Name: Dr. Pramod B.

Thakur
Class: T.Y.B.Sc
Subject: Analytical Chemistry

Title of Topic: Redox Titrations

 T.Y.B.Sc
Analytical Chemistry Paper
IV- USCH504, UNIT- II
2.1 Redox Titrations

By Dr. P. B. Thakur
 Redox Titrations
 General Introduction
 Theory of Redox indicator
 Criteria for choosing an indicator for redox
titration
 Use of diphenyl amine and ferroin as redox
indicators
 Construction of Titration curve in the case of
 One electron system [Ex. Fe(II) Vs Ce(IV)]
 Multielectron system [Ex. Fe(II) Vs KMnO4 ]
General Introduction:
 Redox = Reduction + Oxidation
 Reduction = Addition of electron
Mz+ + n e- M(z-n)+
example: Ce4+ + 1 e- Ce3+
 Oxidation = Removal of electron
Mz+ - n e- M(z+n)+
example: Fe2+ - 1 e- Fe3+
 Redox titration involve the titration reaction
where transfer of electron between the
reactant (titrand) and titrant takes place.
Criteria for reaction in redox titration

 Reaction should be rapid

 Reaction should go to the completion

 Reaction should be stoichiometric

 Reaction should provide easy detection of

end point
 General reaction
Oxi1 + Red2 Red1 + Oxi2
Oxi1 & Oxi2 = Oxidizing agent
Red1 & Red2 = Reducing agent
example: Fe+2 + Ce+4 Fe+3 + Ce+3
Oxi1 + Red2 Red1 + Oxi2
Number of electrons donated and number of electrons accepted
should be equal
Since two Redox couple are present, the electrode potential of each
redox couple must be identical which will be the electrode potential of the
system
Esystem = E Fe+2 / Fe+3 = E Ce+3 / Ce+4
Esystem is the potential which is referred as the
electrode potential of the system
 Redox Indicator:
 Electrode potential is the parameter Reducing

which changes during the course of

agent

titration and magnitude of the change is

maximum in the vicinity of the equivalence
point.
 So indicator used for redox titration must
change color due to sudden change in the
electrode potential of the system at the
equivalence point. Oxidizing

 Such indicator are known as Redox agent

Indicator.
 Theory of Redox Indicator:

 Certain organic compounds are capable

to undergo oxidation-reduction
reactions and the color of the
oxidized form of indicator in solution
is significantly different than that of
reduced form
 If In = any redox indicator, then
In (ox) + ne- In (Red)

By using Nearst equation, the electrode potential

of the indicator can be given as,

EIn = EoIn - 0.05916 X log [ In(Red) ]………eq 1

n [ In(ox) ]
EoIn is the standard electrode potential of indicator
which is constant for given redox indicator. n =
number of electrons
So, EIn will depend on the ratio of [ In(Red) ]
[ In(ox) ]
So, Colour of the indicator in the solution
will depend on the ratio of [ In(Red) ]
[ In(ox) ]
as colour is depend on potential EIn

Because when EIn changes, the ratio of the

reduced form of indicator to the oxidized
form of indicator will change.
The colour of reduced form will dominant when
[ In(Red) ] ≥ 10 or [ In(ox) ] ≤ 10
[ In(ox) ] [ In(Red) ]

The colour of Oxidized form will dominant when [

In(ox) ] ≥ 10 or [ In(Red) ] ≤ 10
[ In(Red) ] [ In(Ox) ]
By substituting these in eq 1, we get
EIn = EoIn ± 0.05916
n
Criteria for choosing an indicator for redox
titration

EIn = EoIn ± 0.05916

n
From the above equation, it is clear that the
potential at which a colour transition will
occur depend on the standard potential of
the indicator system.
Hence the transition potential of the redox
indicator must be equal to or nearly equal
to the equivalence point potential of the
system to give accurate end point at
equivalence point.
Oxidation-Reduction Indicators
Indicator Colour Transition
Oxidized form Reduced form Potential (EoIn)
Nitroferron Pale blue Red 1.25 v

Ferroin Pale blue Red 1.06 v

Diphenyl amine- Purple Colourless 0.84 v

Sulphonic acid

Diphenyl amine Violet Colourless 0.76 v

Methylene blue Colourless Blue 0.53 v

Indigo Blue Colourless 0.36 v

tetrasulfonate
Use of organic molecule as redox
indicators
 The redox indicators are organic molecule
that undergo structural changes upon
being oxidized or reduced.

