Experiment Number: 02

Date: August 25, 2023

Name: k.nemalnath reddy

Registration number: 2023003651

Estimation of Chromium (VI) in

Potassium Dichromate.

Objective:
To learn about

 To understand about dichrometry reactions of redox titrations.

 To know the action of external indicator and its structural changes during the course of reaction.

 To identify the importance of phosphoric acid in the reaction.

Introduction:
Estimation of Chromium (VI) in potassium dichromate by titration against standard solution of
Mohr’s salt.

Significance:

 Chromium is used to harden steel, to manufacture chromium steels (stainless steel), namely
Nickel, Chromium steels of high tensile strength, more resistant to corrosion and shocks.

 Chromium plating can be used to give a polished mirror finish to steel.

 Chromium compounds are used as industrial catalysts and pigments.

 Chromium is important in the metabolism of fats and carbohydrates.

Theory:

Potassium dichromate (K2Cr2O7) acts as an oxidizing agent in the presence of sulphuric acid or
hydrochloric acid oxidizes ferrous iron to ferric iron, getting it self reduced to a green colored
chromic (Cr+3) salt. Mohr’s salt is a reducing agent with the formula (NH4)2SO4.FeSO4.6H2O.

In acid solution, the reduction of potassium dichromate may be represented as: K2Cr2O7 + 4H2
SO4 ® K2 SO4 +Cr2 (SO4 )3 + 4H2O+ 3(O) K2Cr2O7 +8HCl ® 2KCl + 2CrCl3 + 4H2O +3(O) From either
of these equations it follows that the equivalent weight of potassium dichromate is one sixth of
the molecular weight.

The nascent oxygens so liberated oxidize iron (II) to iron (III).

K2Cr2O7 + 4H2 SO4 ® K2 SO4 +Cr2 (SO4 )3 + 4H2O+ 3(O) 6FeSO4 + 3H2 SO4 +3(O) ® 3Fe2 (SO4 )3 +
3H2O K2Cr2O7 + 7H2 SO4 + 6FeSO4 ® K2 SO4 +Cr2 (SO4 )3 + 3Fe2 (SO4 )3 + 7H2O

Diphenylamine (DPA) is used as an external indicator to locate the end point in this titration.
Potassium dichromate, being an oxidizing agent, will also oxidize diphenylamine. The oxidation of
iron (II) to iron (III) imparts green color to the iron (II) solution due to the formation of chromic
sulphate, which deepens to blue green color shortly before the end point of the titration.

The oxidation of DPA imparts intense purple or bluish violet color and it represents the end point
of the titration.

The standard reduction potential values of the active species involved in this titration are as
follows.

Species
E0Reduction Values
+1.33V
Cr6+/Cr3+
Fe3+/Fe2+ +0.77V
DPA(oxidized)/DPA +0.76V

Following the potential values, it is clear that dichromate having highest value (+1.33V) acts as an
oxidizing agent and it will first oxidize DPA preferentially and then Fe2+. As a result, the solution in
the conical flask first gets a bluish violet color which then turns to unclear green color. This leads
to ambiguity in sharp detection of the end point. To avoid this, syrupy phosphoric acid is added,
which reacts with Fe3+ forming stable ferric phosphate. In other words, the Fe3+ ion gets
 stabilized and more Fe2+ ions gets oxidized to Fe3+ , as a result of which the oxidation potential
value of iron increases or, its reduction potential values decreases. The reduction potential value
of iron drops from +0.77V to +0.62V. As a result, dichromate oxidizes Fe2+ first and then DPA. This
facilitate in clear visualization of the end point.

Species
E0Reduction Values
+1.33V
Cr6+/Cr3+
Fe3+/Fe2+ +0.62V
DPA(oxidized)/DPA +0.76V

When once all the ferrous ions completely oxidized with dichromate, an excess drop of dichromate
will oxidize the indicator DPA. This gives a purple or bluish violet color to the solution and it is the
endpoint.

Materials and Equipment:

Chemicals: Mohr’s salt, potassium dichromate, sulphuric acid, phosphoric acid and diphenylamine
Apparatus: Standard volumetric flask, pipette, burette, conical flask, beakers, funnel and glass rod.

