In the Laboratory
A Variety of Electrochemical Methods in a Coulometric
Titration Experiment
A. Ltz
Institut fr Physikalische Chemie der Universitt Mnchen, Munich, Germany
Introduction and General Description of the Experiment
Coulometric titration represents a direct application of
Faradays laws of electrolysis and is one of the methods that
appear most frequently in instrumental analysis courses (1).
Whereas most earlier articles on coulometric analysis in this
Journal (220) concentrated on single methods applied to single
substances, this note presents an experiment that utilizes a
variety of methods of coulometric titration and electrochemical
endpoint indication applied to a mixture of KI and HCl. The
experiment, which was introduced in our practical course in
physical chemistry some years ago, uses common laboratory
equipment of moderate cost. The coulometric current source
can easily be constructed from low-cost, readily available elec-
tronic components.
The iodide content of the mixture of KI and HCl is de-
termined by titration with bromine generated at the anode
from bromide:
4 Br { 2 Br 2 + 4 e{
2 I { + Br 2 I 2 + 2 Br {
I 2 + Br 2 + 2 Br { 2 I Br 2{
There is also a direct oxidation of I { leading to the same turn-
over of electrical charges for the same amount of I{ consumed
and IBr2{ produced:
2 Br { Br 2 + 2 e{
2 I { I 2 + 2 e{
I 2 + Br 2 + 2 Br { 2 I Br 2{
The titration is followed with a twin polarizable platinum
electrode whose indication can be understood qualitatively
from the amount of the easily reducible I 2 and (after the end-
point) Br2 present during the titration (Fig. 1, top) (21). The
electrolysis current of the twin polarizable platinum electrode
is smaller than that of the coulometric electrolysis by approxi-
mately a factor of 1000, so the change in concentrations induced
by the indicator electrode pair is negligible.
Analysis of the chloride content is performed indirectly
by titration of the acid at the cathode:
2 H2O + 2 e{ H2 + 2 HO{
and
2 H+ + 2 e{ H2
The indicator is a glass electrode combined with a Ag/AgCl
reference electrode (Fig. 1, center).
Finally I { and Cl { are determined simultaneously by anodic
dissolution of a silver wire:
Ag + X { Ag X + e{ ; X = I, Cl
JChemEd.chem.wisc.edu Vol. 75 No. 6 June 1998 Journal of Chemical Education
The course of the titration is recorded with a silver electrode
(Fig. 1, bottom).
A source of confusion with coulometric titration using
electrochemical detection is the presence of two pairs of
electrodes. The first pair is used for the generation of the
titrating speciesfor example, Ag+, in the method presented
last. Actually, the above chemical reactions take place at only
one electrode of the pair, the working electrode, whereas the
second electrode, the counter electrode, is necessary for closing
the current circuit. The counter electrode is placed in a separate
compartment with electrolytic connection to the working
electrode in order to avoid interference with the reactions at
the working electrode. Depending on whether the counter
electrode is the cathode or anode, hydrogen from an acidic
solution or oxygen from an alkaline solution is generated at
the counter electrode in the present experiments. Whereas
the working and counter electrode carry a current of approxi-
mately 10 mA, much smaller currents flow through the pair
of electrodes that dip into the solution surrounding the
working electrode and monitor the course of the titration.
In the case of potentiometric measurements (determination
of Ag+ and H+ concentrations, in the present experiments)
the current through the monitoring electrodes is virtually
zero, and is very low (in the A range) in amperometric mea-
surements (e.g. monitoring the concentration of I 2).
Some Details of the Experiment
The students get a mixture of HCl and KI whose abso-
lute and relative content is unknown to them (20 5 mL of
each of two 0.01 M solutions), dilute it to 100 mL, and take
20-mL aliquots. These are filled to approximately 50 mL with
the chemicals listed in the third column of Table 1.
In each of the three titrations, the working electrode and
the counter electrode dip into solutions in different beakers
connected with a salt bridge filled with 1 M KNO3 solution.
The ends of the bridge are plugged with agar-agar gel up to
a length of 1 to 2 cm (3% solution in hot water, solidified in
the bridge). The use of a salt bridge avoids the problem of
diffusion between the anodic and cathodic compartments. The
bridges are stored in KNO3 solution in separate containers
for the three titrations (1-L plastic containers that solid
chemicals are delivered in) and can be reused until they lose
their plugs by accident.
In the titration of I { and Cl { with Ag+, a straight silver wire
of 0.5 mm diameter and 5 cm length is used as the working
electrode, of which approximately 2 cm dips into the solution.
It can be reused once or twice after being cleaned by draw-
ing across sandpaper. The potential of the silver electrode for
the endpoint detection (not to be confused with the silver
wire) is measured against a glass electrode because the KNO3
775
 In the Laboratory

I = 10.6 mA solution of the reference electrode of commercially available

50 combined silver electrodes was often found to contain halides
under the conditions of the practical course. The connection
40
of the glass electrode to the pH/mV-meter must be made with
Current / A

30
a shielded coaxial cable whose shield is at the potential of
the silver electrode in our setup.
20 The twin polarizable platinum electrode used for the
bromometric titration is stored dry. The other platinum elec-
10 trodes used in the experiment are cylindrical, approximately
0.5 cm in diameter and 0.3 cm in length. All are commer-
100 200 300 400 500 600 700 800 cially available. Further details of the experiment are collected
Time / s in Table 1.

