ATOMIC ABSORPTION AND

EMISSION SPECTRA

Ch. Devadasu
Asst. Professor,
Department of PA & QA
Joseph von Fraunhofer (1823)
 Atomic absorption
• Eight dark lines (A to H) in the solar spectrum were explained by
Fraunhofer in 1823 by the phenomenon of atomic absorption.

• Certain elements in the outer core of the sun absorb radiation of

specific wavelengths characteristic of the element.

• Absorption by sodium atoms gives rise to the intense line at 589.3

nm (D-line) in solar spectrum.
SOLAR SPECTRUM

589.3nm
• The excitation of electrons in atomic orbitals to
higher energy states may be induced by thermal
energy or electromagnetic radiation if the
energy of the radiation exactly matches to the
difference between the upper and lower energy
states.
Partial energy levels of sodium during the absorption of thermal
energy or electromagnetic radiation
• Atomic absorption spectrophotometry is a
technique for the quantitative determination
of metallic elements and metalloids, which is
based on the measurement of the absorption
of monochromatic light by ground state
atoms.
Kirchhoff and Bunsen( in the middle of the 19 th century )
 Atomic emission

• When certain atomic samples are heated, light

of characteristic colour is observed.
• This is due to the emission of visible radiation
at wavelengths characteristic of the elements
in the sample.
• The electrons of the gaseous atoms are in orbitals which have
specific energy levels that are characteristic of the element.
• The electrons in the outer orbitals of the atoms may absorb
thermal energy and may be promoted one or more higher energy
states.
• Absorption of energy is a specific quantity which is
corresponding to the difference between the energy levels.
• This process is called excitation.
• Deactivation of thermally excited atoms to lower
energy states occur very rapidly and photons of light
are emitted.
• The light photons have energy that is exactly equal to
the difference between the upper and lower energy
states.

E  E U  E L

hc


• Where h = Planck's constant
• 4.132 × 10-15 e.V.s
• C= speed of light = 3 × 108 m/s

1240
E 
 nm

As the atomic energy are characteristic of the element, the

energies and wavelengths of light emitted are also
characteristic of the element.
• The atomic emission spectrum of sodium consists of approximately 20
lines, the most intense of which occurs at 589.3 nm.
• The line at 589.3 nm is emitted when valence electrons thermally excited
electrons (from the 3s orbital to the 3p orbital) return to the ground state.
• The difference between the energy levels of the 3p and 3s orbitals
corresponds with the wavelength is calculated from Bohr’s equation,

1240
λnm 
(2.1  0)

= 589 nm
• Less intense lines at 330.2 nm and 819 nm are
due to 4p 3s and 3d 3p
respectively.

Flame emission spectrometry (flame photometry) and

emission spectrography are based on the measurement
of light emitted from thermally excited atoms.