Inquiry Question 1: How are the ions present in the environment identified and measured?
Conduct investigations to measure the concentration of cations and anions in solution using gravimetric analysis and precipitation titrations
A focused answer to the HSC Chemistry Module 8 dot point on quantitative wet-chemistry analysis. The full gravimetric workflow (precipitate, filter, dry, weigh), worked sulfate-as-barium-sulfate calculation, the Mohr precipitation titration of chloride with silver nitrate, sources of error, and worked HSC past exam questions.
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What this dot point is asking
NESA wants you to use a precipitation reaction to measure concentration two ways: by weighing the dried precipitate (gravimetric analysis) or by titrating a known precipitant to a colour-change endpoint (precipitation titration, typically the Mohr method for chloride). You should know the workflow, the calculations, and the most common sources of error.
The answer
Gravimetric analysis: the workflow
- Weigh the sample accurately on an analytical balance.
- Dissolve in a measured volume of water, and acidify with the appropriate dilute acid to remove carbonate and other interferents.
- Add excess precipitating reagent to drive the precipitation to completion.
- Digest the precipitate by warming, which grows crystals and reduces co-precipitation.
- Filter through pre-weighed filter paper (ashless) or a sintered glass crucible.
- Wash the precipitate with a small volume of distilled water (and a dilute solution of a common ion to suppress dissolution).
- Dry to constant mass in an oven (or ignite to a known oxide).
- Weigh the dried precipitate.
The mass of the precipitate gives moles, which converts back to moles (and mass) of the original ion via the stoichiometry of the precipitation equation.
The apparatus and workflow for the gravimetric method are shown below:
The canonical example: sulfate as barium sulfate
For a sample of mass that gives a precipitate of mass :
Acidify with dilute first; this removes carbonate (which would otherwise precipitate as ) but does not dissolve .
Other common gravimetric pairs
| Target ion | Precipitate weighed | Acid used |
|---|---|---|
| dilute | ||
| dilute | ||
| (then ignite to ) | / buffer | |
| or | dilute | |
| (or ignite to ) | acetate buffer |
Precipitation titration: the Mohr method
Use when you want speed and do not need part-per-billion precision. The classic Mohr titration measures :
- Titrant: standardised (commonly 0.1 mol/L).
- Indicator: a few drops of .
- End-point: the first persistent red-brown colour of .
The chemistry has two stages. While free chloride remains:
When chloride is exhausted, the next drop of reacts with chromate to give a red-brown precipitate, signalling the end-point:
has a higher than , so precipitates first. The chromate stays in solution until all chloride is consumed.
Calculation pattern for a precipitation titration
For volume of titrant and concentration :
Convert to g/L by multiplying by 35.5 g/mol.
An owned illustrative titration curve shows why the endpoint is sharp:
pH window for the Mohr method
The titration must be run at pH 7 to 9.5.
- Below pH 6.5: chromate protonates to dichromate, which is soluble with silver. No coloured end-point.
- Above pH 10: and brown precipitate, consuming titrant and falsifying the result.
Adjust with or a phosphate buffer if needed.
Sources of error
Gravimetric:
- Incomplete precipitation if insufficient precipitant is added (use a clear excess).
- Co-precipitation of impurities (acidify to remove carbonate; dilute the sample to reduce inclusion).
- Particle loss through the filter (digest the precipitate first to grow larger crystals).
- Incomplete drying (dry to constant mass; reweigh after a second drying cycle).
- Hygroscopic precipitates absorb moisture during weighing (cool in a desiccator).
Precipitation titration:
- pH out of range distorts the end-point.
- Slow precipitate formation makes the end-point hard to spot; swirl thoroughly.
- Indicator concentration: too much chromate masks the white-to-red change.
- Coloured samples (sea water with biological matter, for example) hide the end-point.
When to choose which
| Need | Gravimetric | Precipitation titration |
|---|---|---|
| Highest precision | Yes (0.1% or better) | Moderate (1%) |
| Fast turnaround | No (hours to days) | Yes (minutes per sample) |
| Many samples | No | Yes |
| Trace analysis (ppb) | No (both unsuitable, use AAS or UV-vis) | No |
Examples in context
Example 1. Sulfate in mine drainage at Cobar. EPA contractors monitoring acid mine drainage from the Cobar copper mine in central NSW use gravimetric analysis to measure sulfate. A 50.0 mL aliquot is acidified with HCl and treated with excess to precipitate . The precipitate is filtered through pre-weighed filter paper, washed, dried at 110 degrees C overnight and weighed. A typical mass of 0.282 g corresponds to mol, giving mmol L or 2300 mg L, far above the 250 mg L aesthetic guideline. The result feeds discharge licence compliance.
