Complex Ions and Precipitation Reactions

Among the most common reactions in the qualitative analysis are those involving the formation or decomposition of complex ions and precipitation reactions. These reactions may be performed directly by adding the appropriate anion, or a reagent such as H2S or NH3 may dissociate in water to furnish the anion. Strong acid may be used to dissolve precipitates containing a basic anion. Ammonia or sodium hydroxide may be used to bring a solid into solution if the cation in the precipitate forms a stable complex with NH3 or OH-. A cation is usually present as a single principal species, which may be a complex ion, free ion, or precipitate. If the reaction goes to completion the principal species is a complex ion. The precipitate is the principal species if most of the precipitate remains undissolved. If a cation forms a stable complex, the addition of a complexing agent at 1 M or greater generally will convert the free ion to complex ion. The dissociation constant Kd can be used to determine the extent to which a cation is converted to a complex ion. The solubility product constant Ksp can be used to determine the fraction of cation remaining in a solution after precipitation. Kd and Ksp are both required to calculate the equilibrium constant for dissolving a precipitate in a complexing agent. Complexes of Cations with NH3 and OH- Cation NH3 Complex OH- Complex Ag+ Ag(NH3)2+ -- Al3+ -- Al(OH)4- Cd2+ Cd(NH3)42+ -- Cu2+ Cu(NH3)42+ (blue) -- Ni2+ Ni(NH3)62+ (blue) -- Pb2+ -- Pb(OH)3- Sb3+ -- Sb(OH)4- Sn4+ -- Sn(OH)62- Zn2+ Zn(NH3)42+ Zn(OH)42-