Introduction

The term "infra red" covers the range of

the electromagnetic spectrum between
0.78 and 1000 mm. In the context of infra
red spectroscopy, wavelength is measured
in "wavenumbers", which have the units
cm-1. wavenumber = 1 / wavelength in
centimeters
• It is useful to divide the infra red region
into three sections; near, mid and far infra
red;
• RegionWavelength range
(mm)Wavenumber range (cm-1)Near0.78
- 2.512800 - 4000Middle2.5 - 504000 -
200Far50 -1000200 - 10
• The most useful I.R. region lies between
4000 - 670cm-1.
• Theory of infra red absorption
• IR radiation does not have enough energy
to induce electronic transitions as seen
with UV. Absorption of IR is restricted to
compounds with small energy differences
in the possible vibrational and rotational
states.
• For a molecule to absorb IR, the vibrations or
rotations within a molecule must cause a net
change in the dipole moment of the molecule.
The alternating electrical field of the radiation
(remember that electromagnetic radation
consists of an oscillating electrical field and an
oscillating magnetic field, perpendicular to each
other) interacts with fluctuations in the dipole
moment of the molecule. If the frequency of the
radiation matches the vibrational frequency of
the molecule then radiation will be absorbed,
causing a change in the amplitude of molecular
vibration
• Molecular rotations

• Rotational transitions are of little use to the

spectroscopist. Rotational levels are
quantized, and absorption of IR by gases
yields line spectra. However, in liquids or
solids, these lines broaden into a
continuum due to molecular collisions and
other interactions.
• Molecular vibrations

