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Volumetric analysis: acid-base titrations (SACE Stage 2 Chemistry)

Syllabus dot point

“Apply volumetric analysis using acid-base titrations to determine unknown concentrations.”

9 min read

Quick answer

Volumetric analysis uses a titration of accurately measured volumes to find an unknown concentration. You standardise one solution against a primary standard, titrate it against the unknown to an indicator endpoint, then use n=cVn = cV and the mole ratio from the balanced equation to calculate the unknown concentration. The routine is always: moles of the known, apply the mole ratio, then divide by volume (or scale through any dilution).

Jump to a section
  1. What this dot point is asking
  2. Lead worked calculation
  3. Key terms
  4. The central relationship
  5. Choosing the indicator
  6. Back-titration
  7. Technique and reliability
  8. Why it matters for monitoring
  9. Exam-style questions

What this dot point is asking

SACE expects you to perform the full calculation reliably, justify your choice of indicator, and explain the role of standard solutions, primary standards and the difference between equivalence point and endpoint.

Lead worked calculation

Finding the concentration of HCl

25.00 mL25.00\ \text{mL} of hydrochloric acid is titrated against 0.105 mol L−10.105\ \text{mol L}^{-1} sodium hydroxide. The average concordant titre is 22.40 mL22.40\ \text{mL}. Find the concentration of the acid.

Step 1: Write the balanced equation and identify the mole ratio

Before any numbers, you need the stoichiometry. Hydrochloric acid and sodium hydroxide react in a simple neutralisation, and writing the equation tells you exactly how many moles of one species correspond to how many moles of the other.

HCl+NaOH→NaCl+H2O\text{HCl} + \text{NaOH} \rightarrow \text{NaCl} + \text{H}_2\text{O}

The coefficients are all 11, so the mole ratio of HCl\text{HCl} to NaOH\text{NaOH} is 1:11:1. This is the link that lets you transfer information from the standard solution to the unknown.

Step 2: Calculate moles of the standard (NaOH)

The sodium hydroxide solution is the standard here: its concentration is accurately known. You use the titre, which is the volume of NaOH delivered by the burette, converted to litres, together with the known concentration to find the number of moles actually delivered at the endpoint.

n(NaOH)=cV=0.105×22.401000=0.105×0.02240=2.352×10−3 moln(\text{NaOH}) = cV = 0.105 \times \frac{22.40}{1000} = 0.105 \times 0.02240 = 2.352 \times 10^{-3}\ \text{mol}

Step 3: Transfer to moles of the unknown (HCl) using the ratio

Because the ratio is 1:11:1, every mole of NaOH that reacted corresponds to exactly one mole of HCl in the flask. If the ratio were different (for example 2:12:1 for sulfuric acid), you would multiply or divide accordingly.

n(HCl)=n(NaOH)=2.352×10−3 moln(\text{HCl}) = n(\text{NaOH}) = 2.352 \times 10^{-3}\ \text{mol}

Step 4: Find the concentration by dividing by the volume of the unknown

The 2.352×10−3 mol2.352 \times 10^{-3}\ \text{mol} of HCl was contained in the 25.00 mL25.00\ \text{mL} pipette volume. Dividing moles by volume (in litres) gives concentration. This is simply rearranging n=cVn = cV to solve for cc.

c(HCl)=nV=2.352×10−30.02500=0.0941 mol L−1c(\text{HCl}) = \frac{n}{V} = \frac{2.352 \times 10^{-3}}{0.02500} = 0.0941\ \text{mol L}^{-1}

Final answer: c(HCl)=0.0941 mol L−1c(\text{HCl}) = 0.0941\ \text{mol L}^{-1}

Key terms

Standard solution and primary standard

A standard solution has an accurately known concentration. A primary standard is a pure, stable, non-hygroscopic solid of high and known molar mass (e.g. anhydrous sodium carbonate or potassium hydrogen phthalate) that can be weighed accurately and dissolved to a known volume, giving a standard solution directly. Sodium hydroxide is not a primary standard because it absorbs water and carbon dioxide from the air, so its true mass of NaOH\text{NaOH} is uncertain; it must be standardised against a primary standard before use.

