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Introduction
Theory of Infrared Spectroscopy
In order to understand the theory of Infrared (IR) absorption spectroscopy, one has to understand the
phenomenon of vibrational rotational spectra. Let us 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 (Hookes 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
d 2 r1
d 2 r2
m1 2 K (r re ) ;
m 2 2 K (r re )
. . . . (1)
dt
dt
Where K is proportionality constant known as force constant; it is regarded as a measure of the stiffness of
the bond; m1 and m2 are the masses of the two atoms; r1 and r2 are the positions of atom 1 and 2 relative to
the centre of gravity of the molecule. Now we know that
m2
m1
r1
r;
and r2
r
. . . . (2)
m1 m 2
m1 m2
On substituting equation (2) in (1), we get
m1 m2 d 2 r
2 K (r re )
. . . . (3)
m1 m2 dt
As re is constant its differentiation with respect to t will be zero; so
d 2 (r re )
d 2r
. . . . (4)
dt 2
dt 2
From equations (3) and (4), we get
d 2 (r re )
. . . . (5)
K (r re )
dt 2
m1 m2
If (r re ) x (displacement of atoms ) ; and
(reduced mass of the molecule) then
m1 m2
m1 m 2
m1 m2
d 2x
Kx
dt 2
d 2x
K
x 0
2
dt
2
d x
2x 0
2
dt
or
. . . . (6)
. . . . (7)
Equation (7) is the expression of a simple harmonic motion with frequency of vibration ()
1 K
. . . . (8)
2
2
where is angular frequency and equal to
Energy Levels: Since bond of a diatomic molecule vibrate with a frequency, , it associates with certain
energy known as vibrational energy. This energy may be evaluated from Schrodingers equation by the
expression
_
Ev
v 12 hc
. . . . (9)
where
v is the vibrational quantum number and can have values of 0,1,2,.etc, because the energy is
quantized.
_
. . . . (10)
c
2c
Suppose we consider a diatomic molecule which undergoes transition from an upper vibrational
level v to lower vibrational level v. The change in vibrational energy will then be given as
_
. . . . (11)
_
E
(v " v ' ) hc
(v " v ' )
. . . . (12)
h
h
The selection rule for vibrational quantum number of the harmonic oscillator is restricted to
v v " v ' 1
So that the wave number of spectral line arising due to transition between v = 1 and v = 0 will be given by
_
1
k
cm-1
. . . . (13)
2 c
From the above discussion, when a diatomic
Energy curve for Simple
Harmonic Oscillator
molecule considers as simple harmonic oscillator, the
V=9
energy of transition between any two successive vibrational
V=8
V=7
levels may be same i.e. the vibrational levels are even E
V=6
n
V=5
spacing. However it is observed experimentally that e
V=4
r
vibrational energy levels less and less separated as v g
V=3
Energy curve for
increases. So a diatomic molecule behaves as anharmonic y
V=2
Anarmonic
Oscillator
V=1
oscillator and the energy curve is shown in the fig.
_
V=0
Internuclear Distance
Energy diagram of Anharmonic Oscillator
It may be noted that the atoms in a molecule are not held rigidly. The molecule may be visualized as
consisting of balls of different sizes tied with springs of varying strengths. Here balls and springs
correspond to atoms and bonds respectively. When the molecule absorbs IR radiation, two kinds of
fundamental vibrations are occurred: those are:
a) Stretching vibrations: In this type of vibrations, the distance between the two atoms increases or
decreases but the atoms remain in the same bond axis. There are two types of stretching vibrations:
i) Symmetric stretching: In this type, the movement of the atoms with respect to a particular atom in a
molecule is in the same direction i.e. both the atoms either approach the central atom or depart from the
central atom.
ii) Asymmetric stretching: In these vibrations, one atom approaches the central atom and the other departs
from it.
b) Bending vibrations: In this type of vibrations, the positions of the atoms change with respect to the
original bond axis. This type of vibrations are may be observed in non-linear molecules. These are of four
types:
i) Scissoring: In this type two atoms approach to each other. i.e. the bond angle will change.
ii) Rocking: In this type, the movement of the atoms takes place in the same direction.
iii) Wagging: The two atoms move up and below the plane with respect to the central atom.
iv) Twisting: In this type, one of the atoms moves up the plane while the other moves down the plane with
respect to the central atom.
