FACTORS AFFECTING

EQUILIBRIUM
4

factors :
Concentration
Pressure
Temperature
Catalyst

LE CHATELIERS PRINCIPLE
Definition

:
if a system at equilibrium is disturbed, the
equilibrium moves in the direction which tend
to reduce the disturbance ,
( and as a result of that , achieves a new
equilibrium position )

Effect of concentration
A + B C + D
2. If A or B is increased ,
Rate of forward reaction increases
Concentration of C and D increases
Rate of reverse reaction increases
Rate of forward reaction = rate of reverse
reaction
New equilibrium achieved
1.

 3.Position

of equilibrium changes

Equilibrium

constant unchanged

 4.

Examples :
a.Fe3+(aq) + SCN-(aq) [FeSCN]2+(aq)
Yellow
deep red
At equilibrium ,colour of solution = red
i) [Fe3+] increased ,
Equilibrium shifts right , solution more red
ii) [SCN-] decreased,
Equilibrium shifts left , red solution lightens

 b.2CrO42-(aq)

+ 2H+(aq)Cr2O72-(aq) + H2O

Yellow
orange
At equilibrium , colour of solution = orange
i) Add H+ ,
Concentration of H+ increases
Equilibrium shifts right, solution more orange

 ii)

Add OH- ,
OH- neutralises H+ , [H+] decreased ,
Equilibrium shifts left , solution turns yellow

Effect of pressure

1.Pressure exerted depends on no. of moles of

gases ( no of moles , pressure )
2.Changes in pressure :
a. pressure
Equilibrium will shift so as to decrease pressure
Equilibrium will shift to a direction which produces
fewer no of moles of gases
b. pressure , equilibrium will shift so as to increase
pressure
Equilibrium will shift to a direction which produces
more no of moles of gases

3.Example

1 N2O4 (g) 2 NO2 (g)

pale yellow
brown
Colour of mixture : brown
Forward reaction is accompanied by an increase in no
of moles of gases (1)
If pressure ,
Equilibrium will shift to a direction which produces less
no of moles of gases
equilibrium shifts left
Observation : mixture becomes less brown

 4.

Effect of changes in pressure :

Little effect on equilibrium where overall
difference in no of moles of gases is small
Eg 4NH3(g) + 5O2(g) 4NO(g) +6H2O(g)

9 moles
10 moles

small difference

 5.No

effect on equilibrium if no overall

change in no of moles of gases :
Eg H2(g) + I2(g) 2HI (g)

2 moles
2 moles
6.Position

of equilibrium changes

Equilibrium

constant is unchanged

Effect of temperature
1.Changes

in temperature :
a.Temperature , equilibrium shifts to a
direction to cool system down
Absorbs heat ( endothermic rxn favored)
b.Temperature , equilibrium shifts to a
direction to increase temperature
Evolves heat ( exothermic rxn favored )

2.Example

N2O4(g) 2NO2 (g) H= +58 kJmol-1

pale yellow
brown
Colour of mixture : brown
Forward reaction is endothermic (1)
(Therefore reverse reaction is exothermic)

 If

temperature increases ,
Equilibrium shifts to a direction which absorbs
heat ( endothermic reaction )
Equilibrium shifts right
More NO2 forms
Observation

: mixture becomes more brown

 3.Changes

in temperature has no effect on

equilibrium where H for the reaction is zero
4.Position of equilibrium and equilibrium
constant changes
5. Note :Temperature increase , rate of
forward and reverse reaction increase
However rate of endothermic reaction
increases more

Effect of catalyst (catalysis)

1.Positive

catalyst increases rate of reaction

by providing an alternative route with a lower
activation energy ( Ea )

(With

a different mechanism)
Definition : Activation energy is the minimum
energy required for a reaction to occur

2. Enthalpy diagram : eg reversible exothermic reaction

Energy

Decrease in Ea
Ea forward
(uncatalysed) E forward
a
(catalysed)
Reactants

Ea reverse
Ea reverse

(uncatalysed)

(catalysed)
H

Products
Reaction pathway

 3.Ea

for both forward and reverse reactions

lowered by the same amount
Rate of both reactions increased by the same
extent
Equilibrium position unchanged
Equilibrium constant unchanged
4.Catalyst only results in equilibrium
achieved more quickly

Summary
Factors affecting equilibrium
Influence

Equilibrium
constant

Equilibrium
position

Change in
conc

No change

Changes

Change in
pressure

No change

Changes

Addition of
catalyst

No change

No change

Change in
temp

Changes

Changes

Questions

Br2 + H2O

2H+ + Br- + OBr-

brown / orange
colourless
Colour of solution : brown / orange
Add HCl :
[H+] increase (1)
equilibrium shifts left (1)
Solution becomes more brown (1)

 Add

NaOH,
OH- neutralises H+ , [H+] decrease (1)
Equilibrium shifts right (1)
Solution becomes less brown (1)

2H2 + CO CH3OH H positive

Temperature

decreased,
Forward rxn is endothermic (1)
When temp , equilibrium shifts left (1)
Formation of methanol decreases (1)

 Pressure

increased
Forward rxn is accompanied by a decrease in
the no of moles of gases (1)
When pressure , equilibrium shifts right (1)
Formation of methanol increases (1)