Redox Titrations

UNIT 10 REDOX TITRATIONS

Structure
10.1 Introduction
Objectives
10.2 Redox Reactions and Redox Potential
Redox Reaction as Two Half Reactions
Redox Potential
10.3 Electrochemical Cells
Nernst Equation
Cell Potential
Redox Equilibrium Constant
10.4 Redox Titration Curves
10.5 Redox Indicators
10.6 Redox Titrations in Nonaqueous Solvents
Criteria for Solvent Selection
Characteristics of Common Nonaqueous Solvents
10.7 Applications of Redox Titrations
Oxidimetric Reagents
Reductimetric Reagents
10.8 Summary
10.9 Terminal Questions
10.10 Answers

10.1 INTRODUCTIOIN
You have learnt about the theory and applications of acid-base titrations in Units 7, 8
and 9 of Block 3. A large number of analytical determinations make use of another
important kind of titration, namely, redox titration. As the name suggests these
titrations are based on oxidation-reduction reactions. In contrast to acid-base titrations
in which the titration reaction involves the formation of undissociated molecules of a
weak electrolyte (water or a weak acid), a redox titration reaction is associated with
the transfer of electrons. The electrons are transferred from a reducing agent to an
oxidising agent. Oxidation-reduction or redox reactions are widely used in the
titrimetric determination of both inorganic and organic compounds.

In this unit we begin with a brief review of the concept of redox reactions and redox
potential. Then we shall take up the measurement and significance of standard
reduction potentials. It will be followed by the calculation of the cell potential in the
course of a titration. The theory of redox indicators and the redox titrations in the
nonaqueous solvents will be followed by a few important applications of redox
titrations in analytical determinations. In the next unit you would learn about
complexometric titrations having extensive analytical applications.

Objectives
After studying this unit, you will be able to:
• define oxidation and reduction,
• explain the terms like electrode potential, cell potential and redox potential,
• calculate the cell potential for a given cell,
• calculate the equilibrium constant for a redox reaction and predict the direction
of the reaction,
• construct a titration curve for a redox reaction and compute the equivalence
point,

5
Estimations Based on • select a suitable indicator for a given redox titration on the basis of potential at
Redox and
equivalence point, and
Complexation
Equilibria Studies • carry out the determination of different inorganic and organic substances by
performing their redox titrations with suitable oxidising or reducing agents.

10.2 REDOX REACTIONS AND REDOX POTENTIAL

You would recall from your earlier studies that the oxidation process results in the loss
of one or more electrons by an atom or an ion, e.g. in case of iron we can write the
process as follows.
Fe 2+ 
→ Fe 3+ + e
Here, the ferrous ions are getting oxidised to ferric ions by the loss of one electron.
Reduction, on the other hand, is the process which results in the gain of one or more
electrons by an atom or an ion, e.g., the chlorine gets reduced to chloride ions by
gaining electrons, as shown below.
→ 2Cl −
Cl 2 + 2e 
Further, oxidation and reduction are always found to occur together in a reaction. In
other words, electron loss of one substance is always accompanied by an electron gain
on the part of the other and consequently there are no free electrons in a chemical
system. Such reactions are termed redox reactions and are also termed electron
transfer reactions. Let us take the example of the reaction between the Ce4+ and Fe2+
ions as given below.

Ce4+ + Fe2+
Ce3+ + Fe3+

Here, the electron lost by ferrous ion are picked up by Ce4+ ions and as you can see
You would recall that the that there are no free electrons in the reaction. The transfer of electrons from one
oxidation is defined as an
species of the reactants to another can be rationalised in terms of changes in the
increase in the oxidation
number of an element.
oxidation number. An oxidation-reduction reaction is accompanied by an increase in
Reduction is defined the oxidation number of a given species and a complementary decrease in oxidation
analogously as a decrease number of another species. In the example given above, the oxidation number of iron
in the oxidation number. increases from 2 to 3 whereas that of cerium decreases from 4 to 3.

10.2.1 Redox Reaction as Two Half Reactions

As a redox reaction involves both oxidation and reduction components, it is possible
to divide the total reaction into two half reactions. These clearly demonstrate which
species gains electrons and which loses them. This can be suitably illustrated by the
reaction between iron (II) and cerium (IV) given above. This reaction can be divided
into two half reactions as shown below.

Fe2+ Fe3+ + e ( Oxidation)

Ce4+ + e Ce3+ (Reduction)

The first reaction shows oxidation of iron (II), the second reaction depicts the
reduction of cerium (IV). On adding the half reactions, the electrons cancel out and we
get the overall equation. This method of expressing a redox reaction as two half
reactions provide a kind of flexibility to the concept of redox reactions.

The species possessing strong affinity for electrons cause the oxidation of other
substances by abstracting electrons from them. These species are called oxidising
agents. In the process, the oxidising agents are themselves reduced. In the above
reaction, for example, cerium (IV) ions act as oxidising agents and are consequently
reduced to cerium (III) ion. On the other hand the species that readily give up

6
electrons cause the reduction of other substances. These are called reducing agents Redox Titrations
and in this process, a reducing agent itself gets oxidised. Thus, in the above example,
iron (II) ions act as reducing agents and are consequently oxidised to iron (III) ions.

10.2.2 Redox Potential

If a system contains both an oxidising agent and its reduction product, there will be
equilibrium between them and the electrons. If an inert electrode, such as platinum, is
placed in such a redox system, for example, one containing Fe (III) and Fe (II) ions, it Fe2+
Fe3+
will assume a definite potential indicative of the position of the equilibrium. If the
system tends to act as an oxidising agent i.e., it will take electrons from platinum,
leaving the latter positively charged. On the other hand, if the system has reducing Fe2+ Fe3+
properties i.e., electrons will be given to the metal, which will acquire a negative
charge. The magnitude and sign of the potential on the platinum electrode will thus be
a measure of the oxidising or reducing properties of the system.

Different oxidising / reducing agents differ from one another in their strength. An
oxidising agent can behave as a reducing agent in the presence of a stronger oxidising
agent. The reaction can be depicted as under.

Oxidising agent (I) + Reducing agent (II) 

→ Reducing agent(I) + Oxidising agent (II)

For a reaction of the above type, where we have a pair of oxidising-reducing agents
such that either of the species can act as an oxidising or a reducing agent, the direction
of the reaction is determined by comparing the redox potential of the
oxidising/reducing agents. The redox potential is a quantitative characteristic of the
oxidising/reducing power of a reagent. Let us try to understand the meaning and the
significance of redox potential.

Significance of Redox Potentials

In order to obtain the comparative strengths of oxidising agents, it would be necessary
to measure the potential difference between the platinum and the solution relative to a
standard or a reference under standard experimental conditions. The reference
electrode used is the standard or normal hydrogen electrode whose potential is
taken as zero at all temperatures. The standard experimental conditions for redox
systems are those in which the ratio of the activity of the oxidant to that of the
reductant is unity. Hence for the following electrode,
Fe3+ Fe2+
the standard redox cell would be written as follows: You would recall that in a
cell notation a single
Fe3+ (a = 1)
Pt, H2 H+ (a = 1) Pt vertical line indicates a
Fe2+ (a = 1) solid liquid interface
whereas a double vertical
The potential measured in this way is called the standard redox potential or line represents a salt
standard reduction potential. The standard reduction potentials for a number of bridge.
redox systems are given in Table 10.1.

