Spectroscopic Methods

Lab EXPT. 3 DETERMINATION OF CHROMIUM AND

MANGANESE IN A MIXTURE
Structure
3.1 Introduction
Objectives
3.2 Principle
3.3 Requirements
3.4 Solutions Provided
3.5 Procedure
3.6 Observations and Calculations
3.7 Result
3.8 Precautions

3.1 INTRODUCTION
In the previous two experiments you have learnt about the spectrophotometric
determination of the concentration of iron and nickel ions respectively by calibration
plot method. In these experiments the metal ions were converted into suitable
complexes that were coloured and formed the basis for their determination. In this
experiment you would learn about the simultaneous determination of two species whose
UV-VIS spectra have overlapping regions. You would recall that you have learnt about
this aspect of UV-VIS spectrophotometry in subsection 2.6.4 of Unit 2 of MCH-003
course. It would be worthwhile to have a relook at the same.

In this experiment you would determine the amount of chromium and manganese in a
given mixture. These are present as dichromate and manganate ions respectively. In fact
this determination mimics the determination of the amount of chromium and
manganese in alloy steels wherein these are oxidised to dichromate and permanganate
ions respectively. The spectra of these ions overlap to certain extent. In the next
experiment you would learn about the determination of methylethyl ketone‒an
important industrial solvent.

Objectives
After studying and performing this experiment you should be able to:
• explain the principle underlying simultaneous spectrophotometric determination
of species with overlapping spectrum,
• carry out absorbance measurements for solutions on a spectrophotometer and
draw its UV-VIS spectrum,
• determine the wavelength of maximum absorption in the spectrum and compute
the corresponding molar absorption coefficient,
• calculate the concentrations of chromium and manganese in a mixture from the
absorption measurements of the mixture at two different wavelengths,
• apply and adapt the method of simultaneous determination for other similar
combination of ions.

3.2 PRINCIPLE
On dissolution of alloy steel containing chromium and manganese, we get these
elements as their ions; Cr3+ and Mn2+ ions respectively. In the determination, these are
oxidised respectively to dichromate and permanganate ions using potassium persulphate
and potassium periodate, respectively. The orange red coloured dichromate shows

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maximum absorption ( λmax ) at 440 nm while for the pink coloured permanganate the
λmax is at 545 nm. However, permanganate also absorbs at 440 nm to a smaller extent.
Similarly, dichromate ions also have small absorption at 545 nm (Fig.3.1.)

You would recall from

subsection 2.6.4 of Unit 2
of MCH-003 course that
in order to determine
these species we need to
find two wavelengths
where molar absorption
coefficient of two species
is different and it is
desirable that the
wavelengths are such
where the ratio of molar
absorptivities is largest.

Fig. 3.1: Schematic diagrams of the visible spectra of potassium dichromate and potassium
permanganate in 1M sulphuric acid, indicating the overlapping of the spectra and the
relative values of molar absorption coefficients
In simple words, both the species absorb at the wavelengths of maximum absorptions
mentioned above. Thus, the absorption of the solution containing a mixture of
dichromate and permanganate ions at these wavelengths would be the sum of the
absorbances of the two species. It can be shown that the absorbances of these two ions
obey Beer-Lambert’s law when measured individually and also in a mixture in presence
of 0.5 M sulphuric acid.

Under these conditions we can write the following expression assuming a unit path The general expressions
length. for the simultaneous
equations are:
A440 = ε Cr, 440 [Cr2 O 72− ] + ε Mn,440 [Mn O −4 ] … (3.1)
Aλ1 = C1 (ε 1 ) λ1 + C2 (ε 2 ) λ1

A545 = ε Cr, 545 [Cr2 O 72− ] + ε Mn,545 [Mn O −4 ] … (3.2) Aλ2 = C1 (ε1 )λ2 + C2 (ε 2 )λ2
Here, the meaning of the terms used is self evident. For example, ε Cr, 545 refers to the
molar absorption coefficient at 545 nm for chromium as dichromate ion; A440 refers to
the absorbance of the mixture at 440 nm and [Cr2 O 72− ] represents the concentration of
dichromate ions and so on. We need to solve these simultaneous equations to determine
both the species without their separation.

Solving Eq. (3.1) and (3.2) we get the following expressions for the concentrations of
dichromate and permanganate ions.
A440 (ε MnO− ) 545 − A545 (ε MnO − ) 440
[Cr O ] =
2
2−
7
4 4

(εCr O 2− ) 440 (ε MnO − ) 545 − (ε MnO − ) 440 (εCr O 2− ) 545

… (3.3)
2 7 4 4 2 7

[
A545 − (ε Cr O2− ) 545 Cr2 O 72− ]
[MnO ] =
−
4
2 7

(ε MnO− ) 545
… (3.4)
4

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Spectroscopic Methods Thus, the concentrations of the two ions can be obtained from the absorbance
Lab measurements at 440 and 545 nm, if we know the molar absorption coefficients for both
the ions at these wavelengths. The values of the molar absorption coefficients are
obtained from absorbance measurements of pure solutions of the two substances at the
designated wavelengths.