 We will consider the two examples

1. Use of diphenyl amine as redox
indicators
2. Use of ferroin as redox indicators
Use of diphenyl amine as redox
indicators

N
H
 Diphenyl is the first indicator used in the
redox titration by Knop in 1924 for the
titration of Fe(II) with K2Cr2O7.

 In the presence of a strong oxidizing

agent, diphenyl amine undergoes a series
of reaction as follows:
2 irreverssile Reaction
N
H
Diphenyl amine (Colourless)

N N 2H+ 2e-
H H
Diphenyl benzidine (Colourless)

N N 2H+ 2e-

Diphenyl benzidine violet (Purple)

 The main indicator reaction is the transfer of Diphenyl
benzidine to Diphenyl benzidine violet (Purple).

 The transition potential is 0.76 v at 250C for diphenyl amine

indicator.

 In titration of Fe(II) & K2Cr2O7 the equivalence poin

potential is 1.17 V.

 The transition potential of indicator and equivalence point

potential should be equal or nearly equal to give colour
change at the equivalence point.

 The transition potential of diphenyl amine indicator is less

than that of equivalence point potential, so colour change will
occur before the equivalence point which will introduce error
in measurement.
 To avoid such error, mixture of sulphuric acid and
phosphoric acid is used.

 Sulphuric acid form the diphenyl benzidine sulphonate

salt which increases the solubility of the indicator in
aqueous medium due to which transition potential of the
indictor increases to 0.85 v from previous 0.76 v

 Phosphoric acid forms stable colourless ferric phosphate

complex which considerably decrease the equivalence
potential value.

 So, the equivalence point potential is now closer to the

transition potential of indicator due to which colour
change will takes place close to the equivalence point.
Use of Ferroin as redox indicators
 Ferroin is organic compound known as 1,10
phenonthrolines or orthophenanthrolines.

N N
 It is capable of forming intensely coloued,
highly stable complexwith Fe(II).
 The complex is called Ferroin and represented
as (Phen)3.Fe+2

 It can be shown as below 2+

N N

3 Fe2+ N Fe N
N N
N N

 The indicator reaction involves,

(Phen)3.Fe+3 + e- = (Phen)3.Fe+2
(Pale Blue) (Red)
EoRed = 1.06 v
 Transition potential of ferroin indicator is
1.06 v
 In the titration of Fe(II) Vs Ce(IV), the
equivalence point potential is 1.105 v
 As the transition potential of ferroin
indicator is very close to equivalence
point potential of Fe(II) and Ce(IV)
system, the ferroin is the most suitable
indicator for this sysyem which gives
colour change at exactly equivalence point
Construction of Titration curve
 For Redox titration, titration curve is the
plot of electrode potential of the system
Versus volume of the titrant (reduing or
oxidizing agent).

 Electrode potential of the system can be

obtained by setting up electrochemical
cell or by calculating theoretically using
nearst equation.
Construction of Titration curve
 Construction of the titration curves and
calculation of Esystem In aqueous medium
in case of:
(1)One electron system
eg. Fe(II) Vs Ce(IV)
[Titraton where H3O+ or OH- do not
participate directly in the redox reaction.]
(2) Multielectron system
eg. Fe(II) Vs KMnO4
[Titraton where H3O+ or OH- participate
directly in the redox reaction.]
 Titration curve of Fe(II) Vs Ce(IV)
 In this redox titration, acid solution of Fe(II) is
titrated with standard solution of Ce(IV).
 Consider the titration of 10 cm3 of 0.1 M Fe+2 with 0.1
M Ce+4 solution in the presence of H2SO4.
 The titration reaction correspond to this can be given as
Fe+2 + Ce+4 Fe+3 + Ce+3

 The electrode potential of the system at each stage of

the titration can be calculated by using Nearst equation
as below,
At the beginning of the titration:
 At the beginning of the titration, No Ce+4
Ce+4 is added to Fe+2 solution, so Titrant

solution will contain only Fe+2 ions.

 Electrode potential is determined from

Fe+2/ Fe+3 redox couple

 At the beginning no Fe+3 will be present

so at this stage the electrode potential 10 cm3

is not significant. of 0.1

M Fe+2
 Before the equivalence point:
1. When 2 cm3 0.1 M Ce+4 is added
Fe+2 + Ce+4 Fe+3 + Ce+3
When 2 cm3 0.1 M Ce+4 has been added to Ce+4
10 cm3, 0.1 M Fe+2 solution, then 2 cm3 of Titrant

Fe+2 will oxidized in to Fe+3 So, resulting

concentration of Fe+3 will be
[Fe+3] = 2 X 0.1
12
and 8 cm3 of Fe+2 will remain unreacted,
So, concentration of Fe+2 will be

[ Fe ] =
+2
8 x 0.1 10 cm3
of 0.1

12
M Fe+2

[Fe+2] = 8 = 4
By using Nearst equation, electrode potential can be
given as

Esystem = EoPt/ +2
Fe - Fe
+3
- 0.05916 X log [Fe+2]

n [Fe+3]
EoPt/ Fe+2- Fe+3 = Standard electrode potential
= 0.771 V
n = no of electrons involved = 01
[Fe+2] = 4
[Fe+3]
So we get,
Esystem = 0.771- 0.05916 X log [4]

= 0.771- 0.05916 X 0.6021

2. When 5 cm3 0.1 M Ce+4 is added
Fe+2 + Ce+4 Fe+3 + Ce+3
When 5 cm3 0.1 M Ce+4 has been added to Ce+4
10 cm3, 0.1 M Fe+2 solution, then 5 cm3 of Titrant

Fe+2 will oxidized in to Fe+3 So, resulting

concentration of Fe+3 will be
[Fe+3] = 5 X 0.1
15
and 5 cm3 of Fe+2 will remain unreacted,
So, concentration of Fe+2 will be

[ Fe ] =
+2
5 x 0.1 10 cm3
of 0.1

15
M Fe+2

[Fe+2] = 1
By using Nearst equation, electrode potential can be
given as

Esystem = EoPt/ +2
Fe - Fe
+3
- 0.05916 X log [Fe+2]

n [Fe+3]
EoPt/ Fe+2- Fe+3 = Standard electrode potential
= 0.771 V
n = no of electrons involved = 01
[Fe+2] = 1
[Fe+3]
So we get,
Esystem = 0.771- 0.05916 X log [1]

= 0.771- 0.05916 X 0
3. When 9.9 cm3 0.1 M Ce+4 is added
Fe+2 + Ce+4 Fe+3 + Ce+3

When 9.9 cm3 0.1 M Ce+4 has been added to

Ce+4
10 cm3, 0.1 M Fe+2 solution, then 9.9 cm3 Titrant

of Fe+2 will oxidized in to Fe+3 So,

resulting concentration of Fe+3 will be
[Fe+3] = 9.9 X 0.1
19.9
and 0.1 cm3 of Fe+2 will remain unreacted,
So, concentration of Fe+2 will be

[ Fe ] =
+2
0.1 x 0.1 10 cm3
of 0.1

19.9 M Fe+2

[Fe+2] = 0.1 = 0.0101

By using Nearst equation, electrode potential can be
given as

Esystem = EoPt/ +2
Fe - Fe
+3
- 0.05916 X log [Fe+2]

n [Fe+3]
EoPt/ Fe+2- Fe+3 = Standard electrode potential
= 0.771 V
n = no of electrons involved = 01
[Fe+2] = 0.0101
[Fe+3]
So we get,
Esystem = 0.771- 0.05916 X log [0.0101]

= 0.771- 0.05916 X [-1.9956]

3. At equivalence point
When 10 cm3 0.1 M Ce+4 is added

Fe+2 + Ce+4 Fe+3 + Ce+3 Ce+4

When 10 cm3 0.1 M Ce+4 has been added to 10 Titrant

cm3, 0.1 M Fe+2 solution, then all Fe+2 will

oxidized in to Fe+3. Similarly all Ce+4 will
reduced in to Ce+3.
So, at equivalence point, two redox couple are
present are as follows,
Fe+2 - Fe+3 and Ce+4 - Ce+3

Hence, the potential of the system will be 10 cm3

of 0.1

the sum of the potential of this two redox M Fe+2

couple
By using Nearst equation, electrode potential of the
two redox couple system can be given as

Esystem = EoPt/ +2
Fe - Fe
+3
- 0.05916 X log [Fe+2]

n [Fe+3]
+ EoPt/ +3
Ce - Ce
+4
- 0.05916 X log [Ce +3
]

n [Ce+4]
= 2 equivalence point potential
2 E eq. Point potential =
EoPt/ Fe
+2 +3
- Fe + EoPt/
– 0.05916 X log [Fe+2] [Ce+3]
Ce
+3
- Ce
+4

