EXPT.

3 POTENTIOMETRIC TITRATION OF
STRONG ACID WITH A STRONG BASE
USING QUINHYDRONE ELECTRODE
Structure
3.1 Introduction
Objectives
3.2 Principle
3.3 Requirements
3.4 Procedure
3.5 Calculations
3.6 Results

3.1 INTRODUCTION
We have already disused pH-metry in detail in the unit 3 of MCH -004 course. In this
experiment you are going to perform a titration of a strong acid against a strong base
and EMF change during titration is measured by potentiometer. The equivalence point
of the titration is detected by plotting a titration curve.

Objectives
• After performing this experiment you will be able to:
• Discuss how the potential of quinhydrone electrode is dependent on pH of the
solution,
• perform a titration of a strong acid with a strong base using quinhydrone,
• determine the equivalence point of the titration of the strong acid by plotting
titration curve using potential change values and amount of base added during
titration,
• estimate the strength of the given solution of a strong acid,
• state the advantages of quinhydrone electrode, and
• practice the precautions while performing a potentiometric titration experiment.

3.2 PRINCIPLE
Quinhydrone
This is an equilibrium mixture of quinone and hydroquinone.

This can not be used in strongly base solution (pH>9) because the equilibrium will be
disturbed.
Quinone - hydroquinone system involves the equilibrium
O OH
C6H4O2 + 2H+ + 2e ⇌ C6H6O2
(Quinone) (hydroquinone)
Q QH2
For this reduction reaction, the potential developed on the platinum electrode immersed O OH
in this system is given by Nernst equation. Quinone Hydroquinone

0.0591 [ H + ] 2 [Q ]
Ecell = Eo + log
2 [QH 2 ]

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SpectroscopicMethods Instead of taking quinone & hydroquinone a small amount of quinhydrone, which is an
Lab. equimolar compound of quinone Q and hydroquinone QH2 is taken.

QH2 is a weak acid; its ionisation is very small particularly if the pH of the solution is
less than 7. Therefore, the concentration of hydroquinone, QH2 is same as that of
quinone Q i.e.
[Q]/[QH2] = unity
and hence the Nernst equation may be written as,
= Eo + 0.0591 log [H+] at 25 oC

= Eo – 0.0591 pH
The standard electrode potential of quinhydrone electrode
Eo = + 0.6996 V

E = 0.6996 – 0.0591 pH
Thus the potential of quinhydrone electrode is dependent on pH of the solution i.e.
quinhydrone electrode behaves as a reversible hydrogen electrode.

This is less expensive than hydrogen electrode since it can be set up easily simply by
adding a pinch of quinhydrone to the solution and inserting a Pt electrode for making
electrode connections.

The basic reaction involved in the neutralisation of an acid with a base is

H+ (aq) + OH¯(aq) ⇌ H2O ...(1)

Therefore, the indicator electrode to be selected is obviously an electrode reversible to
H+ ions. e.g. Hydrogen electrode, glass electrode or quinhydrone electrode. For better
results and simple experimentation the latter electrode is commonly used. The cell setup
using quinhydrone electrode is:
SCE│quinhydrone (acid solution)│pt ... (2)
A known volume of the acid is taken in the beaker.

The potentiometer circuit setup and typical apparatus set up are given in Fig. 3.1 and
3.2, respectively.

Fig. 2.1: Circuit diagram for a laboratory potentiometer

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 Fig. 3.2: Typical apparatus set up for potentiometric titration
Standard NaOH is taken in the burette and is added in small volume each time.
The value of potential is noted after each addition.

A graph is plotted by taking the volume of NaOH added along x-axis and the
corresponding voltage on the y-axis.

A steep rise in the curve indicates the equivalence point [see Fig. 3.3 (a)].

Fig. 3.3: Titration curves: (a) typical plot of EMF vs. volume; (b) typical first derivative
titration curve; and (c) typical second derivative titration curve

3.3 REQUIREMENTS
Apparatus
Burette, pipette, volumetric flasks, beakers, magnetic stirrer, potentiometer with
standard cell, SCE, platinum indicator electrode, connecting wires etc.

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SpectroscopicMethods Chemicals
Lab.
Hydrochloric acid. sodium hydroxide and quinhydrone.

3.4 PROCEDURE
1. Take 25.0 cm3 of the standardized hydrochloric acid (use same HCl which you
have standardized for the Experiment 1) in a 100 cm3 beaker (or any other
measured volume enough to allow the indicator and reference electrodes to dip
into solution).