Fe3+, Ni2+, Co2+ and V2+ also absorb in these regions, therefore these should be absent
from the analyte solution.

3.3 REQUIREMENTS
Apparatus Chemicals
Spectrophotometer/ Filter photometer 1 Potassium dichromate
Matched cuvette 2 Potassium permanganate
Volumetric flasks (1 litre) 1 Sulphuric acid
Volumetric flasks (250 cm3) 2
Graduated pipette (10 cm3) 1
Beakers (100 cm3) 10
Weighing bottle 1
Burettes 2

3.4 SOLUTIONS PROVIDED

i) 1 M sulphuric acid (Reference blank): It is prepared by adding (with constant
swirling) 53.3 cm3 of analytical grade concentrated sulphuric acid into a one litre
flask containing about 500 cm3 of distilled water, allowing the flask to cool and
making up the volume using distilled water.

ii) Potassium dichromate (0.002 M) in 1M sulphuric acid: It is prepared by

accurately weighing 0.1471 g of analytical grade potassium dichromate and
quantitatively transferring to a 250 cm3 volumetric flask and adding sufficient
amount of 1 M sulphuric acid to dissolve it. Once the compound dissolves the
volume is made upto the mark with 1M sulphuric acid.

iii) Oxalic acid (0.005 M): It is prepared by accurately weighing 0.063 g of oxalic
acid and quantitatively transferring to a 100 cm3 volumetric flask and adding
sufficient amount of water to dissolve it. Once dissolved the volume is made upto
the mark with distilled water.

iv) Potassium permanganate (0.002 M) in 1 M sulphuric acid: It is prepared as

follows.
• Weigh about 1.8 g A.R. potassium permanganate and dissolve in 50 cm3 of
distilled water taken in a 100 cm3 beaker.
• Heat the solution to boiling and gently continue for about fifteen minutes.
• Cool the solution and filter through a plug of glass wool in the funnel.
• Take 10 cm3 of the filtrate in a 100 cm3 beaker and dilute to 100 cm3 with
1M sulphuric acid.
• Standardise the solution by titrating with a standard solution of oxalic acid
in acidic medium.
• Calculate the volume of the solution required to prepare 250 cm3 of
0.002 M solution.

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 • Take the requited volume of the standardised solution of potassium
permanganate in a 250 cm3 volumetric flask. Make up the volume with 1M
sulphuric acid.

v) Sample solution: prepared by suitably mixing the 0.002 M solutions of

potassium dichromate and potassium permanganate to make 10 cm3 of the
mixture and adding 10 cm3 of 1M sulphuric acid to it.

3.5 PROCEDURE
The procedure for the experiment can be divided into three components. These are
given below.
a) Determination of molar absorption coefficients of dichromate and permanganate
ions
b) Establishing the additivity of absorbance values of dichromate and permanganate
ions
c) Determination of the concentrations of dichromate and permanganate ions in the
mixture.
Follow the instructions given below in the sequential order to accomplish these tasks.

a) Determination of molar absorption coefficients for dichromate and

permanganate ions

1. Pipette out 20 and 40 cm3 respectively of the 0.002 M stock solution of

potassium dichromate into two 100 cm3 standard flasks and make up the
volume with 1M sulphuric acid. This would give 0.0004 M and 0.0008 M
solutions respectively of potassium dichromate. Mark the flasks
accordingly.
2. Pipette out 20 and 40 cm3 respectively of the 0.002 M stock solution of
potassium permanganate into two 100 cm3 standard flasks and make up the
volume with 1M sulphuric acid. This would give 0.0004 M and 0.0008 M
solutions respectively of potassium permanganate. Mark the flasks
accordingly.
3. Measure the absorbance values at 440 nm and 545 nm for the stock
solutions (0.002 M) of potassium dichromate and potassium permanganate
and the dilutions prepared in step 1 and 2. Make measurements in cuvettes
of 1 cm path length and use 1M sulphuric acid as the reference. Record the
values in Observation Table 3.1.
4. Calculate the molar absorption coefficients for potassium dichromate and
potassium permanganate at 440 nm and 545 nm as per the expressions
given under column 4 and 6 and record appropriately in the Observation
Table 3.1.

b) Establishing the additivity of absorbance values of dichromate and

permanganate ions at 440 and 545 nm

1. Take two clean burettes and fill them with 0.0008 M potassium dichromate
and 0.0004 M potassium permanganate respectively.
2. Take 7 beakers of 100 cm3 capacity labelled from 1 to 7 and transfer the
solutions of 0.0008 M potassium dichromate, 0.0004 M potassium
permanganate and 1M sulphuric acid as per the details given in column 2, 3
and 4 of the Observation Table 3.2.

