Infrared Spectroscopy (IR)

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 Infrared Absorption Spectroscopy (IR)

Infrared (IR) spectroscopy provides a simple and rapid

instrumental technique that can give evidence for the presence of
various functional groups (identification of organic compounds).
If you had a sample of unknown identity, for example, among the
first thing you would do is obtain an infrared spectrum, along
with determining its solubility in common solvents and its melting
and/or boiling point.
The infrared spectrum of an organic compound provides a unique
fingerprint, which is readily distinguished from the absorption
patterns of all other compounds.

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 Common Spectroscopic Methods based on Electromagnetic Radiation

Type Spectroscopy Usual wavelength range Usual wave number range, cm-1 Type of quantum
transition
Gamma-ray emission 0.005-1.4 Å - Nuclear
X-ray absorption, emission, 0.1-100 Å - Inner electron
fluorescence,and diffraction
Vacuum uv absorption 10-180 nm 1x106 to 5x104 Bonding electrons
uv-vis absorption, emission, 180-780 nm 5x104 to 1.3x104 Bonding electrons
and fluorescence
IR absorption and Raman 0.78-300 m 1.3x104 to 3.3x101 Rotation/
scattering vibration of
molecules
Microwave absorption 0.75-3.75 mm 13-27 Rotation of molecules
Electron spin resonance 3 cm 0.33 Spin of electrons in a
magnetic field
Nuclear magnetic resonance 0.6-10 m 1.7x10-2 to 1x103 Spin of nuclei in a
magnetic field
1 Å = 10-10 m = 10-8 cm
1nm = 10-9 m = 10-7 cm
1mm = 10-6 m = 10 –4 cm
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 Infrared Spectral Regions
The infrared spectrum is conveniently divided into;

❖ Near
❖ Mid
❖ Far
radiation
Region Wavelength Range Wavenumber Range Frequency Range
(µm) (cm-1) (Hz)
Near 0.78 to 2.5 12,800 to 4000 3.8x1014 to 1.2x1014
Middle 2.5 to 50 4000 to 200 1.2x1014 to 6.0x1012
Far 50 to 1000 200 to 10 6.0x1012 to 3.0x1011
Most Used 2.5 to 15 4000 to 670 1.2x1014 to 2x1013
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 Representation of an Electromagnetic Wave

Electric Field

Direction of Propagation

Electromagnetic radiation is conveniently represented as electric

and magnetic fields that undergo in phase, sinusoidal oscillations
at right angles to each other and to the direction of propagation.
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 ELECTROMAGNETIC RADIATION

Frequency :
the number of oscillations of the
field that occur per second and is
equal to 1/p (p: period)

Wavelength :
linear distance between any two
equivalent points on successive
waves (for example successive
maxima or minima)

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 ELECTROMAGNETIC RADIATION
Velocity of Propagation (vi):
Multiplification of the frequency () in cycles per second by the
wavelength () in meters per cycle gives the velocity of propagation
vi in meters per second:
vi = i

Velocity of Radiation (c):

is the product of the wavelength,  and the frequency, ;

c = 
The relation between frequency, , of the light and energy, E, is defined as;
E=h
h is the Planck constant. 7
 ELECTROMAGNETIC RADIATION
Whenever a molecule interacts with radiation, a quantum of energy
(or photon) is either emitted or absorbed. In each case, the energy of
the quantum of radiation must exactly fit the energy gap such as E1-
E0.

The energy of the quantum is related to the frequency by the

following equation;
E=h

E3
E2
E1
Eo 8
 ELECTROMAGNETIC RADIATION

The wavenumber :
Reciprocal of the wavelength in cm, and the unit of wavenumber is cm-1.
Wavenumber is widely used in IR spectroscopy. The wavenumber is a useful unit
because, in contrast to wavelength, it is directly proportional to the frequency.

 = 1/=/c

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Infrared absorption spectrum of dichloromethane

Wavenumber (cm-1)

In contrast to most UV and visible spectra,

an array of maxima and minima is observed in IR spectrum. 10
 Infrared Absorption Spectroscopy (IR)
❖ Infrared radiation causes atoms and groups of atoms of organic
compounds to vibrate with increased amplitude about the
covalent bonds that connect them.

