Unit 9 Indicators and titration curves
Key unit competence: Evaluate the relationship between titration curves, the type of acid–base titration involved and the choice of indicator.
Key ideas
- An acid–base indicator is a weak acid (HIn) whose acid form and conjugate base form (In−) have different colours: HIn ⇌ H+ + In−. The colour changes over a range of about pKIn ± 1; the end point is when [HIn] = [In−] (pH = pKIn).
- Common indicators: methyl orange, pH 3.1–4.4 (red → yellow); methyl red, 4.4–6.2 (red → yellow); bromothymol blue, 6.0–7.6 (yellow → blue); phenolphthalein, 8.3–10.0 (colourless → pink).
- A titration curve plots pH against volume of titrant. The equivalence point is where moles of acid and base match exactly; the curve is steepest there. Choose an indicator whose range lies in the vertical part of the curve.
- Strong acid–strong base: start pH 1, vertical part about pH 3–11, equivalence pH 7: any common indicator. Weak acid–strong base: start about pH 3, a buffer region, vertical part about 7–11, equivalence pH about 8.7: phenolphthalein. At half-equivalence pH = pKa.
- Strong acid–weak base: vertical part about 3–7, equivalence pH about 5.3: methyl orange (or methyl red). Weak acid–weak base: no sharp vertical part, so no indicator is suitable (use a pH meter or conductivity).
- Sodium carbonate titrated with HCl shows TWO equivalence points: CO32− + H+ → HCO3− at about pH 8.3 (phenolphthalein), then HCO3− + H+ → H2O + CO2 at about pH 3.8 (methyl orange); the second needs twice the volume of the first.
Common misconceptions
- "The end point and the equivalence point are always the same." No: The end point is when the indicator changes; with a well-chosen indicator it is very close to the equivalence point.
- "The equivalence point is always at pH 7." No: Only for strong acid–strong base; weak acid–strong base gives pH > 7, strong acid–weak base pH < 7.
- "Any indicator works for any titration." No: The indicator's range must fall within the steep part of the curve.
Worked examples
Example 1. Sketch (describe) the pH curve for 25.0 cm3 of 0.10 mol dm−3 ethanoic acid titrated with 0.10 mol dm−3 NaOH and mark its key points.
Solution
Start: pH about 2.9 (weak acid).
Buffer region: pH rises slowly; at 12.5 cm3 (half-equivalence) pH = pKa = 4.74.
Equivalence at 25.0 cm3: steep rise from about pH 7 to 11, with the equivalence point near pH 8.7 (ethanoate is basic).
After equivalence: levels off near pH 12.5–13 (excess NaOH). Suitable indicator: phenolphthalein.
Example 2. Explain how an indicator works, using phenolphthalein as an example.
Solution
Phenolphthalein is a weak acid, HIn (colourless); its anion In− is pink: HIn ⇌ H+ + In−.
In acid, high [H+] pushes the equilibrium left: colourless.
When alkali is added, OH− removes H+, the equilibrium shifts right: pink.
The colour changes between pH 8.3 and 10.0, centred on pKIn ≈ 9.3.
Practice questions
Define the end point of a titration.
Show answer
The point at which the indicator changes colour.
Common mistake: Saying it is when the burette is empty.
Why must only a few drops of indicator be used?
Show answer
The indicator is itself a weak acid and would react with the titrant, changing the titre.
Common mistake: Saying more indicator gives better colour.
Give the pH at equivalence for HCl with ammonia: above, below or equal to 7?
Show answer
Below 7 (about 5.3).
Common mistake: Saying 7.
What is the pH at the half-equivalence point of a weak acid titration equal to?
Show answer
pKa of the acid.
Common mistake: Saying 7.
Name a suitable indicator for HCl with NaOH.
Show answer
Methyl orange or phenolphthalein (both fall in the vertical part).
Common mistake: Saying only universal indicator.
How can the Ka of a weak acid be found from its titration curve?
Show answer
Read the pH at half the equivalence volume; pH = pKa, Ka = 10−pKa.
Common mistake: Reading the pH at the equivalence point.
Why is universal indicator not used for titrations?
Show answer
It changes colour gradually over a wide range, so there is no sharp end point.
Common mistake: Saying it is too expensive.
Write the equation for the second stage of the titration of Na2CO3 with HCl.
Show answer
HCO3− + H+ → H2O + CO2
Common mistake: Writing CO32− + 2H+ → CO2 + H2O as stage 2.
Why does a weak acid–strong base titration curve start at a higher pH than a strong acid one of equal concentration?
Show answer
The weak acid is only partly ionised, so [H+] is lower.
Common mistake: Saying the weak acid is more dilute.
Name the region of a weak acid titration curve where pH changes slowly.
Show answer
The buffer region.
Common mistake: Calling it the equivalence region.
Matching and drag-and-drop
Matching
Match each item in column A with the correct answer in column B. Write the letter next to each number.
Column A Column B 1. Methyl orange changes colour in the pH range: a. 3.1–4.4 2. For a strong acid–strong base titration, the pH at equivalence is: b. pink 3. Titrating Na2CO3 with HCl gives how many equivalence points? c. 7 4. Phenolphthalein in alkali is: d. Two Show answer
1 → a (3.1–4.4) · 2 → c (7) · 3 → d (Two) · 4 → b (pink)
- Red to yellow.
- Neutral salt.
- CO32− → HCO3− → H2CO3.
- In− form.
Drag and drop
Choose the correct word or phrase from the box for each gap. One word in the box is not needed.
equivalence point · pH = 14 · pH = pKa · 8.3–10.0- The steep part of a titration curve is near the .
- Phenolphthalein changes colour in the pH range .
- At the half-equivalence point of a weak acid–strong base titration .
Show answer
1: equivalence point · 2: 8.3–10.0 · 3: pH = pKa
- Small volume gives a big pH change.
- Colourless to pink.
- [HA] = [A−].
Matching
Match each item in column A with the correct answer in column B. Write the letter next to each number.
Column A Column B 1. An acid–base indicator is usually: a. pKIn 2. The first equivalence point of Na2CO3 with HCl is detected with: b. a weak acid whose two forms have different colours 3. The colour change of an indicator happens at about pH =: c. phenolphthalein 4. Same titration: 30.0 cm3 of NaOH added. Find the pH. d. 11.96 Show answer
1 → b (a weak acid whose two forms have different colours) · 2 → c (phenolphthalein) · 3 → a (pKIn) · 4 → d (11.96)
- HIn ⇌ H+ + In−.
- About pH 8.3.
- [HIn] = [In−].
- Step 1. Excess OH− = 0.00300 − 0.00250 = 5.0 × 10−4 mol in 55.0 cm3.
Step 2. [OH−] = 9.09 × 10−3; pOH = 2.04.
Step 3. pH = 11.96.
Drag and drop
Choose the correct word or phrase from the box for each gap. One word in the box is not needed.
changes slowly · red · yellow to blue · yellow- Bromothymol blue changes from .
- In the buffer region of a weak acid titrated with NaOH, the pH .
- Methyl orange in acid is .
Show answer
1: yellow to blue · 2: changes slowly · 3: red
- Range 6.0–7.6.
- Mixture of HA and A−.
- HIn form.