Year 11 Chemistry Module 2 ⏱ ~40 min Lesson 17 of 20

Back Calculations
& Unknown Concentrations

In quantitative analysis chemists often know the product and need to work backwards — using a precipitate mass or titration result to find the concentration of an unknown solution. This appears in nearly every HSC Chemistry exam.

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Back Calculation Pathway

Titration: n(standard) = c × V → ÷ ratio → n(unknown) → c = n ÷ V(flask)

Gravimetric: m(precipitate) → n = m ÷ MM → ÷ ratio → n(unknown) → c = n ÷ V

Average titre: discard rough; average concordant results (within 0.10 mL)
⚠️ Volume in the flask (aliquot) is used to find c(unknown). Volume from the burette (titre) is used to find n(standard). Swapping these is the most common error in this lesson.

Know

  • Back-calc starts with known product/standard, finds unknown
  • Concordant = titres within 0.10 mL of each other
  • Rough titre is always discarded
  • Primary standard: known mass → standardise unknown solution

Understand

  • Why excess reagent guarantees complete reaction in gravimetric analysis
  • The flask-vs-burette volume distinction
  • How non-1:1 ratios affect back calculations

Can Do

  • Find c(unknown) from titration data — 1:1 and non-1:1 ratios
  • Find c(unknown) from precipitate mass in gravimetric data
  • Calculate average concordant titre correctly
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Think First

In a titration, the standard solution is in the burette and the unknown solution is in the conical flask. If you know the concentration of the standard and the volume it takes to reach the endpoint, how would you work backwards to find the concentration of the unknown — and which volume goes into the formula c = n ÷ V for each substance?

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Key Terms
MoleThe SI unit for amount of substance; contains exactly 6.022 × 10²³ particles.
Avogadro's Number6.022 × 10²³ — the number of particles in one mole of a substance.
Molar MassThe mass of one mole of a substance, measured in g/mol.
Limiting ReagentThe reactant that is completely consumed first, limiting the amount of product formed.
Empirical FormulaThe simplest whole-number ratio of atoms in a compound.
Molecular FormulaThe actual number of atoms of each element in a molecule of a compound.

Misconceptions to Fix

Wrong: A catalyst increases the yield of products in an equilibrium reaction.

Right: A catalyst speeds up both forward and reverse reactions equally; it does not change equilibrium yield.

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The Back Calculation Method

A back calculation works in the opposite direction to a forward stoichiometry problem. Instead of "given reactant, find product", you work "given product, find unknown reactant".

KNOWN ✓ c(std) V(titre) concentration of standard + average concordant titre n = c×V moles of standard n(std) from burette reading × coeff ÷ coeff moles of unknown n(unk) via mole ratio ÷V(flask) ANSWER ✓ c(unknown) = n ÷ V(flask) concentration of unknown solution
Interactive: Back-Titration Stepper

Concordant Titres

Multiple titrations are performed to ensure reliability. The first trial (rough) is always discarded. Remaining results within 0.10 mL of each other are concordant — average those only.

Example: Rough = 21.8 mL, T1 = 22.4 mL, T2 = 22.5 mL, T3 = 22.3 mL
T1 and T3 differ by 0.1 mL ✓; T2 and T3 differ by 0.2 mL — marginal. Use T1, T2, T3 if all within 0.2 mL and question doesn't specify stricter criteria.
Average = (22.4 + 22.5 + 22.3) ÷ 3 = 22.4 mL

Primary Standard Back Calculation

A known mass of a pure primary standard is dissolved to a known volume, giving a precisely known concentration. This standard is then titrated against the unknown solution.

Steps: m(primary standard) ÷ MM → n(total) ÷ V(total) → c(standard) → n(aliquot) = c × V(aliquot) → apply ratio → n(unknown) → c = n ÷ V(flask)

Worked Example 1 — Titration back-calc, 1:1 ratio

Standard → [Unknown]
25.0 mL of NaOH (unknown concentration) is titrated against 0.100 mol/L HCl. Concordant titres: 22.3, 22.4, 22.3 mL. Find [NaOH]. HCl + NaOH → NaCl + H₂O.
  1. 1
    Average concordant titre
    V(HCl) = (22.3+22.4+22.3)÷3 = 22.33 mL = 0.02233 L
  2. 2
    n(HCl) — the known burette solution
    n(HCl) = 0.100 × 0.02233 = 2.233×10⁻³ mol
  3. 3
    Ratio 1:1 → n(NaOH) = 2.233×10⁻³ mol
  4. 4
    c(NaOH) using flask volume = 25.0 mL
    c(NaOH) = 2.233×10⁻³ ÷ 0.0250 = 0.0893 mol/L
✓ Answerc(NaOH) = 0.0893 mol/L

