U.V.
-VISIBLE SPECTROSCOPY
Dr. Vijay Kumar Singh
Assistant Professor
Institute of Pharmacy
Bundelkhand University, Jhansi
Email:
[email protected] Chromophores
A moiety of a molecule responsible for selective
absorption of radiation in a given range.
The chromophore invariably contain double or triple
bonds and includes the C≡C, C=C, nitro (-NO2) and
nitroso (-N=O) groups, azo (-N=N-) group the carbonyl
(>C=O) and thiocarbonyl (>C=S) groups etc.
Auxochromes
These moieties itself does not act as a chromophore but
when attached to a chromophore it shifts the absorption
maxima towards longer wavelength along with an increase
in the intensity of absorption. Ex. OH, NH2, CH3 and NO2
groups etc.
When -NH2 is attached to benzene ring its absorption
changes from λmax=255 (εmax=203) to λmax=280
(εmax=1430).
Spectral Shifts
Bathochromic shift – shift to longer λ; lower energy
(red shift)
Hypsochromic shift – shift to shorter λ; higher energy
(blue shift)
Hyperchromic effect – an increase in intensity(ε)
Hypochromic effect – a decrease in intensity (ε)
Spectral Shifts
λ
Solvent effect on absorption spectra
The solvent in which the absorbing species is dissolved
also has an effect on the spectrum of the absorbing
species.
Peaks resulting from nπ* transitions are shifted to
shorter wavelengths (blue shift), with increase in solvent
polarity. This arises from increased solvation of the lone
pair, which lowers the energy of the n orbital.
Solvent effect contd.
Bathochromic effect (i.e. red shift) is seen for π π* transitions.
This is caused by attractive polarisation forces between the
solvent and the absorber, which lower the energy levels of both
the excited and unexcited states. This effect is greater for the
excited state, and so the energy difference between the excited
and unexcited states is slightly reduced - resulting in a small red
shift.
This effect also influences nπ* transitions but is
overshadowed by the blue shift resulting from solvation of lone
pairs.
Solvent effect contd.
Relative order of stabilization: n > π* > π
π* π*
n
π
π* orbitals are
more stabilized
n orbitals are more stabilized comparison to π
comparison to π*
Solvent effect contd.
n * transitions are also very sensitive to H-
bonding. Alcohols as well as Amines form hydrogen
bonding with solvent molecules. Such transitions occur
because of non-bonding electrons on the hetero atom and
thus, transition requires greater energy.
Solvent effect contd.
Summary
The increase in polarity of the solvent generally shifts
nπ* and n* transitions to shorter wavelength
(blue shift) while π π* transitions shifts to longer
wavelength (red shift).