❖ Since the functional groups of organic molecules include

specific arrangements of bonded atoms, absorption of IR
radiation by an organic molecule will occur at specific
frequencies depending on the characateristic of the types of
bonds and atoms present in the specific functional groups of
that molecule.

❖ These vibrations are quantized, as they occur, the compounds

absorb IR energy in particular regions of the IR portion of the
spectrum. 11
 Infrared Absorption Spectroscopy (IR)
Infrared spectroscopy, as all forms of spectroscopy, depends on the;

interaction of molecules or atoms with electromagnetic radiation.

The infrared spectrum of a sample is recorded by;

passing a beam of infrared light through the sample.

When the frequency of the IR is the same as the vibrational (or

rotation) frequency of a bond, absorption occurs.
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 How Infrared Absorption Spectroscopy (IR) Works?
1.Absorption of infrared radiation is limited largely to molecular
species for which small energy differences exists between various
vibrational and rotational states.

2. In order to absorb infrared radiation, a molecule must undergo

a net change in dipole moment as a consequence of its
vibrational and rotational motion. Only under these
circumstances can the alternating electrical field of the radiation
interact with the molecule and cause changes in the amplitude
(genlik) of one of its motions.

3. If the frequency of the radiation matches the natural

frequency of the vibration (or rotation), the IR photon is
absorbed, and the amplitude of the vibration increases. 13
Dipole Changes During Vibrations and Rotations
Dipole moment can be defined as the product of magnitude of
charges and the distance of separation between the charges.

For example, the charge distribution around a molecule such as hydrogen

chloride is not symmetric, because the chlorine has a higher electron density
than the hydrogen. Thus, hydrogen chloride has a significant dipole moment
and is said to be polar.
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 Which Types of Species or Molecules Does Not
Absorb IR?
1. No net change in dipole moment occurs during the vibration or
rotation of homonuclear species such as O2, N2, or Cl2, so such
compounds cannot absorb in the infrared.

2. Symmetric molecules (or bonds) do not absorb IR radiation

since there is no dipole moment.

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 Types of Molecular Transitions
There are three types of molecular transitions that occur in IR:
a) Rotational transitions
• When an asymmetric molecule rotates about its center of mass, the
dipole moment seems to fluctuate.
• E for these transitions correspond to  < 100 cm-1

b) Vibrational-rotational transitions

• complex transitions that arise from changes in the molecular dipole

moment due to the combination of a bond vibration and molecular
rotation.

c) Vibrational transitions
• The most important transitions observed in qualitative mid-IR
spectroscopy.
 = 13,000 – 675 cm-1 16
 Types of Molecular Vibrations
1. Stretching - A stretching vibration involves a continuous change in the
interatomic distance along the axis of the bond between two
atoms.

2. Bending - Bending vibrations are characterized by a change in an angle

between two bonds.

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 The atoms in a CH2X2 group, commonly found in organic compounds and where
X can represent any other atom. Six of these vibrations involve only
the CH2 portion:

Symmetry
Symmetric Antisymmetric
Direction

Radial Streching
Antisymmetric
Symmetric stretching (νs)
stretching (νas)

Latitudinal Bending
Scissoring (δ) Rocking (ρ)

Longitudinal Twisting (τ) Bending

Wagging (ω)
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 Mechanical Model of Stretching Vibrations
The characteristic of an atomic stretching
vibration can be approximated by a
mechanical model consisting of two masses
connected by a spring.

A disturbance of one of those masses along

the axis of the spring results in a vibration
called a simple harmonic motion.

If the mass is displaced a distance y from its

equilibrium position by application of a force
along the axis of the spring, the restoring
force F is proportional to the displacement
(Hooke’s Law)

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 Mechanical Model of Stretching Vibrations
Simple harmonic oscillator:

• Hooke’s Law: F = -ky

where: F = Force
k = Force Constant
(depends on stiffness
of spring)
y = Displacement

• Natural oscillation frequency of a mechanical oscillator depends on:

a) mass of the object
b) force constant of the spring (bond)
• The oscillation frequency is independent of the amount of energy
imparted to the spring. 20
 • Wavenumber of absorption of radiation can be predicted with a
modified Hooke’s Law;

where:  = wavenumber of the abs. peak (cm-1)

c = speed of light (3 x 10 10 cm/s)
1 1
1 k 2
 k  2
k = force constant for the bond (N/m)
 =   = 5.3 x10 −12  
2c      = reduced mass of the atoms (kg)

Mx •My Where: Mx = mass of atom x in kg

=
Mx + My My = mass of atom y in kg

• Force constants are expressed in N/m (N = kg•m/s2)

- Range from 3 x 102 to 8 x 102 N/m for single bonds
- 500 N/m is a good average force constant for single bonds when
predicting k.
- k = n(500 N/m) for multiple bonds where n is the bond order 21
 Example
Calculate the approximate wavenumber of the fundamental absorption peak
due to the stretching vibration of a carbonyl group C=O.
Solution
The mass of carbon atom in kg is given by
12𝑥10−3 𝑘𝑔/𝑚𝑜𝑙 −26
𝑀𝑥 = 𝑥1 𝑎𝑡𝑜𝑚 = 2.0𝑥10 𝑘𝑔
6.0𝑥1023 𝑎𝑡𝑜𝑚𝑠/𝑚𝑜𝑙 k for the typical
double bond is about
Similarly, for oxygen; 500x2=1x103 N/m.

16𝑥10−3 𝑘𝑔/𝑚𝑜𝑙
𝑀𝑦 = 23 𝑥1 𝑎𝑡𝑜𝑚 = 2.7𝑥10−26 𝑘𝑔
6.0𝑥10 𝑎𝑡𝑜𝑚𝑠/𝑚𝑜𝑙

And the reduced mass and the wavenumber;

2𝑥10−26 𝑥 2.7𝑥10−26 Mx •My

𝜇= = 1.1𝑥10−26 𝑘𝑔 =
2.0 + 2.7 𝑥10 −26 Mx + My

1𝑥103 𝑁/𝑚
𝜈ҧ = 5.3𝑥10−12 𝑠/𝑐𝑚 = 1.6𝑥103 𝑐𝑚 −1
1.1𝑥10−26 𝑘𝑔 22
 Anharmonic Oscillators
In reality, bonds act as anharmonic oscillators because as atoms get close, they
repel one another, and at some point, a stretched bond will break, thus, the
potential energy can be expected to rise more rapidly than the harmonic
approximation preditcs.

Such curves depart from

the harmonic behaviour by
varying the degrees,
depending on the nature of
the bond and the atoms
involved.

Curve 1: Harmonic oscillator

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Curve 2: Anharmonic oscillator
 Overtone (multiples of given frequency)
Results from excitation from ground state to higher energy states.
Quantum theory indicates that the only
transitions that can take place are those in
which the vibrational quantum number changes
by unity (of v=1).
Anharmonicity leads to deviations. At higher
quantum numbers, E becomes smaller (curve
2), as a result, transitions of v=2 or 3 are
observed.
Such transtions are responsible for the
appearance of overtone lines at frequencies
approximately two or three times that of
fundamental line. The intensity of the overtone
absorption is frequently low, and the peaks
may not be observed.
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 Qualitative Applications of Mid-Infrared Absorption
Identification of an
organic compound
from a spectra is a two
step process. The first
step involves
determining what
functional groups are
most likely present by
examining group
frequency region.
The second step
involves a comparison
of the spectrum of the
unknown with the
spectra of pure
compounds that
contain all of the
functional groups
found in the first step.
(3600-1200 cm-1) (1200-700 cm-1)
 Group Frequency Region (usually about 3600-1200 cm-1):
Although most group frequencies fall in the range of 3600 to 1200 cm-1, a few fall in
the fingerprint region. These include the C-O-C stretching vibration about 1200 cm-1
and the C-Cl stretching vibration at 700 to 800 cm-1.

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 Fingerprint Region (1200-700 cm-1):

Small differences in
the structure and
constitution of a
molecule result in
significant changes in
the distribution of
absorption peaks in
this region of the
spectrum.