The equivalence point is where stoichiometrically equivalent amounts of acid and base have reacted, as defined by the balanced equation. The endpoint is where the chosen indicator changes colour. A well-chosen indicator makes the endpoint coincide with the equivalence point as closely as possible, so the titre is a true measure of the reacting amounts.

The central relationship

Moles from concentration and volume

n=c Vn = c\,V

where nn is amount in mol\text{mol}, cc is concentration in mol L−1\text{mol L}^{-1}, and VV is volume in litres\text{litres}. Always convert mL\text{mL} to L\text{L} (divide by 10001000) before substituting.

The general procedure for any titration calculation:

  1. Write the balanced equation and read off the mole ratio.
  2. Calculate moles of the standard reactant from n=cVn = cV using the titre.
  3. Use the mole ratio to find moles of the analyte.
  4. Account for any dilution or aliquot scaling.
  5. Divide by the relevant volume to get the concentration (or multiply by MM for a mass).

Choosing the indicator

The pH at the equivalence point depends on the salt formed, so the indicator must change colour within the steep part of the titration curve at that pH.

  • Strong acid with strong base (e.g. HCl\text{HCl} and NaOH\text{NaOH}): equivalence pH =7= 7; the vertical region is wide, so methyl orange or phenolphthalein both work.
  • Weak acid with strong base (e.g. ethanoic acid and NaOH\text{NaOH}): the salt is basic, equivalence pH >7> 7; use phenolphthalein (range 8.38.3 to 10.010.0).
  • Strong acid with weak base (e.g. HCl\text{HCl} and NH3\text{NH}_3): the salt is acidic, equivalence pH <7< 7; use methyl orange (range 3.13.1 to 4.44.4).

Back-titration

When an analyte reacts slowly, is insoluble, or is a solid such as an antacid, you add a known excess of one reagent, then titrate the leftover excess with a second standard. The amount that reacted with the analyte is the difference. For example, an antacid containing CaCO3\text{CaCO}_3 is dissolved in a measured excess of standard HCl\text{HCl}; the unreacted HCl\text{HCl} is then titrated with standard NaOH\text{NaOH}, and n(HCl reacted with carbonate)=n(HCl added)−n(HCl titrated)n(\text{HCl reacted with carbonate}) = n(\text{HCl added}) - n(\text{HCl titrated}).

Technique and reliability

  • Rinse the burette and pipette with the solution they will hold; rinse the conical flask with distilled water only (residual water does not change the moles delivered into it).
  • Perform a rough trial titre, then repeat for concordant titres within 0.10 mL0.10\ \text{mL} of each other and average only those.
  • Read the burette to ±0.05 mL\pm 0.05\ \text{mL} at the bottom of the meniscus at eye level to avoid parallax.
  • The final answer can be no more precise than the least precise data; match significant figures accordingly.
Forgetting the mole ratio and the dilution scale

The two most common SACE errors are assuming a 1:11:1 ratio and ignoring aliquot or dilution scaling. For H2SO4+2NaOH\text{H}_2\text{SO}_4 + 2\text{NaOH}, two moles of base react per mole of acid, so the ratio is essential. When only an aliquot of a made-up solution is titrated, you must multiply back up by VtotalValiquot\dfrac{V_\text{total}}{V_\text{aliquot}} to recover the amount in the whole flask. Also always convert mL\text{mL} to L\text{L} before using n=cVn = cV.

Why it matters for monitoring

Acid-base titration delivers quantitative water-quality data, such as total acidity, alkalinity or the concentration of a dissolved species, using simple, low-cost equipment. It is the benchmark technique against which instrumental methods such as AAS and chromatography are calibrated, and it underpins quality control across food, environmental and industrial laboratories.

Exam-style questions

Questions in the style of SACE Board exam questions on this dot point, each with a worked answer. They are written by ExamExplained unless tagged "Past paper"; the year shows the paper a question is modelled on.

