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S3631 Analytical Chemistry I

Redox titrations

Compiled by A/Prof S. Louw and Dr. H. Lotfy

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Redox Titrations
• A redox titration is based on an oxidation-
reduction reaction between analyte and titrant.
• Consider the titration of iron (II) (in 1 M HClO4)
with standard cerium (IV), monitored
potentiometrically with Pt and calomel
electrodes. See Harris and Lucy, 10 Edition, Fig. 16-1 th

• Titration reaction:
Ce4+ + Fe2+ → Ce3+ + Fe3+

Fe3+ + e- ⇌ Fe2+ E° = 0.767 V

Ce4+ + e- ⇌ Ce3+ E° = 1.70 V
Note: The titration reaction goes to completion after each addition of titrant (i.e. large K)

S.C.E || Ce4+, Ce3+, Fe3+, Fe2+ | Pt

See Harris and Lucy, 10th Edition, Fig. 16-1

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Redox titration curves can be divided

into three regions:
• Before the equivalence point
species present: Fe2+, Fe3+, Ce3+
• At the equivalence point
species present: Fe3+, Ce3+, (Ce4+)
• After the equivalence point
species present: Fe3+, Ce3+, Ce4+

See Harris
and Lucy,
10th Edition,
Fig. 16-2

Before the equivalence point

• If we add just one drop of the cerium (IV) solution
from the burette, some of the iron (II) ions will be
oxidized. As a consequence the beaker would still
contain a large number of unreacted iron (II) ions,
but also some iron (III) ions as well.
• All of the cerium (IV) ions added would have been
converted to cerium (III). The solution in the
beaker now represents an iron (III) / iron (II) half-
cell, although not at standard conditions.
• Thus the cell potential will be near, but not equal
to EFeo
3+ 2+
/ Fe

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At the equivalence point

• If we continue to add cerium (IV) solution, the
number of iron (II) ions is gradually reduced
and eventually only very few are left.
• At this stage the next few drops of cerium (IV)
solution convert all the remaining iron (II) ions
into iron (III), and some of the cerium (IV) ions
are left unreacted.

After the equivalence point

• Once this happens we no longer have an iron (III)
/ iron (II) half-cell. Instead we have a solution in
which there are a large number of cerium (III)
ions and a smaller number of cerium (IV) ions.
• The solution in the beaker now behaves as a
cerium (IV) / cerium (III) half-cell (although not a
standard one).
• Thus the cell potential will be near, but not equal
o
to 𝐸𝐶𝑒 4+ Τ𝐶𝑒 3+

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Region 1: before the equivalence point

Since the reaction’s stoichiometry is 1:1 and the
equilibrium constant is large, any Ce4+ that is added
reacts with an equal molar amount of Fe2+:
moles Fe2+ remaining = (moles Fe2+ initial) – (moles Fe2+ used)
moles Fe3+ produced = moles Fe2+ used
• ES.C.E = 0.241 V
• 𝐸 = 𝐸+ − 𝐸−
[Fe2+ ]
• 𝐸 = 0.767 − 0.05916log − 0.241
[Fe3+ ]
[Fe2+ ]
• 𝐸 = 0.526 − 0.05916log
[Fe3+ ]

Region 2: At the equivalence point

• A stoichiometric amount of titrant has been added and
the major constituents of the solution are the products of
the titration reaction, Fe3+ and Ce3+. From the
stoichiometry of the reaction we know that:
[Fe3+] = [Ce3+]
• The only source of Fe2+ and Ce4+ is the reversed reaction of
the titration reaction
• The stoichiometry of the reverse reaction tell us that they
must be equal:
[Fe2+] = [Ce4+]
• The data is not immediately available to solve the Nernst
equation for either half independently, but simultaneous
equations can be solved to obtain the electrode potential.

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The Nernst equations for the analyte and titrant half – reactions are:

𝑜 0.05916 [𝐹𝑒 2+ ]
𝐸𝐹𝑒 = 𝐸𝐹𝑒 3+ Τ𝐹𝑒 2+ − log
𝑛𝐹𝑒 [𝐹𝑒 3+ ]

𝑜 0.05916 [𝐶𝑒 3+ ]
𝐸𝐶𝑒 = 𝐸𝐶𝑒 4+ Τ𝐶𝑒 3+ − log
𝑛𝐶𝑒 [𝐶𝑒 4+ ]
Adding the equations together gives:
Fe2+ [Ce3+ ]
2𝐸+ = 2.467 − 0.05916log
Fe3+ [Ce4+ ]

