Electrochemistry

LEC 06

06.13 Potentiometric titration

What you can learn about
 Potentiometric titration
 Redox reaction
 Nernst equation
 Quantitative analysis

Principle and tasks

In a potentiometric titration the
equivalence point is detected by
monitoring the electromotive force
(e.m.f.) of an electrochemical cell
formed by an indicator electrode
coupled with a convenient reference
electrode. The potential of the indicator electrode, and hence the e.m.f.
of the cell, is a measure of the activity (approximately the concentration) of the ionic species in the electrolyte solution. A potentiometric
titration on the iron(II)/cerium(IV)
redox system with a 0.1 molar
iron(II) sulphate solution is performed to determine the concentration of an unknown iron(II) solution.

What you need:

Cobra3 Chem-Unit
Power supply 12V/2A
Data cable, RS232
Software Cobra3 Chem-Unit
Adapter, BNC-plug/socket, 4mm
Reference electrode, AgCl
Platinum electrode
Connecting cord, l = 1000 mm, blue
Magnetic stirrer, mini
Magnetic stirrer bar, l = 15 mm
Separator for magnetic bars
Retort stand, h = 750 mm
Right angle clamp
Holder for 2 electrodes
Spring balance holder
Burette clamp, roller mounting
Burette, 50 ml, lateral stopcock
Analytical balance with data output, 110 g
Weighing dishes, 80 5014 mm
Beaker, 1000 ml, short
Beaker, 250 ml, tall
Volumetric flask, 100 ml
Volumetric flask, 500 ml
Graduated pipette, 25 ml
Volumetric pipette, 10 ml
Pipettor
Graduated cylinder, 250 ml
Funnel, glass, do = 80 mm
Funnel, glass, do = 55 mm
Pasteur pipettes
Rubber bulbs
Spoon
Wash bottle, 500 ml
86 Laboratory Experiments Chemistry

12153.00 *
12151.99
14602.00
14520.61 *
07542.26 *
18475.00
45206.00
07363.04
47334.93
46299.01
35680.03
37694.00
37697.00
45284.01
03065.20
37720.00
36513.01
45024.93
45019.05
36017.00
36004.00
36548.00
36551.00
36602.00
36578.00
36592.00
36630.00
34459.00
34457.00
36590.00
39275.03
33398.00
33931.00

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1
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2
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Potentiometric redox titration curve for the Fe(II)/Ce(IV) system.

Iron-II sulphate, 500 g

Cerium-IV disulphate, 25 g
Sulphuric acid, 95-98%, 500 ml
Water, distilled, 5 l
PC, Windows 95 or higher

30072.50
31194.04
30219.50
31246.81

Potentiometric titration
with Cobra3 Chem-Unit

1
1
1
1

P3061340

Changes in the equipment required for use of the Basic-Unit:

(instead of * above mentioned)
Cobra3 Basic-Unit
Measuring module, pH/Potential
Software Cobra3 pH/Potential

Potentiometric titration
with Cobra3 Basic-Unit
PHYWE Systeme GmbH & Co. KG D - 37070 Gttingen

12150.00
12101.00
14509.61

1
1
1

P3061311

LEC
06.13

Potentiometric titration

Related concepts
Potentiometric titration, redox reaction, Nernst equation, quantitative analysis.

2. Determine the concentration of an unknown iron(II) solution.

3. Discuss the general form of the titration curve in terms of the
Nernst equation.

Principle
In a potentiometric titration, the equivalence point is detected by
monitoring the electromotive force (e.m.f.) of an electrochemical
cell formed by an indicator electrode coupled with a convenient
reference electrode. The potential of the indicator electrode, and
hence the e.m.f. of the cell, is a measure of the activity (approximately the concentration) of the ionic species in the electrolyte
solution.

