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 covalent bond will
show some degree of selective IR absorption
• If we plot absorbance or transmittance against frequency the result
is an infrared spectrum.
Introduction

Infrared (IR) spectroscopy: based on IR absorption by molecules as undergo

vibrational and rotational transitions.

rotational transitions
Potential Energy (E)

Vibrational transitions

Interatomic Distance (r)

Potential energy resembles classic Harmonic Oscillator

 IR radiation is in the range of 12,800 – 10 cm-1 or l = 0.78 – 1000 mm
- rotational transitions have small energy differences
• ≤ 100 cm-1, l > 100 mm
- vibrational transitions occur at higher energies
- rotational and vibrational transitions often occur together

Typical IR spectrum for Organic Molecule

% Transmittance

Wavenumber (cm-1)
Typical IR spectrum for Organic Molecule
- many more bands than in UV-vis, fluorescence or phosphorescence
- bands are also much sharper
- pattern is distinct for given molecule
• except for optical isomers
- good qualitative tool
• can be used for compound identification
• group analysis
- also quantitative tool
• intensity of bands related to amount of compound present
- spectra usually shown as percent transmittance (instead of absorbance)
vs. wavenumber (instead of l) for convenience
Hexane

Hexene
Hexyne
 Infrared Spectrum of 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 = hν.
• 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 the 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
Theory of IR Absorption

Molecular Vibrations

i) Harmonic Oscillator Model:

- approximate representation of atomic stretching
- two masses attached by a spring

E = ½ ky2

where:
y is spring displacement
k is spring constant
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 m1m2
n 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)
dt2
d2r2
m2 = -K(r-re) (2)
dt2
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 r
and r 2 = (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
m1m2 d2r (5)
= -K(r-re)
m1+m2 dt2

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

be zero, i.e.,
d2r d2 (r-re) (6)
dt2 = dt2
Substituting the above equation in equation (5) yields
m1m2 d2 (r-re) -K(r-r ) (7)
2
= e
m1+m2 dt
 m1m2
put r-re = x and = μ (8)
m1+m2
On substituting equation (8) in (7), we get
d2x
μ 2 = -Kx
dt
d 2x K x
or + = 0 (9)
dt 2 μ
d 2x
or 2 + ω 2x
= 0 (10)
dt
ω 2 = K/μ or ω = 𝑘
where 𝜇 (11)
Equation (10) is the expression of simple harmonic motion with
frequency of vibration (ν) as follows
𝜔 1 𝑘
𝜈= =
2𝜋 2𝜋 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).
To convert this frequency to wave numbers,
divide the eq. 12 by the velocity of light c:

1 𝑘
ν=ω= cm-1
2𝜋𝑐 𝜇
 Energy levels
Vibrational energies, Eν like all other energies for any particular vibrational
system may be evaluated from Schrondiger’s equation. The energy values
for the energy of a linear harmonic oscillator are of the following type :

Ev = (v + ½ )hcω where ω = ν/c = ω/2πc (1)

In equation (1), v is the vibrational quantum number and can have values of
0,1,2,… etc and ω is the vibrational frequency of the oscillator in terms of
wave numbers.
One can deduce a very important result from equation (1) when the
oscillating molecule is in the lowest vibrational state, i.e., when v = 0, the
energy E0 may be given by
E = ½hcω (2)
0

Where E0 is known as zero-point energy of molecule. Thus, even at absolute

zero, when the translational and rotational motion cease, vibrational motion
still exists. 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.
Suppose we consider a diatomic molecule which undergoes
transition from an upper vibrational level νI to lower vibrational
level νII. The change in vibrational energy will then be given as
ΔEν = EIν - EIIν= (vI + ½ )hcω - (vII + ½ )hcω
or ΔEν = (vI – vII) hcω

The frequency of transition in wave numbers may be written as

(vI – vII) hcω

ΔE = (vI – vII) ω
εν = hc =
ν
hc

So that the frequency of spectral line arising due to transition

between v=1 and v=0 will be given as
1 𝑘
εν =1 0=
ω = cm-1
2𝜋𝑐 𝜇
 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.
Since the vibrational levels are equally spaced, transitions between any two
neighbouring 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.
Change in the vibrational energy of a diatomic
molecule possessing dipole moment is given by
𝐸𝑣′ −𝐸𝑣′′
𝜈=
ℎ
𝜈 𝐸𝑣′ −𝐸𝑣′′
ωB = = ; ωB is the number of radiation emitted
𝑐 ℎ𝑐
Substituting the values of 𝐸𝑣′ − 𝐸𝑣′′ in the above equation,
1 1
ωB = 𝑣′+ ℎ𝑐𝜔 − 𝑣" + ℎ𝑐𝜔
2 2
ℎ𝑐
1 1
= 𝑣′ +
2
𝜔 − 𝑣" +
2
𝜔

