Experiment no.

35
Aim: Potentiometric titration of a strong acid strong base using quinhydrone electrode
Apparatus required: Burette, pipette, volumetric flasks, beakers, magnetic stirrer,
potentiometer with standard cell, SCE, platinum indicator electrode, connecting wires etc.
Chemicals required: Hydrochloric acid. sodium hydroxide and quinhydrone.
Theory: 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.
Principle:
Quinhydrone
This is an equilibrium mixture of quinone and hydroquinone.
This cannot be used in strongly base solution (pH>9) because the equilibrium will be disturbed.
Quinone - hydroquinone system involves the equilibrium

For this reduction reaction, the potential developed on the platinum electrode immersed in this
system is given by Nernst equation.

Instead of taking quinone & hydroquinone a small amount of quinhydrone, which is an

equimolar compound of quinone Q and hydroquinone QH2 is taken. QH2 is a weak acid; its
ionization 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 o C = 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 neutralization 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.
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)].

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.
3. Carry out necessary connections.
4. Standardize 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.
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 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. Second derivative curve (∆2 E/∆V2)
against the volume (V) can also be drawn. Second derivative curve (∆2 E/∆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.
Calculations:
From the plotted graph, the volume of alkali used corresponding to the equivalence point =
0.85V cm3
Applying the molarity equation M1V1 = M2V2
(Hydrochloric acid) (Sodium hydroxide) Molarity of sodium hydroxide solution will be
M2 = 0.5 mol dm–3
Result:
Strength of the sodium hydroxide solution is 10 mol dm–3