[Fe+3] [Ce+4]
At equivalence point, [Fe+3] = [Ce+3] and
[Fe+2] = [Ce+4]
[Fe+2] [Ce+3] = 1
EoPt/ +2
Fe - Fe
+3
= Standard electrode potential
= 0.771

EoPt/ +3
= Standard electrode potential
Ce - Ce
+4

= 1.44
Substituting these values in above equation, we get
2 E eq. Point potential = 0.771 + 1.44 – 0.05916

X log [1]
= 0.771 + 1.44
E eq. Point potential = 2.211 = 1.105 v
2
E eq. Point potential = 1.105 v
 4. After the equivalence point
When 10.1 cm3 0.1 M Ce+4 is added

Fe+2 + Ce+4 Fe+3 + Ce+3 Ce+4

When 10.1 cm3 0.1 M Ce+4 has been added Titrant

then 0.1 ml Ce+4 will be in excess.

At this stage, only Ce+4 - Ce+3 redox couple is

responsible for electrode potential and it
calculated as

Esystemt = EoPt/ +3
Ce - Ce
+4
- 0.05916 X log [Ce+3] 10 cm3
of 0.1
n [Ce+4] M Fe+2
EoPt/ +3
Ce - Ce
+4
= 1.44 v

[Ce+4] = 0.1 X 0.1

20.1 and
[Ce+3] = 10 X 0.1
20.1
[Ce+3] = 10 = 100
[Ce+4] 0.1

Esystem = EoPt/ +3
- 0.05916 X log [Ce+3]
Ce - Ce
+4

n [Ce+4]
= 1.44-0.05916 X log [100]
Esystem = 1.322 v
 4. After the equivalence point
When 11 cm3 0.1 M Ce+4 is added

Fe+2 + Ce+4 Fe+3 + Ce+3 Ce+4

When 11 cm3 0.1 M Ce+4 has been added Titrant

then 1 ml Ce+4 will be in excess.

At this stage, only Ce+4 - Ce+3 redox couple is

responsible for electrode potential and it
calculated as

Esystemt = EoPt/ +3
Ce - Ce
+4
- 0.05916 X log [Ce+3] 10 cm3
of 0.1
n [Ce+4] M Fe+2
EoPt/ +3
Ce - Ce
+4
= 1.44 v

[Ce+4] = 1 X 0.1
21 and
[Ce+3] = 10 X 0.1
21
[Ce+3] = 10 = 10
[Ce+4] 1

Esystem = EoPt/ +3
- 0.05916 X log [Ce+3]
Ce - Ce
+4

n [Ce+4]
= 1.44-0.05916 X log [10]
Esystem = 1.381 v
Volume in Cm3 of 0.1 M
Ce+4 added Esystem in V

0.0 -

2.0 0.735

5.0 0.771

9.9 0.889

10.0 1.105

10.1 1.322

11.0 1.381

12.0 1.400
Titration curve of Fe(II) Vs Ce(IV) titration

1.6
1.4
1.2
1
0.8
Esystem 0.6
0.4
0.2
0
2 5 9.9 10 10.1 11 12
Volume of 0.1 M Ce(IV) added
Titration curve of Fe(II) Vs KMnO4
 Additional Example

Titration curve of Fe(II) Vs Cr2O7-2

 Titration curve of Fe(II) Vs Cr2O7-2
 In this redox titration, acid solution of Fe(II) is
titrated with standard solution of K2Cr2O7-2.
 Consider the titration of 10 cm3 of 0.1 M Fe+2 against
with 0.0167 M K2Cr2O7-2 at pH 1.
 The titration reaction correspond to this can be given as
6Fe+2+Cr2O7-2 +14H3O+ 6Fe+3+2Cr+3 + 21H2O

 The electrode potential of the system at each stage of

the titration can be calculated by using Nearst equation
as below,
At the beginning of the titration:
 At the beginning of the titration, No
Cr2O7-2 is added to Fe+2 solution, so
solution will contain only Fe+2 ions.

