Chemical Equilibrium-2

Le Châtelier’s Principle
• When a stress is applied to a system in dynamic equilibrium, the system

changes to relieve the stress.
• When an equilibrium system is subjected to a change in temperature,
pressure, or concentration of a reacting species, the system responds by
attaining a new equilibrium that partially offsets the impact of the change.
• System stressors:
• Concentration of reactants or products
• Temperature
• Pressure
The Effect of Changes in Concentration
N2(g) + 3H2(g) ⇄ 2 NH3(g);
An additional 1.00 mol NH3 into the 10.0 L flask.

Adding any quantity of NH3 to a constant-volume equilibrium mixture makes
Qc larger than Kc. (Qc ˃ Kc)
Net change occurs in the direction that reduces [NH3] that is, to the left, or in
the reverse direction.
Notice that reaction in the reverse direction increases [N2] and [H2], further
decreasing the value of Qc. 2
[NH 3 ]
Kc =
[N 2 ][H 2 ]3
Effects of Pressure or Volume Change on Equilibrium
There are three ways to change the pressure of a constant-temperature
equilibrium mixture.
1. Add or remove a gaseous reactant or product. The effect of these actions on
the equilibrium condition is simply that caused by adding or removing a
reaction component, as described previously.
2. Add an inert gas to the constant-volume reaction mixture. This has the
effect of increasing the total pressure, but the partial pressures of the reacting
species are all unchanged. An inert gas added to a constant-volume equilibrium
mixture has no effect on the equilibrium condition.
3. Change the pressure by changing the volume of the system. Decreasing the
volume of the system increases the pressure, and increasing the system volume
decreases the pressure. Thus, the effect of this type of pressure change is
simply that of a volume change.
When the volume of an equilibrium mixture of gases is reduced, a net change occurs in the
direction that produces fewer moles of gas. When the volume is increased, a net change occurs
in the direction that produces more moles of gas.
The equilibrium mixture in previous Figure has its volume reduced to one-
tenth of its original value by increasing the external pressure. To see how the
equilibrium amounts of the gases change, let’s first rearrange the equilibrium
constant expression to the form
There is only one way in which the ratio of moles of gases will increase in
value: The number of moles of SO3 must increase, and the numbers of moles
of SO2 and O2 must decrease. The equilibrium shifts in the direction producing
more SO3 to the right.
• Figure suggests a way of decreasing the volume of gaseous mixture at
equilibrium by increasing the external pressure.
• One way to increase the volume is to lower the external pressure.
• Another way is to transfer the equilibrium mixture from its original container
to one of larger volume.
• A third method is to add an inert gas at constant pressure; the volume of the
mixture must increase to make room for the added gas.
• The effect on the equilibrium, however, is the same for all three methods:
Equilibrium shifts in the direction of the reaction producing the greater
number of moles of gas.
Note: Keep in mind that an inert gas has no effect on an equilibrium
condition if the gas is added to a system maintained at constant volume, but
it can have an effect if added at constant pressure.
Note: In which direction the equilibrium will shift in either direction depends on the reaction stoichiometry.
Reaction that shifts left when pressure increases,
but shifts right when pressure decreases
Consider the reaction: PCl5(g) ⇄ PCl3(g) + Cl2(g);
- Forward reaction results in more gas molecules.

- Pressure increases as reaction proceeds towards equilibrium.
- When mixture is compressed, pressure increases, and reverse
reaction occurs to reduce pressure;
- When volume expands and pressure reduces, forward reaction
occurs to compensate.
Reactions not affected by pressure changes
Consider the following reactions:

H2(g) + Cl2(g) ⇄ 2HCl(g);
- Reaction has same number of gas molecules in reactants and products.

