INORGANIC CHEMISTRY (LAB MANUAL)

REDOX TITRATIONS

Titrations involving oxidizing and reducing agents are termed as oxidation-

reduction or redox titrations.

The phenomenon of oxidation and reduction plays an important role in our

day-to-day life. For example, digestion of food in our body, the fading of the
colour of our clothes, the rusting of iron and the functioning of a battery
involve oxidation reactions. Many of the industrial processes like extraction of
metals are based on reduction process.

A reducing agent is an electron donor

Fe2  Fe3  e

An oxidizing agent is an electron acceptor


Cl2  2e-  2Cl

The oxidation-reduction reaction is


Cl2  2Fe2+  2Fe3+  2Cl

Such electron transfer reactions are commonly called oxidation-reduction or


redox reactions. These reactions involve change in oxidation state or
transfer of electrons among reacting substances. The electrons are
transferred from a reducing agent to an oxidizing agent. The reducing agents
are generally sodium oxalate, ferrous sulphate, ferrous ammonium sulphate,
oxalic acid etc. The commonly employed oxidizing agents are acidified
potassium permanganate, acidified potassium dichromate, iodine solutions
etc.

Different types of redox titrations are named on the basis of

oxidizing/reducing agents involved. Redox titrations involving KMnO4 and
K2Cr2O7 are referred to as PERMANGANATOMETRY and CHROMATOMETRY
respectively. Other types of redox titrations using KI (Source of I2) or Iodine
directly are called IODOMETRY and IODIMETRY respectively.

Oxidation-Reduction : Redox Potential

Strength of an oxidizing agent or reducing agent is expressed in terms of
Normal or Standard potential.

oxidising agent (Oxidant) + ne- reducing agent (reductant)

OR
ox + ne- red

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For such a system, the Nernst equation takes the form

2.303RT [ox]
E  EO  log10
nF [red]

Where E is the formal potential at the specified concentration, n is the

number of electrons involved in the half reaction, R is a gas constant (8.314

J mol-1 K-1) T is the absolute temperature and F is the Faraday constant
(96,500 C)
E O is the standard electrode potential and is characteristic of a particular
system.
RT
At 25°C, (2.303 ) = 0.05915
F
 0.05915 [ox]
 E  EO  log
n [red]


The solution potential can be calculated if we know the concentrations of the


two forms, i.e. [ox] and [red]. Also, knowing the chemical reaction involved
and the potential of the solution, we can use Nernst equation to evaluate the
relative concentrations of oxidized and reduced forms.

Some of the redox systems with their standard reduction potentials are given
in the following table 2.1.

Table 2.1 Standard reduction potentials of some redox systems.

Oxidized form Reduced form E O (Volts)

MnO4- Mn2+ 1.51
Cr2O72- Cr3+ 1.33
Fe3+ Fe2+  0.76
Sn4+ Sn2+
0.15

Table 2.1 indicates that MnO4- is the strongest oxidizing agent and Sn4+ is the
weakest one among those listed above.

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Titration Curves

According to Nernst equation,

0.05915 [ox]
E  EO  log
n [red]

The potential of a given reaction depends upon the relative concentrations of

oxidized/reduced forms. In the course of a redox titration, the solution

potential also changes, since the concentration of oxidized and reduced forms
goes on changing. At the completion of a reaction i.e., when either of the
forms gets exhausted, there is a sharp change in potential. Using the Nernst
equation, it is possible to calculate theoretically variation of potential during
the course of titration, which is called redox titration curve. A representative
redox titration curve for the titration of iron (II) ammonium sulfate solution
with 0.02 M potassium permanganate solution is shown in figure 1.

Figure 1. Titration of a iron (II) ammonium sulfate solution with 0.02

M potassium permanganate solution

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Redox titrations can also be followed by measuring the potential of the
solution with the help of a potentiometer.

Redox Indicators

In the redox titrations, we need a chemical species that can change colour in
the potential range corresponding to the sharp change at the end point. A
chemical substance, which changes colour when the potential of the solution
reaches a definite value, is termed as an oxidation-reduction or redox
indicator. It is necessary, while choosing a redox indicator for a particular
titration to ensure that its redox potential lies within that of the system.

Inox + ne- Inred

colour A colour B

A redox indicator may be defined as a substance whose oxidized form is of

different colour from that of its reduced form. The oxidation and reduction of
the indicator is readily reversible.

Indicators used in redox titrations are of three types:

i) Self-Indicating: In permanganatometric titrations, one of the

reacting species (KMnO4) changes colour at the end point and is
called self-indicator.
ii) External-Indicators: These indicators are not added internally to
the reaction medium but are used externally in the form of small
droplets on a white tile. For example, potassium ferricyanide,
[K3Fe(CN)6] is used as an external indicator in the chromatometry.
However, the method of using external indicator has become
obsolete as it introduces errors in quantitative volumetric analysis.
It was employed when no suitable internal indicators were available
for redox titrations.
iii) Internal-Indicators: Internal indicators are the substances which
are added to the titration flask in which titration is carried out. In
case of chromatometry, the indicator such as 1% diphenylamine
needs to be added to the titrating mixture. Such indicators are
called internal indicators.

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Chromatometry

In chromatometry, acidified potassium dichromate is used as an oxidizing

agent to estimate ferrous (Fe2+) ions in the given solution. Potassium
dichromate is not so powerful an oxidizing agent as potassium permanganate
but it has the following advantages over the permanganate.

i) potassium dichromate is a stable salt and is available in pure

state and thus serves as an excellent primary standard.
ii) Unlike KMnO4, it does not oxidize HCl to chlorine gas and
thus, the titration can be carried out in the presence of
hydrochloric acid also.
iii) it does not attack organic compounds and rubber.

However, potassium dichromate acts as an oxidizing agent only in the acidic

medium, while potassium permanganate can act as an oxidizing agent both
in acidic and alkaline media. Also, KMnO4 acts as a self indicator while a
redox indicator is necessarily used in chromatometry, since the orange
coloured dichromate ions, Cr(VI), are converted to the green coloured
chromium ions,Cr(III). The green colour of chromium (III) ions produced
makes it difficult to find the end point without the use of redox indicator.

2
Cr2O7  14H+  6e  2Cr3+  7H2O (E O = 1.33 V)
(Cr in +6 state) (Cr in +3 state)

[Fe2+  Fe3+ + e-]6 (EO = 0.77 V)


----------------------------------------------------------------------
2
Cr2O7  6Fe 2 14H+ 2Cr3+  6Fe 3 +7H2O
----------------------------------------------------------------------

Since one mole of dichromate ions react with six moles of Fe2+ ions in

solution, the molarities can be expressed by the following equation.

Amount of K2C r2O7

Stoichiometric ratio =
Amount of Fe2+

MFe2  VFe2   6M 2 V 2

Cr2O7 Cr2O7

Thus each mol of potassium dichromate reacts quantitatively with six mol of
iron (II).


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Indicators and the end point detection

The titrations involving dichromate can be carried out by using either an

internal or external indicator.

i) External indicator
The external indicator is one, which is not added directly into the
solution to be titrated but made to react with the reaction mixture
separately to locate the end point. 0.1% solution of potassium
ferricyanide acts as an external indicator in the oxidation of ferrous
to ferric.

Ferrous ions react with potassium ferricyanide to produce a deep

blue colour (Turnbull’s blue) of ferro-ferricyanide as follows:

3Fe2+ + 2[Fe(CN)6]3-  Fe3[Fe(CN)6]2

blue complex
(Turnbull’s blue)
Potassium ferricyanide does not give any colour with ferric salts.

Potassium ferricyanide cannot be used as internal indicator (cannot

be added to the titration mixture) because it will react with ferrous
ions to give a blue complex and the colour formation is irreversible.
Freshly prepared potassium ferricyanide is used by placing a
number of small drops on a dry groove tile (or place a series of
drops of the indicator on a glazed tile).

Withdraw a drop of titration mixture near the end point and bring
the same in contact with the indicator on the tile. As long as the
ferrous ions are present in the reaction mixture, a blue colour will
be produced on mixing a drop of the titration mixture with the
indicator drop. When all the ferrous ions have been converted into
ferric ions, a drop of the reaction mixture will not produce any blue
colour. The disappearance of any blue colour indicates the end
point.

ii) Internal indicator

The most commonly used internal indicators in chromatometry are:

a) 1% solution of diphenylamine in conc. H2SO4 (chemically pure).

b) 0.2% aqueous solution of sodium diphenylamine sulphonate.
c) N-Phenylanthranilic acid.

