Experiment I

Determination of Iron(II)in Mohr Salt Solution Using Potassium Dichromate

Theory

As an oxidant, potassium dichromate has certain advantages over potassium

permanganate, but, since it is less powerful, its use is much more limited. However,
since it is obtained in a state of high purity and its solution in water is stable indefinitely
it can be used as a primary standard which is also a huge advantage behind its usage.

The half reaction for the dichromate system is:

Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O E° = 1.33 V

An important application of the dichromate ion (Cr2O72) is in its reaction with iron(II)
in which it is often preferred to the permanganate ion MnO4.

The relevant half reaction is:

Fe2+ → Fe3+ + e- E° = -0.77 V or Fe3+ + e- → Fe2+ E° = 0.77 V

hence, the total reaction is:

Cr2O72- + 6Fe2+ + 14H+ → 2Cr3+ + 6Fe3+ + 7H2O E° = 0.56 V

Unlike permanganate, titration against a dichromate solution requires an indicator.

Usually, Barium Diphenylamine Sulfonate (B D S) is used for a titration of Fe2+ with
K2Cr2O7. The colour change for this indicator is green to blue-violet and the standard
electrode potential is near 0.78 V.
The indicator aspect of such titrations
Diphenylamine and its derivatives have been successfully used as redox indicators. The
explanation is that colorless diphenylamine is irreversibly oxidized to colourless
diphenylbenzidine in a two-electron reaction

Diphenylbenzidine is then able to act as a two-electron reversible redox indicator to give

the purple-violet diphenylbenzidine violet

However, since diphenylamine is not very soluble in water, a more soluble derivative
of it like the 4-sulfonic acid is popularly used.
The barium salt of diphenylaminesulfonate is used as the indicator in this redox
titration. The following is the sequence of reactions on the part of the indicator when the
dichromate ion is present as excess following complete oxidation of Fe2+ to Fe3+.

( )
2
Ba 2+ O3S N [O] O3S N
H
N
H
SO3
H 2
Barium salt of diphenylbenzidine sulfonate
Barium salt of diphenylamine sulfonate (colorless)
(colorless)

2
O3S N N SO3

Barium salt of diphenylbenzidine violet sulfonate

(blue-violet)

Formal potentials of the diphenylamine derivatives are in the range 0.7–1.1 V.

The colour change of such titrations at the end point are shown below

In order to get a sharp end point, the standard reduction potential of the Fe3+/Fe2+ couple
needs to be lowered so that all Fe2+ present in solution is oxidized to Fe3+ and only then
the indicator shows a change in colour. This is achieved by adding phosphoric acid
(H3PO4) to the solution prior to the start of the titration. The standard electrode potential
for Fe3+ → Fe2+ reaction is lowered to ~ 0.61 V because H3PO4 stabilizes the Fe3+
formed in solution (as a result of oxidation of Fe2+) forming the stable species
[FeIII(HPO4)(H2O)5]+. Moreover, since the formed species [FeIII(HPO4)(H2O)5]+ is
colourless it helps to detect the color change more clearly and accurately during
titration, which in case of titrations is often referred to as detecting a sharp end point.

NB: The barium salt of the sulphonate of a Diphenylamine is used as the indicator
instead of the Diphenylamine compound itself for its enhanced solubility in
water.
Preparation of 250 ml (N/10) standard K2Cr2O7 solution
Method
About 1.2 g (precisely 1.225 g) of pure K2Cr2O7 is accurately weighed using a digital
balance followed by a complete transfer of the solid to a 250 ml volumetric flask using a
funnel. After dissolving the orange coloured solid completely, the volume is made up to
the mark by adding distilled water drop by drop with the help of a dropper.
The flask is then stoppered and the solid dissolved by shaking or turning the flask
upside down to make the solution homogeneous.

Strength of K2Cr2O7 solution with appropriate factor.

If exactly 1.225 g is weighed and transferred to a volumetric flask then the solution is
0.1 N or . However, if during weighing K2Cr2O7 that amount is not taken exactly

which is more likely then the amount taken divided by the amount that had to be taken
is referred to as the factor for the desired concentration.
Therefore if somebody weighed 1.237 g instead of 1.225 g, then the factor for the
desired strength for his or her solution would be . Hence the solution

would be termed as 1.0098 . Again if someone weighed under the desired weight that

had to be taken then the factor obviously would be less than 1.