• The positions of atoms in a molecules are

not fixed; they are subject to a number of
different vibrations. Vibrations fall into the
two main catagories of stretching and
bending.
• Stretching: Change in inter-atomic
distance along bond axis
• Bending: Change in angle between two
bonds. There are four types of bend:
• Rocking
• Scissoring
• Wagging
• Twisting
•
• Vibrational coupling In addition to the vibrations
mentioned above, interaction between vibrations can
occur (coupling) if the vibrating bonds are joined to a
single, central atom. Vibrational coupling is influenced by
a number of factors;
• Strong coupling of stretching vibrations occurs when
there is a common atom between the two vibrating
bonds
• Coupling of bending vibrations occurs when there is a
common bond between vibrating groups
• Coupling between a stretching vibration and a bending
vibration occurs if the stretching bond is one side of an
angle varied by bending vibration
• Coupling is greatest when the coupled groups have
approximately equal energies
• No coupling is seen between groups separated by two or
more bonds
• SELECTION RULE :
• SELECTION RULE 1) ABSORPTION OF CORRECT
WAVELENGTH OF RADIATION (MATCHING OF
FREQUENCY A molecule will absorb suitable radiation
when its natural frequency of vibration matches with the
frequency of incident radiation (i.e. a net transfer of
energy takes place and it results in a change in the
amplitude of molecular vibration) Natural frequency of
HCl molecule is 8.7 X 1013Hz(vib/sec)or(2890 cm-1)
When IR radiation will allow to pass on HCl sample and
transmitted radiation is analyzed .It is observed that part
of radiation which has same frequency 8.7X1013 HZ is
absorb. Thus remaining has been transmitted so gives
characteristic value of HCl
• 2) DIPOLE MOMENT :
• 2) DIPOLE MOMENT “A molecule will
absorb IR radiation if the change in the
vibrational state is associated with the
change in the dipole moment of the
molecule” μ = q x r A dipole moment
arises from a separation of charges in a
molecule : μ =dipole moment (Coulomb
·meters) q =magnitude of charges r
=vector going from –ve charge to +ve
charge
• SELECTION RULE OF VIBRATIONAL
QUANTUM NUMBER :
• 3)SELECTION RULE OF VIBRATIONAL
QUANTUM NUMBER Based on the
harmonic oscillator model (Δv = ±1) Here
+ absorption & - emission or Vibrational
quantum number change by unity
• Harmonic oscillator Anharmonic oscillator Overtones and
fundamental band
So far as harmonic oscillator model is consider the lower vibration
state can be explain (v - v´=1) but for higher vibrational state the
selection rule may fail because vibrational energy levels are less
separated as the vibration state increases (But for harmonic
oscillator model it is not true ) Overtones and fundamental band can
not be explain by Harmonic oscillator model. So vibrational diatomic
molecule can be explain well using anharmonic oscillator model
Anharmonic oscillator model can explain the selection rule for all
transition . For real molecule they don’t obey simple harmonic
motion. Because the bonds are also real Therefore anharmonic
oscillator model consider Therefore energy difference goes on
decreasing as quantum no. increasing Δv = ±1, ±2, ±3……
(overtone lines) is possible but they are having extremely low
intensity. This are known as overtones (they are weaker)
• they found that when a ball was
suspended on a spring from a horizontal
wall, the frequency of vibration or
oscillation, n, depended only on the mass
of the ball and the stiffness of the spring.
The term A is a constant of the
proportionality. By varying the mass of the
ball and the stiffness of the spring, they
were able to uncover the following simple
relationship between frequency, mass and
force constant:
• Suspending a ball and spring from a
horizontal surface is a special case of the
more general situation when you have two
more comparable masses attached to
each other. Under these circumstances,
when two similar masses are attached to a
spring, the relationship between frequency
of vibration, mass and force constant is
given by:
• where m, represents the product of the masses divided by their sum
(m1m2)/(m1+m2). This latter term is found in other physical
relationships and has been given the name, the reduced mass. It
can easily be seen that equation 2 is a special case of the more
general relationship given by equation 3. If we consider m1to be
much larger than m2, the sum of m1+ m2 m1 and substituting this
approximation into (m1m2)/(m1+m2) m2. Substituting m2 into
equation 3 where m2 is the smaller of the two masses gives us
exactly the same relationship as we had above when the ball was
suspended from a horizontal wall. The horizontal wall is much more
massive than the ball so that the vibration of a smaller ball has very
little effect on the wall. Despite their simplicity, equations 2 and 3
play an important role in explaining the behavior of molecular
systems. However, before we discuss the important role these
equations play in our understanding of infrared spectroscopy, we
need to review some of the properties of electromagnetic radiation,
particularly radiation in the infrared range.
• Number of possible vibrational modes
:Number of possible vibrational modes
CAN WE KNOW THE POSSIBLE
VIBRATION? YES, but how? 3N-5 for
linear molecules 3N-6 nonlinear molecules
N: number of atoms in a molecules BUT
WHAT IS 3N, 5 & 6. HOW’S IT COME?
• Atoms are never fixed in the space but
move about continuously Each atom may
be said to posses three degrees of
freedom of movement, and thus in N-atom
(polyatomic molecule) Molecule there will
be 3N degrees of freedom (That means 3
coordinates are needed to locate a point in
space. And each coordinate corresponds
to one degree of freedom for one of the
atom ,so a molecule containing N-atom is
said to have 3N degree of freedom )
• From this 3 types of motion 1) TRANSLATION
MOTION Corresponds to the movement of the
entire molecule through space while the position
of the atoms relative to each other remain fixed.
In this sence, the molecule may be considered
as a single particle with the mass of the
molecule located at its center of gravity and
possesses three degree of translation freedom
OR Defination of translation motion require 3
coordinates and thus this common motion
requires 3 of the 3N degree of freedom
• 2)ROTATIONAL MOTION :Another 3
degree of freedom are needed to describe
the rotational motion of the molecule. (i.e.
poly atomic molecule has generally 3
degree of rotation freedom) But in the
special case of linear molecule all the
atom lie on a straight line and only 2
rotation can be define (because rotation
around the bond axis is not possible)
2)ROTATIONAL MOTION
• 3)VIBRATIONAL MOTION :Now the rest
i.e. substrate transition & rotation motion
from 3N degree of freedom i.e. 3N-6 ( for
non linear molecule) 3 of translation
motion + 3 of rotational motion=6 & 3N-
5(for linear molecule) 3 of translation
motion + 2 of rotational motion=5
3)VIBRATIONAL MOTION
• Now out of this normal vibration no. of
stretching and bending vibration can be
calculated For stretching vibration =N -1
For bending vibration =2N -5(non linear)
i.e. [(3N - 6)-(N -1)]=2N -5 =2N-4(linear)
i.e. [(3N - 5)-(N -1)] =2N – 4 Examples:
O2, N2, Cl2: 3N-5 =3x2-5 = 1, only one
vibration mode CO2 3N-5 =3x3-5 =
4(linear molecule) H2O 3N-6 =3x3-6 = 3
• FACTOR THAT PRODUCED LESS NO.
OF PEAKS THAN EXPECTED :FACTOR
THAT PRODUCED LESS NO. OF PEAKS
THAN EXPECTED The symmetry of a
molecular vibration result in no change in
the dipole moment (i.e. in co2 only 2 peak
out of 4) The energy of two or more
vibrations are identical (same or
degenerate) The absorption intensity is so
low as to be undetectable by means
(detector) The vibration energy is in the
wL region beyond the range of the
instrument
• INSTRUMENTATION

SOURCE SAMPLE REFRENCE TRANSDUCER

MC
INFRARED SOURCE :INFRARED SOURCE IR
source consist of an inert solid that is heated
electrically to a temperature between 1500 and
2200 K The material is chosen so that its
emission approximates As closely as possible to
that of black body radiator. (in candescent solid-
the glow due to the great heat) We get
continuum radiation approximating that of black
body results
What is this black body radiation? It is truly continuum
radiation is produced when solid are heated
incandescence Thermal radiation of this kind, which is
called black body radiation, is characteristic of temp. of
emitting surface rather than the material of which the
surface is composed.

