4.

ESTIMATION OF Fe2+ BY POTENTIOMETRIC TITRATION

Expt. No.:4 Date:9 AUG 2016

Group No. 1

Aim
To estimate the amount of ferrous ion present in the whole of the given
solution by potentiometric redox titration.

Principle
Potentiometric titrations depend upon the measurement of emf between the
reference electrode and an indicator electrode. When a solution of ferrous ion is
titrated with a solution of potassium dichromate, the following redox reaction takes
place.
2
6 Fe 2 Cr2 O7 14 H 6 Fe 3 2Cr 3 7 H 2 O

During this titration Fe2+ is converted into Fe3+, whose concentration increases. At the
end point, there will be a sharp change due to removal of all Fe 2+ ions.

In this method a cell is set up which consists of calomel electrode as

reference and an oxidation reduction system as indicator electrode. In this case the
oxidation-reduction system consists of excess of Fe 2+ ions which in turn is oxidized
to Fe3+ ions by potassium dichromate during the course of titration.

K 2Cr2O7 + 6FeSO4 + 7H 2SO4 K 2SO4 +Cr2 (SO4 ) 3 + 3Fe 2 (SO4 )3 + 7H 2O

This reaction changes the activity of Fe 2+ and Fe3+ ions in the solution. Thus
change in electrode potential of Fe3+ / Fe2+ system takes place accordingly. Since the
emf of the cell depends on electrode potential of indicator electrode, the emf
measurement can be used to determine the equivalence point of titration of Fe 2+
against dichromate solution.
The oxidation potential of this redox system is given by
E = E0 + (RT/F) ln [Fe3+] / [Fe2+]
Where E0 is the redox potential of the ferrous - ferric system
 R = 8.314 J/K/mol,
F = 96500 coulombs
The potential difference between two electrodes which causes the flow of current
from higher oxidation potential to lower oxidation potential is called emf of the cell.

When K2Cr2O7 is added to the system, Fe2+ is converted into Fe3+ whose
concentration increases with the progressive addition of K 2Cr2O7. The observed emf
will gradually increase. At the end point, there will be a sharp increase due to
sudden removal of all Fe2+ ions. A plot between emf measured E Vs volume of
K2Cr2O7 added and E / V Vs average volume of K 2Cr2O7 added is drawn and the
end point is determined graphically.
Procedure:
Transfer the given unknown ferrous ion solution in to a clean 100 mL standard
flask. Make up the solution upto the mark with distilled water and mix well. 10 mL of
made up Fe2+ solution is pipetted out into a clean 100 mL beaker and a platinum
electrode is inserted. A cell is formed by connecting this with saturated calomel
electrode, through a salt bridge and connected to the potentiometer. One mL of
potassium dichromate solution is added to the beaker, stirred well and emf is
measured. The titrant is added in steps by 1 mL and corresponding emf is measured.
When the rise of emf is rapid the amount is reduced to 0.2 mL per step and the
measurements are continued till the rise is more gradual. The titrant added is
increased to 1mL per step beyond the equivalence point. Record the emf reading
after each addition.

Plot two graphs by taking

1. EMF in y-axis and volume of K 2 Cr2 O7 added in x-axis,

2. E/ V in y-axis and average volume of K 2 Cr2 O7 added in x-axis.

From the graph the end point is determined and from the endpoint the strength and
hence the amount of Fe2+ ion present in one litre of the given solution is calculated.
Equivalent Weight of Fe2+ ion is 55.85.
Graphs:
Graph between Volume of K 2 Cr2 O7 Vs. EMF
800

700

600

500

400
EMF (V)
300

200

100

0
0 2 4 6 8 10 12 14

Volume of K2Cr2O7 (in ml)

A graph between Vavg Vs E / V

1200

1000

800

600
EMF (Volts)

400

200

0
7.3 7.7 8.1 8.5 8.9 9.3 9.7 10.1
7.1 7.5 7.9 8.3 8.7 9.1 9.5 9.9 10.3

Volume of K2Cr2O7 (in ml)

Observation and Calculation:
Rough titration
Strength of Standard Potassium dichromate = 0.1 N
Volume of ferrous solution = 20 mL.
volum
emf e
50 0
118 1
148 2
169 3
187 4
205 5
223 6
247 7
295 8
602 9
632 10
653 11
659 12
670 13

Fair Titration
Strength of Standard Potassium dichromate = 0.1 N
Volume of ferrous solution = 20 mL.
VOL OF AVERAGE
SINO K2Cr2O7 emf E V E/V VOLUME
1 0 50
2 7 255 54 7 7.71 7.1
3 7.2 261 6 0.2 30 7.3
4 7.4 273 12 0.2 60 7.5
5 7.6 275 2 0.2 10 7.7
6 7.8 287 12 0.2 60 7.9
7 8 293 6 0.2 30 8.1
8 8.2 338 45 0.2 225 8.3
9 8.4 548 210 0.2 1050 8.5
10 8.6 570 22 0.2 110 8.7
11 8.8 589 19 0.2 95 8.9
12 9 607 18 0.2 90 9.1
13 9.2 617 10 0.2 50 9.3
14 9.4 621 4 0.2 20 9.5
15 9.6 630 9 0.2 45 9.7
16 9.8 637 7 0.2 35 9.9
 17 10 642 5 0.2 25 10.1

CALCULATIONS

Volume of K 2 Cr2 O7 (from derivative graph, E/V vs. Avg. volume)

(V1) = 8.5mL.

Normality of K 2 Cr2 O7 (N1) = 0.1 N.

Volume of Fe2+ solution (V2) = 20 mL.
Normality of Fe2+ solution (N2) = 0.0425N

Amount of Fe2+ present in 1 litre of the given solution= Eq. wt. (55.85) x Normality

= 2.374 g
Result:
1. Equivalence point determined from the graph = 8.5 mL.
2. The amount of Fe2+ ion present in one litre of the given solution = 2.374 g

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