We know that more energy is required to stretch a spring than that required to bend it. Thus,
stretching absorptions of a bond appear at high frequencies (higher energy) as compared to the bending
absorptions of the same bond. The various stretching and bending vibrations of a bond occur at certain
quantized frequencies, when IR radiation is passed through the substance. The energy required for various
vibrations can be calculated by the expression:
_
1
k
cm-1
2 c
Modes of Vibrations
Bending
Stretching
Symmetric Asymmetric
In plane
Scissoring
Out plane
Rocking
Wagging
Twisting
Type of
compound
Alkanes
Alkenes
Alkynes
Aromatic rings
Aldehydes
Frequency
(in cm-1)
2850 2960
3010 3100
3300
3000 3100
2650 2880
Monomeric
alcohols, phenols
Hydrogen bonded
alcohols, phenols
Amines
Nitriles
3600 - 3650
CO
3200 - 3400
OH
3300 - 3500
2210 - 2260
CN
NO
Bond
C C
C == C
C C
C == C
O
||
C
Type of
compound
Alkanes
Alkenes
Alkynes
Aromatic rings
Carbonyl
compds,
carboxylic acids,
esters
Alcohols, ethers,
acids, esters
Hydrogen bonded
acids
Amines
Nitro compounds
Frequency
(in cm-1)
600 1500
1620 - 1680
2100 2660
1500 - 1600
1680 - 1760
1000 - 1300
2500 3000
1180 1360
1330 - 1540
In such cases, asymmetric vibrations always take place at higher frequency compared with the
symmetric vibrations. These are known as coupled vibrations because these vibrations occur at different
frequencies than that required for isolated CH stretching. Similarly, coupled vibrations of CH3 group
occur at different frequencies compared to CH2 group.
Symmetriic Stretching
Asymmetriic Stretching
Symmetriic Stretching
Asymmetriic Stretching
Some times it is found that two different vibrational levels are having nearly the same energy. If
such vibrations belong to the same species, then a mutual perturbation of energy may occur, causing the
shift of one towards lower frequency and the other towards higher frequency. It is also accompanied by a
substantial increase in the intensity of the respective bands.
1) the term
given to accidental degeneracy arising in polyatomic molecules in
which two different vibrational states accidentally possess approximately
the same energy and interact with each other.
2. Electronic Effects: Electronic effects such as inductive effect, mesomeric effect, field effect etc.
influence the absorption frequency of the bonds. Under the influence of these effects, the bond strength
(force constant) of the bond changes, so that its absorption frequency shifts from the normal value. For
example, the presence of an alkyl group in the carbonyl compounds causes +I effect, which gives rise to
the weakening of the >C=O bond. Due to this, absorption takes place at lower frequency. Similarly, the
presence of electro-negative group (I effect) increases the absorption frequency. The absorption
frequencies of >C=O bond of some carbonyl compounds are given below for comparison.
Influence of + I Effect group
i) Formaldehyde (HCHO)
ii) Acelaldehyde (CH3CHO)
iii) Acetone (CH3COCH3)
1750 cm-1
1745 cm-1
1715 cm-1
1715cm-1
1725cm-1
1740cm-1
Conjugation of pi bonding electrons or lone pair of electrons (mesomeric effect) lowers the strength
of the bond and thus lowers the frequency of absorption. For example, >C=O stretches at 1706cm-1 in
methyl vinyl ketone; at 1693 cm-1 in acetophenone and benzamide and at 1730 cm-1 in phenyl acetate.
