We introduced the concept of equilibrium in Chapter 11, where you learned that a liquid and a vapor are in equilibrium when the number of molecules evaporating from the surface of the liquid per unit time is the same as the number of molecules condensing from the vapor phase. Vapor pressure is an example of a physical equilibrium because only the physical form of the substance changes. Similarly, in Chapter 13, we discussed saturated solutions, another example of a physical equilibrium, in which the rate of dissolution of a solute is the same as the rate at which it crystallizes from solution.
In this chapter, we describe the methods chemists use to quantitatively describe the composition of chemical systems at equilibrium, and we discuss how factors such as temperature and pressure influence the equilibrium composition. As you study these concepts, you will also learn how urban smog forms and how reaction conditions can be altered to produce H2 rather than the combustion products CO2 and H2O from the methane in natural gas. You will discover how to control the composition of the gases emitted in automobile exhaust and how synthetic polymers such as the polyacrylonitrile used in sweaters and carpets are produced on an industrial scale.
- 15.1: The Concept of Equilibrium
- At equilibrium, the forward and reverse reactions of a system proceed at equal rates. Chemical equilibrium is a dynamic process consisting of forward and reverse reactions that proceed at equal rates. At equilibrium, the composition of the system no longer changes with time. The composition of an equilibrium mixture is independent of the direction from which equilibrium is approached.
- 15.2: The Equilibrium Constant
- The law of mass action describes a system at equilibrium in terms of the concentrations of the products and the reactants. For a system involving one or more gases, either the molar concentrations of the gases or their partial pressures can be used. The equilibrium constant can be defined in terms of forward and reverse rate constants via the law of mass action.
- 15.3: Interpreting and Working with Equilibrium Constants
- The magnitude of the equilibrium constant, K, indicates the extent to which a reaction will proceed: If K is a large number, it means that the equilibrium concentration of the products is large. In this case, the reaction as written will proceed to the right (resulting in an increase in the concentration of products) If K is a small number, it means that the equilibrium concentration of the reactants is large.
- 15.4: Heterogeneous Equilibria
- An equilibrated system that contains products and reactants in a single phase is a homogeneous equilibrium; a system whose reactants, products, or both are in more than one phase is a heterogeneous equilibrium.
- 15.5: Calculating Equilibrium Constants
- Various methods can be used to solve the two fundamental types of equilibrium problems: (1) those in which we calculate the concentrations of reactants and products at equilibrium and (2) those in which we use the equilibrium constant and the initial concentrations of reactants to determine the composition of the equilibrium mixture. When an equilibrium constant is calculated from equilibrium concentrations, concentrations or partial pressures are use into the equilibrium constant expression.
- 15.6: Applications of Equilibrium Constants
- The reaction Quotient (\(Q\) or \(Q_p\)) has the same form as the equilibrium constant expression, but it is derived from concentrations obtained at any time. When a reaction system is at equilibrium, \(Q = K\). Graphs derived by plotting a few equilibrium concentrations for a system at a given temperature and pressure can be used to predict the direction in which a reaction will proceed. Points that do not lie on the line or curve are nonequilibrium states.
- 15.7: Le Chatelier'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. Adding a catalyst affects the reaction rates but does not alter equilibrium.
- 15.E: Exercises
- These are homework exercises to accompany the Textmap created for "Chemistry: The Central Science" by Brown et al.