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IR SPECTROSCOPY
Milind Shamrao Thakare
Pratap College Amalner
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OVERVIEW
• INTRODUCTION
• THEORY
• FACTORS AFFECTING VIBRATIONAL FREQUENCY
• SAMPLING TECHNIQUES
• INSTRUMENTATION
• INTERPRETATION
• APPLICATION
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Introduction
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Spectroscopy
Spectroscopy is the measurement and
interpretation of EMR absorbed or emitted,
when the organic molecule or atoms or ions of a
sample move from one energy state to another.
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Definition
IR spectroscopy can be defined as a method for
the identification of substances based on their
absorption of IR wavelength.
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IR RADIATION

Electromagnetic spectrum

g-rays X-rays UV IR Microwave Radio

Visible
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Wave number Wave length

Near IR 14000-4000cm-1 0.8-2.5µm

Mid IR 4000-400cm-1 2.5-25µm

Far IR 400-10cm-1 25-1000µm

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Theory
• IR radiation in the range 10,000- 100 cm-1 is
absorbed.
• Frequency of absorption depends on relative
masses, the force constant, and geometry of
atoms.
• Converted to energy of molecular vibration.
• The absorption is quantized.

• Vibrational spectra is appear as bands.

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• A molecule absorbs a selected frequencies of IR.

• Absorption corresponding to 8-40 KJ/mol
• Not have sufficient energy to cause the excitation
of electrons, it can cause vibrations.
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Criteria for absorption

• Not all bonds are capable of absorbing IR.

1. Dipole moment-
▫ To absorb IR, a molecule must undergo net change
in dipole moment as it vibrate.
▫ Electric field of radiation can interact with
molecule- change amplitude of vibration.
▫ Eg: Hydrochloride.

1. Correct wavelength
▫ Applied IR frequency =Natural frequency of
vibration
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Calculation of stretching frequency:

• By Hooks law;

▫ v - vibrational frequency
▫ k - force constant
▫ µ= (m1.m2)/(m1+m2)
▫ m1 and m2 –mass of atom 1 and 2 respectively.
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Molecular vibrations
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• The relative positions of atoms in a molecule are

not fixed but fluctuate continuously as a
consequence of vibrations and rotations.

• Two types of fundamental vibrations are there,

▫ Stretching
▫ Bending
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Stretching vibrations
• Involves continuous change in inter atomic
distance along the axis.

• Two types:
▫ Symmetrical stretching-stretching/ compression
in symmetrical way.

▫ Asymmetric stretching-one bond is stretching

while other is compressing.
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symmetrical
H

asymmetrical

H
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Bending vibrations:
• Involves change in bond angle between bonds
with a common atom or the movement of
group of atoms to the reminder of molecule.

• Two types:
▫ In-plane
▫ Out-of plane
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In plane bending vibrations

• Scissoring- atoms H

move towards and C

away from each other.
H

H
• Rocking- The
structural unit swings C

back and forth in the H

plane.
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Out of plane bending vibrations

• Wagging: The
structural unit swings H

back and forth out of C

the plane H

• Twisting: structural
unit rotate about the H

bond which joins to C

the rest of the H

molecule
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Degree of freedom
• Each atom has 3 degrees of freedom
• N-atom molecule there will be 3N degree of freedom.

• Translation - the movement of the entire molecule while

the positions of the atoms relative to each other remain
fixed

• Rotational transitions – inter-atomic distances remain

constant but the entire molecule rotates with respect to
three mutually perpendicular axes.
Translation Rotational
Non linear 3 3
linear 3 2
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Number of vibrational degree of freedom

For molecules having N atoms in them

• Nonlinear molecules= 3N - 6
Eg : H2O (3x3)-6=3

• Linear molecules= 3N -5
Eg : N2 (3x2)-5=1
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Why not 3N-6/3N-5 bands in IR

Spectrum?

• The theoretical number of fundamental

vibrations (absorption frequencies) will seldom
be observed.
• Overtone and combined tone increase the
number of bands.
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Reasons for decrease in number of bands are-

• Bands which are so close that they coalesce.