It is to note that some cases, inductive effect dominates over mesomeric effect whereas reverse holds
for other cases.
3. Hydrogen Bonding: Weak electrostatic attractive forces arise between covalently bonded hydrogen and
more electronegative atom is known as hydrogen bond. Hydrogen bonding gives rise to downward
frequency sifts. Stronger the hydrogen bonding grater the absorption sift towards lower frequency from
normal value. As nitrogen atom is less electronegative than an oxygen atom, hydrogen bonding in amines
is weaker than that in alcohols and thus the shifts of absorption frequencies in amines are less than that of
alcohols. For example, alcohols exhibit intermolecular hydrogen bonding and give OH stretching at
3400 3200cm-1 while free OH stretching absorbs near 3600cm-1. Amines show NH stretching at
3500cm-1 in free state (i.e. in dilute solutions) while in condensed phase spectra, absorption takes place at
3300-1. In enols and chelates, hydrogen bonding is exceptionally strong and absorption due to OH
stretching takes place at very low values.
It is possible to distinguish two types of hydrogen bonds viz. intra-molecular (with in the molecule)
and inter molecular (between different molecules) hydrogen bonding by the infrared technique.
Generally, intermolecular hydrogen bonds give broad bands, whereas intramolecular hydrogen bonds
give sharp and well defined bands. Intermolecular hydrogen bonds are concentration dependent, so on
dilution, the intensities of such bands decrease and finally disappear. Intramolecular bonds are
independent of concentration. The effect of intramolecular bonding on frequency of absorption is less
when compare with that of inter molecular bonding.
INSTRUMENTATION
The usual optical materials, glass or quartz absorb strongly in the infrared region, consequently the
apparatus for measuring infrared spectra is different from that for the visible and ultraviolet regions. The
main parts of an IR spectrometer are as follows and the block diagram of the instrument is shown in the fig.
Mirror
Light
Source
Referenc
e
Chopper
Sample
Mirror
Recorder
Detector
Half Mirror
Amplifier
Monochromator
3. Monochromator
iii) steady
a) Incandescent Lamp: Since incandescent lamp produces near IR radiation, an ordinary incandescent
lamp is generally used in the near IR instruments. However, this fails in the far and middle IR
regions because i) it is glass enclosed and ii) has low spectral emissivity.
b) Nernst Glower: It consists of a hallow rod which is about 30 mm in length and 2mm in diameter. It
is composed of rare earth oxides such as zirconia, yttria and thoria. Nernst glower is non-conducting
at room temperature and must be heated externally to bring it to a conducting state. It is generally
iii) Mull Technique: In this technique, the finely ground solid sample is mixed with Nujol (mineral oil)
to make a thick paste and the paste is spread between IR transmitting windows. This is then
mounted in a path of infrared beam and the spectrum is run. However, although Nujol is transparent
throughout IR region, it absorbs at 2915, 1462, 1376 and 719cm-1.
iv) Pressed Pellet Technique: In this technique a small amount of finely ground solid sample is mixed
with powdered potassium bromide in 1:100 ratio. The finely ground mixture is then passed under
very high pressure in a press (at least 25,000 p sig) to form a small pellet (about 1 2 mm thick and
1cm in diameter). The resulting pellet is transparent to IR radiation and is run as such.
The following are some important advantages of this method:
1. KBr is transparent to throughout the IR region. So, no absorption bands appear at 2915,
1462, 1376 and 719cm-1.
2. KBr pellets can be stored for longer time.
3. As the concentration of the sample can be suitably adjusted in the pellet, it can be used for
quantitative analysis.
4. The resolution of the spectrum is superior to that of mull technique.
However, the pressure pellet technique has the following disadvantages:
1. It always has an absorption at 3450 cm-1 from the OH group of moisture present (always) in
the sample.
