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Changes in Concentration
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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: N 2 (g ) + 3H 2 ( g) 2NH3 ( g )
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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
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Changes in Pressure
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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: N 2 (g ) + 3H 2 ( g ) 2NH3 (g )
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Equilibrium 215
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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
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Changes in Temperature
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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: N 2 (g ) + H 2 ( g) 2NH3 ( g)
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The formation of ammonia is exothermic (liberating heat), so the reaction could be written as: N 2 ( g) + 3H 2 (g) 2NH3 (g) + heat
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 CaCO3 ( s) a b c d e f add CO2 remove CO2 add CaO increase T decrease V add a catalyst CaO(s) + CO2 (g )
Answers: a b c d e f 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
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