• Bands which are too weak to be observed.
• Occurrence of a degenerate band.
• Lack of change in molecular dipole moment.
• Fundamental frequencies outside 4000-400 cm-1
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Eg:

• CO2 is linear 3x3-5 =4 degree of freedom.

But
▫ Symmetric stretching- no change in dipole
▫ Bending vibrations are equivalent (degenerate)
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Factors influencing vibrational frequencies

• Calculated value of frequency of absorption for a

particular bond is never exactly equal to its
experimental value.
▫ Electronic effects – inductive and field effect
▫ Ring size
▫ Hydrogen bonding
▫ Vibrational coupling
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• Inductive effect:
Wave no
Electro Stronger bond  cm-1
negative/ Negative Acetone 1715
inductive Increased force
electron constant  chloroacetone 1725
withdrawing
Wave number Dichloroacetone 1740
rises
Tetrachloroacetone 1778

H-CHO 1750
Electro Positive Weaker bond 
positive/ inductive
effect Decrease force CH3-CHO 1745
electron constant 
attracting
Wave number
decreases
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Field effect:
• Lone pair of electrons on two atoms influences
each other through space, can change vibrational
frequency of both groups.
• Eg: O- haloacetophenone
CH3
Electrostatic repulsion due to lone
pair off electrons
:

C = O:
Change the state of hybridization
of C=O
:

X:
Absorption occurs at higher wave
:

number
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Ring size
• Ring strain causes large shift to higher frequency
7 6 5 4 3
membered membered membered membered membered
ring ring ring ring ring
1702 cm-1 1715 cm-1 1745 cm-1 1780 cm-1 1850 cm-1

Increased ‘s’ character

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Hydrogen bonding
• Remarkable downward frequency shift.
• Stronger H bond- greater the shift towards lower
wave number.
▫ Free alcohol - sharp OHstr band
▫ H bonded alcohol - broad OHstr band

• OH of phenol – condensed to polymeric  wide

envelope of O-Hstr
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Vibrational coupling
• Isolated C-H bond – only one str frequency
• For methylene (-CH2-) –two coupled vibrations of
different frequency. ( asymmetric and symmetric)

C=O str
Fundamental+ Amide 1600- 1700cm-1
fundamental N-H def

C-H str
Fundamental + Aldehydes 2800- 2700 cm-1
overtone C-H def
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Sampling techniques
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1) Solid samples:
• Mull technique
• Pressed pellet technique
• Solids run in solutions
• Solid film

2) Liquid samples

3) Gaseous sample
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Mull technique:
• Grinding 2-5mg of sample in smooth agitate
mortar.
• Powdered sample + Nujol  paste
• Paste between the two plates of salt.

• The oil has few absorption bands at 2857, 1449

and 1389 cm-1
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Pressed pellet technique:

1mg Sample+ 100mg KBr

powder

pressed in hydraulic press

transparent disc 
inserted in sample holder.
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Solids films:
• Amorphous solid samples melted between salt
plates allowed to form solid film.
• For qualitative purpose.

Solids run in solution

• Solid + suitable solvent  solution
• Kept in cells for liquids
• Solvents- non associated
solvents- CS2, CCl4,
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Liquid sample:
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Gaseous sample:

• Vapors in specially designed

cells.
• End walls made up of
Sodium chloride.
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Instrumentation
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Dispersive infra red spectrometers

• Instrument produce a beam of IR radiation
• Mirrors divide it into 2 parallel beam of equal
intensity.
• Sample is placed in one beam, other is used for
reference.
• The beam is then passed through mono-
chromator which disperse into a continuous
spectrum.
• The detector senses the ratio b/w intensities of
sample and reference beam.
• Signals is amplified and recorded.
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Dispersive infra red spectrometers

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Radiation sources
• Consist of inert solid
• Heated electrically

▫ Nernst glower
▫ Globar source
▫ Mercury arc
▫ Incandescent wire source
▫ Tungsten filament
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Nernst glower
• Composed of rare earth oxides- zirconium, yttrium
and thorium
• Hollow tube (2-5cm x 1-3mm)
• Platinum leads at one end

• Large negative temp. coefficient.

