Potentiometric Titration of Cerium

Solution
Valentin Uzunov (author), Tom Ronay (lab partner) and Hans Harshfield (lab partner)
PSU ID#: 964100377
CHM 229H, Lab Rm 269, Submitted: 5/16/2014
ABSTRACT
The following experiment demonstrates the practical application of potentiometry as an analytical tool
in chemical analysis. A new solution of ammonium cerium(IV) sulfate ((NH
4
)
4
Ce(SO
4
)
4
2H
2
O) was
prepared and 5.57 mL of the solution was titrated with 0.03 M solution of iron sulfate heptahydrate
(FeSO
4
.7H
2
O). The equivalence point was reached after 9.5 mL of titrant was added with corresponding
a solution potential of 0.8 V in reference to an Ag | AgCl reference electrode. Qualitative analysis of the
results determined the initial concentration of the Cerium(IV) sample solution was 0.08 M.

EXPERIMENTAL
From a newly prepared solution of cerium(IV) sulfate, 5.75 mL were sampled and titrated with 0.03 M
solution of FeSO
4
.7H
2
O. Using a graphite electrode connected through a voltmeter, to a non-commercial
Ag | AgCl reference electrode (constructed using the method described by Ahn, Reuland, and Chadd
(1992)), the solution potential was sampled after each incremental addition of titrant. The potential of
the solution was sampled at 0.5 mL increments over the first 8 mL and then reduced to 0.2 mL near the
equivalence point. The solution for vigorously mixed after each incremental addition and voltage was
allowed to stabilizes or give two consistent readings before making taking a final reading.

RESULTS
Table 1 - Summary results of potentiometry titration of Cerium(IV) solution
Analyte (Ce
4+

(aq)) volume
(mL)
Titrant
([Fe
2+
] (aq))
(M)
Equivalence Point
Initial
[Ce
4+
]
(M)
Volume of
Titrant
added (mL)

vs.
Ag | AgCl (V)

(V) vs
Ag | AgCl (V)
5.75 0.03 9.5 0.8 1.0 0.08

The results of the experiment summarized in table 1 show that the equivalence point was reached
after 9.5 mL of FeSO
4
.7H
2
O were added. The equivalence point was approximated by finding the secant
slopes between raw data points, and then between secant slopes, in order to approximate the first and
second derivatives. An interval between 8.8 mL and 10 mL was selected to represent a closed interval
containing the equivalence point. A line of best fit over the same interval was determined for the second
derivative. The equation of the line was solved for zero, corresponding to an approximated value of the
inflection point in the titration curve. A linear fit over the corresponding interval on the titration curve
was also fitted and solved using the inflection point volume to approximate the potential at the
equivalence point. The approximations obtained in this way seemed appropriate, when compared to a
visual estimations of titration curve (Figure 1) and raw data.

Figure 1 Shows the change in analyte solution potential with respect to titrant volume added. The approximate first and
second derivatives over each interval are also shown. The gray dashed line is the linear trend line over the interval 8.8 mL and 10
mL for the second derivate, with an equation f(x) = -0.3363(x) + 3.196 and regression coefficient of 0.8453. The red dashed trend
line is the titration trend line over the same interval with equation g(x) = -0.2952(x) + 3.5839 and a regression coefficient of
0.9893.
The [Ce
4+
] concentration was determined by rearranging eq. 1 to solve for the initial
concentration.

eq. 1
Example:

= 0.08 M (1 sig fig)
where the final volume is the sum of the initial analyte volume and the volume of titrant added
to reach equivalence.
At the equivalence point virtually all Ce
4+
is reduced to Ce
3+
and all Fe
2+
is oxidized to Fe
3+

[Ce
3+
] = [Fe
3+
] eq. 2
[Ce
4+
] = [Fe
2+
]
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
0 2.5 5 7.5 10 12.5 15 17.5 20 22.5 25
P
o
t
e
n
t
i
a
l

(
V
)

Volume (mL)
Volts
d2/dx
d1/dx
However small amounts of Ce
4+
and Fe
2+
still remain due Le Chateliers principle at equilibrium.
In order to determine the standard cell potential at equilibrium, the Nernst equation (eq 3) of
both reactions which describe the cell voltage can be added together and solved [4].

eq. 3
Example:

----------------------------------------------------

Where

and

are the standard reduction potentials for Fe3+ and Ce4+. Because at
equilibrium [Ce
3+
] = [Fe
3+
] and [Ce
4+
] = [Fe
2+
] the reaction quotient in the log expression is equal
to unity. Simplifying the expression

From this, the cell voltage is calculated using eq. 4:

eq. 4
Example:

Where E
ref
was 0.197 V [1], the standard reduction potential for the Ag | AgCl electrode in a
saturated KCl solution and E
cell
was the determined potential at equivalence.