Estimation of Ferrous iron (Fe2+) in Mohr salt using standard K2Cr2O7 solution
Method
25 ml of the iron(II) stock solution is transferred into a 250 ml conical flask using a
pipette. The solution is then diluted to 150 ml with distilled water. Subsequently, 25 ml
4N H2SO4 is added followed by 5 ml syrupy H3PO4. 5 drops of BDS indicator is then
added and the solution is titrated against standard K2Cr2O7 solution running it from a
burette with constant stirring of the conical flask until the first prominent blue-violet
coloration appears.

The burette-reading is noted and the titration is repeated at least thrice.

Calculation:

1000 ml 1N K2Cr2O7 solution ≡ 55.847 g of Fe(II) ≡ 392.143 g of Mohr salt

Experiment II
Determination of the Total Hardness of Water
Theory:
Hardness of water arises primarily due to dissolved bicarbonate, chloride, sulphate salts
of Ca2+ and Mg2+ ions and may be estimated by titration with a chelating agent ethylene
diaminetetraacetic acid (EDTA) using Eriochrome-Black-T (EBT) as indicator in what
is known as a complexometric titration since a complex is formed with the metal ions
either by the substance used as the titrating agent or by the indicator material. EDTA &
EBT both individually form complex compounds with these metal ions.

Ca2+ and Mg2+ ions form stable complexes with EDTA in the pH range 8-11. The
stability order of the metal-complexes formed either with EDTA or with EBT in
solution follows the sequence: Ca-EDTA complex > Mg-EDTA complex > Mg-EBT
complex >Ca-EBT complex. Accordingly, EDTA first reacts with free Ca2+ ions, then
with free Mg2+ ions, then with the Mg-EBT & Ca-EBT complexes (wine-red colour) i.e.
with Ca2+ ions bound to EBT and Mg2+ ions bound to EBT. Hence, towards the end of
the titration the bare EBT indicator (blue colour) is set free. Consequently, there is a
colour change from wine-red to blue (colour of free EBT indicator) denoting the end
point of the titration.

Hardness is expressed in parts of CaCO3 (equivalent of Ca and Mg salts) per million

parts of water i.e., in ppm.

Eriochrome-Black-T Indicator (EBT): It is a typical complexometric titration

indicator, also known as Solochrome Black-T and is obtained as mono sodium salt. It
contains two dissociable phenolic protons and is often abbreviated as H2D.

In the experimental pH range (8-11) EBT (Na+H2D) exists as HD2 (one of the two
phenolato -OH is now deprotonated) in its free form and exhibits a blue colour.
Metal ions like Ca2+ and Mg2+ react with the indicator in the pH range 8-11 (in presence
of NH3/NH4Cl buffer solution) to form a wine-red metal-indicator complex.

M2+ + HD2 (free indicator, blue) = MD (Metal-Indicator, wine-red) + H+

EDTA (Y2) finally expels the indicator out from the metal complex with EBT, setting
free the EBT (HD2) and forming the stronger metal-EDTA complex (colourless) during
the course of titration. This event is reflected by the end point colour being a clear blue.

MD + Y2 (EDTA soln, colourless) + H+ = MY (Metal-EDTA, colourless) + HD2

(free indicator, blue)
Standard EDTA solution is supplied.
Titration Procedure:
25 ml of the hard water sample is taken in a 250 ml conical flask. 25 ml deionized
water is added. 5 ml NH3/NH4Cl buffer solution (to maintain a pH of 8-11) and 30-40
mg EBT (with KNO3) indicator. The mixture is then shaken to obtain a wine-red
colouration. This is then titrated with a standard EDTA solution running it from a
burette until the initial wine-red colour changes to clear blue. The titration is repeated
for concordant results.

Calculation:
1000 ml of (M/100) EDTA solution  1000 ml of (M/100) CaCO3
 1 g of CaCO3 (since Mol. Wt. of CaCO3 = 100)
 V ml of f (M/100) EDTA solution  (1 x V x f)/1000 g of CaCO3 (f = strength of
(M/100) EDTA)
 V x f x 103 g of CaCO3
[25 ml of hard water  V ml of (M/100) EDTA solution V: Burette reading]

25 parts of the hard water sample contains V x f x 103 parts of CaCO3 (since density
of water  1 at room temperature)
106 parts of hard water will therefore contain (V x f x 103 x 106)/25 parts of CaCO3
 Total hardness = V x f x 40 ppm
EBT is blue in a buffered solution at pH 10. It turns red when Ca2+ ions are added.