• Emit radiation over wide range and remains steady
over a long period.

Disadvantages:
• Fragile
• Auxiliary heater
• Over heating
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Globar source
• Rod of sintered silicon carbide. (5cm x 5mm).
• Positive coefficient of resistance.
• Self starting and electrically heated
• Enclosed in water cooled brass tube

• Less intense.
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Mercury arc
• For far IR region
• High pressure Hg arc, enclosed in quartz
jacketed tube, at 1 atm
• Passage of electricity through vapor  internal
plasma source  IR radiation
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Incandescent wire loop

• Tightly wound spiral of Nichrome wire.
• No water cooling
• Less maintenance
• Less intense than other sources.

Tungsten filament lamp

• Tightly wound spiral of tungsten wire.
• For near IR
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Sample holders
• Constructed of rock salt.
• Path length is adjusted with Teflon.
• Filled and emptied with hypodermic needles.
• Foggy due to moisture.
Care:
▫ Moisture free samples
▫ Fingers should not be come in contact
▫ Prevent contamination with silicones
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Monochromator
• To select desired frequency from radiation
source.
▫ Prism monochromator
▫ Grating monochromator

• Material used: Halogen salt

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Detectors
• Thermal detectors
(IR heating potential difference ∞ amt of radiation)

▫ Thermocouple
▫ Bolometer
▫ Golay cell

• Photo detectors
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Thermocouple
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Bolometer
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Golay cell
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FT Optical System Diagram

Light He-Ne gas laser
source

(ceramic)

Beam splitter
Movable mirror

Sample chamber

(DLATGS)
Fixed mirror
Detector
Interferometer
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Michelson interferometer FT-IR

Moving mirror

IR Source

Stationary
mirror
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Constructive and destructive

interferences
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Comparison Dispersion
Spectrometer
• The dispersion
Spectrometer takes several
minutes to measure an IR
spectrum

•Also the detector receives

only a few % of the energy
of original light source.

FT-IR
•FT-IR takes only a few
seconds, to measure an
IR spectrum.

•The detector receives

up to 50% of the energy
of original light source.
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Spectrum
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IR spectrum

• Each dip- band

• 100% transmittance- no absorption.
• Scale of spectrum is not entirely linear.
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Interaction of IR Radiation with

Organic Molecules
• Primary use is to detect functional group.

• All organic functional groups are made up of

multiple bonds and therefore they will show
multiple IR bands.

• Capable of giving sufficient information about

the structure of a compound.
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ALKANES
General structure : R- CH2- R
Wave number

C-H (str) 3000-2840 cm-1

C-H (def) 1470-1450 cm-1

C-H (rock) 1370-1350 cm-1

In long chain alkanes

C-H (rock) 725-720 cm-1

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Eg: Octane
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ALKENES
General structure : R-C=C-R

Wave number

=C-H str 3100-3000 cm-1

=C-H def 1000-650 cm-1

C=C str 1680-1640 cm-1

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Eg: 1-Octene
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ALKYNES
General structure : R- C ≡ C - R

Wave number

- C ≡ C - H str 3333-3267 cm-1

- C ≡ C - H def 700-610 cm-1

-C ≡ C str 2260-2100 cm-1

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Eg: 1-Hexyne
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Aromatic Compounds

General structure : Ar-R

Wave number

C -H str 3100-3000cm-1

C -C str (in ring) 1600-1585cm-1

1500-1400cm-1

C-H bend 900-675cm-1

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Eg: Toluene
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Alkyl Halides
General structure : R-X
Wave number

C-H str 3000-2850 cm-1

C-H def 1300-1150 cm-1

C-X str 850-515 cm-1

eg: C-Cl str 850-550 cm-1

C-Br str 690-515 cm-1

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Eg: 1-Bromopropane
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Alcohols
General structure : R-OH

