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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.

Reviewed by: AI editorial process; not yet individually human-reviewed

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  1. What this dot point is asking
  2. The answer
  3. Examples in context
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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

  1. Weigh the sample accurately on an analytical balance.
  2. Dissolve in a measured volume of water, and acidify with the appropriate dilute acid to remove carbonate and other interferents.
  3. Add excess precipitating reagent to drive the precipitation to completion.
  4. Digest the precipitate by warming, which grows crystals and reduces co-precipitation.
  5. Filter through pre-weighed filter paper (ashless) or a sintered glass crucible.
  6. Wash the precipitate with a small volume of distilled water (and a dilute solution of a common ion to suppress dissolution).
  7. Dry to constant mass in an oven (or ignite to a known oxide).
  8. 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:

Gravimetric analysis: precipitation, filtration and drying workflow A schematic of the gravimetric analysis apparatus train: a beaker of acidified sample with excess precipitating reagent added from a dropper, connected by an arrow to a filter funnel with ashless filter paper collecting the precipitate over a conical flask, connected by an arrow to a drying oven, connected by an arrow to an analytical balance showing the final constant mass. acidified sample + excess reagent ashless filter precipitate collects drying oven to constant mass 0.583 g analytical balance final mass reading Weigh sample, dissolve and acidify, precipitate with excess reagent, digest, filter, wash, dry to constant mass, weigh.

The canonical example: sulfate as barium sulfate

For a sample of mass mm that gives a precipitate of mass mBaSO4m_{BaSO_4}:

n(BaSO4)=mBaSO4233.4n(BaSO_4) = \frac{m_{BaSO_4}}{233.4}

n(SO42)=n(BaSO4)(1:1)n(SO_4^{2-}) = n(BaSO_4) \quad \text{(1:1)}

%SO42=n(SO42)×96.1m×100%\%SO_4^{2-} = \frac{n(SO_4^{2-}) \times 96.1}{m} \times 100\%

Acidify with dilute HClHCl first; this removes carbonate (which would otherwise precipitate as BaCO3BaCO_3) but does not dissolve BaSO4BaSO_4.

Other common gravimetric pairs

Target ion Precipitate weighed Acid used
SO42SO_4^{2-} BaSO4BaSO_4 dilute HClHCl
ClCl^- AgClAgCl dilute HNO3HNO_3
PO43PO_4^{3-} MgNH4PO46H2OMgNH_4PO_4 \cdot 6H_2O (then ignite to Mg2P2O7Mg_2P_2O_7) NH3NH_3/NH4ClNH_4Cl buffer
Pb2+Pb^{2+} PbSO4PbSO_4 or PbCrO4PbCrO_4 dilute H2SO4H_2SO_4
Ca2+Ca^{2+} CaC2O4H2OCaC_2O_4 \cdot H_2O (or ignite to CaOCaO) 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 ClCl^-:

  • Titrant: standardised AgNO3AgNO_3 (commonly 0.1 mol/L).
  • Indicator: a few drops of K2CrO4K_2CrO_4.
  • End-point: the first persistent red-brown colour of Ag2CrO4Ag_2CrO_4.

The chemistry has two stages. While free chloride remains:

Ag(aq)++Cl(aq)AgCl(s)(white)Ag^+_{(aq)} + Cl^-_{(aq)} \rightarrow AgCl_{(s)} \quad \text{(white)}

When chloride is exhausted, the next drop of Ag+Ag^+ reacts with chromate to give a red-brown precipitate, signalling the end-point:

2Ag(aq)++CrO42(aq)Ag2CrO4(s)(red-brown)2Ag^+_{(aq)} + CrO_4^{2-(aq)} \rightarrow Ag_2CrO_{4(s)} \quad \text{(red-brown)}

Ag2CrO4Ag_2CrO_4 has a higher KspK_{sp} than AgClAgCl, so AgClAgCl precipitates first. The chromate stays in solution until all chloride is consumed.

Calculation pattern for a precipitation titration

For volume of titrant VtV_t and concentration ctc_t:

n(Ag+)=ct×Vtn(Ag^+) = c_t \times V_t

n(Cl)=n(Ag+)(1:1)n(Cl^-) = n(Ag^+) \quad \text{(1:1)}

c(Cl)=n(Cl)Vsamplec(Cl^-) = \frac{n(Cl^-)}{V_{sample}}

Convert to g/L by multiplying by 35.5 g/mol.

An owned illustrative titration curve shows why the endpoint is sharp:

Illustrative Mohr titration curve: pAg versus volume of AgNO3 added An owned illustrative titration curve plotting pAg (negative log10 of silver ion concentration) against volume of 0.100 mol per litre silver nitrate added to a 25.00 millilitre chloride sample, showing a gradual rise, then a sharp inflection (equivalence point) at 18.00 millilitres, then a gradual rise again as excess silver nitrate dilutes into solution. 10 7.5 5 2.5 0 equivalence point 18.00 mL, sharp inflection 0 10 18 26 35 Volume of 0.100 mol/L AgNO3 added / mL (illustrative ExamExplained curve) Curve is flat while excess Cl- consumes added Ag+, then jumps sharply once Cl- is exhausted.

