Infrared

Spectroscopy

Dr. Mohammad Shariare

Associate Professor
North South University
OVERVIEW
 Principles
 Application and usage
 Strength
 Limitation
 Theory of IR – molecular vibration
 Introduction and types of vibration
 Number of fundamental vibration
 Factors influencing intensity of absorption in IR spectra
 Factors influencing vibrational frequencies
 Instrumentation
 Sample type and sampling technique
 Application of IR in structure elucidation
 Application of IR for identification (Fingerprint region)
 Near Infrared analysis (NIRA)
PRINCIPLES
 Infrared spectroscopy is the measurement of the wavelength and
intensity of the absorption of infrared light by the bonds of the
molecules in the sample. Mid-infrared is energetic enough to
excite molecular vibrations to higher energy levels.
 The wavelength of infrared absorption bands is characteristic of
specific types of chemical bonds and infrared spectroscopy finds
its greatest utility for identification of organic and organometallic
molecules.

Near-infrared: 0.8
Near-infrared -2.5 m, 12500 - 4000 cm-1
Mid-infrared: 
Mid-infrared 2.5 - 50 m, 4000 - 400 cm-1
Far-infrared:
Far-infrared 50 - 1000 m, 200 - 10 cm-1
APPLICATION AND USAGE
• Identification of all types of organic and many types of inorganic compounds by

matching spectrum of unknown compound with reference spectrum

(fingerprinting)

• Determination of functional groups in organic materials

• Quantitative determination of compounds in mixtures

• Determination of molecular conformation (structural isomers) and

stereochemistry (geometrical isomers)

• Determination of molecular orientation (polymers and solutions)

• Identification of molecular orientation in polymer films

• Detection of molecular impurities or additives present

• Identification of polymers, plastics, and resins

 STRENGTH AND LIMITATION
Strength
 Provides a complex fingerprint which is unique to the compound being examined

 Computer control of instruments means that matching of the spectrum of a compound to

its standard fingerprint can now be readily carried out

Limitation
• Minimal elemental information is given for most samples.
• Background solvent or solid matrix must be relatively transparent in the spectral region
of interest.
• Molecule must be active in the IR region. (When exposed to IR radiation, a minimum of
one vibrational motion must alter the net dipole moment of the molecule in order for
absorption to be observed.)
• Rarely used for quantitative analysis due to difficulties in sample preparation
• Usually can only detect gross impurities in samples
• Sample preparation requires a great degree of skill, when KBr disc are being prepared
VIBRATION
 Vibration of a molecule is considered to be unique physical property and characteristics of
the molecule
 Any change in shape of the molecule- stretching of bonds, bending of bonds, or internal
rotation around single bonds causes vibration
 For a molecule to absorb IR, the vibrations or rotations within a molecule must cause a net
change in the dipole moment of the molecule.
 Can a vibration change the dipole moment of a molecule?
 Asymmetrical stretching/bending and internal rotation change the dipole moment of a
molecule.
 Symmetrical stretching/bending does not.
 If the frequency of the radiation matches the vibrational frequency of the molecule then
radiation will be absorbed, causing a change in the amplitude of molecular vibration.
VIBRATION

 Clearly a single vibrational energy change is accompanied by a large number of

rotational energy changes

 For a vibration at 4111 cm-1 (the stretch in H2), how many vibrations occur in a
second?

120 trillion vibration per second!!!!

 MOLECULAR
VIBRATIONS
Infrared radiation is largely thermal energy

It induces stronger molecular

vibrations in covalent bonds,
which can be viewed as springs
holding together two masses, or
atoms.

Specific bonds respond to (absorb) specific frequencies

For a simple diatomic molecule,

this model is easy to visualize:
The IR Spectroscopic Process
• As a covalent bond oscillates – due to the oscillation of the dipole
of the molecule – a varying electromagnetic field is produced

• The greater the dipole moment change through the vibration, the
more intense the EM field that is generated
The IR Spectroscopic Process
 When a wave of infrared light encounters this oscillating EM field
generated by the oscillating dipole of the same frequency, the
two waves couple, and IR light is absorbed

 The coupled wave now vibrates with twice the amplitude

“coupled” wave

EM oscillating wave
from bond vibration
IR-ACTIVE AND
INACTIVE
 A polar bond in an assymetric molecule is usually IR-
active.
 Majority of organic molecule have plenty of assymetry

 A nonpolar bond in a symmetrical molecule (O2 or N2) will

absorb weakly or not at all.