Table 10.1: Standard reduction potentials (E0) * for some redox systems at 298 K
Half reaction E0, Volts
F2 + 2e 2F + 2.65
2- + 2.01
S2O8 + 2e 2SO42-
Co3+ + e Co2+ + 1.82

7
Estimations Based on + 1.70
Redox and
Pb4+ + 2e Pb2+
Complexation - + 1.69
MnO4 + 4H+ + 3e MnO2 + 2H2O
Equilibria Studies
BrO3- + 6H+ + 5e 1/2 Br2 + 2H2O + 1.52

- + 1.52
MnO4 + 8H+ + 5e Mn2+ + 4H2O
Ce4+ + e Ce3+ + 1.44
Cl2 + 2e 2Cl- + 1.36

Cr2O72- + 14H+ + 6e 2Cr3+ + 7H2O + 1.33

Tl3+ + 2e Tl+ + 1.25

MnO2 + 4H + + 2e Mn2+ + 2H2O + 1.23
O2 + 4H+ + 4e 2H2O + 1.23
- + 1.20
IO3 + 6H+ + 5e 1/2 I2 + 3H2O
- + 1.07
Br2 + 2e 2Br
HNO2 + H+ + e NO + H2O + 1.00
2Hg2+ + 2e Hg22+ + 0.92
- + 0.86
Cu2+ + I + e CuI
Ag+ + e Ag+ (s) + 0.80
_ + 0.79
Hg2+
2 + 2e 2Br
Fe3+ + e Fe2+ + 0.77

BrO3- + 3H2O + 6e + 0.61

Br -+ 6OH -
MnO-4 + 2H2O + 2e MnO2 + 4OH - + 0.60

MnO-4 + e + 0.56
2-
MnO4
H3AsO4 + 2H+ + 2e H3AsO3 + H2O + 0.56
- + 0.54
Cu2+ + Cl + e CuCl
+ 0.54
I2 + 2e 2I-
[Fe(CN)6]3+ + e [Fe(CN)6]4- + 0.36

IO3- + 3H2O + 6e - + 0.26

I -+ 6OH
Cu2+ + e Cu+ + 0.15
Sn4+ + 2e Sn2+ + 0.15
2- 2- + 0.08
S4O6 + 2e 2S2O3
2H+ + 2e H2 + 0.00
Ni2+ + 2e Ni (s) - 0.25
V3+ + e V2+ - 0.26
Cr3+ + e Cr2+ - 0.41

8
 U4+ + e U3+ - 0.61 Redox Titrations

- - - - 0.67
AsO4 + 3H2O + 2e H2AsO3 + 4OH
Zn + 2e Zn (s) -0.76
Al3+ + 3e Al (s) -1.66
Mg2+ + 2e Mg(s) -2.38
Ca2+ + 2e Ca (s) - 2.87
K+ + e K (s) - 2.92
Li+ + e Li (s) - 3.04
*
A negative E0 means that the redox couple is a stronger reducing agent than H+ / H2 couple
while a positive value means that the redox couple is a weaker reducing agent than hydrogen
couple.

These redox potentials enable us to predict which ion will oxidise or reduce other ions
at unit activity (or molar concentration). The most powerful oxidising agents are those
which are at the upper end of Table 10.1 and most powerful reducing agents are at
bottom end of the table. For example, the standard reduction potential for the
reduction of Ce (IV) ions is highly positive, that is the reduction of cerium (IV) ions is Ce4+ + e Ce3+
quite spontaneous, so Ce (IV) acts as a strong oxidising agent. On the other hand, the
standard reduction potential for the Zn (II) ions is negative, meaning thereby that the
Zn2+ + 2e Zn
reduction of zinc ions is not favourable. Therefore, Zn (II) ion is a weak oxidising
agent, while metallic zinc is a strong reducing agent.

It is important to mention here that for many oxidants, the pH of the medium is of
great importance since they are generally used in acidic media. For example, in
measuring the standard redox potential of the MnO −4 , Mn2+ system, i.e.,

MnO 4− + 8H + + 5e → Mn 2 + + 4 H 2 O
it is necessary to state that hydrogen activity is unity. It needs to be emphasised that
standard redox potentials do not give any information about the speed of the reaction.
In some cases, a catalyst has to be added to enable the reaction to proceed with
reasonable velocity.

SAQ 1
Using Table 10.1 determine which of the two ions, Fe (II) or Cr (II) would be easily
oxidised.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
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…………………………………………………………………………………………...

10.3 ELECTROCHEMICAL CELLS

The direct transfer of electrons from an electron donor to the electron acceptor in a
redox reaction can be best illustrated by immersing a piece of zinc in a copper (II)
sulphate solution. It is observed that copper is deposited at the surface of the metal.
The copper ions migrate to the zinc electrode and get reduced there by extracting
electrons from it; the zinc metal dissolves and generates Zn2+ ions in the solution. It is
important to mention here that such an transfer of electrons can still be accomplished

9
Estimations Based on
Redox and
Complexation
Equilibria Studies
The electrical potential
existing between zinc and
copper electrodes is a
measure of this driving
force and can be easily
measured by a voltmeter,
V, placed in circuit.
The electrode potential,
which is a measure of the
chemical driving force of
a half-reaction, is affected
by the concentration. The
concentrations of
reactants and products in
a half-reaction have a
marked effect on
electrode potential.
10
even when the electron donor and accepter are kept away from each other. This can be
achieved in an electrochemical cell as shown in Fig.10.1.
Fig. 10.1: Schematic diagram of a simple electrochemical cell
The electrochemical cell shown in Fig.10.1 is called Daniel cell. In this set up the
direct contact between metallic zinc and Cu2+ ions is prevented by connecting the two
electrodes with the help of a salt bridge. The salt bridge contains a saturated solution
of an inert electrolyte like KNO3 in agar agar gel. In such a situation, the electrons are
transferred by means of the external circuit and within the cell the current is carried by
the ions. This electron transfer continues until the Cu2+ and Zn2+ concentrations
achieve levels corresponding to the equilibrium for the reaction.
Zn + Cu2+ Zn2+ + Cu
When this stage is reached, there will be no further flow of electrons. It is important to
note that the overall reaction and the position of its equilibrium is the same regardless
of the manner in which the reaction is carried out.
An electrochemical cell is capable of producing electrical energy because of the
tendency of reacting species to transfer electrons and thus achieve the condition of
equilibrium. A cell operated in such a way is called a galvanic cell and is used to
produce electric energy. The voltage produced by an electrochemical cell is directly
related to the equilibrium constant for the particular oxidation-reduction process
involved. The measurement of these potentials constitutes an important source of
numerical values for these constants.
10.3.1 Nernst Equation
In our arguments above, we mentioned that the activity of different species in an
electrode reaction is unity. However, this need not be always true. Nernst showed that
for the electrode reaction:
M n + (aq ) + ne → M (s)
the electrode potential at any concentration measured with respect to
standard hydrogen electrode is given by the following equation called Nernst
equation.
RT [M ]
E M n + / M = E M0 n + / M − ln
nF [ M n + ]
where E0 is the standard electrode potential (characteristic of the particular half
reaction), R is the gas constant, T is the absolute temperature, n is the number of
electrons participating in the reaction and F is the Faraday’s constant. The logarithm
term is the ratio of the concentrations of the reduced and oxidised forms of the species.
It is customary to employ concentrations rather than activities of reactants and
products and the same are given in molarities (for ionic and molecular species). For
gaseous species, the pressure in atmosphere is used. The concentration of pure Redox Titrations
substances such as solids (precipitates) and liquids (water) is taken to be unity. As the
numerator in the logarithm term in equation is the concentration of metal, a pure
substance, it is taken as 1 and the equation becomes,
RT 1
E M n + / M = E M0 n + / M − ln
nF [ M n + ]
After substituting common logarithm for natural logarithms and inserting numerical
values for the constants and assuming the temperature as 298K, we can write the
equation as given below.
0.059 1
E M n + /M = E M0 n + /M − log
n [M n + ]
Let us write the Nernst equation for some half reactions.
I Half reaction Cu2+ + 2e Cu

0 0.059 1
Nernst equation E Cu 2+ /Cu = E Cu 2+
/Cu
− log
2 [Cu 2 + ]
The electrode potential varies with the logarithm of the reciprocal of the molar
Cu2+ ion concentration in the solution (the activity of metallic copper is taken as
unity).

II Half reaction 2H+ + 2e H2

0.059 pH
Nernst equation E 2H + / H = E 0 − log + 22
2 2H + / H 2 2 [H ]
pH2 represents the partial pressure of hydrogen (expressed in atmospheres).
Ordinarily, it will be very close to atmospheric pressure.

