Le Chatelier's Principle for AP Chemistry (page 2)
Practice problems for these concepts can be found at:
- Equilibrium Multiple Choice Review Questions for AP Chemistry
- Equilibrium Free-Response Questions for AP Chemistry
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 product will be formed. But is there anything that can be done to produce more? Yes, there is—through the application of Le Châtelier's principle. Le Châtelier, 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 reactants 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 chemical 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 (NH3) 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 Kc or Kp would 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 concentration 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:
Note that there are 4 mol of gas (1 of nitrogen and 3 of hydrogen) on the left side and 2 mol on the right. If the container is made smaller, the pressure will increase and the equilibrium will shift to the right because 4 mol would be converted to 2 mol. The concentrations of nitrogen and hydrogen gases would decrease, and the concentration of ammonia would increase.
Remember: Pressure effects are only important for gases.
Changes in Temperature
Changing the temperature changes the value of the equilibrium constant. It also changes the amount of heat in the system and can be treated as a concentration effect. To treat it this way, one must know which reaction, forward or reverse, is exothermic (releasing heat).
One last time, let's consider the Haber reaction:
The formation of ammonia is exothermic (liberating heat), so the reaction could be written as:
If the temperature of the reaction mixture were increased, the amount of heat would be increased and the equilibrium would shift to the left to consume the added heat. In doing so, the concentration of nitrogen and hydrogen gases would increase and the concentration of ammonia gas would decrease. If you were in the business of selling ammonia, you would probably want to operate at a reduced temperature, in order to shift the reaction to the right.
Consider the following equilibrium (endothermic as written), and predict what changes, if any, would occur if the following stresses were applied after equilibrium was established.
- add CO2
- remove CO2
- add CaO
- increase T
- decrease V
- add a catalyst
- Left—the equilibrium shifts to remove some of the excess CO2.
- Right—the equilibrium shifts to replace some of the CO2.
- No change—solids do not shift equilibria unless they are totally removed.
- Right—endothermic reactions shift to the right when heated.
- Left—a decrease in volume, or an increase in pressure, will shift the equilibrium toward the side with less gas.
- No change—catalysts do not affect the position of an equilibrium.
Practice problems for these concepts can be found at: