INFRARED SPECTROSCOPY

THE ELECTROMAGNETIC SPECTRUM

high Frequency (n) low

high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 mm 25 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long

 IR-REGION: 12,800 - 10 cm-1

REGION WAVE WAVE FREQUENCY

LENGTH NUMBER RANGE
λ (μm) υ (cm-1) Hz

NEAR 0.78 - 2.5 12800 - 4000 3.8x1014-1.2x1014

MIDDLE 2.5 - 25 4000 - 400 1.2x1014 - 6x112

FAR 25 - 1000 400 -10 6x1012- 30x1011

MOST 2.5 -15 4000 - 670 1.2x1014-2x1013

USED
• When infrared light is passed through a sample of an organic
compound some of the frequencies are absorbed, while other
frequencies are transmitted through the sample without being
absorbed.
• Hence in order to absorb IR radiation a molecule must go a net
change in dipole moment due to its vibration or rotation motion
A dipole moment arises from a separation of charges in a molecule
μ=qxr
μ =dipole moment (Coulomb ·meters)
q =magnitude of charges
r =vector going from –ve charge to +ve charge
• This means that nearly all molecules containing polar covalent
bond will show selective IR absorption
• If we plot absorbance or transmittance against frequency or the
wave number or wavelength the result is an infrared spectrum.
 Infrared
InfraredSpectrum
Spectrumof
ofHexane
Hexane

100

bending
C—H stretching
%T

bending bending

CH3CH2CH2CH2CH2CH3

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw-Hill Companies, Inc. All rights
reserved.
• The alkane molecules will only absorb infrared light of a
particular frequency if there is an energy transition within
the molecule such that ∆E = h√. The transitions involved in
infrared absorption are associated with vibrational changes
within the molecule; for example, the band near 3000 cm -1
has exactly the same frequency as a C –H bond undergoing
stretching vibrations.
• The bands around 1400 cm-1 corresponds to the frequency
of the bending vibrations of C-H bonds, and are called the C-
H (bend) absorptions. Alternatively bending vibrations are
referred to as deformations, so that C-H deformation bands
can be labeled as C-H def.
Most organic compound are fairly large & their
resultant vibration spectra are complex.

-To introduce the basic concept governing vibrational spectra a simple

diatomic covalent bond will be consider as a spring with atomic masses at
either end
-The stiffness of the spring is described by a force constant, k

M1 Force constant, k M2
Ball and spring representation of 2 atom of molecule vibrating in the
direction of bond
 Types of Vibration

Stretching Bending

Scissoring
Symmetric
Wagging
In plane
Out of plane
Rocking
Asymmetric
Twisting
 TYPES OF MOLECULAR VIBRATION

Stretching vibrations

Without change bond angle

Symmetric Asymmetric
Stretching Stretching
Isolated vibration
Symbol nu Without change Symbol nu
bond axis
 Bending Vibrations
In plane

Scissoring
Rocking
Symbol s Symbol rho ρ
 Bending Vibrations

Out of plane

Wagging Twisting
Symbol ω Symbol tau,τ
 If such a simple system is put in to motion ( by stretching and releasing)
the induced vibration of the masses are adequately described by
Hooke’s law of simple harmonic motion

Hooke’s law :
Frequency of motion
1 k m1 m2
 mr 
2 mr m1  m2
n = frequency
k : Force constant (dynes /cm)
mr = reduced mass (mass of largest atom)
 Vibrating diatomic molecule- simple harmonic oscillator
Consider a diatomic molecule associated with a dipole moment.

The vibratory motion of the nuclei of diatomic molecule may be

similar to the vibration of a linear harmonic oscillator. In such oscillator, the
force tending to restore an atom to its original state is proportional to the
displacement of the vibratory atom from the original position (Hooke’s law).

