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Engineering Chemistry Notes

Unit – V, Spectroscopic Techniques

A) UV-visible spectroscopy

Electromagnetic radiation: As light travels in the form of waves, when it is associated with electrical
and magnetic fields it is called as electromagnetic radiation.

Introduction / Interaction of Radiation with Matter

Electromagnetic radiations are the transverse waves and formed due to oscillation of a charge or by
oscillation of magnetic field. The characteristics of an electromagnetic radiation are,

(i) All the electromagnetic radiations travel at 3 × 10 8 m/sec in vacuum but the velocity decreases
when the wave interacts with electrons of matter.
(ii) The speed (V) of the wave is given by, V = wavelength × frequency
(iii) They posses properties of both wave and particle.
(iv) Energy in the photons of the EMR is given by, E = h − c / λ.

Fundamentals of Spectroscopy

Spectroscopy deals with interaction of electromagnetic radiation with matter. Due to these
interactions,
energy is absorbed or emitted by the matter. Measurement of radiation frequency indicates the
change in energy involved.

Spectroscopy involves measurement of spectrum of a sample containing atoms or molecules.

Spectrum is a graph of intensity of absorbed or emitted radiations by sample versus frequency (v) or
wavelength (λ)

The study of spectroscopy can be carried out under following heads :

1) Atomic spectroscopy: It deals with interaction of electromagnetic radiations with atoms.
2) Molecular spectroscopy: It deals with interaction of eletromangnetic radiations with molecules.
This results in transitions between rotational, vibrational and electronic energy levels.

Spectroscopy is of two types: Absorption spectroscopy and Emission spectroscopy

1) Absorption spectroscopy: In absorption spectroscopy, a beam of polychromatic light falls on a
sample. Some part of light is absorbed by the sample and remaining part is transmitted. The intensity
of
transmitted light coming from sample is measured at different wavelengths by suitable photo
detector. Then this information is presented as a graph of intensity of absorbed radiations.

2) Emission spectroscopy: In this technique, sample is subjected to intense source of energy like
electric arc. As a result, sample is vaporized and electrons in the sample are excited to higher
energy state. When these electrons come back to ground state energy level, they emit radiations.
These radiations are analyzed by spectrophotometer to generate spectrum that gives information
about atoms present in the sample.

Like atoms, even molecules possess a set of discrete energy levels, which are of three types:

a) Electronic energy levels b) Vibrational energy levels c) Rotational energy levels

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a) Electronic energy levels: At room temperature the molecules are in the lowest energy levels E 0.
When the molecules absorb UV-visible light from electromagnetic radiation, one of the outermost
electrons from pi - bond, sigma bond or a lone pair is promoted to higher electronic energy state.

b) Vibrational energy levels: Vibrational energy levels are of less energy than electronic energy
levels. The spacing between vibrational energy levels are relatively small. When infrared radiation is
absorbed molecules are excited from one vibrational level to another. Thus, during vibrational
excitation molecule begins to vibrate.

c) Rotational energy levels: The spacing between these levels is even smaller than vibrational energy
levels. The order of spacing of energy levels is as follows.

∆E rotational < ∆E vibrational < ∆E electronic

Whenever electronic transition occurs by absorption of UV radiation it is accompanied by

vibrational and rotational excitations. Similarly, absorption of infrared radiation leads to vibrational
and rotational excitation.

This wavelength at which there is a maximum absorption is called l max. This is a characteristic
property of molecule from sample.

Fig. 2.16: Electromagnetic spectrum

Lambert-Beer Laws of Absorption

Lambert’s Law

The rate of decrease in intensity of radiation is directly proportional to path length of solution, when
the monochromatic light passes through a solution of constant concentration.
Where, I0 = Intensity (radiant power) of the incident radiation
dx = Small thickness of solution or path length
Beer’s Law dI = Small decrease in intensity of light = I0 – It

The rate of decrease in intensity of light is proportional to concentration of solution for a fixed
thickness of solution.
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Combined Lambert-Beer’s Law :

Lambert-Beer’s law can be stated as “absorption of a light by solution is directly proportional to the
concentration of solution and the path length”.

By taking unit concentration of sample in solution (C = 1 mole/lit) and unit length of path (x = 1
cm), the absorbance observed will be the value of the constant in Lambert-beer’s equation.

A=∈·x·C
 is known as molar absorptivity, or molar extinction coefficient constant.

