Precipitation & Solubility Rules
In 2014, the city of Flint, Michigan switched its water supply and within months, lead levels in tap water exceeded safe limits by 27 times — because the new water was corroding old pipes and dissolving Pb²⁺ ions into every glass. Engineers turned to precipitation chemistry: add the right ion, form an insoluble solid, filter it out.
Practise this lesson
Four printable worksheets that build from the foundations up to exam-style questions — start at whatever level suits you.
A water treatment plant receives water contaminated with dissolved lead ions from old pipes. The lead is invisible — the water looks perfectly clear. Engineers add a chemical to the water and within seconds a white solid forms and sinks to the bottom, taking the lead with it.
Key facts
- The NAGSAG solubility rules and their exceptions
- Common precipitates and their colours
- What spectator ions are
Concepts
- Why mixing two clear solutions can produce a solid
- The difference between molecular, full ionic, and net ionic equations
- How precipitation is used in water treatment
Skills
- Apply solubility rules to predict if a precipitate forms
- Write molecular, full ionic, and net ionic equations
- Identify spectator ions in a reaction
When two clear solutions are mixed and a white or coloured solid instantly appears, you have just witnessed a precipitation reaction — two ions met in solution and found they could not stay dissolved together. You can predict which combinations do this before mixing, using one tool: the NAGSAG solubility rules.
| Ion | Solubility | Insoluble Exceptions |
|---|---|---|
| NO₃⁻ (nitrate) | All soluble | None |
| NH₄⁺ (ammonium) | All soluble | None |
| Group 1 metal ions | All soluble | None |
| SO₄²⁻ (sulfate) | Mostly soluble | Ba²⁺, Pb²⁺, Ca²⁺ |
| Cl⁻, Br⁻, I⁻ (halides) | Mostly soluble | Ag⁺, Pb²⁺ |
| CO₃²⁻ (carbonate) | Mostly insoluble | Group 1, NH₄⁺ |
| OH⁻ (hydroxide) | Mostly insoluble | Group 1, Ba²⁺ |
NAGSAG solubility rules: Nitrates, Ammonium salts, Group 1 salts, Acetates — all soluble (no exceptions); Sulfates — mostly soluble except Ba²⁺, Pb²⁺, Ca²⁺; halides mostly soluble except Ag⁺, Pb²⁺; carbonates, hydroxides, sulfides mostly insoluble except with Group 1 or NH₄⁺.
Pause — copy the highlighted rule into your book before moving on.
Explain it: Using the NAGSAG rules, predict whether a precipitate forms when aqueous lead(II) nitrate Pb(NO₃)₂ is mixed with aqueous potassium iodide KI. Name the precipitate and explain your reasoning. (2–3 sentences)
We just saw that NAGSAG rules let us predict which ionic combinations form precipitates. That raises a question: how do we write equations that show exactly which ions react and which are bystanders? This card answers it → the three levels of ionic equation, from molecular to net ionic.
There are three levels of equation for precipitation reactions. Using the reaction of Pb(NO₃)₂(aq) with KI(aq) as the example:
Pb(NO₃)₂(aq) + 2KI(aq) → PbI₂(s) + 2KNO₃(aq)
Pb²⁺(aq) + 2NO₃⁻(aq) + 2K⁺(aq) + 2I⁻(aq) → PbI₂(s) + 2K⁺(aq) + 2NO₃⁻(aq)
Pb²⁺(aq) + 2I⁻(aq) → PbI₂(s)
The net ionic equation removes spectator ions, showing only the ions that react: e.g. Pb²⁺(aq) + 2I⁻(aq) → PbI₂(s). Never split the precipitate into ions — it is an insoluble solid lattice, not free aqueous ions.
Add the highlighted rule to your notes before the check below.
Match it: Match each equation type to its correct description for the reaction between Pb(NO₃)₂(aq) and KI(aq).
- Molecular equation
- Full ionic equation
- Net ionic equation
- Spectator ions
- K⁺(aq) and NO₃⁻(aq) — appear unchanged on both sides
- Pb²⁺(aq) + 2I⁻(aq) → PbI₂(s)
- Pb²⁺(aq) + 2NO₃⁻(aq) + 2K⁺(aq) + 2I⁻(aq) → PbI₂(s) + 2K⁺(aq) + 2NO₃⁻(aq)
- Pb(NO₃)₂(aq) + 2KI(aq) → PbI₂(s) + 2KNO₃(aq)
We just saw how to write net ionic equations that isolate exactly which ions react to form a precipitate. That raises a question: where are these precipitation reactions actually used in the real world? This card answers it → water engineers use the same reactions to remove toxic heavy metal ions from contaminated water supplies.