SACE 2022-style4 marks
All the sodium benzoate in a 20.0 mL20.0\ \text{mL} soft-drink sample was converted to benzoic acid and made up to 100.0 mL100.0\ \text{mL}. A 25.0 mL25.0\ \text{mL} portion was titrated with 0.0010 mol L−10.0010\ \text{mol L}^{-1} NaOH\text{NaOH} (benzoic acid and NaOH\text{NaOH} react 1:11:1); the average titre was 5.05 mL5.05\ \text{mL}. Calculate the concentration, in mol L−1\text{mol L}^{-1}, of sodium benzoate in the soft drink, to the appropriate number of significant figures.
Show worked answer →

Work from the titre back to the original drink.

Step 1: n(NaOH)=cV=0.0010×5.051000=5.05×10−6 moln(\text{NaOH}) = cV = 0.0010 \times \dfrac{5.05}{1000} = 5.05 \times 10^{-6}\ \text{mol}. (1 mark)

Step 2: the 1:11:1 ratio gives n(benzoic acid in 25.0 mL)=5.05×10−6 moln(\text{benzoic acid in } 25.0\ \text{mL}) = 5.05 \times 10^{-6}\ \text{mol}. (1 mark)

Step 3: scale to the full 100.0 mL100.0\ \text{mL}: n=5.05×10−6×100.025.0=2.02×10−5 moln = 5.05 \times 10^{-6} \times \dfrac{100.0}{25.0} = 2.02 \times 10^{-5}\ \text{mol}. This equals the moles of sodium benzoate in the original 20.0 mL20.0\ \text{mL} sample. (1 mark)

Step 4: c=nV=2.02×10−50.0200=1.0×10−3 mol L−1c = \dfrac{n}{V} = \dfrac{2.02 \times 10^{-5}}{0.0200} = 1.0 \times 10^{-3}\ \text{mol L}^{-1} (2 significant figures, matching the 0.00100.0010 data). (1 mark)

SACE 2021-style5 marks
A 1.325 g1.325\ \text{g} sample of impure anhydrous sodium carbonate was dissolved and made up to 250.0 mL250.0\ \text{mL}. A 25.00 mL25.00\ \text{mL} aliquot required 24.10 mL24.10\ \text{mL} of 0.1000 mol L−10.1000\ \text{mol L}^{-1} HCl\text{HCl} for complete reaction: Na2CO3+2HCl→2NaCl+H2O+CO2\text{Na}_2\text{CO}_3 + 2\text{HCl} \rightarrow 2\text{NaCl} + \text{H}_2\text{O} + \text{CO}_2. Calculate the percentage by mass of Na2CO3\text{Na}_2\text{CO}_3 in the sample. (M(Na2CO3)=105.99 g mol−1M(\text{Na}_2\text{CO}_3) = 105.99\ \text{g mol}^{-1}.)
Show worked answer →

Step 1: n(HCl)=cV=0.1000×0.02410=2.410×10−3 moln(\text{HCl}) = cV = 0.1000 \times 0.02410 = 2.410 \times 10^{-3}\ \text{mol}. (1 mark)

Step 2: the 2:12:1 ratio gives n(Na2CO3 in aliquot)=12(2.410×10−3)=1.205×10−3 moln(\text{Na}_2\text{CO}_3 \text{ in aliquot}) = \tfrac{1}{2}(2.410 \times 10^{-3}) = 1.205 \times 10^{-3}\ \text{mol}. (1 mark)

Step 3: scale to the full 250.0 mL250.0\ \text{mL}: n=1.205×10−3×250.025.00=1.205×10−2 moln = 1.205 \times 10^{-3} \times \dfrac{250.0}{25.00} = 1.205 \times 10^{-2}\ \text{mol}. (1 mark)

Step 4: m(Na2CO3)=nM=1.205×10−2×105.99=1.277 gm(\text{Na}_2\text{CO}_3) = nM = 1.205 \times 10^{-2} \times 105.99 = 1.277\ \text{g}. (1 mark)

Step 5: % by mass=1.2771.325×100=96.4%\%\text{ by mass} = \dfrac{1.277}{1.325} \times 100 = 96.4\%. (1 mark)

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