Wave number

O-H str 3500-3200 cm-1

C-O str 1260-1050 cm-1

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Eg: Ethanol
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KETONES
General structure : R-CO-R

Wave number

C=O str

aliphatic ketones 1715 cm-1

α,β-unsaturated ketones 1685-1666 cm-1

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Eg: 2-Butanone
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Aldehydes
General structure : R-CHO

Wave number

H-C=Ostr 2830-2695 cm-1

C=O str

aliphatic aldehyde 1740-1720 cm-1

α,β-unsaturated aldehydes 1710-1685 cm-1

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Eg: Butaraldehyde
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CARBOXYLIC ACIDS
General structure : R-COOH

Wave number

O-H str 3300-2500 cm-1

C=O str 1760-1690 cm-1

C-O str 1320-1210 cm-1

O-H bend 1440-1395 cm-1

950-910 cm-1
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Eg: Hexanoic acid

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ESTERS
General structure : R-COOR

Wave number

C=O str

aliphatic esters 1750-1735cm-1

α,β-unsaturated 1730-1715cm-1

C-O str 1300-1100cm-1

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Eg: Ethyl acetate

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Amines
General structure : R- NH2
Wave number
N-H str 3400-3250cm-1
1O amines 3400-3300cm-1
3330-3250cm-1

2Oamines 3350-3310cm-1
3O amines no bands

N-H bend (1O only) 1650-1580cm-1

N-H wag 910-665cm-1

C-N str
aromatic amines 1335-1250cm-1

aliphatic amines 1250-1020cm-1

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Eg: Aniline
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NITRO GROUP

General structure: R-NO2

Wave number

N-O str (asymmetric) 1550-1475cm-1

N-O str(symmetric) 1360-1290cm-1

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Eg: Nitromethane
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Recent Advancements
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Attenuated Total Reflectance Spectroscopy

( ATR Spectroscopy)
• Utilizes the phenomenon of Total Internal
Reflection
• Angle of incidents > critical angle
• The beam penetrates a fraction of a wavelength
beyond the reflecting surface.
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• when a material that selectively

absorbs radiation, the beam
loses energy at the wavelength
where the material absorbs.
• The resultant attenuated
radiation is measured.
• plotted as a function of
wavelength and gives rise to the
absorption spectral
characteristics of the sample.
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Applications
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Quantitative analysis
• Based on the determination of the concentration of
one of the functional group of the compound being
estimated.
• Concentration is determined using
Beer- lamberts law
A = I1/I0 = abc

A∞ c ; ‘a’ and ‘b’ are constant.

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Qualitative analysis
• By comparison with reference spectra.

• Group frequency region: (3700-1500cm-1)

▫ Hydrogen bonding region
 By str vibration between hydrogen and other atom (O-H)
▫ Triple bond region
 Triple bond produce a peak in the region 2700-1850 cm-1
▫ Double bond region
 Compound having double bond- peak at 1850- 1500cm-1

• Finger print region: (1500-700cm-1)

▫ Identity of a compound
▫ Due to bending vibrations
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Miscellaneous applications
• Study of progress of reaction.
• Detection of impurities.
• Tautomerism.
• Functional group identification.
• Presence of water in sample.
• Industrial applications.
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Conclusion
Infrared spectroscopy is certainly one of the most
important analytical techniques available to
today’s scientists for the determination of
identity and molecular structure of organic
compounds
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References
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• William Kemp; Organic Spectroscopy; 3rd edition; page

no:20-94.

• Robert M Silverstein; Spectrometric Identification of

Organic Compounds; 6th edition; page no:71-109.

• Skoog, Holler, Crouch; Instrumental Analysis; 5th

edition; page no:477- 528.

• John R Dyer; Application of Absorption Spectroscopy;

page no:23-33.
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• H.Kaur; Instrumental Method of Chemical

Analysis; 6th edition; page no:181-184,192-195.
• P.S Kalsi Spectroscopy of organic compound; 6th
edition, page no 67,74.
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Thank you