 Electrode potential is determined from

Fe+2/ Fe+3 redox couple

 At the beginning no Fe+3 will be present

so at this stage the electrode potential 10 cm3
of 0.1
is not significant. M Fe+2
 Before the equivalence point:
1. When 2 cm3 0.0167 M Cr2O7-2 is added

6Fe+2+Cr2O7-2 +14H3O+ 6Fe+3 + 2Cr+3 +

Cr2O7-2
Titrant

21H2O
When 2 cm3 0.0167 M Cr2O7-2 has been
added to 10 cm3, 0.1 M Fe+2 solution, then 2
cm3 of Fe+2 will oxidized in to Fe+3 So,
resulting concentration of Fe+3 will be,
[Fe+3] = 2 X 0.1
12
and 8 cm3 of Fe+2 will remain unreacted, So, 10 cm3
of 0.1
concentration of Fe+2 will be M Fe+2

[ Fe+2] = 8 x 0.1 [Fe+2] = 4

+3
By using Nearst equation, electrode potential can be
given as

Esystem = EoPt/ +2
Fe - Fe
+3
- 0.05916 X log [Fe+2]

n [Fe+3]
EoPt/ Fe+2- Fe+3 = Standard electrode potential
= 0.771 V
n = no of electrons involved = 01
[Fe+2] = 4
[Fe+3]
So we get,
Esystem = 0.771- 0.05916 X log [4]

= 0.771- 0.05916 X 0.6021

 2. When 5 cm3 0.0167 M Cr2O7-2 is added
6Fe+2 + Cr2O7-2 +14H3O+ 6Fe+3 + 2Cr+3
+ 21H2O
When 5 cm3 0.0167 M Cr2O7-2 has been Cr2O7-2
Titrant

added to 10 cm3, 0.1 M Fe+2 solution, then

5 cm3 of Fe+2 will oxidized in to Fe+3 So,
resulting concentration of Fe+3 will be
[Fe+3] = 5 X 0.1
15
and 5 cm3 of Fe+2 will remain unreacted, So,
concentration of Fe+2 will be
[ Fe+2] = 5 x 0.1 10 cm3

15 of 0.1
M Fe+2

[Fe+2] = 1
[Fe+3]
By using Nearst equation, electrode potential can be
given as

Esystem = EoPt/ +2
Fe - Fe
+3
- 0.05916 X log [Fe+2]

n [Fe+3]
EoPt/ Fe+2- Fe+3 = Standard electrode potential
= 0.771 V
n = no of electrons involved = 01
[Fe+2] = 1
[Fe+3]
So we get,
Esystem = 0.771- 0.05916 X log [1]

= 0.771- 0.05916 X 0
3. When 9.9 cm3 0.0167 M Cr2O7-2 is added
6Fe+2 + Cr2O7-2 +14H3O+ 6Fe+3 + 2Cr+3
+ 21H2O
When 9.9 cm3 0.0167 M Cr2O7-2 has been Cr2O7-2

added to 10 cm3, 0.1 M Fe+2 solution, then

Titrant

9.9 cm3 of Fe+2 will oxidized in to Fe+3 So,

resulting concentration of Fe+3 will be, [Fe+3]
= 9.9 X 0.1
19.9
and 0.1 cm3 of Fe+2 will remain unreacted,
So, concentration of Fe+2 will be
10 cm3
[ Fe ] =
+2
0.1 x 0.1 of 0.1
M Fe+2
19.9
[Fe+2] = 0.1 = 0.0101
By using Nearst equation, electrode potential can be
given as

Esystem = EoPt/ +2
Fe - Fe
+3
- 0.05916 X log [Fe+2]

n [Fe+3]
EoPt/ Fe+2- Fe+3 = Standard electrode potential
= 0.771 V
n = no of electrons involved = 01
[Fe+2] = 0.0101
[Fe+3]
So we get,
Esystem = 0.771- 0.05916 X log [0.0101]

= 0.771- 0.05916 X [-1.9956]

3. At equivalence point
When 10 cm3 0.0167 M Cr2O7-2 is added

6Fe+2 + Cr2O7-2 +14H3O+ 6Fe+3 + 2Cr+3 Cr O -2

2 7

+ 21H2O Titrant

When 10 cm3 0.0167 M Cr2O7-2 has been added

to 10 cm3, 0.1 M Fe+2 solution, then all Fe+2 will
oxidized in to Fe+3. Similarly all Cr2O7-2 will
reduced in to Cr+3.
So, at equivalence point, two redox couple are
present are as follows,
Fe+2 - Fe+3 and Cr+3 - Cr2O7-2
10 cm 3

Hence, the potential of the system will be of 0.1

M Fe +2

the sum of the potential of this two redox couple

The respective Half reactions are

Fe+3 + e- Fe+2 and

Cr2O7-2 + 14 H3O+ +6e- 2Cr+3 + 21 H2O

Potential of Fe+2- Fe+3 redox couple is given as,

Eeq = Eo +2
Fe - Fe
+3
- 0.05916 X log [Fe+2].....eq 1

1 [Fe+3]