2. The high pressure involved in the formation of pellet may cause for polymorphic changes in
crystallinity in the sample. Some times, substitution of legend by bromide may be possible.
3. The method is not successful for some polymers which are difficult to grind with KBr.
b) Sampling of liquids: Samples that are liquids at room temperature are usually put directly into
rectangular cells made of NaCl, KBr or ThBr and their IR spectra are obtained directly. The sample
thickness is in the range of 0.01 0.05 mm which should give the transmittance between 15 to 20%.
For double beam spectrometers, matched cells which have the same thickness, are generally
employed. One cell will contain the sample while the other will contain solvent used in the sampling.
All cells should be protected from moisture because the cells dissolve in water. For similar reasons,
organic liquid samples must dry before pouring into the cell.
c) Sampling of gases: The gas sample cell is similar
to the cell for liquid samples, in which the surfaces
in the light path are made of NaCl or KBr. The
cells which are used for gases are larger usually
they are about 10cm long, but they may upto 1m
long. Multiple reflections can be used to make the
effective path length as long as 40m, so that the gas
can be analyzed. The gas must not react with cell
windows and the reflecting surfaces.
Monochromators: The radiation source emits radiations of all frequencies in desired region. Since the
sample absorbs only at certain frequencies, it is necessary to select those desired frequencies from the
radiation source. Monochromator is an optical device which resolves a broad band of spectrum into narrow
band of radiation with high spectral purity. The essential components of a monochromator are entrance slit,
exit slit and dispersing unit which is either a prism or a diffraction grating. There are mainly two types: (a)
prism monochromators and (b) grating monochromators.
a) Prism monochromators: Radiation from the sample is focused upon the entrance slit, then it is
collimated by a lens or mirror so that parallel beam falls upon the dispersing unit. When a beam of
radiation passes through the interface between two different media, such as air and glass, bending
Longer wave
lengths
Shorter wave
lengths
Dispersion of light
Litrow
mirror
Litrow
mirror
Prism
Pris
Entrance
slit
Off-axis
parabolic
mirror
Off-axis
parabolic
mirror
Entrance
slit
1
2
3
4
Plane
mirrors
Exit slit
Exit
slit
b) Grating Monochromator: Grating monochromators are more effective than prism monochromators.
The grating is a series of parallel straight lines cut into a plane surface. Dispersion by grating follows
the law of diffraction and the mathematical relation as:
n d ( Sin i Sin )
Where n is order (a whole number), is the wavelength of the radiation; d is the distance
between the grooves, i is the angle of incidence of radiation and is the angle of dispersion of a
particular radiation of wavelength. So, at a grating, resolution of light occurs because light of
different wavelengths is dispersed at different angles.
Reflection gratings are more common than prism. The gratings may be constructed from a wide
variety of materials such as aluminum. Several gratings, each with different rulings (lines/cm) are
necessary to cover the wide range of IR spectra.
Grating monochromators possess the following advantages over prism monochromators.
i) Grating can be made with materials like aluminum which are not effected by moisture
ii) Grating monochromators can be used over considerable wavelength ranges.
Top view
Side view
Diffraction of radiation
Detectors: Except in the near IR, where a photoconductivity cell is generally used, thermal detectors are
normally used in the IR spectroscopy. As the radiant power of IR radiation is low, the detector signal will
also be low, a preamplifier is fixed to the detector and the radiation is modulated with low frequency light
interrupter. Various types of detectors used in IR spectroscopy are:
a) Bolometers: A bolometer is based upon the fact that the electrical resistance of a metal increases
approximately 0.4% for every degree raise of temperature. A bolometer usually consists of a thin
metal conductor. When radiation, such as IR radiation, falls on this conductor, its temperature raises
and with the result its resistance will increase. So the degree of change in resistance is regarded as a
measure of the amount of radiation that has fallen on the bolometer.