2. Add a pinch of quinhydrone to saturate the solution. Dip the indicator (Pt) and
reference (SCE) electrodes in the above acid solution as shown in Fig. 3.2.

3. Carry out necessary connections as shown in Fig. 3.1.

4. Standardise the potentiometer using a standard cell, before replacing it with the
working cell.

5. Add 1-2 cm3 of 0.1 N NaOH solution from the burette, operate the magnetic
stirrer for 2 minutes, stop it, wait for 1 minute and measure the E.M.F.

6. Repeat the above step, each time adding one or two more cm3 of NaOH at a time
and go on noting the EMF after each addition.

7. When the volume reached near about 1 cm3 of the expected equivalence point.
(approximate), add the solution from the burette in 0.5 cm3 instalments and note
the potential each time.

8. Continue adding these instalments even after the equivalence point (This can be
easily observed from the change in the measured potentials). The change
becomes very small. Continue for another 3-4 additions & note the potential
readings.

9. Record the observations in the Observation Table 1.

10. Plot the following graphs has from the data obtained in the above table.

a) Plot the graph by taking the EMF on the y-axis and volume of NaOH added
on the x-axis. The graph will look like the Fig. 3.3 (a). The volume
corresponding to steep rise in the potential is the equivalence point.

b) Locate the exact end point of the titration by plotting

∆E/∆V along y-axis for small instalments of the titrant in the vicinity of the
equivalence point against the volume of alkali. There is a maximum in the
plot at the equivalence point Fig. 3.3 (b). Second derivative curve
(∆2E/∆V2) against the volume (V) can also be drawn as shown in Fig. 3.3
(c). Second derivative curve (∆2E/∆V2) is zero at the point where the slope
of the ∆E/∆V curve is maximum. The point where this curve cuts the x-axis
is the equivalence point.

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Observations

Observation Table 1: Titration of HCL vs. NaOH

Sr.No. Volume (V) of EMF (E) of the ΔV ΔE Δ E/ Δ V

NaOH added cell (millivolts)
(cm3)

1. 0.0 … … …

2. 2.0

3. 4.0 … … …

4. 6.0 … … …

5. 8.0 … … …

6. 10.0 … … …

7. 12.0 … … …

8. 14.0 … … …

9. 16.0 … … …

10. 18.0 … … …

11. 20.0 … … …

12. 22.0 … … …

13. 23.0 … … …

14. 24.0 … … …

15. 24.5 … … …

16. 25.0 … … …

17. 25.5 … … …

18. 26.0 … … …

19. 26.5 … … …

20. 27.0 … … …

21. 28.0 … … …

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SpectroscopicMethods
Lab. 3.5 CALCULATIONS
From the plotted graph, the volume of alkali used corresponding to the equivalence
point = ……………V cm3
Applying the molarity equation

M1V1 = M2V2
(Hydrochloric acid) (Sodium hydroxide)
Molarity of sodium hydroxide solution will be
M 1V1
M2 = mol dm–3
V2

3.6 RESULT
Strength of the sodium hydroxide solution is ………… mol dm–3

Standardisation of Potentiometer
Circuit of a potentiometer is given in Fig. 3.1

Different steps involved in the standardization:-

1. Connect the galvanometer G, battery Eb, and standard cell W to their appropriate
terminals on the potentiometer. Check the polarity of the battery and standard cell
and make the proper connections.
2. Note the room temperature and find out the voltage of the standard cell at that
temp from the temp-voltage change provided with the Weston cell and set the
potential dials to that of the standard cell.
3. Set the galvanometer to the lowest sensitivity and press the standardisation key K
for a moment. The spot of the galvanometer will move in one direction or other.
4. Adjust the course and fine rheostats so that there is no deflection in the spot when
the standardisation key is pressed.
5. Now increase the sensitivity of the galvanometer and adjust the fine rheostat so
that there is no deflection in the spot.
6. The potentiometer is now standardised and is ready for measurement of any
unknown E.M.F.
7. Do not disturb the Rheostats used for standardisation and now connect to the
unknown cell whose EMF is to be measured instead of the standardisation cell.
8. Repeat the same, now changing the potentiometer dial to get the balance point in
the galvanometer. The potential on the dial will give the potential of the unknown
cell.

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