Dr.

Piya Seth, Assistant Professor in Chemistry Page 1

Redox Titration
During any titration process the relative amount of the titrant increases and the analyte decreases in
the reaction mixture.. When redox couples are involved in such titrations, it acquires different
potentials at different stages of the titration. Before the equivalence point, the potential of the system
is governed by the potential of the analyte and after the equivalence pointnt is reached it gets controlled
by the titrant. At equivalence point the system remains in equilibrium, so the potential of both the
analyte and titrant system will be same.

Let us consider the potential profile during titration of Mohr’s salt solution [i.e. Fe(II)] by KMnO4 in
acid medium.

Overall Reaction: MnO4- + 5Fe2+ + 8H+ Mn2+ + 5 Fe3+ + 4 H2O

E°Fe3+/Fe2+= 0.77V and E°MnO4-/Mn2+

/Mn2+= 1.51V

Fig. 1. Colour change during the titration of Fe(II) by KMnO4

Let us titrate 100 ml 0.1 N Mohr’s salt solution ((Fe2+) with 0.1 N KMnO4 solution and the medium is
maintained with 1(M) acidity (H+). Before the equivalence point the potential is calculated by using
Fe3+/Fe2+ (analyte) couple and after the equivalence point it is calculated by using MnO4-/Mn2+
(Titrant) couple.

1. When 1 ml KMnO4 added: After addition of 1 ml KMnO4 equivalent amount of Fe2+ will be
oxidized to Fe3+. So using Nernst Equation for Fe 3+/Fe2+ couple we get,
Fe2++
E = E° - 0.059 log
1 Fe3++
When 0 ml KMnO4 added, [Fe3+]: [Fe2+] = 1:99, Hence, E= +0.65 V

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2. When 50ml KMnO4 added: After addition of 50ml KMnO4 equivalent amount of Fe2+ will be
oxidized to Fe3+. So [Fe3+]: [Fe2+] = 50:50
As a result E= +0.77 V
3. When 90ml KMnO4 added: After addition of 90ml KMnO4 equivalent amount of Fe2+ will be
oxidized to Fe3+. So [Fe3+]: [Fe2+] = 90:10
As a result E= +0.83 V
4. When 99ml KMnO4 added: After addition of 99ml KMnO4 equivalent amount of Fe2+ will be
oxidized to Fe3+. So [Fe3+]: [Fe2+] = 99:1
As a result E= +89 V
5. When 99.9ml KMnO4 added: After addition of 99.9ml KMnO4 equivalent amount of Fe2+ will be
oxidized to Fe3+. So [Fe3+]: [Fe2+] = 99.9:0.1
As a result E= +95 V
6. When 100ml KMnO4 added: At equivalence point the system is at equilibrium,
So, Eeq = n1E1°+n2E2°/(n1+n2) V
= 5×1.51+1×0.77/6 V = 1.39 V
7. When 100.1 ml KMnO4 added: After the equivalence point is reached the potential of the system
will be calculated by MnO4-/Mn2+ couple. So addition of 100.1 ml KMnO4 gives
[MnO4-]:[Mn2+ ]= 0.1:100. By using Nernst equation we get
Mn2+
E = E° - 0.059 log
5 MnO4-
E= 1.47 V
8. When 101 ml KMnO4 added: After addition of 101 ml KMnO4, the [MnO4-]:[Mn2+ ] becomes
1:100.
Thus, E= 1.49 V
9. When 110 ml KMnO4 added: After addition of 110 ml KMnO4, the [MnO4-]:[Mn2+ ] becomes
10:100.
Thus, E= 1.50 V
When these calculated potentials (E in Volt) are plotted against the volume of KMnO 4
(Titrant) added the following curve is obtained.

Fig. 2. Change of Potential during the progress of titration of Fe2+ by MnO4- in acid medium.

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In this titration no redox indicator is required as KMnO4 acts as a self indicator and the equivalence
point can be detected by the pale pink colouration (Stable for 30 Sec). But that is not the case with
other titrants e.g. K2Cr2O7, Na2S2O3 etc.