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Spectroscopic Methods 3. Measure the absorbance values of the resulting solutions using 1M
Lab sulphuric acid as the reference and record your observations in the column
5 and 7 of Observation Table 3.2. You must use cuvettes having a path
length of 1 cm.
4. Calculate the absorbance values for the mixtures of potassium dichromate
and potassium permanganate at 440 nm and 545 nm by using Eq. (3.1) and
Eq. (3.2) respectively and record them in the column 6 and 8 of
Observation Table 3.2.
5. Compare the observed and calculated absorbance values for the validation
of additivity. Record your observations in the space provided after
Observation Table 3.2.

c) Determination of the concentrations of dichromate and permanganate ions

in the mixture.

1. Measure the absorbance values of the given sample solution taken in a

cuvette of path length equal to 1 cm. Use 1M sulphuric acid as the
reference and record your observations in the column 1 and 2 of
Observation Table 3.3.
2. Calculate the concentration of potassium dichromate and potassium
permanganate in the mixture by using Eq.(3.3) and Eq. (3.4) respectively
and record your results in the column 3 and 4 of Observation Table 3.3.

3.6 OBSERVATIONS AND CALCULATIONS

A. Determination of molar absorption coefficients for dichromate and
permanganate ions

Observation Table-3.1: Determination of molar absorption coefficients for

K2Cr2O7 and KMnO4 at 440 and 545 nm
A: Potassium dichromate
Column
1 2 3 4 5 6
S. No. Concentration Absorbanc ε 440 mm # Absorbance ε545 mm #
of K2Cr2O7 e at 440 A at 545 nm A
cK 2Cr2O7 nm = 440 nm = A545nm = 545nm
cK 2Cr2O7 cK 2Cr2O7
= A440 nm
1 0.002
2 0.0004
3 0.0008
Average = Average =
B: Potassium permanganate
S. No. Concentration Absorbance ε 440 mm # Absorbance ε545 mm #
of KMNO4 at 440 nm A at 545 nm A545nm
= 440 nm =
cKMnO4 = A440 nm cKMnO4 = A545nm cKMnO4

1 0.002
2 0.0004
3 0.0008
Average = Average =

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# the expression is valid only if the absorbance measure is made in a cuvette of path
length=1cm.
The molar absorption coefficients for the [Cr2 O 72− ] and [Mn O −4 ] ions are found to be:

ε 440 nm [Cr2 O 72− ] =

ε 545 nm [Cr2 O 72− ] =

ε 440 nm [Mn O −4 ] =

ε 545 nm [Mn O −4 ] =

B. Establishing the additivity of absorbance values of dichromate and

permanganate ions at 440 and 545 nm

Observation Table 3.2: The observed and calculated absorbance values for
the mixtures of potassium dichromate and potassium permanganate.

Column

1 2 3 4 5 6 7 8
S. No. Volume of Volume of Volume Absorbance Absorbance
0.0008 M 0.0004 M of 1 M at 440 nm at 545 nm
K2Cr2O7 KMnO4 H2SO4 = A440 nm = A545nm
(cm3) (cm3) (cm3)
Obsd. Calc.* Obsd. Calc.**

1. 50 0 1

2. 40 10 1

3. 30 20 1

4. 25 25 1

5. 20 30 1

6. 10 40 1

7. 0 0 1

* The absorbance value is calculated as per Eq. (3.1.)

** The absorbance value is calculated as per Eq. ( 3.2.)

Write your conclusions about the additivity of the absorbance values here.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

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Spectroscopic Methods C. Determination of the concentrations of dichromate and permanganate ions
Lab in the mixture.

Observation Table 3.3: Determination of the concentrations of dichromate

and permanganate ions in the mixture

Absorbance Absorbance cK 2Cr2O7 cKMnO4

at 440 nm at 545 nm
= A440 nm = A545nm A440 (ε MnO − ) 545 − A545 (ε MnO − ) 440 [
A545 − (ε Cr O 2 − ) 545 Cr2 O 72− ]
= 4 4
= 2 7

(ε Cr O 2 − ) 440 (ε MnO − ) 545 − (ε MnO − ) 440 (ε Cr O 2 − ) 545 (ε MnO − ) 545

2 7 4 4 2 7 4

cK 2Cr2O7 =

cKMnO4 =

3.7 RESULT
i) The concentrations of potassium dichromate in the given mixture is found to be
=............M

ii) The concentrations of potassium permanganate in the given mixture is found to be

= ............M

3.8 PRECAUTIONS

• All the reagents used must be of AR grade.

• All the glassware used must be quite clean.
• The measurements should preferably be made in cuvettes of 1 cm path length. (In
the absence of these the expressions given for calculation of molar absorption
coefficients and concentrations would need to be modified.)

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