The precipitation reactions you've just learned are the same reactions municipal water engineers use to remove dissolved toxic metals from contaminated water supplies.
Heavy metal ions such as Pb²⁺, Hg²⁺, and Cd²⁺ dissolve from corroded pipes and industrial runoff. They are colourless and tasteless — contaminated water looks identical to clean water. Treatment adds a reagent that triggers precipitation:
Pb²⁺
Pb²⁺
Hg²⁺
To remove a heavy metal ion from water, add a reagent whose anion forms an insoluble compound with the target cation — e.g. add Na₂S to precipitate Hg²⁺ as HgS(s). The precipitate is removed by filtration; excess reagent must be controlled to avoid secondary contamination.
Pause — write the highlighted point into your book.
Fill the gap: To remove dissolved Hg²⁺ ions from contaminated water, engineers add Na₂S solution. The Hg²⁺ ions combine with S²⁻ ions to form [___](s), a black insoluble solid that can be removed by filtration.
Worked examples · reveal as you go
Predict whether a precipitate will form when aqueous barium chloride (BaCl₂) is mixed with aqueous sodium sulfate (Na₂SO₄). If a precipitate forms, name it, give its colour, and write the molecular equation with state symbols.
For the reaction in Worked Example 1, write (a) the full ionic equation and (b) the net ionic equation. Identify the spectator ions.
Key Tools — This Lesson
Common errors · the 3 traps that cost marks
Common misconception
All ionic compounds dissolve in water because water is polar.
Fix: Water dissolves many ionic compounds through ion-dipole interactions, but not all. Solubility depends on the balance between lattice energy and hydration energy. Compounds with very high lattice energy (e.g., AgCl, BaSO₄) are insoluble despite water's polarity.
Splitting the precipitate into ions in the ionic equation
When writing the full ionic equation, students split all compounds into ions including the precipitate — producing something like Ba²⁺(aq) + SO₄²⁻(aq) → Ba²⁺(aq) + SO₄²⁻(aq).
Fix: Only dissolve (aq) species into their ions. The precipitate, labelled (s), exists as an insoluble ionic lattice — not free ions in solution — so it is never split. Write the precipitate formula intact: Ba²⁺(aq) + SO₄²⁻(aq) → BaSO₄(s). The net ionic equation is then just this line — there are no spectator ions in this example.
Cancelling ions that are not truly identical on both sides
Students cancel an ion from the full ionic equation even when it appears in a different state or formula on each side (e.g. one side has Cu²⁺(aq) and the other has Cu(s)).
Fix: Spectator ions must appear with the same formula, charge, and state (aq) on both sides before they can be cancelled. If an ion changes state (e.g. Cu²⁺(aq) is reduced to Cu(s)), it is NOT a spectator — it is a participant. Cancel only ions that are completely unchanged on both sides of the full ionic equation.
Quick-fire practice · 5 reps +2 XP per reveal
Aqueous silver nitrate AgNO₃(aq) is mixed with aqueous sodium chloride NaCl(aq). Does a precipitate form?
Possible products: AgCl (Ag⁺ + Cl⁻) and NaNO₃ (Na⁺ + NO₃⁻)
NaNO₃: Group 1 → soluble. AgCl: halide with Ag⁺ → insoluble exception → white precipitate forms.
Molecular: AgNO₃(aq) + NaCl(aq) → AgCl(s) + NaNO₃(aq)
Spectator ions: Na⁺ and NO₃⁻
Net ionic: Ag⁺(aq) + Cl⁻(aq) → AgCl(s)
Aqueous potassium carbonate K₂CO₃(aq) is mixed with aqueous calcium chloride CaCl₂(aq). Does a precipitate form?
Possible products: CaCO₃ (Ca²⁺ + CO₃²⁻) and KCl (K⁺ + Cl⁻)
KCl: Group 1 → soluble. CaCO₃: carbonate with Ca²⁺ (not Group 1, not ammonium) → insoluble → white precipitate forms.
Molecular: K₂CO₃(aq) + CaCl₂(aq) → CaCO₃(s) + 2KCl(aq)
Spectator ions: K⁺ and Cl⁻
Net ionic: Ca²⁺(aq) + CO₃²⁻(aq) → CaCO₃(s)
Aqueous sodium sulfate Na₂SO₄(aq) is mixed with aqueous potassium nitrate KNO₃(aq). Does a precipitate form?