III Half reaction -

Cr2O7 + 14H+ + 6e 2Cr3+ + 7H2O

Nernst Equation

0 0.059 [Cr 3+ ] 2
E Cr O 2− /Cr3+ = E Cr O 2 − /Cr 3 +
− log
2 7 2 7 n [Cr2 O 7 ] 2 [ H + ]14
0.059 [Cr 3+ ] 2
=1.33 − log
6 [Cr2 O 7 ] 2− [H + ]14
In this case, the potential depends not only on the concentration of Cr3+ and
Cr2O72 − ions but also on the pH of the solution. −

10.3.2 Cell Potential

When two electrodes combine to give a cell, the potential of the cell depends on the
concentrations of the species involved in both the electrodes or the half cells. We can
develop a suitable Nernst equation for the same also. Let us do this for the Daniel cell
described above. The cell potential of the Daniel cell can be determined by taking the
electrode potentials of the two electrodes for any given concentration of Cu2+ and Zn2+
ions. Let us write the expressions for the reactions at cathode and anode,
0 RT 1
Reaction at Cathode: E Cu 2+ /Cu = E Cu 2+
/Cu
− ln 2+
2F [Cu (aq )]

11
Estimations Based on
Redox and
Complexation Reaction at Anode:
Equilibria Studies
0 RT 1
E Zn 2 + / Zn = E Zn 2+
/ Zn
− ln 2+
2 F [ Zn (aq )]

The cell potential, E cell = E Cu 2+ / Cu − E Zn 2+ / Zn

0 RT 1 0 RT 1
= E Cu 2+
/ Cu
− ln − E Zn 2+
/ Zn
+ ln
2 F [Cu 2 + (aq )] 2 F [ Zn 2 + (aq )]

0 0 RT 1 RT 1
= ( E Cu 2+
/ Cu
− E Zn 2+
/ Zn
)− ln − ln
2 F [Cu 2+ (aq )] 2 F [ Zn 2 + (aq )]

RT [ Zn 2+ (aq )]
E cell = E (0cell ) − ln
2 F [Cu 2+ (aq )]
Taking clue from here, we can write a generalised Nernst equation for any cell. For a
cell with the following general equation
aA + bB + . . . + ne cC + dD + . . .

The Nernst equation would be

RT [C] c [D] d .....
E = E0 − ln
n [A] a [B] b .....
Converting to the logarithm to the base ten and substituting the values of constants and
the temperature as 298 K, we get the following.
0.059 [C] c [D] d ......
E = E0 − log
n [A] a [B]b ......
Let us take an example to learn how to write the Nernst equation for a given cell
reaction.

Example 10.1
Compute the standard electrode potential of the cell in which the following reaction
takes place and write the Nernst equation for the cell. (You may use Table 10.1 for the
data required.)
Ni(s ) + 2Ag + (aq ) → Ni 2 + (aq) + 2 Ag (s )

Solution
In such a situation we need to identify the species getting oxidised and the one getting
reduced. In other words we need to identify the oxidation and reduction half reactions.
In this case as you can see that the nickel is getting oxidised to nickel ions while silver
ions are getting reduced to metallic silver. The reactions being,
Ni(s) (aq) → Ni 2+ (aq) + 2e
2Ag + (aq) + 2e → 2 Ag (s)
The standard reduction potentials for the two redox systems are – 0.25 V and 0.80 V
respectively. The standard cell potential would be [0.80 – (– 0.25) = 1.05 V]

The Nernst equation for the cell with given cell reaction would be as follows.

12
 RT [ Ni 2+ (aq )] Redox Titrations
= E cell = 1.05 − ln V
2 F [ Ag + (aq )] 2

0.0592 [Ni 2+ (aq)]

= 1.05 − ln V
2 [Ag + (aq)] 2

10.3.3 Redox Equilibrium Constant

The equilibrium constant of a redox reaction can be obtained by the application of
Nernst equation. It provides information regarding the direction and extent of the
reaction.

Let us consider two redox systems that involve the same number of electrons.
Ox1 + ne Red1
Red2 Ox2 + ne

Ox1 + Red2 Red1 + Ox2

The equilibrium constant for the reaction can be written as follows.

[Red 1 ] [Ox 2 ]
K =
[Ox 1 ] [Red 2 ]
For the above two systems, Nernst equations for the reduction potentials can be
written as follows.
0.059 [Red 1 ]
E1 = E10 − log
n [Ox 1 ]
0.059 [Red 2 ]
E 2 = E 20 − log
n [Ox 2 ]
When the systems are at equilibrium i.e., E1 = E2, then we have the following
expressions.
0.059 [Red 1 ] 0.059 [Red 2 ]
E10 − log = E 20 − log
n [Ox 1 ] n [Ox 2 ]
Rearranging the equation and substituting the equilibrium constant into the expression,
we get the following relation
0.059 [Red1 ] 0.059 [Red 2 ]
E10 − E20 = log − log
n [Ox1 ] n [Ox 2 ]
0.059 [Red1 ] [Red 2 ]
= ( log − log )
n [Ox1 ] [Ox 2 ]
0.059 [Red1 ] [Red 2 ]
= log ( − )
n [Ox1 ] [Ox 2 ]
0.059 [Red1 ] [Ox 2 ]
= log(
n [Ox1 ] [Red 2 ]
0.059
= log K
n
n ( E1o − E2o )
log K =
0.059
If the number of electrons interchanged is not the same (n1 ≠ n2), the following
equation can be derived.

13
Estimations Based on
Redox and log K = n1 n 2
(E0
1 − E 20 )
Complexation 0.059
Equilibria Studies
Let us take an example to learn about the application of Nernst equation in calculating
the equilibrium constant of a reaction.

Example 10.2
Calculate the equilibrium constant of the following reaction and predict the direction
of the reaction
Sn4+ (aq) + 2Fe2+(aq) Sn2+(aq) + 2Fe3+(aq)
0 0
Given, ESn 4+
, / Sn 2 +
= 0.14 V ; E Fe3+
/ Fe2 +
= 0.77 V

Solution
Substituting the given values of the standard electrode potentials, we get
0.14 − 0.77
log K = 1 × 2 ( ) = − 21.3
0.059
K = 10− 21.3
The extremely low value of equilibrium constant suggests that the equilibrium lies far
to the left.

SAQ 2
Calculate the electrode potential of a half cell containing an aqueous solutions of
0.100 M KMnO4 and 0.100 M MnCl2 having a pH = 1.000.
(Note: You may use Table 10.1.)

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
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10.4 REDOX TITRATION CURVES

In redox titrations, the concentration of the substances or ions involved in the reaction
continuously keeps changing in the course of the titration. Hence, the redox potential
of the solution must also change (the phenomenon may be compared to the change of
the pH of solution during acid-base titrations). By plotting the redox potential
corresponding to different points in the titration, a titration curve similar to the curve
obtained in an acid-base method is obtained. This can be illustrated by computing the
titration curve for a titration of 100 cm3 of 0.1M iron (II) with 0.1 M cerium (IV) in
the presence of dilute sulphuric acid.
Fe2+ + Ce4+ Fe3+ + Ce3+

This titration involves Fe3+/Fe2+ and Ce4+/Ce3+ ion electrode systems (let us call them
as 1 and 2). These can be represented by Nernst equation as follows.

14
 0.059 [Fe 2+ ] Redox Titrations
E1 = E10 − log ;
1 [Fe 3+ ]

0.059 [Ce 3+ ]
E 2 = E 20 − log
1 [Ce 4+ ]

[Fe 2+ ]
E1 = 0.75 − 0.059 log
[Fe 3+ ]

[Ce 3+ ]
E 2 = 1.45 − 0.059 log
[Ce 4+ ]
As you know, the equilibrium constant of the above reaction can be written as follows.
[Ce 3+ ] × [Fe 3+ ]
log K = log
[Ce 4+ ] × [Fe 2+ ]
n (E1o − E o2 )
also, log K =
0.059
1
= (1.45 − 0.75)
0.059
= 11.84

K = 7 × 1011
As the value of the equilibrium constant is quite large, the above reaction goes almost
to completion.