Suppose the bond between the two nuclei of a diatomic molecule is

distorted from its equilibrium length re to a new length r. then the restoring
forces on each atom of the diatomic molecule will be given by
d2r1
m1 = -k(r-re) (1)
dt 2

d 2r 2
m2 = -k(r-re) (2)
dt 2

where k is the proportionality constant and known as force constant ; it is

regarded as the stiffness of the bond ; r1 and r2 are the positions of atom 1 and
2 relative to the centre of gravity of the molecule.
we know m2 r
r1 = (3)
m1+m2
m1
and r2 = r (4)
m1+m2

Where m1 and m2 are the masses of two atoms of a vibrating

diatomic molecule. On substituting equation (3) in (1), we get
m 1 m 2 d2 r (5)
= -k(r-re)
m1+m2 dt2

As re is a constant, its differentiation with respect to time t will

be zero, i.e.,
d2 r d2 (r-re) (6)
dt2 = dt2
Substituting the above equation in equation (5) yields
m1m2 d2 (r-re) (7)
= -k(r-re)
m1+m2 dt 2
 m1 m2 μ (8)
put r-re = x and =
m1+m2
On substituting equation (8) in (7), we get
d2 x
μ 2 = -kx
dt

or d2 x x = 0 (9)
2 +
k
dt μ
d2 x
or 2 + ω x= 0
2 (10)
dt
where ω2= k/μ or ω= √k /μ (11)

Equation (10) is the expression of simple harmonic motion with

frequency of vibration (ν) as follows
ν = ω/2π = 1/2π√k /μ Hz (12)
where k is a force constant expressed in dynes per cm and μ is
the reduced mass of the system(Eq.8).
Problems:
• 1. The fundamental vibrational frequency of
HCl is 2,890 cm-1. Calculate the force constant
of this molecule.
• 2.Calculate the approximate wave number of
the fundamental absorption peak due to the
stretching vibrations of a carbonyl group.
The force constant for a double bond has an
approximate value of 1 x 106 dynes/cm. The
masses of carbon and oxygen atoms are 1
x10-23 and 2.6 x 10-23 g per atom.
Solution 1:
μ= 1.673 X 10-27 kg
k =4π2c2ν2 μ = 483 N.m-1

1 Newton per meter = 1000 dynes per cm

Problem 2. Calculate the approximate wave number of the
fundamental absorption peak due to the stretching vibration of a
carbonyl group.(The atomic masses of carbon and oxygen atoms
are 1.99 x 10-26 kg and 2.66 x 10-26 kg. Force constant = 1 x 10 3
N/M).
Solution:
μ= 1.99 x 10-26 x 2.66 x 10-26/ (1.99+ 2.66) x 10-26
= 1.14 x 10 -26

From Hooke’s law : ν = 1/2ᴨ (k/μ) ½

ν = 4.7171 x 1013 Hz
Wave number = ν/c= 4.7171 x 10 13/ 3 x 10 8 = 1.57 x 10 5 m -1
To convert this frequency to wave numbers, divide the eq. 1 by the velocity
of light c:

ν = ω/2 πc = (1/2πc) √k /μ cm-1

Vibrational energies, like all other molecular energies, are quantized and the
allowed vibrational energies for any particular system may be calculated from
the Schrodinger. For the simple harmonic oscillator the equation as follows

E ν = (v+1/2) hν Joules (v= 0,1,2,……)

Where v is called vibrational quantum number.
or
ε ν = Eν/hc = (v+1/2) ω cm-1
If v=0 then εo = 1/2 ω cm-1

Where εo is known as zero point energy. Thus even at absolute zero atoms of
diatomic molecule can never be completely at rest relative to each other.
In general the zero point energy depends on the classical vibration frequency
and hence on the strength of the chemical bond and the atomic masses.
 Selection rule for the vibrational spectra
Selection rule for the harmonic oscillator under going vibrational changes
is : Δv = ± 1
Vibrational spectra observable only in those molecule if the vibration can
interact with radiation, (if the vibration involves a change in the dipole
moment of the molecule). Thus vibrational spectra observable only in
heteronuclear diatomic molecules since homonuclear molecules have no
dipole moment.
Applying the selection rule we have:
Ε v+1→v = (v+1+ ½ ) ω – (v+ ½ ) ω = ω cm-1 for emission
Ε v→v+1 = (v+1+ ½ ) ω – (v+ ½ ) ω = ω cm-1 for absorption
what ever the initial value of v the vibrational levels are equally
spaced, transitions between any two neighboring states will give rise to the
same energy. Further , energy levels expressed in cm-1 gives directly the
wave number of the spectral line absorbed or emitted. In absorption, for
instance, the vibrating molecule will absorb energy only from radiation with
which it can coherently interact and this must be radiation of its own
oscillation frequency.
 6

3
energy
2

V=0

Internuclear distance
re cm-1

ω
So far as harmonic oscillator model is consider the lower
vibration state can be explained (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 combination band can not be explained

by Harmonic oscillator model. So vibrational diatomic
molecule can be explained well using anharmonic
oscillator model
Harmonic oscillator

