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FACTORS THAT AFFECT CHEMICAL EQUILIBRIUM
Le Chatelier’s Principle
Le Chatelier’s principle states that any stress on the system (∆P, ∆ T, change in reactant or product concentration) causes the system to adjust so as to partially offset the change and establish a new equilibrium.
Changes In Concentration
The effect of concentration changes can be understood by considering the effect of changes in reactant and product molecule collisions or by solving the Law of Mass Action.
The effects of concentration changes can be determined qualitatively by inspection of the equilibrium expression or by calculating Qc values for initial reactant and product concentration in the equilibrium expression.
Changes In Volume and Pressure
Pressure has a small and generally negligible effect on equilibria in the liquid or solid state reactions. (An exception is the huge pressures involved in the graphite-diamond transition.)
In gas phase reactions, pressure changes affect the equilibrium if the reaction produces a change in the number of moles of gas.
Pressure change can be brought about by changing the volume of the system or by adding or removing one of the reaction components.
Example: If a gas reaction causes the number of moles of gas to double, the system pressure at constant volume will double.
According to Le Chatelier’s principle, an imposed increase in the system pressure will drive the reaction to the left (restoring the system equilibrium. This pressure change can be created by a piston that changes the system volume.
The CaCO3(s) ↔ CaO(s) + CO2(g) equilibrium will shift left with a pressure increase
The H2(g) + I2(g) ↔ 2HI equilibrium is unaffected by pressure changes.
The CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l) equilibrium is unaffected by pressure.
The 3H2(g) + N2(g) ↔ 2 NH3(g) equilibrium shifts right with a pressure increase.
What happens to the same reactions when the pressure change is caused by adding or removing one of the reaction components?
Changes In Temperature
Equilibrium constants change with changes in temperature. (K is only constant for constant T.) In general, a temperature increase favors an endothermic reaction and a temperature decrease favors an exothermic reaction. To remember this, think of heat as a reactant or product in a reaction and think how its addition or removal form a system will affect the outcome.
Heat + A ↔ B (endothermic)
Increasing temperature causes the equilibrium to shift to the right since heat is needed to force the reaction.
The Effect of A Catalyst
A catalyst affects only the speed of a reaction. A catalyst has no effect on the position of equilibrium.
A catalyst has an equal effect on lowering the Eact of the forward and the backward reaction