Common-ion effect
The common-ion effect is a phenomenon in chemical equilibria where the addition of an ion that is already present in the equilibrium system shifts the position of the equilibrium, typically suppressing the dissociation or solubility of the involved species according to Le Chatelier's principle.[1][2] This effect occurs when a soluble compound introduces a "common ion"—an ion shared between the added compound and the equilibrium species—leading to a reduction in the concentration of that ion from the equilibrium reaction.[1][2] In the context of solubility equilibria, the common-ion effect significantly decreases the solubility of sparingly soluble ionic salts.[2] For instance, the solubility of silver chloride (AgCl), governed by the equilibrium AgCl(s) ⇌ Ag⁺(aq) + Cl⁻(aq) with a solubility product constant (Ksp) of 1.8 × 10−10, is approximately 1.3 × 10−5 M in pure water but drops to about 1.8 × 10−9 M in a 0.10 M NaCl solution due to the added Cl⁻ ions shifting the equilibrium leftward.[2] This principle can also be applied to prevent precipitation by maintaining ion concentrations below saturation levels through controlled addition of common ions.[2] The common-ion effect extends to acid-base equilibria, particularly for weak acids and bases, where it influences pH and ionization extent.[1][3] For a weak acid like acetic acid (CH3COOH ⇌ H⁺ + CH3COO⁻), adding sodium acetate (NaCH3COO) introduces excess CH3COO⁻, driving the equilibrium left and decreasing [H⁺], which raises the solution's pH.[1] A similar suppression occurs in weak base systems; for example, adding ammonium chloride (NH4Cl) to ammonia (NH3 + H2O ⇌ NH4⁺ + OH⁻) provides NH4⁺, reducing [OH⁻] and lowering basicity, as demonstrated by the fading of phenolphthalein indicator color from pink to colorless.[3] This aspect is crucial in buffer solutions, where common ions from conjugate pairs stabilize pH against changes.[4]Definition and Mechanism
Definition
The common-ion effect refers to the reduction in the degree of ionization of a weak electrolyte or the solubility of a sparingly soluble ionic compound when another ionic compound sharing a common ion is introduced into the solution, causing a shift in the chemical equilibrium.[5] This phenomenon occurs because the added common ion increases the concentration of one of the products in the dissociation equilibrium, suppressing further dissociation to maintain the equilibrium constant.[2] The effect applies broadly to ionic solutions involving weak electrolytes, such as acids and bases that partially dissociate, and to sparingly soluble salts that establish low-concentration equilibria in water.[5] Unlike the general influence of ionic strength, which alters ion activities through electrostatic interactions across all species in solution, the common-ion effect specifically arises from the mass-action response to the elevated concentration of the shared ion.[6] This process presupposes the concept of ionic dissociation, where a compound separates into its constituent ions in solution, as exemplified by the equilibrium for a weak acid:\ce{HA ⇌ H+ + A-}
The introduction of additional \ce{A-} ions from an external source shifts this equilibrium to the left, reducing the concentration of \ce{H+}.[2] The underlying driver is Le Chatelier's principle, which predicts that the system will counteract the change by favoring the reverse reaction.[5]