CHEMISTRY

UNIT 2 MODULE 2
Infrared Spectroscopy
Energies in infra-red radiation correspond to the energies involved in bond vibrations.
In order for a molecule to be IR active, it must be associated with changes in the permanent dipole i.e.
only molecules which have a dipole (partially positive and negative charges) would undergo IR absorption
What causes some frequencies to be absorbed?
Each frequency of light (including infra-red) has a certain energy. If a particular frequency is being absorbed as
it passes through the compound being investigated, it must mean that its energy is being transferred to the
compound.
Energies in infra-red radiation correspond to the energies involved in bond
vibrations.
Bond stretching
In covalent bonds, atoms are not joined by rigid links - the two atoms are held
together because both nuclei are attracted to the same pair of electrons. The two
nuclei can vibrate backwards and forwards - towards and away from each other - around an average position.
The diagram shows the stretching that happens in a carbon-oxygen single bond. There will, of course, be other
atoms attached to both the carbon and the oxygen. For example, it could be the carbon-oxygen bond in methanol,
CH3OH.

The energy involved in this vibration depends on things like the length of the bond and the mass of the atoms at
either end. That means that each different bond will vibrate in a different way, involving different amounts of
energy.
Bonds are vibrating all the time, but if you shine exactly the right amount of energy on a bond, you can kick it
into a higher state of vibration. The amount of energy it needs to do this will vary from bond to bond, and so
each different bond will absorb a different frequency (and hence energy) of infra-red radiation.
Bond bending
CHARACTERISTIC INFRARED ABSORPTION FREQUENCIES
Bond
C-H

Compound Type
Alkanes
CH3 Umbrella Deformation

Frequency range, cm-1

2960-2850(s) stretch
1470-1350(v) scissoring and bending
1380(m-w) - Doublet - isopropyl, t-butyl

C-H

C-H

C-H

Alkenes

3080-3020(m) stretch
1000-675(s) bend

Aromatic Rings

3100-3000(m) stretch

Phenyl Ring Substitution Bands

870-675(s) bend

Phenyl Ring Substitution Overtones

2000-1600(w) - fingerprint region

Alkynes

3333-3267(s) stretch
700-610(b) bend

C=C Alkenes

1680-1640(m,w)) stretch

Alkynes

2260-2100(w,sh) stretch

CC

C=C Aromatic Rings

1600, 1500(w) stretch

C-O

Alcohols, Ethers, Carboxylic acids, Esters

1260-1000(s) stretch

C=O

Aldehydes, Ketones, Carboxylic acids, Esters

1760-1670(s) stretch

Monomeric -- Alcohols, Phenols

3640-3160(s,br) stretch

Hydrogen-bonded -- Alcohols, Phenols

3600-3200(b) stretch

Carboxylic acids

3000-2500(b) stretch

O-H

3500-3300(m) stretch

N-H

Amines

C-N

Amines

1340-1020(m) stretch

CN Nitriles

2260-2220(v) stretch

NO2

Nitro Compounds

1650-1580 (m) bend

1660-1500(s) asymmetrical stretch

1390-1260(s) symmetrical stretch

v - variable, m - medium, s - strong, br - broad, w - weak

The table is used in conjunction with an IR spectrum to determine what functional groups are present in an
organic molecule.
Sample preparation for IR spectroscopy
Gaseous samples require little preparation beyond purification, but a sample cell with a long path length
(typically 5-10 cm) is normally needed, as gases show relatively weak absorbances.

Liquid samples can be sandwiched between two plates of a high purity 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 will not introduce any lines onto the spectra. Some salt plates
are highly soluble in water, so the sample and washing reagents must be anhydrous (without water).
Solid samples can be prepared in four major ways. The first is to crush the sample with a mulling agent (usually
Nujol) in a marble or agate mortar, with a pestle. A thin film of the mull is applied onto salt plates and measured.

The second method is 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 crushed in a mechanical die
press to form a translucent pellet through which the beam of the spectrometer can pass.

The third technique is 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. Care is
important to ensure that the film is not too thick otherwise light cannot pass through. This technique is suitable
for qualitative analysis.

The final method is to use microtomy to cut a thin (20-100 micrometre) 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.

It is important to note that spectra obtained from different sample preparation methods will look slightly
different from each other due to differences in the samples' physical states.
Limitations
Note that to determine the structure of an unknown compound, IR Spectroscopy can only determine the
functional groups present. In order to fully elucidate the structure, other techniques are required such as:- Mass
Spectroscopy and NMR (Nuclear Magnetic Resonance) Spectroscopy.

Practice Questions from past papers.