Pabitra Kumar Mani, Assoc. Prof.

, ACSS, BCKV
Class 13
Redox titrations,
permanganometry, iodometry etc.
Redox Titrations
Basics
Potassium Permanganate
Potassium Dichromate
Cerium IV
Iodine
This valuable and powerful oxidising agent was first introduced
into titrimetric analysis by F. Margueritte for the titration of iron(II).
In acid solutions, the reduction can be represented by the
following equation
The standard reduction potential in acid solution, E
0
has been
calculated to be 1.51 volts; hence the permanganate ion in
acid solution is a strong oxidising agent. Sulphuric acid is the
most suitable acid, as it has no action upon permanganate in
dilute solution. With HCl, there is a likelihood of the reaction
In the HCl , permanganate can oxidize Cl
-
to Cl
2
, which can be a source
of positive errors as permanganate is consumed in this reaction.
(E
red
Cl
2
/Cl
-
)= +1.36V
Permanganometry
Permanganate titration
KMnO
4
Powerful oxidant that the most widely used.

Eq. Wt.(=M/5): In strongly acidic solutions (1M H
2
SO
4
or HCl, pH s 1)
MnO
4

+ 8H
+
+ 5e- = Mn
2 +
+ 4H
2
O E
o
= 1.51 V
violet color colorless manganous
KMnO
4
is a self-indicator.

In feebly acidic, neutral, or alkaline solutions (E=M/3)
MnO
4

+ 4H
+
+ 3e- = MnO
2
(s) + 2H
2
O E
o
= 0.59 V
brown manganese dioxide solid

In very strongly alkaline solution (2M NaOH or Ba (OH)
2
) (E=M/1)
MnO
4

+ e- = MnO
4
2
E
o
= 0.56 V
green manganate
E=M/4 (in HF or NH
4
HF
2
Medium)


MnO
4

+ 4e
-
+ 6F
-
+ 8H
+
= [MnF
6
]
3
+ 4H
2
O
III
Trivalent Fluoro magnate anion
In the analysis of iron ores, (solution is frequently effected in
conc. HCl); the Fe
+3
is reduced and the Fe
+2
is then determined in
the resultant solution.
If Cl
-
is present, to prevent its oxidation in acidic medium (1-2
N) by MnO
4
-
about 25 mL of Zimmermann and Reinhardt's
solution (preventive solution) has to be used.
It is prepared by dissolving 50 g of crystallised (MnSO
4
,4H
2
O) in
250 mL water, adding a cooled mixture of 100 mL conc.H
2
SO
4

and 300 mL water, followed by 100 mL H
3
PO
4
. The manganese
(II) sulphate (presence of Mn
+2
) lowers the oxidation potential of
the MnO
4
-
- Mn(II) couple (-1.20V) and thereby makes it a weaker
oxidising agent; the tendency of the permanganate ion to oxidise
chloride ion is thus reduced.( E
o
of Cl
-
/Cl
2
is much higher)
Estimation of Fe
+2
| |
| |
2
8
4
Mn
H MnO
log
5
0.0591
- -1.52 E
+
+

=
positive
See Vogels book
Determination of Nitrite:

Nitrites react in warm acid solution (40
0
C) with permanganate
solution in accordance with the equation:


If a solution of a nitrite is titrated in the ordinary way with
potassium permanganate, poor results are obtained, because
the NO
2
-
soln has first to be acidified with dil.H
2
SO
4
. Nitrous
acid is liberated, which being volatile and unstable, is partially
lost.
If, however, a measured volume of std. KMnO
4
soln, acidified
with dil.H
2
SO
4
, is treated with the nitrite solution, added from a
burette, until the permanganate is just decolorised, results
accurate to 0.5-1 per cent may be obtained
5NO
2
-
+ 2MnO
4
-
+ 6H
+
= 5NO
3
-
+ 2 Mn
2+
+ 3H
2
O
Preparation of 0.1 N potassium permanganate solution
KMnO
4
is not pure. Distilled water contains traces of organic
reducing substances which react slowly with permanganate to form
hydrous managnese dioxide. MnO
2
promotes the autodecomposition
of permanganate.
1) Dissolve about 3.2 g of KMnO
4
(mw=158.04) in 1000ml of water,
heat the solution to boiling, and keep slightly below the boiling
point for 1 hr. Alternatively , allow the solution to stand at room
temperature for 2 or 3 days.
2) Filter the liquid through a sintered-glass filter crucible to remove
solid MnO
2
.
3) Transfer the filtrate to a clean stoppered bottle freed from grease
with cleaning mixture.
4) Protect the solution from evaporation, dust, and reducing vapors,
and keep it in the dark or in diffuse light. Preserve it in amber
coloured glass bottle.
5) Standardise from time to time. If in time managanese dioxide
settles out, refilter the solution and restandardize it.
Ordinary distilled water is likely to contain reducing
substances (traces of organic matter, etc.) which will react with
the KMnO
4
to form MnO
2
. The presence of the manganese
dioxide is very objectionable because it catalyses the auto-
decomposition of the permanganate solution on standing
Permanganate is inherently unstable in the presence of Mn
+2

