FACTORS AFFECTING THE

STATE OF EQUILIBRIUM :
LE CHATELIERS
PRINCIPLE

FACTORS AFFECTING THE STATE OF

EQUILIBRIUM
Chemical equilibrium is a very delicate system that
represents a perfect balance between forward and
reverse reaction. A small disturb in the equilibrium
may shift the equilibrium position either to right
forming more products or to left forming more
reactants. This reaction by the system is of course
temporary and eventually the system will come back
to equilibrium. This phenomenon can be expressed in
the form of Le Chateliers Principle.

LE CHATELIERS PRINCIPLE
An important and very interesting qualitative
principle governing the equilibrium is the principle of
Le Chatelier. This principle, which is named after the
French chemist Henry Louis Le Chatelier (18501936), may be stated as follows:
if an external stress is applied to a system at
equilibrium, the system will tend to react in such way as
to relieve the applied stress and tries to reestablish the
equilibrium

In chemical reaction terminology, the stress

means change in concentration, pressure, volume or
temperature. Le Chateliers principle can be
understood either qualitatively or quantitatively
doing some problems. However, we restrict

LE CHATELIERS PRINCIPLE
If the concentration of A increases, the system reacts to consume
some of it.

If a reactant is added, the equilibrium position shifts to the

right.
If the
If a concentration
product is added,
the equilibrium
position
to the
of B decreases,
the system
reactsshifts
to consume
left.of it.
some
If a reactant is removed, the equilibrium position shifts to
the left.
substances
that appear
the expression
for shifts
Q canto the
Only
If a product
is removed,
the in
equilibrium
position
have
an effect.
right.
A change in concentration has no effect on the value of K.

The Effect of Change in Concentration

The Effect of Added Cl2 on the PCl3-Cl2-PCl5 System

Concentration (M)
Original equilibrium

PCl3(g) +
0.200

Disturbance
New initial
Change
New equilibrium

Cl2(g)
0.125

PCl3(g)
0.600

+0.075
0.200

0.200

0.600

-x

-x

+x

0.200 - x

0.200 - x

0.600 + x
(0.637)*

The effect of added Cl2 on the PCl3-Cl2-PCl5 system.

PCl3(g) + Cl2(g)

PCl5(g)

When Cl2 (yellow curve) is added, its

concentration increases instantly
(vertical part of yellow curve) and then
falls gradually as it reacts with PCl3 to
form more PCl5. Equilibrium is reestablished at new concentrations but
with the same value of K.

Predicting the Effect of a Change

Sample Problem in Concentration on the
Equilibrium Position
PROBLEM: To improve air quality and obtain a useful product,
chemists often remove sulfur from coal and natural gas
by treating the contaminant hydrogen sulfide with O 2:
2H2S(g) + O2(g)
2S(s) + 2H2O(g)
What happens to
(a) [H2O] if O2 is added?
(b) [H2S] if O2 is added?
(c) [O2] if H2S is removed?
PLAN: We write the reaction quotient to see how Qc is affected by
each disturbance, relative to Kc. This effect tells us the
direction in which the reaction proceeds for the system to
reattain equilibrium and how each concentration changes.

SOLUTION:
Qc = [H2O]
2
2
[H
2S] [O2]
(a) When O2 is added, Q decreases and the reaction proceeds to the
right until Qc = Kc again, so [H2O] increases.
(b) When O2 is added, Q decreases and the reaction proceeds to the
right until Qc = Kc again, so [H2S] decreases.
(c) When H2S is removed, Q increases and the reaction proceeds to
the left until Qc = Kc again, so [O2] increases.
(d) The concentration of solid S is unchanged as long as some is
present, so it does not appear in the reaction quotient. Adding
more S has no effect, so [H2S] is unchanged.

The effect of change in Pressure

(Volume)
Pressure does not have any effect on concentrations
of species that are present in solid, liquid or solution
form. On the other hand, the change in pressure
affects the concentrations of gases. According to
ideal gas law, pressure and volume are inversely
proportional to each other; the greater the pressure,
the smaller the volume, and vice versa. Thus, it is
just enough to understand the affect of change in
pressure on the equilibrium system

Changing the concentration of a gaseous component

causes the equilibrium to shift accordingly.

Adding an inert gas has no effect on the equilibrium

position, as long as the volume does not change.
This is because all concentrations and partial pressures remain
unchanged.

Changing the volume of the reaction vessel will cause

equilibrium to shift if ngas 0.

Changes in pressure (volume) have no effect on the

value of K.

When the volume of an equilibrium mixture of gases

is reduced, a net reaction occurs in the direction
producing fewer moles of gases. When the volume is
increased, a net reaction occurs in the direction
producing more moles of gases.
The effect of a change in pressure (volume) on a
system at equilibrium.

The effect of change In Temperature

A change in concentration, pressure or volume
alters the position of the equilibrium but not the
magnitude (value) of the equilibrium constant.
However, the change in temperature changes the
value of the equilibrium constant. To understand
the effect of temperature, we must know whether
the reaction is endothermic (absorption of heat) or
exothermic( release of heat).

To determine the effect of a change in temperature

on equilibrium, heat is considered a component of
the system.

Heat is a product in an exothermic reaction (DHrxn < 0).

Heat is a reactant in an endothermic reaction (DHrxn > 0).

 An increase in temperature adds heat, which favors the

endothermic reaction.
A decrease in temperature removes heat, which favors
the exothermic reaction.

Raising the temperature of an equilibrium

mixture shifts the equilibrium condition in the
direction of the endothermic reaction.
Lowering the temperature causes a shift in the
direction of the exothermic reaction.

The effect of a Catalyst in an Equilibrium

The function of a catalyst is to speed up the reaction
by lowering the activation energy. The catalyst lowers
the activation energy of the forward reaction and
reverse reaction to the same extent. Due to this,
there is no shift in equilibrium or the change in trhe
value of the equilibrium constant. Therefore, we
conclude that the catalyst has no effect on the
equilibrium system. Therefore:
A catalyst speeds up a reaction by lowering its
activation energy. A catalyst therefore speeds up the
forward and reverse reactions to the same extent.
A catalyst causes a reaction to reach equilibrium more
quickly, but has no effect on the equilibrium position.

Note: The presence of a catalyst does not change the

numerical value of the equilibrium constant.

The function of a catalyst is to change the

mechanism of a reaction to one having a lower
activation energy.
A catalyst has no effect on the condition of
equilibrium in a reversible reaction.

Effects of Various Disturbances on a

System at Equilibrium