Common-ion effect 2026-10-18
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 at fixed gives
Thus the molar solubility decreases continuously as increases. At , the derivative is ; for a very large common-ion background, the rationalized expression approaches . The solubility product is fixed within this model even while the molar solubility changes.
Neglecting beside replaces by . This approximation always overestimates the exact molar solubility, since it neglects the B anions supplied by AB itself. For , its relative error has an exact simple form:
At , , approximately too high. At , and , approximately 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.
Figure 1.
Common-ion suppression and the error from neglecting the solid's own B anions
. Original curves for the same stipulated AB model, with exact molar solubility and approximation. The exact curve reaches at ; the approximation diverges there. The lower panel shows its exact relative error, with markers at and . No curve represents experimental measurements of a named substance. Details.
For a desired fractional relative error at most , substituting into the exact balance gives the equivalent criterion
For this model, a tolerance requires . 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 even when this bound is met.
Ion product Created 2026-10-14 Updated 2026-10-18
The ion product evaluates the same dissolved-ion thermodynamic activity product as the solubility product, but at the current composition rather than necessarily at chemical equilibrium. For AB, ; its concentration counterpart is . Compare with only under compatible activity coefficient assumptions.[ref]
For other stoichiometries, use the dissolution coefficients as powers: gives . A solubility product is not itself the molar concentration dissolved; even in the ideal AB model in pure water, that concentration is .
Molar solubility 2026-10-18
The molar solubility is the amount of substance of a specified solid dissolved per volume of saturated chemical solution, under stated conditions. It counts dissolved formula units, not the sum of all dissolved ion concentrations. For AB with no initial A or B and no competing chemical reactions, one-to-one stoichiometry gives . For an AB solid, the corresponding concentrations are and .[ref]
Relative to the specified solid, favors dissolution if that solid is available; favors precipitation; equality marks saturation. These comparisons identify a driving direction favored by thermodynamics, not a reaction rate.[ref]
A proof outline comes from the reaction Gibbs free energy for dissolution:
Here is the molar gas constant and the absolute temperature. If , the logarithm is positive, making the reverse transfer into solid favorable. At equality the bulk driving difference vanishes. Equality can also occur at the boundary where the last solid disappears, but it is not a universal constraint on every solid-free chemical solution.
Solubility product 2026-10-14
The solubility product is the equilibrium constant for dissolution of a specified solid into its dissolved ions. For a pure bulk AB solid at the chosen temperature, pressure and standard states,
The pure bulk solid's thermodynamic activity is one in this convention. Coexisting solid and chemical solution at chemical equilibrium give this equality. If all available solid dissolves, the final chemical solution may instead be undersaturated; do not impose equality merely because a salt was initially added.[ref]
Using the thermodynamic activity definition , with activity coefficients and reference molar concentration , gives the independent conversion
Thus is dimensionless, while the conditional concentration form has units for this one-to-one model. Treating as constant requires a justified fixed or approximately fixed activity coefficient product. Changing ionic strength can change that product even at fixed temperature; changing temperature can change the equilibrium constant itself. Specify the solid thermodynamic phase too: different crystal polymorphs need not have the same solubility product.