ions:
Potassium permanganate solutions may be standardised using

Primary standards : arsenic(III) oxide or sodium oxalate

Secondary standards : metallic iron etc.
4 MnO
4
-
+2H
2
O = 4 MnO
2
+3O
2
+4 OH
-
2MnO
4
-
+3Mn
2+
+ 2H
2
O = 5 MnO
2
+ 4H
+
Standardization of KMnO
4
solution
Standardization by titration of sodium oxalate Na
2
C
2
O
4
.2H
2
0 (primary standard)
(Fowler and Bright) :
C
2
O
4
2-
= 2CO
2
+ 2 e
-
E
red
= +0.77V
2KMnO
4
+5 Na
2
(COO)
2
+8H
2
SO
4
= 2MnSO
4
+K
2
SO
4
+5Na
2
SO
4
+10 CO
2
+ 8H
2
O











The reaction between oxalic acid and potassium permanganate can be represented
as:
2KMnO
4
+ 5 H
2
C
2
O
4
+3H
2
SO
4
= 2MnSO
4
+K
2
SO
4
+10 CO
2
+ 8H
2
O

In ionic form the reaction can be represented as:
2MnO
4
-
+ 5 C
2
O
4
2-
+ 16H
+
= 2Mn
2+
+ 10 CO
2
+ 8H
2
O
This titration is carried out in warm conditions (60
o
C). The reaction at room
temperature is slow because of the equilibrium nature of this reaction. CO
2
is highly
soluble in water and thus heating removes all dissolved CO
2
out of the solution
driving the reaction in forward direction.
Also at low temperature, the reduction of permanganate may not be
complete producing Mn(III) (in the form [Mn(C
2
O
4
)
3
]
3-
). The formation of this
species introduce errors in titrations as no. of electrons utilized here are different as
compared to production of Mn
2+
.
Standardization of KMnO
4
solution
by Arsenic(III) oxide
This procedure of H.A.Bright, which utilises As(III) oxide as a
primary stand. and KI or potassium iodate (KIO
3
) as a catalyst
for the reaction, is convenient in practice and is a trustworthy
method for the standardisation of permanganate solns.
As
2
O
3
weighed, dissolved in 3N NaOH, H
2
SO
4
(4N) added, a
drop of very dilute KIO
3
added as catalyst and titrated by
MnO
4
-
.
Titration of K
2
Cr
2
O
7
with Mohrs salt.

K
2
Cr
2
O
7
a strong oxidizing agent (E
red
= +1.33V) but, not as strong
oxidizing agent as permanganate (E
red
= +1.51V). It is widely used in redox
titrations because of several advantages over permanganate. Unlike
KMnO4, K
2
Cr
2
O
7
is available in high purity and is highly stable upto its
melting point.
Its aqueous solutions are not attacked by organic matter and thus
composition of aqueous solution does not change on keeping. The
aqueous solutions are quite stable towards light.
It is an excellent primary standard and its standard solutions can
be prepared by direct weighing of an amount of it and dissolving in a
known volume of distilled water.

