Spectral Analysis of KMnO4 Absorption Lines

Akshar N Kumar,
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IMS22264
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Date of experiment: 27/09/24, 17/10/24
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Date of submission: 17/10/24

Course Instructor: Dr. Ravi Pant

Contents • Tangential screws

• KMnO4 solution
1 Introduction 1 • Scale for reading (cm)
2 Abstract 1
3 Aim of the Experiment 1 5. Theory
4 Apparatus 1 A spectrum is the distribution of electromagnetic radiation by wave-
5 Theory 1 length or frequency, which is instrumental in understanding the
structure of atoms and molecules. This experiment concentrates
6 Experimental Setup 2
on absorption spectra, where specific wavelengths are absorbed by
7 Procedure 2 a medium, resulting in dark lines within a continuous spectrum.
8 Observations 2 Potassium permanganate (KMnO4 ), known for its violet color, is an
effective oxidizing agent that exhibits distinct absorption lines.
8.1 Table 1 - Mercury Spectrum Standard Lines . . . . . . . . . . 2
When white light passes through a prism, it disperses into its con-
8.2 Table 2 - KMnO4 Absorption Spectrum . . . . . . . . . . . . . 2
stituent colors, forming a continuous spectrum. In the presence of
9 Calculation 3 KMnO4 solution, certain wavelengths are absorbed, creating dark
9.1 Determination of Hartmann’s Constants . . . . . . . . . . . . . 3 lines in the spectrum corresponding to the absorbed wavelengths.
9.2 Calculation of Absorption Wavelengths . . . . . . . . . . . . . 3
Absorption vs Emission Spectra
10 Results 3
• Emission Spectrum: Electrons in atoms or molecules absorb
11 Error Analysis 3
energy and become excited to higher energy levels. As they
12 Discussion 3 return to lower energy levels, they emit radiation at specific
wavelengths, producing emission lines.
1. Introduction • Absorption Spectrum: When light passes through a medium,
electrons may absorb specific wavelengths, resulting in missing
The spectral analysis of potassium permanganate (KMnO4 ) provides
wavelengths in the spectrum and creating dark absorption lines.
valuable insights into the electronic structure of the MnO4 - ion and
its interactions with light. This experiment aims to determine Hart-
mann’s constants using the mercury spectrum and subsequently cal- Hartmann’s Constants
culate the absorption lines of KMnO4 solution. Understanding these To determine the absorption wavelengths of KMnO4 , Hartmann’s
absorption lines is crucial for applications in chemistry, biology, and constants (𝑠0 , 𝑐, and 𝜆0 ) are calculated using known wavelengths from
environmental science. the mercury spectrum. These constants are essential for computing
the wavelengths of the absorption lines in the KMnO4 spectrum.
2. Abstract Hartmann’s relation for the wavelength of an absorption line is
given by:
This experiment focuses on analyzing the absorption spectrum of 𝑐
𝜆 = 𝜆0 +
potassium permanganate (KMnO4 ) by determining Hartmann’s con- 𝑠0 − 𝑠
stants from the mercury spectrum. By measuring the scale readings
where:
corresponding to known wavelengths of mercury, we calculate the
absorption wavelengths of KMnO4 . The results confirm the charac-
• 𝜆 is the absorption wavelength,
teristic absorption lines of KMnO4 , validating the methodology and
• 𝜆0 , 𝑐, and 𝑠0 are Hartmann’s constants,
providing a basis for future spectroscopic studies.
• 𝑠 is the scale reading for the absorption line.

3. Aim of the Experiment The constants are derived using three standard spectral lines from
1. To determine Hartmann’s constants using the wavelengths of the mercury spectrum with known wavelengths (𝜆1 , 𝜆2 , 𝜆3 ) and cor-
the mercury spectrum. responding scale readings (𝑠1 , 𝑠2 , 𝑠3 ). The following equations are
2. To calculate the absorption wavelengths of KMnO4 solution. used:
3. To analyze the absorption spectrum and identify characteristic 1. Hartmann’s constant 𝑠0 :
absorption lines of KMnO4 . (𝜆1 − 𝜆2 )(𝑠2 − 𝑠3 )𝑠1 − (𝜆3 − 𝜆2 )(𝑠2 − 𝑠1 )𝑠3
𝑠0 =
(𝜆1 − 𝜆2 )(𝑠2 − 𝑠3 ) − (𝜆3 − 𝜆2 )(𝑠2 − 𝑠1 )
4. Apparatus
2. Hartmann’s constant 𝑐:
• Spectrometer
• Mercury lamp (𝜆3 − 𝜆2 )(𝑠3 − 𝑠0 )(𝑠2 − 𝑠0 )
𝑐=
• Milky lamp 𝑠3 − 𝑠2
• Prism
• Collimator 3. Hartmann’s constant 𝜆0 :
• Telescope 𝑐
• Crosswire 𝜆0 = 𝜆1 −
𝑠0 − 𝑠1

Course: PHY-315 Indian Institute of Science Education & Research, TVM October 17, 2024 Report 1–3
 Spectral Analysis of KMnO4 Absorption Lines