Anharmonic oscillator

Overtones and

fundamental band
 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 energy difference goes on

decreasing as quantum no. increasing Δv =±1,
±2, ±3……
(overtone lines) is possible. But they are having
extremely low intensity. These are known as
overtones (they are weaker)
A purely empirical expression which fits this curve to a good
approximation was derived by P.M. Morse, and is called the Morse
function: [1-exp{a(req-r)}]2

E= Deq[1-exp{a(req-r)}]2 (1)
Deq = the dissociation energy for a
particular molecule
a = a constant for a particular
diatomic molecule and
req = the value of internuclear
distance which corresponds to a
minimum of Morse curve.
When equation (1) is used in the Schrodinger’s equation, the
values of allowed vibrational energy levels are as follows

Eν = (v + ½ )hcωe - (v + ½)2 hcx ωe + (v + ½)3 hcy ωe +….

(2)

Where ωe = equilibrium frequency of the molecule expressed in

wave numbers, and x,y,… = the anharmonic constants.
The selection rule for all the transitions in anharmonic oscillator
may be given as:
Δv = + -1, +
- 2, - 3,……
+
For the transition in which
(i) v=1 to v=0 gives fundamental band.
(ii) v=2 to v=0 gives first overtone (second anharmonic)
(iii) v=3 to v=0 gives second overtone (third anharmonic), etc

The energy change when a transition results from an upper level

vI to the lower level vII will be given by
EvI-EvII = (vI-vII) hc ωe – [ vI(vI+1) – (vII(vII+1)] xhc ωe
where v is the vibrational quantum number in the initial
state.
For fundamental band, v=1 to v=0
ν1 = (1-2x) ωe
For the first overtone band, v=2 to v=0
ν2 = (1-3x)2 ωe
For the second overtone band, v=3 to v=0
ν3 = (1-4x)3 ωe
Where ν1 ,ν2 ,ν3 , are the frequencies of the
origins or centres of fundamental, first and second,
overtone respectively
 Diatomic Vibrating Rigid Rotator
Diatomic molecules are considered which can execute rotations
and vibrations simultaneously. Such a system is termed as a
rotating vibrator or a rotating oscillator.

If there is no interaction of vibration and rotation, the total

energy of the vibrating rotator would be given by the sum of
vibrational and rotational energies. (1)
Etotal = Erot + Evib
Diatomic molecule as a harmonic oscillator and a rigid rotator.
The combined energy of such a system is given by

= (v h2 (2)
Evr = Etotal + ½ )hcω + J(J+1)
8π2I
It can be proved very easily that the selection rules for combined
motions are the same as those for each separately. Therefore,

Δv = ±1, ΔJ = ±1
The frequency of spectral lines arising due to transition between
the two states can be calculated by using equation (2). Suppose a
simultaneous transition from vibrational level v’ to v’’ and from
rotational level J’ to J’’ occur. Now the change in energy, on using
equation (2), may be put as
h2
E’vr - E’’vr= (v’ – v’’)hcω + [J’(J’+1)- J’’(J’’+1)] (3)
8π I
2

And the corresponding frequency of radiation, which arises due

to this transition, will be given by
E’ - E’’vr
ν = vr
hc h2
= (v’ – v’’)hcω + 2 [J’(J’+1)- J’’(J’’+1)]
8π I
hc
 = (v’ – v’’) ω + B [J’(J’+1)- J’’(J’’+1)] (4)

where B = h/8π2Ic
= (v’ – v’’) ω + B (J’2 + J’- J”2-J’’)
= (v’ – v’’) ω +B (J’ – J’’) (J’+J’’+1) (5)
As the vibrations are assumed to be harmonic, the possible
Vibrational transitions are those in which v’-v’’=1. Thus, equation
(5) becomes ν = ω +B(J’ – J’’) (J’+J’’+1) (6)

From equation (6) it is evident that the frequencies of the lines will
evidently vary with the values of J’ and J’’. Thus ,
(i) ΔJ = +1, i.e., J’= J’’+ 1 or J’- J’’= 1
So that the equation (6) becomes as
ν(R)= ω + 2B (J’’+ 1) cm-1 where J’’ = 0,1,2, etc (6)
(ii) ΔJ = -1, i.e., J’’= J’+ 1 or J’- J’’= -1,
So that the equation (6) becomes as