As a consequence a
close match between
two spectra in this
fingerprint region
constitutes strong
evidence for the
identity of the
compounds.
 FTIR Spectra of Toluene
The output from the instrument is referred as a spectrum. Most commercial
instruments present a spectrum with the wavenumber decreasing from left to
right.
 Characteristic Infrared Absorption of groups
Group Frequency Range (cm-1) Intensity* (m-s)
A. Alkyl
C-H stretching 2853-2962 (s)
Isopropyl, - CH(CH3)2 1380-1385 and 1365-1370 (s)
Tert-Butyl, - C(CH3)3 1385-1395 (m)
~1365 (s)
B.Alkenyl (out of plane C-H bending)
C-H (stretching) 3010-3095 (m)
C=C (stretching) 1620-1680 (v)
R-CH=CH2 985-1000 (s)
R2-C=CH2 880-900 (s)
cis-RCH=CHR 675-730 (s)
trans- RCH=CHR 960-975 (s)
C. Alkynyl
≡CH (stretching) ~3300 (s)
C≡C (stretching) 2100-2260 (v)
D. Aromatic
Ar-H (stretching) ~3030 (v)
Aromatic substitution type
(C-H out-of-plane bendings)
monosubstituted 690-710 (very s)
730-770 (very s)
730-770
o-Disubstituted 735-770 (s)
m-Disubstituted 680-725 (s)
750-810 (very s)
p-Disubstituted 800-860 (very s)
E. Alcohols, Phenols, and Carboxylic Acids
O-H (stretching)
Alcohols, phenols (dilute solutions) 3590-3650 (sharp, v)
Alcohols, phenols (hydrogen bonded) 3200-3550 (broad, s)
Carboxylic acids (hydrogen bonded) 2500-3000 (broad, v)
F. Aldehydes, Ketones, Esters, Carboxylic Acids, and Amides
C=O (stretching) 1630-1780 (s)
Aldehydes 1690-1740 (s)
Ketones 1680-1750 (s)
Esters 1735-1750 (s)
Carboxylic Acids 1710-1780 (s)
Amides 1630-1690 (s)
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*Abbreviations: s = strong, m= medium, w = weak, v = variable, ~ = approximately.
 Vibrational Coupling
The energy of a vibration and thus the wavelength of its absorption peak may be
influenced (or coupled) by other vibrations in the molecule.
As an example of coupling effects, let us consider the infrared spectrum of
carbon dioxide:
If no coupling occured between two C=O bonds, an absorption peak would be
expected at the same wavenumber as the peak for the C=O stretching vibration in an
aliphatic ketone (about 1700 cm-1). However, experimentally, carbon dioxide exhibits
two absorption peaks, the one at 2330 cm-1 and the other 667 cm-1.

in plane bending

out of plane bending

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 Infrared Instruments
Four types of instruments for infrared absorption measurements are
available for commercial sources:

1. Dispersive grating spectrophotometers (for qualitative analysis)

2. Multiplex instruments (FTIR; for both qualitative and quantitative
analysis)
3. Nondispersive photometers (quantitative analysis of a variety of
organic species in the atmosphere)
4. Reflectance photometers (for analysis of solids encountered in
agriculture and industry)
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Dispersive grating spectrophotometers

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Fourier Transform Infrared (FT-IR)
Spectrometers

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 Fourier Transform Infrared Spectrometers
❖ This type of instrument employs an interferometer. FTIR has greatly
improved the quality of infrared spectra and minimized the time required
to obtain data.

❖ The majority of commercially avialable FTIR instruments are based upon the
Michelson interferometer.

❖ Interferometers are widely used in science and industry for the

measurement of small displacements, refractive index changes and surface
irregularities. In analytical science, interferometers are used in FTIR
instruments to analyze light containing features of absorption or emission
associated with a substance or mixture.

❖ Detectors are not fast enough to respond to power variations at high

frequency (1012 to 1015 Hz) so the signal is modulated by a Michelson
interferometer to a lower frequency that is directly proportional to the high
frequency. 34
 Michelson Interferometer
The Michelson interferometer is a device that
splits a beam of radiation into two beams of nearly
equal power and then recombines them in such a
way that intensity variations of the combined
beam can be measured as a function of differences
in the lengths of the paths of the two halves.