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A redox indicator exhibits two different characteristic colours in

oxidized and reduced forms. The diphenylamine indicator is
suitable when the potential of the solution is 0.73 to 0.79 V. At
potentials below this range, the reduced form, i.e., the
diphenylamine form is more predominant and the solution,
therefore, is colourless. On the other hand, at a solution potential
0.79 V, the oxidized form diphenyl benzidine violet is predominant
and the solution appears blue violet and marks the end point. When
Fe2+ ions get converted to Fe3+ ions, the potential increases
gradually. At equivalence point, all the ferrous ions are oxidized
and there is a sudden jump in the potential. This increase in the
redox potential of the solution is sufficient to cause the oxidation of
the indicator.

2 N

diphenylamine

ox

H H
+
N N + 2H + 2e

diphenylbenzidine (colourless)

+
N N + 2H + 2e

diphenylbenzidine (violet)

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Ferric ions, which are generated during the course of reaction,

might prematurely oxidize the indicator. Therefore, the liberated
ferric ions need to be removed from sphere of action i.e., the
premature oxidation of the indicator is avoided by masking ferric
ions with syrupy phosphoric acid. H3PO4 forms an undissociated
ferric hydrogen phosphate complex [Fe(HPO4)]+ results in lowering
the potential of ferric-ferrous system. As a result, we get a sharp
change in the colour at the end-point.

When N-phenylanthranilic acid is used as an indicator for

dichromate titrations, there is no need to add phosphoric acid as
the premature oxidation of the indicator does not occur. At the end
point, the colour changes from green to violet red i.e., oxidized
form of this indicator is violet-red (purple-red) and reduced form is
colourless.

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EXPERIMENT 4

AIM

To determine the strength of given ferrous ammonium sulphate

(Mohr’s salt) solution by titrating it with potassium dichromate
solution (≈M/40), using 1% Diphenylamine as an internal indicator.
Prepare a standard solution of Mohr’s salt.

Learning Objectives

 Preparation of standard ferrous ammonium sulphate solution.

 Standardization of K2Cr2O7 solution
 Finding the molarity of ferrous ammonium sulphate solution
(unknown).
 Application of chromatometry.

Requirements

Apparatus
Chemicals
Burette (50 cm3)----------1 Ferrous ammonium sulphate
FeSO4.(NH4)2SO4.6H2O
Pipette (10 cm3)----------1
Sulphuric acid (1M)
3
Conical flasks (250 cm )----------2
Phosphoric acid (85%)
Standard Volumetric flask ----------1
(100 cm3) Potassium dichromate solution
(≈M/40)
Wash bottle for distilled water ------1
1% solution of diphenylamine
Weighing bottle -----------1

Burette stand -----------------1

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Theory
2
Cr2O7  14H+  6e  2Cr3+  7H2O (E O = 1.33 V)
(Cr in +6 state) (Cr in +3 state)

[Fe2+  Fe3+ + e-]6 (EO = 0.77 V)


----------------------------------------------------------------------
2
Cr2O7  6Fe 2 14H+ 2Cr3+  6Fe 3 +7H2O
----------------------------------------------------------------------

M1V1  6M2V2

where M1 and M2 represent the molarities of ferrous and potassium
dichromate solutions and V1 and V2 represent their volumes, respectively.

Procedure

a) Preparation of standard ferrous ammonium sulphate solution

(known solution)

 Transfer a known weight of Mohr’s salt (by indirect method) into

a 100 cm3 standard volumetric flask.
 Add a test tube of dilute sulphuric acid to the volumetric flask to
prevent hydrolysis of the Fe2+ ions.
 Dissolve the Mohr’s salt in distilled water and make up the
volume of solution carefully with distilled water.
 Make the solution homogeneous. Invert the flask, six to ten
times, to mix thoroughly.

b) Standardization of K2Cr2O7 solution

 Wash the burette with tap water, rinse with distilled water and
then with K2Cr2O7 solution.
 Fill up the burette with the given K2Cr2O7 solution and mount the
burette on a stand.
 Remove the air bubble, if any, from the nozzle of the burette
and note the initial reading of the burette and record it in the
observation Table I.
 Pipette out 10.0 cm3 of standard solution of Mohr’s salt into a
clean 250 cm3 titrating flask.
 Add one test tube (10-15 cm3) of dil. H2SO4 (1M) to the solution
in the titration flask.
 And then add half test tube of syrupy phosphoric acid (or one
test tube of 1:1 mixture of dil. H2SO4 - phosphoric acid).

