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Spectroscopy I
PS03CORC01_PS03CIPC01_PS03CINC01_PS03CPHC01_PS03CANC01
Unit: I
A
Atomic Absorption Spectroscopytomic Absorption Spectroscopy
Atomic Absorption SpectroscopyAtomic Absorption Spectroscopy
I.1. Introduction
Spectroscopy is the study of the interaction between matter and electromagnetic
radiation.
Atomic absorption, along with atomic emission, was first used by Guystav Kirchhoff
and Robert Bunsen in 1859 and 1860, as a means for the qualitative identification of atoms.
Although atomic emission continued to develop as an analytical technique, progress in atomic
absorption languished for almost a century. Modern atomic absorption spectroscopy was
introduced in 1955 as a result of the independent work of A. Walsh and C. T. J. Alkemade. 18
Commercial instruments were in place by the early 1960s, and the importance of atomic
absorption as an analytical technique was soon evident.
I.2. ABSORPTION OF RADIATION BY ATOMS
AAS is based on the absorption of radiant energy by free gas phase atoms. In the
process of absorption, an atom changes from a low-energy state to a higher energy state.
Gas phase atoms do not vibrate in the same sense that molecules do. Also, they have
virtually no rotational energy. Hence no vibrational or rotational energy is involved in the
electronic excitation of atoms. As a result, atomic absorption spectra consist of a few very
narrow absorption lines, in contrast to the wide bands of energy absorbed by molecules in
solution.
Each element has a specific number of electrons “located” in an orbital structure that is
unique to each element. The lowest energy electronic configuration of an atom is called the
ground state.
The ground state is the most stable electronic state. If energy ∆E of exactly the right
magnitude is applied to a free gas phase atom, the energy will be absorbed. An outer electron
will be promoted to a higher energy, less stable excited state. The frequencies and wavelengths
of radiant energy capable of being absorbed by an atom are predicted from ∆E = hν = hc/λ. The
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