Possible products: Na₂SO₄ (Na⁺ + SO₄²⁻ — same compound, stays dissolved) and KNO₃ (K⁺ + NO₃⁻)
NaNO₃ (alternative pairing): Group 1 → soluble. K₂SO₄: Group 1 → soluble.
Both possible products are soluble. No precipitate forms — no reaction.
Q1 (4 marks): Explain what a spectator ion is and why it does not appear in the net ionic equation. Use the reaction between potassium iodide and lead(II) nitrate as your example. Write the full ionic equation and identify the spectator ions.
Q2 (4 marks): Predict and describe what happens when aqueous iron(III) chloride (FeCl₃) is mixed with aqueous sodium hydroxide (NaOH). (a) Use solubility rules to predict whether a precipitate forms, and identify it with its colour. (1 mark) (b) Write the balanced molecular equation with state symbols. (1 mark) (c) Write the net ionic equation. (1 mark) (d) Identify the spectator ions. (1 mark)
Earlier you read about Flint, Michigan (2014), where Pb²⁺ ions dissolved from corroding pipes made tap water toxic. Now you can answer it precisely: engineers added phosphate ions (PO₄³⁻). Lead phosphate — Pb₃(PO₄)₂ — is insoluble. The Pb²⁺ and PO₄³⁻ ions met in solution and immediately precipitated as a white solid: 3Pb²⁺(aq) + 2PO₄³⁻(aq) → Pb₃(PO₄)₂(s). The solid was filtered out and the lead concentration dropped.
This works because when two ionic solutions mix, every possible ion combination is instantly tested against the solubility rules — whichever combinations are insoluble precipitate immediately. You can predict this before mixing, which is exactly what water engineers do when choosing a reagent.
Now revisit your initial response. What did you get right? What has changed in your thinking?
Look back at your initial response in your book. Annotate it with what you now understand differently.
Pick your answer, then rate your confidence — that tells the system what to drill next.
Q1. 8. Explain what a spectator ion is and why it does not appear in the net ionic equation. Use the reaction between potassium iodide and lead(II) nitrate as your example. Write the full ionic equation and identify the spectator ions.
Q2. 9. Predict and describe what happens when aqueous iron(III) chloride (FeCl₃) is mixed with aqueous sodium hydroxide (NaOH). (a) Use solubility rules to predict whether a precipitate forms, and identify it with its colour. (1 mark) (b) Write the balanced molecular equation with state symbols. (1 mark) (c) Write the net ionic equation. (1 mark) (d) Identify the spectator ions. (1 mark)
Q3. 10. A water treatment facility receives water contaminated with dissolved mercury(II) ions (Hg²⁺). An engineer proposes adding sodium sulfide (Na₂S) to the water to remove the mercury. (a) Write the net ionic equation for the removal of Hg²⁺ using Na₂S. (1 mark) (b) Use solubility rules to justify why mercury(II) sulfide (HgS) precipitates. (1 mark) (c) Evaluate one advantage and one limitation of using precipitation to remove heavy metals from water supplies. (2 marks) (d) The engineer adds excess Na₂S to ensure complete mercury removal. Assess the risk this creates. (1 mark)
📖 Comprehensive answers (click to reveal)
Activity 1 — Predicting Precipitates
1. AgNO₃ + NaCl: Ions: Ag⁺, NO₃⁻, Na⁺, Cl⁻. Products: AgCl (Ag⁺ + Cl⁻ — insoluble, white precipitate), NaNO₃ (soluble). Net ionic: Ag⁺(aq) + Cl⁻(aq) → AgCl(s)
2. K₂CO₃ + CaCl₂: Ions: K⁺, CO₃²⁻, Ca²⁺, Cl⁻. Products: CaCO₃ (insoluble, white precipitate), KCl (Group 1 → soluble). Net ionic: Ca²⁺(aq) + CO₃²⁻(aq) → CaCO₃(s)
3. Na₂SO₄ + KNO₃: Ions: Na⁺, SO₄²⁻, K⁺, NO₃⁻. All possible products (NaNO₃, K₂SO₄) involve Group 1 → all soluble. No precipitate forms.