At the equivalence point [Fe3+] = [Ce3+] and [Fe2+] = [Ce4+], therefore

the log term is 0 and then:
2𝐸+ = 2.467 V ⇒ 𝐸+ = 1.23 V
Cell potential: 𝐸 = 𝐸+ − 𝐸− = 1.23 − 0.241 V = 0.99 V

Region 3: After the equivalence point

The solution contains both products and excess

titrant:
moles Ce4+ remaining = moles Ce4+ added - moles Ce4+ used
moles Ce3+ produced = moles Ce4+ used
• ES.C.E = 0.241 V
• 𝐸 = 𝐸+ − 𝐸−
[Ce3+ ]
• 𝐸 = 1.70 − 0.05916log − 0.241
[Ce4+ ]

[Ce3+ ]
• 𝐸 = 1.459 − 0.05916log
[Ce4+ ]

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We can summarize the conclusions of this

section as follows:

• Before the equivalence point: use Nernst

equation for the analyte.
• At the equivalence point: derive an
appropriate equation (i.e. solve
simultaneous equations).
• After the equivalence point: use Nernst
equation for the titrant.

Example
50 mL of 0.05 M Fe2+ is titrated with 0.1 M Ce4+
(in 1.0 M H2SO4). Calculate the electrode
potential of the solution after addition of:
• 5.0 mL of Ce4+,
• at the equivalence point, and
• after the addition of 25.1 mL of the titrant.

E oFe3+ /Fe2+ = 0.68 V (1 M H 2SO 4 )

E oCe 4+ /Ce3+ = 1.44 V (1M H 2SO 4 )

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Solution
• After the addition of 5.0 ml of Ce4+
Fe  = 550 +0.51 = 9.09110
3+ −3
M

Fe  = 50 550.05 − 5 550.1 = 0.03636 M

2+

0.0592 0.03636
E + = 0.68 − log = +0.64 V
1 9.09110-3

• Before the equivalence point it is convenient

to use the iron half cell because there is very
little Ce4+ present.

• At the equivalence point:

0.0592 [Fe 2+ ]
E Fe = E o Fe3/Fe 2+ − log
n Fe [Fe3+ ]

0.0592 [Ce3+ ]
E Ce = E o Ce4+ /Ce3+ − log
n ce [Ce4+ ]

Fe2+ [Ce3+ ]
2𝐸+ = 2.12 − 0.05916log
Fe3+ [Ce4+ ]

At the equivalence point [Fe3+] = [Ce3+] and [Fe2+] = [Ce4+],

therefore the log term is 0 and then:
2𝐸+ = 2.12 V ⇒ 𝐸+ = 1.06 V

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• After the equivalence point (addition of 25.1

ml Ce4+)

Ce  = 2575.01.1  0.03342 M

3+

Ce  = 25.1 0.75

4+ 1 − 50  0.05
.1
 1.332  10 −4
M

0.0592 0.03342
E + = 1.44 − log = + 1.3 V
1 1.332 10 -4

Exercise
• Demonstration 16-1, p. 386 (Harris & Lucy)

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Redox indicators
Starch-iodine complex:
• Starch is the indicator of choice for redox titrations involving
iodine.
• However, in actual fact starch is not a redox indicator, but
simply responds specifically to the presence of I2, with which
it forms an intense blue complex.

See Harris
and Lucy,
10th Edition,
Fig. 16-5

Methods using iodine

• When a reducing analyte is titrated with iodine
(to produce I-), the method is called iodimetry:
I2 (s) + 2e- ⇌ 2I- (aq)

• However, in iodometry, an oxidizing analyte is

added to excess I- to produce iodine, which is
then titrated with standard thiosulfate solution.
• Molecular iodine is only slightly soluble in water,
but its solubility is enhanced by complexation
with iodide:
I2 (aq) + I- ⇌ I3-
Iodine Iodide Triiodide

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Use of starch indicator

• In iodimetry (titration with I3-), starch can be
added at the beginning of the titration.
• The first drop of excess I3- after the equivalence
point causes the solution to turn dark blue.

• In iodometry (titration of I3-), I3- is present

throughout the reaction up to the equivalence
point.
• Starch should not be added until immediately
before the equivalence point, otherwise some
iodine tends to remain bound to starch particles
after the equivalence point is reached (i.e. in this
case it is the absence of the dark blue colour that
signals the endpoint)

References
• D. C. Harris and C. A. Lucy, Quantitative
Chemical Analysis, Tenth Edition.

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