ULTRAVOILET SPECTROSCOPY

BY
FARAH KHAN

MSC CHEMISTRY
PRESENTATION TOPIC:
WHATTO LOOK FOR IN
ULTRAVOILET SPECTRUM?
 Ultraviolet Spectroscopy
o UV spectroscopy involves absorption spectroscopy where molecules interact with UV
radiation and produce absorption spectra in the range of 200nm to 400nm.

o The UV range in electromagnetic spectra is subdivided into two.

Far or Vacuum UV region; 10nm-200nm
Near OR QUARTZ UV region; 200nm-400nm

o UV spectroscopy is a molecular spectroscopic method arising due to transition of

valence electrons in a molecule from the ground state energy (E) to the higher state (E1).

o Then the difference in change of energy is

E1-E2 = hv
What is ultraviolet radiation?
 Ultraviolet (UV) is a form of electromagnetic radiation with 
wavelength from 10 to 400 nm shorter than that of visible light,
but longer than X-rays.
 UV radiation is present in sunlight, It is also produced by 
electric arcs and specialized lights, such as mercury-vapor lamps
, tanning lamps, and black lights.
Principle of UV spectroscopy:
 UV spectroscopy measure the response of a sample to UV rang of
electromagnetic radiation.
 1. In UV spectroscopy, the sample is irradiated with the broad spectrum
of the UV radiation
 2. If a particular electronic transition matches the energy of a certain
band of UV, it will be absorbed
 3. The remaining UV light passes through the sample and is observed
 4. From this residual radiation a spectrum is obtained with “gaps” at
these discrete energies – this is called an absorption spectrum
o Absorption Spectra
 When sample molecules are exposed
to light having an energy that
matches a possible electronic
transition within the molecule, some
of the light energy will be absorbed
as the electron is promoted to a
higher energy orbital.
The significant features:
1) Λ max
2) ε max intensity of maximum
absorption)
UV SPECTRUM OF ISOPRENE SHOWING
MAXIMUM ABSORPTION AT 222nm
 Energy absorbed in the UV region by valence electrons causes
transition from ground state to excited state.
 The valence electrons are excited from bonding to an antibonding
orbitals.
 The energy required for various transition are in the following order
 n→∏* < ∏→∏* < n→σ* < σ→σ*
TYPES OF ELECTRONS ARE INVOVLED IN UV
SPECTROSCOPY

σ electrons
 These electrons are involved in saturated bonds.
 The amount of energy required to excite electrons are high.
 σ Electrons do not absorbed near UV region, but absorbed in far UV
region.

Π electrons
 These electrons are involved in unsaturated compounds.
 Typically, compounds with π bonds are trienes and aromatic compounds

n electrons
 These electrons are not involved in bonding between atoms in
molecules.
 So it is called not bonded electrons
 Eg organic compounds containing nitrogen oxygen or halogens.
Theory of UV
Spectroscopy :
 UV visible absorption spectra originate from electronic transitions
 These transitions involving promotion of valence electrons
 Since various energy levels of molecules are quantized,
[1] σ - σ * transition
The transition or promotion of an electron from a
bonding sigma orbital to the associated antibonding
sigma orbital is σ - σ * transition. It is a high energy
process because σ bonds are generally very strong
and absorption band occurs in the far UV region
(125_135nm).Eg Saturated Hydrocarbons.
 EXAMPLE:
Methane(125nm)
Ethane(135nm)
Cyclopropane(130nm)
[2] n - σ * transition
Transition or promotion of an electron from a non-
bonding orbital to an antibonding sigma orbital is
designated as n - σ * transition. Compounds
containing non bonding electrons on a heteroatom
are capable of absorption due to n - σ *
Transitions. These transitions require lower energy
than σ- σ* transitions.
 EXAMPLE
Saturated Hydrogen containing with
unshared electyrons pairs (Oxygen,
Nitrogen,Sulphur,or Halogen) OR non
bonding electrons are capable of n - σ *
transition.
[3] π- π* transition
The transition or promotion of an
electron from a π bonding orbital to a
π antibonding orbital is designated π-
π* transition.
 EXAMPLE
These type of transitions occur in
compounds containing
Alkene,carbonyl compound and aromatic
compounds. one or more covalently
unsaturated groups like C=C,C=O,NO2 etc.,
π- π* Transitions require lower energy than
n - σ * transitions.
Aromatic compounds show a number of bands.
B benzenoid (B) band:
 This band is due to π- π* Transitions in aromatic or hetro
aromatic molecules .
 The benzene shows a broad absorption band containing
peak between 230-270nm.
 When a chromophoric group is attached to benzene ring,
the B-band are observed at longer wavelength.

Compound Transition λ max 'ε max

Benzene π-π* 255 215

Phenol π-π* 270 1450

Ethylenic (E) band:
 This band is due to the electronic transition in the
benzenoid system of three ethylenic bonds are in closed
cyclic conjugation
 These are further characterized as E1 and E2 bands.
 The E1 band of benzene , which appears at lower
wavelength (184nm )
 Is more intense than E2 band occurs at longer
wavelength (204 nm).

compound E1 Band E2 Band E1 Band E2 Band

λ max Ε max λ max Ε max

Benzene 184 50,000 204 79,000

Naphthalene 221 133,000 286 9,300

 K band:
 This band exhibited by aromatic compounds with the
benzene ring directly attached to a group containing
multiple bond.
 Eg: Styrene , Benzaldehydes etc.

Compound Transition λ max Ε max

Acetophenone π- π* 240 13,000

1,3-Butadiene π- π* 217 21,000

[4] n - π* transition
 The transition or promotion of an electron from a non-
bonding orbital to a π antibonding orbital is designated
n - π*. This transition reqires lowest energy.
 These transition is exhibit a weak band in their
absorption spectrum.
 The peak due t this transition is called R band .
 In aldehyde and ketones the band due to this transition
occur in the rang of 270 to 300nm.
 In aldehydes and ketones this arises from excitation of
a lone pair of electrons in the 2py orbitals of the oxygen
atom into the antibonding orbitals of the carbonyl group
 When hydrogen is replaced by methyl group in an
aldehyde group , this result in a shift of band due to the
shorter wavelength.
R Band:

 R-Band transition originate due to n-π* transition of a single

chromophoric group and having at least one lone pair of
electrons on the hetero atom
 These are less intense with ε max value below 100.

COMPOUND Transition Λ max Ε max

(nm)

Acetone n-π* 270 15

Acetone n-π* 293 12

Formation of Band or
Why Band Form?
 The spectrum consist of sharp peaks and each peak will
correspond to the promotion of electron from one
electronic level to another.
 During promotion, the electron moves from a given
vibrational and rotational level within one electronic
mode to the other within the next electronic mode.

 Thus, there will be a large no of possible transitions

Hence, not just one but a large no. of wavelengths which
are close enough will be absorbed resulting in the
formation of bands .
 APPLICATIONS OF UV:

 Detection of Impurities
 Structure
elucidation of organic
compounds
 quantitative
determination of
compounds that absorb UV radiation.
 Kinetics
of reaction can also be studied
using UV spectroscopy.
 Molecular weight determination.
 As HPLC detector
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