Infrared spectroscopy

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Infrared spectroscopy[1] (IR spectroscopy) is the subset of spectroscopy that deals with the infrared region of the electromagnetic spectrum. It covers a range of techniques, the most common being a form of absorption spectroscopy. As with all spectroscopic techniques, it can be used to identify compounds or investigate sample composition. Infrared spectroscopy correlation tables are tabulated in the literature.

Background and Theory

The infrared portion of the electromagnetic spectrum is divided into three regions; the near-, mid- and far- infrared, named for their relation to the visible spectrum. The far-infrared, approximately 400-10 cm-1 (1000–30 μm), lying adjacent to the microwave region, has low energy and may be used for rotational spectroscopy. The mid-infrared, approximately 4000-400 cm-1 (30–1.4 μm) may be used to study the fundamental vibrations and associated rotational-vibrational structure. The higher energy near-IR, approximately 14000-4000 cm-1 (1.4–0.8 μm) can excite overtone or harmonic vibrations. The names and classifications of these subregions are merely conventions. They are neither strict divisions nor based on exact molecular or electromagnetic properties.

Infrared spectroscopy exploits the fact that molecules have specific frequencies at which they rotate or vibrate corresponding to discrete energy levels (vibrational modes). These resonant frequencies are determined by the shape of the molecular potential energy surfaces, the masses of the atoms and, by the associated vibronic coupling. In order for a vibrational mode in a molecule to be IR active, it must be associated with changes in the permanent dipole. In particular, in the Born-Oppenheimer and harmonic approximations, i.e. when the molecular Hamiltonian corresponding to the electronic ground state can be approximated by a harmonic oscillator in the neighborhood of the equilibrium molecular geometry, the resonant frequencies are determined by the normal modes corresponding to the molecular electronic ground state potential energy surface. Nevertheless, the resonant frequencies can be in a first approach related to the strength of the bond, and the mass of the atoms at either end of it. Thus, the frequency of the vibrations can be associated with a particular bond type.

Simple diatomic molecules have only one bond, which may stretch. More complex molecules have many bonds, and vibrations can be conjugated, leading to infrared absorptions at characteristic frequencies that may be related to chemical groups. For example, the atoms in a CH2 group, commonly found in organic compounds can vibrate in six different ways: symmetrical and antisymmetrical stretching, scissoring, rocking, wagging and twisting (see [1]).

The infrared spectrum of a sample is collected by passing a beam of infrared light through the sample. Examination of the transmitted light reveals how much energy was absorbed at each wavelength. This can be done with a monochromatic beam, which changes in wavelength over time, or by using a Fourier transform instrument to measure all wavelengths at once. From this, a transmittance or absorbance spectrum can be produced, showing at which IR wavelengths the sample absorbs. Analysis of these absorption characteristics reveals details about the molecular structure of the sample.

This technique works almost exclusively on samples with covalent bonds. Simple spectra are obtained from samples with few IR active bonds and high levels of purity. More complex molecular structures lead to more absorption bands and more complex spectra. The technique has been used for the characterization of very complex mixtures.

Sample preparation

Gaseous samples require little preparation beyond purification, but a sample cell with a long pathlength (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 micron) 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.

Typical method

Typical apparatus

A beam of infrared light is produced and split into two separate beams. One is passed through the sample, the other passed through a reference which is often the substance the sample is dissolved in. The beams are both reflected back towards a detector, however first they pass through a splitter which quickly alternates which of the two beams enters the detector. The two signals are then compared and a printout is obtained.

A reference is used for two reasons:

  • This prevents fluctuations in the output of the source affecting the data
  • This allows the effects of the solvent to be cancelled out (the reference is usually a pure form of the solvent the sample is in)

Summary of absorptions of bonds in organic molecules

IR summary version 2.jpg

Wavenumbers listed in cm-1.

Uses and applications

Infrared spectroscopy is widely used in both research and industry as a simple and reliable technique for measurement, quality control and dynamic measurement. It is of especial use in forensic analysis in both criminal and civil cases, enabling identification of polymer degradation for example. It is perhaps the most widely used method of applied spectroscopy.

The instruments are now small, and can be transported, even for use in field trials. With increasing technology in computer filtering and manipulation of the results, samples in solution can now be measured accurately (water produces a broad absorbance across the range of interest, and thus renders the spectra unreadable without this computer treatment). Some machines will also automatically tell you what substance is being measured from a store of thousands of reference spectra held in storage.

By measuring at a specific frequency over time, changes in the character or quantity of a particular bond can be measured. This is especially useful in measuring the degree of polymerization in polymer manufacture. Modern research machines can take infrared measurements across the whole range of interest as frequently as 32 times a second. This can be done whilst simultaneous measurements are made using other techniques. This makes the observations of chemical reactions and processes quicker and more accurate.

Techniques have been developed to assess the quality of tea-leaves using infrared spectroscopy. This will mean that highly trained experts (also called 'noses') can be used more sparingly, at a significant cost saving.[2]

Infrared spectroscopy has been highly successful for applications in both organic and inorganic chemistry. Infrared spectroscopy has also been successfully utilized in the field of semiconductor microelectronics[3]: for example, infrared spectroscopy can be applied to semiconductors like silicon, gallium arsenide, gallium nitride, zinc selenide, amorphous silicon, silicon nitride, etc.

See also


  1. Wikipedia contributors. Infrared spectroscopy [Internet]. Wikipedia, The Free Encyclopedia; 2008 Sep 29, 01:44 UTC [cited 2008 Oct 2]. Available from:
  2. Luypaert, J.; Zhang, M.H. & Massart, D.L. (2003), "Feasibility study for the use of near infrared spectroscopy in the qualitative and quantitative analysis of green tea, Camellia sinensis (L.)", Analytica Chimica Acta, 478(2), Elsevier, pp. 303–312 
  3. Lau, W.S. (1999). Infrared characterization for microelectronics. World Scientific. 

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