Example 2. Mohr titration of chloride in NSW pool water. Aquatic centre managers at the Sydney Olympic Park Aquatic Centre run weekly Mohr titrations to confirm chloride concentration in saltwater pools. A 25.0 mL pool sample is titrated against standardised 0.100 mol L silver nitrate using potassium chromate as indicator. The first persistent red tint of marks the end point. A titre of 12.50 mL gives mol, hence mol L or 1775 mg L, sitting in the operating range for salt chlorination. The HSC Mohr titration framework is the same chemistry the pool operator runs in the plant room.
Try this
Q1. Outline the steps of a gravimetric analysis for sulfate ions in water. [3 marks]
- Cue. Acidify, add excess , filter the precipitate, wash, dry to constant mass, weigh, calculate moles and concentration.
Q2. A 100 mL water sample yields 0.247 g of after addition of excess . Calculate in mol L. [3 marks]
- Cue. mol; mol; mol L.
Q3. Mohr's method titrates with . (a) Write the equation for the indicator end point. (b) Explain why the pH must be between 7 and 9.5. (c) State one source of error in the Mohr titration. [2+2+1 marks]
- Cue. (a) . (b) Acidic conditions protonate chromate to dichromate; basic conditions precipitate AgOH. (c) Co-precipitation of bromide or iodide; impure water blank.
Exam-style practice questions
Practice questions written in the style of NESA exam questions on this dot point, with worked answer explainers. The year tag is the paper they imitate, not the source.
2022 HSC5 marksA 1.20 g sample of fertiliser was dissolved in water and acidified with dilute HCl. Excess barium chloride solution was added. The precipitate was filtered, washed, dried and weighed. Its mass was 0.583 g. Calculate the percentage by mass of sulfate in the fertiliser. Identify two sources of error in this gravimetric analysis.Show worked answer →
A 5 mark answer needs the stoichiometry, the mass calculation, the percentage and at least two specific error sources.
Step 1: Identify the precipitate. Sulfate plus barium gives :
Molar mass of = 137.3 + 32.1 + 4(16.0) = 233.4 g/mol.
- Step 2: Moles of
- mol.
- Step 3: Moles of sulfate
- 1:1 ratio, so mol.
- Step 4: Mass of sulfate
- Molar mass of = 32.1 + 4(16.0) = 96.1 g/mol. Mass = g.
- Step 5: Percentage
- sulfate by mass.
Error sources (any two of):
- Incomplete precipitation if insufficient is added; mass of is too low.
- Co-precipitation of impurities (carbonate, phosphate) gives high mass unless the solution is acidified first.
- Loss of fine particles through the filter; mass is too low. Use ashless filter paper and double-filter if needed.
- Incomplete drying; residual water mass is too high.
- Loss during transfer between beakers and filter funnel.
Markers reward (1) the equation, (2) correct moles, (3) the percentage, (4) two valid error sources each with the direction of the error.
2020 HSC4 marksA 25.00 mL sample of seawater was titrated with 0.100 mol/L using potassium chromate as the indicator (Mohr method). The endpoint was reached when 22.40 mL of titrant had been delivered. Calculate the chloride concentration in g/L and explain why this method requires a neutral to slightly basic solution.Show worked answer →
A 4 mark answer needs the titration calculation in mol/L, conversion to g/L, and the chemical reason for the pH constraint.
- Step 1: Moles of
- mol.
- Step 2: Moles of
- 1:1 reaction , so mol.
- Step 3: Concentration in mol/L
- mol/L.
- Step 4: Concentration in g/L
- Molar mass of = 35.5 g/mol. Concentration = g/L.
- Why neutral to slightly basic
- The Mohr method relies on a sharp end-point when the second precipitate, red , forms after all is consumed. Two pH constraints apply:
- Too acidic (): chromate protonates to dichromate, , which does not form an insoluble silver salt. The end-point is lost.
- Too basic (): silver hydroxide (and then dark ) precipitates before the chromate end-point, consuming titrant and giving a high result.
Typical buffered range is pH 7 to 9.5.
Markers reward (1) correct moles of titrant, (2) 1:1 stoichiometry, (3) g/L conversion, (4) the chemical reason for both pH limits.