=>
 MOLECULAR
VIBRATIONS
In Infrared spectroscopy the absorbed energy brings about predominant
changes in the vibrational energy which depend upon –
1. Masses of the atom present in the molecule
2. Strength of the bond
3. The arrangement of atoms within the molecule
oIt has been found that no two compounds except the enantiomers can
have similar Infrared spectra.
How does the mass influence the vibration?

H2 I2

MM =2 g/mole
MM =254 g/mole

The greater the mass - the lower the wavenumber

How much movement occurs in the
vibration of a C-C bond?
stretching vibration
154 pm
For a C-C bond with a bond
length of 154 pm, the
variation is about 10 pm.
10 pm

bending vibration
For C-C-C bond angle a
10 pm
change of 4o is typical.
4o
This moves a carbon atom
about 10 pm.
Strong bond will absorb strong IR radiation
TYPES OF VIBRATIONS
There are two types of bond vibration: 1) Fundamental & 2) Non fundamental
1) Fundamental:
• Stretch – Vibration or oscillation along the line of the bond

H H
C C
H H

symmetric asymmetric

• Bend – Vibration or oscillation not along the line of the bond

H H H H
C C C C
H H H
H
scissor rock twist wag
in plane out of plane
TYPES OF VIBRATIONS
Non-Fundamental vibration:
Overtone: Transitions from ground (V=0) to the second
excited state (V=2) with IR radiation absorption give rise
relatively weak bands known as overtone
Combination band: When two vibrational frequencies in
a molecule couple to give rise to a vibration of a new
frequency within the molecule and when such a vibration is
IR active it is called a combination band.
Difference band: The observed frequency, in this case,
results from the difference between two interacting bands.
AN IR SPECTRUM IN TRANSMISSION MODE

The graph above shows a spectrum in transmission mode.

This is the most commonly used representation and the one found in most
chemistry and spectroscopy books. Therefore we will use this representation.
FACTORS INFLUENCING INTENSITY
OF ABSORPTION IN IR SPECTRA
The intensity of an IR band is affected by two primary factors:

Whether the vibration is one of stretching or bending

Electronegativity difference of the atoms involved in the bond

• For both effects, the greater the change in dipole moment in a

given vibration or bend, the larger the peak.

• The greater the difference in electronegativity between the

atoms involved in bonding, the larger the dipole moment

• Typically, stretching will change dipole moment more than

bending
CLASSIFICATION OF IR BANDS
IR bands can be classified as strong (s), medium (m), or weak (w), depending
on their relative intensities in the infrared spectrum. A strong band covers most
of the y-axis. A medium band falls to about half of the y-axis, and a weak band
falls to about one third or less of the y-axis.
INFRARED ACTIVE BONDS
Not all covalent bonds display bands in the IR spectrum. Only polar bonds
do so. These are referred to as IR active.

The intensity of the bands depends on the magnitude of the dipole moment
associated with the bond in question:

 Strongly polar bonds such as carbonyl groups (C=O) produce strong bands.
 Medium polarity bonds and asymmetric bonds produce medium bands.
 Weakly polar bond and symmetric bonds produce weak or non observable
bands.
INFRARED BAND SHAPES
Infrared band shapes come in various forms. Two of the most common are
narrow and broad. Narrow bands are thin and pointed, like a dagger. Broad
bands are wide and smoother.

A typical example of a broad band is that displayed by O-H bonds, such as

those found in alcohols and carboxylic acids, as shown below.
NUMBER OF FUNDAMENTAL
VIBRATION
 Absorption of radiation with energy equal to the difference between two
vibrational energy level will cause a vibrational transition to occur
 Transition from the ground state (V =0) to the first excited state (V=1) absorb
light strongly and give rise to intense bands called the fundamental bands
 Transition from the ground state to the second excited state (V=2) with the
absorption of IR radiation give rise to weak bands, called overtones.
 Polyatomic molecules may exhibit more than one fundamental vibrational
absorption band. The number of these fundamental bands is related to the
degrees of freedom in a molecule
 Each atom has three degrees of freedom corresponding to the three axes
necessary to describe its position relative to the other atom in a molecule.
 When atoms combine to a molecule no degrees of freedom are lost, that is the
total number of degrees of freedom of a molecule will be equal to 3n where n is
the number of atoms in a molecule
NUMBER OF FUNDAMENTAL
VIBRATION
 A molecule with finite dimension will be made up of rotational, vibrational and
translational degrees of freedom
 So 3n degrees of freedom = translational + Rotational + Vibrational
 Since only three coordinates are necessary to locate a molecule in space
therefore a molecule has always three translational degrees of freedom

