EXPT.

1 - EXTERNAL INDICATOR
Aim:

To determine the strength of given solution of ferrous ammonium

sulphate by titrating against standard N/40 K2Cr2O7 using potassium ferricyanide
as an external indicator.

Principle:
Acidic K2Cr207 is a strong oxidizing agent. When it is added to ferrous ammonium
sulphate solution containing dilute H2SO4, only FeSO4 is oxidized and (NH4)2SO4
remains unchanged hence not shown in the equation. The reactions taking place
are as follows:
K2Cr2O7 + 4H2SO4
K2SO4 + Cr2(SO4)3 + 4H2O+ 3O
6FeSO4+ 3H2SO4+3O
3Fe2(SO4)3+ 3H2O
The complete reaction is:
K2Cr2O7+ 6FeSO4+7 H2SO4
3Fe2(SO4)3 + K2SO4+ Cr2(SO4)3+7H2O
Or ionically,

(Cr2O7)-2 + 14H+ + 6Fe2+
6 Fe3+ + 2Cr3+ + 7H2O

The end point on potassium dichromate titration is usually determined by using

two types of indicator. External indicator was once employed when no internal
indicator was available. Here the indicator cannot be added to the solution to be
titrated, but is placed in the depressions of a white glazed groove tile. About
0.1% solution of potassium ferricyanide acts as external indicatior. Freshly
prepared pot. Ferricyanide indicator is used because the old solution of it
becomes contaminated with potassium ferrocyanide. The use of potassium
ferricyanide as an external indicator is the best known example in the titration of
iron with dichromate. As long as ferrous ion is present in the titration mixture, the
indicator will turn blue on the transfer of solution. The appearance of blue colour
is due to the formation of ferroferricyanide (Turnbulls blue) according to flowing
reaction.
2K3Fe(CN)6 + 3FeSo4
Fe3[Fe(CN)6]2 + 3 K2SO4
Ferrous ferricyanide
Dark blue complex

Usually at the end point (all Fe+2 ions are oxidized to Fe+3) the color of the
indicators drop becomes light brownish yellow due to reaction of indicator with
Fe+3 ions to produce brown colored ferric ferricyanide complex.
Fe2(SO4)3 + 2K3[Fe(CN)6]
3K2SO4 + 2Fe[Fe(CN)6]
Brown

Thus, at the end point, the indicator fails to produce blue color when treated with
a drop of titration mixture.

Regents:
0.1% solution of potassium ferricyanide, standard N/40 K2Cr2O7 potassium
dichromate, ferrous ammonium sulphate, dilute sulphuric acid.

Apparatus:
Pipettes, burette, conical flask, glass rod, test tubes, white glazed tile.

Procedure:
Rinse and fill burette with standard N/40 K2Cr2O7 solution.
Pippette out 10ml of given ferrous ammonium sulphate solution in a clean conical
flask and add to it about equal volume of dilute H2SO4.
Put a series of drops of indicator (potassium ferricyanide solution) with the help
of glass rod, on a white tile/ plate.
Titrate the ferrous ammonium sulphate with standard solution of K2Cr2O7 from
the burette.
Near end point, take a drop of titration mixture and put it on one of these drops
on time and see the color.
A strong blue color will be produced. Continue the titrations and repeat the
process at different intervals and when the color of indicator drop does not give
blue color, the end point is reached.
Note the reading of the burette. Repeat the titration to get the exact end point.

Observations:
Burette: standard N/40 K2Cr2O7 solution
Pipette: 10 ml of ferrous ammonium sulphate solution
Indicator: 0.1% solution of potassium ferricyanide (freshly prepared)
Colour change: yellow to brown

Observation Table:

Burette Reading (ml)

Sr. No

Vol. of FAS used

Initial

Final

Vol of K2Cr207
used (ml)

1.

10ml

0.0ml

ml

2.

10ml

0.0ml

ml

3.

10ml

0.0ml

ml
V2=.........ml

Calculation:
Volume of unknown ferrous ammonium sulphate X normality of unknown ferrous
ammonium sulphate = Volume of standard K2Cr2O7 X normality
10 X N1 = V2 (Burette reading) X 0.025
N1=

0.025 X Burette reading

10

Strength = Normality of ferrous ammonium sulphate X Eq. weight of ferrous

ammonium sulphate
=..................................gm/lit

Result:
The strength of given
.....................gm/liter.

unknown

ferrous

ammonium

sulphate

is