There is certain wavelength which is absorbed maximum and it is known as

λmax. This wavelength is selected to analyse the sample by
spectrophotometers

 Principle and instrumentation involved in UV-visible spectroscopy

Principle:
Following principles are involved in UV-visible spectrophotometry:

1. Beer’s law : The absorbance of the monochromatic light from UV-visible region is proportional
to concentration of the solution, for the constant path length.

2. The absorption of λmax from UV-visible region causes excitation of bonding electrons in a
covalent bond to higher energy antibonding orbitals e.g. σ σ*, π π*, non-bonding electrons
(lone pair) to π* etc.

(The electrons in a stronger covalent bond require higher energy for excitation which is available
from a shorter wavelength UV light and electrons in a weaker covalent bond require lower energy
for excitation which is available in visible light wavelengths.)
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Instrumentation in UV-Visible Spectrophotometry (Spectrophotometer) :

1) Light source (Source of radiation): The source of radiation should provide sufficient intensity over
the wavelength region. It has high intensity. The most common radiation sources used are hydrogen
discharge lamp, quartz halogen lamps, deuterium gas discharge tube, mercury arc.

Fig. 2.19: Single beam UV/visible spectrophotometer

2) Monochromator: A monochromator selects light of a particular wavelength. It consists of entrance

slit, collimator, a grating or prism, exit slit. A good monochromator provides very narrow
wavelength band. Glass prisms are used for work in the visible region, quartz prisms are used for
UV-region.

3) Sample cell: It holds the sample either in the form of solution or as such. Quartz cuvettes are used
in UV spectroscopy but for visible spectroscopy glass cuvettes can be used.

4) Detector: Transmitted light from sample cell falls on the detector where it is converted into
electric current. It converts light energy directly into electrical energy. The output current of photo
detector is directly proportional to the intensity of light falling on it.
For UV spectroscopy: Photoelectric cell, photomultiplier tube, photovoltaic cell can be used as
photodetector.

5) Recorder: It is a display device, which automatically draws the spectrum. The signal from
monochromator is recorded onx-axis while the absorbance of the sample is displayed on y-axis. The
absorption of light (EMR) by a substance is governed by certain laws, namely, Beer's law and
Lambert's law.

Theory of Electronic Transitions: Energy absorbed from the ultraviolet –visible region causes
excitation of electrons to higher energy state.

1. σ-electrons: These electrons are involved in saturated or sigma bonds.

2. π-electrons: These electrons are involved in unsaturated (double or triple bonds) compounds and
aromatics.
3. n-electrons: These are the electrons of outermost energy level (valence shell) of atom, which have
not participated in bonding. They are also called as lone pair of electrons and are present in p-
orbitals. e.g. organic compounds containing nitrogen, oxygen, sulphur, halogens.

 Types of Electronic Transitions :-

4 allowed transitions : σ σ* ; n σ* ; 𝜋 𝜋*; n 𝜋*

2 non-allowed / forbidden transitions : σ 𝜋 *; 𝜋 σ*

Relative energies of these transitions are:

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1) σ → σ* transition : These transitions can occur in compounds, in which all the electrons are
involved in single (sigma) bonds and there are no lone pair of electrons on any atom in the molecule.

e.g. saturated hydrocarbons like ethane, methane. As the energy required for the transition is very
large, the absorption band occurs in the far ultraviolet region (100 to 135 nm).

2) n → π* transition : These type of transitions are shown by unsaturated molecules (containing

multiple bonds) which also contain atoms with lone pair of electrons like oxygen, nitrogen, halogen
etc.

Eg. C = 𝑁̈ , C = 𝑂̈ , 𝑁̈ = 𝑂̈ show this transition. In aldehydes, ketones, cyanides, -N=O, etc the
transition occurs due to excitation of electron from p-orbital (lone pair of electron) to antibonding π*
orbital. [at longer wavelength around 300 nm].

3) n → σ* transition : Saturated compounds with atoms having lone pair of electrons can undergo
this transition, and the bands are observed in the near UV region (150-225 nm). If this transition is
observed in the compound having π π* transition, then the λmax for this transition shifts to the
longer wavelength.

Eg. Alcohols (R-OH), amines (R-NH2), alkyl halides (R-X) etc.

4) π → π* transition: π electrons in a bonding orbital is excited to corresponding antibonding orbital

π * orbital . Compounds containing multiple bonds like alkene, alkynes, carbonyl, nitriles, aromatic
compounds undergo this transition.