Practice questions
Original practice questions graded from foundation to exam level, each with a full worked solution. Try them before revealing the solution.
foundation3 marksState the chemical formula of the precipitate formed, and the acid used to pre-treat the sample, for a gravimetric determination of (a) sulfate ions and (b) chloride ions.Show worked solution →
A 3-mark identify needs the correct precipitate formula AND the correct pre-treatment acid for each ion.
(a) Sulfate. Precipitate: . Pre-treatment acid: dilute (removes carbonate without dissolving ).
(b) Chloride. Precipitate: . Pre-treatment acid: dilute (prevents precipitation of other silver salts, such as silver carbonate or silver phosphate, that would co-precipitate and inflate the mass).
Marking criteria: 1 mark for the correct sulfate precipitate and acid, 1 mark for the correct chloride precipitate and acid, 1 mark for correctly linking each acid to the impurity it suppresses.
foundation4 marksOutline, in order, the eight steps of a gravimetric analysis procedure from receiving a solid sample to obtaining a final mass, naming the purpose of the digestion and washing steps.Show worked solution →
The eight-step workflow.
- Weigh the sample accurately.
- Dissolve in a measured volume of water and acidify to remove interferents.
- Add excess precipitating reagent to drive precipitation to completion.
- Digest (warm) the precipitate.
- Filter through pre-weighed ashless paper or a sintered crucible.
- Wash the precipitate with a small volume of distilled water or a common-ion wash solution.
- Dry to constant mass.
- Weigh the dried precipitate.
Purpose of digestion. Warming grows larger, purer crystals, which reduces co-precipitation of impurities and reduces loss of fine particles through the filter.
Purpose of washing. Removes soluble impurities (mother liquor) adhering to the precipitate surface without dissolving an appreciable amount of the precipitate itself.
Marking criteria: 1 mark for the steps in the correct order (accept minor step-combination), 1 mark for identifying excess reagent as necessary for complete precipitation, 1 mark for the purpose of digestion, 1 mark for the purpose of washing.
core5 marksA 0.850 g sample of an ionic chloride salt is dissolved in water and treated with excess silver nitrate solution. The precipitate of silver chloride is filtered, washed, dried and weighed, giving a mass of 1.146 g. Calculate the percentage by mass of chloride in the original sample, to 3 significant figures. (, .)Show worked solution →
Step 1: write the precipitation equation (1:1 stoichiometry).
Step 2: moles of precipitate.
Step 3: moles of chloride (1:1 ratio).
Step 4: mass of chloride.
Step 5: percentage by mass in the original sample.
Rounded to 3 significant figures (matching the 3 s.f. in the 0.850 g and 1.146 g data): .
Marking criteria: 1 mark for the correct 1:1 stoichiometric equation, 1 mark for correct moles of , 1 mark for correctly carrying the 1:1 ratio to chloride, 1 mark for the mass of chloride, 1 mark for the correct percentage to 3 significant figures with a percent sign. Note the true experimental percentage would likely differ slightly from any theoretical value if the sample were of known formula, due to the error sources discussed in the text (co-precipitation, incomplete drying, particle loss).
core5 marksThe titration curve below is an owned illustrative plot of pAg (that is, ) versus volume of added to a 25.00 mL chloride sample, showing a sharp inflection (equivalence point) at 18.00 mL. (a) Identify the equivalence point volume from the curve and explain why the curve shows a sharp jump there rather than a gradual change. (b) Calculate the original chloride concentration in mol/L.Show worked solution →
(a) Equivalence point and shape. The equivalence point is read from the steepest part of the curve, where the graph shows the inflection at 18.00 mL. Before the equivalence point, added is almost completely consumed by the still-plentiful , so free (and hence pAg) barely changes. Right at the equivalence point, one more drop of titrant causes a large relative change in free because there is essentially no left to consume it, producing the sharp vertical jump in pAg. Past the equivalence point, pAg falls more gradually again as excess simply dilutes into the growing volume.
(b) Concentration calculation.
Marking criteria: (a) 1 mark for correctly reading 18.00 mL from the graph, 1 mark for explaining the sharp jump in terms of being exhausted so free rises sharply. (b) 1 mark for correct moles of , 1 mark for the 1:1 stoichiometric ratio, 1 mark for the correct final concentration with units.
core6 marksA student determines chloride in a bore-water sample two ways: gravimetrically (precipitating and weighing ) and by Mohr titration. Compare the two methods in terms of precision, speed and suitability for testing 40 bore-water samples in a single day, and justify which method the student should choose.Show worked solution →
- Precision
- Gravimetric analysis is inherently more precise (typically 0.1% or better) because it relies on a direct mass measurement on an analytical balance, which is a highly precise instrument, and avoids the subjectivity of judging a colour-change endpoint by eye. The Mohr titration is somewhat less precise (around 1%) because the endpoint judgement (first persistent red-brown tinge) introduces small operator-dependent variation.
