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16.13: Formation of Complex Ions

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Formation of Complex Ions

16.13: Formation of Complex Ions

A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN or OH. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination chemistry—the topic of another chapter in this text.

The equilibrium constant for the reaction of a metal ion with one or more ligands to form a coordination complex is called a formation constant (Kf) (sometimes called a stability constant). For example, the complex ion [Cu(CN)2] is produced by the reaction


The formation constant for this reaction is


Alternatively, the reverse reaction (decomposition of the complex ion) can be considered, in which case the equilibrium constant is a dissociation constant (Kd). As per the relation between equilibrium constants for reciprocal reactions described, the dissociation constant is the mathematical inverse of the formation constant, Kd = Kf−1.

As an example of dissolution by complex ion formation, consider what happens when aqueous ammonia is added to a mixture of silver chloride and water. Silver chloride dissolves slightly in water, giving a small concentration of Ag+ ([Ag+] = 1.3 × 10−5 M):


However, if NH3 is present in the water, the complex ion, [Ag(NH3)2]+, can form according to the equation:


This text is adapted from Openstax, Chemistry 2e, Section 15.2: Lewis Acids and Bases.

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