But, v’ – v” = 1 or v’ = v” + 1
 ωB = (v” + 1 + ½ ) ω - (v” + ½ ) ω

Or ωB = ω
Or ωB = ω or νB = ν
That is frequency of radiated light is equal to vibrational
frequency of the oscillator.
From the above equation, we can conclude that
vibrational spectrum should consist of single lines
provided there are no accompanying rotational energy
changes.
 6

3
energy
2

V=0
re

Internuclear distance
cm-1

As the selection rule is restricted to Δv = ± 1, each mode of vibration yields

only one band.
 When the harmonic oscillator model is considered, the lower
vibration state can be explained (v’ – v”=1) but for higher
vibrational state the selection rule fails.
 Experimentally it is observed that vibrational energy levels are
less separated as the vibration state (v) increases, whereas
harmonic oscillator results in even spacing.
 Overtones and fundamental band can not be explain by
Harmonic oscillator model. So vibrational diatomic molecule
can be explained 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 is considered.

In this model, the energy difference goes on

Decreasing as quantum no. increasing Δv =±1, ±2, ±3……
(overtone lines) is possible but they are having
extremely low intensity.
 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 values of y,z ….are
diminishing rapidly, and are important only at large values of v.
The selection rule for all the transitions in anharmonic oscillator may be given
as:
Δv = + -1, - 2, -3,……
+ +
Thus we can rewrite the equation as

εν= (v + ½ )ωe – x (v + ½)2 x ωe cm-1

εν= (v + ½ )ωe [1- x(v + ½) cm-1

Compare the zero point energy of harmonic oscillator with that of anharmonic
oscillator.
ε0= ½ ωe [1- ½ x ] cm-1
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
where v is the vibrational quantum number.
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.
Harmonic oscillator

Anharmonic oscillator

Overtones and

fundamental band
 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.
Etotal = Erot + Evib (1)

Diatomic molecule as a harmonic oscillator and a rigid rotator.

The combined energy of such a system is given by

Evr = Etotal = (v + ½ )hcω + h2 (2)

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

2
E’vr - E’’vr = (v’ – v’’)hcω + h [J’(J’+1)- J’’(J’’+1)] (3)
8π2I
And the corresponding frequency of radiation, which arises due to this transition, will
be given by
E’vr - E’’vr
ν =
hc
2
= (v’ – v’’)hcω + h [J’(J’+1)- J’’(J’’+1)]
8π2I
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
(6)
ν = ω + B (J’ – J’’) (J’+J’’+1)

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.
 INSTRUMENTATION

TRANSDUCER

SAMPLE

MC
SOURCE

REFERENCE
Infrared
Spectrum
1) The source of IR radiation:
Requirement - a source of radiant energy
emitting radiation which is -
 Intense enough for detection
 Steady
 Extend over desired wavelengths
a) Incandescent Lamp – In the near IR
instruments it’s useful. However, it fails to in the
far IR because of the glass enclosure, has low
spectral emissivity.
b) Nernst Glower – Hollow rod, 2 mm diameter, 30 mm
length.
- Rare earth metal oxides (Zr, Ce, Th) heated electrically.
- It’s non conducting at Room Temp.
- Generally heated to a temp. of 1000o – 1800o C.
- It emits a radiation at about 7100 cm-1.
Advantages – emits radiations of wide range of wavelength,
with steady intensity over long period of time.
Disadvantage – Frequent mechanical failure, concentration
of energy in the visible and near IR regions.
c) Globar – Rod of sintered SiC, which is about 50 mm
length and 4 mm in diameter.
- On heating in the range of 1300 – 1700 oC, it emits IR
radiation. It emits maximum at 5200 cm-1.
Advantages -
- It is self starting, has positive temperature coefficient
- It works at wavelengths longer than 650 cm-1.
Disadvantages –
Intensity is less compared to Nernst Glower.
d) Mercury arc – if the radiation in the far IR region is
required, (wave no.<200 cm-1), sources described above
are not effective.
- To overcome this Beckman devised quartz-mercury
lamp.
- Heated quartz envelope emits radiations at shorter
wavelengths, whereas, the mercury plasma provides the
longer wavelengths.
2. Monochromators –
To select the desired frequency.
Two types –
Prism monochromator, Grating monochromator
a) Prism monochromator –
 It’s a dispersive material, transmitting the IR
radiation (metal halide slats).
 Glass and quartz absorb IR radiation and
unsatisfactory for IR.
 NaCl is the most common prism salt.
 However, Metal salts are thermally, mechanically
unstable, soluble in water
 Single Pass Monochromator

Double Pass Monochromator

 b) Grating Monochromator:
 Higher dispersion can be achieved.
 Wide range of materials can be used.
 Various combinations of transmission or
interference filters with or without gratings are
used.

