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Infrared Spectroscopy Notes

This document discusses infrared spectroscopy and its use in analyzing organic compounds. It explains that IR spectroscopy works by detecting the absorption of infrared radiation by the bonds in a molecule during vibrational motions. Only bonds with a changing dipole moment, like asymmetric stretches, will be IR active. The document outlines the basic procedure for analyzing liquid, solid, and gas samples by IR spectroscopy. It notes some limitations, such as an inability to determine full molecular structures. Finally, it discusses how IR spectroscopy can be used to identify functional groups and monitor air pollutants through their characteristic absorption peaks.

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200 views9 pages

Infrared Spectroscopy Notes

This document discusses infrared spectroscopy and its use in analyzing organic compounds. It explains that IR spectroscopy works by detecting the absorption of infrared radiation by the bonds in a molecule during vibrational motions. Only bonds with a changing dipole moment, like asymmetric stretches, will be IR active. The document outlines the basic procedure for analyzing liquid, solid, and gas samples by IR spectroscopy. It notes some limitations, such as an inability to determine full molecular structures. Finally, it discusses how IR spectroscopy can be used to identify functional groups and monitor air pollutants through their characteristic absorption peaks.

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Makeeda
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Form 6 Chemistry

Infrared Spectroscopy

At the end of this lesson, you should know:


● Explain the origin of absorption in IR spectroscopy
● Describe the basic steps involved in analyzing samples by IR spectroscopy
● Comment on the limitation associated with the use of IR Spectroscopy
● Deduce the functional groups present in organic compounds from IR spectra
● Cite examples of the use of IR spectroscopy in the monitoring of air pollution

The origin of absorption in IR spectroscopy


All the atoms in molecules are in continuous vibration with respect to each other, as their bonds
stretch and bend. Since the vibrational energies within molecules are quantized, for the molecule to
absorb energy which leads to an increase in the amplitude of vibrational motions of the bonds, specific
frequencies of infrared (IR) radiation can be absorbed.
Not all bonds within a molecule absorb in the infrared region, even if the frequency of the radiation
exactly matches that of the bond vibration. Only bonds that have a dipole are capable of absorbing
infrared radiation; the frequency of the bond vibration must match the infrared frequency.
Symmetric bonds such as those in Cl2 or N2 do not show infrared absorption. IR activity must involve
vibrations that result in a change of dipole moment.
The vibrations causes changes in dipole of the molecules – asymmetric stretching vibrations generally
occur at higher frequencies (lower λ) than symmetric stretching vibrations and stretching vibrations
occur at higher frequencies than bending vibrations.

Figure 1. Bending and Stretching in SO2 molecule


Figure 2. Bending and Stretching in CO2 molecule

The scale used is wavenumber which is the number of waves per cm, i.e. the reciprocal of the
wavelength (1/λ) and quoted in cm-1.
NB. Larger wavenumbers = shorter λ values = higher energies
Wavenumbers greater than 1500cm-1 the absorption are due to the stretching modes of specific
functional groups. These can assist in determining the structure. The stretching and vibration of other
groups in the molecule give rise to a complex of series of absorption bands at wavenumbers below
1500cm-1, these occur at positions that are characteristic of the entire molecule. This is called
fingerprint region. Like human fingerprint, the pattern in this region is unique for each molecule, and
this can be used to confirm the identity of the molecule (at level this region is not analyzed).

The basic steps involved in analyzing samples by IR spectroscopy


Samples for investigation by infrared spectroscopy may be gases, liquids or solids.
For Liquids
● Place a drop of the compound between two plates of sodium chloride (ideal because NaCl is
transparent to infrared radiation) (the arrangement being supported in the beam)
● Place the salt plates and sample in the machine
● Record reading
For Solids
● Grind the solid compound with a drop of liquid hydrocarbon (Nujol), this forms a mull (Nujol
is used as it is a saturated hydrocarbon and transparent over a wide range of the IR Spectrum)
● Press/smear the mull between two sodium chloride plates
● Insert sample and sodium chloride plates in the machine
● Record reading
OR
● Mix the solid sample with powdered potassium chloride or bromide
● Compress the mixture under vacuum into a disc
● Insert disc in the beam in the machine
● Record reading

Problems associated with NaCl plates


● They are brittle and can break easily
● They are opaque below 600cm-1, and cannot be used in this range
● NaCl is hygroscopic and must be stored in a desiccator or stored above ambient temperatures
to avoid damage due to atmospheric moisture
● It cannot be used with aqueous solutions as it is water soluble, additionally, it would be soluble
in other polar solvents and therefore must be polished or replaced occasionally
Using water as a solvent for IR determination can:
● Damage the NaCl end walls
● Not dissolve most organic compounds
● Absorb IR radiation
● Forms hydrogen bonds with certain molecules, which can shift their absorbances

Limitations associated with the use of IR Spectroscopy


IR spectroscopy is a useful technique for providing some information about the structure of organic
molecules. However, IR spectroscopy does not provide sufficient details for it to be used alone in
determine the structure of compounds. The goal of IR spectroscopic analysis is to determine the
chemical functional groups in the sample. Other techniques must be used with IR spectroscopy for
structure determination.

Examples of the use of IR spectroscopy in monitoring of air pollutants


This method is sensitive, rapid and highly specific for a variety of compounds.
● Monitoring air pollution – it can be used to detect and analyzed air pollutants that absorb IR
radiation e.g. carbon monoxide and sulphur dioxide.
● Forensic science
● Breathalyzer test or intoximeter
● Laboratory identification or organic compounds
● Identification of functional groups
● Analysis of petroleum hydrocarbons
Deducing functional groups present in organic compounds from IR spectra
An IR spectrum consists of peaks that are associated with a particular molecular vibration or
combination of vibrations, and the complexity of the spectrum shows the number of possible IR-active
vibrations, which is dependent on the complexity of the molecule. Absorption due to certain bonds
occur in the same general region of the spectrum irrespective of the structure of the rest of the
molecule. This enables different functional groups within a molecule to be identified – the strength of
absorption, the shape of the peak and the position of the absorption aid in identification of the
molecule. Slight shifts in absorption occur in similar species because of changing environments.
The data booklet in the syllabus (which is given in exam) has a list of characteristic infrared
absorptions.
Example of IR spectrum

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