Equipment
Cobra3 Chem-Unit
Power supply 12 V/2 A
Data cable, RS232
Software Cobra3 Chem-Unit
Adapter, BNC-plug/socket, 4 mm
Reference electrode, AgCl
Platinum electrode
Connecting cord, l = 1000 mm, black
Magnetic stirrer, mini
Magnetic stirrer bar, l = 15 mm
Separator for magnetic bars
Retort stand, h = 750 mm

Tasks
1. Perform a potentiometric titration on the iron(II)/cerium(IV)
redox system with a 0.1 molar iron(II) sulphate solution to
determine the factor for cerium(IV) sulphate solution.

12153.00*
12151.99
14602.00
14520.61*
07542.26*
18475.00
45206.00
07363.05
47334.93
46299.01
35680.03
37694.00

1
1
1
1
1
1
1
1
1
1
1
1

Fig. 1. Experimental set-up.

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen

P3061340

LEC
06.13

Potentiometric titration

Right angle clamp

Universal clamp
Holder for 2 electrodes
Spring balance holder
Burette clamp, roller mounting
Burette, 50 ml, lateral stopcock
Analytical balance, with data output, 110 g
Weighing dishes, 85 x 85 x 7 mm
Beaker, 1000 ml, short
Beaker, 250 ml, tall
Volumetric flask, 100 ml
Volumetric flask, 500 ml
Graduated pipette, 25 ml
Volumetric pipette, 10 ml
Pipettor
Graduated cylinder, 250 ml
Funnel, do = 80 mm
Funnel, do = 55 mm
Pasteur pipettes
Rubber bulbs
Spoon
Wash bottle, 500 ml
Iron-II sulphate, 500 g
Cerium-IV disulphate, 25 g
Sulphuric acid, 95-98%, 500 ml
Water, distilled, 5 l
PC, Windows 95 or higher

37697.00
37715.00
45284.01
03065.20
37720.00
36513.01
48802.93
45019.05
36017.00
36004.00
36548.00
36551.00
36602.00
36578.00
36592.00
36630.00
34459.00
34457.00
36590.00
39275.03
33398.00
33931.00
30072.50
31194.04
30219.50
31246.81

2
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
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1

Changes in the equipment required for use of the Basic-Unit:

(instead of * above mentioned)
Cobra3 Basic-Unit
12150.00 1
Measuring module, pH/Potential
12101.00 1
Software Cobra3 pH/Potential
14509.61 1
Set-up and procedure1
Set up the experiment as shown in Fig. 1.
Prepare the solutions required for the experiment as follows:
0.1 molar Ce(SO4)2 solution: Pour 200 ml of distilled water
into a 1000 ml beaker, add a magnetic stirrer bar and place
the beaker on the magnetic stirrer. Using a graduated
pipette, carefully add 11.2 ml of concentrated sulphuric acid
to the distilled water under continuous agitation to achieve
an approximately 1 molar sulphuric acid solution. Dissolve
20.215 g of cerium(IV) sulphate (Ce(SO4)24 H2O) quantitatively in this acid. To accelerate the dissolution process, heat
the solution slightly. When the cerium salt has dissolved
completely, allow this solution to cool down and then transfer it quantitatively to a 500 ml volumetric flask. Make up to
the mark with distilled water.
0.1 molar FeSO4 solution: Weigh 2.78 g of iron(II) sulphate
(FeSO47 H2O) into a 100 ml volumetric flask, add some distilled water to dissolve it, then make up to the mark with distilled water.