It may be noted that upto the equivalence point of the titration, cerium(IV) solution
added will only oxidise iron(II) to iron(III); since K is large all the cerium ions
would be consumed and the ratio [Fe2+] / [ Fe3+] would change. Therefore, we can
compute the cell potential by using the Nernst equation for the Fe3+ / Fe2+ half cell.
Let us compute the cell potential as a function of the progress of the reaction.

a) Potential before starting the titration

In the beginning of the titration, the solution would contain only Fe2+ ions and may
have traces of Fe3+ due the aerial oxidation of the solution. As the concentration of the
tripositive ion is too small, the calculation of the potential has no meaningful
significance.

b) Potential after the addition of 10 cm3 of 0.1 M cerium (IV)

As the titrand and titrant have same concentration, on addition of 10 cm3 of the titrant
10% of the ferrous ions would have got oxidised to ferric ions and the relative
concentrations of the two ions would be Fe2+ : Fe3+ :: 90:10. In other words,
[Fe 2+ ] 90
3+
= (approx.)
[Fe ] 10
We can compute the cell potential as following.
90
E = 0.75 − 0.059 log
10
= 0.75 − 0.06 = 0.69 V (approx.)

15
Estimations Based on c) Potential after the addition of 50 cm3of 0.1 M cerium (IV)
Redox and
Complexation It can be calculated as follows.
Equilibria Studies
[Fe 2+ ] 50
=
[Fe 3+ ] 50
50
E = 0.75 − 0.059 log
50
= 0.75 − 0 = 0.75 V

d) Potential after the addition of 90 cm3 of 0.1 M cerium (IV)

[Fe 2 + ] 10
= (approx.)
[Fe 3+ ] 90
10
E = 0.75 − 0.059 log
90
= 0.75 + 0.06 = 0.81 V (approx.)

e) Potential after the addition of 99 cm3 of 0.1 M cerium (IV)

[Fe 2 + ] 1
= (approx.)
[Fe 3+ ] 99
1
E = 0.75 − 0.059 log
99
= 0.75 + 0.12 = 0.87 V (approx.)

f) Potential after the addition of 99.9 cm3 of 0.1 M cerium (IV)

Preequivalence point potential
[Fe 2 + ] 0.1
3+
= (approx.)
[Fe ] 99.9
0.1
E = 0.75 − 0.059 log
99.9
= 0.75 + 0.18 = 0.93 V (approx.)

g) Potential after the addition of exactly 100 cm3 of 0.1 M cerium (IV)
Equivalence point potential
[Fe 2+ ] = [Fe 3+ ] ; [Ce 3+ ] = [Ce 4+ ]

E1 + E 2 0.75 + 1.45
= = 1.10 V
2 2
After this stage there won’t be any free ferrous ions, with further addition of the
reagent, it is the ratio [Ce3+] / [Ce4+] which will change. Therefore, for the
further computation of the titration curve we need to use the ratio of the
concentrations of these ions and the Nernst equation for the Ce4+/Ce3+ half cell
will be used.

h) Potential after the addition of 100.1 cm3 of 0.1 M cerium (IV)

Postequivalence point potential.
The added excess (0.1 cm3) of the titrant will be as Ce4+ while the earlier 100
cm3 of the titrant would have got reduced to Ce3+ ions.

16
 [Ce 3+ ] 100 Redox Titrations
4+
= (approx.)
[Ce ] 0.1
100
E = 0.145 − 0.059 log
0.1
= 1.45 − 0.18 = 1.2 V (approx.)

i) Potential after the addition of 101 cm3 of 0.1 M cerium (IV)

[Ce3+ ] 100
4+
= (approx.)
[Ce ] 1

100
E = 0.145 − 0.059 log
1
= 1.45 − 0.12 = 1.33 V (approx.)

j) Potential after the addition of 110 cm3 of 0.1 M cerium (IV)

[Ce 3+ ] 100
4+
= (approx.)
[Ce ] 10
100
E = 0.145 − 0.059 log
10
= 1.45 − 0.06 = 1.39 V (approx.)

k) Potential after the addition of 190 cm3 of 0.1 M cerium (IV)

[Ce 3+ ] 100
4+
= (approx.)
[Ce ] 90
100
E = 0.145 − 0.059 log
90
= 1.45 − 0 = 1.45 V (approx.)
The above results of the calculations can be plotted as a titration curve as shown
in Fig. 10.2.

Fig. 10.2: Calculated titration curve of 100 cm3 of 0.1 M iron (II) with 0.1 M cerium (IV)
solution

17
Estimations Based on The general appearance of the curve is similar to that for an acid base titration. It may
Redox and be noted that the potential, which changes slowly in the early stages of the titrations,
Complexation
changes very abruptly as the titration passes through the equivalence point. The
Equilibria Studies
magnitude of potential change evidently depends on the difference between the
standard potentials of the two redox systems that are involved; the greater the
difference, the greater is the change of potential at the equivalence point. Further, the
curve is symmetric about the equivalence point when oxidants and reductants react in
equimolar amounts or exchange same number of electrons per molecule (as in the
above titration). The curve would, however, would not be symmetric about the
equivalence point when the two redox systems exchange different number of electrons
per molecule.

Redox titration curves are usually independent of dilution because Nernst equation
contains the ratio of the concentrations of reduced and oxidised forms, which does not
alter with dilution. It is worth mentioning here, that the break in the potential on the
titration curve can be used in the selection of an indicator for the redox titration.

SAQ 3
The solution potential at the equivalence point in a titration of 0.1 M Ce (IV) solution
with 0.1 M Fe (II) solution has been worked out to be 1.10 V. What will be the
potential at equivalence point if the concentration of titrant and the titrand were
0.01 M each?

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10.5 REDOX INDICATORS

A redox indicator is a compound which can undergo a redox reaction and change
colour depending on the potential of the solution. The oxidised and reduced forms of
the indicator have different colours. The indicator reaction may be represented as
follows.
Inox + ne Inred
(colour X) (colour Y)
where, Inox is the oxidised form of the indicator having colour X and Inred is the
reduced form of the indicator having a different colour, Y. The potential of the above
half reaction can be represented in terms of Nernst equation as given below.
0 0.059 [In red ]
E = E ox / red − log
n [In ox ]
E0Ox, Red is the standard reduction potential for the indicator half reaction. As the colour
intensity is proportional to the concentration of the species causing it, the Nernst
equation for the indicator half cell may be rewritten as given below.
0 0.059 Intensity of colour Y
E = E ox / red − log
n Intensity of colour X
Thus, the redox indicator will show colour X if the intensity of this colour (oxidised
form) is at least 10 times greater than the intensity of the colour Y. Similarly, the
indicator will show colour Y if the intensity of the colour is 10 times more than that of
the colour X. In other words colour X will be seen when the solution potential is as
follows.

18
 0 0.059 1 Redox Titrations
E = E ox / red − log
n 10
0 0.059
E = E ox / red +
n
And colour Y will be seen when the solution potential is as follows.
0 0.059
E = E ox / red − log 10
n
0 0.059
E = E ox / red −
n
At intermediate potential values of the solution, the indicator will show a mixture of
colour X and Y. From these expressions we can conclude that a redox indicator
involving 1 electron in the half reaction requires a potential change of 2 × 0.059/1
(~0.12 V) to change colour from one form to the other. For indicators involving 2
electrons in their half-reactions, a potential change of 2 × 0.059/2 (~0.060 V) will be
sufficient to cause the colour change. The potential range of the colour change for a
redox indicator can be calculated theoretically on the basis of their standard potential
0
values as, E ox / red ± 0.059/n V.

Let us take an example of the titration of iron (II) with cerium (IV) in acidic medium
having 1M sulphuric acid. In this titration 1, 10-phenanthroline iron (II) sulphate is
used as an indicator. The indicator is called Ferroin and is prepared by dissolving
1,10 phenanthroline and iron(II) sulphate in 3:1 molar ratio. Three molecules of 1,10
phenanthroline are coordinated to an iron(II) cation to form red octahedral indicator
complex which is frequently written as [ Fe (Phen)3]2+.

