Chem 27.

1 Potentiometric Redox Titration 1

Experiment 10 Potentiometric Redox Titration
Garcia, Nikko Benjamin H.; Cruz, Wendell Mark
Group 10, Chem27.1, WEJ1, Mr. Dmitri Cordova
October 2, 2013

I.Abstract
Potentiometry refers to a set of analytical methods that measure the electric potential of an
electrochemical cell. This method is functional in detecting the presence of unsuspected species within colored
or turbid solutions. Potentiometric titration is based on the measurement based on titrant volume and is not
dependent on measuring absolute values of E
cell
. Both the reference electrode (Cu/ Cu
2
) and indicator electrode
(carbon rod) were submerged in Fe(NH
4
)
2
(SO
4
)
2
6H
2
O or the Mohrs salt which acted as the analyte and the
reducing agent while being titrated with KMnO4 which acted as the oxidizing agent. The electron potential was
read after every addition of KMnO4. 0.01 M KMnO
4
was computed from the readings with the use of the titration
curve, first and second derivatives. The unknown containing the Fe acted as the reducing agent, was titrated
with the 0.01M KMnO
4
. It was computed that the sample contains 5.58 % Fe. The voltmeter must be in good
and working condition to avoid errors.

II.Keywords: Potentiometry; Redox Reactions; Titration; Cell Potential; Reference Electrode, Indicator Electrode

III.Introduction
Measurements in potentiometry are gathered
with the use of a potentiometer which is also known
as the voltmeter. A voltmeter is a device used for
measuring potential of an electrochemical cell without
drawing a current or changing what the cell is
composed of. The change in potential that happens
between the electrodes of the electrochemical cells is
a measurement of tendency for the reaction to
continue from a non-equilibrium state to equilibrium
state.
Electrodes almost have no delays and
interferences and provide a quick and safe manner of
quantitatively determining numerous important and
significant anions and cations. The electrochemical
cells of the potentiometer are built in such a way that
one of the half-cells provides a known reference
potential, and the potential of the other half-cell
provides the concentration of the analyte. By
convention, the reference electrode which is the half-
cell having a known electrode potential that remains
constant at the same temperature and is independent
of the composition of the analyte solution, is called
the anode. In addition to that, the ideal reference
electrode must give a stable potential so that all
changes in E
cell
are attributed to the indicator
electrode. Also, the ideal reference electrode should
be easy to make and to use. An indicator electrode
has a potential that varies in a known way with
variations in the concentration of an analyte. The
potential of the indicator electrode in a potentiometric
electrochemical cell is proportional to the
concentration of analyte.
Potentiometric titration involves measurement
of the potential of a suitable indicator electrode as a
function of titrant volume. Data acquired through this
method is more reliable than the data collected from
titrations that make use of chemical indicators
especially with colored solutions. In contrast to direct
potentiometry, potentiometric titration is based on the
measurement of titrant volume and is not dependent
on measuring absolute values of E
cell
. However, it is
dependent on having a titrant of accurately known
concentration.
In this experiment, the students were able to
construct a potentiometric redox titration curve and
solve for the %Fe in a sample.

IV. Experimental
For the preparation of the Cu/Cu
2+
electrode,
we had to prepare a makeshift electrode utilizing a 5-
cm long Pasteur pipet. We then plugged its tapered
end tightly with a cotton ball. The tip of the pipet
should then be dipped in a saturated solution
containing KCl or KNO
3
until the cotton is fully
soaked. Utilizing another pipet or dropper, the tube
was filled with 0.1 M CuSO
4
solution. Next, a copper
wire was looped around a metal rod of smaller
diameter than the pipet. We also left a few portions of
the rod uncoiled for the voltmeter leads. We inserted
the coiled wire into the pipet and proceeded to plug
the open portion of the pipet with modeling clay to fix
the position of the wire. This was also done to seal
the tube and prevent the leakage of the CuSO
4