Alkenes generally absorb in the region 170 - 205 nm and are difficult to record by
spectrophotometer. However, molecules containing two or more conjugated double bonds absorb
above 200 nm and can be easily recorded.

Terms in UV-Visible Spectrophotometry:

1. Chromophore: The part of a molecule responsible for imparting color, are called as
chromospheres. OR The functional groups containing multiple bond and capable of absorbing
radiations above 200 nm due to n → π* & π → π* transitions. e.g. NO2, N=O, C=O, C=N, C≡N,
C=C, C=S, etc
Important points:
a) Conjugated double bonds if present in compound, shifts the λmax to longer wavelengths.
b) Conjugation of –C=C- and carbonyl group shifts the λmax to longer wavelengths eg. Ethylene,
acetone.

2. Auxochrome: The functional groups attached to a chromophore which modifies the ability of
the chromophore to absorb light, altering the wavelength or intensity of absorption.
OR The functional group with non-bonding electrons that does not absorb radiation in near UV
region but when attached to a chromophore alters the wavelength & intensity of absorption.
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3. Bathochromic Shift (Red Shift): When absorption maxima (λmax) of a compound shifts to
longer wavelength, it is known as bathochromic shift or red shift
• The effect is due to presence of an auxochrome or by the change of solvent. e.g. An auxochrome
group like –OH, -OCH3 causes absorption of compound at longer wavelength.

E.g.; In alkaline medium, p-nitrophenol shows red shift. Because negatively charged oxygen
delocalizes more effectively than the unshared pair of electron.

4. Hypsochromic Shift (Blue Shift): When absorption maxima (λmax) of a compound shifts to
shorter wavelength, it is known as hypsochromic shift or blue shift.
• The effect is due to presence of an group causes removal of conjugation or by the change of
solvent.
E.g; Aniline shows blue shift in acidic medium, due to loss of conjugation.

5. Hyperchromic Shift: When absorption intensity (ε) of a compound is increased, it is known as

hyperchromic shift.
• If auxochrome introduces to the compound, the intensity of absorption increases.
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6. Hypochromic Shift: When absorption intensity (ε) of a compound is decreased, it is known as

hypochromic shift. CH3 Naphthalene 2-methyl naphthalene ε = 19000 ε = 10250

Applications of UV-Visible Spectroscopy:

1. Qualitative analysis of organic compounds : The UV-VIS spectrum of an unknown organic

compound is compared with the spectra of various known compounds, to identify compound
qualitatively.

2. Detection of impurities in the organic compounds.

3.Quantitative analysis : This is based upon Beer’s law i.e. A 𝖺 C

Absorbance of the λmax by solutions of known concentration are noted. A plot of Absorbance Vs
conc. gives straight line through origin from this graph, conc. of ‘unknown’ corresponding to its
absorbance, is accurately known

4. Chemical kinetics : As Absorbance is directly proportional to concentration of reactant or product,

with the progress of reaction the change in extent of absorption per minute can help for speed of
reaction.

5. Structural information : From the λmax which is a characteristic value for different chromophores
and chromophore – auxochrome the structural parts in organic molecules, can be known.

6. Dissociation constants of weak acid or weak base : From the absorption of max by known conc.
of weak acid, ratio [A –] / [HA] can be calculated to find the Ka for weak acid.

Fig. 2.21: finding unknown concentration of a solution

 B) Infrared Spectroscopy

Infrared Spectroscopy is the study of interaction of infrared light with a molecule. This can be analyzed
in three ways by measuring absorption, emission and reflection. It is used by chemists to determine
functional groups in molecules. IR Spectroscopy measures the vibrations of atoms, and based on this it
is possible to determine the functional groups.

Infrared radiation is largely thermal energy. It induces stronger molecular vibrations in covalent bonds.

Principle:
If a molecule absorbs IR radiation, it gets excited to higher vibrational energy level (vo → v1). The type
of IR radiation absorbed by molecules is unique and depends on nature of chemical bonds and functional
groups present. On absorption, stretching or bending type of vibrational changes occur in molecules
which provides information about the presence or absence of certain functional groups.

Frequency of absorption of radiation can be predicted with a modified Hooke’s Law.

Where: n = wave number of the abs. peak (cm-1)

c = speed of light (3 x 1010 cm/s)
k = force constant
m = reduced mass of the atoms

 Types of Molecular vibrations

The atoms in molecules undergo a number of different vibrations. Vibrations fall into the two main
categories of A) stretching and B) bending.