2+

N N

3 + Fe2+ Fe

N N

The colour change of the indicator is due to the oxidation of Fe (II) to Fe (III) in the
indicator. The reduced iron (II) form of the indicator has an intense red colour
whereas the oxidised iron (III) indicator complex is pale blue. The indicator half-
reaction can be written as given below.

[ Fe (Phen)3 ]3+ + e [ Fe (Phen)3 ]2+ ; E 0 = 1.06 V

Why don’t you calculate the range of solution potential at which the ferroin indicator
would change colour.

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19
Estimations Based on You seem to have calculated correct, it is 1.00 to 1.12 V, as the indication involves
Redox and only one electron, it will show one colour at E = E0 – 0.06 V (1.06 – 0.06 = 1.00 V)
Complexation
and other at E = E0 + 0.06 V (1.06 + 0.06 = 1.12 V ).
Equilibria Studies
As has been discussed earlier, the potential at the equivalence point is the mean of the
two standard redox potentials. The potential at equivalent point for the titration of
0.1M Fe(II) with 0.1 M cerium(IV) solution will be 1.10 V. Ferroin is a suitable
indicator for the titration as it changes from deep red to pale blue at a redox potential
of 1.12 V. The indicator will therefore be present in the red form after the addition of
just 0.1 percent excess of cerium (IV) solution, the potential rises to 1.27 V and the
indicator is oxidised to pale blue form. The titration error is evidently negligibly small.

It is important to mention here that diphenylamine is one of the earliest redox

indicators. It was introduced by Knoop for the titration of iron (II) with potassium
dichromate. The reduced form of the indicator is colourless and the oxidised form has
a deep violet colour. In the presence of a strong oxidising agent, diphenylamine
undergoes the following reactions:
H H H

2 N N N + 2H+ + 2 e

Diphenylamine Phenylbenzidine
(colourless) (colourless)

N N + 2H+ + 2 e
E0 = 0.76'
Diphenylbenzidine
(violet)

The first reaction involving the formation of colourless diphenylbenzidine is

irreversible, the second, however, giving a violet product, is reversible and is the true
indicator reaction. However, this indicator suffers from the drawback that its solution
must be prepared in concentrated sulphuric acid. The sulphonic acid derivatives of
diphenylamine are frequently used instead.
H

HO3S N

Diphenylamine sulphonic acid

The barium or sodium salt of this acid are soluble in water and may be used to prepare
aqueous indicator solutions. The standard potentials values of some redox indicators
along with the colour of the oxidised and reduced form are compiled in Table 10.2.

Table 10.2: The standard transition (reduction) potential values and the colour
of the oxidised and reduced form of some redox indicators
Indicator Colour of the Colour of the Std. transition
reduced form oxidised form potential, E0
Indigo tetrasulfate Colourless Blue 0.36
Methylene blue Colourless Blue 0.53
Diphenylamine Colourless Violet 0.76
Barium diphenylamine Colourless Red-violet 0.84

20
 sulfonate Redox Titrations
Erioglaucine A Yellow- green Blue- red 1.00
Tris (5-methyl-1,10- Red Pale-blue 1.02
phenanthroline) iron (II)
sulfate
Tris (1, 10-phenanthroline) Red Pale-blue 1.11
iron (II) sulfate
Tris (5-nitro-1,10-phenana- Red Pale-blue 1.25
throline) iron (II) sulfate
(nitroferroin)

SAQ 4
Compute the potential at which the indicator 5 – nitro ‒ 1, 10 phenanthroline would
acquire the colour of the oxidised form of the indicator. The indicator reaction can be
given as under.
[ Fe (5- Nitro-Phen)3 ]3+ + e [ Fe (5- Nitro-Phen)3 ]2+ ; E0 = 1.19 V

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10.6 REDOX TITRATIONS IN NONAQUEOUS SOLVENTS

The discussion so far on the redox reaction was confined to aqueous solution.
However, as a number of analytical determinations are carried out in nonaqueous
media, it would be worth while to learn about the redox titration in nonaqueous
solutions. The scope of redox reactions can be extended by using nonaqueous solvents
as media of titrations in place of water. Redox titrimetry in nonaqueous media has a
wide scope for the determination of compounds which have the following
characteristics.
i) The compounds are insoluble in water.
ii) The compounds react with water through hydrolysis or oxidation.
iii) The compounds are decomposed by the medium of aqueous redox titrations i.e.,
acids, bases, etc.

10.6.1 Criteria for Solvent Selection

The following are the properties that are to be considered while selecting a solvent for
use in nonaqueous redox studies.

i) The solvent should be resistant to the attack by the reagent. This permits
reactions to be carried out over a wide range of potentials. This is so because
some of the nonaqueous solvents may extend the range towards reducing
conditions while others may do so towards oxidising conditions. For example,
dimethyl formamide can be used as a solvent for redox titrations involving
powerful reductants, such as Cr(II) but is oxidised even by mild oxidising
agents. On the other hand, nitrobenzene is resistant to oxidation but susceptible
to reduction whereas, acetonitrile is resistant to both oxidation and reduction.
This makes it a good choice as a solvent for redox determinations in
nonaqueous media.

21
Estimations Based on ii) The solvent should be capable of keeping reactants and, if possible, products as
Redox and well in solution. As you know electron transfer reactions tend to be slow unless
Complexation
appreciable portions of the reactants are present in the ionic form. The dielectric
Equilibria Studies
constant of the solvent must therefore be kept very high so as to minimise ion
pairing that slows down the reaction rates. Acetic acid (dielectric constant 6.2)
has good stability but is poor in providing sufficient salt dissociation.
Acetonitrile is resistant to oxidation or reduction, on the other hand the high
dielectric constant (36) of acetonitrile encourages salt ionisation.

iii) In addition to the above considerations the solvent should be easy to handle. Let
us take up some such issues related to the ease of handling.
a) Some solvents may have favourable resistance and dielectric
characteristics but are sometimes difficult to purify. A significant source
of error and hence such solvents are ignored.
b) Some solvents tend to react with or absorb atmospheric components and
need to be protected from exposure to air, e.g. acetonitrile and
dimethylformamide take up water even on brief exposure to atmosphere
and ethylenediamine tends to absorb carbon dioxide.
c) Many solvents like ammonia, sulphur dioxide, hydrogen sulphide,
nitrosyl chloride etc. have low boiling points and require low
temperature conditions. As a solvent working at room temperature is an
ideal choice, such solvents with low boiling points are not desirable.
Similarly, the high melting points of a number of solvents likes N-
methylacetamide makes them unfit for the purpose.
d) Some solvents are toxic and hence are discouraged for use in analytical
applications. For examples, hydrogen cyanide (b.p. 25.7o C, dielectric
constant 106.8) would be very useful solvent but the problems associated
with its handling and disposal due to its toxicity make it generally
undesirable medium.

10.6.2 Characteristics of Common Nonaqueous Solvents

The above discussion has raised issues regarding the desirable attributes of a solvent to
be employed for redox determination. Let us now learn about the characteristics of the
commonly employed nonaqueous solvents. Some of the commonly used solvents for
redox determination are given below.

Acetic acid: It has a low dielectric constant, is difficult to purify and is not convenient
to handle. That is, it fails to meet the criteria mentioned in the previous subsection.
Yet, it has been more widely used as an analytical medium than any other solvent; this
probably is because of its availability at low cost and its history of analytical use as
solvent for acid-base titrations. The most common oxidation-reduction titrant used in
this solvent is lead (IV) acetate. The oxidations by lead (IV) acetate are slow and
require the presence of an acid or base during the titration to increase the rate of the
reaction. Perchloric acid and Sodium acetate (strong base in acetic acid) have been
found satisfactory for this purpose. These compounds help in the formation of ionic
species in acetic acid, which are able to undergo rapid reactions.

