Infrared Spectrometry

Principle Instrument Qualitative Analysis Quantitative Analysis

Infrared Light

Energy of IR photon insufficient to cause electronic excitation but can cause vibrational or rotational excitation

Selection Rule of Infrared Spectrum

Molecule must have change in dipole

moment due to vibration or rotation to absorb IR radiation. Homonuclear diatomic molecules will have no IR spectrum. Molecule dipole moment interacts with IR photon electric field. Absorption causes increase in vibration amplitude/rotation frequency.

Molecules with permanent dipole moments () are IR active

Types of Molecular Vibrations

Stretchchange in bond length

symmetric stretching

asymmetric stretching

Types of Molecular Vibrations

Bendchange in bond angle

scissoring
wagging

rocking
twisting/torsion

Vibrational Modes: To determine the vibration of polymolecule we need to consider: -motion of the entire molecule in space -rotational motion of the molecule around its centre of gravity -Motion of each atom (individual vibrations). Molecule containing N atoms have 3N degree of freedom

Normal Modes of Vibration

Linear molecule of N atoms: normal

modes = 3N - 5 Nonlinear molecule of N atoms: normal modes = 3N - 6

Only some modes may be IR active

The three fundamental vibrations for sulfur dioxide

How many vibrational modes?

2 atoms (H2) - 1 vibration

3 atoms (H2O) - 3 vibrations

3 atoms (CO2) - 4 vibrations 4 atoms (H2CO) - 6 vibrations

Vibrational coupling :
In addition to the vibrations mentioned above, interaction

between vibrations can occur (coupling) if the vibrating bonds are joined to a single, central atom. Vibrational coupling is influenced by a number of factors; Strong coupling of stretching vibrations occurs when there is a common atom between the two vibrating bonds Coupling of bending vibrations occurs when there is a common bond between vibrating groups Coupling between a stretching vibration and a bending vibration occurs if the stretching bond is one side of an angle varied by bending vibration Coupling is greatest when the coupled groups have approximately equal energies No coupling is seen between groups separated by two or more bonds

Instrumentation: Sources

Instrumentation: Transducers

Fourier Transform Instruments

Michelson interferometer

Fourier Transform

Time Frequency
FT

FTIR advantages
High S/N ratios

Rapid (<10 s)
Reproducible

High resolution (<0.1 cm-1)

Inexpensive

Qualitative and Quantitative Analysis

Gases-fill gas cell

(a) transparent windows (NaCl/KBr) (b) long pathlength (10 cm) - few molecules Liquids-fill liquid cell (a) solute in transparent solvent - not water (b) short pathlength (0.015-1 mm) Solids-make semi-transparent pellet with KBr

Qualitative Analysis
Step One: Identify

functional groups Step Two: Compare with standard spectra

Quantitative Analysis
IR more difficult than UV-VIS complex spectra weak incident beam low sensitivity solvent absorption IR mostly used for rapid qualitative but not quantitative analysis