Constant-Current Source and Other Electronic

10
I = 10.6 mA Equipment
9 The electrolysis current in our experiment is fixed to 10.6
8
mA, which results in an electrolysis time of about 6 min for
the acidimetric titration and twice as much for the other two
pH

7
titrations.
6 The constant-current source (Fig. 2, upper part) runs
5
between +15 and {10 V for a wide regulation range. The
current is boosted by a transistor, since in our experience a
4
common 741 operational amplifier is too much stressed by
0 100 200 300 400 500 600 700 delivery of 10 mA during longtime use.
Time / s The voltage of 140 mV for the twin polarizable electrode
is obtained from the circuit of Figure 2, lower part, whose
feedback resistor of 10 k transforms 1 A of indicator current
to 10 mV at the output. This circuit has its own power supply,
I = 10.6 mA
which means that the twin polarizable electrode is floating
0
with respect to the electrodes of the constant-current circuit.
Data collection during the titration was first done by
Potential / mV

-100
-200
-300
-400
0 100 200 300 400
Time / s
Figure 1. Coulometric titration of a KI/HCl mixture. Thin lines: first
derivatives of the thick titration curves. Dashed lines: end points.
Top: bromometric titration of I { with a twin polarizable platinum
electrode as indicator. Center: acidimetric titration of HCl with a
monitoring glass electrode. Bottom: titration of I { and Cl { with a
silver electrode. Performance: 20 mL 0.01 N K I and HC l analyzed;
found: (top) 19.9 0.1 mL K I, (center) 19.9 0.2 mL HC l, (bottom)
19.7 0.3 mL K I and 20.5 0.5 mL HC l (40.2 0.5 mL halide).
Errors calculated from estimated errors of the end points.
reading from the pH/mV-meter in regular intervals. We later
connected a recorder to the pH/mV-meter, but found that the
students were so much engaged with handling the recorder
that the titration itself threatened to become an appendage
of the recorder. The situation improved greatly when the
recorder was equipped with a switch by which preset bias and
span for each of the three titrations could easily be established.
500 600 700 800 900
We now run the experiment with a Toshiba T2100 laptop
computer appropriately programmed for the experiment in
Visual Basic. This is how the three parts of Figure 1 were
produced. Since the pH/mV-meter that we use did not have
a digital data output, the computer was equipped with a AD-
converter interface (PCM-DAS16D/12, ComputerBoards
Inc., Mansfield, MA). Severe hum on the analog signal line
due to the different floating potentials was suppressed by
a 330-k /1- F filter incorporated in a connector of the
signal line.

Table 1. Electrodes and Solutions for Coulometric Titration of KI/HCl Mixtures

Beaker 1 Beaker 2
Monitoring/ Counter
Working
Ion Electrolytea Reference Electrode/
Electrode
Electrode Electrolyte
I{ Pt (anode) HNO3b + KBr Pt/Pt Pt/HNO3b
+ {
H (Cl ) Pt (cathode) H2O + KCl glass/Ag, AgCl Pt/1 M KOH
I {, Cl { Ag wire (anode) HNO3b + Ba(NO3)2 Ag/glass Pt/HNO3b
a20 mL KI/HCl mixture + 30 mL liquid listed + 2 g salt listed. bConcn 0.1 M.

776 Journal of Chemical Education Vol. 75 No. 6 June 1998 JChemEd.chem.wisc.edu

 In the Laboratory

Concluding Remarks
As Figure 1 shows, the performance is good, the only
difficulty being the uncertainty in the location of the first
endpoint in the simultaneous titration of I { and Cl {, also well
known from the corresponding volumetric titration. We be-
lieve that this experiment with its variety of electrochemical
methods and its internal check of the consistency of the results
is a valuable addition to the range of experiments performed
in the course.
Acknowledgments
I thank Mr. Horbach and Mr. Bachmeier for assembling
the electronic equipment. The very useful comments of the
three referees are gratefully acknowledged.
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Figure 2. Top: constant current (~10 mA) source for the coulometric
titration. Bottom: 140 mV supply for the twin polarizable electrode
and conversion of the indicator current to voltage.

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