13.1 Chemical Equilibria
A reaction is at equilibrium when the amounts of reactants or products no longer change. Chemical equilibrium is a dynamic process, meaning the rate of formation of products by the forward reaction is equal to the rate at which the products re-form reactants by the reverse reaction.
13.2 Equilibrium Constants
For any reaction that is at equilibrium, the reaction quotient Q is equal to the equilibrium constant K for the reaction. If a reactant or product is a pure solid, a pure liquid, or the solvent in a dilute solution, the concentration of this component does not appear in the expression for the equilibrium constant. At equilibrium, the values of the concentrations of the reactants and products are constant. Their particular values may vary depending on conditions, but the value of the reaction quotient will always equal K (Kc when using concentrations or KP when using partial pressures).
A homogeneous equilibrium is an equilibrium in which all components are in the same phase. A heterogeneous equilibrium is an equilibrium in which components are in two or more phases. We can decide whether a reaction is at equilibrium by comparing the reaction quotient with the equilibrium constant for the reaction.
13.3 Shifting Equilibria: Le Châtelier’s Principle
Systems at equilibrium can be disturbed by changes to temperature, concentration, and, in some cases, volume and pressure; volume and pressure changes will disturb equilibrium if the number of moles of gas is different on the reactant and product sides of the reaction. The system's response to these disturbances is described by Le Châtelier's principle: The system will respond in a way that counteracts the disturbance. Not all changes to the system result in a disturbance of the equilibrium. Changing pressure or volume will not significantly disturb systems with no gases or with equal numbers of moles of a gas on the reactant and product side.
|Effects of Disturbances of Equilibrium and K|
|Disturbance||Observed Change as Equilibrium is Restored||Direction of Shift||Effect on K|
|reactant added||added reactant is partially consumed||toward products||none|
|product added||added product is partially consumed||toward reactants||none|
|decrease in volume/increase in gas pressure||pressure decreases||toward side with fewer moles of gas||none|
|increase in volume/decrease in gas pressure||pressure increases||toward side with more moles of gas||none|
|temperature increase||heat is absorbed||toward products for endothermic, toward reactants for exothermic||changes|
|temperature decrease||heat is given off||toward reactants for endothermic, toward products for exothermic||changes|
13.4 Equilibrium Calculations
The ratios of the rate of change in concentrations of a reaction are equal to the ratios of the coefficients in the balanced chemical equation. The sign of the coefficient of x is positive when the concentration increases and negative when it decreases. We learned to approach several basic types of equilibrium problems. When given the concentrations of the reactants and products at equilibrium, we can solve for the equilibrium constant; when given the equilibrium constant and some of the concentrations involved, we can solve for the missing concentrations; and when given the equilibrium constant and the initial concentrations, we can solve for the concentrations at equilibrium. We also learned that a negative value for ΔG indicates a spontaneous process; a positive ΔG indicates a nonspontaneous process; and a ΔG of zero indicates that the system is at equilibrium. We also saw how free energy, spontaneity, and equilibrium relate.