 Grating is essentially a series

of parallel straight lines cut in
to a plane surface.
 Dispersion follows the law of
diffraction, nλ=d(sin i ± sin θ)

Advantages of grating monochromator:

• Grating can be made with materials like aluminium, which are not attacked by moisture.
• Grating can be used over considerable wavelength ranges.
Sample cells and Sampling of substances:
• Samples in all the three phases have to be
handled.
• Material containing sample must be
transparent to IR radiation.
Sampling of solids:
i. Solids run in solution
ii. Solid films
iii. Mull technique - IR spectra of solid that are not
soluble in IR transparent solvent or are not
conveniently pelleted in KBr are often obtain by
dispersing the analyte with mulling agent.
 In Mull technique, A drop of the solution of sample in mulling
agent (2-10 mg of finely ground sample is taken with a 1-2 drop of
mulling agent) is placed on a alkali metal disc and the solvent is
allowed to evaporate, leaving a film of the solute, or the entire
solution is placed in a liquid sample cell.
 But can not be used for all the solids because the suitable solvents
are limited and there is no single solvent which is transparent
throughout the IR region.
 The problem is arise that it is not suitable for aliphatic C—C and
C—H vibration.
 Because NUJOL, refined mineral oil absorbs IR radiation in the
region below 1340 cm-1 and giving a peak of HC, Which interferes
in the analysis.
 Other mulling agent is FLOUROLUBE i.e. halogenated polymer,
fluorinated HC mull, perflouro kerosene or hexa flourobutane.
 iv) Pressed Pellet Technique:
Small amount of the finely ground solid sample is
mixed with 100 times its weight of KBr powder.
Advantages over Nujol method –
1. Bands due to mulling agent is avoided.
2. KBr pellets can be stored for long period.
3. Can be used for quantitative analysis.
4. Resolution is superior.
Disadvantages –
1. Always has a band at 3450 cm-1 due to OH group
of moisture.
2. High pressure involved during the preparation of
pellets may bring about polymorphic changes in
crystallinity of the sample.
3. Not suitable for polymers.
 2) LIQUID

• Liquid can be sampled in no. of different way depending

on the sample characteristics such as volatile,
composition and corrosively (towards the cell material)
and the overall absorptive.

• One of the simplest and most popular method i.e. to

sandwich the liquid between two IR window typically
made from NaCl or KBr thus producing a capillary film
this is certainly and rapid procedure.
• A verity of cells are available for liq. Samples.
• The optical path length required for a liquid is usually
less than 1 mm and spacer of different thickness
used with demountable cell to establish a suitable
path length.
• Liquid cells are thus available as variable or fixed.
In liquid, sampling the solvent generally used are -
Acetone, ether, Methane, Cyclohexane, hexane, CS2,
CCl4, CHCl3, toluene, benzene, tetrachloroethyelene
etc.
 When the amount of liquid sample is small or
when a suitable solvent is un available it is
common practice to obtain spectra on the pure
(neat) liq.
 Commonly a drop of the neat liquid is put
between 2 rock salt plates to give a layer that
has thickness of 0.01mm or less than examined
by putting in beam path
 3 GAS
• Gas cell for IR often constructed with a cylindrical
glass body and are usually about 10 cm length
• To the end of the cell are attached disk of
appropriate window material with wax, epoxy
cement or pressure plates.
• For trace analysis (at ppm level) such as in air
pollution studies ad breath analysis very long path
length can be (up to 30m) obtain using multiple
reflection cells with gold surface mirror.
Double beam spectrophotometer
 DETECTORS or TRANSDUCERS
There are 3 types of detector (transducer)

1) THERMAL DETECTOR
2) PYROELECRIC DETECTOR
3) PHOTON (QUANTUM) DETECTOR
 THERMAL DETECTOR

• Thermal detector whose response depend on heating effect.

• Which alters the physical properties of transducers such as
resistance.
• Transducer changes thermal energy in to an electric signal.
The electric signal is amplified and routed to the read out
device.
• But the problem of measuring IR radiation by thermal means
is compounded by thermal noise from the surrounding for
this reason thermal transducers are housing in a vacuum and
are carefully shielded from thermal radiation emitted by other
near by objects.
• Therefore temp. of room is maintained .
 i) 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
junctions

• Junction is usually blackened (to improve its heat absorb

capacity) With black metallic oxides.