Worked Example 2 — H₂SO₄ vs NaOH, non-1:1 ratio

Non-1:1 Ratio
25.0 mL of H₂SO₄ (unknown) is titrated with 0.200 mol/L NaOH. Average titre = 18.50 mL. Find [H₂SO₄]. H₂SO₄ + 2NaOH → Na₂SO₄ + 2H₂O.
  1. 1
    n(NaOH)
    n(NaOH) = 0.200 × 0.01850 = 3.700×10⁻³ mol
  2. 2
    Ratio NaOH:H₂SO₄ = 2:1
    n(H₂SO₄) = 3.700×10⁻³ ÷ 2 = 1.850×10⁻³ mol
  3. 3
    c(H₂SO₄) in 25.0 mL flask
    c = 1.850×10⁻³ ÷ 0.0250 = 0.0740 mol/L
✓ Answerc(H₂SO₄) = 0.0740 mol/L

Worked Example 3 — Primary standard (Na₂CO₃ vs HCl)

Primary Standard
0.530 g of Na₂CO₃ is dissolved to 100.0 mL. 25.0 mL aliquots are titrated against HCl. Average titre = 24.5 mL. Find [HCl]. Na₂CO₃ + 2HCl → 2NaCl + H₂O + CO₂. (Na = 22.990, C = 12.011, O = 15.999)
  1. 1
    n(Na₂CO₃) in full solution
    MM = 105.99; n = 0.530 ÷ 105.99 = 5.001×10⁻³ mol
  2. 2
    n in 25.0 mL aliquot
    c = 5.001×10⁻³ ÷ 0.100 = 0.05001 mol/L
    n(aliquot) = 0.05001 × 0.0250 = 1.250×10⁻³ mol
  3. 3
    Ratio 1:2 → n(HCl)
    n(HCl) = 1.250×10⁻³ × 2 = 2.500×10⁻³ mol
  4. 4
    c(HCl) from titre
    c(HCl) = 2.500×10⁻³ ÷ 0.0245 = 0.102 mol/L
✓ Answerc(HCl) = 0.102 mol/L

Worked Example 4 — Gravimetric back calculation

Precipitate → [unknown]
25.0 mL of BaCl₂ solution reacts with excess Na₂SO₄. 0.699 g of BaSO₄ precipitate forms. Find [BaCl₂]. BaCl₂ + Na₂SO₄ → BaSO₄↓ + 2NaCl. (Ba = 137.33, S = 32.06, O = 15.999)
  1. 1
    n(BaSO₄)
    MM(BaSO₄) = 233.39; n = 0.699 ÷ 233.39 = 2.995×10⁻³ mol
  2. 2
    Ratio 1:1 → n(BaCl₂) = 2.995×10⁻³ mol
  3. 3
    c(BaCl₂)
    c = 2.995×10⁻³ ÷ 0.0250 = 0.120 mol/L
✓ Answerc(BaCl₂) = 0.120 mol/L
⚠️

Common Mistakes

Using titre volume instead of flask volume for c(unknown)
The unknown is in the flask (25.0 mL aliquot). Its concentration = n ÷ V(flask). The titre volume from the burette belongs to the standard solution. Swapping these gives an answer off by the ratio of the two volumes.
✓ Fix: Label clearly — Flask = unknown. Burette = standard. c(unknown) = n ÷ V(flask). Never use titre volume for c(unknown).
Forgetting the non-1:1 ratio
H₂SO₄ + 2NaOH is the classic trap. If you skip the 2:1 ratio and assume 1:1, your answer for [H₂SO₄] is exactly double the correct value. This is reliably tested every few years in the HSC.
✓ Fix: Write the balanced equation and circle the ratio before calculating. n(H₂SO₄) = n(NaOH) ÷ 2, not n(NaOH) × 1.
Including the rough titre in the average
The rough titre is always larger than the true endpoint because students deliberately overshoot on the first run to find the approximate endpoint range. It must always be discarded. Including it biases the average upward, giving a systematic error in c(unknown).
✓ Fix: Identify and discard the rough titre first. Average only concordant results (within 0.10 mL of each other).

📓 Copy Into Your Books

🔍 Back Calc Steps

  • 1. n(standard) = c × V(titre)
  • 2. Apply mole ratio
  • 3. c(unknown) = n ÷ V(flask)
  • Always use V in litres

🧪 Concordant Titres

  • Discard rough (first) titre always
  • Concordant = within 0.10 mL
  • Average concordant results only
  • Use average in calculation

⚗️ Primary Standard Path

  • m ÷ MM → n(total) ÷ V = c
  • n(aliquot) = c × V(aliquot)
  • Apply ratio → n(HCl)
  • c(HCl) = n ÷ V(titre)

⚠️ Volume Rules

  • Flask volume → c(unknown)
  • Titre volume → n(standard)
  • Total volume → c(product in mixture)
  • NEVER mix these up

📝 How are you completing this lesson?

