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15.1 Precipitation and Dissolution

The equilibrium constant for an equilibrium involving the precipitation or dissolution of a slightly soluble ionic solid is called the solubility product, Ksp, of the solid. When we have a heterogeneous equilibrium involving the slightly soluble solid MpXq and its ions Mm+ and Xn–:


We write the solubility product expression as:


The solubility product of a slightly soluble electrolyte can be calculated from its solubility; conversely, its solubility can be calculated from its Ksp, provided the only significant reaction that occurs when the solid dissolves is the formation of its ions.

A slightly soluble electrolyte begins to precipitate when the magnitude of the reaction quotient for the dissolution reaction exceeds the magnitude of the solubility product. Precipitation continues until the reaction quotient equals the solubility product.

A reagent can be added to a solution of ions to allow one ion to selectively precipitate out of solution. The common ion effect can also play a role in precipitation reactions. In the presence of an ion in common with one of the ions in the solution, Le Châtelier’s principle applies and more precipitate comes out of solution so that the molar solubility is reduced.

15.2 Lewis Acids and Bases

G.N. Lewis proposed a definition for acids and bases that relies on an atom’s or molecule’s ability to accept or donate electron pairs. A Lewis acid is a species that can accept an electron pair, whereas a Lewis base has an electron pair available for donation to a Lewis acid. Complex ions are examples of Lewis acid-base adducts. In a complex ion, we have a central atom, often consisting of a transition metal cation, which acts as a Lewis acid, and several neutral molecules or ions surrounding them called ligands that act as Lewis bases. Complex ions form by sharing electron pairs to form coordinate covalent bonds. The equilibrium reaction that occurs when forming a complex ion has an equilibrium constant associated with it called a formation constant, Kf. This is often referred to as a stability constant, as it represents the stability of the complex ion. Formation of complex ions in solution can have a profound effect on the solubility of a transition metal compound.

15.3 Multiple Equilibria

Several systems we encounter consist of multiple equilibria, systems where two or more equilibria processes are occurring simultaneously. Some common examples include acid rain, fluoridation, and dissolution of carbon dioxide in sea water. When looking at these systems, we need to consider each equilibrium separately and then combine the individual equilibrium constants into one solubility product or reaction quotient expression using the tools from the first equilibrium chapter. Le Châtelier’s principle also must be considered, as each reaction in a multiple equilibria system will shift toward reactants or products based on what is added to the initial reaction and how it affects each subsequent equilibrium reaction.

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