Infrared Spectroscopy

• Infrared radiation stimulates molecular

vibrations.
• In the IR region of the electromagnetic
spectrum, the absorption of radiation by a
sample is (4000-400 cm-1) due to changes in
the vibrational energy states of a molecule.
• Useful in identifying presence or absence of
functional groups
• one of the most powerful tools available to the
chemists for identifying pure organic and inorganic
compounds
• with the exception of a few homonuclear molecules,
such as O2, N2 and Cl2, all molecular species absorb
infrared radiation.
• with the exception of chiral molecules in the
crystalline state, each molecular species has a unique
infrared absorption spectrum.
• an exact match between the spectrum of a
compound of known structure and that of an analyte
unambiguously identifies the latter
• Infrared spectroscopy is a less satisfactory tool
for quantitative analysis than its ultraviolet
and visible counterparts because the narrow
peaks that characterize infrared absorption
usually leads to deviations of the Beer’s law.
• Where modest precision suffices, the unique
nature of infrared spectrum provide a degree
of selectivity in a quantitative measurement
that may offset these undesirable
characteristics.
 The infrared spectrum
Designation Abbreviated Wavelength Wave number
12821-3333
Near Infrared NIR 780–3000 nm
cm-1
Mid Infrared MIR 3000–50000 nm 3333-200 cm-1
 INFRARED SPECTROSCOPY
• Methane H H H H H H

C C C

H H H H H H

Asymmetrical Symmetrical Bending or scissoring

stretching stretching

H H H H H H

C C C

H H H H H H

Rocking or in Twisting or out- Wagging or

plane bending of-plane out-of-plane
bending bending
Stretching
Bending
Bending
• Only vibrations that cause a change in ‘polarity’ give
rise to bands in IR spectra
• Any change in shape of the molecule- stretching of
bonds, bending of bonds, or internal rotation around
single bonds

What vibrations change the dipole moment of a

molecule?
• Asymmetrical stretching/bending and internal rotation
change the dipole moment of a molecule. Asymmetrical
stretching/bending are IR active.

• Symmetrical stretching/bending does not. Not IR active

• The number of ways a molecule can vibrate is
related to the number of atoms, and thus the
number of bonds, it contains. For even a
simple molecule, the number of possible
vibrations is large. For example, n-butanal
(CH3CH2CH2CHO) has 33 vibrational modes,
most differing from each other in energy.
N-butanal
• The IR spectra contrast strongly with the usual UV
and visible spectra. The difference arises in the
nature of the interaction between the absorbing
molecules and their environment. This interaction (in
condensed phases) has a great effect on electronic
transitions occurring within a chromophore,
broadening the absorption lines so that they tend to
coalesce into wide regions of absorption. In the IR,
on the other hand, the frequency and absorptivity
due to a particular bond usually show only minor
alterations with changes in its environment (which
includes the rest of the molecule). The lines are not
likely to be broadened so as to coalesce.
 Absorption peaks
Wavenumber, Wavelength,
cm-1 µm
O─H Aliphatic and aromatic 3600-3000 2.8-3.3
NH2 Also secondary and 3600-3100 2.8-3.2
tertiary
C─H Aromatic 3150-3000 3.2-3.3
C─H Aliphatic 3000-2850 3.3-3.5
C≡N Nitrile 2400-2200 4.2-4.6
C≡C─ Alkyne 2260-2100 4.4-4.8
COOR Ester 1750-1700 5.7-5.9
C=O Aldehydes and ketones 1740-1660 5.7-6.0
CONH2 Amides 1720-1640 5.8-6.1
C=C─ Alkene 1670-1610 6.0-6.2
Ф─O─ Aromatic 1300-1180 7.7-8.5
R
 Qualitative analysis
• Identification of the functional groups in a
molecule is seldom sufficient to permit
positive identification of the compound, and
the entire spectrum from 2.5 to 15 µm must
be compared with that of known compounds.
Collections of spectra are available for this
purpose and computer are of great help in
that regard.
Instruments Designs for
Infrared Absorption
• The simplest instrument for IR absorption
spectroscopy is a filter photometer similar to
that for UV/Vis absorption.
• These instruments have the advantage of
portability and typically are used as
dedicated analyzers for gases such as HCN
and CO.
Double beam dispersive instruments
• are preferred over single-beam optics because
the sources and detectors for infrared
radiation are less stable than that for UV/Vis
radiation.
• it is easier to correct for the absorption of
infrared radiation by atmospheric CO2 and H2O
vapor when using double-beam optics.
 Infrared Instruments
• An infrared spectrophotometer is an instrument that passes
infrared light through an organic molecule and produces a
spectrum that contains a plot of the amount of light
transmitted on the vertical axis against the wavelength of
infrared radiation on the horizontal axis. In infrared spectra
the absorption peaks point downward because the vertical
axis is the percentage transmittance of the radiation through
the sample.
• Absorption of radiation lowers the percentage transmittance
value. Since all bonds in an organic molecule interact with
infrared radiation, IR spectra provide a considerable amount
of structural data.
Infrared Instruments
 Optical Materials.
• Lenses are almost never used in IR
spectrophotometers, but are replaced by front-
surface concave mirrors. Mirrors have many
advantages, for which the often used in the UV and
visible, as well as the IR. They have not chromatic
aberration, which means that they focus all
wavelengths in the same point; they can be made
of sturdy materials such as metal or aluminized
glass, without regard to optical transmission, and
they are easier to mount.
Fourier Transform Infrared Spectrocopy

•Simpler mechanically
•Better rate signal-noise
•Faster
•The calibration of the wavelength is
internally made by a laser.
Fourier transform infrared spectrometers can be
obtained for as little as $15,000–$20,000, although
more expensive models are available.

