Infrared Spectroscopy-IR

Common Applications
Identification of compounds by matching spectrum of
unknown compound with reference spectrum
(fingerprinting)
Identification of functional groups in unknown substances
Identification of reaction components and kinetic studies
of reactions
Identification of molecular orientation in polymer films
Detection of molecular impurities or additives present in
amounts of 1% and in some cases aslow as 0.01%
Identification of polymers, plastics, and resins
Analysis of formulations such as insecticides and
copolymers

Complementary or Related Techniques

Nuclear magnetic resonance provides
additional information on detailed molecular
structure
Mass spectrometry provides molecular mass
information and additional structural
information
Raman spectroscopy provides complementary
information on molecular vibration. (Some
vibrational modes of motion are IR-inactive
but Raman-active and vice versa.)- NOT
INCLUDED IN THIS COURSE

Introduction
Infrared (IR) spectroscopy is one of the
most common spectroscopic techniques
used by organic and inorganic chemists
it is the absorption measurement of
different IR frequencies by a sample
positioned in the path of an IR beam.
The main goal of IR analysis is to
determine the chemical functional groups
in the sample.
Different functional groups absorb
characteristic frequencies of IR radiation.

IR Frequency Range
Region

range (m)

Wave number range,

cm-1

Frequency Range

Near

0.78-2.5

12, 000 to 4000

3.8x1014- 1.2x1014

Middle

2.5-50

4000 to 200

1.2x1014- 6.0x1012

Far

50-1000

200 to 10

6.0x1012- 3.0x1011

Most used

2.5-15

4000 to 670

1.2x1014- 2.0x1013

FT-IR Instrument
1. The Source: Infrared energy is emitted from a glowing blackbody source. This beam passes through an aperture which
controls the amount of energy presented to the sample
(and, ultimately, to the detector).
2. The Interferometer: The beam enters the interferometer
where the spectral encoding takes place. The resulting
interferogram signal then exits the interferometer.
3. The Sample: The beam enters the sample compartment
where it is transmitted through or reflected off of the
surface of the sample, depending on the type of analysis
being accomplished. This is where specific frequencies of
energy, which are uniquely characteristic of the sample, are
absorbed.
4. The Detector: The beam finally passes to the detector for
final measurement. The detectors used are specially
designed to measure the special interferogram signal.
5. The Computer: The measured signal is digitized and sent to
the computer where the Fourier transformation takes
place. The final infrared spectrum is then presented to the
user for interpretation and any further manipulation.

FT-IR Instrument- Schematic

Michaelson Interferometer

Stationary mirror

HeNe laser

Beam Splitter

Source
Moving mirror
PMT
Sample

Detector

Michaelson Interferometer

Interferometers employ a beamsplitter which takes the incoming infrared beam and divides it
into two optical beams.

One beam reflects off of a flat mirror which is fixed in place. The other beam reflects off of a flat
mirror which is on a mechanism which allows this mirror to move a very short distance
(typically a few millimeters) away from the beamsplitter.

The two beams reflect off of their respective mirrors and are recombined when they meet back
at the beamsplitter.

Because the path that one beam travels is a fixed length and the other is constantly changing as
its mirror moves, the signal which exits the interferometer is the result of these two beams
interfering with each other.

The resulting signal is called an interferogram which has the unique property that every data
point (a function of the moving mirror position) which makes up the signal has information
about every infrared frequency which comes from the source.

This means that as the interferogram is measured, all frequencies are being measured
simultaneously.

Thus, the use of the interferometer results in extremely fast measurements.

Because the analyst requires a frequency spectrum (a plot of the intensity at each individual
frequency) in order to make an identification, the measured interferogram signal can not be
interpreted directly.

A means of decoding the individual frequencies is required. This can be accomplished via a wellknown mathematical technique called the Fourier transformation. This transformation is
performed by the computer which then presents the user with the desired spectral information
for analysis.

IR Spectrum

IR absorption information is generally presented in the form of a spectrum

with wavelength or wavenumber as the x-axis and absorption intensity or
percent transmittance as the y-axis

Theory of Infrared
Dipole changes During Vibrations and Rotations
IR absorption - a molecule must undergo a net change in dipole moment
due to vibrational or rotational motion.
Homonuclear species such as O2, N2 or Cl2 no net change in dipole
moment occurs during vibration or rotation.
Eg. The charge distribution around a molecule of HCl is not symetric
because the Cl has a higher electron density than the hydrogen.
HCl has a significant dipole moment and known as polar molecule
Dipole moment: determined by the magnitude of the charge difference
and the distance between the two centre of centre of charge.
as a HCl vibrates, a regular fluctuation in dipole moment occurs, an a
field is established that can interact with the electrical field associated
with radiation. If the frequency of the radiation exactly matches a natural
vibrational frequency of the molecule, a net transfer of energy takes
place that results in a change in the amplitude of the molecular vibration,
absorption of the radiation is the consequence. Similarly, the rotation of
asymmetric molecules around their centres of mass result in a periodic
dipole fluctuation that can interact with radiation.