ν(P) = ω - 2B(J’+ 1) cm-1 where J’ = 0,1,2, etc (7)

On combining equations (6) and (7), we get

ν = ω +2B m cm-1
Where m = ±1, ±2, ±3……etc. The value of m cannot be zero
because this would imply value of J’ or J” to be -1 which is not
possible.
 Diatomic Molecule as anharmonic oscillator and a
non-rigid rotator
Assume a diatomic molecule to be anharmonic oscillator and
non-rigid rotator. It is assumed that there is no interaction of
vibration and rotation. Then it may be
Evr = Etotal = Erot + Evib
The combined energy of a diatomic molecule will be given by

Evr = hc [ {B J(J+1) – DJ2(J+1)2+…….} + { (v+½) we – x(v+½)2 we +y(v+½)3 we)}]

(1)
It can be proved that the selection rules for the combined motions
remain same as those for each separately, thus
=
Δv ±1, ±2, ±3
ΔJ = ±1
The frequency of spectral lines arising due to transition between
the two states may be evaluated by using equation (1). For a good
infrared spectrometer possing a resolving power of about 0.5 cm,
the value of D can be neglected. Thus equation (1) become as
 Evr = hc BJ(J+1) + (v+½) we hc– x(v+½)2 we hc (2)

Suppose we consider only v=0 to v=1 transition. Now designate rotational quantum
number in v=0 state as J’’ and v=1 state as J’. Frequency of transition can be written as

ν = (v’-v’’) ωe - [ v’(v’+1) – v’’(v’’+1)] xe ωe + B (J’-J’’) (J’+J’’+1) cm-1

E’ – E’’
ν =
hc
ν = [{hcBJ’(J’+1)+(1+½)wehc–x(1+½)2wehc } – {hcBJ’’(J’’+1)+(0+½)wehc–x(0+½)2wehc
hc

ν = ν0 + B (J’ - J’’) (J’ + J’’ + 1) cm-1

ν0 = we ( 1 – 2x ) (3)
Where

The value of B remains the same in upper and lower vibrational states because we have
taken rotation to be independent of the vibrational changes. Thus we can write
(i) when ΔJ = +1, i.e., J’= J’’+ 1 or J’- J’’= 1

ν(R) = ν0 + 2B (J’’+ 1) cm-1 where J’’ = 0,1,2, etc (4)

(ii) when ΔJ = -1, i.e., J’’= J’+ 1 or J’- J’’= -1,

ν(P) = ν0 - 2B (J’+ 1) cm-1 where J’ = 0,1,2, etc (5)

On combining equation (4) and (5), we get

ν = ν0 + 2Bm cm-1

Where m = ±1, ±2, ±3……etc. The value of m cannot be zero because this would imply
value of J’ or J” to be -1 which is not possible. The ν0 is generally termed as an origin.

Equation (5) represents the vibration-rotation spectrum. Such spectrum would contain
equally spaced lines with a spacing of 2B on either side of the bond origin ν0 . As the
value of m cannot be zero, no line will appear at ν0 and thus Q branch will be absent.
 ΔJ= -1 ΔJ= +1
6

2
1
J’= 0

2
1
J’’=0

3B 3B
4 B
P6 P5 P4 P3 P2 P1 Vv R0 R1 R2 R3 R4 R5
Normal modes of vibrations in polyatomic
molecules
(3n-6) for non linear molecules
And (3n-5) for linear molecules.
n = no. of atoms in a molecule
Modes of vibrations for H2O molecule:
3 x 3- 6 = 3
Symmetric Stretching γ1 = 3652 cm-1
Asymmetric Stretching γ2 = 3756 cm-1
And in plane scissoring γ3 = 1515 cm-1
CO2 molecule:
3 x 3- 5= 4 modes of vibrations.
γ sym is IR inactive
γ asym = 2350 cm-1
γ inplane and γout of plane , deformation vibrations are degenerate
and appear at 666 cm-1
 Actual number of modes of vibrations will be altogether
different from those calculated theoretically
In polyatomic molecules the actual modes of vibrations will be altogether
different from those calculated theoretically. The main reasons for all this
are:
1. The overtones and combination of tones may increase the number of
modes of vibrations.
2.Vibrations that do not fall in the IR region cannot be observed in the IR
spectrum.
3. Some weak vibrational bands, if present cannot be seen in the IR
spectrum
4. Some vibrational bands, which are having the slightly different
frequencies overlap each other and appear as one band in the IR
spectrum.
5. Some vibrational bands may degenerate and appear at the same place
in IR spectrum
6. If there occurs no required change in dipole character of the molecule,
no band will appear in the IR spectrum.
Factors influencing vibrational frequencies