• One junction between 2 dissimilar metal is heated with IR

radiation other junction is kept at const. temp.
ii) 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.
 iii) 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.
 PYROELECTRIC DETECTOR

• The most recently developed IR detector is pyroelectric

detector.
• It is constructed from single crystalline wafers of pyroelectric
material which are insulator (dielectric material ) with varying
thermal and electric properties.
• Certain crystal such as TGS (tri glycine sulphate
((NH2,CH2,COOH)3.H2SO4), DTGS (deuterated triglycine
sulfate), Lithium tantalat(LITAO3), Lithium niobate (LINbO3) are
the important Pyroelectric material used in IR detectors.
• This crystal possesses internal electric polarizations. This
internal property is taken in account.
• Crystal is placed between 2 electrodes one of which is IR
transparent.
• When IR radiation fall on crystal its temp. is change, which
alters the charge distribution across the crystal, which can be
detected as the current in the external electric circuit
connecting the 2 side of the capacitor.
• The magnitude of this current is proportional to the surface
area of crystal and the rate of change of polarization with
temp. This is known as pyroelectric effect.
• Pyroelectric crystals lose their residual polarization when they
are heated to a temp. Called the Curie point
Modes of vibration of atoms in polyatomic molecules:
 In a polyatomic molecule each atom is having 3 degrees of
freedom.
 Thus a molecule of n atoms has 3n degrees of freedom.
 For a non linear molecule three degrees of freedom
describe rotation and thee describe translation.
 Remaining 3n – 6 degrees are vibrational degrees of
freedom or fundamental vibrations.
 In linear molecules only two degrees of freedom are
required to describe rotation (three are required to describe
translation.
 Thus 3n – 5 vibrational degrees motion.
According to the nature of vibration, normal vibrations can be
divided in to two main groups.
1. Stretching vibration – Atoms move along the bond axis in which
bond length increases or decreases periodically (at regular
intervals).
2. Bending vibration – Bond angle changes. Example – twisting,
rocking and torsional
Bending vibrations are called deformation vibrations.
There will be 2n – 5 bending vibrations for non cyclic and linear
molecules and these appear at lower frequencies.
Stretching vibrations appear at higher frequencies.
Accordingly, the force constant of stretching vibrations is higher
than that of bending vibrations.
 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
Without change
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
Modes of vibration of water molecule:
Triatomic non linear, 3 x 3 – 6 = 3 modes of vibration.
ν1 = 3652 cm-1; ν2 = 1515 cm-1; ν3 = 3756 cm-1
Modes of vibration of CO2 molecule:
Triatomic linear, 3 x 3 – 5 = 4 modes of vibration.
 Applications of IR Spectroscopy:

Identification of substances
Some characteristic infrared absorption frequencies
BOND COMPOUND TYPE FREQUENCY RANGE, cm-1
C-H alkanes 2850-2960 and 1350-1470
alkenes 3020-3080 (m) and

1000 RCH=CH2 910-920 and 990-

R2C=CH2 880-900
cis-RCH=CHR 675-730 (v)
trans-RCH=CHR 965-975
aromatic rings 3000-3100 (m) and

770 monosubst. 690-710 and 730-

ortho-disubst. 735-770

810 (m) meta-disubst. 690-710 and 750-

para-disubst. 810-840 (m)

alkynes 3300

all abs. strong unless marked: m, moderate; v, variable; b, broad

 Some characteristic infrared absorption frequencies
BOND COMPOUND TYPE FREQUENCY RANGE, cm-1

O-H alcohols or phenols 3200-3640 (b)

C=C alkenes 1640-1680 (v)

aromatic rings 1500 and 1600 (v)

C≡C alkynes 2100-2260 (v)

C-O primary alcohols 1050 (b)

secondary alcohols 1100 (b)
tertiary alcohols 1150 (b)
phenols 1230 (b)
alkyl ethers 1060-1150
aryl ethers 1200-1275(b) and 1020-1075 (m)

all abs. strong unless marked: m, moderate; v, variable; b, broad

 Carbon-Carbon
Bond Stretching
• Stronger bonds absorb at higher frequencies:
– C-C 1200 cm-1
– C=C 1660 cm-1
– CC 2200 cm-1 (weak or absent if internal)
• Conjugation lowers the frequency:
– isolated C=C 1640-1680 cm-1
– conjugated C=C 1620-1640 cm-1
– aromatic C=C approx. 1600 cm-1 =>