Potential of Cr+3- Cr2O7-2 redox couple is given as,

Eeq = EoCr+3- Cr O - 0.05916 X log

2 7
-2
[Cr+3]2
6 [Cr2O7-2][H3O+]14
Multiplying both side of this equation by 6, we get
6Eeq = 6EoCr+2- Cr O - 0.05916 X log [Cr+3]2
2 7
-2

1 [Cr2O7-2][H3O+]14
........eq 2
By Adding eq 1 and eq 2, we get
Eeq + 6Eeq = Eo Fe+2- Fe+3 + 6EoCr+3- Cr O - 0.05916
2 7
-2

1
X log [Fe+2].[Cr+3]2
[Fe+3].[Cr2O7-2][H3O+]14

The stoichiometry at equivalence point is,

[Fe+3] = 3 [Cr+3]
[Fe+2] = 6 [Cr2O7-2]
Substituting these values in above equation, we get
7Eeq = Eo +2
Fe - Fe
+3
+ 6EoCr+3- Cr O - 0.05916
2 7
-2

1
X log 6[Cr2O7-2].[Cr+3]2
3[Cr+3].[Cr2O7-2][H3O+]14

7Eeq = Eo +2
Fe - Fe
+3
+ 6EoCr+3- Cr O - 0.05916
2 7
-2

1
X log 6[Cr2O7-2].[Cr+3]2
3[Cr+3].[Cr2O7-2][H3O+]
7Eeq = Eo +2
Fe - Fe + 6EoCr+3- Cr O - 0.05916
+3
2 7
-2

1
X log 2[Cr+3]
[H3O+]14
Potential at equivalence point, thus depend upon
concentration of product as well as
concentration of H+ ions at pH 1,
[H+] = [H3O+] ~ 10-1 and
[Cr+3] = 0.0167
Eo Fe+2- Fe+3 = 0.771 v and EoCr+3- Cr O = 1.36 v
2 7
-2

7Eeq = 0.771+ 6 X1.36-0.05916 X log [2x0.0167]

[10-1]14
Eeq = 1.167 v
4. After the equivalence point
When 10.1 cm3 0.0167 M Cr2O7-2 is added

When 10.1 cm3 0.0167 M Cr2O7-2 has been added

then 0.1 ml Cr2O7-2 will be in excess.
At this stage, only Cr+3- Cr2O7-2 redox couple is
responsible for electrode potential and it
calculated as
E = EoCr+3- Cr O - 0.05916 X log
2 7
-2
[Cr+3]2

n [Cr2O7-2][H3O+]14
[Cr2O7-2] = 0.1 X 0.0167 = 8.31 X 10-5
20.1
[Cr+3] = 10 X 0.0167 = 8.31 X 10-3
 EoCr+3- Cr2O7-2 = 1.36 v and [H3O+] = 10-1

Putting all these values in above equation

E = 1.36 - 0.05916 X log [8.31 X 10-3]2

6 [8.31 X 10-5][10-1]14

E = 1.232
4. After the equivalence point
When 11 cm3 0.0167 M Cr2O7-2 is added

When 11 cm3 0.1 M Ce+4 has been added then 1

cm3 Cr2O7-2 will be in excess.

At this stage, only Cr+3- Cr2O7-2 redox couple is

responsible for electrode potential and it
calculated as

E = EoCr+3- Cr O - 0.05916 X log

2 7
-2
[Cr+3]2

n [Cr2O7-2][H3O+]14
EoCr+3- Cr2O7-2 = 1.36 v

[Cr2O7-2] = 1 X 0.0167 = 7.952 X 10-4

21
[Cr+3] = 10 X 0.0167 = 7.952 X 10-3
21
[H3O+] = 10-1
n = 6
E = 1.36 - 0.05916 X log [7.952 X 10-3]2
6 [7.952 X 10-3][10-1]14
E = 1.242 v
Volume in Cm3 of 0.0167 M
Cr2O7-2 added Esystem in V

0.0 -

2.0 0.735

5.0 0.771

9.9 0.889

10.0 1.169

10.1 1.232

11.0 1.242

12.0 1.260
Titration curve of Fe+2 Vs Cr2O7-2 titration

1.4
1.2
1
0.8
Esystem 0.6
0.4
0.2
0
2 5 9.9 10 10.1 11 12

Volume of 0.1 M Cr2O7-2 added