 Common-ion effect

The common-ion effect is the change in a chemical equilibrium caused by adding an ion already participating in it. In the fixed-activity coefficient AB model, adding the common B anion lowers the molar solubility. The shared ion participates regardless of which salt supplied it.^[ref]

The preceding solubility product and material balance give a short proof without a qualitative slogan. Taking a derivative of $s_{\ast }^2+c_0{s}_{\ast }=K_{\mathrm{sp},c}$ at fixed $K_{\mathrm{sp},c}$ givesThus the molar solubility decreases continuously as $c_0$ increases. At $c_0=0$, the derivative is $-1/2$; for a very large common-ion background, the rationalized expression approaches $K_{\mathrm{sp},c}/c_0$. The solubility product is fixed within this model even while the molar solubility changes.

Neglecting $s_{\ast }$ beside $c_0$ replaces $s_{\ast }(c_0+s_{\ast })=K_{\mathrm{sp},c}$ by $c_0{s}_{\mathrm{app}}=K_{\mathrm{sp},c}$. This approximation always overestimates the exact molar solubility, since it neglects the B anions supplied by AB itself. For $c_0>0$, its relative error has an exact simple form:At $c_0=0.030\mathrm{M}$, $s_{\mathrm{app}}=0.003333333\mathrm{M}$, approximately $10.1\%$ too high. At $c_0=0.100\mathrm{M}$, $s_{\ast }=0.000990195\mathrm{M}$ and $s_{\mathrm{app}}=0.001000000\mathrm{M}$, approximately $0.990\%$ too high. A small solubility product by itself does not justify the approximation: the common-ion background must be large compared with the resulting molar solubility.

For a desired fractional relative error at most $\epsilon >0$, substituting $s_{\ast }/c_0\le \epsilon$ into the exact balance gives the equivalent criterionFor this model, a $5\%$ tolerance requires $c_0\ge 0.0436436\mathrm{M}$. This bound concerns only the algebraic approximation. In a real chemical solution, changes in ionic strength and activity coefficients, or competing chemical reactions, can invalidate a constant $K_{\mathrm{sp},c}$ even when this bound is met.