DISCUSSION

The current experiment demonstrates the use of potentiometry as an analytical tool for redox titrations.
Potentiometry is specifically the passive measurement of potential in an analyte solution, using an
indicator electrode (anode), a reference electrode (cathode) and a voltmeter. The change in potential is
then related to the concentration of the analyte. The current experimental titration involved 5.75 mL
ammonium cerium(IV) sulfate ((NH
4
)
4
Ce(SO
4
)
4
2H
2
O) titrated with 0.03 M solution of iron sulfate
heptahydrate (FeSO
4
.7H
2
O). From the net ionic equation of the titration:
Ce
4+
(aq) + Fe
2+
(aq) Ce
3+
(aq) + Fe
3+
(aq) (rxn. 1)
the reaction shows, ferrous ion (Fe
2+
) was oxidized to ferric ion (Fe
3+
) giving up an electron and reducing
cerium(IV) (Ce
4+
) to cerium(III) (Ce3+) in the process. The titration takes place in a voltaic cell, using
carbon graphite rod electrode and an Ag|AgCl reference electrode. The electromotive force (emf)
generated by the reaction was measured with a voltmeter. As the reaction progresses and the relative
concentrations of reducing agent (Fe
3+
) and oxidizing agent change (Ce
4+
) change, so does the emf
measured. This change is the basis for determining the equivalence point of the titration, at which point
the concentration of analyte and titrant are equal. From the volume of titrant added and its
concentration, the concentration of the analyte was then be determined using the stoichiometry of the
balanced equation. It is noted from Figure 1, that after the point of equivalence was reached, because
Fe
2+
is stronger reducing agent then Ce
3+
the reaction continues in the forward direction after the
equivalence point was passed.
Results of the experiment summarized in table 1, show that that the cerium(IV) concentration of the
analyte was 0.08 M, with cell reduction potential of 1.0 V in reference to the Ag | AgCl electrode. The Ag
| AgCl reference electrode used, was constructed following the method described by Ahn at al., (1999).
The electrode design had been confirmed to provide reasonably accurate and consistent readings in
previous experiments [1,2]. However, it must be acknowledged that the reference electrode could be a
source of error that should be addressed if a higher degree of precision and accuracy of results are
required.
In the process of the potentiometric titration after several unsuccessful titrations it was concluded that
the titration success depends strongly on the how fresh the stock solution was. This is because Ce
4+

oxidizes in water [3] and the rate of the oxidation is temperature dependent. At room temperature if a
stock solution is left overnight it will produce unreliable results next day. This error was corrected by
using a freshly prepared stock solution prior to the titration.
The current experiment demonstrates the steps and analytical analysis necessary in redox
titrations, using potentiometry as an indicator. Experimental results can be improved by using a
commercial reference electrode, which is calibrated, with data logging computer software, over
more trials. More accurate qualitative analysis could also be performed in this manner.

CITATIONS
[1] - Ahn, M K; Reuland, D J; and Chadd, K D: Electrochemical measurements in general chemistry lab
using a student-constructed Ag-AgCl reference electrode", Journal of Chemical Education, 1992, 69(1),
74
[2] - Uzunov, V., Ronay, T. R., & Harshfield, H. Construction of Ag | AgCl Reference Electrode and
Application. PSU Lab 5 report.
[3] - Cerium - Ce. (n.d.). Cerium (Ce). Retrieved May 15, 2014, from
http://www.lenntech.com/periodic/elements/ce.htm
[4] - Redox Titrations. (n.d.). . Retrieved May 15, 2014, from
http://chem320.cs.uwindsor.ca/Notes_files/320_l15.pdf