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Acid-base indicators: WACE Year 12 Chemistry

Syllabus dot point

“Explain how acid-base indicators work as weak acid equilibria and select an appropriate indicator for a titration”

8 min read

Quick answer

An acid-base indicator is itself a weak acid whose acid form (HIn\text{HIn}) and conjugate base form (In−\text{In}^-) have different colours. Changing the pH shifts this equilibrium, changing the colour. An indicator changes colour over a range of about two pH units centred on its pKa\text{p}K_a. You choose an indicator whose colour change range falls on the steep part of the titration curve, at the equivalence point.

What this dot point is asking

An acid-base indicator is a substance that changes colour depending on the pH of the solution. Most are weak organic acids (or bases) where the protonated and deprotonated forms absorb different wavelengths of light.

Acid-base indicator

A weak acid (or base) whose acid form and conjugate base form have distinctly different colours, so that the colour observed depends on the pH of the solution.

How indicators work

Represent the indicator as a weak acid HIn\text{HIn}:

HIn(aq)⇌H+(aq)+In−(aq)\text{HIn}(aq) \rightleftharpoons \text{H}^+(aq) + \text{In}^-(aq)

where HIn\text{HIn} is one colour and In−\text{In}^- is another. In acidic solution the high [H+][\text{H}^+] pushes the equilibrium to the left (Le Chatelier), so the HIn\text{HIn} colour dominates. In basic solution [H+][\text{H}^+] is low, the equilibrium shifts right, and the In−\text{In}^- colour dominates. For example, with litmus the HIn\text{HIn} form is red and the In−\text{In}^- form is blue.

Colour change range is about pKa

The eye sees the colour change when the two forms are present in comparable amounts, which occurs near pH=pKa\text{pH} = \text{p}K_a of the indicator. The visible transition spans roughly pKa±1\text{p}K_a \pm 1, about two pH units.

The colour change range

Because the colour switches over the range where neither form completely dominates, each indicator has a characteristic transition interval. Common examples:

  • Methyl orange: red to yellow, range about pH 3.1 to 4.4.
  • Bromothymol blue: yellow to blue, range about pH 6.0 to 7.6.
  • Phenolphthalein: colourless to pink, range about pH 8.3 to 10.0.

Choosing an indicator for a titration

The key skill is matching the indicator to the equivalence point of the titration. You want the indicator to change colour exactly where the titration curve is steepest, so the colour change is sharp and corresponds to the equivalence point.

  • Strong acid with strong base: equivalence point at pH 7, with a very steep curve from about pH 3 to 11. Almost any of the common indicators works.
  • Strong acid with weak base: equivalence point is acidic (below 7). Use methyl orange.
  • Weak acid with strong base: equivalence point is basic (above 7). Use phenolphthalein.
Selecting an indicator

Question

A student titrates ethanoic acid (a weak acid) with sodium hydroxide (a strong base). Which indicator, methyl orange or phenolphthalein, should they use and why?

Solution

A weak acid titrated with a strong base gives a salt of a weak acid (sodium ethanoate), whose solution is basic, so the equivalence point lies above pH 7. The chosen indicator must change colour in that basic region.

Phenolphthalein changes over pH 8.3 to 10.0, which lies on the steep part of this titration curve, so it gives a sharp end point at the equivalence point. Methyl orange (pH 3.1 to 4.4) would change far too early, well before the acid is neutralised, so it is unsuitable. The student should use phenolphthalein.

End point versus equivalence point

Two terms are easy to confuse. The equivalence point is the point in a titration where the amount of titrant added is stoichiometrically equal to the amount of analyte present, a property of the chemistry alone. The end point is where the indicator actually changes colour, a property of the indicator you chose. They coincide only when the indicator's transition range straddles the equivalence-point pH. Choosing well makes the difference between them negligible, which is why indicator selection is a marked skill in WACE volumetric analysis.

Universal indicator and why titrations avoid it

Universal indicator is a mixture of several indicators that gives a continuous colour change across the whole pH scale, useful for estimating pH but useless for a titration. Because it changes gradually it gives no sharp end point, so it cannot pin down the equivalence volume to within a drop. A single indicator with a narrow transition range, matched to the equivalence-point pH, changes colour over the addition of roughly one drop on the steep part of the curve, giving the precise end point a titration needs.

