increase the yield of ammonia.
b) As the forward reaction is exothermic
reaction.

Changes in concentration and pressure
will alter the position of equilibrium, but
not equilibrium constant, Kc.

Value of Kc will change when temperature
changes.
If forward reaction is exothermic, then when
temperature increases, value of Kc decreases.
If forward reaction is endothermic, when the
temperature increases, value of Kc increases.
 H2(g) + I2(g) 2HI(g)
Initial concentration Equilibrium concentration Kc
(mol L-1) (mol L-1)
[H2]0 [I2]o [HI]0 [H2]eqm [I2]eqm [HI]eqm

0.1000 0.10 0.000 0.0222 0.0222 0.156 49.4

0.0015 0.00 0.127 0.1500 0.1350 0.100 49.4

0.0000 0.00 0.400 0.0442 0.0442 0.311 49.5

Changing concentration of reactant or product

does not change Kc.
 PCl3(g) + Cl2(g) PCl5(g)
Total Pressure mole of PCl5 mole of PCl3 = Kp
(atm) mole of Cl2 (atm-1)

1 0.702 0.298 10.27

2 0.785 0.215 10.27
3 0.822 0.178 10.27
4 0.846 0.154 10.27
5 0.861 0.139 10.27
6 0.873 0.127 10.27
7 0.883 0.117 10.27

Increase pressure does not change Kp.

le chateliers_WMV V9.wmv
2NO2(g) N2O4(g)
Temperature Kp H
(Kelvin) (atm-1) (kJ mol-1)

298 0.115 58.0

350 3.89 57.9
400 47.9 57.7
450 347 57.6
500 1700 57.4
600 17800 57.1

Increase temperature increases Kp value for

endothermic reaction
Equilibrium Decomposition of N2O4

Copyright Cengage Learning.

All rights reserved 29
N2(g) + 3H2(g) 2NH3(g)
Temperature Kp H
(Kelvin) (atm-1) (kJ mol-1)

298 6.76x105 -92.4

400 4.07x101 -96.9
500 3.55x10-2 -101.3
600 1.66 x10-3 -105.8
700 7.76x10-5 -110.2
800 6.92 x10-6 -114.6

Increase temperature decreases Kp value for

exothermic reaction

Catalyst increases the rate of both
forward and reverse reaction to same
extent.

The reaction reaches equilibrium faster
but it does not alter the equilibrium
position or equilibrium constant.

No change in yield as well.
Industrial conditions
 Why not higher pressure?

Higher pressure will move the equilibrium
position to the right as the forward reaction
involves decrease in number of moles of gases.
(4 moles of gas
2 moles of gas)

BUT: Higher cost involved when higher
pressure is employed, which includes:
building reaction vessel which withstand high P.
operating cost: pumping gases at higher pressure.
Increase safety risks.
 Why not lower temperature?

Lower temperature increase the yield of
ammonia as the forward reaction, which is
an exothermic reaction, is favoured.

BUT lower temperature, lower rate.

Slow production, increase cost of
manufacture considerably.

Normally, a catalyst is used to increase
rate of reaction but it does not affect the
equilibrium position.
 Optimum conditions

le chateliers 2_WMV V9.wmv

 It took over 6500
experiments at different
temperatures and
pressures carried out by
the German engineer
Carl Bosch to work all
this lot out.
He got a Nobel Prize for
it in 1931!
(Haber got his Nobel
Prize in 1918)
 Percentage yields in homogeneous gas equilibrium reaction at
different temperatures and pressures.

200kPa 600 kPa 1000kPa

4000C 25% 40% 60%
5000C 20% 35% 55%
6000C 15% 30% 50%
7000C 10% 25% 45%
8000C 5% 20% 40%

Use the data in the table to help in answering the following

questions:
(a) State whether the forward reaction involves an increase or
decrease in the number of moles of gas. Give reasons to your
answer.
(b) State whether the forward reaction is endothermic or
exothermic. Give your reasoning.
 Percentage yields in homogeneous gas equilibrium reaction at
different temperatures and pressures:

200kPa 600 kPa 1000kPa

4000C 25% 40% 60%
5000C 20% 35% 55%
6000C 15% 30% 50%
7000C 10% 25% 45%
8000C 5% 20% 40%

As the pressure increases, the percent of yield increases.

This indicates the equilibrium position shifts to right.

The equilibrium position moves from more moles to fewer
moles side when pressure is increased.

Hence, the forward reaction involves reduction in number
of moles of gas.
 Percentage yields in homogeneous gas equilibrium reaction at
different temperatures and pressures:

200kPa 600 kPa 1000kPa

4000C 25% 40% 60%
5000C 20% 35% 55%
6000C 15% 30% 50%
7000C 10% 25% 45%
8000C 5% 20% 40%

As the temperature increases, the percent of yield decreases.

This indicates the reverse reaction is favored at higher temperature.

The endothermic reaction is favored when temperature is
increased.

The reverse reaction is endothermic reaction. Hence the forward
reaction is exothermic reaction.

The solubility of a solid will be lowered if
a similar ion present in the solution.

This effect is called common ion effect.

Mg(OH)2 (s) Mg2+ (aq) + 2OH-(aq)

If 0.5 M NaOH is added then a common ion
is introduced to the system:
NaOH(aq)
Na+(aq) + OH-(aq)

As suggested by Le Chateliers principle,
when the [OH-] increases, the equilibrium
moves to left.

More solid Mg(OH)2 remained in solid,
instead of forming aqueous ions.

Solubility of Mg(OH)2 decreases.

Calculate the solubility of Mg(OH)2 (Ksp=
5.6 x10-12) in a 0.5 M NaOH solution.
Mg(OH)2(s) Mg2+(aq) 2O H-(aq)

I 0.00 0.50
C x 2x
E x 0.50 + 2x

Ksp = [Mg2+][OH-]2
Ksp = [Mg2+][OH-]2
5.6 x10-12= (x)(0.50+2x)2
2x is negligible compared to 0. 50 since Ksp
is 5.6 x10-12
5.6 x10-12 = (x)(0.50)2
= 0.25 x
x = 2.24 x10-11
solubility of Mg(OH)2 in 0.5 M NaOH
= 2.24 x10-11 mol per liter of 0.5 M NaOH.
 Increase concentration, the equilibrium position shifts to
opposite direction.
Reduce concentration, the equilibrium position moves to the
concentration direction help to increase the amount of species that has been
removed.

Increase pressure, system moves from more moles side

to fewer moles side.
Decrease pressure, system moves to direction involving
Pressure increase in number of moles of gas.
(gas) If both sides of reaction have equal number of moles of
gas, then no change in equilibrium position

Increase in temperature favour the endothermic reaction.

Temperature Decrease in temperature will move to direction involving
exothermic reaction.
 Equilibrium

Law of mass Le Chatelier

Characteristics
action Principle

Kc Application Concentration Pressure Temperature

Common ion
Ksp Effect