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: AgOHAgOH and brown Ag2OAg_2O precipitate, consuming titrant and falsifying the result.

Adjust with NaHCO3NaHCO_3 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 BaCl2BaCl_2 to precipitate BaSO4BaSO_4. 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 n(SO42)=0.282/233.39=1.21×103n(SO_4^{2-}) = 0.282 / 233.39 = 1.21 \times 10^{-3} mol, giving [SO42]=24[SO_4^{2-}] = 24 mmol L1^{-1} or 2300 mg L1^{-1}, far above the 250 mg L1^{-1} 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 L1^{-1} silver nitrate using potassium chromate as indicator. The first persistent red tint of Ag2CrO4Ag_2CrO_4 marks the end point. A titre of 12.50 mL gives n(Cl)=0.100×0.01250=1.25×103n(Cl^-) = 0.100 \times 0.01250 = 1.25 \times 10^{-3} mol, hence [Cl]=0.0500[Cl^-] = 0.0500 mol L1^{-1} or 1775 mg L1^{-1}, 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 BaCl2BaCl_2, filter the BaSO4BaSO_4 precipitate, wash, dry to constant mass, weigh, calculate moles and concentration.

Q2. A 100 mL water sample yields 0.247 g of AgClAgCl after addition of excess AgNO3AgNO_3. Calculate [Cl][Cl^-] in mol L1^{-1}. [3 marks]

  • Cue. n(AgCl)=0.247/143.32=1.72×103n(AgCl) = 0.247 / 143.32 = 1.72 \times 10^{-3} mol; n(Cl)=1.72×103n(Cl^-) = 1.72 \times 10^{-3} mol; [Cl]=0.0172[Cl^-] = 0.0172 mol L1^{-1}.

Q3. Mohr's method titrates ClCl^- with AgNO3AgNO_3. (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) 2Ag++CrO42Ag2CrO4(s,red)2Ag^+ + CrO_4^{2-} \rightarrow Ag_2CrO_{4(s, red)}. (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 BaSO4BaSO_4:

Ba(aq)2++SO42(aq)BaSO4(s)Ba^{2+}_{(aq)} + {SO_4^{2-}}_{(aq)} \rightarrow BaSO_{4(s)}

Molar mass of BaSO4BaSO_4 = 137.3 + 32.1 + 4(16.0) = 233.4 g/mol.

Step 2: Moles of BaSO4BaSO_4
n=0.583/233.4=2.498×103n = 0.583 / 233.4 = 2.498 \times 10^{-3} mol.
Step 3: Moles of sulfate
1:1 ratio, so n(SO42)=2.498×103n(SO_4^{2-}) = 2.498 \times 10^{-3} mol.
Step 4: Mass of sulfate
Molar mass of SO42SO_4^{2-} = 32.1 + 4(16.0) = 96.1 g/mol. Mass = 2.498×103×96.1=0.2402.498 \times 10^{-3} \times 96.1 = 0.240 g.
Step 5: Percentage
(0.240/1.20)×100%=20.0%(0.240 / 1.20) \times 100\% = 20.0\% sulfate by mass.

Error sources (any two of):

  1. Incomplete precipitation if insufficient BaCl2BaCl_2 is added; mass of BaSO4BaSO_4 is too low.
  2. Co-precipitation of impurities (carbonate, phosphate) gives high mass unless the solution is acidified first.
  3. Loss of fine particles through the filter; mass is too low. Use ashless filter paper and double-filter if needed.
  4. Incomplete drying; residual water mass is too high.
  5. 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 AgNO3AgNO_3 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 AgNO3AgNO_3
n=0.100×0.02240=2.240×103n = 0.100 \times 0.02240 = 2.240 \times 10^{-3} mol.
Step 2: Moles of ClCl^-
1:1 reaction Ag++ClAgClAg^+ + Cl^- \rightarrow AgCl, so n(Cl)=2.240×103n(Cl^-) = 2.240 \times 10^{-3} mol.
Step 3: Concentration in mol/L
c=2.240×103/0.02500=0.0896c = 2.240 \times 10^{-3} / 0.02500 = 0.0896 mol/L.
Step 4: Concentration in g/L
Molar mass of ClCl^- = 35.5 g/mol. Concentration = 0.0896×35.5=3.180.0896 \times 35.5 = 3.18 g/L.
Why neutral to slightly basic
The Mohr method relies on a sharp end-point when the second precipitate, red Ag2CrO4Ag_2CrO_4, forms after all ClCl^- is consumed. Two pH constraints apply:
  • Too acidic (pH<6.5pH < 6.5): chromate protonates to dichromate, 2CrO42+2H+Cr2O72+H2O2CrO_4^{2-} + 2H^+ \rightleftharpoons Cr_2O_7^{2-} + H_2O, which does not form an insoluble silver salt. The end-point is lost.
  • Too basic (pH>10pH > 10): silver hydroxide AgOHAgOH (and then dark Ag2OAg_2O) 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: BaSO4BaSO_4. Pre-treatment acid: dilute HClHCl (removes carbonate without dissolving BaSO4BaSO_4).