Acetonitrile: It is a versatile solvent for a large number of interesting analytical

electron transfer reactions. The reasons for its popularity include a convenient liquid
range, ready availability (as a by product of acrylonitrile synthesis), wide
electrochemical range, moderate dielectric constant and low toxicity. However, it has
the disadvantage of being difficult to purify and has a tendency to polymerise in the
presence of acids and bases. It is a powerful solvent for a wide range of organic
compounds and a number of inorganic salts, though it solvates anions of low

22
polarisability relatively poorly with the result that many anionic metal chlorides for Redox Titrations
example, are slightly soluble. On the other hand, salts with higher polarisable anions
such as iodide and thiocyanate, and predominantly covalent chlorides such as zinc
chloride typically are quite soluble. The purification of acetonitrile is difficult and
time consuming. The available potential range in acetonitrile extends from about
+ 2.2 V to – 3.1 V versus Ag/Ag+ (0.01 M) as reference couple.

Dimethylformamide: It is a solvent for which only a few applications as an analytical

redox solvent have been reported but is of considerable promise. It has a dielectric
constant close to that of acetonitrile, nitromethane and dimethyl acetamide. It
dissolves many organic and inorganic compounds, has a wide liquid range and is
thermally stable. In addition, it is readily available; and it has low toxicity upon
inhalation or on contact with skin. The useful electrochemical range extends past – 2.5
V versus the aqueous saturated calomel electrode, making it useful for a variety of
studies. However, susceptibility to oxidation limits its utility in the anodic direction.
The calomel electrode is not stable in this solvent and an aqueous saturated calomel
electrode with a suitable bridge or a silver-silver ion electrode is the best choice in
electrochemical work. Purification of dimethylformamide is however fairly
straightforward.

Dimethylsulphoxide: It has received considerable attention as an electrochemical

solvent and has some promise for homogenous analytical oxidations/reductions. Its
excellent solvent properties for organic compounds and ability to act as a mild oxidant
in conjunction with a number of reagents have made it of interest recently in organic
synthesis. It is also a good solvent for many organic compounds and has a potential
range of over 4.0 V. Dimethylsulphoxide, though not very toxic, still careful handling
of toxic substances in conjunction with this solvent is desirable.

Many other solvents such as acetone, lower aliphatic alcohols tetrahydrofuran,

dioxane, morpholine, nitromethane and nitrobenzene have been used in nonaqueous
redox titrimetry, but they only find limited applications.

SAQ 5
Enlist the conditions under which it becomes pertinent to use nonaqueous medium for
the titrimetric determination of oxidising/reducing agents.

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10.7 APPLICATIONS OF REDOX TITRATIONS

Having learnt about the basics aspects of redox reaction, the parameter characterising
these reactions and their determination, the meaning and significance of redox
titration, we are now equipped to learn about the applications of redox titrations. Let
us learn about some common oxidimetric and reductimetric applications of redox
titrations. In oxidimetric titrations the oxidising agents are used to determine the
reducing and while is reductimetric agents are employed for the determination of
oxidising agents.

23
Estimations Based on 10.7.1 Oxidimetric Reagents
Redox and
Complexation
Equilibria Studies i) Potassium permanganate
Potassium permanganate is a powerful and versatile oxidising agent as it can be
used in acidic, neutral or alkaline medium. It has specific applications in
different media. In acidic medium, KMNO4 is a strong oxidising agent as it
gets reduced to Mn2+ ions as per the following reaction.
MnO −4 + 8H + + 5e → Mn 2 + + 4H 2 O E 0 = 1.51V
In neutral medium potassium permanganate is reduced to manganese dioxide
and again acts as an oxidising agent.
MnO −4 + 4H + + 3e → MnO 2 + 2H 2 O E 0 = 1.68 V
On the other hand in strongly alkaline medium, the oxidising property of
permanganate is attributed to its reduction to mangnate ion.
MnO −4 + e → MnO 24- E o = 0.67 V

In typical determination of reducing agents using KMnO4, a standard solution of

KMnO4 is prepared by dissolving a slightly more than the calculated amount in
required volume of water, boiling for half an hour or so and filtering off the
precipitated MnO2. The solution so obtained is then standardised against sodium
oxalate (a primary standard). KMnO4 not being a primary standard is a big
disadvantage. Besides, while preparing, its solution needs to be filtered off
MnO2 after prolonged period of storage also. More so its solution needs to be
stored in dark so as to check formation of MnO2 catalysed by light. The
standardization of KMnO4 by oxalic acid can be represented by the following
equation,
5C2 O 24 − + 2MnO −4 + 16H + → 10CO2 + 2Mn 2 + + 8H 2 O
The oxidation of oxalate with permanganate at room temperature is slow and
hence heating is required. The end point is marked by pink colour imparted to
the solution by the first drop of oxidant added in excess. In this way KMnO4
acts as a self indicator. This property of KMnO4 is an added advantage. The
oxidant is commonly used for the analysis of iron(II), As(III), H2O2 and NO −2
ion, the corresponding equations being as follows.
5Fe2 + + MnO −4 + 8H + → 5Fe3 + + Mn 2 + + 4H 2 O

5As 2 O3 + 4MnO −4 + 12H + → 5As 2 O5 + 4Mn 2 + + 6H 2 O

5H 2O 2 + 2 MnO −4 + 6H + → 5O 2 + 2Mn 2 + + 8H 2 O

5NO-2 + 2 MnO −4 + 6H + → 5NO-3 + 2 Mn 2 + + 3H 2O

It is important to mention that a difficulty arises when iron (II) is titrated with
permanganate in the presence of hydrochloric acid. High results are obtained
due to the oxidation of chloride ions by the oxidant.
2MnO −4 + 10Cl − + 16H + → 5Mn 2 + + 5Cl 2 + 8H 2 O
This reaction which normally does not occur rapidly enough to cause serious
error, is induced by the presence of iron (II). Its effect can be avoided by
preliminary removal of chloride. In alkaline medium, permanganate easily
oxidises iodides, cyanides, thiocyanates and many organic substances.

24
ii) Cerium (IV) salts Redox Titrations
Cerium (IV) sulphate is a powerful oxidising agent in acidic medium.
Ce 4+ + e → Ce 3+
The E0 values are 1.70 V in HClO4 ; 1.60 V in HNO3 and 1.42 V in H2SO4
solutions. Ceric sulphate is a primary standard and solutions are remarkably
stable. It can be stored almost indefinitely and may be employed in the
determination of reducing agents in the presence of high concentrations of
hydrochloric acid, in contrast to potassium permanganate. The reagent has an
intense yellow colour and if the solutions are not too dilute, the end point may
be detected without an indicator. However, it is not used as a self indicator and
it is preferable to use a suitable indicator such as ferroin, N-phenylanthranilic
acid or 5,6- dimethylferroin. Cerium(IV) solutions are standardised with
arsenic(III) oxide or with sodium oxalate solution. Cerium(IV) solution may be
prepared by dissolving Cerium(IV) sulphate but usually ammonium
hexanitratocerate (NH4)2 [Ce(NO3)6] is used for this purpose.

iii) Potassium dichromate

It is a strong oxidant in acidic medium; the reduction equation being the
following.
2-
Cr2O7 + 14H+ + 6e 2Cr3+ + 7H2O ; Eo = 1.33 V

Potassium dichromate is a primary standard and is obtainable in a high state of

purity. Its standard solution can, therefore, be prepared by direct weighing. The
end point in titrations with dichromate ion is generally detected by using
suitable redox indicators such as diphenylamine, sodium diphenylamine-
sulphonate and N-phenylanthranilic acid, etc.

Although, potassium dichromate is a weaker oxidising agent than KMnO4, it

can be used in acidic medium to determine most compounds that can be titrated
with KMnO4 . Potassium dichromate possesses an advantage over permanganate
that it does not oxidise chloride ion and consequently can be used to determine
iron(II) in hydrochloric acid medium.
6Fe2 + + Cr2 O27 − + 14H + → 2Cr 3 + + 6Fe3 + + 7H 2O
The determination of Fe(II) is probably the most important application of
K2Cr2O7.

iv) Potassium bromate

It is also a strong oxidant in acidic medium.
-
BrO3 + 6H+ + 6e Br - + 3H2O ; E 0 = 1.44 V

Potassium bromate is a primary standard as the reagent can be obtained in a

pure state. Its standard solution can be prepared by direct weighing. The end
point in titrations with bromate is indicated by the yellowish colour due to
bromine released from the slight excess of reagent added.
-
BrO3- + 6H+ + 5Br 3Br2- + 3H2O

The end point may also be detected by irreversible bleaching of azo indicators
such as methyl orange, methyl red etc. by bromine. The reagent is used in
hydrochloric acid for the direct determination of arsenic(III), antimony(III),
tin(II), hydrazine, etc.

