UV Spectroscopy

-Ms. Bansari Bharatbhai Patel

Introduction

 UV-Vis spectroscopy is an analytical technique that measures the amount of discrete

wavelengths of UV or visible light that are absorbed by or transmitted through a sample in
comparison to a reference or blank sample.
 The wavelength range of UV visible spectroscopy lies between 200-800 nm.
 UV absorption spectra arises from transition of electrons from lower to higher energy
levels and the UV emission spectra arises from the reverse type of transition.
Electronic Transition
 When a molecule absorbs UV radiation, the electrons in the molecules undergoes transition
from lower to higher energy levels or molecular orbit. The energy difference can be
denoted as:
E= hv
 The energy required for transition is determined by energy difference between ground state
Eo and excited state E1 of the electron.
E1-Eo = hv
 There are three types of electrons involved in the organic molecules. They are:
 Sigma electrons: They are involved on saturated bonds. For e.g.: bond between carbon and
hydrogen in paraffins. The amount of energy required to excite theses electrons are very high than
that produced by UV light and hence it does not get excited by UV radiation and so they are
useful as solvents.
 Pi- electrons: They are involved on unsaturated hydrocarbons. E.g.: Trienes and aromatic
compounds.
 n electrons: They are not involved on bonding between atoms and molecules. E.g.: organic
compounds containing nitrogen, oxygen and halides.
Types of Transition
 s ® s * 
 An electron in a bonding s orbital is excited to the corresponding antibonding orbital. The
energy required is large. For example, methane (which has only C-H bonds, and can only
undergo sigma to sigma* transitions) shows an absorbance maximum at 125 nm.
Absorption maxima due to sigma to sigma* transitions are not seen in typical UV-Vis.
spectra (200 - 700 nm)
 n ® s* 
 Saturated compounds containing atoms with lone pairs (non-bonding electrons) are
capable of n - s* transitions. These transitions usually need less energy than s - s *
transitions. They can be initiated by light whose wavelength is in the range 150 - 250 nm.
The number of organic functional groups with n - s* peaks in the UV region is small.
 n - pi* and pi - pi*
 Most absorption spectroscopy of organic compounds is based on transitions of n or p
electrons to the p* excited state. This is because the absorption peaks for these transitions
fall in an experimentally convenient region of the spectrum (200 - 700 nm). These
transitions need an unsaturated group in the molecule to provide the p electrons.
 The change in energy values for different molecules are in following order:
n ® s*  < pi - pi* < n ® s* < s ® s * 
 Terminologies

 The Chromophore
 Compounds which absorb light of wavelength in the range 400 – 800 nm are colored to the human eye.
A chromophore is any part of a substance which is responsible for imparting color to the substance.
Thus, nitro group is a chromophore which imparts yellow in color. Aryl conjugated azo compound is
another important example of chromophore which produce color to azo dyes. Thus, the term
chromophore can be defined as any isolated covalently group that shows characteristic absorption in the
UV- or the visible region. Some other important chromophores are ethylenic, acetylenic, carbonyls,
acids, esters, nitrile group etc.
 The Auxochrome
 An auxochrome can be defined as any group which does not itself act as a chromophore but whose
presence in a compound brings about a shift of the absorption band towards the red of the spectrum (i.e.
longer wavelength). Some common auxochromes are – OH, -OR, -NH2, -NHR, -NR2, -SH etc. This
effect is due to its ability to extend the conjugation of a chromophore by the sharing of non-bonded
electrons. For example, benzene shows an absorption at 255 nm (λmax = 203) whereas aniline absorbs
at 280 nm. Thus amino group is an auxochrome.
Absorption and intensity shift
 Bathochromic effect or red shift:
 When the absorption maximum is shifted towards longer wavelength due to the presence
of a chromophore or by the change of solvent then the effect is called bathochromic shift.
Such shift towards longer wavelength is called red shift.
 Hypsochromic shift or blue shift:
 When the absorption wavelength is shifted toward the shorter wavelength then the effect is
called hypsochromic shift. This is commonly known as blue shift. This effect is due to the
removal of conjugation or change in polarity of the solvent. The absorption maximum of
aniline is 280 nm whereas in acidic medium it is shifted to 203 nm. It is because in acidic
medium the lone pair of electron on nitrogen atom forms bond with acidic hydrogen and
hence electron pair is no longer present and conjugation is removed.
 Hyperchromic shift:
 When the intensity of the absorption maximum is increased the effect is called
Hyperchromic shift. i.e. λmax increases. The incorporation of an auxochrome in an organic
molecule usually increases the intensity of absorption and hence exhibits hyperchromic
shift.
 Hyperchromic shift:
 It is the shift where intensity of absorption maximum decrease. When the geometry of a
molecule is distorted due to the introduction of group this type of shift may take place. For
example, biphenyl absorbs at 250 nm, whereas 2- methyl biphenyl absorbs at 237 nm.