The difference in path lengths for the two beams in

the figure is termed as the retardation, . A plot of
output power from the detector (radiant power
data , P) versus  is called as interferogram.
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Schematic diagram of a Michelson interferometer, configured for FTIR

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 The radiation striking the detector after passing through the interferometer will generally
be much lower in frequency than the source frequency. The relationship between the two
frequencies is readily derived by reference to P(t) versus  plot. One cycle of signal occurs
when the mirror moves a distance that corresponds to one half a wavelength (/2). If the
mirror is moving at a constant velocity of vM and  is the time required for the mirror to
move /2 cm, it can be expressed as below;

𝜆
𝑣𝑀 𝜏 =
2

The frequency of the signal at the detector is simply the reciprocal of ;

1 2𝑣𝑀
𝑓= =
𝜏 𝜆

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 The relationship between the optical frequency of the radiation and
the frequency of the interferogram
• The frequency of the
radiation () is directly
related to the frequency
of the interferogram (f).

2 m
f = 
c
 = frequency of radiation
f = frequency of inteferogram
m = velocity of the mirror
c = speed of light (3.00 x 1010 cm/s)

Comparison of interferograms and optical spectra

• FT-IR spectrometers use a polychromatic source and collect the entire

spectrum simultaneously and decode the spectrum by Fourier Transform.38
39
 IR Sources
1. Nernst glower -constructed of a rod of a rare earth oxide (lanthanide) with
platinum leads.

2. Globar - Silicon carbide rod with water cooled contacts to prevent arcing.

3. Incandescent wire - tightly wound wire heated electrically. Longer life

but lower intensity.

Others are; mercury arc, tungsten filament lamp, carbon dioxide laser source
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 Detectors – measure minute changes in temperature.
1. Thermal detectors
• Have a slow response time, so they are not well suited to FT-IR.
2. Pyroelectric detectors
• Constructed of crystalline wafers of pyroelectric materials (triglycine
sulfate) which are insulators (dielectric materials) with very special
thermal and electrical properties.
• Have a fast response time and are well suited for FT-IR.
3. Photoconducting detectors
• Constructed of a semiconducting material (lead sulfide,
mercury/cadmium telluride, or indium antimonide) deposited on a
nonconducting glass surface and sealed in an evacuated envelope to
protect the semiconducting material from the environment.

• Fast response time comparing to pyroelectric detectors and are well suited
for FT-IR. 41
 Advantages of FTIR

• Enhanced signal-to-noise ratio

• Rapid Scanning with good spectra being attainable in a few
seconds in most cases
• High resolutions (<0.1 cm-1)
• Highly accurate and reproducible frequency determinations

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 Infrared Absorption Spectroscopy (IR)

One of the great advantages of infrared spectroscopy is that

virtually any sample in any state may be analysed;

❖ Liquids ❖ Powders

❖ Solutions ❖ Films

❖ Pastes ❖ Fibres
❖ Gases

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 Sample Handling Techniques
Gas Samples:
The spectrum of gas sample can be obtained by
permitting the sample to expand into an evacuated cell.

Solutions:

The demountable cell is designed

for liquid sample. They have Teflon
spacers to allow variation in path
length. Cells can be filled or emptied
with a syringe. 44
 Sample Handling Techniques
Pure Liquid:
When the amount of the sample is small or
when a suitable solvent is unavailable, the
spectra of liquid is obtained. A drop of the
liquid is squeezed between two rock-salt
plates to give a layer that has a thickness of
0.01 mm or less. The two plates that held
together then mounted in the beam path.

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 Sample Handling Techniques
Solid:

Disk Method: A grinded sample

(0.5-2 mg) is tightly mixed with
dried KBr (100 mg) in a mortar by
using a pestle. The obtained very
fine particled mixture is pressed
under vacuum (5-15 kg/cm2) to
obtain a transparent disk. This disk
is placed in the light path of IR
radiation and its IR spectrum is
recorded.

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 Sample Handling Techniques
Solid:
Mull Method: A finely powdered
sample (2 to 5 mg, <2 µm) is
combined with Nujol (a brand of
mineral oil by Plough Inc) in a mortar
and pestle to make a mull (a very
thick suspension). This mull is
sandwiched between sodium chloride
plates before being placed in the
spectrometer. The disk is placed in
the light path of IR radiation and its IR
spectrum recorded.