25
Estimations Based on
Redox and 3As3+ (Sb3+ ) + BrO3− + 6H + → 3As5+ (Sb5 + ) + Br − + 3H2O
Complexation
Equilibria Studies 3Sn 2 + + BrO3− + 6H + → 3Sn 4 + + Br − + 3H 2O

3N 2H 4 + 2BrO3− → 3N 2 + 2Br − + 6H 2O
There are many compounds, which do not react with bromate as such but with
bromine liberated from reaction between bromate and bromide, and to
accomplish this, an excess of bromide is added to the solution. Bromine thus
liberated is used for quantitatively saturating the double bond and in substitution
reactions.

C C Br
+ Br2
C Br C

OH OH
Br Br

+ 3 Br2 + 3 HBr

Br
The above reactions are used in the determination of unsaturated organic
compounds, phenols, aniline, salicylic acid, etc. Particular mention may
however be made of the substitution reaction with 8-hydroxyquinoline (oxine)
for the indirect determination of various metals. The metal is precipitated as
sparingly soluble oxinate, which is filtered off and heated with potassium
bromate and bromide, resulting in the bromination of oxine.

OH OH
N N Br

+ 2 Br2
+ 2 HBr

Br

The unreacted bromine is determined by adding a solution of potassium iodide

and titrating the liberated iodine with thiosulphate.

v) Potassium iodate
The compound is available in a high state of purity and consequently serves as a
primary standard as its standard solution can be prepared by direct weighing.
The reaction of iodate with iodide is analogous to bromate-bromide reaction.
This reaction is very useful for the generation of known amount of iodine.
IO3− + 5l− + 6H + → 3l2 + 3H 2O
In hydrochloric acid solutions (3-6 M), the reduction of iodate occurs to iodine
monochloride and it is under these conditions that it finds its maximum use.

IO3- + 6H+ + CI - + 4e ICI + 3H2O

26
 Oxidation of iodate in strong hydrochloric acid medium infact proceeds through Redox Titrations
the following stages.

IO 3- + 6H+ + 6e I - + 3H2O

IO3- + 5I - + 6H+ 3I2 + 3H2O

IO3- + 2I2 + 6H+ 5I+ + 3H2O

Free iodine is liberated in the initial stages but as more iodate is added, iodine is
oxidised to iodine monochloride and the dark colour (due to iodine) of the
solution gradually disappears. The reaction has been used for the determination
of many reducing agents. Starch cannot be used as an indicator as the blue
starch-iodine complex is not formed at high concentration of the acid. Carbon
tetrachloride or chloroform is added to the solution being titrated in a glass
stopperred conical flask. The end point is marked by the disappearance of the
last trace of violet colour (due to iodine) from the organic solvent. The method
suffers from the drawback that vigorous shaking is required after addition of
each instalment of the oxidant.

vi) Iodine
The I2/2I‒ couple is of medium oxidising power. Whereas iodine is a
weak oxidant, iodide is a relatively weak reductant. Hence, the I2/I– redox
couple can be used for the determination of both reductant as well as oxidants.

I2 + 2e 2I - E 0 = 0.54

I2 + red 2I - + Ox

If the couple to be determined has a standard potential lower than 0.54 V, the
reaction would proceed to the right (or iodine would oxidise the reduced form of
the compound). In case the couple to be determined has a potential higher than
0.54 V, the reaction would proceed to the left (or iodide will be oxidised by the
oxidised form of the couple).

Iodine is sparingly soluble in water and its aqueous solution is prepared by

adding potassium iodide. Though in such a solution, iodine is in the form of a
tri-iodide ion I3- , but for sake of simplicity, iodine is usually expressed as I2 in
its reactions.

I2 + 2l - 2I3-

Iodine solutions are standardised by means of arsenous oxide (a primary

standard) or sodium thiosulphate (to be standardized first). Starch is generally
used as an indicator; the solution turns blue at the end point.

Among the substances which can be titrated directly with a standard iodine
solution are hydrogen sulphide, stannous, arsenite and sulphurous acid.
I2 + H2S S + 2I- + 2H+

Sn2+ + I2 Sn4+ + 2I-

H3AsO3 + I2 + H2O H3AsO4 + 2I- + 2H+

27
Estimations Based on
Redox and H2SO3 + I2 + H2O SO2-4 + 2I- + 4H+
Complexation
Equilibria Studies Many oxidants are capable of converting iodide quantitatively to free iodine
which can be titrated with a standard solution of sodium thiosulphate.

Ox + I - I2 + Red

I2 + 2S2O2-
3
2-
2I- + S4O6

The end point can be detected by adding starch. The blue colour disappears at
the end point. In this manner, potassium iodide can be used for the
determination of copper (II), MnO2, Cl2, Br2, BrO 3− , Cr2 O 72− , etc.

2 Cu2+ + 4I‒
I2 + 2CuI

MnO2 + 4I‒ + 4H+
Mn2+ + 2I2 + 2H2O

Cl2 (or Br2) + 2I‒
I2 + 2Cl‒ (or 2 Br − )

BrO 3− + 6I‒ + 6H+
3I2 + Br − + 3H2O

Cr2 O 72− + 6I‒ + 14H+
3I2 + 3Cr3+ + 7H2O

The method in which iodine is used for the determination of reductants is called
iodimetry. The method in which iodide is used for the determination of
oxidants is called iodometry.

10.7.2 Reductimetric Reagents

Standard solutions of reducing agents are not used as widely as oxidising agents,
because most of them are oxidised by dissolved and atmospheric oxygen. They are,
therefore, less convenient to prepare and use. Thiosulphate is the only common
reducing agent that is stable to air oxidation and can be kept for long periods of time.
This is the reason that Iodometric titrations are so popular for determining oxidising
agents. However, stronger reducing agents than iodide are sometimes required.

i) Iron
It is a weak reductant. Iron(II) is slowly oxidised by air in sulphuric acid
solution and finds common use.

Fe3+ + e Fe2+ E 0 = 0.77 V

Its standard solution is prepared from Mohr’s salt FeSO4. (NH4)2SO4.6H2O and
standardised against primary standard K2Cr2O7, or by titration with a
standardised KMnO4 or cerium(IV) solution. The end point in titrations
involving iron(II) is detected by using redox indicators such as ferroin, N-
phenyl anthranilic acid etc. In the presence of concentrated sulphuric acid at
0oC, iron(II) is used for the determination of nitrates, nitro compounds,
indophenols, etc.

ii) Chromium (II) and Titanium(III)

These two are very powerful reducing agents, but they are readily oxidised by
air and consequently are difficult to handle. The reduction equations and the
standard potential are as follows.

28
 Cr 3+ + e → Cr 2+ E0 = – 0.41 V Redox Titrations

TiO 22+ + 2H + + e → Ti 3+ + H 2 O E0 = 0.04 V

Chromium (II) has been used for the titrations of oxidised forms of copper, iron,
silver, gold, bismuth, uranium, tungsten, etc. Titanium (III) has, however, been
used for the titrations of iron(III), copper(II), tin(IV), chromate, vandate and
chlorate.

SAQ 6
Iodine can be used for the determination of oxidising as well as reducing agents.
Illustrate with the help of examples.

…………………………………………………………………………………………...
…………………………………………………………………………………………...

10.8 SUMMARY
Chemical reactions involving oxidation-reduction are widely used in volumetric
analysis. Redox reactions are also called electron transfer reactions since oxidation
proceeds with loss of electrons while reduction is accompanied by gain of electrons
and both the processes must occur together and must compensate for each other. The
separation of redox reactions into its components i.e. half-reactions, is a suitable way
of indicating species that gains electrons and the one that looses electrons.

