CAPE CH U2 M2 6 INFRARED SPECTROSCOPY

Origin of Infrared Spectra

IR transitions relate to vibrational changes and therefore require less energy than the electronic level transitions and
therefore occur at a higher wavelength (range 2.5 x 10-3 cm to 2 x 10-4 cm, usually expressed in terms of wavenumbers, 1/λ ,
range 400cm-1 to 4600cm-1).
Species which will absorb light in the Infrared region of the spectrum
In order for a vibrational mode in a molecule to be IR active, it must be associated with changes in the permanent dipole.
See Wikipedia.org/ infrared spectroscopy for symmetrical and antisymmetrical stretching, scissoring, rocking, wagging and twisting animation.
Figure 7 Types of molecular vibrations

Basic Steps in Analysing Samples Using Infrared Spectroscopy

Plates of a high purity salt (sodium chloride, or common salt, or potassium bromide or calcium fluoride) must be used. The
plates are transparent to the infrared light and will not introduce any lines onto the spectra. The salt plates are highly soluble
in water, so the sample and washing reagents must be anhydrous (without water).

A. Gas samples require a cell with long pathlength.

B. Liquid samples must be anhydrous and can be sandwiched between two plates.
C. Solid samples can be prepared by crushing the sample with a mulling agent (usually Nujol) in a mortar, with
a pestle. A thin film of the mull is applied onto salt plates and measured.
An alternative 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 compressed in a mechanical die press
to form a translucent disc through which the beam of the spectrometer can pass.

Functional Groups and their Absorbances

Group Wavenumber cm-1
– OH ‘free’ 3580 to 3670 broad, strong
– NH2 3350 to 3500 strong
– OH alcohols 3230 to 3550 broad, strong
– OH in acids 2500 to 3300 broad, strong
– C= O 1680 to 1750 sharp, strong
–C=C– 1610 to 1680 medium
– C – O – in alcohols 1000 to 1300 strong
Limitations Associated with the Use of IR Spectroscopy
Used to identify functional groups present; usually used in conjunction with other spectroscopic methods.
Each molecular species has a unique infrared absorption spectrum. An exact match between the spectrum of a known
structure and the spectrum of an unknown analyte unambiguously identifies the analyte.

Examples of the Use of Infrared Spectroscopy

1. Carbon dioxide
2. Sulphur dioxide
Figure 8 Typical IR spectrum

Also the spectra of CO2 and SO2 are worthy of comparison (Figure 9) with 3 peaks visible in the
spectrum of SO2 while only 2 are evident in the CO2 spectrum (the symmetric stretch of the CO2 does
not give rise to a change in dipole and is therefore not IR active).

Figure 9 IR spectra of CO2 and SO2

(a) CO2

(b) SO2