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Important
Important
Important
Le Chatelier’s Principle
Changes in Concentration
According to Le Chatelier’s principle, adding additional reactant to a system will shift the
equilibrium to the right, towards the side of the products. By the same logic, reducing
the concentration of any product will also shift equilibrium to the right.
The converse is also true. If we add additional product to a system, the equilibrium will
shift to the left, in order to produce more reactants. Or, if we remove reactants from the
system, equilibrium will also be shifted to the left.
This can be illustrated by the equilibrium of this reaction, where carbon monoxide and
hydrogen gas react to form methanol:
CO+2H2⇌CH3OH
Changes in Pressure
Consider the reaction of nitrogen gas with hydrogen gas to form ammonia:
N2+3H2⇌2NH3ΔH=−92kJ mol−1
Note the number of moles of gas on the left-hand side and the number of moles of gas
on the right-hand side. When the volume of the system is changed, the partial pressures
of the gases change. If we were to decrease pressure by increasing volume, the
equilibrium of the above reaction would shift to the left, because the reactant side has
greater number of moles than the product side. The system tries to counteract the
decrease in partial pressure of gas molecules by shifting to the side that exerts greater
pressure.
Lastly, for a gas-phase reaction in which the number of moles of gas on both sides of
the equation are equal, the system will be unaffected by changes in pressure,
since Δn=0.
What would happen to the equilibrium position of the reaction if an inert gas, such as
krypton or argon, were added to the reaction vessel? Answer: nothing at all. Remember
that the system will always shift so that the ratio of products and reactants remains
equal to Kp or Kc. An inert gas will not react with either the reactants or the products, so
it will have no effect on the product/reactant ratio, and therefore, it will have no effect on
equilibrium.
Changes in Temperature
The effect of temperature on equilibrium has to do with the heat of reaction. Recall that
for an endothermic reaction, heat is absorbed in the reaction, and the value of ΔH is
positive. Thus, for an endothermic reaction, we can picture heat as being a reactant:
heat+A⇌BΔH=+
For an exothermic reaction, the situation is just the opposite. Heat is released in the
reaction, so heat is a product, and the value of ΔHΔH is negative:
A⇌B+heatΔH=−
For an exothermic reaction, heat is a product. Therefore, increasing the temperature will
shift the equilibrium to the left, while decreasing the temperature will shift the equilibrium
to the right.
EXAMPLE
In which direction will the equilibrium shift if the temperature is raised on the following reaction?
N2O4(g)⇌2NO2(g) ΔH=+57.2
Our heat of reaction is positive, so this reaction is endothermic. Since this reaction is
endothermic, heat is a reactant. By Le Chatelier’s principle, increasing the temperature will shift
the equilibrium to the right, producing more NO . 2