(b) Chloride. Precipitate: AgClAgCl. Pre-treatment acid: dilute HNO3HNO_3 (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.

  1. Weigh the sample accurately.
  2. Dissolve in a measured volume of water and acidify to remove interferents.
  3. Add excess precipitating reagent to drive precipitation to completion.
  4. Digest (warm) the precipitate.
  5. Filter through pre-weighed ashless paper or a sintered crucible.
  6. Wash the precipitate with a small volume of distilled water or a common-ion wash solution.
  7. Dry to constant mass.
  8. 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. (M(AgCl)=143.3 g mol1M(AgCl) = 143.3\ \text{g mol}^{-1}, M(Cl)=35.5 g mol1M(Cl) = 35.5\ \text{g mol}^{-1}.)
Show worked solution →

Step 1: write the precipitation equation (1:1 stoichiometry).

Ag(aq)++Cl(aq)AgCl(s)Ag^+_{(aq)} + Cl^-_{(aq)} \rightarrow AgCl_{(s)}

Step 2: moles of AgClAgCl precipitate.

n(AgCl)=mM=1.146 g143.3 g mol1=7.998×103 moln(AgCl) = \frac{m}{M} = \frac{1.146\ \text{g}}{143.3\ \text{g mol}^{-1}} = 7.998 \times 10^{-3}\ \text{mol}

Step 3: moles of chloride (1:1 ratio).

n(Cl)=7.998×103 moln(Cl^-) = 7.998 \times 10^{-3}\ \text{mol}

Step 4: mass of chloride.

m(Cl)=n×M=7.998×103 mol×35.5 g mol1=0.2839 gm(Cl^-) = n \times M = 7.998 \times 10^{-3}\ \text{mol} \times 35.5\ \text{g mol}^{-1} = 0.2839\ \text{g}

Step 5: percentage by mass in the original sample.

%Cl=0.2839 g0.850 g×100%=33.4%\%Cl^- = \frac{0.2839\ \text{g}}{0.850\ \text{g}} \times 100\% = 33.4\%

Rounded to 3 significant figures (matching the 3 s.f. in the 0.850 g and 1.146 g data): %Cl=33.4%\%Cl^- = 33.4\%.

Marking criteria: 1 mark for the correct 1:1 stoichiometric equation, 1 mark for correct moles of AgClAgCl, 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, log10[Ag+]-\log_{10}[Ag^+]) versus volume of 0.100 mol L10.100\ \text{mol L}^{-1} AgNO3AgNO_3 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 Ag+Ag^+ is almost completely consumed by the still-plentiful ClCl^-, so free [Ag+][Ag^+] (and hence pAg) barely changes. Right at the equivalence point, one more drop of titrant causes a large relative change in free [Ag+][Ag^+] because there is essentially no ClCl^- left to consume it, producing the sharp vertical jump in pAg. Past the equivalence point, pAg falls more gradually again as excess Ag+Ag^+ simply dilutes into the growing volume.

(b) Concentration calculation.

n(Ag+)=c×V=0.100 mol L1×0.01800 L=1.80×103 moln(Ag^+) = c \times V = 0.100\ \text{mol L}^{-1} \times 0.01800\ \text{L} = 1.80 \times 10^{-3}\ \text{mol}

n(Cl)=n(Ag+)=1.80×103 mol(1:1 stoichiometry)n(Cl^-) = n(Ag^+) = 1.80 \times 10^{-3}\ \text{mol} \quad \text{(1:1 stoichiometry)}

c(Cl)=nVsample=1.80×103 mol0.02500 L=0.0720 mol L1c(Cl^-) = \frac{n}{V_{sample}} = \frac{1.80 \times 10^{-3}\ \text{mol}}{0.02500\ \text{L}} = 0.0720\ \text{mol L}^{-1}

Marking criteria: (a) 1 mark for correctly reading 18.00 mL from the graph, 1 mark for explaining the sharp jump in terms of ClCl^- being exhausted so free Ag+Ag^+ rises sharply. (b) 1 mark for correct moles of Ag+Ag^+, 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 AgClAgCl) 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 AgClAgCl 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 (2CrO42+2H+rightleftharpoonsCr2O72+H2O2CrO_4^{2-} + 2H^+ \\rightleftharpoons Cr_2O_7^{2-} + H_2O), 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 Ag+Ag^+ before chloride is exhausted, at a similar or even lower silver concentration, but Ag+Ag^+ 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 ClCl^-. (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 NaHCO3NaHCO_3) 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.

ExamExplained