Black body radiation is produced by the innumerable

atomic and molecular oscillation excited in the
condensed solid by thermal energy. It is clear that a very
high temp. is needed for thermal excitation The
maximum radiant intensity at this temp. occur between
5000-5900 cm-1 Problems with Infrared from sun 99% of
infrared rays are absorbed by water in our atmosphere
At higher wave length the intensity fall is smoothly until it
is about 1% of max. intensity But on shorter wavelength
side the decrease is much more rapid 10000 5000 670
cm-1 1 2 15 μm
• Nujol mull

• A mull is a suspension of a solid in a liquid. Under these

conditions, light can be transmitted through the sample
to afford an acceptable infrared spectrum. The
commercial sample of Nujol, or mineral oil, which is a
long chain hydrocarbon is often used for this purpose.
Most solids do not dissolve in this medium but can be
ground up in its presence. A small mortar and pestle is
used for this purpose. If the grinding process gives rise
to small particles of solid with diameters roughly the
same as the wavelength of the infrared radiation being
used, 2-5 microns, these particles will scatter rather than
transmit the light. The effect of poor grinding is illustrated
in Figures 29 and 30 for a sample of benzoic acid. If you
find this type of band distortion with either a Nujol mull or
a KBr pellet (discussed below), simply continue grinding
the sample up until the particles become finer.
• The major disadvantage of using a Nujol mull is
that the information in the C-H stretching region
is lost because of the absorptions of the mulling
agent. A spectrum of Nujol is shown in Figure 5.
To eliminate this problem, it may be necessary
to run a second spectrum in a different mulling
agent that does not contain any C-H bonds.
Typical mulling agents that are used for this
purpose are perfluoro- or
perchlorohydrocarbons. Examples include
perchlorobutadiene, perfluorokerosene or a
perfluorohydrocarbon oil.
• DETECTORS :DETECTORS or
TRANSDUCERS There are 3 types of detector
(transducer) 1) THERMAL DETECTOR 2)
PYROELECRIC DETECTOR 3) PHOTON
(QUANTUM) DETECTOR