A schematic diagram of bolometer is shown in fig. In
this, a thin metal conductor is made one arm of the
Wheatstone bridge which is irradiated with IR radiation. A
similar strip of metal is used as the balancing or reference
arm of the bridge which is not exposed to radiation. When no
radiation falls on the bolometer, the bridge is balanced with
the help of variable resistance which is another arm of bridge.
When IR radiation falls on the bolometer, the bridge becomes
unbalanced due to change in the electrical resistance, which
causes a current flow through the galvanometer. The amount
of current flow through the galvanometer is a measure of the
intensity of the radiation falling on the detector. The
response time of a thermocouple is about 4 m sec.
Fixed
Resistance
Reference Strip
(Light shielded)
G
Indicator
Strip
Variable
Resistance
h
Schematic diagram of a Bolometer
b) 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. When one junction of the metals is heated by irradiation with IR
radiation, an electrical potential is developed due to the temperature gradient and this potential is
directly proportional to the intensity of the radiation upon falls on it.
A schematic diagram of thermocouple is shown in
Light barrier
fig. A thermocouple is made by welding together at
Metal A
each end of two wires of different semiconductor
Hot Junction
Cold
materials of high thermoelectric efficiency.
A
(Block body)
Junction
thermocouple is closed in an evacuated steel casing (to
avoid losses of energy by convection) with a KBr
T2
window. One welded joint (called cold junction) is kept
h
T1
Metal B
at a constant temperature and is not exposed to IR
radiation. The other welded joint (called hot junction)
Schematic digram of a Thermocouple
is exposed to the IR radiation which increases the
temperature of the junction. In order to increase the energy gathering efficiency, it is usually a block
body. The temperature difference between two junctions 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.
c) 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 focused on lead sulphide, its conductance increases and causes more current to
flow. Response time is 0.5 m sec.
Recorder and Amplifier:
Infrared Spectrum
The infrared (4000 650cm-1) is of prime importance for the study of an organic compound. The
pattern of absorption in this region is unique to any particular compound, just as a persons fingerprints are
unique. Since infrared spectra contain a large number of bands, the possibility that two different compounds
will have the same infrared spectrum is exceedingly fewer. For this reason an infrared spectrum has been
called the fingerprint of a molecule.
Functional Group Region: The region from 4000 1500cm-1 to the left in the IR spectrum is useful for the
identification of functional groups. This region shows absorption arising from stretching of all bonds of the
molecule. For example, an alcohol shows the absorption band at 3640 3610cm-1 due to OH stretching
and another band at 1200 1000cm-1 region due to CO stretching. This region is functional group region.
The IR spectra of compounds having same functional groups may be identical in this region.
Fingerprint Region: The region from 1500 650cm-1 is very important for structural elucidation, usually
complex since both stretching and bending modes of the bonds give rise to absorption here. In this region
correlation of an individual band with a specific functional group is often difficult. However each organic
compound has its own unique absorption pattern in this region. This part of the spectrum is therefore called
as fingerprint region. Although the functional group region of the spectrum may appear the same for similar
compounds, the absorption patterns of the fingerprint region are entirely different.
Intensity of the Absorption Bands: The bands in the IR spectrum are classified by intensity: strong,
medium, weak and variable. The potion of all bands is given in cm-1. Certain bonds such as OH
stretching absorb the radiation strongly, while certain bond (ex. CH stretching) absorb weakly. However,
the number of similar groups in the molecule changes the relative strengths of the absorption bands. For
example, octane molecule has many CH bonds, the collective effect of the CH absorption gives a band
which is strong.
Applications of IR Spectroscopy
Infrared spectrum is a highly characteristic property of a substance and so it can be useful for
chemical investigation. The important applications of infrared spectroscopy are given as follows:
I. Identification of Substances: Infrared spectroscopy is used to establish whether a given sample of an
organic compound is identical with another or not. Since infrared spectrum contains large number of
absorption bands, the probability that any two different compounds will produce identical spectra is
almost zero. For this reason an infrared spectrum is called the fingerprint of the molecule. Thus if
two samples give identical spectra under similar conditions of measurement, the samples must be
identical. However, if two substances give different spectra they must be different samples.