What is FT spectrocopy?
 Preparing and containing samples
• Only few materials are transparent to IR
radiation and can be used to contain the
sample. Most common are halogen salts:
NaCl, KBr, etc.
 Gases
• Gaseous samples require a sample cell with a long
pathlength to compensate for the diluteness. The
pathlength of the sample cell depends on the concentration
of the compound of interest. A simple glass tube with
length of 5 to 10 cm equipped with infrared transparent
windows at both ends of the tube can be used for
concentrations down to several hundred ppm. Sample gas
concentrations well below ppm can be measured with a
multipass spectroscopic absorption cells in which the
infrared light is guided with mirrors to travel through the
gas.
Multipass absorption cells

White’s cell
Multipass absorption cells

Pfund’s cell

Herriot’s Cell
 Liquids
• Liquid samples can be sandwiched between
two plates of a salt (commonly sodium
chloride, or common salt, although a number
of other salts such as potassium bromide or
calcium fluoride are also used). The plates are
transparent to the infrared light and do not
introduce any lines onto the spectra.
 Solids
• to crush the sample with an oily mulling agent (usually Nujol) in a marble
or agate mortar, with a pestle. A thin film of the mull is smeared onto salt
plates and measured
• to grind a quantity of the sample with a specially purified salt (usually
potassium bromide) finely (to remove scattering effects from large
crystals). This powder mixture is then pressed in a mechanical press to
form a translucent pellet through which the beam of the spectrometer can
pass.
• the "cast film" technique, which is used mainly for polymeric materials.
The sample is first dissolved in a suitable, non hygroscopic solvent. A drop
of this solution is deposited on surface of KBr or NaCl cell. The solution is
then evaporated to dryness and the film formed on the cell is analysed
directly.
• The final method is to use microtomy to cut a thin (20–100 µm) film from
a solid sample. This is one of the most important ways of analysing failed
plastic products for example because the integrity of the solid is
preserved.
• The molecule absorbs a specific quantum of energy to move
from a vibrational energy to the next, the energy provided
to do this is infrared radiation in the electromagnetic
spectrum. Infrared spectroscopy exploits the fact molecules
can bend and stretch.
• Basically, as molecules absorb infrared radiation, the
covalent bonds bend and stretch the molecule and they
gain more vibrational energy. As they move to higher
vibrational energy levels, the frequency of the vibration
increases.
• All molecules absorb infared radiation (disregarding O2, N2
and other homonuclear molecules). Thus infrared
spectroscopy is a useful technique. However for a molecule
to absorb infrared, the bending and stretching vibrations
must change the overall dipole moment of the molecule.
• The strength of the bonds affects the type of energy absorbed by
the molecules. For example a C-C bond absorbs lower infrared
energy than a C≡C bond. The C≡C bond has more bond energy as
it is a stronger bond, and so absorbs higher infrared radiation
energies.
• The mass of the atoms attached to each bond also affects the type
of radiation energy absorbed. The lower the mass of the atoms in
the bond, the higher the absorption. For example a C-H bond will
absorb higher frequencies of infared than a C-O bond.
• Each bond in the molecule is the part that is vibrating, so bond
types affect this.
• Infrared is thus a powerful tool in determining the bonds in the
molecules, using this information. The chemical structures can
also be found which is useful (i.e. Drug design.)
 Qualitative analysis
• Infrared is the best at giving us the functional groups
(determine properties of the molecule) of a molecule,
and it’s structure. The substance can thus be
identified.
• The energy of radiation absorbed and released
depends on:
– The strengths and characteristics of the bonds. As stated it
takes different amounts of energy, and so different
wavelengths to stretch bonds, for example a C-H bond
compared to a C-O bond. A graph of ethanol is shown
below.
• The environment and other bonds in the molecule as
the wavelength absorbed depends on the entire
molecular structure. As an example propanoic acid
and methyl ethanoate have the same molecular
formula but different structures. Both compounds
have an absorption band at 1700cm- due to both
having a C=O bond.

• However, methyl ethanoate has a C-H bond so has a

band at 3000cm-, proponic acid has an O-H bonds and
thus a band at 2700 to 3600cm-. The band for the C=O
bond is different in width however as each compound
may have absorbed this wavenumber differently due
to different types of C=O bonds, varying vibrations.
• Not only is the normal bond absorption bands showing, but so
too are the possible bond distortions. No two molecular
compounds are identical in bonds or bonding environment, so
infrared spectroscopy can give us a fingerprint of each compound.
Each bond has its own specifically different wavenumber. Going
downwards the graph shows absorbance.
• Narrow peaks in the IR spectrum represent the peak corresponds
to one particular type of vibration of a bond (one very specific
wavenumber) as every bond/functional group will have varying
levels of vibrational energy as they have varying levels of
absorbance.
• Very broad bands indicate overlapping energies due to vibrational
changes (refer to table below for overlapping energy examples.)
Peaks are described as strong, medium or weak. Strong peaks are
when a high proportion of the molecules absorb a given
wavenumber.
• Infrared spectrum above 1000cm- is used to identify
functional groups. Wavelengths less than 1000cm- is
characteristic of a particular compound. This region is
made up mostly of bending and stretching of the entire
molecule so is unique to individual compounds, thus
called the fingerprint region. So if an unknown substance
has the same spectrum below 1000cm- to a known
substance they are most likely the same. Those above
1000cm- are identified as they will have specific wave
numbers to other known functional groups.
• There is overlapping, so for certain identification of
functional groups the entire molecule’s spectrum is
compared to a computerised sprectrum library.