• The calculated frequency (by Hook’s law) can

not be exactly equal to the experimental
value.
• The differences arises due to the fact that
vibrations of each group gets influenced by
the structure of the molecule in the
immediate neighborhood of the bond.
• Frequency shifts also occur on working with
the same substance in different states.
Factors :
1. Coupled vibrations and Fermi resonance:
• It is expected that one stretching absorption frequency for
an isolated C-H bond but in --CH2 two absorption occur
corresponds to symmetric and asymmetric vibrations.
• In such cases asymmetric stretching vibration always takes
place at higher wave number compared with symmetric
vibrations. These are known as coupled vibrations.
Simillarly, CH3 coupled vibrations occur at different
frequencies compared to CH2 group.
• Acid anhydrides are having two C=O str. absorptions
between 1850-1800 and 1790-1745 cm-1 due to sym and
asymmetric stretching. This kind of wide spread of
absorption band can be explained the transfer of energy
from fundamental to over tones and back again known as
coupled pendulums called fermi resonance
•
2.Electronic effects

+ I effect: Introduction of alkyl groups:

• Formaldehyde 1750 cm-1

• Acetaldehyde 1745 cm-1
• Acetone 1715 cm-1

• Conclusion: Lengthening and weakening of

the bond
-I effect:

Acetone 1715 cm-1

Chloroacetone 1725 cm-1
Dichloroacetone 1740 cm-1

Conclusion; Shortening and strengthening of

the bond
 Hydrogen bonding
Hydrogen bonding gives rise to downward frequency
shifts. Stronger the hydrogen bonding greater the
absorption shift towards lower wave number from the
normal value.
Generally, intermolecular hydrogen bonding give broad
bands whereas bands arising from intramolecular
hydrogen bonds are sharp and well defined.
Intra molecular hydrogen bonds are independent of
concentration.
Sharp peak, Broad peak,
independent on concentration
concentration dependent
 IR spectrum of amines
• The FTIR spectrum of amines show characteristic absorption
bands due to N-H Stretching, N-H bending and C-N stretching.
• The number and position of bands depends upon the class to
which the amine belongs
• Primary and secondary amines exhibit moderately weak
absorption at 3500-3200 cm-1. However primary amines have
two such bands in this region while secondary amines show
only one band. Tertiary do not exhibit such band
• Primary amines exhibit moderately strong N-H bending bands
at 1650-1560 cm-1 and 900-650 cm-1 while secondary amines
show weak bands of this type around 1600-1500 cm-1
• The C-N stretching bands of aliphatic amines
appear in the region 1230 cm-1 to 1030 cm-1,
weak bands; However the aromatic amines
exhibit two strong bands at 1360-1180 cm-1

• The salts of amines such as hydrochloride

show a broad band in the 3000-2000cm-1
region which is typical of ammonium ion.
Correlation chart
3500-3300 cm-1 N-H Stretch
3500-3200 O-H Stretch
3100-3000 C-H Stretch alkenes
3000-2850 C-H Stretch alkanes
1760-1665 C=O Stretch aldehydes,
ketones and esters
1680- 1640 C=C Stretch alkenes
 INSTRUMENTATION

TRANSDUCER

SAMPLE

MC
SOURCE

REFERENCE
Infrared
Spectrum
 Single beam spectrophotometer

Littrow Prism
mirror

Detector

☼
Sample
Chopper
Double beam spectrophotometer
 INFRARED SOURCE
The source is always some form of the filament which is maintained at red or
white heat by an electric current
1. Incandescent lamp: It works in the near IR but fails in the far IR because
it is glass enclosed and has a low spectral emissivity.
2. Nerst Glower. It is Fabricated from rare earth oxides
(e.g. ZrO2+Y2O3)
Diameter 1-2 mm length 20 mm
Pt. leads are sealed to the end of cylinder
to permit electric connection
When electric current pass it glows ,at
temp 1200-2200 k
Main disadvantage is it requires external heating, and it undergoes
frequent mechanical failure
3.THE GLOBAR SOURCE