solution.
The next set of procedures involved the
preparation and standardization of KMnO
4
.
Theoretically, we must weigh 0.47 g of the KMnO
4

crystals to prepare 300 mL of 0.01 M solution. We
would then take the crystals and dissolve them in 100
mL distilled water. Enough distilled water is added to
make 300 mL of the solution. The resulting solution
should be stored in a colored container. Next, we
should weigh three batches of 0.3-0.4 g
Fe(NH4)
2
(SO4)
2
6H
2
O into a 100-mL beaker. 20 mL
of distilled water is added to dissolve. 5 mL of 2 M
Chem 27.1 Potentiometric Redox Titration 2

H
2
SO
4
is immediately added. The solutions should be
mixed well.
Using a burette, we added 2.0 mL KMnO
4

titrant solution into the 3 beakers. We then dipped a
carbon rod and a Cu/Cu
2+
reference electrode in the
beaker with the electrodes connected to the terminals
of the voltmeter. This is done to measure the
reduction potential as the titration progresses. 2.0 mL
KMnO
4
supplements were added and potentials were
also measured. The addition was repeated until 20
mL of the KMnO
4
solution has been added to the
solution.
Afterwards, 1.0 ml increments of the titrant
were added with the potentials read and recorded in
between additions. This was done until the volume of
the titrant has reached 30 mL. The volume of the
titrant and the observed potential were recorded. All
the data gathered were then used to plot a graph to
determine the equivalence point and the molarity of
the KMnO
4
solution. As we have prepared 3 beakers
of the analyte solution, we have executed 3 trials and
have produced and recorded 3 sets of data for
plotting.
In the analysis of the unknown, we pipetted
approximately 10 mL of the unknown sample into a
100 mL volumetric flask. Enough distilled water was
added to dilute it to mark. 10 mL of the diluted sample
was pipetted into a 100 mL beaker. 5 mL of 2 M
H
2
SO
4
were added into the solution and was mixed
well. The same set of steps from the previous titration
was done to our solution. 2.0 mL increments of the
titrant were added until it reached 20 mL. Then, 1.0
mL portions were added until the volume of the titrant
reached 30 mL. All of these were done while
recording the potential in between. 3 trials were done.
Again, the data gathered were used to plot a graph to
determine the equivalence point and to calculate the
weight of Fe in the sample.

V. Results
For the results, we were given theoretical
values for the analysis of the unknown. We then
proceeded to assume the concentration of the KMnO
4

solution as 0.01M.










Figure 1. Titration Curve of the Analysis of the
Unknown
y = 0.029x + 0.2265
R = 0.8004
0.000
0.200
0.400
0.600
0.800
1.000
1.200
1.400
1.600
0 10 20 30 40 50
E

C
e
l
l

(
V
)

V in mL
Titration Curve

first derivative second derivative
V
(mL)
E cell
(V)
Vav
e
d Ecell/
dV
Vave
2
d
(dEcell/dVave2
)
1 0.358

3 0.389 2 0.0155

5 0.406 4 0.0085 3 -0.00035
7 0.418 6 0.006 5 -0.00125
9 0.429 8 0.0055 7 -0.00025
11 0.439 10 0.005 9 -0.00025
13 0.450 12 0.0055 11 0.00025
15 0.462 14 0.006 13 0.00025
17 0.479 16 0.0085 15 0.00125
19 0.510 18 0.0155 17 0.0035
21 1.169 20 0.3295 19 0.157
23 1.175 22 0.003 21 -0.16325
25 1.178 24 0.0015 23 0.00075
27 1.179 26 0.0005 25 -0.0005
29 1.181 28 0.001 27 0.00025
31 1.182 30 0.0005 29 -0.00025
33 1.183 32 0.0005 31 0
35 1.183 34 0 33 -0.00025
37 1.184 36 0.0005 35 0.00025
39 1.185 38 0.0005 37 0
Chem 27.1 Potentiometric Redox Titration 3


