282x Filetype PPTX File size 0.61 MB Source: cms.gcg11.ac.in
Introduction
UV spectroscopy involves the measurement of absorption of
light in the visible and ultraviolet regions (visible region 400-
800 nm ; uv region 200-400nm) by the substance under
investigation. Since the absorption of light involves the
transition from one electronic energy level to another within a
molecule, UV spectroscopy is also known as electronic
spectroscopy. This technique is complementary to fluorescence
spectroscopy, in that fluorescence deals with transitions from
the excited state to the ground state, while absorption
measures transitions from the ground state to the excited
state.
Principle of absorption spectroscopy
Molecules containing π-electrons or non-bonding electrons (n-
electrons) can absorb the energy in the form of ultraviolet or
visible light to excite these electrons to higher anti-bonding
molecular orbitals. The more easily excited the electrons (i.e.
lower energy gap between the HOMO and the LUMO), the longer
the wavelength of light it can absorb.
A very important condition for a molecule to absorb
electromagnetic radiation is that the energy of photon of radiation
must be equal to the energy difference between two vibrational or
rotational or electronic energy states of the molecule. A record of
the amount of radiation absorbed or transmitted by a given
sample as function of wavelength of radiation is called absorption
spectrum.
Beer’s Lambert law
When a beam of monochromatic light is passed through a
substance dispersed in a non-absorbing solvent,
absorption of light is directly proportional to molar
concentration of the absorbing substance as well as path
length of the sample substance.
Using the Beer-Lambert law:
where A is the measured absorbance, in Absorbance Units
(AU), is the intensity of the incident light at a given
wavelength, is the transmitted intensity, L the path length
through the sample, and c the concentration of the absorbing
species. For each species and wavelength, ε is a constant
known as the molar absorptivity or extinction coefficient.
Electronic
excitations
sigma to sigma* transition :
very high energy required
consequently occur at short
wavelength. Eg: methane.
n to sigma* transition: occur at
long wavelength than sigma to
sigma*. Eg: methyl chloride .
n to pi*transition: require small
amount of energy and take place
within the range of ordinary uv
spectrophotometer. Eg : carbonyl
group of saturated aldehydes and
ketones.
pi to pi* transitions : relatively
high energy requirement than n
to pi * transitions and absorption
generally takes place outside the
ordinary uv region. Eg : aldehydes
and ketones.
Effect of conjugation
conjugation of double
bonds lowers the energy
required for electronic
transition, molecules
containing conjugated
systems absorb radiations of
longer wavelength than in
case of non conjugated
systems.
Eg: 1,3-butadiene shows
max at 217 nm in contrast to
ethylene which shows at
175nm.
energy gap between
HOMO and LUMO decreases.
as the gap decreases
position of energy moves to
longer wavelength which falls
within the ordinary uv region.
no reviews yet
Please Login to review.