 Silicon carbide rod, 50 mm length ,5 mm D

It is self starting
 Electrically heated at 1300-1500 k
 Advantage of +ve temp. coefficient of resistance
 Main disadvantage is that it is a less intense source than

the Nernst glower

4. MERCURY ARC
 Used for far IR region (above 50 μm)

 High pressure Hg arc is used (1 atm pressure)

 Passage of electricity through the vapour, forms an internal plasma source

that provides continuum radiation in far IR
Advantages of using laser are:
1. A single, intense frequency source replaces the multi-lined
mercury lamp. Thus, no filtering is necessary.
2. The line width of a laser line is smaller than the mercury excited
line, therefore the resolution will be better.
3. The greater ease in focusing and collimating the radiation
because of highly coherent character of laser light.
4. A large number of exciting frequencies are available and thus it
is possible to study colored solutions without causing any
electronic transitions. This is of utmost practical importance in
the study of solutions of inorganic salts because many of them
are colored compounds
 .

Optical path and monochromator.

• The beam is guided and focused by mirrors silvered on their surfaces.

Normally a focus is produced at the point where the sample is to
be placed.

• Ordinary lenses and mirrors are not suitable as glass absorbs

strongly over most of the frequencies used.

• Any windows which are essentially made of mineral salts like NaCl
and KBr are used

• Similarly monochromators made of a rock salt or potassium

bromide prisms and gratings are used. Gratings give better
resolution than prisms
 Detectors
Two main types are in common use.
One sensing the effect of heat due to radiation
and the other depending on photoconductivity.

In both, greater the effect( temp. and photoconductivity rise) at a

given frequency, the greater the transmittance and less the
absorbance.
Bolometers: A bolometer is based upon the fact that the electrical
resistance of a metal increases approximately 0.4 % for every
Celsius degree increase of temperature. A bolometer usually
consists of a thin metal conductor. When radiation such as IR falls
on this conductor, its temperature changes. As the resistance of a
metallic conductor changes with temperature, the degree of
change in resistance is regarded as a measure of the amount of
radiation that has fallen on the bolometer. The response time for
Thermocouple
 The thermocouple detector is based upon the fact
that an electrical current will flow when two
dissimilar metal wires are connected together at
both ends and a temperature difference exists
between the two ends.
 The end exposed to the infrared radiation is called
the ‘ hot junction. In order to increase the energy
gathering efficiency, it is usually a black body.
 The other connection, the cold junction is thermally
insulated and carefully screened from stray light.
 The electricity which flows is directly proportional to
the energy difference between the two connection
 A thermocouple is made by welding together at each end of
two wires of different semiconductor materials of high
thermoelectric efficiency.
 If two welded joints are kept at different temperatures, a
small electrical potential is developed between the joints.
 A thermocouple is closed in an evacuated steel casing with a
KBr (or CsI) window to avoid losses of energy by convection.
 In the IR spectroscopy, one welded joint, cold junction is kept
at a constant temperature and is not exposed to IR radiation,
but the other welded joint , hot junction is exposed to the IR
radiation which increases the temperature of the junction.
 The temperature difference between the two junction
generates potential difference which depends on how much
IR radiation falls on the hot junction .
 The response time of a thermocouple is about 60 m sec
Golay Cell
 It is generally used in several commercial spectrophotometers.
 It consists of a small metal cylinder which is closed by a
blackened metal plate at one end and by a flexible metalized
diaphragm at the other.
 After filling the cylinder with xenon, it is sealed.
 When IR radiation is allowed to fall on the blackened metal
plate, it heats the gas which causes it to expand.
 The resulting pressure increase in the gas deforms the
diaphragm which separates two chambers.
 Light from a lamp is made to fall on the diaphragm which
reflects the light on to a photocell.
 Motion of the diaphragm changes the output of cell.
 The signal seen by the phototube is modulated in accordance
with the power of the radiant beam incident on the gas cell
The Golay detector possesses the same sensitivity as a
thermocouple detector in the mid-infrared region.
It is best suited when working at wavelength greater than
about 15μ.
Golay cell is some what less convenient than many other
detectors because it is more expensive and bulky.
Advantages:
• It can be used for wide wavelength range.
• Its response is linear over the entire wavelength range from
the ultraviolet through the visible and infrared into the
microwave range to wavelength about as long as 7 mm.
• The Golay detector’s response time is about 10-2 sec, much
faster than that of the bolometer, thermistor or
thermocouple.
 Photoconductivity Cell
• This is a non thermal
detector of greater
sensitivity.
• It consists of a thin layer of
lead sulphide or lead
telluride supported on glass
and enclosed into an
evacuated glass envelope.
• When IR radiation is focussed
on lead sulphide or lead
telluride, its conductance
increases and causes more
current to flow.
• Response time is 0.5 m sec
• Advantages • Disadvantage
• It has high sensitivity • When operated at room
• Good speed of temperature, it has a
response of IR very restricted range.
usually limited to near
infrared. The range can
be broadened by drastic
cooling.
Why there is a need for FTIR?
1. If useful information required in energy
limited area i.e. from 400 cm-1 to 20 or 10 cm-
1
sources become weak and detectors
become insensitive
2. By conventional means it is difficult to
obtaining good signal-to-noise ratios
If two beams of light of the same wavelength are brought
together in phase, the beams reinforce each other and
continue down the light path.
However, if two beams are out of phase, the destructive
interference takes place. This interference is at a maximum
when the two beams of light are 180ᵒ out of phase.
Advantage is taken of this fact in the Fourier transform
spectrometer.
This system is based on the Michelson-Morely experiment
used to measure the influence of the earth’s rotation on
the speed of light.
 M1

