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Chemistry of Aqueous Solutions

Topic 6 of 6

Common ions and silver-ammonia complexes

Explain why an added ion can suppress dissolution while complex formation promotes it.

A-Level 9476 (2026-2027)

A common ion and a ligand pull the dissolution equilibrium in opposite directions

Ksp stays fixed at fixed temperature, but the free-ion concentrations respond.

Adding Cl- to saturated AgCl solution increases a product concentration and favours precipitation, reducing the salt's solubility. If a 0.0100 mol dm-3 chloride background dominates the tiny dissolved contribution, [Ag+] ≈ Ksp/[Cl-] = 1.80 × 10-8 mol dm-3. The approximation must be checked when the background common-ion amount is not large.

Ammonia binds free silver ions: Ag+(aq) + 2NH3(aq) ⇌ [Ag(NH3)2]+(aq). Removing free Ag+ lowers [Ag+][Cl-] below Ksp, so more AgCl dissolves. The total dissolved silver can increase while the free Ag+ concentration remains small. Ksp uses the free ion, not the sum of free and complexed silver.

The silver-ion and ammonia tests for halides
HalideWith aqueous AgNO3 after acidifying with dilute HNO3With aqueous ammonia
Cl-White AgCl precipitate.Dissolves in dilute ammonia.
Br-Cream AgBr precipitate.Does not readily dissolve in dilute ammonia; dissolves in concentrated ammonia.
I-Yellow AgI precipitate.Remains insoluble in concentrated ammonia under the test conditions.

Nitric acid removes interfering carbonate or hydroxide without introducing a halide. Hydrochloric acid would introduce chloride and give a false positive. The ammonia trend reflects the balance between the very small solubility products and complex formation, rather than a claim that ammonia breaks every silver-halide lattice equally easily.

Check your understandingWhy can acidifying a clear silver-ammonia solution make AgCl reappear when chloride is still present?Think it through, then reveal the answer
H+ converts NH3 to NH4+, reducing the free ligand concentration. The silver-ammonia complex dissociates, free Ag+ rises and the ionic product can exceed Ksp, so AgCl precipitates again.