Linear molecule
Total degrees of freedom, 3n = 3 + 2 + vibrational degrees of freedom
So vibrational degrees of freedom = 3n – 3 – 2 = 3n – 5
Vibrational degrees of freedom for linear CO2 molecule will be 4, hence for
carbon dioxide molecule theoretical number of fundamental band should be four.
Non - Linear molecule
Total degrees of freedom, 3n = 3 + 3 + vibrational degrees of freedom
So vibrational degrees of freedom = 3n – 3 – 3 = 3n – 6
Vibrational degrees of freedom for non-linear C6H6 molecule will be 30, hence for
FACTORS INFLUENCING
VIBRATIONAL FREQUENCIES
 Coupled vibration  Hydrogen bonding

Fermi Resonance
 Electronic effect
• Inductive effect
• Mesomeric effect
• Field effect
Fermi Resonance
When a fundamental vibration couples with an overtone or combination band, the couple
vibration is called Fermi resonance. Fermi resonance is often observed in carbonyl
compounds. Fermi resonance can be explained by saying that a molecule transfers its
energy from fundamental to overtone and back again. This type of resonance gives to a
pair of transitions of equal intensity. An example of Fermi resonance is given by
aldehydes in which C – H stretching absorption usually appears as a doublet (2820cm-1
and 2720cm-1) due to the interaction between C – H stretching (fundamental) and the
overtone of C – H deformation (bending).
INSTRUMENTATION
Two types of instrument are commonly used for obtaining
IR Spectra:
• Dispersive instruments: which use a monochromator
to select each wave number in turn in order to monitor
its intensity after the radiation has passed through the
sample and used in the mid-IR region for spectral
scanning analysis.
• Fourier transform IR (FTIR) systems: which use an
interferometer which generates a radiation source in
which individual wave numbers can be monitored within
1 s pulse of radiation without dispersion being required
and quite popular in the far-IR and mid-IR spectrometry.
 Dispersive IR spectrophotometers
Modern dispersive IR spectrophotometers are invariably double-beam
instruments, but many allow single-beam operation via a front-panel switch.

Simplified diagram of a double beam infrared spectrometer

 Dispersive spectrophotometers Designs

Null type instrument

Fourier Transform Infrared Spectrometer (FTIR)

The Fourier transform method provides an alternatives to

the use of monochromators based on dispersion.

In conversional dispersive spectroscopy, frequencies are

separated and only a small portion is detected at any
particular instant, while the remainder is discarded. The
immediate result is a frequency-domain spectrum.

Fourier transform infrared spectroscopy generates time-

domain spectra as the immediately available data, in which
the intensity is obtained as a function of time.
Single-beam FTIR Spectrometer
 Advantages of FTIR

• very high resolution (< 0.1 cm –1 )

Resolution governed by distance movable mirror travels

• very high sensitivity (nanogram quantity)

can be coupled with GC analysis

• High S/N ratios - high throughput

Few optics, no slits mean high intensity of light

• Rapid (<10 s) analysis

• Reproducible and
• Inexpensive
 Sample and sampling technique
State
Almost any solid, liquid or gas sample can be analyzed. Many sampling
accessories are available.
Amount
Solids 50 to 200 mg is desirable, but 10 μg ground with transparent matrix (such
as KBr) is the minimum for qualitative determinations;
Liquids 0.5 μL is needed if neat, less if pure.
Gases 50 ppb is needed.
Analysis Time
Estimated time to obtain spectrum from a routine sample varies from 1 to 10 min
depending on the type of instrument and the resolution
 Liquid samples
• Pure or soluted in transparent solvent – not water (attacks windows)
•The sample is most often in the form of liquid films (“sandwiched”
between two NaCl plates)
• Adjustable pathlength (0.015 to 1 mm) – by Teflon spacer
 Solid samples
• Spectra of solids are obtained as alkali halide discs (KBr), mulls
(e.g. Nujol, a highly refined mixture of saturated hydrocarbons) and
films (solvent or melt casting)