Oxidising and reducing agents may differ among themselves in strengths. For
obtaining comparative values of their strengths, it is essential to measure under
standard experimental conditions, the potential difference between the platinum and
their solutions relative to a standard of reference. The reference electrode is the
standard hydrogen electrode and its potential is taken as zero. The standard
experimental conditions for redox systems are those in which the ratio of the activity
(or the molar concentration) of the oxidant to that of the reductant is unity.

An understanding of the oxidising and reducing tendency of a substance can be

obtained from an electrochemical cell, which develops an electrical potential from the
tendency of the reacting species (to transfer electrons) and thereby approach the
condition of equilibrium. The voltage produced by an electrochemical cell is directly
related to the equilibrium constant for the particular oxidation- reduction process
involved as well as the extent to which the existing concentration of the participants
differ from their equilibrium values. Measurement of such potential, in fact constitutes
an important source of numerical values for equilibrium constants for redox reactions.
The electrode potential which is a measure of the chemical driving force of a half-
reaction is affected by the concentration. The dependence of the redox potential of a
system on the ion concentration of the reduced and oxidised forms is expressed by the
Nernst equation.

As regards the suitability of a redox reaction to volumetric analysis, it is desirable that

the equilibrium is reached very rapidly following each addition of the titrant and the
indicator is available for locating the end-point with reasonable accuracy. The
equilibrium constant of a redox reaction which provides information regarding the
direction and extent of the reaction, can be derived by the application of the Nernst
equation with the standard potential data serving as a guide.

The redox indicators are used to determine the end point in a redox titration. These are
the substances which undergo redox reactions and their oxidised and reduced forms
differ in colour from each other. The colour-changes of redox indicators can be

29
Estimations Based on calculated theoretically on the basis of its standard potential values. A good redox
Redox and indicator should have a sharp colour change, preferably reversible, at the equivalence
Complexation
point. Hence it is extremely important to examine the changes in the potential that
Equilibria Studies
occur in the course of a redox titration and pay particular attention to those changes
that are more pronounced in the region of the equivalence point. In brief, the potential
of the redox system at the equivalence point is of a particular importance from the
standpoint of indicator selection.

The scope of the redox reactions can be extended by using organic solvents as media
of titration in place of water. Redox titrimetry in nonaqueous media has a wide scope
for the determination of compounds which are (i) insoluble in water, or (ii) react with
water through hydrolysis or oxidation, or (iii) are decomposed by the media i.e. acids,
bases, etc. of aqueous redox reactions.

Potassium permanganate, cerium(IV), potassium dichromate, potassium bromate,

potassium iodate and iodine are commonly used oxidimetric agents. These are used to
determine the oxidising agents on the other hand iodide, iron (II), chromium(II) and
titanium(III)) are commonly used agents for determining the reducing agents that is
theses are reductimetric agents.

10.9 TERMINAL QUESTIONS

1. Describe overall redox reaction and then half- reactions involved when a piece
of copper metal is placed in a solution of silver ion and the copper is coated
with metallic silver and the solution acquires a characteristic blue colour.

2. A solution is 10 −3 M in Cr2 O 72− and 10 −2 M in Cr3+. If the pH is 2.0, what is the

potential of the half reaction? You may consult Table 10. 1 for the reaction
involved.

3. Calculate the potential for a platinum electrode immersed in a solution that is

10 −2 M in KBr and 10 −3 M in Br2. the electrode reaction is as follows.

Br2 (aq) + 2e 2Br - E 0 = 1.087 V

4.

5. Calculate the redox potential of Sn4+, Sn2+ system, if the Sn 4+ ion concentration
is 0.1 g ion/dm3 and the Sn2+ ion concentration is 0.0001 g ion/dm3.

6. Consult Table 10.1 on the standard reduction potentials for the following
substances and list the oxidising agents in the decreasing order of oxidising
capability and reducing agents in the decreasing order of reducing capability.
MnO −4 , Ce3+, Cr3+, IO −3 , Fe3+, I‒, H+, Zn2+.

7. Calculate the equilibrium constant for the reaction:

-
MnO4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O

Given :
E0 2+
= 1.52 V
MnO −
4 /Mn

E0 = 0.77 V
Fe3+ / Fe2 +

8. Calculate the potential at the equivalence point in the titration of tin(II) with
cerium(IV):

30
 Sn2+ + 2Ce4+ Sn4+ 2Ce2+ Redox Titrations

Given:
0
E Sn 4+
/Sn 2 +
= 0.15 V
E 0Ce 4 + / Ce3+ = 1.44 V

9. A solution of Fe2+ is titrated with an oxidising agent. Calculate the potential of

the Fe3+, Fe2+ couple when the following percentages of Fe2+ have been
oxidised.

a) 10% (b) 25% (c) 33% (d) 50% (e) 99% (f) 99.9%
Given:
E0 Fe 3 + / Fe 2 +
= 0.77 V

10.10 ANSWERS

Self Assessment Questions

1. The reduction potential for Fe (III) is more positive as compared to that of Cr
(III) which means that Fe (III) is easier to be reduced than Cr (III). This in turn
means that Cr (II) would be easier to be oxidised.

2. From Table 10.1 the reduction of MnO4 – to Mn2+ is given by the following
equation
-
MnO4 + 8H+ + 5e Mn2+ + 4H2O EO = 1.52 V

The Nernst equation would be

0.059 [Mn 2 + ]
E cell = E (θcell) − log
5 [ MnO −4 ][ H + ]8

As the pH is 1.00, the concentration of H+ ions would be 1 × 10–1

Substituting the values in the equation

0.059 [0.100]
E cell = 1.52 − log = 1.43V
5 [0.100][0.1]8

E1 + E 2
3. The potential at the equivalence point is given as and it does not
2
depend on the concentration of the reactants. Therefore the potential would be
1.10 V.

4. As the potential range of the colour change for a redox indicator is given as,
0
E ox / red ± 0.059/n V; where, n is the number of electrons involved in the
indicator redox reaction. As only one electron is involved in the redox reaction
of the given indicator, the potential range would be
0.1 ± 0.059/n = 0.1 ± 0.059/1 = 0.1± 0.059 = 1.18 to 1.25

the indicator range would be 1.18 – 1.25 V

31
Estimations Based on 5. It is advisable to use nonaqueous medium of titration for the determination of
Redox and compounds which
Complexation
Equilibria Studies i) are insoluble in water.
ii) react with water through hydrolysis or oxidation.
iii) are decomposed by the medium of aqueous redox titrations i.e., acids,
bases, etc.

6. The I2 /2I– couple is of medium oxidising power. Therefore, iodine acts a weak
oxidant and gets reduced to I– ions. This can be used for the determination of
weak reducing agents. For example,

Sn2+ + I2
Sn4+ + 2I‒

The method in which iodine is used for the determination of reductants is

called iodimetry. Similarly, I– ions can get oxidised to I2 and can be used for
the determination of weak oxidising agents. In such cases, the determination is
performed indirectly. The oxidants quantitatively convert iodide ions to free
iodine which is then titrated with a standard solution of sodium thiosulphate.
For example,

2 Cu2+ + 4 I‒
I2 + 2 CuI

I 2 + 2S2 O 32 −
2I + S 4 O 62 −

The method in which iodide is used for the determination of oxidants is called
iodometry.

Terminal Questions
1. The overall reaction would be as follows.
Cu(s) + 2Ag + (aq) → Cu 2 + (aq.) + Ag(s)
While the half reactions would be as follows.
Cu(s) → Cu 2 + (aq) + 2e
2 Ag + (aq) + 2e → 2 Ag (s)

2. 1.06 V

3. 1.117 V

4. 0.24 V

5. The decreasing order of the oxidising capability of the oxidising agents

is: MnO −4 , IO 3− , Fe3+, H+, Zn2+.
The decreasing order of the reducing capability of the reducing agents is as
follows.
I‒, Cr3+, Ce3+

6. K = 3 × 1063

7. E = 0.5 8 V

8. (a) 0.71 V (b) 0.74 V (c) 0.75 V (d) 0.77 V (e) 0.89 V (f) 0.95 V

32