- Speed
- Gravimetric analysis is slow: it requires precipitation, digestion, filtration and drying to constant mass, which typically takes many hours to more than a day per sample (including cooling in a desiccator and possibly a second drying cycle to confirm constant mass). The Mohr titration is fast, taking only minutes per sample once the titrant is standardised.
- Suitability for 40 samples in one day
- Gravimetric analysis is impractical for 40 samples in a single day because of the drying time alone; even with several ovens running in parallel, achieving constant mass for that many crucibles in one working day is unrealistic. The Mohr titration can comfortably process 40 samples in a single day, since each titration takes only a few minutes plus rinsing and refilling the burette.
- Justification
- The student should choose the Mohr precipitation titration for this task. While it sacrifices some precision compared with the gravimetric method, the difference (around 1% versus 0.1%) is small relative to typical variation in bore-water chloride levels, and the enormous time saving makes it the only realistic option for processing 40 samples in one day. Gravimetric analysis would instead be justified if only one or two samples needed the highest achievable accuracy, for example for a regulatory reference measurement.
Marking criteria: 1 mark for correctly comparing precision, 1 mark for correctly comparing speed, 1 mark for correctly reasoning that gravimetric analysis cannot realistically process 40 samples in a day, 1 mark for correctly reasoning that Mohr titration can, 1 mark for a clear final recommendation, 1 mark for the recommendation being properly justified by weighing precision against practicality rather than just restating the comparison.
exam8 marksA council water lab reports a chloride result from a Mohr titration that is noticeably higher than the result later obtained by gravimetric analysis of on the same sample. Evaluate THREE plausible sources of this discrepancy, explain the direction each would push the Mohr result, and recommend the single most likely cause given that the sample is river water with a naturally cloudy brown tint and a measured pH of 6.2.Show worked solution →
This is an 8-mark EVALUATE: markers reward a judgement that uses the specific stimulus (turbid, tinted, pH 6.2), not a generic list of errors.
Band 6 PLAN.
- State three candidate error sources for the Mohr result specifically, each with the direction of the effect (too high or too low).
- Use the given evidence (pH 6.2, brown tint/cloudiness) to argue which is most likely.
- End with an explicit recommendation, not a neutral list.
- Candidate 1: pH out of range (too acidic)
- The Mohr method requires pH 7 to 9.5. At pH 6.2, some chromate indicator is protonated to dichromate (), which does not form a red silver precipitate. The titrator must add MORE titrant than the true equivalence point before enough unprotonated chromate remains to give a visible colour change, so this error pushes the Mohr result HIGHER than the true value, consistent with the observation.
- Candidate 2: obscured endpoint from colour/turbidity
- The natural brown tint and cloudiness of river water make the pale pink-to-red colour change harder to see against the background colour. An operator waiting for a colour that is more visible against the brown background is likely to over-titrate, again giving a titre (and hence a chloride result) that is HIGHER than the true value.
- Candidate 3: co-precipitation with other halides or ions
- If bromide or iodide is present, they also precipitate with before chloride is exhausted, at a similar or even lower silver concentration, but reacts with them as if they were chloride, mole for mole. This makes the apparent chloride result too HIGH, since some of the titrant reacted with other anions, not just . (Gravimetric analysis by mass would report a similarly inflated combined-halide mass, so this candidate is less able to explain a MOHR-SPECIFIC discrepancy relative to gravimetric.)
- Recommendation
- Given the stated evidence, the pH of 6.2 is the most likely dominant cause: it falls clearly below the required 7 to 9.5 window and directly interferes with the chromate indicator chemistry itself, whereas the brown tint mainly makes an already-correct endpoint harder to judge (a smaller effect) and co-precipitation of other halides would likely also elevate the gravimetric result, which was NOT reported as elevated. The lab should buffer the sample to pH 7 to 9.5 (for example with dilute ) before repeating the Mohr titration to test this explanation.
Marker's note: top-band answers (1) give the correct direction (too high, not too low) for at least two candidates with a chemical mechanism, not just an assertion, (2) explicitly connect the pH 6.2 evidence to the chromate protonation equilibrium, (3) use the cloudy/tinted evidence to justify a SEPARATE, smaller contributing error rather than conflating it with the pH cause, and (4) end with a specific, testable recommendation rather than a vague "check the method" statement.