A) Stretching:
In this type of vibrations, the bond length is increased or decreased at regular intervals. There are two
types of stretching vibrations - Symmetrical stretching and asymmetrical stretching.

i) Symmetric stretching: These involve relative movement of atoms in same plane and in same
direction
i.e. in symmetrical pattern

ii) Asymmetric stretching: These involve relative movement of atoms in same plane but in
opposite direction i.e. in symmetrical pattern

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 B) Bending:

In this type of vibrations, a change in bond angle occurs between bonds with a common atom, or there is
a movement of a group of atoms with respect to the remaining molecule without movement of the atoms
in the group with respect to one another.
The bending vibrations are also called as deformation vibrations. They are of two types.
a) In-plane Bending vibrations b) Out of plane Bending vibrations

a) In plane bending- In these types of vibrations, there is a change in bond angle. This type of
bendingtakes place within the same plane. In plane bending are of two types.

i. Scissoring: in this bond angle decreases

ii. Rocking: in this the bond angle is maintained but both bonds moves within the same plane.

b) Out of plane bending- This type of bending takes plane outside of the plane of molecule.
i. Wagging: in this both atoms move to one side of the plane
ii. Twisting: in this one atom is above the plane and the other is below the plane

 Vibrations of Diatomic and Polyatomic Molecules:

Vibration modes are simple to calculate for diatomic or triatomic molecules but are somewhat more
complex in polyatomic molecules.

Number of fundamental vibrations in the molecule can be calculated from its degree of freedom.

A molecule containing n atoms, has 3n degrees of freedom.

3n = Translational modes + Rotational modes + Vibrational Mode

For a non-linear molecule, out of the 3N degrees of freedom, three describe rotation and three describe
translation and remaining (3N-6) degrees vibration degrees of freedom.

In a linear molecule, only two degrees of freedom are required to describe rotation and three describe
translation. Thus the remaining (3N-5) degrees are vibration degrees of freedom.

Linear Molecules: (3N - 5) degrees of freedom

Non-Linear molecules: (3N - 6) degree of freedom
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Following table shows fundamental modes of vibrations for different molecules.

No. of Geometry of Fundamental modes of

Molecule
atoms molecule vibrations
H2O 3 Non-linear 3
NH3 4 Non-linear 6
CH4 5 Non-linear 9
C2H6 8 Non-linear 18
C6H6 12 Non-linear 30
NO 2 linear 1
CO2 3 linear 4

 Conditions of Absorption of IR Radiations (Requirements of IR Absorption)

Energy of IR photon is insufficient to cause electronic excitation but can cause vibrational or
rotational excitations.

For a molecule to absorb IR radiations, it has to fulfill following requirements –

1) Dipole moment (Electric dipole): A bond or molecule must have a permanent dipole moment. If not,
then, some of its vibrations must produce an induced dipole moment in order to have an absorbance in
the IR spectrum.

 Magnitude of dipole moment determined by- i) charge ii) separation of charge

A molecule can only absorb IR radiation when its absorption causes a change in dipole moment (electric
dipole). Such vibrations are said to be IR active.

When the molecule having dipole moment is kept in the beam of IR radiation, the field will exert forces
on the electric charges in the molecule. Opposite charges will experience force in opposite directions.
This tends to decrease in separation of atoms. Thus, dipole moment changes.

Symmetrical diatomic molecules like H2, Cl2, O2, N2 do not possess electrical dipole. They cannot be
excited by infrared radiations and thus do not give rise to IR spectra. Such molecules are IR inactive.

2) Correct frequency of radiation: A molecule absorbs radiations only when the natural frequency of
vibration of some part of a molecule (i.e. atom or group of atoms present in molecule) is same as the
frequency of incident radiation.
When frequency of vibration of a bond and frequency of IR radiation used for excitation, match
perfectly then only IR energy is absorbed.

Example: natural frequency of vibration of HCl molecule is about 8.7x1013 sec-1. When IR radiation is
passed through HCl sample and transmitted radiation is analysed by IR spectrophotometer, it is observed
that part of radiation which has frequency 8.7x1013 sec-1 is missing from transmitted radiation. Thus the
part of radiation with that frequency has been absorbed by HCl molecule and remaining frequencies of
radiation transmitted. Thus, the frequency 8.7x1013 sec-1 is characteristic of HCl molecule.

