UV SPECTROSCOPY

Absorption spectra
 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.
 Chromophore
• A chromophore is the part of a molecule responsible for its
color. The color arises when a molecule absorbs certain
wavelengths of visible light and transmits or reflects others.
The chromophore is a region in the molecule where the energy
difference between two different molecular orbitals falls within
the range of the visible spectrum. Visible light that hits the
chromophore can thus be absorbed by exciting an electron from
its ground state into an excited state.
 Auxochrome
• An auxochrome is a functional group of atoms with nonbonded
electrons which, when attached to a chromophore, alters both the
wavelength and intensity of absorption. If these groups are in direct
conjugation with the pi-system of the chromophore, they may
increase the wavelength at which the light is absorbed and as a result
intensify the absorption. A feature of these auxochromes is the
presence of at least one lone pair of electrons which can be viewed as
extending the conjugated system by resonance .
Changes in position and intensity of absorption

 Bathochromic(red) shift: it involves the shift of absorption

maximum towards longer wavelength. It can be brought about by-
attachment of auxochrome to chromophore, conjugation of two
or more chromophoric groups, using solvent of lower polarity.
 Hypsochromic(blue) shift: it involves the shift of absorption
maximum towards shorter wavelength. It may be brought about
by- removal of conjugation, using solvent of higher polarity.
 Hyperchromic effect: this effect involves an increase in the
intensity of absorption. It is brought about by introduction of
auxochrome.
 Hypochromic effect: it involves decrease in the intensity of
absorption. It is brought about by introduction groups which
distort the geometry of the molecule.
 Solvent effects
 n to pi* transition: increase  Pi to pi* transition: increase
in polarity of solvent shifts in polarity of solvent shifts
the transition to shorter the transitions to longer
wavelength(blue shift). wavelength(red shift).
Woodward fieser rules for calculating absorption maxima
 Assignment-I
 Define the term spectroscopy.

 Why are spectroscopic methods being increasing used for structure

determination?

 Why are spectroscopic techniques based upon absorption spectroscopy and not
emission spectroscopy?

 What is the range of uv-visible spectroscopy?

 How can you distinguish between cis- and trans- stilbenes?

 When p-aminophenol is dissolved in water, wavelength maximum is at longer

wavelength than in acid solution. Explain.

 Discuss electronic energy levels and electronic transitions in UV?

 What is Beer’s Lambert law of absorption?

Explain the principle of absorption spectroscopy?

Explain the following terms:

1. Bathochromic shift 2. Hypsochromic shift 3. auxochrome
4. Chromophore 5. molar absorptivity

Explain application of UV spectroscopy in determination of

configuration of geometrical isomers by taking examples.

Explain how does the UV spectrum of butadiene differ from that of

ethylene.

By taking examples, show the factors which cause a Bathochromic

shift in UV spectrum.

Discuss absorption laws in UV spectroscopy.

Explain effect of solvent on n to pi* and pi to pi* transitions.