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Analytical Aspects of Absorption


Spectroscopy, (UV and Visible
Spectroscopy)

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The word spectroscopy is derived from spectrum which means a bend of different
colours formed due to difference in wavelength and skopin means examination or
evaluation.

Thus, spectroscopy is the branch of science that deals with the examination or
evaluation of spectrum.
Absorption spectroscopy refers to spectroscopic techniques that measure the
absorption of radiation, as a function of frequency or wavelength, due to its interaction
with a sample. The sample absorbs energy, i.e., photons, from the radiating eld. The
intensity of the absorption varies as a function of frequency, and this variation is the
absorption spectrum. Absorption spectroscopy is performed across the electromagnetic
spectrum.
Electromagnetic radiation(EMR) is absorbed or emitted when the molecule atom or ion TOP
of the sample move from one energy state to another energy and the change in
rotational, vibrational and/or electronic energies are measured.

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1/25/2018 Analytical Aspects of Absorption Spectroscopy, (UV and Visible Spectroscopy) | PharmaTutor

Theory
The wavelength range of UV radiation is 200 nm- 400 nm. There are mainly two types of
UV region.
1. 200 nm- 400 nm that is called near ultraviolet region.
2. Below 200 nm that is called far ultraviolet region.

The wavelength of visible radiation is 400 nm- 800 nm.


Wavelength in UV and visible region is expressed in nanometers or in angstroms.
Absorption is expressed in terms of wave number (cm-1).

Absorption spectra arise from transition of electron or electrons within a molecule from
a lower electronic energy level to a higher electronic energy level. Ultraviolet emission
spectra arise from the reverse types of transition. For the radiation to cause electronic
excitation, it must be in the UV region of the EMR spectrum.
Radiation in this region is of su cient energy to cause electronic transition of outer
valence electrons.
Both organic and inorganic species exhibit electronic transitions in which outermost or
bonding electrons are promoted to higher energy levels.
Electronic transitions are associated with vibrational as well as rotational transitions.
A compound appears coloured if it selectively absorbs light in the visible region. The
main function of absorbed energy is to raise the molecule from ground energy state ( E0 )
to higher excited energy state ( E1 ). The difference is given by:

ΔE= E1- E0 = hv = hc/λ

ΔE depends upon how tightly the electrons are bound in the bonds and accordingly,
absorption will occur in UV or visible range, for example;
If the electrons of a molecule are tightly bound as in compounds containing sigma
bonds (e.g. saturated compounds) no light of region will be absorbed. The light of UV
region will only be absorbed and hence compound appears colourless.
If the electrons of molecule are loosely bound as in unsaturated compound. Such
absorption may occur in visible region and substance will appear as coloured.

Energy absorbed in the ultraviolet region produces change in the electronic energy of the
molecule that is resulting from transitions of valance electrons in the molecule. There
are three types of electrons in organic molecules.
a) σ (sigma) electrons- they are found in saturated systems like alkane. They require
large amount of energy for their excitation and hence do not show absorption in UV
region. Their absorption band is appeared in vacuum UV region. Hence, compounds
containing σ- bonds do not absorb in near UV region. For example saturated
hydrocarbons are transparent in near UV region and thus they can be used as solvents.

b) ∏ (pie) electrons- they are found in multiple bonds. They are generally mobile
electrons. Since ∏- bonds are weak bonds, the energy produced by UV radiation can
excite ∏- electrons to higher energy levels.

c) n (non-bonding) electrons- valance electrons which do not participate in chemical


bonding in molecule are called as non bonding electrons or n- electrons. These are
located principally in atomic orbital of N, O, S and halogens(X) as a lone pair of electrons.
They can be excited by UV radiation.

FIND MORE :-

Types of Transition EMR Spectra


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electrone-transition.html) radiation.html)

Beer-Lambert's Law Instrumentation


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law.html) of-absorption-spectroscopy.html)

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Effect of Solvent
Applications
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UV spectroscopy (/taxonomy/term/2079)
Visible Spectroscopy (/taxonomy/term/2080)

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