Titration: Which Volume Belongs to Which Substance? Burette Standard solution c known V = from titration c × V = n Calculation n(standard) → ratio → n(unknown) c = n ÷ V(unknown) Conical Flask Unknown solution c = ? V = from pipette (fixed) ⚠ Do not swap the volumes! The burette volume belongs to the standard; the pipette volume belongs to the unknown.
🔍 Activity 1 — Back Calculation Drill

Titration and Gravimetric Calculations

Identify flask vs burette for each problem before calculating.

1 25.0 mL NaOH titrated with 0.150 mol/L HCl. Average titre = 20.0 mL. Find [NaOH].

n(HCl) = 0.150 × 0.0200 = 3.00×10⁻³; ratio 1:1; n(NaOH) = 3.00×10⁻³c(NaOH) = 3.00×10⁻³ ÷ 0.0250 = 0.120 mol/L

2 20.0 mL H₂SO₄ titrated with 0.100 mol/L NaOH. Average titre = 16.0 mL. Find [H₂SO₄]. (H₂SO₄ + 2NaOH → Na₂SO₄ + 2H₂O)

n(NaOH) = 0.100 × 0.0160 = 1.60×10⁻³; ratio 2:1n(H₂SO₄) = 1.60×10⁻³ ÷ 2 = 8.00×10⁻⁴c(H₂SO₄) = 8.00×10⁻⁴ ÷ 0.0200 = 0.0400 mol/L

3 Titres: Rough = 21.0, T1 = 22.5, T2 = 22.6, T3 = 22.4 mL. (a) Which are concordant? (b) Calculate average titre.

(a) T1, T2, T3 are concordant (Rough discarded). T1–T3: 22.4–22.6, range = 0.2 mL. T1 and T3 are within 0.1 mL; T2 is 0.1–0.2 from T3/T1.
(b) Average = (22.5 + 22.6 + 22.4) ÷ 3 = 22.5 mL

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Revisit — Think First

At the start of this lesson, you thought about how to work backwards from a titration to find the concentration of an unknown solution, and which volume to use for each substance.

The key is: n(standard) = c(standard) × V(titre, from burette). Apply the mole ratio. Then c(unknown) = n(unknown) ÷ V(aliquot, from flask). The burette titre is used for the standard solution; the flask (aliquot) volume is used for the unknown. Swapping these is the most common error. In gravimetric back-calculations, start from the precipitate mass instead of a titre.

Reflect: how did your initial thinking compare to what you've learned?

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MC

Multiple Choice

5 random questions from a replayable lesson bank — feedback shown immediately

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Extended Questions

ApplyBand 3

6. 0.424 g of Na₂CO₃ (MM = 105.99) is dissolved to 100.0 mL. 25.0 mL aliquots are titrated against HCl. Titres: Rough = 19.8, T1 = 21.3, T2 = 21.4, T3 = 21.2 mL. Na₂CO₃ + 2HCl → 2NaCl + H₂O + CO₂. (a) Calculate the average concordant titre. (b) Find [HCl]. 5 MARKS

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AnalyseBand 4

7. 40.0 mL of AgNO₃ solution reacts with excess NaCl. 1.148 g of AgCl precipitate forms. (a) Find [AgNO₃]. (b) Explain why NaCl must be in excess. AgNO₃ + NaCl → AgCl↓ + NaNO₃. (Ag = 107.87, Cl = 35.453) 4 MARKS

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AnalyseBand 4

8. A student standardises an NaOH solution using oxalic acid dihydrate (H₂C₂O₄·2H₂O, MM = 126.07) as a primary standard. They dissolve 0.756 g in 250.0 mL water. 25.0 mL aliquots are titrated against NaOH. The equation is: H₂C₂O₄ + 2NaOH → Na₂C₂O₄ + 2H₂O. Titres: Rough = 24.5, T1 = 25.8, T2 = 25.7, T3 = 25.9 mL. (a) Identify the concordant titres and calculate the average. (b) Find c(NaOH). (c) State one reason why oxalic acid dihydrate is suitable as a primary standard. 6 MARKS

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EvaluateBand 5

9. A student performs a back-calculation titration but accidentally reads the flask volume (25.0 mL) as 0.250 mL when inputting into their calculation. They use this value as V(unknown) in c = n ÷ V. (a) Describe the effect this error has on their calculated concentration — will it be too high or too low, and by what factor? (b) Explain how a chemist could detect this error without redoing the experiment. 4 MARKS