It is to be noted that the individual d- or l- optical isomers of an enantiomeric pair always give
identical spectra when taken in solution, but in solid state these may give different spectra.
II. Identification of functional groups: Infrared spectroscopy is used to identify the functional groups
present in the molecule. Identification of some important functional groups are given as follows:
a) Hydroxy compound:
Alcohols: The OH bond of OH group gives characteristic absorption band (due to OH
stretching) in the infrared spectrum. But it is significantly influenced by hydrogen bonding. Thus in
monomeric state, an alcohol gives sharp absorption band at 3640 3610cm-1. In the associated state
involving inter molecular hydrogen bonding, a strong broad band appears at 3400 3200cm-1, while
in intramolecular hydrogen bonding, the absorption band appears at 3570 3450cm-1.
In addition, alcohols also exhibit a strong and broad band in the 1200 1000cm-1 region due to
CO stretching. However, exact location of CO stretching band depends upon the nature of the
alcohol as shown below.
Class of alcohol
Position of CO stretching band
Primary alcohol
1050 cm-1
Secondary alcohol
1100 cm-1
Tertiary alcohol
1150 cm-1
Phenols: As in case of alcohols, phenols exhibit a strong and broad band in the range 3600
3200cm-1 due to OH stretching. However, the CO stretching band appears in a higher region at
1230cm-1 as compared with alcohols.
b) Aldehydes and Ketones: The infrared spectra of aldehydes and ketones are much useful in detecting
the presence of compounds. The carbonyl group /\ C O in these classes of compounds exhibits a
strong stretching band at 1700cm-1 ; the actual position of the band depending upon the nature of
groups attached to the carbonyl group.
Compound
\
/
C O
stretching
Compound
\
/
C O
stretching
band (cm-1)
1740 - 1720
1710 - 1690
1685 - 1675
band (cm-1)
1725 - 1705
1690 - 1680
1670 - 1660
1780
1740
RCHO
The progress of the reaction can be studied by examining the gradual disappearance of absorption of
due to OH stretching at 3600 3650cm-1 and consequent gradual increasing the absorption band at
1680 1760cm-1 due to stretching of carbonyl group. Similarly, IR spectroscopy can be very useful in
determining whether the reaction proceeds or not.
V. Detection of impurities: With the help of IR spectroscopy, it is possible to determine whether a given
sample is pure or not provided the spectrum of pure sample is available. The spectrum of the given
sample is compared with the spectrum of pure sample. If both the spectra are identical, the sample is
pure, otherwise the sample contains impurities.
VI. Identification of Isomers: IR spectra are useful for identifying isomers. This is may not be possible by
the chemical methods. Although functional isomers (they are differ in functional groups) can be easily
differentiated, positional isomers are difficult, because they differ in carbon skeleton which is not
possible from IR spectra.
a) Geometrical Isomers: In general trans isomers are more symmetric than cis and consequently the
dipole moment of cis isomer is higher than that of trans isomer. Hence, trans isomer gives a simple
IR spectrum than cis isomer. If there is no hetero atom substituent bonded to SP2 C atom, cis and
trans isomers give separate C==C absorption bands, because of the wagging vibrations take place at
different positions. However, if SP2 C atom is bonded with an hetero atom, the stretching
vibrations of the ==CX bond is higher by 20 40cm-1 in trans isomers than cis isomers.
b) Conformers: Conformers differ very slightly in their energy content, and in most cases a given
compound occurs as a mixture. Identification of individual conformers requires very sensitive
methods. Since there is difference in absorption of IR radiation by 1cm-1 corresponds to 0.003 k
cal per mole, IR spectra can be useful for distinguishing the conformers, if the spectra are recorded
at a higher resolution.