-Reducing or increasing the volume will cause equal effect on both sides
no net reaction will occur.
Effect of Temperature
• Increasing the temperature causes the equilibrium to shift in the direction that absorbs heat.
• 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.
• We can think of changing the temperature of an equilibrium mixture in terms
of adding heat (raising the temperature) or removing heat (lowering the
temperature).
• According to Le Châtelier s principle, adding heat favors the reaction in which
heat is absorbed (endothermic reaction). Removing heat favors the reaction
in which heat is evolved (exothermic reaction).
The Effect Temperature on Equilibrium
• Consider the following exothermic reaction:
N2(g) + 3H2(g) ⇄ 2NH3(g); Ho = -92 kJ,
• The forward reaction produces heat

• When temperature increases, reverse reaction will take place to absorb the heat, it
will cause a net reverse reaction.
• If heat is removed to reduce temperature, a net forward reaction will occur to
produce heat.
The Effect Temperature on Equilibrium
Consider the following endothermic reaction:

CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g), Ho = +205 kJ
- Endothermic reaction absorbs heat

- If heat is added to increasing the temperature, it will cause a net
forward reaction.
- If heat is removed to reduce the temperature, it will cause a net
reverse reaction.
Effect of a Catalyst on Equilibrium
• Adding a catalyst to a reaction mixture speeds up both the forward
and reverse reactions. Equilibrium is achieved more rapidly, but the
equilibrium amounts are unchanged by the catalyst.
Question 5
Question 6
2.000 mole of H2 gas and 2.000 mole of I2 vapor are introduced

into a 1.00-liter sealed flask. The mixture is heated to a certain
temperature and the following reaction occurs until equilibrium
is established.
H2(g) + I2(g) ⇄ 2HI(g)
At equilibrium, the mixture is found to contain 2.580 mole of
HI. (a) What are the concentrations of H2, I2 and HI at
equilibrium? (b) Calculate the equilibrium constant Kc.
Calculating Equilibrium Constant
for reaction: H2(g) + I2(g) ⇄ 2HI(g)
————————————————————————————
H2(g) + I2(g) ⇄ 2 HI(g)
————————————————————————————
Initial (mole) : 2.0 2.0 0.000
Change in (mole): -1.29 -1.29 + 2.58
Equilibrium (mole): 0.71 0.71 2.58
Equilibrium (M): 0.71 0.71 2.58
————————————————————————————
[HI]2
Kc = [H 2 ][I 2 ] = 13.20
Question 7
1.500 mole of HI is introduced into a 1.00 liter sealed flask and
heated to a certain temperature. Under this condition HI
decomposes to produce H2 and I2 until an equilibrium is
established. An analysis of the equilibrium mixture shows that
0.200 mole of HI has decomposed. Calculate the equilibrium
concentrations of H2, I2 and HI, and the equilibrium constant
Kc for the following reaction:
H2(g) + I2(g) ⇄ 2HI(g),
Calculating Equilibrium Constant
The reaction: H2(g) + I2(g) ⇄ 2HI(g), proceeds from

right to left.
————————————————————————————
H2(g) + I2(g) ⇄ 2HI(g)
————————————————————————————
Initial (mole): 0.000 0.000 1.500
Change in (mole): +0.100 +0.100 -0.200
Equil’m (mole) 0.100 0.100 1.300
————————————————————————————
Kc = 169
References
1. General Chemistry: Principles and Modern Applications / Ralph H.
Petrucci, F. Geoffrey Herring ...[et al.]. 10th ed.

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Le Châtelier’s Principle

• When a stress is applied to a system in dynamic equilibrium, the system

An additional 1.00 mol NH3 into the 10.0 L flask.

Consider the reaction: PCl5(g) ⇄ PCl3(g) + Cl2(g);

- Forward reaction results in more gas molecules.

Consider the following reactions:

- Reaction has same number of gas molecules in reactants and products.

• The forward reaction produces heat

Consider the following endothermic reaction:

- Endothermic reaction absorbs heat

2.000 mole of H2 gas and 2.000 mole of I2 vapor are introduced

The reaction: H2(g) + I2(g) ⇄ 2HI(g), proceeds from

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