Quantitative Analysis by Colorimetric Methods

Experiment No. 1
Object :
(a) To verify Beer-Lambert's law for the solution of KMnO4.
(b) To determine the concentration of a solution of KMnO4 by Colorimetric Method.

Basic Principles : Concepts and Equations :

When light (monochromatic) falls upon a medium, a portion of the incident light is absorbed
within the medium, and the remainder is transmitted.
If the intensity of incident light is expressed by Io, that of the absorbed light by Ia, that of the
transmitted light by It, then
Io = Ia + It
In spectrophotometry we measure the intensity of light and characterize its change by the sub-
stance. This change is typically expresses as percent transmittance or absorbance.

Transmittance (T) :
The fraction of the incident light transmitted by a thickness l of the medium, is called Transmit-
tance and is given by :

Absorbance (A) :
The reciprocal of Transmittance is called Absorbance (A) or Optical Density (OD), Absorbance can be
defined as the base-ten logarithm of the reciprocal of the transmittance and is given by :

A = log = log = - log T = (2- log % T)

Beer - Lambert Law :
Lambert Law : Relationship between transmitted light and thickness of the medium.
Beer Law : Relationship between transmitted light and concentration of the substance .
Combining these two laws :
A=acl
where
a = molar absorption coefficient or molar absorptivity or molar extinction coefficient
(it is a constant for a given molecule at a given wavelength of light.)
c = concentration of the absorbing substance . in mol/L = M
l = thickness of the medium, ie, the length of the cell containing the solution, usually 1 cm

This is the fundamental equation of Colorimetriy (spectrophotometry).

This law states that the amount of radiation absorbed or transmitted by a solution or medium is an
exponential function of the concentration of the absorbing substance present and of the length of the
path of the radiation through the sample.
(1)
Dr S K Mishra, Chemistry Department, Agra College, Agra
Requirements :
Apparatus :
Photoelectric colorimeter 113 (Systronics, India)
Matched Cuvette 2
Volumetric flasks (1 litre) 1
Volumetric flasks (500 ml) 2
Volumetric flasks (250 ml) 2
Volumetric flasks (100 ml) 6
Pippette (10 ml, 20 ml, 25 ml) 1
Graduated pipette (10 ml) 1
Weighing Tube 1
Chemicals :
Potassium Dichromate
Potassium Permanganate
Sulphuric Acid (18 M) .
DDW

Preparation of Solutions :

STOCK SOLUTIONS :
(i) 1 M Sulphuric acid (Reference blank) - It is prepared by adding (with constant swirling) 53.3 ml
of analytical grade concentrated sulphuric acid in to a one litre flask containing about 500 ml of dis-
tilled water, allowing the flask to cool and making up the volume using distilled water.
(iii) Potassium permanganate (0.0063 M) in 1 M sulphuric acid: It is prepared accurately weighing
15.8034 g of analytical grade potassium permanganate and quantitatively transferring to a one litre
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. (Molecular weight of KMnO4 =
158.03 g/mol)

WORKING SOLUTIONS :

Following working solutions of Potassium permanganate were prepared by

dilution with 1 M sulphuric acid.
• 0.05 M (7.9018 g/L)
• 0.025 M (3.9508 g/L)
• 0.0125 M (1.9754 g/L)
• unknown
• 0.003125 M (0.4938 g/L)
and make up the volume with 1M sulphuric acid.

(2)
Dr S K Mishra, Chemistry Department, Agra College, Agra
Observation :
Table- Absorbance for KMnO4 at 440 and 545 nm

S.N. Concentration Absorbance

of KMnO4 at 440 nm

1. 0.05 M (7.9018 g/L)

2. 0.025 M (3.9508 g/L)
3. 0.0125 M (1.9754 g/L)
4. unknown
5. 0.003125 M (0.4938 g/L)

Plotting the graph - concentration vs absorbance

Take concentration in ppm or molar on X axis and correspondind absorbance on Y axis and draw the
graph.

CALCULATION :
(1) The graph. between absorbance against concentration is straight line which proves the validity of
Beer-Lambert's law.

(2) Concentration of KMnO4 :

By the intrapolation from the graph, the concentration of unknown solution of KMnO4 is ------ M.

RESULT :

1. The plots of absorbance against concentration for solutions of Potassium permanganate is

straight line, thus Beer-Lambert Law is verified.

2. The concentrations of Potassium permanganate in the given given solution is found to be =

................ M

(3)
Dr S K Mishra, Chemistry Department, Agra College, Agra