Figure 2. First Derivative Plot of the Analysis of the
Unknown


Figure 3. Second Derivative Plot of the Analysis of the
Unknown

VI. DISCUSSION

A. Preparation of Cu/Cu
2+
reference electrode
The tip of the Pasteur pipette was tightly
packed with cotton so that the CuSO
4
solution would
not drip and contaminate the analyte. After being
immersed in KCl, the cotton functioned as the salt
bridge which is needed to maintain electrolyte
balance and potential of each solution. It is important
to maintain the electrolyte balance of each solution
because it is the potential difference between each
solution that produces the electric current measured
by the voltmeter. The CuSO
4
solution in the pipette
was for oxidizing the copper wire, which generates
the electrode potential read in the voltmeter. Copper
wire was used because the metal electrode in a
solution that contains ions of that metal develops the
potential difference between the metal and the
solution. The clay was placed on top of the open
portion of the pipette to clog and seal it and stop the
CuSO
4
solution from leaking and also to keep the
copper wire in place.

B. Preparation and standardization of KMnO
4
solution
Aqueous solutions of permanganate are not
that stable due to water oxidation: 4MnO
4
-
+ 2H
2
O
4MnO
2(s)
+ 3O
2(g)
+ 4OH
-
. Even though the
equilibrium constant of this reaction shows that
products are favored since the decomposition
reaction is slow, the reaction is still catalyzed by light,
heat, acids and other factor. This is the reason why
the volumetric flask of KMnO4, during its preparation,
was covered in foil to prevent it from undergoing
photodecomposition. Photodecomposition or
photolysis is the chemical decomposition by the
action of radiant energy or light. This can lead to
negative errors since the amount of ions to react
would have been consumed or broken down already
by the light even before the reaction. Potassium
permanganate is a very strong pH dependent
oxidizing agent. If the solution is basic in nature
instead of being acidic, a different reaction would
occur for the permanganate ion. This can be given by:
2MnO
4
+ 3C
2
O
4
+ 4OH2MnO
2
+ 6CO
3
+2H
2
O.
Sulfuric acid was added to the
Fe(NH
4
)
2
(SO
4
)
2
6H
2
O solution in order to prevent the
oxidation of Fe
2+
by keeping the equilibrium of the
following equation to the left: 4Fe
2+
+ O
2
+ (4+2x) H
2
O
2Fe
2
O
3
xH
2
O + 8 H
+
. The relative reactions
involved in the standardization are as follows:

R: MnO
4
- + 8H
+
+ 5e
-
Mn
2+
+ 4H
2
O
O: Fe
2+
Fe
3+
+ 5e
-
Over-all:MnO
4
-
+ 8H
+
+Fe
2+
Mn
2+
+ Fe
3+
+ 4H
2
O

Mohrs salt (Fe(NH
4
)
2
(SO
4
)
2
6H
2
O) is much
more stable when it is exposed to oxygen present in
the surrounding air. This is very important because
Fe(II) sulfate tends to be oxidized to Fe(III). Its
oxidation is pH dependent, occurring readily at high
pH levels or basic conditions.
The entire setup of the experiment is what
constitutes a cell. A cell used for potentiometric
determination is composed of a reference electrode, a
salt bridge, an analyte solution, an indicator electrode
and a potential measuring device, on this case, the
voltmeter. The carbon rod is the indicator electrode
which was immersed in the analyte solution which is
the Fe(NH
4
)
2
(SO
4
)
2
6H
2
O solution. The KCl in cotton
is the salt bridge of the setup. The Copper-Copper(II)
y = -0.0003x + 0.028
R = 0.0022
-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0 10 20 30 40
d

E

c
e
l
l

V ave
First Derivative
y = -0.0002x + 0.003
R = 0.001
-0.2
-0.15
-0.1
-0.05
0
0.05
0.1
0.15
0.2
0 10 20 30 40
d