Why this matters

Choosing the right indicator is essential for accurate volumetric analysis, the quantitative technique used to find unknown concentrations. A mismatched indicator gives a false end point and a wrong result, so this dot point links directly to the titration calculations elsewhere in Unit 3.

Ignoring the equivalence point pH

The biggest error is choosing an indicator by habit rather than matching its range to the equivalence point. Using phenolphthalein for a strong acid with a weak base, or methyl orange for a weak acid with a strong base, gives an end point that does not coincide with neutralisation. Another slip is treating the end point and the equivalence point as identical; they coincide only when the indicator is well chosen.

Exam-style questions

Questions in the style of SCSA 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.

WACE 2021-style6 marks
An indicator HIn\text{HIn} is a weak acid with Ka=1.0×10−5K_a = 1.0 \times 10^{-5}. Its acid form HIn\text{HIn} is yellow and its conjugate base In−\text{In}^- is blue. (a) Write the equilibrium and the expression for KaK_a. (b) Calculate the pH\text{pH} at which [HIn]=[In−][\text{HIn}] = [\text{In}^-]. (c) State the approximate pH\text{pH} range over which the colour change is seen, and the colour at pH 3\text{pH}\ 3.
Show worked answer →

A 6 mark question rewards the equilibrium, the half-colour pH, and the range with reasoning.

(a) HIn(aq)⇌H+(aq)+In−(aq)\text{HIn}(aq) \rightleftharpoons \text{H}^+(aq) + \text{In}^-(aq), with

Ka=[H+][In−][HIn].K_a = \frac{[\text{H}^+][\text{In}^-]}{[\text{HIn}]}.

(b) When [HIn]=[In−][\text{HIn}] = [\text{In}^-] they cancel in the expression, leaving Ka=[H+]K_a = [\text{H}^+]. So [H+]=1.0×10−5 mol L−1[\text{H}^+] = 1.0 \times 10^{-5}\ \text{mol L}^{-1} and

pH=−log⁡10(1.0×10−5)=5.0.\text{pH} = -\log_{10}(1.0 \times 10^{-5}) = 5.0.

This is the pKa\text{p}K_a, the midpoint of the colour change.

(c) The visible transition spans about pKa±1\text{p}K_a \pm 1, so roughly pH 4\text{pH}\ 4 to pH 6\text{pH}\ 6. At pH 3\text{pH}\ 3 the high [H+][\text{H}^+] pushes the equilibrium left so HIn\text{HIn} dominates: the solution is yellow.

Markers reward the correct KaK_a expression, pH=pKa=5.0\text{pH} = \text{p}K_a = 5.0, the ±1\pm 1 range and the yellow (acid-form) colour at low pH.

WACE 2023-style5 marks
Explain, in terms of the indicator equilibrium and the shape of the titration curve, why phenolphthalein is a suitable indicator for the titration of 0.100 mol L−1\text{0.100 mol L}^{-1} ethanoic acid with 0.100 mol L−1\text{0.100 mol L}^{-1} sodium hydroxide, but methyl orange is not.
Show worked answer →

A 5 mark explain answer needs the equivalence-point pH, the curve shape, and both indicators justified.

Ethanoic acid is a weak acid; titrated with the strong base NaOH\text{NaOH} it forms sodium ethanoate, the salt of a weak acid. The ethanoate ion hydrolyses, CH3COO−(aq)+H2O(l)⇌CH3COOH(aq)+OH−(aq)\text{CH}_3\text{COO}^-(aq) + \text{H}_2\text{O}(l) \rightleftharpoons \text{CH}_3\text{COOH}(aq) + \text{OH}^-(aq), so the equivalence point is basic, near pH 8.7\text{pH}\ 8.7. The titration curve has its steep, near-vertical region in the basic range (about pH 7\text{pH}\ 7 to pH 10\text{pH}\ 10).

Phenolphthalein changes colour over pH 8.3\text{pH}\ 8.3 to 10.010.0, which lies on this steep section, so its end point coincides with the equivalence point and the colour change is sharp. Methyl orange changes over pH 3.1\text{pH}\ 3.1 to 4.44.4; this is reached while there is still a large excess of acid, far before the equivalence point, giving a false and gradual end point.

Markers reward the basic equivalence point (with hydrolysis), the steep region of the curve, and matching only phenolphthalein's range to that region.

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