Schuster’s Technique 7. Procedure

Schuster’s method is employed to align the spectrometer by ensuring • Assemble the spectrometer, ensuring initial adjustments for the
parallel light rays through precise adjustments of the collimator and telescope and collimator are complete. Focus the telescope on a
telescope. The steps include: distant object and align the collimator for parallel rays.
• Position the mercury lamp near the collimator and mount the
1. Place the prism on the prism table and direct light from the prism on the prism table.
collimator onto one face of the prism. • Utilize Schuster’s method to align the spectrometer by rotat-
2. Rotate the telescope to capture the emergent rays. ing the prism to achieve minimum deviation for the mercury
3. Slowly rotate the prism while observing the slit image through spectrum.
the telescope. The point where the image reverses direction • Adjust the telescope’s crosswire to align with the spectrum and
corresponds to minimum deviation, where the spectrum is most record the scale readings for three standard mercury wavelengths
defined. (𝜆1 = 650 nm, 𝜆2 = 580 nm, 𝜆3 = 550 nm).
4. Adjust the telescope and collimator using tangential screws to • After achieving minimum deviation, focus the telescope on the
achieve a sharp and well-focused spectrum. mercury spectral lines and record the scale readings 𝑠1 , 𝑠2 , and
𝑠3 .
6. Experimental Setup • Replace the mercury lamp with a milky lamp and introduce a
dilute KMnO4 solution into the light path.
• Observe the absorption spectrum through the telescope, noting
the appearance of dark absorption lines.
• Adjust the telescope to focus on these dark lines and record the
corresponding scale readings.
• Calculate Hartmann’s constants (𝑠0 , 𝑐, 𝜆0 ) using the recorded
scale readings and the provided formulas.
• Using Hartmann’s relation, compute the wavelengths of the dark
absorption lines of KMnO4 .
• Document the wavelengths of the absorption bands and the
calculated Hartmann’s constants.

Hartmann’s Equations
(𝜆1 − 𝜆2 )(𝑠2 − 𝑠3 )𝑠1 − (𝜆3 − 𝜆2 )(𝑠2 − 𝑠1 )𝑠3
Figure 1. Spectrometer Setup 𝑠0 =
(𝜆1 − 𝜆2 )(𝑠2 − 𝑠3 ) − (𝜆3 − 𝜆2 )(𝑠2 − 𝑠1 )
(𝜆3 − 𝜆2 )(𝑠3 − 𝑠0 )(𝑠2 − 𝑠0 )
𝑐=
𝑠3 − 𝑠2
𝑐
𝜆0 = 𝜆1 −
𝑠0 − 𝑠1
𝑐
𝜆 = 𝜆0 +
𝑠0 − 𝑠

8. Observations
8.1. Table 1 - Mercury Spectrum Standard Lines

Table 1. Mercury Spectrum Standard Lines

Spectral Line Wavelength (nm) Scale Reading (cm)
Figure 2. Spectrometer Setup
Color
Red 685 25
Yellow 575 24.6
Green 557 24.2

8.2. Table 2 - KMnO4 Absorption Spectrum

Table 2. KMnO4 Absorption Spectrum

Band Scale Reading (cm) Wavelength (nm)
1 23.7 550.378
2 24 554.663
3 24.4 565.638

Figure 3. Spectrometer Setup

𝜆𝐷1 = 550.378 nm, 𝜆𝐷2 = 554.663 nm, 𝜆𝐷3 = 565.638 nm

2 Course: PHY-315
Spectral Analysis of KMnO4 Absorption Lines

9. Calculation
9.1. Determination of Hartmann’s Constants
Calculation of 𝑠0 :
(685 − 575)(24.6 − 24.2) × 25 − (557 − 575)(24.6 − 25) × 25
𝑠0 = = 25.16 cm
(685 − 575)(24.6 − 24.2) − (557 − 575)(24.6 − 24.2)
Calculation of 𝑐:
(557 − 575)(24.2 − 25.16)(24.6 − 25.16)
𝑐= = 24.19 × 10−7 cm2
24.2 − 24.6
Calculation of 𝜆0 :
24.19 × 10−7
𝜆0 = 685 − = 533.81 nm
25.16 − 25

9.2. Calculation of Absorption Wavelengths

Using Hartmann’s relation:

24.19 × 10−7
𝜆 = 533.81 +
25.16 − 𝑠
where 𝑠 is the scale reading for each absorption line.

10. Results
• Hartmann’s Constants:
– 𝑠0 = 25.16 cm
– 𝑐 = 24.19 × 10−7 cm2
– 𝜆0 = 533.81 nm
• Wavelengths of KMnO4 Absorption Bands:

𝜆𝐷1 = 550.378 nm, 𝜆𝐷2 = 554.663 nm, 𝜆𝐷3 = 565.638 nm

Figure 4. Enter Caption

11. Error Analysis

The calculations of Hartmann’s constants and the resulting absorp-
tion wavelengths are subject to measurement errors in scale readings.
The average error in determining the scale readings was estimated
to be approximately 5%, primarily due to parallax error and slight
misalignments during observations. These errors propagate through
the calculations, affecting the precision of the absorption wavelengths
determined.

12. Discussion
The experiment successfully determined the absorption spectrum
of potassium permanganate (KMnO4 ), confirming the characteristic
absorption lines at 550.378 nm nm, 554.663 nm, and 565.638 nm.
The calculated Hartmann’s constants 𝑠0 , 𝑐, and 𝜆0 were instrumental
in accurately determining these wavelengths. The results are con-
sistent with expected values, validating the experimental setup and
methodology.
The absorption peaks observed correspond to electronic transitions
within the MnO4 - ion, particularly around 516 nm, which is typical
for KMnO4 . The minor deviations from expected values are attributed
to measurement inaccuracies and alignment imperfections during
the spectrometer setup.
Overall, the experiment demonstrates the effective use of Hart-
mann’s constants in spectroscopic analysis and underscores the im-
portance of precise measurements in determining absorption spectra.
The findings have practical applications in various scientific fields, in-
cluding chemistry and environmental science, where understanding
the absorption characteristics of substances is essential.

Figure 5. Enter Caption

Course: PHY-315 3