Chapter 12 72
 Carbon-Hydrogen Stretching
Bonds with more s character absorb at a higher
frequency.
– sp3 C-H, just below 3000 cm-1 (to the right)
– sp2 C-H, just above 3000 cm-1 (to the left)
– sp C-H, at 3300 cm-1
IR spectra of ALKANES
C—H bond “saturated”
(sp3) 2850-2960 cm-1
+ 1350-1470 cm-1

-CH2- + 1430-1470
-CH3 + “ and 1375
-CH(CH3)2 + “ and 1370, 1385
-C(CH3)3 + “ and 1370(s), 1395 (m)
 n-pentane

2850-2960 cm-1
3000 cm-1
sat’d C-H

1470 &1375 cm-1

CH3CH2CH2CH2CH3
n-hexane

CH3CH2CH2CH2CH2CH3
cyclohexane

no 1375 cm-1
no –CH3
IR of ALKENES
=C—H bond, “unsaturated” vinyl
(sp2) 3020-3080 cm-1
+ 675-1000
RCH=CH2 + 910-920 & 990-1000
R2C=CH2 + 880-900
cis-RCH=CHR + 675-730 (v)
trans-RCH=CHR + 965-975

C=C bond 1640-1680 cm-1 (v)

 1-decene

unsat’d
C-H

3020-
3080
cm-1 910-920 &
990-1000
C=C 1640-1680 RCH=CH2
IR spectra BENZENEs
=C—H bond, “unsaturated” “aryl”
(sp2) 3000-3100 cm-1
+ 690-840
mono-substituted + 690-710, 730-770
ortho-disubstituted + 735-770
meta-disubstituted + 690-710, 750-810(m)
para-disubstituted + 810-840(m)

C=C bond 1500, 1600 cm-1

 ethylbenzene

3000-
3100
cm-1
Unsat’d
1500 & 1600
C-H 690-710,
Benzene ring
730-770
mono-
IR spectra ALCOHOLS & ETHERS

C—O bond 1050-1275 (b) cm-1

1o ROH1050
2o ROH1100
3o ROH1150
ethers 1060-1150

O—H bond 3200-3640 (b)

 O-H and N-H Stretching
• Both of these occur around 3300 cm-1, but
they look different.
– Alcohol O-H, broad with rounded tip.
– Secondary amine (R2NH), broad with one sharp
spike.
– Primary amine (RNH2), broad with two sharp
spikes.
– No signal for a tertiary amine (R3N)
 1-butanol

3200-3640 (b) O-H

C-O 1o

CH3CH2CH2CH2-OH
 methyl n-propyl ether

no O--H

C-O ether
 An Amine
IR Spectrum
 Carbonyl Stretching

• The C=O bond of simple ketones,

aldehydes, and carboxylic acids absorb
around 1710 cm-1.
• Usually, it’s the strongest IR signal.
• Carboxylic acids will have O-H also.
• Aldehydes have two C-H signals around
2700 and 2800 cm-1.
2-butanone

C=O
~1700 (s)
An Aldehyde
IR Spectrum
 O-H Stretch of a
Carboxylic Acid
This O-H absorbs broadly, 2500-3500 cm-1, due
to strong hydrogen bonding.
 Variations in
C=O Absorption
• Conjugation of C=O with C=C lowers the
stretching frequency to ~1680 cm-1.
• The C=O group of an amide absorbs at an even
lower frequency, 1640-1680 cm-1.
• The C=O of an ester absorbs at a higher
frequency, ~1730-1740 cm-1.
• Carbonyl groups in small rings (5 C’s or less)
absorb at an even higher frequency.
 An Amide
IR Spectrum
Carbon - Nitrogen Stretching

• C - N absorbs around 1200 cm-1.

• C = N absorbs around 1660 cm-1 and is much
stronger than the C = C absorption in the
same region.
• C  N absorbs strongly just above 2200 cm-1.
The alkyne C  C signal is much weaker and is
just below 2200 cm-1 .
 A Nitrile
IR Spectrum
Other Applications –
Studying the progress of reaction
Detection of impurities
Identification of Isomers – geometrical, conformers, tautomers
In inorganic chemistry – modes of vibrations, Lower symmetry
complexes (in the case of mixed ligands), Formation of chelates
Miscellaneous applications –
Determination of purity - sharpness of the bands
Shape or symmetry of a molecule – number of bands (modes of
vibrations)
Presence of water molecule –
Measurement of Paints and Varnishes, examination of old paintings
 Strengths and Limitations
• IR alone cannot determine a structure.
• Some signals may be ambiguous.
• The functional group is usually indicated.
• The absence of a signal is definite proof that
the functional group is absent.
• Correspondence with a known sample’s IR
spectrum confirms the identity of the
compound.