Infrared Spectroscopy

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 as low 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 3.8x10
14
- 1.2x10
14

Middle 2.5-50 4000 to 200 1.2x10
14
- 6.0x10
12

Far 50-1000 200 to 10 6.0x10
12
- 3.0x10
11

Most used 2.5-15 4000 to 670 1.2x10
14
- 2.0x10
13

FT-IR
Instrument
1. The Source: Infrared energy is emitted from a glowing
black-body 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
Source
Stationary mirror
Moving mirror
Sample
Detector
Beam Splitter
PMT
HeNe laser
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 well-known 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 O
2
, N
2
or Cl
2
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 Asymmetric
In plane rocking In plane scissoring
Out of plane
wagging
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 Frequency range,
cm
-1

Intensity
C-H Alkanes 2850-2970
1340-1470
Strong
Strong
C-H Alkenes (C=C) 3010-3095
675-995
Medium
Strong
C-H Alkynes (CC) 3300 Strong
C-H Aromatic ring 3010-3100
690-900
Medium
Strong
O-H Monomeric alcohols, phenols
Hydrogen-bonded alcohols, phenols
Monomeric carboxylic acids
H-bonded carboxylic acids
3590-3650
3200-3600
3500-3650
2500-2700
Variable
Variable
(sometimes broad)
Medium
Broad
N-H Amines, amides 3300-3500 Medium
C=C Alkenes 1610-1680 Variable
C=C Aromatic rings 1500-1600 Variable
CC Alkynes 2100-2260 Variable
C-N Amines, amides 1180-1360 Strong
CN Nitriles 2210-2280 Strong
C-O Alcohols, ethers, carboxylic acids, esters 1050-1300 Strong
C=O Aldehydes, ketone,-COOH, esters 1690-1760 Strong
NO
2
Nitro compounds 1500-1570
1300-1370
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:

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
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


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

Indicates:
Is an OH band present? an alcohol or phenol
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 -NO
2
bands? a nitro compound

IR Spectroscopy Tutorial: Alkanes

The spectra of simple alkanes are characterized by absorptions due to CH stretching and
bending (the CC 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, beta-unsaturated 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