After absorbing the correct frequency of radiation the molecule vibrates at increased amplitude. This
occurs at the expense of the energy of IR radiation which has been absorbed.
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  Symmetrical molecules do not absorb IR radiation since they do not have dipole moment (O 2,
F2, H2, Cl2)
 Diatomic molecules with dipole moment are IR-active (HCl, HF, CO, HI)
 Molecules with more than two atoms may or may not be IR active depending on whether they
have permanent net dipole moment

IR Absorption frequency depends on:

 Masses of atoms in the bonds

 Geometry of the molecule
 Strength of bond
 Other contributing factors

Region Energy (kJ/mol) Wavenumber (cm-1) Wavelength (µm)

Near IR 150-50 12800-4000 0.8-2.5

Mid IR 50-2.5 4000-200 2.5-50
Far IR 2.5-0.1 200-10 50-1000
Most used 15-2.5 4000-670

The important components of IR spectrophotometer are as follows:

1) Source : For IR radiations, one of the following sources can be used.

a) Nerst filament: It consists of mixture of rare earth oxides such as zirconium oxide, yttrium oxide
and erbium oxide.
b) Globar: It is a silicon carbide rod.

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c) Incandescent wire: It is a spiral wire of nichrome.
d) Mercury arc: High pressure mercury arc which consists of quatz tube containing mercury vapours can
be used.

2) Monochromator: Prisms or gratings are used as monochromators. They are used to select
radiation of desired frequencies. Prisms are normally made of alkali metal halides like NaCl, KBr.
3) Sample cells and sampling of substances : Infrared spectra can be obtained for solid, liquid or
gases (neat or in solution form). Material containing sample must be transparent to the IR
radiation, so the material made out of certain salts like NaCl, KBr, LiF etc. are used.

Sampling of solid can be done by

a) Solid run in solution: Solid substance is dissolved in non aqueous solvent. A drop of solution is
placed on the disc of alkali halide. Solvent is dried to give thin film on surface.
b) Solid film technique: Used for amorphous solid. Sample is deposited on KBr or NaCI cell by
evaporation of solution of solid.
c) Pressed pellet technique: Sample is finely ground with KBr and pressed to pellet.
d) Mull technique: Sample is mixed with Nujol (mineral oil) and mulled to a make fine paste. A
thin film is applied on KBr pellet.

Sampling of liquids: Liquid sample can be sandwiched using sample cells of KBr or NaCl.

Sampling of gases: Sample cells made of KBr or NaCl can be used for the purpose.

4) Detectors: In IR spectroscopy, thermal detectors are used

a) Thermocouple: It uses two wires of different materials welded together. One of the two
welded joints is hot junction, becomes hotter because of IR radiations than the other joint.
A small electrical potential develops between the joints due to temperature difference. The
resulting current is directly proportional to the IR radiation falling on detector.

b) Bolometer : Platinum or nickel is used to form bolometer. It is a type of resistance

thermometer used to detect and measure weak thermal radiation. Change in resistance is observed
due to change in temperature.

c) Golay detector: It is a sensitive gas thermometer containing Xenon.

5) Amplifier and Recorder: Amplifier amplies the signals from detector and sends to recorder.
Sophisticated recorders give IR spectra of a compound as a graph of percentage transmission of IR
radiation versus wavelength or frequency or wave number (IR spectrum).

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Parts of IR
Spectrum

The electromagnetic radiations having wavelength range 0.8 to 200 µ or wave number range 12800 to
50 cm-1 are infrared radiations.
Far infrared region infrared radiations.

The infrared region is further divided into three regions- Near infrared region, middle infrared region
and far infrared region.

Middle infrared region is further subdivided into functional group region, fingerprint region,
regioncharacteristic for aromatic compounds.

1. Functional group region: The region from 4000- 1500 cm-1 (2.5-6.5 µ) is called functional group
region. This part of IR spectrum contains absorption bands due to stretching vibrations of
functional groups like O - H, N - H, C -H. etc

The common functional groups show absorption bands in this region. The exact position of
absorption depends on force constant, masses of atoms, environment of bond.

2. Finger Print Region 1500 to 909 cm-1

These absorption band due to stretching and bending vibrations. Here unknown compound can
compared with other to identify the compound.

3. Aromatic Region 909 to 607 cm-1

Detection for aromatic character of compounds. ie ortho, meta , para substitution.

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