Redox Indicators are mostly organic dyes and are themselves redox couples having specific
standard reduction potentials. They do not participate in the redox titration, and have distinctly
different colours in their oxidized and reduced forms.
Indox + ne IndRed where, EInd = EInd - 0.059 log [IndRed]
n [InOx]
To detect the colour of any of the form it should have 10 times more concentration. i.e. to detect
[InOx]
10
[InRed]
colour of the oxidized form it must have and to detect the colour of reduced form it
[InRed]
10
[InOx]
must have . Hence the colour change can be detected at the transition potential (Colour
change potential) given by
Etp = EInd0 +
- 0.059
n
To get the best result, Etp should lie at the potential close to that attained at the equivalence point. i.e.
Eeq ≈ Etp.

Some common redox indicators:

Diphenylamine (insoluble in water) undergoes irreversible oxidation to colourless diphenylbenzidine
which in turn suffers a reversible oxidation to form diphenylbenzidine violet.

Fig. 3. Mechanism of colour change of Diphenylamine indicator

Due to low solubility of free Diphenylamine it is replaced by its sulfonic acid derivative. The sodium
or Ba salt of Diphenylamine-4-sulphonic acid is used as indicator in the form of 0.2% aq soln. The
formal potential EInd = 0.85 V (0.5M H2SO4)

Fig. 4. Barium Diphenylamine 4-Sulphonate (BDS) indicator

Ferroin Indicator has the chemical formula [Fe(O-phen)3]SO4, where O-phen is 1,10-phenanthroline,
a bidentate ligand. The redox couple is [Fe-(O-phen)3]3+/[Fe-(O-phen)3]2+, E0Ind = 1.14 V having
colour pale blue and red respectively.
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Fig. 5. Structure of Ferroin indicator.

Table for some common redox indicators with their transition potentials (Colour change potentials)

Indicator Colour in Colour in E°Ind at pH=0

Oxidised form Reduced form
Methylene Blue Blue colourless 0.53
Diphenylamine Blue-violet colourless 0.76
Diphenylamine- Red-violet colourless 0.85
sulfonic acid
N-phenyl anthranilic Red-violet colourless 1.08
acid
Ferroin [Fe(II)- Pale blue Red 1.14
phenantroline]
Tris (5-nitro-1,10- Pale blue Red violet 1.25
phenanthroline)iron

Choice of Redox Indicator:

1) Let us consider the redox titration of Mohr’s salt solution with Potassium Dichromate.
Dichromate ion Cr2O72- oxidizes Fe(II) to Fe(III) itself being reduced to chromium(III) ions.

Cr2O72-+ 14H+ + 6 Fe2+ 2Cr3+ + 6 Fe3+ + 7H2O

E°Fe3+/Fe2+= 0.77V and E° Cr2O72-/Cr3+ = 1.33V

The reduction potential at equivalence point for this system

Eeq = n1E1°+n2E2°/(n1+n2) V
= (6×1.33 + 1×0.77) /7 V = 1.25 V
In fact the potential break at the equivalence point lies in the range 0.95 V- 1.30 V. The indicator
must have its colour changing potential (Etp) in this range.
Now the reduction potential value of di phenylaminesulfonic acid system is E° Ind = +0.0.85V which is
near to that of ferrous-ferric system (E°Fe3+/Fe2+= 0.77V) and also far away from the potential at
equivalence point Eeq = 1.25V. Thus phosphoric acid is required in this titration as it reacts with the

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product Fe3+ ion to form the complex ion [Fe(HPO4)]+, thus lowering the formal potential of the
Fe(III)/Fe(II) system thereby increasing its reducing power. Thus the end point is sharper.

Fig. 6. Colour change during the titration of Fe2+ by Cr2O72- in acid medium with BDS indicator.

2) Another example is oxidation of Fe2+ by Ce4+ in acid medium.

Ce4+ + Fe2+ Ce3+ + Fe3+

E°Fe3+/Fe2+ = 0.77V and E° Ce4+/Ce3+ = 1.44V

The reduction potential at equivalence point for this system

Eeq = n1E1°+n2E2°/(n1+n2) V
= (1.44+0.77)/2 = 1.10 V

In fact the equivalence point potential lies in the range 1.0 to 1.20 V in H 2SO4 medium. So, the
suitable indicator for this titration is Ferroin (Etp= 1.14+0.059 V). When all the Fe2+ ions are titrated a
slight excess of Ce4+ ion will bring about the oxidation of the indicator to change the colour. The
indicators having transition potential (Colour change potential) slightly less than 1.10 V are not
suitable for this titration. Because they will change their colour before the arrival of actual
equivalence point.

Fig. 7. Colour change during the titration of Fe2+ by Ce4+ in acid medium with Ferroin indicator.

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