In <Preferences>, under <pH/Potential>, select <Potential> as

mode and <mV> as unit. Under menu prompt <Displays>, set
the Range to 300 1300 mV, and set Digital Display 1 to
<Potential>. Under <Diagrams>, select <Line diagram> for
Diagram 1, <Potential> for Diagram 1a, and <from 0 to 20 ml>
and <no auto range> for the display range. Confirm your entries
with <OK>.
After having made these settings, press <Continue> to reach the
field for the recording of measured values. Arrange the displays
as you want them.
Adjust the magnetic stirrer to a medium stirring speed. Record
the first point measured (for V = 0.0 ml) by pressing <Save
value>. Add the cerium(IV) sulphate solution in increments of
0.2 ml. After each addition, wait 30 s before saving the value.
Carry on in this manner until a
total of 20 ml has been added. Stop the measurement. Save the
data with <File> <Save measurement as...>.
Fig. 3 shows the graph as it is presented by the programme
when the measurement is stopped.
You can have the equivalence point of the curve shown with
<Detect point of equivalence> under the menu prompt
<Analysis>. Mathematically it is the maximum in the plot of the
differential E/V as a function of V.
Theory and evaluation
The potentiometric redox titration performed here involves the
oxidation of iron(II) by the oxidising agent cerium(IV) according to
Fe2+(aq) + Ce4+(aq) S Fe3+(aq) + Ce3+(aq)
The potential of a platinum indicator electrode in contact with a
solution of these ions will clearly vary as the titration proceeds.
To monitor these changes, a second reference electrode (here
Ag(s) AgCl(s) Cl-(aq)) is immersed in the solution to complete the electrical circuit. The cell can be expressed in terms of
the Fe3+, Fe2+ couple
Ag(s)
AgCl(s)
KCl (aq,3M)

Fe3+(aq), Fe2+(aq)
Pt

later in terms of the Ce4+,Ce3+ couple

Ag(s)
AgCl(s)
KCl (aq,3M)

Fig. 2:

Ce4+(aq), Ce2+(aq)
Pt

Measurement parameters

Pipette 10 ml of the 0.1 molar iron(II) sulphate solution into a

250 ml glass beaker, dilute to a total volume of 150 ml, add a
magnetic stirrer bar and place the beaker on the magnetic stirrer. Attach the burette to the support rod of the magnetic stirrer
and fill it with 0.1 molar cerium(IV) sulphate solution. Immerse
the reference electrode and the platinum electrode carefully in
the solution and ensure that the magnetic stirrer bar is free to
rotate. Use the BNC 4 mm adapter to connect the two electrodes to the pH input of the Cobra3 Chem-Unit. Call up the
Measure programme in Windows and enter <Chem-Unit> as
measuring instrument. Set the measurement parameters as
shown in Fig. 2.

P3061340

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen

LEC
06.13

Potentiometric titration

The dependence of the potential of the indicator electrode on

the activities of the various ionic species in solution is given by
the following equivalent Nernst equations
EFe3+, Fe2+ = EFe3+, Fe2+ +

RT aFe3 
ln
F
aFe2 

(1a)

ECe4+, Ce3+ = ECe4+, Ce3+ +

RT aCe4 
ln
F
aCe3 

(1b)

(4)

cFe3 
and insertion in Eq. 2a gives:
cFe2 

2E = EFe3+, Fe2+ ECe4+, Ce3+ - 2EAg
AgCl
Cl-

RT cFe3 
ln
F
cFe2 

- EAg
AgCl
Cl-

E=
(2a)

E = ECe4+, Ce3+ - EAg
AgCl
ClRT cCe4 

= ECe4+, Ce3+ +
ln
F
cCe3 

- EAg
AgCl
Cl-

(2b)

(5)

- EAg
AgCl
Cl-

1
ln 1EFe3  ,Fe2   ECe4  ,Ce3  2  EAg
AgCl
Cl2

(6)

It follows then that the e.m.f. of the cell at the equivalence point
is independent of the reaction concentrations.
With the following standard electrode potentials:


E Fe3+,Fe2+


E Ce4+,Ce3+

0.771 V

1.610 V

and the reference potential of the Ag(s)
AgCl(s)
Cl-(aq) electrode

at 20C:

in which, for the sake of simplicity, ionic activities have been

replaced by ionic concentrations.
Up until the equivalence point (at which an exactly stoichiometric amount of sample has been added to the titrant) changes in
the electrical potential of the solution, and hence in the e.m.f. of
the cell, are effectively controlled by Eq. 2a, since the Ce(IV) ions
added are continually consumed in the redox reaction. After the
equivalence point practically all the Fe(II) in solution has been
oxidised and the solution potential is now determined by the
concentration ratio cCe4+ /cCe3+. The equivalence point is thus
discernible as a rapid rise in the solution potential from that of
the Fe3+, Fe2+ couple to that of the Ce4+, Ce3+ couple (see Fig.
3).
The detailed shape of the E versus V curve recorded here is
characteristic of potentiometric titrations. At the equivalence
point we have cCe4+ = cFe3+ and cCe3+ = cFe2+.
By replacing the Ce concentrations cCe in Eq. 2b we obtain:

Fig. 3:

- EAg
AgCl
Cl-

and, after dividing by 2:

E = EFe3+, Fe2+ - EAg
AgCl
Cl-

RT cFe2 


E = E Ce4+,Ce3+ +
ln
F
cFe3 

RT cFe3 


E = E Ce4+,Ce3+ +
ln
F
cFe2 
Readjusting this for ln

The cell e.m.f. is thus expressible as

= EFe3+, Fe2+ +

and from this:

(3)

EAg
AgCl
Cl- = 0.210 V

the equivalence point is expected to correspond to a cell potential of 0.98 V.
The standardisation factor f for the 0.1 M cerium(IV) sulphate
solution, which corrects for any discrepancy between the formal
concentration (0.1 M) and the actual concentration, is expressed
as:
f

10
V1

(7)

V1 = volume of cerium(IV) solution consumed for 10 ml of the

0.1 M iron(II) solution
Fig. 4:

Parameters of the channel modification

Potentiometric redox tiration curve for the Fe(II)/Ce(IV)

system

U0

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen

P3061340

LEC
06.13

Potentiometric titration

The concentration of the unknown iron(II) sulphate solution is

obtained by:
cCe4  f V2
(8)
cFe2 

V3
cFe2+
cCe4+
f
V2
V3

Concentration of the unknown iron(II) sulphate solution

Concentration of the cerium(IV) sulphate solution
Factor for the cerium(IV) sulphate solution
Total volume of the cerium(IV) sulphate solution
Volume of the titrated unknown iron(II) sulphate solution

Addition of x ml of 0.1 M Ce(IV) sulphate solution corresponds to

the addition of x 10-4 mol Ce(IV) cations and, since the equilibrium for the reaction lies well to the product side, results in the
formation of x 10-4 mol Fe(III) cations.
Initially 10-3 mol Fe(II) cations are present in a total sample volume of 150 ml. The concentration of Fe(III) cations following the
addition of x ml of titrant is thus
0.1 x
150  x

(9)

1  0.1 x
150  x

(10)

cFe3 

Fig. 5 shows that an approximately straight line form is indeed

attained and verifies the use of the Nernst equation to describe
the behaviour of the potentiometric titration performed here. You
can have the slope of the curve shown with <Show slope...>
under the menu prompt <Analysis>.

Data and results

From Fig. 3 you can see that the equivalence point occurs at
V = 10.16 ml, which corresponds to a cell e.m.f. of 852.2 mV.
The discrepancy between this value and the calculated value of
980 mV may be due to a number of factors. The reference electrode potential may have a potential somewhat different to the
value of 210 mV assumed above. The possibility of an impure
iron(II) sulphate sample already contaminated by the presence of
iron(III) may also be of relevance. Also the response of the Fe3+,
Fe2+ and Ce4+, Ce3+ redox couples to dissolved oxygen in the
solutions has not been taken into account.

Fig. 5:

Verification of the Nernst equation

and that of Fe(II) cations

cFe2 

According to Eq. 2a a plot of the cell e.m.f. E against

ln (cFe3+/cFe2+) should be a straight line of gradient 25.3 mV (at
20C) up to the equivalence point.
To obtain a presentation of this, mark the second part of the titration curve, including the equivalence point, by using <Mark> in
the menu bar, and then use the function <Cut> to cut it out. In
addition, delete the value for V = 0 ml in the data table. Now you
can have the diagram calculated with <Channel modification>
under menu prompt <Analysis>. For this, set the parameters as
given in Fig. 4.

P3061340

ln (cFe3+/cFe2+)

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen