UNIT - 2

Ultra-violet and Visible Spectroscopy

Introduction

The alternate title for this technique is Electronic spectroscopy since it involves the promotion of
electrons (σ, π, π* electrons) from the ground state to the higher energy state.

It is very useful to measure the number of conjugated double bonds and also aromatic conjugation
within the various molecules.

It also distinguishes between conjugated and non-conjugated systems, α,β-unsaturated carbonyl

compounds from β,γ-analogues, homoannular and heteroannular conjugated dienes etc.,

For visible and ultra-violet spectrum, electronic excitations occur in the range 200-800 mμ and involve
the promotion of electrons to the higher energy molecular orbital.

Substances absorbing in the visible range will appear coloured to the human eye. The wavelength of
particular radiation absorbed can also be expressed in terms of frequency or energy in Kcal.mole-1

The range of UV-Visible Spectra

1μ = 10-4 cm

1mμ = 1 nm = 10-7 cm = 10 Å

Let us calculate the energy associated with radiations having wavelength 280 mμ

𝜆 = 280 𝑚𝜇 = 280 × 10−7 𝑐𝑚

We know that, 𝐸 = ℎ𝜈
𝑐
=ℎ × 𝜆
( ℎ = 6.62 × 10−27 𝑒𝑟𝑔𝑠 𝑠𝑒𝑐. )

Avogadro’s number 𝑁 = 6.023 × 1023

4.18 × 107 𝑒𝑟𝑔𝑠 = 1 𝑐𝑎𝑙𝑜𝑟𝑖𝑒

6.62 × 10−27 × 3 × 1010 × 6.023 × 1023

𝐸= 𝐾𝑐𝑎𝑙 𝑚𝑜𝑙𝑒 −1
280 × 10−7 × 4.18 × 107 × 103

≅ 100 𝐾𝑐𝑎𝑙 𝑚𝑜𝑙𝑒 −1

A record of the amount of light absorbed by the sample as a function of the wavelength of light in mμ or
nm units is called absorption spectrum which generally consists of absorption bands.

The Absorption Laws

There are two laws which govern the absorption of light by the molecules. These are:

Lambert’s law

Beer’s law.

1. Lambert’s law:

It states that, when a beam of monochromatic radiation passes through a homogeneous absorbing
medium, the rate of decrease of intensity of radiation with thickness of absorbing medium is
proportional to the intensity of the incident medium.

Mathematically, the law is expressed as,

𝑑𝐼
− = 𝑘𝐼
𝑑𝑥

where 𝐼 = intensity of radiation after passing through a thickness x, of the medium

𝑑𝐼 = infinitesimally small decrease in the intensity of radiation on passing through infinitesimally

small thickness, dx of the medium.

𝑑𝐼
= rate of decrease of intensity of radiation with thickness of the absorbing medium.
𝑑𝑥

𝑘 = proportionality constant or absorption coefficient. Its value depends upon the nature of the
absorbing medium.

Let I0 be the intensity of radiation before entering the absorbing medium (x=0).

Then I, the intensity of radiation after passing through any thickness, say x of the medium can be
calculated as:
𝐼 𝑥=𝑥
𝑑𝐼
∫ = − ∫ 𝑘. 𝑑𝑥
𝐼0 𝐼 𝑥=0

𝐼 𝐼
or ln = −𝑘𝑥 𝑜𝑟 = 𝑒 − 𝑘𝑥
𝐼0 𝐼0

𝐼 = 𝐼0 𝑒 − 𝑘𝑥

The intensity of radiation absorbed, 𝐼𝑎𝑏𝑠 is given by:

𝐼𝑎𝑏𝑠 = 𝐼0 − 𝐼 = 𝐼0 ( 1 − 𝑒 − 𝑘𝑥 )
The above Lambert’s law equation can also be written as,

𝐼 = 𝐼0 10− 𝑎𝑥

where a = extinction coefficient of the absorbing medium

𝑘
(𝑎 = )
2.303

2. Beer’s law:

This law states that, when a beam of monochromatic radiation is passed through a solution of an
absorbing substance, the rate of decrease of intensity of radiation with thickness of the absorbing
solution is proportional to the intensity of incident radiation as well as the concentration of the solution.

Mathematically, this law stated as,

𝑑𝐼
− = 𝑘 ′ 𝐼𝑐
𝑑𝑥

where c = concentration of the solution in moles litre-1.

K’ = molar absorption coefficient and its value depends upon the nature of the absorbing
substance.

Suppose I0 be the intensity of the radiation before entering the absorbing solution. (when x = a), then
the intensity of radiation, I after passing through the thickness x, of the medium can be calculated,
𝐼 𝑥=𝑥
𝑑𝐼
∫ = − ∫ 𝑘 ′ . 𝑐𝑑𝑥
𝐼0 𝐼 𝑥=0

′ 𝑐𝑥
or 𝐼 = 𝐼0 𝑒 − 𝑘

The above equation can also be written as,

′
𝐼 = 𝐼0 10− 𝑎 𝑐𝑥

𝑘′
Here 2.303 = 𝑎′ where 𝑎′ = molar extinction coefficient of the absorbing solution.

Beer-Lambert Law

𝐼0
𝑙𝑜𝑔 = ∈. 𝑐. 𝑙 = 𝐴
𝐼

where, 𝐼0 = Intensity of incident light

𝐼 = Intensity of transmitted light

𝑐 = Concentration of solution in moles litre-1

 𝑙 = Path length of the sample (usually 1 cm)

∈ = Molar extinction coefficient (or molar absorptivity)

𝐴 = Absorbance

Example 1.

2.5 X 10-4 M solution of a substance in a 1 cm length cell at λmax 245 nm has absorbance 1.17, calculate
∈𝑚𝑎𝑥 for this solution.
𝐴
We know that, ∈𝑚𝑎𝑥 = 𝐶𝑙

Here, A = 1.17, c = 2.5 X 10-4 M, l = 1 cm

Substituting the values, we get,

1.17
∈𝑚𝑎𝑥 =
2.5 × 10−4 𝑚𝑜𝑙 𝑙 −1 × 1 𝑐𝑚

1.17 × 104 × 103

=
2.5 𝑚𝑜𝑙. 𝑐𝑚−3 × 1 𝑐𝑚

= 0.468 × 107 𝑐𝑚2 𝑚𝑜𝑙 −1

Dissociation Energy

The energy required to dissociate a molecule into its constituent atoms is called dissociation energy.

Predissociation Spectra

In certain electronic bands, e.g., sulphur vapours, the discontinuous structure is present due to the
quantization of vibration. The bands show a diffuse appearance instead of a rotational fine structure.
These are called predissociation spectra, and have been observed particularly for polyatomic molecules
such as SO2, NH3, NO2 etc.

Measurement of Absorption Intensity

It may be noted that the intensity of absorption is directly proportional to the transition probability. An
allowed transition will have ∈𝑚𝑎𝑥 value greater than 1000 while those having low probability will have
its value less than 1000.

Selection rules:

The various electronic transitions which are governed by certain restrictions are called selection rules.
These are:

(i) The transitions which involve a change in the spin quantum number of an electron during
the transition do not occur. Thus, singlet-triplet transitions are forbidden.
(ii) The transitions between orbitals of different symmetry do not occur. For example, n→π*
transition is symmetry forbidden.

The wavelength of light corresponding to maximum absorption is written as λmax.

Theory of Electronic Spectroscopy

When the molecule absorbs ultraviolet or visible light, its electrons get promoted from the ground state
to the higher energy state.

In the ground state, the spins of the electrons in each molecular orbital are essentially paired.

In the higher energy state, if the spins of the electrons are paired, then it is called an excited singlet
state.

On the other hand, if the spins of the electrons in the excited state are parallel, it is called an excited
triplet state.

The triplet state is always lower in energy than the corresponding excited singlet state.

Therefore, triplet state is more stable as compared to the excited singlet state.

In the triplet excited state, electrons are farther apart in space and thus, electron-electron repulsion is
minimized.
Normally the absorption of ultraviolet or visible light results in singlet ground state to excited singlet
state transition, i.e., excitation proceeds with the retention of spins.

An excited singlet state is converted to excited triplet state with the emission of energy as light.

The transition from singlet ground state to excited triplet state is symmetry forbidden.

The higher energy states are designated as high energy molecular orbitals and also called anti-bonding
orbitals.

The highly probable transition due to absorption of quantized energy involves the promotion of one
electron from the highest occupied molecular orbital to the lowest available unfilled molecular orbital.

In most of the cases, several transitions occur resulting in the formation of several bands.

Types of Electronic Transitions

According to the molecular orbital theory, when a molecule is excited by the absorption of energy (UV
or visible light), its electrons are promoted from a bonding to an anti-bonding orbital.

1. σ to σ* transitions: The anti-bonding orbital which is associated with the excitation of σ electron is
called σ* anti-bonding orbital. So σ to σ* transition takes place when σ electron is promoted to anti-
bonding orbital. It is represented as σ→ σ* transition.

2. n to π* transitions: When a non-bonding electron n, gets promoted to an anti-bonding sigma orbital

σ*, then it represents n→σ* transition.

3. π to π* transitions: π→π* transition represents the promotion of π electrons to an anti-bonding π*

orbital.

4. n to π* transitions: When non-bonding n electron is promoted to anti-bonding π* orbital, it represents

n→π* transition.

The energy required for various transitions obey the following order:

σ →σ* > n→σ* > π→π* > n→π*

1. σ to σ* transitions

This type of transition is a high energy process since σ bonds are, in general, very strong.

The organic compounds in which all the valence shell electrons are involved in the formation of sigma
bonds do not show absorption in the normal ultra-violet region, i.e., 180-400 mμ.

For saturated hydrocarbons, like methane, propane etc. absorption occurs near 150 mμ (high energy).

The excitation of sigma bond electron to σ* level occurs with net retention of electronic spin. It is called
excited singlet state which may, in turn, gets converted to excited triplet state.

2. n to π* transitions

This type of transition takes place in saturated compounds containing one hetero atom with unshared
pair of electrons (n electrons).

Some compounds undergoing this type of transitions are saturated halides, alcohols, ethers, aldehydes,
ketones, amines etc.

Such transitions require comparatively less energy than that required for σ→σ* transitions.

3. π to π* transitions

This type of transition occurs in the unsaturated centers of the molecule, i.e., in compounds containing
double or triple bonds and also in aromatics.

The excitation of π electron requires smaller energy and hence, transition of this type occurs at longer
wavelength.

A π electron of a double bond is excited to π* orbital. For example, alkenes, alkynes, carbonyl
compounds, cyanides, azo compounds etc. show π to π* transition.

4. n to π* transitions

In this type of transition, an electron of unshared electron pair on hetero atom gets excited to π* anti-
bonding orbital.

This type of transition requires least amount of energy out of all transitions discussed above and hence
occurs at longer wavelengths.

Chromophore

All those compounds which absorb light of wavelength between 400-800 mμ appear coloured to the
human eye.

Exact colour depends upon the wavelength of light absorbed by the compound. Originally, a
chromophore was considered any system which is responsible for imparting colour to the compound.
It is defined as any isolated covalently bonded group that shows a characteristic absorption in the
ultraviolet or the visible region.

Auxochrome

An auxochrome can be defined as any group which does not itself acts as a chromophore but whose
presence brings about a shift of the absorption band towards the red end of the spectrum (longer
wavelength).

Bathochromic Shift

It is an effect by virtue of which the absorption maximum (λmax) is shifted towards longer wavelength
due to the presence of an auxochrome or by the change of solvent. Such an absorption shift towards
longer wavelength is called red shift or bathochromic shift.