Source

M2
 A schematic diagram consists of four optical arms, usually at right angles to each
other with a beam splitter at their point of intersection.
 Radiation passes down the first arm and is separated by a beam splitter into two
perpendicular half-beams of equal intensity that pass down into other arms of the
spectrometer. At the ends of these arms the two half-beams are reflected by
mirrors back to the beam splitter, where they recombine and are reflected together
onto the detector.
 If the initial radiation is at one wavelength and in phase with itself and the side
arm paths are equal in length, then, when two half-beam are recombined, they will
still be in phase, reinforcing each other , and the maximum signal will be
obtained on the detector.
 If the mirror in one arm is moved up by one quarter of a wavelength, then the
half-beams will be one-half of a wavelength out of phase with each other, that is,
they will interfere with each other.
 In practice, the mirror in one arm is kept stationary and that in the second arm is
moved slowly in the direction of the beam splitter. The net signal falling on the
detector will then be a cosine wave with the usual maxima and minima when
plotted against the travel of the mirror.
Cosine wave occurs exactly ¼ cylcle earlier the
corresponding point on the sine wave
 The frequency of the cosine signal is equal to
f= 2v/λ
Where f = frequency , v = velocity of the moving mirror,

λ = wavelength of radiation
(A cosine wave is a signal waveform with a shape identical to that of a sine
wave, except each point on the cosine wave occurs exactly 1/4 cycle earlier
than the corresponding point on the sine wave)
 The frequency of modulation is therefore proportional to both the
wavelength of the incident radiation and the velocity of the mirror
 The resolution is dependent on linear movement of the mirror. The
velocity of the mirror can be controlled by using a laser beam.
 As the total distance travelled increases, the resolution improves.
 The sample in the FTIR is exposed to the entire radiation beam at the
same time and absorption effects at all wavelength modify the final signal.
This is known as the multiplex advantage and it greatly increases the
sensitivity and accuracy .
 Comparison between FTIR and Dispersive IR

Dispersive IR Fourier Transform IR

1. There are many moving parts, 1. Only the mirror moves during an
resulting in mechanical slippage and experiment
wear
2. Calibration against reference spectra is 2. Use of a laser provides high frequency
required to measure frequency accuracy (0.01 cm-1)
3. Stray light within the instrument 3. Stray light does not affect the
causes spurious readings detector, since all signals are
modulated
4. Slow scan speeds make dispersive 4. Rapid scan speeds permit monitoring
instruments too slow for monitoring sample undergoing rapid change
systems undergoing rapid change 5. The sample is not subject to thermal
5. The samples is subjected to thermal effects
effect from the focused beam
 Applications of IR spectroscopy
1.Identification of components
2. Determination of molecular structure
3. Studying the progress of reactions
4. Detection of impurities
5. Isomerism in organic chemistry
6. Quantitative analysis
 Limitation of IR spectroscopy
1.It is not possible to know the molecular
weight of a substance
2.Does not provide the information of the
relative positions of different functional
groups on a molecule.
3. From the single spectrum of an unknown
substance it is not possible to know whether it
is a pure compound or a mixture of
compounds