Chapter 5.

Le Châtelier’s
Principle & Catalysis
 Le Châtelier’s Principle

“If a system at equilibrium is disturbed by a change in

temperature, pressure, or the concentration of one of
the components, the system will shift its equilibrium
position so as to counteract the effect of the
disturbance.”
 The Effect of Changes in Temperature

Co(H2O)62+(aq) + 4 Cl(aq) ↔ CoCl4 (aq) + 6 H2O (l)

 Sample Exercise 11 Using Le Châtelier’s Principal to Predict shifts in Equilibrium
Consider the equilibrium

In which direction will the equilibrium shift when (a) N2O4 is added, (b) NO2 is removed, (c)
the total pressure is increased by addition of N2(g), (d) the volume is increased, (e) the
temperature is decreased?

Solve: (a) The system will adjust to decrease the concentration of the added N2O4, so the equilibrium shifts to the
right, in the direction of products.
(b) The system will adjust to the removal of NO2 by shifting to the side that produces more NO2; thus, the
equilibrium shifts to the right.
(c) Adding N2 will increase the total pressure of the system, but N2 is not involved in the reaction. The partial
pressures of NO2 and N2O4 are therefore unchanged, and there is no shift in the position of the equilibrium.
(d) If the volume is increased, the system will shift in the direction that occupies a larger volume (more gas
molecules); thus, the equilibrium shifts to the right. (where the volume was decreased.)
(e) The reaction is endothermic, so we can imagine heat as a reagent on the reactant side of the equation. Decreasing
the temperature will shift the equilibrium in the direction that produces heat, so the equilibrium shifts to the left,
toward the formation of more N2O4. Note that only this last change also affects the value of the equilibrium constant,
K.
 Sample Exercise 12 Predicting the Effect of Temperature on K
(a) Using the standard heat of formation data in Appendix C, determine the standard
enthalpy change for the reaction

(b) Determine how the equilibrium constant for this reaction should change with
temperature.
Solve: (a) Recall that the standard enthalpy change for a reaction is given by the sum of the
standard molar enthalpies of formation of the products, each multiplied by its coefficient in the
balanced chemical equation, less the same quantities for the reactants. At 25 oC, ΔHf for
NH3(g) is –46.19 kJ/mol. The ΔHf values for H2(g) and N2(g) are zero by definition because
the enthalpies of formation of the elements in their normal states at 25 oC are defined as zero.
Because 2 mol of NH3 is formed, the total enthalpy change is

(b) Because the reaction in the forward direction is exothermic, we can consider heat a product
of the reaction. An increase in temperature causes the reaction to shift in the direction of less
NH3 and more N2 and H2. This effect is seen in the values for Kp. Notice that Kp changes
markedly with changes in temperature and that it is larger at lower temperatures.
Chemical Equilibrium : Le Châtelier’s Principle
Le Châ telier’s Principle

1.) What Happens When a System at Equilibrium is Perturbed?

➢ Change concentration, temperature, pressure or add other chemicals

➢ Equilibrium is re-established
- Reaction accommodates the change in products, reactants, temperature,
pressure, etc.
- Rates of forward and reverse reactions re-equilibrate
Chemical Equilibrium : Le Châtelier’s Principle
Le Châ telier’s Principal

1.) What Happens When a System at Equilibrium is Perturbed?

➢ Le Châtelier’s Principal:

- the direction in which the system proceeds back to equilibrium is such that
the change is partially offset.

Consider this reaction:

At equilibrium:
To return to equilibrium
(balance), some (not all)
CO and H2 are converted
to CH3OH
Add excess CO(g):

If all added CO was converted to CH3OH, then reaction

would be unbalanced by the amount of product
 Chemical Equilibrium : Le Châtelier’s Principle
Le Châ telier’s Principal

2.) Example:

Consider this reaction:

[ Br - ][Cr2O72- ][ H + ]8
K= = 1  10 11 at 25 o C
[ BrO3- ][Cr 3+ ]2

At one equilibrium state:

[H + ] = 5.0 M [Cr2O72- ] = 0.10 M [Cr 3+ ] = 0.0030 M

[Br − ] = 1.0 M [BrO3- ] = 0.043 M
 Chemical Equilibrium : Le Châtelier’s Principle
Le Châ telier’s Principal

2.) Example:

What happens when:

[Cr2O72- ] increased from 0.10 M to 0.20 M

According to Le Châtelier’s Principal, reaction should go back to left to
off-set dichormate on right:

Use reaction quotient (Q), Same form of equilibrium equation, but not at
equilibrium:

Q=
[ Br - ][Cr2O72- ][ H + ]8
=
(1.0 )(0.20 )(5.0 )8
= 2  10 11  K
[ BrO3- ][Cr 3+ ]2 (0.043 )(0.0030 )2
 Chemical Equilibrium : Le Châtelier’s Principle
Le Châ telier’s Principal
2.) Example:
Because Q > K, the reaction must go to the left to decrease numerator and increase
denominator.

Continues until Q = K:

1. If the reaction is at equilibrium and products are added (or reactants removed), the
reaction goes to the left

2. If the reaction is at equilibrium and reactants are added ( or products removed), the
reaction goes to the right
 Chemical Equilibrium : Le Châtelier’s Principle
Le Châtelier’s Principle

3.) Affect of Temperature on Equilibrium

Combine Gibbs free energy and Equilibrium Equations:

D − (DH o − TDS )
o
− G
K =e RT =e RT

=e
− D(H o

RT
+ DS
R
)
− DH o DS o
=e RT e R

Only Enthalpy term is temperature dependent:

− DH o
K(T )  e RT
 Chemical Equilibrium : Le Châtelier’s Principle
Le Châtelier’s Principle

3.) Affect of Temperature on Equilibrium

1. Equilibrium constant of an endothermic reaction (DHo = +) increases

if the temperature is raised.
D
DH = +

2. Equilibrium constant of an exothermic reaction (DHo = -)decreases if

the temperature is raised.

D
DH = -
 Chemical Equilibrium : Le Châtelier’s Principle
Le Châtelier’s Principle

4.) Thermodynamics vs. Kinetics

➢ Thermodynamics predicts if a reaction will occur

- determines the state at equilibrium

➢ Thermodynamics does not determine the rate of a reaction

- Will the reaction occur instantly, in minutes, hours, days or years?

DG = -

spontaneous

Diamonds Graphite
- While reaction is spontaneous, takes millions of years to occur
 Adding Catalysts

A catalyst lowers the activation

energy for both the forward
and the reverse reactions.
A catalyst therefore speeds up
the forward and reverse
reactions equally.
A catalyst speeds up the rate
at which equilibrium is
achieved, but the equilibrium
mixture and K remain exactly
the same.
Catalysts

Catalysts increase the rate

of both the forward and
reverse reactions.
Catalysts

When one uses a catalyst,

equilibrium is achieved
faster, but the equilibrium
composition remains
unaltered.
 The Haber Process

The transformation of nitrogen and hydrogen into

ammonia (NH3) is of tremendous significance in
agriculture, where ammonia-based fertilizers are of
utmost importance.
The Haber Process

If H2 is added to the system,

N2 will be consumed and the
two reagents will form more
NH3.
The Haber Process

This apparatus helps push

the equilibrium to the right
by removing the ammonia
(NH3) from the system as a
liquid.