Hypsochromic Shift

It is an effect by virtue of which the absorption maximum (λmax) is shifted towards shorter wavelength.
The absorption shifted towards shorter wavelength is called blue shift or hypsochromic shift.

It may be caused by the removal of conjugation and also by changing the polarity of the solvent.

Instrumentation

A spectrometer is a device which detects the percentage transmittance of light radiation when light of
certain intensity and frequency range is passed through the sample.

There are three basic components in a spectrometer.

(i) A suitable radiant energy source

(ii) A filter or monochromator to cut off the unwanted radiation and isolate a narrow band of
suitable radiation.
(iii) A detector for measuring the intensity of transmitted radiation.

The sample solution taken in a transparent container is placed between the monochromator and the
detector. A signal processor and readout are attached to the detector.
The block diagram of an ultraviolet-visible spectrometer is shown in the fig.

1. Radiation Sources

There are two types of radiation sources for the UV-visible regions. They are:

Thermal sources

Electric discharge sources.

Thermal sources: The tungsten filament lamp is used as a thermal source in the visible region. The major
portion of the emitted radiation energy of this source falls in the near infrared region.

Electric discharge sources: Low pressure (0.2 to 2.0 mm) hydrogen discharge tubes are used in the
ultraviolet region. Generally, a low voltage tube (40 V, dc) is used.

Deuterium lamps can also be used for the 165-375 nm region.

2. Filters and Monochromators

In all absorption measurements it is necessary to eliminate all unwanted radiation and to select a
narrow band of wavelength from the broad spectrum radiation source. To achieve this, filters or
monochromators or sometimes both are used.

Filters: There are two types of filters:

(i) Absorption filters:- Absorption filters operate by selectively absorbing the unwanted radiation
thereby permitting a narrow range of radiation through them.
(ii) Interference filters:- An interference filter is obtained by coating a thin semi-reflecting film of silver
on both sides of a transparent dielectric material, magnesium fluoride or calcium fluoride. It destructs
interference of the waves except a narrow band of waves which are transmitted.

Monochromators: A monochromator is a device for producing a narrow beam of radiation with a

provision to vary the wavelength of the radiation.

The principal parts of a monochromator are:

an entrance slit

a collimating lens or concave mirror to focus the light

a dispersing element which may be a prism or a grating and

an exit slit.

3. Cells or Cuvettes

The essential requirement of a cell or a sample container is that it should be transparent to all
radiations. Quartz or fused silica cells are commonly used.

4. Detectors

Many detectors are used in the UV-visible spectrophotometers. The two important detectors are:

Phototube

Photomultiplier

Phototube: It consists of a semi-cylindrical cathode and a wire anode encased in an evacuated

transparent tube.

The inner surface of the cathode is coated with a photosensitive material which is a mixture of an alkali
metal, alkali metal oxide, silver metal and silver oxide.

When the transmitted radiation strikes the cathode (C), photoelectrons are emitted and are attracted to
the anode A, from where they are returned through the external circuit.

The resulting photoelectric current, which is proportional to the radiant energy is measured.

Photomultiplier: As in the case of a phototube, the radiation striking the photocathode of a

photomultiplier results in the ejection of electrons which are accelerated by a positive potential to a
second photosensitive surface (dynode), where each photoelectron in turn produces five or six
secondary electrons.

These secondary electrons are led to a third surface (dynode), where the number of electrons is
increased by a factor of five or six.
This is repeated at least ten times and the net effect is that the signal is amplified by a million times.

Applications of UV-visible Spectroscopy

UV-visible spectroscopy has been mainly applied for

the detection of functional groups (chromophore)

the extent of conjugation

detection of polynuclear compounds by comparision

distinction in conjugated and non-conjugated compounds

distinction between equatorial and axial conformations

determination of strength of hydrogen bonding