IR Spectroscopy

Kezia Bess
IR RADIATION
Infra-red radiation includes electromagnetic radiation in the wavelength range from 2,500 to
16,000 nm, with a corresponding frequency range from 1.9x1013 to 1.2x1014 Hz.

This portion of the IR region used for analysis of organic compounds in not directly adjacent to
the visible spectrum

The energy of photons in this part of the infra-red is not large enough to excite electrons but
instead, may induce vibrational excitation covalent bonds

These bonds are not rigid but can be thought of as springs that can stretch and bend

Molecules experience a variety of vibrational motions, characteristic of their component atoms.

Consequently, virtually all organic compounds will absorb infrared radiation that corresponds in
energy to these vibrations
WHY DO MOLECULES ABSORB IR RADIATION?
Covalent molecules like methane, the electron clouds bonding the C and H atoms allow the nuclei
to vibrate in two ways, stretching and bending

Covalent bonds have a natural frequency of vibration

A molecule absorbs infrared radiation whose frequency is the same as the natural vibration of the
bond in the molecule. The energy associated with the vibration is quantised

The energy absorbed increases the amplitude of the vibration of the bonds

IR absorption occurs when there is some type of charge separation within the molecule (the
molecule is polar; has a dipole) and the vibration results in a change in the dipole moment of the
molecule. Symmetric molecules such as H2 and Cl2 do not absorb in the IR region but HBr will
IR ANALYSIS
Groups such as C-H, O-H C=O absorb radiation with wavenumbers in the region
1300 cm-1 -3000 cm-1.

Specific peaks indicate the presence of these groups in the molecule. This is
called the band region of the spectrum and compounds of the same homologous
series have near identical spectra.

Peaks in the 600 cm-1- 1300 cm-1 region gives information about the structure of
the whole molecule and this is called the fingerprint region. This region can
distinguish between molecules with the same functional group.
IR SPECTROMETER
CHARACTERISTICS OF AN IR SPECTRUM
The energy absorbed as a result of molecular vibrations depends on the masses of the atoms and
the bond strength

Each type of bond absorbs IR radiation of a specific frequency

Different types of vibration in particular bonds give rise to absorptions in particular regions of the
spectrum ( C-H stretching vibrations are at higher frequencies than the absorption due to C-H
bending vibrations)

The IR spectrum shows the percentage of radiation transmitted. It appears as a series of dips (
inverted peaks) where particular bonds have absorbed radiation

The position of the peaks is given by the wavenumber measured in cm-1

[frequency(Hz) / speed of light (cm/s]

IR APPLICATIONS
Detection of pollutants (FTIR) CO SO2 O3

Forensic analysis

Polymer analysis

Quality assurance and control

Coatings and surfactants

Pharmaceutical and food industry concentration of various compounds in

products
LIMITATIONS OF IR SPECTROSCOPY
It cannot be used to identify non-polar substances

It cannot be used to identify substances that are electrolytes or have ionic

components

It provides information about the type of groups present ( including functional

groups) but not always about the structure of the molecule as a whole
IR VS. RAMAN SPECTROSCOPY
In transitions between vibrational energy levels of molecules, the photons emitted are detected
with two spectroscopic techniques, the Infra-red (IR) and Raman Spectroscopy. The main
difference between the two techniques lies in the nature of the molecular transitions taking
place.

For a transition to be Raman active there must be a change in the polarizability of the molecule
during the vibration. This means that the electron cloud of the molecule must undergo positional
change.

The strong bands in the IR spectrum of a compound corresponds to weak bands in the Raman and
vice versa.
IR VS. RAMAN SPECTROSCOPY
For IR detectable transition, the molecule must undergo dipole moment change during vibration.
When a molecule is symmetrical, e.g. O2, we cannot observe any IR absorption lines, since the
molecule cannot change its dipole moment. In a molecule with a center of symmetry, vibrations
that are Raman active are IR inactive and vice-versa

This complimentary nature is due to the electrical characteristic of the vibration. If a bond is
strongly polarised, a small change in its length such as that occurs during a vibration, will have
only a small additional effect on polarisation.
IR VS. RAMAN SPECTROSCOPY
Vibrations involving polar bonds ( C-O , N-O , O-H ) are comparatively weak Raman scatterers.
Such polarised bonds, carry their charges during the vibrational motion, ( unless neutralised by
symmetry factors), which results in a large net dipole moment change and produce strong IR
absorption band.

Conversely, relatively neutral bonds ( C-C , C-H , C=C ,) suffer large changes in polarizability during
a vibration, though this is less easy to visualise. But the dipole moment is not similarly affected
and vibrations that predominantly involve this type of bond are strong Raman scatterers but weak
in the IR.
Raman
Due to scattering of light by vibrating molecules
Vibration is Raman active if it causes a change in
polarizability
Molecule does not need to possess a permanent dipole
moment
Water can be used as a solvent
Simple sample preparation, sample can be in any state
Gives indication of covalent character
Instrument cost is expensive. Requires high-stability laser
sources and sensitive amplification equipment to detect the
weak signal
Uses a monochromatic beam or laser, in the visible, near-
infrared, or near ultraviolet range of the electromagnetic
spectrum
The Raman spectrum mainly comprises the elastic scattered
light line (Rayleigh) and two equally distanced lines Stokes
and anti-Stokes, with the second being rather weak and
difficult to detect
Infrared
Results from absorption of light by vibrating molecules
Vibration is IR active if it causes a change in dipole moment
Vibration in concern should have a change in dipole moment
due to that vibration
Water cannot be used as a solvent
Elaborate sample preparation. Gaseous samples can rarely be
used
Gives indication of ionic character in molecule
Inexpensive in comparison to Raman
A monochromatic beam is used in the infrared region of the
electromagnetic spectrum. The wavelength here increases or
decreases over time, in order to observe all the absorption
lines within a specific range of the infrared region
The IR technique shows irregular absorbance (or
transmittance) lines, depending on the material investigated.