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 And finally add 6-8 drops of 1% diphenylamine indicator to the
titration mixture and place the titration flask over a glazed tile.
 Run in K2Cr2O7 solution slowly (0.5 cm3 at a time) from the
burette, while giving a swirling motion to the titration flask.
(Hold the stop-cock of the burette by left hand and the conical
flask by right hand.)
 Continue the addition of K2Cr2O7 solution until a persistent
violent colour is obtained.
 Note the final reading of the burette and record it in Table I.
 The difference between the two readings of burette gives the
volume of Cr2O72- required to completely oxidize 10.0 cm3 of
Fe2+ ions.
 Repeat the titrations to get at least two concordant readings.
 Record all the readings in Table I.

c) Finding the molarity of the given Mohr’s salt solution

(unknown)

 Repeat the above procedure of titration with the given Mohr’s

salt solution.
 Record all the readings in Table II.

Observations and Calculations

a) Preparation of standard ferrous ammonium sulphate solution

Mass of the weighing bottle + ferrous ammonium sulphate = m1

=……….g

Mass of weighing bottle after transference = m2 =……….g

 Mass of ferrous ammonium sulphate transferred into 100 cm3

standard volumetric flask = (m2 - m1)
=m
= ……….g

Molar mass of ferrous ammonium sulphate = 392.15 g mol-1

Molarity of ferrous ammonium sulphate solution (M1)

 mass 1000  3
=    mol dm
molar mass V(in cm )
3

 m 1000  3
=    mol dm
392.15 100 cm 
3


= ……………… mol dm3
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b) Standardization of K2Cr2O7 solution

Table-I

Standard ferrous ammonium sulphate Vs potassium dichromate

solution

Volume of Burette Readings

standard
Volume of
S. Mohr’s salt
K2Cr2O7
No. solution Initial Final
used (cm3)
pipetted
(cm3)

1 10.0

2 10.0

3 10.0

Molarity of standard Mohr’s salt solution = M1

=………. mol dm-3
Volume of standard Mohr’s salt solution pipetted = V1 = 10.0 cm3
Volume of K2Cr2O7 solution used = V2 = ………cm3
(From Table – I)
Molarity of K2Cr2O7 solution = M2 = ?
Using Molarity equation,
M1V1  6M2V2
MV
Molarity of dichromate solution, M2 = 1 1 = ……….mol dm-3
6V2




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c) Finding the molarity of given solution of ferrous ammonium
sulphate

Table – II
Given ferrous ammonium sulphate Vs potassium dichromate
solution

Volume of Burette Readings

given ferrous
ammonium Volume of
S.
sulphate K2Cr2O7
No. Initial Final
solution used (cm3)
pipetted
(cm3)

1 10.0

2 10.0

3 10.0

Molarity of K2Cr2O7 solution = M3 = M2 =…… mol dm-3

Volume of K2Cr2O7 solution used (from Table - II) = V3 =……… cm3
Volume of given Mohr’s salt solution pipetted = V4 = 10.0 cm3
Molarity of given Mohr’s salt solution = M4 = ?
Using the molarity equation,
M4V4  6M3V3

6M 3V3
Molarity of given Mohr’s salt solution, M4 = = ………. mol dm-3
 V4
 Strength of given ferrous ammonium sulphate solution
= (molarity) x (molar mass)
= M4 x (392.15 g mol-1)

= ………………. g dm-3

Precautions

The internal indicator, 1% diphenylamine has to be handed carefully since it

has been dissolved in concentrated sulphuric acid.

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Hazards of chemicals used

 Potassium dichromate is carcinogenic and should be handled carefully.

The compound is also corrosive and exposure may produce severe eye
damage.
 Potassium dichromate is one of the most common culprits in causing
chromium dermatitis.
 Hexavalent chromium compounds are generally more toxic than
trivalent chromium compounds. Chromium(VI) compound is a known
cancer hazard.
 Phosphoric acid is corrosive, causes severe irritation and burns to
every area of contact. It is harmful if swallowed or inhaled.
 Wear safety glasses, gloves and work in a ventilated area.

Applications of chromatometry

Titrations involving acidified potassium dichromate solution can be employed

to

i) determine the percentage of iron in a sample of iron wire.

ii) determine ferrous and ferric iron in a solution.
iii) determine the percentage of ferric iron in the given sample of ferric alum.
iv) determine the percentage of iron in an iron ore, such as haematite
(Fe3O4) or spathic iron ore (FeCO3).

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