• THERMAL DETECTOR :THERMAL

DETECTOR Thermal detector whose response
depend on heating effect. Which in terns alters
the physical properties of transducers such as
resistance It is a transducer that changes
thermal energy in to an electric signal. The
electric signal is amplified and routed to the read
out device
• THERMOCOUPLE :1)THERMOCOUPLE
Most widely used IR detector Consist of 2
pieces of metal such as “Bi” which are
joined with dissimilar metal such as “sb”
(antimony) and form a pair of junction (2
jn) Jn. Is usually blackened (to improve its
heat absorb capacity) With black metallic
oxides One jn between 2 dissimilar metal
is heated with IR radiation other jn. Kept at
const. temp..
• PRINCIPLE “A CHANGE IN THE TEMP.
AT THE BOTH DIFF.JN. BETWEEN 2
UNLIKE METAL CAUSES AN ELECTRIC
POTENTIAL TO DEVELOPE BETWEEN
SPECIES” Or “DUE TO DIFRENCE IN
WORK FUNCTION OF METALS WITH
TEMP. A SMALL VOLTAGE DEVELOP
ACROSS THE THERMOCOUPLE”
• This potential diff. is depend (proportional)
to the amt of IR radiation falling on hot jn.
Whole assembly is evacuated in still
housing with IR transparent KBr window to
minimize conductivity heat loss. Capable
to responding temp. diff. of 10-6 k
corresponding to potential diff. of 6-8 μV/
μW Advantage that independent of
response with change in wave length
“THERMOPILE” ?
• 2) THERMISTOR or BOLOMETER When
irradiation by IR beam produced an
increase in resistance of the metal strip
which measured with a whetstone bridge
A potential diff. between the 2 elements
produced a proportional voltage difference
• 3)PNEUMATIC DETECTOR or GOLAY
DETECTOR :3)PNEUMATIC DETECTOR or
GOLAY DETECTOR Pneumatic detectors
respond to change in vol. of non absorbing gas
or liq with temp. change In pneumatic device if
gas is used as medium called golay detector
Here the absorbing radiation heats an inert gas
(usually xenon) in a pneumatic chamber behind
the plate and cause the gas to expand As the
gas expands the flexible diaphragm at the
opposite end of the chamber from the metallic
plate is pushed outward
• Applications of IR Spectroscopy to Inorganic
Molecules. Many so-called inorganic
compounds are in reality largely organic, and for
these we look for the same functional group
bands in the IR as we do for purely organic
compounds. However, the infrared spectra of
relatively simple, purely inorganic compounds
containing only a few atoms--specifically,
inorganic salts containing polyatomic (complex)
ions--are quite distinctive and can be used to
rapidly identify the ions. Consider a simple
inorganic salt, such as KNO2. On the basis of
the empirical formula, we might naively expect
there to be a total of 3(4)-6 = 6 normal modes of
vibration associated with this material. However,
this assumes that KNO2 is covalent.
• In fact, KNO2 consists of an ionic lattice of K+
and NO2- ions arranged in an infinite and very
regular array. The crystal consists of essentially
isolated K+ ions and NO2- ions. Thus we are
able to consider the vibrational modes of the
cation and anion independently of one another.
In this case, since the potassium ions are
monatomic, they have no vibrations (3(1)-3 = 0),
so we need only consider the nitrite anions. The
VSEPR (Valence Shell Electron Pair Repulsion)
Theory predicts a bent structure for the nitrite
ion. We thus anticipate three normal vibrational
modes for NO2-, corresponding to the diagrams
drawn earlier for H2O, and they should all be
infrared active.
• Indeed, three bands are observed in the
IR spectrum of KNO2: the symmetric
stretch at 1335 cm-1, the asymmetric
stretch at 1250 cm-1, and the bending
vibration at 830 cm-1 (bending vibrations
occur in general at lower frequencies than
stretching vibrations). The frequencies of
these vibrations are about the same
regardless of counter ion, substantiating
the independence of the anion and cation
in the crystal.
• C-H aldehydes

• Before concluding the discussion of the carbon hydrogen bond, one

additional type of C-H stretch can be distinguished, the C-H bond of
an aldehyde. The C-H stretching frequency appears as a doublet, at
2750 and 2850 cm-1. Examples of spectra that contain a C-H
stretch of an aldehyde can be found in Figures 14 and 15. You may
(should) question why the stretching of a single C-H bond in an
aldehyde leads to the two bands just described. The splitting of C-H
stretching frequency into a doublet in aldehydes is due to the
phenomema we called "Fermi Resonance". It is believed that the
aldehyde C-H stretch is in Fermi resonance with the first overtone of
the C-H bending motion of the aldehyde. The normal frequency of
the C-H bending motion of an aldehyde is at 1390 cm-1. As a result
of this interaction, one energy level drops to ca. 2750 and the other
increases to ca. 2850 cm-1. Only one C-H stretch is observed for
aldehydes that have the C-H bending motion of an aldehyde
significantly shifted from 1390 cm-1.
• Primary amines and amides derived from
ammonia
The N-H stretching frequency in primary amines
and in amides derived from ammonia have the
same local symmetry as observed in CH2. Two
bands, a symmetric and an asymmetric stretch
are observed. It is not possible to assign the
symmetric and asymmetric stretches by
inspection but their presence at approximately
3300 and 3340 cm-1 are suggestive of a primary
amine or amide. These bands are generally
broad and a third peak at frequencies lower than
3300 cm-1, presumably due to hydrogen
bonding, is also observed. This is illustrated by
the spectra in Figures 18 and 19 for n-butyl
amine and benzamide.
• Esters, aldehydes, and ketones

• Esters, aldehydes, and ketones are frequently

encountered examples of molecules exhibiting a
C=O stretching frequency. The frequencies,
1735, 1725, 1715 cm-1 respectively, are too
close to allow a clear distinction between them.
However, aldehydes can be distinguished by
examining both the presence of the C-H of an
aldehyde (2750, 2850 cm-1) and the presence of
a carbonyl group. Examples of an aliphatic
aldehyde, ester, and ketone are given in Figures
14, 34, 36, and 35, respectively.
• Nitro group

• The final functional group we will include in this

discussion is the nitro group. In addition to being
an important functional group in organic
chemistry, it will also begin our discussion of the
importance of using resonance to predict effects
in infrared spectroscopy. Let's begin by drawing
a Kekule or Lewis structure for the nitro group.
You will find that no matter what you do, it will be
necessary to involve all 5 valence