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✅ Comprehensive Answers

❓ Multiple Choice

1. B — c(unknown) = n ÷ V(flask). The flask volume is the aliquot of the unknown solution.

2. C — n(HCl) = 0.200 × 0.0150 = 0.00300; ratio 1:1; c(NaOH) = 0.00300 ÷ 0.0250 = 0.120 mol/L.

3. A — n(NaOH) = 0.100 × 0.020 = 0.00200; ratio 2:1; n(H₂SO₄) = 0.00100; c = 0.00100 ÷ 0.025 = 0.0400 mol/L.

4. D — Discard rough (22.1). Average T1, T2, T3 = (23.4+23.5+23.3)÷3 = 23.4 mL.

5. B — n = 0.212 ÷ 105.99 = 2.000×10⁻³; c = 2.000×10⁻³ ÷ 0.250 = 0.00800 mol/L.

6. C — The rough titre (18.4) must be discarded. T1 = 19.8, T2 = 19.6, T3 = 20.1. Range = 20.1 − 19.6 = 0.5 mL, which exceeds 0.1 mL — not strictly concordant. In practice, students should ideally repeat to get truly concordant results. If forced to average T1–T3: (19.8+19.6+20.1)÷3 = 19.83 mL. The student's inclusion of the rough titre in their average is an error regardless.

7. A — In a back-calculation titration, the unknown solution (acetic acid) goes in the flask (aliquot) and the standard solution (standardised NaOH) goes in the burette. The titre of NaOH gives n(NaOH), then the mole ratio gives n(acetic acid), and dividing by the flask volume gives c(acetic acid). Option B has the burette and flask swapped.

📝 Short Answer Model Answers

Q6 (5 marks):

(a) Discard rough (19.8). T1=21.3, T2=21.4, T3=21.2 — all within 0.2 mL, concordant. Average = (21.3+21.4+21.2)÷3 = 21.3 mL

(b) n(Na₂CO₃) = 0.424 ÷ 105.99 = 4.001×10⁻³; c = 4.001×10⁻³ ÷ 0.100 = 0.04001 mol/L n(aliquot) = 0.04001 × 0.0250 = 1.000×10⁻³; ratio 1:2; n(HCl) = 2.000×10⁻³ c(HCl) = 2.000×10⁻³ ÷ 0.02130 = 0.0939 mol/L

Q7 (4 marks):

(a) MM(AgCl) = 143.32; n = 1.148 ÷ 143.32 = 8.010×10⁻³; ratio 1:1; n(AgNO₃) = 8.010×10⁻³ c(AgNO₃) = 8.010×10⁻³ ÷ 0.0400 = 0.200 mol/L

(b) If NaCl is not in excess, some Ag⁺ ions would remain in solution unreacted. The precipitate mass would be less than the amount corresponding to all the AgNO₃ present. The calculated n(AgNO₃) would be too small, giving an underestimate of c(AgNO₃). Excess NaCl ensures all Ag⁺ is precipitated, so the mass of AgCl accurately reflects the full quantity of AgNO₃.

Q8 (6 marks):

(a) Discard rough (24.5). T1 = 25.8, T2 = 25.7, T3 = 25.9. Range = 25.9 − 25.7 = 0.2 mL. These are within 0.2 mL — concordant (using standard HSC criterion of ≤0.2 mL). Average = (25.8+25.7+25.9) ÷ 3 = 25.8 mL

(b) n(H₂C₂O₄) = 0.756 ÷ 126.07 = 5.997×10⁻³ mol; c = 5.997×10⁻³ ÷ 0.250 = 0.02399 mol/L n(aliquot) = 0.02399 × 0.0250 = 5.997×10⁻⁴; ratio 1:2; n(NaOH) = 1.199×10⁻³ c(NaOH) = 1.199×10⁻³ ÷ 0.02580 = 0.04647 mol/L ≈ 0.0465 mol/L

(c) Oxalic acid dihydrate is suitable as a primary standard because it has a high molar mass (126.07 g/mol), which reduces the relative error in weighing; it is stable, non-hygroscopic, available in high purity, and does not absorb CO₂ or water vapour from the air appreciably during weighing.

Q9 (4 marks):

(a) If 0.250 mL is used instead of 25.0 mL, the denominator is 100 times too small (0.000250 L instead of 0.025 L). Since c = n ÷ V, a smaller V gives a larger c. The calculated concentration will be 100× too high (a factor of 100 error).

(b) A chemist could detect this error by: (i) checking the units — 0.250 mL is implausibly small for a pipette measurement; a standard pipette delivers 25.0 mL not 0.250 mL; (ii) comparing the calculated concentration with expected values for a typical solution (e.g., a concentration of 40 mol/L for NaOH is physically impossible, as NaOH is only soluble to about 25 mol/L); (iii) checking the recorded experimental data against the flask volume stated in the method.

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Boss Battle

Boss Battle — Back Calculations & Unknown Concentrations

Put your knowledge of back-titration calculations and determining unknown concentrations to the test. Answer correctly to deal damage — get it wrong and the boss hits back. Pool: lessons 1–17.

Mark lesson as complete

Tick when you've finished all activities and checked your answers.