Le Cha
^
telier’s Principle
At a given temperature, a reaction will reach equilibrium with the production of a certain
amount of product. If the equilibrium constant is small, that means that not much prod-
uct will be formed. But is there anything that can be done to produce more? Yes, there is—
through the application of Le Cha^telier’s principle. Le Cha^telier, a French scientist,
discovered that if a chemical system at equilibrium is stressed (disturbed) it will reestablish
equilibrium by shifting the reactions involved. This means that the amounts of the reac-
tants and products will change, but the final ratio will remain the same. The equilibrium
may be stressed in a number of ways: changes in concentration, pressure, and temperature.
Many times the use of a catalyst is mentioned. However, a catalyst will have no effect on
the equilibrium amounts, because it affects both the forward and reverse reactions equally.
It will, however, cause the reaction to reach equilibrium faster.Changes in Concentration
If the equilibrium system is stressed by a change in concentration of one of the reactants or
products, the equilibrium will react to remove that stress. If the concentration of a chemi-
cal species is decreased, the equilibrium will shift to produce more of it. In doing so, the
concentration of chemical species on the other side of the reaction arrows will be decreased.
If the concentration of a chemical species is increased, the equilibrium will shift to consume
it, increasing the concentration of chemical species on the other side of the reaction arrows.For example, again consider the Haber process:If one increases the concentration of hydrogen gas, then the equilibrium shifts to the
right to consume some of the added hydrogen. In doing so, the concentration of ammonia
(NH 3 ) will increase and the concentration of nitrogen gas will decrease. On the other hand,
if the concentration of nitrogen gas was decreased, the equilibrium would shift to the left
to form more, the concentration of ammonia would decrease, and the concentration of
hydrogen would increase.
Again, remember that the concentrations may change, but the value of Kcor Kpwould
remain the same.Changes in Pressure
Changes in pressure are significant only if gases are involved. The pressure may be
changed by changing the volume of the container or by changing the concentration of a
gaseous species (although this is really a change in concentration and can be treated as a con-
centration effect, as above). If the container becomes smaller, the pressure increases because
there is an increased number of collisions on the inside walls of the container. This stresses
the equilibrium system, and it will shift to reduce the pressure. This can be accomplished by
shifting the equilibrium toward the side of the equation that has the lesser number of moles
of gas. If the container size is increased, the pressure decreases and the equilibrium will shift
to the side containing more moles of gas to increase the pressure. If the number of moles of
gas is the same on both sides, changing the pressure will not affect the equilibrium.
Once again, consider the Haber reaction:Ng Hg 22 ()+ 32 () NHg 3 ()Ng Hg) 2NHg 22 ()+ 3 ( 3 ()214 Step 4. Review the Knowledge You Need to Score High