Alkali halide discs:

1. A milligram or less of the fine ground sample mixed with about
100 mg of dry KBr powder in a mortar or ball mill.
2. The mixture compressed in a die to form transparent disc.
Mulls
1. Grinding a few milligrams of the powdered sample with a mortar
or with pulverizing equipment. A few drops of the mineral oil
added (grinding continued to form a smooth paste).
 Solid samples
ATTENUATED TOTAL REFLECTION (ATR) TECHNIQUE
- Uses high refractive index optical element

- Called internal reflection element (IRE) or ATR crystal (germanium, ZnSe,

silicon, diamond)

DIFFUSE REFLECTANCE TECHNIQUE

- DR OR DRIFTS
- Used to obtain IR or NIR spectrum from a rough surface
- Beam penetrates sample to about 100 µm
- Reflected light is scattered at many angles and scattered radiation
is collected with a large mirror
- Good for powdered samples (sample is dispersed in the KBr
powder)
INFORMATION OBTAINED FROM IR SPECTRA
• IR is most useful in providing information about the presence or
absence of specific functional groups.

• IR can provide a molecular fingerprint that can be used when

comparing samples. If two pure samples display the same IR
spectrum it can be argued that they are the same compound.

• IR does not provide detailed information or proof of molecular

formula or structure. It provides information on molecular fragments,
specifically functional groups.

• Therefore it is very limited in scope, and must be used in conjunction

with other techniques to provide a more complete picture of the
molecular structure.
Finger print region:

The region below 1500cm-1 (600 – 1400cm-1) is IR region is termed

as “Finger print region”. This region is important for comparing the
identity of two compounds and also for the detection of certain
functional groups like ester, ether etc. This area of spectrum is usually
complex since many absorption bands are located here, especially
those due to bending vibrations as well as C – C, C – O, C – N
stretching vibrations. As there are more bending than stretching
vibrations in a molecule the finger print region contain many
absorption bands of varying intensities which makes this region of
particular importance in establishing the identity of a compound by
comparison with on authentic sample.
 IR ABSORPTION RANGE
The typical IR absorption range for covalent bonds is 600 - 4000 cm-1. The graph
shows the regions of the spectrum where the following types of bonds normally
absorb. For example a sharp band around 2200-2400 cm-1 would indicate the
possible presence of a C-N or a C-C triple bond.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
 THE FINGERPRINT REGION

Although the entire IR spectrum can be used as a fingerprint for the purposes of
comparing molecules, the 600 - 1400 cm-1 range is called the fingerprint region.
This is normally a complex area showing many bands, frequently overlapping each
other. This complexity limits its use to that of a fingerprint, and should be ignored by
beginners when analyzing the spectrum. As a student, you should focus your
analysis on the rest of the spectrum, that is the region to the left of 1400 cm-1.

Focus your analysis on this region. This is where most stretching Fingerprint region: complex and difficult to
frequencies appear. interpret reliably.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 IR SPECTRUM OF ALKANES
Alkanes have no functional groups. Their IR spectrum displays only C-C and C-H
bond vibrations. Of these the most useful are the C-H bands, which appear
around 3000 cm-1. Since most organic molecules have such bonds, most organic
molecules will display those bands in their spectrum.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
IR SPECTRUM OF ALKENES
Besides the presence of C-H bonds, alkenes also show sharp, medium bands
corresponding to the C=C bond stretching vibration at about 1600-1700 cm-1.
Some alkenes might also show a band for the =C-H bond stretch, appearing
around 3080 cm-1 as shown below. However, this band could be obscured by the
broader bands appearing around 3000 cm-1 (see next slide)

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003
IR SPECTRUM OF ALKYNES
The most prominent band in alkynes corresponds to the carbon-carbon
triple bond. It shows as a sharp, weak band at about 2100 cm-1. The
reason it’s weak is because the triple bond is not very polar. In some
cases, such as in highly symmetrical alkynes, it may not show at all due to
the low polarity of the triple bond associated with those alkynes.