K
2
Cr
2
O
7
acts as oxidizing agent in acidic medium only:
The neutral aqueous solution of K
2
Cr
2
O
7
is 1:1 equilibrium mixture of
dichromate and chromate, a consequence of hydrolysis of dichromate
ions.
Cr
2
O
7
2
+ H
2
O = 2 CrO
4
2
+ 2H
+

Orange yellow
Chromate ions are weaker oxidizing agent than dichromate. Thus oxidizing
strength of dichromate is reduced in neutral solution.
3
4 1
2
7 2
0
Cr
H O Cr
log
6
0.0591
- E E
+
+

=
( )( )
2
2 -
14
2 3
10
10 10
log
6
0.0591
- 33 . 1 E

=
27 -
0 1 log
6
0.0591
- 33 . 1 E =
|
.
|

\
|
+ =
6
0.0591
x 27 33 . 1 E
V 06 . 1 E
| |
| |
2
3
0
Fe
Fe
0.0591log - E E
+
+
=
15 . 0
0.003
0.0591log - 771 . 0 - E =
V 671 . 0 - E=
| || |
| |
2
8
4
0
Mn
H MnO
log
5
0.0591
- E E
+
+

=
( )( )
( ) 005 . 0
00 . 1 02 . 0
log
5
0.0591
- 51 . 1 - E
8
=
V 52 . 1 - E
V 79 . 0
103 . 0
0.05
0.0591log - 771 . 0 - E E
Fe Mn
= = =
Methods Involving Iodine
Iodimetry: a reducing analyte is titrated directly with
iodine (to produce I

).
Iodometry, an oxidizing analyte is added to excess I

to
produce iodine, which is then titrated with standard
thiosulfate solution.

Iodine only dissolves slightly in water. Its solubility
is enhanced by interacting with I
-



A typical 0.05 M solution of I
2
for titrations is
prepared by dissolving 0.12 mol of KI plus 0.05 mol of
I
2
in 1 L of water. When we speak of using iodine as a
titrant, we almost always mean that we are using a solution
of I
2
plus excess I

.
The direct iodometric titration method (Iodimetry) refers
to titrations with a standard solution of iodine.
The indirect iodometric titration method (Iodometry)
deals with the titration of iodine liberated in chemical
reactions.
The normal oxidation potential of the reversible system:
2I
-
I
2
+ 2e
in most iodometric titrations, when an excess of iodide ion
is present the tri-iodide ion is fromed
since iodine is readily soluble in a solution of iodide. The
half-cell reaction is better written:
I
2
(aq) + I
-
I
3
-
I
3
-
+2e 3I
-
and the standard oxidation potential is -0.5355
volt. Iodine or the tri-iodide ion is therefore a
much weaker oxidising agent than potassium
permanganate, potassium dichromate, and
cerium(IV) sulphate.

In most direct titrations with iodine (iodimetry) a
solution of iodine in potassium iodide is employed,
and the reactive species is therefore the tri-
iodide ion I
3
-
.

Strictly speaking, all equations involving reactions
of iodine should be written with I
3
-
; rather than
with I
2
e.g.
The normal oxidation potential of the iodine-iodide system is
independent of the pH of the solution so long as the latter is
less than about 8; at higher values iodine reacts with
hydroxide ions to form iodide and the extremely unstable
hypoiodite, the latter being transformed rapidly into iodate and
iodide by self-oxidation and reduction:
I
2
+ 2S
2
O
3
-
2I
-
+ S
4
O
6
-2
I
2
+ H
2
S S + 2I
-
+ 2H
+
I
2
+ SO
3
-2
+H
2
O 2I
-
+ SO
4
-2
I
2
+ SnCl
2
+2HCl 2I
-
+ SnCl
4 +
2H
+
the reaction is completely reversible. At pH values between 4
and 9, arsenite can be titrated with iodine solution.
In strongly acid solutions, however, arsenate is reduced
to arsenite and iodine is liberated. Upon titration with sodium
thiosulphate solution, the iodine is removed and the reaction
proceeds from right to left
By suitable control of the pH of the solution, it is sometimes
possible to titrate the reduced form of a substance with iodine,
and the oxidised form, after the addition of iodide, with sodium
thiosulphate. Thus with the arsenite-arsenate system:
H
3
ASO
3
+ I
2
+ H
2
O H
3
AsO
4
+ 2 H
+
+ 2I
-
Preparation and Standardization of Solutions
Acidic solutions of I
3
-
are unstable because the excess I

is
slowly oxidized by air:

In neutral solutions, oxidation is insignificant in the absence of
heat, light, and metal ions. At pH 11, triiodide
disproportionates to hypoiodous acid (HOI), iodate, and iodide.
An excellent way to prepare standard I
3
-
:
is to add a weighed quantity of potassium iodate to a small excess
of KI. Then add excess strong acid (giving pH 1) to produce I
2
by
quantitative reverse disproportionation:
Two important sources of error in titrations involving iodine are: (a) loss of iodine
owing to its appreciable volatility; and (b) acid solutions of iodide are oxidised by
oxygen from the air:
4I
-
+ O
2
+ 4H
+
2I
2
+ 2 H
2
O

IO
3
-
+ 5I
-
+ 6H
+
3I
2
+ 3H
2
O

Fact File 1: Introduction to iodometric and iodimetric titrations
Third: Iodometric titration

Analyte of unknown
concentration
Titrant
-standrard solutions: sodium thiosulfate
-known concentration
2 Cu
2+
+ 4I
-
2CuI + I
2


I
2
+ 2S
2
O
3
2-
2I
-
+ S
4
O
6
2-


Starch-Iodine complex

Starch solution(05~ 1%) is not redox indicator.
The active fraction of starch is amylose, a polymer of the sugar o-
D-glucose ( 1,4 bond).
The polymer exists as a coiled helix into which small molecules
can fit.

In the presence of starch and I

, iodine molecules form long

chains of I
5

ions that occupy the center of the amylose helix.

[I I I I I]

[I I I I I]

Visible absorption by the I
5

chain bound within the helix gives

rise to the characteristic starch-iodine color.
Structure of the repeating unit of the
sugar amylose.
Schematic structure of the starch-
iodine complex. The amylose chain
forms a helix around I
6
unit.
View down the starch helix, showing
iodine, inside the helix.
Starch is the indicator of choice for those procedures
involving iodine because it forms an intense blue
complex with iodine. Starch is not a redox indicator;
it responds specifically to the presence of I
2
, not to a
change in redox potential.
The active fraction of starch is amylose, a polymer of
the sugar -d-glucose.
In the presence of starch, iodine forms I
6
chains
inside the amylose helix and the color turns dark
blue
Starch-Iodine Complex
Common Titrant for Oxidation Reactions
Iodine (Solution of I
2
+ I
-
)
I
3
-
is actual species used in titrations with iodine


Either starch of Sodium Thiosulfate (Na
2
S
2
O
3
) are used as
indicator
K = 7 x 10
2
Before
endpoint

Before
endpoint

At
endpoint

I
3
-
+ Starch

I
3
-
I
3
-
+ S
2
O
3
2-
SOLUTION

Determination of Cu
+2
:

2Cu
+2
+ 4I
-
CuI + I
2

Acetic acid buffer pH ~4.5 or better NH
4
HF
2
buffer.
In presence of free mineral acid, at pH<3, dissolved O
2

liberate I
2
from I
-
also.
The elments which interferes with the iodometric
determination are iron, arsenic and antimony, Trivalent
iron is reduced by iodide:
2Fe
3
+ + 2I
-
2Fe
2+
+ I
2

but by addition of excess of fluoride, the iron(III) is
converted into the complex [FeF
6
]
3-
, which yields so
small a concn of Fe
+3
ions that it has no oxidising action
upon the iodide.
DETERMINATION OF THE AVAILABLE CHLORINE IN Bleaching powder
the hypochlorite solution or suspension is treated with an
excess of a solution of potassium iodide, and strongly
acidified with acetic acid:
Ca(OCl)+ KI +HAc CaCl
2
+ I
2
+ H
2
O + KAc
The liberated iodine is titrated with standard sodium
thiosulphate solution.
Determination of hypochlorite in bleaches [CaCl(OCl)H
2
O]:
OCl

+ 2I

+ 2H
+
Cl

+ I
2
+ H
2
O
(unmeasured excess KI)
I
2
+ 2 S
2
O
3
2
2I

+ S
4
O
6
2

Indicator: soluble starch (|-amylose)
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