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Principle:
In acid medium, direct titration of Fe(II) + Fe(III) mixture with standard K2Cr2O7 solution gives
the titre value (V1) corresponding to the amount of Fe2+. To estimate Fe3+ present in the
mixture, it is first reduced to Fe2+ with Al-foils and the resulting solution is then titrated with
the same standard K2Cr2O7 solution. This titre value (V2) corresponds to the total iron (Fe2+ +
Fe3+). The difference (V2V1) corresponds to the amount of Fe3+.
3Fe3 + Al 3Fe2+ + Al3+
In acid medium K2Cr2O7 quantitatively oxidizes Fe2+ to Fe3+:
Cr2O72 + 14H+ + 6Fe2+ 2Cr3+ + 6Fe3+ + 7H2O
1/6 mol Cr2O72 1 mol Fe2+ = 1 equivalent
1000 ml 1 N K2Cr2O7 solution 55.85 gm Fe2+
H3PO4 (or NH4HF2) stabilizes Fe3+ by complex formation which is essential for indicator action
of BDS.
Chemicals required:
a) standard N/20 K2Cr2O7 solution (to be prepared by accurate
weighing)
b) N/20 Mohr’s salt solution
c) 4 N H2SO4
d) syrupy H3PO4 or NH4HF2
e) saturated aqueous solution of BDS indicator
f) Aluminium foil
Procedure:
1. Determination of Fe2+:
Pipette out an aliquot of 25 ml from the supplied Fe(II) + Fe(III) mixture in a 250 ml conical
flask. Add 25 ml of 4 N H2SO4, 3 ml syrupy H3PO4 (or 1-2 gm of NH4HF2) and 3-4 drops of
BDS indicator. Titrate with standard N/20 K2Cr2O7 solution until the colour of the solution
just changes from green to violet. The titre value (V1) corresponds to Fe(II) only. Calculate the
amount of Fe(II) in gm per litre present in the supplied solution.
1. Determination of total iron (Fe2+ + Fe3+):
Pipette out an aliquot of 25 ml from the supplied Fe(II) + Fe(III) mixture in a 500 ml conical
flask. Add 25 ml conc. HCl and a few pieces of A. R. Al-foils to the solution. Heat carefully
and shake by swirling the flask till the yellow colour of the Fe(III) solution is discharged (add
1-2 more pieces of Al-foils if the yellow colour of the solution still persists). Note that the foils
are completely disintegrated to give a clear solution. Dilute the solution with 100 ml of
distilled water to maintain the acidity to 2 N. Titrate the solution with same standard N/20
K2Cr2O7 solution until the colour changes from green to violet. The titre value (V2) corresponds
to total iron (Fe2+ + Fe3+) and the difference (V2V1) give the amount of Fe(III). Calculate the
amount of Fe(II) and Fe(III) in gm per litre present in the supplied solution.
Calculations:
1000 ml 1 N K2Cr2O7 55.85 gm Fe2+
V1 ml y N K2Cr2O7 55.85 V1 y/1000 gm Fe2+
Now 25 ml solution contains Fe2+ = 55.85 V1 y/1000 gm
1000 ml solution contains Fe2+ = (55.85 V1 y/1000) 1000/25 gm
So, the amount of Fe(II) ions present in the supplied solution = _______ gm per litre.
So, the amount of Fe(III) ions present in the supplied solution = _______ gm per litre.