Theory of Infrared
Rotational Transitions
The energy required to cause a change in rotational is minute (small)
and corresponds to radiation of 100 cm-1 or less (>100m)
Rotational levels are quantized;
i) Absorption by gases in the far IR region is characterized by
discrete, well-defined line
ii) Absorption by liquids or solids intramolecular collisions and
interactions cause broadening of the lines in to a continuum.
Vibrational/Rotational Transitions
Vibrational energy levels are also quantized for most molecules the
energy differences between quantum states correspond to the mid-IR
region.
The IR spectrum of a gas usually consists of closely spaced lines,
because there are several rotational energy state for each vibrational
state.
On the other hand, rotation is highly restricted in liquids and solids, in
such sample, discrete vibrational/rotational lines disappear, leaving only
somewhat broadening vibrational peaks.

Types of molecular vibration

i)

Stretching: involves a continues change

in the inter atomic distance along the
axis of the bond between two atoms. 2
types: Symetric stretching and asymetric
stretching

ii)

Bending: characterized by a change in

the angle between two bonds. 4 types of
bending vibrations: scissoring(bending),
rocking, wagging and twisting.

Stretching and Bending

Symmetric

In plane rocking

Out of plane wagging

Asymmetric

In plane scissoring

Out of plane twisting

The IR spectrum ( Dudley Williams pg 30)

A complex molecule-many vibrate modes involve in the

whole molecule

However, these molecular vib. are largely associated with the

vib. of individual bonds and called localized vibrations.

These localized vibrations are useful for the identification of

functional groups, such as the stretching vibs of:
Single bond (O-H & N-H) and all kinds of triple and double
bonds, all of which occur with frequency greater than
1500cm-1

The stretching vib. of other single bonds, most bending

vibrations and the soggier vibration of the molecule as a
whole give rise to a series of absorption bands at lower
energy, below 1500cm-1, the position of which are
characteristic of that molecule (Fingerprint region).

Full spectrum of cortisone acetate , pg 31

Full spectrum of cortisone acetate , pg 31

Strong absorption from the stretching

vibrations above 1500cm-1, showing that
the presence of each of the functional
groups:
O-H group
3 diff C=O groups
The weaker absorption of the C=C
double bond
finger print region below 1500cm-1

Identification of IR spectrum (organic comp)

Two step processes:

Determine what functional groups are present-examining the

group frequency region (3600 1200cm-1)

Detailed comparison of the spectrum of the unknown with

the spectra of pure compounds that contain all of the
functional groups found in the first step. The fingerprint
region (1200-600cm-1) is useful due to small differences in
the structure and constitution of a molecule result in
significant changes in the appearance and distribution of
absorption peaks in this region. Consequently, a close match
between two spectra in the fingerprint region (as well as
others) constitutes almost certain evidence for the identity
of the compound yielding the spectra.

Table of group frequency for organic group

Bond

Type of compound

C-H

Alkanes

C-H

Alkenes (C=C)

C-H
C-H

Alkynes (CC)
Aromatic ring

O-H

Monomeric alcohols, phenols

Hydrogen-bonded alcohols, phenols
Monomeric carboxylic acids
H-bonded carboxylic acids

Frequency range,
cm-1
2850-2970
1340-1470
3010-3095
675-995
3300
3010-3100
690-900
3590-3650
3200-3600
3500-3650
2500-2700

Intensity

N-H
C=C
C=C
CC
C-N
CN
C-O

Amines, amides
Alkenes
Aromatic rings
Alkynes
Amines, amides
Nitriles
Alcohols, ethers, carboxylic acids, esters

3300-3500
1610-1680
1500-1600
2100-2260
1180-1360
2210-2280
1050-1300

Strong
Strong
Medium
Strong
Strong
Medium
Strong
Variable
Variable
(sometimes broad)
Medium
Broad
Medium
Variable
Variable
Variable
Strong
Strong
Strong

C=O
NO2

Aldehydes, ketone,-COOH, esters

Nitro compounds

1690-1760
1500-1570
1300-1370

Strong
Strong
Strong

IR Spectroscopy Tutorial: How to analyze IR spectra

The distinctive bands of the common functional bands:

3500-3300 cm-1

NH stretch

amines

3500-3200 cm-1

OH stretch

alcohols, a broad, strong

band

3100-3000 cm-1

CH stretch

alkenes

3000-2850 cm-1

CH stretch

alkanes

1760-1665 cm-1

C=O stretch

ketones, aldehydes,
esters

1680-1640 cm-1

C=C stretch

alkenes

i) Begin by looking in the region from 4000-1300. Look at the CH

stretching bands around 3000:

Indicates:
Are any or all to the right of 3000?

alkyl groups (present in most organic

molecules)

Are any or all to the left of 3000?

a C=C bond or aromatic group in the

molecule

ii) Look for a carbonyl in the region 1760-1690. If there is such a band:
Indicates:
Is an OH band also present?

a carboxylic acid group

Is a CO band also present?

an ester

Is an aldehydic CH band also present?

an aldehyde

Is an NH band also present?

an amide

Are none of the above present?

a ketone

Look for a broad OH band in the region 3500-3200 cm-1. If there is such a band:
Indicates:

an alcohol or phenol

Is an OH band present?

Look for a single or double sharp NH band in the region 3400-3250 cm-1. If
there is such a band:
Indicates:
Are there two bands?

a primary amine

Is there only one band?

a secondary amine

Other structural features to check for:

Indicates:

Are there CO stretches?

an ether (or an ester if there is a

carbonyl band too)

Is there a C=C stretching band?

an alkene

Are there aromatic stretching bands?

an aromatic

Is there a CC band?

an alkyne

Are there -NO2 bands?

a nitro compound

IR Spectroscopy Tutorial: Alkanes

The spectra of simple alkanes are characterized by absorptions due to CH stretching and bending (the C
C stretching and bending bands are either too weak or of too low a frequency to be detected in IR
spectroscopy). In simple alkanes, which have very few bands, each band in the spectrum can be assigned.
CH stretch from 30002850 cm-1
CH bend or scissoring from 1470-1450 cm-1
CH rock, methyl from 1370-1350 cm-1
CH rock, methyl, seen only in long chain alkanes, from 725-720 cm-1

IR Spectroscopy Tutorial: Alkenes

Alkenes are compounds that have a carbon-carbon double bond, C=C.The stretching vibration of the
C=C bond usually gives rise to a moderate band in the region 1680-1640 cm-1.
Stretching vibrations of the C=CH bond are of higher frequency (higher wavenumber) than those of
the CCH bond in alkanes.

C=C stretch from 1680-1640 cm-1

=CH stretch from 3100-3000 cm-1

=CH bend from 1000-650 cm-1

IR Spectroscopy Tutorial: Aromatics

The =CH stretch in aromatics is observed at 3100-3000 cm-1. Note that this is at slightly higher frequency than is the CH
stretch in alkanes.
Aromatic hydrocarbons show absorptions in the regions 1600-1585 cm-1 and 1500-1400 cm-1 due to carbon-carbon stretching
vibrations in the aromatic ring.

CH stretch from 3100-3000 cm-1

overtones, weak, from 2000-1665 cm-1

CC stretch (in-ring) from 1600-1585 cm-1

CC stretch (in-ring) from 1500-1400 cm-1

IR Spectroscopy Tutorial: Alcohols

Alcohols have characteristic IR absorptions associated with both the O-H and the C-O stretching vibrations.

OH stretch, hydrogen bonded 3500-3200 cm-1

CO stretch 1260-1050 cm-1 (s)

IR Spectroscopy Tutorial: Ketones

The carbonyl stretching vibration band C=O of saturated aliphatic ketones appears at 1715 cm-1.
Conjugation of the carbonyl group with carbon-carbon double bonds or phenyl groups, as in alpha, betaunsaturated aldehydes and benzaldehyde, shifts this band to lower wave numbers, 1685-1666 cm-1

C=O stretch:
aliphatic ketones 1715 cm-1
, -unsaturated ketones 1685-1666 cm-1

IR Spectroscopy Tutorial: Aldehydes

The carbonyl stretch C=O of saturated aliphatic aldehydes appears from 1740-1720 cm-1. As in ketones, if the carbons
adjacent to the aldehyde group are unsaturated, this vibration is shifted to lower wavenumbers, 1710-1685 cm-1

HC=O stretch 2830-2695 cm-1

C=O stretch:

aliphatic aldehydes 1740-1720 cm-1

alpha, beta-unsaturated aldehydes 1710-1685 cm-1