UV VISIBLE SPECTROSCOPY

THEORY , INTRODUCTION AND INSTRUMENTATION

INTRODUCTION
 When a molecule is placed in front of a UV lamp then some of the light gets
absorbed and some remains unaffected.
 Light is absorbed according to the electronic structure of the molecule and
energy changes when a electrons promotes from ground state to excited
state.
 The energy transition from E1 to E2 is the energy equal to energy of
wavelength absorbed.
 ∆E = (E2-E1) = hc/λ
 A molecule can only absorb a particular frequency, if there exists within the
molecule an energy transition of magnitude
 £ = hv
 ultraviolet-visible RANGE- 190-400 nm and 400-800 nm : changes in electronic
energy levels within the molecule (extent of π electron systems, presence of
conjugated unsaturation, and conjugation with nonbonding electrons).
THEORY OF UV VISIBLE SPECTROSCOPY
 When a molecule absorbs energy then its orbitals are effected.
 Firstly electrons gains the energy and one electron flips from its ground state to its
excited state that is of the highest energy level while other electrons remains unaffected.
 For almost 10-15 sec electrons comes in a excited state and in that duration atoms of the
molecule does not move : FRANCK CONDON PRINCIPLE
 The transition will appear when one electron from the highest occupied molecular orbital
to the lowest available unfilled orbital.
 As a molecule absorbs energy, an electron is promoted from an occupied orbital to an
unoccupied orbital of greater potential energy. Generally, the most probable transition
is from the highest occupied molecular orbital (HOMO) to the lowest unoccupied
molecular orbital (LUMO). The energy differences between electronic levels in most
molecules vary from 125 to 650 kJ/mole (kilojoules per mole).
 When a transition is forbidden then the probability of transition occurrence is low. Not all
of the transitions that at first sight appear possible are observed. Certain restrictions,
called selection rules, must be considered.
 One important selection rule states that transitions that involve a change in the spin
quantum number of an electron during the transition are not allowed to take place;
they are called “forbidden” transitions.
 For most molecules, the lowest-energy occupied molecular orbitals are the σ orbitals,
which correspond to σ bonds. The π orbitals lie at somewhat higher energy levels, and
orbitals that hold unshared pairs, the nonbonding (n) orbitals, lie at even higher energies.
The unoccupied, or antibonding orbitals (π * and σ *), are the orbitals of highest energy.
 Here a diagram of energy transition is giving in which several orbitals are involved.
 In alkanes, promotion of an electron from a low-lying a orbital to a high-energy σ
antibonding orbital. Very short wavelength is required (190nm).
 In alkenes several transitions are available, but the lowest-energy transition is the most
important: this is the π to π* transition, which is responsible for the absorption band
around 170-190 nm in unconjugated alkenes.
 In saturated aliphatic ketones the lowest-energy transition involves the non
bonding electrons on oxygen, one of which can be promoted to the relatively
low-lying π* orbital: this n to π* transition is 'forbidden' in symmetry terms and
therefore the intensity is low, although the wavelength is long (around 280 nm).
 Two other transitions available are n to σ'* and π to σ*: these are both 'allowed'
transitions and give rise to strong absorption bands, but the energy involved is
higher than for n toπ * ; therefore, the wavelength of the absorption is shorter
(around 185 for n to σ* and around 160 for π to π*). The most intense band for
these compounds is always due to the π to π* transition.
 In conjugated dienes the π orbitals of the separate alkene groups combine to
form new orbital as in the diagram.
 Conjugated dienes, therefore, show absorption at much longer wavelength than
do isolated alkene groups, a typical value being around 217 nm.
 EFFECT OF CONJUGATION:In the presence of conjugated double bonds, the
electronic energy levels of a chromophore move closer together. As a result,
the energy required to produce a transition from an occupied electronic energy
level to an unoccupied level decreases, and the wavelength of the light
absorbed becomes longer.
 Law of light absorption
 BEER LAMBERT LAW
 Beer's law relates the absorption to the concentration of absorbing solute, and Lambert's law
relates the total absorption to the optical path length.


Log I0/I = Єcl = A/cl

 I0 is the intensity of the incident light (or the light intensity passing through a reference cell),
 I is the light transmitted through the sample solution,
 Log I0/I is the absorbance (A) of the solution (formerly called the optical density, c is the
concentration of solute.
 I is the path length of the sample and Є is the molar absorptivity (formerly called the
molecular extinction coefficient) and it is dimensionless.
 Chromophores. Originally, the term chromophore was applied to the
system responsible for imparting color to a compound.
 (The derivation is from the Greek chromophores, or color carrier.) Thus, in
azo dyes the aryl conjugated azo group (Ar- N = N - Ar) is clearly the principal
chromophore ; in nitro compounds the yellow color is carried by - N02 etc .
 The term has been retained within an extended interpretation to imply any
functional group that absorbs electromagnetic radiation, whether or not a
'color' is thereby produced.
 Thus, the carbonyl group is a chromophore in both ultraviolet and infrared
terms, even though one isolated C=O group is insufficiently 'powerful' to
impart color to a compound. (An isolated carbonyl group, as in acetone ,
absorbs ultraviolet light around 280 nm.)
 AUXOCHROME: An auxochrome was an earlier-defined term for a group
that could enhance the color-imparting properties of a chromophore without
being itself a chromophore, examples being -- O R , -NH2, -NR2, etc .
 The synergist effect of auxochromes is coupled with their ability to extend
the conjugation of a chromophore by sharing of the nonbonding electrons.
CONVENTIONS
 Absorption spectra in organic work are most often plotted with increasing Є
on the ordinate, and with wavelength (A) on the abscissa increasing from left
to right.
 a few spectrometers plot absorbance 'upside-down' to the normal convention.
 When a change in solvent or a change in a substituent causes λmax for a
band to shift , we can unambiguously state whether the shift occurs to longer
wavelength or to shorter wavelength. (Thus, conjugation of an alkene group
causes a shift to longer wavelength of the π - π* band.)
 Bathochromic shift (or red shift) is a shift to longer wavelength (that is,
toward the red end of the spectrum).
 Hypsochromic shift (or blue shift) is a shift to shorter wavelength. (The
expression blue shift is most confusing, since it could be applied to a shift
from 300 nm TO 250 nm , a direction that is receding from the wavelength of
blue light.)
 A hyperchromic effect is one that leads to increased intensity of absorption,
a hypochromic effect is the opposite.
Instrumentation
 It consists of three main components : light source , monochromator and
detector.
1. Light source: The light source is usually a deuterium lamp, which emits
electromagnetic radiation in the ultraviolet region of the spectrum.
A second light source, a tungsten lamp, is used for wavelengths
in the visible region of the spectrum.
 MONOCHROMATOR : The monochromator is a diffraction grating , its role is to
spread the beam of light into its component wavelengths. A system of slits
focuses the desired wavelength on the sample cell. The light that passes
through the sample cell reaches the detector, which records the intensity of
the transmitted light l .
 DETECTOR : The detector is generally a photomultiplier tube, although in
modern instruments photodiodes are also used.
 . In a typical double-beam instrument, the light emanating from the light
source is split into two beams, the sample beam and the reference beam.
 When there is no sample cell in the reference beam, the detected light is
taken to be equal to the intensity of light entering the sample .
 The sample cell must be constructed of a material that is transparent to
the electromagnetic radiation being used in the experiment.
 For spectra in the visible range of the spectrum, cells composed of glass or
plastic are generally suitable.
 For measurements in the ultraviolet region of the spectrum, however, glass
and plastic cannot be used because they absorb ultraviolet radiation.
 Instead, cells made of quartz must be used since quartz does not absorb
radiation in this region.
 The instrument design just described is quite suitable for measurement at
only one wavelength. If a complete spectrum is desired, this type of
instrument has some deficiencies.
 A mechanical system is required to rotate the monochromator and provide a
scan of all desired wavelengths.
 This type of system operates slowly, and therefore considerable time is
required to record a spectrum.
 A modern improvement on the traditional spectrophotometer is the diode-
array spectrophotometer.
 A diode array consists of a series of photodiode detectors positioned side by
side on a silicon crystal.
 Each diode is designed to record a narrow band of the spectrum. The diodes
are connected so that the entire spectrum is recorded at once.
 This type of detector has no moving parts and can record spectra very
quickly.
 Furthermore, its output can be passed to a computer, which can process the
information and provide a variety of useful output formats.
 Since the number of photodiodes is limited, the speed and convenience
described here are obtained at some small cost in resolution.
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