Activity 2 — Water Treatment Table
Row 1 (Pb²⁺, with Na⁺ Cl⁻): Add Na₂CO₃ or Na₂SO₄. With Na₂CO₃: PbCO₃(s) white precipitate forms. Net ionic: Pb²⁺(aq) + CO₃²⁻(aq) → PbCO₃(s)
Row 2 (Cu²⁺, with Na⁺ NO₃⁻): Add NaOH. Cu(OH)₂(s) pale blue precipitate forms (Cu²⁺ + OH⁻; copper is not Group 1 so Cu(OH)₂ insoluble). Net ionic: Cu²⁺(aq) + 2OH⁻(aq) → Cu(OH)₂(s)
Row 3 (Fe³⁺, with K⁺ SO₄²⁻): Add KOH or NaOH. Fe(OH)₃(s) rust brown precipitate (Fe³⁺ + OH⁻; iron not Group 1 so Fe(OH)₃ insoluble). Net ionic: Fe³⁺(aq) + 3OH⁻(aq) → Fe(OH)₃(s)
Why not NaCl for Pb²⁺? The Cl⁻ ion is already present in solution. Adding NaCl increases the Cl⁻ concentration but PbCl₂ is only slightly soluble (not completely insoluble like PbSO₄ or PbCO₃) — significant Pb²⁺ would remain in solution. Additionally, the Cl⁻ ion already present means no driving force for additional precipitation from NaCl.
❓ Multiple Choice
1. C — PbI₂: Pb²⁺ is an exception for iodides → insoluble. The others: Na₂CO₃ (Group 1 → soluble), (NH₄)₂SO₄ (ammonium → soluble), KOH (Group 1 → soluble).
2. B — The precipitate is AgCl(s). Na⁺ and NO₃⁻ remain dissolved unchanged — spectator ions.
3. B — CaCO₃ is an insoluble ionic solid (not free ions). It must be written as CaCO₃(s) in any ionic equation.
4. D — Cu²⁺ + 2OH⁻ → Cu(OH)₂(s). Spectator ions Na⁺ and SO₄²⁻ are removed. Options A and B are molecular/full ionic equations, not net ionic. Option C is incorrect (CuSO₄ is soluble).
5. A — A white solid forming and persisting (cannot be redissolved) confirms new substance PbSO₄(s) produced — strongest evidence of chemical change. Temperature change alone is insufficient; cloudiness could be physical.
6. C (Band 5) — PbCl₂ is only slightly soluble (it sits at the borderline of the solubility exceptions), meaning Pb²⁺ concentration would not drop to safe levels. Also, Cl⁻ ions added to drinking water have taste/health implications.
7. B (Band 6) — Both BaSO₄ and CaSO₄ are insoluble sulfates (both are exceptions to the solubility rules), so Na₂SO₄ would precipitate both. Na₂CO₃ would also precipitate both (BaCO₃ and CaCO₃ are insoluble). BaSO₄ is substantially less soluble than CaSO₄, so at carefully controlled reagent concentrations, BaSO₄ precipitates preferentially — but this precision is not expected at Year 11 level. Option B is the best available answer at this level.
Short Answer Model Answers
Q8 (4 marks): A spectator ion is an ion that appears unchanged (same formula, same state) on both sides of the full ionic equation — it does not participate in the reaction [1]. It is excluded from the net ionic equation because it plays no role in forming the product [1]. Full ionic equation for Pb(NO₃)₂ + 2KI: Pb²⁺(aq) + 2NO₃⁻(aq) + 2K⁺(aq) + 2I⁻(aq) → PbI₂(s) + 2K⁺(aq) + 2NO₃⁻(aq) [1]. Spectator ions: K⁺(aq) and NO₃⁻(aq) — they appear unchanged on both sides [1].
Q9 (4 marks): (a) Fe(OH)₃ — rust brown precipitate. Fe³⁺ with OH⁻: iron is not Group 1 → hydroxide insoluble; Na⁺ with Cl⁻ → NaCl soluble [1]. (b) FeCl₃(aq) + 3NaOH(aq) → Fe(OH)₃(s) + 3NaCl(aq) [1 — balanced with state symbols]. (c) Fe³⁺(aq) + 3OH⁻(aq) → Fe(OH)₃(s) [1]. (d) Spectator ions: Na⁺(aq) and Cl⁻(aq) [1].
Q10 (5 marks): (a) Hg²⁺(aq) + S²⁻(aq) → HgS(s) [1]. (b) HgS is a sulfide with a non-Group 1, non-ammonium cation → falls under "generally insoluble" rule for sulfides; very low solubility confirms precipitation [1]. (c) Advantage: converts dissolved invisible ions into filterable solids, removing them effectively and at relatively low cost [1]. Limitation: not all heavy metal compounds are sufficiently insoluble to reduce contamination below safe limits, or may require precise stoichiometry [1]. (d) Excess Na₂S introduces S²⁻ ions into the treated water, which is itself toxic/harmful and constitutes secondary contamination — negating the purpose of treatment [1].
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