Terminal alkynes, that is to say those where the triple bond is at the end
of a carbon chain, have C-H bonds involving the sp carbon (the carbon
that forms part of the triple bond). Therefore they may also show a sharp,
weak band at about 3300 cm-1 corresponding to the C-H stretch.

Internal alkynes, that is those where the triple bond is in the middle of a
carbon chain, do not have C-H bonds to the sp carbon and therefore lack
the aforementioned band.

The following slide shows a comparison between an unsymmetrical

terminal alkyne (1-octyne) and a symmetrical internal alkyne (4-octyne).
IR SPECTRUM OF ALKYNES

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
IR SPECTRUM OF A NITRILE
In a manner very similar to alkynes, nitriles show a prominent band around 2250
cm-1 caused by the CN triple bond. This band has a sharp, pointed shape just
like the alkyne C-C triple bond, but because the CN triple bond is more polar, this
band is stronger than in alkynes.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
IR SPECTRUM OF AN ALCOHOL
The most prominent band in alcohols is due to the O-H bond, and it appears as a
strong, broad band covering the range of about 3000 - 3700 cm-1. The size and
broad shape of the band dominate the IR spectrum and make it hard to miss.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 IR SPECTRUM OF ALDEHYDES AND
KETONES
Carbonyl compounds are those that contain the C=O functional group. In
aldehydes, this group is at the end of a carbon chain, whereas in ketones it’s in
the middle of the chain. As a result, the carbon in the C=O bond of aldehydes is
also bonded to another carbon and a hydrogen, whereas the same carbon in a
ketone is bonded to two other carbons.

Aldehydes and ketones show a strong, prominent, stake-shaped band around

1710 - 1720 cm-1 (right in the middle of the spectrum). This band is due to the
highly polar C=O bond. Because of its position, shape, and size, it is hard to
miss.

Because aldehydes also contain a C-H bond to the sp2 carbon of the C=O bond,
they also show a pair of medium strength bands positioned about 2700 and 2800
cm-1. These bands are missing in the spectrum of a ketone because the sp2
carbon of the ketone lacks the C-H bond.

The following slide shows a spectrum of an aldehyde and a ketone. Study the
similarities and the differences so that you can distinguish between the two.
IR SPECTRUM OF ALDEHYDES AND
KETONES

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 IR SPECTRUM OF A CARBOXYLIC ACID
A carboxylic acid functional group combines the features of alcohols and ketones
because it has both the O-H bond and the C=O bond. Therefore carboxylic acids
show a very strong and broad band covering a wide range between 2800 and
3500 cm-1 for the O-H stretch. At the same time they also show the stake-shaped
band in the middle of the spectrum around 1710 cm-1 corresponding to the C=O
stretch.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 IR SPECTRA OF AMINES
The most characteristic band in amines is due to the N-H bond stretch, and it appears as a
weak to medium, somewhat broad band (but not as broad as the O-H band of alcohols). This
band is positioned at the left end of the spectrum, in the range of about 3200 - 3600 cm-1.

Primary amines have two N-H bonds, therefore they typically show two spikes that make this
band resemble a molar tooth. Secondary amines have only one N-H bond, which makes
them show only one spike, resembling a canine tooth. Finally, tertiary amines have no N-H
bonds, and therefore this band is absent from the IR spectrum altogether. The spectrum
below shows a secondary amine.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 IR SPECTRUM OF AMIDES
The amide functional group combines the features of amines and ketones because
it has both the N-H bond and the C=O bond. Therefore amides show a very
strong, somewhat broad band at the left end of the spectrum, in the range between
3100 and 3500 cm-1 for the N-H stretch. At the same time they also show the
stake-shaped band in the middle of the spectrum around 1710 cm-1 for the C=O
stretch. As with amines, primary amides show two spikes, whereas secondary
amides show only one spike.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
References:
J. Workman, A.W. Springsteen, “Applied
Spectroscopy”, Academic Press, 1998.
J.M. Hollas, “Modern Spectroscopy”, John
Wiley&Sons, 1996.
B. Stuart, W.O. George, D.J. Ando, “Modern Infrared
Spectroscopy”, John Wiley&Sons, 1997.
Organic Chemistry, 5th Edition L. G. Wade, Jr.
Elementary Organic Spectroscopy, by Y.R. Sharma