Procedure:
 The given potassium dichromate solution is diluted up to the mark of volumetric flask with
distilled water carefully.
 The flask is stoppered tightly and is shaken thoroughly about 3 to 5 minutes for complete
homogenization.
 10.0 ml of standard Mohr’s salt solution is pipetted out into a clean conical flask carefully.
 40.0 ml of distilled water, 5.0 ml of 1:1 dilute sulphuric acid and 3.0 ml of syrupy
phosphoric acid are added with a measuring cylinder.
 One or Two drops diphenylamine indicator is added directly to the conical flask contents.
 The burette is filled with the above potassium dichromate solution after rinsing with the
same solution and then initial reading is noted.
 Now the conical flask contents are titrated against potassium dichromate solution with
constant thorough shaking until the color changes from colorless - pale green, - dark green
– bluish green to bluish violet,which is the end point of the reaction.
 The final reading of the burette is noted without parallax error. Titrations are repeated
until 2 or 3 concurrent results are obtained.

Data and Observations:

The results are tabulated in Table II.

Table II: Titration of potassium dichromate solution with a standard solution of Mohr’s salt.
 Normality of standard solution of Mohr’s salt is = N

Indicator: 1 or 2 drops of diphenylamine solution.

Color change at the end point: Bluish green to bluish violet.

Sl. No. Volume of Burette readings Burette readings Burette readings

Mohr’s salt Volume of Volume of Volume of
solution taken in K2Cr2O7 K2Cr2O7 K2Cr2O7 solution
ml (V3) solution Initial solution Final Final(ml)consumed
(ml) (ml) consumed in ml -initial(ml)
in ml (V4)
01 10ml 0 14.1 14.1
02 10ml 14.1 28.3 14.2
03 10ml 28.4 42.3 13.9

Average =14.1+14.2+13.9/3=42.2/3=14.06ml(V4).

Calculations and Results:

By the law of equivalence,

N3V3 = N4V4

N3 = Normality of Mohr’s salt solution = 0.05N

V3 = Volume of Mohr’s salt solution = 10ml

N4 = Normality of potassium dichromate solution = ?

V4 = Volume of potassium dichromate solution = 14.06ml

 N4 = V3 N3 / V4

=0.05*10/14.06

=0.035N

Normality of unknown potassium dichromate solution =0.035 N

Eq.wt.of chromium (VI) in potassium dichromate = At. wt./6 =104/6 =17.33.

Amount of chromium (VI) present in 1000 ml of solution = Normality of an unknown dichromate

solution  equivalent weight of chromium (VI) = 0.03517.33 = 0.606 g.

Amount of chromium (VI) present in the given 100 ml solution = Amount present in 1000 ml of
solution / 10 =0.606/10 =0.060 g.

Report: The amount of chromium(VI) present in a given 100 ml of an unknown solution is =0.060 g.

Conclusion:
 The objective of the experiment was successfully achieved by accurately determining the Chromium
(VI) in potassium dichromate by titration against standard solution of Mohr’s salt.

The calculated concentration was 0.060mol/g, indicating that the experiment was carried out
effectively.

References:
 Experiments in Applied Chemistry, S. Rattan, S. K Kataria and Sons.
 Vogel’s textbook of quantitative chemical analysis, J. Mendham, R. C. Denney, J. D. Barns,
M. Thomas, B. Sivasankar, Pearson India Education, 6th Edition.

The student remarks on experiment:

Questions:

1) Which is stronger oxidizing agent potassium dichromate or potassium permanganate? Justify.

2) Write the structure of diphenylamine and di-phenylbenzidine.

3) Why sulphuric acid is usually used in redox titration? Why not HCl or HNO3?

4) Is it possible to quantitatively determine Cr ions by this method?

Sources of Error:

1. regular water instead of distilled water.

2. No Care is taken while preparing cement solution .
3. There may be any leakage from burette.
4. Before using any solution, not shaking it properly.
5. While noting burette reading for permanganometry not took any care since permanganate is
violet colour.

Safety:

Precautions:
 Care should be taken while preparing cement solution.
 There should not be any leakage from burette.
 Before using any solution, shake it properly.
 While noting burette reading for permanganometry much care should be taken since
permanganate is violet colour.

Remarks:

No remarks regarding the experiment.

NOTES: