UV VISIBLE SPECTROSCOPY

ELECTRONIC TRANSITION

The absorption of UV or visible radiation corresponds to the excitation of outer

electrons. There are three types of electronic transition which can be considered;

1. Transitions involving , , and n electrons

2. Transitions involving charge-transfer electrons
3. Transitions involving d and f electrons (not covered in this Unit)

When an atom or molecule absorbs energy, electrons are promoted from their
ground state to an excited state. In a molecule, the atoms can rotate and vibrate
with respect to each other. These vibrations and rotations also have discrete energy
levels, which can be considered as being packed on top of each electronic level.

Absorbing species containing , , and n electrons

Absorption of ultraviolet and visible radiation in organic molecules is restricted to

certain functional groups (chromophores) that contain valence electrons of low
excitation energy. The spectrum of a molecule containing these chromophores is
complex. This is because the superposition of rotational and vibrational transitions
on the electronic transitions gives a combination of overlapping lines. This appears
as a continuous absorption band.

Possible electronic transitions of , , and n electrons are;

* Transitions

An electron in a bonding  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 * transitions) shows an absorbance maximum
at 125 nm. Absorption maxima due to * transitions are not seen in typical
UV-Vis. spectra (200 - 700 nm)

n* Transitions

Saturated compounds containing atoms with lone pairs (non-bonding electrons) are
capable of n* transitions. These transitions usually need less energy
than * transitions. They can be initiated by light whose wavelength is in the
range 150 - 250 nm. The number of organic functional groups with n* peaks
in the UV region is small.

n* and * Transitions
Most absorption spectroscopy of organic compounds is based on transitions
of n or  electrons to the * 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  electrons.

Molar absorbtivities from n* transitions are relatively low, and range from 10

to100 L mol-1 cm-1 . * transitions normally give molar absorbtivities between
1000 and 10,000 L mol-1 cm-1 .

The solvent in which the absorbing species is dissolved also has an effect on the
spectrum of the species. Peaks resulting from n* transitions are shifted to
shorter wavelengths (blue shift) with increasing solvent polarity. This arises from
increased solvation of the lone pair, which lowers the energy of the n orbital. Often
(but not always), the reverse (i.e. red shift) is seen for * 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 n* transitions but is overshadowed by the blue shift resulting
from solvation of lone pairs.

CHROMOPHORE

The term chromophore was previously used to denote a functional group of some other
structural feature of which gives a color to compound. For example- Nitro group is a
chromophore because its presence in a compound gives yellow color to the compound. But
these days the term chromophore is used in a much broader sense which may be defined as
“any group which exhibit absorption of electromagnetic radiation in a visible or ultra-visible
region “It may or may not impart any color to the compound. Some of the important
chromophores are: ethylene, acetylene, carbonyls, acids, esters and nitrile groups etc. A
carbonyl group is an important chromophore, although the absorption of light by an isolated
group does not give rise to any colour in the ultra-violet spectroscopy.

Types of chromophores: 
Two types of chromophores are known.
1. Chromophores in which the groups have π electrons undergo π-π* transitions. For
examples:-ethylenes, acetylenes etc.
2. Chromophores having both π- electrons and n (non-bonding) electrons undergo two types
of transitions. i.e., π-π* and n-π*, for examples: - carbonyls, nitriles, azo compounds and
nitro compounds etc.

AUXOCHROMES: 
It is a group which itself does not act as a chromophore but when attached to a chromophore,
it shifts the adsorption towards longer wavelength along with an increase in the intensity of
absorption. Some commonly known auxochromic groups are: -OH, -NH2, -OR, -NHR, and –
NR2. For example:- When the auxochrome –NH2 group is attached to benzene ring. Its
absorption change from λ max 225 (ɛmax 203) to λmax 280 (εmax1430). All auxochromes
have one or more non-bonding pairs of electrons. If an auxochromes is attached to a
chromophore, it helps is extending the conjugation by sharing of non-bonding pair of
electrons as shown below.     
CH2=CH–NR2---------------->CH2-CH-NH2
The extended conjugation has been responsible for bathochromic effect of auxochromes.
SPECTRAL SHIFTS

Absorption and Intensity Shifts

1. Bathochromic shift/effect (Red shift)

2. Hypsochromic shift/effect (Blue shift)

3. Hyperchromic effect

4. Hypochromic effect

Bathochromic shift/effect (Red shift):

It is an effect due to which the absorption maximum is shifted towards longer wavelength for
the presence of an auxochrome or by the change of polarity of solvent. The n → π* transition
for carbonyl compounds experiences red shift when the polarity of solvent decreased.

Hypsochromic shift/effect (Blue shift):

It is an effect due to which the absorption maximum is shifted towards shorter wavelength for
the removal of conjugation (auxochrome) or by the change of polarity of solvent. In aniline,
absorption maximum occurs at 280 mµ as the pair of electorns on nitrogen atom is in
conjugation with π bond system of the benzene ring but in acidic solutions, a blue shift occurs
at shorter wavelength (~203 mµ). In aniline ion formed in acidic solution, the electron pair is
no longer present and hence conjugation is removed.
Hyperchromic shift/effect:

It is an effect due to which the intensity of absorption maximum (εmax) increases. For
example, the B-band for pyridine at 257 mµ εmax 2750 is shifted to 262 mµ εmax 3560 for
2- methyl pyridine. Introdcution of an auxochrome usually increases intensity of absorption.

Hypochromic effect:

It is defined as an effect due to which the intensity of absorption maximum decreases, i.e.,
extinction coefficient, εmax . For example, biphenyl absorps at 250 mµ εmax 19000 whereas
2-methyl biphenyl absorbs at 237 mµ, εmax 10250 (εmax decreases). Introduction of methyl
group distorts the geometry of the molecules thus, cause hypochromic effect.

Solvent Effect
Solvents play an important role in UV spectra. Compound peak could be obscured by the
solvent peak. So a most suitable solvent is one that does not itself get absorbed in the region
under investigation. A solvent should be transparent in a particular region. A dilute solution
of sample is always prepared for analysis. Most commonly used solvents are as follows.

Solvent λ of absorption

Water 191 nm

Ether 215 nm

Methanol 203 nm

Ethanol 204 nm

Chloroform 237 nm

Carbon tetrachloride 265 nm

Benzene 280 nm 

Tetrahydrofuran 220 nm

LAWS GOVERNING ABSORPTION OF RADIATION

When a beam of light falls on a solution or homogeneous media, a portion of light is

absorbed within the medium while the remaining is transmitted through the medium.  Thus
if I0 is the intensity of radiation falling on the media, Ia is the amount of radiation absorbed
and It as the amount of radiation transmitted then,

I0=Ia+ It
Where I = Intensity of Incident light

Ia = Intensity of absorbed light

I t = Intensity of transmitted light

c = molar concentration of sample

b = Length or thickness of the sample cell (cm)

Lambert’s Law :

When a monochromatic light passes through an absorbing medium at right angles to the
plane of surface of medium or solution, the rate of decrease in intensity with thickness of
medium (b) is proportional to the intensity of incident light. In other words the intensity of
transmitted light decreases exponentially as the thickness of medium increases arithmetically.
DEVIATION FROM BEER LAMBERT’S LAW

True deviation : True deviations are related to the concentration of the absorbing substance. Beers
law holds good only for dilute solutions. 

Chemical deviation : Chemical deviations arise if the absorbing species undergo chemical changes
such as association, complex formation, dissociation, hydrogen bonding, hydrolysis, ionization or
polymerization

Instrumental Deviation :

Only monochromatic light gives beers law use of polychromatic light gives negative deviation.

Any fluctuations in intensity of light, change in the sensitivity of detector, improper slit width can
lead to deviation from beer lamberts law.