(
d
E
c
e
l
l
/
d
V
a
v
e
)

ave Vave
Second Derivative
Chem 27.1 Potentiometric Redox Titration 4

sulfate electrode is the reference electrode, based on
the redox reaction with participation of the metal (Cu)
and its salt CuSO
4
. The reference electrode does
not depend on the concentration of the analyte. It is
used for measuring the electrochemical potential and
is the most commonly used reference electrode. The
E
cell
is computed based on this equation:
Cu
2+
+ 2e
-
Cu
0
. It is an anode since it is used for
oxidation.
C. Analysis of the unknown
In the analysis of the unknown, we were
given 10 mL of an unknown sample. It was to be
transferred into a 100 mL volumetric flask and diluted
to mark. Afterwards, 3 10-mL aliquots from the diluted
unknown solution should be pipetted into 3 100 mL
beakers. The unknown solution includes Fe in its
composition; as we are to calculate the weight of the
Fe from the sample.
Just before titration, 5 mL of 2 M H
2
SO
4
was
added to the unknown. This is to reduce the pH of the
solution to make it acidic. In acidic analyte, the
permanganate ion is reduced to Mn
2+
that is more
efficient for oxidizing Fe. In basic solutions, the
permanganate ion is reduced to MnO
4
-
.
The volume of titrant added is controlled and
kept to increments so as to produce a clear graph of
the titration. Adding large quantities of the titrant
might cause a sudden substantial increase or
decrease in the electric current. Keeping a detailed
graph is critical because we need to determine the
equivalence point from the graphs produced.
To solve for the weight of Fe, we make use of
the overall redox reaction.
MnO
4
+ 5Fe
2+
+ 8H
+
Mn
2+
+ 5 Fe
3+
+ 4H
2
O
And from that, we could derive a formula to
determine the weight of Fe from the unknown sample.
We should not forget the dilution factor because we
dealt with aliquots in the titration.

0.01 M KMnO
4
x 0.02 L x 5 mol Fe/1 mol MnO
4
x
55.845 g/1 mol Fe x 100/10 = 0.55845 g Fe
%Fe= 0.55845 g Fe/ 10 mL x 100 = 5.58% Fe

VII.CONCLUSION AND RECOMMENDATIONS
In analyzing oxidation-reduction titrations,
Potentiometry is an alternative and more accurate
method when handling colored solutions, since it
deals with a change in electrochemical potential
instead of a change in color. An electrochemical cell
is used to determine the potentials, which will be
measured by a potentiometer. This technique was
used in order to determine the % of Fe present within
a sample. To attain this, the potential of the solution
was measured after each addition of the titrant,
KMnO
4
, then the data was plotted, and using this for
the computation, it was found that sample contained
5.58 % Fe.
There are numerous possible sources of error in
the experiment. Personal errors, such as: an
inaccurate measurement of the reagents or the
contaminations of these, and personal judgment or
bias as to the reading of the voltmeter. Although
unavoidable, it could be minimized through following
proper laboratory techniques and bymaking sure that
the solutions are covered when left to standby. Only
one person must be assigned in reading the voltmeter
so that her bias towards reading would be constant.
The decomposition of the titrant could also partake in
the errors. Colored solutions, like KMnO
4
must be put
in a container covered with foil all the time. Next,
since the reference electrode was self-made, it is
highly possible that the cotton was not tight enough to
hinder the CuSO
4
solution from escaping the
pipet,thus causing a fluctuating reading from the
voltmeter. The students are advised to check for
leaks before proceeding. Lastly, instrumental error
plays a major role, because the functionality of each
voltmeter was not ensured. It is recommended that
the students be provided with functional and accurate
voltmeter.

VIII. REFERENCES

Skoog DA, West DM, Holler FJ, and Crouch SR.
Fundamentals of Analytical Chemistry. 8
th
ed.
Singapore: Cengage Learning Asia Pte. Ltd.;
2010.
I hereby certify that I have given substantial
contribution to this report.



Garcia, Nikko


Cruz, Wendell